JPH02230240A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material having excellent color reproducibility and image preservable property by incorporating lipophilic fine particles obtd. by emulsion dispersion of a specific magenta coupler and a polymer compd. which is insoluble in water and is soluble in org. solvents into a silver halide emulsion layer. CONSTITUTION:The silver halide emulsion layer contains the lipophilic fine particles obtd. by the emulsion dispersion of the magenta coupler which is expressed by formula I and has <=600mol.wt. and the polymer compd. which is insoluble in water and is soluble in org. solvents. In the formula I, Z denotes a nonmetal atom. group necessary for forming a nitrogenous heterocyclic group; X denotes a hydrogen atom or the group which can be eliminated by reaction with the oxidant of a color developing agent; R denotes a hydrogen atom or a substituent. The light resistance of the photosensitive material having the excellent color reproducibility is improved in this way and the seating property is effectively prevented. The image preservable property is thus improved.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide color photographic material having excellent color reproducibility and image storage stability. [Background of the Invention] Conventionally, in color photographic paper used for direct viewing, a combination of a yellow coupler, a magenta coupler and a cyan coupler is usually used. Among these, most of the magenta couplers that have been widely used in the past have been 5-virazolone rings. This 5-
The dye formed from pyrazolone couplers has a wavelength of 430 nm.
It has a yellow component due to the presence of unnecessary absorption in the vicinity, and has the disadvantage of not being able to sufficiently reproduce a vivid blue color. On the other hand, unlike the conventionally used 5-virazolone magenta couplers, the recently developed pyrosoloazole couplers have no side absorption near 430 nm, so they basically have poor color reproducibility. It has the advantage of being advantageous. However, it is known that magenta dyes obtained from virazoloazole-based magenta couplers are inferior in image storage stability, especially light resistance, compared to magenta dyes obtained from 5-virazolone-based magenta couplers, and improvements in this are strongly desired. ing. Conventional techniques for improving the light resistance of Kagura include, for example, Japanese Patent Application Laid-open Nos. 63-44658 and 63-25064.
No. 8, No. 64-537 and wo-88 1 0072
No. 3 discloses a technique for emulsifying and dispersing a water-insoluble and organic solvent-soluble polymerer together with a coupler. When this technique is applied to a virazoloazole magenta coupler, it is possible to improve the light resistance, but the effect is not sufficient if the sample is stored under high temperature and high humidity conditions. Further, the use of the above-mentioned polymers also causes a problem of deterioration in color development. Therefore, in order to maintain or improve color development, techniques are used such as allowing a high boiling point organic solvent to coexist with the Kabra polymer or introducing many hydrophilic groups (sulfonamide bond, ether bond, etc.) into the diffusion-resistant group of the coupler. . However, in this case, during storage of the image, a new phenomenon occurs in which some of the components that make up the lipophilic particles move to the surface of the photographic constituent layer (hereinafter referred to as "sweating"), which tends to cause a significant deterioration of image quality. Problems have become clear. As described above, regarding the technology of improving the light fastness of silver halide photographic light-sensitive materials with excellent color reproducibility using biradroazole-based magenta couplers, and effectively preventing perspiration and improving image retention, There is still nothing that is satisfactory, and improvements are strongly desired. [Object of the Invention] Therefore, the first object of the present invention is to provide a silver halide photographic material with excellent color reproducibility. A second object of the present invention is to provide a silver halide photographic material which has excellent light resistance, is prevented from sweating, and has good image storage stability. A third object of the present invention is to provide a silver halide photographic material with excellent color development. [Structure of the Invention] The above object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers has the following general formula [M A halogenated compound characterized by containing lipophilic fine particles obtained by emulsifying and dispersing a magenta coupler represented by -I) with a molecular weight of 600 or less and a water-insoluble and organic solvent-soluble polymer compound in coexistence. This is achieved using silver photographic materials. General Formula (M-I) In the formula, 2 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent. Next, the present invention will be explained in more detail. Molecular weight 6 having the structure represented by the general formula (M-I)
The magenta coupler of the present invention, which is 00 or less, will be explained. General Formula (M-I) Y In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by 2 may have a substituent. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. The substituent represented by R is not particularly limited, but typical examples include alkyl, aryl, anilino, acylamino, sulfonamide, alkyl, arylthio, alkenyl, cycloalkyl, etc. Halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sul7ynyl, phosphonyl, acyl, carbamoyl, sulf, famoyl, cyano, alkoxy,
Allyloxy, heterocyclicoxy, siloxy, acyloxy, carbamoyloxy, amine, alkylamino, imide, ureido, sulfamoylamino, alkoxyluponylamino, aryloxyluponylamino, alkoxycarbonyl, aryloxycarbonyl, heterocycle Examples include thio groups, subiro compound residues, bridged hydrocarbon compound residues, and the like. The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched. The aryl group represented by R is preferably a phenyl group. Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group. Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group. Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above. The alkenyl group represented by R preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched. The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred. Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulf7ynyl groups, arylsulf7ynyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, Aryloxyphosphonyl group, arylphosphonyl group, etc.; Acyl group includes alkylcarbonyl group, arylcarbonyl group, etc.; Carbamoyl group includes alkylcarbamoyl group, arylcarbamoyl group, etc.; sulfamoyl group includes alkylsul7amoyl group,
Arylsulfamoyl groups, etc.; Acyloxy groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc. ; As the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; as a heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, a 2-chenyl group , 2-pyrimidinyl group, 2-penzothiazolyl group, etc.; as the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferred, such as 3,
4.5.6-tetoltetrahydrobiranyl-2-oxy group, l-7phenyltetrazol-5-oxy group, etc.; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-penzothiazolisilethio group, 2,4-di7enoxy 1.3.5 triazole-6-thio group, etc.; As a siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide Groups include succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc. Subiro compound residues include subiro [3.3]hebutane=1-yl, etc.; citrus hydrocarbon compounds The residue is bicyclo[2,2.1
1-hebutan-1-yl, tricyclo [3.3.1.1
``・1]decane-1-yl, 7,7-dimethyl-bicyclo[2.2.l]hebutan-1-yl, etc. Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X Examples include halogen atoms (chlorine, bromine, fluorine, etc.), alkoxy, aryloxy, heterocyclicoxy, acyloxy, sulfonyloxy, alkoxyluponyloxy, aryloxyluponyl, alkyloxalyloxy, alkoxyoxalyloxy For example, the following general formula [ Represented by M-1f) ~ [M-■]. hydrogen atom, aryl group, alkyl group, or heterocyclic group), preferably a halogen atom, especially a chlorine atom.Also, as a nitrogen-containing heterocycle formed by 2 or Z' is a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, etc., and examples of the substituents that the ring may have include those described for R above. What is more specific is N-N-
NH General formula [M-■] In the general formula [M-f[) to [M-■], R1 to R
．． and X have the same meanings as R and X above. Also, preferred among the general formulas [M-I] are those represented by the following general formula [M-■]. In the formula R. , X and Zl have the same meanings as R, X and 2 in the general formula [M-1)i::. Among the magenta couplers represented by the general formulas [M-1t) to [M-■], particularly preferred are the general formulas [M-n]
It is a magenta coupler represented by . The most preferred substituents R and R on the heterocycle are those represented by the following general formula [M-II]. General formula [:M-I! ) ,,I RIo C-Rll where R . , R l. and Rl1 each have the same meaning as R above. Further, the above Rs, R+. and 2 in Rll. For example, R
, and R1. may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and Rll may be bonded to the ring to form a bridged hydrocarbon compound residue. . Among the general formula [M-■], (i) R, ~
R. When at least two of them are alkyl groups, (ii
) R@~Rll, for example, one of them, RIl, is a hydrogen thickener, and the other two, R and R. . is combined with the root carbon atom to form a cycloalkyl. Furthermore, it is preferable among (i) that two of R and to Rll are alkyl groups and the other one is a hydrogen atom or an alkyl group. Most preferred is R, ~Rll
This is the case when all three are alkyl groups. In addition, substituents which the ring formed by 2 in general formula [M-I] and the ring formed by z1 in general formula [M-■] may have, and general formulas [M-1f) to ( M
-Vl), ~R. Finally, the following general formula (M-
Those represented by X) are preferred. General formula [M-X) - R'- SO , - R'' In the formula, R1 represents an alkylene group, and R2 represents an alkyl group, a cycloalkyl group, or an aryl group. The alkylene group represented by R1 is preferably a straight chain The moiety has 2 or more carbon atoms, more preferably 3 to 6 carbon atoms, regardless of whether it is linear or branched.The alkyl group represented by R2 preferably has 6 to 20 carbon atoms.
It does not matter whether it is straight chain or branched. The cycloalkyl group represented by R2 is preferably a 5- to 6-membered one. The aryl group represented by R2 is preferably a 7-enyl group, and may further have a substituent. The molecular weight of magenta kaglar represented by general formula (M-1) must be 600 or less, but most preferably 40
It is 0-550. Specific examples of the magenta coupler of the present invention represented by general formula [M-1] are listed below, but are limited to M-1 Molecular weight M-5 CH3 M-2 473.1 M-6 M M-7 M -4 578.3 M M-9 M-10 M-11 M-16 M-17 M-18 M-19 CH, M-12 M-13 529.2 565.2 M-14 M 15 M-20 565 .2 M-21 557.3 543.2 M-22 M-23 543.2 CHs CHs 559.6 587.2 530.8 557.3 571.3 579.2 M-24 M M-26 M-27 M-32 M-33 M-34 M-35 M-28 M-29 M-30 M-31 M-36 M-37 M M-39 L H 1 Fl 2 1 CH. 527.2 M-40 M-41 M-42 81N 1N M-46 M-47 M-48 Heheichihe M-43 523.1 539.1 M-44 487.1 M-45 HeeN -NM 566.2 M-50 567.2 M-51 594. 3 524.1 577.7 554.1 563.2 M 543.2 M-53 M-54 531.1 The above coupler was published in the Journal of the Chemical Society.
calSocity) *Birkin (Perkin)
I (1977). 2047-2052, U.S. Pat.
-43659, 60-172982 and 60-
It can be synthesized by referring to No. 190779 and the like. The coupler usually contains lxlO-3 per mole of silver halide.
moles to 1 mole, preferably l x 10-'' moles to 8X
A range of 10-' moles can be used. The coupler of the present invention can also be used in combination with other types of magenta couplers. Next, the polymer compound (hereinafter referred to as a polymer, copolymer, etc.) according to the present invention will be specifically explained. (1) Vinyl polymers and copolymers To be more specific about the heptanomers forming the vinyl polymers and copolymers, examples of acrylic esters include methyl acrylate, ethyl acrylate, isopropylacrylate, butyl acrylate, t -butyl acrylate, amyl acrylate, hexyl acrylate,
2-ethylhexyl acrylate, t-octyl acrylate, 2-chloroethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, methoxybenzyl acrylate, cyclohexyl acrylate, tetrahydrofuric acid Furyl acrylate, phenyl acrylate, 2,2-dimethyl-3
-Hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2
-i-proboxyacrylate, 2-(2-methoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (additional mole number n = 9), 1-
Examples include promoter 2-methoxyethyl acrylate. Examples of methacrylic esters include methyl methacrylate, ethyl methacrylate, globil methacrylate, butyl methacrylate, isobutyl methacrylate,
amyl methacrylate, cyclohexyl methacrylate, pendyl methacrylate, octyl methacrylate,
Sulfopyl methacrylate, N-ethyl-N-7 enylaminoethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, triethylene glycol monomethacrylate, Examples include 2-methoxyethyl methacrylate, 2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, and ω-methoxypolyethylene glycol methacrylate (number of moles added: n-6). Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl 7-enyl acetate, vinyl benzoate, vinyl salicylate, etc. can be mentioned. Examples of acrylamide include acrylamide, ethyl acrylamide, probylacrylamide, butylacrylamide,

[-Butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, diacetone acrylamide, etc. ;
Examples of methacrylamide include methacrylamide, methylmethacrylamide, ethylmethacrylamide, proylmethacrylamide, butylmethacrylamide, t-
Butylmethacrylamide, cyclohexylmethacrylamide, pendylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, β~cyanoethylmethacrylamide, N-(2 -acetoacetoxyethyl) methacrylamide and the like. Further, examples of olefins include dicyclopentadiene, ethylene, propylene, i-1/tene, 1-bentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, putadiene, 2,3-dimethylptadiene, and the like. Can be done. Examples of the styrenes include styrene, methylstyrene, trimethylstyrene, ethylstyrene, chloromethylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, and vinylbenzoic acid methyl ester. Examples of crotonate esters include butyl crotonate,
Examples include hexyl crotonate. Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like. Examples of the 7-malate diesters include diethyl 7-malate, dimethyl 7-malate, and dibutyl fumarate. Examples of other heptanomers include: Allyl compounds, such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate, etc. Vinyl ethers, such as methyl vinyl ether, butyl vinyl ether, methoxyethyl vinyl ether,
Dimethylaminoethyl vinyl ether, etc.: Vinyl ketones, such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; Vinyl heterocyclic compounds, such as vinyl pyridine, N-vinylimidazole, N-vinyl oxazolidone, N-vinyl triazole, Examples include N-vinylpyrrolidone, etc.: glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.; unsaturated nitriles, such as acrylonitrile, methacrylic nitrile, etc. The polymer used in the present invention may be a homopolymer of the above heptanomers, or, if necessary, a copolymer consisting of two or more heptanomers. Furthermore, the polymer used in the present invention may contain a heptanomer having an acid group shown below to the extent that it does not become water-soluble, but preferably 2
The content is 0% or less, more preferably not at all. Acrylic acid, methacrylic acid, itaconic acid, maleic acid,
Monoalkyl itaconate, monoalkyl maleate, citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, acryloyloxyalkyl sulfonic acid, acryloyloxyalkyl sulfonic acid, methacryloyloxyalkyl sulfonic acid, acrylamide alkyl sulfonic acid, methacrylamidoalkyl Examples include sulfonic acid, acryloyloxyalkyl phosphate, methacryloyloxyalkyl phosphate, and the like. These acids are alkali metals (e.g. Na, K, etc.)
Alternatively, it may be a salt of ammonium ion. As monomers forming the polymer used in the present invention, acrylate-based, methacrylate-based, acrylamide-based and methacrylate-based monomers are preferred. The polymer formed from the above heptanomer can be obtained by a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and a latex polymerization method. As the initiators used in these polymerizations, water-soluble polymerization initiators and lipophilic polymerization initiators are used. Examples of water-soluble polymerization initiators include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; 4.
Sodium 4'-azobis-4-cyanovalerate, 2.2
Water-soluble azo compounds such as '-azobis(2-amidinoproban) hydrochloride and hydrogen peroxide can be used. Examples of the lipophilic polymerization initiator include azobisisobutyronitrile, 2.2''-azobis-2,4-dimethylvalenitrile'), 1.1'-azobis(cyclohexanone-l-carponitrile), 2. Lipophilic azo compounds such as dimethyl 2'-azobisisobutyrate and diethyl 2'-azobisisobutyrate, penzoyl peroxide, lauryl peroxide, diisopropylberoxy dicarponate, and di-t-butyl peroxide may be mentioned. (2) Polyester resin obtained by condensing a polyhydric alcohol and a polybasic acid. As a polyhydric alcohol, HO- R+ - OH (
Glycols or polyalkylene glycols having a structure in which R+ is a hydrocarbon chain having 2 to about 12 carbon atoms, especially an aliphatic hydrocarbon chain are effective; as polybasic acids,
HOOC-R! - Cool (R represents a simple bond or a hydrocarbon chain having 1 to 12 carbon atoms) is effective. Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, 1.2-propylene glycol, 1.3-7'robylene glycol, trimethylo-J-repropane, 1.4-butanediol, imbutylene diol, 1. 5-pentanediol, neopentyl glycol, 1,6-hexanediol, ■,8-octanediol, 1,9-nonanediol, l,101decanediol, glycerin, diglycerin, triglycerin, 1-methyl Examples include glycerin, erythritol, mannitol, sorbitol, and the like. Specific examples of polybasic acids include oxalic acid, succinic acid, glutaric acid, adivic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, Examples include citraconic acid, heptatalic acid, isophthalic acid, terephthalic acid, tetralactalic acid, methaconic acid, isohimelic acid, cyclopentadiene-maleic anhydride adduct, rosin-maleic anhydride adduct, and the like. (3) Polyesters Obtained by Ring-Opening Polymerization These polyesters are obtained from β-probiolactone, ε-cabrolactone, dimethyl piolactone, and the like. (4) Other polymers Polycarbonate resin obtained by polycondensation of glycol or dihydric phenol with carbonate ester or phosgene, polyurethane resin obtained by polyaddition of polyhydric alcohol and polyhydric incyanate, or polyhydric amine. Examples include polyamide resins obtained from polybasic acids. The number average molecular weight of the polymer used in the present invention is not particularly limited, but is preferably 200,000 or less, more preferably 5,000 to 100,000. The ratio (weight ratio) of the polymer of the present invention to the coupler is:
l:20-20:l is preferable, more preferably 1:
The ratio is 10-10:1. Specific examples of the polymer used in the present invention are shown below, but the invention is not limited thereto. (The composition of the copolymer is
Shown in weight ratio. ) A-1 Poly(N-see-butylacrylamide)
A-2 Poly(N-t-butylacrylamide) A-
3 Diacetone acrinoleamide methynole methacrylate copolymer (25:75) A-4 Polycyclohexyl methacrylate A-5N
-t-Butylacrylamide methyl methacrylate copolymer (60:40) A-6 A-7 A-8 A-9 A-1O A-11 A-12 A-13 Yaichi]4 A-15 A-16 A-17 A-18 A-19 A-20 A-21 Poly(N,N-dimethylacrylamide) Poly(t-butyl methacrylate) Polyvinyl acetate Polyvinyl glopionate Polymethyl methacrylate Polyethyl methacrylate Polyethyl acrylate Vinyl rubinyl acetate Alcohol copolymer (90:10) Polybutyl acrylate polybutyl methacrylate polyisobutyl methacrylate polyisopropyl methacrylate polyoctyl acrylate butyl acrylate acrylamide copolymer (95:
5) Stearyl methacrylate-acrylic acid copolymer (90
: 10) Methyl methacrylate-vinyl chloride copolymer (70:3
0) A-22 Methyl methacrylate-styrene copolymer (
90:10) A-23 Methyl methacrylate-ethyl acrylate copolymer (50:50) A-24 Butyl methacrylate-methyl methacrylate-styrene copolymer (50:20:A-25 Vinyl acetate-acrylamide copolymer (85) :15) A-26 Vinyl chloride-vinyl acetate copolymer (65:A
-27 Methyl methacrylate-acrylic nitrile copolymer (65:35) A-28 Butyl methacrylate-pentyl methacrylate-N-vinyl-2-pyrrolidone copolymer (38:3
8:24) A-29 Methyl methacrylate-butyl methacrylate-isobutyl methacrylate-acrylic acid copolymer (
37:29:25:9) A-30 Butyl methacrylate-acrylic acid copolymer A-31 A-32 A-33 A-34 A-35 A-36 A-37 A-38 A-39 Combination (95:5 ) Methyl methacrylate-acrylic acid copolymer (95:5
) Penzyl methacrylate-acrylic acid copolymer (93:
7) Butyl methacrylate-methyl methacrylate-benzyl methacrylate-acrylic acid copolymer (35:35:
25:5) Butyl methacrylate-methyl methacrylate-penzyl methacrylate copolymer (40:30
:30) Diacetone acrylamide-methyl methacrylate copolymer (50:50) Methyl vinyl ketone-isobutyl methacrylate copolymer (55:45) Ethyl methacrylate-butyl acrylate copolymer (
70:30) Diacentacrylamide doptyl acrylate copolymer (60:40.) Methyl methacrylate-1-styrene methacrylate-diacetone acrylamide copolymer (40:4L20) A-40 Butyl acrylate styrene methacrylate - diacetone acrylamide copolymer (70:20:
10) A-41 Stearyl methacrylate-methyl methacrylate-acrylic acid copolymer (50:40:1O) A-42 Methyl methacrylate-styrene-vinyl sulfonamide copolymer (70:20:10)A
-43 Methyl methacrylate-phenyl vinyl ketone copolymer (70:30) A-44 Butyl acrylate-methyl methacrylate-butyl methacrylate copolymer (35:35:30) A-45 Butyl methacrylate-N-vinyl-2- Pyrrolidone copolymer (90:10) A-46 Polypentyl acrylate A-47 Cyclohexyl methacrylate-methyl methacrylate-propyl methacrylate A-48 A-49 A-50 A-51 A-52 8-53 A A -55 A-56 A-57 Polypentyl methacrylate methyl methacrylate-butyl methacrylate copolymer (65: 35) Vinyl acetate vinyl probionate copolymer (75
: 25) Butyl methacrylate-3-acryloxybutane-1
- Sodium sulfonate copolymer (97:3) Butyl methacrylate-methyl methacrylate-acrylamide copolymer (35:35:30) Butyl methacrylate-methyl methacrylate-vinyl chloride copolymer (37:36:27) Butyl methacrylate Tortose styrene copolymer (82:12) t-Butyl methacrylate-methyl methacrylate copolymer (70:30) Poly(N-t-butyl methacrylamide) N-t-butylacrylamide-methyl 7-enyl methacrylate copolymer ( 60:40) A-58 Methyl methacrylate-acrylonitrile copolymer (70:30) A-59 Methyl methacrylate-methyl vinyl ketone copolymer (38:72) A-60 Methyl methacrylate-styrene copolymer (
75:25) A-61 Methyl methacrylate-hexyl methacrylate copolymer (70:30) A-62 Butyl methacrylate-acrylic acid copolymer (85:15) A-63 Methyl methacrylate-acrylic acid copolymer (80 :20) A-64 Methyl methacrylate-acrylic acid copolymer (90:10) A-65 Methyl methacrylate-acrylic acid copolymer (98:2) A-66 Methyl methacrylate-N-vinyl-2-pyrrolidone copolymer Combined (90:10) A-67 Butyl methacrylate-vinyl chloride copolymer A A-69 A-70 A-71 A-72 A-73 A-74 A-75 A-76 A-77 A-78 Combined (90 : 10) Butyl methacrylate-styrene copolymer (70 :
30) 1.4-Butanediol-adipic acid polyester ethylene glycol-sebacic acid polyester polyprolactam polypropiolactam polydimethylbutylacrylamide Nt-butylacrylamide dimethylaminoethyl acrylamide copolymer (85:l5 ) N-t-butyl methacrylamide-vinyl pyridine copolymer (95:5) maleic acid diethyl acrylamide-butynolea azilate copolymer (65:35) N-t-butylacrylamide-2-methoxyethyl acrylate copolymer Polymer (55: 45) ω-methoxypolyethylene glycol methacrylate (number of moles added n-
6) Monomethyl methacrylate (40:60) A-79 ω-methoxypolyethylene glycol acrylate (additional mole number n = 9)-Nt-butylacrylamide (25:75) A-80 Poly(2-methoxyethyl acrylate)
A-81 Poly(2-methoxyethyl methacrylate) A-82 Poly(2-(2-methoxyethoxy)ethyl acrylate) A-83 2-(2-butoxyethoxy)ethyl acrylate methyl methacrylate (58:42) A- 8
4 Poly(oxycarponyloxy-1.4-7enyleneisobutylidene-1,4-7enylene) A-85 Poly(oxyethyleneoxycarbonyl) An insoluble and organic solvent soluble polymer compound is dissolved in a low boiling point and/or water soluble organic solvent as necessary, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution using a stirrer, homogenizer, colloid mill, etc. , 7 After emulsifying and dispersing using a dispersion means such as a low jet mixer or an ultrasonic device,
It may be added to the desired hydrophilic colloid layer. Low boiling point and/or water-soluble organic solvents may be removed from the prepared dispersion by distillation, noodle washing, or ultrafiltration. Examples of the low-boiling organic solvent include ethyl acetate, butyl acetate, ethyl probionate, secondary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, and cyclohexanone. Examples of water-soluble organic solvents include methyl alcohol, ethyl alcohol, acetone, and tetrahydrofuran. These organic solvents can be used in combination of two or more types, if necessary. Alternatively, in the presence of a coupler, monomer components of the monomer or copolymer obtained by suspension polymerization, solution polymerization or bulk polymerization are similarly dispersed in a hydrophilic binder. The method described in JP-A-60-107642 may also be used. The above-mentioned dispersion contains a high-boiling point organic solvent, and examples of commonly used high-boiling point organic solvents include phenol derivatives, phthalate esters, phosphate esters, citric acid esters, and benzoic acid esters that do not react with the oxidized form of the developing agent. Organic solvents having a boiling point of 150° C. or higher, such as esters, alkylamides, fatty acid esters, and trimesic acid esters, are used. In the present invention, the high boiling point organic solvent has a dielectric constant of 6.
Those less than 0 are preferably used. As the high boiling point organic solvent preferably used in the present invention, any compound having a dielectric constant of less than 6.0 can be used. The lower limit is not particularly limited, but the dielectric constant is 1.
9 or more is preferable. Examples include esters such as phthalic esters and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds having a dielectric constant of less than 6.0. Further, in the present invention, a high boiling point organic solvent having a vapor pressure at i o o'c of 0.5 mmHg or less is preferred. More preferably, heptatarates or phosphoric acid esters in the high boiling point organic solvent are used. Note that the organic solvent may be a mixture of two or more types, and in this case, the dielectric constant of the mixture may be less than 6.0. Note that the dielectric constant in the present invention refers to the dielectric constant at 30°C. Examples of the 7-talic acid esters advantageously used in the present invention include those represented by the following general formula [HA]. General formula [HA] In the formula, RM18 and RI42 are each an alkyl group,
Represents an alkenyl group or an aryl group. However, RNI
and Rll! The total number of carbon atoms in the group represented by is 9
〜32. More preferably, the total number of carbon thicknesses is 16 to 24. RMI and Rl4 of the general formula [HA]! The alkyl group represented by is linear or branched, such as butyl group, bentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, These include pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. The aryl group represented by R11 and RH2 is a phenyl group, naphthyl group, etc., and the alkenyl group is a hexenyl group, heptenyl group, octadecenyl group, etc. These alkyl groups, alkenyl groups and aryl groups are
It may have a single or multiple substituents, and examples of substituents for alkyl and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, and alkoxy carbonyl groups. , as a substituent for the aryl group, for example, a halogen atom,
Examples include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxy group. Two or more of these substituents are alkyl groups,
It may be introduced into an alkenyl group or an aryl group. Phosphate esters advantageously used in the present invention include those represented by the following general formula [HB]. General formula [HB] Xi? In, R. 3, R. ．． and Roll each represent an alkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms represented by R N3+ R H4 and RHs is 24 to 54. The alkyl group represented by RM3, R■ and R■ in the general formula [HB] is, for example, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group. , tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, etc. These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. Preferably R. 3, R. , and R■ are alkyl groups,
For example, 2-ethylhexyl group, n-octyl group, 3.
5.5-trimethylhexyl group, n-nonyl'tss
n-decyl group % SeC-decyl group, sec-dodecyl group, t-octyl group and the like. Specific examples of the high boiling point organic solvent are shown below, but the present invention is not limited thereto. Exemplary organic solvent H-1 H-2 C. H. H-3 H-4 H-8 H-5 H-9 H-10 H-6 H-11 CH. CI, H-12 H-7 H-13 H-14 H-15 H-16 H-17 H-18 H-19 H-20 H-21 H-22 In the present invention, the high boiling point organic solvent is silver halide. 0.0 per mole. Ol mol to 10 mol, preferably 0.0 mol
It can be used in a range of 5 mol to 5 mol. The silver halide used in the present invention includes any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodide. The silver halide grains preferably used in the present invention are 90
It is preferable that the silver chloride content is mol % or more, the silver bromide content is 10 mol % or less, and the silver iodide content is 0.5 mol % or less. More preferred is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%. The silver halide grains may be used alone or in combination with other silver halide grains having different compositions. Further, it may be used in combination with silver halide grains having a silver chloride content of 90 mol % or less. In addition, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more,
The ratio of silver halide grains having a silver chloride content of 90 mol% or more to all silver halide grains contained in the emulsion layer is 6.
It is 0% by weight or more, preferably 80% by weight or more. The composition of the silver halide grains may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. Further, when the composition inside and outside the particle is different, the composition may change continuously or discontinuously. There is no particular restriction on the particle size of the silver halide grains, but in consideration of other photographic performance such as rapid processability and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.2 μm. range. The particle diameter can be measured by various methods commonly used in the field of photography. A representative method is Loveland's "Particle Size Analysis Method" (A.S.T.M. Symposium on Light Microscope, 1955).
94-122) or "The Theory of Photographic Processes" (by Mies and James, 3rd edition, published by Macmillan, 1966, Chapter 2). The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area. The particle size distribution of the silver halide grains may be polydisperse or monodisperse. Preferably, the coefficient of variation in the particle size distribution of silver halide grains is 0.22 or less, more preferably 0.22 or less. They are monodisperse silver halide grains of 15 or less. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is defined by the following equation. Here, ``i'' represents the particle size of each particle, and ni represents the number thereof. The grain size here refers to the diameter in the case of spherical silver halide grains, and in the case of grains with shapes other than cubic or spherical, the diameter when the projected image is converted to a circular image of the same area. . In the present invention, the silver halide grains used in the emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different. Further, the soluble silver salt and the soluble halide salt may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferable. Furthermore, as a type of simultaneous mixing method, the pAg-controlled dodable jet method described in JP-A-54-48521 and the like can also be used. Furthermore, if necessary, a silver halide solvent such as thioether may be used. Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound, or a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation. The silver halide grains used in the present invention may have any shape. One preferred example is {10
0} plane as the crystal surface. Also, U.S. Patent No. 4, [3.756], U.S. Pat.
No., JP-A-55-26589, JP-A-55-4273
Specifications such as No. 7, The Journal of Photographic Science (J.Photogr.Sci)
．． Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literature such as 2-1.39 (1973) and used. Furthermore,
Particles having twin planes may also be used. The silver halide grains used in the present invention may be of a single shape or may be a mixture of grains of various shapes. In the present invention, the silver halide grains used in the emulsion are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt, iron Metal ions can be added to the inside of the particles and/or on the surface of the particles using salts or complex salts, and reduction-sensitized nuclei can be formed inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. can be given. In the emulsion containing silver halide grains, unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or the emulsion may be left containing them. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643. In the present invention, the silver halide grains used in the emulsion may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain. Preferably, the particles are particles on which latent images are mainly formed. In the present invention, the breast tissue is chemically sensitized by a conventional method. In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensitive methods can be used alone or in combination. In the present invention, the emulsion can be optically sensitized to a desired wavelength range using a sensitizing dye. Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holobolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxazole dyes, and the like can be used. The dye-forming coupler used in the silver halide photographic light-sensitive material of the present invention is usually selected so that a dye that absorbs light in the sensitivity spectrum of the emulsion layer is formed for each emulsion layer, and is blue-sensitive. A yellow dye-forming coupler is used in the emulsion layer, a magenta dye-forming coupler is used in the green-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above. In the present invention, the yellow dye-forming coupler is
Acylacetanilide couplers can be preferably used. Among these, penzoylacetanilide and bivaloylacetanilide compounds are advantageous. In the present invention, as the cyan dye-forming coupler, a cyan coupler represented by the following general formula CI) or (II) is preferable. General formula CI) 0H Z' In the formula, R' represents an alkyl group or an aryl group. R2
represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Further, R3 may cooperate with R1 to form a ring. Z1 represents a hydrogen atom, and t: represents a group capable of being separated by reaction with an oxidized product of an aromatic primary amine color developing agent. General formula [■] 0 sweet l" In the formula, R'li represents a ballast group. RS is the number of carbon atoms l
-6 represents an alkyl group 21 represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. In the cyan coupler represented by the general formula CI)
The alkyl group represented by Rl preferably has 1 to 32 carbon atoms, and these groups may be linear or branched, and include those having substituents. The aryl group represented by Rl is preferably a phenyl group, including those having substituents. The alkyl group represented by R2 preferably has 1 to 32 carbon atoms, and these alkyl groups may be linear or branched, and include those having substituents. The cycloalkyl group represented by R2 has 3 to 1 carbon atoms.
2 is preferred, and these cycloalkyl groups also include those bearing substituents. The aryl group represented by R2 is preferably a phenyl group, including those having substituents. The heterocyclic group represented by R2 is preferably a 5- to 7-membered one, may have a substituent, and may be fused. R2 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and the alkyl group and the alkoxy group include those having a substituent, but % Rl is preferably a hydrogen atom. Also, the ring formed jointly by %R' and R3 is 5 to 6
A membered ring is preferable, and examples of the group which can be separated by reaction with the oxidized product of the color developing agent represented by Z' in the general formula (1) include a halogen atom, an alkoxy group,
Examples include an aryloxy group, an acyloxy group, a sulfonyloxy group, an acylamino group, a sulfonylamino group, an alkoxyluponyloxy group, an aryloxyluponyloxy group, and an imide group (including those each having a substituent), but preferably, These are a halogen atom, an aryloxy group, and an alkoxy group. Among the above-mentioned cyan couplers, those represented by the following general formula (1-A) are particularly preferred. General formula (IA) OH In the formula, %RA1 represents a phenyl group substituted with at least one halogen atom, and these phenyl groups further include those having a substituent other than a halogen atom. RA! has the same meaning as Rl in the general formula (1). XA represents a halogen atom, an aryloxy group or an anolekoxy group, and includes those having a substituent. Typical specific examples of the cyan coupler represented by the general formula [1] are shown below. Specific examples of the above-mentioned cyan couplers include Japanese Patent Application No. 61-21.853, pages 26 to 35, and JP-A-60-225155, lower left column on page 7 to lower right column on page 10. column, JP-A No. 60-222853, page 6, upper left column to page 8, lower right column, and JP-A-59-185335, page 6, lower left column to page 9, upper left column. 5.
It contains a diacylamino cyan coupler and can be synthesized according to the methods described in these specifications and publications. In the present invention, the amount of cyan coupler added is preferably 2 x 10-'' to 8 x 10-' mol per 1 mol of silver halide, particularly preferably IXIO-'' to 5
It is within the range of Ichiho mole. In the cyan coupler represented by the general formula (n),
The alkyl group represented by Ha may be linear or branched, and includes those having substituents. R6 is preferably an alkyl group having 1 to 6 carbon atoms. The pallast group represented by R6 is an organic group having a size and shape that imparts sufficient bulk to the coupler molecule to substantially prevent the coupler from diffusing from the layer to which it is applied to other layers. be. Preferred ballast groups are those represented by the following general formula. (II-B) -CH-0-Ar RBI Rml represents an alkyl group having 1 to 12 carbon atoms;
"" represents an aryl group such as a phenyl group, and this aryl group includes those having a substituent. Z2 has the same meaning as Zl in the general formula CI). Specific examples of the coupler represented by the general formula (I[) will be shown below, but the invention is not limited thereto. Specific examples of cyan couplers that can be preferably used in the present invention, including these, are listed in Japanese Patent Publication No. 49-11572.
No., JP-A-61. No. -3142, No. 61-9652,
6l-9653, 61-39045, 61-
No. 50136, No. 61-99141, No. 61-105
It is described in No. 545, etc. The cyan dye-forming coupler represented by the general formula (n) is usually used in an amount of 1 x 10-'' mole to 1 mole of silver halide.
It can be used in an amount of 1 mol, preferably 1 x 10-'' mol to 8 x 10 mol. Gelatin is advantageously used as the binder (or protective colloid) used in the silver halide photographic light-sensitive material of the present invention. However, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymeric substances such as single or copolymers are also used. The silver halide photographic material of the present invention may further contain a hardening agent, a color clouding preventive agent, an image stabilizer, an ultraviolet absorber, a plasticizer, a latex, a surfactant, a matting agent, a lubricant, and a charging agent. Additives such as inhibitors can be optionally used. The silver halide photographic material of the present invention can form an image by performing color development treatment known in the art. Silver halide of the present invention Color developing agents used in color developing solutions in the processing of photographic light-sensitive materials include aminophenol i and p-7 22-diamine derivatives, which are widely used in various color photographic processes. In addition to the above-mentioned primary aromatic amine color developing agent, known developer component compounds can be added to the color developing solution applied to the development of silver halide photographic light-sensitive materials. The pH value of the developer is usually above 7, most commonly about 10 to 13. The color development temperature is usually above 15°C, typically 20°C.
~50°C. For rapid development, it is preferable to carry out the process at 30°C or higher. Furthermore, the silver halide photographic light-sensitive material of the present invention is preferably processed with a color developing solution containing no baseyl alcohol. The silver halide photographic material of the present invention is subjected to a bleaching treatment and a fixing treatment after color development. Bleaching treatment may be performed simultaneously with fixing treatment. After the fixing process, a washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination. [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. Example-1 (Preparation of silver halide emulsion) By neutral method and simultaneous mixing method, 6 types *l silver halide 1 shown in Table 1l were prepared.
2+119 addition per mole*2 IXIO-' mole addition per mole of silver halide*3 0 per mole of silver halide
．． 9 mmol added*4 0.7 per mol of silver halide
Addition of mmol *5 0.2 mmol added per mole of silver halide Each silver halide emulsion was treated with STB-1 shown below as an emulsion stabilizer after completion of chemical sensitization at a concentration of 2 x 10-' per mole of silver halide. Mol added. [SD-1] [SD2] [SD-3] [STB-11 ■ SOsH-N(CtHs)s (Preparation of silver halide color photographic light-sensitive material) Polyethylene is coated on one side of a paper support, and polyethylene is coated on the other side. Each layer having the structure shown in Table 1 was coated on a support laminated with polyethylene containing titanium oxide on the first layer side to prepare a multilayer silver halide color photographic light-sensitive material. The coating solution was prepared as follows. First layer coating liquid Yellow coupler (Y-1) 26.7g, stain inhibitor (HQ-1) 0.67g and high boiling point organic solvent (DN
P) Add 60 mQ of ethyl acetate to 13.3 g and dissolve.
This solution was converted into a 10% gelatin aqueous solution containing lθ% sodium alkylna-7talenesulfonate IO + md.
A yellow coupler dispersion was prepared by emulsifying and dispersing 0.0a using a homogenizer. This dispersion was mixed with a sensitive silver chlorobromide emulsion (lOg in terms of E m-1 in terms of silver) and a coating gelatin solution to prepare a first layer coating solution. The second to seventh layer coating solutions were also prepared in the same manner as the eleventh coating solution. However, the magenta coupler dispersion used in the third layer coating solution was prepared as follows. Magenta coupler dispersion (dispersion of document No. Il2)
Magenta Cobra (M-21) 12.0g, dye image stabilizer (ST-1) 6.0g, same (S
T-2) 3.0g, stain inhibitor (H Q
-1) 0.3g1 high boiling point organic solvent (DOP)9.
0g and an exemplary compound (A-
2) Add and dissolve 40mα of ethyl acetate to 9.0g, and add this solution to 200ml of 10% gelatin aqueous solution containing 10m4 of 10% sodium alkylnaphthalene sulfonate.
2 was emulsified and dispersed using a homogenizer to prepare a magenta coupler dispersion. In addition, the following compound (H-1) was used as a hardening agent for gelatin.
．． 08g/m" added. Phthalate) Book (Millimonole/IIl ST-1 ST-2 CI2) The obtained sample was measured using a sensitometer KS-7 (manufactured by Konica Corporation).
After wedge exposure using green light and processing according to the following color development processing steps, the following evaluations were performed. [Processing process] Color development 3 minutes 30 seconds Bleach fixing at 33 degrees Celsius 1 minute 30 seconds Washing with water at 33 degrees Celsius
3 minutes Temperature: 33°C Color developer formulation N-ethyl-N-β-methanesulfonamidoethyl 3-methyl-4-aminoaniline sulfate 4.9g Hydroxylamine sulfate 2.0g Potassium carbonate 25.09 Sodium bromide
0.6g anhydrous sodium sulfite
2.0g benzyl alcohol
13+++l2 polyethylene glycol (average degree of polymerization 400) 3. On+Q
Add water to make 1Q, and add sodium hydroxide to pH 10.0.
Adjust to. Bleach-fix solution formulation Ethylenediaminetetraacetic acid iron (I[) sodium salt 6.0g Ammonium thiosulfate loOg Sodium bisulfite 10g Sodium metabisulfite 3g Add water to make IQ, and adjust to pal 7.0 with aqueous ammonia. <Light resistance> The obtained sample was exposed to sunlight at 60°C and 70% RH.
VS open stand) for one month, and the initial concentration l. Evaluation was made by determining the density reduction rate (%) of the dye image at O. <Sensitivity> Expressed as the reciprocal of the exposure amount required to obtain a density of 0.8, and expressed as the relative sensitivity when the sensitivity of the reference sample is multiplied by 100. Sweat The obtained sample was stored under conditions of 85° C. and 60% RH for 10 days, and the deterioration of gloss due to sweating of the oil agent on the surface of the sample was visually evaluated. ◎ No "sweating" is observed. ○ [Sweating J is hardly observed. △ Wakachi "sweating" can be seen, but it is acceptable as a product. × There is considerable "sweating" and it cannot be used as a product. XX ``Sweating'' seriously impairs image quality. The results are shown in Table-2. Comparative coupler 1 Molecular weight 837.5 Comparative coupler 2 Molecular weight 720.3 As is clear from Table 2, Sample No. 1 using the comparative coupler. Sample No. 1 using only the polymer compound of the present invention in lOl~109. IO2. Although the light resistance of IO5.108 is improved compared to the samples not using the polymer compound, the effect is small and a decrease in sensitivity is observed. Sample No. using a high boiling point organic solvent. 10
3.106 and 109 have a small decrease in sensitivity, but they cause perspiration, which impairs image quality. On the other hand, when the magenta coupler of the present invention was used, sample No. of the present invention using the polymer compound of the present invention. ill. 112,114.11
6 and 118 to 123 all have suppressed sweating,
It can be seen that this is a good sample with a large effect of improving light resistance and a small decrease in sensitivity. Furthermore, when compared among the samples of the present invention, Sample No. 1 uses a combination of the polymer compound of the present invention and a high boiling point organic solvent with a dielectric constant of less than 6.0, which is preferably used in the present invention. 112, 114.116 and ll8-1
Sample No. 21 is sample No. 21 that does not use a high boiling point organic solvent. 1
In terms of sensitivity compared to Sample No. 1i, sample No. 1 also uses a high boiling point organic solvent with a dielectric constant of 6.0 or more. 122 and 12
It can be seen that it is superior to No. 3 in terms of light resistance. or,
Sample No. 1 using a preferable magenta coupler of the present invention having a molecular weight of 550 or less. 114, 116 and 118~
Sample No. 1.23 was found to be an excellent sample with no sweating properties, and sample No. 1.23 using the preferred magenta coupler of the present invention having a substituent represented by the above general formula [M-X]. 1
．． It can be seen that samples 12 and 118 to 123 are excellent in sensitivity. Example-2 First layer blue-sensitive silver chlorobromide emulsion Em- in Example-1
1. The green-sensitive chlorobromide emulsion E+n-2 of the third layer and the red-sensitive silver chlorobromide emulsion Em-3 of the fifth layer were converted to Em-4. E
Multi-layer silver halide color was prepared in the same manner as in Example 1 except that m-5 and Em-6 were changed, and the magenta power blur polymer compound and high boiling point organic solvent of the third layer were changed as shown in Table 3. A photographic material was produced. The obtained sample was subjected to wedge exposure in the same manner as in Example-1, processed according to the following color development process, and then evaluated in the same manner as in Example-1. The results are shown in Table-3. [Processing process] Temperature Time color development 35.0±0.3°C 45 seconds bleach fixing 35. Of 0.5℃ 45 seconds stabilization 30-34℃ 90 seconds drying 60-80℃
60 seconds color developer pure water
800mQ. Triethanolamine
109N, N-diethylhydroxyamine
5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite 0.39l-Hydoxyethylidene 1,1-diphosphonic acid l,09ethylenediaminetetraacetic acid 1.0g Catechol-3,5-disulfonic acid disodium salt 1.0gN monoethyl-N -β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g optical brightener (4-4' diaminostilbendisulfonic acid derivative) ]. ．． 09 Potassium Carbonate 279 Add water to bring the total volume to IQ and adjust to pH = 10.10. Bleach-fix solution Ferric ammonium dihydrate ethylenediaminetetraacetic acid 60 9 Ethylenediaminetetraacetic acid 39 Ammonium thiosulfate (70% aqueous solution) 100 mα Ammonium sulfite (40% aqueous solution) 27.5 mQ Add water to make 1Q, potassium carbonate or ice Adjust pH to −6.2 with acetic acid. Stabilizing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 yethylene glycol 1.0 9l-hydoxyethylidene-1,l-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g water Ammonium oxide (20% aqueous solution) 3.09 Ammonium sulfite
3.0g optical brightener (4.4'-diaminostirpene disulfonic acid derivative) 1.
Add 5g of water to make tQ, and dilute with sulfuric acid or potassium hydroxide.
Adjust to H-7.0. Comparative coupler 4 Molecular weight: 877.6 Comparative coupler 5 As is clear from Table 3, among the samples using the comparative coupler, the sample using only the polymer compound of the present invention has a lower molecular weight than the sample using no polymer compound. Although the light resistance is improved, the effect is small, and a decrease in sensitivity is observed. Samples using high-boiling point organic solvents have a small decrease in sensitivity, but are prone to sweating, which impairs image quality. On the other hand, when the magenta coupler of the present invention is used, all of the samples of the present invention using the polymer compound of the present invention have suppressed sweating, have a large effect of improving light resistance, and have a small decrease in sensitivity. Recognize. Furthermore, when comparing among the samples of the present invention, samples in which the polymer compound of the present invention and a high-boiling point organic solvent with a dielectric constant of less than 6.0, which is preferably used in the present invention, are used in combination are those in which a high-boiling point organic solvent is used in combination. It can be seen that the sensitivity is excellent for samples with no In addition, it was found that a sample using the preferred magenta coupler of the present invention having a molecular weight of 550 or less was an excellent sample without sweating property, and had a substituent represented by [M-X] in the above general formula. It can be seen that the sample using the preferred magenta coupler of the present invention is excellent in sensitivity. Also, sample no. 218 magenta coupler M-4, M-
8, M-28. M-33. M-35, M-3
7. The effects of the present invention were also obtained with samples in which the polymer compounds were replaced with A-5 and A-77 in M-53, respectively. Example-3 Sample No. of Example-2. The magenta coupler in the third layer of No. 212 was replaced with Comparative Coupler 6 shown below, and the amount of green-sensitive silver chlorobromide emulsion added in the third layer was 0.31 g/m in terms of silver.
Sample No. 30 was prepared in the same manner as in Example-2 except that
I got 1. Next, the negative film obtained by photographing and developing the color checker (manufactured by Macbeth) with Konica Color G 212 and 301 to evaluate the color reproducibility of each hue. As a result, blue red and magenta are sample no. 21
It was found that 2 was better. Example 4 Equimolar amounts of silver nitrate aqueous solution and potassium bromide aqueous solution were simultaneously added to gelatin aqueous solution at 50°C for 50 minutes by double jet method to create an emulsion consisting of cubic silver bromide grains with an average grain size of 0.15 μm. I got it. To this emulsion, a silver nitrate aqueous solution and a sodium chloride/potassium bromide mixed aqueous solution (molar ratio 1:1) were added simultaneously to form cubic cores consisting of a silver bromide core and a silver chlorobromide shell with an average grain size of 0.225 μI. /Shell type emulsion (EMP-1) was prepared. In addition to the above emulsions, core/shell type emulsions as shown in Table 4 below were prepared by varying the addition times of the silver nitrate aqueous solution and the halogen salt aqueous solution. Table 4 Using the obtained emulsions EMP-1 to 4 as a support,
An emulsion layer, a non-emulsion layer, and a back layer having the structures shown in Table 5 were coated in order from the first layer onto a 140 μm thick paper support coated on both sides with polyethylene to directly prepare a positive color light-sensitive material. In the table, the additive amounts are shown in mg/dm''. However, silver halide emulsion and yellow colloidal silver are silver equivalent values. Table 5 (Additives used) RD l RD-2 GD-1 BD-1 *mg/mol AgX In addition, HA- ■ HA-2 was used as a hardening agent for the emulsion layer side and the back layer. CG- 1 so- i SO- 2 SO CH3 HA- 1 α) CH CHtl AO- 1 DH HA-2 UV- 1 ST- 1 ST-2 UV-2 ST-3 After that, it was treated according to the treatment steps shown below.The obtained materials were evaluated for light resistance and perspiration in the same manner as in Example-1.The obtained results are shown in Table 6. Processing temperature and processing time) (1) Immersion (color developer) at 38°C (2) Capri exposure (3) Color development (4) Bleach-fixing (5) Stabilization treatment (6) Drying (processing solution composition) Color development Liquid Benzyl alcohol Ethylene glycol Potassium nitrite Potassium bromide Sodium chloride Potassium carbonate 10 mα 15 m (1 2.Og 1.5g 0.2g 30.0g 8 seconds 1 lux for 10 seconds 38°C 2 minutes 35°C 60 seconds 25-30°C 1 minute 30 seconds 75-80°C 1 minute Hydroxylamine sulfate polyphosphoric acid (TPPS) N-ethyl-N-β-methanesulfonami-3-methyl-
4-aminoaniline sulfate optical brightener (4.4'-diaminostilbendisulfonic acid derivative) Add potassium hydroxide water to make a total volume of 14, bleach-fix solution ethylenediaminetetraacetic acid ferric ammonium dihydrate ethylenediaminetetraacetic acid thio Ammonium sulfate (70% solution) Ammonium sulfite (40% solution) Add water to bring the total volume to 112, and adjust the pH with potassium carbonate and glacial acetic acid.
Adjust to 7.1. Stabilizing liquid 5-chloro-2-methyl-4-inthiazolin-3-one ethyleneglyfur The pH was adjusted to 0.20. 3.0g 2.5g Doethyl-5.0g 1.0g 2.0g 3g 100 mQ 27.5 m(1um or 1.09!-Hydroxyethylidene-1,l-diphosphonic acid 2.5g
Bismuth chloride 0.2g Magnesium chloride 0.1g Ammonium hydroxide (28% aqueous H2) 2.0g Sodium nitrilotriacetate 1.0g Add water to bring the total volume to 1/2, and adjust to pH 7. with ammonium hydroxide or sulfuric acid.
Adjust to 0. Note that the stabilization treatment was performed using a countercurrent method with a two-tank configuration. As is clear from Table 6, when the comparative coupler is used, the light resistance is improved when the polymer compound of the present invention is used, but the degree of perspiration is deteriorated. On the other hand, it can be seen that when the coupler and polymeric compound of the present invention are used, the effect of improving light resistance is large and sweating is also effectively prevented. [Effects of the Invention] According to the present invention, a silver halide photographic material which has excellent color reproducibility and light fastness and prevents deterioration of image quality due to perspiration was obtained.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is represented by the following general formula [M-I]. 1. A silver halide photographic material comprising lipophilic fine particles obtained by emulsifying and dispersing a magenta coupler having a molecular weight of 600 or less and a water-insoluble and organic solvent-soluble polymer compound in coexistence. General formula [M-I] ▲ Numerical formulas, chemical formulas, tables, etc. It may have. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. ]