JPH02308246A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic sensitive material having superior antistatic property even after development and inhibiting the sticking of dust by incorporating a specified electrically conductive polymer into a photosensitive silver halide emulsion layer. CONSTITUTION:When a photosensitive silver halide emulsion layer is formed on a support to obtain a photographic sensitive material, an electrically conductive polymer obtd. by oxidation-polymerizing a comp. represented by general formula I is incorporated into the constituent layer of the sensitive material. In the formula I, Y is a group capable of forming a polymer by oxidation polymn., X is a combining group, R1 is optionally substd. alkylene and R2 is H, optionally substd. alkyl, alkenyl, alkynyl, aryl, acyl, carbamoyl or sulfonyl. A concrete example of the compd. represented by the formula I is represented by formula I-1.

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 having good antistatic properties, and in particular, to a silver halide photographic light-sensitive material that has improved dust retention after processing without impairing coating properties. Silver halide photographic material (
(hereinafter referred to as "photosensitive 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. This accumulated electrostatic charge can cause a number of problems, the most serious of which is due to the discharge of the accumulated electrostatic charge before the development process. When the photosensitive emulsion layer is exposed to light and the photographic film is developed, dot-like spots or dendritic or feather-like wire rings are produced. 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 described above, such electrostatic charges are generated due to contact and separation between mechanical parts during the production of photographic light-sensitive materials or in various types of automatic image forming machines.

In particular, static marks are more likely to occur in recent years due to the increased sensitivity of photographic materials and the increased exposure to harsh handling such as high-speed coating, high-speed photography, and high-speed automatic processing. . 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 used as they are, 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. Performance such as not reducing adhesive strength is required, and the application of antistatic agents to photographic materials is subject to numerous restrictions.

One way to eliminate these problems caused by static electricity is to increase the electronic 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 method is particularly effective for removing dust after treatment.

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

(Problems to be Solved by the Invention) However, these substances exhibit specificity depending on the type of film support and photographic composition, lose conductivity after processing and cause dust, and exhibit humidity dependence. It is extremely difficult to apply these substances to photographic materials because they cause static at low humidity, deterioration of photographic performance, coating properties, and transparency, and deterioration of adhesive properties. It was 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 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 further achieved by containing a conductive polymer obtained by oxidative polymerization of at least one of the compounds represented by the following general formula [1].

General formula (1) (wherein, Y represents a group capable of forming a polymer through oxidative polymerization, X represents a linking group, R3 represents an optionally substituted alkylene group, and R2 represents a hydrogen atom or each substituted does not represent an alkyl group, alkenyl group, alkynyl group, aryl group, acyl group, carbamoyl group or sulfonyl group that may be substituted.

a represents O or 1, b represents an integer from 1 to 4,
m represents an integer from 1 to 3, and n represents an integer from 2 to 30.

However, when b>1, -(X)-+(R1-Oi1
h+.

may be the same or different. Further, when m>1, (Rl-0)yRz may be the same or different.

Further, when n≧3, n R1s may be the same or different.) General formula (1) will be explained in more detail.

Yba oxidative polymerization (chemical oxidative polymerization or electrolytic oxidative polymerization)
represents a group capable of forming a polymer, specifically the residue of an aromatic compound or a heterocyclic compound containing oxygen, nitrogen, sulfur, etc. as a heteroatom. Preferred examples of Y include amino aromatic compound residues, hydroxy aromatic compound residues (including polyhydroxy forms, monoyl residues, triazole residues, oxazole (including iso forms) residues), which may be substituted, respectively. , thiazole (including isoforms), zotriazole residue, benzoxazole residue, benzothiazole residue, purine residue, quinoline residue, isoquinoline residue, benzodiazine residue, f group, phenazine residue, phenoxazine residue group, pyrazolodiazole residue, pyrazolodiazole residue, pyrazoloazole residue, benzopyrazoloazole residue, etc. Zl is 0, S or N
A (A represents a hydrogen atom or a substituted or unsubstituted alkyl group). Y is particularly preferably an aniline residue,
They are phenol residue, dihydroquine benzene residue, and residue.

X represents a linking group, and specifically, it is represented by +L(J+-)h)Fh-χ*KJs. Here, Jl, J2, and J3 may be the same or different, -o-, -s-, -co-1-so, -, -
Examples include oco-, -coo-1-0CON-, and the like. R3 represents a hydrogen atom, an optionally substituted alkyl group, a phenyl group, or an aralkyl group; R'
represents an alkylene group having 1 to 4 carbon atoms. R5 represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.

J8, J2, J are preferably -CO-1-5O1-
, -CONB-1-8O□N11-, -Nll-CO-
, -NH-50! -1-0-, -11HCO1iH-1
-S-, -CO□-5-0CO-, -Noco, - and -0CONII-.

X2, X, and X may be the same or different,
Each represents an optionally substituted alkylene group, arylene group, or aralkylene group. Preferably carbon number 1-4
alkylene group, arylene group having 6 to 9 carbon atoms, and substituted arylene group.

p, 9, r and S represent O or 1.

R3 represents an alkylene group which may be substituted, but -C
IlICICII! , particularly preferably -CHl
Cl+, -1-C]1□CHCIh-.

Blind H Rz represents a hydrogen atom or an alkyl group, alkenyl group, alkynyl group, aryl group, acyl group, carbamoyl group or sulfonyl group, which may each be substituted,
Preferably it is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, methyl group or ethyl group, particularly preferably a methyl group.

a represents 0 or 1, b represents an integer from 1 to 4, preferably l or 2, particularly preferably l; 0m represents an integer from 1 to 3, preferably l or 2, particularly preferably is 1. n represents an integer from 2 to 30, preferably from 3 to 25, particularly preferably from 4 to 20.

However, when b > 1, b electric currents (-rR, -0\R2- may be the same or different. Also, when mal, -(R+-0)yRt
may be the same or different. Also, when n≧3,
The n R1s may be the same or different.

Examples of the optionally substituted substituents for Y, X, A, and R1 are a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, and 411Col? 6.

), a hydroxyl group, and a group that forms a hydroxyl group by hydrolysis. R6 represents an alkyl group, a phenyl group, or an aralkyl group. R7 and R8 may be the same or different and represent a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group.

Furthermore, the alkyl group, alkoxy group, phenyl group, and aralkyl group in the above-exemplified substituents may be further substituted, and examples of the substituent include a hydroxyl group, a nitro group, an alkoxy group having 1 to 4 carbon atoms, -CQR', -5O! l?
', a halogen atom, a cyano group, an amino group (which may be further substituted with an alkyl group), and the like. R9 is R
It is synonymous with h. 1710 and 1711 may be the same or different and have the same meaning as R7.

Next, specific examples of the compound represented by the general formula [1] will be shown, but the compounds of the present invention are not limited thereto.

1-2 Mixture of the compound shown in 1-1 with an average n number n'; 12 1-3 Mixture 1-4 of the compound shown in 1-1 with an average n number nζ15 Mixture 1-4 of the compound shown in 1-1 with an average n number nζ7 Mixture 1-5 The average number of compounds shown in 1-1 is n! ==
5 mixture 1-6 A mixture of the compound shown in 1-1 with an average n number nζ20 1-8 A mixture of the compound shown in 1-7 with an average n number n'' and a mixture of 12!-9r-7 with an average n number Mixture of nζI5 + - to r-7 Compounds with average n number nζ5 (average n @ n'-, mixture of 7) (average n number nζ
12) (Mixture with average n number nζ7) (Mixture with average n number nζ9) (Mixture with average n number n!=i15) (Mixture with average n number nζ7)! In the compound shown in -211-20, Z, =S[-2
In the compound shown in 21-20, Ha=N11 (mixture with average n number nζ9) (mixture with average n@nζ11) (mixture with average n number n ''r 7) (average n number n!=, mixture of 7 ( mixture with average n number n!=i7)!(C11□C1I□O)-CI+.

(Mixture with average n number nζ7) A synthesis example of compound 1-7 is shown below. Other compounds can also be synthesized in accordance with this method.

[Synthesis Example 1; Synthesis of compound 1-7] Polyethylene glycol methyl ether (nζ7, ^I
drjch, hereinafter abbreviated as PEO (?)) 1.0
0 d under ice cooling fj14', N at 15°C or less
aH (paraffin dispersion, purity 60%) 12.0g (
0.30 mol) was added gradually. After addition, cool with water for 30 minutes.
After stirring for minutes, 31.5 g (0.20 mol) of orthochloronitrobenzene was gradually added at below 20°C.
After stirring for 30 minutes, add a small amount of hydrochloric acid to neutralize, add 100 d of chloroform and 30 g of magnesium sulfate.
I got it. After removing magnesium sulfate, column purification was performed using chloroform as a developing solvent and silica gel as a carrier to obtain 33.1 g of 0-nitroP E O (7) benzene.

The above 0-nitroP E O (7) was subjected to catalytic reduction under high pressure (20a Lm) using 20g of benzene, 100d of methanol, 0.5g of Pd-C catalyst and hydrogen gas, and Pd-C
After removing the catalyst, methanol was condensed with i4 to form compounds 1-
I got 16a of 7.

Elemental analysis value (%): C-1 N-calculated value (n=
7) 58.5 8.58 3.25 measurement! 59.1 8.29 3.36 The conductive compound of the present invention can be obtained by oxidative polymerization using one or more compounds represented by general formula [I], but during oxidative polymerization, , -C One or more monomers other than the compound represented by the formula [I] may be used.Also, the compound represented by the general formula [I] is polymerized at the initial stage of polymerization, and then the compound represented by the -11 formula [I] may be used. ] or a monomer other than the compound represented by the formula [I], or a monomer other than the compound represented by the general formula (+) may be used at the initial stage of polymerization, and then , general formula [
A compound represented by formula (1) may be used, and furthermore, general formula (1) and another compound may be copolymerized at any polymerization time.

The conductive compound of the present invention contains at least 1 mol% of the compound represented by the general formula [I], preferably 10 to 10% by mole.
It can be obtained by oxidative polymerization using 0 mol%.

Compounds that may be copolymerized include aromatic compounds or heterocyclic compounds containing oxygen, nitrogen, sulfur, etc. as heteroatoms, and specifically, phenolic amino aromatic compounds (e.g., aniline). , hydroxyaromatic compounds (including polyhydroxy forms (e.g. dihydroxybenzene)), oxazole (including iso form), thiazole (including iso form), pyridine, diazine, dutriazole, benzoxazole, benzothiazole, purine , quinoline, isoquinoline, veridine, phenazine, phenoxazine, pyrazolotriazole, pyrazolodiazole, pyrazoloazole, and benzopyrazoloazole.

Z2 has the same meaning as Zl above.

As the oxidative polymerization method that can be carried out in the present invention, commonly used chemical oxidative polymerization methods or electrolytic oxidative polymerization methods can be used.

Polymers produced by chemical oxidative polymerization are prepared by dissolving or dispersing a compound represented by the general formula (N) in water or any organic solvent (which may contain water), and heating the mixture at 60'C to -20°C (preferably It can be obtained by gradually dropping catalyst (oxidizing agent) 18 liquid at 20''C to 0°C).

In this case, an aqueous dispersion of the polymer can also be obtained by using a suitable dispersant (eg, polyvinyl alcohol, gelatin, surfactant, cellulose, polyvinylpyrrolidone, cationic polymer).

Polymers produced by electrolytic oxidation polymerization are produced by dissolving or dispersing the compound represented by general formula [I] and a conductive salt in water or an organic solvent that can dissolve the conductive salt, and dipping the positive electrode and page turner for 80 minutes. “C~-20°C (preferably 30°C~0°C)
It can be obtained by a constant voltage method, a constant potential method, or a constant current method. Preferably, a constant voltage method is used.

Examples of catalysts that can be used in the chemical oxidative polymerization method include chlorides such as ferric chloride and cupric chloride, sulfates such as ferric sulfate and cupric sulfate, lead dioxide, and manganese dioxide. Examples include metal oxides, peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, quinones such as benzoquinone, halogens such as iodine and bromine, and potassium ferricyanide. Specific examples of these are disclosed in JP-A-63-213518, JP-A-63-193926, and JP-A-63-193926.
No. 2-116665, No. 62-104832, No. 63
-215717, 63-69823, 63-1
No. 01415, No. 60-58430, etc.

The amount of catalyst varies depending on the properties of the compound of the invention and the catalyst used, but the molar ratio of catalyst/compound of the invention is 0.
．． A range of 0.01 to 1O can be used.

Electrode materials that can be used in the electrolytic oxidative polymerization method include gold III electrodes (e.g., Pt, Ni, Cu
, Sn, Zn), carbon electrodes (e.g. Francie carbon), gold afII electrodes (e.g. 5n(it, 1
nJz) etc. Further, it is preferable to use a separate reference electrode.

Conductive salts that can be used in the electrolytic oxidative polymerization method include alkali metal cations (Li, Na, KΦ, etc.)
, No", No!・Cation, onium cation (Et4N・, BuJ・, [1u3P function, etc.) and negative ion (BF4e, AsF, θ, ^sF6θ, SbF&', 5
bcz,e,,pphe,'czo4θ,AZF,”
,,AZF,θ,NiF4ze,ZrPhg8,Tr
Pbffi8, B1°Ct,. 'θ, H5Oa6, S0
Salt consisting of 4'θ, C1θ, 8'8, po), sulfonic acid 72t7 (CIIzCallaSOse, ca
usso, e, CF, Sotθ, polystyrene sulfonic acid, etc.), salts containing carboxylic acid anions such as HCOOL+ and sodium polyacrylate, chlorides such as FeCl, and organic amine salts such as pyridine hydrochloride. etc. can be mentioned.

Examples of solvents that can be used in the chemical oxidative polymerization method and the electrolytic oxidative polymerization method include organic solvents (e.g., acetonitrile, dimethyl sulfuric acid, N,N-dimethylacetamide, N,
N-dimethylformamide, dimethyl sulfoxide,
Examples include sulfuran, formamide, dimethoxyethane, propylene carbonate, γ-butyl lactone, dioxane, methanol, ethanol, nitrobenzene, tetrahydrofuran, nitromethane, etc.), water, or a mixture of both.

Furthermore, a conductive compound may be added during chemical oxidative polymerization or electrolytic oxidative polymerization. As a conductive compound,
Inorganic acids (e.g. 11C!, HzSOs, II C/
O,,BF4), 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), organic bases (e.g. pyridine , triethanolamine). At the time of chemical oxidative polymerization, the above-mentioned conductive salt may be added.

Specific examples and synthesis examples of the present invention are shown below.

[Synthesis Example 2; Synthesis of Compound 1 of the Invention by Chemical Oxidative Polymerization] 2.16 g of Compounds I to 7, 1O-1Li (J
Stir 20 g of On and 0.15 d of hydrochloric acid and add lO'
An aqueous ammonium persulfate solution (ammonium persulfate/water = 1.14 g/10 m) was added dropwise over 1 hour. After the dropwise addition, the mixture was stirred for 3 hours, filtered, washed with water, and dried under vacuum at 80°C to obtain 1.85 g of Compound I of the present invention.

[Synthesis Example 3: Synthesis of an aqueous dispersion of Compound 1 of the Wood Invention by chemical oxidative polymerization method] In a 300 d 3 flask, 5 g of dextran, 10 g of compound 1-7, and 120 d of distilled water were placed and stirred under a nitrogen atmosphere. Add 48I of distilled water to this solution at room temperature while
40.3 g of FeCls 611zO dissolved in d 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
KAS [! 5ALIES CO[lP CEL
LULO5E TLIBING C-65 (manufactured by Sanko Junyami Co., Ltd.) was used to obtain an aqueous dispersion of Compound 1 of the present invention.

The average particle size of the resulting aqueous dispersion particles was 1105 nm (measured with a COIILTE II-N4 type submicron particle analyzer (manufactured by Coulter Electronics)).

Additionally, this aqueous dispersion is stable when stored at either 20°C or 5"C, and there is no sedimentation or aggregation of particles after 3 months of storage at either temperature. Ta.

Furthermore, there was no evidence of corruption.

C Synthesis Example 4: Synthesis of Compound 1 of the Present Invention by Electrolytic Oxidative Polymerization Method] 6.5 g of Compound 1-7, 7.5 C of LiCZO4, and 500 ml of acetonitrile were mixed while stirring, and a constant voltage was applied to both the positive and negative electrodes using PTL. Electrolytic polymerization was carried out for 30 minutes using the method (3V, 2/C) to obtain a film of compound 1 of the present invention (23-) on the negative electrode. Compound 1 was peeled off from the negative electrode and pulverized to obtain 0.42 g of the compound of the present invention.

[Synthesis Example 5] Compounds 2 to 21 of the present invention were synthesized according to Synthesis Examples 2 to 4 below.

[Synthesis Example 6] Synthesis of Comparative Compound 1> In Synthesis Example 3, instead of compound 1-7, aniline]O
Comparative compound 1 was obtained using g. The average particle size was 100 n-.

[Synthesis example 7] Comparative compounds 2 to 4 were synthesized according to Synthesis Example 2.4.

The conductive polymer of the present invention may be added to at least one of the constituent layers of the photographic light-sensitive material, for example, at least one of the halogen northern limit emulsion layer or other constituent layers of the photographic light-sensitive material.
It is a layer. Other constituent layers include, for example, a surface protective layer, a back layer, an intermediate layer, and an undercoat layer. Particularly preferred are a surface protective layer, a back layer, and an undercoat layer.

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

To add the conductive polymer of the present invention to a photographic material,
The powdered compound may be dissolved or suspended in water or an organic solvent such as methanol, isopropanol, acetone, etc., or a mixed solvent thereof, and then added to the coating solution for the surface protective layer or back layer, or the above-mentioned The aqueous dispersion may be added to the coating solution as it is, including dip coating, air knife coating, spraying, dipping, or extrusion coating using a hopper as described in U.S. Pat. No. 2,681,294.
Coating can be performed by a method such as a gravure coating method, a bar code method, or a spin code method.

In addition, when the conductive compound of the present invention is in the form of powder or lumps, mechanical pulverization methods (e.g., ball mill, dient mill,
fine particles (preferably, the average particle size is 0.5 ta or less, particularly preferably 0.0
．． 31! m or less), it can be applied by being included in the coating liquid. In this case, various surfactants, polymer compounds, or inorganic stabilizers may be added to stabilize the particles in the coating solution.

Further, if desired, 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 the conductive polymer used in the present invention is preferably 0.0001 to 2.0 g, preferably 0.0005 to 0.7 g, particularly 0.001 to 0.0 g per square meter of the photographic window light material. 3g is preferred.

The conductive polymers of the present invention may be used in combination of two or more.

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,
- black-and-white photosensitive materials for ray, black-and-white photosensitive materials for printing, etc.),
Ordinary multilayer color photosensitive materials (e.g. color negative film, color reversal film, color positive film, color negative film for movies, etc.)
Examples include infrared photosensitive materials for laser scanners and color photosensitive materials for X-ray.

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 Licenses-1ng), Volume 92, 10
pp. 7-110 (December 1971) and Research Disclosure magazine.
urt3>, vol. 176, pp. 22-31 (December 1978), vol. 238.

The description on pages 44-46 (1984) can be referred to.

The photographic emulsion layer or other hydrophilic colloid layer of the photographic light-sensitive material produced using the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, 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, alkylene oxide derivatives (e.g. 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-ionic materials such as polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. surfactant; alkyl carboxylate,
Al-cow sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurine, sulfosuccinate, sulfoalkyl polyoxyethylene alkylphenyl Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as ethers and polyoxyethylene alkyl phosphates; amino acids, aminoalkyl sulfones MM, aminoalkyl sulfates or phosphoric esters,
Ampholytic surfactants such as alkyl betaines and amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and aliphatic or heterocyclic Cationic surfactants such as phosphonium or sulfonium salts can be used.

These include Ryohei Oda et al.'s "Surfactants and Their Applications" (Yokoshoten, 1964), Hiroshi Horiguchi's "New Surfactants" (Sankyo Publishing ■, 1975), and "Matsuku Cations Detergent and Emulsifier". (Manufcation Divisions, MC Publishing Company, 1985) (rMc Cutch
eon's Detergents & Emulsi
Mc CuLcheon Divisio
ns, MC Publicis++ing Co, +198
5)), JP-A-60-76741, JP-A No. 62-1723
．． No. 13, No. 62-173459, No. 62-2152
No. 72, etc.

In addition, in the present invention, other antistatic agents may be used in combination,
For example, in particular, the fluorine-containing surfactants or polymers described in JP-A-62-215272, JP-A-60-76742
No. 60-80846, No. 60-80848, No. 60-80839, No. 60-76741, No. 58-
Nonionic surfactants described in JP-A No. 208743, etc., or JP-A-57-204540 and JP-A No. 6
Conductive polymer or latex (nonionic, anionic, cationic,
(both sexes) can be used.

Inorganic antistatic agents include ammonium, alkali metal, alkaline earth metal halogen salts, nitrates, perchlorates, sulfates, acetates, phosphates, thiocyanates, etc. Conductive tin oxide, zinc oxide, or a composite oxide obtained by doping antimony or the like with these metal oxides described in No. 57-118242 and the like 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 single or copolymers of polyvinylimidazole, polyvinylpyrazole, 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, bentanediol, butanediol, 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 have a spherical, spherical,
It may have a crystal shape such as a plate shape, or a composite shape of these crystal shapes.
Disclosure Volume 225, N[122534,2
0-58 pages, JP-A-58-127921, JP-A No. 58-1
They may be tabular grains as described in No. 13926, or may be composed of a mixture of grains of various crystal 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 sensitization can be imparted to the inside of the particle and/or the particle surface by placing the particle in an appropriate reducing atmosphere.

The silver halide emulsion may be freed of unnecessary soluble salts after the growth of silver halide grains has finished, or may be allowed to remain in the silver halide emulsion. It can be carried out based on the method described in Section.

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

Silver halide emulsions may have any grain size distribution. Emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (monodisperse emulsions) may be used. The monodisperse emulsion referred to here refers to one in which the standard deviation of the grain size distribution divided by the average grain size is 0.20 or less, where the grain size is spherical halogenated emulsion. In the case of silver, the diameter is shown; in the case of particles with a shape other than spherical, the diameter is shown when the projected image is converted to a circular image of the same area.) may be used alone or in combination of several types. A polydisperse emulsion and a monodisperse emulsion may be mixed and used.

Further, the emulsion used in the present invention is disclosed in US Pat. No. 2,996.
No. 382, No. 3,397,987, No. 3,705,8
As described in No. 58, 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. Here, JP-A-61-48
It is preferable to further use the mercapto compound described in No. 832 in combination to suppress capri and improve storage stability over time.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidas, soles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.: mercaptopyrimidines; mercaptotriazines , thioketo compounds such as oxazolinthione, niazaindenes, eg triazaindenes, tetraazaindenes 11! (especially 4-hydroxy substituted (1,3,3a,7)
Tetraazaindene, pentaazaindene, etc.;
Many compounds known as anti-capri agents or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.

The hydrophilic colloid layer of the photographic material of the present invention can contain polymer latexes well known in the art, such as homopolymers or copolymers of alkyl acrylate or polystyrene, and copolymers of vinylidene chloride. Polymer latex is disclosed in Japanese Patent Application Laid-Open No. 61-2301.
It may be stabilized in advance with a nonionic surfactant as described in No. 36.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, and quaternary ammonium for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain 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 black or various dyes such as oxonol dyes, azo dyes, azomethine dyes, styryl dyes, anthraquinone dyes, merocyanine dyes and tri(or di)allylmethane dyes may be used. Cationic polymers or latexes may then be used to prevent the dye from diffusing out of the antihalation layer.

These are Research Disclosure 1761°NQ
17643, Section 4. Furthermore, a magenta dye as described in JP-A-61-285445 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,
It is possible to use so-called mantle agents made of polystyrenes, methyl methacrylate-styrene sulfonic acid copolymer described in JP-A-63-216046, particles containing fluorine groups as described in JP-A-61-230136, etc. can.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer and other constituent layers. 3,5
-triacryloyl-hexahydro-8-triazine,
l, 3-vinylsulfonyl-2-propatol, etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-5-)riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination.

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

(In the formula CHtICH-5ow-CHth-8, B represents a divalent group, but may be omitted.

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

Research Disclosure as a developing agent.

Volume 176, page 29 Developing a
The one described in the section of gents J is 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, in JP-A No. 62-21
It is described in detail in No. 5272.

The developing process for the photographic light-sensitive material of the present invention may be either a process that forms a silver image (black and white development process) or a process that forms a color image.If an image is created by the reversal method, first black and white development process is performed. A negative development process is performed, followed by white exposure or color development by treatment with a bath containing a fogging agent. (Silver dye bleaching may be used, in which a silver image is created and this is used as a bleaching catalyst to bleach the dye.) The black and white development process includes a development process, a 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. Further, 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, or the developing process may be performed using a lithium developer as the developing solution.

Color development processing includes a color development processing process, a bleaching processing process,
A fixing process, a water washing process and, if desired, 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 to perform the bleach-fixing process. You can also do color development, bleaching,
It is also possible to carry out a monobath processing step using a one-bath development, bleach-fix processing solution in which fixing can be carried out in 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, a color developing agent, or An activator treatment step may be carried out in which the precursor is contained in the photosensitive material and the developing treatment is carried out using an activator solution, or the activator treatment can be applied to the monobath treatment.

The treatment temperature is usually selected in the range of 10°C to 65°C, but it may also be 65°C, preferably 25°C.
Processed between °C and 45 °C.

The black-and-white developer used in the black-and-white development process is commonly used in processing 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, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, surface overdevelopment inhibitors consisting of trace amounts of iodides and mercapto compounds, etc. can be mentioned.

Furthermore, in the case of X-ray photosensitive materials, efforts have been made to shorten the development processing time. Furthermore, means for simplifying processing have also been developed, and the conductive compound 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 Polyvinylidene chloride/itaconic acid (copolymerization molar ratio 97
A polyethylene terephthalate support (PET thickness: 175 IJs, vinylidene chloride layer thickness: 0.74) was prepared by applying: 3) and stretching on two wheels at 220°C.

After corona discharge treatment on one side of this support, poly(vinylidene chloride/itaconic acid/ethyl acrylate) (copolymerization molar ratio 92:3:5, added as an aqueous dispersion>(0,
05g/rd), gelatin aqueous solution (0.05g/rd)
, dichloro-hydroxytriazine soda (0,01g
/n(), p-octylphenoxy poly(polymerization degree 10
) A composition consisting of oxyethylene ether (0,005 g/bo) and the conductive polymer of the present invention or comparative compound shown in Table 1 was coated and dried at 140° C. to form an undercoat conductive layer. Furthermore, gelatin (0,2
R/m), α-sulfodihexyl succinate sodium salt (0,002 g/n(), poly(styrene/
divinylbenzene) (copolymerization ratio 98:2, average particle size 2.
Og) (0.02 g/I) and 1,3-divinylsulfonyl-2-propanol (0.005 g/I) were applied to form an undercoat protective layer.

Further, only the undercoat protective layer was coated on the other side of the support.

- j ws of 1 ゛The following dyes were ball milled by the following method. Water (21,
7d) and 6,7% Triton X-200? Surfactant aqueous solution (2,65g) (Rohm & llaa
(manufactured by S company) was placed in a 60ml screw cap bottle. 1.00 g of the dye below was added to this solution. Zirconium oxide (
Add ZrO) beads (40d) (2am diameter),
The lid was secured, the container 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, h). 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.

A dye surfactant (sodium p-octylphenylethoxyethoxyethanesulfonate) and a hardener (bis(vinyl-sulfonylmethyl)ether) were added to the dye-gelatin dispersion. The dispersion produced in this way is
Next, apply a dye coating amount of 0.08 on the base obtained in 1-1).
g/rrf, gelatin coating 110.4 g/rrf, surfactant 0.026 g/rrf and hardener 0.016 g
/rTI was applied to both sides.

30 g of gelatin, 5 g of potassium bromide, 0 potassium iodide in 12 of water in 1-3
．． Add 05 g of silver nitrate solution (5 g as silver nitrate) and iodizing power 'J0.
An aqueous solution of potassium bromide containing 73 g was added over 1 minute using a double jet method. Furthermore, a silver nitrate aqueous solution (145 g after removing 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 start of addition. After this, 0.37 g of potassium iodide aqueous solution was added.

After the addition was completed, soluble salts were removed at 35°C by the sedimentation method, the temperature was raised to 40°C, and 60 g of gelatin was continuously added.
pll was adjusted to 6.5. , the temperature was raised again to 56°C, and the sensitizing dye anhydro-5,5°-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt 650a+
After adding g, chemical sensitization using gold and sulfur sensitization was performed. The obtained emulsion had a hexagonal plate shape, a projected area diameter of 0.854, and an average thickness of 0.158.

This emulsion was added with 4-hydroxy-6-methyl- as a stabilizer.
1, 3, 3a,? -tetrazaindene and 2,6-bis(
hydroxyamino)-4-diethylamino-1,3,5
-) Added riazine and trimethylolpropane.

Furthermore, the following compounds were added <350rsg/rtf
) Furthermore, p-octylphenoxyjethoxyethoxyethanesulfonate sodium 0.01g/rd as a coating aid, dodecylbenzenesulfonate sodium 0.005g/rd, polybotacium p-vinylbenzenesulfonate 0.03g/fff as a thickener, and a polymer. latex (poly)
[Ethyl acrylate/methacrylic acid = 97/3] Particles containing poly[degree of polymerization 10] oxyethylene poly[degree of polymerization 3]
Oxyglyceryl dodecyl ether [3% by weight of particles]
adsorbed, average particle size = O, l*) 0.
4g/rrf, sodium polyacrylate (molecular weight 20
0.1 g/nf, 0.04 g/rrf of 1.2-bis(vinylsulfonylacetamido)ethane, and 0.05 g/nf of trimethylolpropane were added.

l-1 gelatin 1.2g/rrl polyacrylamide (molecular weight 45,000) 0.2g/bodextran (molecular weight 38,000) 0.2g/n
f Sodium polyacrylate 0.02g/r
rf polystyrene sulfonate soda 0.01g/r
RF colloidal silica (particle size 0.02-) 0.0
1g/Povoli (degree of polymerization 10) oxyethylene cetyl ether 0.02g/Povoli (
Polymerization degree 10) Oxyethylene poly(polymerization degree 3) Glyceryl p-octylphenyl ether 0.02g/rrlC
, 11.

CaF+vSOJ(CHzCIlzO)r(Cllgh
SOJa 0.0018/ITrO, 0005g/r
+( C11゜・I CvFltcONll(CIIthN-CIl□COO
θ 0.001g/Bo ■ C1l.

C, H.

C,F,SO,N(C8IC11ZOＤ-CIItCI
ICIl□0)-, H舊0)1 0.005g/rrf OH0.01g/Potassium nitrate 0.05g/rr
fp-t-octylphenoxyethoxyethoxyethoxyethanesulfonic acid sodium salt 0.01 g/rr
f4-hydroxy-6-methyl-1°3.3a,? -Tetrazaindene 0.04 g/rr
f Cetyl balmitate (0 particle size 0.114 dispersed with sodium dodecylbenzenesulfonate) 0.005g
/rrf dimethylsiloxane (dispersed with dioctyl-α-sodium sulfosuccinate. Particle size 0.12u) 0.005g
/ 0.005 g of liquid paraffin (dioctyl-α dispersed with sodium monosulfosuccinate. Particle size: 0.11μ)
#+r Polymethyl methacrylate fine particles (average particle size 3.8-54.8-2.8 I!m abundance 80% by weight or more) 0.04g/po5
The gelatin concentration is 4 for the above emulsion layer and protective layer for - and blue, respectively.
A solution was prepared so as to have a wt% concentration and was used as a basic formulation for each layer.

and! The base prepared in step-1) and coated with the dyed layer in step 1-2) was coated on both sides with a coating silver amount of 1.9 g/nf on one side. 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.

The samples prepared as shown in Table 1 were evaluated as follows.

Note that 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 Hou M10g Hydroquinone 83.3g Diethylene glycol 40g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 11.0g5-
Methylbenzotriazole 2g Adjust to 11 with water (adjust to pH 10.60).

Fixer Concentrate> Ammonium thiosulfate 560g Sodium sulfite 60g Ethylenediaminetetraacetic acid disodium trihydrate 0.10g Sodium hydroxide 248 Make IN with water (adjust to pH 5.10 with acetic acid).

<Development processing process> Developing tank 6. ! M 35℃xlO,5
Second fixing tank 6.54! 35°CX9
Second flush tank 6. ! M! 20'C
X 7.5 seconds dry
50°CDry to Dry processing time 0 45
seconds (total processing time including umbrella drying) When starting the development process, each tank was filled with the following processing solution.

Developing tank: 333 d of the above developer concentrate, 667 ml of water, and 10 d of starter containing 2 g of potassium bromide and 1.8 g of acetic acid were added to adjust the pH to 10.15.

Fixing tank 2: fixer fil liquid 250Ii and water 75
〇(1) Static mark test After conditioning the unexposed sample at 25°C and 10% IF for 2 hours, we tested the static mark on the sample against various materials in a dark room under the same air conditioning conditions. After rubbing the film with a rubber roller and a urethane roller to see if it would cause stains, it was developed with the developer described above, fixed, and washed with water, and the degree of occurrence of static marks was investigated.

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: Some static marks are observed.

C: Significant occurrence of static marks is observed.

D: Static marks are observed almost on the entire surface.

(2) Test with dust The sample (20 cm
X 20CIl) was thoroughly rubbed with gauze, and the adhesion of cigarette ash was examined. Evaluation was performed in the following four stages.

A: No dust was observed at all.

B: A little dust was observed.

C: Considerable dust was observed.

D= Severe dust adhesion was observed.

The dust stain test was conducted on both samples before and after development.

(3) Adhesion Test After the sample was left in an atmosphere of 150% R1+ at 25° C. for two weeks, an adhesion test was conducted in the following manner. The surface tested here was the surface provided with the base coat conductive layer.

(a) Adhesion test method for dry film On the surface to be tested, make 36 squares by making 7 cuts at 1 interval vertically and horizontally, and then apply adhesive tape (for example, Nitto Electric Industry Co., Ltd.) Attach knit tape) and quickly peel it off in a 180° 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 0.

Adhesive strength sufficient for practical use as a photographic material is one that is classified as grade A of the above three-level evaluation.

(Iff) Wet film adhesion test method At each stage of development, fixation, and water washing, scratch the film in the processing solution at the X mark using an iron pen, and then rub it strongly with your fingertip 5 times along the X line. Adhesion strength was evaluated during maximum peeling.

A case where the constituent layer does not peel off after the scratch is removed is graded A, a case where the maximum peeling is less than 5 minutes is graded B, and other cases are grade 0.

Adhesive strength sufficient for practical use as a photographic material is one that is rated at 8 or higher out of the above three grades, preferably classified as A grade.

(4) Coating properties The coating properties of the emulsion layer and protective layer were visually evaluated in 1-5 above.

The results are shown in Table 1. As can be seen from Table 1, the control sample 1-1, which does not contain the conductive polymer of the present invention, is significantly inferior in terms of static mark generation and dust adhesion.

On the other hand, samples 1-2 to 1 using the conductive polymer of the present invention
-4 was excellent in all evaluations, but samples 1-5 to 1-7 using conductive agent particles other than the present invention were accompanied by deterioration in adhesion, and sample 1 using conductive polymer -8
It can be seen that this is accompanied by static marks, deterioration of dust adhesion after processing, and deterioration of adhesion.

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 L 2 1L to 100g of silver per mol of silver in an aqueous gelatin solution kept at 50°C.
In the presence of XlO-' 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.
A silver chlorobromide monodispersed emulsion of 2- was prepared. (chloride 1195
(mol%) This emulsion was desalted by the flocculation method,
lag of thiourea dioxide per m mole and 0
．． 6 figs of chloroauric acid was added and aged at 65°C until maximum performance was obtained.

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

4X10-' mol/Ag mol KB r 20 mg
/rrrPolysretin sulfonic acid sodium salt 40 mg/Po2
．． 6-dichloro-6-hydroxy-! , 3.5-) Sodium riazine salt 30 tsg/I This coating solution was coated at a coating rate of 3.5 g/I.

2-2 The following compounds were further added to the 3I layer of Example 1. Note that the gelatin content was 1.5 g/rrf.

Dodecylbenzenesulfonic acid sodium salt 0.05g/nf
Sodium acetate 0.03g/i5
-Nitroduran 0.015g/rd
1.3-divinylsulfonyl-2-proparonol 0.05g/n1
N-perfluorooctanesulfonyl-N-propylglycinobotadium salt 2 +ig/ethyl acrylate latex (average particle size 0.14) 0.2 g/
Pogelatin 0.01g/Polyethyl acrylate latex (particle size 0.06m) 0.01g
/ rrlCo C0 NHC (CIIJzCIlzSOJa 0C11zC
)1tOcOc11zcIIzs(ltclI=cII
zO,003g/Po conductive agent (see Table 2) -Ba...
Gelatin 2.5 g/PoC
11i-CC-CII CC-Cll51.3-divinylsulfonyl rune 2-propatool 150 yag/poethyl acrylate latex (average particle size 0.14) 900 mg/
n(dihexyl-α-sulfosuccinate sodium salt 35 tag/r
rr Dodecylbenzenesulfonic acid sodium salt 35 mg/n1
-5 BA・i 几Produced in the same manner as the undercoat protective layer of Example 1. Note that the gelatin content was 1.0 g/pot.

The coating sample was a PET base with only the vinylidene chloride undercoat layer of Example 1 applied to both sides (no conductive undercoat layer).
A back lower layer, a bank layer and a back protective layer were simultaneously coated in this order on one side, 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.

Samples 2-2 to 2 created using the conductive polymer of the present invention
-4 is the static mark occurrence rate as seen from Table 2.
It has excellent dust retention and adhesive properties.

On the other hand, control sample 2-1 and samples 2-6 to 2-8 using comparative compounds cannot satisfy all of the static marks, dust, coating properties, and adhesive properties.

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 a silver chlorobromide monodispersed emulsion was prepared as sample 202 of Example 3 of JP-A No. 63-264740.
Color photographic negative film samples 3-1 to 3-8 were prepared in exactly the same manner as in Example 2, except that the composition of the photosensitive layer was changed from the first layer to the 14th layer. (Processing was done in JP-A-63-26
4740, Example 3).

Samples 3-2 to 3-4 of the present invention satisfied all of the characteristics of static adhesive, dust adhesion, adhesion, and coatability.

On the other hand, comparative samples 3-5 to 3-8 and control sample 3-
No. 1 could not satisfy all of the above performance requirements.

Example 4 JP-A-63-2 on one side of cellulose triacetate support
The photosensitive N composition of Sample 104 of Example 2 of No. 64740 was applied. The back layer on the other side was coated with the following composition.

Conductive agent (see Table 3) Diethylene glycol 10 tag/I (applied using a mixed solvent of acetone/methanol/water) 1 Bag 111 L Diacetyl cellulose 200 mg/Istearin III 10 tx
g/pocetyl stearate 20 mg
/rrf Silica particles (particle size 0.34) 30
mg/rd (coated using a mixed solvent of acetone/methanol/water) The treatment was in accordance with Example 2 of JP-A-63-264740.

The obtained samples 4-1 to 4-8 were evaluated in the same manner as in Example 1, respectively.

Samples 4-2 to 4-4 of the present invention satisfied all of the static marks, dust, adhesion, and coating properties, and excellent images were obtained.

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

Example 5 Weighed 1.5 g of sodium dodecyl nitrate into a 12-3 flask equipped with a stirring device and a reflux tube, and added 300 g of water.
The reaction vessel was then heated at 75° under a stream of cold air.
The temperature is raised to C and stirred at 200 rpm. Here, 3%
40 g of potassium persulfate aqueous solution was added, 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 over 3 hours.

3% potassium persulfate Lo 6 times in total every 30 minutes after the start of dripping
g was added. After the completion of dropping the monomer mixture, the reaction vessel was kept at 75° C. for another 2 hours to obtain an aqueous 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 7.5.

2゜4-dichloro-6-hydroxy-1,3,5-) riazine sodium salt was added in an amount of 4% by weight of the copolymer into the aqueous dispersion of the copolymer obtained in step II K. Furthermore, the average particle size 2
A liquid to which polystyrene fine particles were added such that 1.0 mg/rrf of polystyrene fine particles of - was added was used as a coating liquid for the first undercoat layer.

A biaxially stretched polyethylene terephthalate film with a thickness of 100-1/30 cm was subjected to corona discharge treatment under the following conditions. The film transport speed was 30 m/min, and the gap between the corona discharge electrode and the polyethylene terephthalate film was 1.
8 mm, and the power was 200 watts. The above coating solution for the first undercoat layer was coated on both sides of the polyethylene terephthalate treated with corona discharge using a bar coater method to a dry film thickness of 0.1 -, and dried at 185°C. This layer is called the first undercoat layer.

Corona discharge was performed on the undercoat layer on the emulsion layer side prepared using the above-mentioned ILJJUU method, with a film transport speed of 30 m/min, a distance between the corona discharge electrode and the film of 1.8 mm, and a power of 120 watts. Vinylidene chloride/methyl methacrylate/
Methyl acrylate/acrylonitrile/acrylic acid (
An aqueous dispersion of a copolymer (90/4.5/4/l 10.5% by weight) was applied using a gravure coater to a dry film thickness of 0.4 trm, and the coating was carried out at 120°C. This layer is called the second undercoat layer.

On top of the 2N undercoat prepared in 20.3.c), a treatment was applied at 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 an N force of 250 watts.
On top of that, as the third layer of undercoat, apply the undercoat liquid of the following prescription knee (a) by extrusion method to 20 d/n (17 d/n).
It was dried at 0'C to form a third undercoat layer on the side of the emulsion layer.

knee a + -3+' lugelatin
1.0% by weight methyl cellulose
0.05% by weight C1□lhs (ClbCIl
gO)n+lI 0.03% by weight water was added to make the emulsion layer side undercoat to 100% by weight or more.

- On the opposite side of the polyethylene terephthalate film with the emulsion layer side undercoat prepared in step 5-1), apply the first emulsion layer side undercoat.
A first layer of undercoat on the back layer side was applied in exactly the same manner as the layer.

A second back layer side undercoat layer was prepared on top of the back layer side undercoat 1N obtained in the previous section (a) of Robar in exactly the same manner as the second emulsion layer side undercoat layer.

The film was conveyed at a speed of 30 m/min, and the gap between the corona discharge electrode and the film was set at 1.
8 mm and a power of 250 watts, and a coating solution of the following prescription bar (a) was applied thereon at a rate of 20 d/n to form a third undercoat layer on the back layer side.

Bar a Tsuma 1' Gelatin 1.0% by weight Methyl cellulose 0.05% by weight C+ x II t
5o(CHtcIl to)-roll
Add 0.03% water by weight 100
wt% -5-3 halonone per mole of silver in an aqueous gelatin solution maintained 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.
A silver chlorobromide monodisperse emulsion of 2 Misaki was prepared. (Silver chloride 95 mol%) This emulsion was desalted by the flocculation method,
T! lag of thiourea dioxide and 0.6 mg of chloroauric acid per mole were added and aged at 65°C until maximum performance was obtained.

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

2X10-''mol/Agmol 4X10-''mol/Agmol KBr 20
mg/rd polystyrene sulfonic acid sodium salt 40mg/a2.
6-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 30 mg/m This coating solution was coated at a coating amount of 3.5 g/m.

52'' L elbow gelatin 1.5 g/rr
fSing fine particles (average particle size 44) 50
B/Idodecylbenzenesulfonic acid sodium salt 50 mg/■f
H 5-nitroindazole 1.5 mg 7M
1.3-Divinylsulfonyl-2-provalonol 50 wrg#r
rN-perfluorooctanesulfonyl-N-propylglycinobotadium salt 2 erg/M ethyl acrylate latex (average particle size 0.14) 300 mg
/bogelatin 2.5 g/
A C1b-CC=CII CC-CHll, 3-divinylsulfonyl-2-propatol 150 g/ethyl acrylate latex (average particle size 0.1-) 900 mg
/ posihexyl-α-sulfosuccinate sodium salt 35 mg 7M dodecylbenzenesulfonic acid sodium salt 35 B/bo 6
Ba i Solid gelatin 0.8 g/polymethyl methacrylate fine particles (average particle size 34) 20 mg/c
d-dihexyl-α-sulfosuccinate sodium salt 10 mg/rd
Dodecylbenzenesulfonic acid sodium salt 1.0 mg/sodium polyacetate 40 11 g/po The development process was carried out using the FG-660 automatic processor manufactured by Fuji Photo Film Co., Ltd., and the developing solution and fixing solution were GRD-1 and GRF manufactured by the same company.
-1 under the treatment conditions of 38°C and 20 seconds. The drying temperature at that time was 45°C.

The obtained samples 5-1 to 5-8 were evaluated in the same manner as in Example 1, respectively.

Samples 5-2 to 5-4 of the present invention satisfied all of the static marks, dust, adhesion, and coating properties, and also had excellent images.

On the other hand, control sample 5-1 and comparative sample 5-5-5-
No. 8 cannot satisfy all of these requirements, and it is clear that the present invention is superior to the conventional technology.

Claims (1)

[Scope of Claims] 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 compound represented by the following general formula [I]. 1. A silver halide photographic material comprising a conductive polymer obtained by oxidative polymerization of at least one of the following. General formula [I] Y-[-(X)-_a-{-(R_1-O)-_nR_
2}_m]_b (where Y represents a group capable of forming a polymer through oxidative polymerization, X represents a linking group, R_1 represents an optionally substituted alkylene group, and R_2 represents a hydrogen atom or each substituted represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group, a carbamoyl group, or a sulfonyl group, which may be substituted. a represents 0 or 1, b represents an integer from 1 to 4,
m represents an integer from 1 to 3, and n represents an integer from 2 to 30. However, when b>1, -(X)-_a-{-(R_
1-O)-_nR_2}_m may be the same or different. Also, when m>1, -(R_1-O)-_n
R_2 may be the same or different. Further, when n≧3, the n R_1s may be the same or different. )