JPH02282246A - 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 specified heterocyclic compd. CONSTITUTION:A polymer obtd. from a heterocyclic compd. represented by the formula is incorporated into at least one of the constituent layers of a sensitive material. In the formula, each of R<1>-R<4> is H, halogen, alkyl, etc., and X is O, S, Te, etc. The polymer may be obtd. by subjecting the thiophene to oxidation polymn, in acetonitrile in the presence of KBF4 and 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 particularly to a silver halide photographic light-sensitive material having 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 when the photographic film is processed. It is to produce a dotted sub-7 l□, or a dendritic or feather-like linear velocity. 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 adhering 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 the photographic light-sensitive material 1 or in various automatic photographing machines.

Particularly in recent years, as photographic materials have become more sensitive and are subjected to harsh handling such as high-speed coating, high-speed photography, and high-speed automatic processing, the appearance of static marks has become even more likely. Furthermore, there is a problem in that dust is produced 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 problems caused by static electricity is to increase the electrical conductivity of the surface of the photographic material so that the static charges can be dissipated in a short period of time before the accumulated charges are discharged. This is an effective means especially for removing dust after processing.

Therefore, methods have been considered to improve the conductivity of supports and various types of cloth surface layers in photographic materials, and attempts have been made to use various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers, etc. I've been exposed to it.

(Problems to be Solved by the Invention) However, these substances exhibit specificity depending on the type of film support and the photographic composition, and may lose conductivity and become dusty after processing, or may be sensitive to humidity. When these substances are applied to photographic light-sensitive materials, they may be addictive and cause static at low humidity, or may be accompanied by deterioration of photographic performance, coatability, or transparency, or deterioration of adhesion. This was extremely confusing.

Furthermore, JP-A-64. The above-mentioned problems have not been solved with the polyphosphazene described in US Pat. No. 4,237,194 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 heterocyclic compound represented by the following general formula (I).

Here, R1, R2, R3 and R4 are hydrogen atoms, halogen atoms (e.g. fluorine, chlorine, bromine), alkyl groups,
Oryl group, hydroxyl group, alkoxy group, aryloxy group, amino group, alkylamino group, nitro group, cyano group,
-NHCOR' N HS O2R"S OR5S 07R5S
Ol! N R6COR5CON R6R7R7 C0OH, -COOR' , -3O, tlSH, represents a heterocyclic group (eg, 1-heriazole, thiazole, henzthiazole, furan, pyridine, quinaldine, henzoxazole, pyrimidine, oxazole, imidazole). 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.

X represents 0.5XTe or Se.

When X is other than S, RI and R2 or R1 and R1 and/or R2 and R4 may form a ring. Also,
When X is S, R1 and R3 and/or R2 and R4 may form a ring.

In these cases, the ring may contain one or more heteroatoms.

Furthermore, the alkyl group, aryol group, alkoxy group, aryoloxy group, and alkylamino group of R', R2, R', and R4 described above may be further substituted. Further, the alkyl group and aryl group of R5, R6 and R7 described above may also be further substituted.

Examples of these substituents include alkoxy groups (e.g.
methoxy, methoxy), aryloxy groups (e.g., phenyloxy), alkoxycarbonyl groups (e.g., methoxycarbonyl), acylamino groups (e.g., acetylamino), carbamoyl groups, alkylcarbamoyl groups (e.g., methylcarbamoyl, ethylcarbamoyl)
, dialkylcarbamoyl groups (e.g. dimethylcarbamoyl), arylcarbamoyl groups (e.g. phenylcarbamoyl), alkylsulfonyl groups (e.g. eva, methylsulfonyl), arylsulfonyl! (e.g., phenylsulfonyl), argylsulfonamide groups (e.g., methanesulfonamide), arylsulfonamide groups (e.g., phenylsulfonamide), sulfamoyl groups, alkylsulfamoyl groups (e.g., t, ethylsulfamoyl), dialkylsulfamoyl group (e.g. dimethylsulfamoyl), alkylthio group (e.g. methylthio), arylthio group (e.g. phenylthio), amino group, alkylamino group, cyano group, 1・
and halogen atoms (eg, fluorine, chlorine, and bromine), and when two or more of these substituents are present, they may be the same or different.

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

Hereinafter, a method for producing a polymer obtained from a heterocyclic compound will be explained.

The polymer obtained from the heterocyclic compound shown in formula (1) of the present invention can be synthesized by a known chemical oxidative polymerization method or electrochemical oxidative polymerization method used for the synthesis of conductive polymers.

As the chemical oxidative polymerization method, generally known methods such as those shown below can be used, but the method is not limited thereto. For example, C. Khulbe et al.
Polymer Science Polymer Chemistry Edition
ience Polymer Chemistry E
(1982), Vol. 20, p. 1089 (1982), reports that when pyrrole is oxidized with potassium persulfate J in an aqueous solution, a black powder polymer is precipitated.

The solvent used in the chemical oxidative polymerization method of the present invention is not particularly limited and varies widely depending on the polymerization conditions.

For example, water, acetonitrile, Bendani 1-lyl, propionitrile, dimethylformamide, propylene carbonate 1-, dimethylacetamide', dimethyl sulfoxide, etc. are used, but are not limited to these.

As the catalyst used for chemically oxidatively polymerizing the heterocyclic compound in the present invention, any known catalyst used for -C can be used. For example, chlorides such as ferric chloride and cupric chloride, sulfates such as ferrous sulfate and cupric sulfate, metal oxides such as lead dioxide and manganese dioxide, potassium persulfate, ammonium persulfate, and Examples include peroxides such as hydrogen oxide, quinones such as henzoquinone, halogens such as iodine and bromine, and potassium ferricyanide.

Specific examples of these can be found in Japanese Patent Application Laid-open Nos. 6321.3518 and 6321.3518.
No. 3-193926, No. 62-1.16665, No. 6
2-104.832, 63215717, 63
-69823, 63101415, 60-58
4.30 etc. The amount of catalyst will vary depending on the properties of the heterocycle and the catalyst used. However, in general, the catalyst/heterocyclic compound molar ratio is 0.
．． The range is from 01 to 10, preferably from 1 to 5.

The reaction temperature in chemical oxidative polymerization is 0 to 100°C1
Preferably it is 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.
1 to 50 hours.

Further, the above chemical oxidative polymerization may be performed in the presence of a dispersant and a surfactant in an aqueous solvent, and the heterocyclic compound is chemically oxidatively polymerized to obtain an aqueous dispersion. In other words, put polyvinyl alcohol, thiophene, and distilled water in a flask, and use it as a catalyst while stirring under a nitrogen atmosphere.
Fecp3 water? The method of dropping 8 liquids is mentioned, but
It is not limited to these.

When an aqueous dispersion is obtained by chemical oxidative polymerization, the reaction temperature and reaction time of the oxidizing agent may be the same as in the case of the general chemical oxidative polymerization described above.

In addition, solvents that can be used to produce aqueous dispersions include water such as distilled water and ion-exchanged water, but organic solvents that are miscible with water (for example, alcohols such as ethanol and methanol, acetonyl, , dimethyl sulfate, N,N-dimethylacetamide) may be mixed. further polymerizes,
A co-solvent may be used if the heterocyclic compound is insoluble in these solvents.

Dispersants used in the production of aqueous dispersions include nonionic polymers, amphoteric polymers, cationic polymers, and anionic polymers, specific examples of which are listed below, but are not limited to these.

Examples of nonionic polymers include hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, dextran, pullulan, polyvinyl alcohol,
Examples include polyacrylamide' and polyhinylpyrrolidone.

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

Examples of cationic polymers include polymers that are water-soluble and have at least one type of quaternary ammonium base, ogisonium base, sulfonium base, etc. in their structure.

Specific examples of cationic polymers include, but are not limited to, the following compounds.

(-CI-12-CI(-)- CH:1 CH.

CT"+ 3 Cll3COO8 -(-CH2-CI-19- E CH2-CH→- (-CH2 CH3 C+ -O Cll1COO0 (CHz C1(-)- ) 1@ + CH2CI(→- Anionic polymer dispersant Any commonly used polymer having anionic surface properties can be used. Preferably, it is a latex produced by emulsion polymerization. The anionic surface properties can be introduced by various methods.

For example, a latex having anionic surface properties is synthesized by polymerizing an ethylenically unsaturated monomer 1 containing an anionic group, such as a sulfonic acid group, or a mixture 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. .

Additionally, anionic surface properties may be achieved by using anionic surfactants in latex 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.

CJzHz, C00Na CIBH:17 C○0Na CIt H23CON CHz COON aH3 C+ lH23CON CH2CH2COON a H
3 CH2C00c , H, 7 NaO3SCHCOOC8H H2,CH=CHCHzSO,JNa H23CHCHz CH2SO3Na H zHzso(CJ('z)<5OaNaSO,Na 71(33CON CH2CIt 2 S O:+N
aH3 SO, Na SO3Na a CH2COOH,, HI 3 N aO:+ S Cl-I C00C6HI3C,2
H250S O3N a CH3 C1+ H23CON HCH2CH2CH2N C
H]Cρ0 CH.

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

Examples of anionic surfactants include those used in the production of latexes having anionic surface properties as described above.

Examples of cationic surfactants include the following.

Examples of nonionic surfactants include the following.

Cl2H250 (CH2CHzOLoHCH.

C1□H,,NHCρ0 C+6H330 (CHzCI(zo)zoHH3 CH3 CH25 N-CH.

01゜ CH.

I-1 H3 CH33 11-CH2COO8 Hw Polyoxyethylene sorbitan tristearin lecithin CH3 C11H2* CON HCI(zCHzCI(z
N CH2COO"'H3 acid ester n=30 CH3 3Hz7c ON HCH2CH2CH2N CH2C
000CH.

CH CH3 EISH31CONHCH2CH2CHz-N-Cl2
H250 (2CH2SCh"'H3 Examples of amphoteric surfactants include the following.

Hs 2H2゜N -CH□CO○0 CH3 The amount of the dispersant used for dispersing the heterocyclic compound is 1 to 300% by weight, preferably 5 to 300% by weight based on the heterocyclic compound.
It is 200% by weight. Moreover, various surfactants are 0.01 to 50% by weight, preferably 0.01 to 50% by weight, based on the compound of the present invention.
It is preferable to use 1 to 20% by weight.

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

Furthermore, 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, but preferably added before or both before and after polymerization. Furthermore, when performing treatments such as dialysis and ultrafiltration, they may be added after the treatment.

Conductive compounds that can be used in the present invention include alkali metal cations (1-i', 1 for Na', etc.), NO
+, NO2゛, cation, onium cation (Et4N
”, BudN”, BLI3P”, etc.) and negative ions (B
F4-, As F4-, As F6SbF+
, -1sbcβb-, P F6- , Cll04AeF
4-,Aj! F6-, Ni F4"-, ZrF6"
T i F6”-, T i Fb”-, Bloc 11
o"\CIB r", F-, H3O4-, SOa"-
etc.), sulfonic acid anions (CH, C, H4
SO3C6H5S 03-, CF:+S 03-
etc.), salts containing carboxylic acid anions such as HCOOLi, FeCj! Chlorides such as 3, and organic amines, inorganic acids (e.g.) ICE, H2SO, H
(1!0., HBF4), 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 these. It is not limited to these.

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-phtadiene rubber, butadiene rubber, Synthetic rubbers such as isoprene rubber, butyl rubber, nitrile rubber, chloroprene rubber, and ethylene-propylene rubber, polyvinyl acetate-based polymers, polystyrene-based polymers, polyethylene-based polymers, poly(meth)acrylic acid ester-based polymers, etc. can be used. but,
It is not limited to these. Preferably, these polymeric compounds are emulsions.

Next, the electrochemical oxidative polymerization method will be described below.

As the electrochemical oxidation polymerization method, generally known methods such as those shown below can be used, but the method is not limited thereto.

For example, Takashi Kaneto et al.
21, No. 9, p. 567 (1,982) reported that when thiophene is electrolytically polymerized in acetate nitrile in which AgCβ04 is dissolved, a polythiophene fill J is generated at the working electrode. is reported.

The solvent, reaction temperature and reaction time used in the electrochemical oxidative polymerization method of the present invention may be the same as those used in the chemical oxidative polymerization described above.

Further, doping may be performed using a polyelectrolytic compound used in the production of an aqueous dispersion.

Hereinafter, specific examples of the polymer obtained from the heterocyclic compound of the present invention and the aqueous dispersion of the heterocyclic compound polymer and the synthesis method thereof will be shown.

Synthesis Example 1 (Synthesis of aqueous dispersion 1) In a 300 me 3 inch flask, mites 1-stran 5 were added.
g.

Take thiophene Log and 120 mF of distilled water and add 4 ml of distilled water to this solution at room temperature while stirring under nitrogen atmosphere.
．． 50 g of FeCj dissolved in 8 ml! 3.6I]2
0 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 (VIS
KASE 5ALES C0RP CELLUI, O5
E TUBIN [; C-65 Sanko Junyaku (manufactured by Co., Ltd. is used)
, a water-containing liquid of polythiophene was obtained.

The average particle size of the obtained polythiophene particles was 10 Qnm (measured with a COULTER-N4 type submicron particle analyzer (manufactured by Coulter Electronics). In addition, this aqueous dispersion was stored for 20 minutes. It is stable when carried out at ℃ and even at 5℃ to prevent spoilage.
After 3 months, there was no sedimentation or agglomeration of particles at either temperature. Furthermore, there was no evidence of corruption.

Synthesis Example 2 (Synthesis of Aqueous Dispersion 2) As a surfactant, 50.05 g of triglyceride lauryl sulfate
,! As a result of synthesis and dialysis in the same manner as in Synthesis Example 1 except that 10 g of tributylammonium henzenesulfonate salt was added together with thiophene as an electrolytic salt, a stable polythiophene aqueous dispersion (average particle size 80 nm) was obtained as in Synthesis Example 1.
I got it.

Synthesis Example 3 (Synthesis of Aqueous Dispersion 3) Synthesis and dialysis were performed in the same manner as in Synthesis Example 1, except that 5 g of polyvinylpyrrolidone was used instead of dextran, and 12 g of 3-methylthiophene was used instead of thiophene. A stable poly (3-methylthiophene) aqueous dispersion that similarly exhibits no decay or particle aggregation? V, (average particle size: 40 nm) was obtained.

Synthesis Example 4 (Synthesis of Aqueous Dispersion 4) C1z H250 (CH2C
As a result of synthesis and dialysis in the same manner as in Synthesis Example] except that 0.5 g of H,0) and 40 g of ammonium persulfate were used instead of FeC1!3'6Hzo, a stable average particle size of 60 nm was obtained as in Synthesis Example J. An aqueous dispersion of polythiophene was obtained.

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

. H Synthesis Example 23 (Synthesis of Compound 1) In a 300 ml 3 flask, 10 g of thiophene (
C1HJaNBFa 5 g and aceI nitrile 20
Take Qmfl and add 50 g of Fef dissolved in 30 ml of distilled water to this solution at room temperature while stirring under nitrogen atmosphere.
:l! 3.6H20 was added dropwise over 30 minutes. As the mixture was added, heat was generated and a black solid was formed. 2 more
After stirring for an hour, the obtained solid was collected by filtration and dried to obtain Compound 1.

Synthesis Examples 24-32 (Synthesis of Compounds 2-10) Synthesis Example 2
In the same manner as in 3, the monomers shown in the table below were chemically oxidized and polymerized,
Compounds 2-10 were obtained. Here, the amount of monomeric conductive salt is the same as in Synthesis Example 23.

Synthesis Example 33 (Synthesis of Compound 11) 2 g of thiophene, 4 g of (C4Hq)aNBFa, and 200 ml of acetonitrile! The electrolyte is dissolved in Ag/AgC!, a PT plate is used as the working electrode and the counter electrode, and Ag/AgC! is used as the reference electrode.
When electrochemical polymerization was carried out using an electrode at a constant voltage of 0.5 V for 30 minutes, a polythiophene film was produced on the working electrode. The obtained film was peeled off from the electrode and dried to obtain Compound 11.

Synthesis Examples 34-40 (Synthesis of Compounds 12-18) Similarly to Synthesis Example 33, the monomers shown in the table below were electrochemically polymerized to obtain Compounds 12-18. Here, the amounts of monomer and conductive salt are the same as in Synthesis Example 33.

Synthesis Example 42 (Synthesis of Comparative Compound 2) 2 g of pyrrole, 4 g of (C4HQ)4NBFa, and 200 ml of acetonyl 1-lyl! The electrolyte was prepared by dissolving thiophene, a PT plate was used as the working electrode, a PT plate was used as the counter electrode, and a saturated Calo synthesis example 41 (synthesis of comparative compound 1) was used as the reference electrode. When the synthesis was carried out, a solid precipitated. The obtained solid was collected by filtration and dried to obtain Comparative Compound 1.

Comparative Compound 4 was obtained by synthesizing in the same manner as in Synthesis Example 42 using aniline hydrochloride instead of pyrrole.

The compound represented by the general formula (I) of the present invention is added to at least one of the silver halide emulsion layers or other constituent layers of the photographic material A, 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 photosensitive material, the powder is dissolved or suspended in water or an organic solvent such as methanol, isopropanol, acetone, etc., or a mixed solvent thereof, and then the surface is preserved. It may be added to a coating solution for a layer or a vine layer, or it may be added as the aqueous dispersion as described above, and it may be applied by dispersing, air knife coating, spraying, or as described in U.S. Pat. No. 2,681,294. It is coated by an extrusion coating method using a hopper, as described in U.S. Pat.
．． Two or more layers may be applied simultaneously by the method described in Japanese Patent No. 898, No. 3,526,528, or the antistatic film 1 may be immersed in a liquid. Further, if necessary, an antistatic liquid (solution alone or containing a binder) containing the compound of the present invention may be further coated on the protective layer.

The amount of each compound represented by the general formula [1] of the present invention is 0.0001 per square meter of the photographic material.
~2.0g is preferably present, preferably 0.000
The amount is 5 to 0.7 g, particularly preferably 0001 to 0.3 g.

Two or more of the compounds represented by the general formula [1] of the present invention may be mixed.

The photographic material according to the present invention may be a conventional black-and-white silver halide photographic material (for example, black-and-white photographic material, 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,
(color negative film for movies, etc.) and infrared light sensitive materials for racer scanners.

Photographic sensitization of the present invention (types of silver halide used in the silver halide emulsion layer, surface protective layer, etc., manufacturing method, chemical sensitization method, antifoggants, stabilizers, hardeners, antistatic agents,
There are no particular restrictions on couplers, plasticizers, lubricants, coating aids, matting agents, brighteners, spectral sensitizers, dyes, ultraviolet absorbers, etc. For example, Product Licensing Magazine (Pr.
oduct Licensing) Volume 92, 107-11
Page 0 (December 1971) and Research Disclosure Lt.
) Volume 176, pages 22-31 (December 1978), 2
The description in Vol. 38, pp. 44-46 (1984) can be referred to.

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

For example, saponins (steroids), alkylene oxide derivatives (such as polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, non-containing materials such as alkylene gellicol algylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. Ionic surfactants; alkyl carboxylates, alkyl sulfonates, alkyl hanzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, Acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as sulfosuccinates, sulfoargyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. anionic surfactants including amino acids, aminoargylsulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic surfactants; Cationic surfactants such as quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, 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 J (Sankyo Publishing ■, 1975)," and "Matsuku Cations Decousients and Emulsifiers" by Hiroshi Horiguchi. ” (
Mc Cut Visions, MC, Publishing Company 1985) (Mc Cut
cheon's Detergents & Emu
Mc Cutcheon Div.
isions, MC Publishing Co, 1
985) ), Japanese Patent Application Laid-open No. 60-76741, Japanese Patent Application No. 13398-1981, Japanese Patent Application No. 6116056, Japanese Patent Application No. 61-3
No. 2462, etc.

In addition, in the present invention, other antistatic agents may be used in combination (for example, the fluorine-containing surfactants or polymers described in Japanese Patent Application No. 61.-32462, JP-A No. 60-7674).
No. 2, No. 60-80846, No. 60-80848,
No. 60-80839, No. 60-76741, No. 51
(Nonionic surfactants described in Japanese Patent Laid-open No. 208743, etc., or conductive polymers or latex (nonionic, anionic In addition, inorganic antistatic agents include ammonium, alkali metal, alkaline earth metal halogen salts, nitrates, perchlorates, sulfates, acetates, phosphates, Thiocyanate, etc. are also disclosed in JP-A-57-11
It is possible to use conductive tin oxide, zinc oxide, or a composite oxide in which antimony or the like is added to conductive tin oxide, zinc oxide, or these metal oxides as described in No. 824-2.

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 sulfate esters; 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 single or copolymers of polyvinylimidazole, polyvinylpyrasol, and the like.

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.

Polyols such as trimethylolpropane, tantanediol, phthanediol, ethylene glycol, glycerin, and sorbitol can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention.

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 also have spherical, spherical,
It may have a crystal shape such as a plate shape, or it may have a composite shape of these crystal shapes. Further Hari Search Disclosure 22 Evening Volume A
, 2233 II, , 20-evening page f (/91v3≠l
), Tokikai Shoyu g-/, 17ri, 2/ issue, same ta-/13
The tabular grains described in No. 92A may also be used. 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 ( Metal ions are added using a small amount (including complex salts) selected from the group consisting of complex salts, and metal ions are added inside 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 applying 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. When the salts are removed, line 5 can be performed based on the method described in Research Disclosure A'711t3f1.

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 rhodide 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 divided by the average grain size, the diagonal is 00.20 or less.The grain size is the diameter in the case of spherical silver halide, and the projection of the diameter in the case of grains with shapes other than spherical. (This shows the diameter when the image is converted into a circular image with the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

Furthermore, the emulsion used in the present invention is US Pat.
G,! , 3,397. tar r7, 370j,
♂! A mixed emulsion of a light-sensitive silver halide emulsion and an internally overlapped silver halide emulsion or an emulsion used in combination in a separate layer may be used as described in ♂.

Here, the special request is shown/70. It is preferable to further use a mercapto compound described in tl♂ in terms of suppressing fog and improving 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. benzotriazoles, nitrobenzotriazoles, mercaptotetrazo-yv (especially /-phenyl-y-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines, thioketo compounds such as oxadorinthion; azaindenes , for example triazaindenes, tetraazaindenes (especially μm hydroxy-substituted ('+ 3+ 38+ 7
) tetraazaindene), pentaazaindene nat; benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfonic acid amides and the like.

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, it 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 oxide or its derivatives such as ethers, esters, and amines, thiony5'1 methyl compounds, and thiomorpholines. , quaternary ammonium 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. Carbon black or various dyes such as oxonol dyes, azo dyes, aryl tin dyes, styryl dyes, anthraquinone dyes, merocyanine dyes and tri(or di)allylmethane dyes may be used for this purpose. Cationic polymers or latexes may then be used to prevent the dye from diffusing out of the antihalation layer.

These are Research Disclosure Volume 17 A,
``A≠3,'' described in item (■).Furthermore, a magenta dye as described in Japanese Patent Application No. 127TT3 may be used to improve the color tone of developed silver.

The hydrophilic colloid layer used in the present invention includes colloidal silica, barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, and methyl methacrylate-methacrylate described in Japanese Patent Application No. 2-001gq.
Styrene sulfonic acid copolymer, JP-A-Sho t/-230/3
A so-called matting agent made of particles containing fluorine groups as described in No. 1 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 (/, 3.
s-Triacryloyl-hexahydro-5-)riazine, l,3-vinylsulfonyl-2-propatournato)
, active halogen compound (,2,1,t-dichloro-t-
Hydroxy-5-)riazine], mucohalogen acids (mucochloric acid, mucophenoxychlore, etc.), etc. can be used alone or in combination.

The hardening agent preferably used is a vinyl sulfone compound represented by the following general formula.

(CH2=CH-8o2-CH2=CH In the formula, A represents a covalent group, but may be omitted.

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

As a developing agent, Research Disclosure No. 77
Volume Otsu, page 29, “Developing agents
” may be used.

Hydroquinone and pyrazolidones are particularly preferably used.

In the present invention, a coupler that develops yellow, cyan, or magenta may be used, for example,
21tt, No. 2.

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 produced by the reversal method, a black-and-white negative development process is first performed, and then a color development process is performed 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 a photosensitive 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, , development process, fixing process,
A water washing process is performed. 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. Alternatively, a developing agent or its precursor may be incorporated into the photosensitive material, and the developing process may be performed 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 a stabilizing process if necessary are performed, but instead of the process using a solution and the process using a fixer, a /bath bleach-fixer is used to perform bleaching. A fixing process can be carried out, or a monopass process can be carried out using a one-bath development, bleach-fixing treatment solution in which color development, annotation, and fixing can be carried out in a one-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 processes, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution, or an activator process may be performed in the monopass process. Can be applied.

The treatment temperature is usually selected in the range of 100C to 0C, but it may be higher than 0C.

Preferably, it is processed at 0C-≠j0C for one night.

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

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, 2-methylbenzimidazole, and methylbenzthiazole, water softeners such as polyphosphoric acid, and surface overdevelopment inhibitors consisting of trace amounts of iodide and mercapto compounds. can be mentioned.

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 [I] of the present invention can provide extremely excellent photographic materials for these recent processing techniques. reactor.

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

Example 1 l-1) Preparation of hace Polyvinylidene chloride/itaconic acid (polymerization molar ratio 97
After coating 1), a polyethylene terephthalate support (PET thickness 175 μm and 1 vinylidene chloride layer thickness 0.7 μm) was prepared by biaxially stretching at 220'c, and poly(vinylidene chloride/vinylidene chloride/ Itaconic acid/ethyl acrylate; polymerization molar ratio 92:3:5, added as an aqueous dispersion) (0,01, g/rd) Seratin aqueous solution (001 g/rrr), dichloro-hydroxytriazine soda (0,01 g/n ( ), p-octylphenoxypoly (degree of polymerization 10) oxyethylene ether (0
, 03g/d> and the compound in Table 1 (in the case of a solid substance, pulverize (particle size 0.1 μm) or as an aqueous solution and add it as it is in the case of an aqueous dispersion).
After coating, it was dried at 140°C to form an undercoat conductive layer. Furthermore, after corona treatment, gelatin (0.2g #
), α-sulfodihexyl succinate sodium salt (0, Oo2g/m), poly(styrene/divinylbenzene, polymerization ratio 98:2) (average particle size 2.0 μm, 0.02 g/m),
02g/m2), 1. , 3-divinylsulfonyl 2
-Propertool (0,005g/m) was applied to create a protective undercoat layer. Also, only a protective undercoat layer was applied on one side.

1-2) Structure of dyed layer Method 1 of Nippon Paper Industries The following dyes were ball milled by the following method. Water (21,7 m#) and 6.7% Tri tonX-2
00” surfactant aqueous solution (2,65g) (Rohm &
(sold by Haas) in a 60m2 screw cap bottle. A 1.00 g sample of dye was added to this solution. Zirconia oxide 1, (ZrO) beads (40”) (
2ays diameter) was added, the container with a tight lid was placed in the mill, and the contents were ground for 4 days. 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.

The surfactant p-octylphenylethoxyethoxyethoxyethane sodium sulfonate and the hardener (bis(vinyl-sulfonylmethyl)ether) were added to the dye-gelatin melt. The melt produced from the latter mixture was then applied onto the aforementioned haze at a dye coverage of 0.08 g/r.
n', gelatin coating amount 0.4 g/m, surfactant 0.
0.026 g/m and hardener 0.016 g/rd.

■-3) Composition of emulsion layer 30 g of gelatin, 5 g of potassium bromide, 0 potassium iodide in water 11
．． Add 0.5 g of silver nitrate aqueous solution (5 g as silver nitrate) and 0.73 g of potassium iodide into a container kept at 75°C while stirring.
An aqueous solution of potassium bromide containing was added over 1 minute using a double jet method. Furthermore, silver nitrate aqueous solution (145 as silver nitrate)
g) and an aqueous potassium bromide 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, soluble salts were removed at 35°C by the sedimentation method, the temperature was raised to 40°C, and 60g of gelatin was twisted.
H was adjusted to 6.5. The temperature was raised again to 56°C, and the sensitizing dye anhydro-5,5'di-chloro-9-ethyl-3,
Chemical sensitization was carried out using gold and sulfur sensitization to which 650 ml of 3'-cy(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt was added.

The obtained emulsion had a hexagonal plate shape with a projected area diameter of 0°85μ.
The average thickness of m1 was 0.158 μm.

4-hydroxy-6methyl-1 was added to this emulsion as a stabilizer.
．． 3.3a, 7-chitrazaindene and 26-bis(hydroxyamino)-4-diethylamino-1,3,5-)
Riazine and trimethylolpropane were added.

Furthermore, the following compound was added (350 μ/m') N(C2
115)2 In addition, p-octylphenoxyjethoxyethanesulfonic acid sodium 0.01g/M1 dodecylhenzenesulfonate 0.005g/171 as a coating aid, and polypotassium p-vinylbenzenesulfonate 0.03g as a thickener. /rtr, polymer latex (polymer
[Ethyl acrylate/methacrylic acid -97/3) particles adsorbed with poly [degree of polymerization 10] oxyethylene poly [degree of polymerization 3] oxyglyceryl r-decyl ether [3% by weight of particles], average particle size -0 , 1 μm) 0.
4. g/d, sodium polyacrylate (molecular weight 200,000) 0, Ig/po, 1,2-bis(vinylsulfonylacetamido)ethane 0.04 g/n? , trimethylol.

1-4) Composition of protective layer Mugelatin 1.2 g/m polyacrylamide (molecular weight 45,000) 0.2 g/m mudextran (molecular weight 38,000) 0.2 g/n (molecular weight 38,000) Thorium 0.02 g/m Sodium polystyrene sulfonate 0.01 g/Bomb Colloidal strength (particle size 0.02 μm) 0.04 g/m
(Polymerization degree 10) Oxyethylene cetyl ether 0.02g/n? Mupoli (
Degree of polymerization: 10) Oxyethylene poly (degree of polymerization: 3) Glyceryl-p-octylphenyl ether 0.02 g/mC3H.

Mu CJ+ 7sOJ+CHzC1-120+T+CIIz
1. SO, Na0, 001g/m 0005g/m HI C9F, ,C0N1+-(-CH2-)-3N -C
II2COOe0゜001 glrd MUCBF17SO2N + Cl1z (JIzOsu 1 piece ÷
CIhCHCHzO+ *HO■ o, oo 5g/rrr H Mupotassium nitrate 0.01g/nf 0, 05g/bomb p-Momonoctylphenoxyethoxyethoxyethoxyethanesulfonic acid sodium salt 0.02g/mmu 4-hydroxy-6-methyl- 1,3,3a, 7 Tetrazaindene 0 Cetyl mbalmitate (particle size 0.11 μm dispersed with sodium dovucylbenzenesulfonate) 0.005 g/m Muscimethylsiloxane (dispersed with sodium dioctyl-α-sulposuccinate).

Particle size: 0.12 μm) Liquid paraffin (dispersed with dioctyl-alpha-sulfosuccinate sodium. Particle size: 0.11 μm) Polymethyl methacrylate fine particles (average particle size: 3.8 μm, 4.8 to 2.8 μm) 04g/ m o, 005 g/m 0.005 g/rnf abundance of 80% or more) 0.04 g/m A solution was prepared so that the gelatin concentration was 4 wt % for each of the above emulsion layer and protective layer, and the base of each layer was It was prescribed.

Then, the amount of silver coated on the heath made in 1-1) is 1.
It was applied to both sides at a concentration of 9 g/m. 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 Sodium sulfite 200g Diethylenetriaminepentaacetic acid 6.7g Potassium carbonate
16.7g Boric acid 10g
Hydroxynon 83.3g Diethylene glycol 40g 4-Hydromethyl-4 Methyl-1-phenyl-3 Viladuridone 5-Methylhensitriazole 0g Adjust to 14 with water (pH 10) ~ Sodium ethylenediaminetetraacetate trihydrate hydroxide - Make up to 1 part with water (add acetic acid).

automatic developing machine Developing tank 6, 5p Fixing tank 6.51 Washing tank 6.5β drying drying Dry to Dry processing time (adjust to 60).

60g 0g ■(5 0, lOg 2 4, g 1 0 61 laps 1 second processing 35° CXI 0.5 seconds 35° cx 9 seconds 20°C x 7 5 seconds 5 0°C 45 seconds When starting development processing Each tank was filled with the following treatment solution.

Developing tank 2 3 3 ml of the above developer concentrate, 6 ml of water
A starter IQmffi containing 67 ml and 2 g of potassium bromide and 18 g of acetic acid was added to pH
was set to 1.0.15.

Fixing tank: 250 ml of fixer concentrate and 750 ml of water! (1) Static mark test After conditioning an unexposed sample at 25°C and 10% RI for 2 hours, we tested the static mark on various materials in a dark room under the same air conditioning conditions. 8.
After rubbing as much as possible with a rubber roller and a urethane roller, the film was developed with the developer described above, fixed, and washed with water, and the degree of static mark formation was examined.

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

8. No static marks were observed at all B:
Slightly visible C: Significant scratch marks D: Appeared almost on the entire surface (2) Rubbish test Temperature and humidity 25°C. 1. Sample (2
(0 cm x 20 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.

P, I // was a little eight ninja.

C; was significantly observed.

D... was strongly recognized.

(3) Transmittance test Using an unexposed sample that had been developed and fixed as described in (1), the total amount of light was measured. vi! Transmittance was measured. Sample 1-■ (con I-roll) based [I first 1
00, and the relative value to that is the relative transmittance.
Shown in the table. The total light transmittance is ASTMll-100.
It was measured according to 3.

(4) Adhesiveness test After the completed sample was left in an atmosphere of 25°C and 50% RH for two weeks, an adhesiveness test was conducted in the following manner. The surfaces tested here were the surfaces provided with the antistatic layers of Haas A to G.

(B) Adhesion test method for dry film On the surface to be tested, make 36 cuts by making 7 cuts at 5+im intervals vertically and horizontally, and then apply adhesive tape (for example, Nitto Electric Industries , 2, toe tape) and quickly peeled off in a 180° direction.In this method, if the unpeeled portion is 90% or more, it is grade A, if it is 60% or more, it is grade B, and if it is less than 60%, it is grade 0. Adhesive strength that is sufficient for practical use as a photographic material is one that is classified as A grade out of the three-level evaluation.

(0) Wet film adhesion test method At each stage of development, fixation, and water washing, mark scratches on the film in the processing solution as X marks using an iron pen, and then use the tip of your finger to mark scratches (
Adhesive strength was evaluated during maximum peeling along the line x times.

If the constituent layers do not peel off more than the scratches, it is grade A, and the maximum peeling Tl
When J is within 51, it is classified as B class, and other times as 0 class.

What is the adhesion strength that is sufficient for practical use as a photographic material?
On the bottom of the grade evaluation, it is preferably classified as grade I3 or higher.

/ As can be seen from Table 1, the control 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 17 using the electrically conductive agent invented by the strength tree were excellent in all evaluations, but sample 1-8 using the electrically conductive agent particles other than the invention had deteriorated permeability and adhesion. Accordingly, it can be seen that Samples 1-4 to 1-7 using conductive polymers were accompanied by deterioration in dust adhesion and deterioration in adhesion after static mark treatment.

In particular, samples 1-4 to 1-6 had good surface conditions and excellent images.

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

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

Example 2 2-1) Silver halide emulsion layer formulation In an aqueous gelatin solution kept at 50°C,
In the presence of X10" moles of rhodium chloride, an aqueous silver nitrate solution and a mixed aqueous solution of sodium chloride and potassium bromide were simultaneously added at a constant rate for 30 minutes to obtain an average particle size of 0.2
A silver chlorobromide monodisperse emulsion of μ was prepared. ((1 composition: 95 mol%) This emulsion was desalted by the flocculation method, and 1 μg of thiourea dioxide and 0.6 mg of chloroauric acid were added per mole of silver, and the highest performance was achieved at 65°C. It was left to ripen until it was obtained.

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

2XIO-' mol/A g1 mol I (4,
mg/rtr polystyrene sulfonic acid sodium salt 40■/, 12.6
-Dichloro-6-human waxy 1.3.5-1-Ryazine 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. The gelatin content was 1.5 g/n.

F Decylbenzenesulfonate sodium salt 0.05g/rrfSodium acetate 0.03g/m5-Nitroindazole 0.015g/m1.3-Divinylsulfonyl 2-propatol 0.05g/=N-perfluorophthanesulfonyl N-propylglycinepotadium salt ethyl acrylate latex 7x (average particle size 0.1μ) O9 2■/% 2g/rrr 2-3) Bank lower layer formulation/gelatin 0.01g/n (0 polyethyl acrylate latex ( Particle size 0.06 μm> 0.005g/rrro(
7CH2Cl + 65 (-CIlz-C)
I→-1°CO Q NHC(CHs)zcHzsO:+Na OCHzC
1lzOCOC1lzCHzSOzCH=CHzO10
03g/m ・Conductive agent hack layer formulation in Table 2 Gelatin C-CIl = C1 2゜5 g/m C----C-C113 II 1 03K SO! 40■/1ri SO, K 03K 1.3-divinylsulfonyl 2-propanol ethyl acrylate latenox (average particle size 0.1μ) in SO3 80mg/n (150mg/m 900mg/m 35■/, (Dodecylbenzenesulfonic acid sodium salt 35■/m'2-5
) Bank protective layer formulation Prepared in the same manner as in Example 1. Gelatin is 1, og7
It was set as m.

The coating sample was a PET haze in which only the vinylidene chloride undercoat layer of Example 1 was applied on both sides (no conductive undercoat layer), and the hack underlayer, hack layer, and hack protection layer were simultaneously coated on one side in this order, and the other side. It was created by coating an emulsion layer and an emulsion protective layer on the side.

Table 2 shows the evaluation results of the obtained samples.

As can be seen from the table, Samples 2-2 to 2-7 prepared using the conductive agent of the present invention were excellent in all aspects of static mark occurrence, dust adhesion, permeability, and adhesiveness.

On the other hand, control sample 2-1 and samples 2-7 to 2-13 using comparative conductive agents cannot satisfy all of the static marks, dust, permeability, and adhesiveness.

Moreover, the surface condition was good and the image was also excellent, especially in samples 2-4 to 2-7.

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 3-13 were prepared in exactly the same manner as in Example 2, except that the composition of photosensitive layer 2 was changed from the 1st layer to the 14th layer. (Processing is JP-A-63-
26474.0 Example 3 was followed. ) Samples 3-2 to 3-7 of the present invention were satisfactory in terms of static marks, image unevenness, fixer staining property, and coatability.

On the other hand, comparative samples 3-8 to 3-13 and control sample 3
-1 could not satisfy all of the above performance.

Example 4 JP-A-63-26 on one side of cellulose triacetate support
The photosensitive layer composition of Example 2 Sample 104 of 4740 was coated. The hack layer on the other side was coated with the following composition.

(Bank 1st layer) Compound of the present invention (exactly the same compound as Example 1 and the same amount added) Diethylene glycol l0m1r/r+((
(Coated using a mixed solvent of acetone/methanol/water) (Hack 2nd layer) Diacetyl cellulose 200/lri Stearic acid 10 Cetyl stearate 1-20 Silica particles (particle size 0.3 μm) 30 (Acetone/ The treatment was carried out in accordance with Example 2 of JP-A-63-264740.

The obtained samples 4-1 to 4-13 were evaluated in the same manner as in Example 1, respectively.

Samples 4-2 to 4-7 of the present invention were satisfactory in terms of 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
3 could not satisfy all of these requirements.

Example 5 Synthesis of poly (methyl methacrylate-ethyl co-acrylate-co-acrylic acid) 1.5 g of 1P Mitsurofura equipped with a stirring device and a reflux tube
Weigh out and dissolve in 300 cc of water.

Next, the temperature of the reaction vessel was raised to 75°C under a nitrogen stream, and the temperature was increased to 20°C.
Stir at Orpm. 40 g of a 3% aqueous potassium persulfate solution was added thereto, and then a mixed solution of 150 g of methyl methacrylate, 87.5 g of ethyl acrylate, and 12.5 g of acrylic acid was added dropwise in the shade for 3 hours. Every 30 minutes after the start of the dropwise addition, 3% potassium persulfate Log was added six times per side. 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.

To the aqueous dispersion of this copolymer, 2,4 dichloro, 6 hydroxy 1,3,51-riazine sodium salt was added in an amount of 4% by weight based on the copolymer, and polystyrene fine particles with an average particle size of 2 μm were added at each level. A liquid to which polystyrene fine particles were added so that the coating was 1.0 .mu./M was used as a coating liquid for the first undercoat layer.

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 1.8 fins, and the electric power was 200 watts. An aqueous dispersion of the copolymer synthesized by the above method was applied on both sides of the polyethylene terephthalate treated with corona discharge.
It was coated to a dry film thickness of m and dried at 185°C. This layer is called the first undercoat layer. On top of that, corona discharge treatment was performed at a film transport speed of 30 m/min, a gap between the corona discharge electrode and the polyethylene terephthalate film of 1.81, and a power of 120 watts, and then vinylidene chloride:methyl methacrylate-1: Methyl acrylate: acrylonitrile: acrylic acid = 90:4.5:4:I:0.
5. Apply 0.75 μm of aqueous dispersion of copolymer to both sides by weight%.
It was coated to a dry film thickness of m and dried at 120°C. Furthermore, one side of the second undercoat layer made of this vinylidene chloride copolymer was treated with a film transport speed of 30 m/min, a gap between the corona discharge electrode and the polyethylene terephthalate film of 1.8 mm, and a power of 250 watts. On top of that, apply 20ml of undercoat liquid of the following formulation (1) as the third layer of undercoat.
It was coated on one side at a ratio of 1/rd and dried at 170'C to serve 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 bank side undercoat was made in the same manner as the emulsion side undercoat (however, the undercoat liquid was 2 ml/m). .

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 bank layer and undercoat layer on the opposite side, in order from the support side, a hack layer of the following formulation (4),
A bank protective layer of the following formulation (5) was applied, and samples 5-1~
5-12 was created.

f],) Undercoat 3rd layer formulation gelatin 1.0% by weight methylcellulose 0.05% by weight surfactant, Cl2H
250 (CH2CH20LoHO403% by weight Add water to 100.0% by weight (2) Silver halide emulsion layer formulation Q2 per mole of silver in an aqueous gelatin solution kept at 50°C
In the presence of
, 2μ silver chlorobromide monodisperse emulsion was prepared. (CZ composition 9
5 mol %) This emulsion was desalted by the flocculation method, and 1 μ of thiourea dioxide and 0.6 μ of chloroauric acid were added per mole of silver until the maximum performance was obtained at 65 “C. Only ripeness has given rise to pretense.

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

n-ClJzs 2XIO-2 mol/A g 1 mol■ 4×1.0-' mol/A g1 mole Br 20g
/m polystyrene sulfonic acid sodium salt 40■/, f2.6
-Dichloro-6-hydroxyl 1.3.5-triazine sodium salt 30 µ/m' This coating solution was coated to give a coated silver amount of 3.5 g/m.

(3) Emulsion protective layer formulation Gelatin 5iOz fine particles (average particle size 4μ) Sodium dodecylbenzenesulfonate salt 1.5g/rrr 50■/= 50oz/1 5~Nitroindazole 1.3-divinylsulfonyl 2-propatol N -Perfluorophthanesulfonyl-N-probylglycinebotadium salt ethyl acrylate latix (average particle size 0.1 μ) 15 mg/m' 50 mg/g 2/M 300 mg/n (Compound (4) of the present invention Layer formulation Gelatin 2.5 g/m C-C1l = CI+ -C-CL II ll 5U:lNa 3 O3K OJ 4,0 mg/rr? o3K SO3 to 80■/m' 113-Divinylsulfonyl 2-propatol Ethyl acrylate latix (average particle size 0.1 μ) Dihexyl α-sulpozacnate sodium salt Dodecylbenzenesulfonic acid 150 μ/d 900 μ/M 35 mg/Isodium salt 35+++ g/Bo(
5) Back protective layer prescription gelatin 0.8g/polymethyl methacrylate fine particles (average particle size 3μ) 20mg/posihexyl α-sulfosacnate sodium salt 10mg/bododecylbenzenesulfonic acid sodium salt 10■/sodium polyacetate 40. mg/po development processing is
The processing was carried out using an FC-660 automatic processor manufactured by Fuji Photo Film Co., Ltd., using GR11-1 and GRF-1 as developing solutions and fixing solutions manufactured by Fuji Photo Film Co., Ltd. at 38'C for 20 seconds. The drying temperature at that time was 45°C.

The obtained samples 5-1 to 5-13 were evaluated in the same manner as in Example 1, respectively.

Samples 5-2 to 5-7 of the present invention satisfied all of the static masking, image unevenness, fixer staining property, and coatability, and the images were also excellent.

On the other hand, control sample 5-1 and comparative samples 58 to 5-1
No. 3 cannot satisfy all of these requirements, and it is clear that the present invention is superior to the conventional techniques.

Claims (4)

[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 heterocyclic compound represented by the following general formula (I). A silver halide photographic material comprising a polymer obtained from a compound. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R^1, R^2, R^3, and R^4 are hydrogen atoms, halogen atoms, alkyl groups, aryl groups, hydroxyl groups, and alkoxy groups. , aryloxy group, amino group, alkylamino group, nitro group, cyano group, -NHCOR^5--N
HSO_2R^5, -SOR^5, -SO_2R^5,
-SO_2NR^6, -COR^5, -CONR^6,
-COOH, -COOR^5, -SO_3H-, -SH
, represents a heterocyclic 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. X represents O, S, Te or Be. If X is other than S, R^1 and R^2 or R^1 and R^
3 and/or R^2 and R^4 may form a ring together. Furthermore, when X is S, R^1 and R^3 and/or R^2 and R^4 may form a ring. In these cases, the ring may contain one or more heteroatoms. (2) Claim (1) characterized in that the polymer obtained from the heterocyclic compound represented by general formula (I) is obtained by chemical oxidative polymerization or electrochemical oxidative polymerization. silver halide photographic material. (3) The halogen according to claim (1), wherein the polymer obtained from the heterocyclic compound represented by general formula (I) is obtained from an aqueous dispersion of a heterocyclic compound polymer. Silver chemical photographic material. (4) The heterocyclic compound aqueous dispersion is obtained by oxidative polymerization of a pyrrole compound in the presence of one or more dispersants and surfactants. ) The silver halide photographic material described in item ).