JPH0610744B2 - Silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, and in particular, it has excellent coating properties and does not adversely affect photographic characteristics. The present invention relates to a silver halide photographic light-sensitive material having good antistatic property without causing troubles due to adhesion of water-insoluble matter and generation of water-insoluble matter.

BACKGROUND OF THE INVENTION A silver halide photographic light-sensitive material (hereinafter referred to as a photographic light-sensitive material) generally comprises a support having an electrically insulating property and a photographic constituent layer. Electrostatic charges are often accumulated by contact friction or delamination with surfaces of the same or different materials. This accumulated electrostatic charge causes many obstacles, but the most serious obstacle is when the photosensitive emulsion layer is exposed by developing the photographic film by discharging the accumulated electrostatic charge before the development processing. It is the formation of spotted spots or dendritic or feather-like line spots. This is the so-called static mark, which significantly impairs the commercial value of photographic film. For example, if it appears on a medical or industrial X-ray film, it will lead to a very dangerous judgment. This phenomenon becomes apparent only after development and is one of the very troublesome problems. Further, these accumulated electrostatic charges may cause a secondary failure such as dust adhering to the film surface or non-uniform coating.

As described above, such electrostatic charges are often accumulated during the manufacture and use of the photographic light-sensitive material. For example, in the manufacturing process, the contact friction between the photographic film and the roller or the winding and rewinding process of the photographic film is performed. It is caused by separation of the support surface and the emulsion surface in the above. In the finished product, the base surface and the emulsion surface are separated when the winding of the photographic film is changed, or the machine portion of the X-ray film in the automatic photographing machine or the fluorescent intensifying screen is used. It is caused by contact separation between the two. It is also generated by contact with other packaging materials. The static marks of the photographic light-sensitive material, which are induced by the accumulation of such electrostatic charges, become more noticeable as the sensitivity of the photographic light-sensitive material increases and the processing speed increases. In particular, in recent years, the occurrence of static marks has become more likely due to the increased sensitivity of photographic light-sensitive materials and the increased opportunities for severe handling such as high-speed coating, high-speed photography, and high-speed automatic development processing. .

In order to eliminate these problems due to static electricity, it is preferable to add an antistatic agent to the photographic light-sensitive material. However, as the antistatic agent that can be used in the photographic light-sensitive material, the antistatic agent generally used in other fields cannot be used as it is, and various restrictions peculiar to the photographic light-sensitive material are imposed. That is, the antistatic agent that can be used in the photographic light-sensitive material, in addition to having excellent antistatic performance, does not adversely affect the photographic characteristics of the photographic light-sensitive material, the film strength of the photographic light-sensitive material, and the adhesion resistance. Applying antistatic agents to photographic light-sensitive materials requires performance such that fatigue of the processing liquid of photographic light-sensitive materials is not accelerated, transport rollers are not contaminated, and adhesive strength between constituent layers of photographic light-sensitive materials is not reduced. Doing is subject to numerous restrictions.

One way to eliminate these electrostatic disturbances is to increase the electrical conductivity of the surface of the photographic light-sensitive material so that the electrostatic charge can be dissipated in a short time before the accumulated charge is discharged.

Therefore, conventionally, a method of improving the conductivity of the support of the photographic light-sensitive material and various coated surface layers has been considered, and various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers and the like have been tried to be used. Came. Among them, the surfactant is important in terms of antistatic ability. For example, U.S. Pat. No. 3,082,123
No. 3, No. 3,201,251, No. 3,519,561, No. 3,625,695,
West German Patent Nos. 1,552,408 and 1,597,472, JP-A-49
-85,826, 53-129,623, 54-159,223, 48-1
No. 9,213, Japanese Patent Publication Nos. 46-39,312, 49-11,567, 51-4
6,755, the same anion described in 55-14,417,
Betaine and cationic surfactants, or JP-A-52-8
0023, West German Patent Nos. 1,422,809, 1,422,818,
Nonionic surfactants described in Australian Patent No. 54,441 / 1959 are known.

However, these materials show specificity depending on the type of film support and photographic composition, and give good results for certain film supports and photographic emulsions and other photographic components, but other different film supports. Doesn't help the body and photographic components in antistatic purposes at all,
Alternatively, even if the antistatic property is excellent, the photographic properties such as sensitivity, fog, graininess, and sharpness of the photographic emulsion are adversely affected, the developing solution is contaminated, and deposits are formed on the roller. However, it has been extremely difficult to apply these substances to photographic light-sensitive materials.

Further, the antistatic technique using a nonionic surfactant is closely related to the coating agent used together. However,
Although they have certainly made progress in antistatic performance, they do not consider the contamination of the developing solution or the contamination of the transport roller, which causes a serious film failure. . For example, it is described in JP-B-51-9610 that an ethylene oxide addition polymer of a phenol formalin condensate has excellent antistatic properties even when used in combination with various coating agents. However, the method of the patent does not solve the trouble due to contamination in the developing process.

That is, the roller stain, which is considered to be caused by the dried deposit on the transport roller, is extremely bad, which is a problem as uneven density of the film.

Further, JP-A-53-29715 and JP-A-60-76741 describe a photographic light-sensitive material containing a specific anionic surfactant and a polyoxyethylene nonionic surfactant. Similarly, improvement of film failure due to contamination of the developing solution or contamination of the transport roller cannot be obtained.

It is known to use a fluorine-containing surfactant as another means for improving antistatic performance. This method is intended to reduce the generation of static marks by reducing the power generation property of the film by utilizing the negative charging property of the fluorine group. For example, British Patent No. 1,259,398 and US Patent No. 4,01
3,696, JP-B-48-43130, JP-A-48-52,223, 50
-16525, 52-127974, 54-48520, 55-25077
No., etc. In addition, JP-A-60-76742 and 60-808
No. 49 discloses a technique in which a fluorine-containing compound and a nonionic surfactant are used in combination.

However, according to these methods, although the charging performance is improved in some cases, various problems found in the developing process, that is, uneven density due to contamination of the transport roller caused by contamination of the processing liquid, are not sufficiently solved.

By the way, various kinds of surfactants are added to the photographic light-sensitive material in order to coat the support uniformly. In recent years, a large amount of surfactant has been used to cope with high-speed coating accompanying the increase in production amount.

However, the use of a large amount of the above-mentioned surfactants including the antistatic material deteriorates the physical properties of the film, deteriorates the developability, and particularly deteriorates the wettability and inhibits the penetration of the development solution. However, it is a factor that hinders rapid processing of photographic light-sensitive materials. Further, since a surfactant is also used in the production of the polymer latex contained to enhance the film properties of the hydrophilic colloid film, JP-B-45-18415, JP-A-45-18415
In 51-130217 and 56-19047, various attempts have been made to reduce the amount of the surfactant, but the above-mentioned drawbacks have not been improved yet.

[Object of the Invention] A first object of the present invention is to provide a photographic light-sensitive material having good antistatic ability without adversely affecting coatability and film strength of a photographic coating solution.

A second object of the present invention is to provide a photographic light-sensitive material in which static marks are less likely to occur when processed rapidly.

[Structure of the Invention] The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one photographic constituent layer on a support, wherein at least one of the photographic constituent layers has a water-soluble polymer, a latex and a nonionic surfactant. It was achieved by including an agent.

[Specific Structure of the Invention] Examples of the water-soluble polymer used in the present invention include synthetic water-soluble polymers and natural water-soluble polymers, and any of them can be preferably used in the present invention.
Among these, the synthetic water-soluble polymer includes, for example, those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group in the molecular structure. Examples of nonionic groups include ether groups, ethylene oxide groups, and hydroxy groups, and examples of anionic groups include sulfonic acid groups or salts thereof, carboxylic acid groups or salts thereof, phosphoric acid groups or salts thereof, and the like. Can be given. Further, as the natural water-soluble polymer, for example, those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group are included in the molecular structure.

As the water-soluble polymer, in both cases of synthetic water-soluble polymer and natural water-soluble polymer, those having an anionic group and those having a nonionic group and an anionic group can be preferably used. In the present invention, the water-soluble polymer may be dissolved in 100 g of water at 20 ° C. by 0.05 g or more, preferably 0.1 g or more.

Examples of the synthetic water-soluble polymer include those containing the repeating unit of the following general formula [P] in an amount of 10 to 100 mol% in one molecule of the polymer.

General formula [P] In the formula, R ₁ is a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (including those having a substituent, for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), a halogen atom. (Eg chlorine atom) or —CH ₂
Represents COOM, L is -CONH-, -NHCO-,
Represents -COO-, -OCO-, -CO- or -O-, and J is an alkylene group, preferably having 1 to 10 carbon atoms.
And alkylene groups (including those having a substituent. For example, methylene group, ethylene group, propylene group, trimethylene group, butylene group, hexylene group, etc.), arylene groups (including those having a substituent, such as phenylene group, etc. ), Or (M represents an integer of 0-40, n represents an integer of 0-4 More preferably, —SO ₃ M is the most preferable. M represents a hydrogen atom or a cation, R ₂ represents an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.), R ₃ , R ₄ , R ₅ , and R ₆ , R ₇ and R ₈ represent an alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, hexadecyl group, etc.), X represents an anion, p and q each represent 0 or 1.

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

The synthetic water-soluble polymer of the present invention can be easily synthesized by various methods such as solution polymerization, bulk polymerization and suspension polymerization.

For example, in solution polymerization, a mixture of monomers having a suitable concentration in a suitable solvent (eg, ethanol, methanol, water, etc.) (usually 40% by weight or less, preferably 10 to 25% by weight with respect to the solvent) is used. A polymerization initiator (for example,
In the presence of benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) at a suitable temperature (eg 40
The copolymerization reaction is carried out by heating to 120 to 120 ° C, preferably 50 to 100 ° C. Thereafter, the reaction mixture is poured into a medium in which the produced water-soluble polymer is not dissolved, the product is allowed to settle, and then dried to separate and remove the unreacted mixture. The molecular weight of the water-soluble polymer of the present invention is 1,
It is 000 to 1,000,000, preferably 2,000 to 200,000.

The molecular weight of the water-soluble polymer of the present invention is represented by the number average molecular weight, and the measurement was also made by gel permeation chromatography HLC-802A manufactured by Toyo Soda Co., Ltd. in terms of standard polystyrene.

Synthesis Example 1 (Exemplified Compound SP-18) 50 g of 3-sulfopropyl acrylate potassium salt (0.
22 mol), 3.0 g of 4,4'-azobis (4-cyanovaleic acid), and 200 ml of degassed water were placed in a three-necked flask, and this mixture 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. Then, the precipitate was filtered, washed with acetone, and dried in air at 60 ° C to obtain a polymer SP-18 of the present invention. The yield was 45 g (90% of theoretical yield), and the number average molecular weight was Mn = 4,300.

Synthesis Example 2 (Exemplified Compound SP-21) 52 g (0.50 mol) of styrene, 36 g (0.50 of acrylic acid)
Mol), 4,4'-azobis (4-cyanovaleic acid)
5.0 g and 500 ml of degassed ethanol were placed in a three-necked flask, and this mixture 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 carried out to obtain a polymer SP-21 of the invention. The yield is 80 g (9 of the theoretical yield).
1%) and number average molecular weight Mn = 2,600.

Synthesis Example 3 (Exemplified Compound SP-42) 52 g (0.40 mol) of hydroxyethyl methacrylate, 137 g (0.60 mol) of sodium 2-acrylamido-2-methylpropanesulfonate, 4,4′-
Azobis (4-cyanovaleric acid) (5.0 g) and degassed water-ethanol = 80/20 V% solution (500 ml) were placed in a three-necked flask, and the mixture was reacted at 80 ° 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 SP-42 of the present invention. Yield 180g
(95% of theoretical yield), the number average molecular weight was Mn = 5,300.

As the natural water-soluble polymer, it is described in detail in the comprehensive technical sample collection of water-soluble polymer water-dispersible resin (Business Development Center Publishing Department), but lignin, starch, pullulan, cellulose, alginic acid, dextran, dextrin, guar gum. , Gum arabic, glycogen, laminaran,
Likenin, nigeran and the like and derivatives thereof are preferred.

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

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

Further, among natural water-soluble polymers, a glucose polymer, and a derivative thereof are preferable, and among the glucose polymer and a derivative thereof, starch, glycogen, cellulose, lichenin, dextran, nigeran and the like are preferable,
Dextran and its derivatives are particularly preferable.

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 a culture solution of a dextran-producing bacterium such as leuconostoc and mesenteroides. Thus, the separated dextran sucrase can be obtained by reacting with saccharides. 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.

In addition, a dextran modified product is a dextran sulfate ester in which a sulfate group is present in the dextran molecule by an ester bond, and a salt thereof, a carboxyalkyl dextran in which a carboxyalkyl group is present in the dextran molecule by an ether bond, and a dextran molecule. Carboxyalkyl dextran sulfate having a sulfate group as an ester bond and a carboxyalkyl group as an ether bond, and a salt thereof, a dextran phosphate ester in which a phosphate group is present as an ester bond in a dextran molecule, and a salt thereof, a dextran molecule Examples thereof include a hydroxyalkyl dextran having a hydroxyalkyl group introduced therein.

The use of these dextran compounds in a silver halide photographic light-sensitive material is disclosed in Japanese Patent Publication No. 35-11989, U.S. Pat. No. 3,762,92.
No. 4, Japanese Patent Publication No. 45-12820, No. 45-18418, No. 45-40149
No. 46-31192 is known,
These dextrans are directly used in silver halide emulsion,
Alternatively, it is contained in a gelatin layer 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.

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, from the viewpoint of latex dispersion stability. Most preferred are sulfate esters.

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 a hydrochloric acid organic solvent such as pyridine or 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. In addition to this, alkali metal oxides such as sodium and potassium, calcium
Reaction with oxides or hydroxides of alkaline earth metals such as magnesium, ammonia, etc. gives dextran sulfate and carboxyalkyl sulfate salts, respectively.

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 products with an arbitrary degree of substitution within the range of 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.

The carboxyalkyl dextran, dextran sulfate, and carboxyalkyl dextran sulfate thus produced may be produced in various kinds by various combinations of the limiting viscosity of the starting dextran and the carboxyalkyl substitution degree of the sulfate substitution degree of the product. You can

Further, as the water-soluble polymer of the present invention, a polymer having a hydrophilic group and an ethylenic double bond in the molecular structure can be used, and for example, the following general formulas [I], [II] or [II
It is desirable that the polymer is mainly composed of the compound represented by the formula [I].

Here, as the hydrophilic group, the same groups as those described for the synthetic water-soluble polymer can be mentioned.

General formula [I] [In the formula, R ₁ is a divalent organic group, M ₁ is a hydrogen atom or 1
Represents a valent cation, n ₁ is 30 to 95 mol%, n ₂
Represents 70 to 5 mol%. ] General formula [II] [In the formula, R ₂ is a hydrogen atom or an alkyl group, M ₂ ,
M _{3, M 4} and _{M 5} each represents a hydrogen atom or a monovalent cation, _{n 3} is 30 to 95 mol%, _{n 4} is 7
0 to 0 mol% and n ₅ represent 70 to 0 mol%. However,
n ₄ + _{n 5} is 70 to 5 mol%. ] General formula [III] [In the formula, R ₃ is a hydrogen atom or an alkyl group, M ₆ ,
M ₇ , M ₈ and M ₉ each represent a hydrogen atom or a monovalent cation, n ₆ is 30 to 70 mol% and n ₇ is 5
˜50 mol%, n ₈ represents 70 to 5 mol%. However,
_{n 7} + n ₈ is 70 to 30 mol%. Next, the general formulas [I], [II] and [III] will be specifically described. Examples of the divalent organic group represented by R ₁ include ethylene, trimethylene, tetramethylene, hexamethylene, propenylene, 3, 6-dioxaoctane-
Divalent residue of aliphatic hydrocarbon such as 1,8-diyl, 2,2-dimethyltrimethylene, propylene and 1,4-cyclohexylene, or 1,2-dichloroethylene, 2-chlorotrimethylene, 2-bromo Aliphatic hydrocarbons substituted with halogen atoms, cyano groups, alkyloxy groups, aryloxy groups, etc., such as trimethylene, 1-cyanomethylethylene, 1-chloromethylethylene, 1-methoxymethylethylene, 1-phenoxyethylene. Divalent residue of 1,4-phenylene, 1,3-tolylene-2-chloro-
Substituted with a divalent residue of an aromatic hydrocarbon such as 1,4-phenylene, 2-cyano-1,4-phenylene, 2-methoxy-1,5-phenylene or a halogen atom, a cyano group, an alkyloxy group, etc. Divalent residue of aromatic hydrocarbon, or 1,1 '-(1,4-phenylene) dimethyl, 2,2'-(2-chloro-1,4-phenylene) diethyl, 2,2'- Examples thereof include a divalent residue of an aliphatic hydrocarbon such as (2-cyano-1,4-phenylene) diethyl or a divalent residue of an aliphatic hydrocarbon bonded to an aryl group substituted with a halogen atom, a cyano group or the like. To be

M ₁ , M ₂ , M ₃ , M ₄ and M ₅ represent a hydrogen atom or a monovalent cation of an alkali metal such as lithium, sodium or potassium, or an ammonium cation. As the polymer having a hydrophilic group and an ethylenic double bond in the molecular structure, the compound represented by the general formula [I] is preferable.

Next, representative specific examples of the polymer of the present invention will be listed as examples below, but the present invention is not limited thereto. The method for synthesizing these polymers is described in JP-A-55-50240.

D-1 _(However, n _1: n 2 = 50 mol%: 50 mol%, a number average molecular weight _(M n) = about 10,000) D-2 (However, n ₁ : n ₂ = 30 mol%: 70 mol%, M _n = about 6,000
0) D-3 _(Where, n _1: n 2 = 95 mol%: 5 mol%, _{M n} = about 20,000
0) D-4 (However, n ₁ : n ₂ = 70 mol%: 30 mol%, M _n = about 30,0
00) D-5 D-6 D-7 D-8 (However, n ¹ : n ² = 30 mol%: 70 mol%, M _n =
About 15,000) D-9 D-10 ^{(Where, n 1: n 2: n} 3 = 80 mol%: 10 mol%:
10 mol%, M _n = about 6,000) D-11 D-12 D-13 ^{(Where, n 1: n 2: n} 3 = 50 mol%: 45 mol%:
5 mol%, M _n = about 15,000) The latex used in the present invention is mainly composed of a hydrophobic polymer, and such a polymer is roughly classified into a condensation polymer and a vinyl polymer. As the condensation polymer, polyamide, polypeptide, polyester, polycarbonate,
Examples thereof include polyanhydrides, polyurethanes, polyureas, polyethers and the like. The unsaturated compound polymer is a vinyl group addition polymer, and is a homopolymer of aliphatic hydrocarbon, aromatic, vinyl alcohol, nitrile, acryl, methacryl, acrylonitrile, halogen, etc. And copolymers of these combinations.

By using the water-soluble polymer of the present invention in combination, a hydrophobic polymer of any composition can be stably contained in the hydrophilic colloid layer, and therefore the composition is not particularly selected in terms of performance, but the production of latex From the above easiness, a polyester or vinyl polymer is preferably selected.
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,
Examples thereof include acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl ketones, polyfunctional monomers, vinyl heterocyclic compounds, glycidyl esters and unsaturated nitriles.

Specific examples of these polymerizable unsaturated compounds include acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, and 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 and the like can be mentioned.

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, 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-methoxy polyethylene glycol methacrylate (additional mol number n = 6) and the like.

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

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, bromstyrene, vinylbenzoic 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.

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

Examples of the fumarate diesters include diethyl fumarate, dimethyl 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. Acrylamide, β-cyanoethylacrylamide, N- (2-acetoacetoxyethyl)
Examples include acrylamide.

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, N
-(2-acetoacetoxyethyl) methacrylamide and the like can be mentioned.

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

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

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

Examples of the vinyl heterocyclic compound include vinyl pyridine, N-vinyl imidazole, N-vinyl oxazolidone, N-vinyl triazole and N-vinyl pyrrolidone.

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 etc .; citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid such as acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid; methacryloyloxyalkyl Sulfonic acids such as methacryloyloxymethyl sulfonic acid, methacryloyloxyethyl sulfonic acid, methacryloyloxypropyl sulfonic acid and the like; Krill amide alkylsulfonic 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
Examples thereof include sodium 3-allyloxy-2-hydroxypropane sulfonate and the like. These acids may be salts of alkali metals (eg Na, K, etc.) or ammonium ions. Further, as other polymerizable unsaturated compounds, U.S. Patent Nos. 3,459,790 and 3,43.
No. 8,708, No. 3,554,987, No. 4,215,195, No. 4,2
The crosslinkable monomers described in JP-A-47,673 and JP-A-57-205735 can be used. Specific examples of such a crosslinkable monomer include N- (2-
Acetoacetoxyethyl) acrylamide, N- {2-
(2-acetoacetoxyethoxy) ethyl} acrylamide and the like can be mentioned.

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-dimethyvaleronitrile), 1,1'-azobis (cyclohexanone-1-carbonitrile) dimethyl, 2,2'-
Azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, sodium 4,4'-azobis-4-cyanovalerate, 2,2'-azobis (2-amidinopropane) hydrochloride, etc. Peroxides of compounds, benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, t-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, hydrogen peroxide And persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate, potassium bromate, and ceric ammonium nitrate.

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

Latex production method Production example 1 A 1000 ml four-necked flask was equipped with a stirrer, thermometer, dropping funnel, nitrogen introducing tube, and reflux condenser, and 350 cc of pure water was added 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, the
Pass nitrogen gas for minutes. 4.5 g of sodium dodecylbenzene sulfonate was added, and then a solution of 0.45 g of ammonium persulfate dissolved in 10 cc of water was added as an initiator, followed by 40 g of butyl acrylate and 50 g of styrene in a dropping funnel for about 1 hour. And drop it. 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).

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

Production Example 3 Ethyl acrylate 90 as the polymerizable unsaturated compound
g, and using potassium persulfate as an initiator, synthesis was carried out in the same manner as in Production Example 1 except that polymerization was carried out at 70 ° C. to obtain a latex liquid (c).

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

Production Example 5 A latex liquid (e) was obtained in the same manner as in Production Example 2 except that Alkanol XC was used instead of sodium dodecylbenzenesulfonate.

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

Production Example 7 A 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, and 3 parts of sodium dodecylbenzenesulfonate were used.
Parts by weight, third dodecyl mercaptan 0.2 parts by weight, tripotassium phosphate 0.3 parts by weight, ammonium persulfate 0.3 parts by weight, water 100
Polymerization temperature of 50 ° C., polymerization pressure of 5 atm and polymerization time of 18 hours were charged, and after completion of the reaction, residual monomers were distilled off to obtain latex (g).

Production Example 8 192.1 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 introduction 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 an aqueous ammonia 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).

In the present invention, the amount of latex used is 10% or more and 300% or less, preferably 3% by weight, based on 100 of gelatin.
It is 0% or more and 200% or less. If the amount of latex used is too small, the effect 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 water-soluble polymer used in the present invention is 0.5% or more and 30% or less by weight ratio with respect to latex 100,
It is preferably 1% or more and 15% or less. If the amount of the water-soluble polymer used is too small, the sufficient effect is not exhibited, and if the amount is too large, the coating properties of gelatin, especially during high-speed coating, pose problems.

Next, the nonionic surfactant used in combination with the above water-soluble polymer and latex will be described.

The nonionic surfactants preferably used in the present invention include the following general formulas [NI], [N-II] and [N-].
III] can be mentioned.

General formula [NI] General formula [N-II] General formula [N-III] In the formula, R ₁ represents a hydrogen atom or an alkyl group, an alkenyl group or an aryl group having 1 to 30 carbon atoms, and those groups each having a substituent are also included. R ₁ is preferably an alkyl group having 4 to 24 carbon atoms, an alkenyl group,
Aryl group, particularly preferably hexyl group, dodecyl group, isostearyl group, oleyl group, t-butylphenyl group, 2,4-di-t-butylphenyl group, 2,4-
Examples thereof include di-t-pentylphenyl group, p-dodecylphenyl group, m-pentadecaphenyl group, t-octylphenyl group, 2,4-dinonylphenyl group and octylnaphthyl group.

A is -O-, -S-, -COO-, -OCO-, An alkyl group including one having a substituent is shown. ) Is represented.

R ₂ , R ₃ , R ₇ and R ₉ are each a hydrogen atom, an alkyl group,
It represents an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, and these groups include those each having a substituent.

R ₆ and R ₈ represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, and these groups each have a substituent. Is also included.

R ₆ and R ₈ are preferably an aryl group such as an alkyl group having 1 to 20 carbon atoms, a phenyl group and a p-chlorophenyl group, —OR ₁₅ (wherein R ₁₅ is an alkyl group having 1 to 20 carbon atoms or an aryl group). And those groups having a substituent are also included. The same shall apply hereinafter) and an alkoxy group and an aryloxy group, a halogen atom such as a chlorine atom and a bromine atom, an acyl group represented by —COR ₁₅ . -NR ₁₆ COR ₁₅ (wherein _{R 16} represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. the same below.) an amide group represented _by, -NR 16 _SO 2 R
Sulfonamide represented by ₁₅ It is an yl group. Of these, R ₆ and R ₈ are more preferably an alkyl group or a halogen atom, and most preferably a tertiary alkyl group such as a t-butyl group, a t-amyl group and a t-octyl group.

R ₂ , R ₃ , R ₇ and R ₉ are preferably hydrogen atoms or the groups mentioned above as preferred ones of R ₆ and R ₈ . Of these, R ₇ and R ₉ are particularly preferably hydrogen atoms.

R ₄ and R ₅ represent a hydrogen atom, an alkyl group or an aryl group, and these groups include those having a substituent. R ₄ and R ₅ are particularly preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a furyl group or the like.

R ₄ and R ₅ , R ₆ and R _7, and R ₈ and R ₉ may be linked to each other to form a ring, for example, a cyclohexyl ring. Further, in the general formula [N-III], the substituents on the phenyl ring may be left-right asymmetric.

n ₁ , n ₂ , n ₃ and n ₄ are the average number of moles of ethylene oxide added, which is a number of 2 to 5, and particularly preferably 5 to 30. n ₃ and n ₄ may be the same or different.

m is an integer of 2 to 50.

These compounds are described in, for example, U.S. Patent Nos. 2,982,651 and 3,4.
28,456, 3,457,076, 3,454,625, 3,552,97
No. 2, No. 3,655,387, Japanese Patent Publication No. 51-9610, JP-A No. 53-2971
5, JP-A-54-89626, JP-A-58-203435, JP-A-58
-208743, Hiroshi Horiguchi, "New Surfactants" (Sankyo Publishing 1975
Year) etc.

Next, specific examples of the nonionic surfactant preferably used in the present invention will be shown.

Compound Example N-1 N-2 N-3 N-4 N-5 N-6 N-7 N-8 N-9 N-10 N-11 N-12 N-13 N-14 N-15 N-16 N-17 N-18 N-19 N-20 N-21 N-22 N-23 N-24 N-25 N-26 N-27 N-28 N-29 N-30 N-31 N-32 N-33 N-34 N-35 N-36 N-37 N-38 N-39 N-40 N-41 N-42 N-43 N-44 N-45 N-46 N-47 Two or more kinds of these nonionic surfactants may be used in combination.

The amount of the nonionic surfactant of the present invention to be used varies depending on the form, type, coating method, etc. of the silver halide photographic light-sensitive material to be used, but in general, silver halide photographic light-sensitive material 1
It may be 0.1 to 1000 mg per m ² , and particularly preferably 0.5 to 200 mg.

In the present invention, the water-soluble polymer and the latex are used together with the nonionic surfactant in at least one of the photographic constituent layers, and it is particularly preferably used in the surface protective layer or the back surface layer.

As the binder of the photographic constituent layer, gelatin or a gelatin derivative may be used in combination.

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, octahedron or tetradecahedron, or may have an irregular shape such as a sphere or a plate. It may have a crystalline form. In these particles, {1
Any ratio of the {00} plane to the {111} plane can be used. or,
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.

[Examples] Examples of the present invention will be given below, but the invention is not limited thereto.

(1) Preparation of Sample A silver halide emulsion layer having the following composition was coated on a polyethylene terephthalate film support having an undercoat thickness of 180 μ, and a protective layer having the following composition was further coated thereon and dried. A black and white silver halide photographic light-sensitive material was prepared. The water-soluble polymer of the present invention, a nonionic surfactant and a latex were added to the protective layer.

The number of repellents per 30 cm × 30 cm applied area was visually observed.

(Emulsion layer) Thickness: 5μ Composition gelatin 2.5 g / m ² Silver iodobromide (silver iodide 1.5 mol%) 5 g / m ² 1-Phenyl-5-mercaptotetrazole 25 mg / m ² (Protective layer) Thickness: About 1 μ composition and coating amount Gelatin 0.9 g / m ² 2,6-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10
mg / m ² Nonionic surfactant of the present invention 40 mg / m ² Latex of the present invention 0.8 g / m ² Water-soluble polymer 40 mg / m ² (2) Antistatic ability determination method: Static antistatic ability causes static marks It was decided by the measurement. The static mark generation test was carried out by a method of generating static marks by pressing the rubber sheet on the protective layer side of the unexposed light-sensitive material, pressing it with a rubber roller from above, and then peeling it off.

The static mark generation test was conducted at 25 ° C. and 25% RH. The humidity of the test piece of the sample was adjusted under the above conditions for 24 hours.

In order to evaluate the degree of generation of static marks, each sample was developed with a developer having the following composition at 20 ° C. for 5 minutes.

Development composition N-methyl-p-aminophenol sulfate 4 g Anhydrous sodium sulfite 60 g Hydroquinone 10 g Sodium carbonate (monohydrate) 53 g Potassium bromide 25 g Water is added to make 1.

The evaluation of the static mark was based on the following 5 grades.

A: No static mark was observed.

B: Static marks are slightly generated.

C: Static marks are considerably generated.

D: Static marks are remarkably generated.

E: Static marks are generated on the front surface.

(3) Photographic property test method: Sensitivity and fog were measured by Konishi Roku Photo Industry Co., Ltd. sensitometer KS
It measured using the -1 type. Sensitivity is the reciprocal of the amount of exposure that gives a density of fog +0.7, and is expressed as the specific sensitivity with 100 as the same day sensitivity of the control sample.

(4) Measurement of roller contamination degree The sample was cut into a 30.5 cm × 17.1 cm square. After uniform exposure so that the optical density after development is 1.0, it is continuously processed with an automatic development processor (which has a silicone transport roller and consists of three baths: a developing bath, a fixing bath, and a washing bath). 50 sheets were developed. After sufficiently drying the washing squeeze roller, the appearance of streak-shaped density unevenness occurring at the tip of the 51st sample was examined.

The evaluation of the roller contamination degree was based on the following four-stage criteria.

A: No uneven density is observed.

B: A little density unevenness occurs.

C: Density unevenness considerably occurs.

D: The density unevenness remarkably occurs.

(5) Film physical property test method The dimensional change rate accompanying development processing was measured using a pin 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.

The results are shown in the table.

As is apparent from the results in the table, the present invention has excellent coating properties without adversely affecting photographic characteristics and film physical properties, has good antistatic performance, and has a low roller contamination degree.

 ─────────────────────────────────────────────────── --- Continuation of front page (56) References JP-A-55-25077 (JP, A) JP-A-60-80849 (JP, A) JP-A-60-87323 (JP, A) JP-A-58- 153925 (JP, A) JP 60-661 (JP, B2)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photographic constituent layer on a support, wherein at least one photographic constituent layer contains gelatin or a derivative thereof as a binder, and a synthetic water-soluble polymer or latex. And a nonionic surfactant are separately contained, and the latex is contained in an amount of 30 to 200% by weight with respect to gelatin or a derivative thereof, and the synthetic water-soluble polymer is included in an amount of 1 to 15% by weight with respect to the latex. A silver halide photographic light-sensitive material characterized by: