JPH02282247A - 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, etc., R<1> and R<2> or R<1> and R<3> and/or R<2> and R<4> may form a ring and R<5> is H, alkyl, etc. The polymer obtd. from the compd. represented by the formula, e.g., pyrrole is preferably produced by chemical or electrochemical oxidation polymn. The polymer is also preferably produced by subjecting the pyrrole compd. to oxidation polymn, in the presence of one or more kinds of dispersants such as gelatin and a surfactant.

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 light-sensitive material "hereinafter referred to as photographic light-sensitive material" (hereinafter referred to as 1).

(Prior Art) Photographic materials generally consist of an electrically insulating support and a photographic layer, so contact friction or peeling occurs between surfaces of the same or different materials during the manufacturing process and during use of the photographic materials. Electrostatic charge often builds up as you move. 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 the development process. When this happens, it produces dotted cotton tufts or dendritic or feather-like cotton tufts. This is what is called a static mark, and it significantly reduces the commercial value of photographic film, and in some cases causes the film to lose its commercial value altogether.

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

As mentioned above, such electrostatic charges are generated due to contact separation between mechanical parts and the like during the production of photographic photosensitive materials* or in various automatic photographing machines.

Particularly in recent years, 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 have made scratch marks more likely to occur. There is. 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 unique to photographic light-sensitive materials.
Zuru. In other words, antistatic agents that can be used in photographic light-sensitive materials not only have excellent antistatic properties, but also do not have an adverse effect on photographic properties such as the sensitivity of photographic +A fi, fog, graininess, and sharpness. That is, photographic sensitivity +41'
It should not have an adverse effect on the film strength of the second l, it should not have an adverse effect on the adhesion resistance, it should not hasten the fatigue of the processing solution of the photographic light-sensitive material, it should not contaminate the conveying roller, and it should not have an adverse effect on the film strength of the photographic light-sensitive 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 reduce the electrical conductivity of the surface of the photographic material so that the static charge can be dissipated in a short period of time before the accumulated charge is discharged. This is an effective means especially 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, and may cause dust to lose conductivity after processing. , these substances are humidity dependent and may cause static at low humidity, or may be accompanied by deterioration of photographic performance, coatability, or transparency, or may cause deterioration of adhesion. It was extremely difficult to apply.

Furthermore, the above-mentioned problems have not been solved with the polyphosphazene described in JP-A No. 64-6875 and the polyaniline described in U.S. Pat. No. 4,2371.94.

(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.

Second, the present invention aims to provide a photographic material that has excellent antistatic properties even after development and is free from dust.

Thirdly, it is necessary 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 halogenated photosensitive material containing a polymer obtained from a heterocyclic compound represented by the following format (1).

General formula (1) where R1 and R2 or R1 and R3 and/or R2 and R4
together form a ring. In this case, one or two in the ring
may contain more than one heteroatom.

Furthermore, R1, R2, R3 and R4 are hydrogen atoms, halogen atoms (e.g. fluorine, chlorine, bromine), alkyl groups,
Aryl group, hydroxyl group, alkoxy group, aryloxy group, amino group, alkylamino group, 21,4 group, cyano group, -N l-I COR'N HS O2R6S OR
6S O2R6SO,NR'-COR6-CONR
'R8Re C001(, -C00R6S O3H 2N, heterocyclic group (e.g. triazole, thiazole,
Henzthiazole, furan, pyridine, quinaldine, henzoxazole, pyrimidine, oxazole, imidazole). R5 represents a hydrogen atom, an alkyl group or an aryl group. R6 represents an alkyl group or an aryl group. R7 and R11 may be the same or different and represent a hydrogen atom, an alkyl group or an aryl group.

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

where R1 and R2 or R1 and R3 and/or R2 and R4
together form a ring. In this case, one or two in the ring
may contain more than one heteroatom.

Furthermore, R1, R2, R3 and R4 are hydrogen atoms, halogen atoms (e.g. fluorine, chlorine, bromine), alkyl groups,
Aryl group, hydroxyl group, alkoxy group, aryloxy group, amino group, alkylamino group (may be ring-fused), 21.4 group, cyano group, N II COR''' -Nl
'(SO2R'''-3OR'5O7R'= -3o
□NR7-COR'CONR', -COOI(, -C
OOR6RI' S 011 (--S I-1, represents a heterocyclic group (e.g., triazole, thiazole, henzthiazole, furan, pyridine, quinaldine, henzoxazole, pyrimidine, oxazole, imidazole). R5 is a hydrogen atom, an alkyl group or represents an aryl group.R6 represents an argyl group or an aryl group.

R7 and R8 may be the same or different and represent a hydrogen atom, an alkyl group or an aryl group.

Furthermore, an alkyl group, an aryl group, an alco=t-cy group, an aryloxy group of R1, R2, R3 and R4 in "2.
The alkylamino group may be further substituted. Also,
The above-mentioned R', R', R7 and R8's alni)-yl group and ari-yl group may also be further substituted (mulberry). Examples of these substituents include alkoxy groups (e.g. , methoxy, ethoxy), aryoloxy groups (e.g., phenyloxy), alkoxycarbonyl groups (e.g., methoxycarbonyl), acylamino groups (
For example, acetylamino), carbamoyl group, alkylcarbamoyl group (e.g., methylcarbamoyl, ethylcarbamoyl), dialkylcarbamoyl group (e.g.,
dimethylcarbamoyl), arylcarbamoyl group (e.g. phenylcarbamoyl), alkylsulfonyl group (e.g. methylsulfonyl), arylsulfonyl group (e.g. phenylsulfonyl), alkylsulfonamide group (e.g. methanesulfonamide), sulfonamide groups (e.g. phenylsulfonamide),
Sulfamoyl group, alkylsulfamoyl group (e.g. ethylsulfamoyl), dialkylsulfamoyl W (e.g. dimethylcarbamoyl), alkylthio group (e.g. methylthio), arylthio group (e.g.
phenylthio), amine groups, alkylamino groups, cyano groups, nitro groups, halogen atoms (e.g. fluorine, chlorine,
(bromine), and when there are two or more of these substituents, 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.

CH3C2I].

CH.

CH3 CH3 Cz Hs ■] [( CH:1 CH:l Hereinafter, a method for producing a polymer obtained from a heterocyclic compound will be described.

The polymer obtained from the heterocyclic compound represented by the general formula (I) 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, C1Khulbe et al.
science Polymer Chemistry
Edition) Volume 20, Page 1089 (1982)
reported that when pyrrole was oxidized with potassium persulfate in an aqueous solution, a black powder polymer 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, henzonitrile, propionitrile, dimethyl sulfoxide, dimethyl formamide, propylene carbonate, dimethyl acetamide, etc. are used, but are not limited to these.

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

Specific examples of these are disclosed in JP-A-63-213518 and JP-A-63-213518.
No. 3-193926, No. 62-116665, No. 62
-104832, 6321, 5717, 63-
No. 69823, No. 63101415, No. 60-584
It is described in No. 30, etc. The amount of catalyst varies depending on the properties of the compound represented by formula (T) and the catalyst used. However, in general, the molar ratio of catalyst/-compound of general formula 1) ranges from 0.01 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. For example, put polyvinyl alcohol, thiophene, and distilled water in a flask, and add F as a catalyst while stirring under a nitrogen atmosphere.
eCj2. Examples include, but are not limited to, a method of dropping an aqueous solution of.

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

In addition, solvents that can be used to produce an aqueous dispersion 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, acetonitrile, dimethyl sulfate, N,N-dimethylacetamide) may be mixed. If the heterocyclic compound to be further polymerized is insoluble in these solvents, a co-solvent may be used.

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, polyvinylpyrrolidone, and the like.

Examples of amphoteric polymers include gelatin, 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, oxonium base, sulfonium base, etc. in their structure.

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

-(-C' N2 CH->- C=N N3 N　HC-N　T(2 N1-cho2・C1(3CO○0 (-CH2 H3 Cl C-○ ・C) (3C00゜ c) l 3 CH.

Cl1JCOO0 (-CI(2 CI-)) As the component used as the anionic light molecule, a commonly used and known polymer having anionic surface properties can be used. Preferably, a latex produced by an emulsion polymerization method is used. Anionic surface properties can be introduced in a variety of ways, for example by polymerizing ethylenically unsaturated monomers with anionic groups, such as sulfonic acid groups, or mixtures with ethylenically unsaturated monomers, which possess anionic surface properties. It is a method for synthesizing latex. Salts of 2-acrylamido-2-methylpropanesulfonic acid and vinylhenzenesulfonic acid can be used for this purpose, but ethylene can introduce anionic surface properties into other polymers. Polymer unsaturated monomers 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 to be used are listed below, but are not limited to gore.

Examples of anionic surfactants include the following.

C,,N25COONa Cllll37COONa C+ + H2z CON CHz C○0NaCH* C+ IH23CON CH2CH2COON aH3 CH□C00C,H,7 Na03SCHCOOCeH+v N2. Cl-CHCN25o3Na +HHCI-(C1'1zCH2SO3NaH21-f2SO(5sO2Na of CI-1, 1-
(3, C0NCH2CH25○3 NaH3 03Na 0JNa CH2COOHbH1:+ pJa ○] S Cl-I C00Cb Hl 3C
I2H250S 03N a Further, specific examples of the surfactant used in the production of 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.

Cl-1.

C, 2H2r, NH CeL) CI 2 H250 (CH2CH20) lo HCI
b 1 block 330 (CI'I2 CHz O) 20
HCI(.

CI-1.

C+zl■z.

N-Cl■.

CI! 0 CH.

H 0-1゜C++HziCONHCIIzCN(zCJ(z-CI
Examples of IJ le tl 3 acid ester nonionic surfactants include the following.

H ~26 CH3 Examples of amphoteric surfactants include the following.

CH.

C+ z H2S N CH2C○0°CH.

CH* Cl6H33N CH2CO00 CH.

C,,H2,C0NHCH2CT(2CH2-NC)1
2COO0CI.

H3 CI3H27CONHCH□CH2CH2-, NCH2
COO○ H3 ''+H3 CON I-i CH2CH2CH2 N-CH2CH2CH, CH25○3゜ H3 The amount of dispersant used for dispersing the heterocyclic compound is 1 to 300% by weight, preferably 5% by weight based on the heterocyclic compound. ~
It is 200% by weight. In addition, various surfactants have the general formula (
+) 0.01 to 50% by weight based on the compound represented by
, preferably 0. 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.

Moreover, a conductive compound can be added to the aqueous dispersion of the present invention in order to further improve the conductivity of the molded article. These conductive compounds may be added before or after oxidative polymerization, 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 (Li", Na"K1, etc.), NO'
, NO2', cation, onium cation (Et4
N”, BuaN”, Bu3P”, etc.) and negative ions (B
F4-, As F4-, As FbSbF6
−． 5bcxa-, PFb-, C1204A A F
4-, AIFb-, NIF4'-, Z
rF62T i Fb2-, T i F6"-,
B+oCj2+o"\CffBr-, F-, H3O4-
, SO4”-, etc.), sulfonic acid anions (C
H3Cb l-(,lS O3c6H9SO,-,CF
: ISO, -, etc.), salts containing carboxylic acid anions such as HCOOL i, chlorides such as FeCβ3, and organic amines, inorganic acids (e.g. HCA, H
2S O, HCe o , HB F a), organic acids (e.g. toluenesulfonic acid, I-fluoromethylsulfonic acid, sulfonic acids such as polystyrene sulfonic acid, formic acid, acetic acid, polyacrylic acid) carboxylic acid)
Or, 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-butadiene rubber, butadiene rubber, Synthetic rubbers such as isoprene rubber, butyl rubber, nitrile rubber, chloroprene rubber, ethylene-propylene rubber, polyvinyl acetate polymers, polystyrene polymers, polyethylene polymers, poly(meth)acrylate ester polymers, etc. can be used. , but not limited to these. Preferably, these polymeric compounds are emulsions.

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, G. Tourillon et al.
nal of Electroanalytical
Chemistry) et al., vol. 135, p. 173 (198
2) Indole (C4H9)4HCAO4? It has been reported that electropolymerization in dissolved acetonitrile produces a polyindole film on the working electrode.

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.

Dobin may also be used with a conductive 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) 5 g of dextran was placed in a 300+++f 30 flask.
Take pyrovirol log and 120 ml of distilled water and add 4 ml of distilled water to this solution at room temperature while stirring under nitrogen atmosphere.
70 g of F,e CC3.6H20 dissolved in 8 ml 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 (VrS
KASIE 5ALES C0RP CELLIILO
5E TUBING C-65 made by Sanko Junyaku 0 Sakaki)
, an aqueous dispersion of polypyrovirol was obtained.

The average particle size of the obtained polypyrovirol particles was 120 nm.
(measured with COULTER-N4 type submicron particle analyzer (Coulter Electronics@)).

Moreover, when this aqueous dispersion was stored at 20°C,
It is also stable even at 5°C 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, 0.05 g of sodium lauryl sulfate
,,As a result of synthesis and dialysis in the same manner as in Synthesis Example 1, except that log benzenesulfonic acid l-butylammonium salt was added together with pyrovirol as a conductive salt, Synthesis Example 1
Polypyrovirol aqueous dispersion (average particle size 1
00 nm) was obtained.

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 indole was used instead of pyropyrrole. A stable aqueous polyindole dispersion (average particle size: 140 nm) in which no aggregation of particles was observed was obtained.

Synthesis Example 4 (Synthesis of aqueous dispersion 4) Instead of dextran, Cl 2 Hz s O(CH
2CH20) 0, 5 g, Fe Cj23
-6 As a result of synthesis and dialysis in the same manner as in Synthesis Example except that 50 g of ammonium persulfate was used instead of H20, a polypyrovirol aqueous dispersion having a stable average particle size of 80 nm as in Synthesis Example 1 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.

Synthesis Example 23 (Synthesis of Comparative Compound 1) Indole log in a 300 ml 3 tube flask.

(C4H9)aNBF45 g and acetonitrile 20
Take 0 ml and add 70 g of FeC dissolved in 30 ml of distilled water to this solution at room temperature while stirring under nitrogen atmosphere.
β3.6H20 was added dropwise over 30 minutes. As the mixture was added, heat was generated and a black solid was formed. After further stirring for 2 hours, the obtained solid was collected by filtration and dried to obtain Compound 1.

Synthesis Examples 24-32 (Synthesis of Compounds 2-1o) Synthesis Example 2
In the same manner as in 3, the i-mers shown in the table below were chemically oxidized and polymerized,
Compounds 2-1o were obtained. Here, the amount of monomeric conductive salt is the same as in Synthesis Example 23.

Synthesis Example 33 (Synthesis of Compound 11) Using 2 g of indole, (C4Hq), and 44 g of NBF dissolved in 200 ml of acetonitrile as an electrolyte, a PT plate was used as a working electrode and a counter electrode, and an Ag/Agc1 electrode was used as a reference electrode. When electrochemically polymerized for 30 minutes at a constant voltage of .8 V, a polyindole film was formed 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) Synthesis Example 4
Monomers shown in the table below were electrochemically polymerized in the same manner as in Example 5 to obtain Compounds 12 to 18. Here, the amounts of monomer and conductive salt are the same as in Synthesis Example 33.

Synthesis Example 41 (Synthesis of Comparative Compound 1) Synthesis was carried out in the same manner as Synthesis Example 23 except that 10 g of virol was used instead of indole, and a solid was precipitated. The obtained solid was collected by filtration and dried to obtain Comparative Compound 1.

Synthesis Example 42 (Synthesis of Comparative Compound 2) 2 g of indole and 44 g of (C4H9)4NB F were dissolved in 200 g of acetonitrile as electrolyte solution 38. A PT plate was used as a working electrode and a counter electrode, and a saturated calomel electrode was used as a reference electrode. When electrochemical polymerization was carried out using a constant voltage of 0.5 V for 30 minutes, a polypyrrole film was formed on the working electrode. The obtained film was peeled off from the electrode and dried to obtain Comparative Compound 2.

Synthesis Example 43 (Synthesis of Comparative Compound 3) Comparative Compound 3 was obtained by synthesizing in the same manner as Synthesis Example 41 using aniline hydrochloride instead of virol.

Synthesis Example 44 (Synthesis of Comparative Compound 4) Synthesis Example 4 using aniline hydrochloride instead of virol
Comparative compound 4 was obtained by synthesizing in the same manner as 2.

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

When the surface protective layer, bank 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 represented by the general formula (1) used in the present invention to a photographic light-sensitive material, the powder is dissolved or suspended in water, an organic solvent such as methanol, isopropanol, acetone, etc., or a mixed solvent thereof. After that, it may be added to the coating solution for the surface protective layer or hack layer, or it may be added as the aqueous dispersion as described above, and it may be added to Disopco-1 by air knife coating, spraying, or U.S. Patent No. 2,681. ,29
It is coated by the extrusion coating method using a hopper as described in US Pat. No. 3,508.94.
No. 7, No. 2,941,898, No. 3526.528, etc., two or more layers may be applied simultaneously, or they may be immersed in an antistatic liquid.

Further, if necessary, an antistatic liquid (solution alone or containing a binder) containing the compound of the present invention may be further coated on the protective layer.

The usage amount of each compound represented by the general formula (r) of the present invention is 0.0001 per square meter of the photographic light-sensitive material.
~2.0g is preferably present, preferably 0.000g.
The amount is 5 to 0.7 g, particularly preferably 0.001 to 0.3 g.

Two or more types of each of the polythianaphthene compounds 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 films for movies, etc.), infrared light sensitive materials for racer scanners, etc.

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, pine I agents, brighteners, spectral sensitizers, dyes, ultraviolet absorbers, etc.
oduct Licensing) Volume 92, 107-11
Page 0 (December 1971) and Research Disclosure (1? esearchDisclosure)
Volume 176, pages 22-31 (December 197f1), same 2
The description in Vol. 38, 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 JJ, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g., development acceleration). Various surfactants may be included for various purposes such as increasing contrast, increasing contrast, and increasing sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/Voripl:I pyrene glycol condensate,
Polyethylene glycol alkyl ethers or polyethylene glycol alcohol:) - aryl ethers, polyethylene glycol esters, polyethylene glycol albicune esters, polyalkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicone), glycidol derivatives ( Nonionic surfactants such as alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates,
Alkylhenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkylpolyoxyethylene algyl phenyl ether chains, Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as polyoxyethylene alkyl phosphates; amino acids, aminoalkylsulfonic acids, amino Ampholytic surfactants such as alkyl sulfates or phosphates, alkylhetaines, and amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, and heterocyclic quaternary ammoniums such as pyridinium and imidazolium. Cationic surfactants such as salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

These are Ryohei Oda et al. [Surfactants and their Applications] (Maki Shoten, 1964), Hiroshi Horiguchi "New Surfactants" (Sankyo Publishing ■, 1975), and "Hook Cations Detergents and Emulsions". Fires J (
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 the present invention, other antistatic agents may also be used in combination, for example, the fluorine-containing surfactants or polymers described in Japanese Patent Application No. 6132462, Japanese Patent Application Laid-Open Nos. 60-76742 and 60-80846. No. 60-80848, No. 6
No. 0-80839, No. 60-7674.1, No. 58-
208743, etc., or also JP-A-57-204-540,
Conductive polymers or latexes (nonionic, anionic, cationic, amphoteric) described in Japanese Patent Application No. 61-32462 may be used. Also, examples of inorganic antistatic agents include ammonium, alkali metals, and alkali+B:! H metal salts, 1iii salts, perchlorates, sulfates, acetates, phosphates, thiocyanates, etc. are also used as conductive tin oxides as described in JP-A-57-118242, etc. ,
A composite oxide obtained by doping zinc oxide or these metal oxides with antimony or 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.
can also be used.

For example, seratin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, sodium alkinate, dexI-lan, starch KA & Sugar derivatives such as polyvinyl alcohol, polyvinyl alcohol moiety acecolyte, poly-N-vinyl bi-1 coliton, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinyl virazole, etc., as single or copolymers. You can see and discover the synthetic hydrophilic polymer materials.

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

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

In the hydrophilic colloid layer of the photographic light-sensitive material of the present invention, polyols such as trimethylolpropane, tantanediol, butandionopeethylene glycol, glycerin, and sorbitol can be used as plasticizers.

The silver halide grains in the photographic emulsion used in the photographic light-sensitive material of the present invention are regular (re) grains such as cubes and octahedrons.
It may have a spherical or plate-like crystal shape, or it may have a composite shape of these crystal shapes. A, 22 Evening 3 Q,
ao~ty page (lliggυ3g/), JP-A-Shoj, l'-/
, No. 279.2/, and No. 3r//3722. 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 at least seven types selected from complex salts (including 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 placing the particle in an appropriate reducing atmosphere.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure A/7.44f-311.

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

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). When divided by the average grain size, the value is 0, -!0 or less.Here, the grain size is the diameter in the case of spherical silver halide, and in the case of grains with a shape other than spherical, This indicates the diameter when the projected image is converted into a circular image of the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

Further, the emulsion used in the present invention is disclosed in US Patent λ.

97 otsu, 3 and 2, same 3, 3 tough, ri f7, same 3゜70j
As described in , and 5'g, a mixed emulsion of a light-sensitive silver halide emulsion and an internally puffed silver halide emulsion or an emulsion used in combination in a separate layer may be used.

Here, it is preferable to further use the mercapto compound described in Japanese Patent Application Shojter/70jgg from the viewpoint 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. such as benzotriazoles, nitrobencitriazoles, mercaptotetrazoles (especially l-phenyl-j-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines, such as thioketo compounds such as oxadorinthion; azaindenes, such as triazoles; Zaindenes, tetraazaindenes (% 4I--hydroxy substitution ('+ 3t 3a, 7
) tetraazaindenes], tetraazaindenes; 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 well known in the industry, such as a homopolymer or copolymer of alkyl acrylate or a copolymer of vinylidene chloride. /-λ30/31. (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 contains, for example, polyalkylene oxide or its ether, derivatives such as estenopeamine, thionityl compounds, thiomorpholines, quaternary It may also contain 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 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. In that case, the dye is anti-
- Cationic polymers or latex may be used to prevent diffusion from the ration layer.

These are Research Disclosure / Volume 7J! ,
/ 71≠3, described in item ■. In addition, in order to improve the color tone of developed silver, a patent application was filed in Showa 1. Magenta dyes such as those described in No. o-127tt3 may also be used.

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 as described in the patent application No. -Styrene sulfonic acid copolymer, JP-A-1/-230
t31. It is possible to use a so-called matting agent made of particles containing fluorine groups as described in No.

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.), activated vinyl compounds (/, 3.S
-) lyacryloylhexahydro-5-) riazine, l
, 3-vinylsulfonyl-2-prono? Solnato),
Active halogen compounds such as (2,≠-dichloro-t-hydroxy-5-)riazine, mucohalogen acids (mucochloric acid, mucophenoxychloric acid nat), and the like can be used alone or in combination.

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

(CH22cn-so2-CH2-)-2A In the formula, A represents a monovalent group, but it may also be used.

The photographic material of the present invention contains a developing agent.

As a developing agent, Research Disclosure No. 17
Volume 1, page 2 rDeveloping age -
The one listed under ntsJ 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, Japanese Patent Application No. 1987;/-3
It is described in detail in No. 2≠6λ.

The developing process for the photographic light-sensitive material of the present invention may be either a process for forming a silver image (black and white development process) or a process for forming a color image. If an image is to be produced by the reversal method, a black and white negative development step is first carried out, and then a color development process is carried out by applying white exposure or processing with a bath containing a fogging agent. (Silver dye bleaching may also be used, in which a dye is contained in 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 are performed as necessary, but instead of the process using a bleach solution and the process using a fixer, a l-bath bleach-fix solution is used for bleach-fixing. It is also possible to carry out a monobath processing step using a l-bath development, bleach-fix processing solution in which color development, bleaching and fixing can be carried out in a bath.

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

The treatment temperature is usually selected in the range of 1000 to 6 t'(', but it may be set to a temperature exceeding 6 0 C).

Preferably, the treatment is performed with 2s OC-≠s Oc.

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, and methylbenzthiazole, water softeners such as BoIJ phosphoric acid, and surface overdevelopment inhibitors consisting of trace amounts of iodide and mercapto compounds. etc. can be mentioned.

Furthermore, in the case of X-ray sensitive materials, efforts have been made to shorten the development processing time. Furthermore, means to simplify processing have also been developed, and the compound represented by the general formula [■] 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 l-1) Preparation of base Polyvinylidene chloride/itaconic acid (polymerization molar ratio 97:
After coating 3), a polyethylene terephthalate support (PET thickness 175 μm and vinylidene chloride layer thickness 0.7 μm) was biaxially stretched at 220°C, and poly(vinylidene chloride/itaconic acid) was coated on one side after corona discharge treatment. /ethyl acrylate; polymerization molar ratio 92:3:5, added as an aqueous dispersion) (0,01g/m) gelatin aqueous solution (0°0
1g/n? ), dichloro-hydroxytriazine soda (0.01g/bo), p-octylphenoxypoly(
Degree of polymerization 10) Oxyethylene ether (0,038/n
? ) and the compounds in Table 1 (in the case of solids, pulverization (particle size 0
．． After coating a barcode with a liquid consisting of 1 μm (1 μm) or an aqueous solution (added directly in the case of an aqueous dispersion), the undercoat conductive layer was dried at 140°C. Further, after corona treatment, gelatin (0.2 g/m), α
-sulfodihexyl succinate sodium salt (000
2g/m), poly(styrene/divinylbenzene, polymerization ratio 98:2) (average particle size 2.0μm, 0.02g/m
), 1,3-divinylsulfonyl 2-propatol (
0,005 g/m) to create an undercoat protective layer.

Also, only a protective undercoat layer was applied on one side.

5 1-2) Construction of the dyed layer 9b Method The following dyes were ball milled by the following method. Water (21,7 mff) and 6.7% TritonX-
2000 surfactant aqueous solution (2,65g) (Rohm
& l1aas), 60m2 screw m11m
I put it in. A 1.00 g sample of dye was added to this solution. Zirconium oxide (ZrO) beads (40'l-
) (2 m 11 diameter) was added, the container with a tight lid was placed in the mill, and the contents were ground for 4 days. Remove the container and dilute the contents with a 12.5% aqueous seratin solution (8,0g
) was added. The fresh mixture was placed in the roll mill for 10 minutes to reduce foam, and the resulting mixture was then filtered to remove Zr.
O beads were removed.

0O11 Coating method The surfactant sodium p-octylphenylethoxyethoxyethanesulfonate and the hardener (bis(vinyl-sulfonylmethyl)ether) were added to the dye-gelatin melt described above. The melt produced from the latter mixture was then added to the .
08g/+d, gelatin coating amount 0.4g/n (, surfactant 0.026g/m and hardener 0.016g/m
It was applied to both sides so that

1-3) Constituent of emulsion layer 30g gelatin 1 5g 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 potassium iodide into a container kept at 75°C while stirring.
An aqueous potassium bromide solution containing g was added by double jet method over 1 minute. Furthermore, silver nitrate aqueous solution (14 as silver nitrate)
5 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 was completed, soluble salts were removed at 35°C by a sedimentation method, the temperature was raised to 40°C, 60 g of gelatin was additionally twisted, and the pH was adjusted to 6.5. Raise the temperature again to 56°C,
After adding 650 μ of the sensitizing dye anhydro-5,5'di-chloro-9-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt, gold and sulfur sensitization was performed together. Chemical sensitization was applied.

The obtained emulsion has a hexagonal plate shape and a projected area diameter of 085 μm.
, the average thickness was 0.158 μm.

This emulsion was added with 4-hydroxy-6methyl-L as a stabilizer.
3,3a,7-chitrazaindene and 2,6-his (
hydroxyamine)-4-diethylamino-1,3,5
4 riazine and trimethylolpropane were added.

Furthermore, the following compound was also added (350+ng/m) N(C
2+15)Z Further, as a coating aid, p-octylphenoxyjethoxyethanesulfonic acid sodium 0.01 g/M1F decylhensensulfonate 0.005g/%, as a thickener, polybotacium p-vinylhenszenesulfonate 0.01g/M1. 03g/n? , polymer latex (poly [ethyl acrylate-1-/methacrylic acid-97/33 particles) [polymerization degree 10] oxyethylene poly [polymerization degree 3]
Oxyglyceryl dodecyl ether [3% by weight of particles]
(average particle size -0.1 μm) 0.4 g
/m', sodium polyacrylate (molecular weight 200,000) 0
．． 1 g/n (,1,2-bis(vinylsulfonylacetamido)ethane 0.04 g/n?, 1 helimethylol.

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. 2g/mm Sodium polyacrylate o, 02g/n? Sodium styrene sulfonate O, O1g/rrf Mucolloidal silica (particle size 0.02μm) 0.04. g/m Poly (Polymerization degree 10) Oxyethylene cetyl ether 0.02 g/m Poly (Polymerization degree 10) Oxyethylene poly (Polymerization degree 3) Glyceryl-p-octylphenyl ether 0.02 g/ml C, l+7 Mu C, l+ 7 So z N +CHzcH20-)-14C1l
2→-,5O3Na0.001g/m 0゜0005g/m C)13 C9F , ,C0NI+(-CI+□-),-,N-
Cl1□COO8001g/m C3)17 CIIF17SOZN (CHzCHzO→]■÷CH
zCHCII. 0+3H0,005g/n(mu) Potassium nitrate 0.01g/m O,05g/n? Mupt Octylphenoxyethoxyethoxyethoxyethanesulfonic acid sodium salt 0,02g/m Mu4-hydroxy-6-methyl-1,3 , 3a, 7 Tetrazaindene 0 Cetyl mupalmitate (particle size 011 μm dispersed with sodium todecylhenzenesulfonate) Muscimethylsiloxane (dispersed with sodium dioctyl-α-sulbosuccinate).

Particle size 0.12 μm) 0.005 g/mm liquid paraffin (dispersed with dioctyl-α-sodium sulfosuccinate. Particle size 0.11 μm) Polymethyl methacrylate fine particles (average particle size 3.8 μm, 4.8-2 .8 μ 04, g/m 0.005 g/m 0.005 g/mf 0.04 g/m A solution was prepared so that the gelatin concentration was 44% for each of the above emulsion layer and protective layer. This was the basic formulation for each layer.

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/rrr. 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
16.78 Boric acid
1.0g Hydroxynon 83.
3 g diconylene glycol) and 4 Q g
Hydroxymethyl-4 Methyl-1-phenyl-3 Pyrazolidone 5-methylbenzotriacey 0g 0g (Adjusted to pH 10.60 once).

le Make 1β with water Fixer concentrate ammonium thiosulfate sodium sulfite Ethylenediaminetetraacetic acid Sodium dihydrate sthorium hydroxide Adjust to 11 with water (p with acetic acid) ).

Automatic processor developing tank 6.5β Fixing tank 6.5β Washing tank 6,51 Dry to Dry Processing time 60g 0g 0.10g 4g 1 (Adjust to 5,10 seconds processing 35°C x 10.5 seconds 35°C x 9 seconds at 20°C x 7.5 seconds at 50°C for 45 seconds When starting the development process, each tank was filled with the following processing solution.

Developing tank 2 333 ml of the above developer concentrate, 667 ml of water
A starter IQ+++f containing mR and 2 g of potassium bromide and 1.8 g of acetic acid was added to bring the pH to 10.15.

Fixing tank 2 250 d of the above fixer concentrate and 750 ml of water (1) Static mark test After conditioning the unexposed sample at 25°C and 10% RH for 2 hours, test the sample in a dark room under the same air conditioning conditions. After rubbing it with a rubber roller and a urethane roller to see how the static mark will form on the material,
The film was developed with the developer described above, fixed, and washed with water, and the degree of static mark generation was examined.

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

A: No scratch marks were observed at all.B:
〃 Slightly observed C: Significant static marks D: 〃 Appeared almost on the entire surface (2) Test with dust Sample (20cI11) under conditions of temperature and humidity of 25°C and 10% RH.
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.

B: A little was observed.

C; 〃 was considerably recognized.

D: 8 was violently attacked.

(3) Transmittance test An unexposed sample was developed and fixed as described in (1) using a ZAMBLE, and its total light transmittance was measured.

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

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

(4) Adhesiveness Test 1 ~ After the completed sample was left in an atmosphere of 25° C. and 150% RH for two weeks, an adhesiveness test was conducted in the following manner. The surfaces tested here are the surfaces provided with the antistatic layers of Hayes A to G.

(b) Adhesion test method for dry film On the surface to be tested, make 36 first cuts by making 7 cuts at 5 increments in the vertical and horizontal directions, and then apply adhesive tape (for example, Nitto Electric Industry Co., Ltd. Attach the knit tape) and quickly peel it off in the 1806 direction. In this method, if the unpeeled portion is 90% or more, it is graded A, if it is 60% or more, it is graded B, and if it is less than 60%, it is graded 0. Adhesive strength that is sufficient for practical use as a photographic material is one that is classified as grade A of the above three-level evaluation.

(b) Wet film adhesion test method At each stage of development, fixation, and water washing, mark scratches on the film in the processing solution with an X mark using an iron pen, and use the tip of your finger to strongly (5
Adhesive strength was evaluated during maximum peeling along the x line.

A case where the constituent layers do not peel off more than scratches is given as A grade, a case where the maximum peeling rate is within 5III is graded as B grade, and other cases as 0 grade.

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

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 16 using the electrically conductive agent invented by the forceps were excellent in all evaluations, but sample 1-7 using the electrically conductive agent particles other than the invention had poor permeability and adhesion. Experiments using conductive polymers! It can be seen that samples ``41-8 to 1-12 are associated with deterioration in dust adhesion and deterioration in adhesion after static mark treatment.

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.

Also, in the present invention, samples 1-4 to 1-6 using an aqueous dispersion
had a particularly excellent surface condition.

Example 2 2-1) Silver halide emulsion layer formulation In an aqueous gelatin solution kept at 50°C,
In the presence of X 10-S mol of rhodium chloride, an aqueous silver nitrate solution and a mixed aqueous solution of thorium chloride and potassium bromide were simultaneously added at a constant rate for 30 minutes to obtain an average particle size of 0.
．． A 2μ silver chlorobromide monodisperse emulsion was prepared. (Cj2 composition: 95 mol%) This emulsion was desalted by the flocculation method, and 1 µ of diourea dioxite and 0.6 µ of chloroauric acid were added per mole of silver, and the maximum performance was reached at 65°C. Only ripening until obtained gave birth to a pretense.

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

-CBLs 2 x 104 mol/Ag 1 mol 1 4 x 1. O-' mole/A g1 mole Br 2
On+g/m polystyrene sulfonic acid sodium salt 4.0mg/m26
-Dichloro-6-hydroxy-1,3,5-triazinina I.Rium salt 30 µ/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. Note that the gelatin content was 1.5 g/m.

Dodecylbenzenesulfonic acid thorium salt 0.05g/m Sodium acetate o, 03g/mH 5-Nitroindazole 0.015g/bo 1.3-
Divinylsulfonyl 2-propatol O N-perfluorophthanesulfonyl-N-propylglycine bothadium salt Ethyl acrylate latex (average particle size 0.1 μ) 0 2■/, (2g/m 05g/n (2-3) Hack lower layer formulation - Gelatin 0.01g/mO Polyethyl acrylate latex (particle size 0.06 μm) 0.005g/m' (C
l1zCtl-)-6s (CH2-C11
→-3゜co c.

NIIC(C1l,)zCH2SOJa OC+1
．． C11□0COC112C112SO, Cl1=CI
+20, 003g/mj ・Table 2 Conductive Agent Hack Layer Formula Gelatin 2゜5g/m O3K 0JK 40■/d OJ OJa 03K SO3 with 13-divinylsulfonyl 2-propaturu ethyl acrylate-Y latex (average particle size 0.1 μ) Dihegysil-α-sulbozacnate sodium salt SO, 80 μ/M 150 mg/BO 900 μ/1 35 μ/rrr Dodecylhenzenesulfonic acid mono-lium salt 35 mg/n (2-
5) Hack protective layer formulation Prepared in the same manner as in Example 1. In addition, gelatin is 1.0g
/rtr.

The coating sample was prepared by applying only the vinylidene chloride undercoat layer of Example 1 on both sides (no conductive undercoat layer), and simultaneously coating the puncture underlayer, hack layer, and hack protection layer on one side in this order, and on 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.

Samples Fl 2-2 to 2- created using the conductive agent of the present invention
As can be seen from the table, Sample No. 6 is excellent in all aspects of static mark generation, dust sticking, permeability, and adhesiveness.

On the other hand, Con 1 to Roll samples 2-1 and Samples 2-7 to 2-12 using comparative conductive agents have static marks, dust,
It is not possible to satisfy both transparency and adhesion.

In addition, in particular, samples 2-4 to 2-6 had good surface conditions and excellent images.

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 as Example 3 Sample 2 of JP-A-63-26474.0.
02 Composition of Photosensitive Layer Color photographic negative film samples 3-1 to 3-12 were prepared in exactly the same manner as in Example 2, except that the first layer was changed to the 14th layer. (Processing is JP-A-63-
264.74.0 Example 3 was followed. ) Samples +43-2 to +43-6 of the present invention satisfied all of the static marks, image unevenness, fixer staining property, and coatability.

- Comparative samples 3-7 to 3-12 and control sample 3-1 could not satisfy all of the above performance.

Example 4 JP-A-63-26 on one side of triacetic acid Celsus support
The photosensitive layer composition of Example 2 Sample 104 of 4.740 was coated. The hack layer on the other side was coated with the following composition.

(Hack 1st layer) Compound of the present invention (exactly the same compound as in Example I, the same amount added) Diethylene glycol lQmg/rnf (Coated using a mixed solvent of acetone/methanol/water) (Hack 2nd layer ) Diacetyl cellulose 200 INg/n (Stearic acid 10 Cetyl stearate 1.20 Silica particles (particle size 0.3 μm) 30 (Coated using a mixed solvent of acetone/methanol/water) 264740, according to Example 2.

The obtained samples 4-1 to 4-12 were evaluated in the same manner as in Example 1, respectively.

Samples 4-2 to 4-6 of the present invention satisfied static marks, image unevenness, fixer contamination, and coatability, and excellent images were obtained.

On the other hand, control sample 4-1 and comparative samples 4-7 to 4-1
2 could not satisfy all of these requirements.

Example 5 Poly(methyl meccrylate-co-edyl acrylate)
Synthesis of Coacrylic Acid) Weigh out 1.5 g of B Mitsurofura, which is equipped with a stirrer and a reflux tube, and dissolve it in 300 cc of water.

Next, the temperature of the reaction vessel was raised to 75°C under a nitrogen stream, and the temperature was increased to 20°C.
Stir at 0 rpm. Add 40 g of 3% potassium persulfate aqueous solution F4, then add 150 g of methyl methacrylate.
g Ethyl acrylate 87.5g, acrylic acid 12.5g
A mixed solution of was added dropwise in the shade for 3 hours. After the start of the dropwise addition, 10 g of 3% potassium persulfate was added six times in total every 30 minutes. After the monomer mixture was added dropwise, the reaction vessel was kept at 75°C for another 2 hours, and the copolymer with an average molecular weight of 250,000 was washed with water.
I got dinner. 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 of the copolymer, and polystyrene fine particles with an average particle size of 2 μm were added at each level. is 1. A solution to which polystyrene fine particles were added such that the coating was 0 .mu./m' was used as a coating solution for the first undercoat layer.

A biaxially stretched polyethylene terephthalate film having a thickness of 100 μm and 3 Q cm was subjected to a corona discharge treatment under the following conditions. The film transport speed was 30 fn/min, the gap between the corona discharge electrode and the polyethylene terephthalate film was 1,
3++++, the electricity was 200 waso1. An aqueous dispersion of the copolymer synthesized by the above method was applied on both sides of 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, the film transport speed was 30 m/min, the gap between the corona discharge electrode and the polyethylene terephthalate film was 1.8 ml+, and the electric power was 1.
Corona discharge treatment was carried out at 20 Watts, and the -1- was treated with vinylidene chloride dimethylmethacryle-1...methyl acrylate:acrylonide-9CJ:4.5:4. :L.0.5, by weight, an aqueous dispersion of a copolymer was coated on both sides to a dry film thickness of 0.75 μm, and dried at 120°C. Further, on one side of the second undercoat layer made of this vinylidene chloride copolymer, a gap of 1.8 f between the corona discharge electrode and the polyethylene terephthalate film was set at a film conveyance speed of 30 m/min.
1 power was applied at 250 Wano 1~, and on top of that, as the third layer of undercoat, the following undercoat solution (11) was applied to one side at 20 mβ/, ?, dried at 170°C, and the emulsion side was undercoated. And so.

Next, on the other side, the same compound of the present invention as in Example 1 was added to the third undercoat layer formulation, and the second side was undercoated in the same manner as the emulsion side undercoat (however, the undercoat liquid was 2 mβ/m'). And so.

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

(1) Undercoat 3rd layer prescription gelatin 1.0% by weight methylcellulose 0.05% by weight surfactant, C+zH
zsO (CH2CHzO') + oHO, 03% by weight Add water 100.0% by weight (2)
Silver halide emulsion layer formulation 2X per mole of silver in an aqueous gelatin solution kept at 50°C.
An aqueous solution of silver nitrate and a mixed aqueous solution of thorium chloride and potassium bromide were simultaneously added at a constant rate for 30 minutes in the presence of 10-' moles of rhodium chloride to obtain an average particle size of 0.2.
A silver chlorobromide monodisperse emulsion of μ was prepared. (CtV.Mi composition: 95 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. It was only matured until the performance was achieved.

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

n-C. □１１. .

2 X LO-2 mol/A g 1 mol I (4,
20mg/m polystyrene sulfonic acid mono-lithium salt 40mg/m2,
6-dichloro-6-hydroxy-1. ．． 3. ．． 5-1-Reazin sodium salt 30mg/m Coating amount of silver 3.5ε/n? It was applied so that

(3) Emulsion protective layer formulation Seratin 5iOz grains (average particle size 4μ) Sodium dodecylbenzenesulfonate salt 0■ ■ 5g/rrf 50■/m' 50■/, f Compound of the present invention (4) Bank layer formulation Gelatin 2.5 g/m 5-Nitroindazole 1.3-divinylsulfonyl 2-propatol N-perfluorophthanesulfonyl-N-probylglycine bothadium salt ethyl acrylate tratix (average particle size 0.1 μ) 15 mg/m 50 ■/m 2■/rTr 300■/m' SO, K OJ 03Na o3K 03 0.1 μ) Dihexyl α-sulfosacnate sodium salt Dodecylbenzenesulfonic acid 150 μ/M 900 μ/d 35 mir/m Sodium salt 35 mg/bo (5)
Back protective layer prescription gelatin 0.8g/bopolymethyl methacrylate fine particles (average particle size 3//) 20mg/nf dihexyl-α-sulfosacnate sodium salt xomg/pododecylbenzenesulfonic acid sodium salt 10/]Tf sodium acetate 40mg The /po development process was carried out at 38 DEG C. for 20 seconds using an FC-660 automatic processor manufactured by Fuji Photo Film Co., Ltd. and GRD-1 and GRF-1 manufactured by the same company as the developing solution and fixing solution. The drying temperature at that time was 45°C.

The obtained samples 5-1 to 5-12 were evaluated in the same manner as in Example 1, respectively.

Samples 5-2 to 5-6 of the present invention satisfied all of the static marks, image unevenness, fixer staining property, and coatability, and the images were also excellent.

On the other hand, control sample 5-1 and comparative samples 57 to 5-1
No. 2 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 and R^2 or R^1 and R^3 and/or R
^2 and R^4 together form a ring. In this case, 1 in the ring
may contain one or more heteroatoms. Furthermore, R^1, R^2, R^3 and R^4 are hydrogen atoms, halogen atoms, alkyl groups, aryl groups, hydroxyl groups, alkoxy groups, aryloxy groups, amino groups, alkylamino groups, nitro groups, cyano groups. group, -NHCOR^6, -N
HSO_2R^6, -SOR^6, -SO_2R^6,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, -COR^6, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, -COOH, -COOR^6, -SO_3H-, -SH
, represents a heterocyclic group. R^5 represents a hydrogen atom, an alkyl group or an aryl group. R^6 represents an alkyl group or an aryl group. R^7 and R^8 may be the same or different and represent a hydrogen atom, an alkyl group or an aryl group. (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 ).