Silver halide photographic material containing a polymer with a photographically useful group which is rendered non-diffusive by cross-linking

A silver halide photographic material is described comprising at least one layer which contains at least PA0 (1) a polymer comprising as constitutional components thereof a repeating unit having a photographically useful group and at least one repeating unit having a sulfinic acid group or a sulfinate group, and PA0 (2) a compound having at least one functional group capable of reacting with at least one of a sulfinic acid group and sulfinate group and at least one functional group capable of reacting with at least one of a sulfinic acid group, a sulfinate group and a primary amino group. Said photographic group-containing polymer (1) may be fixed in a photographic layer according to the present photographic material, and does not substantially migrate therefrom during development or other photographic treatment, thus resulting in formation of color images of high density.

FIELD OF THE INVENTION 
The present invention relates to photographic materials, and, in 
particular, to silver halide photographic materials containing at least 
one polymer containing a photographically useful group, and which is 
rendered non-diffusive by crosslinking to each other and/or with gelatin 
using a compound having two or more functional groups capable of reacting 
with a sulfinic acid group or a primary amino group. 
BACKGROUND OF THE INVENTION 
Each layer of a silver halide photographic material contains, in general, 
various kinds of photographic additives, such as coupler, ultra-violet 
absorbent, anti-oxidant, stabilizer, color-stain inhibitor, anti-fogging 
agent, dye, etc.; and various methods have heretofore been proposed for 
fixation of specific photographic additivess in a specific layer 
comprising gelatin or the like hydrophilic binder. 
For instance, one prior art method is disclosed, for example, in U.S. Pat. 
Nos. 2,322,029, 2,360,289, 2,533,514 and 2,801,170, where a hydrophobic 
coupler having an oil-soluble group and a photographically useful group is 
dissolved in a solvent having a high boiling point, and the resulting 
solution is dispersed in a hydrophilic polymer solution to obtain a 
coupler-dispersion, which is coated on a photographic support. Another 
prior art method is disclosed, for example, in Japanese Patent Application 
(OPI) No. 59943/76 (The term "OPI" as used herein refers to a published 
unexamined Japanese Patent Application.), where a hydrophobic coupler 
having an oil-soluble group and a photographically useful group is 
dissolved in a water-compatible organic solvent and an aqueous polymer 
latex is gradually added to the resulting solution and admixed therewith 
to incorporate said hydrophobic coupler in said latex particles, and then 
the mixture obtained is dispersed in a hydrophilic polymer and then coated 
on a photographic support. 
However, these prior art methods include some troublesome defects as 
mentioned below. The former method requires an emulsification step 
requiring a large amount of energy, and the coupler, etc., are often 
deteriorated during said step, and thus, this is not always advantageous. 
On the other hand, in the latter method, the amount of the hydrophobic 
coupler to be incorporated in the latex particles must inevitably be 
limited in order to prevent the aggregation of said latex particles, and, 
therefore, desired photographic characteristics can not always be 
obtained. 
In addition to said above prior art methods, still another methods are 
known, as disclosed, e.g., in Research Disclosure, No. 190, pp. 65-66 
(1980), U.S. Pat. Nos. 3,926,436 and 4,397,943, and German Pat. No. 
1,547,863, where coupler, ultra-violet absorbent and stabilizer are added, 
each in the form of a water-soluble polymer, to a hydrophilic polymer 
binder, and the solution obtained is coated on a photographic support. 
However, this method is also defective in that the water-soluble polymers 
are not rendered sufficiently non-diffusive and so these are apt to flow 
out in a developer during development. In order to provide 
non-diffusiveness to a polymer, water-soluble polymers have been 
developed, having a reactive group such as vinylsulfone group, active 
ester group, active methylene group, primary amino group, epoxy group, 
etc. together with a photographically useful group, said reactive group 
being able to be cross-linked with gelatin directly or via a hardening 
agent, for example, as described in Research Disclosure, No. 17825 (1979), 
U.S. Pat. Nos. 4,215,195, 3,859,096 and 3,625,694 and Japanese Patent 
Application (OPI) Nos. 27139/83 and 142524/81. 
However, said photographically useful group-containing water-soluble 
reactive polymer do not have sufficient reactivity with gelatin or a 
hardening agent, and so to provide complete non-diffusiveness to said 
polymers is difficult. For example, in the case of a water-soluble polymer 
which has a photographically useful group a coupler residue capable of 
forming a dye by coupling with an oxidation product of an aromatic primary 
amine developing agent, if said polymer is not sufficiently made 
non-diffusive, color stain is apt to occur, and furthermore the polymer 
often flows out during development treatment, resulting in decrease of the 
density of the formed images. In the case of a water-soluble polymer 
having a residue derived from a reductive color stain-inhibitor as a 
photographically useful group, if the non-diffusiveness of said polymer is 
insufficient, the polymer also includes problems of color-stain and 
decrease of the density of the formed images. 
In addition, said conventional reactive groups such as vinylsulfone group, 
active ester group, active methylene group and epoxy group are per se 
hydrophobic. Accoridngly, if the polymers themselves containing such 
hydrophobic group are to be made water-soluble, it is necessary to 
copolymerize them with a substantial amount of hydrophilic monomer, in 
addition to a monomer having said reactive group or a monomer having a 
photographically useful group. Under the situation, the ratio of the 
amount of said monomers having the reactive group or a photographically 
useful group must be limited. However, if the ratio of the reactive 
group-containing monomer is made small, sufficient non-diffusiveness 
cannot be attained; and if the ratio of the photographically useful 
group-containing monomer is made small, sufficient photographic 
characteristics cannot be attained. These have been troublesome problems. 
SUMMARY OF THE INVENTION 
One object of the present invention is to provide a novel method for 
fixation (i.e. attainment of non-diffusiveness) of a compound having a 
photographically useful group in a definite layer. 
The other object of the present invention is to provide a silver halide 
photographic material having improved photographic characteristics, which 
has a photographically useful group-containing polymer as being fixed 
(i.e. made non-diffusive) in a definite layer by a novel method. 
Accordingly, the present invention provides a silver halide photographic 
material comprising at least one layer which contains at least 
(1) a polymer comprising as constitutional components thereof a repeating 
unit having a photographically useful group and at least one repeating 
unit having a sulfinic acid group or a sulfinate group, and 
(2) a compound having at least one functional group capable of reacting 
with at least one of a sulfinic acid group and sulfinate group and at 
least one functional group capable of reacting with at least one of a 
sulfinic acid group, a sulfinate group and a primary amino group. 
DETAILED DESCRIPTION OF THE INVENTION 
"Photographically useful group" as used herein refers to a substituent 
derived from photographic compounds which may be used in silver halide 
photographic materials, including a photographic dye, development 
inhibitor, development accelerator, coupler, competing coupler, 
development inhibitor-releasing compound (DIR compound), developing agent, 
development auxiliary, bleaching inhibitor, bleaching accelerator, 
bleaching accelerator-releasing compound (BAR compound), silver halide 
solvent, silver complexing agent, fogging agent, anti-fogging agent, 
stabilizer, chemical sensitizer, spectral sensitizer, de-sensitizer, 
ultra-violet absorbent, antioxidant, development accelerator-releasing 
compound, as well as precursors thereof. 
Preferred examples of photographically useful group-containing repeating 
units which may be used in the present invention include those represented 
by formula (A) 
##STR1## 
wherein R is hydrogen atom or an alkyl group having from 1 to 6 carbon 
atoms; 
Y is 
##STR2## 
wherein R has the same meaning as above; L is a divalent bonding group 
having from 1 to 12 carbon atoms; 
X is --O--, --CO--, --CO.sub.2, --SO.sub.2 --, 
##STR3## 
wherein R has the same meaning as above; Q is a photographically useful 
group; and 
l, m, and n are each independently 0 or 1. 
Preferred embodiments of the photographically useful group-containing 
repeating units of said formula (A) are explained in greater detail in the 
following description. 
R represents hydrogen atom or an alkyl group having from 1 to 6 carbon 
atoms such as methyl group, ethyl group, n-propyl group, iso-propyl group, 
n-butyl group, tert-butyl group, iso-butyl group, sec-butyl group, n-amyl 
group, tert-amyl group, or n-hexyl group; and is especially preferably a 
hydrogen atom, a methyl group, or an ethyl group. 
Y represents 
##STR4## 
R is selected from the group as mentioned above; for example, 
##STR5## 
and in particular, Y is especially preferably 
##STR6## 
L represents a divalent bonding group having from 1 to 12 carbon atoms, for 
example, an alkylene group such as methylene group, ethylene group, 
methylmethylene group, dimethylmethylene group, trimethylene group, 
tetramethylene group, pentamethylene group, hexamethylene group, 
octamethylene group, or decamethylene group; or an arylene group such as 
o-phenylene group, m-phenylene group, p-phenylene group, or naphthylene 
group; or 
##STR7## 
(in which R has the same meaning as above, and A and B represent an 
alkylene group having from 1 to 10 carbon atoms or an arylene group having 
from 6 to 10 carbon atoms), such as 
EQU --CH.sub.2 NHCOCH.sub.2 --, 
EQU --CH.sub.2 NHCOCH.sub.2 CH.sub.2 --, 
EQU --CH.sub.2 CH.sub.2 NHCOCH.sub.2 --, 
EQU --CH.sub.2 CH.sub.2 NHCOCH.sub.2 CH.sub.2 --, 
EQU --CH.sub.2 CH.sub.2 CH.sub.2 NHCOCH.sub.2 CH.sub.2 -- 
##STR8## 
or --A--CO.sub.2 --B-- (in which R, A, and B have the same meanings as 
above), such as 
EQU --CH.sub.2 OCOCH.sub.2 --, 
EQU --CH.sub.2 OCOCH.sub.2 CH.sub.2 --, 
EQU --CH.sub.2 CH.sub.2 OCOCH.sub.2 --, 
EQU --CH.sub.2 CH.sub.2 OCOCH.sub.2 CH.sub.2 --, 
EQU --CH.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.2 CH.sub.2 --, 
##STR9## 
A part of hydrogen atoms in said alkylene group and arylene group may, 
optionally, be substituted by an aryl group (such as a phenyl group, or a 
tolyl group), nitro group, hydroxyl group, cyano group, an alkoxy group 
(such as a methoxy group), an aryloxy group (such as a phenoxy group), an 
alkylcarbonyloxy group (such as an acetoxy group), an arylcarbonyloxy 
group (such as a benzoyloxy group), an alkylcarbonylamino group (such as 
an acetylamino group), an arylcarbonylamino group (such as a benzoylamino 
group), a carbamoyl group, an alkylcarbamoyl group (such as a 
methylcarbamoyl group or ethylcarbamoyl group), a dialkylcarbamoyl group 
(such as a dimethylcarbamoyl group), an arylcarbamoyl group (such as a 
phenylcarbamoyl group), an alkylsulfonyl group (such as a methylsulfonyl 
group), an arylsulfonyl group (such as a phenylsulfonyl group), an 
alkylsulfonamido group (such as a methanesulfonamido group), an 
arylsulfonamido group (such as a phenylsulfonamido group), a sulfamoyl 
group, an alkylsulfamoyl group (such as an ethylsulfamoyl group), a 
dialkylsulfamoyl group (such as a dimethylsulfamoyl group), an 
arylsulfamoyl group, carboxyl group, an alkoxycarbonyl group (such as 
methoxycarbonyl group), a halogen atom (such as a fluorine atom, chlorine 
atom, bromine atom), etc. 
L is especially preferably a methylene group, ethylene group, 
methylmethylene group, dimethylmethylene group, trimethylene group, 
tetramethylene group, pentamethylene group, m-phenylene group, p-phenylene 
group, --CH.sub.2 NHCOCH.sub.2 --, --CH.sub.2 NHCOCH.sub.2 CH.sub.2 --, 
--CH.sub.2 OCOCH.sub.2 CH.sub.2 --, or --CH.sub.2 CH.sub.2 OCOCH.sub.2 
CH.sub.2 --. 
X represents --O--, --CO--, --CO.sub.2 --, --SO.sub.2 --, 
##STR10## 
R has the same meaning as above; and especially preferably --O--, --CO--, 
--CO.sub.2 --, --SO.sub.2 --, --CONH--, --NHCONH--, --NHCO.sub.2 --, 
--NHCOCH.sub.2 CH.sub.2, or --SO.sub.2 CH.sub.2 CH.sub.2 --. 
Q represents a photographically useful group. 
For example, Q represents a coupler group capable of forming a dye by 
coupling with an aromatic primary amine developing agent. As for a cyan 
coupler group, a phenoltype group of the following formula (I)-1 or a 
naphthol-type group of the following formula (I)-2 is preferred. The 
asterisk mark * hereinafter shows the position of the bond to X. 
##STR11## 
In said formulae (I)-1 and (I)-2, R.sub.1 represents an alkyl group, an 
alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, 
an alkoxycarbamoyl group, an aliphatic amido group, an alkylsulfamoyl 
group, an alkylsulfonamido group, an alkylureido group, an arylcarbamoyl 
group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido 
group or an arylureido group; p is an integer of 0 to 3, and q is an 
integer of 0 to 4. 
Z.sub.1 represents hydrogen atom, a halogen atom, sulfo group, an acyloxy 
group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an 
alkylthio group, an arylthio group or a heterocyclic thio group. 
Groups recited for R.sub.1 and Z.sub.1 may, optionally, be substituted. 
Examples of substituents thereon include an aryl group (such as phenyl 
group), nitro group, hydroxy group, cyano group, sulfo group, an alkoxy 
group (such as methoxy group), an aryloxy group (such as phenoxy group), 
an acyloxy group (such as acetoxy group), an acylamino group (such as 
acetylamino group), an alkylsulfonamido group (such as methanesulfonamido 
group), an alkylsulfamoyl group (such as methylsulfamoyl group), a halogen 
atom (such as fluorine atom, chlorine atom, bromine atom), carboxyl group, 
an alkylcarbamoyl group (such as methylcarbamoyl group), an alkoxycarbonyl 
group (such as methoxycarbonyl group), an alkylsulfonyl group (such as 
methylsulfonyl group), an alkylthio group (such as .beta.-carboxyethylthio 
group), etc. In the case that said group is substituted by two or more of 
said substituents, these may be same or different. 
As for a magenta coupler group, pyrazolone-type, pyrazolotriazole-type, and 
imidazopyrazole-type groups of the following formulae (I)-3 through (I)-14 
are preferred. 
##STR12## 
R.sub.2 represents a conventional substituent which is well known as a 
substituent on 1-position of a 2-pyrazolin-5-one coupler, for example, an 
alkyl group, a substituted alkyl group (such as a halo-alkyl group, e.g., 
fluoroalkyl, or a cyano-alkyl group, a benzyl-alkyl group), an aryl group 
or a substituted aryl group (examples of substituents thereon is an alkyl 
group such as a methyl group or ethyl group), an alkoxy group (such as a 
methoxy group or ethoxy group), an aryloxy group (such as a phenyloxy 
group), an alkoxycarbonyl group (such as a methoxycarbonyl group), an 
acylamino group (such as an acetylamino group), a carbamoyl group, an 
alkylcarbamoyl group (such as a methylcarbamoyl group or ethylcarbamoyl 
group), a dialkylcarbmoyl group (such as a dimethylcarbamoyl group), an 
arylcarbamoyl group (such as a phenylcarbamoyl group), an alkylsulfonyl 
group (such as a methylsulfonyl group), an arylsulfonyl group (such as a 
phenylsulfonyl group), an alkylsulfonamido group (such as a 
methanesulfonamido group), an arylsulfonamido group (such as a 
phenylsulfonamido group), a sulfamoyl group, an alkylsulfamoyl group (such 
as an ethylsulfamoyl group), a dialkylsulfamoyl group (such as a 
dimethylsulfamoyl group), an arylsulfamoyl group, an alkylthio group (such 
as a methylthio group), an arylthio group (such as a phenylthio group), 
cyano group, nitro group, a halogen atom (such as a fulorine atom, 
chlorine atom, bromine atom), etc. In case said group is substituted by 
two or more of said substituents, these may be same or different. 
Especially preferably, substituents are halogen atom, alkyl group, alkoxy 
group, alkoxycarbonyl group and cyano group. 
R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, 
R.sub.11 and R.sub.12 are each independently a hydrogen atom or hydroxyl 
group, or represent an unsubstituted or substituted alkyl group 
(preferably having from 1 to 20 carbon atoms, such as a methyl group, 
propyl group, t-butyl group, trifluoromethyl group, tridecyl group), an 
aryl group (preferably having from 6 to 20 carbon atoms, such as phenyl 
group, 4-t-butylphenyl group, 2,4-di-t-amylphenyl group, 4-methoxyphenyl 
group), a heterocyclic group (such as a 2-furyl group, 2-thienyl group, 
2-pyrimidinyl group, 2-benzthiazolyl group), an alkylamino group 
(preferably having from 1 to 20 carbon atoms, such as a methylamino group, 
diethylamino group, t-butylamino group), an acylamino group (preferably 
having from 2 to 20 carbon atoms, such as an acetylamino group, 
propylamido group, benzamido group), an anilino group (such as phenylamino 
group, 2-chloroanilino group), an alkoxycarbonyl group (preferably having 
from 2 to 20 carbon atoms, such as a methoxycarbonyl group butoxycarbonyl 
group, 2-ethylhexyloxycarbonyl group), an alkylcarbonyl group (preferably 
having from 2 to 20 carbon atoms, such as an acetyl group, butyl-carbonyl 
group, cyclohexylcarbonyl group), an arylcarbonyl group (preferably having 
from 7 to 20 carbon atoms, such as a benzoyl group, 4-t-butylbenzoyl 
group), an alkylthio group (preferably having from 1 to 20 carbon atoms, 
such as a methylthio group, octylthio group, 2-phenoxyethylthio group), an 
arylthio group (preferably having from 6 to 20 carbon atoms, such as a 
phenylthio group, 2-butoxy-5-t-octylphenylthio group), a carbamoyl group 
(preferably having from 1 to 20 carbon atoms, such as an N-ethylcarbamoyl 
group, N,N-dibutylcarbamoyl group, N-methyl-N-butylcarbamoyl group), a 
sulfamoyl group (preferably NH.sub.2 SO.sub.2 -- and a group having from 1 
to 20 carbon atoms, such as an N-ethylsulfamoyl group, 
N,N-diethylsulfamoyl group, N,N-dipropylsulfamoyl group) or an alkyl 
sulfonamido group (preferably having from 1 to 20 carbon atoms, such as a 
methanesulfonamido group), an arylsulfonamido group (preferably having 
from 6 to 20 carbon atoms, such as benzenesulfonamido group, 
p-toluenesulfonamido group). 
Z.sub.2 represents hydrogen atom, a halogen atom, or a split off group 
which is bonded at a coupling position via an oxygen, nitrogen, or sulfur 
atom. In the case Z.sub.2 is bonded at a coupling position via an oxygen, 
nitrogen, or sulfur atom, said atom is bonded with an alkyl group, an aryl 
group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl 
group, an arylcarbonyl group or a heterocyclic ring residue. In addition, 
in case Z.sub.2 is bonded at a coupling position via nitrogen atom, this 
may form, including said nitrogen atom, a 5- or 6-membered ring (such as 
an imidazolyl group, pyrazolyl group, triazolyl group, or tetrazolyl 
group). 
As for a yellow dye forming coupler group, an acylacetanilide-type group of 
formula (I)-15 and benzoylacetanilide-type groups of formulae (I)-16 and 
(I)-17 are preferred. 
##STR13## 
R.sub.13, R.sub.14, R.sub.15 and R.sub.16 each independently represents a 
hydrogen atom or a substituent which is conventional and well known in a 
yellow coupler group, for example, an alkyl group, an alkenyl group, an 
alkoxy group, an alkoxycarbonyl group, a halogen atom, an alkoxycarbamoyl 
group, an aliphatic amido group, an alkylsulfamoyl group, an 
alkylsulfonamido group, an alkylureido group, an alkyl-substituted 
succinimido group, an aryloxy group, an aryloxycarbonyl group, an 
arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an 
arylsulfonamido group, an arylureido group, carboxyl group, sulfo group, 
nitro group, cyano group or thiocyano group. 
Z.sub.3 represents hydrogen atom or --OR.sub.17 (in which R.sub.17 
represents an aryl group, a substituted aryl group or a heterocyclic 
group), or represents 
##STR14## 
wherein R.sub.18 and R.sub.19 each independently represents hydrogen atom, 
a halogen atom, a carboxylic acid ester residue, an amino group, an alkyl 
group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an 
alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, a 
substituted or unsubstituted phenyl group, or a heterocyclic ring, or 
represents 
##STR15## 
wherein W.sub.1 is an atomic group necessary for forming a 4 to 7 membered 
ring together with 
##STR16## 
Especially preferred among the foregoing are 
##STR17## 
wherein R.sub.20, R.sub.21, and R.sub.22 each independently represents a 
hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an acyl 
group; W.sub.2 represents an oxygen atom or a sulfur atom; R.sub.23 and 
R.sub.24 each independently represents a hydrogen atom, an alkyl group, an 
aryl group, an alkoxy group, an aryloxy group or hydroxy group. 
Preferred examples of repeating units of the above-described formula (A), 
which have as a photographically useful group a coupler group capable of 
forming a dye by coupling with an aromatic primary amine developer, are 
set forth below. 
##STR18## 
Q in the above-mentioned formula (A) may represent a group derived from a 
development inhibitor, and examples thereof are described, e.g., in U.S. 
Pat. Nos. 3,227,554, 3,384,657, 3,615,506, 3,617,291 and 3,733,201, and 
British Pat. No. 1,450,479. Preferred development inhibitor residues are 
represented by the following formulae (II)-1 through (II)-6, which are 
described in Japanese Patent Application (OPI) No. 145135/79. 
##STR19## 
In the above formulae, R.sub.25 represents a hydrogen atom, an alkyl group 
containing from 1 to 6 carbon atoms, phenyl group or a substituted phenyl 
group; and R.sub.26 represents hydrogen atom, a halogen atom, an alkyl 
group containing from 1 to 4 carbon atoms, or nitro group. 
Preferred examples of repeating units having a photographically useful 
group of a development inhibitor residue which are included in the scope 
of said formula (A) are set forth below. 
##STR20## 
Q in the formula (A) may represent a group derived from a developing agent, 
and examples thereof are described, e.g., in U.S. Pat. Nos. 2,193,015, 
2,108,243, 2,592,364, 3,656,950, 3,658,525, 2,751,297, 2,289,367, 
2,772,282, 2,743,279, 2,753,265 and 2,304,953. 
Preferred developing agents capable of yielding said group Q are 
aminophenols, phenylenediamines, hydroquinones, and pyrazolidones as 
described in Japanese Patent Application (OPI) No. 145135/79, and residues 
of the following formulae (III)-1 through (III)-6 are especially 
preferred. 
##STR21## 
In the above formulae, R.sub.25 and R.sub.26 have the same meanings as set 
forth above; R.sub.27 represents hydrogen atom, an alkyl group containing 
1 to 4 carbon atoms, a hydroxyalkyl group containing from 1 to 4 carbon 
atoms (such as a hydroxymethyl group or hydroxyethyl group) or a 
sulfoalkyl group containing from 1 to 4 carbon atoms; and R.sub.28 
represents an alkyl group containing from 1 to 20 carbon atoms or an aryl 
group containing 6 to 20 carbon atoms. 
Preferred examples of repeating units having as a photographically useful 
group a developing agent group, which are included in the scope of said 
formula (A) are set forth below. 
##STR22## 
Q in the formula (A) may represent a group derived from a bleaching 
inhibitor, and examples thereof are described in U.S. Pat. Nos. 3,705,801 
and 3,715,208 and German Pat. OLS No. 2,405,279. Groups of the following 
formulae (IV)-1 through (IV)-4, which are derived from bleaching 
inhibitors, are especially preferred, as described in Japanese Patent 
Application (OPI) No. 145135/79. 
##STR23## 
In the above formulae, R.sub.28 has the same meaning as described above. 
Preferred examples examples of repeating units having a photographic group 
of a bleaching inhibitor group which are included in the scope of said 
formula (A) are set forth below. 
##STR24## 
Q in the formula (A) may represent a residue derived from an ultra-violet 
absorbent, and examples thereof are described, e.g., in U.S. Pat. Nos. 
4,431,726, 4,178,303, and 4,207,253, and Japanese Patent Application (OPI) 
Nos. 178351/83, 185677/83, 111942/83 and 27139/83. Groups of the following 
formulae (V)-1 through (V)-4, which are derived from ultra-violet 
absorbents, are especially preferred. 
##STR25## 
In the above formulae, R.sub.13, R.sub.14, R.sub.17 and R.sub.27 have the 
same meanings as described above; R.sub.29 and R.sub.30 each independently 
represents cyano group, an aryl group (such as phenyl group, tolyl group), 
an alkyl group (such as a methyl group, ethyl group, butyl group, or hexyl 
group), an alkoxycarbonyl group (such as an ethoxycarbonyl group or 
propoxycarbonyl group), an arylsulfonyl group (such as a phenylsulfonyl 
group), or an alkylsulfonyl group (such as a methylsulfonyl group). 
Preferred examples of repeating units having as a photographically useful 
group an ultra-violet absorbent group which are included in the scope of 
said formula (A) are set forth below. 
##STR26## 
Q in the formula (A) may represent a group derived from a dye, and examples 
thereof are described in, for example, Japanese Patent Application (OPI) 
No. 145135/79. 
Preferred dyes are triarylmethane-type, azo-type, anthraquinone-type, 
merocyanine-type, oxonole-type, arylidene-type and styryl-type dyes. 
Preferred examples of repeating units having as a photographically useful 
group a dye group which are included in the scope of said formula (A) are 
set forth below. 
##STR27## 
Examples of sulfinic acid group or sulfinate group containing repeating 
units which may be used in the present invention include those represented 
by the formula (B) 
##STR28## 
wherein R has the same meaning as defined in the case of the 
above-described formula (A); U represents a divalent bonding group 
containing from 1 to 20 carbon atoms; T represents a sulfinic acid group 
or a sulfinate group; and r is 0 or 1. 
In the repeating units of said formula (B), R is especially preferably a 
hydrogen atom, methyl group, or ethyl group. 
U represents a divalent bonding group having 1 to 20 carbon atoms, for 
example, an alkylene group (such as a methylene group, ethylene group, 
trimethylene group, or hexamethylene group), a phenylene group (such as an 
o-phenylene group, p-phenylene group, or m-phenylene group), an 
arylene-alkylene group (such as 
##STR29## 
in which R.sub.29 represents an alkylene group containing from 1 to 12 
carbon atoms), --CO.sub.2 --, --CO.sub.2 --R.sub.30 -- (wherein R.sub.30 
represents an alkylene group, group, a phenylene group or an 
arylenealkylene group), --CONH--R.sub.30 -- (in which R.sub.30 has the 
same meaning as above), or 
##STR30## 
(in which R and R.sub.30 have the same meanings as described above); and 
in particular, the following are especially preferred. 
##STR31## 
T represents a sulfinic acid group or a sulfinate group. The cation to form 
said sulfinate group is preferably mono- or tri-valent. In case said 
cation is di-valent or more, the pair anions may comprise any other 
anion(s) such as --SO.sub.2.sup..crclbar. Ba.sup.2.sym. Cl.sup..crclbar. 
or --SO.sub.2.sup..crclbar. Al.sup.3.sym. Cl.sub.2.sup.2.crclbar. in 
addition to the repeating unit of the formula (B). Preferred cations are 
ammonium ion and metal ions, and alkali metal ions (such as sodium ion, 
potassium ion) are especially preferred. 
Preferred examples of repeating units of said formula (B) are set forth 
below. 
##STR32## 
Photographic polymers which may be used in the present invention may 
additionally contain other repeating units in addition to the 
photographically useful group-containing repeating unit of the 
above-described formula (A) and the sulfinic acid group or sulfinate 
group-containing repeating unit of the above-described formula (B). 
Preferred examples of monomers useful for forming said additional repeating 
units are ethylene, propylene, 1-butnene, 1-vinylimidazole, styrene, 
sodium vinylbenzenesulfonate, potassium vinylbenzylsulfonate, 
.alpha.-methylstyrene, vinyltoluene, sodium vinylsulfonate; and 
mono-ethylenic unsaturated esters of fatty acids (such as vinyl acetate, 
allyl acetate), monoethylenic unsaturated amides of fatty acids (such as 
N-vinylacetamide, N-vinylpyrrolidone), ethylenic unsaturated 
mono-carboxylic acid or di-carboxylic acid esters (such as methyl 
acrylate, ethyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 
n-butyl methacrylate, benzyl acrylate, 2-ethylhexyl acrylate, cyclohexyl 
methacrylate, furfuryl acrylate, diethyl maleate, diethyl itaconate), 
ethylenic unsaturated monocarboxylic acid amides (such as acrylamide, 
dimethyl-acrylamide, methacrylamide, diacetoneacrylamide, 
acryloyl-morpholine, sodium acrylamide-2-methylpropane-sulfonate, 
methacryloyl-morpholine), mono-ethylenic unsaturated compounds (such as 
acrylonitrile), and dienes (such as butadiene, isoprene); and in 
particular, highly hydrophilic compounds are especially preferred among 
them. 
In the photographic polymers of the present invention, the content of the 
photographically useful group-containing repeating unit is preferably from 
20 to 98 wt.% and especially preferably from 30 to 90 wt.%; the content of 
the sulfinic acid group or sulfinate group-containing repeating unit is 
preferably from 2 to 50 wt.% and more preferably from 4 to 40 wt.%; and 
the content of other additional repeating unit(s) is preferably 70 wt.% or 
less. 
The polymer couplers of the present invention preferably have a molecular 
weight of from 5.times.10.sup.3 to 1.times.10.sup.7. If the molecular 
weight is too small, the polymer is apt to easily move, but on the 
contrary, if the molecular weight is too large, the polymer is difficult 
to coat on a photographic support. The preferred molecular weight of the 
polymers falls within the range of from 1.times.10.sup.4 to 
2.times.10.sup.6. 
Preferred examples of the polymers which may be used in the present 
invention are set forth below, with the values set forth beside the 
parentheses for each type of repeating unit indicating the molar % content 
thereof. 
##STR33## 
As compound (2) which is used in the present invention i.e., a compound 
having at least one functional group capable of reacting with at least one 
of a sulfinic acid group and a sulfinate group and at least one other 
functional group capable of reacting with at least one of a sulfinic acid 
group, a sulfinate group and a primary amino group, photographic 
gelatin-hardening agent is preferred. 
Preferred photographic gelatin-hardening agents which may be used in the 
present invention include, for example, an aldehyde (such as formaldehyde, 
glyoxal, glutaraldehyde), a ketone (such as diacetyl, cyclopentane-dione), 
an N-methylol compound (such as dimethylol-urea, 
methylol-dimethylhydantoin), a dioxane derivative (such as 
2,3-dihydroxy-dioxane), an active vinyl compound (such as 
1,3,5-triacryloyl-hyxahydro-s-triazine, bis(vinylsulfonyl)methylether, 
N,N'-ethylene-bis(vinylsulfonylacetamide)), an active ester (such as 
di-N-hydroxysuccinimido-succinate), an active halogen compound (such as 
2,4-dichloro-6-hydroxy-s-triazine), a mucohalogenic acid (such as 
mucochloric acid, mucophenoxychloric acid), an isoxazole, a 
dialdehyde-starch, a 1-chloro-6-hydroxytriazinylatedgelatin, a high 
molecular weight active vinyl compound, a high molecular weight active 
ester compound, etc. Examples of said hardening agents are described, 
e.g., in U.S. Pat. Nos. 1,870,354, 2,726,162, 2,870,013, 2,893,611, 
2,992,109, 3,047,394, 3,057,723, 3,103,437, 3,325,287, 3,362,827, 
3,490,911, 3,539,644, and 4,161,407; British Pat. Nos. 676,628, 825,544, 
and 1,270,578; German Pat. Nos. 872,153, 1,090,427, 2,749,260; Japanese 
Patent Publication No. 7133/59, and Japanese Patent Application (OPI) Nos. 
66841/81 and 142524/81. 
Among said gelatin-hardening agents, active vinyl compounds, especially 
vinylsulfonyl compounds and precursors thereof, are preferred. 
Vinysulfonyl compounds which may be used in the present invention include 
those described, e.g., in Japanese Patent Publication No. 13563/74, U.S. 
Pat. No. 3,539,664, and Research Disclosure, RD No. 17458. Preferred 
vinylsulfonyl compounds and precursors thereof are represented by the 
following formulae (C) and (D). 
EQU (CH.sub.2 .dbd.CH--SO.sub.2).sub.2 A (C) 
EQU (XCH.sub.2 CH.sub.2 --SO.sub.2).sub.2 A (D) 
In the above formulae, A represents a divalent bonding group; and X 
represents a mono-valent organic group which may be removed from the 
formula (D) in the form of a compound of HX to form a compound of the 
formula (C). 
A is, for example, an alkylene group, preferably having from 1 to 10 carbon 
atoms, or a phenylene group, and said alkylene group may optionally 
contain an ether bond or an amido bond in the chain thereof. Said alkylene 
and phenylene may optionally be substituted with, for example, an alkyl 
group (preferably having from 1 to 5 carbon atoms, a halogen atom (e.g., 
chlorine atom), or a hydroxy group. In particular, A is preferably an 
alkylene group, and especially preferably --CH.sub.2 -- --CH.sub.2 
OCH.sub.2 --, 
##STR34## 
or --CH.sub.2 CONH--(CH.sub.2).sub.n NHCOCH.sub.2 --, in which n is 2 or 
3. 
X is preferably a halogen atom, an acyloxy group (preferably, 
alkylcarbonyloxy group having from 2 to 4 carbon atoms, and an 
arylcarbonyloxy group having from 7 to 11 carbon atoms) or a sulfonyloxy 
group (preferably, an alkylsulfonyloxy group having from 1 to 6 carbon 
atoms and an arylsulfonyloxy group having from 6 to 10 carbon atoms), and 
especially preferably a chlorine atom, acetoxy group, or 
methanesulfonyloxy group. 
Examples of preferred gelatin-hardening agents are given belosw, which, 
however, do not whatsoever restrict the scope of the present invention. 
##STR35## 
The amount of the compound (2) to be used in the present invention may be 
widely varied, in accordance with the use and the object of the 
photographic materials to be formed. In general, said amount is from 0.05 
to 10 molar times, and preferably from 0.1 to 2.0 molar times, the amount 
of the sulfinic acid group or the sulfinate group contained in the polymer 
(1) used in the present invention. When the amount of the compound (2) is 
too small the fixation of the polymer is not sufficient, on the other 
hand, when the amount is too large the layer of the photographic material 
becomes difficult to swell, which prevents impregnation of a processing 
solution to the layer. Upon deciding the amount of compound (2) the amount 
which is used for hardening gelatin should also be taken into account. 
The polymer (1) and the compound (2) which are used in the present 
invention are in general incorporated in the same layer; or alternatively 
may be incorporated in different photographic layers. In the latter case, 
one compound diffuses into a layer containing the other compound, and as a 
result, the two compounds come to exist in the same layer. Incorporation 
of the compounds in different layers is preferably applied in the case 
that, if both of the compounds used in the present invention were to be 
added in one coating solution, the viscosity of said coating solution 
would increase too much and the coating solution is difficult to handle.

Some examples to illustrate the synthesis of polymers which may be used in 
the present invention are described below. 
SYNTHESIS EXAMPLE 1 
Synthesis of 
poly(2'[(1-hydroxy-2-naphthoylamino)ethyl]acrylanidido-co-potassium-p-viny 
lbenzenesulfinate-co-sodium 2-acrylamido-2-methylpropanesulfonate) (CP-4) 
14.0 g of 2'[(1-hydroxy-2-naphthoylamino)ethyl] acryanilide, 7.0 g of 
potassium p-vinylbenzenesulfinate, 12.6 g of 
2-acrylamido-2-methylpropanesulfonic acid, 60 ml of DMF, 60 ml of methanol 
and 12 ml of 5N-sodium hydroxide aqueous solution were put in a reaction 
container having a capacity of 300 ml, and the content was fully purged by 
the use of nitrogen gas. Afterwards, the whole was heated at 60.degree. 
C., and then 0.175 g of 2,2'-azobisisobutyronitrile was added thereto and 
continuously heated for 4 hours. The reaction sample was cooled to room 
temperature and then put in 600 ml of acetone. Thus crystallized 
precipitate was separated by filtration, and then dried in vacuum, to 
obtain 21.6 g of the desired polymer. Yield: 62%. 
SYNTHESIS EXAMPLE 2 
Synthesis of 
poly(1-(2,5-dichlorophenyl)-3-methacryloylamino-2-pyrazolin-5-one-co-potas 
sium p-vinylbenzenesulfinate-co-sodium 
2-acrylamido-2-methylpropanesulfonate) (MP-1) 
10.5 g of 1-(2,5-dichlorophenyl)-3-methacryloylamino-2-pyrazolin-5-one, 6.0 
g of potassium p-vinylbenzenesulfinate, 13.5 g of 
2-acrylamido-2-methylpropanesulfonic acid, 60 ml of DMF, 60 ml of methanol 
and 14 ml of 5N-sodium hydroxide aqueous solution were put in a reaction 
container having a capacity of 300 ml, and the content was fully purged by 
the use of nitrogen gas. Afterwards, the whole was heated at 60.degree. 
C., and then 0.15 g of 2,2'-azobisisobutyronitrile was added thereto and 
continuously heated for 4 hours. The reaction sample was cooled to room 
temperature and then put in 600 ml of acetone. Thus crystallized 
precipitate was separated by filtration and then dried in vacuum, to 
obtain 15.5 g of the desired polymer. Yield: 49%. 
SYNTHESIS EXAMPLE 3 
Synthesis of 
poly(1-(2,4,6-trichlorophenyl)-3-(2-chloro-3-acrylamidobenzamido)-2-pyrazo 
lin-5-one-co-potassium p-vinylbenzenesulfinate-co-sodium 
2-acrylamido-2methylpropanesulfonate) (MP-7) 
The above entitled polymer was synthesized analogously to the synthesis 
Example 2, using 
1-(2,4,6-trichlorophenyl)-3-(2-chloro-3-acrylamidobenzamido)-2-pyrazoline- 
5-one. Yield: 53%. 
SYNTHESIS EXAMPLE 4 
Synthesis of 
poly(4'-chloro-3'-[.alpha.-(4-methoxycarbonylphenoxy)-.alpha.-pivaloylacet 
amido]acrylanilido-co-potassium p-vinylbenzenesulfinate-co-sodium 
2-acrylamido-2-methylpropanesulfonate) (YP-3) 
10.5 g of 
4'-chloro-3'-[.alpha.-(4-methoxycarbonylphenoxy)-.alpha.-pivaloylacetamido 
]acrylanilide, 6.0 g of potassium p-vinylbenzenesulfinate, 13.5 g of 
2-acrylamido-2-methylpropane-sulfonic acid, 60 ml of DMF, 60 ml of 
methanol and 14 ml of 5N-sodium hydroxide were put in a reaction container 
having a capacity of 300 ml, and the content was fully purged by the use 
of nitrogen gas. Afterwards, the whole was heated at 60.degree. C., and 
then 0.15 g of 2,2'-azobisisobutyronitrile was added thereto and 
continuously heated for 4 hours. The reaction sample was cooled to room 
temperature and then put in 600 ml of acetone. Thus crystallized 
precipitate was separated by filtration and then dried in vacuum, to 
obtain 17.2 g of the desired polymer. Yield: 55%. 
SYNTHESIS EXAMPLE 5 
Synthesis of 
poly(3-methacryloylamino-4-methyl-2-pyrazolin-5-one-co-potassium 
p-vinylbenzenesulfinate) (DP-4) 
23.4 g of 3-methacryloylamino-4-methyl-2-pyrazolin-5-one, 10.1 g of 
potassium p-vinylbenzenesulfinate, 70 ml of DMF and 60 ml of methanol were 
put in a reaction container having a capacity of 300 ml, and the content 
was fully purged by the use of nitrogen gas. Afterwards, the whole was 
heated at 60.degree. C., and then 0.23 g of 2,2'-azobisisobutyronitrile 
was added thereto and continuously heated for 4 hours. The reaction sample 
was cooled to room temperature and then put in 800 ml of acetone. Thus 
crystallized precipitate was separated by filtration and then dried in 
vacuum, to obtain 20.4 g of the above-entitled polymer. Yield: 61%. 
The compounds of the present invention may be incorporated in the same one 
layer in the form of a mixture of two or more kinds of said compounds. 
Also, a particular compound may be incorporated in two or more different 
layers. 
The polymer (1) and the compound (2) may be incorporated in any layer of a 
photographic material, such as, a silver halide emulsion layer, a 
protective layer, an interlayer, and a subbing layer depending on the aim 
of use of the polymer. 
For introduction of the polymer (1) and the compound (2) of the present 
invention into silver halide emulsion layers, water-soluble compounds 
among said compounds may be incorporated in a silver halide emulsion in 
the form of an aqueous solution thereof; water-insoluble compounds may be 
dispersed in a hydrophilic colloid and the resulting dispersion 
incorporated in a silver halide emulsion. The polymer (1) and the compound 
(2) may be incorporated separately. The silver halide emulsion thus 
containing the compounds of the present invention is thereafter coated on 
a photographic support. In the same manner the compounds can be 
incorporated to other layers. Furthermore, the compound (2) may be 
impregnated to a photographic material as a solution after completion of 
coating of all layers. 
The amount of the polymer (1) to be used in the present invention is 
determined, depending upon the property and the use of the photographic 
material to be formed, for example, upon the layer to which the polymer is 
to be added, the kind of compounds to be co-used, and the means for 
treating the photographic material. 
The silver halide photographic materials of the present invention may be 
applied to color negative films, color reversal films, color positive 
film, color photographic papers, color reversal photographic papers or a 
color diffusion transfer-system or silver dye bleachingsystem color 
photographic materials. The materials may also be applied to black and 
white photographic materials such as black and white photographic films, 
X-ray films, photo-engraving films, black and white photographic papers, 
aerial photographic films, microfilms, facsmimile films phototypesetting 
films, photographic papers, graphic films, etc. 
Gelatins which may be used in the silver halide photographic materials of 
the present invention may be a so-called alkali-treated (or lime-treated 
gelatin, which is dipped in an alkaline bath, prior to the extraction of 
gelatin, in the manufacture procedure thereof, or an acid-treated gelatin, 
which is dipped in an acidic bath, or a double-dipped gelatin, which is 
subject to said both alkali and acid treatments; or, it may also be an 
enzyme-treated gelatin, as described in "Bull, Soc. Sci. Photo, Japan", 
No. 16, page 30 (1966). In addition, partially hydrolyzed gelatins having 
a low molecular weight which is obtained by heating the above-mentioned 
various kinds of gelatins in a hot-water bath or reacting those with a 
protease may also be used in the present invention. 
The above-described gelatins, to which the compounds of the present 
invention may be applied, may optionally be partially substituted by a 
collodial albumin, a casein, a cellulose derivative such as 
carboxymethylcellulose or hydroxyethylcellulose, an agar, a sodium 
alginate, a saccharide derivative such as starch derivative, a synthetic 
hydrophilic colloid such as polyvinyl alcohol, poly-N-vinylpyrrolidone, 
polyacrylic acid co-polymer or polyacrylamide, or a derivative thereof or 
a partially hydrolyzed product thereof; or otherwise may also optionally 
be partially substituted by a gelatin derivative obtained by modification 
of functional amino, imino, hydroxyl and/or carboxyl group(s) contained in 
the gelatin molecule with a reagent having one reactive group capable of 
reacting with said functional groups, or by a gelatin-graft polymer 
obtained by graft-polymerization of gelatin with other high molecular 
substance. 
Examples of reagents which may be used for formation of said gelatin 
derivatives are, for example, isocyanates, acid chlorides, and acid 
anhydrides as described in U.S. Pat. No. 2,614,928; acid anhydrides as 
described in U.S. Pat. No. 3,118,766; bromoacetic acids as described in 
Japanese Patent Publication No. 5514/64; phenylgylcidylethers as described 
in Japanaese Patent Publication No. 26845/67; vinylsulfone compounds as 
described in U.S. Pat. No. 3,132,945; N-allylvinylsulfonamides as 
described in British Pat. No. 861,414; malemide compounds as described in 
U.S. Pat. No. 3,186,846; acrylonitriles as described in U.S. Pat. No. 
2,594,293; polyalkyleneoxides as described in U.S. Pat. No. 3,312,553; 
epoxy compounds as described in Japanese Patent Publication No. 26845/67; 
acid esters as described in U.S. Pat. No. 2,763,639; and alkanesultones as 
described in British Pat. No. 1,033,189. 
A number of high molecular weight substances which may be grafted with 
gelatin, are known, and described e.g., in U.S. Pat. Nos. 2,763,625, 
2,831,767, and 2,956,884; Polymer Letters, Vol. 5, p. 595 (1967); Phot. 
Sci. Eng., Vol. 9, p. 148 (1965); J. Polymer Sci., A-1, Vol. 9, p. 3199 
(1971), etc. For example, polymers and copolymers of so-called vinyl 
monomers such as acrylic acid, methacrylic acid or an ester, amide or 
nitrile derivative thereof, or styrene, may be used for said 
graft-polymerization. In particular, hydrophilic vinyl polymers or 
copolymers which are somewhat compatible with gelatin are especially 
preferred, including polymers or copolymers of acrylic acid, acrylamide, 
methacrylamide, hydroxy-alkyl acrylate, hydroxylalkyl methacrylate, etc. 
The photographic materials of the present invention may optionally contain, 
in the photographic emulsion layers or other layers thereof, synthetic 
polymers other than the above-described polymers, such as a 
water-dispersible vinyl-polymer in the form of a latex, especially 
preferably a compound capable of increasing the dimensional stability of 
the photographic material, singly or in the form of a mixture of said 
compounds, or, if necessary, in the form of a combination of said compound 
with other hydrophilic water-permeable colloid. 
The photographic materials of the present invention may further contain a 
matting agent. Fine particles of a water-insoluble organic or inorganic 
compound are preferred as said matting agent, having an average diameter 
of from 0.2 to 10 .mu.m, and especially preferably from 0.3 to 5 .mu.m. 
In the case wherein the photographically useful group-containing polymer to 
be used in the present invention is a yellow polymer-coupler, this coupler 
is in general incorporated in a blue-sensitive emulsion layer; in the case 
wherein the coupler is a magenta polymer-coupler, it is generally 
incorporated in a green-sensitive emulsion layer; and in the case wherein 
the coupler is a cyan polymer-coupler, it is generally incorporated in a 
red-sensitive emulsion layer. However, different combinations than those 
mentioned above may also be used, if desired. Couplers other than the 
polymer-couplers of the present invention may analogously be incorporated 
in an appropriate emulsion layer, if co-used. Examples of other couplers 
than the polymer-couplers of the present invention, which may be co-used 
together with the present polymer-couplers, are polymer-couplers which do 
not contain any monomer unit represented by the above-described formula 
(B) as well as polymer-couplers represented by the above-described 
formulae (I)-1 through (I)-17 in which the position marked with an 
asterisk (*) is bound to a substituent of R.sub.1 as defined in the 
formula (I)-1. 
Said couplers may be either 4-equivalent or 2-equivalent to silver ion. In 
addition, they may also be colored couplers having a color-correcting 
activity, or so-called DIR-couplers which may release a development 
inhibitor during development. 
Besides said DIR coulers, a non-coloring DIR-coupling compound may be 
included, which may form a colorless reaction product after coupling and 
which may release a development inhibitor during development. Compounds 
other than said DIR-couplers may also be used which may release a 
development inhibitor during development. 
For introduction of the coupler in a silver halide emulsion layer in the 
present invention, a known method may be used, for example, as described 
in U.S. Pat. No. 2,322,027. For instance, the coupler to be incorporated 
in a silver halide emulsion layer is first dissolved in an alkyl phthalate 
(such as dibutyl phthalate, dioctyl phthalate), a phosphate (such as 
diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctylbutyl 
phosphate), a citrate (such as tributyl acetyl-citrate), a benzoate (such 
as octyl benzoate), an alkylamide (such as diethyllaurylamide), a fatty 
acid ester (such as dibutoxyethyl succinate, diethyl azelate), a trimesate 
(such as tributyl trimesate); or in an organic solvent having a boiling 
point of about 30.degree.-150.degree. C., for example, a lower alkyl 
acetate (such as ethyl acetate, butyl acetate), ethyl propionate, 
secondary butyl alcohol, methylisobutylketone, .beta.-ethoxyethyl acetate, 
methylcellosolve, etc.; and then the resulting solution is dispersed in a 
hydrophilic colloid. Said high boiling point-organic solvent and low 
boiling point-organic solvent may be used together in the form of a 
mixture thereof. 
Apart from said method, another dispersion method by the use of a polymer 
substance may also be used for the introduction of the coupler, e.g., as 
described in Japanese Patent Publication No. 39853/76 and Japanese Patent 
Application (OPI) No. 59943/76. 
In the case that the coupler has an acid group such as a carboxylic acid or 
sulfonic acid group said coupler may be introduced in a hydrophilic 
colloid in the form of an alkaline aqueous solution thereof. 
The photographic emulsion layer of the photographic materials of the 
present invention may contain any silver halide selected from silver 
bromide, silver bromoiodide, silver chloroiodide, silver bromochloride, 
and silver chloride. 
The average particle size of silver halide particles in the photographic 
emulsion in the present invention is not specifically limitative, but is 
preferably 3.mu. or less. Regarding the average particle size of silver 
halide particles, in the case of particles that are spherical or nearly 
spherical, the diameter of the particle is measured on the basis of the 
projected area thereof, and in case the particles are cubical, the length 
of the side is measured also on the basis of the projected area thereof, 
and the size is designated by the average of the measured values. 
The particle size distribution may be broad or narrow. 
The silver halide particles in the photographic emulsion of the present 
invention may have a regular crystalline form such as a hexahedrom or 
octahedron form; or otherwise may have an irregular crystalline form such 
as a spherical or plate-like form; or in addition, may have a composite 
crystalline form compising the combination of said regular and irregular 
forms. Moreover, these silver halide particles may comprise a mixture of 
various crystalline forms. 
An emulsion containing ultra-flat plate-like silver halide particles, in 
which the diameter of the particle is larger than the thickness thereof by 
5 times or more, in a proportion of 50% or more of the total projected 
area, may also be used in the photographic materials of the present 
invention. 
The silver halide particles of the present invention may have different 
inner phase and surface layer phase. Said particles may form a latent 
image mainly on the surface parts thereof, or otherwise, may form the same 
mainly in the inner parts thereof. 
The photographic emulsions to be used in the present invention may be 
prepared according to conventional methods as described in Chimie et 
Physique Photographique, by P. Glafkides, Paul Montel Co., (1967); 
Photographic Emulsion Chemistry, by G. F. Duffin, The Focal Press Co. 
(1966); or Making and Coating Photographic Emulsion, by V. L. Zelikman, et 
al., The Focal Press Co., (1964). The preparation of the present 
photographic emulsions may be carried out by any of acid method, neutral 
method, or ammonia method, according to said conventional means. In a 
reaction system where a soluble silver salt is reacted with a soluble 
halide, any conventional means such as one-side admixture method, 
simultaneous admixture method or a combination of said methods may be 
utilized. 
A so-called reverse-admixture method may also be used, where silver halide 
particles are formed in the presence of an excess silver ion. As one 
embodiment of the simultaneous admixture method, a so-called 
controlled-double jet method may be used, where the pAg value in the 
liquid phase necessary to form silver halide particles is determined, and 
kept at the determined value. According to said method, a silver halide 
emulsion comprising particles having a regular crystalline form and a 
uniform particle size may be obtained. 
Two or more kinds of silver halide emulsions which have been prepared 
separately may be used together in the form of a mixture thereof. 
During the formation of silver halide particles or during the physical 
ripening step thereof, a cadmium salt, a zinc salt, a lead salt, a 
thallium salt, an iridium salt or a complex salt thereof, a rhodium salt 
or a complex salt thereof, or an iron salt or a complex salt thereof may 
co-exist in the reaction system. 
Silver halide emulsions are in general chemical-sensitized. For the 
chemical-sensitization, for example, methods as described in Die 
Grundlagender Photographischen Processe mit Silberhalogeniden, by H. 
Freiser, Akademische Verlagsgessellshaft, (1968), pp 675-734, may be used. 
More precisely, a sulfur-sensitization method where a sulfur-containing 
compound capable of reacting with an active gelatin is used; a reductive 
sensitization method using a reductive substance; and a noble 
metal-sensitization method using a noble metal compound may be used for 
the chemical-sensitization of the silver halide emulsions of the present 
invention, and said methods may be carried out singly or in the 
combination of two or more methods. 
The photographic emulsions to be used in the present invention may 
additionally contain various kinds of additives, in order to prevent the 
photographic materials from being fogged during the manufacture thereof or 
during the preservation or photographic treatment thereof, or to stabilize 
the photographic characteristics of said materials. 
For example, various kinds of conventional compounds which are known as 
anti-fogging agents or as stabilizers may be added to the present 
photographic emulsions, such as an azole compound, a mercaptopyrimidine 
compound, a mercaptotriazine compound, a thiocarbonyl compound, an 
azaindene compound, a thiosulfonic acid compund, a sulfinic acid compound, 
and a sulfonamide compound. 
The photographic materials of the present invention may contain, in the 
photographic emulsion layer or in other hydrophilic colloid layer, a 
coating auxiliary and various kinds of surfactants, for the purpose of 
static charge prevention, improvement of slide property, emulsification 
and dispersion, blocking inhibition, and improvement of photographic 
characteristics (e.g., development acceleration, high contrast 
reproduction, and sensitization). 
For instance, various kinds of surfactants may be used for said purpose, 
including non-ionic surfactants such as saponins (steroid type), 
alkyleneoxide derivatives, glycidol derivatives, fatty acid esters of 
polyhydric alcohols and alkylesters of saccharides; anionic surfactants 
containing an acid group such as carboxyl group or sulfo group; ampholytic 
surfactants such as aminoalkylsulfinic acid and alkylbetains; and cationic 
surfactants such as alkylamine salts and quaternary ammonium salts. 
The photographlic emulsion layer of the present photographic materials may 
further contain other additives for the purpose of increasing sensitivity 
and contrast, and for acceleration of development, including 
polyalkyleneoxides and ester, ether and amine derivatives thereof, and 
thioether compounds, thiomorpholines, quaternary ammonium salt compounds, 
urethane derivatives, urea derivatives, imidazole derivatives and 
3-pyrazolidone derivatives. 
The present photograhic materials may contain, in the photographic emulsion 
layer or in other hydrophilic colloid layer, a dispersion of a synthetic 
polymer which is insoluble or hardly soluble in water, for the purpose of 
improvement of dimension stability. For example, polymers or copolymers of 
an alkyl (meth)acrylate and/or (meth)acrylamide and/or styrene, optionally 
with a (meth)acrylic acid, hydroxyalkyl (meth)acrylate and/or 
styrenesulfonic acid, may be used for said purpose. 
The photographic emulsions to be used in the present invention may be 
spectral-sensitized by the use of methine dyes or the like other dyes. 
Examples of dyes which may be used for said spectral-sensitization are 
cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine 
dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol 
dyes. Especially preferred dyes among them are cyanine dyes, merocyanine 
dyes and complex merocyanine dyes. These dyes may have any basic 
heterocyclic nucleus which is conventionally contained in cyanine dyes, 
including pyrroline, oxazoline, thiazoline, pyrrole, oxazole, thiazole, 
selenazole, imidazole, tetrazole and pyridine nuclei; fused nuclei 
comprising said nucleus and an alicyclic hydrocarbon ring; and fused 
nuclei comprising said nucleus and an aromatic hydrocarbon ring, such as 
indolenine, benzindolenine, indole, benzoxazole, napthoxazole, 
benzothiazole, naphthothiazole, benzoselenazole, benzimidazole and 
quinoline nuclei. These nuclei may be substituted on carbon atoms. 
Merocyanine dyes and complex merocyanine dyes may contain a ketomethylene 
structure-containing 5 or 6 membered heterocyclic ring nucleus such as 
pyrazolin-5-one, thiohydantoin, 2-thiooxazolidine-2,4-dione, 
thiazolidine-2,4-dione, rhodanine, and thio-barbituric acid nuclei. 
These sensitizing dyes may be used singly or in the form of a mixture 
thereof, and the use of a combination of sensitizing dyes is often 
preferred for the purpose of supersensitization. 
The present photographic emulsion may further contain other dyes which 
themselves have no spectral-sensitization activity, or other substances 
which do not substantially absorb any visible radiation, but have 
supersensitization activity, together with the above-mentioned sensitizing 
dyes. For example, amino-styryl compounds which are substituted by an 
nitrogen-containing heterocyclic ring group (e.g., as described in U.S. 
Pat. Nos. 2,933,390 and 3,635,721); aromatic organic acid/formaldehyde 
condensation products (e.g., as described in U.S. Pat. No. 3,743,510); and 
cadmium salts and azaindene compounds may be added to the photographic 
emulsion for said purpose. 
When the hydrophilic colloid layer in the photographic materials of the 
present invention contains dye-stuffs or ultraviolet absorbent, these may 
be mordanted by the use of a cationic polymer or the like. 
The photographic materials of the present invention may contain as an 
anti-fogging agent, a hydroquinone derivative, an aminophenol derivative, 
a gallic acid derivative, or an ascorbic acid derivative. 
The photographic materials of the present invention may contain in the 
hydrophilic colloid layer thereof an ultra-violet absorbent. For example, 
aryl-substituted benzotriazole compounds (e.g., as described in U.S. Pat. 
No. 3,533,794); 4-thiazolidone compounds (e.g., as described in U.S. Pat. 
Nos. 3,314,794 and 3,352,681); benzophenone compounds (e.g., as described 
in Japanese Patent Application (OPI) No. 2784/71); cinnamate compounds 
(e.g., as described in U.S. Pat. Nos. 3,705,805 and 3,707,375); butadiene 
compounds (e.g., as described in U.S. Pat. No. 4,045,229); and benzoxazole 
compounds (e.g., as described in U.S. Pat. No. 3,700,455) may be used. In 
addition, ultra-violet absorbing coupler (such as .alpha.-naphthol-type 
cyan couplers) and ultra-violet absorbing polymers may also be used. Said 
ultra-violet absorbents may be mordanted in a special layer if desired. 
The photographic materials of the present invention may contain, in the 
hydrophilic colloid layer thereof, a water-soluble dye, as a filter dye, 
for the purpose of irradiation prevention, or for various other purposes. 
Such water-soluble dyes include oxonole dyes, hemioxonole dyes, styryl 
dyes, merocyanine dyes, cyanine dyes, and azo dyes. Oxonole dyes, 
hemioxonole dyes and merocyanine dyes are preferred. 
The photographic materials of the present invention may additionally 
contain a known color-deterioration inhibitor or a color image-stabilizers 
which may be used singly or in the form of a mixture of two or more kinds 
thereof Conventional color-deterioration inhibitors which may be used in 
the present invention are, for example, hydroquinone derivatives (e.g., as 
described in Japanese Patent Application (OPI) No. 10539/84), gallic acid 
derivatives, p-alkoxyphenols and bisphenols. 
For the photographic treatment of the photographic materials of the present 
invention may be utilized conventional means. In accordance with the 
object and the use of the photographic materials, any conventional 
photographic treatment may be applied thereto, such as a black and white 
photographic treatment for formation of silver images, or other 
photographic treatment for formation of color images (e.g., a color 
development system, diffusion transfer system, or silver dye bleaching 
system). 
The developer to be used for said black and white photographic treatment 
may contain a conventional developing agent such as dihydroxybenzenes or 
aminophenols, and other conventional additives. 
The color development system comprises steps of color development, silver 
bleaching and fixation (or bleach-fix); and the silver dye bleaching 
system comprises steps of black and white development, dye-bleaching, 
silver-bleaching (or simultaneous dye and silver bleaching) and fixation. 
A color developer to be used for said color development comprises, in 
general, an alkaline aqueous solution containing a color developing agent. 
As said color developing agent conventional aromatic primary amine 
developing agents such as phenylenediamines may be used. Said color 
developer may additionally contain a pH buffer, an anti-fogging agent, a 
development inhibitor, a preservative, a development accelerator, a color 
forming coupler, a competing coupler, a fogging agent, and an auxiliary 
developing agent. 
The silver bleaching treatment may be carried out together with the 
fixation treatment. As a silver bleaching agent, polyvalent metal 
compounds such as iron (III)-compounds, peroxides, and quinones may be 
used. 
Any conventional fixing agent may be used in the fixation solution, for 
example, thiosulfates, thiocyanates and organic sulfur-compounds may be 
used. 
A PQ-type black and white developer is used, in general, in black and white 
development in the silver dye bleaching system. 
In the dye-bleaching step, dyes are reduced and bleached by the use of a 
developed silver which has been formed in the photographic material and 
which acts as a catalyst. The dye-bleaching solution may contain an acid 
agent (such as a mineral acid or an organic acid), a compound which may 
form a silver salt or a silver complex (such as potassium bromide or 
thiourea), and dye-bleaching accelerator catalyst (such as pyrazine, 
phenazine, or naphthoquinone). 
The present invention will be explained in greater detail by reference to 
the following examples, which, however, are not intended to be interpreted 
as limiting the scope of the present invention. In the examples, a polymer 
having a coupler residue (as a photographically useful group) and a 
polymer having a residue derived from a developing agent (as a 
photographically useful group) were used. 
EXAMPLE 1 
Layers, each comprising the components as set forth below, were coated on a 
cellulose triacetate film support, to obtain a sample (A). 
1. Silver halide emulsion layer: 
Red-sensitive silver bromoiodide emulsion (Silver iodide: 5 mole%) 
Coated Silver Amount: 1.1 g/m.sup.2 
Gelatin: 1.2 g/m.sup.2 
Polymer coupler CP-4: 0.63 g/m.sup.2 
2. Protective layer 
Gelatin: 1.0 g/m.sup.2 
Hardening agent HH-1 0.08 g/m.sup.2 (used as a compound (2)): 
Other samples (B) through (H) were analogously prepared, with the provisio 
that a magenta polymer coupler was added to a green-sensitive silver 
bromoiodide emulsion layer and a yellow polymer coupler was added to a 
blue-sensitive silver bromoiodide emulsion layer. 
The thus obtained samples were subjected to wedge exposure with white light 
at a color temperature of 4800.degree. K. and then to photographic 
treatments to obtain color images. The density of each of the thus-formed 
color images was determined. 
Next, each sample was irradiated with a fluorescent light (20000 luxes) for 
one day. The difference between the density of the color image before the 
fluorescent irradiation and that after said irradiation was obtained. The 
color-fastness of the formed color image was evaluated on the basis of 
said difference. 
The following Table 1 shows the maximum density of each of the samples (A) 
through (H) and the color retention percentage* (as defined below) at a 
color density of 1.0 of each sample. Hardening agent HH-1 can be 
represented by the formula 
##STR36## 
TABLE 1 
__________________________________________________________________________ 
Sample 
Polymer coupler (g/m.sup.2) 
Maximum density 
Color retention percentage (%) 
__________________________________________________________________________ 
A CP-4 0.63 1.95 89 Present invention 
B CH-1 0.72 1.80 80 Comparative sample 
C MP-1 1.00 1.01 92 Present invention 
D MP-7 1.05 1.12 90 " 
E MH-1 0.48 0.97 65 Comparative sample 
F MH-2 1.20 0.89 66 " 
G YP-3 1.56 1.18 87 Present invention 
H YH-1 2.00 1.09 80 Comparative sample 
__________________________________________________________________________ 
(Compound described in Example 15 of U.S. Pat. No. 4,421,915) 
##STR37## 
- - 
(Compound described in Japanese Patent Application (OPI) No. 28744/83) 
##STR38## 
- - 
(Compound described in Example 18 of U.S. Pat. No. 4,421,915) 
##STR39## 
- - 
(Compound described in Example 17 of U.S. Pat. No. 4,421,915) 
##STR40## 
The Table-1 proves that the polymer coupler of the present invention, whic 
has a sulfinic acid group as a reactive group, does not migrate into the 
development solution, and therefore a higher maximum density may be 
attained. Other polymer couplers having an active methylene group as a 
reactive group, as described in U.S. Pat. No. 4,421,915 or Japanese Patent 
Application (OPI) No. 28744/83 are inferior to said polymer coupler of the 
present invention. 
In addition, it is apparent that the polymer couplers of the present 
invention form excellent color images (especially magenta images) which 
have high color-fasteness to light. 
From the above results, it is recognized that the use of the polymers of 
the present invention having as a photographically useful group a coupler 
group remarkably improve the photographic characteristics, especially the 
maximum density of the color images formed and the color-fastness thereof 
to light. 
EXAMPLE 2 
Layers each comprising the components as set forth below were coated on a 
cellulose acetate film support, to obtain a sample (I). 
1. Red-sensitive emulsion layer: 
Silver bromoiodide emulsion (silver iodide: 5 mole%) 
Coated Silver Amount: 1.6 g/m.sup.2 
Gelatin: 2.0 g/m.sup.2 
Tricresyl phosphate: 0.5 g/m.sup.2 
Coupler C-1: 0.7 g/m.sup.2 
Hardening agent HH-1 0.05 g/m.sup.2 (used as a compound (2)): 
2. Intermediate layer: 
Polymer color-stain inhibitor DP-4: 0.11 g/m.sup.2 
Gelatin: 0.4 g/m.sup.2 
3. Magenta coupler layer: 
Coupler M-1: 0.6 g/m.sup.2 
Gelatin: 1.2 g/m.sup.2 
Tricresyl phosphate: 0.5 g/m.sup.2 
Hardening agent HH-1: 0.05 g/m.sup.2 
Other samples (J) and (K) were prepared analogously, with the proviso that 
the sample (J) did not contain the polymer color-stain inhibitor DP-4, and 
that the sample (K) contained 0.24 g of DPH-1 instead of DP-4. 
Thus formed samples were exposed and photographically treated analogously 
to Example 1, and the density of each of the formed color images were 
determined analogously. The following Table-2 shows the results. 
TABLE 2 
______________________________________ 
Color-stain inhibitor 
Maximum density 
Sample (g/m.sup.2) Cyan Magenta 
______________________________________ 
I DP-4 (0.11) 1.56 0.01 present 
sample 
J -- (--) 1.41 0.13 comparative 
sample 
K DPH-1 (0.24) 1.46 0.07 comparative 
sample 
______________________________________ 
DPH-1 (Compound described in Example of Japanese Patent Application (OPI) 
NO. 27139/81) 
##STR41## 
The data of Table-2 indicates that the polymer colorstain inhibitor of the 
present invention, which has a sulfinic acid group as a reactive group, 
does not migrate during development treatment, and appears to 
substantially trap the excess oxidation product of the developing agent, 
which was formed in the red-sensitive emulsion layer. Therefore, magenta 
development in the upper layer can be well restrained, as compared with 
the other comparative samples. In addition, it is recognized that the 
polymer color-stain inhibitor of the present invention can firmly be fixed 
in the intermediate layer, and thus, this does not hinder the cyan-color 
development in the red-sensitive emulsion layer, resulting in formation of 
cyan-color images of high density. 
It is apparent from the above results, that the polymer color-stain 
inhibitor of the present invention, which contains a residue derived from 
a developing agent as a photographically group, has an excellent 
color-stain inhibitory effect. 
##STR42## 
While the invention has been described in detail and with reference to 
specific embodiments thereof, it will be apparent to one skilled in the 
art that various changes and modifications can be made therein without 
departing from the spirit and scope thereof.