Method for processing silver halide photosensitive materials including the replenishing of washing water having a controlled amount of calcium and magnesium compounds

In a method for processing silver halide photosensitive materials comprising developing an exposed silver halide photosensitive material, fixing the developed material and washing it with a washing water, the amount of calcium and magnesium compounds present in the replenishing washing water is reduced to not more than 5 mg/l on the basis of the weight of elemental calcium or magnesium and washing water is replenished in an amount of 1 to 50 times the volume of liquid carried over by the photosensitive material from a bath preceding the washing bath per unit area thereof or that the replenishing washing water is introduced into a washing bath after reducing the amount of calcium and magnesium compounds to the range mentioned above and sterilizing the same. The method makes it possible to substantially reduce the amount of washing water while reliably suppressing turbidity and proliferation of microorganisms in the washing water during and after completion of processing.

BACKGROUND OF THE INVENTION 
(1) Field of the Invention 
The present invention relates to a method for processing silver halide 
(color) photosensitive materials, in particular to a processing method 
which makes it possible to suppress turbidity due to the proliferation of 
bacteria and propagation of mold in a washing bath even when the 
processing is continuously conducted while substantially saving the amount 
of washing water and which provides an excellent processed photosensitive 
material. Moreover, the present invention also relates to an apparatus for 
effectively conducting such a processing method. 
(2) Prior Art 
Recently, it has been proposed to reduce the amount of washing water used 
in water washing and other processes for processing silver halide 
photosensitive materials, in view of environmental protection, exhaustion 
of water resources and enhanced economy. For example, one of such 
techniques for reducing the amount of washing water is proposed by S. R. 
Goldwasser in his article entitled "Water Flow Rates in Immersion-Washing 
of Motion Picture Film", Journal of the Society of Motion Picture and 
Television Engineers, 64, 248-253 (1955) in which saving of the amount of 
washing water is achieved by employing a multistage washing system 
including the use of a plurality of washing tanks and countercurrently 
passing water therethrough. Likewise, U.S. Pat. No. 4,336,324 discloses 
another method comprising directly transferring bleached and fixed 
photosensitive materials to stabilization process without substantially 
passing them through washing process to save the amount of washing water. 
These methods have been adopted in different kinds of automatic processor 
as an effective means for water-saving. 
However, if the water-saving is effected without implementing any other 
means, the retention time of water in a washing bath is substantially 
increased, which results in the proliferation of bacteria and in turn 
causes the formation of suspended matters and the increase in turbidity of 
washing water. Moreover, various molds are liable to proliferate. 
The proliferation of bacteria and molds lower the quality of processed 
(color) photosensitive materials (hereunder simply referred to as 
"photosensitive material(s)", because the bacteria and molds deposit on 
the photosensitive materials. In addition, there remains an inevitable 
problem that mold and/or bacteria severely proliferate on the materials 
processed under such conditions during storage. Besides these problems, 
the proliferation of such microorganisms causes problems such that a 
circulating pumps and filters provided such baths as the washing and 
stabilizing baths become clogged within a very short time and that the 
water becomes rotten and give out a bad smell. 
In order to solve such problems, many attempts have been made, for example, 
Japanese Patent Un-examined Publication No. 57-8542 proposes a method 
which comprises adding an antibacterial or antifungus agent such as 
isothiazolone type agents, benzoisothiazolone type agents to the washing 
bath and/or stabilizing bath. 
The addition of such an antibacterial or antifungus agent is effective to 
solve the foregoing problems. However, the presence thereof in these baths 
may impair the safety of the working environment since they are heated in 
the drying process subsequent to the washing process and evaporate into 
the ambient atmosphere. Therefore, an extra investment is required for 
installing an exhaust system or the like. Furthermore, under the high 
temperature conditions which are likely to occur during summer which is 
quite favorable to the proliferation of bacteria and mold, the 
effectiveness of these antibacterial and/or antifungus agents to suppress 
the proliferation thereof is incomplete. In particular, if an automatic 
processor is stopped for a long time, for example, more than 2 days under 
such a high temperature condition favorable to the proliferation of 
microorganisms, conveying the liquid surfaces by floating bacteria and/or 
mold (hereunder referred to as "a bacterial floating matter") is not 
completely prevented. This bacterial floating matter formed while the 
automatic processor is stopped tends to adhere to the photosensitive 
materials if they are brought into contact with the film by, for instance, 
passing them through the washing bath or by again starting the automatic 
processor, which results., in additional serious troubles. Therefore, it 
is usually required to add antibacterial agents even when the automatic 
processor is out of operation in order to suppress the proliferation of 
bacteria and/or mold or the formation of bacterial floating matter, or 
prior to restarting the automatic processor any treatments such as the 
disposal of the water in the baths are required. Moreover, the use of 
these antibacterial agents causes side effects such that they make the 
processed photosensitive materials quite sticky and these materials are 
liable to adhere to one another or to other materials. Thus, there has not 
yet been proposed a processing method for silver halide photosensitive 
material, which can completely eliminate the foregoing problems 
SUMMARY OF THE INVENTION 
Under such circumstances, the inventors of this invention have conducted 
studies to eliminate aforementioned drawbacks associated with the 
conventional processing methods for silver halide photosensitive materials 
and to develop a new processing method which permits the complete 
elimination of such disadvantages and the substantial saving of the amount 
of washing water. 
Accordingly, it is a principal object of this invention to provide a method 
for processing silver halide photosensitive materials which makes it 
possible to possitively suppress the proliferation of bacteria and mold in 
washing baths while substantially saving the amount of washing water. 
Another object of the present invention is to provide a processing method 
in which the proliferation of bacteria and mold is suppress without using 
any antibacterial or antifungus agents. 
Another object of this invention is to provide a processing method which 
permits the suppression of proliferation of microorganisms on the 
processed photosensitive materials even if the amount of washing water is 
remarkably reduced. 
Another object of the present invention is to provide a processing method 
having a maintenance-free water washing step. 
Another object of the present invention is to provide an apparatus for 
processing silver halide photosensitive materials, which permits the 
effective practice of the foregoing processing methods capable of saving 
the amount of washing water. 
These and other objects of the present invention will be clear from the 
following description. 
The inventors of the present invention found that the foregoing drawbacks 
of the conventional method for processing silver halide photosensitive 
materials can effectively be eliminated by restricting the amount of 
washing water to be replenished to washing bath to a specific range and 
simultaneously limiting the amount of calcium ions and magnesium ions 
present in the washing bath to not more than a specific value The present 
invention has been completed on the basis of these findings. 
In accordance with the present invention, there is provided a method for 
processing silver halide photosensitive materials which comprises color 
developing an exposed silver halide photosensitive material, treating the 
color developed photosensitive material in a fixing process and then 
washing the photosensitive material with washing water, the method 
comprising that the washing water is replenished in an amount of 1 to 50 
times the volume of liquid carried over by the photosensitive material 
from a bath preceding the water washing bath per unit area thereof and 
that the amount of calcium and magnesium compounds present in the 
replenishing washing water are reduced to not more than 5 mg/l 
respectively on the basis of elemental calcium or magnesium (hereunder 
referred to as "first method"). 
According to another aspect of the present invention, there is provided a 
method comprising the steps of reducing the amount of calcium and 
magnesium compounds included in replenishing washing water which is to be 
used in the water washing process to not more than 5 mg/l, respectively, 
on the basis of elemental calcium or magnesium, sterilizing the 
replenishing washing water and then introducing the replenishing washing 
water in a washing bath of water washing process (hereunder referred to as 
"second method"). 
According to a further aspect of the present invention, an apparatus for 
effectively carrying out the foregoing processing methods is also provided 
and comprises a bath for carrying out (color) development process, a bath 
containing a fixing liquid and baths for water washing, wherein the 
apparatus comprises a means for reducing the amount of the content of 
calcium and magnesium compounds included in washing water which is fed to 
the final bath for water washing to not more than 5 mg/l on the basis of 
elemental clacium or magnesium.

DETAILED EXPLANATION OF THE PREFERRED EMBODIMENTS 
In the present invention, the term "water washing" means a process for 
washing out the processing liquid adhering to or absorbed by the processed 
photosensitive materials as well as components of the photosensitive 
materials which have become useless during the processing and thus is a 
process for maintaining the performance of the subsequent processing baths 
and/or assuring a variety of properties of the processed photosensitive 
materials such as shelf stability of images. Therefore, the washing 
process herein referred to includes any processes so far as the 
aforementioned purposes or effects are surely achieved even if liquids 
having any composition are used therein. 
Thus, the methods according to the present invention can be applied to any 
washing processes in a series of development processing for photosensitive 
materials, irrespective of the washing process being an intermediate 
washing, a final washing or the like. 
The first method of this invention will be explained in detail In this 
method, it is desirable that the water washing process comprises at least 
two washing baths, preferably 2 to 6 baths, more preferably 2 to 4 baths 
and it is also desirable to counter-currently introduce the replenishing 
washing water into the baths in an amount of 1 to 50 times, preferably 2 
to 50 times, volume of liquid carried over by the processed photosensitive 
material from a bath preceding the washing bath per unit area thereof and 
more preferably 3 to 30 times volume thereof. Moreover, in the first 
method of this invention, the amount of calcium and magnesium compounds 
included in at least washing water in the final washing bath in the 
washing process is reduced to 5 mg/l or less expressed as elemental 
calcium and magnesium respectively. It is particularly preferred to 
control the concentration of calcium and magnesium in the baths, except 
for the first washing bath, to not more than 5 mg/l, more preferably not 
more than 3 mg and most preferably 2 mg/l or less. 
The control of the amount of magnesium and calcium compounds in each 
washing bath may be accomplished by any known method For example, the 
amount thereof in the washing water (inclusive of replenishing water) can 
be reduced to not more than the above mentioned value by using an ion 
exchange technique, a technique employing zeolite and an reverse osmosis 
technique. These techniques may be used alone or in combination. 
In the ion exchange technique, various cation exchange resins may be used 
herein Preferred examples thereof are those of Na-type capable of 
exchanging Ca, Mg with Na. In addition, H-type cationic ion exchange 
resins may also be used. However, in this case, it is preferable to use 
the resin together with an OH-type anion exchange resin since the pH of 
the processed water becomes acidic when H-type one is used alone. 
In this respect, preferred ion exchange resins are strong acidic cation 
exchange resins which are mainly composed of styrene-divinylbenzene 
copolymer and have sulfonic groups as the ion exchange group. Examples of 
such an ion exchange resin include Diaion SK-1B or Diaion PK-216 
(manufactured and sold by MITSUBISHI CHEMICAL INDUSTRIES LTD.) The basic 
copolymer of these ion exchange resins preferably comprises 4 to 16% by 
weight of divinylbenzene on the basis of the total charge weight of 
monomers at the time of preparation. Moreover, preferred examples of anion 
exchange resins which may be used in combination with H-type cation 
exchange resins are strong basic anion exchange resins which mainly 
comprise styrene-divinylbenzene copolymer and have tertiary or quaternary 
ammonium groups as the ion exchange group. Concrete examples thereof 
include Diaion SA-10A or Diaion PA-418 (also, manufactured and sold by 
MITSUBISHI CHEMICAL INDUSTRIES LTD.). 
Any known methods may be employed when calcium and magnesium ions included 
in washing water are removed with these ion exchange resins. However, it 
is preferred to pass washing water to be treated through a column packed 
with such an ion exchange resin. The flow rate of the water in the column 
is in general 1 to 100 times of volumes of the resin packed therein per 
hour, preferably 5 to 50 times thereof. 
Moreover, the control of the content of calcium and magnesium compounds may 
also be effected using, instead of the ion exchange resins, a chelate 
resin such as those having aminopolycarboxylic acid salt at their 
terminals, which can capture metal ions through a chelating reaction 
The membrane for reverse osmosis installed in the apparatus therefor 
includes, for instance, membrane of cellulose acetate, membrane of 
ethylcellulose.polyacrylic acid, membrane of polyacrylonitrile, membrane 
of polyvinylene carbonate and membrane of polyether sulfone. 
The pressure for passing liquid through the membrane usually falls within 
the range of from 5 to 60 kg/cm.sup.2. However, it is sufficient to use 
the pressure of not more than 30 kg/cm.sup.2 to achieve the purposes of 
the present invention and a so-called low-pressure reverse osmotic 
apparatus drived at a pressure of 10 kg/cm.sup.2 or less is also usable in 
the present invention effectively. 
The structure of the membrane for reverse osmosis may be spiral, tubular, 
hollow fiber, pleated or rod type. 
Zeolites which may be used in the present invention are water-insoluble 
aluminum silicates represented by the following general formula: 
EQU Na(AlO.sub.2).sub.x.(SiO.sub.2).sub.y.Z(H.sub.2 O) 
In the present invention, A-type zeolites having the above general formula 
in which x is equal to y and X-type zeolites in which x is different from 
y may be used. In particular, X-type zeolites are preferred because of 
their high ion exchange capacity with respect to both calcium and 
magnesium. An example of such a zeolite includes molecular sieve LINDE 
ZB-300 (manufactured and sold by Union Carbide Corp.). Zeolites having 
different particle sizes are known However, those having a particle size 
of more than 30 mesh are preferable when packed in a column to come it 
into contact with washing water. 
Furthermore, in the first method of this invention, it is preferred to 
irradiate, with ultraviolet rays, washing water included in at least one 
bath selected from water washing baths and their auxiliary tanks, which 
permits the suppression of proliferation of mold. 
The source of ultraviolet light as used herein may be an ultraviolet lamp 
such as a low pressure mercury vapour discharge tube which emits light of 
253 7 nm in wavelength. In the present invention, preferred are those 
having a power of bactericidal ray ranging from 0.5 W to 7.5 W. 
The ultraviolet lamp may be disposed outside or inside the water to be 
irradiated. 
As already explained above, an antibacterial or antifungus agent is not 
necessarily used in the first method of the present invention However, 
they may be used in the first method depending on purposes 
These antibacterial and antifungus agents which can be used in the first 
method include, for instance, isothiazolone type antibacterial agents such 
as 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one; 
benzoisothiazolone type antibacterial agents such as 
1,2-benzoisothiazolin-3-one; triazole derivatives such as benzotriazole; 
sulfamide type antibacterial agents such as sulfanilamide; organoarsenide 
type mold control agents such as 10,10'-oxybisphenoxyarsine and those 
disclosed in "Bokin Bobaizai No Kagaku (Chemistry of antibacterial and 
mold control agents)", Hiroshi HORIGUCHI, Society of Hygienic 
Engineerings, entitled "Techniques for Sterilization, Pasteurization and 
Mold Control". 
Each of the water washing baths should be adjusted to pH 5 to 9 in the 
first method and pH of washing water supplied to these baths is preferably 
in the range of 4 to 9, more preferably from 6 to 8. 
The second method according to the present invention will now be explained 
in detail. This second method comprises the steps of reducing the amount 
of calcium and magnesium compounds included in replenishing washing water 
used in the water washing process to not more than 5 mg/l, respectively, 
on the basis of elemental calcium and magnesium, preferably to 3 mg/l or 
less and more preferably 2 mg/l and simultaneously sterilizing the 
replenishing washing water and then introducing it into a washing bath of 
water washing process. The control of the amount of calcium and magnesium 
compounds present in washing water can be achieved in the similar manner 
to that explained in connection with the first method. 
In the second method, the term "sterilizing process" means that 
microorganisms such as bacteria and mold present in water to be used as 
washing water and/or washing water to which desired components are added 
are killed, removed or decreased in number prior to circulating them 
through the water washing baths. 
The sterilization may be achieved by, for instance, adding a compound 
having antibacterial action to the replenishing water used as washing 
water or washing water containing necessary components, filtering them 
through a filter of not more than 0.8 .mu. in pore size, heating them or 
irradiating them with ultraviolet rays. However, from the view point of 
reliability in sterilizing effect and magnitude of synergistic effect with 
the reduction of the content of calcium and magnesium compounds, the 
addition of compounds having sterilizing effect and filtration with a 
filter having a pore size of 0.8 .mu. or less are preferred. 
Particularly preferred examples of the compounds having sterilizing effect 
include compounds which release active halogen atoms such as hypochlorous 
acid, dichloroisocyanuric acid, trichloroisocyanuric acid, and salts 
thereof. In addition to those listed in connection with the first method, 
examples thereof further include compounds which release silver ions such 
as silver nitrate, silver chloride, silver oxide or the like. 
Among them, compounds which release active halogen atoms or silver ions are 
preferred since they provide a high synergistic effect with the reduction 
of the amount of calcium and magnesium compounds. Concrete examples 
thereof are as follows: 
COMPOUNDS RELEASING ACTIVE HALOGEN ATOMS 
1. sodium hypochlorite; 
2. sodium dichloroisocyanurate; 
3. trichloroisocyanuric acid; 
4. chloramine T; 
5. chloramine B; 
6. dichlorodimethylhydantoin; 
7. 2-bromo-4'-hydroxyacetophenone; 
8. 1,4-bisbromoacetoxy-2-butene; 
COMPOUNDS RELEASING SILVER IONS 
9. silver nitrate; 
10. silver chloride; 
11. silver bromide; 
12. silver fluoride; 
13. silver perchlorate; 
14. silver chlorate; 
15. silver acetate; 
16. silver sulfate; 
17. silver carbonate; 
18. silver phosphate; 
19. silver sulfite; 
20. silver silicate; 
21. silver bromate; 
22. silver nitrite 
23. silver iodate 
24. silver lactate 
Among these, preferred are sodium hypochlorite, sodium 
dichloroisocyanurate, trichloroisocyanuric acid. Sodium hypochlorite is 
added to the washing water in the form of 5 to 15 % alkaline aqueous 
solution. Sodium dichloroisocyanurate and trichloroisocyanuric acid are 
commercially available in different form such as powder, granules, tablet 
or the like and they may be used depending on the intended purposes. 
Examples of such compounds commercially available include High Light Ace 
G, High Light 60G, High Light Clean or the like which are manufactured and 
sold by Nissan Chemical Industries, Ltd. 
In view of the sterilization effect, these compounds having sterilizing 
action are used in an amount as much as possible, however, there are 
preferably used in an amount as low as possible since by the use of a 
large excess of such compound, the properties of the treated 
photosensitive materials are largely impaired. Therefore, the compounds 
releasing active halogen atoms are preferably used in an amount of 0.1 to 
100 mg per one liter of washing water on the basis of pure compounds, more 
preferably from 1 to 50 mg/l and most preferably from 3 to 30 mg/l. While 
in the case of the compounds releasing silver ions, the amount of the 
compounds is adjusted so that the concentration of silver ions in the 
washing water to be treated falls within the range of 0.005 to 10 mg per 
one liter of washing water and more preferably 0.02 to 1 mg/l. In these 
respects, it is noted that these compounds should be added to the 
replenishing washing water prior to replenishing the same to a washing 
bath. This is because, if the compounds is added to the replenishing water 
after the introduction thereof into the bath i.e., it is added to the 
water contained in the washing bath, these compounds are possibly 
deactivated by the action of components carried over from a bath preceding 
thereto and thus present in the washing bath, for example, reducing agents 
such as thiosulfates, sulfites; oxidizing agents such as 
ethylenediaminetetraacetate-iron (III) complex as well as the components 
dissolved from the photosensitive materials, for instance, silver salts, 
gelatin or the like in the case of the compounds releasing active halogen 
atoms, while in the case of the compounds releasing silver ions, the 
silver ions are converted to silver thiosulfate and as a result they lose 
sterilizing effect. Thus, the addition thereof to the replenishing water 
prior to introducing it to washing bath is critical condition in the 
second method. 
The addition of these compounds having sterilizing effect may be carried 
out by, for example, directly adding to the replenishing washing water 
stored in an auxiliary tank, in the form of powder, tablet, granules or 
the like or adding it to the replenishing water after dissolving it in an 
additional water. Moreover, they may gradually be dissolved by bringing 
them in a solid form packed in a proper container into contact with the 
replenishing washing water. Sodium hypochlorite and Silver nitrate are 
commercially available in the form of solution and, therefore, in such 
case they may be added to the replenishing water as they are or after 
diluting it with a suitable amount of water. 
According to the second method, the sterilization of the replenishing 
washing water is also effected by filtering the same through a filter of 
0.8 .mu.m or less in pore size. The filter used herein should have a pore 
size of not more than 0.8 .mu. in order to assure the elimination of 
microorganisms such as bacteria and mold possibly present in the 
replenishing water, preferably not more than 0.5 .mu. and most preferably 
0.3 .mu. or less. Materials of such filters include, for instance, 
cellulose acetate, ethyl cellulose, polyacrylic acid, polyacrylonitrile 
and polyvinylene carbonate and from the viewpoint of durability cellulose 
acetate such as triacetyl cellulose is preferred among others Examples of 
such filters are those manufactured and sold under the trade name of Fuji 
Microfilter FCE-80W, FCE-45W, FCE-22W cartridges by Fuji Photo Film Co., 
Ltd Microorganisms such as bacteria and mold can effectively be filtered 
off by passing the replenishing water through one of these filters. 
In the second method, microorganisms such as bacteria and mold must not 
completely be removed from the replenishing water by the sterilizing 
treatment. The effect of the present invention can be expected if the 
number of living bacteria present in the treated replenishing washing 
water is not more than 10.sup.3 and preferably 10.sup.2 or less. This is 
one of important results of the synergistic effect with the control of the 
content of calcium and magnesium compounds in the replenishing washing 
water. 
In other words, the inventors have found that if the content thereof is 
reduced to at most 5 mg/l, the proliferation of bacteria and mold in the 
water washing bath is extremely suppressed and as a result different 
troubles accompanied by the formation of bacterial floating matter can 
effectively be eliminated even when an automatic processor is stopped over 
a long period of time as referred to before. Moreover, even if the 
replenishing washing water is stored in a replenishing tank over a long 
term, the putrefaction of the replenishing water never takes place during 
storage thereof. 
In the second method of this invention, the processing for reducing the 
content of calcium and magnesium compounds and for sterilization of the 
replenishing liquid may be carried out in any order, however, it is 
preferred to carry out the reduction of calcium and magnesium content and 
then the sterilization treatment, for the purpose of preventing the 
replenishing water from any contamination possibly caused after the 
sterilization processing. 
The second method of the present invention may widely be applied to water 
washing processes for silver halide photosensitive materials, in 
particular to water washing processes in which the amount of replenishing 
water is largely reduced for the purpose of saving water. For example, it 
is preferred to apply the method to water washing processes to which the 
processed photosensitive materials convey a volume of the lqiuid from the 
bath preceding to the water washing bath and the replenishing water is 
added in an amount 1 to 50 times of volume of that carried over by the 
photosensitive material (per unit area thereof) from the preceding bath. 
The second method is most preferably applied when the washing bath is 
disposed subsequent to a bath having fixing ability and the amount of the 
replenishing water is 1 to 50 times of that carried over from the bath of 
fixing ability. In this case, the replenishing water is preferably 
supplied in an amount of 2 to 50 times, more preferably 3 to 30 times 
thereof and most preferably 5 to 20 times thereof. 
In the water washing process of the second method, the pH of the washing 
water is not critical, however, it is usually adjusted to 3 to 10 and 
preferably 4 to 9. 
To the washing water as used in the aforementioned methods of the present 
invention, there may be added different kinds of compounds according to 
need, although it is preferred not to use additives other than 
antibacterial or antifungus agents (in the case of the second method). 
However, it is also favorable to use chelating agents such as 
ethylenediaminetetraacetic acid which serve to suppress the putrefaction 
of waters such as hard and soft water in water washing baths; metal ions 
such as copper ions which enhance the mold control action or the like. 
The term "stabilizing solution" as used herein means solutions capable of 
achieving an effect of image stabilization which cannot be attained by 
simply washing photosensitive materials with water as explained above and 
an example thereof is a stabilizing solution containing formaline as an 
image stabilizing agent. 
In most of cases, such stabilizing solution is in general used in the final 
processing stage. In such cases, for the purpose of preventing the 
formation of drying marks, various kinds of surfactants such as nonionic 
surfactants are added to the stabilizing solution as an agent for water 
drainage. Moreover, it is also possible to use a chelating agent such as 
those listed below and salts thereof, for instance, sodium, potassium and 
ammonium salts to prohibit the decomposition of formaline by 
microorganisms present therein. 
##STR1## 
These amionocarboxylic acids, aminophosphonic acids, phosphonic acids, 
phosphonocarboxylic acids and salts thereof are in general used in an 
amount of 5.times.10.sup.-5 to 1.times.10.sup.-2 moles/l and preferably 
1.times.10.sup.-4 to 5.times.10.sup.-3 moles/l. 
According to a preferred embodiment of the present invention, the following 
isothiazoline type compounds may be added to the stabilizing solution as 
the sterilizing agent. 
(1) 2-methyl-4-isothiazolin-3-one; 
(2) 5-chloro-2-methyl-4-isothiazolin-3-one; 
(3) 2-methyl-5-phenyl-4-isothiazolin-3-one; 
(4) 4-bromo-5-chloro-2-methyl-4-isothiazolin-3-one; 
(5) 2-hydroxymethyl-4-isothiazolin-3-one; 
(6) 2-(2-ethoxyethyl)-4-isothiazolin-3-one; 
(7) 2-(N-methylcarbamoyl)-4-isothiazolin-3-one; 
(8) 5-bromomethyl-3-(N-dichlorophonylcarbamoyl)-4-isothiazolin-3-one; 
(9) 5-chloro-2-(2-phenylethyl)-4-isothiazolin-3-one; 
(10) 4-methyl-2-(3,4-dichlorophenyl)-4-isothiazolin-3-one. 
The compounds listed above is employed in an amount of 1 to 100 mg/l and 
preferably 3 to 30 mg/l in the stabilizing solution. 
In addition to the aforementioned compounds, the stabilizing solution may 
include other different compounds, for instance, a variety of buffering 
agents for adjusting pH thereof, such as borate, metaborate, borax, 
phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous 
ammonia, monocarboxylic acids, dicarboxylic acids, and polycarboxylic 
acids which are used in a proper combination. 
Furthermore, there may be added a various kind of ammonium salts as an 
agent for adjusting pH of emulsion layer of the photographic material 
after processing, which include, for instance, ammonium chloride, ammonium 
nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite and 
ammonium thiosulfate. 
The methods according to the present invention as explained above may 
effectively be carried out using an apparatus for processing silver halide 
photosensitive materials, which is also an aspect of this invention. A 
preferred embodiment of such an apparatus is shown in FIG. 1. 
As seen from FIG. 1, the apparatus of the present invention mainly 
comprises a bath L.sub.1 for color developemnt, a bath L.sub.2 for 
bleaching and fixing, a first water washing bath T.sub.1, a second water 
washing bath T.sub.2, a third water washing bath T.sub.3, devices UV.sub.1 
and UV.sub.2 for emitting ultraviolet rays, a column packed with an ion 
exchange resin IC, an auxiliary tank A and a pump P. Moreover, it is 
preferred to use a device which comprises an ultraviolet lamp UV connected 
to a power supply code 1, a tube 2 for containing the ultraviolet lamp UV 
and a water resistant cover 3 of rubber as shown in FIG. 2. When the 
device for irradiating the washing water with ultraviolet light is used, 
the washing water is introduced into the container tube 2 through an inlet 
4 and then delivered from an outlet 5 after being irradiated with 
ultraviolet rays therein. In addition, the ion exchange resin IC is 
preferably in the form capable of being automatically replaced with new 
one. 
Apparatuses shown in FIGS. 3 to 6 may also be used in the processing 
methods of the present invention and the same effect as set forth above 
can be expected. In these FIGS. 3 to 6, the reference letters RP and K 
represent an apparatus for reverse osmosis and a cascade exhaust pipe 
respectively and other members are the same as those shown in FIG. 1. 
The processing time of the water washing process in the methods according 
to the present invention is in general in the range of 20 seconds to 3 
minutes, preferably 30 seconds to 2 minutes and the processing is carried 
out at a temperature of 20.degree. to 40.degree. C. and preferably 
30.degree. to 38.degree. C. 
The processing methods according to the present invention can be applied to 
a variety of processes for processing silver halide photosensitive 
materials. The processing methods of the invention with hereunder be 
explained in more detail mainly in connection with the processing method 
for silver halide color photosensitive material, however, it is a matter 
of course that the methods can be applied to processing silver halide 
photosensitive material other than color photosensitive materials. 
The processes for silver halide color photosensitive materials to which the 
methods of this invention can be applied are, for example, as follows: 
A. color development--bleaching and fixing--water washing--drying; 
B. color development--water washing--bleaching and fixing--water 
washing--drying; 
C. color development--bleaching--fixing--water washing--drying; 
D. color development--bleaching--bleaching and fixing--water 
washing--drying; 
E. color development--bleaching--bleaching and fixing--water 
washing--drying; 
F. color development--fixing--bleaching and fixing--water washing--drying; 
G. color development--bleaching--water washing--fixing--water 
washing--stabilization--drying; 
H. color development--bleaching--fixing--water 
washing--stabilization--drying; 
I. color development--bleaching--bleaching and fixing--water 
washing--stabilization--drying; 
J. color development--bleaching and fixing--water 
washing--stabilization--drying; 
K. color development--fixing--bleaching and fixing--water 
washing--stabilization--drying. 
Each of the processing baths will now be explained below. 
COLOR DEVELOPING SOLUTION 
A color developing solution used for the development of the photosensitive 
materials of the present invention is preferably an aqueous alkaline 
solution containing an aromatic primary amine type color developing agent 
as a main component. Although, aminophenolic compounds are useful as the 
color developing agent, p-phenylenediamine type compounds are preferred. 
As examples of the latter, there can be included 
3-methyl-4-amino-N,N-diethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-methanesulfonamidoethylaniline, 
4-amino-3-methyl-N-ethyl-N-.beta.-methoxyethylaniline or sulfate, 
hydrochloride, phosphate, p-toluenesulfonate, tetraphenylborate and 
p-(t-octyl)benzensulfonate thereof. These diamines are generally more 
stable in a salt state than in a free state and, therefore, the salts are 
preferably used. 
Examples of the aminophenol type derivatives are o-aminophenol, 
p-aminophenol, 4-amino-2-methylphenol, 2-amino-3-methylphenol, 
2-oxy-3-amino-1, 4-dimethylbenzene. 
In addition, those described in L. F. A. Mason "Photographic Processing 
Chemistry", Focal Press (1966), pp 26 to 229, U.S. Pat. Nos. 2,193,015 and 
2,592,364 and Japanese Patent Un-examined Publication No. 48-64933 may be 
used. 
These color developing agents may be used in combination if necessary. 
A color developing solution generally contains a pH buffering agent such as 
carbonate, borate and phosphate of alkali metals; a development restrainer 
or antifoggant such as bromide, iodide, benzimidazols, benzthiazols and 
mercapto compounds; a preservative such as hydroxylamine, diethyl 
hydroxylamine, triethanolamine, compounds described in DEOS No. 2622950, 
sulfite and hydrogen sulfite; an organic solvent such as ethylene glycol; 
a development accelerator such as benzylalcohol, polyethylene glycol, 
quaternary ammonium salts, amines, thiocyanate and 
3,6-thiaoctane-1,8-diol; a dye-forming coupler; a competing coupler; a 
nucleus forming agent such as sodium borohydride; an auxiliary developing 
agent such as 1-phenyl-3-pyrazolidone; a thickener; a chelating agent such 
as ethylenediaminetetraacetic acid, nitrirotriacetic acid, 
cyclohexanediaminetetraacetic acid, iminodiacetic acid, 
N-hydroxymethylethylenediaminetriacetic acid, 
diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 
aminopolycarboxylic acids as described in Japanese Patent Unexamined 
Publication No. 58-195845, 1-hydroxyethylidene-1,1'-diphosphonic acid, 
organic phosphonic acids as described in Research Disclosure 18170 (May, 
1979), amino phosphonic acids such as aminotris (methylenephosphonic acid) 
and ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, and 
phosphonocarboxylic acids as described in Japanese Patent Unexamined 
Publications Nos. 52-102726, 53-42730, 54-121127, 55-4024, 55-4025, 
55-126241, 55-65955 and 55-65956, and Research Disclosure 18170 (May, 
1979). 
The color developing agent is generally used in an amount of about 0.1 to 
about 30 g, preferably about 1 to about 15 g per liter of a color 
developing solution. The pH of the color developing solution is generally 
7 or higher and most generally about 9 to about 13. Further, it is 
possible to use an auxiliary solution, in which the concentrations of 
halides, a color developing agent and the like are adjusted, so as to 
decrease the amount of a replenisher for the color developing bath. 
In the methods of this invention, it is preferred that the color developing 
solution is substantially free from benzyl alcohol listed above as an 
example of development accelerator In this respect, the term 
"substantially free from" means that benzyl alcohol is present in the 
color developing solution in an amount of 2 ml or less per liter of the 
latter, preferably 0.5 ml or less and most preferably zero. If benzyl 
alcohol is not included in the color developing solution, a more excellent 
effect is attained. 
The processing temperature in the color developing solution preferably 
ranges from 20.degree. to 50.degree. C. and more preferably from 
30.degree. to 40.degree. C. The processing time is preferably in the range 
of from 20 seconds to 10 minutes and more preferably from 30 seconds to 5 
minutes. 
BLEACHING, BLEACHING-FIXING AND FIXING LIQUIDS 
The photographic emulsion layers after the color development are usually 
subjected to a bleaching process. The bleaching may be carried out at the 
same time with a fixing treatment, as called bleaching-fixing, or may be 
carried out separately In the bleaching-fixing process, a counterflow 
supplement method may be used wherein two or more baths are present and 
the bleaching-fixing solution is fed to the later bath and a overflow 
liquid of the later bath is introduced in the former bath. 
An example of bleaching agent used in the bleaching liquid or the 
bleaching-fixing liquid in the present invention is a ferric ion complex 
which is a complex of ferric ion with a chelating agent such as 
aminopolycarboxylic acid, aminopolyphosphonic acid or salts thereof. The 
aminopolycarboxylic acid salts or aminopolyphosphonic acid salts are an 
alkali metal salt, ammonium salt or water-soluble amine salt of 
aminopolycarboxylic acid or aminopolyphosphonic acid. The alkali metal is, 
for instance, sodium, potassium and lithium and examles of the 
water-soluble amines are alkyl amines such as methylamine, diethylamine, 
triethylamine and butylamine; alicyclic amines such as cyclohexylamine; 
arylamines such as aniline, m-toluidine; heterocyclic amines such as 
pyridine, morpholine and piperidine. 
Typical examples of the chelating agents such as aminopolycarboxylic acid, 
aminopolyphosphonic acid and salts thereof are as follows, however, it 
should be appreciated that the invention is not limited to the following 
specific examples: 
Ethylenediaminetetraacetic acid; 
Disodium ethylenediaminetetraacetate; 
Diammonium ethylenediaminetetraacetate; 
Tetra(trimethylammonium) ethylenediaminetetraacetate; 
Tetrapotassium ethylenediaminetetraacetate; 
Tetrasodium ethylenediaminetetraacetate; 
Trisodium ethylenediaminetetraacetate; 
Diethylenetriaminepentaacetic acid; 
Pentasodium diethylenetriaminepentaacetate; 
Ethylenediamine-N-(.beta.-oxyethyl)-N,N',N'-triacetic acid; 
Trisodium ethylenediamine-N-(.beta.-oxyethyl)-N,N',N'-triacetate; 
Triammonium ethylenediamine-N-(.beta.-oxyethyl)-N,N',N'-triacetate; 
1,2-Diaminopropanetetraacetic acid; 
Disodium 1,2-diaminopropanetetraacetate; 
1,3-Diaminopropanetetraacetic acid; 
Diammonium 1,3-diaminopropanetetraacetate; 
Nitrilotriacetic acid; 
Trisodium nitrilotriacetate; 
Cyclohexanediaminetetraacetic acid; 
Disodium cyclohexanediaminetetraacetic acid; 
Iminodiacetic acid; 
Dihydroxyethylglycine; 
Ethyl ether diaminetetraacetic acid; 
Glycol ether diaminetetraacetic acid; 
Ethylenediaminetetrapropionic acid; 
Phenylenediaminetetraacetic acid; 
1,3-diaminepropanol-N,N,N'-N'-tetramethylenephosphonic acid; 
Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid; 
1,3-propylenediamine-N,N,N',N'-tetramethylenephosphonic acid. 
The ferric ion complex salt may be used in a form of one or more complex 
salt previously prepared or may be formed in a solution using a ferric 
salt, such as ferric sulfate, ferric chloride, ferric nitrate, ferric 
ammonium sulfate and ferric phosphate, and a chelating agent such as 
aminopolycarboxylic acid, aminopolyphosphonic acid and phosphonocarboxylic 
acid. When the complex salt is formed in a solution, one or more ferric 
salts may be used, and one or more chelating agents may also be used. In 
eitehr case of the previously prepared complex salt or the in situ formed 
one, the chelating agent may be used in an excess amount greater than that 
required to form the desired ferric ion salt. Among iron complexes, 
preferred is a complex of ferric ion with aminopolycarboxylic acid and the 
amount thereof used is in the range of 0.1 to 1 mole/l, preferably 0.2 to 
0.4 moles/l in the case of bleaching liquid for photographic color 
photosensitive materials such as color negative films. On the other hand, 
the compound is used in an amount of 0.05 to 0.5 moles/l, preferably 0.1 
to 0.3 moles/l in the bleaching-fixing liquid therefor. Moreover, it is 
used in an amount of 0.03 to 0.3 moles/l, preferably 0.05 to 0.2 moles/l 
in the case of the bleaching and bleaching-fixing liquid for color 
photosensitive materials for print such as color paper. 
To the bleaching liquid and the bleaching-fixing liquid, there may be added 
a bleaching accelerator according to need. Examples of useful bleaching 
accelerators are compounds having a mercapto group or a disulfide group 
such as those disclosed in U.S. Pat. No. 3,893,858; German Patent Nos. 
1,290,812 and 2,059,988; Japanese Patent Un-examined Publication Nos. 
53-32736, 53-57831, 53-37418, 53-65732, 53-72623, 53-95630, 53-95631, 
53-104232, 53-124424, 53-141623 and 53-28426; and Research Disclosure No. 
17129 (July, 1978); thiazoline derivatives such as these disclosed in 
Japanese Patent Un-examined Publication No. 50-140129; thiourea 
derivatives such as those disclosed in Japanese Patent Publication No. 
45-8506; Japanese Patent Un-examined Publication Nos. 52-20832 and 
53-32735; and U.S. Pat. No. 3,706,561; iodides such as those disclosed in 
German Patent No. 1,127,715 and Japanese Patent Un-examined Publication 
No. 58-16235; polyethylene oxides such as those disclosed in German Patent 
Nos. 966,410 and 2,748,430; polyamine compounds such as those disclosed in 
Japanese Patent Publication No. 45-8836; as well as compounds disclosed in 
Japanese Patent Unexamined Publicaiton Nos. 49-42434, 49-59644, 53-94927, 
54-35727, 55-26506 and 58-163940; and iodine and bromine ions. From the 
viewpoint of a high acceleration effect, preferred are compounds having a 
mercapto or a disulfide group among others and in particular, those 
disclosed in U.S. Pat. No. 3,893,858, German Patent No. 1,290,812 and 
Japanese Patent Unexamined Publication No. 53-95630 are preferred. 
In the bleaching or bleaching-fixing solution as used in the present 
invention, bromides such as potassium bromide, sodium bromide and ammonium 
bromide, chlorides such as potassium chloride, sodium chloride and 
ammonium chloride, or iodides such as ammonium iodide may be contained as 
a rehaloganating agent. If necessary, one or more inorganic or organic 
acids and alkali or ammonium salts thereof having a pH buffering ability, 
such as, boric acid, borax, sodium metaborate, acetic acid, sodium 
acetate, sodium carbonate, potassium carbonate, phosphorous acid, 
phosphoric acid, sodium phosphate, citric acid, sodium citrate and 
tartaric acid, anti-corrosives such as ammonium nitrate and guanidine may 
be added. 
The fixing agent used in the fixing or bleaching-fixing liquid may be any 
conventional one, for instance, thiosulfates such as sodium thiosulfate 
and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and 
ammonium thiocyanate; thioethers or thioureas such as 
ethylenebisthioglycollic acid, 3,6-dithia-1,8-octanediol, which are 
water-soluble, silver halide-solubilizing agents. These agents may be used 
alone or in combination. Further, the special bleaching-fixing solution 
consisting of a combination of a fixing agent and a large amount of halide 
such as potassium iodide described in Japanese Patent Unexamined 
Publication No. 51-155354 may be used in the bleaching-fixing process. In 
the present invention, preferred are thiosulfates, in particular, ammonium 
thiosulfate. 
The concentration of the fixing agent in the fixing or bleaching-fixing 
treatment is preferably 0.3 to 2 moles/l. In particular, in the case of 
processing photographic color photosensitive materials, the amount thereof 
is in the range of 0.8 to 1.5 moles/l and in the case of color 
photosensitive materials for print, it ranges from 0.5 to 1 mole/l. 
Generally, the pH value of the fixing or bleaching-fixing solution is 
preferably 3 to 10, more preferably 5 to 9. This is because, if pH value 
is less than the lower limit, the desilvering effect is enhanced, however, 
the liquids are impaired and the cyan dye tends to be converted to leuco 
dye, while if pH is more than the upper limit, the rate of desilvering is 
extremely lowered and there is a tendency to easily cause stains. 
In order to adjust pH, there may be added to the liquids, for example, 
hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonates, 
ammonia, caustic soda, caustic potash, sodium carbonate and potassium 
carbonate according to need. Further, various fluorescent brighteners, 
defoaming agents, surfactants, polyvinylpyrrolidone or organic solvents 
such as methanol may also be added to the bleaching-fixing liquid. 
The bleaching liquid and bleaching-fixing liquid as used herein contain a 
sulfite ion releasing compound, as the preservative, such as sulfites, for 
instance, sodium sulfite, potassium sulfite and ammonium sulfite; 
bisulfites, for instance, ammonium bisulfite, sodium bisulfite and 
potassium bisulfite; and metabisulfites, for instance, potassium 
metabisulfite, sodium metabisulfite and ammonium metabisulfite. These 
compounds are preferably present in an amount of about 0.02 to 0.5 moles/l 
expressed as sulfite ions and more preferably 0.04 to 0.40 moles/l. 
Furthermore, other preservatives such as ascorbic acid, carbonyl bisulfite 
adduct or carbonyl compounds may be used although the bisulfites are 
generally used as the preservative. 
In addition to the foregoing compounds, it is also possible to add 
buffering agents, fluorescent brighteners, chelating agents and mold 
controlling agents according to need. 
The photosensitive materials to which the foregoing processing is applied 
are, for instance, monochromatic paper, monochromataic negataive films, 
color paper or color negative films. 
First of all, in the emulsion layer of the color paper, silver 
chlorobromide having a silver bromide content of 10 mole % or more is 
preferably used. Moreover, the silver bromide content is preferably 20 
mole % or more in order to obtain an emulsion having a sufficient 
sensitivity without causing undesired increase in fogging and in 
particular when rapidity is required in color development processing the 
content of silver halide may be reduced to at most 10 mole % or at most 5 
mole %. Particularly, the use of an emulsion having a silver bromide 
content of 1 mole % or less which is almost pure silver chloride is 
preferred since it makes the color developing process more rapid. 
The photographic emulsion layer of the color negative films as used herein 
may contain any of the following silver halides: silver bromide, silver 
iodobromide, silver iodochlorobromide, silver chlorobromide and silver 
chloride. Preferred are silver iodobromide and silver iodochlorobromide 
having a silver iodide content of not more than 30 mole %. The most 
preferred are silver iodobromides having a silver iodide content of 2 to 
25 mole %. 
The silver halide grains in the photographic emulsions may be so-called 
regular grains having a regular crystal form such as cubic, octahedron or 
tetradeca-hedron. Alternatively, the grains may be of an irregular crystal 
structure such as spherical, or ones having crystal defects such as a 
twinning plane, or composite form thereof. 
Regarding a grain size of silver halide, the grains may be fine grains 
having a size of 0.1 .mu. or less, or may be large size grains having a 
diameter of the projected area of up to 10 .mu.. The photogrpahic emulsion 
may be a monodisperse one containing silver halide grains having a narrow 
grain size distribution or a polydisperse one containing grains of a broad 
size distribution. 
Photographic emulsions to be used in the present invention may be prepared 
according to, for instance, the methods described in P. Glafkides, Chimie 
et Physique Photographique, Paul Montel, 1967; G. F. Duffin, Photographic 
Emulsion Chemistry, Focal Press, 1966; and V. L. Zelikman et al, Making 
and Coating Photographic Emulsion, Focal Press, 1964. That is, any of an 
acid method, neutral method and ammoniacal method may be used. Further, a 
single-jet, simultaneous jet method or a combination thereof may be used 
for reacting a soluble silver salt with a soluble halogen salt. A method 
of forming grains in silver ion-excessive condition, i.e., so-called 
reverse jet method, may be used. As one of the simultaneous jet method, a 
method where pAg is maintained constant in a liquid phase in which silver 
halide is formed, i.e., controlled double jet method, may also be used. 
This method yields silver halide emulsion in which a crystal form is 
regular and a grain size is approximately uniform. 
It is also possible to mix at least two silver halides which have 
separately been formed. 
The aforesaid silver halide emulsion having regular grains is obtained by 
controlling pAg and pH during the formation of grains. Details are 
disclosed in, for instance, Photographic Science and Engineering, vol. 6, 
p 159 to 165 (1962), Journal of Photographic Science, vol. 12, p 242 to 
251 (1964), U.S. Pat. No. 3,655,394 and U.K. Patent No. 1,413,748. 
A typical monodisperse emulsion contains silver halide whose average grains 
size is larger than 0.1 .mu. and of which at least about 95% by weight has 
a grain size within the average grain size .+-.40%. An emulsion containing 
silver halide whose average grain size is about 0.25 to 2 .mu. and of 
which at least about 95% by weight or by number has a grain size within 
the average grain size .+-.20% may be used in the present invention. 
Methods for the preparation of such an emulsion are described in U.S. Pat. 
Nos. 3,574,628 and 3,655,394 and U.K. Patent No. 1,413,748. Further, 
monodisperse emulsions as described in Japanese Patent Un-examined 
Publication Nos. 48-8600, 51-39027, 51-83097, 53-137133, 54-48521, 
54-99419, 58-37635 and 58-49938 may preferably be used in the present 
invention. 
Use of flat grains in the silver halide photographic emulsion used in the 
invention may provide enhanced sensitivity including improvement in 
efficiency of color sensitization by sensitizing dyes, improved relation 
between sensitivity and graininess, improved sharpness, improvement in 
progress of development, improved covering power and improved cross-over. 
The flat silver halide grain as used herein has a ratio of diameter to 
thickness of 5 or more, such as more than 8 or between 5 and 8. 
The term "diameter of silver halide grain" herein used means a diameter of 
circle which has the same area as the projected area of grain. In the 
present invention, the diameter of the flat silver halide grains is 0.3 to 
5.0 .mu., preferably 0.5 to 3.0 .mu.. 
The thickness thereof is 0.4 .mu. or less, preferably 0.3 .mu. or less, 
more preferably 0.2 .mu. or less. 
Generally, a flat silver halide grain is a disk-like grain having two 
surfaces parallel to each other. Accordingly, the aforementioned 
"thickness" is expressed as the distance between the two parallel surfaces 
constituting a flat silver halide grain. 
Flat silver halide grains in which the grain size and/or thickness thereof 
are made monodisperse may be used as described in Japanese Patent 
Publicaiton No. 11386. 
Monodispersion of flat silver halide grains mentioned above means a 
dispersion system in which 95% of the grains dispersed therein has a grain 
size falling within the range of the number average grain size .+-.60%, 
preferably, .+-.40%. "Number average grain size" herein means the number 
average diameter of the projected area of silver halide grains. 
The flat silver halide grains contained in the emulsion used in the 
invention preferably account for 50% or more of the total projected area, 
more preferably 70% or more, particularly 90% or more. 
Preferred flat silver halide is comprised of silver bromide, silver 
iodobromide, silver chlorobromide, silver chloroiodobromide, silver 
chloride or silver iodochloride. Silver iodochloride is particularly 
preferred in high speed photosensitive materials. In the case of silver 
iodochloride, the content of silver iodide is usually 40 mol % or less, 
preferably 20 mol % or less, more preferably 15 mol % or less. In 
addition, silver chlorobromide and silver bromide are particularly 
preferred in the case of photosensitive materials for print. 
The flat grains may have homogeneous composition or may be composed of two 
or more phases of different halogen compositions. 
For instance, when silver iodobromide is used, flat silver iodobromide 
grains may have layered structure composed of plural phases having 
different iodide contents. For example; Japanese Patent Un-examined 
Publication Nos. 58-113928 and 59-99433 describe preferred examples of 
halide composition of flat silver halide grains and halide distribution in 
grains. Basically, relative contents of iodide included in flat silver 
halide grains in each phases are preferably chosen depending upon 
development conditions for the photosensitive materials containing these 
flat silver halide grains, (such as the amount of a solvent for silver 
halide in a developing solution) and so on. 
The flat silver halide grains may be composite type silver halide crystals 
in which oxide crystal such as PbO and silver halide crystals such as 
silver chloride are connected and silver halide crystals formed by 
epitaxial growth (such as crystals in which silver chloride, silver 
iodobromide or silver iodide is epitaxially grown on silver bromide 
crystal, or crystals in which silver chloride, silver bromide, silver 
iodide or silver chloroiodobromide is epitaxially grown on hexagonal, or 
octahedral silver iodide). Examples of those are described in U.S. Pat. 
Nos. 4,435,501 and 4,463,087. 
Regarding sites of silver halide crystals on which the formation of latent 
image takes place, grains which give a latent image mainly on the surface 
of grains or grains which give a latent image mainly in the inner part of 
the grains may be used. This may be properly selected depending upon, for 
instance, the use of the photosensitive materials which contain the 
aforesaid flat silver halide grains and the depth in the grain to which a 
developing solution to be used for processing the photosensitive materials 
can penetrate so as to develop a latent image. 
A preferred method of using the flat silver halide grains according to the 
present technique is described in detail in Research Disclosure No. 22534 
(January, 1983) and No. 25330 (May, 1985), wherein the method of use the 
same, for instance, on a basis of relation between the thickness and 
optical properties of flat silver halide grains is disclosed. 
Grains may have homogeneous crystal structure or may have silver halide 
compositions different between the inner part and the outer part thereof 
or may have layered structure. Such grains for emulsion are disclosed in 
U.K. Patent No. 1,027,146, U.S. Pat. Nos. 3,505,068 and 4,444,877, and 
Japanese Patent Un-examined Publication No. 58-143331. More than 2 types 
of silver halides which have different compositions may be connected by 
epitaxial connection. Alternatively, silver halide may be connected with 
compounds other than silver halide, such as rhodan silver and lead oxide. 
Such grains for emulsion are disclosed in U.S. Pat. Nos. 4,094,684; 
4,142,900; 4,459,353; 4,349,622; 4,395,478; 4,433,501; 4,463,087; 
3,656,962; and 3,852,067; U.K. Patent No. 2,038,792; and Japanese Patent 
Un-examined Publication No. 59-162540. 
It is also possible to use a mixture of grains having different crystal 
forms. 
Solvents for silver halide are useful to facilitate ripening. For instance, 
it is known that an excess amount of halogen ion is placed in a reactor to 
facilitate ripening. Therefore, it is clear that it is possible to 
facilitate ripening merely by introducing a halide salt solution into a 
reactor. Other ripening agents may also be used. Those ripening agents may 
previously be added to a dispersion medium in a reactor before adding 
silver and halide salts, or may be introduced into a reactor 
simultaneously with the addition of one or more halide salts, silver salts 
and deflocculating agents. Alternatively, the ripening agents may be 
separately introduced in a step of addition of halide salts and silver 
salts. 
As ripening agents other than halogen ion, there are named ammonia or amino 
compounds, thiocyanate salts such as alkali metal thiocyanates, 
particularly sodium or potassium thiocyanate, and ammonium thiocyanate. 
The use of thiocyanate ripening agents is disclosed in U.S. Pat. Nos. 
2,222,264; 2,448,534; and 3,320,069. Thioether ripening agents currently 
used in this field and described in U.S. Pat. Nos. 3,271,157; 3,574,628 
and 3,737,313 may also be used. Alternatively, thione compounds disclosed 
in Japanese Patent Un-examined Publication Nos. 53-82408 and 53-144319 may 
be used. 
Properties of silver halide grains can be controlled by making various 
compounds present in a course of silver halide formation and 
precipitation. Such compounds may be introduced in a reactor in advance 
or, according to a conventional manner, may be added while adding one or 
more salts. As described in U.S. Pat. Nos. 2,448,060; 2,628,167; 
3,737,313; and 3,772,031; and Research Disclosure, vol. 134 (June, 1975), 
13452, properties of silver halide may be controlled by making such 
compounds present in a step of silver halide formation and precipitation 
as compounds of copper, iridium, lead, bismuth, cadmium, zinc, chalcogen 
such as sulfur, selenium and tellurium, gold and precious metals of the 
group VII. Silver halide emulsions may be sensitized by inner reduction of 
grains during the formation and precipitation thereof as described in 
Japanese Patent Publication No. 58-1410 and Moiser et al., Journal of 
Photographic Science, Vol. 25, 1977, 19-27. 
Silver halide emulsions are usually chemically sensitized. The chemical 
sensitization may be conducted using active gelatin as described in T. H. 
James, The Theory of the Photogrpahic Process, 4th ed, Macmillan, 1977, p 
67-76. Alternatively, the chemical sensitization may be carried out using 
sulfur, selenium, tellurium, gold, platinum palladium, iridium or a 
mixture of these sensitizing agents at a pAg of 5 to 10, a pH of 5 to 8 
and a temperature of 30.degree. to 80.degree. C. as described in Research 
Disclosure, vol. 120, 12008 (April, 1974), and ibid, vol. 34, 13452 (June, 
1975), U.S. Pat. Nos. 2,642,361; 3,297,446; 3,772,031; 3,857,711; 
3,901,714; 4,266,018 and 3,904,415 and U.K. Patent No. 1,315,755. 
Preferably, the chemical sensitization is carried out in the presence of 
gold compounds and thiocyanate compounds, or sulfur containing compounds 
described in U.S. Pat. Nos. 3,857,711; 4,266,018; and 4,054,457, or other 
sulfur containing compounds such as hypo, thiourea compounds, rhodanine 
compounds. The chemical sensitization may be conducted in the presence of 
chemical sensitization aids. Useful chemical sensitization aids are, for 
instance, compounds which are known to inhibit fogging and enhacne 
sensitivity in the course of chemical sensitization, such as azaindene, 
azapyridazine and azapyrimidine. Examples of chemical sensitization 
modifying aids are described in U.S. Patent Nos. 2,131,038; 3,411,914; and 
3,554,757; Japanese Patent Un-examined Publication No. 58-126526; and G. 
F. Duffin, Photographic Emulsion Chemistry (Focal Press, 1966), p 138-143. 
In addition to or instead of the chemical sensitization, it is possible to 
conduct reduction sensitization using, for example, hydrogen as described 
in U.S. Pat. Nos. 3,891,446 and 3,984,249. Reduction sensitization may be 
carried out by use of such reducing agents as stannous chloride, thiourea 
dioxide and polyamine or by low pAg (e.g., below 5) treatment and/or high 
pH (e.g., above 8) treatment as described in U.S. Pat. Nos. 2,518,698; 
2,743,182; and 2,743,183. Further, it is possible to enhance color 
sensitization by the chemical sensitization described in U.S. Pat. Nos. 
3,917,485 and 3,966,476. 
Silver halide photographic emulsions used in the invention may spectrally 
be sensitized by methine dyes or others. Dyes to be used include cyanine 
dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, 
holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. 
Particularly useful dyes are those belonging to cyanine dyes, merocyanine 
dyes and complex merocyanine dyes. In those dyes, any nuclei usually used 
in cyanine dyes may be adopted as basically reactive heterocyclic nuclei. 
Namely, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole 
nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole 
nucleus, tetrazole nucleus, pyridine nucleus etc.; nuclei composed by 
fusing an alicyclic hydrocarbon ring with the aforesaid nuclei; and nuclei 
composed by fusing an aromatic hydrocarbon ring with the aforesaid nuclei, 
such as indolenine nucleus, benzindolenine nucleus, indole nucleus, 
benzoxazole nucleus, naphthooxazole nucleus, benzthiazole nucleus, 
naphthothiazole nucleus, benzselenazole nucleus, benzimidazole nucleus, 
quinaline nucleus, may be used. Those nuclei may have substituents on 
their carbon atoms. 
For merocyanine dyes or complex merocyanine dyes, 5 or 6 membered 
heterocyclic nuclei, such as pyrrazolin-5-one nucleus, thiohydantoin 
nucleus, 2-thiooxazolidin-2,4-dione nucleus, thiazolin-2,4-dione nucleus, 
rhodanine nucleus, thiobarbituric acid nucleus, may be used as a nucleus 
having a ketomethylene structure. 
Those sensitizing dyes may be used alone or in combination. A combination 
of sensitizing dyes are often used, particularly, for the purpose of 
supersensitization. 
Substances having no spectral sensitization effect per se or substances 
absorbing substantially no visual lights and showing supersensitization 
may be incorporated in the emulsions together with the sensitizing dyes. 
For instance, aminostilbene compounds substituted with a 
nitrogen-containing 
heterocyclic group, such as described in U.S. Pat. Nos. 2,933,390 and 
3,635,721, aromatic organic acid-formaldehyde condensate, such as 
described in U.S. Pat. No. 3,743,510, cadmium salts and azaindene 
compounds may be incorported. The combinations described in U.S. Pat. Nos. 
3,615,613; 3,615,641; 3,617,295; and 3,635,721, are particularly useful. 
When the emulsion according to the invention is spectrally sensitized, it 
may be carried out at any stage of the preparation of the emulsion. 
Generally, spectrally sensitizing dyes are added to a chemically sensitized 
emulsion before coating. Alternatively, for instance, U.S. Pat. No. 
4,425,426 discloses a method in which the spectrally sensitizing dyes are 
added to the emulsion before or in the course of the chemical 
sensitization. In addition, a method in which the spectrally sensitizing 
agents are added to the emulsion prior to the complete formation of silver 
halide grains is disclosed in U.S. Pat. Nos. 2,735,766; 3,628,960; 
4,183,756 and 4,225,666. 
In particular, U.S. Pat. Nos. 4,183,756 and 4,225,666 disclose that a 
variety of advantages such as improvement in photographic sensitivity and 
enhancement in adsorptivity of silver halide grains to spectrally 
sensitizing dyes are accomplished by adding the spectrally sensitizing 
dyes to the emulsion after stable nucleus for forming silver halide grains 
are formed. 
Known additives for photographs which may be incorporated in photographic 
photosensitive materials are used herein are likewise disclosed in 
Research Disclosure Nos. 17643 and 18716 and the related passages thereof 
are picked up and summarized in the following Table. 
______________________________________ 
Additive RD17643 RD18716 
______________________________________ 
1. Chemical sensitizing 
page 23 page 648, 
agent right column 
2. Sensitivity enhancing page 648, 
agent right column 
3. Spectral sensitizing 
pages 23 and 24 
page 648, 
agent, Supersensitiz- right column 
ing agent to page 649, 
right column 
4. Antifoggant, Fogging 
pages 24 and 25 
page 649, 
stabilizing agent right column 
5. Light absorbing agent, 
pages 25 and 26 
page 649, 
Filter dye, right column 
UV absorbing agent to page 650, 
left column 
6. Antistain agent page 25, right 
page 650, left 
column to right column 
7. Hardening agent page 26 page 651, left 
column 
8. Binder page 26 page 651, left 
column 
9. Plasticizer, Lubricant 
page 27 page 650, 
right column 
10. Coating aid, pages 26 and 27 
page 650, 
Surface activator right column 
11. Antistatic page 27 page 650, 
right column 
______________________________________ 
For the purpose of increase of sensitivity, strengthening of contrast or 
acceleration of development, photographic emulsion layers in the 
photographic materials employed in the invention may contain, for 
instance, polyalkyleneoxide or derivatives thereof such as ethers, esters 
and amine; thioether compounds, thiomorphorines, quaternary ammonium 
salts, urethane derivatives, urea derivatives, imidazole derivatives and 
3-pyrazolidones. For instance, those described in U.S. Pat. Nos 2,400,532; 
2,423,549; 2,716,062; 3,617,280; 3,772,021; and 3,808,003; and U.K. Patent 
No. 1,488,991 may be used. 
For the purpose of prevention of fogging during preparation, storage or 
development of the photosensitive materials, or stabilization of the 
photographic performance, various compounds may be contained in the silver 
halide photographic emulsion used in the present technique. There are 
named antifoggants or stabilizers, for instance, azoles such as 
benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, 
chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, 
mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, 
aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles, 
particularly 1-phenyl-5-mercaptoterazole; mercaptopyrimidines; 
mercaptotriadines; thioketo compounds such as oxazolinethione; azaindenes 
such as triazaindenes, tetraazaindenes, particularly 4-hydroxy substituted 
(1, 3, 3a, 7) tetraazaindenes, and pentaazaindenes benzenethiosulfonic 
acid, benzenesulfinic acid, and benzenesulfonamide. 
Various color couplers may be incorporated in the photosensitive materials 
used in the present invention. "Color coupler" herein means a compound 
capable of forming a dye through coupling reaction with an oxidized form 
of an aromatic primary amine developing agent. Typical examples of useful 
color couplers include naphthol or phenol type compounds, pyrazolone or 
pyrazoloazole type compounds, and linear or heterocyclic ketomethylene 
compounds. Cyan, magenta and yellow color couplers which may be used in 
the present invention are disclosed in the patents cited in Research 
Disclosure, 17643 (December, 1978) VII-D; and 18717 (November, 1979). 
The color couplers incorporated in photosensitive materials are preferably 
made nondiffusible by imparting thereto ballast groups or polymerizing 
them. 2-Equivalent couplers which are substituted with coupling 
elimination groups are more preferable than 4-equivalent couplers in which 
a hydrogen atom is in a coupling active cite, because the amount of coated 
silver can be decreased. Furthermore, couplers in which a formed dye has a 
proper diffusibility, non-color couplers, DIR couplers which release a 
development inhibitor through coupling reaction or couplers which release 
a development accelerator may also be used. 
A typical yellow coupler capable of being used in the present invention is 
an acylacetamide coupler of an oil protect type. Examples of such are 
disclosed in U.S. Pat. Nos. 2,407,210; 2,875,057; and 3,265,506. 
2-Equivalent yellow couplers are preferably used in the present invention. 
Typical examples of such are the yellow couplers of an oxygen atom 
elimination type described in U.S. Pat. Nos. 3,408,194; 3,447,928; 
3,933,501; and 4,022,620, or the yellow couplers of a nitrogen atom 
elimination type described in Japanese Patent Publication No. 58-10739, 
U.S. Pat. Nos. 4,401,752 and 4,326,024, Research Disclosure (RD) 18053 
(April, 1979), U.K. Patent No. 1,425,020, DEOS Nos. 2,219,917; 2,261,361; 
2,329,587; and 2,433,812. .alpha.-Pivaloyl acetanilide type couplers are 
excellent in fastness, particularly light fastness, of formed dye. 
.alpha.-Benzoyl acetanilide type couplers yield high color density. 
Magenta couplers usable in the present invention include couplers of an oil 
protect type of indazolone, cyanoacetyl, or, preferably, pyrazoloazole 
such as 5-pyrazolone and pyrazolotriazole type ones. Among 5-pyrazolone 
type couplers, couplers whose 3-position is substituted with an arylamino 
or acylamino group is preferred from the viewpoint of color phase and 
color density of the formed dye. Typical examples of such are described in 
U.S. Pat. Nos. 2,311,082; 2,343,703; 2,600,788; 2,908,573; 3,062,653; 
3,152,896; and 3,936,015. A elimination group of the 2-equivalent 
5-pyrazolone type couplers is preferably a nitrogen atom eliminating group 
described in U.S. Pat. No. 4,310,619 and an arylthio group described in 
U.S. Pat. No. 4,351,897. The 5-pyrazolone type coupler having ballast 
groups described in European Patent No 73,636 provides high color density. 
As examples of pyrazoloazole type couplers, there are named 
pyrazolobenzimidazoles described in U.S. Pat. No. 3,061,432, preferably 
pyrazole [5, 1-c] [1, 2, 4] triazoles described in U.S. Pat. No 3,725,067, 
pyrazolotetrazoles described in Research Disclosure 24220 (June, 1984) and 
Japanese Patent Un-examined Publication No. 50-33552, and 
pyrazolopyrazoles described in Research Disclosure 24230 (June, 1984) and 
Japanese Patent Un-examined Publication No. 60-43659. Imidazo [1, 
2-b]pyrazoles described in U.S. Pat. No. 4,500,630 is preferred on account 
of small yellow minor absorption of formed dye and fastness Pyrazolo [1, 
5-b] [1, 2, 4] triazole described in U.S. Pat. No. 4,540,654 is 
particularly preferred. 
As the magenta coupler, it is preferred to use a combination of 
2-equivalent magenta couplers of pyrazole elimination type such as those 
disclosed in U.S. Pat. No. 4,367,282 with arylthio group elimination type 
2-equivalent magenta couplers such as those described in U.S. Pat. Nos. 
4,366,237 and 4,522,915. 
Cyan couplers which may be used in the present invention include naphthol 
or phenol couplers of an oil protect type. Typical naphthol type couplers 
are described in U.S. Pat. No. 2,474,293. Typical preferred 2-equivalent 
naphtholic couplers of oxygen atom elimination type are described in U.S. 
Pat. Nos. 4,052,212; 4,146,396; 4,228,233; and 4,296,200. Exemplary phenol 
type couplers are described in U.S. Pat. Nos. 2,369,929; 2,801,171; 
2,772,162; and 2,895,826. 
Cyan couplers which are resistant to humidity and heat are preferably used 
in the present invention. Examples of such are phenol type cyan couplers 
having an alkyl group higher than a methyl group at a metha-position of a 
phenolic nucleus as described in U.S. Pat. No. 3,772,002; 
2,5-diacylaminosubstituted phenol type couplers as described in U.S. Pat. 
Nos. 2,772,162; 3,758,308; 4,126,396; 4,334,011; and 4,327,173; DEOS No. 
3,329,729; and European Patent No. 121,365; and phenol type couplers 
having a phenylureido group at the 2-position and an acylamino gorup at 
the 5-position as described in U.S. Pat. Nos. 3,446,622; 4,333,999; 
4,451,559; and 4,427,767. Cyan couplers in which 5-position of naphtol is 
substituted with a sulfonamide or amide group as described in Japanese 
Patent Un-examined Publication No. 60-237448, Japanese Patent Application 
Nos. 59-264277 and 59-268135 are excellent in fastness of formed image and 
may also be preferably used in the present invention. 
In order to compensate unnecessary absorption in the short-wave region of 
dye formed from magenta and cyan couplers, it is preferred to use a 
colored coupler together in color photosensitive materials used for taking 
photographs. Examples of such are the yellow colored magenta coupler 
described in U.S. Pat. No. 4,163,670 and Japanese Patent Publication No. 
57-39413, the magenta colored cyan coupler described in U.S. Pat. Nos. 
4,004,929 and 4,138,258, and U.K. Patent No. 1,146,368. 
Graininess may be improved by using together a coupler which can form a dye 
being moderately diffusible. As such blur couplers, some magenta couplers 
are specifically described in U.S. Pat. No. 4,366,237 and U.K. Patent No. 
2,125,570 and some yellow, magenta and cyan couplers are specifically 
described in European Patent No. 96,570 and DEOS No. 3,234,533. 
Dye-forming couplers and the aforesaid special couplers may be a dimer or 
higher polymers. Typical examples of polymerized dye-forming couplers are 
described in U.S. Pat. Nos. 3,451,820 and 4,080,211. Examples of 
polymerized magenta couplers are described in U.K. Patent No. 2,102,173, 
U.S. Pat. No. 4,367,282, Japanese Patent Application Nos. 60-75041 and 
60-113596. 
In order to meet properties required for photosensitive materials, two or 
more couplers may be used together in a single photosensitive layer, or 
the same coupler may be introduced in two or more different photosensitive 
layers. 
The standard amount of the colored couplers to be used is 0.001 to 1 mole 
and preferred amount there of is 0.01 to 0.5 mole for yellow couplers, 
0.003 to 0.3 mole for magenta couplers and 0.002 to 0.3 mole for cyan 
couplers per mole of photosensitive silver halide. 
The photosensitive materials according to the invention may contain a 
coupler which releases a development inhibitor in the course of 
development, i.e., a so-called DIR coupler. 
Examples of the DIR coupler are those which release a heterocyclic mercapto 
type development inhibitor as described in U.S. Pat. No. 3,227,554; those 
which release development inhibitors of benzotriazole derivatives as 
described in Japanese Patent Publication No. 58-9942; so-called colorless 
DIR couplers described in Japanese Patent Publication No. 51-16141; those 
which release a nitrogen-containing heterocyclic development inhibitor 
with decomposition of methylol after elimination as described in Japanese 
Patent Un-examined Publication (No. 52-90932; those which release a 
development inhibitor, accompanied with intramolecular nucleophilic 
reaction after elimination as described in U.S. Pat. No. 4,248,962 and 
Japanese Patent Un-examined Publication No. 57-6837; those which release a 
development inhibitor by causing electron transfer via conjugated system 
after elimination as described in Japanese Patent Un-examined Publication 
Nos. 56-14946, 57-154234, 57-188035, 58-98728, 58-209736, 58-209737, 
58-209738, 58-209739 and 58-209740; those which release a diffusible 
development inhibitor whose development inhibiting ability is deactivated 
in a development bath as disclosed in Japanese Patent Un-examined 
Publication Nos. 57-151944 and 58-17932; and those which release reactive 
compounds to form a development inhibitor by reaction in membrane during 
development or to make a development inhibitor inactive as described in 
Japanese Patent Publication Nos. 59-182438 and 59-184248. 
Among the aforesaid DIR couplers, couplers which are preferably used in 
combination with the coupler as used in the invention are developing 
solution deactivation type couplers as described in Japanese Patent 
Un-examined Publication No. 57-151944, timing type couplers as described 
in U.S. Pat. No. 4,248,962 and Japanese Patent Un-examined Publication No. 
57-154234 and reaction type couplers as described in Japanese Patent 
Un-examined Publication No. 60-184248. Particularly preferred ones are the 
developing solution deactivation type DIR couplers described in Japanese 
Patent Un-examined Publication Nos. 57-151944, 58-217932, 50-218644, 
60-225156, and 60-233650, and the reaction type DIR couplers described in 
Japanese Patent Un-examined Publication No. 60-184248. 
The photosensitive materials which can be used in the present invention may 
contain a compound which releases a nucleus-forming agent or a development 
accelerator or precursors thereof (hereinafter referred to as a 
"development accelerator and others") in a form of images during 
development. Examples of such compounds are described in U.K. Patent Nos. 
2,097,140 and 2,131,188 and are couplers which release a "development 
accelerator and others" by coupling reaction with an oxidized form of an 
aromatic primary amine development agent, i.e., DAR couplers. 
The "development accelerator and others" released from the DAR coupler 
preferably has an adsorbing group for silver halide. Examples of such DAR 
couplers are described in Japanese Patent Un-examined Publication Nos. 
59-157638 and 59-170840. Particularly preferred are DAR couplers which 
forms N-acyl substituted hydrazines having a monocyclic or fused cyclic 
hetro ring as an adsorbing group and eliminated at a sulfur or nitrogen 
atom from a coupling active site of a photographic coupler. Examples of 
such couplers are described in Japanese Patent Un-examined Publication No. 
60-128446. 
Compounds which have a development accelerating moiety in a coupler residue 
as described in Japanese Patent Unexamined Publication No. 60-37556 and 
compounds which release a development accelerator by oxidation reduction 
reaction with a development agent as described in Japanese Patent 
Unexamined Publication No. 60-107029 may also be incorporated in the 
photosensitive materials as used in the present invention. 
The DAR couplers are preferably introduced into a photosensitive silver 
halide emulsion of the photosensitive materials used in the present 
invention. Preferably, at least one photosensitive layer contains 
substantially nonphotosensitive silver halide grains as described in 
Japanese Patent Un-examined Publication Nos. 59-172640 and 60-128429. 
The photosensitive materials used in the present invention may contain 
hydroquinone derivatives, aminophenol derivatives, amines, gallic acid 
derivatives, catechol derivatives, ascorbic acid derivatives, colorless 
couplers and sulfonamide phenol derivatives as a anticolorfoggant or a 
color mixing inhibitor. 
Known antidiscoloration agents may be used in the photosensitive materials 
as used in the present invention, such as hydroquinones, 
6-hydroxycumarones, 5-hydroxycumarones, spirocumarones, p-alkoxyphenols, 
hindered phenols such as bisphenols, gallic acid derivatives, 
methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester 
derivatives obtained by silylation or alkylation of the phenolic hydroxyl 
group of these compounds. Further, metal complexes such as 
(bissalicylaldoximato) nickel complex and (bis-N,N-dialkyldithiocarbamato) 
nickel complex may also be used. 
UV absorbers may be added to a hydrophilic colloidal layer in the 
photosensitive materials which can be used in the present invention. For 
instance, benzotriazoles substituted with an aryl group described in U.S. 
Pat. Nos. 3,553,794 and 4,236,013, Japanese Patent Publication No. 51-6540 
and Europe Patent No. 57,160; butadienes described in U.S. Pat. Nos. 
4,450,229 and 4,195,999; cinnamates described in U.S. Pat. Nos. 3,705,805 
and 3,707,375; benzophenones described in U.S. Pat. No. 3,215,530 and U.K. 
Patent No. 1,321,355; and polymeric compound having UV absorbing residues 
described in U.S. Pat. Nos. 3,761,272 and 4,431,726 may be used. 
Fluorescent whitners having a UV absorbing property described in U.S. Pat. 
Nos. 3,499,762 and 3,700,455. Typical UV absorbers are those described in 
Research Disclosure 24239 (June, 1984). 
The photosensitive materials which can be used in the invention may include 
one or more surfactants for various purposes, for instance, as a coating 
assistant or an antistatic, for improvement of slipping, emulsifying 
dispersion, prevention of adhesion or improvement of photographic 
properties such as development acceleration, contrast develoment and 
sensitization. 
The photosensitive materials which may be employed in the present invention 
may contain water-soluble dyes in hydrophilic colloidal layers, which 
serve as filter dyes and further serve to prevent irradiation, or halation 
and so on. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, 
merocyanine dyes, anthraquinone dyes, azo dyes are preferably used. 
Besides, cyanine dyes, azomethine dyes, triarylmethane dyes and 
phthalocyanine dyes are also useful. It is possible to emulsify an 
oil-soluble dyes by oil-in-water dispersion method and add it to 
hydrophilic colloidal layers. 
In order to introduce a lipophilic compound such as photographic couplers 
into a hydrophilic organic colloidal layer of the photosensitive materials 
which can be used in this invention, various methods such as oil-in-water 
dispersion method, latex dispersion method, solid dispersion method and 
alkali dispersion method may be adopted. A proper method may be selected 
depending on chemical structure and physicochemical properties of a 
compound to be introduced. 
The photographic couplers used in the present invention may be added to, 
for instance, one or more silver halide emulsion layers preferably 
according to the latex dispersion method or, more preferably, the 
oil-in-water dispersion method. In the oil-in-water dispersion method, the 
couplers are dissolved in a high boiling organic solvent of a boiling 
point of 175.degree. C. or higher in an atmospheric pressure (hereinafter 
referred to as oil) using, if necessary, a low boiling auxiliary solvent 
together, and are finely dispersed in water or an aqueous binder solution 
of, for instance, gelatin, preferably, in the presence of a surfactant. 
Typical high boiling organic solvents are phthalates described in U.S. Pat. 
Nos. 2,272,191 and 2,322,027, Japanese Patent Un-examined Publication Nos. 
54-31728 and 54-118246; phosphates and phosphonates described in U.S. Pat. 
Nos. 3,676,137, 4,217,410, 4,278,757, 4,326,022 and 4,353,979; benzoates 
described in U.S. Pat. No. 4,080,209; amides described in U.S. Pat. Nos. 
2,533,514, 4,106,940 and 4,127,413; alcohols and phenols described in 
Japanese Patent Un-examined Pubication Nos. 51-27922, 53-13414 and 
53-130028 and U.S. Pat. No. 2,835,579; aliphatic carboxylic esters 
described in Japanese Patent Un-examined Publication Nos. 51-26037, 
51-27921, 51-149028, 52-34715, 53-1521, 53-15127, 54-58027, 56-64333 and 
56-114940, U.S. Pat. Nos. 3,748,141, 3,779,765, 4,004,928, 4,430,421 and 
4,430,422; anilines described in Japanese Patent Un-examined Publication 
No. 58-105147; hydrocarbons described in Japanese Patent Un-examined 
Publication Nos. 50-62632 and 54-99432 and U.S. Pat. No. 3,912,515; 
solvents described in Japanese Patent Un-examined Publication No. 
53-146622, U.S. Pat. Nos. 3,689,271, 3,700,454, 3,764,336, 3,765,897, 
4,075,022 and 4,239,851 and DEOS No. 2,410,914. Two or more high boiling 
organic solvents may be used in combination. For instance, a combination 
of phthalate and phosphate is described in U.S. Pat. No. 4,327,175. 
A dispersion method by polymers described in Japanese Patent Un-examined 
Publication No. 51-59943, Japanese Patent Publication Nos. 51-39853 and 
56-126830, U.S. Pat. Nos. 2,772,163 and 4,201,589 may also be used. 
Gelatin is preferred as a binder or protective colloid which may be used in 
an emulsion layer or an intermediate layer of the photosensitive materials 
as used in the invention, although other hydrophilic colloid may also be 
used. For instance, proteins such as gelatin derivatives, graft polymers 
of gelatin and other polymers, albumin and casein; cellulose derivatives 
such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose 
sulfates; sodium alginate; sugar derivatives such as starch derivatives; 
various synthetic hydrophilic homopolymers or copolymers such as polyvinyl 
alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, 
polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole 
and polyvinylpyrazol. 
For gelatin, lime-treated gelatin for general use, acid-treated gelatin, 
and enzyme-treated gelatin described in Bull. Soc. Sci. Phot. Japan, No. 
16, p 30 (1966) may be used. Further, hydrolyzed gelatin may be used. 
Inorganic or organic hardners may be included in a photographic 
photosensitive layer or any hydrophilic colloidal layers constituting a 
backing layer in the photosensitive materials which may be used in the 
invention. For instance, cromate, aldehydes such as formaldehyde, glyoxal 
and glutaraldehyde, N-methylol compounds such as dimethylol urea are named 
as examples. Active halogen compound such as 
2,4-dichloro-6-hydroxy-1,3,5-triazine, and active vinyl compounds such as 
1,3-bisvinylsulfonyl-2-propanol, 1,2-bisvinylsulfonylacetamide ethane and 
vinyl polymers having a vinyl sulfonyl group on side chains are preferred, 
because these compounds quickly harden hydrophilic colloid such as gelatin 
to provide stable photograhic properties. N-carbamoylpyridinium salts and 
haloamidinium salts are also excellent in hardening speed. 
The methods according to the present invention can be adopted to process a 
multilayered multicolor photographic materials having at least two layers 
of different spectral sensitivities applied on a support. Multilayer 
natural color photographic materials processed according to this invention 
usually have at least one red-sensitive emulsion layer, at least one 
green-sensitive emulsion layer and at least one blue-sensitive emulsion 
layer on a substrate. The order of arrangement of these layers is not 
restricted to a specific one and may be selected according to need. Layer 
arrangement is preferably in an order of red-sensitive layers, 
green-sensitive layers and, then, blue-sensitive layers from the 
substrate. It is possible that an emulsion layer having a certain 
color-sensitivity is comprised of more than one emulsion layers having 
different sensitivities to enhance attainable sensitivity. It is also 
possible to use such layer made up by a three-layered constitution to 
improve graininess. Further, there may be a non-color-sensitive layer 
between two or more emulsion layers having the same color sensitivity. It 
is likewise possible that, between emulsion layers of the same color 
sensitivity, another emulsion layer of a different color sensitivity is 
inserted. 
In multi-layered multi-color photographic materials, there may be provided 
filter layers for absorbing lights of specific wave lengths and/or layers 
for preventing halation. The aforesaid organic dyes as well as colloidal 
silver grains may be used in those light-absorbing layers. 
For the purpose of enhancing sensitivity by reflection of light and 
trapping of development inhibiting substances, non-light-sensitive silver 
halide fine grain emulsion may be used in one or more non-light-sensitive 
layers of multi-layered multi-color photographic materials. 
Generally, cyan-forming couplers are included in red-sensitive emulsion 
layers; magenta-forming couplers in green-sensitive emulsion layers; and 
yellow-forming couplers in blue-sensitive emulsion layers. However, other 
combinations are also permitted. For instance, an IR-sensitive layer is 
combined to yield quasicolorphotographs or materials to be exposed to 
semi-conductor laser. Further, it is possible to admix a coupler which 
forms a dye developing a color other than the complementary color of a 
sensitive light wave length of each layer so as to avoid unnatural hue as 
disclosed in Japanese Patent Publication No. 33-3481. 
In the photographic materials to which the methods according to the 
invention are applied, photographic emulsion layers and other layers are 
coated on a conventional flexible substrate such as a plastic film, paper 
and cloth, or a rigid substrate such as glass, ceramics or metals. 
Examples of useful flexible substrate are films composed of a synthetic or 
semi-synthetic polymer such as cellulose nitrate, cellulose acetate, 
cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene 
terephthalate and polycarbonate, baryta paper and paper coated or 
laminated with .alpha.-olefine polymer such as polyethylene, polypropylene 
and ethylene-butene copolymer. The substrate may be colored with dyes or 
pigments. It may be made black for shielding light. The surface of the 
substrate is generally undercoated to give good adhesion with a 
photographic emulsion layer or the like. It is possible to subject the 
substrate surface to glow discharge, corona discharge, irradiation with UV 
light or flame treatment before or after undercoating. 
For coating the surface of the substrate with photographic emulsion layers 
or hydrophilic colloid layers, various known coating methods may be used, 
such as a dip coating method, roller coating method, curtain coating 
method and extrusion coating method. When occasion demands, the coating 
methods described in U.S. Pat. Nos. 2,681,294; 2,761,791; 3,526,528; and 
3,508,947 may be used for the simultaneous coating with plural layers. 
Various exposure means may be adopted for the photosensitive materials 
which can be processed according to the present invention. Any sources of 
light which radiate radiant rays corresponding to the sensitive wave 
length of the photosensitive materials may be used as a lighting source or 
a writing source of light. Natural light (sun light), incandescents, 
halogen atom sealing lamps, mercury lamps, fluorescent lamps, flash light 
sources such as strobo lamps and metal burning flash lamps are usually 
used. Further, laser of gases, dye solutions or semi-conductors, 
luminescent diodes and plasma light sources may also be used. Fluorescent 
light emitted from a fluorescent body excited by electron beams or the 
like (CRT, etc.), or an exposure means of a combination of microshutter 
arrays using liquid crystal (LCD) or lead zirconate titanate (PLZT) doped 
with lanthanum and a source of light of a linear or plane form may also be 
used. The spectral distribution of light used for exposure may be 
controlled utilizing a color filter according to need. 
The present invention is adopted to process photosensitive materials 
comprised of the foregoing components and having a variety of known 
constructions of layers. Preferred layer constructions are listed below, 
in which as the substrate, there may be mentioned, for instance, flexible 
substrates such as plastic films, paper and cloths; glass, porcelain and 
metals. Among them, preferred are baryta paper and paper laminated with 
polyethylene film in which a white pigment such as titanium oxide and/or a 
bluing dye such as Ultramarine Blue are incorporated. Examples thereof are 
those disclosed in Research Disclosure No. 17643, p 23-27 and ibid, No. 
18716, p 648-650. 
(i) substrate-BL-MC-GL-MC-RL-PC(2)-PC(1); 
(ii) substrate-BL-MC-RL-MC-GL-PC(2)-PC(1); 
(iii) substrate-RL-MC-GL-MC-BL-PC(2)-PC(1); 
(iv) substrate-RL-MC-RL-MC-GL-PC(2)-PC(1); 
(v) substate-BL(2)-BL(1)-MC-GL(2)-GL(1)-MC-RL(2)-RL(1)-PC(2)-PC(1). 
Wherein PC(1) and PC(2) represent non-photosensitive layers, MC an 
intermediate layer, BL a blue-sensitive emulsion layer, GL green-sensitive 
emulsion layer and RL red-sensitive emulsion layer, respectively. 
Heretofore, it has been known that the formation of precipitations such as 
calcium carbonate can be prevented by softening hard water. However, the 
effects of the present invention are surely achieved by softening hard 
water as well as by restricting the amount of replenishing water to a 
specific range and/or sterilizing washing water prior to supplying it to 
washing baths Therefore, these effects result from the synergistic action 
of these two or three factors and have never been expected from the 
aforesaid known fact. 
The present invention can effectively be applied to the processing of any 
silver halide (color) photosensitive materials such as color paper, 
monochromatic paper, reversal color paper, color positive films, color 
negative films, monochromatic negative films, color reversal films, 
monochromatic reversal films, X-ray films, microfilms, copying films, 
direct positive films, printing films and gravure films. 
The processing methods for silver halide photosensitive materials according 
to the present invention will hereunder be explained in more detail with 
reference to unlimitative working examples and the effects practically 
attained will also be discussed in comparison with comparative examples. 
EXAMPLE 1 
A multilayered color photographic paper having a layer structure as 
disclosed in the following Table 1 was prepared on a paper substrate, both 
surfaces of which were laminated with polyethylene films. Each coating 
liquid was prepared according to the following procedures 
Preparation of Coating Liquid for 1st Layer 
To 19.1 g of an yellow coupler (a) and 4.4 g of a dye image stabilizer (b) 
there were added 27.2 ml of ethyl acetate and 7.9 ml of solvent (c) and 
the resultant solution was dispersed in 185 ml of 10% aqueous gelatin 
solution containing 8 ml of 10% sodium dodecylbenzenesulfonate solution to 
form an emulsion. On the other hand, 90 g of a blue-sensitive emulsion was 
prepared by adding the following blue-sensitive sensitizing dye to a 
silver chlorobromide emulsion (silver bromide content=1 mole %; amount of 
silver=70 g/kg) in an amount of 5.0.times.10.sup.-4 moles per mole of the 
silver chlorobromide. The emulsified dispersion and the blue-sensitive 
emulsion prepared above were mixed and the concentration of gelatin was 
adjusted so as to obtain the composition described in Table 1 and thus the 
coating liquid for 1st layer was prepared. 
Coating liquids for second to seventh layers were also prepared according 
to procedures similar to those for preparing the first liquid. In each of 
these layers, sodium salt of 1-oxy-3,5-dichloro-s-triazine was used as a 
hardening agent for gelatin. 
The following spectral sensitizers were used in each of the emulsions: 
##STR2## 
The following dyes were used in each of the emulsions as an irradiation 
resistant dye: 
##STR3## 
The structural formula of the compounds such as couplers used in this 
Example were as follows: 
##STR4## 
TABLE 1 
__________________________________________________________________________ 
Layers Principal composition 
Amount used 
__________________________________________________________________________ 
7th layer gelatin 1.50 g/m.sup.2 
(Protective layer) 
6th layer gelatin 0.54 g/m.sup.2 
(UV absorbing layer) 
UV absorber (h) 0.21 g/m.sup.2 
solvent (j) 0.09 cc/m.sup.2 
5th layer silver chlorobromide (AgBr: 1 mole %) Ag: 
0.26 g/m.sup.2 
(Red-sensitive layer) 
gelatin 0.98 g/m.sup.2 
cyan coupler (k) 0.38 g/m.sup.2 
dye image stabilizer (l) 
0.17 g/m.sup.2 
solvent (m) 0.23 cc/m.sup.2 
4th layer gelatin 1.60 g/m.sup.2 
(UV absorbing layer) 
UV absorber (h) 0.62 g/m.sup.2 
color mixing inhibitor (i) 
0.05 g/m.sup.2 
solvent (j) 0.26 cc/m.sup.2 
3rd layer silver chlorobromide (AgBr: 1 mole %) Ag: 
0.30 g/m.sup.2 
(Green-sensitive layer) 
gelatin 1.80 g/m.sup.2 
magenta coupler (e) 0.34 g/m.sup.2 
dye image stabilizer (f) 
0.20 g/m.sup.2 
solvent (g) 0.68 cc/m.sup.2 
2nd layer gelatin 0.99 g/m.sup.2 
(Color mixing inhibiting 
color mixing inhibitor (d) 
0.08 g/m.sup.2 
layer) 
1st layer silver chlorobromide (AgBr: 1 mole %) Ag: 
0.30 g/m.sup.2 
(Blue-sensitive layer) 
gelatin 1.86 g/m.sup.2 
yellow coupler (a) 0.82 g/m.sup.2 
dye image stabilizer (b) 
0.19 g/m.sup.2 
solvent (c) 0.34 cc/m.sup.2 
Substrate paper laminated with polyethylene (polyethylene situated 
at the side of 1st layer contains a white pigment 
(TiO.sub.2) 
and a bluing dye (Ultramarine Blue)) 
__________________________________________________________________________ 
The photographic paper thus prepared was cut into long band-like paper of 
82.5 mm in width, they were exposed to light by an autoprinter and then 
processed by an autodeveloping machine according to each of the following 
processing steps shown in Table 2. 
TABLE 2 
______________________________________ 
Processing Steps 
Amount 
replenished 
Pro- (per 1 m of 
cessing Volume paper having 
Temp. time of tank 
a width of 
Step .degree.C. 
(sec.) (l) 82.5 mm) 
______________________________________ 
Color Development 
35 45 16 13 ml 
Bleaching-Fixing 
35 45 10 8 ml 
Water Washing (1) Water Washing (2) Water Washing (3) Water Washing 
35 35 35 35 
20 20 20 20 
##STR5## 
Multistage and Countercurrent System 
15 ml 
______________________________________ 
Each of the processing liquids used in these steps had the following 
composition: 
______________________________________ 
(Color Development Liquid) 
Component Mother Liquor 
Replenishing Liquid 
______________________________________ 
Water 800 ml 800 ml 
1-Hydroxyethylidene- 
1.5 ml 1.5 ml 
1,1-diphosphonic acid 
(60% solution) 
Lithium chloride 
1.0 g 1.0 g 
Diethylenetriaminepenta- 
1 g 1 g 
acetic acid 
4,5-Dihydroxy-m- 
1.0 g 1.5 g 
benzenediphosphonic acid 
Sodium sulfite 0.5 g 1.0 g 
Potassium bromide 
0.1 g -- 
Sodium chloride 
1.5 g -- 
Adenine 30 mg 60 mg 
Potassium carbonate 
40 g 40 g 
N-Ethyl-N-(.beta.-methane- 
4.5 g 11.0 g 
sulfonamideethyl)-3- 
methyl-4-aminoaniline 
sulfate 
Hydroxylamine sulfate 
3.0 g 4.0 g 
Fluorescent Whitener 
1.0 g 2.0 g 
(Whitex 4: manufactured 
and sold by Sumitomo 
Chemical Company, Ltd.) 
Polyethyleneimine (50% 
3.0 g 3.0 g 
aqueous solution) 
Water (Amount sufficient to obtain 1 liter 
of each solutions) 
pH (KOH) 10.25 10.80 
______________________________________ 
______________________________________ 
(Bleaching-Fixing Liquid) 
Component Mother Liquor 
Replenishing liquid 
______________________________________ 
Water 700 ml 700 ml 
Ammonium thiosulfate 
150 ml 150 ml 
(70%) 
Sodium sulfite 18 g 25 g 
Ferric ammonium 
55 g 65 g 
ethylenediamine- 
tetraacetate 
Ethylenediaminetetra- 
5 g 10 g 
acetic acid 
pH (adjusted by the 
6.75 6.50 
addition of aqueous 
ammonia or acetic acid) 
Water (Amount required to obtain 1 liter 
of the intended solutions) 
______________________________________ 
Washing Water 
Well water having the following properties was passed through a column 
packed with H-type strong acidic cation exchange resin (manufactured and 
sold under the trade name of Diaion SK-1B by MITSUBISHI CHEMICAL 
INDUSTRIES LTD.) and OH-type strong basic anion exchange resin 
(manufactured and sold under the trade name of Diaion SA-10A by MITSUBISHI 
CHEMICAL INDUSTRIES LTD.) and the resulting soft water was used as washing 
water. 
TABLE 3 
______________________________________ 
Properties of Washing Water 
Before ion exchange 
After ion exchange 
______________________________________ 
pH 6.8 6.6 
Calcium ions 
38 mg/l 0.4 mg/l 
Magnesium ions 
11 mg/l 0.1 mg/l 
Chlorine ions 
32 mg/l 3.3 mg/l 
Residue after 
185 mg/l 20.4 mg/l 
evaporation 
______________________________________ 
The processing was carried out at a rate of 180 m/day an such processing 
was repeated for 6 days. After processing for 6 days, water in the final 
water washing bath was took to charge it in test tubes of 100 ml volume 
and then calcium chloride (CaCl.sub.2.2H.sub.2 O) and magnesium chloride 
(MgCl.sub.2.6H.sub.2 O) were added to each test tube so as to obtain 
calcium and magnesium concentrations listed in Table 4. Thereafter, these 
tubes were maintained in an air thermostat chamber held at 25.degree. C. 
for 10 days and then the samples were examined on turbidity of washing 
water and proliferation of mold at this time. 
The degree of turbidity was determined from absorbance at 700 nm (optical 
path=10 mm) and visual observation, while the proliferation of mold was 
estimated according to visual observation. 
TABLE 4 
__________________________________________________________________________ 
Estimation of Turbidity and Mold 
Turbidity Mold 
Ca Concn. 
Mg Concn. Visual (Visual 
No. 
(mg/l) 
(mg/l) 
Absorbance 
Observation 
Observation) 
__________________________________________________________________________ 
Invention 
1 0.9 0.4 0.002 (-) (-) 
Invention 
2 2 " " (-) (-) 
Invention 
3 3 " " (-) (-) 
Invention 
4 5 " 0.004 (-) (-) 
Comparative 
5 7 " 0.010 (+) (-) 
Example 
Comparative 
6 10 " 0.018 (++) (-) 
Example 
Comparative 
7 20 " 0.023 (++) (-) 
Example 
Invention 
8 0.9 2 0.002 (-) (-) 
Invention 
9 " 3 " (-) (-) 
Invention 
10 " 5 0.004 (-) (-) 
Comparative 
11 " 7 0.005 (-) (+) 
Example 
Comparative 
12 " 10 0.010 (+) (+++) 
Example 
Comparative 
13 " 20 0.019 (++) (++) 
Example 
Invention 
14 2 2 0.002 (-) (-) 
Invention 
15 3 3 " (-) (-) 
Invention 
16 5 5 0.004 (-) (-) 
Comparative 
17 7 7 0.011 (+) (+) 
Example 
Comparative 
18 10 10 0.024 (++) (+++) 
Example 
Comparative 
19 20 20 0.031 (+++) (++) 
Example 
__________________________________________________________________________ 
Explanation of 
Ideograms 
Turbidity 
Mold 
(-) not observed 
not observed 
(+) observed observed 
(in small degree) 
(in small extent) 
(++) observed observed 
(in some degree) 
(in some extent) 
(+++) observed observed 
(in great degree) 
(in great extent) 
As seen from the results shown in Table 4, it is clear that the increase in 
turbidity and the proliferation of mold can surely be prohibited for a 
long period of time by lowering the concentrations of both calcium and 
magnesium in the washing water to not more than 5 mg/l. 
The basic molecular structure of Diaion SK-1B available from MITSUBISHI 
CHEMICAL INDUSTRIES LTD. is as follows: 
##STR6## 
EXAMPLE 2 
The following four kinds of color photographic paper P.sub.1 to P.sub.4 
were prepared: 
______________________________________ 
Color photographic paper P.sub.1 : 
Color photographic paper 
described in Table 1 of 
Example 1. 
Color photographic paper P.sub.2 : 
Similar to the color 
photographic paper P.sub.1 
except that the 7th 
layer had the following 
composition: 
Gelatin 1.33 g/m.sup.2 
Acrylic acid modified 
0.17 g/m.sup.2 
polyvinyl alcohol 
copolymer (degree of 
modification = 17%) 
Color photographic paper P.sub.3 : 
Color photographic paper 
having a layer structure 
and composition of each 
layer shown in Table 5. 
Color photographic paper P.sub.4 : 
Similar to the color 
photographic paper P.sub.3 
except that the 7th 
layer had the following 
composition: 
Gelatin 1.46 g/m.sup.2 
Acrylic acid modified 
0.16 g/m.sup.2 
polyvinyl alcohol 
copolymer (degree of 
modification = 17%) 
______________________________________ 
TABLE 5 
______________________________________ 
Amount used 
Layer Principal Composition 
(g/m.sup.2) 
______________________________________ 
7th layer Gelatin 1.62 
(protective layer) 
6th layer Gelatin 1.06 
(UV absorbing layer) 
UV absorber (h) 0.35 
UV absorbing solvent (c) 
0.12 
5th layer Silver chlorobromide 
0.25 
(Red-sensitive layer) 
(AgBr content = (silver) 
50 mole %) 
Gelatin 1.26 
Cyan coupler (k) 0.50 
Coupler solvent (c) 
0.25 
4th layer Gelatin 1.60 
(UV absorbing layer) 
UV absorber (h) 0.70 
Color mixing inhibitor 
0.20 
(i) 
Solvent for color mixing 
0.30 
inhibitor (c) 
3rd layer Silver chlorobromide 
0.17 
(Green-sensitive 
(AgBr content = (silver) 
layer) 70 mole %) 
Gelatin 1.40 
Magenta coupler (n) 
0.40 
Coupler solvent (g) 
0.20 
2nd layer Gelatin 1.10 
(Intermediate layer) 
Color mixing inhibitor 
0.20 
(i) 
Solvent for color mixing 
0.10 
inhibitor (c) 
1st layer Silver chlorobromide 
0.35 
(Blue-sensitive layer) 
(AgBr content = (silver) 
80 mole %) 
Gelatin 1.54 
Yellow coupler (a) 
0.50 
Coupler solvent (c) 
0.50 
Substrate Paper laminated with polyethylene 
films in which the polyethylene 
situated at the side of 1st layer 
contains a white pigment (such as 
TiO.sub.2) and a bluing dye such as 
Ultramarine Blue. 
______________________________________ 
Magenta coupler (n) 
##STR7## 
In addition to the foregoing compounds, the same spectral sensitizers as i 
Example 1 were used. 
After exposing the color photographic paper P.sub.1 (82.5 mm in width) to 
light utilizing an autoprinter, it was processed by an autodeveloping 
machine according to processing (I) shown in Table 6. In the processing 
(I), five kinds of water washing procedures inclusive of the present 
invention were conducted and results obtained were compared with each 
other. 
TABLE 6 
______________________________________ 
Steps of the Processing (I) 
Pro- 
cessing Volume 
Temp. time of tank 
Amount 
Step .degree.C. 
(sec.) (l) replenished 
______________________________________ 
Color Development 
35 45 16 13 ml 
Bleaching-Fixing 
35 45 10 8 ml 
Water Washing (1) Water Washing (2) Water Washing (3) 
35 35 35 
20 20 20 
##STR8## 
Multistage Countercurrent System The 
amount replenished was hereunder 
described. 
______________________________________ 
______________________________________ 
Water washing process A: 
Tap water having the following 
(Comparative Example) 
properties was replenished in an 
amount 30 ml per unit length (1 m) 
of the color photographic paper. 
pH 7.1 
Calcium ions 21 mg/l 
Magnesium ions 9 mg/l 
Water washing process B: 
Washing water comprises the same 
(Comparative Example) 
tap water as in the water washing 
process A and 5-chloro-2-methyl-4- 
isothiazilin-3-one disclosed in 
Japanese Patent Un-examined 
Publication No. 57-8542 as a mold 
control agent and suspending agent 
in an amount of 0.5 g per liter of 
tap water and the resultant 
washing water was replenished at a 
rate of 30 ml per unit length (1 m) 
of the color photographic paper. 
Water washing process C: 
As shown in FIG. 6, low pressure 
(Comparative Example) 
mercury UV lamps of quartz glass 
having a rated consumed power of 
4W (main wave length = 2537.ANG.) 
were disposed to a washing water 
storage tank for replenishing and 
a final water washing bath. 
Tap water similar to that in the 
water washing process A was 
introduced in the washing water 
storage tank and the tap water was 
replenished in an amount of 30 ml 
per unit length (1 m) of the color 
photographic paper while 
continuously irradiating water in 
the storage tank and the final 
water washing bath with UV light 
during operating the 
autodeveloping machine. 
Water washing process D: 
Tap water similar to that in the 
(Present Invention) 
water washing process A was 
treated with Na-type strong acidic 
cation exchange resin 
(manufactured and sold under the 
trade name of Diaion SK-1B by 
MITSUBISHI CHEMICAL 
INDUSTRIES LTD.) to obtain 
washing water having the following 
properties and the water was 
replenished in an amount of 
30 ml per 1 m of the 
color photographic paper. 
pH 6.9 
Calcium ions 1.6 mg/l 
Magnesium ions 0.5 mg/l 
Water washing process E: 
The water treated with ion 
(Present Invention) 
exchange resin as in the water 
washing process D was replenished 
in an amount of 30 ml per 1 m of 
the color photographic paper while 
irradiating the water with UV 
light as in the case of the water 
washing process C. 
______________________________________ 
In the processing methods including the water washing processes A to E, the 
color photographic paper P.sub.1 of 82.5 mm in width was processed in a 
rate of 180 m per day for 6 days and then the processing was interrupted 
for 4 days. Thereafter, the conditions (turbidity and presence of mold) of 
each of the water washing bath and calcium and magnesium concentration of 
the washing water contained in the final water washing bath were 
determined. Then, the color photographic paper P.sub.1 as well as P.sub.2 
were further processed in the same procedures and baths to determine the 
degree of contamination (stains and deposition of mold or the like on the 
processed photographic paper) as well as adhesion properties thereof when 
two sheets of the processed photographic paper were superposed. The 
concentrations of calcium and magnesium were determined according to 
atomic-absorption spectroscopy. 
Furthermore, in a processing (II) as shown in Table 7 in which the color 
photographic paper P.sub.3 was employed, results obtained were compaired 
between the water washing processes A to E. The processing (II) was 
identical to the processing (I) except for utilizing the following 
processing steps and color developing liquid having the following 
composition. 
TABLE 7 
______________________________________ 
Steps in the Processing (II) 
Pro- Volume 
Temp. cessing of tank 
Amount 
Step (.degree.C.) 
time (l) replenished 
______________________________________ 
Color Development 
38 1 min. 16 24 ml 
40 sec. 
Bleaching-Fixing 
33 1 min. 10 13 ml 
Water Washing (1) Water Washing (2) Water Washing (3) 
33 33 33 
20 sec. 20 sec. 20 sec. 
##STR9## 
Multistage Countercurrent System (The 
amount replenished was hereunder 
described.) 
______________________________________ 
______________________________________ 
(Color Developing Liquid for the Processing (II)) 
Component Mother Liquor 
Replenishing liquid 
______________________________________ 
Water 800 ml 800 ml 
1-Hydroxyethylidene-1,1- 
1.5 ml 1.5 ml 
diphosphonic acid 
(60% solution) 
Diethylenetriaminepenta- 
1.0 g 1.0 g 
acetic acid 
Benzyl alcohol 16 ml 20 ml 
Diethylene glycol 
10 ml 10 ml 
Sodium sulfite 2.0 g 2.5 g 
Hydroxylamino sulfate 
3.0 g 3.5 g 
Potassium bromide 
1.0 g -- 
Sodium carbonate 
30 g 35 g 
N-ethyl-N-(.beta.-methane- 
6.0 g 8.0 g 
sulfonamideethyl)-3- 
methyl-4-aminoamiline 
sulfate 
Water (Amount required to form 1000 ml 
of the intended liquids) 
pH 10.25 10.60 
______________________________________ 
The color photographic paper P.sub.3 was processed for 6 days followed by 
interrupting the processing over 4 days and then the processing was 
continued with the color photographic paper P.sub.3 and P.sub.4 to effect 
estimation of the same properties as before. Results obtained are listed 
in the following Table 8. 
TABLE 8 
__________________________________________________________________________ 
Conditions of Liquid 
Concn. in the 
in each Water Wash- 
Final Water 
ing Bath Color 
Water 
Washing Bath 
Turbidity. 
Prolifer- 
Photo- 
Process- 
Washing 
Ca Mg Color of 
ation of 
graphic 
Contami- 
Adhesion 
No. 
ing Process 
(mg/l) 
(mg/l) 
Liquid Mold Paper 
nant Properties 
Remarks 
__________________________________________________________________________ 
1 (I) A 16 7 (++) (+++) 
P.sub.1 
(++) (+) Comparative 
P.sub.2 
(+) (+) Example 
2 (I) B 15 7 (++) (-) P.sub.1 
(++) (+++) Comparative 
The liquid P.sub.2 
(+) (+++) Example 
was colored 
black 
3 (I) C 15 8 (++) (+++) 
P.sub.1 
(++) (+) Comparative 
P.sub.2 
(+) (+) Example 
4 (I) D 1.9 0.6 (- ) (+) P.sub.1 
(-) (+) Present 
P.sub.2 
(+) (-) Invention 
5 (I) E 1.9 0.5 (-) (-) P.sub.1 
(-) (+) Present 
P.sub.2 
(+) (+) Invention 
6 (II) A 14 7 (+++) (+++) 
P.sub.3 
(+++) 
(++) Comparative 
P.sub.4 
(++) (++) Example 
7 (II) B 15 8 (++) (-) P.sub.3 
(++) (+++) Comparative 
The liquid P.sub.4 
(+) (+++) Example 
was colored 
black 
8 (II) C 16 8 (+++) (+++) 
P.sub.3 
(+++) 
(++) Comparative 
P.sub.4 
(+) (+) Example 
9 (II) D 1.8 0.6 (-) (+) P.sub.3 
(+) (++) Present 
P.sub.4 
(-) (+) Invention 
10 (II) E 2.0 0.6 (-) (-) P.sub.3 
(- - (++) Present 
P.sub.4 
(-) (+) Invention 
__________________________________________________________________________ 
TABLE 9 
______________________________________ 
Explanation of Ideograms Appeared in Table 8 
Turbidity.multidot. Contaminant 
Color of Proliferation 
(Stains.multidot. 
Adhesion 
Liquid of Mold Deposit) Properties 
______________________________________ 
(-) not not not no 
observed observed observed adhesion 
(+) observed observed observed observed 
(in small (in small (in small 
(in small 
degree) degree) degree) extent) 
(++) observed observed observed observed 
(in some (in some (in some (in some 
degree) degree) degree) extent) 
(+++) observed observed observed observed 
(in great (in great (in great 
(in great 
degree) degree) degree) extent) 
______________________________________ 
Estimation of Adhesion Properties 
The adhesion properties listed in Table 8 were determined according to the 
following method: After exposing whole the surface of a photographic 
paper, it was cut into pieces of 3.5 cm.times.6 cm in size followed by 
maintaining them in a controlled chamber held at 25.degree. C. and a 
relative humidity (RH) of 80% for 2 days. Then, parts (3.5 cm.times.3.5 
cm) of the two of them were superposed to one another, applied a load of 
500 g and further maintained in a controlled chamber held at 35.degree. C. 
and RH of 80% for 3 days. Thereafter, they were peeled off and the 
surfaces superposed were observed with respect to adhesion. 
As seen from the results listed in Table 8, it was found that all of the 
turbidity, coloration of liquids and contaminants were observed in every 
water washing processes A, B and C in which the concentrations of calcium 
and magnesium were beyond the range defined in the present invention, 
while in the process of this invention, they were not observed at all. 
This means that the processing method of this invention is quite effective 
to eliminate the foregoing disadvantages. In the water washing process B 
in which 5-chloro-2-methyl-4-isothiazolin-3-one was used, the 
proliferation of mold was positively prohibited. However, the liquid 
turned very black and the photographic paper caused stains, while the 
adhesion properties were also extremely high. On the contrary, in the 
present invention, the adhesion properties were low enough and the 
proliferation of mold was effectively suppressed. In particular, as seen 
from the results observed on the water washing process E, it is found that 
the proliferation of mold is very effectively prohibited. 
Moreover, it was also found that the use of a color photographic paper in 
which the 7th layer contains an acrylic acid modified polyvinyl alcohol 
copolymer provides an improved adhesion property in the processing method 
of the present invention. 
EXAMPLE 3 
The instant Example was carried out to explain the relationship between the 
effects of the present invention and the amount of the washing water used. 
Color photographic paper as used in this example was the same as that used 
in Example 2 i.e., the color photographic paper P.sub.2. Furthermore, the 
processing steps used herein were also the same as those in Example 2 
(Table 6) and the processing liquids were those used in the processing 
(I). 
As washing water, tap water and desalted water treated with an apparatus 
for reverse osmosis, those having the following properties were used in 
this Example. 
______________________________________ 
Properties of the Tap Water used: 
pH 6.6 
Ca ions 26 mg/l 
Mg ions 8 mg/l 
Properties of the Desalted 
pH 6.8 
Water used: Ca ions 1.6 mg/l 
Mg ions 0.3 mg/l 
______________________________________ 
The apparatus for reverse osmosis used herein was provided with a spiral 
type membrane for reverse osmosis of polysulfone having an area of 1.3 
m.sup.2 and the treatment of desalting was carried out under a pressure of 
13 kg/m.sup.2. 
The details of the processing in this Example were shown in Table 10. 
TABLE 10 
______________________________________ 
Detail of the Processing 
Amount 
carried 
over from Amount of Kind of 
preceding water the 
Run- bath (A) replenished 
Ratio washing Amount 
ning *1 (B) *2 (B/A) water processed 
______________________________________ 
1 2.5 ml 400 ml 160 Tap water 
90 m/day 
.times. 6 days 
2 2.5 ml 400 ml 160 Desalted 
90 m/day 
water .times. 6 days 
3 2.5 ml 125 ml 50 Tap water 
90 m/day 
.times. 6 days 
4 2.5 ml 125 ml 50 Desalted 
90 m/day 
water .times. 6 days 
5 2.5 ml 25 ml 10 Tap water 
90 m/day 
.times. 6 days 
6 2.5 ml 25 ml 10 Desalted 
90 m/day 
water .times. 6 days 
7 2.5 ml 5 ml 2 Tap water 
90 m/day 
.times. 6 days 
8 2.5 ml 5 ml 2 Desalted 
90 m/day 
water .times. 6 days 
______________________________________ 
As seen from the above, after processing 6 days, the calcium and magnesium 
concentrations were determined on the washing water in the final bath (3rd 
bath) according to atomic-absorption spectroscopy as well as it was also 
examined on turbidity of water, presence or absence of deposits on the 
processed color photographic paper and on whether mold proliferated on the 
processed color photographic paper when it was maintained under high 
temperature and humidity conditions. 
In Table 10, "amount of liquid carried over by the treated paper from the 
preceding bath (A)" was determined according to the following manner: A 
sample of 1 m in length was collected just before the color photographic 
paper during treating entered into water washing bath and immadiately 
thereafter the sample was immersed in 1 l of distilled water followed by 
maintaining it at 30.degree. C. while stirring with a magnetic stirrer. 
Then, a volume of the liquid was took therefrom, quantitatively analized 
on the concentration of thiosulfate ions C.sub.1 (g/l ) contained therein, 
at the same time the concentration of thiosulfate ions C.sub.2 (g/l ) of 
the fixing liquid in the preceding was also quantitatively determined and 
thus the amount of liquid (A (ml)) carried over from the preceding bath 
was estimated according to the following equation: 
##EQU1## 
In this connection, the quantitative determination of thiosulfate ions was 
carried out by acidic iodine titration after adding formaldehyde to the 
sample to mask the coexisting sulfite ions. 
Moreover, the "amount of water replenished (B)" in Table 10 means that per 
unit length (1 m) of the sample (color photographic paper). 
Test on the proliferation of mold on the processed photographic paper was 
effected as follows: a piece of absorbent cotton wetted with water was 
placed in a plastic schale (a laboratory disk) and a piece (2 cm.times.2 
cm) of the color photographic paper was sticked on the inner surface of a 
cover of the schale and then the schale was closed by placing the cover 
thereon without coming the piece into contact with the absorbent wadding. 
All implements used in this test, such as schale, absorbent wadding and so 
on were previously sterilized prior to the practical use. 
The piece of the color photographic paper was thus maintained at 25.degree. 
C. for 2 weeks and then observed whether mold grew or not. 
Results thus obtained are listed in Table 11. 
TABLE 11 
__________________________________________________________________________ 
Kind of 
Concentration in the 
Turbidity Proliferation 
washing 
final bath Ratio 
of washing 
Degree of 
on the photo- 
Running 
water Calcium 
Magnesium 
B/A water deposition 
graphic paper 
__________________________________________________________________________ 
Comparative 
1 Tap water 
24 mg/l 
8 mg/l 
160 (-) (-) (+) 
Example 
Comparative 
2 Desalted 
1.8 mg/l 
0.5 mg/l 
160 (-) (-) (+) 
Example water 
Comparative 
3 Tap water 
2.1 mg/l 
7.2 mg/l 
50 (+) (+) (++) 
Example 
Present 
4 Desalted 
2.0 mg/l 
0.7 mg/l 
50 (-) (-) (+) 
Invention water 
Comparative 
5 Tap water 
17 mg/l 
7 mg/l 
10 (+++) (+++) (+++) 
Example 
Present 
6 Desalted 
2.4 mg/l 
1.1 mg/l 
10 (-) (-) (-) 
Invention water 
Comparative 
7 Tap water 
16 mg/l 
8 mg/l 
2 (++) (++) (++) 
Example 
Present 
8 Desalted 
2.5 mg/l 
1.3 mg/l 
2 (-) (- ) (-) 
Invention water 
__________________________________________________________________________ 
Explanation of 
(Turbidity of Washing (Proliferation of Mold 
Ideograms 
Water) (Degree of Deposition) 
on the Paper) 
(-) not observed no deposit no proliferation 
(+) observed (in small degree) 
observed (in small degree) 
observed (in small degree) 
(++) observed (in some degree) 
observed (in some degree) 
observed (in some degree) 
(+++) observed (in great degree) 
observed (in great degree) 
observed (in great degree) 
EXAMPLE 4 
There was prepared a multilayered color photosensitive material (hereunder 
referred to as Sample N1) by applying, in order, the following layers, 
each of which had the composition given below, on a substrate of cellulose 
triacetate film provided with an underlying coating. 
Composition of the Photosensitive Layer 
In the following composition, each component was represented by coated 
amount expressed as g/m.sup.2, while as to silver halide, the amount was 
represented by coated amount expressed as a reduced amount of elemental 
silver, provided that the amounts of sensitizing dyes and couplers were 
represented by coated amount expressed as molar amount per unit mole of 
silver halide included in the same layer. 
Sample N1 
1st Layer: Halation Inhibiting Layer 
______________________________________ 
Black colloidal silver 0.18 (silver) 
Gelatin 1.40 
______________________________________ 
2nd Layer: Intermediate Layer 
______________________________________ 
2,5-Di-tert-pentadecylhydroquinone 
0.18 
C-1 0.07 
C3 0.02 
U-1 0.08 
U-2 0.08 
HBS-1 0.10 
HBS-2 0.02 
Gelatin 1.04 
______________________________________ 
3rd Layer: First Red-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.50 (silver) 
(AgI content = 6 mole %; average 
particle size = 0.8.mu.) 
Sensitizing dye IX 6.9 .times. 10.sup.-5 
Sensitizing dye II 1.8 .times. 10.sup.-5 
Sensitizing dye III 3.1 .times. 10.sup.-4 
Sensitizing dye IV 4.0 .times. 10.sup.-5 
C-2 0.146 
HBS-1 0.005 
C-10 0.0050 
Gelatin 1.20 
______________________________________ 
4th Layer: Second Red-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
1.15 (silver) 
(AgI content = 5 mole %; average 
grain size = 0.85.mu.) 
Sensitizing dye IX 5.1 .times. 10.sup.-5 
Sensitizing dye II 1.4 .times. 10.sup.-5 
Sensitizing dye III 2.3 .times. 10.sup.-4 
Sensitizing dye IV 3.0 .times. 10.sup.-5 
C-2 0.060 
C-3 0.008 
C-10 0.004 
HBS-1 0.005 
Gelatin 1.50 
______________________________________ 
5th Layer: Third Red-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
1.50 (silver) 
(AgI content = 10 mole %; average 
grain size = 1.5.mu.) 
Sensitizing dye IX 5.4 .times. 10.sup.-5 
Sensitizing dye II 1.4 .times. 10.sup.-5 
Sensitizing dye III 2.4 .times. 10.sup.-4 
Sensitizing dye IV 3.1 .times. 10.sup.-5 
C-5 0.012 
C-3 0.003 
C-4 0.004 
HBS-1 0.32 
Gelatin 1.63 
______________________________________ 
6th Layer: Intermediate Layer 
______________________________________ 
Gelatin 1.06 
______________________________________ 
7th Layer: First Green-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.35 (silver) 
(AgI content = 6 mole %; average 
grain size = 0.8.mu.) 
Sensitizing dye V 3.0 .times. 10.sup.-5 
Sensitizing dye VI 1.0 .times. 10.sup.-4 
Sensitizing dye VII 3.8 .times. 10.sup.-4 
C-6 0.120 
C-1 0.021 
C-7 0.030 
C-8 0.025 
HBS-1 0.20 
Gelatin 0.70 
______________________________________ 
8th Layer: Second Green-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.75 (silver) 
(AgI content = 5 mole %; average 
grain size = 0.85.mu.) 
Sensitizing dye V 2.1 .times. 10.sup.-5 
Sensitizing dye VI 7.0 .times. 10.sup.-5 
Sensitizing dye VII 2.6 .times. 10.sup.-4 
C-6 0.021 
C-8 0.004 
C-1 0.002 
C-7 0.003 
HBS-1 0.15 
Gelatin 0.80 
______________________________________ 
9th Layer: Third Green-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
1.80 (silver) 
(AgI content = 10 mole %; average 
grain size = 1.5.mu.) 
Sensitizing dye V 3.5 .times. 10.sup.-5 
Sensitizing dye VI 8.0 .times. 10.sup.-5 
Sensitizing dye VII 3.0 .times. 10.sup.-4 
C-16 0.012 
C-1 0.001 
HBS-2 0.69 
Gelatin 1.74 
______________________________________ 
10th Layer: Yellow Filter Layer 
______________________________________ 
Yellow colloidal silver 0.05 (silver) 
2,5-Di-tert-pentadecylhydroquinone 
0.03 
Gelatin 0.95 
______________________________________ 
11th Layer: First Blue-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.24 (silver) 
(AgI content = 6 mole %; average 
grain size = 0.6.mu.) 
Sensitizing dye VIII 3.5 .times. 10.sup.-4 
C-9 0.27 
C-8 0.005 
HBS-1 0.28 
Gelatin 1.28 
______________________________________ 
12th Layer: Second Blue-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.45 (silver) 
(AgI content = 10 mole %; average 
grain size = 1.0.mu.) 
Sensitizing dye VIII 2.1 .times. 10.sup.-4 
C-9 0.098 
HBS-1 0.03 
Gelatin 0.46 
______________________________________ 
13th Layer: Third Blue-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.77 (silver) 
(AgI content = 10 mole %; average 
grain size = 1.8.mu.) 
Sensitizing dye VIII 2.2 .times. 10.sup.-4 
C-9 0.036 
HBS-1 0.07 
Gelatin 0.69 
______________________________________ 
14th Layer: First Protective Layer 
______________________________________ 
Silver iodobromide emulsion 
0.5 (silver) 
(AgI content = 1 mole %; average 
grain size = 0.07.mu.) 
U-1 0.11 
U-2 0.17 
Butyl p-hydroxybenzoate 0.012 
HBS-1 0.90 
______________________________________ 
15th Layer: Second Protective Layer 
______________________________________ 
Particles of polymethylmethacrylate 
0.54 
(diameter = about 1.5 .mu.m) 
S-1 0.15 
S-2 0.10 
Gelatin 0.72 
______________________________________ 
To each layers, there are added a gelatin hardening agent H-1 and a 
surfactant in addition to the aforementioned components. 
Samples N2 and N3 
These Samples N2 and N3 were prepared according to the same procedures as 
those for preparing Sample N1 except that C-10 used in the compositions of 
the third and fourth layers was replaced with C-11 and C-12 respectively. 
##STR10## 
Color negative films thus prepared (Samples N1, N2 and N3) were cut in long 
band-like films of 35 mm in width. Then, a standard object was 
photographed in the open air using the color negative film (Sample N1). 
Thereafter, the color negative film was processed, by an autodeveloping 
machine, according to the processing steps shown in Table 12 and utilizing 
processing liquids given below. 
TABLE 12 
______________________________________ 
Processing Steps 
Pro- 
Pro- cessing Tank Amount 
cessing Temp. Volume Replenished* 
Steps Time (.degree.C.) 
(l) (ml) 
______________________________________ 
Color Development 
2 min. 38 8 15 
30 sec. 
Bleaching-Fixing 
3 min. 38 8 25 
Water Washing (1) Water Washing (2) Water Washing (3) 
30 sec. 30 sec. 30 sec. 
35 35 35 
##STR11## 
(see Table 13) 
Stabilization 
30 sec. 35 4 5 
______________________________________ 
*This was expressed as the amount per unit length (1 m) of the 
photosensitive material (width: 35 mm). 
In the foregoing processing steps, water washing steps (1) to (3) were 
carried out according to countercurrent water washing system from (3) to 
(1). Each processing liquid had the following composition: 
______________________________________ 
Mother Replenishing 
Liquor Liquid 
Component (g) (g) 
______________________________________ 
(Color Developing Liquid) 
Diethylenetriamine- 1.0 1.1 
pentaacetic acid 
1-hydroxyethylidene-1,1- 
2.0 2.2 
diphosphonic acid 
Sodium sulfite 4.0 4.9 
Potassium carbonate 30.0 42.0 
Potassium bromide 1.6 -- 
Potassium iodide 2.0 (mg) -- 
Hydroxylamine 2.4 3.6 
4-(N-ethyl-N-.beta.-hydroxy- 
5.0 7.3 
ethylamino)-2-methylaniline, 
sulfate 
Water (Amount required to obtain 1 
liter of the intended solutions) 
pH 10.00 10.05 
(Bleaching-Fixing Liquid) 
Ferric ammonium ethylene- 
60.0 66.0 
diamine-tetraacetate 
Disodium ethylene- -- -- 
diaminetetraacetate 
Sodium sulfite 12.0 20.0 
Ammonium thiosulfate 
220 (ml) 250 (ml) 
(70% (w/v) aqueous solution) 
Ammonium nitrate 10.0 12.0 
Bleaching agent 0.5 0.7 
##STR12## 
Aqueous ammonia 13.0 (ml) 12.0 (ml) 
Water (Amount required to 
form 1 liter of these solutions) 
pH 6.7 6.5 
(Stabilization Solution) 
Formalin (37% w/v) 2.0 ml 
Polyoxyethylene-p-monononyl 0.3 g 
phenyl ether (average degree 
of polymerization = 10) 
EDTA.2Na 0.05 g 
Water to 1 
pH 5.0-8.0 
______________________________________ 
Water washing processes and other conditions of processing were shown in 
Table 13 below. 
TABLE 13 
__________________________________________________________________________ 
Conditions of Processing 
Amount carried 
Amount Properties of 
over from 
of Water Washing Water 
the Preceding 
Replenishing 
Ratio 
and Replenishing 
Amount 
Running 
Bath (A) *3 
(B) *4 (B/A) 
Washing Water 
Processed 
__________________________________________________________________________ 
1 2 ml 1000 ml 
500 tap water *5 
30 m/day .times. 
10 days 
2 2 ml 1000 ml 
500 ion exchange 
30 m/day .times. 
water *6 10 days 
3 2 ml 100 ml 
50 tap water *5 
30 m/day .times. 
10 days 
4 2 ml 100 ml 
50 ion exchange 
30 m/day .times. 
water *6 10 days 
5 2 ml 20 ml 10 tap water *5 
30 m/day .times. 
10 days 
6 2 ml 20 ml 10 ion exchange 
30 m/day .times. 
water *6 10 days 
__________________________________________________________________________ 
*3 This is the same as that disclosed in Example 3. 
*4 This is the value on the basis of the unit length (1 m) of the 
processed photosensitive material (width = 35 mm). 
*5 The properties of tap water were as follows: 
pH 7.4 
Ca ions 35 mg/l 
Mg ions 6 mg/l 
*6 This ion exchange water was obtained by treating the foregoing tap 
water with an Natype strong acidic cation exchange resin (manufactured an 
sold under the trade name of Diaion SE1B by MITSUBISHI CHEMICAL INDUSTRIE 
LTD.) and had the following properties: 
pH 6.9 
Ca ions 2.5 mg/l 
Mg ions 0.8 mg/l 
After continuing the processing as shown in Table 13 for 10 days, the 
concentrations of calcium and magnesium in the final water washing bath 
(third bath) were determined according to atomic-absorption spectroscopy 
as well as the turbidity of water in each of the water washing baths was 
also inspected. 
Thereafter, the color negative films N1, N2 and N3 were processed and then 
these films were examined on whether the proliferation of mold on the 
processed color negative films was observed or not when they were 
maintained under high temperature and humidity conditions. Results 
obtained are shown in the following Table 14. 
TABLE 14 
__________________________________________________________________________ 
Turbidity 
Kind of 
Concn. in the Final 
of the 
Color 
Water Washing Bath 
Ratio 
Washing 
Negative 
Proliferation 
Running 
Calcium 
Magnesium 
(B/A) 
Water Film of Mold 
__________________________________________________________________________ 
Comparative 
1 34 mg/l 
7 mg/l 
160 (-) N1 (+) 
Example N2 (+) 
N3 (+) 
Comparative 
2 2.5 mg/l 
0.8 mg/l 
160 (-) N1 (+) 
Example N2 (+) 
N3 (+) 
Comparative 
3 27 mg/l 
8 mg/l 
50 (+) N1 (+) 
Example N2 (+) 
N3 (++) 
Present 
4 2.7 mg/l 
0.9 mg/l 
50 (-) N1 (-) 
Invention N2 (-) 
N3 (+) 
Comparative 
5 24 mg/l 
7 mg/l 
10 (++) N1 (++) 
Example N2 (++) 
N3 (+++) 
Present 
6 2.9 mg/l 
1.1 mg/l 
10 (-) N1 (-) 
Invention N2 (- ) 
N3 (-) 
__________________________________________________________________________ 
The meanings of the ideograms (-), (+), (++) and (+++) appearing in this 
Table have already been given above in connection with Table 11. 
As seen from the results given in Table 14, it is clear that the invention 
makes it possible to substantially suppress the turbidity of the washing 
water and the proliferation of mold on the color negative films tested by 
limiting the amount of calcium and magnesium coexisting in the washing 
water if the ratio (B/A) is 50 and 10 which are within the range defined 
in the present invention. 
EXAMPLE 5 
Color paper and color negative films were prepared according to the same 
procedures as those in Example 1 or Example 4 except that the yellow 
couplers, cyan couplers and magenta couplers as used therein were 
partially or completely replaced with those listed below and the resulting 
color paper and color negative films were developed in accordance with 
those described in Example 1 or 4 except for using a desalted water which 
fulfilled the requirements defined in the present invention to wash the 
processed paper or films. The same excellent results as in Examples 1 and 
4 were obtained. 
##STR13## 
EXAMPLE 6 
The procedures as described in Example 4 were repeated except that the 
following processing steps and a developer, a bleaching liquid and a 
bleaching-fixing liquid having compositions described below were employed. 
Accordingly, the water washing process of the present invention provided 
excellent results as in the case of Example 4. 
TABLE 15 
______________________________________ 
Processing Steps (Temp. = 38.degree. C.) 
Tank Amount 
Volume Replenished* 
Step Processing Time 
(l) (ml) 
______________________________________ 
Color Development 
3 min. 15 sec. 10 38 
Bleaching 1 min. 4 18 
Bleaching-Fixing 
3 min. 15 sec. 10 27 
Water Washing (1) 40 sec. 4 -- 
Water Washing (2) 
1 min. 4 27 
Stabilization 40 sec. 4 18 
______________________________________ 
*This value is expressed as that per unit length (1 m) of the color 
photographic paper (35 mm in width). 
In the foregoing processing steps, the water washing steps (1) and (2) were 
carried out according to countercurrent washing system from (2) to (1). 
Moreover, overflow liquid associated with the replenishment of the 
bleaching liquid was introduced into the bleaching-fixing bath. 
__________________________________________________________________________ 
(Color Developing Liquid) 
Mother Liquor 
Replenishing Liquid 
Component (g) (g) 
__________________________________________________________________________ 
Diethylenetriamine- 1.0 1.1 
pentaacetic acid 
1-Hydroxyethylidene-1,1- 
2.0 2.2 
diphosphonic acid 
Sodium sulfite 4.0 4.9 
Potassium Carbonate 30.0 36.0 
Potassium bromide 1.6 0.7 
Potassium iodide 2.0 (mg) 
-- 
Hydroxylamine 2.4 3.6 
4-(N-Ethyl-N-.beta.-hydroxy- 
5.0 5.5 
ethylamino)-2-methylaniline. 
sulfate 
Water (Amount required to form 1 liter 
of the intended solutions) 
pH 10.0 10.05 
__________________________________________________________________________ 
(Bleaching Liquid) 
Mother Liquor and 
Replenishing Liquid 
Component (g) 
__________________________________________________________________________ 
Ammonium bromide 100 
Ferric ammonium ethylenediamine- 
120 
tetraacetate 
Disodium ethylenediaminetetraacetate 
10.0 
Ammonium nitrate 10.0 
Bleaching accelerator 2.0 
(N(CH.sub.3).sub.2 --(CH.sub.2).sub.2 --S--S--(CH.sub.2).sub.2 --N(CH.sub. 
3).sub.2) 
Aqueous ammonia 17.0 (ml) 
Water (Amount required to form 1 liter 
of the intended solution) 
pH 6.5 
__________________________________________________________________________ 
(Bleaching-Fixing Liquid) 
Mother Liquor 
Replenishing Liquid 
Component (g) (g) 
__________________________________________________________________________ 
Ammonium bromide 50.0 -- 
Ferric ammonium ethylene- 
50.0 -- 
diaminetetraacetate 
Disodium ethylenediamine- 
5.0 1.0 
tetraacetate 
Ammonium nitrate 5.0 -- 
Sodium sulfite 12.0 20.0 
Aqueous ammonium 240 (ml) 
400 (ml) 
thiosulfate solution (70%) 
Aqueous ammonia 10.0 
(ml) 
-- 
Water (Amount required to obtain 1 liter 
of the intended solution) 
pH 7.3 8.0 
__________________________________________________________________________ 
EXAMPLE 7 
A multilayered color photographic paper (hereunder referred to as Sample 
P.sub.5) having a layer structure as described in the following Table 15 
was prepared on a paper substrate, both surfaces of which were laminated 
with polyethylene films. Each of coating liquids used in this Example was 
prepared according to the following procedures: 
Sample P.sub.5 
Preparation of Coating Liquid for 1st Layer 
As yellow coupler (a) (19.1 g) and a dye image stabilizer (b) (4.4 g) were 
added to and dissolved in 27.2 ml of ethyl acetate and 7.9 ml of solvent 
(c) and the resultant solution was dispersed in 185 ml of 10% aqueous 
gelatin solution containing 8 ml of 10% sodium dodecylbenzenesulfonate 
solution to form an emulsion. On the other hand, 90 g of a blue-sensitive 
emulsion was prepared by adding the blue-sensitive sensitizing dye as used 
in Example 1 to a silver chlorobromide emulsion (AgBr content=80 mole %; 
Ag content=70 g/kg emulsion) in an amount of 7.0.times.10.sup.-4 moles per 
one mole of the silver chlorobromide. The emulsified dispersion and the 
blue-sensitive emulsion prepared above were admixed with each other and 
the concentration of gelatin was controlled so as to consist with the 
composition listed in Table 16 to obtain a coating liquid for first layer. 
Coating liquids for second to seventh layers were also prepared in 
accordance with procedures similar to those for preparing the first 
coating liquid. In each of these layers, sodium salt of 
1-oxy-3,5-dichloro-s-triazine was used as a hardening agent for gelatin. 
In this Example 7, spectral sensitizing agents, dyes as an irradiation 
resistant dyes used for each emulsion were the same as those used in 
Example 1 provided that in the blue-sensitive emulsion layer the 
corresponding compound was used in an amount of 7.0.times.10.sup.-4 moles 
per unit mole of silver halide. 
The structures of the compounds such as couplers or the like have already 
been described with respect to Example 1 except for the following 
compounds: 
##STR14## 
TABLE 16 
______________________________________ 
Layer Principal Composition 
Amount Used 
______________________________________ 
7th layer Gelatin 1.33 g/m.sup.2 
(Protective layer) 
Acrylic acid modified 
0.17 g/m.sup.2 
polyvinyl alcohol 
copolymer (degree of 
modification = 17%) 
6th layer Gelatin 0.54 g/m.sup.2 
(UV absorbing 
UV absorber (h) 0.21 g/m.sup.2 
layer) Solvent (j) 0.09 g/m.sup.2 
5th layer Silver chlorobromide 
0.26 g/m.sup.2 
(Red-sensitive 
emulsion (AgBr content = 
(Ag) 
layer) 70 mole %) 
Gelatin 0.98 g/m.sup.2 
Cyan coupler (k) 0.38 g/m.sup.2 
Dye image stabilizer (l) 
0.17 g/m.sup.2 
Solvent (m) 0.23 cc/m.sup.2 
4th layer Gelatin 1.60 g/m.sup.2 
(UV absorbing 
UV absorber (h) 0.62 g/m.sup.2 
layer) Color mixing inhibitor (i) 
0.05 g/m.sup.2 
Solvent (j) 0.26 cc/m.sup.2 
3rd layer Silver chlorobromide 
0.16 g/m.sup.2 
(Green-sensitive 
emulsion (AgBr content = 
(Ag) 
layer) 75 mole %) 
Gelatin 1.80 g/m.sup.2 
Magenta coupler (e) 
0.34 g/m.sup.2 
Dye image stabilizer (f) 
0.20 g/m.sup.2 
Solvent (g) 0.68 cc/m.sup.2 
2nd layer Gelatin 0.99 g/m.sup.2 
(Color mixing 
Color mixing inhibitor (d) 
0.08 g/m.sup.2 
inhibiting layer) 
1st layer Silver chlorobromide 
0.30 g/m.sup. 2 
emulsion (AgBr content = 
(Ag) 
80 mole %) 
(Blue-sensitive 
Gelatin 1.86 g/m.sup.2 
layer) Yellow coupler (a) 
0.82 g/m.sup.2 
Dye image stabilizer (b) 
0.19 g/m.sup.2 
Solvent (c) 0.34 cc/m.sup.2 
Substrate Paper laminated with polyethylene 
films (the polyethylene film situated 
at the side of 1st layer contains a 
white pigment (TiO.sub.2) and a bluing dye 
(Ultramarine Blue)) 
______________________________________ 
The multilayered color photographic paper thus prepared was cut into long 
band-like paper of 82.5 mm in width, they were then exposed to light using 
an autoprinter and thereafter processed by an autodeveloping machine 
according to the following processing steps shown in Table 17 below. 
TABLE 17 
______________________________________ 
Processing Steps 
Pro- Tank Amount 
Temp. cessing Volume Replenished* 
Step (.degree.C.) 
Time (l) (ml) 
______________________________________ 
Color Development 
38 1 min. 16 24 
40 sec. 
Bleaching-Fixing 
33 1 min. 10 13 
Water Washing (1) Water Washing (2) Water Washing (3) 
33 33 33 
20 sec. 20 sec. 20 sec. 
##STR15## 
three-stage countercurrent water 
washing system 30 
______________________________________ 
*The amount is expressed as that per unit length (1 m) of the processed 
color photographic paper (82.5 mm in width). 
In the above processing, the amount of the bleaching-fixing liquid carried 
over in the washing bath (1) by the processed color photographic paper 
from the bleaching-fixing bath was 2.5 ml per unit length (1 m) of the 
photographic paper (82.5 mm in width) and the amount of washing water 
replenished was 12 times of the amount of bleaching-fixing liquid carried 
over. 
Each of the processing liquids used in these steps had the following 
composition. 
______________________________________ 
Component Mother Liquor 
Replenishing Liquid 
______________________________________ 
(Color Developing Liquid) 
Water 800 ml 800 ml 
1-Hydroxyethylidene-1,1- 
1.5 ml 1.5 ml 
diphosphonic acid 
(60% solution) 
Diethylenetriaminepenta- 
1.0 g 1.0 g 
acetic acid 
Benzyl alcohol 16 ml 20 ml 
Ethylene glycol 
10 ml 10 ml 
Sodium sulfite 2.0 g 2.5 g 
Hydroxylamine sulfate 
3.0 g 3.5 g 
Potassium bromide 
1.0 g -- 
Sodium carbonate 
30 g 35 g 
Disodium 4,5-dihydroxy- 
1.0 g 1.1 g 
m-benzenedisulfonate 
Fluorescent whitener 
1.0 g 1.5 g 
(stilbene type) 
N-Ethyl-N-(.beta.-methane- 
6.0 g 8.0 g 
sulfonamidethyl)-3-methyl- 
4-aminoamiline.sulfate 
Water (Amount required to obtain 1 liter of the intended liquids) 
pH 10.25 10.60 
(Bleaching-Fixing Liquid) 
Water 400 ml 400 ml 
Ammonium thiosulfate 
150 ml 200 ml 
(70% solution) 
Sodium sulfate 18 g 25 g 
Ferric ammonium 
55 g 65 g 
ethylenediaminetetra 
acetic acid 
Ethylenediaminetetraacetic 
5 g 10 g 
acid 
Water (Amount required to obtain one liter of the intended 
liquids) 
pH (Aqueous ammonia or 
6.75 6.50 
acetic acid) 
______________________________________ 
Washing Water 
(A) Well water having the following properties was passed through a column 
packed with H-type strong acidic cation exchange resin (manufactured and 
sold under the trade name of Diaion SA-1B by MITSUBISHI CHEMICAL 
INDUSTRIES LTD.) and OH-type strong basic anion exchange resin 
(manufactured and sold under the trade name of Diaion SA-10A by MITSUBISHI 
CHEMICAL INDUSTRIES LTD.) to soften the well water and the resultant soft 
water was used as the washing water (hereunder referred to as washing 
water (A)). 
TABLE 18 
______________________________________ 
Properties of the Washing Water 
Before Ion Exchange 
After Ion Exchange 
______________________________________ 
pH 6.8 6.6 
Calcium ions 
31 mg/l 0.4 mg/l 
Magnesium ions 
11 mg/l 0.1 mg/l 
Chlorine ions 
30 mg/l 0.6 mg/l 
Residue after 
150 mg/l 8.7 mg/l 
evaporation 
______________________________________ 
(B) Washing water (B) was prepared by adding sodium dichloroisocyanurate to 
the foregoing ion exchange water (washing water (A)) in an amount of 10 mg 
per liter of the latter. 
(C) Washing water (c) was prepared by adding silver nitrate to the washing 
water (A) in an amount of 0.3 mg/l. 
(D) Washing water (D) was obtained by adding sodium dichloroisocyanurate to 
the well water prior to subjecting it to ion exchange treatment in an 
amount of 10 mg/l. 
The color photographic paper described above was processed at a rate of 180 
m/day for 6 days using each of the foregoing washing water (A) to (D) and 
those to which calcium chloride (CaCl.sub.2.2H.sub.2 O) and magnesium 
chloride (MgCl.sub.2.6H.sub.2 O) were added so that the concentrations 
thereof were consistent with those listed in the following Table 19. 
Thereafter, each washing water was collected in a test tube, followed by 
maintaining at room temperature (about 25.degree. C.) and term (days) 
which elapsed until the formation of a bacterial floating matter on the 
surface of the collected water was observed were determined. 
TABLE 19 
______________________________________ 
Term (days) 
elapsed till 
the Formation 
of Bacterial 
Ca Mg floating 
Washing Concn. Concn. 
matter was 
No. Water (Mg/l) (mg/l) 
observed 
______________________________________ 
Present 1 A 1.1 0.3 5 days 
Invention 
Present 2 A 3 3 5 days 
Invention 
Present 3 A 5 5 4 days 
Invention 
Comparative 
4 A 10 10 2 days 
Example 
Present 5 B 0.9 0.4 at least 
Invention 10 days 
Present 6 B 2 2 at least 
Invention 10 days 
Present 7 B 3 3 at least 
Invention 10 days 
Present 8 B 5 5 7 days 
Invention 
Comparative 
9 B 10 10 2 days 
Example 
Present 10 C 1.2 0.5 at least 
Invention 10 days 
Present 11 C 3 3 at least 
Invention 10 days 
Present 12 C 5 5 6 days 
Invention 
Comparative 
13 C 10 10 2 days 
Example 
Comparative 
14 D 31 9 1 day 
Example 
______________________________________ 
As shown in Table 19, it is clear that the formation of bacterial floating 
matter is substantially suppressed by reducing the concentrations of 
calcium and magnesium to not more than 5 mg/l respectively and 
simultaneously sterilizing the washing water. 
EXAMPLE 8 
The procedures similar to those in Example 6 were repeated except that a 
photographic paper (hereunder referred to as Sample P.sub.6) prepared 
according to a manner given below was used instead of the color 
photographic paper P.sub.5 and that the mother liquor and the replenishing 
liquid for color development from which benzyl alcohol and ethylene glycol 
were removed were used and the same test as in Example 7 was carried out. 
Results obtained are summarized in the following Table 20-2. 
Sample P.sub.6 
On a paper substrate, both surface of which were laminated with 
polyethylene films, a multilayered color photographic paper having a layer 
structure shown in Table 20-1 was prepared. The coating liquids used were 
prepared according to the following procedures: 
Preparation of Coating Liquid for 1st Layer 
An yellow coupler (a) (19.1 g) and a dye image stabilizer (b) (4.4 g) were 
added to and dissolved in 27.2 cc of ethyl acetate and 7.7 cc of solvent 
(c) and the resultant solution was dispersed in 185 cc of 10% aqueous 
gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate 
solution to form an emulsion. On the other hand, another emulsion was 
prepared by adding the following blue-sensitive sensitizing dye to a 
silver chlorobromide emulsion (AgBr content=90.0 mole %; Ag content=70 
g/kg emulsion) in an amount of 5.times.10.sup.-4 moles per mole of silver 
halide. These two emulsions prepared above were mixed with one another and 
adjusting the composition so as to be coinsident with that in Table 20-1 
to obtain a coating liquid for 1st layer. Other coating liquids for second 
to seventh layers were also prepared in the same manner as described 
above. As the hardening agent for gelatin in each layer, sodium salt of 
1-oxy-3,5-dichloro-s-triazine was used. 
As the spectral sensitizing dye in each layer, the following compounds were 
used. 
##STR16## 
The following compound was added to the red-sensitive emulsion layer in an 
amount of 2.6.times.10.sup.-3 moles per mole of silver halide: 
##STR17## 
Moreover, to each of the blue-sensitive emulsion layer, the green-sensitive 
emulsion layer and the red-sensitive emulsion layer, there was added 
1-(5-methylareidophenyl)-5-mercaptotetrazole in an amount of 
8.5.times.10.sup.-5, 7.7.times.10.sup.-4 or 2.5.times.10.sup.-4 moles per 
mole of silver halide tetrazaindene was added to the blue-sensitive 
emulsion layer and the green-sensitive emulsion layer in an amount of 
1.2.times.10.sup.-2 and 1.2.times.10.sup.-2 moles per mole of silver 
halide respectively. 
For the purpose of preventing irradiation, the following dyes were added to 
the emulsion layers: 
##STR18## 
TABLE 20-1 
______________________________________ 
Layer Principal Composition 
Amount Used 
______________________________________ 
7th layer Gelatin 1.33 g/m.sup.2 
(Protective 
Acrylic acid modified poly- 
0.17 g/m.sup.2 
layer) vinyl alcohol copolymer 
(degree of modification = 
17%) 
Liquid paraffin 0.03 g/m.sup.2 
6th layer Gelatin 0.53 g/m.sup.2 
(UV absorbing 
UV absorber (i) 0.21 g/m.sup.2 
layer) Solvent (k) 0.08 g/m.sup.2 
5th layer Silver halide emulsion 
0.23 g/m.sup.2 (Ag) 
(Red-sensitive 
Gelatin 1.34 g/m.sup.2 
layer) Cyan coupler (l) 0.34 g/m.sup.2 
Dye image stabilizer (m) 
0.17 g/m.sup.2 
Polymer (n) 0.40 g/m.sup.2 
Solvent (o) 0.23 g/m.sup.2 
4th layer Gelatin 1.58 g/m.sup.2 
(UV absorbing 
UV absorber (i) 0.62 g/m.sup.2 
layer) Color mixing inhibitor (j) 
0.05 g/m.sup.2 
Solvent (k) 0.24 g/m.sup.2 
3rd layer Silver halide emulsion 
0.16 g/m.sup.2 (Ag) 
(Green- Gelatin 1.79 g/m.sup.2 
sensitive Magenta coupler (e) 
0.32 g/m.sup.2 
layer) Dye image stabilizer (f) 
0.20 g/m.sup.2 
Dye image stabilizer (g) 
0.01 g/m.sup.2 
Solvent (h) 0.65 g/m.sup.2 
2nd layer Gelatin 0.99 g/m.sup.2 
(Color mixing 
Color mixing inhibitor (d) 
0.08 g/m.sup.2 
inhibiting 
layer) 
1st layer Silver halide emulsion 
0.26 g/m.sup.2 (Ag) 
(Blue-sensitive 
Gelatin 1.83 g/m.sup.2 
layer) Yellow coupler (a) 
0.83 g/m.sup.2 
Dye image stabilizer (b) 
0.19 g/m.sup.2 
Solvent (c) 0.35 g/m.sup.2 
Substrate Paper laminated with polyethylene films 
(the polyethylene film situated at the side 
of 1st layer contains a white pigment 
(TiO.sub.2) and a bluing dye (Ultramarine Blue)) 
______________________________________ 
##STR19## 
TABLE 20-2 
______________________________________ 
Term (days) 
Elapsed Till 
Bacterial 
Ca Mg floating 
Washing Concn. Concn. 
matter was 
No. Water (Mg/l) (mg/l) 
Formed 
______________________________________ 
Present 1 A 0.9 0.4 7 days 
Invention 
Present 2 A 3 3 7 days 
Invention 
Present 3 A 5 5 6 days 
Invention 
Comparative 
4 A 10 10 3 days 
Example 
Present 5 B 1 0.5 at least 
Invention 10 days 
Present 6 B 3 3 at least 
Invention 10 days 
Present 7 B 5 5 at least 
Invention 10 days 
Comparative 
8 B 10 10 3 days 
Example 
Present 9 C 1.3 0.5 at least 
Invention 10 days 
Present 10 C 3 3 at least 
Invention 10 days 
Present 11 C 5 5 9 days 
Invention 
Comparative 
12 C 10 10 3 days 
Example 
Comparative 
13 D 30 9 2 days 
Example 
______________________________________ 
As seen from Table 20-2, according to the processing method of this 
invention in which the concentration of both calcium and magnesium was not 
more than 5 mg/l in the washing water replenished and the latter was also 
sterilized, the formation of bacterial floating matter can substantially 
be suppressed. 
EXAMPLE 9 
A multilayered color photographic paper (hereunder referred to as "Sample 
P.sub.7 ") having a layer structure shown in Table 21 was prepared on a 
paper substrate, the both surface of which were laminated with 
polyethylene films. Coating liquids used for preparing Sample P.sub.7 were 
formulated as follows: 
Sample P.sub.7 
Preparation of Coating Liquid for First Layer: 
An yellow coupler (a) (19.1 g) and a dye image stabilizer (b) (4.4 g) were 
dissolved in 27.2 ml of ethyl acetate and 7.9 ml of solvent (c) and the 
resulting solution was then dispersed in 185 ml of 10% aqueous gelatin 
solution containing 8 ml of 10% sodium dodecylbenzenesulfonate solution to 
form an emulsion. On the other hand, a blue-sensitive sensitizing dye as 
will be shown below was added to a silver chlorobromide emulsion (AgBr 
content=1 mole %; Ag content=70 g/kg emulsion) in an amount of 
5.0.times.10.sup.-4 moles per mole of silver chlorobromide to obtain 90 g 
of blue-sensitive emulsion. The emulsion and the blue-sensitive emulsion 
separately prepared above were admixed with one another and then the 
gelatin concentration of the resultant mixture was adjusted so as to be in 
accord with that in Table 21 to form an intended coating liquid for first 
layer. Other coating liquids for the second to seventh layers were also 
prepared according to the procedures similar to those described above in 
connection with the coating liquid for the first layer. As the hardening 
agent for gelatin in each of the layers, sodium salt of 
1-oxy-3,5-dichloro-s-triazine was used. 
The following spectral sensitizers were used in each corresponding 
emulsion: 
##STR20## 
In each emulsion layer, the following dyes were used as irradiation 
resistant dyes respectively: 
##STR21## 
The compounds such as couplers used in the present Example had the 
following structural formula: 
##STR22## 
TABLE 21 
______________________________________ 
Layer Principal Composition 
Amount Used 
______________________________________ 
7th layer Gelatin 1.33 g/m.sup.2 
(Protective 
Acrylic acid modified poly- 
0.17 g/m.sup.2 
layer) vinyl alcohol copolymer 
(degree of modification = 
17%) 
6th layer Gelatin 0.54 g/m.sup.2 
(UV absorbing 
UV absorber (h) 0.21 g/m.sup.2 
layer) Solvent (j) 0.09 g/m.sup.2 
5th layer Silver chlorobromide 
0.26 g/m.sup.2 (Ag) 
(Red-sensitive 
emulsion (AgBr content = 
layer) 1 mole %) 
Gelatin 0.98 g/m.sup.2 
Cyan coupler (k) 0.38 g/m.sup.2 
Dye image stabilizer (l) 
0.17 g/m.sup.2 
Solvent (m) 0.23 cc/m.sup.2 
4th layer Gelatin 1.60 g/m.sup.2 
(UV absorbing 
UV absorber (h) 0.62 g/m.sup.2 
layer) Color mixing inhibitor (i) 
0.05 g/m.sup.2 
Solvent (j) 0.26 cc/m.sup.2 
3rd layer Silver chlorobromide 
0.16 g/m.sup.2 (Ag) 
(Green- emulsion (AgBr content = 
sensitive 0.5 mole %) 
layer) Gelatin 1.80 g/m.sup.2 
Magenta coupler (e) 
0.48 g/m.sup.2 
Dye image stabilizer (f) 
0.20 g/m.sup.2 
Solvent (g) 0.68 cc/m.sup.2 
2nd layer Gelatin 0.99 g/m.sup.2 
(Color mixing 
Color mixing inhibitor (d) 
0.08 g/m.sup.2 
inhibiting 
layer) 
1st layer Silver chlorobromide 
0.30 g/m.sup.2 (Ag) 
(Blue-sensitive 
emulsion (AgBr content = 
layer) 1 mole %) 
Gelatin 1.86 g/m.sup.2 
yellow coupler (a) 
0.82 g/m.sup.2 
Dye image stabilizer (b) 
0.19 g/m.sup.2 
Solvent (c) 0.34 cc/m.sup.2 
Substrate Paper laminated with polyethylene films 
(the polyethylene film situated at the side 
of 1st layer contains a white pigment 
(TiO.sub.2) and a bluing dye (Ultramarine Blue)) 
______________________________________ 
The color photographic paper thus prepared was cut into continuous 
band-like ones having a width of 82.5 mm followed by exposing them to 
light with an autoprinter and then the exposed paper was processed with an 
autodeveloping machine according to the following processing steps given 
in Table 22. 
TABLE 22 
______________________________________ 
Processing Steps 
Pro- 
cessing Tank Amount 
Temp. Time Volume Replenished* 
Step (.degree.C.) 
(sec) (l) (ml) 
______________________________________ 
Color Development 
35 45 16 13 
Bleaching-Fixing 
35 45 10 8 
Water Washing (1) Water Washing (2) Water Washing (3) Water Washing 
35 35 35 35 
20 20 20 30 
4 4 4 4 
##STR23## 
Drying 80 60 
______________________________________ 
*The value is expressed as that per unit length (1 m) of the processed 
color photographic paper (82.5 mm in width). 
In the foregoing processing steps, the amount of the bleaching-fixing 
liquid carried over, by the color photographic paper during processing, to 
the water washing bath (1) was 2.5 ml per unit length (1 m) of the paper 
and thus the amount of washing water replenished was 6 times of that of 
the bleaching-fixing liquid carried over. 
The formulation of each processing liquid employed was as follows: 
______________________________________ 
(Color Developing Liquid) 
Mother Liquor 
Replenishing Liquid 
Component (g) (g) 
______________________________________ 
Triethanolamine 
8.0 10.0 
N,N-Diethylhydroxyl- 
4.2 6.0 
amine 
Fluorescent Whitener 
3.0 4.0 
(4,4'-diaminostilbene 
type) 
Ethylenediaminetetra- 
1.0 1.5 
acetic acid 
Potassium carbonate 
30.0 30.0 
Sodium chloride 
1.4 0.1 
4-amino-3-methyl-N- 
5.0 7.0 
ethyl-N-{.beta.-(methane- 
sulfonamide)ethyl}-p- 
phenylenediamine.sulfate 
Water (Amount required to obtain 1 liter of the intended 
solutions) 
pH 10.10 10.50 
______________________________________ 
(Bleaching-Fixing Liquid (Mother Liquor and 
Replenishing Liquid)) 
Component Amount 
______________________________________ 
EDTA.Fe(III).NH.sub.4.2H.sub.2 O 
60 g 
EDTA.2Na.2H.sub.2 O 4 g 
Ammonium thiosulfate (70%) 
120 ml 
Sodium sulfite 16 g 
Glacial acetic acid 7 g 
Water (Amount required to form 1 liter of 
the intended solutions) 
pH 5.5 
______________________________________ 
Washing Water A (Comparative Example): Tap water having the following 
properties: 
pH: 7.1 
Ca ions: 23 mg/l 
Mg ions: 8 mg/l; 
Washing Water B (Comparative Example): Washing water B comprised the 
washing water A and 20 mg of sodium dichloroisocyanurate per 1 liter of 
the former; 
Washing Water C (Present Invention): Washing water C was prepared by 
passing the washing water A through a column packed with H-type strong 
acidic cation exchange resin (manufactuared and sold under the trade name 
of Diaion SK-1B by MITSUBISHI CHEMICAL INDUSTRIES LTD.) and OH-type strong 
basic anion exchange resin (manufactured and sold under the trade name of 
Diaion SA-10A by MITSUBISHI CHEMICAL INDUSTRIES LTD.) to form washing 
water having the following properties: 
pH: 6.9 
Ca ion: 1.5 mg/l 
Mg ion: 0.5 mg/l; 
Washing Water D (Present Invention): This comprised the washing water C and 
20 mg of sodium dichlorocyanurate per 1 liter of the former; 
Washing Water E (Present Invention): This was prepared by filtering the ion 
exchange water (the aforementioned washing water C) through a sterilizing 
filter having a pore size of 0.45 .mu. (manufactured and sold under the 
trade name of Microfilter FCE-45W by Fuji Photo Film Co., Ltd.) 
In the processing in which the washing water A to E were used, the color 
photographic paper (Sample P.sub.7) of 82.5 mm in width was processed at a 
rate of 180 m/day for 6 days followed by the out of operation for 7 days 
and it was observed whether there was the formation of bacterial floating 
matter or not during the term of the out of operation in each of the water 
washing baths. Alternatively, the concentrations of calcium and magnesium 
in the final water washing bath at the time of 6 days after the processing 
were determined by atomic-absorption spectroscopy. Thereafter, the Sample 
P.sub.7 was again processed in the same processing liquids to compare the 
degree of contamination of the color photographic papers with each other. 
TABLE 23 
__________________________________________________________________________ 
Concn. in the 
Final Water 
Washing Bath Degree of Contamin- 
Washing 
Ca Mg Formation of 
ation of Photo- 
No. 
water 
(mg/l) 
(mg/l) 
Bacterial Membrane 
graphic Paper 
__________________________________________________________________________ 
Comparative 
1 A 20 9 Observed after 
(++) 
Example 2 days 
Comparative 
2 B 21 8 Observed after 
(++) 
Example 2 days 
Present 
3 C 1.3 0.7 Observed after 
(+) 
Invention 4 days 
Present 
4 D 1.5 0.6 not observed even 
(-) 
Invention after 7 days 
Present 
5 E 1.5 0.7 not observed even 
(-) 
Invention after 7 days 
__________________________________________________________________________ 
As seen from the results in Table 23, it is clear that the formation of 
bacterial membrane and the contamination of the color photographic paper 
are substantially suppressed or prevented by restricting the amount of 
calcium and magnesium in the washing water replenished and sterilizing the 
latter. 
In addition, the concentrations of calcium and magnesium in the final 
washing water were approximately equal to those in the replenishing liquid 
respectively. 
In Table 23, ideograms (-) to () have the following meanings: 
(-) contamination of the color photographic paper is not observed; 
(+) contamination thereof is observed in small extent; 
() contamination thereof is observed in some extent; 
() contamination thereof is observed in great extent. 
EXAMPLE 10 
The same test as in Example 9 was carried out except that the following 
color photographic paper (hereunder referred to as Sample P.sub.8) was 
used instead of Sample P.sub.7. Consequently, results similar to those in 
Example 9 were obtained. 
Sample P.sub.8 
A multilayered color photographic paper having a layer structure shown in 
Table 24 was prepared on a paper substrate, both surfaces of which were 
laminated with polyethylene films. Coating liquids for preparing the 
photographic paper were obtained according to the following procedures: 
Preparation of Coating Liquid for First Layer 
An yellow coupler (a) (19.1 g) and a dye image stabilizer (b) (4.4 g) were 
dissolved in 27.2 cc of ethyl acetate and 7.7 cc of solvent (c) and the 
resultant solution was dispersed in 185 cc of 10% aqueous gelatin solution 
containing 8 cc of 10% sodium dodecylbenzenesulfonate solution to form an 
emulsion. On the other hand, the following blue-sensitive sensitizing dye 
was added to a silver chlorobromide emulsion (AgBr content=1.0 mole %; Ag 
content.times.70 g/kg emulsion) in an amount of 5.0.times.10.sup.-4 moles 
per mole of silver chlorobromide to form a blue-sensitive silver halide 
emulsion. Then, the emulsion and the blue-sensitive emulsion separately 
prepared above were admixed with each other followed by adjusting the 
concentration of the components so as to be consistent with those listed 
in Table 24 to form a coating liquid for first layer. 
Other coating liquids for second to seventh layers were likewise prepared 
according to the same manner as described above. 
In each layer, sodium salt of 1-oxy-3,5-dichloro-striazine was used as the 
hardening agent for gelatin. 
The following spectral sensitizing dyes were used in each corresponding 
layers: 
##STR24## 
The following compound was added to the red-sensitive emulsion layer in an 
amount of 2.6.times.10.sup.-3 moles per mole of silver halide. 
##STR25## 
Moreover, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to each of 
the blue-sensitive emulsion layer, green-sensitive emulsion layer and 
red-sensitive emulsion layer in an amount of 8.5.times.10.sup.-5, 
7.7.times.10.sup.-4 and 7.5.times.10.sup.-4 moles per mole of solver 
halide respective. 
For the purpose of preventing irradiation, the following dyes were added to 
the emulsion layers: 
##STR26## 
TABLE 24 
______________________________________ 
Amount Used 
Layer Principal Composition 
(g/m.sup.2) 
______________________________________ 
7th layer Gelatin 1.33 
(Protective 
Acrylic acid modified poly- 
0.17 
layer) vinyl alcohol copolymer 
(degree of modification = 
17%) 
Liquid paraffin 0.03 
6th layer Gelatin 0.53 
(UV absorbing 
UV absorber (i) 0.21 
layer) Solvent (k) 0.08 
5th layer Silver halide emulsion 
0.23 (Ag) 
(Red-sensitive 
Gelatin 1.34 
layer) Cyan coupler (l) 0.34 
Dye image stabilizer (m) 
0.17 
Polymer (n) 0.40 
Solvent (o) 0.23 
4th layer Gelatin 1.58 
(UV absorbing 
UV absorber (i) 0.62 
layer) Color mixing inhibitor (j) 
0.05 
Solvent (k) 0.24 
3rd layer Silver halide emulsion 
0.36 (Ag) 
(Green- Gelatin 1.24 
sensitive Magenta coupler (e) 
0.31 
layer) Dye image stabilizer (f) 
0.25 
Dye image stabilizer (g) 
0.12 
Solvent (h) 0.42 
2nd layer Gelatin 0.99 
(Color mixing 
Color mixing inhibitor (d) 
0.08 
inhibiting 
layer) 
1st layer Silver halide emulsion layer 
0.30 (Ag) 
(Blue-sensitive 
Gelatin 1.86 
layer) Yellow coupler (a) 
0.82 
Dye image stabilizer (b) 
0.19 
Solvent (c) 0.35 
Substrate Paper laminated with polyethylene films 
(the polyethylene film situated at the side 
of 1st layer contains a white pigment 
(TiO.sub.2) and a bluing dye (Ultramarine Blue)) 
______________________________________ 
The structural formula of each compound used in the Example is as follows: 
##STR27## 
EXAMPLE 11 
A multilayered color photosensitive material having the following layers of 
the compositions given below was formed on a substrate of a cellulose 
triacetate film provided with an underlying coating. 
Composition of the Photosensitive Material 
In the following formulations, the coated amount of silver halide and 
colloidal silver is expressed as the weight of silver per unit area (1 
m.sup.2) of the photosensitive material, that of couplers, additives and 
gelatin is expressed as the weight thereof per unit area (1 m.sup.2) of 
the photosensitive material and that of sensitizing dyes is expressed as 
molar number thereof per mole of the silver halide in the same layer. 
First Layer (Antihalation Layer) 
______________________________________ 
Component Amount 
______________________________________ 
Black colloidal silver 
0.4 
Gelatin 1.3 
Coupler C-1 0.06 
UV absorber UV-1 0.1 
UV absorber UV-2 0.2 
Dispersion oil Oil-1 
0.01 
Dispersion oil Oil-2 
0.01 
______________________________________ 
2nd Layer (Intermediate Layer) 
______________________________________ 
Component Amount 
______________________________________ 
Silver bromide of fine grain 
0.15 
(average grain size = 0.07.mu.) 
Gelatin 1.0 
Coupler C-2 0.02 
Dispersion oil Oil-1 0.1 
______________________________________ 
3rd Layer (First Red-sensitive Emulsion Layer) 
______________________________________ 
Component Amount 
______________________________________ 
Silver iodobromide emulsion 
1.5 (Ag) 
(AgI content = 6 mole %; ratio 
of diameter to thickness = 2.5; 
average grain size = 0.3.mu.) 
Gelatin 0.6 
Sensitizing dye I 1.0 .times. 10.sup.-4 
Sensitizing dye II 3.0 .times. 10.sup.-4 
Sensitizing dye III 1 .times. 10.sup.-5 
Coupler C-3 0.06 
Coupler C-4 0.06 
Coupler C-8 0.04 
Coupler C-2 0.03 
Dispersion oil Oil-1 0.03 
Dispersion oil Oil-3 0.012 
______________________________________ 
4th Layer (Second Red-sensitive Emulsion Layer) 
______________________________________ 
Component Amount 
______________________________________ 
Silver iodobromide emulsion 
1.5 (Ag) 
(AgI content = 6 mole %; ratio of 
diameter to thickness = 3.5; 
average grain size = 0.5.mu.) 
Sensitizing dye I 1 .times. 10.sup.-4 
Sensitizing dye II 3 .times. 10.sup.-4 
Sensitizing dye III 1 .times. 10.sup.-5 
Coupler C-3 0.24 
Coupler C-4 0.24 
Coupler C-8 0.04 
Coupler C-2 0.04 
Dispersion oil Oil-1 0.15 
Dispersion oil Oil-3 0.02 
______________________________________ 
5th Layer (Third Red-sensitive Emulsion Layer) 
______________________________________ 
Component Amount 
______________________________________ 
Silver iodobromide emulsion 
2.0 (Ag) 
(AgI content = 10 mole %; ratio of 
diameter to thickness = 1.5; average 
grain size = 0.7.mu.) 
Gelatin 1.0 
Sensitizing dye I 1 .times. 10.sup.-4 
Sensitizing dye II 3 .times. 10.sup.-4 
Sensitizing dye III 1 .times. 10.sup.-5 
Coupler C-6 0.05 
Coupler C-7 0.1 
Dispersion oil Oil-1 0.01 
Dispersion oil Oil-2 0.05 
______________________________________ 
6th Layer (Intermediate Layer) 
______________________________________ 
Component Amount 
______________________________________ 
Gelatin 1.0 
Compound Cpd-A 0.03 
Dispersion oil Oil-1 
0.05 
______________________________________ 
7th Layer (First Green-sensitive Emulsion Layer) 
______________________________________ 
Component Amount 
______________________________________ 
Silver iodobromide emulsion 
0.7 (Ag) 
(AgI content = 6 mole %; ratio of 
diameter to thickness = 2.5; average 
grain size = 0.3.mu.) 
Sensitizing dye IV 5 .times. 10.sup.-4 
Sensitizing dye VI 0.3 .times. 10.sup.-4 
Sensitizing dye V 2 .times. 10.sup.-4 
Gelatin 1.0 
Coupler C-9 0.2 
Coupler C-5 0.03 
Coupler C-1 0.03 
Compound Cpd-C 0.012 
Dispersion oil Oil-1 0.5 
______________________________________ 
8th Layer (Second Green-sensitive Emulsion Layer) 
______________________________________ 
Component Amount 
______________________________________ 
Silver iodobromide emulsion 
1.4 (Ag) 
(AgI content = 5 mole %; ratio of 
diameter to thickness = 3.5; average 
grain size = 0.5.mu.) 
Sensitizing dye IV 5 .times. 10.sup.-4 
Sensitizing dye V 2 .times. 10.sup.-4 
Sensitizing dye VI 0.3 .times. 10.sup.-4 
Coupler C-9 0.25 
Coupler C-1 0.03 
Coupler C-10 0.015 
Coupler C-5 0.01 
Compound Cpd-C 0.012 
Dispersion oil Oil-1 0.2 
______________________________________ 
9th Layer (Third Green-sensitive Emulsion Layer) 
______________________________________ 
Component Amount 
______________________________________ 
Silver iodobromide emulsion 
1.9 (Ag) 
(AgI content = 10 mole %; ratio of 
diameter to thickness = 1.5; average 
grain size = 0.7.mu.) 
Gelatin 1.0 
Sensitizing dye VII 3.5 .times. 10.sup.-4 
Sensitizing dye VIII 1.4 .times. 10.sup.-4 
Coupler C-11 0.01 
Coupler C-12 0.03 
Coupler C-13 0.20 
Coupler C-1 0.02 
Coupler C-15 0.02 
Dispersion oil Oil-1 0.20 
Dispersion oil Oil-2 0.05 
______________________________________ 
10th Layer (Yellow Filter Layer) 
______________________________________ 
Component Amount 
______________________________________ 
Gelatin 1.2 
Yellow colloidal silver 
0.16 
Compound Cpd-B 0.1 
Dispersion oil Oil-1 
0.3 
______________________________________ 
11th Layer (First Blue-sensitive Emulsion Layer) 
______________________________________ 
Component Amount 
______________________________________ 
Monodispersed silver iodobromide 
1.0 (Ag) 
emulsion (AgI content = 6 mole %; 
ratio of diameter to thickness = 1.5; 
average grain size = 0.3.mu.) 
Gelatin 1.0 
Sensitizing dye IX 2 .times. 10.sup.-4 
Coupler C-14 0.9 
Coupler C-5 0.07 
Dispersion oil Oil-1 0.2 
______________________________________ 
12th Layer (Second Blue-sensitive Emulsion Layer) 
______________________________________ 
Component Amount 
______________________________________ 
Silver iodobromide emulsion 
0.9 (Ag) 
(AgI content = 10 mole %; ratio of 
diameter to thickness = 1.5; average 
grain size = 1.5.mu.) 
Gelatin 0.6 
Sensitizing dye IX 1 .times. 10.sup.-4 
Coupler C-14 0.25 
Dispersion oil Oil-1 0.07 
______________________________________ 
13th Layer (First Protective Layer) 
______________________________________ 
Component Amount 
______________________________________ 
Gelatin 0.8 
UV absorber UV-1 0.1 
UV absorber UV-2 0.2 
Dispersion oil Oil-1 
0.01 
Dispersion oil Oil-2 
0.01 
______________________________________ 
14th Layer (Second Protective Layer) 
______________________________________ 
Component Amount 
______________________________________ 
Silver bromide of fine grain 
0.5 
(average grain size = 0.07.mu.) 
Gelatin 0.45 
Polymethylmethacrylate particles 
0.2 
(diameter = 1.5.mu.) 
Hardening agent H-1 0.4 
n-Butyl p-hydroxybenzoate 
0.012 
Formaldehyde scavenger S-1 
0.5 
Formaldehyde scavenger S-2 
0.5 
______________________________________ 
In each of these layers, a surfactant was incorporated as a coating 
additive in addition to the aforementioned components. The sample thus 
prepared will hereunder be referred to as "Sample N4". 
Nomenclature or the structural formula of the compounds used in this 
Example will be given below: 
##STR28## 
The multilayered color photosensitive material, Sample N.sub.4, was cut 
into continuous band-like ones having a width of 35 mm and there a 
standard object was photographed in the open air utilizing the cut Sample 
N.sub.4. Thereafter, Sample N.sub.4 was processed, by an autodeveloping 
machine, according to the processing steps described in Table 25 given 
below. 
TABLE 25 
______________________________________ 
Processing Steps 
Pro- Processing 
Tank Amount 
cessing Temp. Volume Replenished* 
Step Time (.degree.C.) 
(l) (ml) 
______________________________________ 
Color 3 min. 38 8 45 
Development 
15 sec. 
Bleaching 
1 min. 38 4 20 
Bleaching- 
3 min. 38 8 30 
Fixing 15 sec. 
Water Washing (1) Water Washing (2) 
40 sec. 35 35 
##STR29## 
Two-stage Counter- current Wash- ing 
System 30 
Stabilization 
40 sec. 35 4 20 
______________________________________ 
*This amount is expressed as that per unit length (1 m) of the processed 
photosensitive material (35 mm in width). 
In the foregoing processing steps, the water washing steps (1) and (2) were 
carried out according to a countercurrent water washing system from the 
bath (2) to the bath (1). The processing liquids having the following 
compositions were used in this processing method. 
______________________________________ 
(Color Developing Liquid) 
Mother Liquor 
Replenishing Liquid 
Component (g) (g) 
______________________________________ 
Diethylenetriaminepenta- 
1.0 1.1 
acetic acid 
1-Hydroxyethylidene-1,1- 
2.0 2.2 
diphosphonic acid 
Sodium sulfite 4.0 4.4 
Potassium carbonate 
30.0 32.0 
Potassium bromide 
1.4 0.7 
Potassium iodide 
1.3 (mg) -- 
Hydroxylamine 2.4 2.6 
4-(N-Ethyl-N-.beta.-hydroxy- 
4.5 5.0 
ethylamino)-2-methyl- 
amiline.sulfate 
Water (Amount required to obtain 1 liter of the intended 
solutions) 
pH 10.00 10.05 
______________________________________ 
(Bleaching Liquid) 
Mother Liquor 
and Replenishing 
Component Liquid (g) 
______________________________________ 
Ammonium bromide 100 
Ferric ammonium ethylenediamine- 
120 
tetraacetate 
Disodium ethylenediaminetetraacetate 
10.0 
Ammonium nitrate 10.0 
Bleaching accelerator 2.0 
(N(CH.sub.3).sub.2 ----(CH.sub.2).sub.2 --S-- S--(CH.sub. 2).sub.2 
----N(CH.sub.3).sub.2) 
Aqueous ammonia 17.0 (ml) 
Water (Amount required to form 1 liter of the intended 
solutions) 
pH 6.5 
______________________________________ 
(Bleaching-Fixing Liquid) 
Mother Liquor 
Replenishing Liquid 
Component (g) (g) 
______________________________________ 
Ammonium bromide 
50.0 -- 
Ferric ammonium 
50.0 -- 
ethylenediamine- 
tetraacetate 
Disodium ethylenediamine- 
5.0 1.0 
tetraacetate 
Ammonium nitrate 
5.0 -- 
Sodium sulfite 12.0 20.0 
Aqueous solution of 
240 (ml) 400 (ml) 
ammonium thiosulfate 
(70%) 
Aqueous ammonia 
10.0 (ml) -- 
Water (Amount required to obtain 1 liter of the intended 
solutions) 
pH 7.3 8.0 
______________________________________ 
(Stabilizing Solution) 
Replenishing 
Component Mother Liquor 
Solution 
______________________________________ 
Formalin (30% w/v) 
2.0 ml 3.0 ml 
Polyoxyethylene-p- 
0.3 g 0.45 g 
monononyl phenyl ether 
(average degree of 
polymerization = 10) 
Water (Amount required to obtain 1 liter of the intended 
solutions) 
______________________________________ 
Using the foregoing processing steps, processing liquids and the following 
washing water, a color negative film was processed and results obtained 
were compared with each other. 
______________________________________ 
Washing Water A: 
Tap water as used in Example 9 (Washing 
Comparative Water A); 
Example) 
Washing Water B: 
This was the tap water (washing water A) 
(Comparative containing sodium dichloroisocyanurate 
Example) in an amount of 20 mg per 
liter of the washing water A; 
Washing Water C: 
This was obtained by passing the tap 
(Present water used in Example 9 as washing 
Invention) water A through a column packed with 
strong acidic Na-type cation exchange 
resin (manufactured and sold under the 
trade name of Diaion SK-1B by 
MITSUBISHI CHEMICAL 
INDUSTRIES LTD.); 
Washing Water D: 
This was the foregoing washing water C 
(Present (ion exchange water) to which sodium 
Invention) dichloroiocyanurate was added in an 
amount of 20 mg per liter of the water; 
Washing Water E: 
This was prepared by passing the tap 
(Present water (Washing water A) used in 
Invention) Example 8 through a column packed with 
an X-type zeolite (manufactured and sold 
under the trade name of Molecular Sieve, 
LINDE ZB-300 by UNION SHOWA 
INC.) and then adding sodium dichloro- 
isocyanurate in an amount of 20 mg per 
liter of the ion exchange water. 
______________________________________ 
In every processings in which the foregoing washing water a to E were 
utilized, a color negative film (35 mm in width) was processed at a rate 
of 30 m per day over 10 days followed by the cessation of the processing 
for 10 days and at this stage it was observed whether a bacterial floating 
matter was formed in each water washing bath or not during out of the 
operation. Thereafter, processing of a color negative film N.sub.4 was 
again carried out and the surface thereof was observed on contamination 
for the purpose of comparison. Results obtained are listed in the 
following Table 26. 
TABLE 26 
__________________________________________________________________________ 
Concn. in the Fixal 
Formation of 
Washing 
Washing Bath 
Bacterial 
Contamination 
Processing No. 
Water 
Ca (mg/l) 
Mg (mg/l) 
Membrane 
of the Film 
__________________________________________________________________________ 
(Comparative 
A 22 9.5 After 2 days 
(+++) 
Example) 
(Comparative 
B 24 10 After 2 days 
(+++) 
Example) 
(Present 
C 1.8 0.9 After 5 days 
(+) 
Invention) 
(Present 
D 1.9 1.1 Not observed 
(-) 
Invention) even after 
10 days 
(Present 
E 2.5 2.8 Not observed 
(-) 
Invention) even after 
10 days 
__________________________________________________________________________ 
In Table 26, the meanings of ideograms (-) . . . () are those as defined in 
Example 9. 
As seen from the results shown in Table 26, it is found that the present 
invention makes it possible to substantially suppress the formation of 
bacterial floating matter and the contamination of film in the water 
washing bath even in the processing of the color negative film. 
EXAMPLE 12 
The procedures of Example 11 were repeated except that the following 
processing steps and the processing liquids were used and the washing 
water E was prepared by treating the same tap water as before according to 
reverse osmosis technique using a cellulose acetate film having a surface 
area of 1 m.sup.2 and under a pressure of 15 kg/cm.sup.2) in place of 
X-type zeolite treatment. Consequently, the same results as in Example 11 
were obtained. 
TABLE 27 
______________________________________ 
Processing Steps 
Pro- 
cessing Tank Amount 
Processing 
Temp. Volume Replenished* 
Step Time (.degree.C.) 
(l) (ml) 
______________________________________ 
Color 2 min. 38 8 15 
Development 
30 sec. 
Bleaching- 
3 min. 38 8 25 
Fixing 
Water Washing (1) Water Washing (2) Water Washing (3) 
30 sec. 30 sec. 30 sec. 
35 35 35 
##STR30## 
Three-stage Counter- current Water 
Washing System 10 
Stabilization 
30 sec. 35 4 5 
______________________________________ 
*This is expressed as that per unit length (1 m) of the processed 
photosensitive material (35 mm in width). Moreover, the amount of the 
bleachingfixing liquid carried over from the bleachingfixing bath to the 
water washing bath (1) by the material during processing was 2 ml per uni 
length (1 m) of the material (35 mm in width). 
In the aforementioned processing steps, the water washing steps (1) to (3) 
were carried out according to countercurrent water washing system from the 
bath (3) to the bath (1). The composition of each processing liquid was as 
follows: 
______________________________________ 
Mother Liquor 
Replenishing 
Component (g) Liquid (g) 
______________________________________ 
(Color Developing Liquid) 
Diethylenetriaminepenta- 
1.0 1.1 
acetic acid 
1-Hydroxyethylidene-1,1- 
2.0 2.2 
diphosphonic acid 
Sodium sulfite 4.0 4.9 
Potassium carbonate 
30.0 42.0 
Potassium bromide 
1.6 -- 
Potassium iodide 2.0 (mg) -- 
Hydroxylamine 2.4 3.6 
4-(N-Ethyl-N-.beta.-hydroxy- 
5.0 7.3 
ethylamino)-2- 
methylaniline.sulfate 
Water (Amount required to form 1 liter of the intended solutions) 
pH 10.00 10.05 
(Bleaching-Fixing) 
Ferric ammonium ethylene- 
60.0 66.0 
diaminetetraacetate 
Disodium ethylene- 
10.0 11.0 
diaminetetraacetate 
Sodium sulfite 12.0 20.0 
Ammonium thiosulfate 
220 (ml) 250 (ml) 
(70% w/v aqueous 
solution) 
Ammonium nitrate 10.0 12.0 
Bleaching accelerator 
0.5 0.7 
##STR31## 
Aqueous ammonia 13.0 (ml) 12.0 (ml) 
Water (Amount required to form 1 liter of the intended solutions) 
pH 6.7 6.5 
______________________________________ 
EXAMPLE 13 
The same test as in Example 11 was carried out using the following 
multilayered color photosensitive materials (hereunder referred to as 
Samples N.sub.5 to N.sub.10 instead of Sample N.sub.4 and the same results 
as in Example 11 were obtained. 
Multilayered color photosensitive materials (Samples N.sub.5 to N.sub.10) 
were formed on substrates of cellulose triacetate film provided with 
underlying coating by applying in order layers having the following 
compositions: 
(Composition of the Photosensitive Layer 
The numerical value corresponding to each component represents the coated 
amount thereof expressed as g/m.sup.2 provided that the coated amount of 
silver halide stands for that reduced to the amount of silver. Moreover, 
the coated amount of sensitizing dyes and couplers used is expressed as 
moles per 1 mole of the silver halide contained in the same layer. 
Sample N.sub.5 
1st Layer: Antihalation Layer 
______________________________________ 
Black colloidal silver 0.18 (Ag) 
Gelatin 1.40 
______________________________________ 
2nd Layer: Intermediate Layer 
______________________________________ 
2,5-di-tert-pentadecylhydroquinone 
0.18 
C-1 0.07 
C-3 0.02 
U-1 0.08 
U-2 0.08 
HBS-1 0.10 
HBS-2 0.02 
Gelatin 1.04 
______________________________________ 
3rd Layer: First Red-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.50 (Ag) 
(AgI content = 6 mole %; average 
grain size = 0.8.mu.) 
Sensitizing dye IX 6.9 .times. 10.sup.-5 
Sensitizing dye II 1.8 .times. 10.sup.-5 
Sensitizing dye III 3.1 .times. 10.sup.-4 
Sensitizing dye IV 4.0 .times. 10.sup.-5 
Coupler C-2 0.146 
HBS-1 0.005 
C-10 0.0050 
Gelatin 1.20 
______________________________________ 
4th Layer: Second Red-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
1.15 (Ag) 
(AgI content = 5 mole %; average 
grain size = 0.85.mu.) 
Sensitizing dye IX 5.1 .times. 10.sup.-5 
Sensitizing dye II 1.4 .times. 10.sup.-5 
Sensitizing dye III 2.3 .times. 10.sup.-4 
Sensitizing dye IV 3.0 .times. 10.sup.-5 
C-2 0.060 
C-3 0.008 
C-10 0.004 
HBS-1 0.005 
Gelatin 1.50 
______________________________________ 
5th Layer: Third Red-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
1.50 (Ag) 
(AgI content = 10 mole %; average 
grain size = 1.5.mu.) 
Sensitizing dye IX 5.4 .times. 10.sup.-5 
Sensitizing dye II 1.4 .times. 10.sup.-5 
Sensitizing dye III 2.4 .times. 10.sup.-4 
Sensitizing dye IV 3.1 .times. 10.sup.-5 
C-5 0.012 
C-3 0.003 
C-4 0.004 
HBS-1 0.32 
Gelatin 1.63 
______________________________________ 
6th Layer: Intermediate Layer 
______________________________________ 
Gelatin 
1.06 
______________________________________ 
7th Layer: First Green-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.35 (Ag) 
(AgI content = 6 mole %; average 
grain size = 0.8.mu.) 
Sensitizing dye V 3.0 .times. 10.sup.-5 
Sensitizing dye VI 1.0 .times. 10.sup.-4 
Sensitizing dye VII 3.8 .times. 10.sup.-4 
C-6 0.120 
C-1 0.021 
C-7 0.030 
C-8 0.025 
HBS-1 0.20 
Gelatin 0.70 
______________________________________ 
8th Layer: Second Green-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.75 (Ag) 
(AgI content = 5 mole %; average 
grain size = 0.85.mu.) 
Sensitizing dye V 2.1 .times. 10.sup.-5 
Sensitizing dye VI 7.0 .times. 10.sup.-5 
Sensitizing dye VII 2.6 .times. 10.sup.-4 
C-6 0.021 
C-8 0.004 
C-1 0.002 
C-7 0.003 
HBS-1 0.15 
Gelatin 0.80 
______________________________________ 
9th Layer: Third Green-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
1.80 (Ag) 
(AgI content = 10 mole %; average 
grain size = 1.5.mu.) 
Sensitizing dye V 3.5 .times. 10.sup.-5 
Sensitizing dye VI 8.0 .times. 10.sup.-5 
Sensitizing dye VII 3.0 .times. 10.sup.-4 
C-16 0.012 
C-1 0.001 
HBS-2 0.69 
Gelatin 1.74 
______________________________________ 
10th Layer: Yellow Filter Layer 
______________________________________ 
Yellow colloidal silver 0.05 (Ag) 
2,5-di-tert-pentadecylhydroquinone 
0.03 
Gelatin 0.95 
______________________________________ 
11th Layer: First Blue-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.24 (Ag) 
(AgI content = 6 mole %; average 
grain size = 0.6.mu.) 
Sensitizing dye VIII 3.5 .times. 10.sup.-4 
C-9 0.27 
C-8 0.005 
HBS-1 0.28 
Gelatin 1.28 
______________________________________ 
12th Layer: Second Blue-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.45 (Ag) 
(AgI content = 10 mole %; average 
grain size = 1.0.mu.) 
Sensitizing dye VIII 2.1 .times. 10.sup.-4 
C-9 0.098 
HBS-1 0.03 
Gelatin 0.46 
______________________________________ 
13th Layer: Third Blue-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.77 (Ag) 
(AgI content = 10 mole %; average 
grain size = 1.8.mu.) 
Sensitizing dye VIII 2.2 .times. 10.sup.-4 
C-9 0.036 
HBS-1 0.07 
Gelatin 0.69 
______________________________________ 
10th Layer: First Protective Layer 
______________________________________ 
Silver iodobromide emulsion 
0.5 (Ag) 
(AgI content = 1 mole %; average 
grain size = 0.07.mu.) 
U-1 0.11 
U-2 0.17 
Butyl p-hydroxybenzoate 0.012 
HBS-1 0.90 
______________________________________ 
15th Layer: Second Protective Layer 
______________________________________ 
Polymethylmethacrylate particles 
0.54 
(diameter: 1.5.mu.) 
S-1 0.15 
S-2 0.10 
Gelatin 0.72 
______________________________________ 
In each layer, a hardening agent of gelatin (H-1) and a surfactant were 
added in addition to the foregoing components. 
Samples N.sub.6 and N.sub.7 
Samples N.sub.6 and N.sub.7 were prepared in the same manner as described 
above in connection with Sample N.sub.5 except that equivalent moles of 
C-11 and C-12 was used in 3rd and 4th layers in place of C-10. The 
structural formula or nomenclature of each compound used in preparing 
Samples N.sub.5 to N.sub.7 was as follows. 
##STR32## 
Sample N.sub.8 
1st Layer: Antihalation Layer 
______________________________________ 
Black colloidal silver 0.18 (Ag) 
Gelatin 0.40 
______________________________________ 
2nd Layer: Intermediate Layer 
______________________________________ 
2,5-di-tert-pentadecylhydroquinone 
0.18 
C-1 0.07 
C-3 0.02 
U-1 0.08 
U-2 0.08 
HBS-1 0.10 
HBS-2 0.02 
Gelatin 1.04 
______________________________________ 
3rd Layer: First Red-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.50 (Ag) 
(AgI content = 6 mole %; average 
grain size = 0.8 .mu.) 
Sensitizing dye IX 6.9 .times. 10.sup.-5 
Sensitizing dye II 1.8 .times. 10.sup.-5 
Sensitizing dye III 3.1 .times. 10.sup.-4 
Sensitizing dye IV 4.0 .times. 10.sup.-5 
C-2 0.146 
HBS-1 0.40 
C-10 0.008 
Gelatin 1.20 
______________________________________ 
4th Layer: Second Red-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
1.15 (Ag) 
(AgI content = 5 mole %; average 
grain size = 0.85.mu.) 
Sensitizing dye IX 5.1 .times. 10.sup.-5 
Sensitzing dye II 1.4 .times. 10.sup.-5 
Sensitizing dye III 2.3 .times. 10.sup.-4 
Sensitizing dye IV 3.0 .times. 10.sup.-5 
C-2 0.060 
C-3 0.008 
C-10 0.004 
HBS-2 0.40 
Gelatin 1.50 
______________________________________ 
5th Layer: Third Red-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
1.50 (Ag) 
(AgI content = 10 mole %; average 
grain size = 1.5.mu.) 
Sensitizing dye IX 5.4 .times. 10.sup.-5 
Sensitizing dye II 1.4 .times. 10.sup.-5 
Sensitizing dye III 2.4 .times. 10.sup.-4 
Sensitizing dye IV 3.1 .times. 10.sup.-5 
C-5 0.012 
C-3 0.003 
C-4 0.004 
HBS-1 0.32 
Gelatin 1.63 
______________________________________ 
6th Layer: Intermediate Layer 
______________________________________ 
Gelatin 
1.06 
______________________________________ 
7th Layer: First Green-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.35 (Ag) 
(AgI content = 6 mole %; average 
grain size = 0.8.mu.) 
Sensitizing dye V 3.0 .times. 10.sup.-5 
Sensitizing dye VI 1.0 .times. 10.sup.-4 
Sensitizing dye VII 3.8 .times. 10.sup.-4 
C-6 0.120 
C-1 0.021 
C-7 0.030 
C-8 0.025 
HBS-1 0.20 
Gelatin 0.70 
______________________________________ 
8th Layer: Second Green-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.75 (Ag) 
(AgI content = 5 mole %; average 
grain size = 0.85.mu.) 
Sensitizing dye V 2.1 .times. 10.sup.-5 
Sensitizing dye VI 7.0 .times. 10.sup.-5 
Sensitizing dye VII 2.6 .times. 10.sup.-4 
C-6 0.018 
C-8 0.004 
C-1 0.002 
C-7 0.003 
C-11 0.008 
HBS-1 0.10 
HBS-2 0.05 
Gelatin 0.80 
______________________________________ 
9th Layer: Third Green-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
1.80 (Ag) 
(AgI content = 10 mole %; average 
grain size = 1.2.mu.) 
Sensitizing dye V 3.5 .times. 10.sup.-5 
Sensitizing dye VI 8.0 .times. 10.sup.-5 
Sensitizing dye VII 3.0 .times. 10.sup.-4 
C-6 0.011 
C-1 0.001 
HBS-2 0.69 
Gelatin 1.74 
______________________________________ 
10th Layer: Yellow Filter Layer 
______________________________________ 
Yellow colloidal silver 0.05 (Ag) 
2,5-di-tert-pentadecylhydroquinone 
0.03 
Gelatin 0.95 
______________________________________ 
11th Layer: First Blue-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.24 (Ag) 
(AgI content = 6 mole %; average 
grain size = 0.6.mu.) 
Sensitizing dye VIII 3.5 .times. 10.sup.-4 
C-9 0.27 
C-8 0.005 
HBS-1 0.28 
Gelatin 1.28 
______________________________________ 
12nd Layer: Second Blue-sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.45 (Ag) 
(AgI content = 10 mole %; average 
grain size = 1.0.mu.) 
Sensitizing dye VIII 2.1 .times. 10.sup.-4 
C-9 0.098 
HBS-1 0.03 
Gelatin 0.46 
______________________________________ 
13th Layer: Third Blue=sensitive Emulsion Layer 
______________________________________ 
Silver iodobromide emulsion 
0.77 (Ag) 
(AgI content = 10 mole %; average 
grain size = 1.8.mu.) 
Sensitizing dye VIII 2.2 .times. 10.sup.-4 
C-9 0.036 
HBS-1 0.07 
Gelatin 0.69 
______________________________________ 
14th Layer: First Protective Layer 
______________________________________ 
Silver iodobromide emulsion 
0.5 (Ag) 
(AgI content = 1 mole %; average 
grain size = 0.07.mu.) 
U-1 0.11 
U-2 0.17 
HBS-1 0.90 
Gelatin 0.95 
______________________________________ 
15th Layer: Second Protective Layer 
______________________________________ 
Polymethylmethacrylate particles 
0.54 
(diameter = about 1.5.mu.) 
S-1 0.15 
S-2 0.05 
Gelatin 0.72 
______________________________________ 
To each of these layers, a hardening agent for gelatin (H-1) and a 
surfactant were added in addition to the foregoing components. The 
structural formula and nomenclature of each compounds used in preparing 
Sample N.sub.8 were as follows: 
##STR33## 
Sample N.sub.9 
1st Layer: Antihalation Layer 
A layer of gelatin containing black colloidal silver; 
2nd Layer: Intermediate Layer 
A layer of gelatin containing an emulsified dispersion of 
2,5-di-tert-octylhydroquinone; 
3rd Layer: Low Sensitive Red-sensitive Emulsion Layer (a gelatin layer 
containing the following components): 
______________________________________ 
Silver iodobromide emulsion 
1.6 g/m.sup.2 (Ag) 
(AgI content: 5 mole %) 
Sensitizing dye I 6 .times. 10.sup.-5 moles 
per mole of Ag 
Sensitizing dye II 1.5 .times. 10.sup.-5 
moles per mole 
of Ag 
Coupler EX-1 0.04 moles per 
mole of Ag 
Coupler EX-2 0.003 moles 
per mole of Ag 
Coupler EX-3 0.0006 moles 
per mole of Ag 
______________________________________ 
4th Layer: High Sensitive Red-sensitive Emulsion Layer (a gelatin layer 
containing the following components): 
______________________________________ 
Silver iodobromide emulsion 
1.4 g/m.sup.2 (Ag) 
(AgI content = 10 mole %) 
Sensitizing dye I 3 .times. 10.sup.-5 moles 
per mole of Ag 
Sensitizing dye II 1.2 .times. 10.sup.-5 
moles per mole 
of Ag 
Coupler EX-4 0.01 moles per 
mole of Ag 
Coupler EX-10 0.01 moles per 
mole of Ag 
______________________________________ 
5th Layer: Intermediate Layer 
The same layer as the foregoing 2nd layer; 
6th Layer: Low Sensitive Green-sensitive Emulsion Layer (a gelatin layer 
containing the following components): 
______________________________________ 
Monodisperse silver iodobromide 
1.2 g/m.sup.2 (Ag) 
emulsion (AgI content = 4 mole %) 
Sensitizing dye III 3 .times. 10.sup.-5 moles 
per mole of Ag 
Sensitizing dye IV 1 .times. 10.sup.-5 moles 
per mole of Ag 
Coupler EX-5 0.05 moles per 
mole of Ag 
Coupler EX-6 0.008 moles 
per mole of Ag 
Coupler EX-3 0.0015 moles 
per mole of Ag 
______________________________________ 
7th Layer: High Sensitive Green-Sensitive Emulsion Layer (a gelatin layer 
containing the following components): 
______________________________________ 
Silver iodobromide emulsion 
1.3 g/m.sup.2 (Ag) 
(AgI content = 10 mole %) 
Sensitizing dye III 2.5 .times. 10.sup.-5 
moles per mole 
of Ag 
Sensitizing dye IV 0.8 .times. 10.sup.-5 
moles per mole 
of Ag 
Coupler EX-7 0.017 moles 
per mole of Ag 
Coupler EX-6 0.003 moles 
per mole of Ag 
Coupler EX-8 0.003 moles 
per mole of Ag 
______________________________________ 
8th Layer: Yellow Filter Layer 
A gelatin layer of an aqueous gelatin solution containing yellow colloidal 
silver and an emulsified dispersion of 2,5-di-tert-octylhydroquinone; 
9th Layer: Low Sensitive Blue-sensitive Emulsion Layer (a gelatin layer 
containing the following components): 
______________________________________ 
Silver iodobromide emulsion 
0.7 g/m.sup.2 (Ag) 
(AgI content = 4 mole %) 
Coupler EX-9 0.25 moles per 
mole of Ag 
Coupler EX-3 0.015 moles 
per mole of Ag 
______________________________________ 
10th Layer: High Sensitive Blue-sensitive Emulsion Layer (a gelatin layer 
containing the following components): 
______________________________________ 
Silver iodobromide emulsion 
0.6 g/m.sup.2 (Ag) 
(AgI content = 6 mole %) 
Coupler EX-9 0.06 moles per 
mole of silver 
______________________________________ 
11th Layer: First Protective Layer 
A layer of gelatin containing 5 g/m.sup.2 (Ag) of silver iodobromide 
emulsion (AgI content=1 mole %; average grain size=0.07 .mu.) and an 
emulsified dispersion of an ultraviolet absorber UV-1; 
12th Layer: Second Protective Layer 
A layer of gelatin containing polymethylmethacrylate particles 
(diameter=about 1.5 .mu.). 
In addition to the aforementioned components, each layer contained a 
hardening agent for gelatin (H-1) or a surfactant. The compounds used for 
preparing this Sample were as follows: 
Sensitizing dye I: Pyridinium salt of 
anhydro-5,5'-dichloro-3,3'-di-(.gamma.-sulfopropyl)-9-ethyl-thiacarbocyani 
nehydroxide. 
Sensitizing dye II: Triethylamine salt of 
anhydro-9-ethyl-3,3'-di-(.gamma.-sulfopropyl)-4,5,4',5'-dibenzothiacarbocy 
aninehydroxide. 
Sensitizing dye III: Sodium salt of 
anhydro-9-ethyl-5,5'-dichloro-3,3'-di-(.gamma.-sulfopropyl)-oxacarbocyanin 
e. 
Sensitizing dye IV: Sodium salt of 
anhydro-5,6,5'-6'-tetrachloro-1,1'-diethyl-3,3'-di-{.beta.-[.beta.-(.gamma 
.-sulfopropyl)ethoxy]ethyl}-imidazolocarbocyaninehydroxide. 
##STR34## 
Sample N.sub.10 
1st Layer: Antihalation Layer (A layer of gelatin containing the following 
listed components: 
______________________________________ 
Black colloidal silver 0.18 g/m.sup.2 
Ultraviolet absorber C-1 
0.12 g/m.sup.2 
Ultraviolet absorber C-2 
0.17 g/m.sup.2 
______________________________________ 
2nd Layer: Intermediate Layer (A layer of gelatin containing the following 
components): 
______________________________________ 
2,5-di-tert-pentadecylhydroquinone 
0.18 g/m.sup.2 
Coupler C-3 0.03 g/mm.sup.2 
Silver iodobromide emulsion 
0.15 g/m.sup.2 (Ag) 
(AgI content = 1 mole %; average 
grain size = 0.07.mu.) 
______________________________________ 
3rd Layer: First Red-sensitive Emulsion Layer (A gelatin layer containing 
the following components): 
______________________________________ 
Silver iodobromide emulsion 
0.72 g/m.sup.2 (Ag) 
(AgI content = 6 mole %; average 
grain size = 0.6.mu.) 
Sensitizing dye I 7.0 .times. 10.sup.-5 moles per 
mole of silver 
Sensitizing dye II 2.0 .times. 10.sup.-5 moles per 
mole of silver 
Sensitizing dye III 2.8 .times. 10.sup.-4 moles per 
mole of silver 
Sensitizing dye IV 2.0 .times. 10.sup.-5 moles per 
mole of silver 
Coupler C-4 0.320 g/m.sup.2 
Coupler C-5 0.010 g/m.sup.2 
Coupler C-3 0.050 g/m.sup.2 
______________________________________ 
4th Layer: Second Red-sensitive Emulsion Layer (A gelatin layer containing 
the following components): 
______________________________________ 
Silver iodobromide emulsion 
1.6 g/m.sup.2 (Ag) 
(AgI content = 10 mole %; average 
grain size = 1.5.mu.) 
Sensitizing dye I 5.2 .times. 10.sup.-5 moles per 
mole of silver 
Sensitizing dye II 1.5 .times. 10.sup.-5 moles per 
mole of silver 
Sensitizing dye III 2.1 .times. 10.sup.-4 moles per 
mole of silver 
Sensitizing dye IV 1.5 .times. 10.sup.-5 moles per 
mole of silver 
Coupler C-4 0.050 g/m.sup.2 
Coupler C-6 0.210 g/m.sup.2 
Coupler C-3 0.090 g/m.sup.2 
______________________________________ 
5th Layer: Third Red-sensitive Emulsion Layer (a layer of gelatin 
containing the following components): 
______________________________________ 
Silver iodobromide emulsion 
1.6 g/m.sup.2 (Ag) 
(AgI content = 10 mole %; average 
grain size = 2.0.mu.) 
Sensitizing dye I 5.5 .times. 10.sup.-5 moles per 
mole of silver 
Sensitizing dye II 1.6 .times. 10.sup.-5 moles per 
mole of silver 
Sensitizing dye III 2.2 .times. 10.sup.-5 moles per 
mole of silver 
Sensitizing dye IV 1.5 .times. 10.sup.-5 moles per 
mole of silver 
Coupler C-6 0.180 g/m.sup.2 
Coupler C-3 0.005 g/m.sup.2 
______________________________________ 
6th Layer: Intermediate Layer (a gelatin layer) 
7th Layer: First Green-sensitive Emulsion Layer (a layer of gelatin 
containing the following components): 
______________________________________ 
Silver iodobromide emulsion 
0.55 g/m.sup.2 (Ag) 
(AgI content = 5 mole %; average 
grain size = 0.5.mu.) 
Sensitizing dye V 3.8 .times. 10.sup.-4 moles per 
mole of silver 
Sensitizing dye VI 3.0 .times. 10.sup.-5 moles per 
mole of silver 
Sensitizing dye VII 1.2 .times. 10.sup.-4 moles per 
mole of silver 
Coupler C-7 0.290 g/m.sup.2 
Coupler C-8 0.040 g/m.sup.2 
Coupler C-9 0.060 g/m.sup.2 
______________________________________ 
8th Layer: Second Green-sensitive Emulsion Layer (a layer of gelatin 
containing the components given below): 
______________________________________ 
Silver iodobromide emulsion 
1.5 g/m.sup.2 (Ag) 
(AgI content = 6 mole %; average 
grain size = 1.5.mu.) 
Sensitizing dye V 2.7 .times. 10.sup.-4 moles per 
mole of silver 
Sensitizing dye VI 2.1 .times. 10.sup.-5 moles per 
mole of silver 
Sensitizing dye VII 8.5 .times. 10.sup.-5 moles per 
mole of silver 
Coupler C-7 0.210 g/m.sup.2 
Coupler C-8 0.012 g/m.sup.2 
Coupler C-9 0.009 g/m.sup.2 
Coupler C-10 0.011 g/m.sup.2 
______________________________________ 
9th Layer: Intermediate Layer (a gelatin layer) 
10th Layer: Third Green-sensitive Emulsion Layer (a layer of gelatin 
containing the following components): 
______________________________________ 
Silver iodobromide emulsion 
1.5 g/m.sup.2 (Ag) 
(AgI content = 10 mole %; average 
grain size = 2.0.mu.) 
Sensitizing dye V 3.0 .times. 10.sup.-4 moles per 
mole of silver 
Sensitizing dye VI 2.4 .times. 10.sup.-5 moles per 
mole of silver 
Sensitizing dye VII 9.5 .times. 10.sup.-5 moles per 
mole of silver 
Coupler C-11 0.013 g/m.sup.2 
Coupler C-10 0.070 g/m.sup.2 
______________________________________ 
11th Layer: Yellow Filter Layer (a layer of gelatin containing the 
following components): 
______________________________________ 
Dye Y-1 2.0 .times. 10.sup.-4 moles/m.sup.2 
2,5-di-pentadecylhydroquinone 
0.031 g/m.sup.2 
______________________________________ 
12th Layer: First Blue-sensitive Emulsion Layer (a layer of gelatin 
containing the following components): 
______________________________________ 
Silver iodobromide emulsion 
0.32 g/m.sup.2 (Ag) 
(AgI content = 6 mole %; average 
grain size = 0.4.mu.) 
Coupler C-12 0.73 g/m.sup.2 
Coupler C-13 0.052 g/m.sup.2 
______________________________________ 
13th Layer: Second Blue-sensitive Emulsion Layer (a layer of gelatin 
containing the following components): 
______________________________________ 
Silver iodobromide emulsion 
0.40 g/m.sup.2 (Ag) 
(AgI content = 10 mole %; average 
grain size = 1.0.mu.) 
Sensitizing dye VIII 2.2 .times. 10.sup.-4 moles per 
mole of silver 
Coupler C-12 0.35 g/m.sup.2 
______________________________________ 
14th Layer: Emulsion Layer of finely divided Particles (a layer of gelatin 
containing the following components): 
______________________________________ 
Silver iodobromide emulsion 
0.25 g/m.sup.2 (Ag) 
(AgI content = 2 mole %; average 
grain size = 0.15.mu.) 
______________________________________ 
15th Layer: Third Blue-sensitive Emulsion Layer (a gelatin layer containing 
the following components): 
______________________________________ 
Silver iodobromide emulsion 
1.00 g/m.sup.2 (Ag) 
(AgI content = 10 mole %; average 
grain size = 1.6.mu.) 
Sensitizing dye VIII 2.3 .times. 10.sup.-4 moles per 
mole of silver 
Coupler C-12 0.15 g/m.sup.2 
______________________________________ 
16th Layer: First Protective Layer (a layer of gelatin containing the 
following components): 
______________________________________ 
Ultraviolet absorber C-1 
0.14 g/m.sup.2 
Ultraviolet absorber C-2 
0.22 g/m.sup.2 
______________________________________ 
17th Layer: Second Protective Layer (a gelatin layer containing the 
following components): 
______________________________________ 
Polymethylmethacrylate particles 
0.05 g/m.sup.2 
(diameter = about 1.5.mu.) 
Silver iodobromide emulsion 
0.30 g/m.sup.2 (Ag) 
(AgI content = 2 mole %; average 
grain size = 0.07.mu.) 
______________________________________ 
In addition to the aforementioned components, each layer contained 
4-hydroxy-6-methyl(1,3,3a,7)tetrazaindene as a stabilizer, a hardening 
agent for gelatin (H-1) and a surfactant. 
The components used in preparing the sample were as follows: 
##STR35## 
EXAMPLE 14 
Color papers and color negative films were prepared according to the same 
procedures as in Examples 7 to 13 except that a part or whole of the 
yellow couplers, cyan couplers and magenta couplers as used in these 
Examples were replaced with the following ones and these color papers and 
color negative films were developed in the same manner as those disclosed 
in these Examples followed by washing with washing water from which 
calcium and magnesium were removed according to the present invention. 
Thus, excellent results similar to those attained in Examples 7 to 13 were 
observed. 
##STR36## 
EXAMPLE 15 
An X-ray photosensitive material (manufactured and sold under the trade 
name of HRA by Fuji Photo Film Co., Ltd.) was subjected to a running 
treatment utilizing a developer for X-ray films RD-V and a fixing liquid 
GF-1 (both of them are manufactured and sold by Fuji Photo Film Co., Ltd.) 
TABLE 30 
______________________________________ 
Processing Steps 
Temp. Time Amount Replenished* 
Step (.degree.C.) 
(sec.) (ml) 
______________________________________ 
Development 
35 24 55 
Fixing 30 25 70 
Water Washing 
25 34 70 
Drying 50-55 19 -- 
______________________________________ 
*The value was expressed as the amount per sheet of quart film. 
In the above processing, water washing was carried out according to the 
water washing steps A to D in Example 7. The processing was effected at a 
rate of 5 sheets of quart film per day over 6 days followed by the out of 
the operation over 7 days and it was observed if there was formed a 
bacterial floating matter in the water washing bath during the out of the 
operation. As a result, the same effect as in Example 7 was achieved.