# US 4,396,706 A · Silver halide photographic light-sensitive material and image forming method > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,396,706 A - Document ID: US4396706A - Status: Granted - Kind: A - Application number: 06/279,401 - Filed: 1981-07-01 - Granted: 1983-08-02 - Earliest claimed: 1980-07-01 - Assignees: Fuji Photo Film Co., Ltd. - Inventors: Tsumoru Ishii; Shinji Sakaguchi - Web page: https://patentgrep.com/patent/US4396706A ## CPC - G03C 5/26: Processes using silver-salt-containing photosensitive materials or agents therefor (physical development G03C5/58) - G03C 1/95: rendered opaque or writable, e.g. with inert particulate additives (G03C1/775 takes precedence) - Y10S 430/151: Matting or other surface reflectivity altering material - Y10S 430/162: Protective or antiabrasion layer - G03C: PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES (for photomechanical purposes G03F); PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY (photographic processes characterised by the use or manipulation of apparatus classifiable per se in subclass G03B, see G03B; photomechanical production of textured or patterned surfaces G03F; electrophotography, magnetography G03G) - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract A silver halide photographic light-sensitive material is described containing in its outermost layer a high molecular weight matting agent formed from at least one kind of alkali insoluble synthetic polymer grains having a glass transition point of at least 60.degree. C. and an average grain size of from 0.2 to 10, and said polymer is represented by the formula (I): --A).sub.x (B).sub.y (C).sub.z (I) wherein A represents a divalent group derived from at least one monomer having the formula (II); B represents a divalent group derived from at least one monomer having the formula (III), whose homopolymer has a glass transition point of at least 50.degree. C.; C represents a divalent group derived from an ethylenic unsaturated monomer other than A or B which is capable of copolymerizing with the monomers forming both A and B; x represents the fractional content of group A, which ranges from 0.005 to 0.20 mol/mol of polymer of formula (I); y represents the fractional content of group B, which ranges from 0.50 to 0.995 mol/mol of polymer of formula (I); and z represents the fractional content of group C, which ranges from 0 to 0.495 mol/mol of polymer of formula (I). Formula (II) and formula (III) are disclosed herein. These polymer grains are not removed from the outermost layer by rapid development-processing and exhibit a satisfactory matting effect even after the completion of such processing. ## Claims ### Claim 1 A silver halide photographic light-sensitive material which has on a support at least one light-sensitive silver halide emulsion layer, said material containing in its outermost layer at least one kind of alkali-insoluble synthetic polymer grains having a glass transition point of at least 60.degree. C. and an average grain size of from 0.2.mu. to 10.mu., and said polymer is represented by formula (I) --A).sub.x (B).sub.y (C).sub.z (I) wherein A represents a divalent group derived from at least one monomer having the formula (II); B represents a divalent group derived from at least one monomer having the formula (III), whose homopolymer has a glass transition point of at least 50.degree. C.; C represents a divalent group derived from an ethylenic unsaturated monomer other than A or B which is capable of copolymerizing with the monomers forming both A and B, said divalent group being derived from a member selected from the group consisting of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octylacrylate, tert-octyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, dimethylaminoethyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,3-dihydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, diethylene glycol monoacrylate, triethylene glycol monoacrylate, dipropylene glycol monoacrylate, glycerol monoacrylate, trimethylolethane monoacrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-isopropoxyethyl acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, .omega.-methoxypolyethylene glycol acrylate wherein the addition mol number of ethylene oxide groups is 9, .omega.-lauroxypolyethylene glycol acrylate wherein the addition mol number of ethylene oxide groups is 20, 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, 2-hydroxy-3-chloropropyl acrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N,N-diethylaminopropyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, glycerol monomethacrylate, trimethylolethane monomethacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-ethoxythyl methacrylate, 2-isopropoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy) ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, .omega.-methoxypolyethylene glycol methacrylate wherein the addition mol number of ethylene oxide groups is 6, .omega.-methoxypolyethylene glycol methacrylate wherein the addition mol number of ethylene oxide groups is 23, .omega.-lauroxypolyethylene glycol methacrylate, hexyl acrylamide, octyl acrylamide, 2-acrylamido-2-methylpropane-sulfonic acid, N-(1,1-dimethyl-3-oxobutyl)acrylamide, pentyl methacrylamide, dihexyl methacrylamide, allyl caproate, allyl caprate, allyl laurate, allyl palmitate, allyl stearate, allyl acetoacetate, allyl butyrate, allyloxyethanol, allyl butyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinylethyl butyrate, vinyl valerate, vinyl caproate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl acetoacetate, vinyl lactate, N-vinyloxazolidone, vinylpyridine, vinylpicoline, N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-triazole, N-vinyl-3,5-dimethyltriazole, N-vinyl, pyrrolidone, N-vinyl-3,5-dimethylpyrazole, N-vinylcarbazole, vinylthiophene, N-vinylsuccinimide, N-vinylglutarimide, N-vinylaldipimide, N-methyl-N-vinylformamide, N-ethyl-N-vinylformamide, N-methyl-N-vinylacetamide, N-ethyl-N-vinylacetamide, N-methyl-N-vinylpropionamide, N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-s-caprolactam, N-vinyl-2-pyridone, vinyl methyl ketone, methoxyethyl vinyl ketone, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 5-methyl-1-nonene, 5,5-dimethyl-1-octene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 5-methyl-1-hexene, 4-methyl-1-heptene, 5-methyl-1-heptene, 4,4-dimethyl-1-hexene, 5,5,6-trimethyl-1-heptene, 1-dodecene, 1-octadecene, dioctyl itaconate, dihexyl itaconate, dibutyl itaconate, maleic anhydride, dihexyl maleate, butyl hexyl maleate, dibutyl maleate, dioctyl maleate, dibutyl fumarate, and dioctyl fumarate; x represents the fractional content of group A, which ranges from 0.03 to less than 0.1 mol/mol of polymer of formula (I); y represents the fractional content of group B, which ranges from 0.50 to 0.97 mol/mol of polymer of formula (I); and z represents the fractional content of group C, which ranges from 0 to 0.47 mol/mol of polymer of formula (I), and formula (II) is represented by ##STR7## wherein X, Y and Z each represents hydrogen, an alkyl group having from 1 to 6 carbon atoms, --COR, or --COOR.sub.1 ; Q represents ##STR8## and R represents ##STR9## where R.sub.1 represents a substituted or an unsubstituted alkyl group having from 1 to 18 carbon atoms, an aryl group having from 6 to 18 carbon atoms, or an aralkyl group having from 7 to 12 carbon atoms; R.sub.2 represents hydrogen, a halogen atom, an alkyl group having from 1 to 12 carbon atoms or an alkoxy group having from 1 to 6 carbon atoms; R.sub.3 represents hydrogen, a substituted or an unsubstituted alkyl group having from 1 to 4 carbon atoms, a phenyl group or an aralkyl group having from 7 to 10 carbon atoms; R.sub.4 represents the same groups as R.sub.3 or an --R.sub.5 --CONH).sub.l R.sub.5 --COR.sub.7 group, wherein R.sub.5 represents a divalent aliphatic or an aromatic group (C.sub.1 -C.sub.12), R.sub.7 represents --OM, hydrogen, a substituted or an unsubstituted alkyl group (C.sub.1 -C.sub.4), a phenyl group or an aralkyl group (C.sub.7 -C.sub.10), and l is an integer of 0 to 6; M represents hydrogen or a cation; m is 0 or 1; and n is an integer of from 1 to 4; and formula (III) is represented by ##STR10## wherein D and E each represents hydrogen, a methyl group, a halogen atom, or --COOR.sub.6 ; G represents hydrogen, a methyl group, a halogen atom or --(CH.sub.2).sub.k --COOR.sub.6 ; J represents hydrogen, an aryl group, ##STR11## R.sub.6 represents a substituted or an unsubstituted alkyl group having from 1 to 10 carbon atoms, an aryl group having from 6 to 12 carbon atoms, or an aralkyl group having from 7 to 12 carbon atoms; and k is 0 or 1. ### Claim 2 (depends on 1) A silver halide photographic light-sensitive material as in claim 1, wherein said divalent group A is represented by the formula (II) wherein X, Y and Z each is hydrogen, a methyl group, or --COR, and Q is --(CH.sub.2).sub.m --. ### Claim 3 (depends on 1) A silver halide photographic light-sensitive material as in claim 1, wherein said formula (II) represents acrylic acid, methacrylic acid, maleic acid, itaconic acid or acryloylamino acid. ### Claim 4 (depends on 3) A silver halide photographic light-sensitive material as in claim 3, wherein said formula (II) represents acrylic acid or methacrylic acid. ### Claim 5 (depends on 1) A silver halide photographic light-sensitive material as in claim 1, wherein said monomer B is represented by the formula (III) wherein D and E each is hydrogen and G is a methyl group. ### Claim 6 (depends on 1) A silver halide photographic light-sensitive material as in claim 1, wherein said formula (III) represents a methacrylic acid ester or a styrene. ### Claim 7 (depends on 1) A silver halide photographic light-sensitive material as in claim 1, wherein said formula (II) represents acrylic acid or methacrylic acid, and said formula (III) represents a methacrylic acid ester or a styrene. ### Claim 8 (depends on 7) A silver halide photographic light-sensitive material as in claim 7, wherein z in said formula (I) is zero. ### Claim 9 (depends on 1, 2, 3, 4, 5, 6, 7) A silver halide photographic light-sensitive material as in claim 1, 2, 3, 4, 5, 6, 7, or 8, wherein said outermost layer is a surface protecting layer, and said polymer grains are coated in an amount of from 2 to 500 mg per square meter. ### Claim 10 (depends on 1, 2, 3, 4, 5, 6, 7) A silver halide photographic light-sensitive material as in claim 1, 2, 3, 4, 5, 6, 7, or 8, wherein the average grain diameter of the polymeric grains is from 1.mu. to 8.mu.. ### Claim 11 A method for forming photographic images comprising imagewise exposing and development-processing a silver halide photographic sensitive material wherein during said development-processing excess liquid is removed from the film material surface by squeezing means, wherein said silver halide photographic light-sensitive material has on a support at least one light-sensitive silver halide emulsion layer, said material containing in its outermost layer at least one kind of alkali insoluble synthetic polymer grains having a glass transition point of at least 60.degree. C. and an average grain size of from 0.2.mu. to 10.mu., and said polymer is represented by formula (I) --A).sub.x (B).sub.y (C).sub.z (I) wherein A represents a divalent group derived from at least one monomer having the formula (II); B represents a divalent group derived from at least one monomer having the formula (III), whose homopolymer has a glass transition point of at least 50.degree. C.; C represents a divalent group derived from an ethylenic unsaturated monomer other than A or B which is capable of copolymerizing with the monomers forming both A and B, said divalent group being derived from a member selected from the group consisting of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octylacrylate, tert-octyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, dimethylaminoethyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,3-dihydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, diethylene glycol monoacrylate, triethylene glycol monoacrylate, dipropylene glycol monoacrylate, glycerol monoacrylate, trimethylolethane monoacrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-isopropoxyethyl acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, .omega.-methoxypolyethylene glycol acrylate wherein the addition mol number of ethylene oxide groups is 9, .omega.-lauroxypolyethylene glycol acrylate wherein the addition mol number of ethylene oxide groups is 20, 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, 2-hydroxy-3-chloropropyl acrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N,N-diethylaminopropyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, glycerol monomethacrylate, trimethylolethane monomethacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-ethoxythyl methacrylate, 2-isopropoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy) ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, .omega.-methoxypolyethylene glycol methacrylate wherein the addition mol number of ethylene oxide groups is 6, .omega.-methoxypolyethylene glycol methacrylate wherein the addition mol number of ethylene oxide groups is 23, .omega.-lauroxypolyethylene glycol methacrylate wherein the addition mol number of ethylene oxide groups is 20, hexyl acrylamide, octyl acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, N-(1,1-dimethyl-3-oxobutyl)acrylamide, pentyl methacrylamide, dihexyl methacrylamide, allyl caproate, allyl caprate, allyl laurate, allyl palmitate, allyl stearate, allyl acetoacetate, allyl butyrate, allyloxyethanol, allyl butyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinylethyl butyrate, vinyl valerate, vinyl caproate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl acetoacetate, vinyl lactate, N-vinyloxazolidone, vinylpyridine, vinylpicoline, N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-triazole, N-vinyl-3,5-dimethyltriazole, N-vinyl, pyrrolidone, N-vinyl-3,5-dimethylpyrazole, N-vinylcarbazole, vinylthiophene, N-vinylsuccinimide, N-vinylglutarimide, N-vinyladipimide, N-methyl-N-vinylformamide, N-ethyl-N-vinylformamide, N-methyl-N-vinylacetamide, N-ethyl-N-vinylacetamide, N-methyl-N-vinylpropionamide, N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-s-caprolactam, N-vinyl-2-pyridone, vinyl methyl ketone, methoxyethyl vinyl ketone, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 5-methyl-1-nonene, 5,5-dimethyl-1-octene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 5-methyl-1-hexene, 4-methyl-1-heptene, 5-methyl-1-heptene, 4,4-dimethyl-1-hexene, 5,5,6-trimethyl-1-heptene, 1-dodecene, 1-octadecene, dioctyl itaconate, dihexyl itaconate, dibutyl itaconate, maleic anhydride, dihexyl maleate, butyl hexyl maleate, dibutyl maleate, dioctyl maleate, dibutyl fumarate, and dioctyl fumarate; x represents the fractional content of group A, which ranges from 0.03 to less than 0.1 mol/mol of polymer of formula (I); y represents the fractional content of group B, which ranges from 0.50 to 0.97 mol/mol of polymer of formula (I); and z represents the fractional content of group C, which ranges from 0 to 0.47 mol/mol of polymer of formula (I), and formula (II) is represented by ##STR12## wherein X, Y and Z each represents hydrogen, an alkyl group having from 1 to 6 carbon atoms, --COR, or --COOR.sub.1 ; Q represents ##STR13## and R represents ##STR14## where R.sub.1 represents a substituted or an unsubstituted alkyl group having from 1 to 18 carbon atoms, an aryl group having from 6 to 18 carbon atoms, or an aralkyl group having from 7 to 12 carbon atoms; R.sub.2 represents hydrogen, a halogen atom, an alkyl group having from 1 to 12 carbon atoms or an alkoxy group having from 1 to 6 carbon atoms; R.sub.3 represents hydrogen, a substituted or an unsubstituted alkyl group having from 1 to 4 carbon atoms, a phenyl group or an aralkyl group having from 7 to 10 carbon atoms; R.sub.4 represents the same groups as R.sub.3 or an --R.sub.5 --CONH).sub.l R.sub.5 --COR.sub.7 group, wherein R.sub.5 represents a divalent alphatic or an aromatic group (C.sub.1 -C.sub.12), R.sub.7 represents --OM, hydrogen, a substituted or an unsubstituted alkyl group (C.sub.1 -C.sub.4), a phenyl group or an aralkyl group (C.sub.7 -C.sub.10) and l is an integer of 0 to 6; M represents hydrogen or a cation; m is 0 or 1; and n is an integer of 1 to 4; and formula (III) is represented by ##STR15## wherein D and E each represents hydrogen, a methyl group, a halogen atom, or --COOR.sub.6 ; G represents hydrogen, a methyl group, a halogen atom or --(CH.sub.2).sub.k --COOR.sub.6 ; J represents hydrogen, an aryl group, ##STR16## R.sub.6 represents a substituted or an unsubstituted alkyl group having from 1 to 10 carbon atoms, an aryl group having from 6 to 12 carbon atoms, or an aralkyl group having from 7 to 12 carbon atoms; and k is 0 or 1. ### Claim 12 (depends on 11) A method as in claim 11, wherein said divalent group A is represented by the formula (II) wherein X, Y and Z each is hydrogen, a methyl group or --COR, and Q is --(CH.sub.2).sub.m --. ### Claim 13 (depends on 11) A method as in claim 11, wherein said formula (II) represents acrylic acid, methacrylic acid, maleic acid, itaconic acid or acryloylamino acid. ### Claim 14 (depends on 11) A method as in claim 11, wherein said formula (II) represents acrylic acid or methacrylic acid. ### Claim 15 (depends on 11) A method as in claim 11, wherein said divalent group B is represented by the formula (III) wherein D and E each is hydrogen and G is a methyl group. ### Claim 16 (depends on 11) A method as in claim 11, wherein said formula (III) represents a methacrylic acid ester or a styrene. ### Claim 17 (depends on 11) A method as in claim 11, wherein said formula (II) represents acrylic acid or methacrylic acid, and said formula (III) represents a methacrylic acid ester or a styrene. ### Claim 18 (depends on 17) A method as in claim 17, wherein z in said formula (I) is zero. ### Claim 19 (depends on 11, 12, 13, 14, 15, 16, 17) A method as in claim 11, 12, 13, 14, 15, 16, 17, or 18, wherein said outermost layer is a surface protecting layer, and said polymer grains are coated in an amount of from 2 to 500 mg per square meter. ### Claim 20 (depends on 11, 12, 13, 14, 15, 16, 17) A method as in claim 11, 12, 13, 14, 15, 16, 17, or 18, wherein the average grain diameter of the polymeric grains is from 1.mu. to 8.mu.. ### Claim 21 (depends on 11) A method as in claim 11, wherein said squeezing means is a rubber lips, squeeze rollers or buff rollers.