JPS62115436A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photogrpahic sensitive material having satisfactory dimensional stability, enabling the hardening of each separate specified layer and nearly independent of tailing trouble caused during production by incorporating a water soluble polymer, latex and a polymer hardening agent into a photographic constituent layer. CONSTITUTION:A water soluble polymer, latex and a polymer hardening agent are incorporated into a photographic constituent layer on a support. Any of synthetic and natural water soluble polymers can preferably be used as the water soluble polymer. The latex contains a hydrophobic polymer as the principal component and the hydrophobic polymer can stably be incorporated into the hydrophilic colloidal layer independently of the composition by combining a water soluble polymer with the hydrophobic polymer. Polyester or a vinyl polymer is preferably used as the hydrophobic polymer because it is easily produced. The polymer hardening agent is a polymer having functional groups which can cause a cross-linking reaction with gelatin or a polymer having functional groups which can caused a cross-linking reaction with gelatin through a hardening agent. The especially preferred polymer hardening agent is a (co)polymer of a vinyl monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a silver halide photographic material, and more specifically to a silver halide photographic material. ! The present invention relates to a silver halide photographic light-sensitive material which has good stability, can be hardened layer by layer, and has improved troubles that occur during production, especially trailing troubles that occur in coated layers.

[Background of the Invention J Silver halide photographic materials having a hydrophilic colloid layer prevent the hydrophilic colloid from eluting during the development process, moderately suppress swelling, and resist friction and compression during handling. It is generally hardened with a hardening agent. The hardening agent commonly used is a hydrophilic colloid that has good diffusibility.
For example, if a hardening agent is added to the top layer fabric liquid and multi-layer coating is performed simultaneously, the hardening agent will diffuse within the photosensitive material until the drying process of the photosensitive material is completed. The degree of hardness becomes uniform or continuous.

In recent years, the design of silver halide photographic light-sensitive materials has become more sophisticated, and in light-sensitive materials consisting of two or more layers, it has become necessary to independently control the degree of hardening of the hydrophilic colloid layer for each layer. It is known that a polymer hardener is used as a means for achieving such hardening of each coated layer.

On the other hand, we aim to reduce the gelatin content, and also improve the physical properties of the film, such as dimensional stability before and after development, dimensional stability against moist heat,
It is generally well known that latex is used together with gelatin as a binder for silver halide photographic materials in order to improve flexibility, pressure resistance, and drying properties.

Therefore, the use of latex can also be considered in sensitive materials that are hardened with polymer VJ film-forming agents. For example, JP-A-5
No. 9-12437 contains a polymeric hardener and a latex in a non-photosensitive upper layer to improve reticulation.

However, when such a polymer hardener and a large amount of latex are added to a coating solution for a hydrophilic colloid layer mainly composed of gelatin, fine lumps are formed and trailing layer formation occurs during coating. Product value has dropped significantly.

Furthermore, such tailing failures occur not only when the polymer hardener and latex are present in the same hydrophilic colloid layer, but also when they are present in separate adjacent layers. For example, when multiple layers of a halogen transitive emulsion layer containing latex and a protective layer containing a polymer hardener are simultaneously coated on a support, if the amount of 911 in the latex increases, trailing failure will still occur. For this reason, latex could only be added in a marginal amount, and therefore a silver halide photographic material with sufficiently good dimensional stability could not be obtained.

[Objective of the Invention 1 Therefore, the object of the present invention is to provide a material with good dimensional stability and 11
It is an object of the present invention to provide a silver halide photosensitive material which can be hardened layer by layer and which has improved delivery failures that occur during production.

[Structure of the Invention] The above object of the present invention is achieved by providing a silver halide photographic light-sensitive material containing a water-soluble polymer, a latex, and a polymer hardener in a photographic constituent layer on a support.

[Specific Structure of the Invention] Examples of water-soluble polymers used in the present invention include synthetic water-soluble polymers and natural water-soluble polymers, both of which can be preferably used in the present invention. Among these, examples of synthetic water-soluble polymers include those having, for example, nonionic groups, anionic groups, and nonionic and anionic groups in the molecule + Fi structure. Examples of nonionic groups include ether groups, ethylene oxide groups, hydroxy groups, etc., and examples of anionic groups include sulfonic acid groups or salts thereof, carboxylic acid groups or j8 thereof, phosphorus M groups or salts thereof, etc. can be given.

Natural water-soluble polymers include those having, for example, nonionic groups, anionic groups, and both nonionic and anionic groups in their molecular structures.

As the water-soluble polymer, in both synthetic water-soluble polymers and natural water-soluble 1'1 polymers, those having anionic properties and those having nonionic groups and anionic groups can be preferably used. In the present invention,
A water-soluble polymer is 0.05 (1 or more) dissolved in 100 g of water at 20°C, preferably o, +
g or more.

Examples of synthetic water-soluble polymers include those containing 10 to 100 mol % of repeating units represented by the following general formula [P] in one polymer molecule.

The following is a blank general formula [P] R1 In the formula, R1 is a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (including those having substituents. For example, a methyl group, an ethyl group, a propyl group, butyl group, etc.), halogen atom (e.g. chlorine atom) or -C82
C00M, L is 100Nl-1-1-N) (C
O-1-COO-1-OCO-1-〇〇- or 10-
, J is an alkylene group, preferably having 1 carbon atom
~10 alkylene groups (including those with substituents).

For example, butylene group, ethylene group, propylene group, trimethylene group, butylene group, hexylene group, etc.), arylene group (including those having substituents).

For example, phenylene group), or → CH2CH20+FiV+CH2 thick- (m is 0 to 40
n represents an integer from O to 4, -0M1-NH2, -
3O3M, -〇-P-OM.

! 0M -CR2 represents a hydrogen atom or RJ, and -803M is most preferred. M represents a hydrogen atom or a cation, R2 represents an alkyl group having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), and R3, R4, R5, R6, R7 and R8 are represents an alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, hexadecyl group, etc.), X represents an anion, and Di and q each represent Represents 0 or 1.

Next, specific examples of the synthetic water-soluble polymer of general formula [P] will be given.

Margin below 5P-1 Number average molecular weight P-2 P-3 P-4 P-5 5P-6 SP-7 P-8 CH) 5P-1,0 CH) C○o-tel-1, ch2u- Gar h shi, Usu UP
-11 P-12 CH39,800 P-14 P-15 SP 47 CH.

SP 1.8 P-19 P-20 9,000 P-21 P-22 P-23 P-24 P-25 5P-26 SP-27 CH.

SP-28 P-30 2,100 P-31 So, Na 163.000 P-33 P-34 SP-35CH.

P-36 CH.

■ CH.

5P-47 SP-48 P-49 P-50 15,600 The synthetic water-soluble polymer of the present invention can be easily synthesized by a method such as occasional solution polymerization, bulk polymerization, or suspension polymerization.

For example, in solution polymerization, a mixture of monomers (usually 40% by weight or less, preferably 10 to 25% by weight based on the solvent) in a suitable solvent (e.g., ethanol, methanol, water, etc.) at a suitable temperature is generally used. ) as a polymerization initiator (e.g.
benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) at an appropriate temperature (e.g. 40°C).
The copolymerization reaction is carried out by heating to 120° C., preferably 50 to 100° C.). Thereafter, the reaction mixture is poured into a medium that does not dissolve the produced water-soluble polymer, the product is precipitated, and the unreacted mixture is separated and removed by drying. The molecular weight of the water-soluble polymer of the present invention is from 1,000 to 1,000,000, preferably from 2,000 to 200,000.

d3. The molecular weight of the water-soluble polymer of the present invention is expressed in terms of number average molecular weight, and was measured in terms of standard polystyrene using gel permeation chromatography HLC-802A manufactured by Futanso Co., Ltd. () 1).

Synthesis Example 1 (Exemplary Compound 5P-18> Potassium 3-sulfopropyl acrylate 50[1
(0.22 E-nyl), 4.4'-azobis(4-
Ciatsuvalein iW>3.0g and degassed water 20
Place 3 pieces of 0.0ml in a flask and heat this mixture at 80°C.
Allowed time to react. After the reaction was completed, the reaction solution was poured into acetone with vigorous stirring to precipitate the reaction product. The precipitate was then filtered, washed with acetone, dried in air at 60°C, and the polymer SP-18 of the present invention was added to
It was. The yield was 459 (90% of the theoretical yield), and the number average molecular weight was Mn = 4,300.

Synthesis Example 2 (Exemplary Compound SP-2 1 ) Styrene 52g
(0.5 (1 mol), acrylic acid 36 (+ (
0.50 mol), 4.4'-azobis(4-cyatubarein) 1) 5.0q, and degassed ethanol 5
Put 3 pieces of 00d into a flask and let this mixture flow down 8
Allowed time to react. After the reaction was completed, the mixture was poured into a large amount of ace1-ene while stirring vigorously, and the same treatment as in Synthesis Example 1 was carried out to obtain Polymer 5P-21 of the present invention. Yield: 80g (91% of theoretical yield), number average molecular weight: Mn
= 2,600.

Synthesis Example 3 (Exemplary Compound 5P-42) Hydroxyethyl methacrylate 52g (0.40 mol), Sodium 2-acrylamido-2-methylpropanesulfonate 1371J (0.60 mol), 4.4'-
Three 500g of azobis(4-cyatubaleic acid) and 500g of a degassed water-ethanol-80/20vx solution were placed in a flask, and the mixture was reacted at 80°C for 10 hours. After the reaction was completed, the reaction solution was poured into a large amount of acetone while stirring vigorously to precipitate the reaction product.

The precipitate was then filtered, washed with acetone, and dried in air at 60°C to obtain the polymer 5P-42 of the present invention. Yield: 180g (95% of theoretical yield), number average molecular weight: 1yl
n = 5,300.

Natural water-soluble polymers are described in detail in the comprehensive technical data collection of water-soluble polymer water-dispersible resins (Management Development Center Publishing Department), but include lignin, starch, pullulan, cellulose, alginic acid, dextran, dextrin, and guar gum. , gum arabic, glycogen, laminaran,
Lignin, nigeran, etc., and derivatives thereof are preferred.

Further, as derivatives of natural water-soluble polymers, sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carboxyalkylenated, alkylphosphorylated ones, and salts thereof are particularly preferable.

In the present invention, two or more natural water-soluble polymers may be used in combination.

Furthermore, among natural water-soluble polymers, glucose polymers and their derivatives are preferable, and among glucose polymers and their derivatives, starch, glycogen, cellulose, lignin, dextran, nigeran, etc. are preferable, and dextran and its derivatives are particularly preferable. Derivatives are preferred.

Dextran is a polymer of α-1,61 linked D-glucose, and is obtained by culturing dextran-producing bacteria in the presence of sugars. Dextran sucrase can be obtained from the culture solution by reacting it with sugars. In addition, these native dextrans are reduced to a desired molecular weight by a partial decomposition polymerization method using acid or alkaline enzymes, and the intrinsic viscosity is reduced to 0.
03 to 25 can also be obtained.

In addition, dextran modified products include dextran sulfate esters in which a sulfate group exists in the dextran molecule as an ester bond, and its salts, carboxyalkyl dextran in which the carboxyalkyl group exists in the dextran molecule as an ether bond, and dextran-producing bacteria. Carboxyalkyldextran HM ester in which the sulfate group is present as an ester bond and the carboxyalkyl group is present in the ether bond, and its column, 1-kitran Ill ester in which phosphoric acid ν is present in the ester bond in the dextran molecule, and its 1-n crystal. , hydroxyalkyldextran in which a hydroxyalkyl group is introduced into the molecule of dex1-ran.

The use of these dextrans in silver halide photographic materials is disclosed in Japanese Patent Publication No. 35-11989, U.S. Pat. No. 40149, 46-
As described in No. 31192, these dextrans are incorporated directly into a silver halide emulsion or a gelatin layer to improve the covering power of a silver image, and to improve the maximum temperature and contrast. Improving.

Methods for producing these dextrans and their derivatives are described in detail in these patents.

Among these dextran and its modified products, particularly preferred are dextran sulfate ester, carboxyalkyl dextran Mid ester, and dextran phosphate ester, in which an anionic group is introduced, from the viewpoint of latex dispersion stability. Among them, dextran 6X[u ester is most preferred.

The synthesis of these dextran variants involves using the above-mentioned dextran as a raw material and reacting it with a sulfating agent such as chlorosulfonic acid in the presence of a hydrochloric acidic organic solvent such as pyridine or formamide to form dextran mFIt ester. Obtainable.

Further, when it is reacted with a carboxyalkylating agent such as monochlorocarboxylic acid, carboxyalkyldextran sulfate is obtained.

Furthermore, carboxyalkyldextran can be obtained by using dextran as a raw material and reacting it with a carboxyalkylating agent such as monochlorocarboxylic acid in an alkaline environment. Further, by reacting this with a sulfurizing agent such as chlorosulfonic acid in the presence of a basic solvent such as pyridine or bormamide, carboxyalkyldextran sulfate can be obtained. In addition, oxides of alkali metals such as sodium and potassium, calcium and
By reacting oxides or hydroxides of alkaline earth metals such as magnesium, ammonia, etc., salts of dextran sulfate and carboxyalkyl IaM esters can be obtained, respectively.

Since dextran has three hydroxyl groups that can be substituted per anhydroglucose unit, it is theoretically possible to substitute sulfate groups and carboxyalkyl groups with a maximum degree of substitution of up to 3, but depending on the selection of reaction conditions. It is possible to produce compounds with any degree of substitution within the range of 3 or less.

However, the sum of the degrees of substitution of the sulfate ester group and the carboxyalkyl group cannot exceed 3.

The carboxyalkyl dextran, dextran sulfate ester, and carboxyalkyl dextran 1M ester produced in this manner can be produced in a wide variety of types by varying the intrinsic viscosity of the raw material dextran and the degree of sulfate ester substitution and carboxyalkyl substitution degree of the product. I can do it.

Further, as the water-soluble 4Ji polymer of the present invention, a polymer having a hydrophilic group and an ethylenic double bond in its molecular structure can also be used, for example, the following general formula [VI], [vII
] It is preferable that the polymer is a polymer mainly containing a compound showing ester.

Here, the hydrophilic groups are as described in synthetic water-soluble polymers.
Examples include things similar to komono.

General formula CVI 1 In the formula, R1 is a divalent @ group, Ml is a hydrogen atom or
Rho represents a cation of 30 to 95 mol%, n2
represents 70 to 5 mol%. 1 General formula [vfi] CIl 2 C00H3 CM 2 C0NCl 2 CH2SO3t'l s^
2 [wherein R2 is a hydrogen atom or an alkyl group, M2, M
3, M4 and M5 each represent a hydrogen atom or a cation, n3 represents 30-95 mol%, n4 represents 70-0 mol%, n5 represents 70-0 mol%. However, n4+n5 represents 70-0 mol%. 5 mol%.1 General formula cvm [wherein R3 is a hydrogen atom or an alkyl group, Ma, M
7, Ma and M9 each represent a hydrogen atom or a monovalent cation, n6 is 30 to 70 mol%, and n7 is 5
~50 mol%, n8 represents 70-5 mol%. however,
n7+n8 is 70 to 30 mol%. ] Next, to specifically explain the general formulas [VI], [■co and [VIU], 2 (Ichi's formulas III) represented by R1 include ethylene, 1-rimedylene, tetramethylene, hexamethylene, propenylene, 3゜6 Dioxy4) ΔCran-1,8-diyl, 2,2-dimethyltrimethylene, propylene, 1. /I-Divalent residues of aliphatic hydrocarbons such as cyclohexylene, or 1,2-dichloroethylene, 2-chlorotrimethylene, 2-bromotrimethylene, 1-cyanomethylethylene, 1-chloromethylethylene, 1- 21i1 [i residue, or 1,4-phenylene, 1.
3-tolylene, 2-chloro0-1,4-phenylene, 2-
Cyano~1,4-)1nylene,2-methoxy-1,5-
Divalent residues of aromatic hydrocarbons such as phenylene or divalent residues of aromatic hydrocarbons substituted with halogen atoms, cyano groups, alkyloxy groups, etc., or 1.1'-(1,
4-phenylene)dimethyl, 2.2'-(2-chloro-1,4-phenylene)diethyl, 2.2'-(2-
Examples include divalent residues of aliphatic hydrocarbons such as cyano-1,4-phenylene)diethyl, and divalent residues of aliphatic hydrocarbons bonded to aryl groups substituted with halogen atoms, cyano groups, etc.

M+, M2, Ms, M4 and Ms represent a hydrogen atom, a monovalent cation of an alkali metal such as lithium, sodium or potassium, or an ammonium cation. As the polymer having a hydrophilic group and an ethylenic double bond in its molecular structure, a compound represented by the general formula [Vf] is preferred.

Next, typical examples of the polymer of the present invention will be exemplified below, but the invention is not limited thereto. Methods for synthesizing these polymers are described in JP-A-55-50240.

The following margin (n+: nz = 50 molti: 50 molti, number average molecular weight (Mn) = about 10.000) 70 molti) b%,
Mn = approximately 6,000) 5 mol%, Mn = approximately 20,000) 30 mol%, Mn = approximately 30,000) (However, nl: n2 = 75 mol%: 25%/I/%
, M practice = about 2o, ooci) (however, nl: n2 = 50 mole: 50 mole, eight n = about 25,000) D -12 CONHCH2CH2S○31qa (however, n+: n2 = 5Q mole%: 50 Mol%, Mn=
Approximately 10,000) ■ H3 (However, ns: n2: n3 = 50%%:
(45 mol%: 5 mol%, Mn = approximately 15,000) The latex used in the present invention is mainly composed of hydrophobic polymers, and such polymers are broadly classified into condensation polymers and vinyl polymers. Ru. Examples of condensation polymers include polyamide, polypeptide, polyester, polycarbonate,
Examples include polyacid anhydrides, polyurethanes, polyureas, polyethers, and the like. An unsaturated compound-based polymer is a polymer based on a vinyl group (=I polymer, aliphatic hydrocarbon type, aromatic type,
Examples include single polymers such as vinyl alcohol, nitrile, acrylic, methacrylic, acrylonitrile, and halogen, and copolymers of combinations thereof.

By using the water-soluble polymer of this 51 invention in combination, hydrophobic polymers of any composition can be stably contained in the hydrophilic colloid layer, so the composition is not particularly selected in terms of performance, but latex Polyester or vinyl polymers are preferably selected from the viewpoint of ease of manufacture. The raw material of these polymers is ff13 + unsaturated Cf
The first compound may be a polymerizable unsaturated ethylene compound or a Zinrefine compound. For example, acrylic acid and its esters, methacrylic acid and its esters, crotonic acid and its esters, vinyl esters, maleic acid and its diesters, fumaric acid and its diesters, itaconic acid and its diesters, olefins. , styrenes, acrylamides, methacrylamides, allyl compounds, vinyl ethers, monylketones, polyfunctional esters, monyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, and the like.

Specific examples of these polymerizable unsaturated compounds include acrylic esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ec-7 tyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert
-Octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobuteracrylate, cyanoethyl acrylate, 2-acetyl acrylate]
~xyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate,
Cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2.
2-dimethyl-3-human O-oxypropyl acrylate,
2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-
iso-propoxy acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxybolyethylene glycol acrylate (addition mole Vin-9), 1 -bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate-1-, and the like.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 5ec-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, Chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-7enylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl Methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2
-Methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-7cetoxyethyl methacrylate, 2-7cetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl acrylate, 2-( Examples include 2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, and ω-methoxypolyethylene glycol methacrylate (number of moles added = 6). .

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl acetate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, etc. can be mentioned.

Examples of olefins include dicyclopentadiene, ethylene, butyrene, 1-butene, 1-pentene,
Examples include vinyl chloride, vinylidene chloride, isoprene, chlorobrene, butadiene, 2,3-dimethylbutadiene, and the like.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isobrobylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromstyrene, and vinylbenzoic acid. Examples include methyl ester.

Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like.

Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of the maleic acid diesters include diethyl maleate, dimethyl maleate, diptyl maleate, and the like.

Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibdel fumarate.

Acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Examples include methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, and the like.

Examples of methacrylamide include methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, ter
t-Butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanethylmethacrylamide , N-(2-acetoacetoxyethyl)methacrylamide, and the like.

Examples of allyl compounds include allyl acetate, allyl capronate, allyl laurate, and allyl benzoate.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like.

Examples of the vinyl ketones include methyl vinyl ketone, phenyl vinyl ketone, and methoxyethyl ketone.

Examples of the vinyl heterocyclic compound include vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, and N-vinylpyrrolidone.

Examples of glycidyl esters include glycidyl acrylate and glycidyl methacrylate.

Examples of unsaturated nitriles include acrylonitrile and methacrylatetrile.

Examples of polyfunctional monomers include divinylbenzene, methylene bisacrylamide, and ethylene glycol dimethacrylate.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates, such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; monoalkyl maleates, such as monomethyl maleate, monoethyl maleate, maleic acid; Monobutyl acids, etc. Niditoraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyprolsulfonic acid, acryloyloxypropylsulfonic acid, etc.: methacryloyloxyalkyl Sulfonic acids, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxyethylsulfonic acid, etc.; acrylamide alkylsulfonic acids, such as 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2- Methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.; methacrylamide alkylsulfonic acid, e.g. 2-
methacrylamide-2-methylethanesulfonic acid, 2-
methacrylamide-2-methylpropanesulfonic acid, 2
- methacrylamide-2-methylstansulfonic acid, etc.; acryloyloxyalkyl phosphates, e.g.
Acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc.: Methacryloyloxyalkyl phosphate, such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc.; 3-aryloxy-2 having two hydrophilic groups -sodium hydroxypropanesulfonate, etc. These acids may be salts of alkali metals (eg, Na, Ni, etc.) or ammonium ions. Furthermore, other polymerizable unsaturated compounds include U.S. Patent No. 3.459.790, U.S. Patent No. 3.438.708, U.S. Patent No. 3,554,987,
Crosslinking monomers described in JP-A No. 4.2Is, No. 195, No. 4,247,673, JP-A-57-205735, and the like can be used. An example of such a crosslinking monomer is specifically N-(2-
acetoacetoxyethyl)acrylamide, N-(2-
(2-acetoacetoxyethoxy)ethyl)acrylamide and the like can be mentioned.

Some of these compounds are water-soluble, but
Hydrophobic polymers can be formed by copolymerizing with hydrophobic ones.

The latex production method of the present invention includes a method in which a hydrophobic polymer obtained by solution polymerization is dispersed in water using a surfactant or an organic solvent, and a suspension polymerization method in which polymerization is carried out in an aqueous medium. Although there are legal methods and emulsion polymerization methods, suspension polymerization methods and emulsion polymerization methods are preferable because they reduce the number of manufacturing steps.

Polymerization initiators for vinyl polymers include azobisisobutyratetrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisodimethyl acetate, 2,2'-azobis (4-methoxy-2,4-
dimethyvaleronitrile), 1.1'-azobis(cyclohexanone-1-carbonitrile)dimethyl, 2.2'
-azobisisobutyrate, 4.4'-azobis-4
- Azo compounds such as cyanovaleric acid, sodium 4,4'-azobis-4-cyanovalerate, 2,2'-azobis(2-amidinopropane) hydrochloride, benzoyl peroxide, lauryl peroxide, cumene hydroper Peroxides such as oxide, diisobrobyl peroxydicarbonate, t-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, hydrogen peroxide, potassium persulfate, ammonium persulfate, 1 g! i
Persulfates such as sodium chloride, potassium bromate, ceric ammonium nitrate, and the like are used.

Additionally, peroxides and persulfates can be used as redox initiators in combination with suitable reducing agents. Preferred initiators are those that are water soluble.

Manufacturing method for latex Production example 1 A 1000 d four-bottle flask was equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen introduction tube, and a reflux condenser, and 350 d of purified water was prepared.
Add c and heat until the internal temperature reaches 80°C. During this time, nitrogen gas is introduced, and after the internal temperature reaches 80° C., nitrogen gas is passed for an additional 30 minutes.

Add 4.5 g of sodium dodecylbenzenesulfonate, then add 0.45 g of ammonium persulfate as an initiator.
! A solution of I+ in 10 cc of water is added, and then a mixture of 40 Q of butyl acrylate and 50 cc of styrene is added dropwise using a dropping funnel over about 1 hour. Five hours after the addition of the initiator, the mixture was cooled, adjusted to PT-16 with aqueous ammonia, and filtered to remove dust and coarse particles to obtain a latex liquid (a).

Production Example 2 As a polymerizable unsaturated compound, butyl acrylate 39.
A latex liquid (b) was obtained by synthesizing in the same manner as in Preparation Example 1, except that a mixture of 5(1), 49.5(1) subolene, and 1 g of acrylic acid was used.

Production example 3: 90 g of ethyl acrylate as a polymerizable unsaturated compound
A latex liquid (C) was synthesized in the same manner as in Production Example 1, except that potassium persulfate was used as an initiator and the polymerization was carried out at 70°C.

Production Example 4 A latex liquid (d) was synthesized in the same manner as in Production Example 1, except that Alkanol XC (manufactured by DuPont) was used instead of sodium dodecylbenzenesulfonate.

Production Example 5 Latex liquid (e) was synthesized in the same manner as Production Example 2 except that alkanol XC was used instead of sodium dodecylbenzenesulfonate.

Production Example 6 A latex liquid (r) was synthesized in the same manner as Production Example 3 except that alkanol XC was used instead of sodium dodecylbenzenesulfonate.

Production Example 7 A stirred autoclave was replaced with nitrogen, and 55 parts by weight of styrene, 42 parts by weight of butadiene, and glycidyl methacrylate were added.
I ~ 3 parts by weight, 3 parts by weight of sodium dodecylbenzenesulfonate, 0.2 parts by weight of tertiary dodecyl mercaptan, w
Charge 0.3 layers of tripotassium tetroxide, 20.3 parts by weight of ammonium persulfate, and 100 layers of water, polymerize at 50° C., at 5 atm pressure, for 18 hours, and after the reaction is complete, The remaining monomer was removed by distillation to obtain latex (g).

Production Example 8 Trimelidic anhydride 192.1a (
1.0 mol), ethylene glycol 62.1 fJ (
1.0 mol) and benzyl alcohol 108.1 (+
(1.0 mol) was loaded.

The reaction mixture was heated to 150°C and maintained at this temperature for 4 hours with stirring. Then, distillation of water was started, and the temperature was gradually raised to 190°C over about 9 hours, and then further raised to 205°C.

The obtained polyester was taken out and subjected to cold 11JI assimilation.

100 g of the obtained polyester was dissolved in 250 ηQ of acetone, and 100 v of ammonia aqueous solution with a molar concentration of about 0.01 molar was added.
The acetone solution was slowly poured into the solution under rapid stirring. This mixture was filtered and then heated to 60°C to remove acetone to obtain a latex liquid (h).

In the present invention, the amount of latex used is 100% gelatin.
tffl ratio is 10% or more and 300% or less, preferably 30% or more and 200% or less. If too few machines use latex, the effects of the present invention will not be fully exhibited, and if too many machines use latex, sufficient film strength will not be obtained. Further, the amount of the water-soluble polymer used in the present invention is 0.5% or more and 30% or less, preferably 1% or more and 15% or less, based on 100% of the latex. If the amount of water-soluble polymer used is too small, the sufficient effect will not be exhibited, and if it is too large, problems will arise in the coating properties of gelatin, especially during high-speed coating.

Margin below Next, the polymer hardener used in the present invention will be explained.

The polymer used in the present invention (filming agent) refers to a polymer having a functionality that can crosslink with gelatin, and a polymer having a functionality that can crosslink with gelatin via a hardening agent. The polymers also include modified gelatin products obtained by weakly reacting gelatin with a hardening agent having a low R content.

These polymeric hardeners are described, for example, in U.S. Pat. No. 3,057.
．． No. 723, No. 3,671,256, No. 3.39
No. 6.029, No. 4,161,407, No. 4.207
．． No.109, British r
Patents such as No. 121327 and “The Celery of the Photographic Process” 4th edition (bottom, page 1)
[James et al.], page 94, [Polymeric Amine and Ammonium Solz (E, J., Gutars et al.), page 321, etc., which are known in the art, can be used.

Among these polymeric hardeners! I? j: In L-Imonodoshi, polysaccharide modified products such as dialdehyde IQ 'yt>, modified piratin with pendant gelatin cross-linking agent, and water-soluble polymers with functional groups cross-linked with piratin are shown in graphs 1 to 1. Examples include polymers or copolymers of vinyl monomers having a functional group capable of crosslinking with gelabone.

Particularly preferred is a polymer or copolymer of a vinyl monomer having a functional group that crosslinks with geratin.

Polymers or copolymers made of vinyl monomers having functional groups capable of crosslinking with gelatin include the following general formula [I
], []I], and [I[I] are preferred.

The following margin is General formula [1] %Formula% General formula [11] General formula [I[1] %Formula% Here, R1 is a hydrogen atom, a halogen atom, or a carbon number of 1 to
Represents 4 lower argyl groups, 0 is -Co-, -G
O2-, -CON- (R2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), an alkylene group or an arylene group having 6 to 12 carbon atoms, and -CO2-.

15111a containing at least one divalent group having a carbon atom, or -0-, -N-, -Co-, -8o-, -3O2- 6
Represents a divalent group having 12 carbon atoms.

G represents a group involved in a crosslinking reaction with gelatin. M represents an alkali metal, and m and n each represent 0 or 1 (provided that m+n≧1).

h represents O or 1.

For example, Q includes the following bases:

H3 -CO2-, -CONH-, -CON-.

Margin below For example, L includes the following bases.

-0 month 2CO2CH2- -c+2CO2C+2C+-+2- -C)-12C)-12CO□C)(2C)-12-I
C) (2-)5C02C)-12C)12-IC)'l
2-)7-5CO2CH2CH2-CH2CHCOC)
12- -CH2NHCOCH2CHz -+ Cl-12+-N) (C0CH2cH2-+
CHz 10TN HCOCH2CH2--+CH2+,
,NHCOCH2Cl-1,--c)-12ocH2--C1-(2CH20CH2CH2CH2-C)-1x
? Ha -NCH2CH:+-, -CH2CH2120H2-C
OCHzCHz- -C) -12C0CH2C)-12- -8OC)lze)12- -CH2SOC1-I2CH2- -5O2CH2C) -12- -5O2CH2CH2SO2CH2CHz- -8O2C
HxCH2SO2CHxCHCH2-■ H -9O3CH2CHzCH2- -9O3C) (2COzC) -1zC)42- -9OCH2C) (2CO2C) -I2CH2--,502N
HC)-12C0,2CH2CH2--8O2Nl-1
cH2cI(2CO2CH2CH2--N)(CONH
CH2CHz - -C) (zN)tCONHCt-120Hz--N onlyC
02CH2Cl (2- -C1-1; N1-40020 days 2CH2--CONH
CH2-, -CON)ICH2CHz+.

-CONHCH2CH-CH2-.

-〇〇Nl-4CH2CH2CH2CH2CH2-.

-COCI-12cl→20cOc)-1ze)-12
−.

-CON)ICH2CONHC+-12.

-CON)1cH2cONHcH2CONI-1zcH
2-.

G includes, for example, a group such as dog.

-CH2= CH,, -CH2CH2C1! , -CH,
SO3Na, -NHCH2PO(ONa)
2, N (CHff)2, -0NH4, -0C
H,,NHSO:LNa, -CH2CH2B
r.

-CH2-CH202CCHCe2 1'+02 C2 discharge -COzeH2CN -eo2cH2cO
zczHs-CO2CH2('0N)-12-CO2C
H2COCHs-CO2N=CHCHR-CO2N=C
(C)! 312-COzCH2CHzBr -CO
2C)lzcH2chJH3 -CO2C)12C82θN -Ct-+3c#CH3 The polymer hardener according to the present invention has the general formula [1], [I[1
, [ [ The comonomer used in the copolymerization may be a polymerizable unsaturated ethylenic compound or a diolefin compound. For example, acrylic acid and its esters, methacrylic acid and its esters, crotonic acid and its esters, vinyl esters, maleic acid and its diesters, fumaric acid and its diesters, itaconic acid and its diesters, olefins. , subolenes, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl ketones, polyfunctional monomers,
Examples include vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, and the like.

To give specific examples of these polymerizable unsaturated compounds, examples of acrylic esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, lobetyl acrylate, isobutyl acrylate, 5ec-butyl acrylate, and amyl acrylate. , hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert
-Octyl acrylate, 2-Ooethyl acrylate, 2-pro-ethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-n-rocyclo hexyl acrylate, cyclohexyl acrylate, furfuryl acrylate,
Tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2.2
-dimethyl-3-hydroxypropyl acrylate, 2
-Methoxybenyl acrylate, 3-methoxybutyl acrylate, 2-1 toxyethyl acrylate, 2-i
so-propoxy acrylate, 2-11-oxyethyl acrylate, 2-(2-methoxyethyl-1-xy)T-alacrylate-1-, 1-(2-butoxyethoxy)-acrylate, ω-methoxypolyethylene glycol acrylate (additional 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, and the like.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 5CC-butyl methacrylate, amino methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, Chlorobenzyl methacrylate, ocdyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate-1~ , tetrahydrofurfuryl methacrylate, phenyl methacrylate, talesyl methacrylate, naphthyl methacrylate, 2-human [coxiable methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3 -methoxybutyl methacrylate, 2-ace1hexyethyl methacrylate, 2-acetoacetoxyethyl methacrylate,
2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate-1-, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2- Examples include (2-butoxyethoxy)ethyl methacrylate and ω-methoxypolyethylene glycol methacrylate (n-6 moles).

Examples of vinylnisders include vinyl acetate vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caproate, vinyl chloride [] [1 avidate, vinyl methoxy arethi 1-, vinyl phenyl acetate, vinyl benzoate, [narityl] Examples include vinyl acid.

Examples of olefins include dicyclopencdiene, ethylene, propylene, 1-butene, 1-pentene,
Examples include vinyl chloride, vinyl chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimedelstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromstyrene, and vinylbenzoic acid methyl ester. Examples include.

Nisder crotonates such as 111 include butyl chloropentate, hexyl crotonate, and the like.

Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibdel maleate, and the like.

Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibdel fumarate.

Acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Examples include methoxyethylacrylamide, dimethylaminoedylacrylamide, phenylacrylamide, diethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, and N-(2-acedo-l-xyethyl)acrylamide.

Examples of methacrylamide include methacrylamide, methylmethacrylamide, ethylacrylamide, propylmethacrylamide, butylmethacrylamide, tart
- bunalmeccrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide,
Dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanethylmethacrylamide,
Examples include N-(2-acetoacetoxyethyl)methacrylamide.

Examples of allyl compounds include allyl acetate, allyl caproate, allyl laurate, and allyl benzoate.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like.

Examples of vinyl ketones include methyl vinyl ketone, phenyl vinyl ketone, and methoxyethyl vinyl ketone.

Examples of the vinyl heterocyclic compound include vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, and N-vinylpyrrolidone.

Examples of glycidyl esters include glycidyl acrylate and glycidyl methacrylate.

Examples of unsaturated nitriles include acrylonitrile and methacrylate trile.

Examples of the polyfunctional monomer include divinylbenzene, styrene bisacrylamide, and ethylene glycol dimethacrylate.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates, such as monomethyl itaconate, monobutyl itaconate, monobutyl itaconate, etc.; monoalkyl maleates, such as monomethyl maleate, monoethyl maleate, maleic acid; monobutyl acids, etc.; citranic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid, such as acryloyloxydimethylsulfone, acry[1yloxynibullosulfonic acid, acryloyloxypropyl] Sulfone MQ
etc.: Methacryloyloxyalkylsulfonic acids, such as methacryloyloxyethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.; Acrylamidoalkylsulfonic acids, such as 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamide -2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.: methacrylamide alkylsulfonic acid,
For example, 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, and niacryloxyalkyl phosphates, such as acryloyloxyethyl phosphate,
3-Acryloyloxypropyl-2-phosphate, etc.; Methacryloyloxyalkylbosphates, such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc.:
Examples include sodium 3-allyloxy-2-hydroxypropanesulfonate having two hydrophilic groups. These acids may be salts of alkali metals (eg, Na, Ni, etc.) or ammonium ions. Zaranisonohaku's combinatorial unsaturated compounds include U.S. Patent No. 3,459.
, No. 790, No. 3.438.708, No. 3.55
No. 4.987, No. 4,215,195, No. 4,2
47,673, JP-A No. 57-205735, etc., cross-linking materials can be used. Specific examples of such crosslinkable additives include N-(2-acetoacetoxyethyl)acrylamide, N-(2-(2-7cetoacetoxyethoxy)ethyl)acrylamide, and the like. can.

Next, specific examples of the polymer hardener according to the present invention will be shown, but the present invention is not limited thereto.

5 margin Q g −
Evening punishment D
Target B It
If＞＞
In other words, the silver halide photographic light-sensitive material according to the present invention contains a water-soluble polymer, a latex, and a polymeric hardener in its photographic constituent layers. Used in a photographic constituent layer, or of two adjacent photographic constituent layers, one layer contains latex and the other layer contains a polymer hardening agent, and at least one of these layers contains latex and the other layer contains a polymer hardener. The effect of the present invention is very large when a water-soluble polymer is contained in the water-soluble polymer. In the case of the latter embodiment, it is more preferred to use a water-soluble polymer in the latex-containing layer.

In the present invention, the amount of latex used is 20% to 300% by weight, preferably 50% to gelatin.
% or more and 200% or less. If the amount of latex used is too small, dimensional stability will be poor, and if it is too large, sufficient strength will not be obtained.

Further, the water-soluble polymer used in the present invention has a weight ratio of 0.05% to 20%, preferably 0.1% to 10%, based on Zerabun. If the amount of the water-soluble polymer used is too small, sufficient effects will not be exhibited, and if it is too large, problems will arise in coating properties during the production of sensitive materials, particularly during high-speed coating.

Furthermore, the polymer hardener used in the present invention has a weight ratio of 0.1% to 30%, preferably 0.5% to gelatin.
15% or less. If the amount of polymeric hardener is too small, sufficient hardness cannot be obtained, and if it is too large, problems arise in coating properties.

As a binder for the photographic constituent layer, gelatin or gelatin derivatives may be used in combination with latex.

In addition to lime-treated gelatin, gelatin
of the society of science
Photography of Japan (Bull, So
c, Sci, Phot, Japan,)No,
16.30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Examples of gelatin derivatives include various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkyleonoxides, and epoxy compounds. The product obtained by reacting is used. Specific examples are U.S. Pat.
British Patent No. 861,414, British Patent No. 1,033.189,
It is described in Japanese Patent Publication No. 1,005,784, Japanese Patent Publication No. 42-26845, etc.

The silver halide emulsion of the present invention includes any silver halide used in conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. can be used.

Furthermore, 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. It may be a particle in which an image is mainly formed on the surface, or it may be a particle in which an image is mainly formed inside the particle.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape such as a cube, an octahedron, or a tetradecahedron, or may have an irregular crystal shape such as a spherical or plate shape. It may also have a crystalline form.

In these particles, any ratio of the (100) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The average grain size of the silver halide grains (grain size represents the diameter of a circle with an area equal to the projected area) is preferably 5 μm or less, and particularly preferably 3 μm or less.

The silver halide emulsion of the present invention may have any grain size distribution. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle with a value of 0.20 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. This indicates the diameter when the image is converted into a circular image with the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion of the present invention can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using a precious metal compound such as gold or silver, etc. can be used alone or in combination.

Further, the silver halide emulsion layer may contain a dye-forming coupler to produce a color light-sensitive material.

[Examples] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A silver chloroiodide emulsion containing 74 mol % of silver chloride, 25 mol % of silver bromide, and 1 mol % of silver iodide was added to a silver chloroiodide (:':1'f) emulsion per mol of silver halide. 6 (l of 4-hydroxy-〇-methyl-1.3.3a, 7-te1herari“
Add indene and add aqueous solution of water-soluble polymer to gelatin.1. 0.05g was added as a dry revision to Og, and latex was added at 1.0g per 1.0g of gelatin as a drying wheel, and a polymer hardener was further added. , fjl Ejl 4 on the undercoated polyethylene terephthalate support Vj body
．． Og/12, total of gelatin and latex is 1.9
(It was applied so that it was 1/+12.

Regarding the obtained samples, the vA of occurrence of trailing failure during coating was observed with the naked eye, each slurry was roughly exposed to light, and the following development treatment was performed to examine the dimensional stability.

The results are shown in Table-1.

[Dimensional change rate] The dimensional change rate accompanying the development process was measured using a bottle gauge. The dimension of the exposed sample with a thickness of 200 mm before processing is X1llll+, the dimension after development processing is Ymm,
The rate of change in dimension is determined by the following formula.

Dimensional change rate (%) = ((Y-X) / 200)
x 1o.

In the industry, it is considered that there is no practical problem if the dimensional change rate is ±0.001% or less.

[Tailing failure] A case where no tailing occurred in the coating direction was evaluated as A, a case where one or two cases of tailing occurred in 1 v' was evaluated as B, and a case where more than that occurred as C.

[Processing conditions] Development: 29°C, 30 seconds Fixation: 28°C, 20
Wash with water for 20℃ 2
Dry for 0 seconds at 45°C for 30 seconds Soul image solution (undiluted solution)] Potassium bromide 25g Ethylenediaminetetraacetic acid disu! ~Thulium 1g potassium sulfite (
55% aqueous solution) 90% potassium carbonate
25 Rehydroquinone
10[+5-methylbenzo1-lyazole
100mg 5-21-penzotriazole 1
00mg1-) [Nyl-5-merkabutode1heran-
0m9 5-21-loindazole 50mg1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.5g diethylene glycol
60g Sodium hydroxide Adjust DH to 10.6j Add water to make 500 vQ. (11
H10,6) When using, the above stock solution is diluted to twice the volume with water.

[Fixer] (Part A) Ammonium boric acid 1700 Sodium sulfite 15 (1 Boric acid
6.5g glacial acetic acid
12 reduced sodium citrate (dihydrate) 2.5 (1 Add water to make 275iI2.

(Part B) Add 15 g of aluminum sulfate (18 hydrate), 2.5 g of 98% sulfuric acid, and add 40 g of water.
Finished with TII2.

The method for preparing the solution used is to add about 600 TI (l) of water to Part A 275vR, add Part 840-, and then add water to make it to 10001N.

From the results shown in Margin Table 1 below, it can be seen that the examples of the present invention have good dimensional stability and do not cause tailing failure. On the other hand, sample No. does not use a water-soluble polymer.

Sample No. 11 was found to have tailing failure, and sample No. 12, which did not use latex, had very poor dimensional stability.

Example 2 A silver iodobromide gelatin high-sensitivity emulsion containing 98.5 mol% silver bromide and 1.5 mol% silver iodide was added with halogenated! ! 1
1.2 g of 4-hydroxy-6-methyl-1 per mole
, 3,3a,7-chitrazaindene, 10 g of diethlene glycol, and an aqueous solution of water-soluble polymer was added to 1.0 g of gelatin at a dry weight of 0.05 g.
(1.Additionally, latex (b) was added at a dry weight of 1.0g per 1g of gelatin to obtain an emulsion coating solution.On the other hand, for a protective layer, an aqueous solution of a water-soluble polymer was added to the gelatin solution. Add 0.05g of dry weight to 1oQ, and add 1oQ of polymer hardener.
-4 was added at 0.1 (l) to gelatin 19 to obtain a coating solution.

An emulsion layer and a protective layer were formed on a polyethylene terephthalate support subjected to -F coating, and the silver content of the emulsion layer was 4.0 (+/1
', the protective layer was coated at the same time with gelatin of 1.5 (!/TI'), and samples No. 11 to 4 were coated at 19.

In addition, as a comparative example, sample N was prepared without using a water-soluble polymer.
o, 5 was created. The occurrence of trailing failure in the obtained sample was observed with the naked eye.

The results are shown in Table-2.

Table 2 As is clear from Table 2, even when a layer containing latex and a layer containing a polymer hardener are adjacent to each other, if a water-soluble polymer is present in at least one of the layers, trailing failure occurs. does not occur. In contrast, in the absence of a water-soluble polymer, trailing failures occur even when a layer containing latex and a layer containing a polymeric hardener are adjacent to each other.

Claims (1)

[Claims] A silver halide photographic light-sensitive material characterized in that a photographic constituent layer on a support contains a water-soluble polymer, a latex, and a polymeric hardener.