JP2552444B2 - Silver halide photographic material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material in which a synthetic polymer is contained in a silver halide emulsion layer, and more specifically to a silver halide emulsion layer. The present invention relates to a silver halide photographic light-sensitive material containing a latex colloidalized with a specific hydrophilic polymer.

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 flexibility, pressure resistance and dryness. However, the use of latex seriously affects photographic performance and the like.
For example, desensitization of silver halide emulsions, devitrification during development, color contamination of dyes after development, deterioration of halftone dot quality of photosensitive materials for printing, and the like, and various improvements have been attempted to solve them. For example, U.S. Patent 3,525,620, Belgium Patent 768,558, U.S. Patent 3,142,568, U.S. Patent 3,323,286, Belgium Patent 70
8,347, German patent 2,047,150, British patent 1,498,69
No. 7, as described in JP-A-57-50967,
Some attempt to polymerize the latex with specific activators to ameliorate these drawbacks. However, in this technique, the type of emulsion used was limited, and none of them had any influence on fog, sensitivity and developing characteristics. Therefore, in the latex emulsion-polymerized using a low molecular weight surfactant, the combination of the type of the latex and the silver halide emulsion used is limited, and the amount of latex that can be contained in the emulsion is limited.

JP-A-55-50240, JP-B-55-47371, and JP-A-54-1977
No. 2, JP-A-48-52882, JP-A-48-52883 and the like, in order to solve the above problems, there is a technique of incorporating a latex using a polymer protective colloid into a silver halide emulsion during emulsion polymerization. It is disclosed. These latexes
Although it has little effect on photographic performance, there are problems in production of photographic materials such as devitrification during development, increase in viscosity of coating solution, deterioration of multi-layer property, and cissing during coating. As described above, it is advantageous to use the polymer protective colloid latex for the purpose of improving the physical properties of the film, from the viewpoint of photographic performance, but the devitrification property at the time of development, 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 use a silver halide emulsion which has good compatibility with gelatin and does not cause aggregation upon addition of emulsion to a latex, and which is free from sensitivity deterioration and has less fog increase. It is to provide a photographic light-sensitive material. Another object is to provide a silver halide photographic light-sensitive material using the above emulsion, which does not curl and has a small change in dimension. The above object can be achieved by the following technical means.

[Structure of the Invention] The above object is to provide 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 contains water or a water-miscible organic solvent containing a hydrophilic polymer having at least one anionic functional group having a repeating unit represented by the following general formula [I] in the molecular structure. It is achieved by a silver halide photographic light-sensitive material characterized in that it contains a protective colloidal latex obtained by dissolving it in an aqueous solution and adding a polymerizable unsaturated compound thereto and polymerizing.

[In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, X represents a hydrogen atom, and L represents -CONH-, -COO-, -CO- or -O-. , J represents an alkylene group having 1 to 12 carbon atoms or an arylene group, or CH ₂ CH ₂ O _m CH _{2 n} (m represents an integer of 0 to 40, n represents an integer of 0 to 4), and Q represents -SO ₃ M or (M represents a hydrogen atom or a cation), and p and q each represent 0 or 1. [Specific Structure of the Invention] The latex of the present invention contains water or a water-miscible organic solvent in which a resin obtained by previously polymerizing a polymerizable unsaturated compound is dissolved as it is or in a water-miscible organic solvent. It is dispersed in an aqueous solution and the hydrophilic polymer according to the present invention is added to obtain a stable latex.

A resin obtained by previously polymerizing a polymerizable unsaturated compound is directly used, or a solution obtained by dissolving it in a water-miscible organic solvent is dispersed in an aqueous solution in which the hydrophilic polymer according to the present invention is dissolved to obtain a stable latex.

The polymerizable unsaturated compound is emulsion-polymerized in water using a small amount of a surfactant, and the hydrophilic polymer according to the present invention is added thereto to obtain a stable latex.

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 therein to polymerize to obtain a stable latex.

And the like.

In the above method, a more stable latex can be obtained by adding the hydrophilic polymer of the present invention and then heating the temperature of the liquid to 50 ° C. or higher and then cooling.

Among the above methods, the method of obtaining a latex having good stability and uniform particle size is preferable.

The hydrophilic polymer compound having an anionic functional group referred to in the present invention means a sulfonic acid group as an anionic functional group in the molecular structure, or a salt thereof, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof. It is a hydrophilic polymer having In addition, the hydrophilic polymer compound may be dissolved in 0.05 g or more in 100 g of water at 20 ° C. so that the number average molecular weight is 2
Say more than 000. Preferably, the solubility in water is 0.1 g or more.

As the hydrophilic polymer having an anionic functional group, preferably, a polymer containing the repeating unit of the following general formula [I] in an amount of 10 to 100 mol% in one molecule of the polymer can be mentioned.

In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.) or a halogen atom (eg, chlorine atom, etc.), and X represents a hydrogen atom. , L is -CONH-, -COO-,
Represents -CO- or -O-, and J represents 1 to 12 carbon atoms.
And alkylene groups (including those having a substituent, such as methylene group, ethylene group, trimethylene group, propylene group, butylene group, and hexylene group), arylene groups (including those having a substituent, such as phenylene group). ), Or CH ₂ CH ₂ O _m CH _{2 n} (m is an integer of 0 to 40, n is an integer of 0 to 4), and Q is -SO.
₃ M or Represents M represents a hydrogen atom or a cation, and p and q each represent 0 or 1.

The hydrophilic polymer having the repeating unit represented by the general formula [I] may be a homopolymer of the unit represented by the general formula [I] or may contain other components.

As other components, for example, acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, styrenes, crotonic acid esters, itaconic acid diesters, maleic acid diesters, fumaric acid diesters, acrylamides, Allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional monomers,
Examples thereof include a monomer compound selected from various unsaturated acids or a combination of two or more thereof.

The hydrophilic polymer having an anionic functional group of the present invention may contain other components as a composition. In that case, the anionic functional group is contained in a molar ratio of at least 10% or more, preferably 30% or more. Specific examples are shown below.
(The numbers on the main chain represent the molar ratio.) The latex used in the present invention is mainly composed of a hydrophobic polymer which is made into a protective colloid by the hydrophilic polymer having an anionic functional group according to the present invention, and such a polymer is
They are roughly classified into condensation polymers and vinyl polymers. Examples of the condensation polymer include polyamide, polypeptide, polyester, polycarbonate, polyanhydride, polyurethane, polyurea and polyether. The unsaturated compound-based polymer is an addition polymer based on a vinyl group and is an aliphatic hydrocarbon-based, aromatic-based, vinyl alcohol-based, nitrile-based, acrylic-based, methacrylic-based, acrylonitrile-based,
Examples thereof include halogen-based homopolymers and copolymers obtained by combining these.

By forming a protective colloid with the hydrophilic polymer of the present invention, a hydrophobic polymer of any composition can be stably contained in the hydrophilic colloid layer, so that the composition is not particularly selected in terms of performance, A polyester-based or vinyl-based polymer is preferably selected from the viewpoint of 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, polyfunctional monomers, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles and the like.

To give specific examples of these polymerizable unsaturated compounds,
As acrylic acid esters, 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, penzyl 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-butoxy) Butoxy) ethyl acrylate, .omega.-methoxy polyethylene glycol acrylate (addition molar number n = 9), 1-promo-2-methoxyethyl acrylate, and 1,1-dichloro-2-ethoxyethyl acrylate.

Examples of methacrylic acid esters include 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, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, Cresyl methacrylate, Chill 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-ptoxyethoxy) ethyl. Methacrylate, ω-methoxypolyethylene glycol methacrylate (additional mol number n = 6) and the like can be mentioned.

Examples of vinyl esters include vinyl acetate,
Examples thereof include vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate and the like.

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

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester, etc. Is mentioned.

Examples of crotonic acid esters include butyl crotonic acid, hexyl crotonic acid, and the like.

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

The maleic acid diesters include, for example, diethyl maleate, dimethyl maleate, dibutyl maleate and the like.

Examples of the fumarate diesters include diethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

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

As methacrylamides, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert.
-Butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide,
Dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide,
Examples thereof include N- (2-acetoacetoxyethyl) methacrylamide.

Examples of the allyl compound include allyl acetate, allyl caproate, allyl laurate, and allyl benzoate.

As vinyl ethers, methyl vinyl ether,
Examples thereof include 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 vinyl pyridine and N-
Vinyl imidazole, N-vinyl oxazolidone, N-
Examples thereof include vinyltriazole and N-vinylpyrrolidone.

Examples of the glycidyl esters include glycidyl acrylate and glycidyl methacrylate.

Examples of unsaturated nitriles include acrylonitrile and methacrylonitrile.

Examples of polyfunctional monomers include divinylbenzene, methylenebisacrylamide, ethylene glycol dimethacrylate and the like.

Further, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, for example, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc .; Monoalkyl maleate, for example, monomethyl maleate, monoethyl maleate, malein Acid monobutyl; citraconic acid, styrenesulfonic acid, vinylbenzylsulfonic acid, vinylsulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid;
Methacryloyloxyalkyl sulfonic acids, such as methacryloyloxymethyl sulfonic acid, methacryloyloxyethyl sulfonic acid, methacryloyloxypropyl sulfonic acid, etc .; acrylamidoalkyl sulfonic acids, such as 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2- Methyl propane sulfonic acid, 2-acrylamido-2-methylbutane sulfonic acid, etc .; Methacrylamide amidoalkyl sulfonic acids, such as 2-methacrylamido-2-methylethane sulfonic acid, 2-methacrylamido-2-methylpropane sulfonic acid, 2- Methacrylamido-2-methylbutanesulfonic acid and the like; acryloyloxyalkyl phosphate,
For example, acryloyloxyethyl phosphate, 3-
Acryloyloxypropyl-2-phosphate etc .;
Methacryloyloxyalkyl phosphates such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate and the like; sodium 3-allyloxy-2-hydroxypropane sulfonate having two hydrophilic groups and the like can be mentioned. These acids may be salts of alkali metals (eg Na, K, etc.) or ammonium ions. Still other polymerizable unsaturated compounds include U.S. Pat.Nos. 3,459,790 and 3,4.
38,708, 3,554,987, 4,215,195, 4,
The crosslinkable monomers described in JP-A No. 247,673 and JP-A No. 57-205735 can be used. Specific examples of such a crosslinkable monomer include N- (2
-Acetoacetoxyethyl) acrylamide, N- {2
Examples thereof include-(2-acetoacetoxyethoxy) ethyl} acrylamide.

These polymerizable unsaturated compounds can be roughly classified into a hydrophobic unsaturated compound and a hydrophilic unsaturated compound, but when a hydrophilic unsaturated compound is used, a combination with a hydrophobic unsaturated compound is a stable latex. Is preferred for the formation of Of course, these unsaturated compounds may be used alone or in combination of two or more kinds.

Although water-soluble compounds are included in these compounds, a hydrophobic polymer can be formed by copolymerizing with a hydrophobic compound.

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 a polymerization initiator for vinyl polymers, azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate,
2,2'-Azobis (4-methoxy-2,4-dimethivaleronitrile), 1,1'-azobis (cyclohexanone-1-
Carbonitrile) dimethyl, 2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, 4,4'-
Azo compounds such as sodium azobis-4-cyanovalerate, 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, persulfates such as sodium persulfate, potassium bromate, and ceric ammonium nitrate 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 the present invention, the amount of latex used is 10% or more and 300% or less, preferably 30% or more and 200% or less, by weight ratio to gelatin. If the amount of the latex used is too small, the effect of the present invention is not sufficiently exhibited, and if the amount of the latex used is too large, sufficient film strength cannot be obtained. Amount of the hydrophilic polymer used in the present invention Is 30% or less and 0.1% or more, preferably 15% or less and 0.5% or more by weight ratio with respect to the resin. The same applies to the amount used in emulsion polymerization.

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

For example, in solution polymerization, generally, a mixture of monomers having an appropriate concentration in an appropriate solvent (eg, ethanol, methanol, water, etc.) (usually 40% by weight or less, preferably 10 to 25% by weight based on the solvent) is used. In the presence of a polymerization initiator (eg, benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.), at an appropriate temperature (eg, 40 to 120).
The copolymerization reaction is carried out by heating to 50 ° C, preferably 50 to 100 ° C. Then, the reaction mixture is poured into a medium in which the produced copolymer is not dissolved, and the product is allowed to settle,
Then, the unreacted mixture is separated and removed by drying. The molecular weight of the hydrophilic polymer according to the present invention is 1,000 to 1,0.
It is 00,000, preferably 2,000 to 200,000.

In addition, the molecular weight of the hydrophilic polymer according to the present invention is represented by a number average molecular weight, and the measurement was performed using a Gluvermiation chromatography HLC-802A manufactured by Toyo Soda Co., Ltd. as a standard polystyrene conversion.

Synthesis Example 1 (Exemplified Compound P-6) 50 g of 3-sulfopropyl acrylate potassium salt (0.2
2 mol), 4,4-azobis (4-cyanovaleic acid) 3.0
g and 200 ml of degassed water were put into a three-necked flask, and this mixed solution was reacted at 80 ° C. for 8 hours. After completion of the reaction, the reaction solution was poured into a large amount of acetone with vigorous stirring to precipitate the reaction product. The precipitate is then filtered,
The polymer P-6 of the present invention was obtained by washing with acetone and drying in air at 60 ° C. The yield was 45 g (90% of theoretical yield) and the number average molecular weight was Mn = 4300.

Synthesis Example 2 (Exemplified Compound P) Styrene 52 g (0.50 mol), acrylic acid 36 g (0.50 mol), 4,4-azobis (4-cyanovaleic acid) 5.0 g,
Then, 500 ml of degassed ethanol was placed in a three-necked flask, and this mixed solution was reacted under reflux for 8 hours. After the completion of the reaction, the mixture was poured into a large amount of acetone with vigorous stirring, and then the same treatment as in Synthesis Example 1 was performed to obtain a polymer P. Yield 80g (91% of theoretical yield), number average molecular weight Mn
= 2600.

Synthesis Example 3 (Exemplified Compound P-7) 25.6 g (0.20 mol) of n-butyl acrylate, 183 g (0.80 mol) of sodium 2-acrylamido-2-methylpropanesulfonate, 4,4-azobis (4-cyanovaleic acid) 5.0 g and degassed water-ethanol = 50 / 50v
% Solution 500ml into a three-necked flask and add 75
The reaction was carried out at 0 ° C for 10 hours. After completion of the reaction, the reaction solution was poured into a large amount of acetone with vigorous stirring to precipitate the reaction product. Then, the precipitate was filtered, washed with acetone and dried in air at 60 ° C. to obtain a polymer P-7 of the invention. The yield was 185 g (88% of theoretical yield) and the number average molecular weight was Mn =
It was 6800.

Latex production method Production example 1 A 1000 ml four-necked flask is equipped with a stirrer, thermometer, dropping funnel, nitrogen introduction tube, and reflux condenser, heated with 350 cc of pure water, and heated to an internal temperature of 80 ° C. To do. During this period, nitrogen gas was introduced, and after the internal temperature reached 80 ° C, nitrogen gas was passed through for 30 minutes. 4.5 g of P-6 was added, and then a solution of 0.45 g of ammonium persulfate in 10 cc of water was added as an initiator, followed by 40 g of butyl acrylate and 50 g of styrene.
The mixture is added dropwise with a dropping funnel over about 1 hour.
5 hours after adding the initiator, cool and pH with ammonia water
After adjusting to 6, the mixture was filtered to remove dust and coarse particles to obtain a latex liquid (a).

Production Example 2 As the polymerizable unsaturated compound, butyl acrylate 39.5
A latex liquid (b) was obtained in the same manner as in Production Example 1 except that a mixture of g, 49.5 g of styrene and 1 g of acrylic acid was used.

Production Example 3 Ethyl acrylate 90 was used as the polymerizable unsaturated compound.
g, a latex liquid (c) was obtained 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 2 except that P-7 was used instead of P-6.
A latex liquid (e) was obtained by synthesizing in the same manner as.

Production Example 5 Production Example 3 except that P-7 was used instead of P-6.
A latex liquid (f) was obtained by synthesizing in the same manner as in.

Production Example 6 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 P-7, 0.2 part by weight of third dodecyl mercaptan, and 0.3 part by weight of tripotassium phosphate. Then, 0.3 parts by weight of ammonium persulfate and 100 parts by weight of water were charged, and the polymerization was carried out at a polymerization temperature of 50 ° C., a polymerization pressure of 5 atm and a polymerization time of 18 hours. After the reaction was completed, residual monomers were distilled off to obtain a latex (g ) Got.

Production Example 7 192.1 g (1.0 mol) of trimellitic anhydride, 62.1 g (1.0 mol) of ethylene glycol and 108.1 g of benzyl alcohol were placed in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introducing tube, a distillation device, and a heater. (1.0 mol).

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 the acetone solution was gradually poured into 100 ml of a P-7 aqueous solution having a concentration of about 0.1 molar with rapid stirring. The mixture was filtered, and then heated to 60 ° C. to remove acetone to obtain a latex liquid (h).

Production Example 8 Latex liquid (i) was synthesized in the same manner as in Production Example 1 except that Compound P was used instead of the hydrophilic polymer compound P-6.
I got

In the present invention, the latex colloidalized with the hydrophilic 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.

Gelatin is not only lime-processed gelatin, but also Bulletin of the Society of Scientific Photography of Japan (Bull, Soc, Sc
i, Phot, Japan.) No. 16, page 30 (1966), an oxygen-treated gelatin may be used, or a hydrolyzate or an enzymatic hydrolyzate of gelatin may 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 cubic, octahedral or tetradecahedral, or may have an irregular shape such as spherical or tabular. It may have a crystal form. In these particles,
Any ratio can be used for the {100} plane and the {111} plane. Further, those having a composite form of these crystal forms may be used, 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 used in combination.

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.

[Examples] Hereinafter, specific examples of the present invention will be described in detail, but the embodiments of the present invention are not limited thereto.

Example 1 75 mol% silver chloride, 25 mol% silver bromide, and 1 silver iodide
To a silver chloroiodobromide gelatin emulsion containing 1 mol%, 0.6 g of 4-hydroxy-6-methyl-per mol of silver halide was added.
1,3,3a, 7-tetrazaindene was added, and the compound latex (a) of the present invention was added as a dry weight to give gelatin.
It was added to 1.0 g per 1 g, and after adding mucochloric acid, on a polyethylene terephthalate support that had been subjected to undercoating, the amount of latex and gelatin was 1.9 g / m ² so that the amount of silver was 4.0 g / m ^2. It was applied so as to be m ² .

As a comparison, a sample was prepared in the same manner except that the latex liquid (a) prepared by using sodium dodecylbenzenesulfonate instead of P-6 used in Production Example 1 was replaced with the latex (a). A sample was prepared without adding the latex (a).

The obtained sample was subjected to wedge exposure, and the following treatment was performed to examine the sensitivity, fog, and dimensional stability. The results are shown in Table 1.

[Processing conditions] Image 29 ℃ 30 seconds Settlement 28 ℃ 20 seconds Water wash 20 ℃ 20 seconds Dry 45 ℃ 30 seconds [Developer (stock solution)] Potassium bromide 2.5 g Ethylenediaminetetraacetic 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 170 g Sodium sulfite 15 g Boric acid 6.5 g Glacial acetic acid 12 ml Sodium citrate (dihydrate) 2.5 g Add water to make 275 ml.

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

About 600 ml of water is added to 275 ml of Part A above.
Then add 40 ml of Part B, and then add water to add 1
Make up to 000 ml.

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

The reciprocal of the exposure amount that gives a density of fog +0.7 is defined as the sensitivity, and the specific sensitivity is shown with the same day sensitivity of Sample No. 1 as 100.

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

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

As is clear from Table-1, the comparative latex can be used only in a small amount and the dimensional stability is not good. Moreover, the dimensional stability is not good even for a sample that does not use latex at all. The sample of the present invention has high sensitivity, less fog, and improved dimensional stability as compared with the comparative sample.

Example 2 A sample prepared in the same manner as sample No. 1 except that latex (i) is used instead of latex a is referred to as sample No. 12.

The samples No. 5 and No. 12 of Example 1 were evaluated for devitrification and trailing failure.

[Devitrification] When an unexposed sample was developed, the transparency of the film was A, which showed no decrease in transparency as compared to sample No. 11 containing no latex, and a sample which became extremely slightly milky white. B, and the one having a clear milky white color was designated as C.

The tailing failure] created emulsion surface of the sample observed in detail with a loupe, those tailing generated as dragging the coating direction does not occur at all A, B those on 1 m ² 1 to 2 pieces occurs, it Others were evaluated as C.

The photographic characteristics and dimensional stability were evaluated in the same manner as in Example 1. The obtained results are shown in Table-2.

As described on page 3 of the specification of the present application, and as is clear from the above results, a light-sensitive material using a latex polymerized in the presence of a hydrophilic polymer compound in which an anionic group is a carboxyl group has dimensional stability and Regarding photographic characteristics, there were no major problems, but devitrification and tailing failure were observed.

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Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has a molecular structure represented by the following general formula [I]: A protective colloid obtained by dissolving a hydrophilic polymer having at least one anionic functional group having a repeating unit in water or an aqueous solution containing a water-miscible organic solvent, and adding a polymerizable unsaturated compound to the solution to polymerize the solution. A silver halide photographic light-sensitive material, characterized in that it contains a prepared latex. [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, X represents a hydrogen atom, and L represents-.
CONH -, - COO -, - CO- or an -O-, J ₂ alkylene or arylene group or a CH ₂ CH 1 to 12 carbon atoms is O _m CH _{2 n (m} is 0 to 40 integer, n is 0
Represents an integer of 4; ), Q is -SO ₃ M or (M represents a hydrogen atom or a cation), p and q
Represents 0 or 1, respectively. ]