Silver halide photographic light-sensitive material

A silver halide photographic light-sensitive material excellent in antistatic property and evelopment uniformity is provided, comprising a support having on one side thereof hydrophilic colloidal layers including a silver halide emulsion layer, which is exposed and processed with an automatic processing machine, wherein at least one of the hydrophilic layers contains a water-soluble polymer represented by formula [I] or a water-soluble polymer having a repeating unit represented by formula [II], and a nonionic surfactant represented by formula [IIIa], [IIIb] or [IIIc]. ##STR1##

FIELD OF THE INVENTION 
The present invention relates to a silver halide photographic 
light-sensitive material and an image forming method, more specifically a 
silver halide photographic light-sensitive material excellent in 
antistatic property and development uniformity in processing using an 
automatic processing machine, and a rapid image forming method thereof. 
BACKGROUND OF THE INVENTION 
It is known that incorporating a nonionic surfactant in a hydrophilic 
colloidal layer of a silver halide photographic light-sensitive material 
is effective in reducing the occurrence of static marks caused by 
frictional electrification, peeling electrification and other factors. 
However, containment of a nonionic surfactant in a hydrophilic colloidal 
layer on the silver halide emulsion layer side for improving the 
antistatic property poses a problem of frequent occurrence of uneven 
development in processing using an automatic processing machine. 
Therefore there is a need for a silver halide photographic light-sensitive 
material excellent in antistatic property and development evenness in 
processing using an automatic processing machine, and a rapid image 
forming method. 
SUMMARY OF THE INVENTION 
The object of the present invention is to provide a silver halide 
photographic light-sensitive material excellent in antistatic property and 
development evenness in processing using an automatic processing machine, 
and a rapid image forming method thereof. 
The object of the present invention has been accomplished by: 
1) a silver halide photographic light-sensitive material processed using an 
automatic processing machine, wherein the hydrophilic colloidal layer on 
the silver halide emulsion layer side contains a water-soluble polymer of 
the following formula I or at least one water-soluble polymer comprising 
at least one kind of a repeating unit represented by the following formula 
II, and at least one of nonionic surfactants of the following formula III, 
III' or III", 
More preferred embodyments of the silver halide photographic 
light-sensitive material is 
2) the silver halide photographic light-sensitive material of the above, 
wherein the degree of surface matting on the silver halide emulsion layer 
side is not higher than 50 mmHg, and 
3) an image forming method using the light-sensitive material of term 1) 
above, wherein the total processing time is not longer than 50 seconds. 
Accordingly, the present inventors found that uneven development occurred 
in a photographic light-sensitive material containing a nonionic 
surfactant can be reduced significantly by incorporating at least one kind 
of the hydrophilic polymer of formula I or of the hydrophilic polymer 
comprising a repeating unit represented by formula II into the hydrophylic 
colloidal layer on the silver halide emulsion layer side. 
The inventors also found that the effect of the containment of the above 
compound increases as the degree of surface matting on the silver halide 
emulsion layer side decreases (not higher than 50 mmHg). 
The inventors also found that the effect of the containment of the above 
compounds increases as the total processing time decreases (not longer 
than 50 seconds). 
##STR2## 
In these formulas, R.sub.1 represents a substituted or unsubstituted alkyl 
group having 1 to 30 carbon atoms, an alkenyl group or an aryl group; A 
represents an --O-- group, an --S-- group, a --COO-- group, an 
--N--R.sub.10 group, a --CO--N--R.sub.10 group or an --SO.sub.2 N--R group 
(R.sub.10 represents a hydrogen atom or a substituted or unsubstituted 
alkyl group).

DETAILED DESCRIPTION OF THE INVENTION 
Water soluble polymers represented by formula I used for the present 
invention are described below. 
##STR3## 
wherein A represents a repeating unit represented by the following formula 
A; B and C independently represent a repeating unit comprising a vinyl 
monomer copolymerizable with A. Formula I contains a repeating unit of 
formula A in an amount of 10 to 100 mol % per polymer molecule. Thus, n is 
10 to 100 mol % and m+l is 0 to 90 mol %. 
##STR4## 
wherein R.sub.1 and R.sub.2, independently represent a hydrogen atom, an 
alkyl group, preferably one having 1 to 4 carbon atoms (e.g., methyl 
group, ethyl group, propyl group, butyl group), including one having a 
substituent, a halogen atom such as chlorine, or --CH.sub.2 COOM; a 
represents --CONH--, --NHCO--, --COO--, --OCO--, --CO--, --SO.sub.2 --, 
&gt;NHSO.sub.2 --, --SO.sub.2 NH-- or --O--; b represents an alkylene group, 
preferably one having 1 to 10 carbon atoms (e.g., methylene group, 
ethylene group, propylene group, trimethylene group, butylene group, 
hexylene group), including one having a substituent, an arylene group 
(e.g., phenylene group), including one having a substituent, or an 
aralkylene group including one having a substituent; M represents a 
hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an 
ammonium group or an organic ammonium group; j represents an integer of 0 
or 1, and k represent an integer of 1 to 10; Y represents a hydrogen atom 
or the following: 
##STR5## 
Examples of compounds (water-soluble polymers) represented by formula I are 
given below, which are not to be construed as limitative. 
##STR6## 
The number-average molecular weight (M.sub.n) of the water-soluble polymer 
ranges normally from 500 to 5,000,000, preferably 1,000 to 500,000. 
Water-soluble polymers of the present invention, comprising at least one 
kind of a repeat unit represented by formula II, are described below. 
##STR7## 
wherein R.sub.1 through R.sub.6 independently represent a hydrogen atom, 
an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 
carbon atoms or --SO.sub.3 X, where X represents a hydrogen atom, an atom 
of alkali metal, an atom of alkaline earth metal, an ammonium group or an 
organic ammonium group, and at least one of R.sub.1 through R.sub.6 is 
--SO.sub.3 X. 
A compound having a repeat unit of the above formula II, used for the 
present invention, can be obtained by sulfonating and then polymerizing a 
diene monomer or by polymerizing a diene monomer and then sulfonating. 
With respect to the compound of the present invention, the content of the 
repeat unit represented by formula II is not less than 10 mol %, 
preferably not less than 20 mol %. 
Examples of diene monomers used for the present invention include 
1,3-butadiene, 1,2-butadiene, 1,2-pentadiene, 1,3-pentadiene, 
2,3-pentadiene, isoprene, 1,2-hexadiene, 1,3-hexadiene, 1,4-hexadiene, 
1,5-hexadiene, 2,3-hexadiene, 2,4-hexadiene, 2,3-dimethyl-1,3-butadiene, 
2-ethyl-1,3-butadiene, 1,2-heptadiene, 1,3-heptadiene, 1,4-heptadiene, 
1,5-heptadiene, 1,6-heptadiene, 2,3-heptadiene, 2,5-heptadiene, 
3,4-heptadiene, 3,5-heptadiene and 2-phenylbutadiene, and also various 
branched diene monomers. 
These diene monomers may be used singly or in combination. 
In the above method wherein a diene monomer is sulfonated and then 
polymerized, the sulfonate can be produced by, for example, sulfonating 
the diene monomer as described below while retaining the double bond 
thereof. 
Specifically, using sulfur trioxide as a sulfonating agent, a diene monomer 
can be sulfonated under conventional conditions such as those described in 
Jikken Kagaku Koza, edited by the Chemical Society of Japan, and Japanese 
Patent Publication Open to Public Inspection (hereinafter referred to as 
Japanese Patent O.P.I. Publication) No. 26310/1989. 
Although the sulfonate thus obtained is not subject to limitation as to 
cationic moiety, the cation is preferably hydrogen, alkali metal, alkaline 
earth metal, ammonium, amine or the like from the viewpoint of water 
solubility. 
Such alkali metals include sodium and potassium. Such amines include 
alkylamines such as methylamine, ethylamine, propylamine, dimethylamine, 
diethylamine, triethylamine, butylamine, dibutylamine and tributylamine, 
polyamines such as ethylenediamine, diethylenetriamine and 
triethylenetetramine, morpholine and piperidine. Such alkaline earth 
metals include calcium and magnesium. 
These cations may be exchanged with other cations by various ion exchanging 
techniques. 
A compound of the present invention, having a repeat unit represented by 
the above formula II, may be copolymerized with other monomer 
copolymerizable with the diene monomer (hereinafter referred to as "other 
monomers") in not less than 99% by weight, preferably 1 to 98% by weight, 
and more preferably about 10 to 90% by weight. 
Such other copolymerizable monomers include aromatic compounds such as 
styrene, .alpha.-methylstyrene, vinyltoluene and p-methylstyrene, alkyl 
esters of acrylic or methacrylic acid such as methyl acrylate, ethyl 
acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, 
2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, anhydrides of 
mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, 
crotonic acid, maleic acid, fumaric acid and itaconic acid, aliphatic 
conjugated dienes such as butadiene, isoprene, 2-chloro-1,3-butadiene and 
1-chloro-1,3-butadiene, vinyl cyanide compounds such as acrylonitrile and 
methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl methyl ethyl 
ketone, vinyl methyl ether, vinyl acetate, vinyl formate, allyl acetate, 
methallyl acetate, acrylamide, methacrylamide, N-methylolacrylamide, 
glycidyl acrylate, glycidyl methacrylate, acrolein and allyl alcohol. 
Specifically, a sulfonate of the above diene monomer and, where necessary, 
one or more other monomers copolymerizable therewith are subjected to 
radical polymerization in the presence of a solvent for polymerization 
such as water or an organic solvent using a radical polymerization 
initiator, chain transferring agent and other additives. 
The sulfonated polymer thus obtained can have repeat units represented by 
formulas II' and/or II", as well as a repeat unit represented by formula 
II. 
The unit represented by formula II' and/or II" is contained in an amount of 
0 to 70 mol %, preferably 0 to 50 mol %. This content can be controlled 
according to polymerizing conditions. 
##STR8## 
With respect to formulas II' and II", R.sub.1 through R.sub.6 are identical 
to those defined in the above formula II. 
Although the weight-average molecular weight (Mw) of the sulfonated polymer 
thus obtained varies depending on the use thereof, it is normally 500 to 
5,000,000, preferably 1,000 to 500,000. 
The sulfonated polymer of the present invention may be converted to acid 
forms or salts of alkali metal, alkaline earth metal, ammonium, amine, 
etc. by ion exchanging or neutralization. 
When the monomer sulfonate is formed prior to polymerization, the 
sulfonated polymer thus obtained is neutralized in an aqueous alkali 
solution such as aqueous sodium hydroxide, potassium hydroxide or ammonia 
to yield a water-soluble or hydrophilic polymer salt wherein at least some 
of the sulfone groups have formed salt. Although the sulfonate is not 
subject to limitation as to cation for forming a salt in the sulfone group 
thereof, the cation is preferably hydrogen atom, alkali metal, alkaline 
earth metal, ammonium, amine or the like from the viewpoint of water 
solubility as described above. 
These cations may be exchanged mutually with other cations by various ion 
exchanging techniques. 
An aqueous solution of a water-soluble (co)polymer salt is thus prepared. 
The degree of sulfone group neutralization can be chosen as appropriate, as 
long as the (co)polymer salt is soluble or dispersible in water, and 
sulfone groups may form different salts. 
As described above, a (co)polymer of the present invention can be obtained 
from a sulfonated diene monomer, but alternatively, it can also be 
obtained by polymerizing and then sulfonating a diene monomer. The 
(co)polymer may be produced by any of these methods, which are carried out 
by known procedures. 
Examples of compound having a repeat unit represented by formula II of the 
present invention are given below, which are not to be construed as 
limitative. 
##STR9## 
Some of these compounds are commercially available as "JSR water-soluble 
polymers" from Japan Synthetic Rubber Co., Ltd. 
The water-soluble polymer represented by formula I or formula II is 
contained in an amount of 5 mg to 5 g, preferably 10 mg to 2 g per m.sup.2 
of the photographic material. 
Nonionic surfactant of the present invention represented by formula III, 
III' or III", are described below. 
##STR10## 
In these formulas, R.sub.1 represents a substituted or unsubstituted alkyl 
group having 1 to 30 carbon atoms, an alkenyl group or an aryl group; A 
represents --O--, --S--, --COO--, 
##STR11## 
or --SO.sub.2 N--R.sub.10, wherein R.sub.10 represents a hydrogen atom or 
a substituted or unsubstituted alkyl group. 
R.sub.2, R.sub.3, R.sub.7 and R.sub.9 independently represent a hydrogen 
atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy 
group, a halogen atom, an acyl group, an amide group, a sulfonamide group, 
a carbamoyl group or a sulfamoyl group. R.sub.6 and R.sub.8 independently 
represent a substituted or unsubstituted alkyl group, an aryl group, an 
alkoxy group, a halogen atom, an acyl group, an amide group, a sulfonamide 
group, a carbamoyl group or a sulfamoyl group. With respect to formula 
III". R.sub.4 and R.sub.5 independently represent a hydrogen atom, a 
substituted or unsubstituted alkyl group, or an aryl group. R.sub.4 and 
R.sub.5, R.sub.6 and R.sub.7, and R.sub.8 and R.sub.9, may bind together 
to form a substituted or unsubstituted ring. n.sub.1, n.sub.2, n.sub.3 and 
n.sub.4 independently represent the degree of polymerization of ethylene 
oxide, ranging from 2 to 50, and m represents the degree of 
polymerization, ranging from 2 to 50. 
Examples of preferable compounds of the present invention, represented by 
formula III, III' or III", are given below, which are not to be construed 
as limitative. 
##STR12## 
Also included are exemplified Compound Nos. I-1 through I-7 described on 
page 2 of Japanese Patent O.P.I. Publication No. 55521/1977, and 
exemplified Compound Nos. I-15 through 18, I-20 and 21, I-24, I-29, I-34, 
I-44 and I-60 described on pages 5 through 8 of Japanese Patent O.P.I. 
Publication No. 76741/1985. 
The above compounds can easily be synthesized by adding ethylene oxide to 
respective corresponding fatty acid monoethanolamides and carrying out a 
reaction therebetween. For example, Amizet 5C and Amizet 10C (both 
produced by Nikko Chemical) and other commercial products are categorized 
under this compound 4 and can be used in the present invention. 
Although the amount of the surfactant used varies depending on the shape, 
kind and coating method of the photographic light-sensitive material used, 
it is preferable to use the surfactant in an amount of 1 to 1000 mg, 
particularly 5 to 200 mg per m.sup.2 of photographic light-sensitive 
material. For introducing the surfactant to a layer of the photographic 
light-sensitive material, it is dissolved in water, an organic solvent 
such as methanol, ethanol or acetone, or a mixed solvent of water and an 
organic solvent as above, after which the solution is added to a 
light-sensitive emulsion layer or non light-sensitive auxiliary layer 
(e.g., anti-halation layer, interlayer, protective layer) on the support, 
or is sprayed or coated on the surface of the support, or the photographic 
light-sensitive material is immersed in said solution, followed by drying. 
In this operation, two or more kinds of nonionic and anionic surfactants 
may be used in combination. 
To the emulsion layer or protective layer of the silver halide photographic 
material of the present invention, preferably to the protective layer, may 
be added a matting agent and/or lubricant. 
As one preferred embodiment of the present invention, a silver halide 
photographic material contains a matting agent and the surface of the 
photographic material has a mattness of not more than 50 mmHg. The term 
"mattness" is expressed in smoothness of the surface, which is determined 
under a specific condition by measuring a suction force on an unprocessed 
photographic material which has been stored for three hours under 
23.degree. C. and 48% R.H. The larger the value is, the greater the 
mattness. The measurement of the suction force is carried out using a 
SMOOSTER (produced by Toei Denshi Kogyo K. K.), as described later. 
The silver halide photographic light-sensitive material of the present 
invention is subjected to exposure and processing by using an automatic 
processing machine. A conventional developing solution can be used, as 
exemplified by that containing hydroquinone, 1-phenyl-3-pyrazolidone, 
N-methyl-p-aminophenol or p-phenylenediamine, which can be used alone or 
in combination thereof. 
A developing solution containing an aldehyde hardening agent can be used in 
the silver halide photographic light-sensitive material of the invention. 
For example, a conventional developing solution containing dialdehyde such 
as maleic dialdehyde, or glutaraldehyde, and sodium bisulfites thereof can 
be used. 
In the present invention, an overall processing time refers to the period 
of time through which the photographic material of the present invention 
is inserted to the first roller, which constitute the inlet of an 
automatic processing machine, and thereafter it passes through a 
developing tank, a fixing tank, and a drying tank until it reaches the 
last roller at a drying section outlet. 
The overall processing time is 50 seconds or less, and preferably from 20 
to 50 seconds. A processing time of less than 20 seconds may give rise to 
insufficient sensitivity, or bring about a dye residue or an image poor in 
uniformity. 
The processing is carried out at a temperature of 60.degree. C. or less, 
and preferably from 20.degree. to 45.degree. C. 
An example of particulars of the overall processing time is shown below. 
______________________________________ 
Processing step 
Temperature (.degree.C.) 
Time (sec) 
______________________________________ 
Insertion -- 1.2 
Developing + crossover 
35 14.6 
Fixing + crossover 
33 8.2 
Washing + crossover 
25 7.2 
Squeeze 40 5.7 
Drying 45 8.1 
Total 45.0 
______________________________________ 
EXAMPLES 
The present invention is hereinafter described in more detail by means of 
the following examples. 
The present invention is by no means limited by these examples. 
EXAMPLE 1 
Preparation of Emulsion A 
To 1 l of a solution containing 130 g of KBr, 2.5 g of K1, 30 mg of 
1-phenyl-5-mercaptotetrazole and 15 g of gelatin being stirred at 
40.degree. C., 500 ml of a solution containing 0.5M ammoniacal silver 
nitrate was added in 1 minute. Two minutes later, acetic acid was added to 
obtain a pH of 6.0. One minute later, 500 ml of a solution containing 0.5M 
silver nitrate was added in 1 minute, followed by stirring for 15 minutes, 
after which a formalin condensate of naphthalene naphthalenesulfonate and 
an aqueous solution of magnesium sulfate were added to coagulate the 
emulsion. After supernatant removal, 2 l of 40.degree. C. warm water was 
added, followed by stirring for 10 minutes, after which an aqueous 
solution of magnesium sulfate was added again to coagulate the emulsion. 
After supernatant removal, 300 ml of a 5% gelatin solution was added, 
followed by stirring at 55.degree. C. for 30 minutes, to yield an 
emulsion. 
This emulsion comprised grains having an average grain size of 0.27 .mu.m 
wherein 90% of the total number of grains fell in the grain size range of 
0.1 to 0.70 .mu.m. 
Preparation of Emulsion B 
Using an AgBrI seed emulsion having an average grain size of 0.1 .mu. and 
an AgI content of 6 mol %, an aqueous solution of ammoniacal AgNO.sub.3 
and an aqueous solution of potassium bromide were added by the double jet 
method, and a monodispersed emulsion comprising cubic AgBrI grains having 
an average grain size of 0.25 .mu. and an average AgI content of 0.4 mol % 
was grown. The coefficient of variation (.sigma./r) was 0.17. 
These emulsions A and B were each dissolved immediately before the start of 
chemical ripening. When the solution temperature became constant, a dye of 
the following formula 1 was added, and ammonium thiocyanate, chloroauric 
acid and hypo were added to cause chemical sensitization, and thereafter 
4- hydroxy-5-methyl-1,3,3a,7-tetrazaindene was added thereto. 
##STR13## 
Coating Application of Red-sensitive Emulsions A and B Backing and 
Protective Layers 
A backing-coated support was prepared as follows: First, a backing layer 
coating solution, comprising a dye emulsion dispersion comprising 400 g of 
gelatin, 2 g of polymethyl methacrylate having an average grain size of 6 
.mu.m, 24 g of KNO.sub.3, 6 g of sodium dodecylbenzenesulfonate and 20 g 
of the following anti-halation dye 1, in an amount equivalent to 2 
g/m.sup.2, and glyoxal, was prepared. Separately, an aqueous terpolymer 
dispersion was prepared by diluting to a 10% by weight of a terpolymer 
comprising 50% by weight glycidyl methacrylate, 10% by weight methyl 
acrylate and 40% by weight butyl methacrylate, and this dispersion, as a 
subbing solution, was coated on a polyethylene terephthalate base. On one 
face of the polyethylene terephthalate base, the above backing layer 
coating solution, along with a protective layer coating solution 
comprising gelatin, a matting agent, glyoxal, and sodium 
dodecylbenzenesulfonate, was coated, to yield a support having a backing 
layer. 
The coating weight was 2.0 g/m.sup.2, based on the amount of gelatin 
applied, for each of the backing and protective layers. 
##STR14## 
Preparation of Red-sensitive Photographic Sample Nos. 1-14, 17-43, and 45 
Red-sensitive Silver Halide Emulsion Layer Coating Solution 
To emulsion A or B were added 10 g (per mol of silver halide, the same 
applies below) of trimethylolpropane, 50 mg of nitrophenyl 
triphenylphosphonium chloride, 1 g of ammonium 
1,3-dihydroxybenzene-4-sulfonate, 10 mg of sodium 
2-mercaptobenzimidazole-5-sulfonate, 1 g of C.sub.4 H.sub.9 OCH.sub.2 
CH(OH)CH.sub.2 N(CH.sub.2 COOH).sub.2, 10 mg of 
1,1-dimethylol-1-bromo-1-nitromethane, 
##STR15## 
and others were added to provide a red-sensitive silver halide emulsion 
coating solution. 
Emulsion-side Protective Layer Coating Solution 
The composition is as follows: Figures for the amount of addition are per 
liter of coating solution. 
______________________________________ 
Limed inert gelatin 68 g 
Acid-treated gelatin 2 g 
##STR16## 1 g 
______________________________________ 
Polymethyl methacrylate grains having an average size of 4 .mu.m were added 
to provide a degree of matting shown in Table 1. 
______________________________________ 
Silicon dioxide grains (1.2 .mu.m area-averaged 
0.5 g 
grain size, matting agent) 
Ludox AM (colloidal silica, produced by Du Pont) 
30 g 
2% aqueous solution of 2,4-dichloro-6-hydroxy- 
10 ml 
1,3,5-triazine sodium (hardener) 
35% formalin (hardener) 2 ml 
40% aqueous solution of glyoxal (hardener) 
1.5 ml 
##STR17## 1.0 g 
##STR18## 0.3 g 
##STR19## 0.5 g 
C.sub.4 F.sub.9 SO.sub.3 K 2 mg 
Topcide 300 (produced by Permachem Asia Ltd.) 
45 mg 
Nonionic surfactants of formulas IIIa-IIIc 
(added to all samples but sample No. 1) 
Example compound III-15 0.4 g 
Example compound III-22 2.5 g 
______________________________________ 
On the side opposite to the backing coated side, the silver halide emulsion 
layer coating solution and protective layer coating solution were 
simultaneously coated in this sequence from the support by the slide 
hopper method at a coating speed of 80 m/min, to yield a red-sensitive 
photographic sample. The coating weight of silver was 2.5 g/m.sup.2, and 
the coating weight of gelatin was 2.2 g/m.sup.2 for the emulsion layer and 
1.2 g/m.sup.2 for the protective layer. 
As shown in Table 1, a water-soluble polymer of formulas I or II was added 
to the emulsion layer or protective layer. 
Preparation of Emulsion C 
1) Preparation of Seed Emulsion 
To a 0.05N aqueous potassium bromide solution containing gelatin treated 
with hydrogen peroxide, being stirred vigorously at 40.degree. C., an 
aqueous silver nitrate solution and an equal molar amount of an aqueous 
potassium bromide solution containing gelatin treated with hydrogen 
peroxide were added by the double jet method. 1.5 minutes later, the 
liquid temperature was decreased to 25.degree. C. over a 30-minute period, 
after which 80 ml of aqueous ammonia (28%) was added per mol of silver 
nitrate, and the mixture was stirred for 5 minutes. After addition of 
acetic acid to obtain a pH of 6.0, the resulting reaction mixture was 
desalinized using an aqueous solution of Demol-Na (produced by Kao Atlas) 
and an aqueous solution of magnesium sulfate, after which it was 
re-dispersed in an aqueous gelatin solution, to yield a seed emulsion 
comprising spherical grains having an average grain size of 0.23 .mu.m and 
a coefficient of variation of 0.28. 
2) Grain Growth From Seed Emulsion 
Using the above seed emulsion, grains were grown as follows: To an aqueous 
solution containing ossein gelatin and disodium salt of 
propyleneoxy-polyethyleneoxy disuccinate being stirred vigorously at 
75.degree. C., an aqueous solution of potassium bromide and potassium 
iodide and an aqueous solution of silver nitrate were added by the double 
jet method, while maintaining a pH of 5.8 and a pAg of 9.0. After 
completion of the addition, pH was adjusted to 6.0, and 400 mg/mol AgX of 
an anhydride of sodium salt of 
5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine was added. 
This mixture was further desalinized at 40.degree. C., using an aqueous 
solution of Demol-Na (produced by Kao Atlas) and an aqueous solution of 
magnesium sulfate, after which it was re-dispersed in an aqueous gelatin 
solution. 
A tabular silver iodobromide emulsion (emulsion C) having an average silver 
iodide content of 1.5 mol %, a projected area diameter of 0.96 .mu.m, a 
coefficient of variation of 0.25 and an aspect ratio (projected area 
diameter/grain thickness) of 4.0 was thus obtained. 
Preparation of Green Sensitive Sample Nos. 13, 14, 34 and 35 
To the resulting emulsion C, an anhydride of sodium salt of 
5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine and an 
anhydrous sodium salt of 
5,5'di-(butoxycarbonyl)-1,1'-diethyl-3,3'-di-(4-sulfobutyl)benzimidazoloca 
rbocyanine, in a weight ratio of 200:1, were added at 500 mg per mol of 
silver halide at 50.degree. C. 
Ten minutes later, appropriate amounts of chloroauric acid, sodium 
thiosulfate and ammonium thiocyanate were added to cause chemical 
ripening. 15 minutes before completion of the ripening, potassium iodide 
was added at 200 mg per mol of silver halide, after which 
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added at 3.times.10.sup.-2 
mol per mol of silver halide, and this mixture was dispersed in an aqueous 
solution of 70 g of gelatin. To ripened emulsion C, the following 
additives were added. The amount of addition are per mol of silver halide. 
______________________________________ 
1,1-dimethylol-1-bromo-1-nitromethane 
70 mg 
t-butylcatechol 400 mg 
Polyvinylpyrrolidone (molecular weight 10,000) 
1.0 g 
Styrene-maleic anhydride copolymer 
2.5 g 
Nitrophenyl-triphenylphosphonium chloride 
50 mg 
Ammonium 1,3-dihydroxybenzene-4-sulfonate 
4 g 
Sodium 2-mercaptobenzimidazole-5-sulfonate 
15 mg 
1-phenyl-5-mercaptotetrazole 
10 mg 
Trimethylolpropane 10 g 
C.sub.4 H.sub.9 OCH.sub.2 CH(OH)CH.sub.2 N(CH.sub.2 COOH).sub.2 
1 g 
##STR20## 60 mg 
##STR21## 35 mg 
______________________________________ 
1.2 g of the following dye emulsion dispersion was added to yield a coating 
emulsion. 
Preparation of Dye Emulsion Dispersion 
10 kg of the following dye was dissolved in a mixed solvent of 28 l of 
tricresyl phosphate and 85 l of ethyl acetate at 55.degree. C. This 
solution is designated as oily solution. Separately, 270 l of a 9.3% 
aqueous solution of gelatin containing 1.35 kg of anionic surfactant AS 
was prepared. This solution is designated as aqueous solution. Next, the 
oily solution and the aqueous solution were placed in a dispersing vessel 
and dispersed while keeping the liquid temperature at 40.degree. C. To the 
resulting dispersion were added appropriate amounts of phenol and 
1,1-dimethylol-1-bromo-1-nitromethane, and water was added to make 240 kg. 
##STR22## 
The additives used in the protective layer on the emulsion surface side are 
as follows: The amount of addition are per liter of coating solution. 
______________________________________ 
Limed inert gelatin 68 g 
Acid-treated gelatin 2 g 
Sodium isoamyl-n-decylsulfosuccinate 
0.3 g 
______________________________________ 
Polymethyl methacrylate (matting agent of area-average grain size of 4 
.mu.m) Added to obtain a degree of matting shown in Table 1 
______________________________________ 
Silicon dioxide grains (matting agent of area-average 
0.5 g 
grain size 1.2 .mu.m) 
Ludox AM (colloidal silica, produced by Du Pont) 
30 g 
40% aqueous solution of glyoxal (hardener) 
1.5 ml 
(CH.sub.2 CHSO.sub.2 CH.sub.2).sub.2 O (hardener) 
500 mg 
Topcide 300 (produced by Permachem Asia Ltd.) 
45 mg 
##STR23## 1.0 g 
##STR24## 0.4 g 
##STR25## 0.5 g 
Nonionic surfactants (formulas IIIa through IIIc) 
III-15 0.4 g 
III-22 2.5 g 
______________________________________ 
Using two slide hopper coaters, a 175 .mu.m polyethylene terephthalate film 
base, coated with an aqueous dispersion of a terpolymer comprising 50% by 
weight glycidyl methacrylate, 10% by weight methyl acrylate and 40% by 
weight butyl methacrylate, diluted to a concentration of 10% by weight, 
was coated with an emulsion layer and protective layer on one face and 
with upper and lower backing layers on the opposite face simultaneously at 
a coating speed of 90 m/min and dried in 2 minutes and 15 seconds, to 
yield green-sensitive sample Nos. 15, 16 and 44, wherein the coating 
weight of silver was 2.9 g/m.sup.2 for the emulsion layer and that of 
gelatin was 1.1 g/m.sup.2 for the protective layer. 
The compositions of the backing layer solutions are given below. A 
water-soluble polymer was added as shown in Table 1. 
Backing Layer Coating Solution Compositions 
Two backing layers, i.e., the upper and lower backing layers, were coated, 
in a coating weight of gelatin of 1.2 g/m.sup.2 for the upper layer and 
3.0 g/m.sup.2 for the lower layer. 
The backing layer coating solutions were prepared as follows: 
______________________________________ 
Backing layers 
______________________________________ 
Lower layer coating solution (per liter of coating 
solution) 
Limed gelatin 70 g 
Acid-treated gelatin 5 g 
Trimethylolpropane 1.5 g 
Backing dye A 1.0 g 
Backing dye B 1.0 g 
Aqueous glyoxal solution (40%) (hardener) 
8 g 
Upper layer coating solution (per liter of coating 
solution) 
Limed gelatin 70 g 
Acid-treated gelatin 5 g 
Trimethylolpropane 1.5 g 
Backing dye A 1.0 g 
Backing dye C 1.0 g 
KNO.sub.3 0.5 g 
##STR26## 0.4 g 
##STR27## 0.3 g 
##STR28## 1.0 g 
F.sub.19 C.sub.90 (CH.sub.2 CH.sub.2 O).sub.10 CH.sub.2 CH.sub.2 SO.sub.3 
Na 0.1 g 
2% aqueous solution of sodium salt of 2, 
20 ml 
4-dichloro-6-hydroxy-1,3,5-triazine 
Polymethyl methacrylate grains of an area-average 
1.1 g 
grain size of 6 .mu.m 
C.sub.11 H.sub.23 CONH(CH.sub.2 CH.sub.2 O).sub.5 H 
1.0 g 
Backing dye A 
##STR29## 
Backing dye B 
##STR30## 
Backing dye C 
##STR31## 
______________________________________ 
Evaluation of the Mattness 
The mattness is evaluated with the aid of SMOOSTER(produced by Toei Denshi 
Kogyo K. K.). Thus, utilizing a vacuum type air micrometer, an inflow rate 
of air variable depending upon smoothness of the surface is measured as a 
change of pressure. The mattness is defined as a pressure value expressed 
in mmHg. The larger is the value, the greater the mattness. When measuring 
the mattness, a test sample which has been stored for three hours under 
23.degree. C. and 48% R.H., is placed beneath a head as shown in FIG. 1. 
When a vacuum pump sucks out air inside a tube, the pressure inside the 
tube (P) is read off. 
TABLE 1 
__________________________________________________________________________ 
Water- Coating 
Degree of 
Nonionic 
Total 
soluble weight 
matting 
surfactant 
processing 
Devel- 
No. 
Emulsion 
polymer 
Site of addition 
(mg/m.sup.2) 
(mmHg) 
III-15, III-22 
time oper 
Remark 
__________________________________________________________________________ 
1 B -- -- -- 30 Not added 
45 seconds 
H Comparative 
2 B -- -- -- 100 Added 45 seconds 
H Comparative 
3 B -- -- -- 50 Added 45 seconds 
H Comparative 
4 B -- -- -- 30 Added 45 seconds 
H Comparative 
5 B -- -- -- 30 Added 90 seconds 
H Comparative 
6 B I-2 Emulsion side 
5 30 Added 45 seconds 
H Inventive 
protective layer 
7 B I-2 Emulsion side 
10 30 Added 45 seconds 
H Inventive 
protective layer 
8 B I-2 Emulsion side 
50 100 Added 45 seconds 
H Inventive 
protective layer 
9 B I-2 Emulsion side 
50 50 Added 45 seconds 
H Inventive 
protective layer 
10 B I-2 Emulsion side 
50 30 Added 45 seconds 
H Inventive 
protective layer 
11 B I-2 Emulsion side 
200 30 Added 45 seconds 
H Inventive 
protective layer 
12 B I-2 Emulsion side 
250 30 Added 45 seconds 
H Inventive 
protective layer 
13 A I-2 Emulsion side 
10 30 Added 45 seconds 
H Inventive 
protective layer 
14 A I-2 Emulsion side 
50 30 Added 45 seconds 
H Inventive 
protective layer 
15 C I-2 Emulsion side 
10 30 Added 45 seconds 
H Inventive 
protective layer 
16 C I-2 Emulsion side 
50 30 Added 45 seconds 
H Inventive 
protective layer 
17 B I-3 Emulsion side 
10 30 Added 45 seconds 
H Inventive 
protective layer 
18 B I-3 Emulsion side 
50 30 Added 45 seconds 
H Inventive 
protective layer 
19 B I-5 Emulsion side 
10 30 Added 45 seconds 
H Inventive 
protective layer 
20 B I-5 Emulsion side 
50 30 Added 45 seconds 
H Inventive 
protective layer 
21 B I-6 Emulsion side 
50 30 Added 45 seconds 
H Inventive 
protective layer 
22 B I-12 
Emulsion side 
10 30 Added 45 seconds 
H Inventive 
protective layer 
23 B I-12 
Emulsion side 
200 30 Added 45 seconds 
H Inventive 
protective layer 
24 B I-13 
Emulsion side 
50 30 Added 45 seconds 
H Inventive 
protective layer 
25 B I-16 
Emulsion side 
50 30 Added 45 seconds 
H Inventive 
protective layer 
26 B II-1 Emulsion side 
10 30 Added 45 seconds 
H Inventive 
protective layer 
27 B II-1 Emulsion side 
50 30 Added 45 seconds 
H Inventive 
protective layer 
28 B II-2 Emulsion side 
50 30 Added 45 seconds 
H Inventive 
protective layer 
29 B II-3 Emulsion side 
50 30 Added 45 seconds 
H Inventive 
protective layer 
30 B II-5 Emulsion side 
50 30 Added 45 seconds 
H Inventive 
protective layer 
31 B I-2 Emulsion layer 
10 30 Added 45 seconds 
H Inventive 
32 B I-2 Emulsion layer 
200 30 Added 45 seconds 
H Inventive 
33 B I-5 Emulsion layer 
10 30 Added 45 seconds 
H Inventive 
34 B I-5 Emulsion layer 
200 30 Added 45 seconds 
H Inventive 
35 B I-5 Emulsion layer 
50 100 Added 45 seconds 
H Inventive 
36 B I-5 Emulsion layer 
50 50 Added 45 seconds 
H Inventive 
37 B I-5 Emulsion layer 
50 30 Added 45 seconds 
H Inventive 
38 B I-5 Emulsion layer 
200 30 Added 45 seconds 
K Inventive 
39 B I-2 Emulsion layer 
10 30 Added 45 seconds 
K Inventive 
40 B I-2 Emulsion layer 
200 30 Added 45 seconds 
K Inventive 
41 B II-1 Emulsion layer 
10 30 Added 45 seconds 
K Inventive 
42 B II-1 Emulsion layer 
200 30 Added 45 seconds 
K Inventive 
43 A -- Emulsion layer 
-- 30 Added 45 seconds 
H Comparative 
44 C -- Emulsion layer 
-- 30 Added 45 seconds 
H Comparative 
45 B I-5 Emulsion layer 
100 30 Added 45 seconds 
H Inventive 
I-12 
Protective layer 
100 
__________________________________________________________________________ 
Evaluation of Antistatic Property (Static Marks) 
To evaluate the antistatic property of each obtained sample, static marks 
were evaluated as follows: Sample Nos. 1 through 45 were kept standing in 
an atmosphere of 20% RH for 1 hour, after which they were cut into 
6.times.30 cm pieces. As illustrated in FIG. 1 a 500 gram weight 13 was 
suspended on each piece 12 which was subjected to friction with neoprene 
rubber rod 10 of about 30 mm diameter at a speed of one reciprocal cycle 
per about 0.8 seconds in the direction indicated by arrow in a total of 
five cycles. Then, the piece, remaining unexposed, was processed using the 
Konica X-ray automatic processing machine SRX-501, and macroscopically 
observed for static marks. The antistatic property was evaluated in 
accordance with the following criteria. The results are given in Table 2. 
Evaluation Criteria 
A: Very good 
B: Good 
C: No problem for practical use 
D: Poor 
Evaluation of Uneven Development 
Sample Nos. 1 through 45 were subjected to uniform exposure to tungsten 
light to a density of 1.1.+-.0.1 and then subjected to the following 
developing and other processes, after which they were macroscopically 
evaluated for uneven development. The results are given in Table 2. 
Evaluation Criteria 
A: Very good 
B: Good 
C: No problem for practical use 
D: Poor 
E: Very poor 
TABLE 2 
__________________________________________________________________________ 
Anti- 
Uneven Anti- 
Uneven 
static 
develop- static 
develop- 
No. 
property 
ment Remark No. 
property 
ment Remark 
__________________________________________________________________________ 
1 D C Comparative 
24 A A Inventive 
2 A E Comparative 
25 A A Inventive 
3 A E Comparative 
26 A B Inventive 
4 A E Comparative 
27 A A Inventive 
5 A D Comparative 
28 A A Inventive 
6 A C Inventive 
29 A A Inventive 
7 A B Inventive 
30 A A Inventive 
8 A C Inventive 
31 A B Inventive 
9 A B Inventive 
32 A A Inventive 
10 A A Inventive 
33 A B Inventive 
11 A A Inventive 
34 A A Inventive 
12 A A Inventive 
35 A C Inventive 
13 A B Inventive 
36 A B Inventive 
14 A A Inventive 
37 A A Inventive 
15 A B Inventive 
38 A A Inventive 
16 A A Inventive 
39 A B Inventive 
17 A B Inventive 
40 A A Inventive 
18 A A Inventive 
41 A B Inventive 
19 A B Inventive 
42 A A Inventive 
20 A A Inventive 
43 A E Comparative 
21 A A Inventive 
44 A E Comparative 
22 A B Inventive 
45 A A Inventive 
23 A A Inventive 
-- -- -- -- 
__________________________________________________________________________ 
From the results given in Table 2, it is seen that the samples prepared in 
accordance with the present invention are excellent in antistatic property 
and prevention of uneven development. 
Developing and Other Processes 
Developing was achieved using the following developers and fixer, using the 
automatic processing machine SRX-501 (produced by Konica Corporation) at a 
developing temperature of 35.degree. C. and a fixing temperature of 
33.degree. C. Washing water at 18.degree. C. was supplied at a flow rate 
of 3.5 l per minute. Drying temperature was 45.degree. C. The whole 
processing was performed over a period of time of 45 seconds in total, as 
shown in Table 1. 
______________________________________ 
Processing procedures 
Processing 
temperature Processing Replenishing 
Procedure (.degree.C.) 
time (seconds) 
rate 
______________________________________ 
Feed -- 1.2 
Developing + 
35 14.6 33 cc/10 .times. 
transition 12 inch size 
Fixing + 33 8.2 63 cc/10 .times. 
transition 12 inch size 
Washing + 18 7.2 3.5 l/min 
transition 
Squeezing 40 5.7 -- 
Drying 45 8.1 -- 
Total -- 45.0 -- 
______________________________________ 
Developer H 
Potassium sulfite 70 g 
Trisodium hydroxyethylehtylenediaminetriacetate 
8 g 
1,4-dihydroxybenzene 28 g 
Boric acid 10 g 
5-methylbenzotriazole 0.04 g 
1-phenyl-5-mercaptotetrazole 
0.01 g 
Sodium metabisulfite 5 g 
Acetic acid (90%) 13 g 
Triethylene glycol 15 g 
1-phenyl-3-pyrazolidone 1.2 g 
5-nitroindazole 0.2 g 
Glutaraldehyde 4 g 
Potassium bromide 4 g 
5-nitrobenzimidazole 1 g 
Water was added to 1 l, and sodium hydroxide was 
added to obtain a pH of 10.5. 
Fixer 
Sodium thiosulfate pentahydrate 
4.5 g 
Disodium ethylenediaminetetraacetate 
0.5 g 
Ammonium thiosulfate 150 g 
Anhydrous sodium sulfite 8 g 
Potassium acetate 16 g 
Aluminum sulfate 10-18 hydrate 
10 g 
Sulfuric acid (50 wt %) 5 g 
Citric acid 1 g 
Boric acid 7 g 
Glacial acetic acid 5 g 
Water was added to 1 l, and glacial acetic acid was 
added to obtain a pH of 4.2. 
Developer K 
The same composition as developer H but glutatralde- 
hyde was eliminated. 
______________________________________