JPH1062905A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material superior in antistaticness and restrained from electrostatic trouble after development processing. SOLUTION: This silver halide photographic sensitive material is provided with a dye layer containing dispersed solid dye particles and a photosensitive silver halide emulsion layer successively on one side of a plastic support and on the other side successively with an antistatic layer and a surface layer. A surface resistivity on the antistatic layer side is <=5x10<12> Ω/(square) in an atmosphere of 23 deg.C and 65%RH before the development processing and after that 5x10<9> in an atmosphere of 23 deg.C10%RH. It is preferred to contain a silicone compound and/or fine organic compound particies in the outermost layer on the side of the emulsion layer and to contain fine conductive metal oxide particles in the antistatic layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material which has excellent antistatic properties before development, has an antistatic property on the surface of the photosensitive material after development, and has improved transportability in a projector or the like. Things.

[0002]

2. Description of the Related Art In recent years, the technology for manufacturing photosensitive materials has been remarkably improved and the speed thereof has been increased. Therefore, during the manufacturing process, the same type or different types of materials are subject to contact friction or peeling, so that they are charged with static electricity and dust and dust easily adhere. It tends to cause various spots such as water repellency, desensitization, and fogging, as well as discharging the accumulated static electricity, resulting in a so-called static mark on the photosensitive layer and a fatal defect. Become. For example, it is easily recognized that the occurrence of a static mark on a medical or industrial X-ray film or the like leads to a very dangerous judgment. Unfortunately, this phenomenon cannot be detected until the photosensitive material is developed. The tendency to increase the speed is the same in the photographing and developing processing steps, and in these steps, static electricity is likely to be generated.

[0003] Even after development processing, when image information recorded on a photosensitive material is used in an enlarged manner such as a microfilm or a movie film, dust or the like adhered to the film due to static electricity. Dust makes the image unsightly, which significantly impairs the commercial value.

[0004] For this reason, one method of imparting antistatic properties to the photosensitive material is to dissipate the electrostatic charge before the accumulated charge is discharged by increasing the electrical conductivity of the surface of the photosensitive material. Specifically, it is known to provide a layer containing a conductive polymer, an ionic or nonionic surfactant, colloidal silica, a metal oxide or a composite oxide thereof. However, for example, a surfactant such as a surfactant that elutes in the developing solution during the developing process naturally has not only an antistatic property after the developing process but also a photographic characteristic such as deterioration of the developing solution in some cases. May worsen.
Further, in a low humidity atmosphere such as in winter, an antistatic agent such as a conductive polymer generally cannot exhibit sufficient antistatic performance due to ionic conductivity.

[0005] The antistatic agent is preferably a metal oxide or a composite oxide thereof, because it 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 known, and specific examples thereof include particles described in Japanese Patent Publication No. 1-20736 and JP-A-61-20033.

When the antistatic performance is imparted by using such fine particles of a metal oxide or the like, there is a problem associated with an increase in the speed of the production of the photosensitive material. There is a case where a phenomenon called so-called powder dropping, which is caused to drop off from the film surface and adhere to the roll surface or the like due to contact friction with the inside transport roll or the like, is caused. Regarding this point, conductive metal oxide particles as described in JP-A-8-36239, at least one polymer selected from the group consisting of acrylic resin, vinyl resin, polyurethane resin and polyester resin, and a melamine compound It is known that the problem can be solved by providing an antistatic layer made of a cured product of the above. Another method for eliminating obstacles due to static electricity of the photosensitive material is to adjust the charging sequence on the surface of the photosensitive material so as to reduce the generation of static electricity due to friction and contact as described above.

For example, British Patent No. 1,330,356
No. 1,524,631, U.S. Pat.
No. 475, No. 3,589,906, JP-B 52-26
687, JP-A-49-46733, and JP-A-51-323.
Attempts have been made to use fluorinated surfactants such as those described in No. 22 or the like in light-sensitive materials for this purpose.

[0008] On the other hand, the photosensitive material is used in various devices, machines, cameras, and the like in handling such as rewinding or transporting in the manufacturing process such as coating, drying, and processing, as well as in photographing, developing, printing, and projection. Is often undesirably affected by contact friction between photosensitive material such as photographic materials or contact friction between dust and fiber debris, or contact between photographic photosensitive materials such as between the photosensitive material surface and the back surface. is there. For example, the transportability of the photosensitive material in a camera or other equipment is deteriorated, and film dust is generated in the camera or other equipment.

As a countermeasure, the physical friction is improved by reducing the contact friction of the photographic material so that the photographic material can be smoothly transported through a film magazine, a camera gate, a camera gate such as a projector gate, and the like. There have been proposed several methods for obtaining a photographic light-sensitive material. For example, U.S. Pat.
No. 2,080,317 describes a method for imparting slipperiness to a light-sensitive material film by simultaneously containing dimethyl silicone and a specific surfactant in a photographic emulsion layer or a protective layer as described in U.S. Pat. A method in which a mixture of dimethyl silicone and diphenyl silicone is applied to the back surface of a light-sensitive material film to impart lubricity, and a triphenyl terminal in a protective layer as described in British Patent No. 1,143,118. There is known a method of adding a block of methylphenyl silicone to impart a lubricating property to a light-sensitive material film.

Further, as a method for providing a photosensitive material having both properties of charging property and slipperiness during long-term storage, a polymer matting agent is added to a back layer of a photosensitive material film as described in JP-A-61-42653. A method in which a polyoxyethylene-based surfactant and a silicone-based slip agent are coated on the emulsion protective layer, and a polymer matting agent is coated on the emulsion protective layer of a light-sensitive material film as described in JP-A-61-42654. There has been proposed a method of applying a fluorine-containing surfactant, a polyoxyethylene-based surfactant, or a silicone-based slip agent to the back layer.

[0011]

However, a photosensitive material such as a movie film is conveyed by a machine such as a printer or a projector after the development processing. In recent years, due to demands for faster printers and faster transport systems,
Many of the transport rollers are made of plastic resin, and because of their insulating properties, static electricity tends to be easily generated due to contact friction with a photosensitive material or the like. This phenomenon is caused by contact friction between the surface of the photosensitive material and a roller or the like even when the antistatic layer is provided, and it is often difficult to suppress static electricity in a low humidity atmosphere.

In the case after the development processing, there is no concern about the occurrence of the static mark as described above, but the generated static electricity may cause troubles such as the film not being transported smoothly. As a specific example, in the horizontal platter type projector used in many movie theaters in recent years, when the photosensitive film wound on the platter is sent out from the inside of the roll, the films stick together due to static electricity and are sent out at the center of the platter Troubles that can be entangled in the drive part of the vehicle.

Therefore, the present invention is excellent in antistatic performance,
It is another object of the present invention to provide a silver halide photographic light-sensitive material in which electrostatic damage after development processing is suppressed. More specifically, an object of the present invention is to provide a silver halide photographic light-sensitive material having an antistatic property in which the electric resistance value of the surface of a light-sensitive material is adjusted to a specific range and improved transportability in a projector or the like after development processing. I do.

[0014]

As a result of intensive studies, the present inventor has found that any of the following constitutions (1) to (5) can solve the above-mentioned problems. (1) On one side of the plastic film support,
A dye layer, a photosensitive silver halide photographic emulsion layer are provided in this order, an antistatic layer and a surface layer are provided in this order on the other side, and the dye layer contains solid dispersed dye particles. In the photographic light-sensitive material, the surface electric resistance value on the antistatic layer side is 5 × 10 ¹² Ω / □ or less at 23 ° C. and 65% RH before development, and 23 ° C.
A silver halide photographic material having a density of 5 × 10 ⁹ Ω / □ or more in a% RH atmosphere. (2) The silver halide photographic material as described in (1), wherein the outermost layer on the emulsion layer side contains a silicone compound. (3) The silver halide photographic material as described in (1) or (2), wherein the outermost layer on the emulsion layer side contains organic compound fine particles. (4) The silver halide photographic light-sensitive material according to any one of (1) to (3), wherein a protective layer containing fine particles of a silicone compound and / or an organic compound is provided on the outer surface side of the emulsion layer. . (5) The antistatic layer is made of ZnO, TiO ₂ , Sn
Contains at least one crystalline metal oxide selected from O ₂ , Al ₂ O ₃ , In ₂ O ₃ , and MgO, a composite oxide thereof, or conductive metal fine particles containing a small amount of heteroatoms in these oxides The silver halide photographic light-sensitive material according to any one of (1) to (4), wherein

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be specifically described below. If the surface electric resistance value of the photosensitive material on the antistatic layer side in the present invention is too high or too low, inconvenience occurs.
A preferred range is 5 × 10 ¹² Ω / □ or less at 23 ° C. and 65% RH before development, and 5 × 10 ⁹ Ω / □ or more at 23 ° C. and 10% RH before development. is there. Before the development processing, from the viewpoint of preventing generation of static marks, it is necessary to set the above range after the development processing from the viewpoint of preventing transport trouble of a projector or the like.

For measuring the surface electric resistance value, a DC constant voltage power supply and an ammeter can be used. The principle of measurement utilizes the relationship of Ohm's law E = RI (voltage E, current I, resistance R). A constant voltage E is applied to a predetermined area on the antistatic layer of the photosensitive material, and a current I flowing at that time is measured by an ammeter in the circuit to obtain a standardized electric resistance R per area. (Unit: Ω / □) can be calculated.

A specific device is, for example, a constant voltage power supply TR-300C and an ammeter TR-8 manufactured by Takeda Riken Industry Co., Ltd.
651 and the sample chamber TR-42. STANDARDRE
SISTOR TR-45 is used.

Next, the concept of preventing an electrostatic failure will be described. When the photosensitive material is transported in a projector or the like, static electricity is generated as described above, and the photosensitive material may be charged. It is known that the attenuation of the charged voltage is represented by the following equation. Vt = Vo exp (−t / τ) Vo: initial charged voltage Vt: voltage at time t τ: time constant τ in the above equation is capacitance C, leakage resistance (= electrical resistance)
Τ = CR using R.

The small time constant τ means that even if a large amount of electric charge is generated, it leaks instantaneously and does not become large as the charge amount. Therefore, for the purpose of preventing generation of static marks on the photosensitive material before the development processing, it is preferable that the electric resistance R be small. Since the temperature and humidity are controlled in many places where the photosensitive material before the development processing is handled, the properties can be represented by electric resistance at 23 ° C. and 65% RH under typical conditions. The preferred range is 23 ° C 65% RH
Under an atmosphere, it is 5 × 10 ¹² Ω / □ or less, and more preferably 5 × 10 ¹¹ Ω / □ or less.

However, the smaller the electric resistance value, the less preferable. If the photosensitive material is in a state of not being grounded electrostatically, electrostatic damage is more likely to occur. For example, when the developed photosensitive material is transported by a horizontal platter type projector, etc., the charge of the opposite sign is applied to the photosensitive material in order to cancel the charge due to the static electricity generated by friction with the roller at the center of the horizontal platter. It will be supplied from other parts. When the time constant is small, this supply is performed instantaneously, and the supply source of the charge temporarily becomes electrically biased to supply the charge of one sign. If the photosensitive material is not grounded, the electrical bias will not be eliminated and the photosensitive material will be transported one after another, so that static electricity will continue to be generated due to friction with the rollers. Thus, static electricity damage occurs in the photosensitive material after the development processing.

To prevent this, the time required for canceling static electricity due to friction with the roller is delayed by increasing the electric resistance of the photosensitive material to some extent to increase the time constant, thereby reducing the degree of the electric bias. It is better to reduce it. Since the charging due to friction between the photosensitive material and the roller increases at low temperatures, it is preferably 5 × 10 ⁹ Ω / □ or more as a representative evaluation condition in terms of the properties in a 23 ° C., 10% RH atmosphere.

In the present invention, plastic film supports include, for example, polyethylene terephthalate, polyethylene-2,6-dinaphthalate, polypropylene terephthalate, polybutylene terephthalate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, polycarbonate, Films such as polystyrene and polyethylene can be given. Among these plastic film supports, polyethylene terephthalate is preferable, and a biaxially stretched and heat-fixed 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. Further, the support may be transparent or may contain an anthraquinone dye, dyed silicon, silicon dioxide, alumina sol, chromium salt, zirconium salt, titanium oxide, or 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. The surface on the side on which the antistatic layer (back layer) of the present invention is formed is generally subjected to the same surface treatment. (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 performing a surface activation treatment such as
Once these surface treatments have been carried out, there are two methods: a method in which an undercoat layer is provided and a photographic emulsion layer is coated thereon.

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 that it increases the density and the adhesive strength, and as a result, the affinity of the components contained in the undercoat layer solution with the polar group increases, and the robustness of the adhesive surface increases. Etc.
It is considered that the adhesion between the undercoat layer and the surface of the support is improved.

The method of applying the undercoat layer includes a so-called multilayer method in which a first layer is provided with a layer which adheres well to the 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.
In forming the first undercoat layer and the second undercoat layer of gelatin, a curing agent such as a dichlorotriazine derivative, an epoxy compound, or a vinyl sulfone compound is generally used in combination.

If desired, a swelling agent such as phenol or resorcin may be added to the first undercoat layer, and the amount of addition is 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, as a blocking inhibitor, a matting agent (silicon dioxide, aluminum oxide, barium sulfate, polymethyl acrylate, polystyrene), methyl cellulose, polyvinyl alcohol, or the like can be used.

The 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. It can be applied by an extrusion coating method using a popper described in U.S. Pat. No. 2,681,294. When further providing a second undercoat layer on the undercoat layer,
If necessary, U.S. Pat.
Nos. 8947, 2941898 and 352652
No. 8, two or more layers can be simultaneously coated by the method described in Ozaki et al., “Coating Engineering”, page 253 (published by Asakura Shoten, 1973).

The amount of the first undercoat layer and the amount of the second undercoat layer provided on the first undercoat layer is 0.01 to 0.01% per square meter of the polyester film support as a solid content.
10 g to 10 g is preferable, and particularly preferably 0.2 to 3 g. In the present invention, a hydrophilic colloid layer mainly composed of gelatin 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 carboxymethylcellulose and hydroxyethylcellulose, acrylic acid, methacrylic acid and the like. Grafted gelatin obtained by grafting acid or amide to gelatin,
Polyvinyl alcohol, polyhydroxyalkyl acrylate, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, casein, agarose, albumin, sodium alginate, polysaccharide, agar, starch, grafted starch, polyacrylamide, polyethyleneimine acyl compound, and acrylic acid Methacrylic acid 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. 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, if necessary.

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). Etc.) onto gelatin, grafted gelatin, polyvinyl alcohol, polyhydroxyalkyl acrylate, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymer, casein, agarose, albumin, sodium alginate, polysaccharide, agar, starch, graft Synthetic or natural hydrophilic high-molecular compounds such as starch, polyacrylamide, acylated polyethyleneimine, and their partially hydrolyzed products 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. A physical development nucleus such as silver halide or silver sulfide used in diffusion transfer photography, a photosensitive material such as a diazo compound, various additives, a coupler, and an emulsion polymerization latex polymer 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.

Representative examples of the silicone compound used in the outermost layer on the emulsion layer side of the present invention include, for example, US Pat. No. 3,042,522 and British Patent 955,061.
No. 3,080,317, U.S. Pat.
927, 4,047,958, 3,489,5
No. 67, British Patent No. 1,143,118 and the like. In the present invention, the following general formula (II-1), general formula (II-2) and general formula (II-
Alkyl polysiloxisan represented by 3) is preferably used. More preferably, an alkylpolysiloxane having a polyoxyalkylene chain in a side chain represented by the general formula (II-1) and an alkylpolysiloxane represented by the general formula (II-2) are used.

[0035]

Embedded image

In the formula, R is an aliphatic group such as an alkyl group (preferably having 1 to 18 carbon atoms), a substituted alkyl group (eg, an aralkyl group, an alkoxyalkyl group, an aryloxyalkyl group, etc.) or an aryl group ( For example, a phenyl group). R 'is a hydrogen atom, an aliphatic group such as an alkyl group (preferably having 1 to 12 carbon atoms). Represents a substituted alkyl group or an aryl group (eg, a phenyl group). R "represents an alkyl group (for example, a methyl group) or an alkoxyalkyl group (for example, a methoxymethyl group); A represents a divalent residue of an aliphatic hydrocarbon; n is 0 or an integer of 1 to 12; p is a number of 0 to 50, q is a number of 2 to 50 (preferably 2 to 30), x is a number of 0 to 100, y is a number of 1 to 50, and z is a number of 0 to 50.
X + y + z is a number from 5 to 250 (preferably from 10 to 50).

Specific examples of R include methyl, ethyl, propyl, pentyl, cyclopentyl, cyclohexyl,
Examples include dimethylpentyl, heptyl, methylhexyl, octyl, dodecyl, octadecyl, phenylethyl, methylphenylethyl, phenylpropyl, cyclohexylpropyl, benzyloxypropyl, phenoxypropyl, ethyloxypropyl, butyloxyethyl, phenyl and the like. The group represented by A is methylene, 1-
On-trimethylene, 2-methyl-1-one-trimethylene and the like can be mentioned. Examples of the alkyl group represented by R ′ include a methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl group.

[0038]

Embedded image

The general formula (II-2) is represented by the following general formula (II-2-
A cyclic siloxane having a siloxane unit represented by 1) and a linear siloxane having a siloxane unit represented by the general formula (II-2-1) and a terminal group represented by the following general formula (II-2-2) Is included.

[0040]

Embedded image

In the formula, R ₁ represents an alkyl, cycloalkyl, alkoxyalkyl, arylalkyl, aryloxyalkyl or glycidyloxyalkyl group having 5 to 20 carbon atoms. R ₂ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl, an alkoxyalkyl, an arylalkyl, an aryloxyalkyl and a glycidyloxyalkyl group having 5 to 20 carbon atoms. n is 0 or a number of 1 or more, m is a number of 1 or more, and n + m is 1 to 10.
Represents the number 00. Preferably n + m is from 2 to 500.

R _{1 of the} compound represented by formula (II-2)
Specific examples include, but are not limited to, pentyl, methylpentyl, cyclopentyl, cyclohexyl, dimethylpentyl, heptyl, methylhexyl, octyl, eicosyl, phenylethyl, methylphenylethyl, phenylpropyl, cyclohexylpropyl, pendyloxypropyl, phenoxypropyl, tolyl Oxypropyl, naphthylpropyl, ethyloxypropyl, butyloxyethyl, octadecyloxypropyl, glycidyloxypropyl, glycidyloxybutyl and the like.

[0043]

Embedded image

Wherein R ₃ is an alkyl group having 1 to ₃ carbon atoms;
R ₄ represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms. m is an integer of 0 to 2000.
Representative examples of the compounds represented by formulas (II-1), (II-2) and (II-3) are (II-1-yl) (II-) described in JP-A-61-42653. 2-ii ~ ne) (II-3-i ~
B).

The content of the silicone compound contained in the outermost layer on the emulsion layer side of the present invention is 0.000 per square meter.
The range of 5 to 2.0 g is preferred, and particularly 0.05 to 0.6 g.
It is preferably in the range of g.

Specific examples of the organic compound fine particles used in the present invention include a water-dispersible vinyl polymer such as polymethyl methacrylate, cellulose acetate propionate and starch. In particular, a spherical matting agent of a water-dispersible vinyl polymer such as a homopolymer of an acrylate such as methyl methacrylate, glycidyl acrylate or glycidyl methacrylate, or a copolymer of these acrylates with each other or with another vinyl monomer. preferable.

The content of the fine particles is preferably in the range of 0.01 to 1.0 g per square meter, particularly preferably 0.02 to 1.0 g.
It is preferably in the range of ０．１0.15 gk. The particle size is preferably from 0.2 to 10 μm, particularly preferably from 1.0 to 6.0 μm.

The outermost layer on the emulsion layer side of the present invention may contain a polyoxyethylene surfactant. Specific examples include compounds represented by the following general formula [I-1] [I-2] or [I-3].

[0049]

Embedded image

In the formula, R ₁ represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group having 1 to 30 carbon atoms, and A represents-
O-group, -S- group, -COO- group,

Embedded image (Where R ₁₀ represents a hydrogen atom, a substituted or unsubstituted alkyl group).

R ₂ , R ₃ , R ₇ and R ₉ are a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group. Represents
In the formula, R ₆ and R ₈ represent a substituted or unsubstituted alkyl group, aryl group, alkoxy group, halogen group, acyl group, amide group, sulfonamido group, carbamoyl group or sulfamoyl group. In the general formula [I-3], the substituent on the phenyl ring may be left-right asymmetric. R ₄ and R
₅ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. R ₄ and R ₅ , R ₆ and R ₇ and R ₈
And R ₉ may combine with each other to form a substituted or unsubstituted ring. n ₁ , n ₂ , n ₃ and n ₄ are average degrees of polymerization of ethylene oxide and are 2 to 50 numbers. In addition, m is an average degree of polymerization, and is a number of 2 to 50.

Preferred examples of the present invention are described below.
R ₁ is preferably an alkyl group, an alkenyl group, or an alkylaryl group having 4 to 24 carbon atoms, and particularly preferably a hexyl group, a dodecyl group, an isostearyl group, an oleyl group, a t-butylphenyl group, or a 2,4-diphenyl group. -T-butylphenyl group, 2,4-di-t-pentylphenyl group, p-
Dodecylphenyl group, m-pentadecaphenyl group, t-
Octylphenyl, 2,4-dinonylphenyl, octylnaphthyl and the like. R ₂ , R ₃ , R ₆ , R ₇ ,
R ₈ and R ₉ are preferably methyl, ethyl, i-propyl, t-butyl, t-amyl, t-hexyl, t-octyl, nonyl, decyl, dodecyl, trichloromethyl,
A substituted or unsubstituted aryl group such as a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms such as tripromomethyl, 1-phenylethyl, and 2-phenyl-2-propyl, a phenyl group, and a p-chlorophenyl group; A substituted or unsubstituted alkoxy group represented by OR ₁₁ (where R ₁₁ represents a substituted or unsubstituted alkyl group or aryl group having 1 to 20 carbon atoms; the same applies hereinafter), a chlorine atom, a bromine atom, etc. A halogen atom, an acyl group represented by -COR ₁₁ , -NR ₁₂ SO
An amide group represented by ₂ R _11- (where R ₁₂ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; the same applies hereinafter);
A sulfonamide group represented by NR ₁₂ SO ₂ R ₁₁ —,

Embedded image A carbamoyl group represented by

Embedded image And a sulfamoyl group represented by R ₂ ,
R ₃ , R ₇ and R ₉ may be hydrogen atoms. Of these, R ₆ and R ₈ are preferably an alkyl group or a halogen atom, and particularly preferably a bulky t-butyl group or t-butyl group.
It is a tertiary alkyl group such as an amyl group and a t-octyl group.
R ₇ and R ₉ are particularly preferably a hydrogen atom. That is, a compound of the general formula [I-3] synthesized from a 2,4-disubstituted phenol is particularly preferred.

R_Four, R_FiveIs preferably a hydrogen atom, methyl
Group, ethyl group, n-propyl group, i-propyl group, n-
Heptyl group, 1-ethylamyl group, n-undecyl group,
Substitution of trichloromethyl group, tribromomethyl group, etc.
Or unsubstituted alkyl group, α-furyl group, phenyl group,
Naphthyl group, p-chlorophenyl group, p-methoxyphen
Substituted or unsubstituted groups such as nyl group and m-nitrophenyl group
Is an aryl group. Also, R_FourAnd R_Five, R₆And R₇Passing
And R₈And R₉Are linked to each other to form a substituted or unsubstituted ring
For example, a cyclohexyl ring. This
Of these, R _FourAnd R_FiveIs particularly preferably a hydrogen atom,
An alkyl group having 1 to 8 carbon atoms, a phenyl group, and a furyl group;
You. n₁, N_Two, N_ThreeAnd n_FourIs particularly preferably 5 to
It is a number of thirty. n_ThreeAnd n_FourAre the same or different
good.

These compounds are described, for example, in US Pat.
No. 82,651, No. 3,428,456, No. 3,45
7,076, 3,454,625, 3,55
No. 2,972, No. 3,655,387, Tokiko Sho 51-
No. 9610, JP-A-53-29715, JP-A-54-1979
No. 89626, Japanese Patent Application No. 57-85764, Japanese Patent Application No. 57
No. 90909, Hiroshi Horiguchi, "New Surfactant" (Sankyo Shuppan, 1975). Specific examples include compounds (I-1 to I-3) described in JP-A-61-42653.
7).

Although not necessarily required in the present invention, the surface treatment such as corona discharge treatment is performed not only for the hydrophobic support but also for the hydrophobic support.
It may be performed on the undercoat layer composed of a polymer substance and / or on the second undercoat layer, in which case the adhesion between the treated layers 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 antistatic layer of the present invention,
This is a layer in which conductive metal oxide particles are dispersed in a cured product of an acrylic resin and a melamine compound.

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, MoO ₃ and their composite oxides, and metal oxides containing heteroatoms in addition to these metal oxides can be mentioned.

As the metal oxide, SnO_Two , ZnO,
Al_Two O_Three , TiO_Two , In_Two O_Three, And MgO, Ba
O and MoO_ThreeIs preferable, and SnO_Two , ZnO,
In _Two O_ThreeAnd TiO_Two Are preferred, and SnO_Two Is particularly good
Good. As an example containing a small amount of heteroatoms, ZnO
Al or In, TiO_Two Nb or T
a, In_Two O_Three For Sn and SnO_Two For S
b, Nb or a different element such as a halogen element
1 to 30 mol% (preferably 0.1 to 10 mol%)
Can be mentioned. Addition amount of different elements
Is less than 0.01 mol%, oxide or complex oxidation
30% by mole
If the ratio exceeds the above range, the degree of blackening of the particles increases, and
Not suitable for photosensitive materials. Therefore, the present invention
As the material of the metal oxide particles, metal oxide or composite
Those containing a small amount of a different element with respect to the metal oxide are preferred.
Further, those having an oxygen defect in the crystal structure are also preferable.

The conductive metal oxide particles contain a binder (a total of acrylic resin and melamine compound) in the antistatic layer.
Is preferably 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 the photosensitive material.

The particle size of the conductive metal oxide particles is preferably as small as possible to minimize light scattering, but should be determined using the ratio of the refractive index of the particles to the binder as a parameter. ) Can be determined using the theory of (1). Generally, the average particle size is 0.001 to
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 including 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 metal oxide are added to the coating solution for forming the antistatic layer, they may be added as they are and dispersed, but may be a solvent such as water (including a dispersant and a binder if necessary. It is preferable to add the dispersion liquid dispersed in the above (1).

The antistatic layer of the present invention contains a cured product of an acrylic resin and a melamine compound as a binder for dispersing and supporting the conductive metal oxide particles. 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. The polymer preferably has any one of a methylol group, a hydroxyl group, a carboxyl group and a glycidyl group so that a cross-linking 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 0.0001 to 10 equivalents / 1.
kg, particularly preferably 0.01 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-mentioned composition as a main component, and includes, for example, a monomer having at least one 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. It is a polymer obtained by use.

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 the initial condensate of melamine and formalin include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, and specific commercial products such as Sumitex・ Resin (Su
mitex Resin) M-3, MW, MK, and MC (manufactured by Sumitomo Chemical Co., Ltd.), but are not limited thereto.

Examples of the above-mentioned polycondensate include hexamethylolmelamine resin, trimethylolmelamine resin, trimethyloltrimethoxymethylmelamine resin and the like. MA-1 and MA-2 are commercially available.
04 (Sumitomo Bakelite Co., Ltd.), Beckamine (BEC
KAMINE) MA-S, Beckamin APM and Beckamin J-101 (manufactured by Dainippon Ink and Chemicals, Inc.), Euroid 344 (manufactured by Mitsui Toatsu Chemicals, Inc.), Oka Resin M31 and Oka Resin PWP-8 (Oka Promotion) (Made by Corporation)
And the like, but are not limited to these.

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.

Representative examples include mucochloric acid, mucobromic acid, mucofenoxycyclolic acid, mucophenoxypromic acid, formaldehyde, glyoxal, monomethylglyoxal, 2,3-dihydroxy-1,4 dioxane, 2,3-dioxane 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, methylenebismaleimide, 5-acetyl-1,3-diacryloyl-hexahydro- s-triazine, 1,3,5-triacryloyl-hesahydro-s-triazine and 1,3,
Active vinyl compounds such as 5-trivinylsulfonyl-hexahydro-s-triazine;

2,4-dichloro-6-hydroxy-s-
Triazine sodium salt, 2,4-dichloro-6- (4
-Sulfoanilino) -s-triazine sodium salt,
2,4-dichloro-6- (2-sulfoethylamino)-
Active halogen compounds such as s-triazine and N, N'-bis (2-chloroethylcarbamyl) piperazine;

Bis (2,3-epoxypropyl) methylpropylammonium / p-toluenesulfonate,
1,4-bis (2 ', 3'-epoxypropyloxy)
Butane, 1,3,5-triglycidyl isocyanurate, 1,3-dichridyl-5- (γ-acetoxy-β
-Oxypropyl) isocyanurate, sorbitol polyglycidyl ethers, polyglycerol polyglycidyl ethers, pentaerythritol polyglycidyl ethers, diglycerol polyglycidyl ether,
1,3,5-triglycidyl (2-hydroxyethyl)
Epoxy compounds such as isocyanurate, glycerol polyglycerol ethers and trimethylolpropane polyglycidyl ethers;

Ethyleneimine compounds such as 2,4,6-triethylene-s-triazine, 1,6-hexamethylene-N, N'-bisethyleneurea and bis-β-ethyleneiminoethylthioether; -Di (methanesulfonoxy) ethane, 1,4-di (methanesulfonoxy) butane and 1,5-di (methanesulfonoxy)
Methanesulfonic acid ester compounds such as 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 dust and chromium acetate;

Dehydration-condensed peptide reagents such as N-carbethoxy-2-isopropoxy-1,2-dihydroquinoline and N- (1-morpholinocarboxy) -4-methylpyridium chloride; N, N'-adipo Active ester compounds such as ildioxy dissuccinimide and N, N'-terephthaloyl dioxy dissuccinimide: isocyanates such as toluene-2,4-diisocyanate and 1,6-hexamethylene diisocyanate; and polyamide-polyamine- An epichlorohydrin-based compound such as an epichlorohydrin reactant can be used, but is not limited thereto.

If necessary, a matting agent, a surfactant, a slipping agent and the like can be used in combination in the antistatic layer and the following surface layer of the present invention. As a matting agent,
Examples thereof include oxides having a particle size of 0.001 μm to 10 μm, such as silicon oxide, aluminum oxide, and magnesium oxide, and polymers or copolymers such as polymethyl methacrylate and polystyrene. Examples of the surfactant include known anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. Examples of the slipping agent include phosphoric 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.

The antistatic layer according to the present invention is formed 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) with an acrylic resin or a melamine compound. And an aqueous dispersion or an aqueous solution containing an appropriate additive, followed by mixing (dispersion as necessary) to prepare a coating solution for forming an antistatic layer.

The antistatic layer of the present invention can be prepared by applying the above-mentioned coating solution for forming an antistatic layer to the surface of a plastic film such as polyester (the side on which the photosensitive layer is not provided), for example, a dip coating method. It can be applied 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 plastic film of polyester or the like to be applied may be either before sequential biaxial stretching, 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 μm 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.

In the present invention, a surface layer is provided on the antistatic layer. 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.

Examples of the material for the surface layer include waxes, resins, and rubbers made of homo- or copolymers of 1-olefin unsaturated hydrocarbons such as ethylene, propylene, 1-butene and 4-methyl-1-pentene. (For example, polyethylene, polypropylene, poly-1-butene, poly-4
-Methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer and propylene / 1
-Butene copolymer), rubbery copolymers of two or more of the above-mentioned 1-olefins with conjugated or non-conjugated dienes (eg, ethylene / propylene / ethylidene norbornene copolymer, ethylene / propylene / 1,5-hexadiene) Copolymer and isobutene / isoprene copolymer), 1
A copolymer of an olefin and a conjugated or non-conjugated diene,
(E.g., ethylene / butadiene copolymer and ethylene / ethylidene norbornene copolymer), 1-olefins, particularly copolymers of ethylene and vinyl acetate and their fully or partially saponified products, homo- or copolymers of 1-olefins And a graft polymer obtained by grafting the above conjugated or non-conjugated diene, vinyl acetate, or the like, and a completely or partially saponified product thereof, but are not limited thereto. The compound is
It is described in JP-B-5-41656.

The above-mentioned polyolefins having a carboxyl group and / or a carboxylic acid group are preferred. In the present invention, it is usually used as an aqueous solution or an aqueous dispersion.

The above-mentioned surface layer can be 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 solution (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 the thickness is less than 0.01 μm, it is difficult to apply the coating agent uniformly, so that application unevenness is likely to occur on the product. If the thickness exceeds 1 μm, the antistatic performance and the scratch resistance may be poor.

Next, the silver halide emulsion layer provided on the other side of the photographic support will be described. Various hydrophilic colloids are used in the light-sensitive material of the present invention. Hydrophilic colloids used as binders for photographic emulsions and / or other photographic constituent layers include, for example, gelatin, colloidal albumin, casein, carboxymethylcellulose, cellulose derivatives such as hydroxyethylcellulose, agar, sodium alginate, Examples include sugar derivatives such as starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, poly N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide, or derivatives thereof, and partially hydrolyzed sugars. Optionally, a compatible mixture of two or more of these colloids is used. The most commonly used of these is gelatin.

In the silver halide emulsion layer and other layers, a synthetic polymer compound, for example, a latex-like water-dispersed vinyl compound polymer, especially a compound for increasing the dimensional stability of a photographic material, may be used alone or as a mixture. (Of a heterogeneous polymer) or in combination with a hydrophilic water-permeable colloid. There are many polymers, for example, U.S. Pat. Nos. 2,376,005 and 2,734.
9,137, 2,853,457, 3,06
No. 2,674, No. 3,411,911, No. 3,48
8,708, 3,525,620, 3,63
5,715, 3,607,290, 3,64
No. 5,740, British Patent Nos. 1,186,699 and 1,307,373.

Among these descriptions, alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, sulfoalkyl acrylate, sulfoalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, alkoxy Copolymers and homopolymers selected from alkyl acrylates, alkoxyalkyl methacrylates, styrene, butadiene, vinyl chloride, vinylidene chloride, maleic anhydride and itaconic anhydride are generally used.

The hardening of the silver halide emulsion and / or other photographic constituent layers can be carried out according to a conventional method. Examples of the curing agent include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, and bis (2
-Chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other U.S. Pat.
No. 288,775, No. 2,732,303,
British Patent Nos. 974,723 and 1,167,
No. 207, such as compounds having a reactive halogen, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine,
Other U.S. Pat. Nos. 3,635,718, 3,232,763, 3,490,911, 3,642,486, British Patent 994,869, etc. Compounds having a reactive olefin as shown in

N-Hydroxymethylphthalimide and other US Pat. Nos. 2,732,316 and 2,5
N-methylol compounds as shown in US Pat. No. 86,168, isocyanates as described in US Pat. No. 3,103,437, US Pat.
Aziridine compounds such as those described in US Pat. Nos. 017,280 and 2,983,611, and US Pat. Nos. 2,725,294 and 2,725,295.
Derivatives such as those shown in US Pat.
Carbodiimide compounds such as those described in US Pat. No. 100,704, epoxy compounds such as those described in US Pat. No. 3,091,537,

US Pat. No. 3,321,313,
Nos. 3,534,292, etc., isoxazole compounds, halogenocarboxaldehydes such as mucochloric acid, dihydroxydioxane,
Examples thereof include dioxane derivatives such as dichlorodioxane, N-carbamoylpyridinium salts, haloamidinium salts, and inorganic hardeners such as chromium ban and zirconium sulfate. In place of the above compounds, those in the form of a precursor such as an alkali metal bisulfite aldehyde adduct, a methylol derivative of hydantoin, and a primary aliphatic nitro alcohol may be used.

A silver halide emulsion is usually prepared by mixing a water-soluble silver salt (eg, silver nitrate) solution and a water-soluble halogen salt (eg, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. You. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halide such as chlorinated, iodinated and silver chloroiodobromide can be used.

Various compounds can be added to the silver halide emulsion in order to prevent a reduction in sensitivity and generation of fog during the production, storage or processing of the photographic material. Those compounds are 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene, 3-methyl-benzothiazole, 1-phenyl-5-mercaptotetrazole, and many other compounds such as heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts. Has been known for a long time.

The silver halide emulsion can be chemically sensitized by a conventional method. Chemical sensitizers include, for example, chloroaurate, gold compounds such as gold trichloride, platinum, palladium, iridium, rhodium, salts of precious metals such as ruthenium, and sulfur compounds that react with silver salts to form silver sulfide. , Stannous salts, amines, and other reducing substances.

The silver halide emulsion may be used, if necessary, by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with a styryl dye or the like. Sensitization and supersensitization can be performed.

Further, stilbene, triazine, oxazole and coumarin compounds are used as a brightening agent in the non-photosensitive photographic component layer, and benzotriazole, thiazolidine and cinnamate compounds are used as an ultraviolet absorber. Various photographic filter dyes known as light absorbers may be contained.

In the present invention, if necessary, as a slipping agent or an antiadhesive, for example, US Pat. No. 2,732,30
No. 5, No. 4,042,399, No. 3,12
Amides or esters of fatty acids and polyesters as described in US Pat. No. 1,060 and British Patent 1,466,304, and also British Patent 1,3.
Water insoluble materials as described in US Patent Nos. 20,564, 1,320,565, U.S. Patent 3,121,060, and U.S. Patent 3,617,2.
Surfactants such as those described in U.S. Pat. Further, the protective layer may contain, as a matting agent, an inorganic compound such as silica or strontium barium sulfate having an appropriate particle size, or an organic polymer such as polymethyl methacrylate or polystyrene.

Further, to a photographic constituting layer including a silver halide emulsion layer, in particular, to an antistatic layer provided on the outermost side of the light-sensitive material, as an antistatic agent, for example, US Pat.
No. 97, No. 2,972,535, No. 2,9
No. 72,536, No. 2,972,537, No. 2,
No. 972,538, No. 3,033,679, No. 3,072,484, No. 3,262,807, No. 3,525,621, No. 3,615,531,
No. 3,630,743, No. 3,653,906
No. 3,655,384, No. 3,655,38
6 and British Patents 1,222,154 and 1,235,075 and hydrophilic polymers such as those described in U.S. Pat. No. 2,973,263.
No. 2,976,148, can be used, for example, in US Pat.
Biguanide compounds as described in 4,362, 2,591,590,

For example, see US Pat. No. 2,639,234.
No. 2,649,372, 3,20
Nos. 3,251,076 and 3,457,076, and sulfonic acid type anion compounds described in, for example, U.S. Pat. Nos. 3,317,344 and 3,51.
Phosphate esters and quaternary ammonium salts as described in U.S. Pat.
Nos. 82,157, 2,982,651, 3,399,995, 3,549,369,
Cationic compounds such as those described in U.S. Pat. No. 3,564,043 may also be used, e.g., in U.S. Pat.
Nonionic compounds such as those described in US Pat. No. 695, etc., and amphoteric compounds such as those described in US Pat. No. 3,736,268, and US Pat. No. 2,647,836, for example. Complex compounds such as those described in US Pat.
Organic salts such as those described in JP-A Nos. 17,834 and 3,655,387 can be contained.

The light-sensitive material of the present invention corresponds to a color light-sensitive material using a dye-forming coupler. Color photographic materials are color negative films, reversal films, color negative films for movies,
Refers to color photographic materials for general movies such as color positive films and movie positive films.

A typical example of the color light-sensitive material of the present invention is a halogenated light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially different color sensitivity on a transparent support. It is a silver photographic light-sensitive material. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light.

The preferred silver halide used in the photographic light-sensitive material is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 0.5 mol% to about 30 mol% of silver iodide. . Particularly preferred are from about 2 mol% to about 10 mol%.
Silver iodobromide or silver iodochlorobromide containing up to mol% of silver iodide. Preferred silver halides for use in motion picture color positive films are silver chlorobromide and silver chloride, particularly those having a silver chloride content of 9.5 mol% or more and the remainder being silver bromide (silver iodide). Is preferred.

The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (hereinafter referred to as RD).
No.) 17643 (December 1978) pages 22-23, "I.
No. 18716 (November 1979), p.648, p.307105
(November 1989), pp. 863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glaf)
kides, Chemie et Phisque Photographique Paul Mon
tel, 1967), Duffin's "Photographic Emulsion Chemistry", Focal Press (GF Duffin, Photographic Emulsi)
on Chemistry Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions", by Zerikman, published by Focal Press (V.
L. Zelikman et al., Making and Coating Photograph
ic Emulsion, Focal Press, 1964).

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are described in Research Disclosure (RD) below, and the relevant locations are indicated in the table below.

Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizers, pages 23 to 24, page 648, right column 866 to 868 Super sensitizers, page 649, right column Brightener 24 page 647 page right column 868 page 5. 5. Light absorber page 25-26 page 649 right column page 873 Filter dye ~ page 650 left column ultraviolet absorber agent 6. Binder page 26 page 651 left column pages 873 to 874 7. Plasticizer, lubricant page 27, page 650, right column, page 876 8. Coating aid page 26-27 page 650 right column page 875-876 Surface active agent 9. Antistatic agent, page 27, page 650, right column, pages 876 to 877 Matting agent 878-879

Although various dye-forming couplers can be used in the light-sensitive material of the present invention, the following couplers are particularly preferred. Yellow coupler: Formula (I) of EP502,424A,
A coupler represented by the formula (1) or (2) of EP513,496A (particularly, a coupler represented by Y
-28); a coupler represented by formula (I) of claim 1 of JP-A-5-307248; US Pat. No. 5,066,5;
A coupler represented by the general formula (I) on lines 45 to 55 of column 1 of column 76; paragraph 00 of JP-A-4-274425;
08, a coupler represented by the general formula (I);
Couplers described in claim 1 on page 40 of 381A1 (especially D-35 on page 18); couplers represented by formula (Y) on page 4 of EP447,969A1 (especially Y-1 (17)
US Pat. No. 4,476,21), Y-page 54 (page 41));
9, the couplers represented by formulas (II) to (IV) in rows 36 to 58 of column 7 (particularly II-17, 19 (column 1
7), II-24 (column 19)).

Magenta coupler: JP-A-3-39737
(L-57 (page 11, lower right), L-68 (page 12, lower right),
L-77 (page 13, lower right); EP-4, 257, A-4
−63 (p. 134), A−4 −73, −75 (13
9); M-4, -6 of EP486,956 (26
M-7 (page 27); M-45 of paragraph 0024 of JP-A-6-43611, paragraph 0 of JP-A-5-204106.
036 M-1; paragraph 023 of JP-A-4-362631
7 M-22.

Cyan coupler: JP-A-4-208443
CX-1,3,4,5,11,12,14,15 (1
4 to 16); JP-A-4-43345, C-7,10
(Page 35), 34, 35 (page 37), (I-1), (I
-17) (pages 42 to 43); a coupler represented by formula (Ia) or (Ib) of claim 1 of JP-A-6-67385. Polymer coupler: P-1, P of JP-A-2-44345
-5 (page 11).

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, GB 2,125,
570, EP 96,873B, DE 3,234,533
Are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are described in Formulas (CI), (CII), (CIII), and (CI) described on page 5 of EP 456,257A1.
V) a yellow colored cyan coupler (especially YC-86 on page 84), and a yellow colored magenta coupler ExM-7 described on the EP (page 202, EX-1)
(Page 249), EX-7 (page 251), US Pat.
Magenta colored cyan coupler C described in 3,069
C-9 (column 8), CC-13 (column 10), US
4,837,136 (2) (column 8), WO92 /
Colorless masking couplers of formula (A) of claim 1 of 11575 (especially the exemplified compounds on pages 36 to 45) are preferred.

[0110]

【Example】

(Production of Samples A to F) Biaxial stretching (length and width are 3.3 each)
After fixing by heat at 240 ° C. for 3 minutes, a first undercoat layer and a second undercoat layer having the following composition were formed on one surface of a polyethylene terephthalate film having a thickness of 120 μm on which both surfaces were subjected to corona discharge treatment. In this order, they were 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, an antihalation layer, a blue-sensitive emulsion layer, a color-mixing prevention layer, a red-sensitive emulsion layer, a color-mixing prevention layer, a green-sensitive emulsion layer, and a protective layer are formed on the second undercoat layer as described below. A to F) were prepared.

(First Undercoat Layer Coating Solution) Styrene / butadiene copolymer latex 6.3 parts by weight (styrene / butadiene = 67/30, solid content 40% by weight) 2.4-dichloro-6-hydroxy- 0.2 parts by weight of s-triazine sodium salt 73.5 parts by weight of distilled water 73.5 parts by weight of the first undercoating solution is applied to one surface of the polyethylene terephthalate film, dried at 180 ° C. for 30 seconds, and dried at 0.3 μm. An undercoat layer was formed.

(Second Undercoat Layer Coating Solution) Gelatin 1.6 parts by weight Polystyrene fine particles (average particle size: 2 μm) 0.0 6 〃 The following compound (1) 0.006 〃 The following compound (2) 0 0.006 Glycine 0.05 Distilled water 98.278

The above compound (1) is as shown below.

Embedded image

The above compound (2) is as shown below.

Embedded image

The coating solution for the second undercoat layer was applied onto the first undercoat layer, dried at 170 ° C. for 30 seconds, and dried at 0.15 μm.
m of the second undercoat layer was formed.

(Coating Solution for Antistatic Layer) Acrylic resin aqueous dispersion 2.0 parts by weight (Julima ET410, solid content 20% by weight, manufactured by Nippon Pure Chemical Co., Ltd.) Tin oxide-antimony oxide aqueous dispersion (Table 1) (Average particle size: 0.1 μm; 17% by weight) Polyoxyethylene phenyl ether 0.1 part by weight Melamine compound (Sumitec Resin M-3, manufactured by Sumitomo Chemical Co., Ltd.) 0.3 part by weight Distillation Water was added to adjust the total to 100 parts by weight. Coating the antistatic layer coating solution on the surface of the polyethylene terephthalate film on which no undercoat layer is provided,
After drying at 80 ° C. for 30 seconds, an antistatic layer having a layer thickness of 0.04 μm was formed.

(Surface Layer Coating Solution) 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.) Distilled water was added to adjust the total to 100 parts by weight.

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

Next, on the second undercoat layer of the above-mentioned coated film, layers having the following compositions were applied in multiple layers to prepare a silver halide photographic light-sensitive material. [The numbers represent the coating amount (unit: g / m ² ), and the silver halide emulsion represents the coating amount in terms of silver. ]

[0120] The first layer (hydrophilic colloid layer) (Anti-halation layer: AH layer) Gelatin 1.03 Dye solid dispersion (a) 0.140 ^* 〃 (b) 0.025 ^** * Exemplified Compound (V- It represents the coating amount of 1). ** Indicates the amount of Exemplified Compound (IV-4) applied.

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Second Layer (Blue-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, average halogen composition Br / Cl = 1 mol%: 99 mol%, gold-sulfur sensitized emulsions B1 and B0 having an average grain size of 0.7 μm) 0.4 μm gold-sulfur sensitized 1: 3 mixture of emulsion B2 (silver molar ratio).) 0.50 gelatin 1.66 yellow coupler (ExY) 1.10 solvent (Solv-1) 0.13 solvent (Solv-2) ) 0.13 (Cpd-1) 0.0016 (Cpd-2) 0.0006 (Cpd-3) 0.006 (Cpd-4) 0.03

Third layer (color mixture prevention layer) Gelatin 0.40 (Cpd-5) 0.03 Solvent (Solv-3) 0.03 Solvent (Solv-4) 0.03

Fourth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, average halogen composition Br / Cl = 25 mol%: 75 mol%, gold-sulfur sensitized emulsions R1 and R0 having an average grain size of 0.25 μm) 0.1 μm gold-sulfur sensitized emulsion R2 1: 3 mixture (silver molar ratio)) 0.44 gelatin 2.12 cyan coupler (ExC) 0.97 (Cpd-6) 0.18 (Cpd-5) 0 0.015 Solvent (Solv-5) 0.50 Solvent (Solv-6) 0.32 (Cpd-7) 0.0002 (Cpd-8) 0.003 (Cpd-2) 0.003

Fifth layer (color mixture prevention layer) Gelatin 0.40 (Cpd-5) 0.03 Solvent (Solv-3) 0.03 Solvent (Solv-4) 0.03

Sixth Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, average halogen composition Br / Cl = 25 mol%: 75 mol%, gold-sulfur sensitized emulsions G1 and G0 having an average grain size of 0.25 μm) 0.5 μm gelatin 1.29 Magenta coupler (ExM) 0.61 (Cpd-9) 0.001 (Cpd-5) 0 .1 μm 1: 3 mixture of gold-sulfur sensitized emulsion G2 (silver molar ratio). .012 Solvent (Solv-3) 0.15 (Cpd-10) 0.003 (Cpd-11) 0.002 (Cpd-12) 0.003

Seventh layer (protective layer) Gelatin 0.98 Polymethyl methacrylate (types and coating amounts used for each sample are described in Table 1) Silicone compounds (types and coating amounts used for each sample are shown in Table 1 Described in)

The polymethyl methacrylates (a-1 to 4) shown in Table 1 are the following compounds.

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The silicone compounds (b-1 to b-1) shown in Table 1
2) is a compound shown below.

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The compounds used here are shown below.

[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. To prevent irradiation, the following dyes were added to the emulsion layer (the amount in parentheses indicates the coating amount).

[0137]

Embedded image Further, 1- (m-methyluredophenyl) -5
-Mercaptotetrazole was added.

[Comparative Examples] (Preparation of Samples GL) Formed. Further, the polymethyl methacrylate and the silicone compound in the seventh layer (protective layer) on the emulsion layer side were coated with the coating amount (g / g) shown in Table 1.
m ² ). Other than this, photosensitive materials (samples G to L were prepared in the same manner as in the examples. For samples A to L obtained in the examples and the comparative examples, the occurrence of static marks and the use of a horizontal platter projector as described below were performed. The occurrence of static electricity trouble was evaluated.

(1) Generation of Static Mark The above sample was processed into a long film having a width of 35 mm, conveyed by a printer in a dark room, developed by an automatic developing machine, and then visually inspected. The evaluation was as follows. ：: No static mark is generated. ス タ: Static mark is generated in some places. X: Static mark is frequently generated. (2) Electrostatic trouble in horizontal platter projector. Each 6000 ft horizontal platter type projector (SPECO Systems & products engineering c
Ompany LP-270), and evaluated as follows. ：: No trouble at all △: Films sometimes stick together and are sent out ×: Films are often stuck together and sent out XX: Films stick together and sent out, and the film clings to the center of the platter. The evaluation results are shown in Table 1.

[0140]

[Table 1]

From Table 1, it can be seen that in Examples 1 to 6, the surface resistance before the development treatment was 5 × at 23 ° C. and 65% RH.
10 ¹² Ω / □ or less, and the surface resistance after development processing is 2
It is 5 × 10 ⁹ Ω / □ or more in an atmosphere of 3 ° C. and 10% RH, which means that no static mark is generated and no transport trouble occurs. In Comparative Examples 1 to 4, the surface resistance after the development treatment was 5 × 1 at 23 ° C. and 10% RH atmosphere.
0 ⁹ Ω / □, which indicates that a transport trouble has occurred. In Comparative Examples 5 and 6, the surface resistance before development was 5 × 10 5 at 23 ° C. and 65% RH.
^It exceeds ¹² Ω / □, indicating that a static mark has occurred.

[0142]

As described above, according to the present invention, a silver halide photographic light-sensitive material having no static marks before the development processing and having no transport troubles in a horizontal platter projector or the like after the development processing is obtained. be able to.

Continuing on the front page (72) Inventor Koichi Suematsu 200, Onakasato, Fujinomiya City, Shizuoka Prefecture Inside Fuji Photo Film Co., Ltd. Takeshi Konno 200 Onakazato, Fujinomiya City, Shizuoka Prefecture Inside Fuji Photo Film Co., Ltd.

Claims (5)

[Claims] 1. A dye layer and a photosensitive silver halide photographic emulsion layer are provided in this order 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 a silver halide photographic light-sensitive material in which the dye layer contains solid dispersed dye particles, the surface electric resistance of the antistatic layer side is 5 × 10 ¹² Ω at 23 ° C. and 65% RH before development. / □ or less and 23 after development
A silver halide photographic material having a resistivity of 5 × 10 ⁹ Ω / □ or more in an atmosphere of 10 ° C. and 10% RH. 2. The silver halide photographic material according to claim 1, wherein the outermost layer on the emulsion layer side contains a silicone compound. 3. The silver halide photographic material according to claim 1, wherein the outermost layer on the emulsion layer side contains organic compound fine particles. 4. A silver halide photograph according to claim 1, wherein a protective layer containing silicone compound and / or organic compound fine particles is provided on the outer surface side of said emulsion layer. Photosensitive material. 5. The antistatic layer is made of ZnO, TiO._Two,
SnO_Two, Al_TwoO _Three, In_TwoO_Three, MgO, BaO,
MoO_ThreeAt least one crystalline gold selected from
Oxides or composite oxides of these or heterogeneous
Contains conductive metal particles containing a small amount of atoms
The halogenation according to any one of claims 1 to 4,
Silver halide photographic material.