JPH02304554A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide an excellent antistatic property even after a development processing without adversely affecting the transmittability, adhesiveness and coatability by incorporating a polymer having an isothianaphthene structure into at least one layer of the constituting layers of the photosensitive material. CONSTITUTION:The polymer having the isothianaphthene structure is incorporated into at least one layer of the constituting layers of the photosensitive material. The polymer having the isothianaphthene structure is preferably the polymer having the structural unit expressed by formula I or II. In the formulas I and II, R<1> to R<4> denote a hydrogen atom, halogen atom, etc., X denotes the anion of an electrolyte; m denotes the ratio of the anion per repeating unit and is 0.01 to 1; n denotes a degree of polymn. and is 5 to 1000. The excellent antistatic property even after the development processing is obtd. in this way without adversely affecting the transmittability, adhesiveness and coatability.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic material having good antistatic properties. In particular, a silver halide photographic light-sensitive material [hereinafter referred to as a photographic light-sensitive material] that has no adverse effect on coating properties, no deterioration of i3 transitivity or adhesion, and has excellent antistatic properties even after development processing. It is related to.

(Prior Art) Since a photographic light-sensitive material consists of a support and a photographic layer that have electrical insulation properties, contact and friction between surfaces of the same or different materials during the manufacturing process and during use of the photographic light-sensitive material. Electrostatic charge is often accumulated by being subjected to or peeling. This accumulated electrostatic charge causes many problems, but the most serious problem is that the accumulated electrostatic charge is discharged before the development process. This causes the photosensitive emulsion layer to be exposed to light, resulting in dotted spots or dendritic or feather-like streaks when the photographic film is developed. This is what is called a static mark, and it significantly reduces the commercial value of the photographic film, and in some cases, it completely loses the commercial value. This phenomenon becomes apparent only after development, and is a very troublesome problem. In addition, these accumulated electrostatic charges may cause secondary failures such as dust adhering to the surface of the film before and after processing or the inability to apply uniformly.

Static marks on photographic materials induced by such accumulation of electrostatic charges become more noticeable as the sensitivity of photographic materials increases and processing speed increases. Particularly in recent years, static marks are more likely to occur 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. 6.Furthermore, the number of opportunities to handle processed photographic materials has increased in recent years, and dust has become a serious problem.

In order to eliminate these problems caused by static electricity, it is preferable to add an antistatic agent to the photographic material. However, the antistatic agents that can be used in photographic light-sensitive materials cannot be the same as those commonly used in other fields, and are subject to various restrictions specific to photographic light-sensitive materials. In other words, antistatic agents that can be used in photographic materials have poor antistatic properties before and after processing.
For example, the photographic properties such as sensitivity, fog, graininess, and sharpness of the photographic light-sensitive material should not be adversely affected, the film strength and adhesion resistance of the photographic light-sensitive material should not be adversely affected, and the processing solution for the photographic light-sensitive material should not be fatigued. Application of antistatic agents to photographic materials is subject to numerous restrictions, such as not accelerating the process, not contaminating the transport rollers, and not reducing the adhesive strength between the constituent layers of photographic materials. receive. In particular, an antistatic layer with poor transparency will have an adverse effect on photographic properties.

One way to eliminate these problems caused by static electricity is to increase the electrical conductivity of the surface of the photographic material so that the static charges can be dissipated in a short period of time before the accumulated charges are discharged.

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.

Surfactants are important in terms of antistatic ability in this range, and see, for example, US Pat. Nos. 3,082,123 and 3,201.
No. 251, No. 3,519.561, No. 3,625,6
No. 95, West German Patent No. 18552.408, No. 1,
597.472, JP-A-49-85826, JP-A No. 53
-129623, 54-159223, 48-
No. 19213, Special Publication No. 46-39312, No. 49-1
No. 1567, No. 51-46755, No. 55-1441
Anionic, betaine and cationic surfactants described in No. 7, etc., or Japanese Patent Publication No. 17882/1982,
Japanese Patent Application Publication No. 52-80023, West German Patent No. 1,422
, No. 809, No. 422.818, Australian Patent No. 54.414/1959, and the like are known.

However, these substances exhibit specificity depending on the type of film support and the photographic composition, and do not fully satisfy the above-mentioned performance, making it extremely difficult to apply them to photographic light-sensitive materials.

Furthermore, JP-A No. 64-68751 discloses a photographic material containing a polyphosphazene compound, US Pat. No. 4.23.
No. 7,194 discloses photographic materials containing polyaniline compounds, but these compounds have not been able to solve the above-mentioned problems.

(Problems to be Solved by the Present Invention) The first object of the present invention is to provide a photographic material that has excellent antistatic properties even after development.

The second object is to provide a photosensitive material that is antistatic and does not cause i3 transients or deterioration of adhesive properties.

The third object is to provide a photographic material that is antistatic without adversely affecting coating 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, in which at least one of the constituent layers of the light-sensitive material comprises: This was achieved by a silver halide photographic material containing a polymer having an isothianaphthene structure.

The present invention will be described in detail below.

The polymer having an isothianaphthene structure used in the present invention preferably has the following general formula (1) or (r
It is a polymer having a structural unit represented by l).

m- (1) (I+) where R1
, RZ, R2 and R4 are a hydrogen atom, a halogen atom (e.g. fluorine, chlorine, bromine), an alkyl group, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, an alkylamino method, a nitro group, Cyano group, -N HC
OR', NH301R', SOR', -3o
w R', -CooR', -3o, H, -3ll, -C
oo) [Heterocyclic groups (e.g. triazole, thiazole, henzthiazole, furan, pyridine, quinaldine,
benzoxazole, oxazole, pyrimidine, imidazole). R5 represents an alkyl group or an aryl group, and R1 may be the same or different and represent a hydrogen atom, an alkyl group or an aryl group. Also,
The above R1 and R1, R' and R2, or RZ and R4 may be fused.

Furthermore, the above R1, R2, R2 and R4 are alkyl groups,
The aryl group, alkoxy group, aryloxy group, and alkylamino group may be further substituted. Further, the alkyl group and aryl group of R%, Rh and R1 described above may also be further substituted.

Examples of these substituents include alkoxy groups (e.g.
methoxy, ethoxy), aryloxy groups (e.g. phenyloxy), alkoxycarbonyl groups (e.g. methoxycarbonyl), acylamino groups (e.g. acetylamino), carbamoyl groups, alkylcarbamoyl groups (e.g. methylcarbamoyl, ethylcarbamoyl)
, dialkyl group rouivamoyl group (e.g. dimethylcarbamoyl), arylcarbamoyl group (e.g. phenylcarbamoyl), alkylsulfonyl group (e.g. methylsulfonyl), arylsulfonyl! (for example,
phenylsulfonyl), alkylsulfonamide groups (e.g. methanesulfonamide), arylsulfonamide groups (e.g. phenylsulfonamide), sulfamoyl groups, alkylsulfamoyl groups (e.g. ethylsulfamoyl), dialkylsulfamoyl groups (e.g. dimethylsulfamoyl), alkylthio groups (e.g. methylthio), arylthio groups (e.g. phenylthio), amino 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.

X represents an anion of the electrolyte, m represents the ratio of anion per repeating φ position and is a number from 0.01 to 1, and n represents a degree of polymerization and is a number from 5 to 1000.

Preferably, it is a polymer containing 1 to 100 mol% of the structural unit represented by the general formula (]) or (TI).

Specific examples of monomers having an isothianaphthene structure include isothianaphthene, 5-methylbenzo(C)thiophene, 5-ethylbenzo(C)thiophene, 5-phenylbenzoCC)thiophene, and 4-methylbenzo(C)thiophene. , 4-ethylbenzo(c)thiophene, 4-phenylbenzo(C)thiophene, 4.5-dimethylbenzo[C]thiophene, 4.5-diethylbenzo(C)thiophene, 5.5°-dimethylbenzo(C) thiophene,
4,4°-dimethylbenzo[C]thiophene, 5-methoxybenzo(C)thiophene, 5-ethoxybenzoC
C) Thiophene, 5-phenoxybenzo(C)thiophene, 4-methoxybenzo(C)thiophene, 4-ethoxybenzo(C)thiophene, 4-phenoxybenzo(C)
) Thiophene, 5-aminobenzo(C)thiophene, 5
-Phenylaminobenzo(C)thiophene, 5-methylphenylaminobenzoCC)thiophene, 5-dimethylaminobenzoCC)thiophene, 5-diphenylaminobenzo(C)thiophene, 4-aminobenzoCC)thiophene, 4-phenylaminobenzo (C) Thiophene,
4-methylphenylaminobenzo(C)thiophene, 4
-dimethylaminobenzo(e)thiophene, 4-diphenylaminobenzo(C)thiophene, 5-chlorobenzo(CC)thiophene, 5-cyanobenzo(C)thiophene, 5-nitrobenzo(e)thiophene, 5-acetylbenzo(C)thiophene etc., but are not limited to these.

Hereinafter, a method for producing a polymer having an isothianaphthene structure will be explained.

The polymer having an isothianaphthene structure of the present invention is synthesized by a known chemical oxidative polymerization method or electrochemical oxidative polymerization method used for the synthesis of conductive polymers.

Also, does the structural unit represented by general formula (II) contain an electrolyte? Doping may be performed by performing chemical oxidative polymerization or electrochemical oxidative polymerization in a liquid.

Electrolytes that can be used for doping in the present invention include alkali metal cations (Li", Na', K', etc.), No'No!' cations, and onium cations (E ta N", B ua N"). ,BulP”
etc.) and negative ions (I3F4-18SF4~, AsF, -
-3bF, -1SbCli-PF6-1CIO4-, A
IF2-, AlF6-, N1Fa''-1ZrF,
",'riF,"-1""i F,"\B,oct,
. z-1CI-, B r-, F-, tlsOn-1so
,”, etc.), sulfonic acid anions (CH
s Cb H4SOs −, Cb Hs 5O3-1C
salts containing carboxylic acid anions such as HCOOLi, chlorides such as FeCl, (7), and organic amines, inorganic acids (e.g. HCI-
Hz Sob , CI Oa , l (B F4), 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)
Moreover, it is not limited to these salts.

Generally known methods can be used for the chemical oxidation polymerization method in the present invention, but the method is not limited to these. For example, the method described in the Journal on Organic Chemistry by F.
The method described in Organic Chemistry Vol. 49, p. 3382 (1984) includes the method of oxidizing isothianaphthene with aluminum chloride and 2VA chloride in methylene chloride to obtain a polymer.

The solvent used in the chemical oxidative polymerization method of the present invention is not particularly limited and can be selected from a wide range depending on the polymerization conditions.For example, water, organic solvents (such as propylene carbonate,
acetonitrile, benzonitrile, propionitrile,
(dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide) and mixed solvents thereof, but are not limited thereto.

As the catalyst used for chemically oxidatively polymerizing the monomer having an isothianaphthene structure in the present invention, commonly used and known catalysts can be used. For example, chlorides such as ferric chloride and cupric chloride, ferric sulfate,
Sulfates such as cupric sulfate, metal oxides such as lead dioxide and manganese dioxide, peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, quinones such as benzoquinone, halogens such as iodine and bromine, and ferri Examples include potassium cyanide. Specific examples of these are disclosed in Japanese Patent Application Laid-open No. 1983
-213518, 63-193926, 62-
No. 116665, No. 62-104832, No. 63-2
No. 15717, No. 63-69823, No. 63-101
No. 415, No. 60-58430, etc.

The amount of catalyst will vary depending on the properties of the isothianaphthenic monomer and the catalyst used. However, in general, the molar ratio of catalyst/isothianaphthene structure is in the range of 0.01 to 10, preferably,
It ranges from 1 to 5.

The reaction temperature in chemical oxidative polymerization is -10 to 100°C
, preferably 0 to 50°C. The reaction time is related to the reaction temperature, but is usually 0.1-100 hours, preferably 0.
．． 1 to 50 hours.

The above chemical oxidative polymerization is preferably a method in which a monomer having an isothianaphthene structure is chemically oxidized in an aqueous solvent in the presence of a dispersant and/or a surfactant to obtain a polymer as an aqueous dispersion. . If it can be obtained as an aqueous dispersion, it can be easily added to a coating solution. As a chemical oxidative polymerization method for obtaining an aqueous dispersion, for example, a dispersant (e.g., polyvinyl alcohol), a monomer having an isothianaphthene structure dissolved in methylene chloride, and distilled water are placed in a flask, and the mixture is placed in a nitrogen atmosphere. Add the catalyst (e.g.
A method of dropping an aqueous solution of pacts) is mentioned. However, the method is not limited to this method.

When an aqueous dispersion is obtained by chemical oxidative polymerization, the oxidizing agent, reaction temperature, and reaction time may be the same as those in the general chemical oxidative polymerization described above. Water such as distilled water and ion-exchanged water can be used as a solvent. 8 solvents (e.g. alcohols such as methanol and ethanol, acetonitrile,
Dimethyl sulfate, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide) may be mixed.

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

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 of quaternary ammonium bases, oxonium bases, sulfonium bases, etc. in their structure.

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

-(CHt CH+ CH,COOe CHz -(CH, -C)- ■ -O 〇-(CH2CI(辷■ It is a latex produced by polymerization methods. Anionic surface properties can be introduced in various ways, for example by polymerizing ethylenically unsaturated monomers with anionic groups, e.g. sulfonic acid groups, or mixtures with ethylenically unsaturated monomers. This is a method of synthesizing a latex with anionic surface properties.For this purpose, salts of 2-acrylamido-2-methylpropanesulfonic acid, vinylbenzenesulfonic acid, etc. can be used, but if the polymer has anionic surface properties, Other ethylenically unsaturated monomers that can be introduced can also be used.

Specific examples in this case are listed below, but the invention is not limited thereto.

CH.

C.I.

-(C)I x CH+ CHx CHhsCOO
Na C0OH CH3 COONa COOCH3CC00CHsCH
.

CH3CHl -(CH2-Chivr(CHz c hiπ-COO
HCOONa Additionally, anionic surface properties may be achieved by using anionic surfactants in latex production. Examples of anionic surfactants that can be used in this case include those described below.

Surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

Specific examples of anionic surfactants are listed below, but the invention is not limited thereto.

Examples of anionic surfactants include the following.

C+zHzsCOONa,,C+eH:+rCOONa
.

C+ + II 23 CON Ctl z COON
a , C + + ) I 2: + CON CII
z CII z COON =@.

CH, CH.

NapsSCHCOOCsH+y　　,0■ C+dl+1CONCIlz CHz SOi Na.

Yam C.I.

NaO: + 5CIICOOCb H+s, C
+b11tzO3O3Na.

Examples of cationic surfactants include the following.

CH.

Examples of nonionic surfactants include the following.

C1□IIzsO(CHz CHtO)+. II,
C+J! 3:+0 (C)Iz CH,O:h. 11,
H Polyoxyethylene sorbitan tristearate n-30 0H Examples of the amphoteric surfactant include the following.

CH2GHz CH.

CH3 Hs The amount of nonionic polymer, amphoteric polymer, cationic polymer, and anionic polymer used for water dispersion of the polymer having an isothianaphthene structure is determined by the amount of the monomer having an isothianaphthene structure. 1 to 300%, preferably 5%
~200% by weight. Further, the surfactant is preferably used in an amount of 0.01 to 50% by weight, preferably 0.1 to 20% by weight, based on the monomer having an isothianaphthene structure.

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

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)
Acrylic acid ester polymers etc. can be used, but are not limited to these. Preferably,
These polymer compounds are emulsions.

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

As the electrochemical oxidative polymerization method, generally known methods such as those shown below can be used, but the method is not limited thereto.For example, the method described in the Journal of Organic Chemistry by F.
of Organic Chemistry) No. 49
Vol., p. 3382 (1984), the method of electrolytically polymerizing isothianaphthene in acetonitrile in which Liar is dissolved to obtain polyisothianaphthene on the anode.

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 method described above.

Hereinafter, specific examples of the polymer having an inthianaphthene structure and its aqueous dispersion of the present invention and a method for synthesizing the same will be shown.

Synthesis Example 1 (Synthesis of Aqueous Dispersion I) 5 g of dextran and 100 mJ of distilled water were placed in a 300 mJ 3-tube flask, and 10 g of isothianaphthene dissolved in 10 ml of methylene chloride was added while stirring under a nitrogen atmosphere to obtain a suspension. To this suspension at room temperature, add 30 ml of distilled water.
m 20 g of FeCl3 6H20 dissolved in A'
was added dropwise over 30 minutes.

As the mixture was added, heat was generated and polymerization progressed.

Furthermore, after stirring for 2 hours, dialysis was performed for 2 days to obtain m5KA.
sE 5ALES C0RP CELLtlLOSE
TIIBING C-65 manufactured by Sanko Pure Chemical Industries, Ltd.) was used to obtain an aqueous dispersion of polyisothianaphthene.

The average particle size of the obtained polyisothianaphthene particles was 80n.
m (measured using COULTER-N4 type submicron particle analyzer (manufactured by Coulter Electronics),
Furthermore, this aqueous dispersion was stable whether it was stored at either 20° C. or 50° C., and there was no sedimentation or aggregation of particles when it was stored at either temperature after 3 months. Furthermore, there was no evidence of corruption.

Synthesis Example 2 (Synthesis of Aqueous Dispersion 2) As a surfactant, 0°05g of sodium lauryl sulfate
Synthesis example 1
Similarly, a stable polyisothianaphthene aqueous dispersion (average particle size 65 nm) was obtained.

Synthesis Example 3 (Water dispersion? Synthesis of 3) Result of synthesis and dialysis in the same manner as Synthesis Example 1 except that 6 g of polyvinylpyrrolidone was used instead of dextran and 12 g of 5-methylbenzoCC)thiophene was used instead of inthianaphthene. , a stable poly(5-methylbenzo(c)) with no observed decay or particle aggregation as in Synthesis Example I.
Thiophene) aqueous dispersion (average particle size: 120 nm) was obtained.

Synthesis Example 4 (Synthesis of aqueous dispersion 4) C+z11zsO (C1lzC
IItO) tallo, 5g-FeC15・61f, O
Synthesis and dialysis were performed in the same manner as in Synthesis Example 1, except that 18 g of ammonium persulfate was used instead of 18 g. As a result, a stable aqueous polyisothianaphthene dispersion (average particle size: 150 nm) was obtained in the same manner as in Synthesis Example 1.

Synthesis Examples 5 to 22 (Synthesis of Aqueous Dispersions 5 to 22) The aqueous dispersions shown in the table below were synthesized according to Synthesis Examples 1 to 4. A stable aqueous dispersion was obtained in the same manner as in Synthesis Example 1.

Synthesis Example 23 (Synthesis of Compound 1) Isothianaphthene was added to a 300 mjl 3 flask.
Take 5 g of (C4Hq)*NBFn and 200 ml of acetonitrile and add 70 g of F dissolved in 30 m of distilled water to this solution at room temperature while stirring under nitrogen atmosphere.
eC1,.6H,O was added dropwise over 30 minutes.

As the mixture was added, heat was generated and solid matter was formed. After further stirring for 2 hours, the obtained solid was collected by filtration and dried to form a compound l.
I got it.

Synthesis Examples 24 to 32 (Synthesis of Compounds 2 to 1O) Synthesis Example 23
In the same manner as above, the monomers shown in the following table were chemically oxidized and polymerized to obtain compounds 2 to 1O. Here, the amounts of monomer and electrolyte are the same as in Synthesis Example 23.

Synthesis Example 33 (Synthesis of compound ll) 2 g of isothianaphthene, (CnllJ 4NBF44
g dissolved in 200 ml of acetonitrile as an electrolyte, a platinum plate was used as a working electrode and a counter electrode, and Ag/AgC was used as a reference electrode.
When electrochemical polymerization was carried out using one electrode at a constant voltage of 0.8 μ for 30 minutes, a polyisothianaphthene film was formed on the working electrode. The resulting film was peeled off from the electrode and dried to form the compound l! I got it.

Synthesis Examples 34-40 (Synthesis of Compounds 12-18) Synthesis Example 3
In the same manner as in Example 3, the monomers shown in the following table were electrochemically oxidized and polymerized to obtain compounds 12 to 18.

Here, the amounts of monomer and electrolyte 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 in Synthesis Example 23 except that pyrrole 1Og was used instead of isothianaphthene, and a solid was precipitated. The obtained solid was collected by filtration and dried to obtain Comparative Compound 1.
I got it.

Synthesis Example 42 (Synthesis of Comparative Compound 2) Using 2 g of pyrrole and 4 g of (CallJJBFa) dissolved in 200 ml of acetonitrile as an electrolyte, platinum plates were used as the working and counter electrodes, and a saturated calomel bridge was used as the reference electrode. When electrochemically polymerized for 30 minutes at a constant voltage of .5 ■, 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) Using aniline hydrochloride instead of pyrrole, Synthesis Example 4
Comparative compound 2 was obtained by synthesizing in the same manner as in 1.

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

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

The compound of the present invention was applied to a photographic material by the following method. In the case of a solid product, dissolve it in water or an organic solvent such as methanol, isopropanol, acetone, or a mixed solvent thereof, or pulverize it by ball milling, and then add it to the coating liquid for the surface protection layer or back layer, etc. do. The pulverized compound of the present invention is 0.01 to 0.50
In the case of the above-mentioned aqueous dispersion, it may be added as is. Furthermore, these coating solutions can be applied by dip coating, air knife coating, spraying or U.S. Pat.
No. 81,294, by the method of extrusion coating using a hopper;
No. 08.947, No. 2゜941.898, No. 3,52
6,528, etc., two or more layers may be coated simultaneously or immersed in an antistatic liquid, and if necessary, the protective layer may be further coated with the present invention. An antistatic liquid containing a compound (solution alone or containing a binder) may be added.

The amount of the compound of the present invention used is preferably 0.0001 to 2.0 g, preferably 0.0005 g to 0.7 g, per square meter of the photographic material.
In particular, o,oot~0.3g is preferable, and when it is added as an aqueous dispersion, the above-mentioned amount of solid content is added.

Two or more types of each of the 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, a black-and-white photographic material for close-up,
(black and white photosensitive material for printing, etc.), normal multilayer color photosensitive materials (e.g., color negative film, color reversal film, color positive film, etc.)
(color negative films for movies, etc.), infrared light sensitive materials for laser 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, anticapri agent, stabilizer, hardener, antistatic agent, coupler, There are no particular restrictions on plasticizers, lubricants, coating aids, matting agents, brighteners, spectral sensitizers, dyes, ultraviolet absorbers, etc.
ductLicensing) 92'a 107~
l I 0 page (December 1971) and Research Disclosure magazine (December 1971)
ure) Volume 176, pages 22-31 (December 1978)
, Vol. 238, pp. 44-46 (1984).

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

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene glycols) Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfonate Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as alkyl polyoxyethylene alkyl phenyl ethers and polyoxyethylene alkyl phosphate esters; Ampholytic surfactants such as amino acid chains, aminoalkyl sulfone a[, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl carboxylic acids, amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazo Like Rium? Cationic surfactants such as M ring quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

These are “Surfactants and Their Applications” (4f.) by Ryohei Oda et al.
T Shoten, 1964), “New Surfactants” by Hiroshi Horiguchi (
Sankyo Shuppan Chu, 1975) or “Matsukuriki Chions Detergents and Emulsifiers”
(Hook Cation Visions, MC Publishing Company 1985) (rM
c Cutcheon's Detergent
s&Esulsifiers J (Mc CuLc
heon Divisions +MCPublis
hing Co, 1985)), Japanese Patent Application Publication No. 1986.
-76741, 62-172343, 62-1
No. 73459, No. 62-215272, etc.

In addition, in the present invention, other antistatic agents may be used in combination, for example, especially those described in JP-A-62-109044 and JP-A-62-21.
Fluorine-containing surfactants or polymers described in No. 5272, JP-A No. 1-76742, No. 60-80846, No. 60-80848, No. 60-80839, No. 6
No. 0-76741, No. 58-208743, No. 62-
No. 172343, No. 62-173459, No. 62-2
Nonionic surfactants described in JP-A-57-204540 and JP-A-57-204540, JP-A No. 15272, etc.
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,
Thiocyanate, etc. are also disclosed in JP-A-57-118242.
Composite oxides prepared by doping conductive tin oxide, zinc oxide, or these metal oxides with antimony, etc., 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? Ai forms, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate, dextran, and starch derivatives; polyvinyl A variety of synthetic hydrophilic polymeric substances are used, such as single or copolymers of alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. be able to.

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 or plate-like crystal shape, or it may have a composite shape of these crystal shapes. Further Hari Search Disclosure Volume 225-22534, 20-5
8 pages (198341), JP-A-58-127921,
The tabular grains described in No. 58-113926 may also be used. It may also consist of a mixture of particles of various crystalline forms.

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

In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left in the silver halide emulsion.If the salts are removed, research disclosure magnet 17643 It can be carried out based on the method described in Section.

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 0.20 or less, where the grain size is the diameter in the case of spherical silver halide, and the projection in the case of grains with a shape other than spherical. (This shows the diameter when the image is converted into a circular image of the same area.) may be used alone or in combination of several kinds, or a polydisperse emulsion and a monodisperse emulsion may be mixed.

Further, the emulsion used in the present invention is disclosed in US Pat. No. 2,996.
382, 3,397,987, 3゜705.858
As described in , a mixed emulsion of a light-sensitive silver halide emulsion and an internally fogged silver halide emulsion or an emulsion that is used in combination in a separate layer may be used.

Here, it is preferable to further use the mercapto compound described in JP-A No. 61-48832 in combination to suppress fogging and improve storage stability over time.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines, thioketo compounds such as oxadorinthion; azaindenes,
For example, triazaindenes, tetraazaindene M (
In particular, 4-hydroxy substituted tfA (1,3,3a,7tetraazaindene w4), pentaazaindene, etc.:
Many compounds known as antifoggants or stabilizers can be added, such as henzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and the like.

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 and copolymers of vinylidene chloride. The polymer latex may be stabilized in advance with a nonionic surfactant as described in JP-A-61-230136.

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. Carbon black or various dyes such as oxonol dyes, azo dyes, aryl tin dyes, styryl dyes, anthraquinone dyes, merocyanine dyes and tri(or di)allylmethane dyes may be used for this purpose. Cationic polymers or latexes may then be used to prevent the dye from diffusing out of the antihalation layer.

These are Research Disclosure Volume 176 11h
17643, section ■. 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, and methyl methacrylate-styrene sulfonic acid described in JP-A-63-216046. Copolymer, JP-A-61-2301
A so-called matting agent made of particles containing fluorine groups as described in No. 36 can be used.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other constituent layers. For example, aldehydes R (formaldehyde, glyoxal, geltaraldehyde, etc.), active vinyl compounds (1,3,5
-) lyacryloyl-hexahydro-5-1-lyazine, 1,3-vinylsulfonyl-2-propatur)
, active halogen compounds (2,4-dichloro-6-hydroxy-3-triazine, etc.), mucohalogen M1'! (
mucochloric acid, mucophenoxychloric acid, etc.), etc. can be used alone or in combination.

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

(CHz = CH-5o□-CI!)-z In formula A,
A represents a divalent group, but may be omitted.

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

As a developing agent, Research Disclosure, No. 1
76S, page 29 rDeveloping agent
Those described in the tsJ section can 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, JP-A-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 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 process is first carried out, and then a color development process is carried out by applying a white exposure or processing with a bath containing a capri 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. 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 a stabilizing process are performed if necessary, 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 bleaching. A fixing process can be carried out, or a monobath process can be carried out using a one-bath development, bleach-fixing solution in which color development, bleaching and 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 treatments, instead of the color development treatment step, an activator treatment step may be performed in which a color developing agent or its precursor is contained in the material and the development treatment is performed with an activator solution, or an activator treatment may be performed in the monobath treatment. Can be applied.

The processing temperature is usually selected in the range of 10°C to 65°C,
The temperature may exceed 65°C. Preferably from 25°C
Processed at 45°C.

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

Typical additives include l-phenyl-3-virapritone, developing agents such as metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, etc. Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, and methylbenzthiazole, water softeners such as polyphosphoric acid, and surface overdevelopment inhibitors consisting of trace amounts of iodide and mercapto compounds. can be mentioned.

Furthermore, in the case of X-ray sensitive materials, efforts have been made to shorten the development processing time. Furthermore, means for simplifying processing have also been developed, and the compounds 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) Creation of a base A polyethylene terephthalate support (vinylidene chloride/itaconic acid) (weight molar ratio 97:3) was coated on both sides of a polyethylene terephthalate (PET) film and stretched on two wheels at 220°C. PETII!175#m
, a vinylidene chloride layer (thickness: 0.7 μm) was prepared, and one side was coated with poly(vinylidene chloride/itaconic acid/ethyl alcohol) (weight molar ratio 92:3:
5. Added as an aqueous dispersion; 0. 01 g/+d),
Gelatin aqueous solution (0,01g/rr+), dichlorohydroxytriazine soda (0,01g/m), p-
Octylphenoxy polyoxyethylene ether (polymerization degree 10.0.01 g/n?) and the conductive compound in Table 1 (
0.02 g/n (, water dispersions and water-soluble ones were added as they were, and water-insoluble ones were pulverized and dispersed to a particle size of 21 μm by ball milling in an aqueous Triton X-200 surfactant solution and added. A conductive undercoat was prepared by applying a liquid consisting of (the amount added in the case of solid content) was applied and dried at 140°C.

Furthermore, after corona treatment, gelatin (0.2 g/d) was added on top of the corona treatment.
), α-sulfodihexyl succinate sodium salt (
0,002g/cd), poly(styrene/divinylbenzene) (polymerization ratio 98:2, average particle size 2.0.crm)
, 0. 02g/rr+), 1. A protective undercoat layer was prepared by applying 3-divinylsulfonyl-2-propertool (0, QO 5 g/nl'').On one side, only the protective undercoat layer was applied.

2-2) Preparation of dyed layer 'Resistance F' Award 2) 1-1 Method The following dyes were ball milled by the following method. Water (21.7 mj and 6.7% Triton χ-20
0@ Surfactant aqueous solution (2.65g) (Rohm &
(Sold by l1aas) was placed in a 60m&' screw blue bottle. A 1.00 g sample of dye was added to this solution. Zirconium oxide (ZrO) beads (40ml) (
2 m diameter) was added, the indigo-filled container was placed in a mill, and the contents were ground for 4 days. The container was removed and the contents were added to a 12.5% aqueous gelatin solution (8.0 g).

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

The dye surfactant sodium p-octylphenylethoxyethoxyethanesulfonate and hard TIQ Fl (His(vinyl-sulfonylmethyl)ether) were added to the dye-gelatin melt. The melt produced from the latter mixture was then dye coated 510.0 on the aforementioned base.
8g/r+(, gelatin coating 10.4g/rrf, surfactant 0.026g/n? and hardener 0.016g/r
It was applied to both sides so that it was rr.

1-3) Composition of emulsion layer 30 g of gelatin, 5 g of potassium bromide, 0 potassium iodide in 1 liter of water
．． Add 0.5 g of silver nitrate aqueous solution (5 g as silver nitrate) and 0.73 g of potassium iodide into a container kept at 75°C while stirring.
An aqueous solution of potassium bromide containing was added over 1 minute using a double jet method. Furthermore, silver nitrate aqueous solution (145 as silver nitrate)
g) and an aqueous potassium bromide solution were added by a double jet method.

The addition flow rate at this time was accelerated so that the flow rate at the end of addition was eight times that at the start of addition. After this, 0.37 g of an aqueous potassium iodide solution was added.

After the addition, soluble salts were removed at 35°C by the sedimentation method, the temperature was raised to 40°C, and 60g of gelatin was twisted.
H was adjusted to 6.5. The temperature was raised again to 56°C, and the sensitizing dye anhydro-5,5'-di-chloro-9-ethyl-3
, 3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt 650 μm, and then chemical sensitization using gold and ion sensitization was carried out.

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

This emulsion was added with 4-hydroxy-6-methyl- as a stabilizer.
1,3,3a+ 7-chitrazaindene and 2,6-bis(hydroxyamino)-4-diethylamino-! ,3
．． 5-) Added riazine and trimethylolpropane.

Furthermore, the following compounds were added (350 μ/d): 0.01 g/d of sodium p-octylphenoxyjethoxyethanesulfonate as a coating aid, 0.005 g/d of dodecylbenzenesulfonate, and polybotanium as a thickener. p-vinylbenzene sulfonate 0. 03g
/+d, polymer latex (poly[ethyl acrylate/methacrylic acid = 97/3) particles with poly[degree of polymerization 1
0] Oxyethylene poly [Polymerization degree 3] Adsorbed with 3% by weight of oxyglyceryl dodecyl engineered C particles, average particle size -0.1 μm) 0.4 g/d5 Sodium polyacrylate (molecules 1.2 million )0, 1g/rd,
l,2-bis(vinylsulfonylacetamido)ethane 0.04g/rrr, trimethylol 1-4) Composition of protective layer Mugelatin 1.2g/rd Mupolyacrylamide (molecular weight 45,000) 0.2 glrd Mudextran ( Molecular weight 380,000) 0.2g/n? Sodium polyacrylate 0.02g/n? Sodium mucostyrene sulfonate 0.01 g/n (mucolloidal strength (particle size 0.02 μm) 0.04 g/rr
r (degree of polymerization 10) Oxyethylene cetyl ether 0.02g/+v (degree of polymerization 1
0) Oxyethylene poly(degree of polymerization 3) glyceryl-p-octylphenyl ether 0.02g/n (c3n.

M Cs H+wSOg N1cHz CHz O
Lid CHz) TSO3Na0.001g/rrr O,0005g/rd CH.

Mu Cv F+? C0NH(CHI)TN Hz
Coo”CHz o, 001g/mC:
sHt Mu Cs F+tSCh N1cHz CHz O and'
rr(CHz CHCH20)T FlH 0,005g/n(Potassium nitrate 0.05g/m'p-t-octylphenoxyethoxyethoxyethoxyethanesulfonic acid sodium salt 0.02g/rrlm4
-Hydroxy-6-methyl-1,3°3a,7-chitrazaindene 0.04 g/cd Cetyl mpalmitate (dispersed with sodium dodecylbenzenesulfonate).

Particle size 0.111jm) 0, OO5g/rrr
Muscimethylsiloxane (dispersed with dioctyl-α-sodium sulfosuccinate).

Particle size: 0.12 μm) 0.005 g/mm liquid paraffin (dispersed with dioctyl-α-sodium sulfosuccinate).

Particle size 0.11 μm) 0. OQ5g/+d polymethyl methacrylate fine particles (average particle size 3.8μm, abundance of 4.8~2°8μ 80% or more) 0.04g/m above emulsion layer,
A solution was prepared so that the gelatin concentration was 4 wt% for each protective layer, and this was used as the basic formulation for each layer.

Then, on the base created in 1-■), the amount of coated silver is 1 on one side.
．． 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
16.7g boric acid
10g hydroquinone 8
3.3g diethylene glycol 40g
4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 11.0g5-methylhensitriazole 2g with water! Let it be l (
(adjust to pH 10.60).

Fixer Concentrate> Ammonium thiosulfate 560g Sodium sulfite 60g Ethylenediaminetetraacetic acid disodium dihydrate 0.10g Sodium hydroxide 24g Adjust to It' with water (adjust to pH 5 and IO with acetic acid).

Automatic developing machine Second processing developing tank 6.57! 35℃ x 10.5 seconds fixing tank 6.51' 35℃ x 9 seconds washing tank 6
．． 51 Dry at 20℃ x 7.5 seconds
50° C. Dry to Dry Processing time: 45 seconds When starting the developing process, each tank was filled with the following processing solution.

Developing tank 2: 333mj of the above developer concentrate! , water 657
A starter lO mA+ containing mf and 2 g of potassium bromide and 1.8 g of acetic acid was added to bring the pH to 10.15.

Fixer tank 2 250 ml of the above fixer concentrate and water 7
50nl il+ Static Mark Test After conditioning an unexposed sample at 25°C and 10% R1 for 2 hours, in a dark room under the same air-conditioning conditions, we tested the static marks on various materials. After rubbing with a rubber roller and a urethane roller in order to investigate the occurrence of static marks, the film was developed with the above-mentioned developer, 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:
〃 Somewhat acceptable C;
〃 Considerably observed D: 〃 Observed on almost the entire surface A2) Test with dust Temperature and humidity 25°C, 10%R) Sample (201 x 20
(J) 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: Quite a bit. D: Severe moths. (3) Transmittance test Using an unexposed sample that was developed and fixed as described in (1), the 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) Adhesion test The completed sample was placed in an atmosphere of 25°C and 50% RH for 2 hours.
After leaving it for a week, an adhesion test was conducted using the method described below. The surfaces tested here were the surfaces provided with the antistatic layers of bases A to G.

(a) Adhesion test method for dry film On the surface to be tested, make 36 squares by making 7 cuts at 5 square intervals vertically and horizontally. , knit tape),
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.

(b) Wet film adhesion test method At each stage of development, fixation, and water washing, scratch the film at the x mark using an iron pen in the processing solution, and then scratch it firmly with the tip of your finger.
Adhesive strength was evaluated based on the maximum peeling 11 that occurred along the x line when rubbed twice.

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 within 5 cranes is graded B, and other cases are grade 0.

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.

(5) Evaluation of coated surface condition The coating surface condition was evaluated in the following four stages.

A: No bumps are observed at all.

B: Slightly acceptable.

C: Quite acceptable.

D: Fully recognized.

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 1-5 using the electrically conductive agent invented by Riki were excellent in all evaluations, but samples using electrically conductive agents other than those of the invention! -6 is samples 1-7 to 1 using conductive polymers other than the present invention with deterioration in permeability and adhesion.
-11 is static mark, worsening of dust after processing,
It can be seen that this is accompanied by deterioration of adhesion and coating surface condition.

In addition, in particular, coatings 1-4 to 1-5 had good coated surface conditions and excellent images.

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

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

Example 2 2-1) Silver halide emulsion layer formulation 2X per mole of silver in an aqueous gelatin solution kept at 50°C.
In the presence of 10-' moles of rhodium chloride, an aqueous solution of nitrate 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 2μ silver chlorobromide monodisperse emulsion was prepared. (CIl&1N
(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 1 mol of i, and the emulsion was aged at 65°C until the highest performance was obtained. It made me frown.

The following compound was further added to the emulsion thus obtained.

n-C1zHzs 2X10-2 mole/Ag1 mole + 1XIO-'' mole/Ag1 mol 4X10-'
mol/A g1 mol KBr 2
0mg/m polystyrene sulfonate sodium 40m
g/m lium salt 2.6-dichloro-6-hydroxy-1,3,5-triazine sodium salt 30 g/d This coating solution was coated to give a coating silver amount of 3.5 g/rd.

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/rrl.

Dodecylbenzenesulfonate sodium salt 0.05g/m Sodium acetate 0.03g/rd5-nitroindazole 0.015g/ml, 3-divinylsulfonyl-2-propatol 0.05g/n? N-perfluorooctanesulfonyl-N-probylglycine bottaium salt 2/M ethyl acrylate latex (average particle size 0.1μ) 0.2g/rd0,
1g/rr1 2-3) Back lower layer formulation 0 Gelatin 0.01g/n (0 Polyethyl acrylate latex (particle size 0.06 μm) 0.005g/rrl N IIc (Cll 3) xcII! SOz
Na OC)I gcll tOcOcll g
cll zso zcH=chl zo, 003g/rd 0 Conductive compound in Table 2 0.02g/rrl (Addition method is the same as Example 1) 2-4) Back layer prescription gelatin 2.5g/rrfCH
s C-C=CHCCCHs 30■/n(40■/i80■/n(1,3-divinylsulfonyl-2-propatol 150mg/rd Ethyl acrylate latex (average particle size 0.1μ) 900■/-dihexyl α-Sulfosacnate sodium salt 35■/rriDodecylbenzenesulfonic acid sodium salt 35■/rd2-5
) Back protective layer formulation was prepared in the same manner as in Example 1. Gelatin is 1゜0g
/m.

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 back 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.

As can be seen from the table, Samples 2-2 to 2-5 prepared using the conductive agent of the present invention were excellent in all aspects of static mark occurrence, dust adhesion, i3 transitivity, and adhesiveness.

Prescription control sample 2-1 and samples 2-6 to 2-11 using the comparative base cannot satisfy all of static marks, dust, permeability, and adhesiveness.

In addition, in particular, coatings 2-4 to 2-5 had good coated surface conditions and excellent images.

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

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

Example 3 The emulsion layer having tabular silver halide grains in Example 2 was prepared from Example 3 Sample 202 of JP-A-63-264740.
Color photographic negative film samples 3-1 to 3-11 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 is JP-A-63-2
64740 Example 3 was followed. ) Samples 3-2 to 3-5 of the present invention satisfied all of the requirements for static marking, permeability, and adhesiveness.

On the other hand, comparative samples 3-6 to 3-11 and control sample 3
-1 could not satisfy all of the above performance.

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

(Back 1st layer) Conductive compound (exactly the same compound as in Example I, and the amount added is the same; those insoluble in the solvent shown below were ground by ball milling and added.) Diethylene glycol lO / d (acetone/methanol (Applied using a mixed solvent of /water) (Back No. 2N) Diacetylcellulose 200■/d Stearic acid lO〃Cetyl stearate
20 Silica particles (particle size 0.3 μm)
30 # (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 4-11 were applied in Example 1, respectively. It was evaluated in the same manner.

Samples 4 to 4-5 of the present invention satisfied static marks, dust, transparency, and adhesive properties, and excellent images were obtained.

Prescription control test t44-1 and comparative samples 4-6 to 4-
11 could not satisfy all of these requirements.

Example 5 Synthesis of poly(methyl methacrylate-co-ethyl acrylate-co-acrylic acid) 1.5 g was weighed into a 1FFI Mitsuro flask equipped with a stirring device and a reflux tube, and dissolved 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. 40 g of a 3% aqueous potassium persulfate solution was added thereto, and then a mixed solution of 150 g of methyl methacrylate, 87.5 g of ethyl acrylate, and 12.5 g of acrylic acid was added dropwise over 3 hours. After the start of the dropwise addition, 10 g of 3% potassium persulfate was added six times in total every 30 minutes. After the monomer mixture was added dropwise, the reaction vessel was kept at 75° C. for another 2 hours to obtain an aqueous dispersion of a copolymer with an average molecular weight of 1250,000. This aqueous dispersion was neutralized with a 10% aqueous potassium hydroxide solution to adjust the pH to 7.0.

In the aqueous dispersion of this copolymer, 2,4-dichloro, 6
- Hydroxy 1.3.5 triazine sodium salt was added at 4% by weight of the copolymer, and the average particle size was 2μ for each level.
of polystyrene fine particles.

A liquid to which polystyrene fine particles were added so as to be applied ON/RD was used as a coating liquid for the first undercoat layer.

A 30C11 biaxially stretched polyethylene terephthalate film having a thickness of 100 μm was subjected to a 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.
8IIa, the power was 200 watts. An aqueous dispersion of the copolymer synthesized by the above method was placed on both sides of the polyethylene terephthalate treated with corona discharge to a thickness of 0.1 μm.
The coating was applied to a dry film thickness of 185°C and dried at 185°C.

This layer is called the first undercoat layer. On top of it, discharge treatment is applied at a film transport speed of 30 m/min, a corona discharge electrode with a gap of 1.8 m/min to the polyethylene terephthalate film, and a power of 120 watts. Vinylidene: Methyl methacrylate: Methyl acrylate: Acrylonitrile: Acrylic acid = 90:4. s:4:t:o,5,wt%
An aqueous dispersion of the 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 the vinylidene chloride copolymer, the film was conveyed at a speed of 30 m/min, and the gap between the corona discharge electrode and the polyethylene terecrate film was set to 1.
Processes 8am power at 250 watts, and has 3 primer tubes on top of it.
As N, add 20 ml/undercoating liquid of the following formulation (1).
It was coated on one side so as to have a thickness of m and dried at 170°C to serve as an undercoat on the emulsion side.

Next, on the other side, the same compound of the present invention as in Example 1 was added to the third layer formulation of the undercoat, and a back side undercoat was applied in the same manner as the emulsion side undercoat (however, the undercoat liquid was 2 m 1 /rd). did.

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

+11 Undercoat 3rd layer prescription gelatin 1.0% by weight methyl cellulose 0.05% by weight surfactant, C1
□) 1□0 (C11□C11□0) 1.110.03% by weight Add water 100.0% by weight (2) Silver halide emulsion layer formulation 1 mol of silver in an aqueous gelatin solution kept at 50°C per 2X
In the presence of IO-' moles of rhodium chloride, an aqueous silver nitrate solution and a mixed aqueous solution of sodium chloride and potassium bromide were simultaneously added at a constant rate for 30 minutes to obtain an average particle size of 0.2.
A silver chlorobromide monodisperse emulsion of μ was prepared. CCIMi Sei95
(mol%) This emulsion was desalted by the flocculation method, 1 Akebono of thiourea dioxide and 0.6 μ of chloroauric acid were added per mole of SN, and the emulsion was aged at 65°C until the highest performance was obtained. It caused a fog.

The following compound was further added to the emulsion thus obtained.

n-01□ [1□ 2XlO-'' mol/A g 1 mol l lXl0-' mol/Ag/mo/Lz4 X
I O-'mol/Ag17KBr2
0 g/rr! Sodium polystyrene sulfonate 4
0 .mu./M lithium salt 2.6-dichloro-6-hydroxy-1,3,5-triazine sodium salt 30 w/rd This coating solution was coated to give a coated silver of 13.5 g/rrr.

(3) Emulsion retention 3i layer prescription gelatin 1.5g/m5iO1
Fine particles (average particle size 4μ) 50■/d Dodecylbenzenesulfonic acid sodium salt 50■/n (5-nitroindazole 15I+++r/m1.3
-Divinylsulfonyl-2-propatol 5Q+og/mN -Perfluorooctanesulfonyl-N-propylglycine botadium salt 2111r/n (ethyl acrylate latex average particle size 0.1μ) 0.2g/m100
■/d Conductive compound 0.02g/n? (4) Back layer prescription gelatin 2.5g/m30■/M) Rico Na 40■/rtr 1.3-divinylsulfonyl-2-propatol 150■/d Ethyl acrylate latex (average particle size 0.1μ) 900 ■/d Dihexyl-α-sulfosacnate sodium salt 35 ■/d Dodecylbenzenesulfonic acid sodium salt 35 ■/d (5)
Back protective layer prescription gelatin 0. 8g/rrr Polymethyl methacrylate fine particles (average particle size 3μ) 20■/d Dihexyl-α-sulfosacnate sodium salt lO■/d Dodecylbenzenesulfonic acid sodium salt lO■/rrr Sodium acetate 40■/Irr Development processing is as follows: F(,-660 automatic processor manufactured by Fuji Photo Film Co., Ltd., developer and fixer are GRD-ISGRF-1 manufactured by Fuji Photo Film Co., Ltd.)
The treatment was carried out at 38° C. for 20 seconds. The drying temperature at that time was 45°C.

The obtained samples 5-1 to 5-11 were evaluated in the same manner as in Example 1, respectively.

Tests 05-2 to 5-5 of the present invention satisfied all of the static marks, dust, transparency, and adhesive properties.
The images were also excellent.

On the other hand, control sample 5-1 and comparative samples 5-6 to 5-
No. 11 cannot satisfy all of these requirements, and it is clear that the present invention is superior to the conventional technology.

(Effects of the Invention) As described above, according to the present invention, it is possible to provide a photographic material that has excellent antistatic properties even after development without adversely affecting transparency, adhesion, and coatability. can.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment 1. Indication of the case 2008/2007 Patent Application No. 1 J4 Jti No. 2, Title of the invention Silver halide photographic light-sensitive material 3, Person making the amendment Relationship to the case Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. Contact information 2 Nishi-Azabu, Minato-ku, Tokyo 106
26-30 No. 4, Subject of amendment The description in the "Detailed Description of the Invention" column 5 of the description and the "Detailed Description of the Invention" section of the description of the contents of the amendment are amended as follows.

■) Page 61, line 5 and correct it.

2) Change r2XlO""mol/A g1 mol" in the second line of page 74 to r2X10-"
Corrected as "mol/Ag1 mole".

3) Page 74, line 3 rlXlo-"mol/Ag1 mol" rlXlo-”mol/Ag1mol” and correct it.

4) Page 74, line 6 r4X10-'mol/Ag1mol' r4X10-' mol/Ag 1 mol" and correct it.

5) Page 74, 5th line from the bottom "2,6-dichloro" "2,4-dichloro" and correct it.

6) 5th line from the bottom of No. 81 "In Example 2" “In Example 1” and correct it.

7) Page 81, second line from the bottom “Implement N2 and J “Example 1” and correct it.

8) "2,4-dichloro,6-hydroxy 1°3.5 triazine sodium salt" on page 84, lines 16-17 was replaced with "2,4-dichloro-6-hydroxy-1°3.5-"
Correct with riazine sodium salt J.

9) Page 88, line 2 '/1 mole of Ag' '/1 mole of Ag' and correct it.

10) Page 88, line 4 '/1 mole of Ag' '/1 mole of Ag' and correct it.

11) Page 88, line 6 r/1 mole of Ag” r/Ag1 mole” and correct it.

12) Page 88, line 10 "2,6-dichloro" "2,4-dichloro" and correct it.

Claims (3)

[Claims] (1) In a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, at least one of the constituent layers of the light-sensitive material contains a polymer having an isothianaphthene structure. Characteristic silver halide photographic materials. (2) The silver halide photographic light-sensitive material according to claim (1), wherein the polymer having an isothianaphthene structure is obtained by chemical oxidative polymerization or electrochemical oxidative polymerization. . (3) The silver halide photographic material according to claim (1), wherein the polymer having an isothianaphthene structure is obtained as an aqueous dispersion by chemical oxidative polymerization.