JP2684438B2 - Antistatic silver halide photographic material and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material containing an antistatic agent and a method for producing the same, and in particular, to a silver halide light-sensitive material having a low surface resistance in a stable manner. The present invention also provides a support for the photographic light-sensitive material that can be produced, and further relates to a method for producing the support for the photographic light-sensitive material.

[Conventional technology]

During manufacture and use of silver halide photographic light-sensitive materials, static electricity tends to be accumulated, and this accumulation of static electricity causes many obstacles. In this charging, for example, in a manufacturing process, a contact portion between a silver halide photographic light-sensitive material (hereinafter simply referred to as a photographic light-sensitive material) and a roller, or a support surface and an emulsion surface in a winding and rewinding process of the photographic light-sensitive material Of the support and the emulsion surface when exposed to a temperature high enough to cause adhesion of the light-sensitive material during use, and also when used for movie cameras and X-ray films. It also occurs when automatic development is used. When these accumulated static electricity is discharged, the photosensitive material is exposed to light, and after development, irregular static marks such as spots, dendritic shapes, and feathers are generated, which increases the commercial value of the photographic photosensitive material. It will be significantly lost. These static marks are one of the very troublesome problems because their existence is unknown until they are developed. Further, the accumulated static electricity causes dust to adhere to the surface of the photosensitive material, and causes secondary failure such as non-uniform failure during coating. In addition, since all the photosensitive material supports are insulative, a large amount of static electricity is accumulated, so that the generation of static marks increases with an increase in processing speed and emulsion sensitivity, resulting in a marked adverse effect.

Various substances have been conventionally used to prevent electrification of photographic light-sensitive materials. These substances are ionic conductive substances or hygroscopic substances, and if the method of imparting conductivity to the photosensitive material and promptly dissipating the electric charge before discharge occurs due to the accumulation of electric charges, it is necessary. Has been used. In use, these substances may be used alone or in combination. In order to directly impart antistatic properties to the support of a photographic light-sensitive material, there is known a method of directly blending such a substance with a polymer substance which is a support or applying it to the surface of the support. In the latter case, a method of applying an antistatic agent alone or by mixing it with a polymer substance such as gelatin, polyvinyl alcohol, cellulose acetate, polyvinyl formal, or polyvinyl butyral is used. For example, Japanese Examined Patent Publication No. 57-56059 discloses a cationic antistatic agent, but this antistatic agent is treated with a mixed solvent of methanol and acetone, and by coating and drying on a cellulose triacetate film,
It is possible to obtain an antistatic layer having a surface resistivity of 10 ⁹ to 10 ¹⁰ Ω.

[Problems to be Solved by the Invention] However, even though the same antistatic agent is used, a problem that static marks sometimes occur occurs, and as a result of examining the cause, the antistatic agent is photographed. When a hydrophobic polymer layer is present on the support of the light-sensitive material or on the support, depending on the distribution state existing in the hydrophobic polymer layer, particularly the maximum position of the concentration of the existing distribution, after the formation of the antistatic layer It has been invented that the surface resistivity of the support of the photographic light-sensitive material becomes high, so that the above-mentioned various electrostatic disturbances occur during the process of manufacturing the photographic light-sensitive material film and when handling the finished product.

The present invention provides a support for a photographic light-sensitive material having a low surface resistivity and good reproducibility by improving the method for forming an antistatic layer on the support of a photographic light-sensitive material. It is an object of the present invention to stably manufacture a photographic light-sensitive material that is not easily affected by static electricity and to provide the product.

[Means for solving the problem]

By measuring the presence state of the antistatic agent from the surface of the support of the photographic light-sensitive material by the etching ESCA method, the one with low surface resistivity is (1) when the antistatic agent is only applied to the support. It was found that the maximum concentration of antistatic agent present was 0.2 μm from the surface. Further, (2) it was found that when the antistatic agent was applied to the support and then the hydrophobic polymer was applied, the maximum concentration of the antistatic agent present was in the hydrophobic polymer. The invention was reached.

The method of manufacturing a support of a photographic light-sensitive material is roughly classified, and a light-transmissive support formed by a solution film forming method or a melt film forming method and a polyolefin such as polyethylene or polypropylene are laminated. There is a light reflective support. The present invention can be applied to a support and a photographic light-sensitive material using them by any of these film forming methods.

In any of the support formed by the solution film forming method, the support formed by the melt film forming method, or the light-reflecting support in which a polyolefin such as polyethylene or polypropylene is laminated, It is possible to form the maximum concentration of the agent within 0.2 μm from the surface of the support by adjusting the characteristics of the antistatic agent and the blending of the solvent and the diluent used when applying the antistatic agent.

However, in the case of a support formed by a solution film forming method, the charge may be changed depending on the type and amount of the volatile components present in the support as well as the combination of the solvent and the diluent used when applying the antistatic agent. The distribution of the existing concentration of the inhibitor is obviously affected by the flatness of the support during coating and drying.

As a result of diligent studies, the present inventors have surprisingly found that if the usual attention is paid to the mixing conditions of solvents and diluents used in coating and the drying conditions, a water-soluble cationic antistatic agent is applied to a support. When the volatile content of the support is 5% or more immediately before coating, the maximum concentration of the antistatic agent can be formed within 0.2 μm from the surface of the support, and further coating and drying are performed. It was sometimes found that the flatness of the support was hardly affected.

Here, the volatile content is the amount of volatile components contained in the support of the photographic light-sensitive material, for example, methylene chloride in the case of cellulose triacetate which is commonly used as a support of photographic light-sensitive materials, It is a volatile organic solvent such as methanol and acetone.

Further, when an antistatic agent is applied to a support and the maximum concentration of the antistatic agent present is within 0.2 μm from the surface of the support, film formation is carried out by a solution film formation method, film formation by a melt film formation method. In any of the above-mentioned supports or light-reflecting supports in which polyolefins such as polyethylene or polypropylene are laminated, the maximum concentration of the antistatic agent present is the hydrophobic polymer when the hydrophobic polymer is coated thereon. A photographic support inside is obtained. Using such a photographic support, it is possible to stably produce a silver halide photographic light-sensitive material having a low surface resistivity.

Antistatic agents that can be used in the present invention include water-soluble polymer compounds described in JP-A-49-3972, styrene-maleic acid copolymers described in JP-A-51-23722, and the like. Anion type antistatic agent of JP-A-2004-96,
The cationic antistatic agents described in JP-A-91165, JP-A-49-121523, JP-A-53-92125 and the like can be mentioned.
Particularly in the present invention, a cationic antistatic agent is preferable. Specifically, the compounds represented by the following general formula (I) described in JP-A-48-91165 are represented by the general formula (I) Provided that R ₁ , R ₂ , R ₃ and R ₄ are substituted or terminally substituted alkyl groups having 1 to ₄ carbon atoms, and A and B are alkylene groups having 1 to 6 carbon atoms, a methyl hydroxide group and a phenylene group. , Or a simple bond, X ₁ ⁻ and X ₂ ⁻ are anions, and n is 10 to 50.

The following general formula (I
Compound represented by general formula (II) In the formula, A and B each represent a linear or branched alkylene, xylylene or cyclohexylene, and the linear or branched alkylene is a double bond triple bond or-(CH ₂ CH ₂ O) in the alkylene. _y -CH ₂ CH ₂ - may have. R ₁ , R ₂ , R ₃ and R ₄ each represent a lower alkyl group, or R ₁ and R ₂ and / or R ₃ and R ₄ may combine to form a nitrogen-containing heterocycle. X ⁻ represents an anion, n represents an integer of 20 to 50, and y represents an integer of 1 to 20.

The following general formula (II) described in JP-A-53-92125 is used.
Compounds represented by general formula (III) In the formula, R ₁ and R ₂ are each an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or an alkenyl group, and these R ₁ and R ₂ may be bonded to each other to form an alkerene chain. R ₃ represents an alkylene group having 10 or less carbon atoms or an aralkylene group. X ₁ ⁻ and X ₂ ⁻ are anions. n is about 10
To 300.

Further, compounds containing the molecular structural elements represented by the following general formulas (IV) to (VIII) can be used. In order to show the scale of the molecular size of each antistatic agent, the number of repetitions is shown by n when it is composed of only the molecular structural element represented by the general formula. It may be a compound which is co-condensed with another type of molecular structural element.

That is, the molecular structural element represented by the following formula (IV) described in JP-A-64-29839 is represented by the general formula (IV) The following general formula (V) described in JP-A No. 64-29840
Molecular structure element represented by General formula (V) The following general formula (VI) described in JP-A-1-245252
Molecular structure element represented by General formula (VI) The following general formula (VI
Molecular structural element represented by I) General formula (VII) The following general formula (VII
Molecular structural element represented by I) General formula (VIII) [Wherein, R ₁ and R ₂ each represent an alkyl group or an aryl group, X ₁ ⁻ and X ₂ ⁻ represent an anion, and n is about 5 to 25].

In addition, compounds represented by the following general formula (IX) described in JP-A-64-88449 are represented by the general formula (IX) Or Can also be preferably used.

The antistatic agent used in the present invention is usually about 1 per m ^2.
It is used in the range of 0.01 to 1.0 g, preferably 0.03 to 0.4 g.

To apply these antistatic agents on photographic supports, water, organic solvents such as methanol, ethanol, acetone, methyl ethyl ketone, ethyl acetate, acetonitrile, dioxane, dimethylformamide, formamide, dimethylsulfoxide, methylcellosolve, ethyl are used. After dissolving using cellosolve or the like or a mixed solvent thereof, spraying, coating, or immersion in the solvent and drying may be performed. Further, it may be used as an antistatic layer by using together with a binder such as gelatin, polyvinyl alcohol, cellulose acetate, cellulose acetate phthalate, polyvinyl formal, polyvinyl butyral and the like.

The support for silver halide photographic film in the present invention includes, for example, a polyolefin such as polyethylene, a cellulose derivative such as cellulose triacetate, a light transmissive film such as polyester such as polyethylene terephthalate, baryta paper, synthetic paper, or paper. And the like, and the like thereof.

Further, the support of the photographic light-sensitive material produced according to the present invention is provided with a non-photosensitive auxiliary layer such as a backing layer, an antihalation layer, an intermediate layer and a protective layer.

An antistatic agent may be contained in each of the above layers in order to further prevent the antistatic property. When it is contained, a layer adjacent to the undercoat layer on the silver halide emulsion layer side, and /
Alternatively, it is a layer adjacent to the outermost surface layer made of the polymer binder of the backing layer. What is the layer adjacent to the undercoat layer?
A non-photosensitive layer which is between the support and the undercoat layer or immediately above the undercoat layer, and an antistatic agent is contained in a layer adjacent to the undercoat layer to prevent electrostatic damage in the manufacturing process of the photographic light-sensitive material. Can be alleviated. When it is added to the layer adjacent to the undercoat layer, it is preferably added to the layer immediately above the undercoat layer. The layer adjacent to the outermost surface layer of the backing layer is a back outermost surface layer containing a cellulose ester, for example, a polymer such as cellulose diacetate, cellulose triacetate, nitrocellulose as a binder, and optionally a matting agent, a slipping agent, a paint, etc. Is a layer adjacent to and immediately below, and by incorporating an antistatic agent in this layer, it is possible to eliminate electrostatic damage at the time of manufacturing, using, and especially using the photographic light-sensitive material.

In the photographic support produced according to the present invention, particularly preferable results are obtained by using a fluorine-containing surfactant and a matting agent together in the surface layer of the backing layer. Greatly effective in prevention. Further, the surface layer may contain additives for various purposes such as a curing agent and a slip agent such as silicone, paraffin and antihalation paint.

Examples of the matting agent that can obtain preferable results include silver halide, barium strontium sulfate, polymethyl methacrylate, metal methacrylate-methacrylic acid copolymer,
Examples include colloidal silica and powdered silica.

Further, as a fluorine-based surfactant that can be used in combination,
The following compound examples can be given. For example, British Patent No. 1,330,356, U.S. Patent Nos. 3,666,478 and 3,589,90.
There is a fluorine-based surfactant described in No. 6. Representative examples of compounds are, for example, N-perfluorooctylsulfonyl-N-propylglycine potassium salt, 2
-(N-perfluorooctylsulfonyl-N-ethylamino) ethyl phosphate, N- [4- (perfluorononenyloxy) benzyl] -N, N-dimethylammonioacetate, N- [3- (N ', N ′, N′-trimethylammonio) propyl] perfluorooctylsulfonamide iodide, and N- (polyoxyethylenyl) -N-propylperfluorooctylsulfoamide [C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) _n H].

An antihalation layer may be provided on the light-transmissive support of the photographic light-sensitive material produced by the present invention. For this purpose, carbon black or various dyes such as oxole dyes, azo dyes, arylidene dyes, stilyl dyes, anthraquinone dyes, merocyanine dyes, and tri- or diallylmethane dyes can be used. As a binder for carbon black dye,
Cellulose acetate (di or mono), polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, polyvinyl formal, polymethacrylic acid ester, polyacrylic acid ester, polythrene, styrene /
Maleic anhydride copolymers, polyvinyl acetate, vinyl acetate / maleic anhydride copolymers, methyl vinyl ether / maleic anhydride copolymers, polyvinylidene chloride, and their derivatives can be used.

The silver halide photographic light-sensitive material in which the support of the present invention can be used is a usual black-and-white silver halide photographic light-sensitive material such as a black-and-white light-sensitive material for photography, a black-and-white light-sensitive material for X-rays, a black-and-white light-sensitive material for printing, and the like. Or, various conventional silver halide photographic light-sensitive materials such as a multi-layer color light-sensitive material such as a color reversal film, a color negative film and a color positive film can be used. It is particularly effective for high-speed rapid processing silver halide photographic light-sensitive materials and high-sensitivity silver halide photographic light-sensitive materials.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

(Measurement) Measurement of surface specific resistance The surface specific resistance is TR based on JIS-K-6911 (1979).
It was measured with an applied voltage of 100 V and a relative humidity of 30% RH using a -8601 type measuring instrument (manufactured by Takeda Riken Co., Ltd.).

Measurement of the presence state of the antistatic agent in the depth direction from the surface While shaving from the surface layer by Ar (argon) etching, ESCA measurement was performed to measure the distribution of the antistatic agent in the depth direction.

Equipment; Shimadzu ESCA-750 type Etching conditions; Gas type: Ar (5 x 10 ^-4 Pa) Accelerating voltage: 2KV Sample current: 4μA Etching interval: 3 minutes x 22 times Etching depth: About 40A / min ESCA measurement conditions; Excited X-ray: MgKα (160W) Measurement peak: Cl ₂ p, C ₁ s data processing; measured ESCA spectrum was subjected to area calculation using a digitizer. This was standardized for each layer by the area of C ₁ s, and the intensity ratio was blotted for each etching time to obtain the distribution in the depth direction.

Measurement of volatile matter Calculated by the following formula.

Volatile content (weight) = (base weight before drying)-(base weight after drying at 115 ° C for 1 hour) (Example 1) The volatile matter before application of the cellulose triacetate film was
8.5% (base A) and 6.0% (base B) 4.
5% (base C) and 3.5% (base D) were coated with the following antistatic coating composition so as to have a concentration of 15 ml / m ² (the cationic polymer coating amount was 50 mg / m ² ). It was dried at 70 ° C for minutes.

Antistatic coating composition Cationic polymer below 3.5g Ethylene glycol 27ml Methanol 600ml Acetone 400ml (Cationic polymer) The above polymer was dissolved in 1% by weight of saline solution in an amount of 0.1% by weight, and ηsp / c (viscosity number) measured at 30% was 0.12. What was applied to the base A was sample A, what was applied to the base B was sample B, what was applied to the base C was sample C, and what was applied to the base D was sample D. The presence state of the antistatic agent was measured.

 The results are shown in Table 1.

From the above results, it was found that Sample A and Sample B having a volatile content before coating of 5% or more had low surface resistivity and the depth of the distribution of the concentration of the antistatic agent from the surface was within 0.2 μm.

Example 2 The following hydrophobic polymer coating composition was applied to the four samples A, B, C and D prepared in Example 1 so that the dry film thickness was 0.2 μm, and dried at 100 ° C. for 3 minutes. .

Hydrophobic polymer coating composition Acetone 850 ml Methanol 150 ml Diacetyl cellulose 9 g SiO ₂ fine particles 0.7 g (average particle size 0.1 μm) Samples A, B, C and D coated on each are designated as samples E, F, G and H respectively The surface resistivity and the presence state of the antistatic agent in the depth direction were measured. Second result
It is shown in the table.

From the above results, it was found that the sample E and the sample F in which the volatile matter before coating was 5% or more had low surface resistivity and the maximum peak of the concentration distribution of the antistatic agent was in the hydrophobic binder.

〔The invention's effect〕

In order to obtain an antistatic photographic film, the present invention regulates the existence state of the antistatic agent from the surface. By setting the volatile content before application to 5% or more, the surface resistivity is low. It is possible to stably produce a silver halide photographic light-sensitive material excellent in prevention property.

Claims (4)

(57) [Claims] 1. A water-soluble cationic antistatic agent is present in a support of a silver halide photographic light-sensitive material with a concentration distribution, and has a maximum concentration distribution within 0.2 μm from the surface of the support, and The silver halide photographic light-sensitive material, wherein the support has a volatile content of 5% or more immediately before the application of the antistatic agent. 2. A system in which a water-soluble cationic antistatic agent is coated on a support of a silver halide photographic light-sensitive material and one or more hydrophobic polymer layers are coated thereon, and the volatile content of the support immediately before coating. Is 5% or more, and the maximum distribution of the concentration of the antistatic agent present is present in the hydrophobic polymer. 3. A water-soluble cationic antistatic agent is present with a concentration distribution in a support formed by a solution film-forming method of a silver halide photographic light-sensitive material, and is 0.2 from the surface of the support.
In order to have the maximum concentration distribution within μm,
In coating the support of the water-soluble cationic antistatic agent on the support of the photographic light-sensitive material, the volatile content of the support immediately before coating is 5% or more. Production method. 4. A system comprising a water-soluble cationic antistatic agent coated on a support formed by a solution film-forming method of a silver halide photographic light-sensitive material, and having one or more hydrophobic polymer layers thereon. When the water-soluble cationic antistatic agent is applied to the support of the silver halide photographic light-sensitive material in order to make the maximum concentration distribution of the antistatic agent present in the hydrophobic polymer, the support just before the application is applied. A method for producing a silver halide photographic light-sensitive material, characterized in that the body has a volatile content of 5% or more.