JPH0836239A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material with an antistatic layer contg. tightly held electrically conductive metal oxide particles. CONSTITUTION:A silver halide photographic sensitive layer is formed on one side of a plastic film substrate and an antistatic layer and a surface layer are successively formed on the other side to obtain the objective silver halide photographic sensitive material. The antistatic layer consists of electrically conductive metal oxide particles and a cured product of at least one kind of polymer selected from among acrylic resin, vinyl resin, polyurethane resin and polyester resin with a melamine compd.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having an antistatic property.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter referred to as "sensitive material") is generally a photosensitive silver halide photographic emulsion layer (hereinafter referred to as "light-sensitive layer") and an antihalation layer on an electrically insulating plastic film support. A layer, a protective layer, an intermediate layer, an undercoat layer, a backing layer (hereinafter referred to as "back layer") and the like are applied and dried.

In recent years, the technique for producing a sensitive material has been remarkably improved, and for example, the coating speed of the undercoat layer or the photosensitive layer, or the cutting and cutting processes have been sped up. Scratches or peeling tend to occur easily due to contact friction with. In addition, the sensitive material is charged with static electricity due to contact friction, and dust (dirt or dust) tends to adhere to the sensitive material. The occurrence of such scratches, peeling, or dust adhesion leads to the formation of various spots such as water repellency, desensitization, and fog. Furthermore, when static electricity accumulated in the photosensitive material is discharged by contact friction, so-called static marks are generated on the photosensitive layer, which is a fatal defect. The tendency of speeding up is the same in the photographing and development processing steps, and static electricity tends to be easily generated in these steps as well.

Further, when the image information recorded on the photosensitive material is further enlarged and used, such as a microfilm and a movie film, the image becomes unsightly due to dust and the like adhering to the film due to static electricity. This will significantly reduce the commercial value of the film shot.

For this reason, it is known that the photosensitive material is provided with an antistatic layer containing a conductive polymer, an ionic or nonionic surfactant, colloidal silica, a metal oxide or a composite oxide thereof. ing. However, for example, a surfactant that elutes in the developing solution during the developing process not only loses the antistatic performance after the developing process but also causes deterioration of photographic characteristics such as deterioration of the developing solution. There are cases. Further, in low humidity such as in winter, an antistatic agent such as a conductive polymer generally cannot exhibit sufficient antistatic performance because of its ionic conductivity. As the antistatic agent, in particular, a metal oxide or a composite oxide thereof, or a composite oxide thereof is used, because it does not deteriorate the photographic performance during the development process and does not depend on the humidity after the development process and exhibits the antistatic property. Fine particles containing a small amount of different kinds of atoms are preferable, for example, Japanese Patent Publication No. 1-20736, Japanese Patent Application Laid-Open No. 61-20033, and Japanese Patent Application Laid-Open No. 4-39.
Japanese Patent No. 651 describes an antistatic layer containing these particles.

Further, as a method for preventing the scratches on the film surface caused by the contact friction between the photosensitive material and the conveying roll during the production of the photosensitive material, for example, Japanese Patent Application Laid-Open No. 1-210 is known.
It is known to use water-soluble methylcellulose and water-dispersible synthetic polymers as described in 947 as polymers for the surface layer (over-coat layer) of the back layer (antistatic layer). And, as a result, the prevention of scratches is improved.

[0007]

In addition to the above-mentioned problems caused by the speeding up of the production of a light-sensitive material, a problem that has recently become particularly apparent is that metal oxide particles, which are antistatic agents, are present in the production process. An example of development is so-called powder falling, which is released from the film surface by contact friction with a transport roll or the like and adheres to the roll surface or the like. Particles that have been desorbed and adhered to rolls, etc., during the manufacturing process,
It may be redeposited on the film to cause defective coating or scratches, resulting in a marked decrease in productivity.

In the manufacturing process of the antistatic layer containing the metal oxide particles, since the layer thickness of the back layer (antistatic layer) is smaller than the particle diameter of the metal oxide particles, a considerable amount of the metal oxide particles are contained. The part protrudes from the surface of the antistatic layer, and even if the surface layer is formed, the protruding part remains, so that the strength of the antistatic layer becomes insufficient when the film is pressed by a roll to form a photosensitive layer. If sufficient, it will be desorbed. According to the study by the present inventors, as a binder for an antistatic layer, a compound of a styrene-maleic acid copolymer and an epoxy compound described in JP-A-4-39651, or JP-A-61-20033. Even when the polyester described in 1) is used, the metal oxide particles cannot be retained so as not to be detached from the photosensitive material during the manufacturing process, and these binders have sufficient strength to prevent detachment. It became clear that there is no. Moreover, since the binder described in Japanese Patent Publication No. 1-20736 has gelatin as a main component,
The resulting antistatic layer has a problem that it has insufficient water resistance and is easily softened by a treatment liquid or the like in a subsequent treatment step.

Accordingly, it is an object of the present invention to provide a silver halide photographic light-sensitive material having an antistatic layer in which conductive metal oxide particles are firmly held. Specifically, an object of the present invention is to provide a silver halide photographic light-sensitive material having no deterioration of antistatic property after development processing, almost no loss of conductive metal oxide particles during the manufacturing process, and further improved scratch resistance. And

[0010]

The above object is to provide a silver halide photographic photosensitive layer on one side of a plastic film support, and an antistatic layer and a surface layer in that order on the other side. In the silver halide photographic material, the antistatic layer comprises conductive metal oxide particles, at least one polymer selected from the group consisting of acrylic resins, vinyl resins, polyurethane resins and polyester resins, and a melamine compound. It can be achieved by a silver halide photographic light-sensitive material characterized by comprising a cured product.

The preferred embodiments of the silver halide photographic light-sensitive material of the present invention are as follows. 1) The conductive metal oxide particles are ZnO, TiO ₂ , S
At least one metal oxide selected from the group consisting of nO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, and composite oxides thereof, or a metal oxide containing a different metal in the metal oxide. Silver halide photographic light-sensitive material. 2) The above silver halide photographic light-sensitive material, wherein the acrylic resin is a polymer composed of at least two kinds of monomers selected from the group consisting of acrylic acid esters and methacrylic acid esters. 3) The vinyl resin is polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinylholmar, polyolefin, ethylene / butadiene copolymer or ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / acrylic ester copolymer). The silver halide photographic light-sensitive material described above. 4) The silver halide photographic light-sensitive material, wherein the polyurethane is a polyurethane derived from polyisocyanate and at least one polyol selected from the group consisting of aliphatic polyester polyols, polyether polyols, polycarbonate polyols, and polyethylene terephthalate polyols. . 5) The silver halide photographic light-sensitive material, wherein the polymer is an acrylic resin. 6) The silver halide photographic light-sensitive material, wherein the polymer is polyurethane. 7) The above silver halide photographic light-sensitive material, wherein the melamine compound is a compound having two or more (preferably three or more) methylol groups or alkoxymethyl groups. 8) The silver halide photographic light-sensitive material, wherein the surface layer is made of a polyolefin having a carboxyl group and / or a carboxylate group. 9) The photographic light-sensitive material as described above, wherein the surface of the plastic film support is subjected to surface activation treatment (preferably corona discharge treatment). 10) The above photographic light-sensitive material in which the plastic film support is biaxially stretched.

The details of the present invention will be described below. In the present invention, as the plastic film support,
Examples thereof include polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, polycarbonate, polystyrene and polyethylene films. Among them, a polyethylene terephthalate film is preferable, and a biaxially stretched and heat-fixed polyethylene terephthalate film is particularly preferable in terms of stability and toughness.

The thickness of the support is not particularly limited, but may be 15 to
The range of 500 μm is generally used, and the range of 40 to 200 μm is particularly preferable because it is advantageous in terms of handling and general versatility. The support may be transparent or may contain dyed silicon, alumina sol, chromium salt, zirconium salt and the like.

In order to firmly adhere the photosensitive layer to the surface of the plastic film support, the following surface treatment is generally performed. Antistatic layer (back layer) of the present invention
A similar surface treatment is generally performed on the surface on which is formed. (1) Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone acid treatment,
After surface activation treatment such as, the method of directly applying a photographic emulsion (coating liquid for forming photosensitive layer) to obtain the adhesive force, and (2) once these surface treatments are performed, an undercoat layer is provided and a photograph is formed on top of this. There are two methods, a method of coating an emulsion layer. Of these, the method (2) is more effective and widely used. In all of these surface treatments, the formation of more or less polar groups on the surface of the support, which was originally hydrophobic, the removal of thin layers which are a negative factor for the adhesion of the surface, and the crosslinking of the surface. It is thought to increase the density and the adhesive strength, and as a result, the affinity of the components contained in the undercoat layer solution with polar groups is increased and the fastness of the adhesive surface is increased. It is considered that the adhesion between the undercoat layer and the surface of the support is improved by the above.

As the method of applying the undercoat layer, a so-called multi-layer method in which a layer which is well adhered to a support is provided as a first layer, and a gelatin layer is applied and formed as a second layer thereon, and a hydrophobic layer are used. There is a single layer method in which only one layer of a resin layer containing both groups and hydrophilic groups is applied. As a method for forming the undercoat layer, for example, a method of forming two undercoat layers, which is a first undercoat layer of a polymeric substance and a second undercoat layer of gelatin, in an aqueous system can be mentioned. Examples of the polymer substance of the first undercoat layer include, for example,
Starting from copolymers starting from monomers selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, polyethyleneimine, epoxy resin grafted gelatin , Nitrocellulose and the like.
A hardener such as a dichlorotriazine derivative or an epoxy compound is generally used in combination to form the first undercoat layer and the second gelatin undercoat layer.

If desired, for example, phenol or resorcin may be added to the first undercoat layer as a swelling agent, and the addition amount is 1 to 10 g per liter of the coating solution for the first undercoat layer. . A hydrophilic polymer may be used in the first undercoat layer, for example, a natural polymer such as gelatin,
Examples thereof include synthetic polymers such as polyvinyl alcohol, vinyl acetate-maleic anhydride copolymer, acrylic acid-acrylamide copolymer, and styrene-maleic anhydride copolymer. Further, it is also possible to use a matting agent (silicon dioxide, polymethyl acrylate, polystyrene), methyl cellulose, polyvinyl alcohol or the like as an antiblocking agent.

The coating solution for the first undercoat layer according to the present invention is a coating method which is generally well known, for example, a dip coating method,
It can be applied by an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or an extrusion coating method using a popper described in US Pat. No. 2,681,294. When a second subbing layer is further provided on the subbing layer, if necessary, US Pat.
No. 3508947, No. 2941898 and No. 3526528, and Ozaki et al., “Coating Engineering”, page 253 (published by Asakura Shoten in 1973). I can.

The coating amount of the first undercoat layer according to the present invention and the second undercoat layer provided on the first undercoat layer is 0.01 to 10 g per square meter of the polyester film support as a solid content. Is preferable, and 0.2 to 3 g is particularly preferable. In the present invention, a hydrophilic colloid layer containing gelatin as a main component is provided as a second undercoat layer on the first undercoat layer.

Examples of hydrophilic polymers other than gelatin used in the second undercoat layer include acylated gelatin such as phthalated gelatin and maleated gelatin, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, acrylic acid and methacryl. Grafted gelatin in which acid or amide is grafted to gelatin,
Polyvinyl alcohol, polyhydroxyalkyl acrylate, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, casein, agarose, albumin, sodium alginate, polysaccharide, agar, starch, graft starch, polyacrylamide, polyethyleneimine acyl compound, and acrylic Acid, methacrylic acid acrylamide, N-substituted acrylamide and N-
A homopolymer or copolymer such as a substituted methacrylamide, or a synthetic or natural hydrophilic polymer compound such as a partial hydrolyzate thereof can be mentioned. These can be used alone or in combination.

If necessary, an antistatic agent, a crosslinking agent, a matting agent, an antiblocking agent, etc. can be added to the hydrophilic polymer as described above.

Next, the photosensitive silver halide photographic emulsion layer (photosensitive layer) used in the present invention will be briefly described. Examples of the binder (hydrophilic organic protective colloid) for the photosensitive layer include acylated gelatin such as gelatin, phthalated gelatin and maleated gelatin, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, acrylic acid, methacrylic acid or amide (acrylamide). Etc.) and the like grafted on gelatin, polyvinyl alcohol, polyhydroxyalkyl acrylate, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, casein, agarose, albumin, sodium alginate, polysaccharides, agar, tempura, Examples include synthetic or natural hydrophilic polymer compounds such as graft starch, polyacrylamide, polyethylenimine acylated products, and partial hydrolysates thereof. Can. These materials can be used alone or as a mixture.

If the binder is a hydrophilic polymer compound as described above, what is added to the binder is not particularly important in the present invention, but these hydrophilic binders are usually used. Physical development nuclei such as silver halide or silver sulfide used in the diffusion transfer photographic method, and various additives such as a sensitizing material such as a diazo compound, a coupler, an emulsion polymerization and a latex polymer are added.

Various materials used for the above-mentioned photosensitive layer, for example, silver halide grains, chemical sensitizers, dyes, polymer latex, surfactants, gelatin hardeners, color couplers, anti-fading agents, antistatic agents, mats. There is no particular limitation on the agent, for example, Research Disclosure (Re
search Disclosure 176, 22-31 (1978)
(December year) can be referred to.

Although the present invention is not always necessary, surface treatment such as corona discharge treatment is carried out not only on the hydrophobic support but also on the undercoat layer made of a polymeric substance and / or the second undercoat layer. In that case, the adhesion between the layers after the treatment is improved.

An antistatic layer of the present invention and a surface layer are provided in this order on the surface of the plastic film support on which the photosensitive layer is not provided. The antistatic layer of the present invention,
A layer in which conductive metal oxide particles are dispersed in a cured product of any one of the following polymers or a mixture thereof and a melamine compound. Acrylic resin, vinyl resin, polyurethane resin and polyester resin are used as the polymer.

As the material of the conductive metal oxide particles, Z
nO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ ,
MgO, BaO and MoO ₃ and their composite oxides,
Further, these metal oxides can further include metal oxides containing different atoms. As the metal oxide, Sn
O ₂ , ZnO, Al ₂ O ₃ , TiO ₂ , In ₂ O ₃ and MgO are preferable, and SnO ₂ , ZnO and In ₂ are further preferable.
O ₂ and TiO ₂ are preferred, SnO ₂ is particularly preferred. As an example containing a small amount of heteroatoms, A for ZnO
l or In, Nb or Ta for TiO ₂ ,
Sn for In ₂ O ₃ and Sb for SnO ₂ ,
Nb or a different element such as a halogen element is 0.01 to
Examples thereof include those doped with 30 mol% (preferably 0.1 to 10 mol%). The amount of different elements added is
If it is less than 0.01 mol%, sufficient conductivity cannot be imparted to the oxide or composite oxide, and if it exceeds 30 mol%, the degree of blackening of the particles is increased and the antistatic layer is darkened. Not suitable for use. Therefore, in the present invention, the material of the conductive metal oxide particles is preferably a material containing a small amount of a different element with respect to the metal oxide or the composite metal oxide. Further, those having an oxygen defect in the crystal structure are also preferable.

The conductive metal oxide particles are added to the antistatic layer by a binder (the above-mentioned polymer and melamine compound).
It is preferably contained in the range of 10 to 1000% by weight, more preferably 200 to 800% by weight. If it is less than 10% by weight, sufficient antistatic properties cannot be obtained, and if it exceeds 1000% by weight, it is impossible to prevent the conductive metal oxide particles from falling off from the photosensitive material.

The particle size of the conductive metal oxide particles is preferably as small as possible in order to minimize light scattering, but it should be determined by using the ratio of the refractive index of the particles and the binder as a parameter. ) Can be used for the calculation. Generally, the average particle size is 0.001
It is in the range of 0.5 μm, preferably in the range of 0.003 to 0.2 μm. Here, the average particle diameter is a value that includes not only the primary particle diameter of the conductive metal oxide particles but also the particle diameter of the higher-order structure.

When the fine particles of the above metal oxide are added to the coating liquid for forming the antistatic layer, they may be added as they are and dispersed, but a solvent such as water (including a dispersant and a binder if necessary). It is preferable to add a dispersion liquid dispersed in (1).

The antistatic layer of the present invention contains a cured product of the above-mentioned polymer (acrylic resin, vinyl resin, polyurethane resin or polyester resin) and a melamine compound as a binder for dispersing and supporting the conductive metal oxide particles. I'm out. In the present invention, from the viewpoint of maintaining a good working environment and preventing air pollution, it is preferable to use a water-soluble polymer or melamine compound, or to use it in a water-dispersed state such as an emulsion. Further, the polymer has any group of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group so that a crosslinking reaction with a melamine compound is possible. A hydroxyl group and a carboxyl group are preferable, and a carboxyl group is particularly preferable. The content of the hydroxyl group or the carboxyl group in the polymer is preferably 0.0001 to 1 equivalent / 1 kg, and particularly preferably 0.001 to 1 equivalent / 1 k.
g is preferred.

Examples of the acrylic resin include acrylic acid, acrylic acid esters such as alkyl acrylate, methacrylic acid esters such as acrylamide, acrylonitrile, methacrylic acid, alkyl methacrylate, methacrylamide, and methacrylonitrile. Mention may be made of homopolymers or copolymers obtained by polymerizing two or more of these monomers. Among these,
A homopolymer of any one of acrylic acid esters such as alkyl acrylate and methacrylic acid esters such as alkyl methacrylate, or a copolymer obtained by polymerizing two or more of these monomers is preferable. For example, a homopolymer of any one of acrylic acid esters and methacrylic acid esters having an alkyl group having 1 to 6 carbon atoms or a copolymer obtained by polymerization of two or more of these monomers may be mentioned. it can. The acrylic resin has the above-mentioned composition as a main component, so that a crosslinking reaction with a melamine compound is possible, for example, by partially using a monomer having any group of a methylol group, a hydroxyl group, a carboxyl group and a glycidyl group. The resulting polymer.

Examples of the vinyl resin include polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinylholimal, polyvinyl butyral, polyvinyl methyl ether, polyolefin, ethylene / butadiene copolymer, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, Examples thereof include vinyl chloride / (meth) acrylic acid ester copolymers and ethylene / vinyl acetate copolymers (preferably ethylene / vinyl acetate / (meth) acrylic acid ester copolymers). Among them, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinylholmar, polyolefin, ethylene / butadiene copolymer and ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / acrylic acid ester copolymer) are preferable. The vinyl resin is a polyvinyl alcohol, an acid-modified polyvinyl alcohol, a polyvinyl formal, a polyvinyl butyral, a polyvinyl methyl ether and a polyvinyl acetate so that a crosslinking reaction with a melamine compound is possible, for example, a vinyl alcohol unit in a polymer. By leaving it as a polymer having a hydroxyl group, for other polymers, for example, a methylol group,
A polymer obtained by partially using a monomer having any one of a hydroxyl group, a carboxyl group and a glycidyl group.

Examples of the polyurethane resin include polyhydroxy compounds (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane), aliphatic polyester polyols and polyether polyols obtained by reacting polyhydroxy compounds with polybasic acids. (Example, any one of poly (oxypropylene ether) polyol, poly (oxyethylene-propylene ether) polyol), polycarbonate-based polyol, and polyethylene terephthalate polyol, or a polyurethane derived from a mixture of these and polyisocyanate. You can In the polyurethane resin, for example, after the reaction between the polyol and the polyisocyanate, the unreacted residual hydroxyl group can be used as a functional group capable of undergoing a crosslinking reaction with the melamine compound.

As the polyester resin, a polymer obtained by reacting a polyhydroxy compound (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane) with a polybasic acid is generally used. In the above polyester resin, for example, a hydroxyl group and a carboxyl group which remain unreacted after the reaction of the polyol and the polybasic acid can be used as a functional group capable of a crosslinking reaction with a melamine compound. Of course, a third component having a functional group such as a hydroxyl group may be added.

Among the above polymers, acrylic resins and polyurethane resins are preferable, and acrylic resins are particularly preferable.

The melamine compound used in the present invention has two or more (preferably three or more) in the melamine molecule.
Examples thereof include a compound containing a methylol group and / or an alkoxymethyl group, and a condensation polymer thereof such as a melamine resin or a melamine-urea resin. Examples of the initial condensation product of melamine and formalin include dimethylolmelamine, trimethylolmelamine,
There are tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, and the like, and specific commercial products thereof include, for example, Sumitex resin (Sumitex resin).
tex Resin) M-3, the same MW, the same MK, the same MC (manufactured by Sumitomo Chemical Co., Ltd.) and the like, but not limited to these. Examples of the condensation polymer include hexamethylolmelamine resin, trimethylolmelamine resin, trimethyloltrimethoxymethylmelamine resin, and the like. Commercially available products include MA-1 and MA-204 (Sumitomo Bakelite Co., Ltd., BECKAMINE MA-S, Beckamine APM).
And Beckamine J-101 (manufactured by Dainippon Ink and Chemicals, Inc.), Euroid 344 (Mitsui Toatsu Chemicals, Inc.)
Manufactured by Oshika Resin M31, Oshika Resin PWP-8 (manufactured by Oshika Shinko Co., Ltd.), and the like, but are not limited thereto.

The melamine compound of the present invention preferably has a functional group equivalent represented by the value obtained by dividing the molecular weight by the number of functional groups in one molecule, which is 50 or more and 300 or less. Here, the functional means a methylol group and / or an alkoxymethyl group. If this value exceeds 300, the curing density will be small and high strength will not be obtained, and if the amount of the melamine compound is increased, the coating property will deteriorate. If the curing density is low, scratches are likely to occur. In addition, the retention of the conductive metal oxide is also reduced. If the functional group equivalent is less than 50, the curing density will be high, but the transparency will be impaired, and even if the amount is reduced, it will not be improved. The addition amount of the aqueous melamine compound of the present invention is 0.1 to 1 with respect to the above polymer.
It is 00% by weight, preferably 10 to 90% by weight.

These melamine compounds may be used alone or in combination of two or more. It can also be used in combination with other compounds, such as CEKMeers and THJa.
mes, "The Theory of the Photographic Process" 3rd edition (1966), U.S. Pat. Nos. 3,316,095, 3,232,764, 3,288,775, and 27,323.
03, 3635718, 3232763, 2732316, 2586168, 31034.
No. 37, No. 3017280, No. 2983611, No. 2725294, No. 2725295, No. 31007.
No. 04, No. 3091537, No. 3321313, No. 3543292, and No. 3125449, and hardeners described in British Patent Nos. 994869 and 1167207. As a typical example,
Mucochloric acid, mucobromic acid, mucophenoxycycloric acid, mucophenoxypromic acid, formaldehyde, glyoxal, monomethylglyoxal, 2,3-dihydroxy-1,4dioxane, 2,3-dihydroxy-
5-methyl-1,4-dioxane succinaldehyde,
Aldehyde compounds such as 2,5-dimethoxytetrahydrofuran and glutaraldehyde and their derivatives; divinylsulfone-N, N'-ethylenebis (vinylsulfonylacetamide), 1,3-bis (vinylsulfonyl) -2-propanol, methylenebis. Maleimide, 5
-Acetyl-1,3-diacryloyl-hexahydro-
Active vinyl compounds such as s-triazine, 1,3,5-triacryloyl-hesahydro-s-triazine and 1,3,5-trivinylsulfonyl-hexahydro-s-triazine; 2,4-dichloro-6-hydroxy -S
-Triazine sodium salt, 2,4-dichloro-6-
Activity of (4-sulfoanilino) -s-triazine sodium salt, 2,4-dichloro-6- (2-sulfoethylamino) -s-triazine and N, N'-bis (2-chloroethylcarbamyl) piperazine Halogen-based compound; bis (2,3-epoxypropyl) methylpropylammonium p-toluenesulfonate, 1,4-bis (2 ′, 3′-epoxypropyloxy) butane,
1,3,5-triglycidyl isocyanurate, 1,3
-Diclycidyl-5- (γ-acetoxy-β-oxypropyl) isosinurate, sorbitol polyglycidyl ethers, polyglycerol polyglycidyl ethers, pentaerythritol polyglycidyl ethers,
Diglycerol polyglycidyl ether, 1,3,5-
Epoxy compounds such as triglycidyl (2-hydroxyethyl) isocyanurate, glycerol polyglycerol ethers and trimethylolpropane polyglycidyl ethers; 2,4,6-triethylene-s-triazine, 1,6-hexamethylene- Ethyleneimine compounds such as N, N′-bisethyleneurea and bis-β-ethyleneiminoethylthioether; 1,2-di (methanesulfonoxy) ethane, 1,4-di (methanesulfonoxy) butane and 1, Methanesulfonic acid ester compounds such as 5-di (methanesulfonoxy) pentane;
Carbodiimide compounds such as dicyclohexylcarbodiimide and 1-dicyclohexyl-3- (3-trimethylaminopropyl) carbodiimide hydrochloride; isoxazole compounds such as 2,5-dimethylisoxazole;
Inorganic compounds such as chromium alum and chromium acetate; N-carbethoxy-2-isopropoxy-1,2-dihydroquinoline and N- (1-morpholinocarboxy) -4-
Dehydration condensation type peptide reagents such as methylpyridinium chloride; active ester compounds such as N, N'-adipoyldioxydisuccinimide and N, N'-terephthaloyldioxydisuccinimodo: toluene-2,4 -Isocyanates such as diisocyanate and 1,6-hexamethylene diisocyanate; and epichlorohydrin-based compounds such as polyamide-polyamine-epichlorohydrin reaction products, but not limited thereto.

If necessary, a matting agent, a surface active agent, a slipping agent and the like may be used in combination in the antistatic layer of the present invention and the following surface layer. As a matting agent,
Examples thereof include oxides such as silicon oxide, aluminum oxide and magnesium oxide having a particle size of 0.001 μm to 10 μm, and polymers or copolymers such as polymethylmethacrylate and polystyrene. Examples of the surfactant include known anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and the like. Examples of the slip agent include phosphoric acid esters of higher alcohols having 8 to 22 carbon atoms or amino salts thereof; palmitic acid, stearic acid, behenic acid and esters thereof; and silicone compounds.

In the antistatic layer of the present invention, the above-mentioned polymer and melamine compound are prepared by dispersing the above-mentioned conductive metal oxide particles as they are or in a solvent such as water (including a dispersant and a binder if necessary) into the above-mentioned polymer and melamine compound. And an aqueous dispersion or an aqueous solution containing appropriate additives, added and mixed (dispersed as necessary) to prepare a coating liquid for forming an antistatic layer. The antistatic layer of the present invention may be prepared by applying the above antistatic layer-forming coating liquid to the surface of a plastic film such as polyester (on the side where the photosensitive layer is not provided) by a well-known coating method such as dip coating or air knife coating. Method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method and the like. The applied plastic film such as polyester may be subjected to sequential biaxial stretching, simultaneous biaxial stretching, uniaxial stretching and re-stretching, or biaxial stretching.
The surface of the plastic support to which the coating liquid for forming an antistatic layer is applied is preferably subjected to surface treatment such as ultraviolet ray treatment, corona treatment and glow discharge treatment in advance.

The layer thickness of the antistatic layer of the present invention is 0.01 to.
The range of 1 μm is preferable, and further 0.01 μ to 0.2 μ
Is preferred. If it is less than 0.01 μm, it is difficult to apply the coating agent evenly, so uneven coating is likely to occur on the product.
If it exceeds m, the antistatic performance and scratch resistance may be poor.

In the present invention, a surface layer is provided on the antistatic layer. The surface layer is provided mainly for improving slipperiness and scratch resistance and for assisting the function of preventing the conductive metal oxide particles from being detached from the antistatic layer. Examples of the material for the surface layer include waxes, resins and rubber-like substances (for example, waxes or homopolymers of 1-olefin unsaturated hydrocarbons such as ethylene, propylene, 1-butene and 4-methyl-1-pentene). Polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-
Penten, ethylene / propylene copolymer, ethylene /
1-butene copolymers and propylene / 1-butene copolymers), rubbery copolymers of two or more of the above 1-olefins with conjugated or non-conjugated dienes (eg ethylene / propylene / ethylidene norbornene copolymers) , Ethylene / propylene / 1,5-hexadiene copolymers and isobutene / isoprene copolymers), copolymers of 1-olefins with conjugated or non-conjugated dienes, (eg ethylene / butadiene copolymers and ethylene / ethylidene copolymers) Norbornene copolymer), 1-olefin, especially ethylene-vinyl acetate copolymer and its complete or partially saponified product, 1-olefin homo- or copolymer grafted with the above conjugated or non-conjugated diene or vinyl acetate Graft polymer and its complete or complete or partial saponification product thereof, Etc. can be mentioned, but not limited thereto. The above compound is described in JP-B-5-41656. The above-mentioned polyolefin having a carboxyl group and / or a carboxylate group is preferable. In the present invention, it is usually used as an aqueous solution or an aqueous dispersion.

Water-soluble methyl cellulose having a methyl group substitution degree of 2.5 or less may be added to the surface layer, and the additive is 0.1% by weight based on the total binder forming the surface layer.
-40% by weight is preferred. The water-soluble methyl cellulose is described in JP-A 1-210947.

The surface layer is formed on the antistatic layer of the present invention by a well-known coating method, for example, a dip coating method,
It can be formed by applying a coating solution (aqueous dispersion or aqueous solution) containing the above binder by an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, or the like. The surface layer preferably has a layer thickness of 0.01 to 1 μm, more preferably 0.01 to 0.2 μm. If the thickness is less than 0.01 μm, it is difficult to uniformly apply the coating agent, so that coating unevenness is likely to occur in the product, and if it exceeds 1 μm, the antistatic performance and scratch resistance may be poor.

[0045]

【Example】

Example 1 (Samples A-1 to A-9, B-1 to B-6 and C-1 to C)
Production of -6) Biaxial stretching (lengthwise and widthwise 3.3 times each),
After heat fixing at 240 ° C. for 10 minutes, one side of a 125 μm-thick polyethylene terephthalate film having both surfaces subjected to corona discharge treatment was provided with a first undercoat layer and a second undercoat layer having the following composition in this order: Formed like. Next, an antistatic layer and a surface layer were formed in this order on the opposite surface of the film as follows. Then, a photosensitive layer was formed on the second undercoat layer as follows, and the photosensitive material (Samples A-1 to A-9,
B-1 to B-6 and C-1 to C-6) were produced.

(Coating liquid for first undercoat layer) Styrene / butadiene copolymer latex 6.3 parts by weight (styrene: butadiene = 67: 30, solid content 40% by weight) 2,4-dichloro-6-hydroxy- s-Triazine 0.2 parts by weight Sodium salt Distilled water 73.5 parts by weight The above coating liquid for the first undercoat layer is applied to one side of the above polyethylene terephthalate film, dried at 180 ° C. for 30 seconds, and 0.3 μm. To form a first undercoat layer.

(Coating Liquid for Second Undercoat Layer) Gelatin 1.6 parts by weight Polystyrene fine particles (average particle size: 2 μm) 0.06 parts by weight Compound of the following (1) 0.006 parts by weight Compound of the following (2) 0.006 parts by weight Glycine 0.05 parts by weight Distilled water 98.278 parts by weight

Compound (1)

[0050]

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Compound (2)

[0052]

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The coating solution for the second undercoat layer is applied on the first undercoat layer and dried at 170 ° C. for 30 seconds to give 0.15
A second subbing layer of μm was formed.

(Coating Liquid for Antistatic Layer) Aqueous Dispersion of Acrylic Resin (Copolymer of (Meth) acrylic Acid Ester; Kind and Amount of Acrylic Resin Used for Each Sample are shown in Tables 1, 2 and 3) ) Tin oxide-antimony oxide dispersion 16.5 parts by weight (average particle size: 0.1 μm; 30% by weight) Polyoxyethylene phenyl ether 0.1 parts by weight Melamine compound (Type and amount of melamine compound used for each sample) Is described in Table 1, Table 2 and Table 3) Distilled water was added to prepare a total of 100 parts by weight. The coating liquid for an antistatic layer was applied to the surface of the polyethylene terephthalate film on which the undercoat layer was not provided, and dried at 180 ° C. for 30 seconds, and then, Tables 1, 2, and 3 were used.
An antistatic layer having the layer thickness described in 1. was formed.

(Coating liquid for surface layer) Polyolefin 3.0 parts by weight (Chemipearl S-120, 27% by weight, manufactured by Mitsui Petrochemical Co., Ltd.) Colloidal silica (Snowtex C, manufactured by Nissan Chemical Co., Ltd.) 2. 0 parts by weight Epoxy compound 0.3 parts by weight (Denacol EX-614B; manufactured by Nagase Kasei Co., Ltd.) Polyethylene sulfonate (molecular weight 1000-5000) 0.1 parts by weight Distilled water 94.6 parts by weight Coating for the surface layer The solution is coated on the antistatic layer, and 1
It was dried at 70 ° C. for 30 seconds to form a surface layer having a layer thickness of 0.03 μm.

Next, a photosensitive layer coating solution having the following composition (1) was dried on the second undercoat layer of the above coating film to a dry thickness of 6.0 μm.
The coating was performed so that the coated silver amount was 5.0 g / m ² . Further, a protective layer having the following composition (2) was coated on the photosensitive layer to prepare a silver halide photographic photosensitive material.

Composition (1) (Photosensitive layer) Gelatin 5 g / m ² Silver chloroiodobromide (Cl: 80 mol% Br: 19.5 mol% I: 0.5 mol%) Chloroauric acid 0.1 g / m ² Polyethylene acrylate latex (the same as that used in US Pat. No. 3,525,620, Example 3) 1.5 g / m ² Sensitizing dye: 3-allyl-5- [2- (1-ethyl) -4 Methyl-2 tetrazoline-5 ylidene-ethylidene] rhodamine 6 mg / m ² antifoggant: 4-hydroxy-6-methyl-1,3,3a-7 sotrazaindene 30 mg / m ² polyoxyethylene compound 20 mg / m ² gelatin hardener : 2-Hydroxy-4,6-dichloro-s-triazine sodium salt 60 mg / m ² Surfactant: p-sodium dodecylbenzenesulfonate 40 mg / m ²

Composition (2) (protective layer) Gelatin 1 g / m ² matting agent: polymethyl methacrylate having an average particle size of 3.0 to 4.0 μm 0.05 g / m ² Surfactant: sodium p-dodecylbenzenesulfonate 0 0.03 g / m ² Gelatin hardening agent: 2-hydroxy-4,6-dichloro-S-triazine sodium salt 0.01 g / m ² (same as used in the above emulsion layer) 50 g / 100 g Gelatin dye 0.3 g / M ² A mixture of the following dyes (1) :( 2) :( 3) (1) :( 2) :( 3) = 1: 1: 1 (weight ratio).

[0059]

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[0060]

[Chemical 4]

[0061]

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Comparative Example 1 (Samples A-10 to A-12, B-7 to B-12 and C-
Preparation of 7 to C-12) In Example 1, as the acrylic resin in the coating liquid for the antistatic layer, acrylic resins of the types and amounts shown in Table 1, Table 2 and Table 3 were used, and the melamine compound Instead, the epoxy compounds of the types and amounts shown in Tables 1, 2 and 3 were used, and the layer thickness of the antistatic layer was changed to the thickness shown in Tables 1, 2 and 3. A silver halide photographic light-sensitive material was prepared in the same manner as in Example 1.

Samples (A) obtained in Example 1 and Comparative Example 1
-1 to A-12, B-1 to B-12 and C-1 to C-1
Regarding 2), the detachability (powder dropping property), scratch resistance, and slipperiness of the conductive particles were evaluated as follows.

(1) Releasability of conductive particles (powder dropping property) The film of the above sample before forming the photosensitive layer (that is, the first and second undercoat layers on one side of the support, and the other side charged) Protective layer, surface layer), 25 ℃, 65% RH
After storing for 3 days in the atmosphere of, the film is processed into a long film of 18 cm width, and the long film is conveyed at a line speed of 100 m / min using a handling test machine, which is a simulated device of an emulsion coating machine, and tested. The lap angle of the machine is 1
After rotating the 80-degree drive roll (flat roll) in the reverse direction for 5 minutes at a peripheral speed of 90 m / min, the amount of the powdery substance adhering to the surface of the drive roll was visually evaluated as follows. . AA: No adhered powder is seen at all BB: Some adhered powder is seen CC: A considerable amount of adhered powder is seen

(2) Scratch resistance After the above sample (having a photosensitive layer) was stored in an atmosphere of 25 ° C. and 65% RH for 3 days, a scratch strength tester (HEID) was used.
Using ON-18, manufactured by Shinto Kagaku Co., Ltd., the load of the pressing 0.025R diamond needle was continuously increased to 0 to 100 g. The load at which scratches started was expressed in grams. It can be said that the larger the value, the better the scratch resistance.

(3) Sliding property The above sample (having a photosensitive layer) was stored in an atmosphere of 25 ° C. and 65% RH for 3 days, and then the dynamic friction coefficient was measured using a dynamic friction coefficient measuring device (manufactured by Toyo Baldwin Co., Ltd.). Was measured. That is, a steel ball having a diameter of 5 mm, to which a load of 20 g was applied, was brought into contact with the surface of the sample film, and the resistance when sliding at a speed of 20 cm / min was detected by a strain gauge.

The evaluation results are shown in Tables 1 to 3.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

Example 2 (Preparation of Samples D-1 to D-6 and E-1 to E-6) Example 1 was repeated except that the antistatic layer was formed as follows. A silver halide photographic light-sensitive material was produced in the same manner as.

(Coating Liquid for Antistatic Layer) Vinyl Resin (Types and Amounts of Acrylic Resin Used in Each Sample are Described in Tables 4 and 5) Tin Oxide-Antimony Oxide Dispersion 16.5 parts by Weight (Average Particle Size) : 0.1 μm; 30% by weight) Polyoxyethylene phenyl ether 0.1 part by weight Melamine compound (Types and amounts of melamine compounds used in each sample are shown in Table 4 and Table 5) Distilled water was added to make a total of 100 It was prepared so as to be part by weight. The antistatic layer coating solution is applied to the surface of the polyethylene terephthalate film on which the undercoat layer is not provided,
It was dried at 180 ° C. for 30 seconds to form an antistatic layer having the layer thickness shown in Table 4 and Table 5.

Comparative Example 2 (Preparation of Samples D-7 to D-12 and E-7 to E-12)
In Example 2, as the vinyl resin in the coating liquid for the antistatic layer, the vinyl resins of the types and amounts shown in Tables 4 and 5 were used, and instead of the melamine compound, the vinyl resins shown in Tables 4 and 5 were used. A silver halide photographic light-sensitive material was produced in the same manner as in Example 2 except that the type and amount of the epoxy compound was used and the thickness of the antistatic layer was set to the thickness shown in Tables 4 and 5.

The samples obtained above were evaluated in the same manner as in Example 1. The results are shown in Tables 4 and 5.

[0075]

[Table 4]

[0076]

[Table 5]

Example 3 (Preparation of Samples F-1 to F-6) A silver halide photograph was prepared in the same manner as in Example 1 except that the antistatic layer was formed as follows. A light-sensitive material was prepared.

(Coating Liquid for Antistatic Layer) Polyurethane Resin Aqueous Dispersion (Type and amount of polyurethane resin aqueous dispersion used for each sample are shown in Table 6) Tin oxide-antimony oxide dispersion 16.5 parts by weight ( Average particle size: 0.1 μm; 30% by weight) Polyoxyethylene phenyl ether 0.1 part by weight Melamine compound (Type and amount of melamine compound used in each sample are listed in Table 6) Total with distilled water is 100 It was prepared so as to be part by weight. The antistatic layer coating solution is applied to the surface of the polyethylene terephthalate film on which the undercoat layer is not provided,
After drying at 180 ° C. for 30 seconds, an antistatic layer having the layer thickness shown in Table 6 was formed.

Comparative Example 3 (Preparation of Samples F-7 to F-12) In Example 3, as the polyurethane resin aqueous dispersion in the coating liquid for the antistatic layer, polyurethane of the types and amounts shown in Table 6 was used. A resin aqueous dispersion was used, and instead of the melamine compound, an epoxy compound of the type and amount shown in Table 6 was used, and the layer thickness of the antistatic layer was set to the thickness shown in Table 6. Example 3
A silver halide photographic light-sensitive material was produced in the same manner as.

The samples obtained above were evaluated in the same manner as in Example 1. Table 6 shows the results.

[0081]

[Table 6]

Example 4 (Preparation of Samples G-1 to G-6) A silver halide photograph was prepared in the same manner as in Example 1 except that the antistatic layer was formed as follows. A light-sensitive material was prepared.

(Coating Liquid for Antistatic Layer) Aqueous Dispersion of Vinyl Acetate / Ethylene / Acrylic Ester Copolymer (Type and amount of copolymer aqueous dispersion used in each sample are shown in Table 7) Tin oxide -Antimony oxide dispersion 16.5 parts by weight (average particle size: 0.1 μm; 30% by weight) polyoxyethylene phenyl ether 0.1 part by weight melamine compound (the type and amount of the melamine compound used in each sample are shown in Table 7). Distilled water was added to prepare a total of 100 parts by weight. The antistatic layer coating solution is applied to the surface of the polyethylene terephthalate film on which the undercoat layer is not provided,
After drying at 180 ° C. for 30 seconds, an antistatic layer having the layer thickness shown in Table 6 was formed.

[Comparative Example 4] (Preparation of Samples G-7 to G-12) In Example 4, as the aqueous dispersion of the copolymer in the coating liquid for the antistatic layer, the type and amount shown in Table 7 were used. An aqueous copolymer dispersion was used, and instead of the melamine compound, an epoxy compound of the type and amount described in Table 7 was used, and the layer thickness of the antistatic layer was determined in Table 7.
A silver halide photographic light-sensitive material was produced in the same manner as in Example 4 except that the thickness described in 1 was used.

The sample obtained above was evaluated in the same manner as in Example 1. The results are shown in Table 7.

[0086]

[Table 7]

Example 5 (Preparation of Samples H-1 to H-6) A silver halide photograph was prepared in the same manner as in Example 1 except that the antistatic layer was formed as follows. A light-sensitive material was prepared.

(Coating Liquid for Antistatic Layer) Polyester Aqueous Dispersion (Type and amount of polyester aqueous dispersion used for each sample are shown in Table 8) Tin oxide-antimony oxide dispersion 16.5 parts by weight (average particle size) Diameter: 0.1 μm; 30% by weight) Polyoxyethylene phenyl ether 0.1 part by weight Melamine compound (Type and amount of melamine compound used in each sample are listed in Table 8) Total 100 parts by weight with addition of distilled water Was prepared so that The antistatic layer coating solution is applied to the surface of the polyethylene terephthalate film on which the undercoat layer is not provided,
After drying at 180 ° C. for 30 seconds, an antistatic layer having the layer thickness shown in Table 6 was formed.

Comparative Example 5 (Preparation of Samples H-7 to H-12) In Example 5, as the polyester aqueous dispersion in the coating liquid for the antistatic layer, the polyester water of the type and amount shown in Table 8 was used. Example 5 except that the dispersion was used and that instead of the melamine compound an epoxy compound of the type and amount listed in Table 8 was used and the layer thickness of the antistatic layer was the thickness listed in Table 8. A silver halide photographic light-sensitive material was produced in the same manner as.

The sample obtained above was evaluated in the same manner as in Example 1. Table 8 shows the results.

[0091]

[Table 8]

[0092]

The antistatic layer of the present invention is a layer in which conductive metal oxide particles are firmly held by a tough film obtained by curing a specific polymer and a melamine compound. Therefore, there is almost no loss of conductive metal oxide particles during the manufacturing process,
Further, it is a silver halide photographic light-sensitive material having improved scratch resistance. In addition, since the conductive metal oxide particles are not detached even after the development treatment, the antistatic property is not impaired.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material in which a silver halide photographic light-sensitive layer is provided on one side of a plastic film support, and an antistatic layer and a surface layer are provided in this order on the other side. In the above, the antistatic layer is composed of conductive metal oxide particles, and a cured product of a melamine compound and at least one polymer selected from the group consisting of acrylic resin, vinyl resin, polyurethane resin and polyester resin. And a silver halide photographic light-sensitive material. 2. The conductive metal oxide particles are ZnO, T
_{iO 2, SnO 2, Al 2} O 3, In 2 O 3, MgO and at least one metal oxide selected from the group consisting of composite oxides, or metal oxide containing further hetero atom in the metal oxide The silver halide photographic light-sensitive material according to claim 1, wherein