Solid photographic processing composition for developing a silver halide photographic light-sensitive material

Disclosed is a solid photographic processing composition for developing a silver halide photographic light-sensitive material comprising a ferric complex of an aminopolycarboxylic acid and a sugar alcohol compound.

FIELD OF THE INVENTION 
The present invention relates to a powder shaped, a granular shaped or a 
tablet shaped solid photographic processing composition for developing a 
silver halide photographic light-sensitive material. 
BACKGROUND OF THE INVENTION 
Silver halide light-sensitive color photographic materials are usually 
processed with a color developing solution, a bleaching solution, a 
bleach-fixing solution, a fixing solution, a stabilizing solution, etc., 
to obtain an image. The respective processing solutions are usually 
contained in a plastic bottle and supplied to customers in the form of a 
processing kit and the customer prepares a working solution, (i.e., a 
starting solution and a replenishing solution) and then use the processing 
solution. 
However, the processing kits have still needed to have a lot of spaces for 
storing them, and the transportation cost of the kits can also in no way 
be slighted. 
For saving the storage space, cutting down the transportation cost and 
reducing the quantity of waste plastic bottles, it may be considered to 
pulverize a photographic processing composition and then to supply it. 
However, a pulverized photographic processing composition has not only 
such a problem that there is an apprehension for the worker's health, 
because the fine powder thereof is whirled up in the air when dissolving 
the composition and he may possibly inhale the flying powder, but also 
such a problem that a whirling processing composition component is mixed 
in another photographic processing composition and thereby a trouble is 
produced in the development process. 
On the other hand, Japanese Patent O.P.I. Publication No. 3-39739(1991) 
discloses granulated agent of aminopolycarboxylic acid ferric complex, 
comprising a re-halogenation agent and having a certain average grain 
diameter. According to this method, since this granulated agent is not 
apparently powder shaped, scattering of the agent may be restricted, 
however, it was found that this had a defect that there is large variation 
of quality in the manufactured product, apparently due to the difference 
of bonding strength between ferric complex and the re-halogenation agent. 
Further, it was found that there is another defect that physical property 
of the granulated agent is changed, with the lapse of time, and, finaly, 
the agent loses function as granulated particle. 
So quality variation in the manufactured product tends to take place when 
the granulated agent is molded by compression molding and hardness of the 
tabular shaped composition manufactured therefrom can be deteriorated. The 
diameter and thickness of the tabular shaped composition expands with the 
lapse of time, and then, it is found that the hardness of the tabular 
shaped composition is deteriorated. Needless to say, expansion of the 
tabular shaped composition leads to a deterioration of a market value, and 
deterioration of the hardness of the tabular shaped composition often 
causes cracking and partial loss by vibration or impact applied during 
transportation, so that they are serious problems as to a quality of the 
tabular shaped composition. 
Further, Japanese Patent O.P.I. Publications No. 5-119454(1993) and No. 
6-19100(1994) disclose a tabular shaped processing composition comprising 
a ferric complex of aminopolycarboxylic acid and a re-halogenation agent. 
Still further, Japanese Patent O.P.I. Publications No. 4-254853(1992) 
discloses a granular shaped composition comprising an aminopolycarboxylic 
acid ferric salt and polyethylene glycol. 
According to this method, components of the granular shaped composition are 
stable, because polyethylene glycol functions as a binder, however, it was 
found that it is not sufficient to solve the variation of physical 
properties of the granular shaped composition. Furthermore, the granulated 
agent is compressed to prepare a tabular shaped composition, so that a 
hardness degradation of the tabular shaped composition with the lapse of 
time is avoided to some extent. However, it was found that cracks of the 
surface of the tabular shaped composition and expansion of the tabular 
shaped composition took place. 
Still further, Japanese patent O.P.I. Publication No. 51-61837(1976) 
discloses a tabular shaped composition comprising a ferric complex of 
aminopolycarboxylic acid and lactose. In accordance to this method, again, 
although the binding force of the tabular shaped compositions may be 
enhanced to some extent, however, this method cannot solve the 
above-mentioned problems of storage under high temperature and low 
humidity conditions. 
After long and intensive research on the solid photographic processing 
composition containing an aminopolycarboxylic acid ferric salt, when a 
sugar alcohol is contained in the solid photographic processing 
composition, the present inventors have discovered the following improved 
results. In a large-scale preparation, a content variation of the solid 
photographic processing composition is small, and the granulated 
properties is stable at the lapse of time, and, when the tabular shaped 
processing composition is prepared by compressing molding, expansion of 
the tabular shaped processing composition and hardness deterioration of 
the tabular shaped processing composition are not occurred. 
SUMMARY OF THE INVENTION 
The object of the present invention is to provide a solid photographic 
processing composition used for silver halide light-sensitive photographic 
materials, which has no variation in the ingredient as a bleaching agent 
and has improved bleaching ability with less problems in the physical 
properties after long period of storage under the conditions of a high 
temperature and a low humidity. 
The above-mentioned object of the present invention is achieved by the 
following items. 
Item 1: A solid photographic processing composition for processing a silver 
halide photographic light-sensitive material, which comprises a ferric 
complex of an aminopolycarboxylic acid and a sugar alcohol compound. 
Item 2: The solid photographic processing composition of item 1, wherein 
said sugar alcohol is contained in an amount of from 0.5% to 30% by 
weight. 
Item 3: The solid photographic processing composition of item 1, wherein 
said photographic processing composition comprises a ferric complex 
hydrate and a decreasing ratio in weight of said photographic processing 
composition after drying at 50.degree. C. is within the range of 0.1% to 
10.0% by weight. 
Item 4: The solid photographic processing composition of item 2, wherein 
said photographic processing composition comprises a ferric complex 
hydrate and a decreasing ratio in weight of said photographic processing 
composition after drying at 50.degree. C. is within the range of 0.1% to 
10.0% by weight. 
Item 5: The solid photographic processing composition of item 1, wherein 
said photographic processing composition is a granular shaped composition, 
and said granular shaped composition is prepared by applying compression 
by making use of a tableting machine. 
Item 6: The solid photographic processing composition of item 2, wherein 
said photographic processing composition is a granular shaped composition, 
and said granular shaped composition is prepared by applying compression 
by making use of a tableting machine. 
Item 7: The solid photographic processing composition of item 4, wherein 
said photographic processing composition is a granular shaped composition, 
and said granular shaped composition is prepared by applying compression 
by making use of a tableting machine. 
Item 8: The solid photographic processing composition of item 1, wherein 
said aminopolycarboxylic acid is represented by Formula I: 
##STR1## 
wherein T.sub.1 represents a hydrogen atom, a hydroxyl group, a carboxyl 
group, a sulfo group, a carbamoyl group, a phosphono group, a phosphonic 
group, a sulfamoyl group, an alkyl group, an alkoxyl group, an 
alkylsulfonamido group, an alkylthio group, an acylamino group, a 
hydroxamic acid, a hydroxyalkyl group or 
##STR2## 
wherein W.sub.1 represents an alkylene group, an arylene group, an 
alkenylene group, a cycloalkylene group, an aralkylene group or 
##STR3## 
wherein X represents --O--, --S--, a divalent heterocyclic group or 
##STR4## 
wherein R.sub.1 through R.sub.5 independently represent a hydrogen atom, a 
hydroxyl group, a carboxyl group, a sulfo group, a carbamoyl group, a 
phosphono group, a phosphonic group, a sulfamoyl group, a sulfonamido 
group, an acylamino group or a hydroxamic group, provided that at least 
one of R.sub.1 through R.sub.5 is a carboxyl group; L.sub.1 through 
L.sub.7 independently represent a group selected from the group consisting 
of an alkylene group, an arylene group, an alkenylene group, a 
cycloalkylene group and an aralkylene group; l.sub.1 trough l.sub.7 
independently represent an integer of zero to six, provided that l.sub.5 
through l.sub.6 are not zero simultaneously. 
Hereinbelow the present invention is explained in detail: 
The present inventors have carried out extensive amount of research and 
experiments and have found the following facts: 
It is known in the art that an aminopolycarboxylic acid ferric complex 
compound, which may be herein below abbreviated as APC-Fe, is used in the 
solid photographic processing composition, however, what was made clear by 
the present invention is that APC-Fe has shows low bonding strength, and 
when a granular shaped processing composition is manufactured, proportion 
of fine powder becomes larger, and it is easily blown off into the air, 
which causes an operational problem and, when a tabular shaped processing 
composition is manufactured, predetermined hardness of the tabular shaped 
processing composition can hardly be obtained and, moreover, there has 
been a problem that the tabular shaped composition is easily broken by 
vibration or impact during transportation. 
In order to enhance the bonding strength of the ACP-Fe, the present 
inventors have tried to decrease weight ratio of the ACP-Fe. However, it 
was found that the bonding strength of the APC-Fe is not affected by the 
weight ratio in the presence of APC-Fe and the similar problem causes. 
Moreover, the reduction of weight ratio of APC-Fe leads to remarkable 
increase of volume of the processing composition, so that it cannot be an 
effective countermeasure to decrease weight ratio of the ACP-Fe. 
Further the present inventors have tried to add some other known 
water-soluble polymers for the purpose of enhancing the bonding strength 
of APC-Fe. 
By the use of lactose and a water-soluble polymer such as polyethylene 
glycol, etc. it is possible to improve the bonding strength, and a 
granular shaped composition or a tabular shaped composition having 
preferable bonding strength may be obtained, however, when granular shaped 
composition or tabular shaped composition manufactured by this method are 
stored under high temperature and low humidity conditions, it was found 
that the bonding strength of the granular shaped composition was rapidly 
decreased after storing, causing large amount of fine powder. 
Further, deterioration of fluidity of the granular shaped composition 
causes a problem that operational performance at the time of dissolution 
is jeopardized. 
When the tabular shaped compositions are stored, expansion in the diameter 
direction and in the thickness direction took place, and the tabular 
shaped composition hardness is deteriorated and the commercial value of 
the tabular shaped composition is also deteriorated. 
Solid photographic processing composition for the silver halide 
light-sensitive photographic material are generally filled up in a sealed 
container, so that humidity condition inside the container is low. And, 
thus, the above-mentioned problem which takes place in the low humidity 
condition was serious. 
Additionally, the solid photographic processing composition of the present 
invention may be stored in high temperature area like as Southeast Asia 
region or the solid composition may be bathed in direct sunlight, and 
therefore, there is so serious problem in practical use under high 
temperature condition mentioned above. 
After carrying out further research based on the above-mentioned knowledge, 
the inventors of the present invention have found that a granular shaped 
composition, with which generation of fine powder, when it is stored under 
low humidity condition and a tabular shaped composition, of which 
expansion and lowering of hardness, are minimized, can be provided by 
incorporating a sugar alcohol compound into a solid photographic 
processing composition for silver halide light-sensitive photographic 
material comprising a ferric complex of an aminopolycarboxylic acid and 
having a bleaching ability. 
It was a surprising and unexpected for the inventors of the present 
invention to find a fact that only additive selected from sugar alcohol 
compound can make up the loss of the bonding strength of APC-Fe, and this 
fact was found after huge amount of research and experiment by the 
inventors of the present invention. 
The solid photographic photographic processing composition for silver 
halide light-sensitive photographic material of the present invention is 
in the form of fine powder shaped composition, a granular shaped 
composition or a tabular shaped composition. 
Preferably, it is in the form of granular shaped compositions or tabular 
shaped compositions. In view of expansion or degradation of hardness, 
which are the main effects of the present invention, it is, most 
preferably, in the form of a tabular shaped composition. 
The term "powder" of the present invention shows aggregation of fine powder 
crystals, and "granular shaped composition" means coarse particles made 
from the powder and having 50 to 5000 .mu.m in size; more preferably, 
100-2000 .mu.m, and most preferably, 200 to 1500 .mu.m in size. 
As for the method of granulation, any conventional methods can be employed, 
including a fluidized bed granulation method, an extrusion granulation 
method, a compression granulation method, a pulverization method, stirring 
granulation method, a fluidity layer granulation method, a spray-dry 
granulation method, etc. 
The term "tabular shaped composition" used in the present invention means 
one which is molded by compression into a predetermined shape from powder 
or granular shaped composition. For the effects of the present invention 
to be exerted most distinguishably, at least a part of the raw materials 
be granulated and, more preferably, all of the raw materials are granular 
shaped. 
Moreover, the solid photographic processing composition of the present 
invention can be manufactured with the use of any conventional compressor 
known in the art, including, for example, a hydraulic compressor, a 
single-engined molding machine, a rotary tabular shaped composition making 
machine, a prequetting machine, etc. can be employed. 
The tabular shaped solid photographic processing composition may be 
optional, however, in view of productivity and easy handling, a 
cylindrical shaped composition is preferable. 
The solid photographic processing composition for silver halide 
light-sensitive photographic material of the present invention comprises 
at least one kind of ferric complex of aminopolycarboxylic acid and it may 
comprise two or more kinds different ferric complexes of 
aminopolycarboxylic acid in combination. 
As for the ferric complex of the aminopolycarboxylic acid, it is preferable 
that the compound is used in the form of a ferric complex of a free acid 
represented by the following formula I! given below and it is more 
preferable to use the above-mentioned ferric complex and the free acid of 
aminopolycarboxylic acid in combination. Particularly preferable 
combination is a free acid of an aminopolycarboxylic acid and a ferric 
complex of the same free acid. 
The above mentioned ferric complex of aminopolycarboxylic acid can be used 
in the form of a potassium salt, a sodium salt, an ammonium salt, etc. and 
the free acid of the aminopolycarboxylic acid may be in the form of a free 
acid, potassium salt, sodium salt, etc. 
As for specific examples of the above-mentioned aminopolycarboxylic acid, 
compounds represented by the following formula I! can be mentioned: 
##STR5## 
wherein T.sub.1 represents a hydrogen atom or a group selected from the 
group consisting of a hydroxyl group, a carboxyl group, a sulfo group, a 
carbamoyl group, a phosphono group, a phosphonic group, a sulfamoyl group, 
an alkyl group, an alkoxy group, an alkylsulfonamide group, an alkylthio 
group, an acylamino group, a hydroxamic acid, a hydroxyalkyl group and the 
group represented as follows; 
##STR6## 
in which W.sub.1 represents an alkylene group, an arylene group, an 
alkenylene group, a cycloalkylene group, or an aralkylene group or a group 
represented by 
##STR7## 
X represents --O--, --S--, a divalent heterocycle or 
##STR8## 
R.sub.1 through R.sub.5 independently represent a hydrogen atom or a group 
selected from the group consisting of a hydroxyl group, a carboxyl group, 
a sulfo group, a carbamoyl group, a phosphono group, a phosphonic group, a 
sulfamoyl group, a sulfonamide group, an acylamino group and a hydroxamic 
group, provided that at least one of R.sub.1 through R.sub.5 is a carboxyl 
group; 
L.sub.1 through L.sub.7 independently represent a group selected from the 
group consisting of a substituted or unsubstituted alkylene group, an 
arylene group, an alkenylene group, a cycloalkylene group and an 
aralkylene group; l.sub.1 trough l.sub.7 independently represent an 
integer of zero to six, provided that l.sub.5 through l.sub.6 are not zero 
simultaneously. 
Specific examples of the ferric complex of aminopolycarboxylic acid 
hydrides represented by the general formula I! are shown below: 
##STR9## 
Among these, (I-1) through (I-8), (I-12), (I-14) through (I-20), (I-22), 
(I-23) and(I-27) can be mentioned as preferable compounds. 
As especially preferable compounds, (I-1), (I-2), (I-6), (I-12), (I-14), 
(I-15) and (I-17) can be mentioned. 
Specific examples of the ferric complex hydrates of aminopolycarboxylic 
acid are given below: 
______________________________________ 
Preferable Amount 
of Water of 
Crystallization in 
Fe(III) Complex of 
Fe(III) Complex of Aminopolycarboxylic 
Aminopolycarboxylic Acid 
Acid 
Amino- Mol number of water 
polycarboxylic 
Counter of crystallization 
No. Acid Cation per a mol of Iron 
______________________________________ 
II-1 I-1 Na.sup.+ 3 
II-2 I-1 K.sup.+ 2 
II-3 I-1 NH.sub.4.sup.+ 
2 
II-4 I-2 Na.sup.+ 3 
II-5 I-2 K.sup.+ 1 
II-6 I-2 NH.sub.4.sup.+ 
1 
II-7 I-3 K.sup.+, H.sup.+ 
1 
II-8 I-3 NH.sub.4.sup.+, H.sup.+ 
1 
II-9 I-5 K.sup.+ 1 
II-10 I-5 NH.sub.4.sup.+ 
1 
II-11 I-14 -- 2 
II-12 I-28 K.sup.+ 1 
II-13 I-26 K.sup.+ 1 
II-14 I-10 -- 1.5 
II-15 I-8 NH.sub.4.sup.+ 
2 
______________________________________ 
The solid photographic processing composition for silver halide 
light-sensitive photographic materials of the present invention comprises 
at least one kind of sugar alcohol, and different kinds of sugar alcohols 
may be used in combination. 
The term `sugar alcohol` of the present invention is a general term for 
polyalcohols corresponding to a primary or a secondary alcohol produced by 
reducing aldehyde group or ketone group of the sugar. 
Specific examples of sugar alcohols used in the present invention are given 
below: 
(III-1) Glycerine 
(III-2) D-Thereitol 
(III-3) L-Threitol 
(III-4) Erythritol 
(III-5) D-Arabitol 
(III-6) L-Arabitol 
(III-7) Adonitol 
(III-8) Xylitol 
(III-9) D-Sorbitol 
(III-10) L-Sorbitol 
(III-11) D-Mannitol 
(III-12) L-Mannitol 
(III-13) D-Iditol 
(III-14) L-Iditol 
(III-15) D-Talitol 
(III-16) L-Talitol 
(III-17 Dulcitol 
(III-18) Allodulcitol 
Among these exemplified compounds, preferable ones are (III-4), (III-9) 
through (III-18) and especially preferable compounds are (III-4), (III-9) 
and (III-11). 
In the present invention, the sugar alcohol used in the solid photographic 
processing composition for silver halide light-sensitive photographic 
material is preferable employed in an amount of not less than 0.5 wt %, 
and is more preferably employed in an amount of not less than 1.0 wt %. 
Furthermore, the sugar alcohol used in the solid photographic processing 
composition for silver halide light-sensitive photographic material is 
preferable employed in an amount of not more than 30 wt %, and is more 
preferably employed in an amount of not more than 20 wt %. 
In the present invention, a decreasing ratio in weight of a photographic 
processing composition after drying at 50.degree. C. is defined as 
follows. 
About 10 g of a photographic processing composition is dried in a 
commercially available electronic moisture meter at 50.degree. C. for 10 
minutes, and then, a decreasing weight is measured under the conditions, 
that is, an atmospheric pressure, a temperature condition of from 
25.degree. to 30.degree. C. and a relative humidity of from 40 to 45%. The 
decreasing weight is defined as a decreasing ratio in weight of a 
photographic composition. 
The solid photographic processing composition of the present invention is 
applied to solid photographic processing composition for bleaching use or 
bleach-fixing, and further, the solid photographic processing composition 
is applied to all other solid photographic composition which comprises a 
ferric complex of aminopolycarboxylic acid.

EXAMPLE 
Hereinbelow the present invention is further explained with reference to 
working examples: 
Example 1 
(Procedure: 1-1) 
Ferric complex of the Exemplified Compound (as shown in Table 1) 1900 g 
Free acid of the above-exemplified compound 100 g 
Potassium bromide 900 g 
Succinic acid 700 g 
Disodium mleate monohydrate 300 g 
Adipic acid 200 g 
Additive-1 as shown in Table 1 as shown in Table 1 
After respective raw materials mentioned above were pulverized into fine 
grains having average grain diameter of not more than 50 .mu.m with a 
hammer-mill, they were granulated in a mixing granulator while mixing and 
spraying water. 
Amount of water used in this step was 100 ml. These granulated products 
were dried at 60.degree. C. for four hours using a commercially available 
fluidized-bed dryer. This is called granulated product (a). 
(Procedure: 1-2) 
To the granulated product (a), 2% by weight of sodium lauroylsarcosine was 
added and after mixing this for three minutes, tabular shaped processing 
composition for bleaching, having diameter of 30 mm, and 11 g in weight a 
tabular shaped composition was prepared by the use of a tablet molding 
machine obtained by modifying Clean Press Collect 18K, a product of 
Kikusui Manufacturing Co., Ltd. 
Thus prepared tabular shaped compositions were sealed up in a packaging 
bag, which is made of aluminium, and stored for two weeks under 
atomospheric conditions of 30% R.H. and 50.degree. C. 
After storage, increased amount of diameter and thickness of the tabular 
shaped composition were measured, to obtain the rate of expansion. 
Further, by the use of s Speed Checker, a product of Okada Manufacturing 
Company Ltd., destructive strength (hardness) with respect to he direction 
towards diameter was measured. 
Results thus obtained are shown in Table 1. 
TABLE 1 
__________________________________________________________________________ 
Rate of Expansion 
after Storage 
Hardness 
Sample 
Exemplified Diameter 
Thickness 
after 
No. Compound 
Additive-1 (wt %) 
(%) (%) Storage 
Remarks 
__________________________________________________________________________ 
1-1 II-6 -- 6.2 8.3 8.0 Comp. 
1-2 II-6 D-Mannitol (0.3) 
3.6 4.2 21.0 Inv. 
1-3 II-6 D-Mannitol (0.5) 
1.7 2.3 32.0 Inv. 
1-4 II-6 D-Mannitol (1.0) 
1.2 1.8 40.0 Inv. 
1-5 II-6 D-Mannitol (5.0) 
1.3 1.9 43.0 Inv. 
1-6 II-6 D-Mannitol (10.0) 
1.3 1.7 46.0 Inv. 
1-7 II-6 D-Mannitol (20.0) 
1.5 1.7 45.0 Inv. 
1-8 II-6 D-Mannitol (30.0) 
2.1 2.5 46.0 Inv. 
1-9 II-6 D-Mannitol (35.0) 
3.9 3.8 49.0 Inv. 
1-10 
II-6 D-Sorbitol (0.5) 
1.6 1.9 42.0 Inv. 
1-11 
II-6 D-Sorbitol (5.0) 
1.2 1.8 53.0 Inv. 
1-12 
II-6 D-Sorbitol (10.0) 
1.1 1.8 55.0 Inv. 
1-13 
II-6 Erythritol (5.0) 
1.3 1.7 40.0 Inv. 
1-14 
II-6 Glycerine (5.0) 
2.2 2.8 28.0 Inv. 
1-15 
II-6 Adnit (5.0) 
2.0 2.6 27.0 Inv. 
1-16 
II-6 PEG600 (5.0) 
8.3 9.9 19.0 Comp. 
1-17 
II-6 PEG2000 (5.0) 
8.1 9.6 25.0 Comp. 
1-18 
II-6 PEG6000 (5.0) 
6.0 7.9 26.0 Comp. 
1-19 
II-6 Lactose (5.0) 
5.7 6.1 14.0 Comp. 
1-20 
II-6 HPC (5.0) 
6.3 7.0 13.0 Comp. 
1-21 
II-1 -- 6.9 9.0 5.0 Comp. 
1-22 
II-3 -- 6.1 7.9 10.0 Comp. 
1-23 
II-8 -- 7.3 8.9 8.0 Comp. 
1-24 
II-9 -- 7.1 8.5 6.0 Comp. 
1-25 
II-1 D-Mannitol (5.0) 
1.5 1.8 40.0 Inv. 
1-26 
II-3 D-Mannitol (5.0) 
1.3 1.7 43.0 Inv. 
1-27 
II-8 D-Mannitol (5.0) 
1.4 1.9 40.0 Inv. 
1-28 
II-9 D-Mannitol (5.0) 
1.4 2.1 39.0 Inv. 
1-29 
II-6 D-Mannitol (4.0) 
1.0 1.2 59.0 Inv. 
D-Sorbitol (2.0) 
__________________________________________________________________________ 
Comp.: Comparison 
Inv.: Invention 
Note) 
PEG = Polyethylene Glycol (The numerical value means average molecular 
weight) 
HPC = Hydroxypropyl Cellullose 
As is obvious from Table-1, it is understood that the samples of the 
present invention, which comprise both a ferric complex of 
aminopolycarboxylic acid and a sugar alcohol can exhibit reduced rate of 
expansion and decrease in the hardness of the tabular shaped composition 
the tabular shaped composition after storage under atomospheric conditions 
of high temperature and low humidity in comparison with comparative 
samples. 
It is also understood that preferable content of sugar alcohol is not less 
than 0.5 wt % and, more preferably, not less than 1.0 wt % and not more 
than 30 wt % and, more preferably, not more than 20 wt %. 
Example 2 
In Example 1, respective granulated products (grains), which were prepared 
according to (Procedure: 1-1), were passed through a sieve with the mesh 
size of 149 .mu.m and 100 g of respective grains having grain size of not 
less than 149 .mu.m were sealed up in the packaging bag made of aluminium, 
and stored for two weeks under the same atomospheric conditions (RH30%, 
50.degree. C.) as in Example 1. 
After storage, respective granular products were subjected to vibration 
test (5-67 Hz/210 sec for 30 mins.) by the use of a Vibration Tester 
BF-UA, a product of IDEX Company. 
After completion of the vibration test, occurrence of fine powder with 
respect to the respective granular products were evaluated by use of sieve 
having a mesh of 100 .mu.m. 
Evaluation was carried out based upon the following standards: 
______________________________________ 
Grade Rate of Occurrence of Fine Powder 
______________________________________ 
E: Excellent 
0-10% 
G: Good 10-20% 
F: Fair 20-30% 
P: Poor 30-50% 
B: Bad 50-70% 
VB: Very Bad 
70-100% 
______________________________________ 
##STR10## 
TABLE 2 
______________________________________ 
Rate of 
Sample 
Exemplified 
Additive-1 Occurrence 
No. Compound (Amount in wt %) 
of Fine Powder 
Remarks 
______________________________________ 
2-1 II-6 -- Bad Comparison 
2-2 II-6 D-Mannit (5.0) 
Excellent 
Invention 
2-3 II-6 D-Sorbitol (5.0) 
Excellent 
Invention 
2-4 II-6 Erythritol (5.0) 
Excellent 
Invention 
2-5 II-6 D-Arabitol (5.0) 
Good Invention 
2-6 II-6 Glycerine (5.0) 
Fair Invention 
2-7 II-6 D-Iditol (5.0) 
Excellent 
Invention 
2-8 II-6 Dulcitol (5.0) 
Excellent 
Invention 
2-9 II-6 D-Threitol (5.0) 
Good Invention 
2-10 II-6 PEG600 Bad Comparison 
2-11 II-6 PEG2000 Bad Comparison 
2-12 II-6 PEG6000 Bad Comparison 
2-13 II-6 Lactose Bad Comparison 
2-14 II-6 HPC Bad Comparison 
2-15 II-1 D-Mannitol Excellent 
Invention 
2-16 II-3 D-Mannitol Excellent 
Invention 
2-17 II-8 D-Mannitol Excellent 
Invention 
2-18 II-9 D-Mannitol Excellent 
Invention 
______________________________________ 
It is obvious from Table 2 that the granular agents prepared according to 
the present invention can minimize, in comparison with comparative 
samples, occurrence of fine powder after storage under high temperature 
and low humidity conditions by incorporating the sugar alcohol of the 
invention in the grain. 
Example 3 
In this Example, tabular shaped compositions were prepared and the 
experiments were carried out in the same manner as in Example 1, except 
that a tabular shaped composition form processing agent for bleaching had 
a diameter of 15 mm and weight of 1.7 g a tabular shaped composition in 
procedure (1-2) of Example 1. Similar results as Example 1 were obtained. 
Thus it was found that the effect of the present invention can be obtained 
independent of the diameter of the tabular shaped composition. 
Example 4 
(Procedure: 4-1) 
Ferric complex of the exemplified compound (as shown in Table 3) 720 g 
Free acid of the above-mentioned exemplified compound 70 g 
Additive-1 (as shown in Table 3) as shown in Table 3 
Sodium carbonate monohydrate 70 g 
After respective raw materials mentioned above were pulverized into fine 
grains having average grain diameter of not more than 50 .mu.m with a 
hammer-mill, they were granulated in a mixing granulator while mixing and 
spraying water. 
Amount of water used in this step was 50 ml. These granulated products were 
dried for three hours using a conventional fluidized-bed dryer at 
60.degree. C. This is called granulated product (b). 
(Procedure: 4-2) 
Ammonium thiosulfite 800 g 
Sodium sulfate 160 g 
Sodium metasulfate 60 g 
Additive-2 (as shown in Table 3) See Table 3 
After respective raw materials mentioned above were pulverized into fine 
grains having average grain diameter of not more than 50 .mu.m with a 
hammer-mill, they were granulated in a mixing granulator while mixing and 
spraying water. 
Amount of water used in this step was 50 ml. These granulated products were 
dried for three hours using a conventional fluidized-bed dryer at 
60.degree. C. This is called granulated product (c). 
To the granulated products (b) and (c), 0.5% by weight of sodium 
lauroylsarcosine was added and after mixing this for three minutes, 
tabular shaped processing composition for bleaching, having diameter of 30 
mm and 10 g in weight a was prepared. 
Thus prepared tabular shaped compositions were sealed up in a packaging 
bag, which is made of aluminium and the same experiment as Example 1 was 
carried out. 
Results obtained are shown in Table 3: 
TABLE 3 
__________________________________________________________________________ 
Expansion Rate 
after Storage 
Hardness 
Sample 
Exemplified 
Additive-1 
Additive-2 
Diameter 
Thickness 
after Storage 
No. Compound 
(wt %) (wt %) (%) (%) (kg) Remarks 
__________________________________________________________________________ 
3-1 II-1 -- -- 5.8 7.7 12.0 Comparison 
3-2 II-1 D-Mannit (1.0) 
-- 1.1 1.4 48.0 Invention 
3-3 II-1 D-Mannit (5.0) 
-- 0.8 1.2 55.0 Invention 
3-4 II-1 D-Mannit (20.0) 
-- 1.5 1.6 53.0 Invention 
3-5 II-1 D-Mannit (30.0) 
-- 1.9 2.2 55.0 Invention 
3-6 II-1 D-Mannit (40.0) 
-- 2.9 3.2 54.0 Invention 
3-7 II-1 -- D-Mannit (5.0) 
2.0 2.8 47.0 Invention 
3-8 II-1 D-Sorbit (5.0) 
-- 1.0 1.2 62.0 Invention 
3-9 II-1 Erythrit (5.0) 
-- 1.3 1.5 49.0 Invention 
3-10 
II-1 Glycerine (5.0) 
-- 1.9 2.3 37.0 Invention 
3-11 
II-1 D-Mannit (5.0) 
PEG2000 (5.0) 
1.0 1.3 56.0 Invention 
3-12 
II-1 PEG6000 (5.0) 
PEG6000 (5.0) 
4.9 6.8 49.0 Comparison 
3-13 
II-1 PEG2000 (5.0) 
PEG2000 (5.0) 
5.9 8.0 38.0 Comparison 
3-14 
II-1 Lactose (5.0) 
Lactose (5.0) 
5.5 7.2 19.0 Comparison 
3-15 
II-1 HPC (5.0) 
HPC (5.0) 
5.1 7.4 27.0 Comparison 
3-16 
II-8 D-Mannit (5.0) 
-- 0.9 1.4 56.0 Invention 
3-17 
II-3 D-Mannit (5.0) 
-- 0.9 1.3 54.0 Invention 
3-18 
II-6 D-Mannit (5.0) 
-- 1.2 1.4 49.0 Invention 
3-19 
II-10 D-Mannit (5.0) 
-- 1.1 1.6 50.0 Invention 
3-20 
II-14 D-Mannit (5.0) 
-- 1.0 1.5 52.0 Invention 
3-21 
II-8 -- -- 5.9 7.5 13.0 Comparison 
3-22 
II-3 -- -- 5.7 7.2 11.0 Comparison 
3-23 
II-6 -- -- 6.7 8.9 9.0 Comparison 
3-24 
II-10 -- -- 5.9 7.9 12.0 Comparison 
3-25 
II-14 -- -- 5.5 7.5 10.0 Comparison 
__________________________________________________________________________ 
It is obvious from Table 3 that according to the present invention, similar 
effects can be obtained with respect to a tabular shaped composition 
bleach-fixing agent, and from results of Samples No. 3-3 and No. 3-7 that 
in the case of a tabular shaped composition made from a mixture of two or 
more kinds of granulated products, the effects of the present invention 
may be obtained by incorporating in the tabular shaped composition 
comprising a ferric complex of aminopolycarboxylic acid at least one sugar 
alcohol and, more preferably in the tabular shaped composition comprising 
APC-Fe the sugar alcohol of the present invention. 
Example 5 
Experiments were repeated in the same manner as Example 4, except that in 
this example, Exemplified Compounds II-1, II-3, II-7, II-9, II-10 and 
II-14 were used, and similar effects of the present invention as obtained 
in Example 4 were observed. 
Example 6 
Mixed granular products prepared by mixing Granular products (b) and (c) 
prepared in Example 4, were passed through a sieve with the mesh size of 
149 .mu.m and 100 g of respective grains having grain size of not less 
than 149 .mu.m were sealed up in the packaging bag made of aluminium, and 
the same experiment as Example 2 was carried out. 
Results are shown in Table 4. 
TABLE 4 
__________________________________________________________________________ 
Rate of 
Occurrence 
Sample 
Exemplified 
Additive-2 
Additive-3 
of Fine 
No. Compound 
(wt %) (wt %) Powder 
Remarks 
__________________________________________________________________________ 
4-1 II-1 -- -- Very Bad 
Comparison 
4-2 II-1 D-Mannit (5.0) 
-- Good Invention 
4-3 II-1 D-Sorbit (5.0) 
-- Good Invention 
4-4 II-1 Erythrit (5.0) 
-- Good Invention 
4-5 II-1 D-Arabit (5.0) 
-- Fair Invention 
4-6 II-1 Glycerine (5.0) 
-- Fair Invention 
4-7 II-1 D-Idit (5.0) 
-- Good Invention 
4-8 II-1 Dulcit (5.0) 
-- Good Invention 
4-9 II-1 D-Threit (5.0) 
-- Fair Invention 
4-10 
II-1 PEG600 (5.0) 
-- Bad Comparison 
4-11 
II-1 PEG6000 (5.0) 
-- Very Bad 
Comparison 
4-12 
II-1 Lactose (5.0) 
-- Very Bad 
Comparison 
4-13 
II-1 HPC (5.0) 
-- Very Bad 
Comparison 
4-14 
II-1 D-Mannit (5.0) 
D-Mannit (5.0) 
Excellent 
Invention 
4-15 
II-1 PEG600 (5.0) 
PEG600 (5.0) 
Bad Comparison 
4-16 
II-8 D-Mannit (5.0) 
-- Good Invention 
4-17 
II-3 D-Mannit (5.0) 
-- Good Invention 
4-18 
II-6 D-Mannit (5.0) 
-- Fair Invention 
4-19 
II-10 D-Mannit (5.0) 
-- Good Invention 
4-20 
II-14 D-Mannit (5.0) 
-- Good Invention 
__________________________________________________________________________ 
It is obvious from Table 4 that the similar effects of the present 
invention can be obtained in the granular agent for bleach-fixing. 
Example 7 
To the granulated product (b) prepared in Example 4, 0.5% by weight of 
sodium lauroylsarcosine was added and after mixing this for three minutes, 
tabular shaped processing composition for bleach-fixing, having diameter 
of 30 mm and 10 g in weight a tabular shaped composition was prepared in 
the same manner as Example 1. 
Thus prepared tabular shaped compositions were sealed up in a packaging 
bag, and the same experiments as in Example 4 were carried out. 
As a result, it was understood that the similar results were obtained and 
that the effects of the present invention is obtainable with respect to a 
tabular shaped processing composition for bleach-fixing. 
Example 8 
Granulated product (b) prepared in Example 4 were passed through a sieve 
with the mesh size of 149 .mu.m and 100 g of respective grains having 
grain size of not less than 149 .mu.m were sealed up in the packaging bag 
made of aluminium and the same experiments as Example 2 were carried out. 
As a result, it was understood that the similar results as those obtained 
in Example 6 were obtained, and, thus, the effects of the present 
invention is obtainable with respect to a tabular shaped processing 
composition for bleach-fixing. 
Example 9 
Granulated products as shown in Table 5, provided that in this example 
amount of water, drying temperature and drying time were varied, to 
prepare granulated products as shown in Table 5. 
After mixing these granulated products with granulated product (c) in the 
same manner as in Example 4, tabular shaped processing composition for 
bleach-fixing, having diameter of 30 mm. and 10 g in weight a tabular 
shaped composition was prepared in the same manner as Example 4. Then thus 
prepared tabular shaped compositions were sealed up in a packaging bag, 
and the same experiments as in Example 4 were carried out. 
Results are shown in Table 5. 
TABLE 5 
__________________________________________________________________________ 
Amount of Hard- 
Molar 
Reduced Rate of Expansion 
ness 
Sam- 
Exempli- 
*1 Number 
Weight by after Storage 
after 
ple 
fied Counter 
of Drying at 
Additive-2 
Additive-3 
Diameter 
Thickness 
Storage 
Re- 
No. 
Compound 
Cathion 
Water 
50.degree. C. 
(wt %) 
(wt %) (%) (%) (kg) 
marks 
__________________________________________________________________________ 
5-1 
II-3 NH.sub.4.sup.+ 
2 0.06 Mannit (5.0) 
PEG6000 (5.0) 
1.1 1.7 24 Inv. 
5-2 
II-3 NH.sub.4.sup.+ 
2 0.12 Mannit (5.0) 
PEG6000 (5.0) 
1.3 1.6 33 Inv. 
5-3 
II-3 NH.sub.4.sup.+ 
2 0.53 Mannit (5.0) 
PEG6000 (5.0) 
1.3 1.8 35 Inv. 
5-4 
II-3 NH.sub.4.sup.+ 
2 1.08 Mannit (5.0) 
PEG6000 (5.0) 
1.3 1.6 48 Inv. 
5-5 
II-3 NH.sub.4.sup.+ 
2 5.82 Mannit (5.0) 
PEG6000 (5.0) 
1.4 1.8 43 Inv. 
5-6 
II-3 NH.sub.4.sup.+ 
2 7.91 Mannit (5.0) 
PEG6000 (5.0) 
2.0 2.3 31 Inv. 
5-7 
II-3 NH.sub.4.sup.+ 
2 9.83 Mannit (5.0) 
PEG6000 (5.0) 
2.1 2.6 29 Inv. 
5-8 
II-3 NH.sub.4.sup.+ 
2 12.11 
Mannit (5.0) 
PEG6000 (5.0) 
3.6 4.1 22 Inv. 
5-9 
II-3 NH.sub.4.sup.+ 
0 0.09 Mannit (5.0) 
PEG6000 (5.0) 
1.1 1.8 21 Inv. 
5-10 
II-3 NH.sub.4.sup.+ 
0 5.73 Mannit (5.0) 
PEG6000 (5.0) 
1.5 1.9 24 Inv. 
5-11 
II-3 NH.sub.4.sup.+ 
0 12.01 
Mannit (5.0) 
PEG6000 (5.0) 
3.8 4.3 20 Inv. 
5-12 
II-10 NH.sub.4.sup.+ 
2 0.07 Mannit (5.0) 
PEG6000 (5.0) 
1.2 1.5 28 Inv. 
5-13 
II-10 NH.sub.4.sup.+ 
2 5.63 Mannit (5.0) 
PEG6000 (5.0) 
1.3 1.6 44 Inv. 
5-14 
II-10 NH.sub.4.sup.+ 
2 11.89 
Mannit (5.0) 
PEG6000 (5.0) 
3.7 3.9 26 Inv. 
__________________________________________________________________________ 
Inv.: Invention 
*CounterCation in the exemplified compound 
As is obvious from Table 5, it is understood that the effects of the 
present invention become distinguished in the case where the tabular 
shaped composition comprises a ferric complex of aminopolycarboxylic acid 
hydrate and a decreasing ratio in weight of said photographic processing 
composition after drying at 50.degree. C. is within the range of 0.1% to 
10.0% by weight. 
Example 10 
Granular products as shown in Table 6, provided that in this example amount 
of water, drying temperature and drying time were varied, to prepare 
granular products as shown in Table 6. 
Tabular shaped processing composition for bleach-fixing agent, having 
diameter of 30 mm and 10 g in weight a tabular shaped composition was 
prepared in the same manner as Example 1. 
Then thus prepared tabular shaped compositions were sealed up in a 
packaging bag, and the same experiments as in Example 4 were carried out. 
Results are shown in Table 6. 
TABLE 6 
__________________________________________________________________________ 
Molar 
Amount of Rate of Expansion 
Hardness 
Sam- 
Exempli- Number 
Reduced Weight 
after Storage 
after 
ple 
fied Counter 
of by Drying at 
Additive-1 
Diameter 
Thickness 
Storage 
No. 
Compound 
Cathion 
Water 
50.degree. C. 
(wt %) 
(%) (%) (kg) Remarks 
__________________________________________________________________________ 
6-1 
II-6 NH.sub.4.sup.+ 
1 0.05 Mannit (5.0) 
1.3 1.7 20 Invention 
6-2 
II-6 NH.sub.4.sup.+ 
1 3.20 Mannit (5.0) 
1.3 1.8 46 Invention 
6-3 
II-6 NH.sub.4.sup.+ 
1 9.62 Mannit (5.0) 
1.5 1.9 37 Invention 
6-4 
II-6 NH.sub.4.sup.+ 
1 12.15 Mannit (5.0) 
2.9 2.9 21 Invention 
6-5 
II-6 NH.sub.4.sup.+ 
0 3.30 Mannit (5.0) 
2.3 2.7 22 Invention 
6-6 
II-3 NH.sub.4.sup.+ 
2 3.42 Mannit (5.0) 
1.4 1.7 47 Invention 
6-7 
II-10 NH.sub.4.sup.+ 
1 3.22 Mannit (5.0) 
1.5 1.6 42 Invention 
__________________________________________________________________________ 
As is obvious from Table 6, as in the case of Example 9, it is understood 
that the effects of the present invention become distinguished in the case 
where the tabular shaped composition comprises a ferric complex of 
aminopolycarboxylic acid hydrate and the amount of reduced weight by 
drying at 50.degree. C. is between 0.1 and 10.0% by weight. 
Example 11 
Respective granulated products (b) prepared in Example 10 were passed 
through a sieve with the mesh size of 149 .mu.m and 100 g of respective 
grains having grain size of not less than 149 .mu.m were sealed up in the 
packaging bag made of aluminium, and the same experiments as Example 2 
were carried out. 
Results are shown in Table 7. 
TABLE 7 
__________________________________________________________________________ 
Decreas- 
ing ratio 
Molar 
in weight Rate of 
Sam- 
Exempli- Number 
after Expansion 
ple 
fied Counter 
of drying at 
Additive-1 
after 
No. 
Compound 
Cation 
Water 
50.degree. C. 
(wt %) 
Storage 
Remarks 
__________________________________________________________________________ 
7-1 
II-6 NH.sub.4.sup.+ 
1 0.05 Mannit (5.0) 
Good Invention 
7-2 
II-6 NH.sub.4.sup.+ 
1 3.20 Mannit (5.0) 
Excellent 
Invention 
7-3 
II-6 NH.sub.4.sup.+ 
1 9.62 Mannit (5.0) 
Good Invention 
7-4 
II-6 NH.sub.4.sup.+ 
1 12.15 
Mannit (5.0) 
Fair Invention 
7-5 
II-6 NH.sub.4.sup.+ 
0 3.30 Mannit (5.0) 
Excellent 
Invention 
7-6 
I-3 NH.sub.4.sup.+ 
2 3.42 Mannit (5.0) 
Excellent 
Invention 
7-7 
I-10 NH.sub.4.sup.+ 
1 3.22 Mannit (5.0) 
Excellent 
Invention 
__________________________________________________________________________ 
As is obvious from Table 7, it is understood that the effects of the 
present invention become distinguished in the case where the tabular 
shaped composition comprises a ferric complex of aminopolycarboxylic acid 
hydrate and a decreasing ratio in weight of photographic processing 
composition after drying at 50.degree. C. is within the range of 0.1% to 
10.0% by weight. 
Experiment 12 
As to the mixtures prepared in Example 9, the same experiments as in 
Example 11 were carried out, to obtain similar results as obtained in 
Example 11.