JPS62103632A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the titled photosensitive material with which the deterioration in sensitivity is obviated and an increase of fogging is low by incorporating a latex contg. a hydrophilic high polymer having a nonionic functional group and anionic functional group as protective colloid into the molecular structure of a silver halide emulsion layer. CONSTITUTION:The hydrophilic high polymer having the nonionic functional group and anionic functional group and latex are incorporated into the molecular structure of the silver halide emulsion layer. The hydrophilic high polymer having the nonionic functional group and anionic functional group in the molecular structure is the hydrophilic high polymer commonly having an ether group, ethylene oxide group, and hydroxy group as the nonionic group and a sulfonic acid group or the salt thereof, carboxylic acid group or the salt thereof, and phosphoric acid group or the salt thereof as the anionic functional group. The dissolution of the hydrophilic high polymer at >=0.05g in 100g water at 20 deg.C is satisfactory. The hydrophilic high polymer has >=2,000 number average mol.wt., preferably has the ethylene oxide group and sulfonic acid group in common and has >=0.1g solubility in water.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material 1'+1 containing a synthetic polymer in a silver halide emulsion layer. More specifically, the present invention relates to a silver halide photographic light-sensitive material in which a silver halide emulsion layer contains latex which has been made into a protective colloid with a specific hydrophilic polymer.

[Background of the Invention] Generally, latex is used together with gelatin as a binder for halogenated photosensitive materials to reduce the gelatin content and improve the physical properties of the film, such as dimensional stability before and after development, dimensional stability against moist heat. , is known to improve flexibility, pressure resistance, and drying properties. However, the use of latex has a significant impact on photographic performance and the like. For example, various improvements have been attempted to solve problems such as desensitization of silver halide emulsions, devitrification during development, color staining of dyes after development, and deterioration of halftone dot quality of photosensitive materials for printing. . For example, US Patent No. 3,525,620, Belgian Patent No. 76
No. 8,558, U.S. Pat. No. 3,142,568, U.S. Patent No. 3.
No. 323.286, Belgian Patent No. 708,347,
German Patent No. 2,047,150, British Patent No. 1,49
As described in Japanese Patent Application Laid-Open No. 8,697 and Japanese Patent Application Laid-Open No. 57-50967, there are attempts to improve these drawbacks by polymerizing latex using a specific activator.

However, this technique is limited in the types of emulsions used, and none of them has any effect on fog, sensitivity, and development characteristics. Therefore, for latex emulsion polymerized using a low molecular weight surfactant, the combination of the type of latex and the silver halide emulsion used is limited, and the amount of latex that can be contained in the emulsion is also limited.

JP-A-55-50240, JP-A-55-47371, JP-A-54-1-9772, JP-A-48-52882,
In order to solve the above problems, Japanese Patent No. 48-52883 discloses a technique in which a latex using a polymeric protective colloid is contained in a silver halide emulsion during emulsion polymerization.

Although these latexes have little effect on photographic performance, they do have problems in the production of photographic materials, such as devitrification during development, increased viscosity of coating liquids, deterioration of multilayer properties, and repellency during coating. be. When using polymer latex to improve the physical properties of the film, it is advantageous to use polymer protective colloid latex from the viewpoint of photographic performance, but it is difficult to avoid devitrification during development and thickening during application. Photographic materials using polymeric protective colloid latex have not yet been put into practical use due to many problems in the manufacturing process, such as the occurrence of compatibility with gelatin. good and
It is an object of the present invention to provide a silver halide photographic light-sensitive material that uses a silver halide emulsion that does not cause aggregation when latex is added to the emulsion, and is free from deterioration in sensitivity and little increase in fog.

Another object is to provide a silver halide photographic material using the above emulsion that is free from curl and exhibits little dimensional change.

The above objective can be achieved by the following technical means.

[Structure of the Invention] The above object 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 at least one nonionic element in its molecular structure. This is achieved by incorporating a hydrophilic polymer and a latex containing a functional group and at least one anionic functional group.

[Specific Structure of the Invention] The latex of the present invention includes: ■ A resin obtained by polymerizing a polymerizable unsaturated compound in advance, as it is, or a solution obtained by dissolving it in a water-miscible organic solvent, containing water or a water-miscible organic solvent. A stable latex is obtained by adding the hydrophilic polymer according to the present invention dispersed in an aqueous solution.

(2) A stable latex is obtained by dispersing the resin obtained by previously polymerizing a polymerizable unsaturated compound as it is or by dissolving the solution in a water-miscible organic solvent in an aqueous solution containing the hydrophilic polymer according to the present invention.

(2) A polymerizable unsaturated compound is emulsion polymerized in water using a small amount of surfactant, and the hydrophilic polymer according to the present invention is added therein to obtain a stable latex.

(2) The hydrophilic polymer according to the present invention is dissolved in water or an aqueous solution containing a water-miscible organic solvent, and a polymerizable unsaturated compound is added thereto and polymerized to obtain a stable latex.

It can be obtained by a method such as

In method (2), a more stable latex can be obtained by heating the hydrophilic polymer according to the present invention to a temperature of 50 DEG C. or higher and then cooling it.

In the above method, method (2) is preferred in order to obtain a latex with good stability and uniform particle size.

In the present invention, a hydrophilic polymer having both a nonionic functional group and an anionic functional group is defined as a hydrophilic polymer having both a nonionic functional group and an anionic functional group.
It is a hydrophilic polymer having both a hydroxy group and a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, and a phosphoric acid group or a salt thereof as an anionic functional group. In addition, hydrophilic polymer means 100 g of water at 20°C.
If the number average numerator is 2, it is sufficient to dissolve 0.050 or more
Meet over 000 things. Preferably, it has both an ethylene oxide group and a sulfonic acid group and has a solubility in water of 0.1 g or more.

The hydrophilic polymer according to the present invention may include a third component in its composition. In that case, the total molar ratio of the two functional groups is at least 10% or more, preferably 30% or more. A specific example is shown below. (The numbers on the main chain represent the molar ratio.) The following margins are 0:I:1 CH.

m n -A-P-650
50+CH, -CH÷ 7300 0OH CH.

P-74060+CHZ C+ 27
000OH CH.

P-86040+CH2-Csu 480
0C00CHzCHaSOsNa CH3 Margin below The latex used in the present invention mainly consists of hydrophobic polymers that have been made into a protective colloid by the hydrophilic polymer according to the present invention. Broadly classified. Examples of condensation polymers include polyamide, polyethylene, polyester, polycarbonate,
Examples include polyacid anhydrides, polyurethanes, polyureas, polyethers, and the like. Unsaturated compound-based polymers are addition polymers with vinyl groups, and include single polymers such as aliphatic hydrocarbon-based, aromatic-based, vinyl alcohol-based, nitrile-based, acrylic-based, methacrylic-based, acrylonitrile-based, halogen-based, etc. and a combination of these.

By forming a protective colloid with the hydrophilic polymer according to the present invention, a hydrophobic polymer of any composition can be stably contained in the hydrophilic colloid layer, so the composition is not particularly selected from a performance standpoint. Preferably, polyester or vinyl-based polymers are selected from the viewpoint of ease of manufacture, latex production) Δ. The unsaturated compound to be polymerized, which is the raw material for the coalescence, 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, styrenes, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl ketones, polyfunctional monomers, vinyl Examples include surface ring 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, n-butyl acrylate, isobutyl acrylate, 5ec-butyl acrylate, amyl Acrylate hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-
Octyl acrylate, 2-chloroethyl acrylate, 2-propyl methacrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylamine 1-noethyl acrylate, benzyl acrylate, methoxybutyl acrylate, 2-chlorocyclohexyl acrylate, cyclo hexyl 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-t
so-propoxy acrylate, 2-but4nidiethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxyboriethylene glycol acrylate 1~(addition) number of moles n=9), 1-bromo-2~
Examples include methoxyethyl acrylate, 1,1-dichloro-2-layer 1-xyethyl acrylate, and the like.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, inpropyl methacrylate, n-methyl methacrylate, isobutyl methacrylate, 5ec-methyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate. , chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, Phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2- and droxyegul methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2- Acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2
-Ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy) ) Ethyl methacrylate, ω-Me1-xypolyethylene glycol methacrylate monolayer (additional mole number n = 6), and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobulate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acedate, vinyl benzoate. , vinyl salicylate, etc.

Examples of olefins include dicyclopentadiene, eburene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene, and the like. .

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromstyrene, vinylbenzoic acid methyl ester, etc. can be mentioned.

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

Further, examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, diptyl itaconate, and the like.

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

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

Acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Examples thereof include methoxyethyl acrylamide, dimylaminoethyl acrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, and N-(2-7cetoacetoxyegyl)acrylamide.

Examples of methacrylamides include methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, ter
t-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylacrylamide,
Dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide,
Examples include N-(2-7cetoacetoxyethyl)methacrylamide.

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

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyedyl 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-vinylpyridine.

Examples of glycidyl esters include glycidyl acrylate and glycidyl methacrylate.

Examples of unsaturated 21-helyl compounds include acryloni-1-lyl and methacrylatelyl.

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

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates, such as monomedyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; monoalkyl maleates, such as monomethyl maleate, monoethyl maleate, maleic acid, etc. Acrylic monobutyl acid, such as ditraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropyl sulfonic acid, etc.: methacryloyloxy Alkyl sulfonic acids, such as nuclyloxymethyl sulfonic acid, methacryloyloxyethyl sulfonic acid, methacryloyloxypropylsulfonic acid, etc.; acrylamide alkyl sulfonic acid,
For example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.: methacrylamide alkylsulfonic acid, e.g.
-Methacrylamide-2-methylethanesulfonic acid, 2
- methacrylamide-2-methylpropanesulfonic acid,
2-methacrylamido-2-methylbutanesulfonic acid, etc.; acryloyloxyalkylbosphates, such as acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc.; methacryloyloxyalkyl phosphates, such as methacryloyloxyethyl phosphate, 3 -methacryloyloxypropyl-2-phosphate, etc.; and sodium 3-aryloxy-2-hydroxypropanesulfonate having two hydrophilic groups. These acids may be salts of alkali metals (such as N31) or ammonium ions. Furthermore, other polymerizable unsaturated compounds include U.S. Patent No. 3.459.790;
No. 3,438.708, No. 3.554.987, No. 4.215.195, No. 4,247,673
Crosslinkable monomers described in 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.

Examples of the polymerization initiator for the vinyl-based m polymer include azopisisobutyronitrile, 2,2'-azobis=(2,4-dimethylvaleronitrile), 2,2'-azobisisoFIAl
Dimethyl, 2,2'-azobis(4-methoxy-2,4
-dimebvaleronitrile), 1.1'-azobis(cyclohexanonemono-carbonyl-1-lyl)dimethyl, 2
．． to 2'-azobisisobutylene 1, 4,4'-azobis-4-cyanovaleric acid, 4,4'-azobis-4-cyanovaleric acid I.lium, 2,2'-azodos (2-amidinopropane) azo compounds such as hydrochloride, benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate,
Peroxides such as t-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, hydrogen peroxide, persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, potassium bromate, nitric acid Ceric ammonium or the like is used.

In addition, peroxides and peroxides can also be used as redox initiators in combination with suitable reducing agents. Preferred initiators are water soluble.

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

The latex production method in the present invention includes a method in which a hydrophobic polymer obtained by solution polymerization is dispersed in water using a surfactant or a solvent or other solvent, and a method in which the polymerization is carried out in an aqueous medium. Although there are 'IQ'1 method and emulsion polymerization method, suspension polymerization method and emulsion polymerization method are preferable because the number of culms required until production is reduced.

In the present invention, the amount of latex used is 100% gelatin.
ff1ffi ratio of 10% or more and 300% or less,
Preferably it is 30% or more and 200% or less. If the amount of latex used is too small, the effect of the present invention will not be fully exhibited, and if the amount of latex used is too large, sufficient membrane strength will not be obtained. Gloss is 0.1% less than 30% in ff1ffi ratio to resin
The content is preferably 15% or less and 0.5% or more. The same applies to R used in emulsion polymerization.

Some of the hydrophilic TQ polymers according to the present invention can be easily synthesized by conventionally known methods such as solution polymerization, bulk polymerization, and suspension polymerization.
can be done.

For example, in solution polymerization, a mixture of AA molecules is generally used at an appropriate concentration in an appropriate solvent (e.g., ethanol, methanol, water, etc.) (usually a mixture of 40% by weight or less, preferably 10 to 25% by weight based on the solvent). by heating to an appropriate temperature (e.g. 40-120°C, preferably 50-100°C) in the presence of a Nakadai initiator (e.g. (benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.)). A copolymerization reaction is carried out.Then, the reaction mixture is poured into a medium that does not dissolve the produced copolymer, the product is precipitated, and the unreacted mixture is separated and removed by drying.The copolymerization reaction of the present invention The molecular quality of coalescence is
1,000 to 1,000,000, preferably 2,0
00 to 200,000.

The molecule 1 of the polymer of the present invention is expressed as a number-average molecular sphere, and the measurement was carried out using a gluvermeation chromatography HLC-802A manufactured by Toyo Soda ISI in terms of standard polystyrene.

Synthesis Example (Exemplary Compound P Single Layer 1) Hydroxyethyl methacrylate 52g (0.40 mol), Sodium 2-acrylamido-2-methylpropanesulfonate 137C1 (0.60 mol) 4.4-azobis(4-cyazubarein 119) 5 ．． Oql and degassed water-ethanol = 80/20V% solution s
Put three of o o, y into a flask, and add this mixture to 80
The reaction was carried out at ℃ for 10 hours. After the reaction was completed, the reaction solution was poured into a large volume of acetone while stirring vigorously to precipitate the reaction product. Next, the precipitate was filtered, washed with acetone, and dried in air at 60°C to obtain P monolayer 1 of the present invention.

Yield 1 is 180g (95% of the theoretical intake) and the number average molecule I
M n =5300.

Manufacturing method for latex Manufacturing example 1 Four 1,000-liter flasks were equipped with a stirrer, a thermometer, one coat of dripping, a nitrogen introduction tube, and a reflux condenser, and 350 liters of pure water was used.
Add CC and heat until the internal temperature reaches 80°C. During this time, nitrogen gas was passed through the chamber, and after the internal temperature reached 80° C., nitrogen gas was passed for another 30 minutes.

Add 4.5 g of P layer 1, then add a solution of 0.45 g of ammonium persulfate dissolved in 10 cc of water as an initiator, and then add 40 g of butyl acrylate and 50 g of styrene (+ mixture in a dropping funnel). It took about an hour,
Drip. Five hours after the addition of the initiator, the mixture was cooled, adjusted to pH 6 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 monolayer ~ 39
．． Latex liquid (b) was synthesized in the same manner as in Production Example 1 except that a mixture of 5(1), 49.5Q styrene, and 1 g of acrylic acid was used.

Production Example 3 As a polymerizable unsaturated compound, ethyl acrylate monolayer ~ 90
g, tut A latex liquid (C) was obtained by synthesizing 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 Production Example 1 except that P-9 was used instead of P-1 layer 1.
Latex liquid (d) was obtained by synthesis in the same manner as above.

Production Example 5 Production Example 2 except that P-9 was used instead of P-1 layer 1.
Synthesize in the same manner as above to obtain latex liquid (C).

Production Example 6 Production Example 3 except that P-9 was used instead of P-1 layer 1.
It was synthesized in the same manner as above to obtain a latex liquid <f).

Production Example 7 A stirred autoclave was replaced with nitrogen, and 55 parts of styrene, 42 parts of butadiene, 3 parts of glycidyl methacrylate, 13 parts of P monolayer, 0.2 parts of tertiary acyl mercaptan, 0.2 parts of triphosphoric acid were added. Potassium 0.3 parts and 4 parts,
Excessive rg! ! 0.3 parts by weight of ammonium acid and 100 parts by weight of water were charged for polymerization, polymerization temperature was 50°C, polymerization pressure was 5 atm, and polymerization time was 1.
Polymerization was carried out for 8 hours, and after the reaction was completed, the remaining monomers were removed by distillation.
Latex (a) was obtained.

Production Example 8 1-limellitic anhydride 192.1 (+
< 1.0 mol), ethylene glycol 62, IC
1 (1,0 mol) and benzyl alcohol 108.1 (
1 (1.0 mol).

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, cooled and solidified.

100 g of the obtained polyester was dissolved in 250 iN of acetone, and 100 g of an aqueous solution of P of about 0.1 molar concentration was added. Q
The acetone solution was slowly poured into the solution with 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 hydrophilic polymer and latex according to the present invention are contained in the silver halide emulsion layer, but if necessary, other photographic constituent layers such as a protective layer, an intermediate layer, an antihalation layer, etc. It is absolutely not advisable to add it to the base layer, backing layer, mordant layer, neutralizing layer, etc.

Although it is advantageous to use gelatin as the hydrophilic colloid layer, gelatin derivatives may be used in combination with gelatin.

In addition to lime-treated gelatin, gelatin
of the society of science
Photography of Japan (Bull, 5o
cSSci%Photo, Japan, )NO, 1
6, p. 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. As gelatin derivatives, various compounds such as gelaboon, acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkyleonoxides, epoxy compounds, etc. The product obtained by reacting is used. Specific examples thereof include U.S. Patent No. 2,614,928, U.S. Pat. No. 3,132,945, 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 may include any of the silver halides used in conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. You can use the following.

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, octahedron, or dodecahedron, 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 (1(to) plane to the (111) plane) can be used.Also, they may have a composite form of these crystal forms, and particles of various crystal forms may be mixed. Good too.

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). When divided by the average grain size, the value is 0.201 (The diameter is not shown 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. The following methods can be used singly or in combination: a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a member metal sensitization method using gold or other metal compounds.

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

[Examples] Specific examples of the present invention will be described in detail below, but the aspects of the present invention are not limited thereto.

Example 1 A silver chloroiododobromide gelatin emulsion containing 75 mol% silver chloride, 25 mol% silver bromide, and 1 mol% silver iodide contains 0.6 g of 4-hydroxy-6 per mole of silver halide. - adding methylmonolayer,3,3a,7-chitrazaindene,
Further, the compound latex (d) of the present invention was added at a dry weight of 1.0 g per 1 g of gelatin, and mucosyl acid was added thereto, and then onto a subbed polyethylene terephthalate support. silver fjl 4.0
Latex and Lord Zeradin are 1. so that Q is /1.
It was applied so that it was 9Q/V.

For comparison, a sample was prepared in the same manner except that the latex liquid (x) made using thorium dodecylbenzenesulfonate instead of the P1 layer 1 used in Production Example 1 was replaced with latex (a>. A sample was prepared without adding a).

The obtained sample was subjected to wedge exposure, subjected to the following processing, and examined for sensitivity, fog, and dimensional stability. The results are shown in the table.

[Processing conditions] Development: 29°C, 30 seconds Fixation: 28°C, 20
Wash with water for 20℃ 2
Dry for 0 seconds at 45℃ 3
0 seconds [Developer (undiluted solution)] Potassium bromide 2.5g Disodium ethylenediaminetetraacetate 1g Potassium sulfite (55% aqueous solution) 90i12 Potassium carbonate 250 Hydroquinone
10 (15-methylbenzotriazole 100mg5-nitrobenzo1-lyazole 100mg1-phenyl-5-mercaptotetrazole 30111g5
- Nitroindazole 50mg 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone o, sg Diethylene glycol 60 (J Sodium hydroxide l) Amount to adjust H to 10.6 Add water to 50
Finish it to 0y6. (DHlo, 6) When using, the above stock solution is diluted twice with water.

[Fixer] (Part A) Ammonium thiosulfate 170 Q sub@
Sodium acid 1513 hou 15!
6.5 (+glacial acetic acid
Add 123g of sodium citrate (dihydrate) and 2.5g of water to make 275mQ.

(Part B) Add 15 g of aluminum sulfate (18 hydrate), 98% sulfuric acid, 2.5 Q water, and finish to 401112.

The method for preparing the solution used is to add about 600 vQ of water to Part A275112, add 40 v(l) of Part B, and then add water to make it to 1000.

[Sensitivity J The measurement was performed using a sensitivity HKS single layer manufactured by Konishiroku Photo Industry Co., Ltd.

The sensitivity was expressed as the reciprocal of the exposure ω that gave a density of fog +0.7, and the sensitivity was expressed as a specific sensitivity with the same-day sensitivity of the control sample as 100.

[Dimensional change rate] Dimensional stability accompanying development 51!1 was measured using a bottle gauge. The dimension change rate of an exposed sample having a length of 200 mm is determined by the following equation, where X mm is the dimension before processing, and Y mm is the dimension after development processing.

Dimensional change rate (% = ((Y-X) / 200) X
100 In the industry, it is considered that there is no problem in practical use if the dimensional change rate is 10.01% or less.

*1 When the same amount of latex (×) as gelatin was used, it agglomerated and could not be coated.

*2 In order to add latex (X) without causing aggregation, the amount was 5 wt% to gelatin, and this was used as a sample.

As is clear from Table 1, sample 1 of the present invention has high sensitivity and low fogging, and compared to comparative samples 3 and 4,
The rate of dimensional change is extremely low. Further, no aggregation occurs as in Comparative Sample 2.

Patent applicant Konishi Roku Photo Industry Co., Ltd. Procedural amendment (Jiri November 7, 1985, October 16, 1985 filed patent application (2) 2, name of invention Silver halide photographic light-sensitive material 3, Who is making the amendment? What is the relationship between the case and the applicant? Address of the patent applicant: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Keio Benko 4, Agent 102 Address Kudan-Rosaka Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone 263-9524 Iris 711% False Specification [2, Claims (1) and 6 , Contents of amendment (1) Claim 1 of the specification is amended as shown in the attached sheet.

(2) The detailed description of the invention in the specification is corrected as follows.

i) On page 4, line 20 of the specification, the phrase "hydrophilic polymer and latex" is corrected to read "latex formed into a protective colloid by a hydrophilic polymer."

it) Page 29 of the specification, lines 13 to 14, “
The phrase ``hydrophilic polymers and latex'' has been corrected to ``latex made into a protective colloid by hydrophilic polymers.''

Attachment Claims (1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers 1: At least one layer 1 of the silver halide emulsion layer is formed during IR production. A silver halide photographic material comprising a latex formed into a protective colloid by a hydrophilic polymer having a nonionic functional group and at least one anionic functional group.

(2) The silver halide photographic material according to claim 1, wherein the latex is obtained by polymerizing a polymerizable unsaturated compound in the presence of the hydrophilic polymer. .

Procedure 7 rll official document (spontaneous) November 7, 1985 Commissioner of the Japan Patent Office Black ff1 Meiweiden2, Name of the invention Silver halide photographic light-sensitive material 3, Relationship to the person making the amendment case Patent applicant address Shinjuku, Tokyo Ward Nishi-Shinjuku 1-26-2 Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Ide Ochu 4, Agent 102 Address Kudan-Rosaka Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone: 263-9524 Column 6 of ``3. Detailed Description of the Invention'' of the specification, Contents of amendment The detailed description of the invention of Akira am is amended as follows.

that's all Procedural amendment (voluntary) December 4, 1986

Claims (2)

[Claims] (1) 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 has at least one nonionic functional group and at least one nonionic functional group in its molecular structure. A silver halide photographic material comprising a hydrophilic polymer having an anionic functional group and a latex. (2) The silver halide photographic material according to claim 1, wherein the latex is obtained by polymerizing a polymerizable unsaturated compound in the presence of the hydrophilic polymer. .