Silver halide photographic material

A silver halide photographic material is disclosed in which a matting agent contained in a coating solution is prevented from settling in solution and peeling off during processing. The silver halide photographic material contains at least one light-sensitive emulsion and at least one surface protective layer on a support. The surface protective layer contains a polymer latex having an average particle size of up to 2 .mu.m and a perticular precipitation amount as measured in a test coating solution or a crosslinked polymer latex having a hydrophilic group.

FIELD OF THE INVENTION 
The present invention relates to photographic material and, more 
particularly, photographic light sensitive material including a matting 
agent (a polymer latex) which when contained in a coating solution does 
not settle out of the same, and which does not peel off the photographic 
light sensitive material during processing. 
BACKGROUND OF THE INVENTION 
Recently, rapid processing at high temperatures during development 
processing of photographic material has become popular. Also, in automatic 
development processing of light-sensitive material, developing solutions 
are required which provide sufficient sensitivity in a short amount of 
time. Light-sensitive materials having excellent developing performance 
and which cause no residual color, even in a short amount of processing 
time, are also required as well as light-sensitive material which drys in 
a short amount of time after washing. Automatic processors may have a 
drying zone built the inside thereof and inferior drying performance of 
the light-sensitive material requires a larger drying zone which results 
in increased size of the automatic processor. Further, generation of large 
amounts of energy results in increasing the temperature in the room in 
which the automatic processor is located. 
Accelerating the drying speed of the light-sensitive material as much as 
possible is desired. Generally, a hardener is added to the light sensitive 
material prior to costing thereof, and swelling rate in an emulsion layer 
and in a surface protective layer in the developing-fixing-rinsing 
processes is decreased to reduce the water content in the light-sensitive 
material before drying. Use of a significant amount of the hardener can 
accelerate drying speed. However, it increases developing time, lowers a 
sensitivity and reduces a covering power. In addition, using significant 
amounts of hardener causes delay of fixing speed of an unexposed silver 
halide grain, deterioration of residual color, and increase in residual 
hypo in the light-sensitive material after processing. Reduced water 
content in the light-sensitive material before the drying can be also 
achieved by decreasing the amounts of hydrophilic material (that is, 
gelatin), synthetic high molecular weight polymer, and hydrophilic low 
molecular weight polymer, contained in the light-sensitive material. In 
general, the hydrophilic low molecular weight polymer is used to prevent 
dry fog of a silver halide grain during a coating process and the removal 
thereof generates a fog on the light-sensitive material. 
Light-sensitive material has been advantageously designed so that the 
amount of binder, particularly gelatin, coated on the light-sensitive 
material is reduced. However, decreasing the coated amount of gelatin in 
an emulsion layer generates increased pressure blackening, accurrence of 
black spots during processing, and layer peeling during processing due to 
reduced layer strength. This means a pickoff generally described in the 
art. Reducing the amount of the binder in a surface protective layer is 
may cause a matting agent contained in a surface protective layer coating 
solution to settle because of reduced protective colloid action by the 
gelatin. Also, in a coated layer, reducing binder levels causes the 
matting agent to be peeled off during processing which can stain a 
processing solution. Polyalkylene oxide, which is a nonionic series 
surface active agent, is conventionally added to a surface protective 
layer as an electrification controlling agent. However, the polyalkylene 
oxide affects a surface charge in the matting agent and accelerates 
settling of the matting agent from a coating solution containing the same. 
As described in JP-A-51-6017 (the term "JP-A" as used herein means an 
unexamined published Japanese patent application), JP-A-61-20028, and 
JP-A-53-7231, the matting agent has an important function, in particular, 
preventing sticking, preventing static marks, and preventing scratchs 
caused when the surface protective layer of a photographic material 
contacts other substances. Conventionally, the matting agent has been 
incorporated into a non-light-sensitive protective layer (hereinafter 
referred to as a protective layer) for the above-mentioned purposes. 
Concentrating of a solution containing polyalkylene oxide, in order to 
increase the protective colloid performance thereof in some cases 
accelerates settling from the solution due to the concentration of the 
polyalkylene oxide in the solution. Reduction of the coated amount of 
polyalkylene oxide causes static marks and inferior transportation of the 
light sensitive material during processing. Further, reducing the amount 
of water soluble polymer causes repelling of coating solution during 
coating and generation of coagulated material. Reducing the amount of 
water soluble polymer also lowers development swelling in case of the same 
drying speed and causes deterioration of covering power and sensitivity. 
The present invention provides a photographic material without the 
above-discussed problems, and a method for producing the same. 
As described in, for example, JP-A-1-154141, JP-A-1-159634, and 
JP-A-1-14574, a matting agent having a hydrophilic group is effective in 
terms of improving the stability of a matting agent in a coating solution 
and preventing the matting agent from peeling off from a coated material. 
However, an excess of hydrophilic groups causes elution of the matting 
agent from a light sensitive material containing the same during 
developing of the light sensitive material, which changes the size and 
amount of the matting agent in the light sensitive material before and 
after processing. Accordingly, glossiness of processed light sensitive 
material is reduced, and sliding performance and separating performance of 
the processed light-sensitive material are also reduced. Further, the 
processing solution used to process the light sensitive material is 
stained. In addition, holes remain in the light sensitive material where 
matting agent particles are removed. These holes resemble a white punched 
hole at a high density portion on a picture and cause deterioration of 
image quality. 
Intensive investigations made by the present inventors resulted in 
obtaining a matting agent which does not dissolve in a processing solution 
due to a hydrophilic group present in the matting agent and due to a cross 
linking reaction with a cross linking agent. It was found by the present 
inventors that the use of a matting agent in accordance with the invention 
provides a light-sensitive material having excellent stability in a 
coating solution and having an excellent handling characteristics and 
image quality. 
SUMMARY OF THE INVENTION 
The first object of the present invention is to provide a photographic 
material which achieves high sensitization in a short processing time, 
while having a sufficiently rapid drying speed, and a method for producing 
the same. Another object is to provide a photographic material in which 
scattering of a coated amount of a matting agent is not caused by the 
settling of the matting agent in a coating solution, and a method for 
producing the same. Another object is to provide a photographic material 
which does not generate a stain in a processing solution due to the 
matting agent peeling and dissolving in the processing solution, and a 
method for producing the same. 
Another object of the present invention is to provide a photographic 
material in which a static mark during handling is non generted, and at 
the same time the material has the above mentioned characteristics, the 
material also having excellent handling characteristics, in particular, 
separating performance and sliding performance, which do not change before 
and after processing, and a method for producing the same. 
A still further object of the present invention is to provide a 
photographic material in which image quality, such as a glossiness and 
haze, does not fluctuate and deteriorate due to the manner of processing 
the material. 
The above mentioned objects of the present invention and other objects have 
been achieved by a photographic material in accordance with the invention, 
which comprises a support provided thereon at least one light-sensitive 
emulsion and at least one surface protective layer comprising a 
hydrophilic colloid and a polymer latex having an average particle size of 
at least 2 .mu.m. The polymer latex standing at 40.degree. C. for 16 hours 
in a test coating solution, generates a precipitate in an amount of up to 
30 weight %, based on the weight of the polymer latex added to the coating 
solution wherein the test coating solution includes: 
______________________________________ 
Ingredient Amount 
______________________________________ 
Gelatin (as a solid matter 500 g 
having a Ca content of at least 2000 ppm 
so as to provide the test coating solution 
with a viscosity of 0.2 to 0.3 poise at 
40.degree. C.) 
Polymer latex (as a solid matter 
47 g 
dispersed in a 5 weight % gelatin solution 
so that the solid matter becomes 10 weight %) 
H.sub.2 O 400 ml 
##STR1## 0.09 g 
C.sub.16 H.sub.33 O(CH.sub.2 CH.sub.2 O) .sub.10H 
0.51 g 
Poly(sodium acrylate) 1.0 g 
(average molecular weight: 400,000) 
______________________________________ 
wherein the dispersion of the polymer latex is added to a solution prepared 
by swelling and dissolving gelatin in water at 40.degree. C. and then the 
other compounds are added and mixed while stirring. 
Furthermore, the above mentioned objects of the present invention and other 
objects have been achieved by a silver halide photographic material 
comprising a support provided thereon at least one light-sensitive 
emulsion layer and at least one surface protective layer containing a 
hydrophilic colloid and a crosslinked polymer latex having a hydrophilic 
group.

DETAILED DESCRIPTION OF THE INVENTION 
The polymer latex or crosslinked polymer latex having a hydrophilic group 
according to the present invention (sometimes hereinafter refered to as 
"matting agent according to the present invention") is incorporated in a 
surface protective layer. As long as the matting agent according to the 
present invention is incorporated in the surface protective layer, it may 
be incorporated or not incorporated in the other photographic constituting 
layers. The surface protective layer is a non-light-sensitive layer 
containing a hydrophilic colloid, is an uppermost layer on the support of 
a light-sensitive material and is provided on the outside of a 
light-sensitive layer from the support. 
Any well-known hydrophilic colloid may be incorporated in the surface 
protective layer, but gelatin is particularly preferred. 
The matting agent according to the present invention precipitates in an 
amount only by up to 30 weight %, preferably up to 20 weight % based on 
the weight of amount added to the above mentioned test coating solution, 
when the test coating solution is left standing at 40.degree. C. for 16 
hours. 
The same gelatin as used for a binder of a light-sensitive material may be 
used for gelatin for the test coating solution. 
The components are added in the above mentioned order at 40.degree. C. 
while stirring at a low speed so that too many foams do not generate and 
the matting agent does not perticipate to thereby prepare a coating 
solution in which all the additives are mixed homogeneously. 
The matting agent which is preferably used in the present invention 
includes the following polymer latexes designated "polymer latex-1" and 
"polymer latex-2", as will be described below, but suitable polymer 
latexes will be apparent to one skilled in the art. 
The polymer latex-1 is a polymer latex having a hydrophilic group. 
Examples of the hydrophilic group which the polymer latex-1 has include a 
carboxyl group, a phosphoric acid group, a sulfonic acid group, or a 
sulfuric acid group. The hydrophilic group preferably is a the carboxyl 
group. 
Preferred monomers having a carboxyl group as the hydrophilic group 
include: acrylic acid, methacrylic acid, itaconic acid, maleic acid, 
fumaric acid, mono-alkyl itaconate, monalkyl maleate, citraconic acid, and 
styrenecarboxylic acid. Phosphoric acid ester of hydroxyethyl acrylate is 
suitable for use as a monomer having a phosphoric acid group. 
Examples of monomers having a sulfonic acid group include: styrenesulfonic 
acid, methacyloyloxypropyisulfonic acid, and 
2-acrylamide-2-methylpropanesulfonic acid. Sulfuric acid ester of 
hydroxyethyl acrylate is suitable as the monomer having a sulfuric acid 
group. 
Monomers having at least one ethylenically saturated double bond are 
suitable for use as a monomer for forming a copolymer in combination with 
the above mentioned monomers. Such monomers may be used in combination. 
Suitable acrylic acid esters include methyl acrylate, ethyl acrylate, 
n-propyl acrylate, iso-propyl acrytate, n-butyl acrylate, iso-butyl 
acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl 
acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 
2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, 
cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, 
benzyl acrylate, methoxy-benzyl acrylate, 2-chlorocyclohexyl acrylate, 
cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, 
phenyl acrylate, 2-hydroxyethyl acrylate, 5-hydroxypentyl acrylate, 
2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 
3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 
2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 
2-(2-butoxyethoxy)ethyl acrylate, .omega.-methoxypolyethylene glycol 
acrylate (an addition mole number n=9), 1-bromo-2-methoxyethyl acrylate, 
and 1,1-dichloro-2-ethoxyethyl acrylate. 
Suitable methacrylic acid esters include methyl methacrylate, ethyl 
methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl 
methacrylate, iso-butyl methacrylate, sec-butyl meth-acrylate, tert-butyl 
methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl 
methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl 
methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl 
methacrylate, 2-(3phenylpropyloxy)ethyl methacrylate, 
dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, 
tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, 
naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl 
methacrylate, triethylene glycol monomethacrylate, dipropylene glycol 
monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl 
methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl 
methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 
2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 
2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl 
methacrylate, .omega.-methoxypolyethylene glycol methacrylate (addition 
mole number n=6), allyl methacrylate, and methacrylic acid 
dimethylaminoethylmethyl chloride salt. 
Suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl 
butylate, vinyl isobutylate, vinyl caproate, vinyl chloroacetate, vinyl 
methoxyacetate, vinyl phenylacetate, vinyl benzoate, and vinyl salicylate. 
Suitable olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 
1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, 
butadiene, and 2,3-dimethylbutadiene. 
Suitable styrenes include styrene, methylstyrene, dimethylstyrene, 
trimethylstyrene, ethytstyrene, isopropylstyrene, chloromethylstyrene, 
methoxystyrene, isoetoxystyrene, chlorostyrene, dichlorostyrene, 
didibromostyrene, trifluoromethylstyrene, and methyl vinylbenzoate. 
Suitable crotonic acid esters include butyl crotonate and hexyl crotonate. 
Suitable itaconic acid diesters include dimethyl itaconate, diethyl 
itaconate, and dibutyl itaconate. 
Suitable maleic acid diesters include diethyl maleate, dimethyl maleate, 
and dibutyl maleate. 
Suitable fumaric acid diesters include diethyl fumarate, dimethyl fumarate, 
and dibutyl fumarate. 
Suitable acrylamides include acrylamide, methylacrylamide, ethylacrylamide, 
propylacrylamide, butylacrylamide, tert-butylacrylamide, 
cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, 
methoxyethylacrylamide, dimethylaminoethylacrylamide, pnenylacrylamide, 
dimethylacrylamide, diethylacrylamide, .beta.-cyanoethylacrylamide, and 
N-(2-acetoacetoxyethyl)acrylamide. 
The methylacrylamide may be, for example, methacrylamide, 
methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, 
butylmethacrylamide, tert-butylmethacrylamide, cyclohexylmethacrylamide, 
benzylmethacrylamide, hydroxymethylmethacrylamide, 
methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, 
phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, 
.beta.-cyanoethylmethacrylamide, and 
N-(2-acetoacetoxyethyl)methacrylamide. 
Suitable allyl compounds include allyl acetate, allyl caproate, allyl 
laurate, and allyl benzoate. 
Suitable vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl 
vinyl ether, methoxyethyl vinyl ether, and dimethylaminoethyl vinyl ether. 
Suitable vinyl ketones include methyl vinyl ketone, phenyl vinyl ketone, 
and methoxyethyl vinyl ketone. 
Suitable vinyl heterocyclic compounds include vinylpyridine, 
N-vinylimidazole, N-vinyloxaziidone, N-vinyltriazole, and 
N-vinylpyrrolidone. 
Suitable glycidyl esters include glycidyl acrylate and glycidyl 
methacrylate. 
Suitable unsaturated nitriles include acrylonitrile and methacrylonitrile. 
Suitable multi-functional monomers include divinylbenzene, 
methylenebisacrylamide, and ethylene glycol dimethacrylate. 
The hydrophilic group-containing polymer may be a copolymer having, for 
example, a mole ratio of methyl methacrylate/methacrylic acid of 1/1, as 
described in U.S. Pat. Nos. 2,992,102 and 3,767,448, the disclosures of 
which are herein incorporated by reference; a copolymer having a mole 
ratio of methyl methacrylate/methacrylic acid of 6/4 to 9/1, as described 
in JP-A-53-7231; a copolymer of ethyl methacrylate/methacrylic acid, as 
described in JP-A-58-66937; and a copolymer of ethyl methacrylate/methyl 
methacrylate/methacrylic acid, as described in JP-A-60-126644. Copolymers 
including a fluorine atom and a hydrophilic group as described in 
JP-A-62-14647 and 62-15543, are suitable for use in the present invention. 
Particles of the foregoing mentioned polymers are preferably used as a 
polymer-latex-1 according to the present invention but the present 
invention will not be limited thereto. 
More Preferred examples of the polymer-latex-1 include a copolymer of 
methyl methacrylate and methacrylic acid having a ratio of 70/30 to 95/5, 
a copolymer of methyl methacrylate/methyl acrylate/methacrylic acid where 
the ratio of methyl acrylate/methacrylic acid is 60/40 to 95/5 and methyl 
acrylane is 0 to 50% based on the amount of methyl methacrylate. 
The polymer latex-1 preferably contains 2 to 70 mole %, more preferably 3 
to 50 mole %, and most preferably 5 to 40 mole %, of the hydrophilic 
group-containing monomer. 
The average particle size of the polymer latex-1 is not less than 2.0 
.mu.m, preferably from 2 to 15 .mu.m, and more preferably from 2 to 6 
.mu.m. The average particle size of the polymer latex of the present 
invention can be measured using Multi Particle Counter manufactured by 
COULTER ELECTRONICS, INC., an electron microscope, or utilizing light 
scattering. 
The polymer latex-2, i.e., a crosslinked polymer latex having a hydrophilic 
group according to the present invention is preferably a copolymer 
including a repeating unit represented by the following Formula (II): 
EQU (A)x (B)y (C)z (II) 
wherein A represents a monomer having a hydrophilic group; B represents a 
crosslinkable monomer; C represents a vinyl monomer other than B and C; 
and x, y and z represent a copoiymerization ratio, in which x is 0.1 to 30 
mole %, y is 0.1 to 30 mole % and z is 0 to 95 mole %. 
The monomer represented by A will now be explained. 
In the present invention, the hydrophilic group is a group which makes the 
polymer easy to dissolve in water by introducing and includes a carboxyl 
group, a phosphoric acid group, a sulfonic acid group, a sulfuric acid 
group. Preferably, the hydrophillic group is a carboxyl group. Examples of 
suitable monomers having a carboxyl group include acrylic acid, 
methacrylic acid, itaconic acid, maleic acid, fumaric acid, itaconate, 
monoalkyl maleate, monoalkyl citraconic acid, and styrenecarboxylic acid. 
Phosphoric acid ester of hydroxyethyl acrylate is suitable for use as a 
monomer having the phosphoric acid group. Examples of suitable monomers 
having a sulfonic acid group include styrenesulfonic acid, 
methacryloyloxypropylsulfonic acid, and 
2-acrylamide-2-methylpropanesulfonic acid. Sulfuric acid ester of 
hydroethyl acrylate is suitable for use as the monomer having a sulfuric 
acid group. 
Acrylic acid and methacrylic acid are preferred as the monomer having a 
hydrophillic group (monomer A). Monomer A may contain two or more kinds of 
monomers. 
Next, the crosslinkable monomer represented by B will be explained. 
Preferably, the crosslinkable monomer is a monomer having two or more 
ethylenically unsaturated groups capable of radical polymerization. For 
example, the crosslinkable polymer may be a polymerizable unsaturated 
carboxylic acid ester of polyhydric alcohol, a polymerizable unsaturated 
alcohol ester of polybasic acid, or an aromatic compound substituted with 
two or more vinyl groups. Examples of suitable crosslinkable polymers 
include ethylene glycol diacrylate, ethylene glycol dimethacrylate, 
triethylene glycol dimethacrylate, tetra-ethylene glycol dimethacrylate, 
1,3-butylene glycol di-methacrylate, trimethylolpropane triacrylate, 
tri-methylolpropane trimethacrylate, 1,4-butanediol di-acrylate, neopentyl 
glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, 
pennaerythritol triacrylate, pentaerythritol tetraacrylate, 
penta-erythritol dimethacrylate, pentaerythritol trimethacrylate, 
pentaerythritol tetramethacrylate, glycerol dimethacrylate, glycerol 
diacrylate, glycerol acroxydimethacrylate, 1,1,1-trishydroxymethylethane 
diacry-late, 1,1,1-trishydroxymethylethane triacrylate, 
1,1,1-trishydroxymethylethane dimethacrylate, 
1,1,1-trishydroxymethylethane trimethacrylate, 
1,1,1-trishydroxymethylpropane diacrylate, 1,1,1-trishydroxymethylpropane 
triacrylate, 1,1,1-trishydroxymethylpropane dimethacrylate, 
1,1,1-trishydroxymethylpropane trimethacrylate, triallyl cyanurate, 
triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, 
diallyl phthalate, and divinylbenzene. 
Preferably, monomer B is ethylene glycol dimethacrylate, ethylene glycol 
diacrylate, or divinylbenzene. 
Monomer B may contain two or more monomers. 
Monomer C may be any suitable monomer as long as it is different from 
monomers A and B. For example, monomer C may be an acrylic acid ester, a 
methacrylic acid ester, a vinyl ester, an olefin, a styrene, a crotonic 
acid ester, a itaconic acid diester, a meleic acid diester, a acrylamide, 
a methacrylamide, an allyl compound, a vinyl ether, a vinyl ketone, a 
vinyl heterocyclic compound, or a glycidyl ester. Preferably, monomer C is 
an acrylic acid ester, a methacrylic acid ester, a vinyl ester, or a 
styrene. 
Suitable acrylic acid esters include methyl acrylate, ethyl acrylate, 
n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl 
acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, and 
hexyl acrylate. Suitable methacrylic acid esters include methyl 
methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl 
methacrylate, n-butyl methacrylate, iso-butyl methacrylate, sec-butyl 
methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl 
methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl 
methacrylate, and octyl methacrylate. Suitable vinyl esters include vinyl 
acetate, vinyl propionate, vinyl butylate, vinyl iso-butylate, and vinyl 
caproate. Suitable styrene includes styrene, methylstyrene, 
dimethylstyrene, trimethylstyrene, ethylstyrene, iso-propylstyrene, 
chloromethylstyrene, and methoxystyrene. Suitable olefins include 
dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl 
chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 
2,3-dimethyl-butadiene. 
Preferably, monomer C is methyl methacrylate, ethyl methacrylate, styrene, 
methyl acrylate, or ethyl acrylate. 
Monomer C may be two or more kinds of monomers the formula II: 
x is 0.1 to 30 mole %, preferably 5 to 30 mole %, more preferably 10 to 25 
mole %, and more preferably 15 to 25 mole %. 
y is 0.1 to 30 mole %, preferably 1 to 25 mole %, more preferably 1 to 20 
mole %, and more preferably 3 to 15 mole %. 
z is 0 to 95 mole %, preferably 50 to 90 mole %, more preferably 60 to 89 
mole %, and more preferably 60 to 84 mole %. 
Examples of suitable the matting agent used in the present invention 
generably represented by Formula (II) are shown below but the present 
invention will not be limited thereto. 
1. MMA/St/MAA/EGDM=36/36/20/8 (mole %) 
2. MMA/MAA/EGDM=75/20/5 
3. MMA/MA/MAA/EGDM=60/15/15/10 
4. MMA/MAA/DVB=75/20/5 
5. MMA/MAA/EGDM=70/25/5 
6. MMA/MAA/EGDM=70/20/10 
7. EMA/AA/DVB=80/15/5 
8. EMA/EA/AA/EGDM=35/35/20/10 
9. MMA/MAA/EGDA=75/20/5 
wherein 
MMA: methyl methacrylate 
MA: methyl acrylate 
MAA: methacrylic acid 
AA: acrylic acid 
EMA: ethyl methacrylate 
EA: ethyl acrylate 
St: styrene 
EGDM: ethylene glycol dimethacrylate 
DVB: divinylbenzene 
EGDA: ethylene glycol diacrylate 
The average particle size of the polymer-latex-2 to be used in the present 
invention is preferably 2 to 15 .mu.m, more preferably 2 to 6 .mu.m. 
The coated amount of the matting agent according to the present invention 
(including polymer-latex-1 and polymer-latex-2) to be contained in the 
surface protective layer, is preferably 0.001 to 0.3 g/m.sup.2, more 
preferably 0.01 to 0.15 g/m.sup.2. 
The amount of the polymer-latex-1 incorporated in the surface protective 
layer is preferably at least 30 weight %, more preferably at least 50 
weight % based on the whole coated amount of the used matting agents. Any 
suitable alkali insoluble matting agent may be used in combination 
therewith. This agent may be, for example, an organic compound such as 
poly-methyl methacrylate and polystyrene, or an inorganic compound such as 
silicon dioxide. Further, two or more kinds of the matting agents 
according to the present invention may be used in the present invention. 
Preferably, the surface protective layer includes the mattinig agent 
according to the present invention in an amount of at least 70 weight %, 
more preferably at least 80 weight %, and more preferably at least 90 
weight % based on the amount of the whole matting agent used on one side 
of the support of the light-sensitive material. 
Particularly preferred is the one having the maximums in a particle size 
distribution in the ranges of 3 .mu.m or more and 3 .mu.m or less. This is 
because while the matting agent having the average particle size of 3 
.mu.m or more controls the peeling property of a light-sensitive material, 
the matting agent having the average particle size of 3 .mu.m or less 
controls mainly the sliding property and glossiness of the light-sensitive 
material. Usually, what causes settling in a coating solution and peeling 
off in a processing is this particle of 3 .mu.m or more. This component of 
3 .mu.m or more is particularly effective in the present invention. 
A preferred particle size distribution in the matting agent according to 
the present invention is shown in the Figure. 
The silver halide photographic material of the present invention preferably 
includes a coated amount of gelatin of up to 0.8 g/m.sup.2, more 
preferably from 0.3 to 0.8 g/m.sup.2, present in the surface protective 
layer containing the matting agent according to the present invention. 
The silver halide photographic material of the present invention preferably 
includes a water soluble polymer contained in the surface protective layer 
containing the matting agent according to the present invention, and the 
coated amount thereof is at least 10 wt % based on the whole coated 
gelatin amount on the side having the surface protective layer containing 
the matting agent of the present invention. 
The silver halide photographic material of the present invention preferably 
includes one or more of the compounds represented by the following 
Formulas (I-1), (I-2) and (I-3) contained in the surface protective layer 
containing the matting agent according to the present invention, in the 
amount of 20 mg/m.sup.2 or more: 
##STR2## 
In the foregoing formulas I-1, I-2 and I-3, R.sub.1 represents a 
substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a 
substituted or unsubstituted alkenyl group having 1 to 30 carbon atoms, or 
a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and 
A repre-sents a --O-- group, a --S-- group, a --COO-- group, a 
--N(R.sub.10)-- group, a --CO--N(R.sub.10)-- group, or a --SO.sub.2 
--N(R.sub.10)-- group, where 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 each represents a hydrogen atom, a 
substituted or unsubstituted alkyl group, a substituted or unsubstituted 
aryl group, a substituted or unsubstituted alkoxy group, a halogen atom, a 
substituted or unsubstituted acyl group, an amide group, a sulfonamide 
group, a carbamoyl group, or a sufamoyl group. 
R.sub.6 and R.sub.8 each represents a substituted or unsubstituted alkyl 
group, a substituted or unsubstituted aryl group, a substituted or 
unsubstituted alkoxy group, a halogen atom, a substituted or unsubstituted 
acyl group, an amide group, a sulfonamide group, a carbamoyl group, or a 
sufamoyl group. In Formula (I-3), the substituents on the phenyl rings 
(R.sub.6, R.sub.7, R.sub.8 and R.sub.9) may be laterally asymmertic. 
R.sub.4 and R.sub.5 each represents a hydrogen atom, a substituted or 
unsubstituted alkyl group, or a substituted or unsubstituted 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 be 
combined with each other to form a substituted or unsubstituted ring. 
n.sub.1, n.sub.2, n.sub.3 and n.sub.4 are the average polymerization 
degrees of ethylene oxide and each are 2 to 50. m is an average 
polymerization degree and is the number of 2 to 50. 
The addded amount of the compound represented by formula (I-1), (I-2) or 
(I-3) is more preferably from 20 to 100 mg/m.sup.2, most preferably from 
20 to 60 mg/m.sup.2. 
Formulas (I-1), (I-2) and (I-3) will be explained in further details. 
R.sub.1 is preferably an alkyl group, an alkenyl group, or an alkylaryl 
group, each having 4 to 24 carbon atoms, and more preferably hexyl, 
dodecyl, isosteraryl, oleyl, t-butylphenyl, 2,4-di-t-butylphenyl, 
2,4-di-t-pentylphenyl, p-dodecylphenyl, m-pentadecaphenyl, t-octylphenyl, 
2,4-dinonylphenyl, or octylnaphthyl. R.sub.2, R.sub.3, R.sub.6, R.sub.7, 
R.sub.8 and R.sub.9 are each preferably: a substituted or unsubstituted 
alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, i-propyl, 
t-butyl, t-amyl, t-hexyl, t-octyl, nonyl, decyl, dodecyl, trichloromethyl, 
tribromomethyl, 1-phenylethyl, and 2-phenyl-2-propyl; a substituted or 
unsubstituted aryl group such as phenyl and p-chlorophenyl; a substituted 
or unsubstituted alkoxy group represented by --OR.sub.11, where R.sub.11 
represents a substituted or unsubstituted alkyl group having 1 to 20 
carbon atoms, or an aryl group; a halogen atom, such as a chlorine atom 
and a bromine atom; an acyl group represented by --COR.sub.11, where 
R.sub. 11 is as defined above an amide group represented by --NR.sub.12 
COR.sub.11, where R.sub.12 represents a hydrogen atom or an alkyl group 
having 1 to 20 carbon atoms; a sulfonamide group represented by 
--NR.sub.12 SO.sub.2 R.sub.11, where R.sub.11 and R.sub.12 are as defined 
above; a carbamoyl group represented by --CON(R.sub.12).sub.2, where 
R.sub.12 is as defined above, or a sulfamoyl group represented by 
--SO.sub.2 N(R.sub.12).sub.2, where R.sub.12 is as defined above R.sub.2, 
R.sub.3, R.sub.7 and R.sub.9 may be a hydrogen atom. R.sub.6 and R.sub.8 
are each preferably an alkyl group or a halogen atom, more preferably a 
tertiary alkyl group such as bulky t-butyl, t-amyl, and t-octyl. R.sub.7 
and R.sub.9 are more preferably a hydrogen atom. The compound of Formula 
(I-3) synthesized from 2,4-disubstituted phenol is particularly preferred. 
R.sub.4 and R.sub.5 are each preferably a hydrogen atom, a substituted or 
unsubstituted alkyl group, such as methyl, ethyl, n-propyl, i-propyl, 
n-hepyl, 1-ethylamyl, n-undecyl, trichloromethyl, and tribromomethyl, or a 
substituted or unsubstituted aryl group such as .alpha.-furyl, phenyl, 
naphthyl, p-chlorophenyl, p-methoxyphenyl, and m-nitrophenyl. R.sub.4 and 
R.sub.5, R.sub.6 and R.sub.7, and R.sub.8 and R.sub.9 may be combined with 
each other to form a substituted or un-substituted ring, for example, a 
cyclohexyl ring. R.sub.4 and R.sub.5 are more preferably a hydrogen atom, 
an alkyl group having 1 to 8 carbon atoms, a phenyl group, and a furyl 
group. n.sub.1, n.sub.2, n.sub.3 and n.sub.4 are more preferably 5 to 30. 
n.sub.3 and n.sub.4 may be the same or different. 
Examples of suitable polyalkylene oxide compounds which may be used in the 
present invention for the compound of formulas I-1, I-2 and I-3 include: 
##STR3## 
Any suitable water soluble polymer may be used in the present invention. 
For example, a synthetic water soluble polymer or a natural water soluble 
polymer may be used. Suitable synthetic water soluble polymers may include 
a nonionic group, an anionic group, or a nonionic group and an anionic 
group in a molecular structure. The nonionic group may be, for example, an 
ether group, an ethylene oxide group, or a hydroxy group. The anionic 
group may be, for example, a sulfonic acid group or the salt thereof, a 
carboxylic acid group or the salt thereof, or a phosphoric acid group or 
the salt thereof. The natural water soluble polymer may include a nonionic 
group, an anionic group, and a nonionic group and an anionic group in a 
molecular structure. 
A polymer having an anionic group, or a polymer having a nonionic group and 
an anionic group, is preferably used as the synthetic or natural water 
soluble polymer. The water soluble polymer dissolves in 100 g of water at 
20.degree. C. in an amount of at least 0.05 g, preferably at least 0.1 g. 
Further, the water soluble polymer according to the present invention has a 
high solubility to both developing and fixing solutions. Preferably, the 
solubility (at 35.degree. C., the developing temperature or the fixing 
temperature) of the water soluble polymer is at least 0.05 g, more 
preferably at least 0.5 g, and most preferably at least 1 g per 100 g of 
the developing solution. A suitable synthetic water soluble polymer 
contains 10 to 100 mole % of the repeating unit represented by the 
following Formula (P) in one molecule of the polymer: 
##STR4## 
wherein R.sub.10 represents a hydrogen atom, a substituted or 
unsubstituted alkyl group, the alkyl group preferably having 1 to 4 carbon 
atoms (where the allyl group may substituted with, or example, a methyl 
group, an ethyl group, a propyl group, or a butyl group), a halogen atom 
(for example, a chlorine atom), or --CH.sub.2 COOM; L represents --CONH--, 
--NHCO--, --COO--, --OCO--, --CO--, or --O--; J represents an alkylene 
group, preferably an alkylene group having 1 to 10 carbon atoms (where the 
alkyl group may be substituted, for example, methylene, ethylene, 
propylene, trimethylene, butylene, and hexylene), an arylene group (where 
the arylene group may be substituted, for example, phenylene), or 
##STR5## 
m represents an integer of 0 to 40, and n represents an integer of 0 to 4. 
or Q represents 
##STR6## 
a hydrogen atom or R.sub.17 M represents a hydrogen atom or a cation; R 16 
represents an alkyl group having 1 to 4 carbon atoms (for example, a 
methyl group, an ethyl group, a propyl group, and a butyl group); 
R.sub.17, R.sub.11, R.sub.12, R.sub.13, R.sub.14 and R.sub.15 each 
represents an alkyl group having 1 to 20 carbon atoms (for example, a 
methyl group, an ethyl group, a propyl group, a butyl group, a hexyl 
group, a decyl group, and a hexadecyl group), an alkenyl group (for 
example, vinyl and aryl), a phenyl group (for example, phenyl, 
methoxyphenyl, and chlorophenyl), or an aralkyl group (for example, 
benzyl); X represents an anion; and p and q each represents 0 or 1. A 
polymer containing acrylamide or methacrylamide is preferred. 
Examples of the suitable synthetic water soluble polymer including a 
repeating unit represented by Formula [P] include: 
______________________________________ 
Mean 
molec- 
ular 
weight 
______________________________________ 
##STR7## 8,000 
##STR8## 15,000 
##STR9## 9,000 
##STR10## 3,100 
##STR11## 3,000 
##STR12## 8,000 
##STR13## 10,000 
##STR14## 9,000 
##STR15## 12,000 
##STR16## 8,000 
##STR17## 11,000 
##STR18## 6,000 
##STR19## 7,800 
##STR20## 
______________________________________ 
n.sub.1 :n.sub.2 =50 mol %:50 mol % number average molecular weight (Mn): 
about 10,000 
The synthetic water soluble polymer according to the present invention 
preferably has the molecular weight of 1,000 to 100,000, more preferably 
2,000 to 50,000. 
Preferably, the natural synthetic water soluble polymer is a glucose 
polymer or a derivative thereof, more preferably, starch, glycogen, 
cellulose, lichenan, dextran, or nigerant and more preferably, dextran or 
a derivative thereof. 
Preferably, the natural water soluble polymers have the molecular weight of 
1000 to 100,000, more preferably 2000 to 50,000. 
The synthetic or natural water soluble polymer may be incorporated into the 
photographic material of the present invention in an amount of preferably 
at least 10%, more preferably from 10% to 30 based on the amount of the 
whole coated amount of gelatin on the side having the surface protective 
layer of the present invention. 
Other various additives and techniques conventionally used for 
manufacturing light-sensitive material according to the present invention 
may be used in the present invention, such as the ingredious and 
techniques identified below and described in the documents also identified 
below: described in the corresponding portions shown below can be used. 
______________________________________ 
Ingredient/Technique 
Document 
______________________________________ 
1) Silver halide 
Right lower column, line 6 from 
emulsion and bottom at p. 8 to right upper 
manufacturing 
column, line 12 at p. 10 of JP-A- 
method thereof 
2-68539; right lower column, line 10 
at p. 2 to right upper column, line 
1 at p. 6 and left upper column, 
line 16 at p. 10 to left lower 
column, line 19 at p. 11 of JP-A- 
3-24537; and JP-A-4-107442. 
2) Chemical Right upper column, line 13 to left 
sensitization 
upper column, line 16 at p. 10 of 
method JP-A-2-68539; and Japanese patent 
application 3-105035. 
3) Anti-fogging Left lower column, line 17 at p. 
agent, & 10 to left upper column, line 7 at 
stabilizer p. 11 and left lower column, line 2 
at p. 3 to left lower column at p. 
4 of JP-A-2-68539. 
4) Color tone Left lower column, line 7 at p. 2 
improving to left lower column, line 20 at 
agent p. 10 of JP-A-62-276539, and left 
lower column, line 15 at p. 6 to 
right upper column, line 19 at p. 
11 of JP-A-3-94249. 
5) Spectral Right lower column, line 4 at p. 4 
sensitizing to right lower column at p. 8 of 
dye JP-A-2-68539. 
6) Surface active 
Left upper column, line 14 at p. 
agent, & anti- 
11 to left upper column, line 9 at 
electrifica- p. 12 of JP-A-2-68539. 
tion agent 
7) Sliding agent, 
Left upper column, line 10 to right 
& plasticizer 
upper column, line 10 at p. 12 and 
left lower column, line 10 to right 
lower column, line 1 at p. 14 of 
JP-A-2-68539. 
8) Hardener Left lower column, line 17 at p. 12 
to right upper column, line 6 at P. 
13 of JP-A-2-68539. 
9) Support Right upper column, lines 7 to 20 at 
p. 13 of JP-A-2-68539. 
10) Crossover cut- 
Right upper column, line 20 at p. 
ting method 4 to right upper column at p. 14 
of JP-A-2-264944. 
11) Dye and Left lower column, line 1 at p. 
mordant 13 to left lower column, line 9 at 
p. 14 of JP-A-2-68539; and left 
lower column at p. 14 to right 
lower column at p. 16 of JP-A-3- 
24537. 
12) Polyhydroxy- Left upper column at P. 11 to left 
benzenes lower column at p. 12 of JP-A-3- 
39948, and EP Patent 452772A. 
13) Layer JP-A-3-198041. 
structure 
14) Development Right upper column, line 7 at p. 
processing 16 to left lower column, line 15 
method at p. 19 of JP-A-2-103037; and 
right lower column, line 5 at p. 
3 to right upper column, line 10 at 
p. 6 of JP-A-2-115837. 
______________________________________ 
EXAMPLES 
The invention will now be described in connection with examples thereos, it 
being understood that the invention is not limited thereto. 
EXAMPLE 1 
Preparation of the tabular grains 
6 g of potassium bromide and 7 g of low molecular weight gelatin having the 
average molecular weight of 15,000 were added to 1 liter of water, and 37 
ml of a silver nitrate aqueous solution (silver nitrate: 4.00 g), and 38 
ml of an aqueous solution 38 ml containing 5.9 g of potassium bromide were 
added to the above solution kept at 55 .degree. C. by a double jet method 
for 37 seconds while stirring. Next, 18.6 g of gelatin were added and then 
89 ml of a silver nitrate aqueous solution (silver nitrate: 9.80 g) was 
added over a period of 22 minutes after the temperature was raised to 
70.degree. C. Then 7 ml of a 25% ammonia aqueous solution was added to 
provide a physical ripening for 10 minutes while maintaining keeping the 
temperature, and then 6.5 ml of a 100% acetic acid solution was added. 
Subsequently, 153 g of the aqueous solution of silver nitrate and the 
aqueous solution of potassium bromide were added by a controlled double 
jet method over a period of 35 minutes while maintaining pAg at 8.5. Then, 
15 ml of a 2N potassium thiocyanate aqueous solution was added. After 
providing a physical ripening for 5 minutes while maintaining the 
temperature, the temperature was then lowered to 35.degree. C. Thus, 
mono-dispersed pure silver bromide tabular grains were obtained having an 
average projected area-corresponding circle diameter of 1.10 .mu.m, an 
average thickness of 0.165 .mu.m, an average aspect ratio of 6.7, and a 
diameter fluctuation coefficient of 18.5%. 
Thereafter, the soluble salts were removed by a settling method. The 
temperature was raised once again to 40.degree. C. and 30 g of gelatin, 
2.35 g of phenoxy ethanol, and 0.8 g of poly(sodium styrenesulfonate) as a 
thickener, were added followed by adjusting pH and pAg to 5.90 and 8.00, 
respectively, with caustic soda and a silver nitrate solution. 
This emulsion was subjected to a chemical sensitization while stirring and 
maintaining the temperature at 56.degree. C. 
First, 1.times.10.sup.-5 mole/mole Ag of the following thiosulfonic acid 
compound-1 was added: 
Thiosulfonic acid compound-1 
EQU C.sub.2 H.sub.5 SO.sub.2 SNa 
and further 0.043 mg of thiourea dioxide was added and the emulsion was 
left standing for 22 minutes to subject it to a reduction sensitization. 
Next, AgI fine grains having the average sphere-corresponding size of 0.03 
.mu.m were added in an amount corresponding to 0.2 mole % per mole of 
silver halide. Then, 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 
and the sensitizing dyes: 
##STR21## 
were added. Further, potassium chloride 0.83 g was added. Subsequently, 
there were added sodium thiosulfate 1.3 mg and the selenium compound-1 2.7 
mg, and further chlorauric acid 2.6 mg and potassium thiocyanate 90 mg 
were added. The solution was cooled down to 35.degree. C. 40 minutes 
later. 
Selenium compound-1 
##STR22## 
Thus, the tabular grains T-1 were prepared. 
Preparation of the coated samples 
The following compounds per mole of silver halide were added to prepare the 
coating solutions for preparing the coated samples. 
______________________________________ 
Gelatin (including gelatin contained in 
108 g 
an emulsion) 
Trimethylol propane 9 g 
Dextrane (average molecular weight: 39,000) 
18.5 g 
Poly(sodium styrenesulfonate) 
1.8 g 
(an average molecular weight: 600,000) 
Hardener/1,2-bis(vinylsulfonylacetoamide)ethane 
the addition amount was adjusted so that a swelling 
ratio became 230%. 
##STR23## 34 mg 
##STR24## 4.8 g 
##STR25## 30 mg 
______________________________________ 
A surface protective layer was coated so that the coated amounts of the 
respective components became as shown below: 
______________________________________ 
Coated 
Composition of the surface protective layer 
amount 
______________________________________ 
Gelatin 0.900 g/m.sup.2 
Poly(sodium acrylate) 0.023 g/m.sup.2 
(average molecular weight: 400,000) 
4-Hydroxy-6-methyl-1,3,3a,7-tetrazaindene 
0.015 g/m.sup.2 
##STR26## 0.013 g/m.sup.2 
C.sub.16 H.sub.33 O(CH.sub.2 CH.sub.2 O) .sub.10H 
0.045 g/m.sup.2 
##STR27## 0.0065 g/m.sup.2 
##STR28## 0.003 g/m.sup.2 
##STR29## 0.001 g/m.sup.2 
Proxel (pH was adjusted to 7.4 with NaOH) 
0.0005 g/m.sup.2 
______________________________________ 
Next, the kind of the matting agent added was changed as shown in Table 1 
and water was added so that the viscosity of the coating solution became 
0.25 poise to thereby prepare the coating solution. Then, the coating 
solution was applied so that the coated amount of the matting agent became 
0.1 g/m.sup.2, whereby the test coated samples 1 to 8 were prepared. 
TABLE 1 
__________________________________________________________________________ 
Average 
Presence of peak 
Settling 
Matting agent No. 
grain size 
of 3 .mu.m or more 
amount* 
Matting agent component 
__________________________________________________________________________ 
1 (Comparison) 
1.8 Presence A: 10% 
MMA/MA/MAA = 70/20/10 
B: 5% 
M.W.: 20,000 
2 (Comparison) 
2.2 Presence A: 45% 
MMA/MA/MAA = 80/15/5 
B: 40% 
M.W.: 22,000 
3 (Invention) 
2.2 Presence A: 5% 
MMA/MA/MAA = 65/20/15 
B: 5% 
M.W.: 24,000 
4 (Invention) 
3.2 Presence A: 25% 
MMA/MA/MAA = 83/10/7 
B: 20% 
M.W.: 30,000 
5 (Comparison) 
3.2 Presence A: 35% 
MMA/MA/MAA = 81/15/4 
B: 25% 
M.W.: 21,000 
6 (Invention) 
3.2 None A: 14% 
MMA/MAA = 90/10 
B: 10% 
M.W.: 24,000 
7 (Invention) 
3.2 Presence A: 5% 
MMA/ST/BA/MA/MAA = 10/30/30/10/20 
B: 5% 
M.W.: 30,000 
8 (Comparison) 
3.2 Presence A: 55% 
MMA/MAA = 80/20 
B: 40% 
M.W.: 22,000 
__________________________________________________________________________ 
*A: matting agent test amount by the test method described in claim 1. 
B: settling amount of the matting agent in the surface protrective layer 
coating solution after leaving for standing at 40.degree. C. for 24 hours 
MMA: methyl methacrylate, MA: methyl acrylate, MAA: methacrylic acid, ST: 
styrene, BA: butyl acrylate (ratio: weight %). 
A support was prepared in the following manner. 
Preparation of a support 
(1) Preparation of the dye dispersion D-1 for coating a subbing layer: 
The dye shown below was treated with a ball mill by the method described in 
JP-A-63-197943. 
##STR30## 
Water 434 ml and the 6.7% aqueous solution 791 ml of the surface active 
agent Triton X-200 (TX-200) were put in a 2 liter ball mill and the dye 20 
g was added to this solution. The beads 400 ml (diameter: 2 mm) of 
zirconium oxide (ZrO) were put therein and the content was crashed for 4 
days. Then, a 12.5% gelatin aqueous solution 160 g was added, and after 
defoaming, the mixture was filtered to remove the ZrO beads. The 
observation of the dye dispersion thus obtained showed that the particle 
sizes of the crashed dye were distributed in the wide range of 0.05 to 
1.15 .mu.m and that the average particle size was 0.37 .mu.m. 
Further, a centrifugal procedure was applied to remove the dye particles 
having the sizes of 0.9 .mu.m or more. Thus, the dye dispersion D-1 was 
obtained. 
(2) Preparation of a support: 
The surface of a biaxially stretched polyethylene terephthalate film with 
the thickness of 183 .mu.m was subjected to a corona discharge treatment, 
and the first subbing layer coating solution having the following 
composition was coated thereon with a wire bar coater so that the coated 
amount thereof became 5.1 ml/m.sup.2, followed by drying at 175.degree. C. 
for one minute. 
Next, the first subbing layer was provided as well on the opposite side of 
the support in the same manner. Polyethylene terephthalate containing 0.04 
wt % of the dye having the following chemical structure was used: 
______________________________________ 
##STR31## 
Butadiene-styrene copolymer latex solution 
79 ml 
(the solid content: 40%, butadiene/styrene 
weight ratio: 31/69) 
Sodium 2,4-dichloro-6-hydroxy-s-triazine 
20.5 ml 
(4% solution) 
Distilled water 900.5 ml 
##STR32## 
was contained as an emulsion 
dispersant in the latex solution in a proportion 
of 0.4 wt % based on a latex solid content 
______________________________________ 
The second subbing layers having the following composition were applied 
layer by layer on the above first subbing layers on the both sides with 
the wire bar coater so that the coated amounts of the respective 
components became as shown below, followed by drying at 150.degree. C.: 
______________________________________ 
Gelatin 160 mg/m.sup.2 
Dye dispersion D-1 (as the solid content of the dye) 
26 mg/m.sup.2 
##STR33## 8 mg/m.sup.2 
##STR34## 0.27 mg/m.sup.2 
Matting agent (polymethyl methacrylate 
2.5 mg/m.sup.2 
with the average grain size of 2.5 .mu.m) 
______________________________________ 
Preparation of a photographic material 
The foregoing emulsion layer and surface protective layer were provided on 
the both sides of the support prepared above by a simultaneous extrusion 
method. The coated silver amount per one side was set at 1.75 g/m.sup.2. A 
coated gelatin amount and a swelling rate determined by a freeze drying 
method with liquid nitrogen were controlled by gelatin added to the 
emulsion layer and a hardener amount. 
Processing: 
Automatic processor: a driving motor and a gear of FPM-9000 manufactured by 
Fuji Photo Film Co., Ltd. were modified to accelerate a transporting 
speed. 
______________________________________ 
Developing solution condensate: 
Potassium hydroxide 56.6 g 
Sodium sulfite 200 g 
Diethylenetriaminepentaacetic acid 
6.7 g 
Potassium carbonate 16.7 g 
Boric acid 10 g 
Hydroquinone 83.3 g 
Diethylene glycol 40 g 
4-Hydroxymethyl-4-methyl-l-phenyl-3- 
22.0 g 
pyrazolidone 
5-Methylbenzotriazole 2 g 
##STR35## 0.6 g 
Water was added to 1 liter 
(pH was adjusted to 10.60) 
Fixing solution condensate: 
Ammonium thiosulfate 560 g 
Sodium sulfite 60 g 
Disodium ethylenediaminetetraacetate 
0.10 g 
dehydrate 
Sodium hydroxide 24 g 
Water was added to 1 liter 
(pH was adjusted to 5.10 with acetic acid) 
______________________________________ 
Before development processing was started, the processing solutions shown 
below were filled in the respective tanks of the automatic processor. 
Developing tank: 10 ml of a starter containing 33 l of the above developing 
solution condensate, 667 ml of water, 2 g of potassium bromide and 1.8 g 
of acetic acid were added and pH was adjusted to 10.25. 
Fixing tank: 200 ml of the above fixing solution condensate and 800 ml of 
water. 
Processing speed: 35 seconds on Dry to Dry. 
Developing temperature: 35.degree. C. 
Fixing temperature: 32.degree. C. 
Drying temperature: 55.degree. C. 
Replenishing amount 
developing solution: 22 ml/10.times.12 inch 
fixing solution: 30 ml/10.times.12 inch 
The respective coated light-sensitive materials thus prepared were cut to 
600 sheets each with a size of 18 cm.times.38 cm and each thereof was 
subjected to a running processing with the automatic processor Model 
CEPROS-M and an automatic feeder without replenishing the fixing solution. 
After processing 600 sheets, 1 liter of the fixing solution was sampled 
and filtered with an FM-22, 47-00 filter. The weight of the filtered 
matters was measured to obtain the results shown in Table 2. The filtered 
residue was observed with a microscope and analyzed with infrared 
spectroscopy to confirm that it was matting agent. 
There was summarized as well in Table 2, the frequency inferior 
transportation caused when the respective light-sensitive materials were 
subjected to the running test under the conditions of 25.degree. C. and 
25% RH. The term "inferior transportation" as used herein means that 
plural sheets are sent at the same time in transporting a film and that 
the film gets caught during transporting with a roller. It will be 
appreciated from the results shown in Table 2 that the light-sensitive 
materials according to the present invention exhibit less peeling off and 
eluting of the matting agent and have excellent transporting performance. 
TABLE 2 
______________________________________ 
Matting agent amount 
Frequency of bad 
in the fixing solution 
transportion 
______________________________________ 
1 0.04 g/liter 10 
2 0.11 g/liter 4 
white turbidity in the 
fixing solution 
3 0.03 g/liter 2 
4 0.03 g/liter 0 
5 0.06 g/liter 1 
6 0.025 g/liter 2 
7 0.15 g/liter 0 
8 0.15 g/liter 2 
white turbidity in the 
fixing solution 
______________________________________ 
EXAMPLE 2 
The light-sensitive materials 2-1 to 2-8 corresponding to the 
light-sensitive materials 1 to 8 prepared in Example 1 were prepared in 
the same manners as those in Example 1, except that the coated amount of 
gelatin contained in the surface protective layer coating solution was 
changed to 0.65 g/m.sup.2. They were subjected to a surface protective 
layer coating solution settling test and the tests of matting agent 
peeling off and an inferior transportation in a running processing in the 
same manner as those in Example 1, whereby the results shown in Table 3 
were obtained. Again, the light-sensitive materials of the present 
invention preformed excellently particularly with the reduced coating 
amount of gelatin. 
TABLE 3 
______________________________________ 
Coated Matting Matting Frequency of bad 
sample agent* agent** transportation 
______________________________________ 
2-1 15% 0.06 g/l 15 
2-2 70% 0.20 g/l 8 
2-3 5% 0.35 g/l 2 
2-4 25% 0.04 g/l 2 
2-5 60% 0.17 g/l 8 
2-6 10% 0.03 g/l 1 
2-7 5% 0.015 g/l 
0 
2-8 80% 0.3% g/l 10 
______________________________________ 
*: Settling amount. 
**: Amount in the fixing agent. 
EXAMPLE 3 
The coating solutions and the light-sensitive materials 3-1 to 3-8 
corresponding to the light-sensitive materials 1 to 8 prepared in Example 
1 were prepared in the same manner as those in Example 1, except that the 
coated amount of the following compound: 
##STR36## 
contained in the surface protective layer coating solution was reduced to 
the level corresponding to a coated amount of 15 mg/m.sup.2. These coating 
solutions were evaluated by the same settling method as that in Example 1 
to find that the matting agent precipitated only in an amount of up to 
10%. Meanwhile, these light-sensitive materials were subjected to 
processing with the automatic processor described in Example 1 at 
25.degree. C. and 10% RH to find that any of the light-sensitive materials 
had the generation of a static mark and was fogged. Accordingly, it was 
confirmed that the decrease in the content of polyethylene oxide could not 
prepare the light-sensitive materials preferred in terms of a handling 
performance while the settling in the coating solution could be prevented. 
EXAMPLE 4 
The light-sensitive materials of the present invention described in 
Examples 1 and 2 were subjected to the following evaluation of 
photographic performances. 
Evaluation of the photographic performances 
The X ray ortho-screen HR-4 manufactured by Fuji Photo Film Co., Ltd. was 
used to expose the light sensitive material for 0.05 second on both sides 
and evaluation was carried out. 
The automatic processor Model FPM-9000 manufactured by Fuji Photo Film Co., 
Ltd. was modified to use it for this experiment. The processing steps 
therefor are shown in the following Table 4. 
TABLE 4 
______________________________________ 
Processing 
bath Processing 
Processing 
solution Processing path Processing 
step amount temperature 
length time 
______________________________________ 
Developing 
15 liter 35.degree. C. 
613 mm 8.8 seconds 
(solution surface area to processing bath 
volume ratio = 25 cm.sup.2 /liter) 
Fixing 15 liter 32.degree. C. 
539 mm 7.7 seconds 
Rinsing 13 liter 17.degree. C. 
263 mm 3.8 seconds 
flowing water 
Squeeze 304 mm 4.4 seconds 
Drying hot air 40.degree. C. 
368 mm 5.3 seconds 
(heat roller 100.degree. C. 2 pairs) 
Total 2087 mm 30.0 
seconds 
______________________________________ 
The processing solutions are as follows: 
______________________________________ 
Development processing 
______________________________________ 
Preparation of the condensed solutions: 
(1) Developing solution: 
Part agent A 
Potassium hydroxide 270 g 
Potassium sulfite 1125 g 
Sodium carbonate 450 g 
Boric acid 75 g 
Diethylene glycol 150 g 
Diethylenetriaminepentacetic acid 
30 g 
1-(N,N-diethylamino)ethyl-5-mercapto- 
1.5 g 
tetrazole 
Hydroquinone 405 g 
4-Hydroxymethyl-4-methyl-1-phenyl- 
30 g 
3-pyrazolidone 
Water was added to 4500 ml 
Part agent B 
Tetraethylene glycol 750 g 
3-3'-Dithiobishydrocinnamic acid 
3 9 
Glacial acetic acid 75 g 
5-Nitroindazole 4.5 g 
1-Phenyl-3-pyrazolidone 67.5 g 
Water was added to 1000 ml 
Part agent C 
Glutaraldehyde (50 wt/wt %) 
150 g 
Potassium bromide 15 g 
Potassium metabisulfite 120 g 
Water was added to 750 ml 
(2) Fixing solution: 
Anunonium thiosulfate (70 wt/vol %) 
3000 ml 
Disodium ethylenediaminetetracetate 
0.45 g 
dihydrate 
Sodium sulfite 225 g 
Boric acid 60 g 
1-(N,N-dimethylamino)-ethyl-5-mercapto- 
15 g 
tetrazole 
Tartaric acid 48 g 
Glacial acetic acid 675 g 
Sodium hydroxide 225 g 
Sulfuric acid (36N) 58.5 g 
Aluminum sulfate 150 g 
Water was added to 6000 ml 
pH 4.68 
______________________________________ 
Preparation of the processing solutions 
The above developing solution was placed in a vessel in the below amounts 
of each part. The vessel is constituted by combining the respective part 
vessels of the part agents A, B and C with the vessels themselves so as to 
make one vessel. 
The above fixing solution was placed in a similar vessel. 
First, 300 ml of an aqueous solution containing 54 g of acetic acid and 
55.5 g of potassium bromide was put in a developing bath as a starter. 
The vessels containing the above processing solutions were inserted in an 
inverted position into drilling blades in the processing solution stock 
tanks disposed at the side of an automatic processor to break the sealing 
membranes provided on the caps, and the respective processing solutions in 
the vessels were placed in the stock tanks. 
The respective processing solutions were placed in a developing bath and a 
fixing bath of the automatic processor in the following ratio by the pumps 
of the automatic processor. 
The replenishing rate was 10 ml/sheet (10 inch.times.12 inch) in both of 
the developing solution and the fixing solution. 
______________________________________ 
Developing solution: 
Part agent A 60 ml 
Part agent B 13.4 ml 
Part agent C 10 ml 
Water 116.6 ml 
pH 10.50 
Fixing solution: 
Condensate 80 ml 
Water 120 ml 
pH 4.62 
______________________________________ 
City water was filled in a rinsing bath. 
Samples in accordance with the present invention had excellent photographic 
performances. 
EXAMPLE 5 
Light-sensitive materials were prepared in the same manner as in Examples 1 
and 2, except that glutaraldehyde was removed from part agent C of the 
developing solution and the processing was carried out with the 
replenishing amounts of the developing solution and the fixing solution 
set at 11 ml/sheet (10 inch x 12 inch) and at a processing time of 30 
seconds. Similar excellent photographic performances were obtained. 
EXAMPLE 6 
The procedure in Example 4 was repeated, except that the developing 
solution and the fixing solution were replaced with the following 
developing solution and fixing solution, processing was carried out with 
replenishing amounts thereof set at 20 ml/sheet (10 inch.times.12 inch), 
and the processing time was 45 seconds. Similar excellent photographic 
performances were obtained. 
______________________________________ 
Developing solution: 
Part agent A 
Potassium hydroxide 28.0 g 
Potassium sulfite 75.0 g 
Diethylenetriaminepeantacetic acid 
2.0 g 
Sodium carbonate 30.0 g 
Hydroquinone 18.0 g 
1-(diethylamino)-ethyl-5-mercapto- 
0.1 g 
tetrazole 
Potassium bromide 1.0 g 
Water was added to 300 ml 
Part agent B 
Triethylene glycol 6.0 g 
5-Nitroindazole 0.3 g 
Acetic acid 40.0 g 
1-Phenyl-3-pyrazolidone 3.5 g 
3-3'-Dithiobishydrocinnamic acid 
0.2 g 
Water was added to 50 ml 
Water was added to make a 1 liter solution 
(pH was adjusted to 10.30). 
The replenshing ratio was: 
Part agent A 300 ml 
Part agent B 50 ml 
Water 650 ml 
COD (chemical oxygen demand) of the above solution 
was about 50,000. 
Fixing solution: 
Part agent A 
Sodium thiosulfate 96.4 g 
Disodium ethylenediaminetetracetate 
0.025 g 
dihydrate 
Sodium metabisulfite 22.0 g 
Water was added to 500 ml 
pH was adjusted with NaOH 5.0 
The replenishing ratio was 
Part agent A 500 ml 
Water 500 ml 
COD of the above solution was about 40,000. 
______________________________________ 
EXAMPLE 7 
Example 1 of the present invention was repeated, except that the method for 
preparing the emulsion was changed to prepare those of various sizes and 
provide plural emulsion layers, whereby there were obtained the same 
gradations as those of SHRS, SHRL, SHRA, SHRC, SHRG, and HRHA (all 
manufactured by Fuji Photo Film Co., Ltd.). 
The embodiment in Example 1 of the present inven-tion was repeated, except 
that the method for preparing the emulsion was changed to prepare those of 
various sizes and provide plural emulsion layers, whereby there were 
obtained the same gradations as those of MINP, MIMA, and MINP (all 
manufactured by Fuji Photo Film Co., Ltd.). 
EXAMPLE 8 
The same procedure as that in Example 1 was repeated, except that the 
matting agent was changed as shown in Table 5. 
TABLE 5 
__________________________________________________________________________ 
Settling amount of 
Matting agent 
Average grain 
matting agent* 
No. size (.mu.m) 
A B Matting agent component** 
__________________________________________________________________________ 
1-1 (Comp.) 
4.0 40% MMA 100 
1-2 (Comp.) 
4.1 60% MMA/MA = 80/20 
1-3 (Comp.) 
3.8 50% MMA/St = 50/50 
1-4 (Inv.) 
3.8 20% 15% MMA/MAA = 80/20 
1-5 (Comp.) 
4.1 55% MMA/St = 48/47 
cross linking agent: ethylene glycol 
dimethacrylate : 5 
1-6 (Inv.) 
4.0 30% 30% MMA/MA/MAA = 70/15/15 
1-7 (Inv.) 
3.9 20% 15% MMA/St/MAA + 36/36/20 
ethylene glycol dimethacrylate : 8 
1-8 (Inv.) 
3.8 15% 10% MMA/MAA = 75/20 
ethylene glycol dimethacrylate : 5 
1-9 (Inv.) 
4.0 10% 10% MMA/MA/MAA = 60/15/15 
ethylene glycol dimethacrylate : 
__________________________________________________________________________ 
10 
*)A: matting agent test amount by the test method described in claim 1. 
B: settling amount of the matting agent in the surface protrective layer 
coating solution after leaving for standing at 40.degree. C. for 24 hours 
**)All the matting agent components had molecular weight of about 60,000. 
The coated light-sensitive materials thus prepared were cut into 600 sheets 
each having a size of 18 cm.times.38 cm, and each was subjected to a 
running processing with the automatic processor Model CEPROS-M and an 
automatic feeder without replenishing the fixing solution. After 
processing 600 sheets, 1 liter of the developing solution was sampled and 
filtered with a FM-22, 47-00 filter. The weight of the filtrated matters 
was measured to obtain the results shown in Table 6. The filtrated residue 
was observed with a microscope and analyzed with an infrared spectroscopy 
to confirm that it was matting agent. 
The number of inferior transportations caused when the light-sensitive 
materials were subjected to a running test at 25.degree. C. and 25% RH are 
summarized in Table 6, wherein matting agent numbers correspond to those 
in Table 5. It will be appreciated from the above results that the 
light-sensitive materials according to the present invention have less 
occurrence of peeling off and eluting of the matting agent and have 
excellent transporting performance. 
TABLE 6 
______________________________________ 
Kind Matting agent 
Frequency 
Light- of amount in the 
of bad 
sensitive 
matting developing transpor- 
matrerial 
agent solution tation 
______________________________________ 
1 1-1 0.15 g/liter 
10 
2 1-2 0.18 g/liter 
6 
3 1-3 0.15 g/liter 
8 
4 1-4 0.04 g/liter 
6 
5 1-5 0.12 g/liter 
6 
6 1-6 0.045 g/liter 
7 
7 1-7 0.01 g/liter 
0 
8 1-8 0.01 g/liter 
0 
9 1-9 0.01 g/liter 
1 
______________________________________ 
EXAMPLE 9 
The light-sensitive materials 9-1 to 9-9 corresponding to the 
light-sensitive materials 1 to 9 prepared in Example 8 were prepared in 
the same manners as those in Example 8, except that the coated amount of 
gelatin contained in the surface protective layer coating solu-tion was 
changed to 0.65 g/m.sup.2. Surface protective layer coating solution 
settling tests and tests of matting agent peel off and an inferior 
transportation were conducted in the same manners as those in Example 1, 
whereby the results shown in Table 7 were obtained, where matting agent 
numbers correspond to those of Table 5. It will be appreciated that the 
light-sensitive materials of the present invention had excellent 
photographic performances, particularly which reduced coated amounts of 
gelatin. 
TABLE 7 
______________________________________ 
Kind Settling Matting agent 
Frequency 
Light- of amount* of 
amount in the 
of bad 
sensitive 
matting matting devoloping 
transpor- 
matrerial 
agent agent solution tation 
______________________________________ 
9-1 (Comp.) 
1-1 60% 0.22 g/liter 
12 
9-2 (Comp.) 
1-2 70% 0.21 g/liter 
10 
9-3 (Comp.) 
1-3 70% 0.20 g/liter 
10 
9-4 (Inv.) 
1-4 30% 0.08 g/liter 
7 
9-5 (Comp.) 
1-5 80% 0.15 g/liter 
7 
9-6 (Inv.) 
1-6 40% 0.056 g/liter 
8 
9-7 (Inv.) 
1-7 20% 0.015 g/liter 
1 
9-8 (Inv.) 
1-8 15% 0.010 g/liter 
1 
9-9 (Inv.) 
1-9 15% 0.015 g/liter 
0 
______________________________________ 
*settling amount of the matting agent in the surface protrective layer 
coating solution after leaving for standing at 40.degree. C. for 24 hours 
 
EXAMPLE 10 
The coating solutions and the light-sensitive materials 10-1 to 10-9 
corresponding to the light-sensitive materials 1 to 9 prepared in Example 
8 were prepared in the same manners as those in Example 1, except that the 
coated amount of the following compound: 
contained in the surface protective layer coating solution was reduced to 
15 mg/m.sup.2. 
These coating solutions were evaluated by the same settling method as that 
in Example 8 resulting in the matting agent being precipitated by only up 
to 10%. Meanwhile, the light-sensitive materials were subjected to 
processing with the automatic processor described in Example 8 at 
25.degree. C. and 10% RH to find that any of the light-sensitive materials 
had the generation of a static mark and was fogged. Accordingly, it was 
confirmed that the decreasing the amount of polkyethylene oxide resulted 
in light-sensitive materials having inferior handling performance, while 
settling of walling agent in the coating solution was prevented. 
EXAMPLE 11 
The light-sensitive materials of the present invention prepared by the 
manufacturing method according to the present invention described in 
Examples 8 and 9 were subjected to evaluation of the following 
photographic performances. 
Evaluation of the photographic performances 
The X ray ortho-screen HR-4 manufactured by Fuji Photo Film Co., Ltd. was 
used to expose the light-sensitive material for 0.05 second on both sides 
and evaluation was carried out. The others were the same as those in 
Example 4 and processing was carried out in the same manner as that in 
Example 4. 
The results showed that the samples of the present invention had excellent 
photographic performances. 
EXAMPLE 12 
The light-sensitive materials were prepared in the same manners as those in 
Examples 8 and 9, except that glutaraldehyde was removed from part agent C 
of the developing solution and processing was carried out with the 
replenishing amounts of the developing solution and the fixing solution 
set at 11 ml/sheet (10 inch.times.12 inch), and at a processing time of 30 
seconds. Similar results were obtained. 
EXAMPLE 13 
The procedure in Example 11 was repeated, except that processing was 
carried out in the developing solution and fixing solution used in Example 
6 with the replenishing amounts thereof set at 20 ml/sheet (10 
inch.times.12 inch), and at processing time of 45 seconds. Similar results 
were obtained. 
EXAMPLE 14 
Example 8 of the present invention was repeated, except that the method for 
preparing the emulsion was changed to prepare emulsions of various sizes 
and provide plural emulsion layers, whereby there were obtained the same 
gradations as those of SHRS, SHRL, SHRA, SHRC, SHRG, and HRHA (all 
manufactured by Fuji Photo Film Co., Ltd.). 
The embodiment in Example 8 of the present invention was repeated, except 
that the method for preparing the emulsion was changed to prepare 
emulsions of various sizes and provide plural emulsion layers, whereby 
there were obtained the same gradations as those of MINP, MIMA, and MINP 
(all manufactured by Fuji Photo Film Co., Ltd.). 
While the invention has been described in detailed with reference to 
specific embodiments, it will be apparent to one skilled in the art that 
various changes and modifications can be made to the invention without 
departing from its spirit and scope.