JPH02282245A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the antistatic performance of a sensitive material, to inhibit the sticking of dust and to prevent the deterioration of transparency and adhesive property due to incorporation by incorporating a polymer obtd. from a polyaniline-contg. aq. dispersion. CONSTITUTION:A polymer obtd. from a polyaniline-contg. aq. dispersion is incorporated into at least one of the constituent layers of a sensitive material. The aq. dispersion is preferably prepd. by subjecting an aniline compd. such as aniline to oxidation polymn. in the presence of one or more kinds of compds. selected among desired high molecular compds. such as hydroxyethylcelluslose and surfactants. The polymer may be incorporated into the protective surface layer, back layer or undercoat of the sensitive material.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material having good antistatic properties, and in particular to a silver halide photographic material that has good antistatic properties, and in particular, it can be used without impairing transparency or coatability, and without impairing dust after processing. This invention relates to an improved silver halide photographic material (hereinafter referred to as photographic material).

(Prior Art) Photographic materials generally consist of an electrically insulating support and a photographic layer, so contact friction or peeling between surfaces of the same or different materials is avoided during the manufacturing process and during use of the photographic materials. Electrostatic charges often accumulate due to exposure to This accumulated electrostatic charge causes many problems, but the most serious problem is that the photosensitive emulsion layer is exposed to light due to the discharge of the accumulated electrostatic charge before processing, and photographic film 1 is developed. It often produces dot-like spots or dendritic or feather-like cotton tufts. This is what is called a static mark, and it significantly reduces the commercial value of photographic film, and in some cases causes the film to lose its commercial value altogether.

Furthermore, these accumulated electrostatic charges may cause secondary failures such as dust adhesion to the film surface or inability to apply uniformly.

As mentioned above, such electrostatic charges are generated due to contact and separation between mechanical parts during the manufacturing of photographic light-sensitive materials or in various automatic photographing machines.

Particularly in recent years, photosensitive materials have become more sensitive and exposed to harsh handling such as high-speed coating, high-speed photography, and high-speed automatic processing, making it more likely that static marks will appear. . Furthermore, there is a problem in that dust may accumulate during various handling stages of the processed film.

In order to eliminate these problems caused by static electricity, it is preferable to add an antistatic agent to the photographic material. However, the antistatic agents that can be used in photographic light-sensitive materials cannot be the same as those commonly used in other fields, and are subject to various restrictions specific to photographic light-sensitive materials. That is, in addition to having excellent antistatic properties, antistatic agents that can be used in photographic light-sensitive materials must not have any adverse effect on photographic properties such as sensitivity, fog, graininess, sharpness, etc. of photographic light-sensitive materials; Does not adversely affect the film strength of the photosensitive material, does not adversely affect the adhesion resistance, does not accelerate the fatigue of the processing solution for the photographic material, does not contaminate the conveyance roller, and does not cause any damage between the constituent layers of the photographic material. Application of antistatic agents to photographic materials is subject to numerous restrictions, as performance such as not reducing adhesive strength is required.

One way to eliminate these electrostatic disturbances is to increase the electrical conductivity of the surface of the photographic material so that the electrostatic charges can be dissipated in a short period of time before the accumulated charges are discharged. . It is an effective means especially for removing waste after processing.

Therefore, methods have been considered to improve the electrical conductivity of supports and various coated surface layers of photographic materials, including various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers, etc. Attempts have been made to use

(Problems to be Solved by the Invention) However, these materials exhibit specificity depending on the type of film support and photographic composition, may lose their conductivity after processing, cause dust buildup, and are humidity-dependent. When these substances are applied to photographic materials, they may cause static at low humidity due to their properties, or may cause deterioration of photographic performance, coating properties, or transparency, or may cause deterioration of adhesive properties. was extremely difficult.

Furthermore, the above-mentioned problems have not been solved with the polyphosphazene described in JP-A-64-68751 and the polyaniline described in US Pat. No. 4,237,194.

(Objective of the Invention) The first object of the present invention is to provide a photographic light-sensitive material that is well prevented from being charged even when it comes into contact with various objects.

A second object is to provide a photographic material that has excellent antistatic properties even after development and is free from dust.

The third object is to provide a photographic material that is antistatic without adversely affecting transparency.

A fourth object is to provide a photographic material that is antistatic and does not deteriorate in adhesive properties.

(Means for Solving the Problems) These objects of the present invention are to provide a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support. This was achieved by a silver halide photographic material containing a polymer obtained from a polyaniline aqueous dispersion.

The method for producing a polyaniline aqueous dispersion will be described below in Section 7.

As a method for producing the aqueous polyaniline dispersion used in the present invention, a known method similar to emulsion polymerization used for producing latex can be used.

For example, there is a method in which polyhinyl alcohol aniline hydrochloride and distilled water are placed in a flask, and an aqueous solution of FeCρ3 is added dropwise as a catalyst while stirring under a nitrogen atmosphere.

A preferred aniline compound used in the present invention is represented by the following general formula (1).

Here, R1 and R2 are hydrogen atoms, halogen atoms (e.g., fluorine, chlorine, bromine), alkyl groups, aryl groups,
hydroxyl group, alkoxy group, aryloxy group, amino group,
Argylamino group (may be fused), nido ofi, Schiff'/49, -N HCOR'N HS Oz R5
S OR” S O2R5R7R? and R4 does not represent a hydrogen atom, an alkyl group or an aryl group. R5 represents an alkyl group or an aryl group.

R6 and R7 may be the same or different and represent a hydrogen atom, an alkyl group or an aryl group.

Furthermore, the above R1 and R2 alkyl groups, aryl groups,
The alkoxy group, aryloxy group, and alkylamino group may be further substituted. In addition, the above R3, R4,
The alkyl groups and aryl groups of R5, R1'' and R7 may also be further substituted.

Examples of these substituents include alkoxy groups (e.g.
methoxy, ethoxy), oryloxy groups (e.g., phenyloxy), alkoxycarbonyl groups (e.g., methoxycarbonyl), acylamine groups (e.g., acetylamino), carbamoyl groups, argylcarbamoyl groups (e.g., methylcarbamoyl), , ethylcarbamoyl), dialkylcarbamoyl groups (e.g. dimethylcarbamoyl), arylcarbamoyl groups (e.g. phenylcarbamoyl), alkylsulfonyl groups (e.g. methylsulfonyl), arylsulfonyl groups (e.g. eva, phenylsulfonyl), alkylsulfones Amide groups (e.g. methanesulfonamide), estersulfonamide groups (e.g. phenylsulfonamide), sulfamoyl groups, alkylsulfamoyl groups (e.g. ethylsulfamoyl), dialkylsulfamoyl groups (e.g. ,
dimethylsulfamoyl), alkylthio groups (e.g.
(methylthio), arylthio group (e.g., phenylthio), amino group, alkylamino group, cyano group, nitro group, halogen atom (e.g., fluorine, chlorine, bromine), and when there are two or more of these substituents, the same It may be the same or different.

Specific examples of the above aniline compounds are shown below, but the invention is not limited thereto.

N H2 NIIz Hz NH□ l-12 NI-■2 NH2 N.H.

NI(2 N　H□ Hz N.H.

NH□ Hz NH2 H2 As the catalyst used for oxidative polymerization of the aniline compound in the present invention, commonly used and known catalysts can be used. For example, chlorides such as ferric chloride and cupric chloride, sulfates such as ferrous sulfate and cupric sulfate,
Examples include metal oxides such as lead dioxide and manganese dioxide, peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, quinones such as henzoquinone, halogens such as iodine and bromine, and potassium ferricyanide.

Specific examples of these are JP-A-63-21.3518, JP-A-63-193926, JP-A-62-II6665, and JP-A-63-193926.
No. 2-104832, No. 63215717, No. 63-
69823 area, 63101415, 60-584
It is described in No. 30, etc. The amount of catalyst will vary depending on the properties of the aniline compound and the catalyst used. However, in general, the molar ratio of catalyst/aniline compound is 0.
．． It ranges from 01 to 10, preferably from ■ to 5.

Solvents that can be used in the production of the aqueous dispersion of the present invention include water such as distilled water and ion-exchanged water, but also organic solvents that are miscible with water (for example, alcohols such as ethanol and methanol, acetonitrile, dimethyl sulfate, etc.). , N,N-dimethylacetamide) may be used in combination.

Specific examples of the dispersant used in producing the aqueous dispersion of the present invention are listed below, but the dispersant is not limited thereto.

Examples of nonionic polymers include hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, dextran, pullulan, polyvinyl alcohol,
Examples include polyacrylamide, polyvinylpyrrolidone, and the like.

Examples of amphoteric polymers include gelatin, collagen, globulin, albumin, casein, and the like.

(4) As the dispersant used as the anionic polymer, commonly used polymers having anionic surface properties can be used. Preferably, it is a latex produced by emulsion polymerization. Anionic surface properties can be introduced in a variety of ways. For example, a latex having anionic surface characteristics is synthesized by polymerizing an ethylenically unsaturated monomer 1 having an anionic group, such as a sulfonic acid group, or a mixture thereof with an ethylenically unsaturated monomer. Salts of 2-acrylamido-2-methylpropanesulfonic acid, vinylhenzenesulfonic acid, etc. can be used for this purpose, but other ethylenically unsaturated monomers that can introduce anionic surface properties into the polymer can also be used. .

Furthermore, anionic surface properties may be achieved by using anionic surfactants in latinx production.

In this case, specific examples of the anionic surfactant used are listed below, but the invention is not limited thereto.

Examples of anionic surfactants include the following.

C,2H,,C00Na C+eH37COONa C+ + H2'3 CON CH2C00N aCl
-13 C+ + H21CON CHz CH2COON a
CH] CH2COOCs Hl7 NaO:1SCHCOOC1lH,7 C+ + H2:lCH-CHCHzS O3N aC
,,H23CHCHzCHzSO:+Na H2H2,○(Cl-12)4S 03N aC+7Hz
zCONCH,CH25O,NaCH'+ CHz COOHb I(+ 3 N a O, 3S CHC00Cb H+ sC+zH
zsOS 03N a Specific examples of the surfactants used in the production of the aqueous dispersion of the present invention are listed below (but are not limited to these).

Examples of anionic surfactants include those mentioned above in Latte Nox Production G with Anionic Surface Characteristics.

Examples of cationic surfactants include the following.

2 guns (2,0 (C112CHxO) ,H C,,HIIO(CH2CH2O)zoHH3 Cl　2　Hzs　NH CI(.

H3 H25 N-CH.

Cβe H CH.

CH'y CIIH2: ICONHCH2CH2CH2N-CH:
l CH.

Polyoxyethylene sorbitan tristearate n-30H Examples of nonionic surfactants include the following.

H Examples of amphoteric surfactants include the following.

CH3 CI 2 H2S N CH2COO0 H3 CH.

C+bH** N-CH2COO8 CH3 lecithin CH.

Cl1H23CONHCH2CH2CH2-NCH2C
OO0H3 CH3 CI]H27CON HCH2CH2CH2= N C
H2COOeCH.

21~ H5 sH3+ CON HC+(zCH2CH2N-CH2
CH2CH2CH2S O3e H3 The amount of nonionic polymer, amphoteric polymer or anionic polymer used for dispersing the polyaniline compound is 1 to 300% by weight, preferably 5 to 2% by weight of the aniline compound.
00% by weight. Moreover, various surfactants are used in amounts of 0.01 to 50% by weight, preferably 0.01 to 50%, preferably 0.01 to 50%, based on the aniline compound.
Use 1-20% heavy background.

The reaction temperature during oxidative polymerization is 0 to 100°C, preferably 5 to 50'C. The reaction time is related to the reaction temperature, but is usually 0.1 to 100 hours, preferably 0.1 to 100 hours.
It is 50 hours.

The aqueous dispersion of the present invention may be used after being subjected to treatments such as dialysis and ultrafiltration.

Moreover, a conductive compound can be added to the aqueous dispersion of the present invention in order to further improve the conductivity of the molded article. These conductive compounds may be added before or after oxidative polymerization, or both, but it is preferable to add them before or both before and after polymerization. Furthermore, when treatments such as dialysis and ultrafiltration are carried out, it may be removed after the treatment.

Conductive compounds that can be used in the present invention include alkali metal cations (1, i'', Na+, etc.), N
O4, NO2+, cation, onium cation (Et4
N”, BL14N”, Bu3r”, etc.) and negative ions (
BF4-, AS F4-, 85F6SbFb-,5
bC1b-, PF6-, Cρ04A1F4-, A,
j2F6-, N1Fn'-, ZrFl, "T i F
b”-, T i Fb”-, Bloc 11o”-1C
pBr r-, F-, H3O,-, SO2''-, etc.), sulfonic acid anions (CH3C, H, IsO:I
CaHsS03-, CF35O, l-, etc.),
a salt containing a carboxylic acid anion such as HC00T-i,
Chlorides such as Fe C13, and organic amines, no m
Acids (e.g. HC1, H2S0a, HC!!, O, 11
HB F , ), organic acids (e.g., sulfonic acids such as toluenesulfonic acid, trifluoromethylsulfonic acid, polystyrene sulfonic acid, carboxylic acids such as formic acid, acetic acid, polyacrylic acid) or limited thereto. It's not something you can do.

Further, the aqueous dispersion of the present invention can be used by blending it with a polymer compound. Polymer compounds that can be blended in the present invention include synthetic resins such as phenol resin, urea resin, melamine resin, silicone resin, vinylidene chloride resin, polystyrene resin, polyethylene resin, vinyl chloride resin, polyamide resin, styrene-butadiene rubber, butadiene rubber, Synthetic rubbers such as imprene rubber, butyl rubber, nitrile rubber, chloroprene rubber, ethylene-propylene rubber, polyvinyl acetate polymers, polystyrene polymers, polyethylene polymers, poly(meth)acrylic acid ester polymers, etc. can be used. , but not limited to these. Preferably, these polymeric compounds are emulsions.

Specific examples and synthesis methods of the polyaniline aqueous dispersion of the present invention are shown below.

Synthesis Example 1 (Synthesis of aqueous dispersion 1) Dextran 5g, Aco 9
F10m! 29 g of FeCIf dissolved in 30 mβ of distilled water was added to this solution at room temperature while stirring under nitrogen atmosphere.
．． 3'6H20 was added dropwise over 30 minutes.

As the mixture was added, heat was generated and the reaction solution turned black.

Furthermore, after stirring for 2 hours, dialysis was performed for 2 days (νl5
KAsE S/ILEs CO1? P CELI
, ULO5IE TUBTNG C-G 5
(manufactured by Sanko Junyaku ■) to obtain an aqueous dispersion of polyaniline.

The average particle size of the obtained polyaniline particles was 60 om (COULTER-N4 type Zabumicron particle analyzer W).
(Made and measured by Coulter Electronics (12)).

Furthermore, this aqueous dispersion was stable whether it was stored at either 20° C. or 5° C., and there was no sedimentation or aggregation of particles when it was stored at either temperature after 3 months. Furthermore, there was no evidence of corruption.

Synthesis Example 2 (Synthesis of Aqueous Dispersion 2) As a surfactant, 0.05 g of sodium lauryl sulfate
．． As a result of synthesis and dialysis in the same manner as in Synthesis Example 1 except that benzenesulfonic acid tributylammonium salt [Og] was added together with aniline as a conductive salt, a stable polyaniline aqueous dispersion (average particle size 55 nm) was obtained as in Synthesis Example 1. ) was obtained.

Synthesis Example 3 (Synthesis of Aqueous Dispersion 3) Synthesis and dialysis were carried out in the same manner as in Synthesis Example 1, except that 6 g of polyvinylpyrrolidone was used instead of dextran and 12 g of o-1 to luidine were used instead of aniline. Similar to 1, a stable poly(o-1-luidine) aqueous dispersion with no rotting or particle aggregation (average particle size of 70°
m> was obtained.

Synthesis Example 4 (Synthesis of aqueous dispersion 4) Cl2H2,○(CH2CH2
0) 0,5g,FeCff. ,・61HzOO Synthesis and dialysis were performed in the same manner as in Synthesis Example 1, except that 25 g of ammonium persulfate was used instead of OO, resulting in Synthesis Example 1. H Similarly stable polyaniline aqueous dispersion (average particle size 1010
0n was obtained.

Synthesis Examples 5 to 22 (Synthesis of Aqueous Dispersions 5 to 22) As a result of synthesizing the aqueous dispersions shown in the table below according to Synthesis Examples 1 to 4, they were stable as in Synthesis Example 1. An aqueous dispersion is obtained.

Synthesis Example 23 (Synthesis of Comparative Compound 1) Add 1 liter of aniline hydrochloride to 3 1-bottle flasks each containing 300 rnl.
Take 5 g of (CaI2)4NB F4 and 200 mf of acetonitrile, and add this solution at room temperature under a nitrogen atmosphere with stirring. 29g of FeCl3.6I]20 dissolved in 30ml of distilled water was added dropwise to the solution over a period of 30 minutes. Heat was generated as the dropwise addition was carried out, and a black solid was formed. After further stirring for 2 hours, the resulting solid Filter things out,
After drying, Comparative Compound 1 was obtained.

Synthesis Example 24 (Synthesis of Comparative Compound 2) 2 g of aniline hydrochloride and 44 g of (C4H9)4NBF were heated with acetonitrile at 200 mA! When electrochemically polymerized using an electrolyte solution at a constant voltage of IV for 30 minutes using a Pt plate as the working and counter electrodes and a saturated calomel electrode as the reference electrode, a polyaniline film was formed on the working electrode. did. The obtained film was peeled off from the electrode and dried to obtain Comparative Compound 2.

Synthesis Example 25 (Synthesis of Comparative Compound 3) 20 g of water-soluble polymer PAS-H-5-L (manufactured by Nittobo Co., Ltd.) having a quaternary ammonium salt instead of dextran
Synthesis was carried out in the same manner as in Synthesis Example 1 except for using , and a black solid was produced. The obtained solid was collected by filtration and dried to obtain Comparative Compound 3.

The polyaniline compound of the present invention is added to at least one of the silver halide emulsion layers or other constituent layers of the photographic light-sensitive material, and may be an undercoat layer. Other constituent layers include, for example, a surface protective layer, a hack layer, an intermediate layer, and an undercoat layer. Particularly preferred locations for addition are the surface protective layer, hack layer, and undercoat.

When the surface protective layer, hack layer or undercoat layer consists of two layers, any of these layers may be used, and on the surface protective layer,
Furthermore, it can also be used as an overcoat.

When applying the compound used in the present invention to a photographic light-sensitive material, the powder is dissolved or suspended in water, an organic solvent such as methanol, isopropanol, acetone, or a mixed solvent thereof, and then a surface protective layer or hack layer is formed. It may be added to a coating solution such as, or it may be added as the aqueous dispersion described above,
It can be applied by dip coating, air knife coating, spraying, or extrusion method using a hopper as described in U.S. Pat. No. 2,681.294.
U.S. Patent No. 3.508,94.7, U.S. Patent No. 2,941.89
No. 8, No. 3,526.528, etc., two or more layers may be applied simultaneously, or they may be immersed in an antistatic liquid. Further, if necessary, an antistatic liquid (containing a solution or a binder) containing the compound of the present invention may be further coated on the protective layer.

The amount of the polyaniline compound of the present invention used is 0.0001 to 2.0 per square meter of photographic light-sensitive material.
g is preferably present, preferably from 0.0005 to 0.
7 g, particularly preferably 0.001 to 0.3 g.

Two or more types of each of the polyaniline compounds of the present invention may be mixed.

As the photographic light-sensitive material according to the present invention, ordinary black-and-white silver halide photographic light-sensitive materials (for example, black light-sensitive material for photography, X-r
black-and-white photosensitive materials for AY, black-and-white photosensitive materials for printing, etc.), ordinary multilayer color photosensitive materials (e.g., color negative film, color rehearsal film, color positive film,
Examples include color negative films for movies) and infrared light sensitive materials for racer scanners.

Types of silver halide used in the silver halide emulsion layer, surface protective layer, etc. of the photographic light-sensitive material of the present invention, manufacturing method, chemical sensitization method, antifoggants, stabilizers, hardeners, antistatic agents, couplers, There are no particular restrictions on plasticizers, lubricants, coating aids, matting agents, brighteners, spectral sensitizers, dyes, ultraviolet absorbers, etc.
duct Licensing) Volume 92, 107-110
Shin (December 1971) and Research Disclosure 1
Reference may be made to the descriptions in Vol. 76, pp. 22-31 (December 1978) and Vol. 238, pp. 44-46 (1984).

The photographic emulsion layer or other hydrophilic colloid layer of the photographic light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, improvement of sheer properties, emulsification dispersion, prevention of adhesion, and improvement of photographic properties (e.g., development acceleration, high contrast). Various surfactants may be included for various purposes such as oxidation, sensitization, etc.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyconytylene glycol esters, polyethylene glycol alkyl ethers) , polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenyl succinic phenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator; alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, acrylic sulfate,
Carboxy groups, sulfo groups, phosphoric acids such as castyl alkyl phosphates, N-acyl-N-alkyl clarins, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. anionic surfactants containing acidic groups such as sulfuric acid ester groups, sulfuric acid ester groups, phosphoric acid ester groups; Surfactants: Alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary salts such as pyridinium, imidazolium, etc.
Cationic surfactants such as ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

These include Ryohei Oda et al.'s "Surfactants and Their Applications" (Maki Shoten, 1964), Hiroshi Horiguchi's "New Surfactants" (Sankyo Publishing Co., Ltd., 1975), and Emulji Fires” (Matsufucation Divisions, MC,
Publishing Company 1 9 8 5 ) (
rMc Cutcheon's Detergen
ts & EmulsifiersJ (Mc CuL
cheon old visions MC Publishing
g Co. 1985)), Japanese Patent Application Publication No. 1986-
No. 76741, Japanese Patent Application No. 61-13398, No. 6116
No. 056, No. 61-32462, etc.

In addition, in the present invention, other antistatic agents may be used in combination, for example, in particular, as disclosed in Japanese Patent Application No. 1983. -3 2 4 6 No. 2, the fluorine-containing surfactant or polymer described in JP-A No. 6
0-7 6 7 4 No. 2, 60 80'84
No.6, No.60-808.18, No.60-808
3 9, 6 0 - 7 6 7 4. No. 1,
Nonionic surfactants described in JP-A No. 58-208743, etc., or JP-A-58-208743, etc.
4. 5 4. No. 0, patent application 1986 1-3 2 4-
Conductive polymers or latexes (nonionic, anionic, cationic, amphoteric) described in No. 6 2 can be used. In addition, as inorganic antistatic agents, ammonium,
Alkali combined pressure, halogen salts of 7 alkali earth metals, nitrates, perchlorates, sulfates, acetates, phosphates, thiocyanates, etc. are also used as conductors as described in JP-A-57-118242, etc. Tin oxide, zinc oxide, or a composite oxide obtained by doping antimony or the like with these metal oxides can be used.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the photographic light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate, dextran, and starch derivatives; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as monopolymers or copolymers such as polyvinylimidazone polyvinylvirazole.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and gelatin hydrolysates or enzymatically decomposed products may also be used.

Among these, it is preferable to use dextran and polyacrylamide together with gelatin.

In the hydrophilic colloid layer of the photographic material of the present invention, polyols such as trimethylolpropane, unkundiol, butanediol, ethylene glycol, glycerin, and sorbitol can be used as plasticizers.

The silver halide grains in the photographic emulsion used in the photographic light-sensitive material of the present invention are regular (regular) grains such as cubes and octahedrons.
It may have a spherical, spherical,
It may have a crystal shape such as a plate shape, or a composite shape of these crystal shapes. Further beam search・
Disclosure, 22! :Makibian, 22nd 3rd≠,! θ
~Evening page (/rigu3≠/), JP-A-31-/,! 7F
,! The tabular grains may be tabular grains described in No. It may also consist of a mixture of particles of various crystalline forms.

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( (including complex salts) to add metal ions to the inside of the particles and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure 1711t3.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

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

Further, the emulsion used in the present invention is disclosed in US Pat. No. 2,926.
3 and! , 3, 3 7. ′? g7, same 3゜70 years old 2
A mixed emulsion of a silver rhodanide emulsion and an internally overlapped silver halide emulsion or an emulsion used together in a separate layer may be used.

Here, the patent application Sho 3;7. It is preferable to further use the mercapto compound described in 1.-/70 tagg in combination to suppress fogging and improve storage stability over time.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl-j-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines, such as thioketo compounds such as oxadorinthion; azaindenes, such as triazoles; Zaindenes, tetraazaindenes (4'-H)"oxy substitution ('+ 3+ 3a+
7) Tetraazaindenes), hantaazaindenes, etc.; compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. may be added. can.

The hydrophilic colloid layer of the photographic material of the present invention may contain a polymer latex such as a homopolymer or copolymer of alkyl acrylate (well known in the art) such as a copolymer of vinylidene chloride. /-230/3 (which may be stabilized in advance with a nonionic surfactant).

For the purpose of increasing sensitivity, increasing contrast, or promoting development, the photographic emulsion layer of the photographic light-sensitive material of the present invention may contain, for example, polyalkylene quinide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary It may also contain ammorum salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

The support used in the present invention can also be provided with an antihalation layer. For this purpose carbon blanks or various dyes such as oxonol dyes,
Examples include azo dyes, arylitine dyes, styryl dyes, anthraquinone dyes, merocyanine dyes, and tri(or di)allylmethane dyes. Cationic polymers or latexes may then be used to prevent the dye from diffusing out of the antinolation layer.

These are Research Disclosure /7.4 volume type/
76≠3, described in item ■. Furthermore, a magenta dye as described in Japanese Patent Application No. 27113, Shoto O-/, may be used to improve the tone of skin image silver.

The hydrophilic colloid layer used in the present invention includes colloidal silica, barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, patent application Sho-Otsu, 2-. Methyl methacrylate-styrene sulfonic acid copolymer described in No. 1'0gφ, JP-A-6/-23
A so-called matting agent made of particles containing fluorine groups as described in No. 0i31 can be used.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other constituent layers. For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), active vinyl compounds (/, :t,
S-triacryloylhexahydro=s-triazine,
/, 3-vinylsulfonyl-2-propatournato),
Active halogen compounds (such as 2,4t-dichloro-A-hydroxy-3-lyazine), mucohalogen acids (mucochloric acid, mucophenoxychloric acid nat), and the like can be used alone or in combination.

The hardener preferably used is a vinyl sulfone compound represented by the following formula.

(CH2=CH-SC2-CH2=CH In the formula, A represents a divalent group (although it may be used).

The photographic material of the present invention may contain a developing agent.

As a developing agent, Research Disclosure No. 17
Volume Otsu, page 27 [Developing age-
Those described in the section ntsJ can be used.

In particular, hydroquinone and pyrazolidones are preferably used at °C.
It will be done.

In the present invention, a coupler that develops yellow, cyan, or magenta may be used.
2 is described in detail in No. 32.

The developing process for the photographic light-sensitive material of the present invention may be either a process for forming a silver image (black and white development process) or a process for forming a color image. If an image is to be produced by the reversal method, a black and white negative development step is first carried out, and then a color development process is carried out by applying white exposure or processing with a bath containing a fogging agent. (Silver dye bleaching may also be used, in which a dye is contained in the light-sensitive material, a black-and-white development process is performed after exposure to create a silver image, and this is used as a bleaching catalyst to bleach the dye.) As a black-and-white development process. are a developing process, a fixing process,
A water washing process should be carried out. When a stopping process is performed after the development process or a stabilizing process is performed after the fixing process, the washing process may be omitted. It is also possible to incorporate a developing agent or its precursor into the photosensitive material and perform the development process using only an alkaline solution. A development process using a lithium developer as a developer may also be performed.

Color development processing includes a color development processing process, a bleaching processing process,
A fixing process, a water washing process and, if necessary, a stabilizing process are carried out, but instead of the process using a bleach solution and the process using a fixer, a l-bath bleach-fix solution is used.
A bleach-fixing treatment step can be carried out, or a monobath treatment step can be carried out using a bath development, bleach-fixing treatment solution in which color development, bleaching and fixing can be carried out in a single bath.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development treatment step, an activator treatment step may be performed in which a color developing agent or its precursor is contained in the material and the development treatment is performed with an activator solution, or an activator treatment may be performed in the monobath treatment. Can be applied.

The processing temperature is usually chosen in the range 10°C to 15-'C, but temperatures above AJ 0C may also be used.

Preferably, the temperature is 20C-≠30C.

The black-and-white developer used in black-and-white development processing is commonly used in the processing of known black-and-white photographic materials, and can contain various additives that are generally added to black-and-white developers.

Typical additives include l-phenyl-3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, etc. Inorganic or organic inhibitors such as potassium bromide, l-methylbenzimidazole, methylbenzthiazole, water softeners such as polyhydrochloric acid, and surface superoxides consisting of trace amounts of iodide and mercapto compounds. Examples include development inhibitors.

Furthermore, in the case of X-ray sensitive materials, efforts have been made to shorten the development processing time. Furthermore, means for simplifying processing have also been developed, and the compound represented by the general formula [1] of the present invention can provide extremely excellent photographic materials for these recent processing techniques. .

The present invention will be illustrated below with reference to Examples, but the present invention is not limited thereto.

Example 1 ■-1) Preparation of heath Polyvinylidene chloride/itaconic acid (polymerization molar ratio 97
: After coating 3), polyethylene terephthalate 1 was biaxially stretched at 220°C. (vinylidene chloride/itaconic acid/ethyl acrylate-I; polymerization molar ratio 92:3:5, added as an aqueous dispersion) (0,01, g/n () gelatin aqueous solution (001 g/m), dichloro-hydroxytriazine soda (0,01g/bo), p-octylphenoxypoly (degree of polymerization 10) oxyethylene ether (0,
After applying a solution consisting of 03g/r+ () and the compound in Table 1 (in the case of the old product, add it as pulverized (particle size 10 μm) or as an aqueous solution, or as it is in the case of an aqueous dispersion) to Harko 1. , and dried at 14.0°C to form an undercoat conductive layer. Furthermore, after corona treatment, gelatin (0
, 2 g/%), α-sulfodihexyl succinate sodium salt (0,002 g/m>, poly(styrene/divinylhensen, polymerization ratio 98:2) (average particle size 20 μm)
,002g/m) ,I,3-divinylsulfonyl-2
Proper tool (0,005 g/n) was applied to create a protective undercoat layer.On one side, only a protective undercoat layer was applied.

(2-2) Composition of the dyed layer Method for separating and removing the microscopic swirls The following dyes were ball milled by the following method. Water (21,7mff) and 6.7% TritonX-2
000 surfactant aqueous solution (2,65g) (Rohm &
(sold from 1LAAS) was placed in a 6ame double-lid bottle. A 1.00 g sample of dye was added to this solution. Zirconium oxide (ZrO) beads (40ml) C2y
am diameter) was added, the container with a tight lid was placed in the mill, and the contents were ground for 4B. The container was removed and the contents were added to a 12.5% aqueous gelatin solution (8.0 g).

The new mixture was placed on a roll mill for 10 minutes to reduce foam, and the resulting mixture was then filtered to remove the ZrO beads.

COO 11 The surfactant p-octyl phenylene ethoxyethoxyethane sulfonic acid sodium and Hard 1111 (bis(vinyl-sulfonylmethyl) ether) were added to the above dye-gelatin melt. The melt produced from the latter mixture was then applied onto the hairs described above with a dye coverage o, 0.
8g/m, gelatin coating amount 0.4g/%, surfactant 0
．． 026 g/rd and hardener 0.01.6 g/r+(
It was applied to both sides so that

1-3) Composition of emulsion layer: 30g of gelatin, 5g of potassium bromide, 0 potassium iodide in 1ρ of water
．． 0.5 g of silver nitrate (5 g as silver nitrate) and potassium iodide were added to a container kept at 75°C with stirring.
An aqueous solution of potassium bromide containing 73 g was added by double jet method over 1 minute. Furthermore, a silver nitrate aqueous solution (145 g as silver nitrate) and a potassium bromide aqueous solution were added by a double jet method. The addition flow rate at this time was accelerated so that the flow rate at the end of addition was eight times that at the beginning of addition. After this, 0.37 g of an aqueous potassium iodide solution was added.

After the addition was completed, soluble salts were removed at 35°C by a sedimentation method, and then the temperature was raised to 40°C, 60 g of gelatin was additionally twisted, and the pH was adjusted to 6.5. Raise the temperature again to 56°C,
After adding 650 μl of the sensitizing dye anhydro-5,5'di-chloro-9-ethyl-3,3'-di(3-sulfoprobyl)oxacarpocyanine hydrooxide sodium salt, gold and sulfur sensitization was carried out. Combined chemical sensitization was applied.

The obtained emulsion had a hexagonal plate shape with a projected area diameter of 0°85μ.
m, and the average thickness was 0.158 μm.

4-hydroxy-6methyl-1 was added to this emulsion as a stabilizer.
．． 3.3a, 7-thitrazaindene and 2,6-bis(hydroxyamino)-4-diethylamine-13,5-triazine, trimethylolpropane were added.

Furthermore, the following compounds were added (350 ■/n ()) Furthermore, as a coating aid, p-octylphenoxyjethoxyethanesulfonic acid sodium 0.01 g/M, dodecylhenzenesulfonate 0.005 g/d, and a thickening agent. as polybotacium p-vinylhenzensulfo-1-0.03g
/m, polymer latex (poly [ethyl acrylate/methacrylic acid-97/3] particles with poly [degree of polymerization 1
0) Oxyethylene poly [degree of polymerization 3] Adsorbed with oxyglyceryl F decyl ether [3% by weight of particles], average particle size -0.1 μm) 0.4. g/m', sodium polyacrylate (molecular weight 200,000) 0.1 g/n (
, 1,2-his(vinylsulfonylacetamido)ethane 0.04 g/m, trimethylol.

1-4) Composition of protective layer Mugelatin 1. 2g/mm polyacrylamide (molecular weight 45,000) 0. 2 g/n (Muchkiss 1 run (molecular weight 38,000) 0.2 g/m Sodium polyacrylate 0.02 g/n (Muccolloidal silica (particle size 0.02 μm ) 0.04g/% Mboli
(Polymerization degree 10) Oxyethylene cetyl ether o, 02g/rrf polymer
(Polymerization degree 10) Oxyethylene poly (Polymerization degree 3) Glyceryl-p-octylphenyl ether 0.02g/m3H7 A Ca1l+ 7SOZN + CH□C1120-
)-T(CHz→-,5O3Na0, 001g/m 0, 0005g/n? CIl:l A C9F19CONH+ CIIZ→-3N -C1
,C000C1(3o o i g/m C:lI+?muC9F,,5OJ(-C)I2C11,0→ko"(-
CIt z CHCH□O→-311 Mupotassium nitrate 0, OIg/m 0, 05 g/m Mu p-t-octylphenoxyethoxyethoxyethanesulfonate sulfonic acid salt 02 g/m Mucy-hydroxy-6-methyl- 133a 7 Tetrazaindene 0゜Cetyl palmitate (particle size 0.11 Nm dispersed in dobcilhensensulfonic acid sodium) 0.005 g/m dimethylsiloxane (dispersed in dioctyl-alpha-sulfocobacic acid sodium).

Particle size: 0゜12μm) 0゜m liquid paraffin (dispersed with dioctyl-α-sodium sulfosuccinate. Particle size: 0.11μm) 0 mm Polymethyl methacrylate-1 Fine particles (average particle size: 3.8μm, 4.8μm) ~2.8 μ 04 g/n (005 g/m 005 g/i abundance of 80% or more) 0.04 g/n (gelatin concentration of 4 wt for each of the above emulsion layer and protective layer)
%? Yong? The word ``night'' was used as the basic formula for each layer.

Then, the amount of silver coated on the heath made in 1-1) is 1.
9g/rn! It was applied to both sides of the binding. The layers were arranged in such a way that the dyeing layer, emulsion layer, and protective layer were arranged in order from the side closest to the support.

Samples prepared as shown in Table 1 were evaluated.

The developer, fixer, and development process were performed as follows.

Developer concentrate> Potassium hydroxide 56.6g sulfite 1
-Rium 200g Diethylenetriaminepentaacetic acid 6.7g Potassium carbonate
16.7g boric acid
1.0 g Hydroxynon 83
．． 3 g diethylene glycol 40 g hydroxymethyl-4 methyl-1-phenyl-3 biraduriton 1], 0 g 5-methylhencitriazole 2
Make up to 1a with g water (adjust pH 0.6 o).

Fixer Concentrate> Ammonium diogate 560g Sodium sulfite 60g Ethylenediaminetetraacetic acid sthorium dihydrate 0.10g Sodium hydroxide 24g Adjust to 11 with water (adjust to pH 5.10 with acetic acid).

Automatic developing machine Second processing developing tank 6
．． 5p 35°cxlo, 5 seconds fixing tank 6.5#
35°cx9 seconds water washing tank 6.5β 20°
cx 7.5 seconds dry
50℃ Dry to Dry processing time 4
When starting the 5-second development process, each tank was filled with the following processing solution.

Developing tank: 333 m of the above developer concentrate, 667 m of water
A starter IQmE containing 1.1 g of potassium bromide and 18 g of acetic acid was added to bring the pH to 1.0.15.

Fixing tank: 250ml of the above fixer concentrate and 70ml of water
R (1) Static mark test After conditioning the unexposed sample at 25°C and 10% RH for 2 hours, test the static mark test of #work<1'1 on various materials in a dark room under the same air conditioning conditions. After rubbing with a rubber roller and a urethane roller to examine the appearance of marks, the film was developed with the developer described above, fixed, and washed with water to examine the degree of static mark formation.

In Table 1, the degree of static mark occurrence was evaluated in the following four stages.

A: No static marks were observed at all B:
Slightly tolerable C: Significant scratch marks are observed D: Marks are observed over the entire surface (2) Test with dust The sample (20 cm x 2
0 cm) was thoroughly rubbed with gauze to examine the adhesion of cigarette ash. Evaluation was performed in the following four stages.

A: No dust was observed at all.

B: A little was observed.

C; was significantly observed.

D: was strongly recognized.

(3) Transmittance Test I - Using an unexposed sample that was developed and fixed as described in (1), its total light transmittance was measured.

Sample 1-] (control) was set as 100, and the relative values relative to that were shown in Table 1 as relative transmittance.

Note that the total light transmittance was measured according to ASTM D-1003.

(4) Adhesion test The completed sample was placed in an atmosphere of 25°C and 50% RH for 2 hours.
After leaving it for a week, an adhesion test was conducted using the method described below. The surface tested here was a surface provided with an antistatic layer of Hess Δ~G.

(a) Adhesiveness test method for dried Filno On the surface to be tested, make 36 cuts by making 5 vertical and 7 horizontal cuts, and apply adhesive tape (
For example, attach a knit tape (manufactured by Nitto Electric Industry II) and quickly peel it off in the 1806 direction. In this method, if the unpeeled portion is 90% or more, it is graded A, if it is 60% or more, it is graded B, and if it is less than 60%, it is graded C. Adhesive strength sufficient for practical use as a photographic material is classified as the lower A class of the above three-level evaluation.

Wet film adhesion test method At each stage of development, fixation, and water washing, mark a scratch on the film in the processing solution with an iron pen, and then rub it firmly with the tip of your finger.
The adhesive strength was evaluated based on the maximum peeling iJ that was achieved by peeling off along the line G of times of strain x.

If the constituent layers do not peel off more than the scratches, it is classified as A grade, maximum peeling rl.
] is within 5 degrees, it is grade B, and the others are grade C.

Adhesive strength sufficient for practical use as a photographic material is one classified as B or higher, preferably grade A of the above three-grade evaluation.

As can be seen from Table 1, the Con I roll sample 1-1, which does not contain the conductive agent of the present invention, is significantly inferior in terms of static mark occurrence and dust adhesion. -Samples 1-2 to 15 using the conductive agent of the invention of strength wood were excellent in all evaluations, but sample 1-6 using the conductive agent particles other than the invention had deteriorated permeability and adhesion. Accordingly, it can be seen that Samples 1-7 to 1-10 using conductive polymers were accompanied by deterioration in dust adhesion and deterioration in adhesion after static mark treatment.

In addition, samples 1-7 to 1-10 had poor surface conditions.

From the foregoing, it is clear that the present invention is significantly superior to the prior art.

Note that excellent surface shapes and images were obtained for both the control sample and the sample of the present invention.

Example 2 2-1) Silver halide emulsion layer formulation Gelatin water kept at 50°C? Silver nitrate water in the presence of 2XIO-5 moles of 1 cosium chloride per mole of silver nitrate in the solution? A silver chlorobromide monodisperse emulsion having an average grain size of 0.2 μm was prepared by simultaneously adding W solution and a mixed aqueous solution of thorium chloride and potassium bromide at a constant rate for 30 minutes. (cI
2 composition (95 mol%) This emulsion was desalted by the flocculation method, and 1 μ of thiourea dioxite and 0.6 μ of chloroauric acid were added per mole of silver, and the highest performance was obtained at 65°C. Even the cram school students were disappointed.

The following compounds were further added to the emulsion thus obtained.

Rho C1□II ZS 2X10-''mol/A g1mol4X1.O-'mol/A, g1mol KBr 20rNg/m
Polystyrene sulfonic acid sodium salt 4.0mg/m2.
6-dichloro-6-hydroxy-1.3.5-1-riazine sodium salt 30 mg/m This coating solution was coated to give a coated silver amount of 3.5 g/m.

2-2) Emulsion protective layer formulation The following compounds were further added to the protective layer of Example 1. Furthermore, Seratin is 1. ．． It was set to 5 g/m.

Dodecylbenzenesulfonic acid sodium salt 0.05 g/mX Sodium acetate 03 g/m Tex (particle size 0.06 μm) 005 g/n (5-2I-loindazole 0.01.5 g/m
1,3-Divinylsulfonyl - 2-propatol 0.05g/mN-Perfluorophthanesulfonyl-N-propylglycine botadium salt 2mg/m Ethyl acrylate latte, alcoholic acid (average particle size 0°11t) 0.2g /rtr
NIIC (CI+3) zcllzsOJ8OC112
CI+20COCII□C1fzSOzC! l”C
1h・Conductive agent 2-4 in Table 2 Bank layer prescription Gelatin CI, -C-□ CI = CI+ 0.003g/n (5g/m C□ C-CI+ 3 03K SO, 2-3) Hack lower layer prescription・Ceratin 01 g/rrf ・Polyethyl acrylate] 5O3K SOJ 1.3-divinylsulfonyl 2-propanol ethyl acrylate latenox (average particle size 0.2μ Fujihexyl-α-sulbosacnate sodium salt SOJ 40 ■/d SO, 80■/,? 150■/I900/m 35■/d Dodecylhenzenesulfonic acid sodium salt 35■/, (2-5
) Huck 8I layer formulation was prepared in the same manner as in Example 1. Furthermore, Seratin Ba1, Og
/ m.

The coating sample was a PET hese with only the vinylidene chloride undercoat layer of Example 1 applied to both sides (no conductive undercoat layer).
A hack underlayer, a hack layer, and a hack protective layer were simultaneously coated in this order on one side of the film, and an emulsion layer and an emulsion protective layer were coated on the other side.

Table 2 shows the evaluation results of the obtained samples.

As can be seen from the table, Samples 2-2 to 2-5 prepared using the conductive agent of the present invention were excellent in all of the static mark occurrence rate, dust adhesion, permeability, and adhesiveness.

On the other hand, Con I roll sample 2-1 and samples 2-6 to 2-10 using comparative conductive agents had static marks, dust,
It is not possible to satisfy both transparency and adhesion.

From the above, it is clear that the present invention is significantly superior to conventional techniques.

Furthermore, the obtained images were excellent, with no unevenness during development and no decrease in sensitivity.

Example 3 In Example 2, the emulsion layer having tabular silver halide grains was prepared from Example 3 Sample 20 of JP-A-63-264740.
Color photographic negative film samples 3-1 to 3-10 were prepared in exactly the same manner as in Example 2, except that the composition of the second photosensitive layer was changed from the first layer to the 14th layer. (Processing is JP-A-63-2
6474.0 Example 3 was followed. ) Samples 3-2 to 3-5 of the present invention satisfied all of the static masking, image unevenness, fixer staining property, and coatability.

On the other hand, comparative samples 3-8 to 3-10 and control sample 3
-1 was unable to satisfy all of the performance requirements listed in item 2.

Example 4 = Acetate cell 1. On one side of the J-S support
The photosensitive layer composition of Example 2 Sample 104 of 26474.0 was coated. The hack layer on the other side was coated with the following composition.

(Hack 1st layer) Compound of the present invention (exactly the same compound as in Example 1 and the same amount added) Diethylene glycol 10 μ/m' (Coated using a mixed solvent of acetone/methanol/water) (Hack 2nd layer) Layer) Diacetylcellulose 200■/, (Stearic acid 10 Cetyl stearate 1-20■/d Silicary particles (particle size 0.3.+rm) 30 (Coated using a mixed solvent of acetone/methanol/water) The treatment was in accordance with Example 2 of JP-A-63-264.74.0.

Obtained sample 4. -1 to 4-10 were evaluated in the same manner as in Example 1, respectively.

Samples 4-2 to 4-5 of the present invention satisfied static marks, image unevenness, fixer contamination, and coatability, and excellent images were obtained.

On the other hand, control sample 4-1 and comparative samples 4-8 to 4-1
0 could not satisfy all of these requirements.

Example 5 Synthesis of poly (methyl meccrylate-ethyl co-acrylate-co-acrylic acid) 1β three-necked flask equipped with a stirring device and a reflux tube], 5
Weigh out g and dissolve it in 300 cc of water.

Next, the temperature of the reaction vessel was raised to 75°C under a nitrogen stream, and
Stir at 00 rpm. Add 40g of 3% potassium persilicate aqueous solution, then add 150g of methyl methacrylate.
A mixed solution of 87.5 g of ethyl acrylate and 12.5 g of acrylic acid was added dropwise over 3 hours. After the start of the dropwise addition, 10 g of 3% potassium persulfate was added six times in total every 30 minutes. After the monomer mixture was added dropwise, the reaction vessel was kept at 75°C for another 2 hours to obtain a water-washed dispersion of a copolymer with an average molecular weight of 250,000. This aqueous dispersion was neutralized with a 10% aqueous potassium hydroxide solution to adjust the pH to 7.0.

In the aqueous dispersion of this copolymer, 2.4 dichloro and 1.6
1 nitroxy], 3.5 triazinina 1 to 3.5% by weight of the copolymer salt was added, and polystyrene with an average particle size of 2 μm was added to each 4L of water (polystyrene was added so that the Atsushi particles were coated at 1.0 mg/m). First coat the liquid containing fine particles.
It was used as a layer coating liquid.

A biaxially stretched polyethylene terephthalate film having a thickness of 100 μrll 30 cm was subjected to a corona discharge treatment under the following conditions. The film transport speed was 30 m/min, the gap between the corona discharge electrode and the polyethylene terephthalate film was 1.81, and the electric power was 200 W[. On both sides of corona discharge treated polyethylene terephthalate, an aqueous dispersion of the copolymer synthesized by the above method was applied at a rate of 0.1
It was applied to a dry film thickness of μm and dried at 185°C. This layer is called the first undercoat layer. On top of that, the film transport speed was 30 m/min, the gap between the corona discharge electrode and the polyethylene terephthalate film was 18 fins, and the electric power was 120 m/min.
After corona discharge treatment with Waso I., vinylidene chloride:methyl methacrylate-1: methyl acrylate:acryloni-1 hel:acrylic acid-90:4. ．． 5:4.
:1:0.5, wt% copolymer aqueous dispersion was applied to both sides to a dry film thickness of 0.75 μm, and heated at 120°C.
It was dried. Furthermore, on one side of the second undercoat layer made of this vinylidene chloride copolymer, the film was conveyed at a temperature of 30 m for 7 minutes, and the gap between the corona discharge electrode and the polyethylene terephthalate film was set at 1.8 cm and the electric power was set at 250 m. Treated with Watsuto and applied the following prescription (1) as the third layer of undercoat on top of it.
Apply the undercoating liquid on one side to 20mβ77m',
It was dried at 170°C and used as an undercoat on the emulsion side.

Next, on the other side, the same compound of the present invention as in Example 1 was added to the third layer formulation of the undercoat, and the same method as for the emulsion side undercoat was applied (however, the undercoat liquid was set at 2 decrement/m') on the hack side. I used it as an undercoat.

Next, apply the following formulation (2) on the undercoat layer on the emulsion side of the support.
A silver halide emulsion of the following formula (3) was further coated. On the opposite side of the hack layer, on top of the undercoat layer, in order from the support side, a hack layer of the following formulation (4),
A hack protective layer of the following formulation (5) was applied, and samples 5-1~
5-12 was created.

(1) Undercoat 3rd layer prescription gelatin 1.0% by weight methyl cellulose 0.05% by weight surfactant, C+zH
zsO(CH2C)T2O) + o HO103 weight% Water weight 100.0% by weight (2) Silver halide emulsion layer formulation 2X per mole of silver in gelatin aqueous solution kept at 50°C
1. Silver chlorobromide with an average particle size of 0.2μ was obtained by simultaneously adding a mixed aqueous solution of silver nitrate, thorium chloride, and potassium bromide for 30 minutes at a constant rate in the presence of O-' moles of rhodium chloride. Eleven single emulsions were prepared. (1 composition: 95 mol%) This emulsion was desalted by the flocculation method,
1. per mole of silver. mg of thiourea dioxylide and 0. 6n++r of chloroauric acid was added to generate the y1 compound at 65°C until maximum performance was obtained.

The following compounds were further added to the emulsion thus obtained.

n-C, 211゜2X10-'' mol/A g1 mol 4, X10-' mol/A g1 mole Br 2f
) n++y/m polystyrene sulfonic acid sodium salt 40■/d2.6-
Cycloro 6-Hydroxyl 1.3.5-1-Ryazine Sodium Salt 30 µ/m', and the second coating solution was applied to give a coated silver amount of 3.5 g/m.

7 (3) Emulsion protective layer prescription Gelatin 5i02 mold particles (average particle size 4μ) Dodecylbenzenesulfonate sodium salt H],, 5g/n? 50 ■/m 50 Ing/n (Compound of the present invention (4) Pack layer formulation gelatin 5 g/rd 5-nitroindazole 1.3-divinylsulfonyl 2-propatol N-perfluorophthanesulfonyl-N-probylglycine Botadium salt ethyl acrylate tratics (average particle size 0.1μ) 15■/11 (50mg/% 2mg/rl 300■/m' SO31 (So, 40■/M o3K SO, 80■/M 13- Divinylsulfonyl 2-propatur ethyl acrylate latix (average particle size 0.1 μ) Dihexyl α-sulfosacnate sodium salt Dodecylbenzenesulfonic acid 150 mg/m 900 mg/m 35 ■/% Sodium salt 35 mg/bo (5)
Puncture protection layer prescription gelatin 0.88/rrrPolymethyl methacrylate fine particles (average particle size 3μ) 20mg/Posihexyl α-sulfosacnate sodium salt 10mg/Bododecylbenzenesulfonic acid sodium salt 10mg/Sodium boacetate 40μ/Bo development processing The FC-660 automatic processor manufactured by Fuji Photo Film Co., Ltd. was used, and the developer and fixer were GRD-1 and GRF-1 manufactured by the same company.
The treatment was carried out at 38°C for 20 seconds. The drying temperature at that time was 45°C.

The obtained samples 5-1 to 5-10 were evaluated in the same manner as in Example 1, respectively.

Samples 5-2 to 5-5 of the present invention satisfied all of the static marks, image unevenness, fixer staining property, and coatability, and the images were also excellent.

On the other hand, control sample 5-1 and comparative samples 56 to 5-1
0 cannot satisfy all of these requirements, and it is clear that the present invention is superior to the conventional technology.

Claims (3)

[Claims] (1) In a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, at least one of the constituent layers of the light-sensitive material contains a polymer obtained from a polyaniline-based aqueous dispersion. A silver halide photographic material characterized by: (2) The polyaniline aqueous dispersion is a nonionic polymer, an amphoteric polymer, an anionic polymer, a cationic surfactant,
It is characterized by being obtained by oxidative polymerization of an aniline compound in the presence of one or more compounds selected from the group consisting of anionic surfactants, nonionic surfactants, and amphoteric surfactants. Claim No. (
The silver halide photographic material described in item 1). (3) The silver halide photographic material according to claim (2), wherein the aniline compound is a compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) Here, R^1 and R^2 are hydrogen atoms, halogen atoms,
Alkyl group, aryl group, hydroxyl group, alkoxy group, aryloxy group, amino group, alkylamino group (may be fused), nitro group, cyano group, -NHCOR^5, -
NHSO_2R^5, -SOR^5, -SO_2R^5
,▲There are mathematical formulas, chemical formulas, tables, etc.▼, -COR^5,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, -COOR^5,
-SO_3H-, -SH, -COOH, represents a heterocyclic group. R^3 and R^4 represent a hydrogen atom, an alkyl group or an aryl group. R^5 represents an alkyl group or an aryl group. R^6 and R^7 may be the same or different and represent a hydrogen atom, an alkyl group or an aryl group.