JPS6353544A - Silver halide photographic sensitive material preventing sweating phenomenon and formation of static mark - Google Patents

Abstract

PURPOSE:To prevent the formation of static marks without causing a sweating phenomenon by using a polymer derived from repeating units of a specified monomer. CONSTITUTION:A polymer derived from repeating units of a monomer represented by formula I is used. In the formula I, each of R1 and R2 is H, 1-4C alkyl or the like, W is H or -COOR4, X is 1-6C alkylene, 6-12C arylene or the like, Y is 0-12C bivalent group having at least one group such as -O- or -SO3-, m=0 or 1 and Q is a UV absorbing group. The polymer may be a homo- or copolymer of the monomer having a UV absorbing group. The polymer is used as latex in a hydrophilic colloidal layer of a silver halide photographic sensitive material such as the protective surface layer, an intermediate layer or a silver halide emulsion layer.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material n (hereinafter referred to as "photographic material"), and in particular, the present invention relates to a silver halide photographic material n (hereinafter referred to as "photographic material"), and in particular, the surface quality can be improved by incorporating a polymer ultraviolet absorber. This invention relates to a photographic material with improved static marks and without the adverse effects of. [Background of the invention 1 Photographic materials include polyethylene terephthalate film,
Alternatively, the light-sensitive photographic emulsion is coated on a support with relatively high electrical insulation, such as laminated paper coated with polyethylene, etc., so that electrostatic charges are reduced during the manufacturing process of the photosensitive material and during use. Accumulation causes sparks to be generated due to air discharge, resulting in various image defects such as dendritic marks, so-called static marks, after development, which can significantly reduce commercial value. Conventionally, attempts have been made to prevent the generation of static marks by blocking ultraviolet light of 300 to 400 rv using ultraviolet absorbers. As ultraviolet absorbers, we use
No., JP-A-53-97425, JP-A No. 53-133033
No. 53-131837, No. 53-134431, No. 59-10944, R2O, No. 18,032,
JP-A-54-18727, British Patent No. 2.083,2
No. 39, No. 2,083,240, JP-A-53-12
9633, British Patent No. 2,083,241, West German Patent Application (OLS) No. 2.118.798, British Patent No. 1,198,337, US Patent No. 3,253,921
No. 3,745,010, No. 3,533,79
No. 4, No. 3,754,919, No. 3, 794.4
No. 93, No. 4,009,038, No. 4,220,
No. 711, No. 4,323,633, R, D, No. 22
．． We tried adding the compounds described in No. 519, etc., but found that the static prevention effect was insufficient and that a sweating phenomenon occurred in which an oil-like substance or a powdery crystal-like substance appeared on the surface of the photographic light-sensitive material. [Object of the Invention] An object of the present invention is to provide a photographic material that does not cause the sweating phenomenon and prevents the generation of static marks. [Structure of the Invention] The present inventors achieved the above object as a result of 12 studies.
In a silver halide photographic light-sensitive material having at least a 11I photosensitive silver halide emulsion layer on a support, a halogenated material containing a polymer derived from a monolayer repeating unit represented by the following general formula [E] It has been discovered that the above object can be achieved by using a silver photographic material. General Formula [I] In the formula, R1 and R2 each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a nitrile, and W represents a hydrogen atom or -COOR4. X has 1 or more carbon atoms
6 alkylene group, C6-12 arylene group, C7-15 arylene alkylene group, -0-1-C
ON-1 However, when W is 100OR+, it represents -CO〇- or -CON-. Y is 10-1-N-1-CO-1
-S-1-SO-1-3O2-1 represents a valent group having 0 to 12 carbon atoms. R3 is an alkyl group having 1 to 6 carbon atoms or 6 to 12 carbon atoms
represents an aryl group, R4, R5 and R6 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 6 carbon atoms.
represents 12 aryl groups. Z represents a group of atoms necessary to form a ring containing at least one nitrogen atom. m is O or 1. However, when X is an arylene group, the number of carbon atoms in Y is not 1. Q represents an ultraviolet absorbing group. [Specific Structure of the Invention] The silver halide photographic material of the present invention has the general formula [
It contains a polymer derived from repeating units of the monomer represented by 11. The general formula [I] will be explained. In the general formula [Equation 1], examples of the alkyl group represented by R1-R6 include methyl group, ethyl group, propyl group, t-butyl group, etc., and examples of the alkylene group represented by X include methylene group. , propylene group,
Examples of the aryl group represented by R3-R6 include a phenyl group, a naphthyl group, and a tolyl group. Examples of the arylene group represented by X include a phenylene group, a tolylene group, and a propyl group. Examples of the arylene alkylene group represented by X include phenylene group, and examples of the arylene alkylene group represented by X include phenylene,
In particular, the -1z- group represented by Y and the ultraviolet absorbing group represented by Q include the following general formulas [111, [Ima
], [llIb], [IV], [Vl, [V1], [
UV-absorbing groups represented by VI], [■] and [rX] are preferred. General formula [■] DiR2°, R3, R4 and R5 each represent a hydrogen atom, an aliphatic group or an aryl group. Yl represents an oxygen atom, a sulfur atom, an ethylene group or a methylene group. Vl and Wl are each a hydrogen atom and -CN. -COR'', -COOR', -3○2 R8, hereafter the margin \R...\8. Here, R6, R, 7 and R8 each represent an aliphatic group or an aryl group, and R9, RIQ, R+1 and R12
each represents a hydrogen atom, an aliphatic group, or an aryl group, and R9 and R+o and R++ and R12 may be connected to each other to form a ring. R1, R2, R3, R4,
At least one of R5, vl and Wl is bonded to a polymerizable group. In the formula, R21 represents an aliphatic group or an aryl group. R'n, R"', R24 and R23' bar FA'
L represents a hydrogen atom, an aliphatic group or an aryl group, R
and R23 may be connected to form a benzene ring or a naphthalene ring. Here, R2 represents a hydrogen atom or an alkyl group. V2 and UW2 i, l respectively -CN, -COR" evening,
\R27 \R31 R2ζ and R:L'7 each represent an aliphatic group or an aryl group, R1, R Tsuba, R3° and R3/ each represent a hydrogen atom, an aliphatic group or an aryl group, and R''X and R, and R30 and R31 may be connected to each other to form a ring.Furthermore, V2 and W2 are connected to aR representing a group of nonmetallic atoms necessary to form a membered or 6-membered acidic keto ring.
At least one of 2', R22, R2J, 2 and W2 is bonded to a polymerizable group. *+ 41 R+3 and R44 are respectively hydrogen in the formula R, R, atom, halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, alkylthio group, arylthio group, amine 1 alkylamim L arylamim L hydroxy group, cyano group , represents an acylamino group, carbamoylphonyl group, sulfamoyl group, sulfonamide group, acyloxy group, or oxycarbonyl group, R41
and Rμ, R'3 and Rf4, or R and R may be connected to each other to form a 5- to 6-membered ring. z2 represents a group of nonmetallic atoms necessary to form a 5- or 6-membered acidic keto ring. +I Sen ◆3 r At least one of R , R , R , R and Z2 is bonded to a polymerizable group. General formula [V]! ;=1 S2 t,s C烹4 Sゆう -1? In the formula R SR ,
R, R, R, R. R5', Ru, RA/ and R are each a hydrogen atom,
Halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, amino group, alkylamino group, arylamino group, hydroxy group, cyam L acylamino group, carbamoyl group, acyl group, sulfonyl group, Represents a sulfamoyl group, a sulfonamide group, an acyloxy group, or an oxycarbonyl group, R5'1 and Rmi, Rゝ3 and ζ, R4 and R, R7 and R, RゝtoR and 0 and R6 ' and R6z may be connected to each other to form a 5- to 6-membered ring. Rゝ6 and R phantom each represent a hydrogen atom, an alkyl group or an aryl group. s/ , 92 93 However, R , R , R , R , R", R"',
S ff f7 60
It is R , R , R , R ,
At least one of R and R is bonded to a polymerizable group. General formula [VI] In the formula, R1'. is a hydrogen atom, an acyl group, a carbamoyl group,
Represents an aliphatic group or an aryl group. 1o1 1al R , R and R″3 are each hydrogen atom, halogen atom, alkyl group, aryl group, acyl group, sulfonyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, amino group, alkylamino group, carbamoyl group, arylamino group, hydroxy group, cyam L acylamino group, sulfamoyl group, sulfonamide group, acyloxy group or oxycarbonyl group. )oo HOt IOYR ,R
, R and R″3 are bonded to a polymerizable group. General formulas [II], [II[a], [II[b], [
■The aliphatic groups represented by R1 and R2' in [V] and [VI] may be saturated or unsaturated, preferably have 1 to 10 carbon atoms, and may have a substituent. , specifically unsubstituted alkyl groups such as methyl, ethyl, n-pentyl, isohexyl, 2-hydroxypropyl, benzyl, phenethyl, ethoxycarbonylethyl, methoxyethoxyethyl, 2,3.3-tetrafluoropropyl, allyl The following groups are mentioned. R1 and R
Examples of the aryl group represented by :' include phenyl, p-
Examples include various groups such as tolyl. The aliphatic group represented by R10o may be saturated or unsaturated, preferably a straight, branched or cyclic group having 1 to 10 carbon atoms, and may have a substituent, specifically methyl- Examples of aryl groups include unsubstituted alkyl groups such as ethyl, 2-ethylhexyl, and cyclohexyl; 2-hydroxypropyl, benzyl, ethoxycarbonylethyl, and allyl; examples of aryl groups include phenyl, tolyl, and other groups; Examples of the group include acetyl, benzoyl, and the like, and carbamoyl groups include methylcarbamoyl, dimethylcarbamoyl, and the like. R2, R3, R4, R5, R6, R', Ra, z2.
Sword 3 R9, RIO, Rli, R+2, R, R, R, R2'
, R1/7, R2J', R29, R3 (J and R
The aliphatic group represented by 3' is an alkyl group having 1 to 2 carbon atoms, and may have a substituent. Specifically, methyl, ethyl, °C-butyl, 2-ethylhexyl, 5
Examples include unsubstituted groups such as ec-dodecyl, and groups such as hydroxyethyl, benzyl, carbamoylmethyl, methoxyethyl, and furyl. Examples of the aryl group include phenyl, p-tolyl, I-aminophenyl, p-methoxyphenyl, p-dodecyloxyphenyl, -monoethoxylponylphenyl, and the like. Examples of the ring formed by connecting R9 and R10, R11 and R12, R2J' and R2, and R30 and R31 include rings such as morpholine, piperidine, and bi-Olysine. The benzene ring and naphthalene ring formed by connecting R22 and R23 may have a substituent, and examples of the substituent include methyl, fluorine, chlorine, methoxy, phenyl, carbamoylrboxy, hydroxy, and phenyloxy. The following groups are mentioned. Examples of the alkyl group represented by R, R and R5'7 include methyl, ethyl, benzyl and the like. Examples of the aryl group represented by R5' and R include groups such as phenyl and p-tolyl. R", R battle, R sticky, Rq, R Shu, R Ai(~R",
Examples of the halogen atoms represented by R, R, R, and R'3 include fluorine, chlorine, and bromine atoms, and examples of alkyl groups include methyl, ethyl, n-propyl, Examples of aryl groups include phenyl, tolyl, mesityl, and chlorophenyl; examples of alkoxy groups include methoxy, Groups such as ethoxy, octyloxy, 2-ethylhexyloxy, and methoxyethoxy; examples of aryloxy groups include phenoxy and 4-methylphenoxy; examples of alkylthio groups include methylthio and propylthio; Examples of arylthio groups include phenylthio groups; examples of alkylamino groups include methylamine, dimethylamino, ethylamine, benzylamino, diallylamino, and cyanoethylamino; examples of arylamino groups include anilino, anisidine, toluidino, Examples of groups such as diphenylamino and acylamino groups include acetylamino,
Groups such as benzoylamino, examples of carbamoyl groups include methylcarbamoylnzoyl, examples of sulfonyl groups include methylsulfonyl and phenylsulfonyl, examples of sulfamoyl groups include ethylsulfamoyl and dimethyl. Examples of sulfamoyl groups include methanesulfonamide and benzenesulfonamide groups; examples of acyloxy groups include acetoxy and benzoyloxy; examples of oxycarbonyl groups include methoxy. Examples include carbonyl, ethoxycarbonyl, phenoxycarbonyl and other groups. R'' and R42, Rq and R44, Rq and R, Ken' and Ra
2, Ra3 and R outside, RS″ and R anchor, R7 and R″2, R″
Groups formed by linking 9 and R2O, and Rtl and R2, include methylenedioxy, tetramethylene, trimethylene, and the like. The 5- or 6-membered acidic keto ring formed by zl and Z2 includes a 1,3-indanedione nucleus, a barbylic acid group (
For example, barbylic acid, 1-phenylbarbylic acid,
1-methyl-3-octylbarbic acid, etc.), 2-
Thiobarbylic acid nuclei (e.g. 2-thiobarbyric acid, 1-ethyl-3-decyl-2-thioparturic acid, etc.), cyclohexane-1,3-dione nuclei (e.g. dimethone-5,5-diethylcyclohexane-1,3- ion), 2,4-diaza-1-alkoxy-3,5-
Dioxocyclohexene nucleus (e.g. 2,4-diaza-1
-ethoxy-4-[3-(2°4-di-tert-amylphenoxy)propyl]-3,5-dioxocyclohexene, etc.), 2,4-thiazolidinedione nuclei (e.g., 3
-Phenyl-2゜4-thiazolidinedione, 3-2-
hydroxyethyl)-2,4-thiazolidinedione, 3
-amino-2,4-thiazolidinedione), 2-iminothiazolidin-4-one nucleus (e.g. 2-phenyliminothiazolidin-4-one, 3-)-2-decyliminothiazolidin-4-one, 3 -ethyl-2-[
2° 4-oxazolidinedione nucleus (e.g. 3-ethyl-2,4-oxazolidinedione, 3-phenyl-2
, 4-oxazolidinedione, etc.), 2-iminooxazolidin-4-one nuclei such as 3-ethyl-2-iminooxazolidin-4-one, 3-phenyl-2-ethyliminooxazolidin-4-one, 3-ethyl- 2-Phenyliminooxazolidin-4-one, 3-ethyl-
2-[3-(2,4-di-tert-amylphenoxy)propylimino]oxazolidin-4-one, etc.),
2-Imituimidazolidin-4-one nucleus (e.g. 2-imino-1,3-diethylimidazolidin-4-one, 2
-decylimino-1-ethyl-3-phenylimidazolidin-4-one, 2-phenylimino-1-phenyl-
3-cyclohexylimidazolidin-4-one, 1,3
-diethyl-2-[3-(2,4-di-tert-amylphenoxy)propylimino]imidazolidine-4-
), isoxazolone nuclei (for example, 3-phenyl-5-isoxacilone, 3-methyl-5-isoxacilone, etc.). -+"l:i"' General formula [VI] In the formula, R/71 and R/') are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, a rhohexyl group, a cyclohexyl group, n-dodecyl group, eicosyl group, methoxyethyl group, ethoxypropyl group, 2-ethylhexyl group, hydroxyethyl group, chloropropyl group, N,N-diethylaminepropyl group, cyanoethyl group, benzyl group, p-butylphenethyl group , p-t-
Octylphenoxyethyl group, 3-(2,4-di
-amylphenoxy)propyl group, ethoxycarbonylmethyl group, 2-(2-hydroxyethoxy)ethyl group,
(2-furylethyl group, etc.), or an aryl M having 6 to 20 carbon atoms (for example, tolyl group, anisyl group, mesityl group, chlorophenyl group, 2,4-di-t-amylphenyl group, naphthyl group, etc.) Furthermore, R/71 and Rqz do not represent a hydrogen atom at the same time. Furthermore, R'71 and R
9U is bonded to form a cyclic amine group (e.g. piperidino group,
morpholim L-pyrrolidino group, hexahydrozevime L-piperazino group, etc.). R, 7, 3 is Siam L-G OOR, 75-1-CON HR, 3, -CO
R? f, or -5O2R/; Da, R/7+ is a cyano group, -GOOR,, -CONHR, <, -C
ORri7 or -8O2Rri4 represents R and R, respectively, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
or represents an aryl group having 6 to 20 carbon atoms,
Or, it has the same meaning as the alkyl group or aryl group represented by R/72. Furthermore, R43 and Rr)1 are combined to form a 1,3-dioxocyclohexane ring (for example, dimedone, 1,3-dioxo-5,5-diethylcyclohexane, etc.), 1.3
-Diaza-2,4,6-drioxocyclohexane ring (
For example, barbylic acid, gophenylbarbylic acid,
1-methyl-3-octylbarbylic acid, 1-ethyl-3-octyloxycarbonylethylpalgoturic acid, etc.), 1°2-diaza-3,5-dioxocyclopentane ring (e.g. 1.2 -Diaza-1,2-dimethyl-3゜5-dioxocyclopentane, 1,2-diaza-1,2
-diphenyl-3,5-dioxocyclopentane, etc.),
or 2,4-diaza-1-alkoxy-3,5-dioxocyclohexene ring (e.g., 2,4-diaza-1-ethoxy-4-[3-(2°4-di[-amylphenoxy)propyl]) -3°5-dioxocyclohexene, etc.). Furthermore, R'71, R'7m, R/73, and R
/7% at least one is bonded to a polymerizable group. In the general formula [■], preferably Rql and R/72 each represent an alkyl group having 1 to 20 carbon atoms, particularly 1 to 6 carbon atoms,
R'73 represents a cyano group or -8O2R/7.5- (especially -8O2RQ5-), and R4p represents a cyano group or -〇〇〇R (especially -GOOR bullet). Rg and 87g are each an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms (particularly preferably R5 is
Phenyl group (e.g. phenyl group, tolyl group, etc.), RQ4
represents an alkyl group having 1 to 20 carbon atoms. General formula [■] In the formula, R? I, Rql, Ry3, R explosion and R?
, respectively represent a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, etc.), an alkyl group having 1 to 2 carbon atoms (e.g. methyl group, isopropyl group, [-butyl group, t-amyl group,
n-octyl group, ethoxypropyl group, hydroxyethyl group, chloropropyl group, benzyl group, cyanoethyl group, etc.), aryl group having 6 to 20 carbon atoms (e.g., phenyl group, tolyl group, mesityl group, chlorophenyl group, etc.), Alkoxy groups having 1 to 20 carbon atoms (e.g., ethoxy, octyloxy, 2-ethylhexyloxy, methoxyethoxy, aryloxy groups having 6 to 20 carbon atoms)
For example, phenoxy group, 4-methylphenoxy group, etc.),
Alkylthio groups having 1 to 20 carbon atoms (e.g., methylthio group, n-octylthio group, etc.), arylthio groups having 6 to 20 carbon atoms (e.g., phenylthio group, etc.), AMILL alkylamino groups having 1 to 20 carbon atoms (e.g., methylamino group, benzylamino group, diethylamino group, etc.), carbon number 6
~20 arylamino groups (e.g., anilino group, diphenylamino group, anisidino group, toluidino group, etc.), hydroxy group, Cia/JJ, nitro group, acylamino group (
For example, acetylamine group, etc.), carbamoyl group (e.g., methylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfonyl group (e.g., methylsulfonyl group, phenylsulfonyl group, etc.), sulfamoyl group (e.g., ethylsulfamoyl group, dimethylsulfonyl group, etc.), famoyl group, etc.),
represents a sulfonamide group (e.g., methanesulfonamide group, etc.), an acyloxy group (e.g., acetoxy group, benzoyloxy group, etc.), or an oxycarbonyl group (e.g., ethoxycarbonyl group, phenoxycarbonyl group, etc.), and RPV and R92, , R9: L and Rc! 3.Rc,
3 and "ts or R? (, and Ryr is ring closed and 5 or 6
May form a membered ring (for example, methylenedioxy group, etc.)
. Rqt is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (e.g., methyl group, isopropyl group, n-butyl group, n-
octyl group, etc.). R'7'7 is a cyano group, -C
OOt%7, -〇〇NHR? 9, -COR? g, or -802RQ, R9? is Siam L-COOR
,,,-CONHR? o1-COR? , also SO2R7
Represents ao, R? 9 and R'? O represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 2 o carbon atoms, respectively. Furthermore, R91, R92, R93, R94, R? ,5”SR
? g,Re,'7,R? At least one of r is bonded to a polymerizable group. Preferably R97, RzZ, R? 3.R
q- and R9,5- are each a hydrogen atom, a halogen atom,
Alkyl group with 1 to 2 carbon atoms, aryl group with 6 to 20 carbon atoms, alkoxy group with 1 to 20 carbon atoms, 6 to 20 carbon atoms
aryloxy group, alkylamino group having 1 to 20 carbon atoms, arylamino group having 6 to 20 carbon atoms, hydroxy group, acylamino group, carbamoyl group, acyloxy group,
Represents an oxycarbonyl group, R1, and R? l, R92
and R? 3. R93 and R9q or Rd and R9s may be ring-closed. R9, represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R? Riha Siam L-COOR? ,
-CONHR? ? , -COROR fu or-
8O2R99, R7F is a cyano group, -COOR
-CON HR,. , -COR? 0, 90 again ・Has-S○2R? , and Ry7 and R? , respectively represent an alkyl group having 1 to 20 carbon atoms and a 7-aryl group having 6 to 20 carbon atoms. More preferably, R, , R, , □, R9 and R each represent a hydrogen atom, and R93 is a hydrogen atom or has 1 to 1 carbon atoms.
5 represents an alkyl group, R9g is a hydrogen atom, R? /7
represents a cyano group, R represents 10 0 OR, and R9
o represents an alkylene group having 1 to 20 carbon atoms, and is bonded to a polymerizable group. General formula [rX] In the formula, R to R are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, an amino group,
alkylamino group, arylamine group, hydroxy group,
Cyam L acylamino group, carbamoyl group, acyl group,
Sulfonyl group, sulfamoyl group, sulfonamide group,
Represents an acyloxy group or an oxycarbonyl group, R/
j and RIQ represent a hydrogen atom, an alkyl group or a phenyl group, R 4 represents a hydrogen atom or a phenyl group, and RJ'
At least one of /~Rr6 is bonded to a polymerizable group. Examples of halogen atoms represented by 821 to 81% include fluorine, chlorine, bromine, etc. Examples of alkyl groups include methyl, ethyl, n-propyl, methoxyethyl, hydroxyethyl, chloropropyl, benzyl, Examples of aryl groups include phenyl, tolylmesityl, and chlorophenyl; examples of alkoxy groups include Sat methoxy, ethoxy, octyloxy, 2-ethylhexyloxy, and methoxyethoxy. Examples of aryloxy groups include phenoxy and 4-methylphenoxy; examples of alkylthio groups include methylthio and propylthio; examples of arylthio groups include phenylthio and alkylamine groups. Examples include methylamine, dimethylamino, ethylamino, benzylamino, diacrylamino, cyanoethylamino, etc. Examples of arylamino groups include anilino, anisidine, toluidino, diphenylamino, etc. Examples of acylamino groups Examples include acetylamine, benzoylamino and other groups,
Examples of carbamoyl groups include methylcarbamoyl and dimethylcarbamoyl; examples of acyl groups include acetyl and benzoyl; examples of sulfonyl groups include methylsulfonyl and phenylsulfonyl; and examples of sulfamoyl groups. Examples of sulfonamide groups include methanesulfonamide, benzenesulfonamide, etc. Examples of acyloxy groups include acetoxy, benzoyloxy, and oxy groups. Examples of carbonyl groups include methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl and the like. The polymer of the present invention may be a homopolymer of a monomer having an ultraviolet absorbing group, a copolymer of two or more of the monomers, or a copolymer of the monomer and a monomer having no ultraviolet absorbing group. It may also be a copolymer with In the case of a copolymer, examples of the comonomer having no ultraviolet absorbing group include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (preferably esters derived from acrylic acids such as methacrylic acid), Lower alkyl esters and amides such as acrylamide, methacrylamide, °C-butylacrylamide, methyl acrylate, methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and lauryl methacrylate, methylenebisacrylamide, etc.), vinyl esters ( (e.g. vinyl acetate and vinyl laurate, etc.), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, e.g. vinyltoluene, divinylbenzene, vinylacetophenone, sulfostyrene and styrene sulfinic acid, etc.), itaconic acid, citraconic acid , crotonic acid, vinylidene chloride, vinyl alkyl ether (such as vinyl ethyl ether), maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinyl and lysine, and the like. Among these, acrylic esters, methacrylic esters, and aromatic vinyl compounds are particularly preferred. Two or more of the above comonomer compounds can also be used together. Specific examples of the monomer represented by the general formula CI] of the present invention are shown below. Below-Yoshi'o)・c-OcocJ's Q-low
−= ~=−tJ −
IJ - (Jhei = 111Q ~ ~ 0
C) 1 engineering. . Q~
~
N low - to
So F3 (J ■ So So's ef3
(2) CH3 Specific examples of the polymer of the present invention are shown below. Exemplary polymers P-1 to P-38: Exemplary monomers [1 body 1 to 38 (7) *Mo,
j? Remer copolymer monomer charge molar ratio P-3
9 Exemplary *Assembly-1: MMA 8:2P-40 Exemplary monomer-3: MMA 5:5P-41 Exemplary monomer-4
:VA:BA 7:1:2 P-42 Exemplary Monomer-8:BA 6:4P-43
Exemplary monomer-11: BA 5:5P-44 Exemplary monomer-12: MMA 7:3P-45 Exemplary monomer-13
:ST:APS6: 3.9: 0. IP-46 example”1il14A-17:EA 7:3
P-47 Exemplary Monomer-18:BA 7:3P-48
Exemplary monomer-19: MMA 6:4P-49 Exemplary monomer-21: VA:ST6:2:2 P-50 Exemplary monomer-23: MMA A: 3P-51
Exemplary monomer-24:BA:MA8:1:1 P-52F/A monomer-26:ST:BA5:4:1 P-53 example monomer-27:MMA 5:5P-54
Exemplary monomer-30: BA 7: 3P-55 Exemplary single door body-32: VA: AA7: 2.9: 0. I P-56 Exemplary Monomer-342B△:AAM7:2:1 P-57 Exemplary Monomer-37:MMA 6:4P-58
Just an example! ! 1 body-38: BA 5:5 MMA-methyl methacrylate, VA-vinyl acetate, BA-n-butyl acrylate, ST-styrene, APS-2-acrylamido-1-propanesulfone MNa 5EA-ethyl acrylate MA-methyl acrylate , AA-acrylic acid, AAM-acrylamide Specific synthesis examples are shown below. Synthesis Example 1 Synthesis of Exemplary 11jtk Form-1 3-Anilinoacroleinanil (29g) and ethylphenylsulfonylacetate (30g) Fjll vinegar! ! (30d) in T85-90"C1,: Heat for 2 hours. Remove acetic anhydride under reduced pressure, add 200 g of ethyl alcohol and ethyl hydroxyethylamine (12 o), and reflux. After the reaction,
Pour into ice water and filter the precipitate. This compound 309 and pyridine 71Q were mixed with 1 acetonitrile.
001ρ, and 709 was added dropwise under 20'Cg. After the dropwise addition was completed, the reaction was allowed to proceed for 1 hour, and acetonitrile was removed, followed by separation and purification by column chromatography to obtain oily target product 25Q. I R, NMRTi [Shi? =. Synthesis Example-2 Synthesis of Exemplary Single Portion-8 *CH2SO2CH2CH2CI! 50g was dissolved in 5001λ of tetrahydrofuran, and 50q of 10% sodium hydroxide was slowly added dropwise thereto while maintaining the temperature at 0 to 5°C. After the dropwise addition was completed, the reaction was continued for another 2 hours, and the resulting salt was a1
Drain and place in ice water. After extraction with ethyl acetate, the precipitated crystals were recrystallized from ethanol to obtain 170 of the desired product. The structure was confirmed by IR and NMR. Synthesis Example 3 Illustrated monomer 12 was dissolved in a 600 ml solution and refluxed. 55 g of ethylene iodide was dropped into this over 2 hours. After the dropwise addition, the reaction was continued for 6 hours and then cooled to air temperature. Add this and reflux again. After 5 hours of reaction, acetonitrile was distilled off, cooled to 60°C, methanol 6001g1 isopropanol 30g
Add and dissolve 0112. Cool with water, cause crystallization, and collect the precipitate by filtration. Add 40g of CH2CH20COCH2ON and 2g of hydroquinone to 131g of triethylamine dissolved in acetonitrile 6501fi, and add anhydrous vinegar'v11 to this mixture.
Add 33g at 50°C. After the dropwise addition, the mixture was refluxed for 2 hours and cooled to temperature V to form a precipitate. This precipitate was recrystallized from acetonitrile, and the target product 25
I got o. The structure was confirmed by IR and NMR. Synthesis Example 4 Synthesis of Exemplified Monomer-17 20g of 2-methoxyethanol was dissolved in 0.59% of hydroquinone monomethyl ether to 100% of 2-methoxyethanol. Reflux in I2 and add methylamine 112. After 1 hour of rapid flow, it was cooled to air temperature and the resulting precipitate was recrystallized from ether.
Five desired objects were obtained. The structure was confirmed by IR and NMR. Synthesis Example 5 Synthesis of Exemplified Monomer-21*-328 g of C6HI is dissolved in 400 tJ2 of acetonitrile in which 0.59 J of hydroquinone monomethyl ether and 131 J of triethylamine are dissolved, and the mixture is refluxed for 2 hours. After the reaction, it is cooled to V temperature. The resulting crystals were recrystallized from acetonitrile to obtain the target compound 10(+. The structure was confirmed by IRSNMR. Synthesis Example 6 Synthesis of Exemplified Monomer-23 30 g of 4-hydroxybenzaldehyde, ethyl cyanacetate 32 g of ester, 51 f; 1 of acetic acid, and 2 Q of ammonium acetate are refluxed in 1001 ρ of ethanol for 4 hours. After the reaction is complete, a precipitate is formed when the reaction solution is poured into water. This precipitate is collected by filtration, and 4 g of pyridine, The mixture was dissolved in 100 d of tetrahydrofuran, and after dropping N HCH2CH2C1 , the temperature was raised to 30°C and reacted for 1 hour.The reaction solution was poured into ice water to cause crystallization, and the obtained crystals were recrystallized from methanol to obtain the desired product. Synthesis Example 7 Synthesis of Exemplified Monomer-27 Dissolve in Dorofuran 300 xi and keep at 0 to 5°C. 20 g of triethylamine is slowly added dropwise there. After completion of the dropwise addition, the reaction is continued for another 2 hours, and the resulting salt is passed through. Tetrahydrofuran was distilled off from the filtrate under reduced pressure, and the obtained crystals were recrystallized from ethanol to obtain 62 g of the target product. After dropping CH2=CH NHCOCH2CH2C1 while keeping it at 0-5℃, it is heated to the lowest temperature and reacted for 2 hours.After the reaction is completed,
Filter the resulting salt and pour the filtrate into ice water. After extraction with ethyl acetate and evaporation of ethyl acetate under reduced pressure, the obtained crystals were recrystallized from methanol to obtain target compound 12a. The structure was confirmed by IR and NMR. Synthesis Example-9 Synthesis of Polymer P-1*-CH2CH2CH2SO3Na 10(1(050
01g aqueous solution was heated at 80°C while deoxidizing it through a nitrogen stream.
Heat until. 350 mg of potassium persulfate is added to this aqueous solution.
A 20N aqueous solution of was added. Next, exemplified monomer-1509
was dissolved in 200 d of ethanol and added. After the addition, stirring was continued for 1 hour, and 150 mg of potassium persulfate was added.
0- Add aqueous solution and react for 1 hour. After the reaction was completed, ethanol was distilled off as an azeotrope of water, the pH was adjusted to 6.0 with 0.1N sodium hydroxide, and the mixture was filtered. The polymer concentration of the latex was 8.2%. Synthesis Example-10 Synthesis of Polymer P-12 Exemplified Monomer-1 in place of Exemplified Monomer-1 of Synthesis Example-9
The desired product was obtained in the same manner as Synthesis Example 9 except that 2 was used. The polymer concentration of the latex was 8.1%. Synthesis Example-11 Synthesis of Polymer P-46 10g of sodium dodecylbenzenesulfonate 5001R
The aqueous solution is heated to 80° C. while being deoxidized through a nitrogen stream. To this aqueous solution, add 350mg of potassium perIIIate.
2012 aqueous solution was added. Next, 45 g of Exemplified Monomer-17 and 5 g of ethyl acrylate were added to 150 d of ethanol.
The mixture was dissolved by heating and added. Rough stirring was continued for 1 hour after the addition, 250 mg of potassium persulfate in 101ρ aqueous solution was added, and after further reaction for 1 hour, ethanol and unreacted monomers were distilled off as an azeotrope of water. TA the I)H to 6.0 with IN sodium hydroxide! ! I..., after...
It's passed. The polymer concentration of the latex was 7.8%, and the exemplified monomer-1
The content of 7 units was 69 mol%. Synthesis Example-12 Synthesis of Polymer P-48 Synthesis Example except that 45 g of Exemplified Monomer-17 in Synthesis Example-11 was replaced with 80 g of Exemplified Monomer-19, and ethyl acrylate 59 was changed to 10 g of methyl methacrylate. Synthesized in the same manner as -11. Latex polymer concentration 12.3%, Exemplary monomer-19
The content of units of 58 mol%. Synthesis Example-13 Synthesis of Polymer P-50 In place of 459 exemplified monomer-17 in Synthesis Example-11, 8
0 g of Exemplified Monomer-23 was synthesized in the same manner as Synthesis Example-11 except that 9.50 g of methyl methacrylate was used instead of 5 g of ethyl acrylate. The polymer concentration of the latex was 15%, and the content of exemplified monomer units was 170 mol%. Synthesis Example-14!1 Synthesis of Coalescence-57 Synthesis Example-11 45 (50g of Exemplified Monomer-37 was used instead of Exemplified Monomer-17 of 59, 1og of ethyl acrylate was used instead of 59 of Synthesis was carried out in the same manner as in Synthesis Example 11 except that methyl methacrylate was used. The polymer concentration of the latex was 7.3%, and the content of exemplified single units was 59 mol%. Synthesis Example 15 Synthesis of combined P-42 50 g of exemplified monomer-8 and n-butyl acrylate 10
g was dissolved in 1501 fl of dioxane and heated under a nitrogen stream for 70 min.
2,2 dissolved in dioxane with stirring at ℃
'-Azobis〈2,4-dimethylvaleronitrile)
After adding 27011 g, the reaction was continued for 4 hours. After the reaction was completed, the reaction solution was cooled to air temperature, poured into 2 L of ice water, and the precipitated solid was collected by filtration. This solid was a polymer containing 58 mole percent units of the exemplified monomer. A latex was produced using this polymer as follows. Polymer 59 is dissolved in ethyl acetate 2011 at 38° C. and a 70% by weight methanol solution of sodium dodecylbenzenesulfonate is added. Next, this was mixed with a 10 weight 1% aqueous solution 70a of gelatin and dispersed using a double cylindrical disperser, and then ethyl acetate and methanol were distilled off under reduced pressure to prepare a latex. Synthesis Example-16 Synthesis of Polymer P-51 In place of 50 g of Exemplified Monomer-8 in Synthesis Example-15, 50 g of Exemplified Monomer-24 was added, and in place of n-butyl acrylate of 109, 5 g of Exemplified Monomer-24 was added. Synthesis example except that lobe tyl acrylate and 4g of methyl acrylate were used.
Synthesis was performed in the same manner as No. 15, and latex was further made. The content of units of Exemplary Monomer-24 in the polymer is 77 mol%
Met. Synthesis Example-17 Synthesis of Polymer P-27 Illustrative monomers-8 and 10 of 5(l) in Synthesis Example-15
Synthesis was carried out in the same manner as in Synthesis Example 15 except that only exemplified monomer 27 of 509 was used instead of n-butyl acrylate of i11, and a latex was also produced. Synthesis Example-18 Synthesis of Polymer P-48 (core-shell type) Sodium salt of oleyl methyl tauride 159-11
The aqueous solution was heated to 80° C. while being deoxidized through an N air current. Add 250 mg of potassium persulfate to this aqueous solution.
Add 1 g of aqueous solution, then 5 g of methyl methacrylate, and react for 1 hour. Ethanol 2001β in which 80 g of Exemplary Monomer-19 and 10 g of methyl methacrylate were dissolved was added to this latex, and then an aqueous solution of 20112 containing 300 mg of potassium persulfate was added, and after further reaction for 1 hour, potassium persulfate 20 (lag of 20 After 1 hour of reaction, ethanol and unreacted monomers were distilled off as an azeotrope of water, the pH was adjusted to 6.0 with 0.0000000000000 sodium hydroxide, and the mixture was filtered. The combined concentration was 8.2%, and the content of exemplified monomer units was 64 mol%. The polymer of the present invention is preferably added as a latex in the silver halide photographic light-sensitive material. Latex In order to add the above polymer as an emulsion polymerization method, the above polymer may be polymerized by an emulsion polymerization method, or a lipophilic polymer obtained by another polymerization method may be dissolved in an RFg medium and dispersed in a latex form in an aqueous gelatin solution. Examples of initiators and their effects can be found in F. A. Bovey, “Emulsion polymers”.
tianJ l ntersciencePubl
ishes I nc New York Published 1
955, pp. 59-93. As the emulsifier used in emulsion polymerization, a compound having surface activity is used, and preferred examples include soaps, sulfonates, sulfates, cationic compounds, amphoteric compounds, and polymeric protective colloids. Examples of these groups and their effects can be found in Belgische Chemi
Scheindustrie Vol. 28, pp. 16-20 (1963). - When dispersing the polymer of Rikiki's invention in the form of a latex in an aqueous gelatin solution, the organic solvent used to dissolve the polymer of the invention may be used before or (less preferably) after coating the dispersion. It is removed during evaporation during drying of the liquid. The proportion of the monomer having an ultraviolet absorber moiety in the polymer of the present invention is generally preferably 5 to 100% by weight, but 35 to 100% by weight is particularly preferable from the viewpoint of film thickness and stability. The polymer of the present invention is used by being added to a hydrophilic colloid layer such as a surface protective layer, an intermediate layer, or a silver halide emulsion layer of a silver halide photographic light-sensitive material. Preferably, it is used in the sex colloid layer. There are no particular restrictions on the use of the polymer of the present invention, but 1
10-3000 mg per square meter, especially 50-20
Preferably it is QOmg. Examples of the silver halide photographic material of the present invention include color negative films, color reversal films, and diffusion transfer method sensitive materials. In the silver halide emulsion used in the light-sensitive material of the present invention, any silver halide used in ordinary silver halide emulsions, such as silver iodobromide and silver halide, can be used. The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method. The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer. 1 m may be a particle that is mainly formed on the surface, or a particle that is mainly formed inside the particle. Further, it may have a regular crystal shape, or it may have an irregular crystal shape such as a spherical shape or a plate shape. Also, any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in combination. or,
A polydisperse emulsion and a monodisperse emulsion may be mixed and used. The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions. The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye. The sensitizing dyes may be used alone or in combination of two or more. Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion. The emulsion layer and other hydrophilic colloid layers can be imitated, and can also contain a plasticizer and a dispersion (latex) of a water-insoluble or M-soluble synthetic polymer. Light-sensitive material for color photography A coupler is used in the emulsion layer of the emulsion layer.The coupler is usually selected so that a dye is formed for each emulsion layer that absorbs light in the light-sensitive spectrum of the emulsion layer. A yellow coupler is used in the green-sensitive emulsion layer, a magenta coupler is used in the green-sensitive emulsion layer, and a cyan coupler is used in the red-sensitive emulsion layer.However, depending on the purpose, silver halide color photographic light-sensitive materials may be produced using different combinations from the above. These couplers may be either 4- or 2- or 3-functional.The couplers include a colored coupler that has a color correction effect and a development inhibitor by coupling with an oxidized form of a developing agent. Development accelerator, bleaching accelerator, developing agent, silver halide solvent, toning agent, hardener, fogging agent, antifogging agent,
Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers, and desensitizers are included. A coupling reaction is carried out with the oxidized product of the aromatic primary amine developer, but a colorless coupler (also referred to as an 8-coupler coupler) that does not form a dye can also be used in combination. As the yellow coupler, known acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. As the magenta coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used. As the cyan coupler, phenol or naphthol couplers are generally used. Among couplers, DiR compounds, image stabilizers, optical brighteners, etc. that do not require handling on the silver halide crystal surface, dispersion of hydrophobic compounds can be performed using the solid dispersion method, latex dispersion method, or oil-in-water emulsion fraction method. Various methods can be used, such as, and can be appropriately selected depending on the chemical structure of the hydrophobic compound. In addition, when it has an acid group, it can also be introduced into the hydrophilic colloid as an alkaline aqueous solution. A color antifogging agent can be used to prevent the oxidized product of the developing agent or the electron transfer agent from moving through the living room, causing color turbidity, deterioration of sharpness, and noticeable graininess. The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer. The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. In these layers and/or in the emulsion layer, 5
Dyes that are leached or bleached from the optical material may be included. A formalin scavenger-1 optical brightener, a matting agent, a lubricant, an image stabilizer, a surfactant, a development accelerator, a development retardant, and a bleach accelerator can be added to the photosensitive material. As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, Sanzuya cellulose, etc. can be used. In order to obtain a black and white image using the photosensitive material of the present invention, a developing step, a fixing step and/or a stabilizing step may be performed.
After exposure, color photographic processing is performed to obtain a dye image. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. In addition, a bleach-fixing process can be performed using a one-bath bleach-fixing solution, or a monobath processing process using a one-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be performed in one bath. You can also do In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development treatment step, an activator treatment step may be performed in which a color development agent or its precursor is contained in the material and the development treatment is performed using an activator solution, or an activator treatment step may be performed in which the color development agent or its precursor is contained in the material and the development treatment is performed using an activator solution. Processing can be applied. [Example 1] Next, examples of the present invention will be shown, but the present invention is not limited thereto. Example 1 A green-sensitive emulsion layer and a protective layer having the following composition were simultaneously coated on a cellulose triacetate transparent base and dried to prepare a sample. First layer: green-sensitive emulsion layer A green-sensitive silver iodobromide emulsion containing 7 mol % of silver iodide and having an average grain size of 12 μm was prepared. Then, per mole of silver halide, 1-(2,4,6-trichlorophenyl)-3 was added as magenta coupler.
-[3-<2.4-di~t-amylphenoxyacetamide)penzamide]-5-pyrazolone, 80 g, as a colored magenta coupler, 1-(2,4,6-trichlorophenyl)-4-(1- naphthylazo)-3-
Weigh out 2.5 g of (2-chloro-5-octadecenylsuccinimidoanilino)-5-lazolone, mix with 1201 g of tricresyl phosphate and 2401 g of ethyl acetate, and dissolve by heating. , then sodium triisopropylnaphthalene sulfonate 5Q and 7.5%
A coupler solution emulsified and dispersed in 550 g of an aqueous gelatin solution was added to the above emulsion. Furthermore, gelatin hardener is added to green-sensitive halogenated Wx.
A coating solution was prepared and applied to give a dry film thickness of 55μ. 2nd layer; Tamotsu:! Layer comparison Ultraviolet absorber and tricresyl phosphate as a high-boiling solvent were heated and dissolved in ethyl acetate (twice the weight of the combined weight of the ultraviolet absorber and tricresyl phosphate), containing sodium triisopropylnaphthalene sulfonate. After adding it to a gelatin solution and emulsifying and dispersing it in a colloid mill, ethyl acetate was removed by evaporation, and the mixture was coated and dried to prepare a comparative sample. On the other hand, a sample according to the present invention (see Table 1) was prepared by coating and drying a polymer UV absorber of the present invention in place of the comparative UV absorber and tricresyl phosphate.The amount of gelatin in the protective layer was as follows: The comparison sample and the sample according to the present invention were both 1QffiQ/100cj. One part of each sample was stored unexposed in an atmosphere of 55°C and 80% RH for 7 days, and then the surface condition 1 (oil ,
The state of appearance of crystals, etc.) was observed. Evaluation was performed in the following three stages. A Little or no appearance B Most appearance C High appearance After moistening the unexposed sample at 25°C and 20% RH for 6 hours at WAm, the emulsion side of the sample was rubbed with a neoprene rubber roller in AAV under the same air conditioning conditions. After sm, development, bleaching, fixing, washing, and stabilization were performed using the following processing solution, and the degree of static mark occurrence was examined. Processing process Temperature Processing time (1) Developer...38℃ 3 minutes 15 seconds (2) Floating
White...38℃ 4 minutes 30 seconds (3) Fixation...
38℃ 4 minutes 20 seconds (4) Washing with water...38℃
3 minutes and 15 seconds (5) Stabilization: 38°C, 1 minute and 05 seconds The compositions of the developer, bleach, fixing bath, and stabilizing bath are as follows. Developer (pH-10,05> Sulfuric acid and droxyamine 2.5g4-amino-3-methyl-N-(β-hydroxyethyl)aniline @acid 4.56Q diethylenetriaminohexaacetic acid 4.75gK2 CO330,
3Q Sodium sulfite 49 Add water to make 11. Bleach bath (1) H-5,70) Ammonium bromide 173980%
of acetic acid 201gEDTA
Fe NH4to3 Q EDTA 27g Add water to make 1. Fixing bath (1) H-6,50) Ammonium thiosulfate 8001 (1 Sodium sulfite 4.6 g Sodium bisulfite 5,09 Add water to make 11. Stabilizing bath (1) H-7,30) 40% formalin 6,6d50%
Polyoxyethylated uryl alcohol 0.6 - Add water to make 11. The degree of occurrence of static marks was evaluated on the following four levels A to D. A: No static marks are observed B: Some static marks are observed C: A considerable amount of static marks are observed D: Static marks are observed almost on the entire surface It is shown in Table 2. As shown in Table 2 below, the samples of the present invention are excellent in surface condition and static marks. Moreover, the sample of the present invention is
Further thinning (for example, for samples 13.19 and 25, gelatin aged 630/1001, for samples 14.15.
811(]/100c for 20.21 and 26
It was found that the sharpness of the image can be improved because there is no deterioration in performance in terms of surface condition and static marks even if the surface condition is reduced to Ii). Example 2 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a multicolor silver halide photographic material. 1st layer: Blue-sensitive silver halide emulsion layer α-pivaloyl-α-(2,4
-dioxo-1-benzylimidazolidin-3-yl)
-2-riO-5-[γ-(2゜4-di-t-amylphenoxy)butyramide]acetanilide at 6.81
tl/100i, blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to silver: 3.2+ag/100cm
, di-butyl phthalate 3.51/100ci,
And gelatin was coated in an amount of 13.511 iJ/100ci. 21st: Intermediate layer 2.5-G with 0.5f of octylhydroquinone
ll/100ai, 0.5B dibutyl phthalate
/ 100I:Ii and gelatin 9.0mg/10
31i: Green-sensitive halogenated limited emulsion layer 1-(2,4,6-dolichlorophenyl)-3-(2-chloro-5=tetradecane) was used as a magenta coupler. Amidoanilino)-5-pyrazolone 4.2mg/1
ooai, green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) converted to silver is 2.5 m Q / 100 ci
, dibutyl phthalate at 3.01 fJ/100aj
, and gelatin were coated at a ratio of 12.0 -/100 -. 4th layer: Interlayer UV absorber (Table 3), dibutyl phthalate, 2.
5-G (-octylhydroquinone (0,51Q/
100 cm ) and gelatin (t2.ou/100
−). (The contents of other materials are shown in Table 3.) 5th layer: Red-sensitive silver halide emulsion layer 2-[α-(2,4-di-1-pentylphenoxy)butanamide]-4°6 as cyan coupler -dichloro-5-ethylphenol at 4.2m9/1oOaj, red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) converted into silver at 3.0IQ/100ci, and tricresyl phosphate at 3.0IQ/100ci. .5H/100ci and gelatin at 11.
It was coated to give a ratio of 5mo/1ooCi. 6th layer: 2 intermediate layers gelatin (10 l (] / 100 ci), a layer containing ultraviolet absorber (Table 3) and dioctyl phthalate. (Other layers are shown in Table 3.) 7th layer: Protective layer gelatin was coated at 8.Oma/100cj.An appropriate amount of gelatin hardener was added to the protective layer.The sample test piece was kept unexposed at 55℃ and 80%R.
After being stored in an H atmosphere for 3 days, the surface condition was visually observed. The evaluation criteria are the same as in Table 3. Also, after conditioning the unexposed sample at 25°C and 20% RH for 6 hours, the emulsion side of the sample was rubbed with a neoprene rubber roller in a dark room under the same air conditioning conditions, and then developed with the following processing solution. After bleaching, fixing, washing and stabilization, the degree of static mark occurrence was examined. The evaluation criteria are the same as in Table 3. [Processing process]! I! Temperature Processing time Color development 33°C 3 minutes 30 seconds Bleach fixing 33
℃ Wash with water for 1 minute 30 seconds 33℃
3 divisions Drying 50-80℃ 2
The components of each treatment solution are as follows. [Color developer] Benzyl alcohol 12-diethylene glycol 10d potassium carbonate
25 g sodium bromide
0.6(]Anhydrous sodium sulfite
2.0g hydroxylamine sulfate
2.5 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate 4.5 g water was added to make the solution 12, and the pH was adjusted to 10.2 km with NaOH. [Bleach-fix solution] Ammonium 5A acid 120g Sodium metabisulfite 150 Anhydrous sodium sulfite 3g EDTA ferric ammonium salt 65g Add water to make 12, and adjust I)H to 6.7 to 6.8. The results are shown in Table 3. Table 3 shows that the samples of the present invention are superior to the comparative samples in terms of surface condition and degree of static mark occurrence. Furthermore, among the samples of the present invention, samples such as Samples 53 and 56, in which the sixth layer had an increased l added, were particularly good. Furthermore, for the samples of the present invention, it was also possible to make the ultraviolet absorber layer thinner. E. Effects of the present invention] As explained in detail above, by using the polymer of the present invention, it is possible to improve static marks and prevent deterioration of surface condition due to storage under harsh conditions. It becomes possible to make the film thinner. Patent applicant Roku Konishi Photo Industry Co., Ltd. Procedural amendment (spontaneous) December 3, 1985 Patent consultant No. 198527 2, Title of invention Silver halide photographic sensitization that prevents sweating phenomenon and static murf generation Material 38 Relationship with the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1
27) Konishi Roku Photo Industry Co., Ltd. Representative Director Keio Benko 4, Agent 102 Address 4-1 Kusho Kita, Chiyoda-ku, Tokyo @ No. 1 Kudan-Rosaka Building Telephone 263-9524 3. Invention of the Specification "Detailed explanation" column (- +7 + ' s "t' / - +86, Contents of amendment (amended as below). (1) Specification f The structural formula of compound 5 of formula 33 is amended as follows 8C-COOH (2) Specifications! The structural formula of compound 33 on page 41 is corrected as follows.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, which is derived from a repeating unit of a monomer represented by the following general formula [I]. A silver halide photographic material containing a polymer. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 are each a hydrogen atom and have a carbon number of 1
-4 represents an alkyl group, a halogen atom or a nitrile, and W represents a hydrogen atom or -COOR_4. X is an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, an arylene alkylene group having 7 to 15 carbon atoms, -O
-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, but when W is -COOR_4 -COO- or ▲mathematical formula,
There are chemical formulas, tables, etc. Represents ▼. Y is -O-, ▲Mathematical formula, chemical formula, table, etc.▼, -CO-, -S-, -SO-, -SO_2-, -SO_
Represents a divalent group having 0 to 12 carbon atoms and having at least one 3- or ▲, which has a mathematical formula, chemical formula, table, etc. R_3 is an alkyl group having 1 to 6 carbon atoms or 6 to 1 carbon atoms
R_4, R_5 and R_6 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Z represents a group of atoms necessary to form a ring containing at least one nitrogen atom. m is 0 or 1. However, when X is an arylene group, the number of carbon atoms in Y is not 1. Q represents an ultraviolet absorbing group. ]