JPH1115109A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material superior in transparency and antistatic property and capable of being smoothly conveyed without being stained with dust. SOLUTION: This silver halide photographic sensitive material is provided on one side of a plastic film support with an antistatic layer containing conductive metal oxide particles and a surface layer in this order, and on the surface of the nonstaticized side of the support with a silver halide photographic sensitive layer. The haze of the staticized support side is <=1.5 and the surface layer has an electric resistance controlled in the range of 8×10<8> -5×10<8> Ω.

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 material having an antistatic property.

[0002]

2. Description of the Related Art In general, a silver halide photographic light-sensitive material (hereinafter referred to as a "light-sensitive material") is provided on an electrically insulating plastic film support on a light-sensitive silver halide photographic emulsion layer (hereinafter referred to as a "photosensitive layer"). It is manufactured by applying and drying a layer, a protective layer, an intermediate layer, an undercoat layer, an antistatic layer (hereinafter also referred to as a “back layer”) and the like.

[0003] In recent years, the technology for manufacturing photosensitive materials has been remarkably improved. For example, the coating speed of the undercoat layer and the photosensitive layer, or the cutting and cutting processes have been accelerated. Abrasion or peeling is likely to occur due to the contact friction with the metal. In addition, the photosensitive material tends to be charged with static electricity due to contact friction, and dust (dust and dust) tends to adhere thereto. The occurrence of such abrasion, peeling, or adhesion of dust causes generation of various spots exhibiting water repellency, desensitization, fogging, and the like. Further, when static electricity accumulated in the photosensitive material is discharged due to contact friction, a so-called static mark is generated in the photosensitive layer, which is a fatal defect. Such a tendency of speeding up is the same in the photographing and developing processing steps, and in these steps, static electricity tends to be easily generated.

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

For this reason, it has been known to provide an antistatic layer containing a conductive polymer, an ionic or nonionic surfactant, colloidal silica, a metal oxide or a composite oxide thereof on a photosensitive material. I have. However, those eluted into the developing solution during the developing process, such as a surfactant, not only lose the antistatic performance after the developing process but also deteriorate the photographic properties such as deterioration of the developing solution. There are cases. In addition, at low humidity such as in winter, antistatic agents such as conductive polymers generally cannot exhibit sufficient antistatic performance due to ionic conductivity. As the antistatic agent, the metal oxide or its composite oxide, or a metal oxide or the like, in particular, exhibits antistatic performance without deteriorating photographic performance during development processing and is not dependent on humidity even after development processing. Fine particles containing a small amount of heteroatoms are preferable. For example, Japanese Patent Publication No. Hei.
No. 651 describes an antistatic layer containing these particles.

[0006] In addition to the above-mentioned problem due to the generation of static electricity caused by the increase in speed in the production of photosensitive materials, a problem that has recently become particularly apparent is that metal oxide particles as an antistatic agent are produced during the production process. Development called so-called powder drop, which falls off from the film surface and adheres to the roll surface or the like due to contact friction with a transport roll or the like, can be mentioned. During the manufacturing process, the particles detached and adhered to a roll or the like may be re-adhered to the film to cause poor application or abrasion, which significantly lowers productivity.

In the manufacturing process of the antistatic layer containing metal oxide particles, the thickness of the back layer (antistatic layer) is smaller than the particle diameter of the metal oxide particles. The portion protrudes from the surface of the antistatic layer, and even if the surface layer is formed, the protruding portion remains. Therefore, when the film is pressed with a roll to form a photosensitive layer or the like, the strength of the antistatic layer is not sufficient. If sufficient, they will be desorbed. Japanese Patent Application Laid-Open No. 8-36239 proposes an antistatic layer in which such a point is improved. That is, such an antistatic layer comprises the metal oxide particles, a cured product of at least one polymer selected from the group consisting of acrylic resin, vinyl resin, polyurethane resin and polyester resin and a melamine compound. is there.

[0008]

The use of an antistatic layer having the above-mentioned metal oxide particles and a cured product of a polymer and a melamine compound has improved the powder drop, but it has been improved with respect to microfilms and movie films. In applications that are particularly severe under such transfer conditions, the conductivity of the antistatic layer cannot be said to be sufficiently high, and adhesion of dust and the like to the film cannot be prevented. Even if the amount of metal oxide particles is increased to improve this, the surface electric resistance is slightly reduced, but the amount of desorbed components is increased, so that the adhesion of dust during transportation is not reduced. The present inventors have found that there is a problem of causing an increase in haze. Therefore, the appearance of an antistatic layer which has good conductivity, has no adhesion of dust and film detachment powder during film transport, and has a low haze is desired.

The present invention has excellent transparency and antistatic properties,
It is an object of the present invention to provide a silver halide photographic light-sensitive material which hardly adheres dust during transportation. Also, the present invention
It is an object of the present invention to provide a silver halide photographic light-sensitive material having excellent transparency and antistatic property and also excellent antistatic property after development processing.

[0010]

SUMMARY OF THE INVENTION The present invention provides a low-charge support comprising a plastic film support provided on one side thereof with an antistatic layer containing conductive metal oxide particles.
And a silver halide photographic light-sensitive material comprising a silver halide photographic light-sensitive layer provided on the surface of the low-charge support on which the antistatic layer is not provided, wherein the haze of the low-charge support is 1 0.5 or less, and the surface electric resistance of the surface layer of the silver halide photographic light-sensitive material is from 8 × 10 ^{6 to} 6
A silver halide photographic material characterized by being in the range of × 10 ⁸ Ω. The surface electric resistance is JIS-K
It is a value measured in accordance with the method described in -6911-1979. The haze is determined according to JIS-K-6714-1977.
Is a value measured according to the method described in "Haze Value".

Preferred embodiments of the silver halide photographic light-sensitive material of the present invention are as follows. 1) The conductive metal oxide particles are acicular particles, and the ratio of the major axis to the minor axis (major axis / minor axis) is 3 to 50 (particularly 1).
0 to 50). 2) The minor axis of the conductive metal oxide particles is 0.001 to 0.
It is in the range of 1 μm (particularly 0.01 to 0.02 μm). 3) The major axis of the conductive metal oxide particles is 0.1 to 5.0 μm.
m (particularly 0.1 to 2.0 μm). 4) The conductive metal oxide particles are composed of ZnO, TiO ₂ , Sn
A particle of at least one metal oxide selected from the group consisting of O ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO and a composite oxide thereof, or a metal oxide further containing a different atom in the metal oxide. Particles. 5) The conductive metal oxide particles are made of antimony-doped SnO ₂ (preferably 0.2 to 2.0% of antimony).
Doped SnO ₂ ) particles. 6) The antistatic layer further includes an acrylic resin as a binder,
It includes a cured product of at least one polymer selected from the group consisting of vinyl resins, polyurethane resins and polyester resins and a melamine compound. 7) The surface layer is made of a polyolefin (carboxyl group and / or
Or a polyolefin having a carboxylate group is preferred). 8) The surface of the plastic film support has been subjected to a surface activation treatment (preferably a corona discharge treatment). 9) Between the plastic film support and the silver halide photographic light-sensitive layer, a first undercoat layer and a second undercoat layer (preferably a layer made of gelatin) are provided in this order on the support surface. . 10) The plastic film support has been biaxially stretched. 11) The surface electrical resistance of the silver halide photographic material after development processing is in the range of 8 × 10 ^{6 to} 6 × 10 ⁸ Ω.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail.
The silver halide photographic light-sensitive material of the present invention comprises a plastic film support, an antistatic layer containing conductive metal oxide particles provided on one side thereof, a surface layer thereon, and an antistatic layer of the support. It has a basic structure comprising a silver halide photographic light-sensitive layer provided on the surface on the side having no silver halide. In the present invention, a laminate comprising a plastic film support and an antistatic layer and a surface layer provided on one side thereof is referred to as a low-charge support. Examples of the plastic film support 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-set polyethylene terephthalate film is particularly preferable in terms of stability, toughness, and the like.

The thickness of the support is not particularly limited.
A range of 500 μm is generally used, and a range of 40 to 200 μm is particularly advantageous and advantageous from the viewpoint of ease of handling and versatility. In addition, the support is in a range that can maintain transparency,
It 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
In general, a similar surface treatment is performed on the surface on which the 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,
(2) a method of directly applying a photographic emulsion (a coating solution for forming a photosensitive layer) to obtain an adhesive force after surface treatment such as (2) once treating these surfaces, providing an undercoat layer, And an emulsion layer coating method. Of these, the method (2) is more effective and widely used. All of these surface treatments involve the formation of more or less polar groups on the originally hydrophobic support surface, the removal of thin layers that are a negative factor for surface adhesion, and the crosslinking of surfaces. It is thought to increase the density and increase the adhesive strength, and as a result, the affinity of the components contained in the undercoat layer forming solution with the polar group increases, and the robustness of the adhesive surface increases It is considered that the adhesiveness between the undercoat layer and the surface of the support is improved by the above method.

As a method of applying an undercoat layer, a so-called multilayer method in which a first layer is provided with a layer which adheres well to a support, and a gelatin layer is formed thereon as a second layer, There is a single-layer method in which only one resin layer containing both a group and a hydrophilic group is applied. Examples of the method for forming the undercoat layer include a method in which a two-layer undercoat layer comprising a first undercoat layer of a polymer substance and a second undercoat layer of gelatin is formed in an aqueous system. As the polymer substance of the first undercoat layer, for example,
Starting from copolymers starting from monomers selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc., polyethyleneimine, epoxy resin grafted gelatin And nitrocellulose.
For forming the first undercoat layer and the second undercoat layer of gelatin, a curing agent such as a dichlorotriazine derivative or an epoxy compound is generally used in combination.

The first undercoat layer may optionally contain, as a swelling agent, for example, phenol, resorcin, etc., in an amount of 1 to 10 g per liter of the first undercoat layer coating solution. . For the first undercoat layer, a hydrophilic polymer may be used, for example, a natural polymer such as gelatin,
Examples include synthetic polymers such as polyvinyl alcohol, vinyl acetate / maleic anhydride copolymer, acrylic acid / acrylamide copolymer, and styrene / maleic anhydride copolymer. Further, a matting agent (silicon dioxide, polymethyl acrylate, polystyrene), methyl cellulose, polyvinyl alcohol, or the like can be used as a blocking inhibitor.

The above-mentioned coating solution for the first undercoat layer can be prepared by a well-known coating method such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, or the like. And an extrusion coating method using a popper described in U.S. Pat. No. 2,681,294. When a second undercoat layer is further provided on the undercoat layer, if necessary, U.S. Pat.
Nos. 508947, 2941898 and 3526
No. 528, "Coating Engineering" 253 by Ozaki et al.
Two or more layers can be simultaneously coated by the method described on page (1973, published by Asakura Shoten).

The coating amount of the first undercoat layer and the second undercoat layer provided on the first undercoat layer is 0.01 to 10 g per 1 m ² of the polyester film support as solids.
And particularly preferably 0.2 to 3 g.
In the present invention, a hydrophilic colloid layer containing gelatin as a main component is generally 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 carboxymethylcellulose and hydroxyethylcellulose, acrylic acid, methacrylic acid. Grafted gelatin obtained by grafting acid or amide to gelatin,
Polyvinyl alcohol, polyhydroxyalkyl acrylate, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymer, casein, agarose, albumin, sodium alginate, polysaccharide, agar, starch, grafted starch, polyacrylamide, polyethyleneimine acyl compound, and acrylic Acid, methacrylic acrylamide, N-substituted acrylamide and N-
A homopolymer or a copolymer such as a substituted methacrylamide, or a synthetic or natural hydrophilic high molecular compound such as a partial hydrolyzate thereof can be given. These can be used alone or in combination.

If necessary, an antistatic agent, a cross-linking agent, a matting agent, an anti-blocking agent and the like can be added to the hydrophilic polymer as described above.

Next, the photosensitive silver halide 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 carboxymethylcellulose and hydroxyethylcellulose, acrylic acid, methacrylic acid or amide (acrylamide). Grafted gelatin obtained by grafting onto gelatin, polyvinyl alcohol, polyhydroxyalkyl acrylate, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, casein, agarose, albumin, sodium alginate, polysaccharite, agar, tempura, Synthetic or natural hydrophilic polymer compounds such as graft starch, polyacrylamide, acylated polyethyleneimine, and partially hydrolyzed products thereof Can. These materials can be used alone or as a mixture.

As long as the binder is a hydrophilic polymer compound as described above, what is added to the binder is not particularly important in the present invention. Physical development nuclei such as silver halide or silver sulfide used in diffusion transfer photography, a photosensitive material such as a diazo compound, various additives, couplers, emulsion polymerization, latex polymers and the like are added.

Various materials used in the photosensitive layer, for example, silver halide grains, chemical sensitizers, dyes, polymer latexes, surfactants, gelatin hardeners, color couplers, anti-fading agents, antistatic agents, mats There are no particular restrictions on the agents and the like. For example, Research Disclosure (Re
search Disclosure) Vol. 176, pp. 22-31 (1978)
December) can be referred to.

Although the present invention is not necessarily required, a surface treatment such as a corona discharge treatment is performed not only on the hydrophobic support but also on the undercoat layer made of a polymer substance and / or the second undercoat layer. In this case, the adhesion between the layers after the treatment is improved.

On the surface of the plastic film support on which the photosensitive layer is not provided, the antistatic layer of the present invention and the surface layer are provided in this order. The order of formation of these layers is generally such that after forming an antistatic layer and a surface layer, a photosensitive layer is provided on an undercoat layer. In the antistatic layer of the present invention,
The haze of the low-charge support obtained by providing the antistatic layer on the support is 1.5 or less, and the surface electric resistance of the surface layer of the obtained light-sensitive material is 8 × 10 ^{6 to} 6 × 10 ⁸ Ω. , The conductivity is given.

The antistatic layer is a layer containing conductive metal oxide particles, and generally further contains a binder. As the conductive metal oxide particles, it is preferable to use needle-like particles having a ratio of the major axis to the minor axis (major axis / minor axis) in the range of 3 to 50. In particular, those having a major axis / minor axis in the range of 10 to 50 are preferred. The minor axis of such acicular particles is preferably in the range of 0.001 to 0.1 μm, particularly preferably in the range of 0.01 to 0.02 μm. The major axis is 0.1 to 5.0 μm.
m, preferably 0.1 to 2.0 μm
m is preferably in the range.

The material of the conductive metal oxide particles is ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂
O ₃ , MgO, BaO, and MoO _3, and their composite oxides, and metal oxides further containing a heteroatom can be mentioned. As the metal oxide, SnO ₂ , ZnO, Al ₂ O ₃ , TiO ₂ , In ₂
O ₃ and MgO are preferable, and SnO ₂ , Zn
O, In ₂ O ₂ and TiO ₂ are preferred, with SnO ₂ being particularly preferred. Examples of containing a small amount of foreign atoms include Al or In for ZnO, Nb or Ta for TiO ₂ , Sn for In ₂ O ₃ , and Sb, Nb or a halogen element for SnO ₂ . An element doped with 0.01 to 30 mol% (preferably 0.1 to 10 mol%) of an element can be given. If the amount of the different element is less than 0.01 mol%, sufficient conductivity cannot be imparted to the oxide or composite oxide, and
If it exceeds mol%, the degree of blackening of the particles increases, and the antistatic layer becomes dark, which is not suitable for use as a light-sensitive material. Therefore, in the present invention, the material of the conductive metal oxide particles preferably contains a small amount of a different element from the metal oxide or the composite metal oxide. Further, those having an oxygen defect in the crystal structure are also preferable. As the conductive metal oxide particles containing a small amount of the dissimilar atom, SnO ₂ particles are preferred antimony-doped, SnO ₂ particles are preferred which are particularly doped antimony 0.2-2.0 mol%. Therefore, in the present invention, the use of metal oxide particles such as antimony-doped SnO ₂ having the dimensions of the short axis and the long axis is advantageous for forming an antistatic layer that is transparent and has good conductivity. is there. Thereby, it has a low-chargeable support having a haze of 1.5 or less, and has a surface electric resistance of 8 × 10 ^{6 to} 6 × 10 ⁸ Ω.
Can be easily obtained.

By using acicular metal oxide particles (eg, antimony-doped SnO ₂ ) having the short-axis and long-axis dimensions, a transparent antistatic layer having good conductivity is advantageously formed. The possible reasons are as follows. In the antistatic layer, the long axis direction of the acicular metal oxide particles extends long in parallel with the surface of the antistatic layer, but the length in the thickness direction of the layer corresponds to the length of the short axis diameter. It only occupies. Such acicular metal oxide particles,
Since the particles are long in the major axis direction as described above, they are easily in contact with each other as compared with ordinary spherical particles, and high conductivity can be obtained even with a small amount. Therefore, the surface electric resistance can be reduced without impairing the transparency. In the needle-like metal oxide particles, the diameter of the minor axis is usually smaller than or approximately the same as the thickness of the antistatic layer, and rarely protrudes from the surface. Because of the slight
It will be almost completely covered by the surface layer provided on the antistatic layer. Accordingly, there is also obtained an advantage that almost no powder dropping, which is the detachment of the protruding portion from the layer, occurs during the transportation of the support for preparing the photosensitive material, and during the transportation of the photosensitive material for photographing and development. Furthermore, the change in surface electric resistance before and after the development processing of the photosensitive material is relatively large in the case of spherical particles,
When the needle-shaped metal oxide is used, it is extremely small, and it can be said that the transportability after the development processing is particularly improved. This is presumed to be due to the fact that, in the case of spherical particles, the arrangement of the particles changes due to the swelling and shrinkage of the film due to the development treatment, and the number of parts in contact with each other decreases.

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

Examples of the acrylic resin include acrylates such as acrylic acid and alkyl acrylate, methacrylates such as acrylamide, acrylonitrile, methacrylic acid and alkyl methacrylate, and monomers of any of methacrylamide and methacrylonitrile. Examples thereof include a homopolymer or a copolymer obtained by polymerization of two or more of these monomers. Among these,
A homopolymer of any one of monomers of acrylates such as alkyl acrylates and methacrylates such as alkyl methacrylate or a copolymer obtained by polymerization of 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-described composition as a main component, and is capable of performing a cross-linking reaction with a melamine compound, for example, 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, polyvinyl folimal, polyvinyl butyral, polyvinyl methyl ether, polyolefin, ethylene / butadiene copolymer, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, Examples thereof include vinyl chloride / (meth) acrylate copolymer and ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / (meth) acrylate copolymer). Among them, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl folimar, polyolefin, ethylene / butadiene copolymer and ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / acrylate copolymer) Is preferred. The vinyl resin is a polyvinyl alcohol, an acid-modified polyvinyl alcohol, polyvinyl folimar, polyvinyl butyral, polyvinyl methyl ether and polyvinyl acetate, so that a crosslinking reaction with the melamine compound is possible, for example, a vinyl alcohol unit in the polymer By leaving a polymer having a hydroxyl group, for other polymers, for example, a methylol group,
A crosslinkable polymer is 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. (Examples include polyurethanes derived from poly (oxypropylene ether) polyol, poly (oxyethylene-propylene ether) polyol), polycarbonate polyol, and polyethylene terephthalate polyol, or a mixture thereof and a polyisocyanate. Can be. In the above polyurethane resin, for example, after the reaction between the polyol and the polyisocyanate, the hydroxyl group remaining unreacted can be used as a functional group capable of a cross-linking 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 polyester resin, for example, after the reaction between the polyol and the polybasic acid is completed, the unreacted hydroxyl group and carboxyl group can be used as a functional group capable of performing a crosslinking reaction with the melamine compound. Of course, a third component having a functional group such as a hydroxyl group may be added.

Of the above polymers, acrylic resins and polyurethane resins are preferred, and acrylic resins are particularly preferred.

The melamine compound used in the present invention includes two or more (preferably three or more) in a melamine molecule.
And a melamine resin or a melamine urea resin which is a condensation polymer thereof. Examples of precondensates of melamine and formalin include dimethylol melamine, trimethylol melamine,
There are tetramethylolmelamine, pentamethylolmelamine, hexamethylolmelamine and the like, and specific commercial products thereof are, for example, Sumitex resin (Sumitex resin).
tex Resin) M-3, same MW, same MK and same MC (above,
Sumitomo Chemical Co., Ltd.) and the like, but are not limited thereto. Examples of the above-mentioned polycondensate include hexamethylolmelamine resin, trimethylolmelamine resin, trimethyloltrimethoxymethylmelamine resin and the like. As a commercial product, MA
-1 and MA-204 (manufactured by Sumitomo Bakelite Co., Ltd.), BECKAMINE MA-S, Beckamine APM, and Beckamine J-101 (manufactured by Dainippon Ink and Chemicals, Inc.) )
Manufactured by Oshika Resin M31 and Oka Resin PWP-8 (manufactured by Oshika Shinko Co., Ltd.), but are not limited thereto.

The melamine compound of the present invention preferably has a functional group equivalent represented by a value obtained by dividing the molecular weight by the number of functional groups in one molecule of from 50 to 300. Here, the functional group indicates a methylol group and / or an alkoxymethyl group. When this value exceeds 300, the cured density is small and high strength cannot be obtained, and when the amount of the melamine compound is increased, the applicability decreases. If the cured density is low, scratches are likely to occur. Also, the holding power of the conductive metal oxide is reduced.
If the functional group equivalent is less than 50, the cured density will be high, but the transparency will be impaired, and even if the amount is reduced, it will not improve. The amount of the aqueous melamine compound of the present invention is 0.1 to 0.1 based on the polymer.
It is 100% by weight, preferably 10-90% by weight.

These melamine compounds may be used alone or in combination of two or more. Also, it can be used in combination with other compounds, for example, CEKMeers and THJa.
mes, The Theory of the Photographic Process, 3rd ed. (1966), U.S. Pat. Nos. 3,331,095, 3,232,767, 3,288,775, and 27323.
No. 03, No. 3635718, No. 3232763, No. 2732316, No. 2586168, No. 31034
No. 37, No. 3017280, No. 2983611, No. 2725294, No. 2725295, No. 31007
And the curing agents described in JP-A Nos. 04, 3091537, 3321313, 3543292 and 3125449, and British Patents 994869 and 1167207. A typical example is
Mucochloric acid, mucobromic acid, mucofenoxycyclolic acid, mucophenoxypromic acid, formaldehyde, glyoxal, monomethylglyoxal, 2,3-dihydroxy-1,4-dioxane, 2,3-dihydroxy-5-methyl-1,4 Aldehyde compounds such as dioxane succinaldehyde, 2,5-dimethoxytetrahydrofuran and glutaraldehyde and derivatives thereof; divinylsulfone-N, N'-ethylenebis (vinylsulfonylacetamide), 1,3-bis (vinylsulfonyl) -2 -Propanol, methylene bismaleimide, 5-acetyl-1,3-diacryloyl-hexahydro-s-triazine, 1,3,5-triacryloyl-hesahydro-s-triazine and 1,3,5-trivinylsulfonyl-hexahi Active vinyl compounds such as dro-s-triazine; sodium 2,4-dichloro-6-hydroxy-s-triazine, 2,4-dichloro-
6- (4-sulfoanilino) -s-triazine sodium salt, 2,4-dichloro-6- (2-sulfoethylamino) -s-triazine and N, N′-bis (2-chloroethylcarbamyl) piperazine and the like An active halogen compound of the formula: bis (2,3-epoxypropyl) methylpropylammonium / p-toluenesulfonate, 1,4-bis (2 ′, 3′-epoxypropyloxy) butane,
1,3,5-triglycidyl isocyanurate, 1,3
-Dicricidyl-5- (γ-acetoxy-β-oxypropyl) isocyanurate, 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 ether; 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, 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-condensed peptide reagents such as methylpyridium chloride; active ester compounds such as N, N'-adipoyldoxysuccinimide and N, N'-terephthaloyldioxydisuccinimide: toluene-2,4- Examples include, but are not limited to, isocyanates such as diisocyanate and 1,6-hexamethylene diisocyanate; and epichlorohydrin compounds such as polyamide-polyamine-epichlorohydrin reactants.

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

The thickness of the antistatic layer of the present invention is from 0.01 to
The range of 1 μm is preferable, and further 0.01 to 0.2 μm
Is preferable. When the thickness is less than 0.01 μm, it is difficult to apply the coating agent uniformly, so that uneven coating is likely to occur on the product.
If it exceeds m, the antistatic performance and the scratch resistance may be poor. The conductive metal oxide particles are preferably contained in the antistatic layer in a range of 10 to 1000% by weight with respect to the binder (eg, the total of the polymer and the melamine compound), and more preferably 200 to 600%. A range of weight% is preferred. If it is less than 10% by weight, sufficient antistatic properties cannot be obtained, and if it exceeds 1000% by weight, the haze is too high.

If necessary, a matting agent, a surfactant, a slipping agent and the like can be used in combination in the antistatic layer of the present invention and the following surface layer. As a matting agent,
Oxide particles having a particle size of 0.001 to 10 μm such as silicon oxide, aluminum oxide, and magnesium oxide, and particles such as polymers or copolymers such as polymethyl methacrylate and polystyrene. Examples of the surfactant include known anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. As a slipping agent, carbon number 8 to 2
(2) phosphate esters of higher alcohols or amino salts thereof; palmitic acid, stearic acid, behenic acid and esters thereof; and silicone compounds.

In the present invention, on the antistatic layer,
A surface layer is provided. The surface layer is provided mainly to improve the slipperiness and scratch resistance, and to assist the antistatic layer in preventing the conductive metal oxide particles from desorbing. Generally, polyolefin is used as the material of the surface layer. Examples of the polyolefin include ethylene,
Waxes, resins and rubbers (for example, polyethylene, polypropylene, poly-1-butene) comprising homo- or copolymers of 1-olefin unsaturated hydrocarbons such as propylene, 1-butene and 4-methyl-1-pentene , Poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer and propylene / 1-butene copolymer), conjugated or non-conjugated with two or more of the above 1-olefins Rubbery copolymers with dienes (e.g., ethylene / propylene / ethylidene norbornene copolymer, ethylene / propylene / 1,5-hexadiene copolymer and isobutene / isoprene copolymer),
Copolymers of 1-olefins with conjugated or non-conjugated dienes (e.g., ethylene / butadiene copolymers and ethylene / ethylidene norbornene copolymers), 1-olefins (especially copolymers of ethylene and vinyl acetate and their complete Or partially saponified product), a graft polymer obtained by grafting the conjugated or non-conjugated diene or vinyl acetate or the like to a homo- or copolymer of 1-olefin, and a completely or partially saponified product thereof. However, the present invention is not limited to this. The compound is
It is described in JP-B-5-41656. Among the above-mentioned polyolefins, those having a carboxyl group and / or a carboxylate group are preferred. In the present invention, it is usually used as an aqueous solution or an aqueous dispersion.

Water-soluble methylcellulose having a degree of methyl group substitution of 2.5 or less may be added to the above-mentioned surface layer, and the additive is used in an amount of 0.1% by weight based on all binders forming the surface layer.
~ 40% by weight is preferred. The water-soluble methylcellulose is described in JP-A-1-210947.

The above-mentioned surface layer is formed on the antistatic layer of the present invention by a generally well-known coating method, for example, a dip coating method.
It can be formed by applying a coating liquid (aqueous dispersion or aqueous solution) containing the above binder or the like 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 thickness of the surface layer is preferably in the range of 0.01 to 1 μm, and more preferably in the range of 0.01 to 0.2 μm. If it is less than 0.01 μm, it is difficult to apply the coating agent uniformly, so that the product tends to have uneven coating. If it exceeds 1 μm, the antistatic performance and scratch resistance may be poor.

[0044]

【Example】

Examples 1-4 and Comparative Examples 1-4 Samples A-1 to A-6, A-11 to A-16 (Example 1, Comparative Example 1); Samples B-1 to B- 6, B-11 to B-16 (Example 2,
Comparative Example 2); Samples C-1 to C-6, C-11 to C-16 (Example 3,
Comparative Example 3); Samples D-1 to D-6, D-11 to D-16 (Example 4,
Comparative Example 4);

Biaxial stretching (length and width 3.3 times each)
After heat setting at 240 ° C. for 10 minutes, a first undercoat layer and a second undercoat layer having the following composition were formed in this order on one side of a 120 μm-thick polyethylene terephthalate film subjected to corona discharge treatment on both sides. It was formed as follows. Next, an antistatic layer and a surface layer were formed in this order on the opposite surface of the film as follows. Next, a photosensitive layer was formed on the second undercoat layer as described below to prepare a photosensitive material (the sample).

(Coating solution for forming first undercoat layer) Styrene / butadiene copolymer latex 15.2 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 Polystyrene fine particles (average particle size: 2 μm) 0.01 parts by weight 84.59 parts by weight distilled water The above-mentioned coating liquid for forming a first undercoat layer is applied to one side of the above polyethylene terephthalate film. And dried at 180 ° C. for 30 seconds to form a 0.3 μm first undercoat layer.

(Coating solution for forming second undercoat layer) Gelatin 1.5 parts by weight Acetic acid (20% aqueous solution) 1.0 parts by weight Compound of the following (1) 0.04 parts by weight Methylcellulose (2% aqueous solution) 33 parts by weight Distilled water 92.63 parts by weight

Compound (1)

[0050]

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The coating solution for forming the second undercoat layer was applied on the first undercoat layer and dried at 170 ° C. for 30 seconds.
A 15 μm second undercoat layer was formed.

(Coating solution for forming antistatic layer) Polymer aqueous dispersion (Type and amount of acrylic resin used for each sample are shown in Table 1,
(See Tables 2, 3 and 4) Conductive Metal Oxide Particles (Types and amounts of metal oxide particles used for each sample are described in Tables 1, 2, 3 and 4) Polyoxyethylene phenyl ether
0.1 parts by weight Curing agent (Type and amount of curing agent used for each sample are shown in Tables 1 and 2,
(See Tables 3 and 4.) Distilled water was added to adjust the total to 100 parts by weight.

The coating solution for forming an antistatic layer was applied to the surface of the polyethylene terephthalate film on which no undercoat layer was provided, and dried at 180 ° C. for 30 seconds.
Antistatic layers having the thicknesses shown in Tables 2, 3 and 4 were formed.

(Coating Solution 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.) 0 parts by weight Epoxy compound 0.3 parts by weight (Denacol EX-614B; manufactured by Nagase Kasei Co., Ltd.) 0.1 parts by weight of polyethylene sulfonate (molecular weight: 1000 to 5000) 94.6 parts by weight of distilled water

The coating solution for a surface layer was applied on the antistatic layer and dried at 170 ° C. for 30 seconds to form a layer having a thickness of 0.03.
A μm surface layer was formed.

Next, a coating liquid for forming a photosensitive layer having the following composition (1) was dried on the second undercoat layer of the above-mentioned coated film to a dry thickness of 6.0.
μm (coating silver amount: 5.0 g / m ² ). Further, a coating solution for forming a protective layer having the following composition (2) was applied on the photosensitive layer to prepare a silver halide photographic material (sample).

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 (same as 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-2tetrazoline-5ylidene-ethylidene] rhodanine 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-dodecylbenzenesulfonic acid sodium 40 mg / m ²

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

[0059]

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[0060]

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[0061]

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Samples obtained in Examples 1 to 4 and Comparative Examples 1 to 4 (Samples A-1 to A-6, A-11 to A-16 (Example 1, Comparative Example 1); Sample B-1 ~ B-6, B-11 ~ B
-16 (Example 2, Comparative Example 2); Samples C-1 to C-6,
C-11 to C-16 (Example 3, Comparative Example 3); Sample D-
1 to D-6 and D-11 to D-16 (Example 4, Comparative Example 4)), surface electric resistance (before and after development), haze, particle detachability (powdering) Sex) was evaluated.

(1) Surface Electric Resistance (SR) The obtained sample was subjected to a pre-development process and a post-development process.
The surface electric resistance was measured according to the method described in JIS-K-6911-1979. The measurement is performed at 23 ° C.
After leaving it for 6 hours in an atmosphere of 65% RH to adjust the humidity, a constant voltage power supply (TR-300C, manufactured by Takeda Riken Industry Co., Ltd.), an ammeter (TR-8651, manufactured by the company) and The measurement was performed using a sample chamber (TR-42, manufactured by the company). (2) Haze The film of the sample before the formation of the photosensitive layer (that is, a low charge having a first and second undercoat layers on one surface of the support and an antistatic layer and a surface layer formed on the other surface) Haze of the non-crystalline support) was measured according to the method described in the haze value of JIS-K-6714-1977. The measurement was performed using a haze meter (NDH-1)
001P, manufactured by Nippon Denshoku Industries Co., Ltd.). (3) Adhesion of dust such as detached conductive particles due to transport The film before forming the photosensitive layer of the sample (that is, the first and second undercoat layers on one surface of the support, and the other surface is charged) The film having the protective layer and the surface layer formed thereon was processed into a long film having a width of 18 cm, stored in an atmosphere of 25 ° C. and 65% RH for 3 days, and then used a handling test machine, which is a simulation device of an emulsion coating machine. To transport a long film at a line speed of 100 m / min.
The drive roll (flat roll) was rotated in the reverse direction and conveyed for 5 minutes at a peripheral speed of 90 m / min, and the amount of powder attached to the drive roll surface was visually evaluated as follows. AA: no attached dust is seen at all BB: little attached dust is seen CC: some attached dust is seen DD: considerable amount of attached dust is seen

Tables 1 to 4 show the composition of the antistatic layer forming material and the evaluation results.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

[Table 3]

[0068]

[Table 4]

As is clear from the results of Tables 1 to 4,
The light-sensitive materials obtained in Examples 1 to 4 have low haze and low surface electric resistance, have transparency necessary for photographic light-sensitive materials, and have excellent characteristics that there is almost no adhesion of dust due to transportation. . On the other hand, even if the photographic light-sensitive materials obtained in Comparative Examples 1 to 4 do not have sufficiently low haze, the surface electric resistance does not decrease so much, and the adhesion of dust due to transportation is inferior to those of Examples. Further, even if the amount of the metal oxide particles is increased, the haze is increased and the amount of desorbed components is increased, so that the adhesion of dust is not improved. Further, in the photographic materials obtained in Examples 1 to 4, the surface electric resistance after development hardly changed from the value before development and was not affected by the development processing, but the photographic materials obtained in Comparative Examples 1 to 4 were obtained. The photosensitive material is affected by the development processing, and the surface electric resistance before and after the development has a large change.

[0070]

The antistatic layer of the silver halide photographic light-sensitive material of the present invention has good conductivity while maintaining low haze. For this reason, the silver halide photographic light-sensitive material of the present invention is excellent in transparency and antistatic property, and hardly adheres dust due to powder dropping during transportation of the photographic material. An antistatic layer having good conductivity while maintaining the above low haze can be advantageously obtained by using needle-like metal oxide particles. Such an antistatic layer hardly causes the conductive metal oxide particles to fall off and has excellent antistatic properties after the development processing, so that there is almost no adhesion of dust due to transportation during development. Therefore, it can be said that the silver halide photographic light-sensitive material of the present invention is useful in a particularly severe application under the transport conditions of a microfilm, a movie film and the like.

Claims (6)

[Claims] 1. A low-charge support having an antistatic layer containing conductive metal oxide particles and a surface layer provided in this order on one side of a plastic film support, and the low-charge support. In a silver halide photographic light-sensitive material comprising a silver halide photographic light-sensitive layer provided on the surface on which the antistatic layer of the body is not provided, the haze of the low-charge support is 1.5 or less; Then, the surface electric resistance of the surface layer of the silver halide photographic material is from 8 × 10 ^{6 to} 6 × 10 ^8.
A silver halide photographic material characterized by being in the range of Ω. 2. The silver halide photographic material according to claim 1, wherein the conductive metal oxide particles are acicular particles, and the ratio of the major axis to the minor axis is in the range of 3 to 50. 3. The method according to claim 1, wherein the conductive metal oxide particles are ZnO, T
Particles of at least one metal oxide selected from the group consisting of iO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO and composite oxides thereof, or a metal further containing a different atom in the metal oxide 3. The silver halide photographic light-sensitive material according to claim 1, which is an oxide particle. 4. The silver halide photographic material according to claim 1, wherein said conductive metal oxide particles are SnO ₂ particles doped with antimony. 5. The antistatic layer according to claim 1, further comprising a cured product of a melamine compound and at least one polymer selected from the group consisting of an acrylic resin, a vinyl resin, a polyurethane resin and a polyester resin. C. The silver halide photographic light-sensitive material described in C. 6. The silver halide photographic light-sensitive material according to claim 1, wherein said surface layer comprises a polyolefin.