JPH0648349B2 - Silver halide photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a synthetic polymer, and more specifically to a hydrophilic colloid layer. , A silver halide photographic light-sensitive material containing a latex.

BACKGROUND OF THE INVENTION In general, latex is used together with gelatin as a binder in a silver halide photographic light-sensitive material to reduce the gelatin content, and the physical properties of the film such as dimensional stability before and after development and dimensional stability against heat and humidity. It is known to improve heat resistance, flexibility, pressure resistance and dryness. However, the use of latex can, for example, desensitize emulsions, devitrification during development,
Since there are serious influences on photographic performance such as color contamination of dyes after development and deterioration of halftone dot quality of printing photosensitive materials, various improvements have been attempted to solve them. For example, U.S. Pat.
5,620, Belgium Patent 768,558, U.S. Patent 3,14
2,568, 3,323,286, Belgian patent 708,347
German patent 2,049,150, British patent 1,498,697
As disclosed in JP-A-59-50969 and the like, there is an attempt to improve these drawbacks by polymerizing a latex using a specific activator. However, the technology
The type of emulsion used was limited, and none of them had any influence on fog, sensitivity, and development characteristics. The emulsion-polymerized latex using a low molecular weight surfactant has a limited combination of the type of the latex and the silver halide emulsion to be used, and the amount of the latex that can be contained in the emulsion.

JP-A-55-50240, JP-B-55-47371, JP-A-54-19772,
JP-A-48-52882, JP-A-48-52883 and the like disclose a technique of incorporating a latex using a polymeric protective colloid into a silver halide emulsion during emulsion polymerization in order to solve the above-mentioned problems. . Although these latexes have little effect on photographic performance, they have problems with devitrification during development, increase in viscosity of coating solution, deterioration of multi-layer property, cissing during coating, and other problems in manufacturing photographic materials. . As described above, it is advantageous to use the polymer protective colloid latex for improving the physical properties of the film from the viewpoint of photographic performance, but the devitrification property at the time of development and the thickening and cissing at the time of coating are advantageous. There are many problems in the manufacturing process such as failures, and photographic materials using polymer protective colloid latex have not yet been put to practical use.

[Object of the Invention] An object of the present invention is to provide a silver halide photographic light-sensitive material having no problems in photographic properties and production of a photographic light-sensitive material even when latex is used, and having excellent film physical properties such as dimensional stability. That is.

[Construction of the Invention] The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers comprises a glucose polymer or a derivative thereof. It is achieved by a silver halide photographic light-sensitive material characterized by containing a latex colloidalized with at least one of a water-soluble polymer and its derivative.

[Specific Structure of the Invention] The natural water-soluble polymer used in the present invention is described in detail in the comprehensive technical data collection of water-soluble polymer water-dispersible resin (published by the Management Development Center). , Pullulan, cellulose, alginic acid, dextran, dextrin, guar gum, gum arabic, glycogen, laminaran, lichenin, nigeran and the like, and derivatives thereof.

As the natural water-soluble polymer derivative, sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carboxyalkylenated, alkylphosphorylated, and salts thereof are particularly preferable.

In the present invention, the natural water-soluble polymer may be used in combination of two or more kinds. Further, among the natural water-soluble polymers, glucose polymers and derivatives thereof are preferable, and among the glucose polymers and derivatives thereof, starch, glycogen, cellulose, lichenin, dextran, nigeran and the like are preferable, and especially dextran. , And derivatives thereof are preferred.

Dextran is a polymer of D-glucose linked with α-1,6 and is generally obtained by culturing a dextran-producing bacterium in the presence of a saccharide, but culturing dextran-producing bacterium such as leuconostoc, mesenteroides and the like. It can be obtained by reacting the separated dextran sucrase with a saccharide from the liquid. In addition, these native dextran are reduced to a desired molecular weight by a partial decomposition polymerization method using an acid or alkaline enzyme, and the intrinsic viscosity is 0.03.
Those in the range of up to 2.5 can also be obtained.

The modified dextran is a dextran sulfate ester in which a sulfate group is present in the dextran molecule through an ester bond, and a salt thereof, a carboxyalkyl dextran in which a carboxyalkyl group is present in the dextran molecule through an ether bond, or a dextran molecule. A carboxyalkyl dextran sulfate ester in which a sulfate group is an ester bond and a carboxyalkyl group is an ether bond, and a salt thereof, a dextran phosphate ester in which a phosphate group is ester-bonded in a dextran molecule, and its Examples thereof include hydroxyalkyl dextran in which a hadrooxyalkyl group is introduced into a salt or dextran molecule.

The use of these dextran compounds in a silver halide photographic light-sensitive material is disclosed in JP-B-35-11989, U.S. Pat.
No. 924, Japanese Patent Publication No. 45-12820, No. 45-18418, No. 45-40149
No. 46-31192 is known,
These dextrans are contained in the silver halide emulsion or the gelatin layer as they are to improve the covering power of the developed silver image, the maximum density and the contrast. The methods for producing these dextrans and their derivatives are described in detail in these patents.

The amount of dextran used for latex synthesis can be any amount from 100 wt% to 0.1 wt% based on the weight of the charged monomers, but if used in a large amount, the viscosity increases and When added to a colloidal solution, it thickens and makes application difficult. If the amount used is too small, the stability of the latex becomes poor.

Therefore, the preferred amount of dextran used is 30 wt% to 0.1 wt%, more preferably 15 wt% to 0.5 wt%, based on the weight of the charged monomers.

Among these dextran and modified products thereof, particularly preferable are dextran sulfate ester, carboxyalkyl dextran sulfate ester, and dextran phosphate ester, in which an anionic group is introduced, in view of dispersion stability of latex. Among them, dextran sulfate ester is most preferable.

In the synthesis of these dextran-modified products, dextran sulfate can be obtained by reacting a dextran as a raw material with a sulfating agent such as chlorosulfonic acid in the presence of pyridine or a hydrochloric acid organic solvent such as formamide. Further reaction with a carboxyalkylating agent such as monochlorocarboxylic acid gives a carboxyalkyl dextran sulfate. In addition, dextran can be reacted with a carboxyalkylating agent such as monochlorocarboxylic acid using dextran as a raw material to obtain carboxyalkyl dextran. Furthermore, by reacting this with a sulfiding agent such as chlorosulfonic acid in the presence of a basic solvent such as pyridine or formamide, a carboxyalkyl dextran sulfate can be obtained. If this is reacted with oxides of alkali metals such as sodium and potassium, oxides or hydroxides of alkaline earth metals such as calcium and magnesium, ammonia, etc., the corresponding salts of dextran sulfate and carboxyalkyl sulfate. Is obtained.

Since dextran has three hydroxyl groups that can be substituted per anhydroglucose unit, theoretically it is possible to substitute sulfate ester groups and carboxyalkyl groups with a maximum degree of substitution of up to 3, but by selecting the reaction conditions It is possible to manufacture a resin having an arbitrary degree of substitution within a range of the degree of substitution of 3 or less. However, the sum of the substitution degrees of the sulfate ester group and the carboxyalkyl group cannot exceed 3.

Many kinds of carboxyalkyl dextran, dextran sulfate, and carboxyalkyl dextran sulfate thus produced can be produced by varying the intrinsic viscosity of the starting dextran and the degree of substitution of sulfate ester and carboxyalkyl substitution of the product. You can

The protective colloid is a hydrophilic polymer on the surface of the hydrophobic particles, which has the ability to stably disperse the hydrophobic particles in water.

The produced protective colloid latex liquid is not a simple mixture of hydrophobic polymer particles and dextran or its derivative, but that dextran or its derivative acts as a protective colloid means that It can be seen that the dispersion stability of the particles is improved and that the viscosity of the protective colloid latex solution is lower than the viscosity of the aqueous solution of the natural water-soluble polymer.

Specifically, the stable latex of the present invention can be obtained by the following method.

A resin obtained by previously polymerizing a polymerizable unsaturated compound as it is, or a liquid obtained by dissolving it in a water-miscible organic solvent is dispersed in water or an aqueous solution containing a water-miscible organic solvent, and a natural water-soluble polymer is added to obtain .

Furthermore, the resin obtained by previously polymerizing the polymerizable unsaturated compound is obtained as it is, or a solution prepared by dissolving it in a water-miscible organic solvent is dispersed in an aqueous solution prepared by dissolving a natural water-soluble polymer.

The polymerizable unsaturated compound may be emulsion-polymerized in water using a small amount of a surfactant, and a natural water-soluble polymer may be added thereto.

It is obtained by dissolving a natural water-soluble polymer in water or an aqueous solution containing a water-miscible organic solvent, adding a polymerizable unsaturated compound therein, and polymerizing.

In the above method, after adding the natural water-soluble polymer,
A more stable latex can be obtained by heating the liquid to 50 ° C. or higher and then cooling it.

In the above method, the above method is preferable in order to obtain a latex having good stability and uniform particle size.

The latex used in the present invention comprises a hydrophobic polymer, and such a polymer is roughly classified into a condensation polymer and a vinyl polymer. Examples of the condensation polymer include polyamide, polypeptide, polyester, polycarbonate, polyanhydride, polyurethane, polyurea and polyether. Vinyl-based polymers are addition polymers based on vinyl groups, such as aliphatic hydrocarbon-based, aromatic-based, vinyl alcohol-based, nitrile-based, acrylic-based, methacrylic-based, acrylonitrile-based, and halogen-based homopolymers and the like. A copolymer obtained by the combination of

By using the glucose polymer or the glucose polymer modified product of the present invention in combination with a protective colloid, a hydrophobic polymer of any composition can be stably contained in the hydrophilic colloid layer. The composition is not selected, but a polyester-based or vinyl-based polymer is preferably selected because of the ease of production of the latex. The polymerizable unsaturated compound as a raw material of these polymers may be a polymerizable unsaturated ethylene 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 and the like. Examples thereof include polyfunctional monomers, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles and the like.

The following can be mentioned as specific examples of these polymerizable unsaturated compounds.

Acrylic esters, such as methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate,
2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl 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-hydroxypropyl 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-methoxypolyethylene glycol acrylate (addition mole number n = 9), 1-bromo- 2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, etc .; Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec- Butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octylmeth Acrylate, 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-hydroxyethyl 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
-Methoxypolyethylene glycol methacrylate (additional mol number n = 6) and the like; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate,
Vinyl methoxyacetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate, etc .; olefins such as dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2 , 3-dimethylbutadiene, etc .; Styrenes such as styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene,
Isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, brom styrene, vinyl benzoic acid methyl ester, etc .; Crotonic acid esters, such as butyl crotonic acid, hexyl crotonic acid, etc .; Itaconic acid diesters , For example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate and the like; maleic acid diesters such as diethyl maleate, dimethyl maleate, dibutyl maleate and the like; fumarate diesters such as diethyl fumarate, dimethyl fumarate , Dibutyl fumarate and the like; acrylamides such as acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, tert-butyl acetate Riruamido, cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxyethyl acrylamide, dimethylaminoethyl acrylamide, phenyl acrylamide, dimethyl acrylamide, diethyl acrylamide, beta-cyanoethyl acrylamide, N-(2-acetoacetoxyethyl)
Acrylamide, etc .; Methacrylamides, for example, methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, tert-
Butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, N
-(2-acetoacetoxyethyl) methacrylamide, etc .; allyl compounds, such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate, etc .; vinyl ethers, such as methyl vinyl ether, butyl vinyl ether, hexyl 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-vinyl imidazole, N-vinyl oxazolidone, N-vinyl. Triazole, N-vinylpyrrolidone, etc .; Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc .; Unsaturated nitriles, such as acetic acid Lilonitrile, methacrylonitrile, etc .; polyfunctional monomers such as divinylbenzene, methylenebisacrylamide, ethylene glycol dimethacrylate, etc .; and acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconic acid, eg itaconic acid Monomethyl, monoethyl itaconate, monobutyl itaconate, etc .; Monoalkyl maleate, such as monomethyl maleate, monoethyl maleate, monobutyl maleate, etc .; citraconic acid, styrenesulfonic acid, vinylbenzylsulfonic acid, vinylsulfonic acid, acryloyloxyalkyl Sulfonic acids such as acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid and the like; methacryloyl Xyalkyl sulfonic acids such as methacryloyloxymethyl sulfonic acid, methacryloyloxyethyl sulfonic acid, methacryloyloxypropyl sulfonic acid and the like; acrylamidoalkyl sulfonic acid,
For example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid and the like; methacrylamide alkylsulfonic acid, for example 2
-Methacrylamido-2-methylethanesulfonic acid, 2
-Methacrylamido-2-methylpropanesulfonic acid,
2-methacrylamido-2-methylbutane sulfonic acid and the like; acryloyloxyalkyl phosphates such as acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate and the like; methacryloyloxyalkyl phosphates such as methacryloyloxyethyl phosphate, 3-methacryloyl Oxypropyl-2-phosphate, etc .; 2 hydrophilic groups
Sodium 3-allyloxy-2-hydroxypropane sulfonate and the like; and these acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions. Still other polymerizable unsaturated compounds include U.S. Pat.
No. 790, No. 3,438,708, No. 3,554,987, No. 4,21
The crosslinkable monomers described in 5,195, 4,247,673, JP-A-57-205735 and the like can be used. Specific examples of such a crosslinkable monomer include N- (2-acetoacetoxyethyl) acrylamide and N- {2- (2-acetoacetoxyethoxy) ethyl} acrylamide.

These polymerizable unsaturated compounds can be roughly divided into hydrophobic unsaturated compounds and hydrophilic unsaturated compounds. When a hydrophilic unsaturated compound is used, it is stable when used in combination with a hydrophobic unsaturated compound. It is preferable in forming a latex. Of course, these unsaturated compounds may be used alone or in combination of two or more kinds.

Some of these compounds include water-soluble ones,
By copolymerizing with a hydrophobic one, a hydrophobic polymer can be formed.

The method for producing the latex in the present invention includes a method in which a hydrophobic polymer obtained by a solution polymerization method is dispersed in water by using a surfactant or an organic solvent, or a suspension weight method in which polymerization is performed in an aqueous medium. Although there are a legal method and an emulsion polymerization method, the suspension polymerization method and the emulsion polymerization method are preferable in that the number of manufacturing steps is reduced.

As the polymerization initiator for the vinyl polymer, azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 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 and 2,2′-azobis (2-amidinopropane) hydrochloride, benzoyl peroxide, lauryl peroxide, cumene hydroperoxide , Diisopropyl peroxydicarbonate, t-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate, sodium persulfate and the like. Sulfates, potassium bromate, ceric ammonium nitrate, etc. are used.

Further, peroxides and persulfates can be used as a redox initiator in combination with a suitable reducing agent. Water-soluble initiators are preferred.

The preferred polymerization temperature varies depending on the initiator used, but is usually 30 to 95 ° C, preferably 40 to 85 ° C.

In producing the latex according to the present invention, the above 4. When performing the method of, the anionic system used in ordinary emulsion polymerization,
The nonionic and cationic surfactants are preferably not used, but may be used in an amount and kind that do not impair the effects of the present invention. In this case, the surfactant which is usually added to the photographic emulsion is preferably added to the latex liquid after completion of the polymerization.

In the present invention, the amount of the latex used is 10% or more and 300% or less, preferably 30% or more and 200% or less, based on 100 weight of gelatin. If the amount of latex used is too small, the effects of the present invention will not be sufficiently exhibited, and if the amount of latex used is too large, sufficient film strength will not be obtained. Further, the natural 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 by weight ratio with respect to latex 100. If the amount of the natural water-soluble polymer used is too small, the sufficient effect cannot be obtained, and if it is too large, the coating property of gelatin, particularly at the time of high-speed coating, causes problems.

The preferred mode of producing the latex in the present invention is as described below.

Glucose polymer in an aqueous solution containing water or a water-miscible organic solvent, or a derivative of the glucose polymer is dissolved, heated while stirring, degassing, after setting the desired temperature, the polymerization initiator is added, Subsequently, a polymerizable unsaturated compound is added or dropped to carry out polymerization for a predetermined time and then cooled.

Incidentally, the glucose polymer or the derivative of the glucose polymer may be dissolved in an aqueous solution containing water or a water-miscible organic solvent after heating and degassing, and the polymerization initiator is heated,
It may be added before degassing.

Latex Production Examples 1 to 11 A 1.1l four-necked flask was equipped with a stirrer, thermometer, dropping funnel, nitrogen introducing tube, and reflux condenser, and dextran with an intrinsic viscosity of 0.210 was used as a raw material. 4.5 g of dextran sulfate sodium salt synthesized by the method described in 1 is added to a flask, 350 cc of pure water is added, and the mixture is heated to an internal temperature of 80 ° C. During this period, nitrogen gas was introduced, and after the internal temperature reached 80 ° C., nitrogen gas was further passed for 30 minutes. Then, a solution of 0.45 g of ammonium persulfate dissolved in 10 cc of water was added as an initiator, and subsequently, a mixture of 40 g of butyl acrylate and 50 g of styrene as a polymerizable unsaturated compound was added dropwise by a dropping funnel over about 1 hour. Five hours after the addition of the initiator, the mixture was cooled, adjusted to pH 6 with aqueous ammonia, and then filtered to remove dust and coarse particles to obtain a latex liquid (a).

2. Butyl acrylate 3 as a polymerizable unsaturated compound
A latex liquid (b) was obtained in the same manner as in Synthesis Example 1, except that a mixture of 9.5 g, styrene 49.5 g and acrylic acid 1 g was used.

3. Butyl acrylate 5 as the polymerizable unsaturated compound
A latex liquid (c) was obtained in the same manner as in Synthesis Example 1 except that a mixture of 0 g, styrene 35 g and maleic anhydride 5 g was used.

4. Ethyl acrylate 9 as the polymerizable unsaturated compound
0 g, potassium persulfate was used as an initiator, and the polymerization was carried out at 70 ° C., except that the polymerization was carried out in the same manner as in Synthesis Example 1 to obtain a latex liquid (d).

5. Except using 0.9 g of dextran sulfate ester salt,
Synthesis was performed in the same manner as in Synthesis Example 1 to obtain a latex liquid (e).

6. Ethyl acrylate 9 as the polymerizable unsaturated compound
A latex liquid (f) was obtained in the same manner as in Synthesis Example 1 except that 0 g was used, 0.45 g of ammonium persulfate and 0.22 g of sodium bisulfite were used as the initiator, and polymerization was carried out at 40 ° C.

7. Ethyl acrylate 8 as the polymerizable unsaturated compound
A latex liquid (g) was obtained in the same manner as in Synthesis Example 4, except that 5 g of 2-acrylamido-2-methylpropanesulfonic acid was used.

8. A latex solution (h) was obtained in the same manner as in Synthesis Example 1, except that 13.5 g of dextran sulfate ester salt was used.

9. Instead of dextran sulfate ester salt
A latex solution (i) was obtained in the same manner as in Synthesis Example 1 except that 3.5 g of carboxymethyl dextran shown in Synthesis Example 2 of No. 12820 was used.

10. Instead of dextran sulfate ester salt,
A latex liquid (j) was obtained in the same manner as in Synthesis Example 1 except that 3.5 g of carboxymethyl dextran sulfate shown in Synthesis Example 1 of 45-12820 was used.

11. Instead of carboxymethyl dextran sulfate ester salt, weight average molecular weight (MW) = 100,000-20
A latex liquid (k) was obtained in the same manner as in Synthesis Example 1, except that 3.5 g of 000 commercially available dextran was used.

Latex Production Example 12 300 ml four-necked flask, a stirrer, thermometer, nitrogen inlet tube,
A reflux condenser is provided, 90 ml of dioxane is added, nitrogen gas is introduced, the internal temperature is heated to 70 ° C., and nitrogen gas is passed for 30 minutes. Stop nitrogen gas Butyl acrylate 60
g and 30 g of styrene were added, and a solution of 0.3 g of azobisisobutyronitrile dissolved in 10 ml of dioxane was added,
Polymerization was carried out at 70 ° C. for 12 hours.

Heat a mixed solvent of 240 cc of water and 120 cc of ethanol to 70 ° C,
Combining 4.5 g of dextran sulfate sodium salt,
The above-mentioned polymerization liquid was added to this while hot, and the mixture was vigorously stirred,
Then, it cooled and obtained the latex liquid (1).

Latex Production Example 13 The stirring autoclave was replaced with nitrogen, and 55 parts by weight of styrene, 42 parts by weight of butadiene, 3 parts by weight of glycidyl methacrylate, 3 parts by weight of sulfate ester salt, 0.2 parts by weight of third dedosyl mercaptan, and tripotassium phosphate. 0.3 parts by weight, 0.3 parts by weight of ammonium persulfate and 100 parts by weight of water were charged, polymerization temperature was 50 ° C., polymerization pressure was 5 atm and polymerization time was 18 hours. After the reaction was completed, residual monomers were distilled off, Latex (m)
Got

Latex Production Example 15 In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introducing tube, a distillation device, and a heater, 192.12 g (1.0 mol) of trimellitic anhydride, 62.1 g (1.0 mol) of ethylene glycol and 108.1 of benzyl alcohol were added. g (1.0 mol) was charged.

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

The obtained polyester was taken out and solidified by cooling. 100 g of the obtained polyester was dissolved in 250 ml of acetone, and into a 100 ml aqueous ammonia solution of about 0.1 molar concentration in which 2.5 g of dextran sulfate ester salt was dissolved, with rapid stirring,
The acetone solution was slowly poured. This mixture is filtered,
Then, the mixture was heated to 60 ° C. to remove acetone to obtain a latex liquid (n).

As shown in the production example, in a glucose polymer, an aqueous solution containing a derivative of a glucose polymer, it is possible to very well emulsion polymerize a hydrophobic vinyl monomer without using an ordinary emulsifier. However, it is found that they are sufficiently effective as a protective colloid.

Generally, various kinds of surfactants are used in a silver halide photographic light-sensitive material, but according to the study by the present inventors, a latex using a normal surfactant as a dispersion stabilizer (emulsifier) is used as a silver halide. When it is contained in the emulsion layer, the surfactant used in the silver halide photographic light-sensitive material is adsorbed on the latex surface, or the surfactant used for polymerization is desorbed from the latex surface, which seriously affects the photographic performance. It had a great influence.

However, the latex made into a protective colloid by the natural water-soluble polymer of the present invention has little adsorption of various surfactants and has little influence on photographic performance. It is considered that this is because the desorption rate from the latex surface protected by the natural water-soluble polymer is extremely slow, but glucose or a glucose modified product has a very small effect on the photographic performance on the latex particle surface. This is probably because a protective colloid layer having a sufficient adsorption density and a sufficient adsorption density is formed.

Therefore, the latex of the present invention is useful as a material which does not adversely affect the silver halide emulsion for any silver halide photographic material and can be used for various purposes. That is, in addition to the dimension-stabilizing binder latex,
It can also be used as an impregnating latex for dispersing a hydrophobic photographic useful compound in a hydrophilic colloid layer, an undercoating latex, a matting agent, a mordant layer, and a neutralizing layer latex.

In the present invention, the latex colloidalized with the natural water-soluble polymer according to the present invention is contained in the silver halide emulsion layer, but if necessary, other photographic constituent layers such as a protective layer, It may be added to the intermediate layer, the antihalation layer, the undercoat layer, the backing layer, the mordant layer, the neutralization layer and the like at all.

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

In addition to lime processed gelatin, gelatin
Of the Society of Scientific
Photography of Japan (Bull, Soc, Sci, Pho
t, Japan.) No. Oxygen-treated gelatin as described on pages 16 and 30 (1966) may be used, or a hydrolyzate or enzymatic hydrolyzate of gelatin may also be used. Examples of the gelatin derivative include various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkyleonoxides, and epoxy compounds in gelatin. What is obtained by reacting is used. Specific examples thereof are U.S. Patent Nos. 2,614,928 and 3,132,945,
3,186,846, 3,312,553, British patent 861,414,
1,033,189, 1,005,784, and Japanese Examined Patent Publication No. 42-26845.

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

The silver halide grain may be one having a uniform silver halide composition distribution within the grain, or may be a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer. The particles may be such that the image is mainly formed on the surface, or the particles are mainly formed inside the particles.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or may have an irregular shape such as a sphere or a plate. It may have a crystalline form. In these particles,
Any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The average grain size of the silver halide grains (the grain size represents the diameter of a circle having 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 having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion. The monodisperse emulsion referred to here is the standard deviation of the grain size distribution. When divided by the average grain size, the value is 0.20 or less, where the grain size is the diameter in the case of spherical silver halide and the projected image in the case of grains other than spherical. The diameter when converted to a circular image of the same area is shown). Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

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

The silver halide emulsion of the present invention can be chemically sensitized by a conventional method. That is, the sulfur sensitizing method, the selenium sensitizing method, the reduction sensitizing method, the noble metal sensitizing method using gold and other noble metal compounds can be used alone or in combination.

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

Example 1 A silver chloroiodobromide gelatin emulsion containing 75 mol% silver chloride, 25 mol% silver bromide, and 1 mol% silver iodide was added to 0.6 g of 4-hydroxy-6 per mol of silver halide. -Methyl-1,3,3a, 7-tetrazaindene was added, and the latex (a-m) of the present invention and the comparative latex (a-to) were added as dry weight to 1.0 g per 1 g of gelatin.
After adding mucochloric acid,
On a subbed polyethylene terephthalate support, the total amount of silver 4.0 g / m ² gelatin and latex was 1.9 g / m ²
Was applied so that

[Production of Comparative Latex] 1. A latex synthesized in the same manner as in Production Example 1 except that 7.0 g of sodium dodecylbenzenesulfonate was used in place of the dextran sulfate sodium salt was used as a comparative latex (a).

2. A latex (b) synthesized in the same manner as in Production Example 2 using 7.0 g of sodium dodecylbenzenesulfonate instead of the dextran sulfate sodium salt.

3. A latex prepared in the same manner as in Production Example 3 using 5.0 g of the activator of the following compound instead of dextran sulfate sodium salt as a latex solution for comparison (C).

4. A latex synthesized in the same manner as in Production Example 4 using 6.0 g of the activator of the following compound instead of dextran sulfate sodium salt was used as a comparative latex (d).

5. Polymerized according to the method described in JP-B-55-47371,
A latex containing polyvinyl alcohol as a protective colloid is used as a comparative latex (e).

6. A latex obtained by copolymerizing a water-soluble monomer, which was polymerized according to the method described in JP-A-51-130217, was used as a comparative latex (f).

7. In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, a distillation device, and a heater, 192.1 g (1.0 mol) of trimellitic anhydride, 62.1 g (1.0 mol) of ethylene glycol and 108.1 g (1.0 mol of benzyl alcohol) were added. ) Was loaded.

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

The obtained polyester was taken out and solidified by cooling. About 100 g of the obtained polyester was dissolved in 250 ml of acetone and about 2.5 g of sodium dodecylbenzenesulfonate was dissolved.
The acetone solution was gradually poured into 100 ml of a molar aqueous ammonia solution with rapid stirring. The mixture was filtered, and then heated to 60 ° C. to remove acetone to obtain a comparative latex liquid (g).

With respect to the obtained sample, observing the occurrence of cissing during coating with the naked eye, further, each sample was subjected to wedge exposure, and the following treatment was performed to determine sensitivity, fog, dimensional stability, devitrification, and cissing. Examined. The results are shown in Table-1.

[Processing conditions] Current image 29 ° C 30 seconds Settling 28 ° C 20 seconds Washing with water 20 ° C 20 seconds Drying 45 ° C 30 seconds [Developer (stock solution)] Potassium bromide 2.5 g Ethylenediamitetraacetic acid disodium 1 g Potassium sulfite (55 % Aqueous solution) 90 ml potassium carbonate 25 g hydroquinone 10 g 5-methylbenzotriazole 100 mg 5-nitrobenzotriazole 100 mg 1-phenyl-5-mercaptotetrazole 30 mg 5-nitroindazole 50 mg 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone 0.5 g Diethylene glycol 60 g Sodium hydroxide Adjust the pH to 10.6 Add water to make 500 ml. (PH 10.6) When using, dilute the above stock solution with water to double volume.

[Fixer] (Part A) Ammonium thiosulfate 170g Sodium sulfite 15g Boric acid 6.5g Glacial acetic acid 12ml Sodium citrate (dihydrate) 2.5g Add water to make 275ml.

(Part B) Aluminum sulfate (18-hydrate) 15 g 98% sulfuric acid 2.5 g Add water to make 40 ml.

To prepare the solution, add about 600 ml of water to 275 ml of Part A above, add 40 ml of Part B, and then add water.
Make up to 1000 ml.

[Sensitivity] The sensitivity was measured using a sensitivity meter KS-1 manufactured by Konishi Rokusha Kogyo KK.

Sensitivity is the reciprocal of the exposure amount that gives a density of fog +0.7,
Sample No. It was displayed as a specific sensitivity with the same day sensitivity of 1 as 100.

[Dimensional change rate] The dimensional stability associated with the development processing was measured using a bottle gauge. The dimension before exposure of a 200 mm long exposed sample is Xm
m, the dimension after development processing is Y mm, and the dimensional change rate is calculated by the following equation.

Dimensional change rate (%) = {(Y−X) / 200} × 100 In the industry, if the dimensional change rate is ± 0.01% or less, there is no practical problem.

[Devitrification] A film having no decrease in transparency after washing with water for development treatment was A, a film having a very slightly milky white color was B, and a film having a slightly milky white color was C.

[Repelling] The number of coated areas per 30 cm × 30 cm was visually observed.

As is clear from Table 1, Samples 1 to 14 of the present invention
Causes less fog, has excellent sensitivity, has a small dimensional change rate, and does not cause devitrification or cissing during coating. On the other hand, the sample 22 that does not use latex has an extremely large dimensional change rate, and the sample No. using the latex synthesized by using the low molecular surfactant is used.
Nos. 15 to 18 are samples in which the photographic characteristics are extremely deteriorated and a known latex using a polymer protective colloid is used.
No. 19 is also inferior in photographic properties, and devitrification and cissing are noticeable. Sample No. 20, which uses a latex obtained by copolymerizing a water-soluble monomer, also has photographic characteristics deteriorated and devitrification and cissing are conspicuous. Sample No. 21, which uses a latex obtained by dispersing a hydrophobic polymer with a low-molecular-weight surfactant, is deteriorated in photographic characteristics, devitrification, and cissing.

Example 2 A silver iodobromide gelatin high-sensitivity emulsion containing 98.5 mol% silver bromide and 1.5 mol% silver iodide was added per mol of silver halide.
1.2 g of 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene, 10 g of diethylene glycol was added, and the latex (a-n) of the present invention and the latex for comparison (a-to) were further added to gelatin 1 as a dry weight.
2-hydroxy-4, added so as to be 1.0 g per g,
After the addition of 6-dichloro-S-triazine sodium salt, this emulsion was coated on both sides of a polyethylene terephthalate support which had been subjected to undercoating, with a silver amount of 4.0 g / m ² , and the total amount of gelatin and latex was 1.9 g / m 2. ^It was applied so as to be ² .

With respect to the obtained sample, the occurrence of repelling at the time of application was observed with the naked eye, and each sample was subjected to wedge exposure, and the following treatment was carried out to obtain sensitivity, fog, and dimensional stability in the same manner as in Example 1. The devitrification property was examined.

Further, a pressure fog test was performed on the obtained sample. The results are shown in Table-2.

[Pressure Fogging] After folding the sample with a folding tester having a slit interval of 2 mm, development processing was performed and the pressure fogging was measured.

Processing Step Development 30 ° C. 45 ″ Fixing 25 ° C. 35 ″ Washing 15 ° C. 35 ″ Drying 45 ° C. 20 ″ Developer composition is as follows.

Phenidone 0.4 g Metol 5 g Hydroquinone 1 g Anhydrous sodium sulfite 60 g Sodium hydrous carbonate 54 g 5-Nitroimidazole 100 mg Potassium bromide 2.5 g Water is added to bring the total volume to 1000 ml to pH 10.20.

As is clear from Table-2, the samples 1 to 14 of the present invention are
It has low fog, excellent sensitivity, low dimensional change rate, and does not cause devitrification or cissing during coating.

Further, when the latex of the present invention is used in a high-sensitivity emulsion, the occurrence of folding fog can be suppressed.

Continuation of the front page (56) Reference JP 59-135456 (JP, A) JP 59-193447 (JP, A) JP 56-9743 (JP, A) JP 48-37488 (JP , A) JP-A-48-52882 (JP, A) JP-A-52-96016 (JP, A)

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, wherein at least one hydrophilic colloid layer comprises a glucose polymer or a derivative thereof, a natural water-soluble polymer and a derivative thereof. A silver halide photographic light-sensitive material comprising a latex colloidized by at least one of the above. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the glucose polymer and its derivative are dextran or dextran derivative. 3. The silver halide photographic light-sensitive material according to claim 2, wherein the dextran derivative has an anionic group. 4. The latex is obtained by polymerizing a polymerizable unsaturated compound in the presence of at least one natural water-soluble polymer consisting of glucose polymer or its derivative and its derivative. A silver halide photographic light-sensitive material according to claim 1.