JPH0728193A - Silver halide sensitive material - Google Patents

Abstract

PURPOSE:To provide a sensitive material equipped with an electrostatic charge preventive excellent in the charge preventing performance with a low relative humidity and in the bonding performance with a support by furnishing at least one layer which contains a specific polymeride. CONSTITUTION:A photosensitive material concerned has at least one sensitive silver halide layer on a support, and also at least one layer which contains a polymeride having a repetitive unit expressed by Formula I and/or II. In Formulae, R1, R5 are hydrogen atom or methyl radical, R2-R4 are alkyl radical, alalkyl radical, aryl radical, at least one of them being the aryl, R6 is aryl radical, L1 is two-valent radical, D is a complex ring of five or six members having one or two nitrogen atoms, X1, X2 are anion, x1-z1, x2-z2 are specific molar fraction, and A is a repetitive unit which has at least two ethylene type unsaturated radical capable of copolymerization and includes at least one of them in the side chain, while B is a repetitive unit which has ethylene type unsaturated radical capable of copolymerization.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a photographic light-sensitive material having excellent antistatic properties, and more particularly to a silver halide photographic light-sensitive material having excellent antistatic properties and adhesiveness.

[0002]

2. Description of the Related Art Since a photographic light-sensitive material generally comprises an electrically insulating support and a photographic layer, there are various photographic light-sensitive materials during the manufacturing process of the photographic light-sensitive material and during use.
Static electricity is easily accumulated on the photosensitive material due to contact friction or peeling. The accumulated electrostatic charges cause various inconveniences for the photosensitive material. For example, when the electrostatic charge accumulated in the photographic light-sensitive material is discharged before the development processing, when the photographic light-sensitive material is subjected to the development processing, the photographic emulsion layer is exposed in a pattern of dots, resins, feathers, etc. It is observed as a so-called static mark. This is a serious matter that loses its value as a photographic light-sensitive material. In other words, this static mark is one of the very troublesome problems in assuring the quality before use because such a defect becomes apparent only after development processing. In addition, the accumulated electrostatic charges tend to cause dust to adhere to the film surface before and after the development processing, and the adhered material also causes unnecessary noise on the photographing screen.

Accumulation of electrostatic charges in such a photographic light-sensitive material increases the sensitivity of the photographic light-sensitive material, speeds up the manufacturing and transporting process,
It has become more and more prominent with the increase in speed of the developing processor, and many antistatic methods have been proposed so far in order to eliminate the trouble due to static electricity of these photographic light-sensitive materials. For example, US Pat. No. 2,882,157, JP-A-55-65950.
No. 51, No. 51-129520, No. 51-42535, No. 54-159222, No.
55-7763, German Patent No. 2,011,366, JP-A No. 53-82876, and other ionic polymer antistatic agents. A typical silver halide photographic light-sensitive material having an antistatic layer exposed on one surface of a light-sensitive film is a color or black-and-white roll film. These have an antistatic composition coated directly on a support and a photosensitive layer coated on the other side of the support. The photosensitive layer often consists of a hydrophilic colloid, such as gelatin, to facilitate the development process. It is necessary that the antistatic layer described above does not interfere with the so-called "emulsion side" coated hydrophilic binder. In other words, when the film itself is rolled up and the antistatic layer is in contact with the hydrophilic layer, it is necessary to prevent physical defects from occurring on both surfaces or layers, and the ion satisfying such conditions is required. It has been quite difficult to find a positive antistatic compound. It is known that ionic polymer compounds generally require the presence of moisture to effectively provide conductivity. When the antistatic layer and the photosensitive layer are in close contact with each other due to the film being rolled up, their surfaces are adhered to each other due to the presence of some water, and the photosensitive layer surface is smooth and glossy even if it does not reach there. So-called ferrotyping (polishing) may occur. Further, since the ionic polymer is generally a water-soluble polymer, it tends to have poor resistance to an aqueous development processing composition, generate scum in a photographic film, and form a brittle layer having poor adhesion. Further, these polymers have a problem that they are dissolved in the developing solution and accumulate in the developing solution, and the silver halide photographic light-sensitive material to be developed thereafter is stained or fogged. . Further, there is a problem that these polymers diffuse into other layers and the antistatic performance is significantly lowered.

In order to solve these problems, US Pat. No. 3,399,995, JP-A-53-45231 and JP-B-58-56858 have been proposed.
No. 55/65950, 55-67746, 61-223736
JP-A No. 62-9346, JP-A-3-129340, and the like propose a water-insoluble antistatic agent which is a cationic cross-linking polymer cross-linked with a cross-linking monomer such as divinylbenzene. These antistatic agents were improved in terms of elution into the processing solution and diffusion of the polymeric antistatic agent to other layers, and they showed good performance. The objective could not be achieved because there are insufficient points in terms of the preventive performance as well as practical characteristics based on other physical properties and chemical properties. As in recent years, the speed of processing such as preparation for development and processing has become faster, and it has become impossible to obtain a product that can satisfy them. When using these cross-linked cationic polymer antistatic agents, it is necessary to add a large amount of antistatic agents to fulfill the charging performance as a photographic film, so that the film strength is reduced, and the adhesion of the antistatic layer is reduced. It has a drawback that it cannot satisfy the properties that the antistatic layer must have, such as deterioration.

[0005]

The present invention has been made to solve the above problems, and an object of the present invention is to have excellent antistatic performance under low relative humidity and excellent adhesiveness to a support. Another object of the present invention is to provide a silver halide photographic light-sensitive material that does not adversely affect photographic characteristics and processing characteristics.

[0006]

The object of the present invention is to provide a photographic light-sensitive material having at least one light-sensitive silver halide layer on a support, which is represented by the following general formula (1) and / or (2). It is achieved by a silver halide photographic light-sensitive material characterized by having at least one layer containing a polymer having a repeating unit.

General formulas (1) and (2):

[0008]

[Chemical 2]

In the general formula (1), R ₁ represents a hydrogen atom or a methyl group, and R ₂ , R ₃ and R ₄ represent an alkyl group, an aralkyl group and an allyl group, respectively.
R ₂ , R ₃ and R ₄ may be the same or different. However, at least one of R ₂ , R ₃ and R ₄ is an allyl group. _{Two of} R ₂ , R ₃ and R ₄ may be linked to form a 5-membered ring or 6-membered ring together with the nitrogen atom. L ₁ is 2
Represents a valent group. X ₁ represents an anion. x ₁ , y ₁ and z ₁ represent mole fractions, x ₁ is 0 to 20%, y ₁ is 0 to 70%, z ₁ is 3
0 to 100%. In the formula, A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain, and B represents a repeating unit having a copolymerizable ethylenically unsaturated group. Indicates a unit.

In the general formula (2), R ₅ represents a hydrogen atom or a methyl group, and R ₆ represents an allyl group. D is a 5- or 6-membered heterocyclic ring having one or two nitrogen atoms. D may have a substituent.
X ₂ represents an anion. x _2, y _2, z ₂ represent mole fractions, x ₂ is 0 to 20%, y ₂ is 0 to 70%, z ₂ is from 30 to 100%. In the formula, A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain, and B represents a repeating unit having a copolymerizable ethylenically unsaturated group. Indicates a unit.

The present invention will be described in more detail below. In the above general formula (1), A represents a copolymerizable monomer having at least two ethylenically unsaturated groups, and examples thereof include divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol. Examples thereof include dimethacrylate, neopentyl glycol dimethacrylate, tetramethylene glycol diacrylate, tetramethylene dimethacrylate and the like, among which divinylbenzene, ethylene glycol diacrylate and ethylene glycol dimethacrylate are preferable.

B represents a copolymerizable monomer unit having a copolymerizable ethylenically unsaturated group, and examples thereof include ethylene, propylene, 1-butene, isobutene, styrene and α.
-Methylstyrene, vinyltoluene, fatty acid family monoethylenically unsaturated ester (eg vinyl acetate, allyl acetate), ethylenically unsaturated monocarboxylic acid ester (eg methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n- Butyl acrylate, n-butyl methacrylate, n-hexyl methacrylate, n-octyl acrylate, benzyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate and acrylonitrile and the like,
Of these, styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate,
Cyclohexyl methacrylate, benzyl acrylate and the like are particularly preferable. B may contain two or more of the above monomer units.

R ₁ represents a hydrogen atom or a methyl group,
R ₂ , R ₃ and R ₄ are each an alkyl group having 1 to 10 carbon atoms,
Represents an aralkyl group, a benzyl group and an allyl group. R ₂ ,
R ₃ and R ₄ may be the same or different. However, at least one of R ₂ , R ₃ and R ₄ is an allyl group. Examples of the nitrogen-containing heterocycle formed by connecting R ₂ , R ₃ and R ₄ or the nitrogen-containing heterocycle represented by D include piperidine, piperazine, quinuclidine, triethylenediamine, pyrrolidine and imidazolidine. Further, examples of the nitrogen-containing heterocycle represented by D include imidazole, imidazoline, pyrazoline, piperazine, pyrazine, pyrimidine, pyridine and the like. Among these, preferred heterocycles include piperidine, piperazine, triethylenediamine, pyrrolidine, quinuclidine, imidazole, pyrazine, pyridine, and the like, with triethylenediamine, piperazine, piperidine, pyrrolidine, and pyridine being particularly preferred. The nitrogen of these heterocycles is used in the reaction as a tertiary amine, but in the case of a secondary amine, it is necessary to introduce a substituent into the nitrogen atom in advance. Further, the carbon atom of these heterocycles may have a substituent.

As the anions of X ₁ and X ₂ , halogen ions such as chlorine ion and bromine ion, alkyl sulfate ions such as methyl sulfate ion and ethyl sulfate ion, methanesulfonate ion, ethanesulfonate ion, benzenesulfonate ion, There are alkyl or aryl sulfonate ions such as p-toluene sulfonate ion, and chlorine ion or bromine ion is particularly preferable.

X ₁ , y ₁ and z ₁ represent mole fractions, and x ₁ is 0
-20%, preferably 1-10%, y ₁ is 0-70%, preferably 0-20%, z ₁ is 30-100%, preferably 70-100%
Is.

L ₁ is an alkylene group having 1 to 10 carbon atoms, an alkenyl group, aralkylene,

[0017]

[Chemical 3]

The crosslinkable cationic polymer of the present invention is characterized by the polymer particles to be obtained, and since it can have a high concentration and high density of the cation component in the particles, it has not only excellent conductivity. No deterioration of conductivity was observed even under low relative humidity, and although the particles were well dispersed in the dispersed state, the adhesion between the particles was also good in the film-forming process after coating, so the film strength was also high. It is strong and has excellent adhesiveness to other substances such as a support. Conventional antistatic agents for cellulose triacetate supports tended to be difficult to adhere to other supports such as polyethylene terephthalate, but the antistatic agent of the present invention was able to surpass them. The crosslinkable cationic polymer of the present invention is disclosed in JP-A-54-159222 and JP-A-55-7763, or an antistatic agent containing only an ionene polymer or JP-A-53-45231 and JP-A-62-9346. It has been found that it has an excellent performance which is incomparable to the antistatic agent based on such a crosslinkable cationic polymer particle.

Specific examples of the polymer of the present invention are shown below.

[0020]

[Chemical 4]

[0021]

[Chemical 5]

[0022]

[Chemical 6]

[0023]

[Chemical 7]

The above-mentioned polymerization is generally carried out by using an anionic surfactant (for example, commercially available from Rohm & House under the name of Triton 770), a cationic surfactant (for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, nonionic surfactant). It is carried out as an emulsion polymerization in the presence of at least one surfactant selected from the agents (eg polyvinyl alcohol) and radical initiation (eg a combination of potassium persulfate and potassium bisulfite).

The reaction temperature for the quaternization of the above reaction is generally 0.
C. to about 10.degree. C., with 40.degree. C. to 70.degree. C. being particularly preferred.

When emulsion-copolymerizing a quaternized monomer, the monomer solution (when the monomers do not dissolve in each other, use an auxiliary solvent such as water, alcohol, acetone, etc.) and polymerization in emulsion water are used. The method is characterized in that an initiator is added at the same time.

The polymerization temperature can be 50 to 100 ° C., but a preferable polymer dispersion can be obtained at 80 to 100 ° C.

The dispersible particulate copolymers described herein are generally in the particle size range of about 0.01 μm to 0.02 μm,
Preferably a particle size in the range 0.05 μm to 0.08 μm is used.

The amount of the polymer of the general formula (1) used in the present invention varies depending on the form to be used, but it is generally 0.01 to 2.0 g, preferably 0.03 to 1.0 g in terms of solid content per 1 m ^{2 of the} photographic light-sensitive material. Is.

Throughout this specification and claims, the term "dispersible polymer" as used herein, refers to a clear or slightly cloudy solution by visual observation, but under an electron microscope as a granular dispersion. It is a polymer.

Synthesis Example 1 [Polymerization of P-1] Polymerization of chloromethylstyrene-latex In a 500 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen gas inlet tube, sodium lauryl sulfate 7.0 g was added. And potassium persulfate were dissolved in 20 ml of distilled water degassed with nitrogen gas. Separately prepared 142.0 g of m- and p-chloromethylstyrene under nitrogen stream, 0.33
g of sodium bisulfite and 0.75 g of sodium lauryl sulphate dissolved in 50 ml of distilled water were heated and stirred at 60 ° C. under a nitrogen stream while simultaneously dropping 2 drops at a time.
Dropped over time. After completion of dropping, the mixture was heated and stirred for another 2 hours. The produced latex was diluted with 500 ml of distilled water, filtered, and the pH was adjusted to 7 with 1N sodium hydroxide solution.

Quaternization and Crosslinking After cooling the latex to 5 ° C., a solution prepared by dissolving 39.0 g of dimethylallylamine in 200 ml of water was added, and the mixture was allowed to stand at room temperature for 1 hour.
Stir for hours. Then, the mixture was heated to 60 ° C. and stirred for 8 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and this reaction solution was added to 5 volumes of acetone with gentle stirring. The precipitated polymer was taken out by filtration and washed three times with the same amount of acetone. The polymer was then filtered off and redispersed in gently stirred methanol to give a 10% solids dispersion.

Synthesis Example 2 [Polymerization of P-1] Synthesis of quaternized monomer A mixture of 121.9 g of chloromethylstyrene dissolved in acetone was placed in a 1000 ml three-necked flask. To this solution was added 60.4 g of dimethylallylamine dissolved in 300 ml of acetone. After completion of the addition, the mixture was heated under reflux for 4 hours and cooled, and the precipitated crystals were filtered to obtain 84.5 g of dimethylallylammonium-Np-vinylbenzyl-chloride (quaternary ammonium monomer).

Copolymerization of quaternary ammonium monomer 10 equipped with a stirrer, cooling pipe, thermometer, nitrogen gas introduction pipe
In a 00 ml four-necked flask, add 300 ml of distilled water and degas with nitrogen, add 1.2 g of polyoxyethylene nonylphenyl ether (Nippon Emulsion Co., Ltd., average number of repeating units of ethylenoxide = 40), and add nitrogen. 90 ° C after air flow
It was heated and stirred. Divinylbenzene 4.0 g and the above cationic monomer 21.0 g dissolved in 50 ml of methanol
Then, a solution prepared by dissolving 0.4 g of 2,2'-azobis (2-aminodipropane) hydrochloride as a polymerization initiator in 20 ml of distilled water was simultaneously added dropwise over 1 hour. After completion of dropping, a solution prepared by dissolving 0.05 g of the above-mentioned polymerization initiator in 5 ml of distilled water was added, and the mixture was further heated and stirred at 90 ° C for 2 hours. Then, the mixture was cooled to room temperature to obtain a crosslinked polymerization dispersion having a solid content of 9.7%. Further, it was slowly added to 8 times acetone with stirring to precipitate a polymer, and the precipitated polymer was taken out by filtration and further 3 times.
It was washed once with 5 volumes of acetone. The polymer was then filtered off and redispersed in gently stirred methanol.
A 10% solids dispersion was obtained.

Synthesis Example 3 [Polymerization of P-4] Polymerization of chloromethylstyrene-latex 50 equipped with a stirrer, a cooling pipe, a thermometer, and a nitrogen gas introducing pipe.
In a 0 ml four-necked flask, 7.0 g of sodium lauryl sulfate and 1.0 g of potassium persulfate were dissolved in 20 ml of distilled water degassed with nitrogen gas and placed. A mixture of 92.0 g of m- and p-chloromethylstyrene, 50.0 g of divinylbenzene, 0.33 g of sodium bisulfite and 0.75 g of sodium lauryl sulfate dissolved in 50 ml of distilled water prepared under a nitrogen stream. 60 ° C with nitrogen stream
While the mixture was heated and stirred, 1 drop was added dropwise at the same time in 2 hours. After completion of dropping, the mixture was heated and stirred for another 2 hours. Dilute the produced latex with 500 ml of distilled water, filter, and
The pH was adjusted to 7 with an aqueous solution of N sodium hydroxide.

Polymerization of Cationic Polymer 52.5 g of p-xylene dichloride was dissolved in 75 g of acetone and placed in a reaction vessel. Dimethylallylamine 28.5
A solution obtained by dissolving 45 g of acetonitrile in 45 g of acetonitrile was added dropwise at room temperature over 1 hour. After the dropwise addition, stirring was continued for 2 hours, and then the white precipitate formed was filtered, washed with 30 g of acetone, and further 10
It was dissolved in 0 g of water and stirred at 50 ° C. for 20 hours. The reaction product was poured into 5 times the amount of acetone, and the white precipitate thus deposited was filtered and dried. The yield was 65.1 g.

Synthesis of Cross-Linked Polymer Containing Cationic Polymer Cross-linking After cooling 1/2 of latex to 5 ° C., a solution prepared by dissolving 65.1 g of the cationic polymer in 200 ml of water was added and stirred at room temperature for 1 hour. Then, it heated at 60 degreeC and stirred for 8 hours. After the reaction was completed, the mixture was cooled and added to 5 volumes of acetone with gentle stirring. The precipitated polymer was filtered out and washed three times with the same amount of acetone. The polymer was then filtered off and redispersed in gently stirred methanol to give a 10% solids dispersion.

The copolymer dispersion of the present invention, when synthesized by latex polymerization, stably exists as particles as an aqueous dispersion, but it is washed with acetone to remove impurities such as unreacted materials. In the case of redispersion with methanol, the dispersion of methanol allows the copolymer to exist more stably, which makes it easier to handle industrially and facilitates coating on a support. However, when it is desired to use it as an aqueous dispersion, it can be used as an aqueous dispersion by reducing the amount of methanol in the methanol dispersion and adding a large amount of water. As a solvent that can be used in addition to methanol, for example, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoacetate, 1-
Methoxy-2-propanol, dimethylformamide,
Formamide, dioxane, acetonitrile and the like can be mentioned, with methanol and ethanol being particularly preferable. As the diluting solvent, for example, acetone, methyl ethyl ketone ethyl acetate, etc. are used, and acetone is particularly preferable among them.

The polymer particle dispersion of the general formula (1) of the present invention is particularly useful as an antistatic layer applied as an excellent antistatic composition to a support directly or through an undercoat layer. In addition to this, a photographic emulsion layer on the side of the undercoat layer and the photographic photosensitive layer
By adding and mixing the copolymer particles of the present invention to a layer mainly containing gelatin as a binder such as a protective layer, an intermediate layer and an antihalation layer, or by providing the layer of the present invention on these layers, these An excellent antistatic effect can be imparted to the layer.

The method of applying the antistatic layer of the present invention includes:
There are methods such as spraying on the surface, dipping in the solution, and coating, but coating is particularly preferable. As a coating method, a general method, specifically, a doctor coat, an extrusion coat, a slide coat, a roller coat, a gravure coat or an extrusion coat method using a hopper described in U.S. Pat.No. 2,681,294 is applied. can do.

The antistatic layer provided by the polymer of the general formula (1) of the present invention may contain additives such as a binder, a matting agent, a surfactant, a slip agent, a curing agent and a high boiling point solvent. Of course, the antistatic function of this layer and also the physical function of the antistatic layer can be further enhanced.

When the polymer of the general formula (1) of the present invention is coated on a support to form an antistatic layer as described above, the binder is mixed and used together without impairing the conductivity. The film strength of the layer can be improved.
Examples of the binder include cellulose diacetate, cellulose acetate butyrate, cellulose nitrate, polyvinyl formal, polyvinyl butyral, and the like, and cellulose diacetate is particularly preferable. Gelatin is preferred as the binder that can be commonly used on the emulsion layer side.

Other physical properties are imparted to the outermost surface of the antistatic layer provided by the polymer of the general formula of the present invention, particularly the antistatic layer provided on one side of the support on the side opposite to the photographic photosensitive layer. Therefore, at least one layer may be provided. This layer may or may not contain the antistatic agent of the present invention. The physical properties of this layer include adhesion prevention, unreasonable contact prevention, slippery property, scratch prevention from an extremely sharp object, charge sequence adjustment, and substance transfer prevention. It is necessary to form the layer. In some cases, a binder is used, and for example, cellulose diacetate, cellulose triacetate, polyvinyl acetal, polyvinyl formal, polystyrene or the like may be used. Examples of the physical property-imparting agent are matting agents; for example, silica particles, spherical particles of polymethylmethacrylate, spherical or powder particles of fluorinated polymers such as vinylidene fluoride, and slip agents; for example, carnauba wax, candelilla wax, perfluoroalkyl. Methacrylate and its copolymers, British patent
1,330,356, U.S. Pat.Nos. 3,666,478, 3,589,906 and the like fluorine-based surfactants such as N-perfluorooctylsulfonyl-N-propylglycine potassium salt, 2- (N-perfluorooctylsulfonyl-N-ethyl Amino) ethyl phosphate, N- [4- (perfluorononenyloxy) benzyl] -N, N-dimethylammonium acetate, N- [3- (N ', N', N'-trimethylammonium) propyl] perfluoro Octylsulfonamide iodide, N- (polyoxyethylenyl) -N-propylperfluorooctylsulfoamide and the like can be mentioned. Polymers or copolymers containing vinyl esters or acrylic esters of higher fatty acids or higher fatty alcohols are also useful.

As the antistatic compound of the present invention, the following high boiling point solvent may be contained together with the copolymer of the general formula (1) of the present invention. Examples thereof include ethylene glycol, propylene glycol, 1,1,1-trimethylolpropane, diethylene glycol, triethylene glycol and the like.

As the support applicable to the polymer of the general formula (1) and / or (2) of the present invention, all those generally used as a photographic light-sensitive material can be used. For example, polyethylene laminated photographic paper, polyolefin-based support such as polypropylene synthetic paper, cellulose ester-based support such as cellulose triacetate, polyester-based support such as polyethylene terephthalate and the like can be mentioned. Other polystyrene,
Films such as polycarbonate may also be suitable. In the present invention, cellulose triacetate (TAC) and polyethylene terephthalate are preferably and effectively applicable.

The undercoat layer for strengthening the adhesion between the support and the gelatin layer or other layers used in the present invention will be described. The undercoat layer depends on the nature of the support. Generally, a solvent-based one is used as the subbing solution for the cellulose triacetate (TAC) support. TAC
As a solvent useful for the undercoating of acetone, methyl ethyl ketone, methanol, isopropanol, methylene chloride, ethylene chloride, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol, ethyl acetate,
Dimethylformamide or the like can be used. TAC
Gelatin is generally used as the undercoat material, but polyvinyl alcohol, partially acetalized polyvinyl alcohol, vinyl acetate-maleic anhydride copolymer is applied as a hydrophilic resin to a mixed solvent solution of acetone, ethyl acetate, and isopropanol. And a method in which a solution in which gelatin: cellulose nitrate is mixed and dispersed in a methylene chloride: acetone: methanol mixed solution is applied.

In addition to the above-mentioned organic solvent-based undercoating, the polyethylene terephthalate (PET) support may be so-called etching solvent (for example, phenol, cresol, etc.) for etching the polyester to adhere the undercoat material by the anchoring effect. Resorcin, chloral hydrate, chlorophenol, etc.) may be used to apply an organic solvent-based or water-based undercoat liquid. This is because polyester has a regular structure in which it is difficult to adhere, and it is necessary to change the surface structure loosely or chemically. For this, other mechanical processing,
Corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment,
Surface activation treatment such as glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone treatment is performed. Good adhesive strength can be obtained by directly applying a photographic emulsion after the above treatment, but in order to further strengthen the adhesive strength, an undercoat layer is provided after these surface treatments or without surface treatment. A film with which a photographic emulsion layer may be provided is obtained. Even with a water-based undercoating agent, the adhesiveness can be easily improved by utilizing the above various treatments as a pretreatment. For example, JP-A-55-67745 and JP-A-59-19941
By the method described in, etc., that is, the corona discharge treatment is performed before and after the undercoating and the acrylic ester-based aqueous latex is applied, a product having satisfactory adhesiveness can be obtained.

When the antistatic layer of the present invention is provided on the polyester support, the above pretreatment or subbing treatment may be performed in advance. After subjecting these supports to corona discharge treatment, for example, n-butyl methacrylate described in JP-A-59-19941: t-butyl methacrylate, styrene and
A quaternary copolymer latex consisting of 2-hydroxyethylmethacrylate, a surface-active agent and a curing agent are applied on an aqueous subbing liquid and dried, followed by corona discharge treatment again, and then gelatin on the photographic emulsion layer side. A desired photographic light-sensitive material can be finished by applying an aqueous solution and an organic solvent-based solution of cellulose diacetate on the antistatic layer side.

The silver halide light-sensitive material according to the present invention is a usual black-and-white photographic light-sensitive material (for example, black-and-white light-sensitive material for photographing, black-and-white light-sensitive material for printing, black-and-white light-sensitive material for X ray,
Etc.), and various conventional multi-layered light-sensitive materials (for example, color negative film, color reversal film, color positive film, etc.). It is particularly effective for high-sensitivity silver halide light-sensitive materials and high-speed rapid processing silver halide light-sensitive materials. Further, the antistatic layer of the present invention is more effective for a silver halide light-sensitive material having a photographic emulsion layer on one side and an antistatic layer on the other side. Specifically, they are roll films of color negative, positive, reversal light-sensitive materials and the like, roll films of X-ray black and white light-sensitive materials for indirect photography and the like.

The silver halide grains and other additives used in the silver halide light-sensitive material of the present invention, such as chemical sensitizers, spectral sensitizing dyes, hardeners, surfactants, color couplers, etc., are particularly limited. , For example, Research Disclosure Volume 176, 22-31
The description on page (December 1978) can be referred to. Further, the description of the above literature can be referred to for the exposure and development methods of the silver halide light-sensitive material of the present invention. The silver halide emulsion will be described below.

The silver halide grain contained in the silver halide photographic emulsion may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The silver halide grains are cubic, octahedral, 14
It may have a regular crystal form such as a face piece, or may have an irregular crystal form such as a spherical shape or a plate shape.
In these grains, any ratio of {100} plane to {111} plane can be used. Further, grains having various crystal forms may be mixed and grains of various crystal forms may be mixed, but twin silver halide grains having two parallel twin planes facing each other are preferable. .

A twin is a silver halide crystal having one or more twin planes in one grain. The twin morphology is classified by Klein and Moiser in the report Photographiesche Correspondents. (Photographishe Korrespondenz)
Volume 99, page 99, volume 100, page 57.

In the present invention, when tabular silver halide grains are used, the average ratio of the diameter to the thickness of tabular grains (also referred to as aspect ratio) is preferably less than 5, more preferably 1.1 or more. Less than 4.5, particularly preferably
It is 1.2 or more and less than 4. This average value is obtained by averaging the ratio of diameter to thickness of all tabular grains.

The diameter of the silver halide grain is indicated by the circle-equivalent diameter of the projected area of the silver halide grain (the diameter of the circle having the same projected area as the silver halide grain),
The thickness is preferably 5.0 μm, more preferably 0.2 to 4.0 μm, and particularly preferably 0.3 to 3.0 μm.

As the silver halide photographic emulsion, any one such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution can be used, but a monodisperse emulsion is preferable.

As the monodisperse silver halide emulsion,
It is preferable that the weight of silver halide contained in the grain size range of ± 20% around the average grain size r is 60% or more, more preferably 70% or more, and still more preferably the weight of all silver halide grains. 80% or more.

Here, the average particle size r is defined as the particle size ri when the product ni × ri ³ of the frequency ni and ri ³ of the particles having the particle size ri is the maximum (three significant digits, the minimum number). Digits and numbers are rounded to 4).

The grain size ri mentioned here is the diameter when the projected image of a silver halide grain of a silver halide grain is converted into a circular image of the same area.

The particle size ri can be obtained by, for example, enlarging the particles with an electron microscope at a magnification of 10,000 to 70,000 and measuring the particle diameter on the print or the area at the time of projection (measurement). The number of particles shall be indiscriminately 1,000 or more.)

A particularly preferred highly monodisperse emulsion of the present invention has a width of distribution of 20 when the width of the distribution is defined by (grain size standard deviation / average grain size) × 100 = width of distribution (%). %
It is the following, and more preferably 15% or less.

The average particle size and standard deviation are obtained from the particle size ri defined above. In the present invention, when silver iodobromide is used as the silver halide, the content of the silver iodide is 4 mol% or more and 15 mol% or less as the average silver iodide content in the entire silver halide grains. It is preferable that the amount is 5 mol% or more and 12 mol% or less, and particularly preferably 6 mol% or more and 10 mol% or less.

The silver halide grains contained in the silver halide photographic emulsion are preferably so-called core / shell type grains in which silver iodide is concentrated.

The core / shell type particles are particles composed of a core that serves as a core and a shell that coats the core, and the shell is formed of one or more layers. The silver iodide contents of the core and the shell are preferably different from each other, and it is particularly preferable that the silver iodide contents of the core portions are maximized.

The silver iodide content of the above core is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 25 mol% or more. The silver iodide content of the outermost shell of the above shells, that is, the shell which usually forms the outermost surface layer is preferably 5 mol% or less, more preferably 0 to 2 mol%. The proportion of the core is preferably 2 to 60% of the volume of the whole particle, more preferably 5 to 50%.

Regarding the silver halide grains contained in the silver halide photographic emulsion, an aqueous solution containing a protective colloid and seed grains are preliminarily present in a reaction vessel, and silver ions, halogen ions or silver halide fine grains are supplied if necessary. It is obtained by crystal growth of seed particles. Here, the seed particles can be prepared by a single jet method or a controlled double jet method well known in the art. The halogen composition of the seed grains is arbitrary and may be any of silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. Silver bromide and silver iodobromide are preferred.

When seed grains are used for preparing a silver halide emulsion, the seed grains may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or may have a spherical or plate shape. It may have an irregular crystal form. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.
It is preferable to use the monodisperse spherical seed particles described in the specification of 2-408178.

The silver halide photographic emulsion can be produced by any of the acidic method, the neutral method and the ammonia method.

In the production of silver halide photographic emulsion,
The halide ion and the silver ion may be mixed at the same time, or the other may be mixed in the presence of either one. Also,
It may be grown by adding halide ions and silver ions successively or simultaneously while controlling the pH and pAg in the mixing vessel, while considering the critical growth rate of the silver halide crystal. The conversion method may be used to change the silver halide composition of the grains at any step of the silver halide formation. Further, halide ions and silver ions may be supplied as fine silver halide particles into the mixing vessel.

In the production of silver halide photographic emulsion,
Known silver halide solvents such as ammonia, thioether, thiourea and the like can be present.

The silver halide grains contained in the silver halide photographic emulsion are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), in the process of forming grains and / or the process of growing grains. Rhodium salt (including complex salt)
And at least one selected from iron salts (including complex salts) can be used to add a metal ion so that these metal elements can be contained inside and / or on the surface of the particles, and the particles are placed in a suitable reducing atmosphere. By this, reduction sensitization nuclei can be imparted to the inside of the grain and / or the surface of the grain.

In the silver halide photographic emulsion, unnecessary soluble salts may be removed after the completion of the growth of silver halide grains, or may be contained. When removing the salts, Research Disclosure (Research D
isclosure, hereinafter abbreviated as RD. ) It can be carried out based on the method described in No. 17,643 Item II.

Conditions other than those mentioned above in the production of the silver halide photographic emulsion according to the present invention are described in JP-A-61-6643.
No. 61, No. 61-14630, No. 61-112142, No. 62-
No. 157024, No. 62-18556, No. 63-92942,
63-151618, 63-l63451, 63-220238.
The optimum conditions can be selected with reference to known methods such as Japanese Patent Publication No. 63-311244 and Japanese Patent Publication No. 63-311244.

The silver halide emulsion can be subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are RD No. 17,643, RD No. 18,716 and RD No.
No.308,119 (Respectively RDl7,643, RDl8,716 and RD
Abbreviated as 308,119. )It is described in. Table 1 shows the locations.

[0075]

[Table 1]

When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, photographic additives that can be used are described in the above RD. Table 2 shows the relevant locations.

[0077]

[Table 2]

The hardener is used in an amount of 1 to 20% by weight, preferably 2 to 10% by weight, based on dry-processed gelatin.

When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, various couplers can be used, specific examples of which are described in RD17,643 and RD308,119 below. Table 3 shows the related description.

[0080]

[Table 3]

These additives are RD308,119 1,007
It can be added to the photographic light-sensitive layer by the dispersion method described in page XIV.

For the color photographic light-sensitive material, the above-mentioned RD308,11 is used.
9 An auxiliary layer such as a filter layer or an intermediate layer described in Section VII-K can be provided.

When the color photographic light-sensitive material is constituted, various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above-mentioned RD308, 119 VII-K can be adopted.

To develop the silver halide photographic light-sensitive material of the present invention, for example, T.W. H. James, Theory of the Photographic Process 4th Edition (Th
e Theory of The Photografic Process Forth Editio
n) Pages 291-334 and the Journal of the American Chemical Society (JournaI of the Ame
rican Chemical Society) Vol. 73, p. 3,100 (1951)
The developers known per se described in 1) can be used. The color photographic light-sensitive material is RD17,6 described above.
43 Development can be carried out by the usual method described on pages 28 to 29, RDl8,716 pages 615 and RD308,119 XIX.

[0085]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

Example 1 A cellulose triacetate (TAC) support was prepared as follows. Sunawa TAC resin flake (Acetification degree 60.3
~ 61.6%) 15.7 parts by weight, triphenyl phosphate 1.6
Parts by weight, methylene chloride: ethanol (84:16)
82.7 parts by weight of a viscous solution (hereinafter referred to as dope) was cast on a rotating endless stainless belt to a thickness of 100 μm after drying, and the dope weight was about 1/10. On the belt, and the dope film is peeled off after one rotation, and while heating and drying while conveying on multiple rotating rolls, when the residual solvent is 10% or less, first place the following below on one side. The coating liquid is applied and dried so as to be 20 ml / m ² on one side, and then the following antistatic processing liquid is applied and dried on the opposite side so as to be 18 ml / m ² , and then the antistatic layer of the antistatic layer is applied. Cellulose diacetate on top of the protective layer liquid
100 mg / m ² , stearic acid 50 mg / m ² and silica matting agent 50 mg / m ² coated and dried to process TA
A C support was prepared and provided for the next production of the light-sensitive material.

(Subtraction liquid) Vinyl acetate-maleic anhydride copolymer 4.3 parts by weight Acetone 550 parts by weight Ethyl acetate 135 parts by weight Isopropanol 40 parts by weight Ultrafine particle silica (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) 0.01
Parts by Weight (Antistatic Processing Liquid (1)) Antistatic Exemplary Compound (P-2, 5, 7, 8, 1 of the present invention
0,13,16,18) and the following comparative compounds (A, B) 8.0 parts by weight each: acetone: methanol (55:45 by weight ratio) mixed solvent 450 parts by weight (antistatic processing liquid (2)) antistatic processing Cellulose diacetate (binder) was added to the liquid (1) in an amount of 2 to 3.34 times that of the antistatic exemplary compound of the present invention to obtain a processing liquid (2).

Comparative compound: (A) compound described in JP-B-60-51693 (B) compound described in JP-B-58-56858

[0089]

[Chemical 8]

The above coated TAC support was overcoated with each layer of the following composition to form a color negative photographic film.

(Photosensitive Layer Composition) A photosensitive material exactly the same as the photosensitive material described in Example 1 of Japanese Patent Application No. 4-267697 was prepared. That is, the first layer is an antihalation layer, the second layer is an intermediate layer, the third to fourth layers are red sensitive emulsion layers, the fifth layer is an intermediate layer, the sixth to seventh layers are green sensitive emulsion layers, and the eighth layer is an eighth layer. A yellow filter layer, a blue-sensitive emulsion layer as the ninth to tenth layers, and a protective layer as the eleventh to twelfth layers.

(Sample processing) The material was cut into a film of 24 pieces of 35 mm width. Antistatic performance and adhesiveness of these samples were evaluated. The control between the compound No. and the sample No. is shown in Table 4.

[Evaluation of Antistatic Performance and Adhesive Strength] The antistatic performance was evaluated by generation of static marks and measurement of surface specific resistance.

1. Static mark test In a dark room adjusted to 23 ° C. and 20% RH, the surface of the unexposed photosensitive material sample, which had been humidity-controlled under the same conditions for 24 hours, was faced down on a rubber sheet. After that, a static mark was generated by pressure-bonding with a rubber roller and then peeling. Each peeled sample was treated with the following developer or the like. [Development Processing] (Process 1.) l. Color development: 3 minutes 15 seconds 38.0 ± 0.1 ° C 2. Bleaching …… 6 minutes 30 seconds 38.0 ± 3.0 ℃ 3. Rinse with water …… 3 minutes 15 seconds 24-41 ℃ 4. Settling …… 6 minutes 30 seconds 38.0 ± 3.0 ℃ 5. Rinse with water …… 3 minutes 15 seconds 24-41 ℃ 6. Stabilization: 3 minutes 15 seconds 38.0 ± 3.0 ° C 7. Dryness ... 50 ° C or less The composition of the processing liquid used in each process is shown below.

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5g Sodium bromide l.3g Nitrilotriacetic acid sodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1l (pH = 10.l) <Bleach> Ethylenediaminetetraacetate iron (LlI) Ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Add water to make 1 liter, and adjust to pH 6.0 with ammonia water. <Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 1 liter and adjust to pH 6.0 with acetic acid <Stabilizing liquid> Formalin (37% aqueous solution) l.5ml Conidax (manufactured by Konica Corporation) 7.5 ml Add water to make 1 liter.

(Static Mark Evaluation Criteria) A: No generation of static marks is observed B: Static marks are slightly generated C: Static marks are considerably generated D: Static marks are significantly generated E: Static marks are generated on the entire surface.

2. Measurement of surface specific resistance value It was measured using a teraohm meter model VE-30 manufactured by Kawaguchi Electric Co., Ltd. in a room whose humidity was adjusted to 23 ° C. and 20% RH. Each sample, which has been conditioned at 23 ° C. and 20% RH for 24 hours, is sandwiched between stainless steel electrodes having an electrode interval of 5 cm and a length of 1 cm, and the value is measured for 1 minute.

3. Adhesive strength 3-1. Test with dry film Make a shallow scratch with a razor on the surface of the antistatic layer side of the sample, and apply a 24 mm wide cellophane tape (cellophane adhesive tape LP made by Nichiban Co., Ltd.) with a length of 3 cm centered on the scratch at a right angle to the scratch. Adhere closely, hold one end of the tape in your hand, and peel off rapidly in the direction of the scratch. The peeled area on the surface of the antistatic layer is calculated and calculated. If 95% or more of the pasted cellophane tape remains, there is no practical problem.

3-2. Test with treatment film The sample was immersed in two kinds of treatment baths at a predetermined temperature for a predetermined time, and the surface of the antistatic layer of the sample was sharply sharpened in a final stabilizing bath. A scratch is made in a grid pattern at the tip, and the whole part of the grid pattern is rubbed in the bath with the palm of the finger, and whether or not the film is peeled off is measured by expressing the peeled area as a percentage. Processing 1
Is a normal treatment bath (described in 1. Static Mark Test above) and treatment 2 is a rapid treatment bath. With the treated film, there is no problem if the area that is not peeled off is practically 95% or more.

(Processing 2) l. Color development: 3 minutes 15 seconds 38.0 ± 0.1 ° C 2. Bleaching …… 45 seconds 38.0 ± 3.0 ℃ 3. Settlement …… 1 minute 45 seconds 38.0 ± 3.0 ℃ 4. Stabilization …… 50 seconds 38.0 ± 3.0 ℃ 5. Drying: 1 minute 00 seconds 40 to 80 ° C or less The composition of the processing liquid used in each process is shown below.

<Color developer> 4-Amino-3-methyl-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.8 g Potassium sulfite 5.0 g Hydroxylamine / 1/2 sulfate 2.5 g Potassium carbonate 30 g Carbonic acid Sodium hydrogen 2.5 g Sodium bromide 1.3 g Potassium iodide 2 mg Sodium chloride 0.6 g Potassium hydroxide 1.2 g Water is added to make 1 liter, and pH is adjusted to 10.06 with potassium hydroxide or 20% sulfuric acid.

<Bleach> Ethylenediaminetetraacetic acid iron (llI) ammonium salt 150 g Ethylenediaminetetraacetic acid diammonium salt 10 g Ammonium bromide 150 g Glacial acetic acid 10 ml The color developer 200 ml Water was added to make 1 l, and ammonia water or glacial acetic acid was used. Adjust to pH 5.8.

<Fixer> Ammonium thiosulfate 150 g Anhydrous sodium bisulfite 12 g Sodium metabisulfite 2.5 g Ethylenediaminetetraacetic acid disodium 0.5 g Sodium carbonate 10 g The bleaching solution 100 ml Water was added to make 1 liter, pH 7 was added using acetic acid and aqueous ammonia. Adjust to .0. <Stabilizing liquid> Formalin (37% aqueous solution) 2 ml 5-chloro-2-methyl-4-isothiazolin-3-one 0.05 g Emulgen 810 1 ml Formaldehyde bisulfite sodium 2 g Add water to make 1 liter, and add ammonia water and 50 Adjust to pH 7.0 with% sulfuric acid.

Evaluation results: The degree of occurrence of static marks was evaluated according to the above evaluation criteria. The surface resistivity of the antistatic surface measured under the same conditions was also measured. The results are shown in Table 4.

[0105]

[Table 4]

As can be seen from Table 4, the comparison between the antistatic compound according to the present invention and the comparative compound clearly shows that the samples (No. 1 to 10) having the antistatic layer consisting of the antistatic compound of the present invention were used. Is the antistatic layer of the compound for comparison (No. 11
It can be seen that the occurrence of static marks is less than in (13) to (13), drying and treatment with a film are excellent, and especially rapid treatment with a film is also excellent.

Example 2. A sample was prepared in exactly the same manner as in Example 1, and the same test method was used. The difference from Example 1 is that the amount of binder is changed by two levels. The results are shown in Table 5.

Evaluation result:

[0109]

[Table 5]

As can be seen from Table 5, the comparison between the antistatic agent compound according to the present invention and the comparative compound clearly shows that the samples (Nos. 1 to 6) having the antistatic layer comprising the antistatic agent compound of the present invention were used. One is the antistatic layer of the comparative compound (No. 7
9 to 9), less static marks are generated, and drying and treatment with a film are also excellent, and in particular, rapid treatment with a film is excellent.

[0111]

It is an object of the present invention to provide a silver halide photographic light-sensitive material having an antistatic layer which is excellent in antistatic performance and adhesion of the antistatic layer.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoichi Saito 1 Konica Stock Company, Sakura-cho, Hino City, Tokyo

Claims (1)

[Claims] 1. A photographic light-sensitive material having at least one light-sensitive silver halide layer on a support, which contains a polymer having a repeating unit represented by the following general formulas (1) and / or (2). A silver halide photographic light-sensitive material having at least one layer. General formulas (1) and (2): In the general formula (1), R ₁ represents a hydrogen atom or a methyl group, and R ₂ , R ₃ and R ₄ represent an alkyl group, an aralkyl group and an allyl group, respectively. R ₂ , R ₃ and R ₄ may be the same or different. However, R ₂ ,
At least one of R ₃ and R ₄ is an allyl group.
_{Two of} R ₂ , R ₃ and R ₄ may be linked to form a 5-membered ring or 6-membered ring together with the nitrogen atom. L ₁ represents a divalent group. X ₁ represents an anion. x ₁ , y ₁ and z ₁ represent mole fractions, x ₁ is 0 to 20%, y ₁ is 0 to 70%, z ₁ is 30 to 100%
Is. In the formula, A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain, and B represents a repeating unit having a copolymerizable ethylenically unsaturated group. Indicates a unit. In the general formula (2), R ₅ represents a hydrogen atom or a methyl group, and R ₆ represents an allyl group. D is a 5- or 6-membered heterocyclic ring having one or two nitrogen atoms.
D may have a substituent. X ₂ represents an anion.
x ₂ , y ₂ and z ₂ represent a mole fraction, x ₂ is 0 to 20%, y ₂
Is 0 to 70% and z ₂ is 30 to 100%. In the formula, A represents a repeating unit having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain,
B represents a repeating unit having a copolymerizable ethylenically unsaturated group.