JPS6214151A - Photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having excellent charging and antiadhesive properties, and capable of obtaining a good sharp picture image by using a particle contg. a polymer having 20-60wt% an unit devided from a monomer selected from an olefins contg. a fluorine atom as a mat agent. CONSTITUTION:The mat agent is composed of the particle contg. the polymer having 10-60wt% the monomer unit derived from at least one of monomers selected from the olefins contg. the fluorine atom in the title material which is made at least one surface of the substrate to a roughened surface with the mat agent. When the titled material contains <=20wt% the monomer unit, a mere insufficient charging effect is obtd. When the titled material contains >=60wt% the monomer unit, the sharpness of the picture image is reduced due to the depression of a compatibility between a hydrophilic colloidal layer and the monomer.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a photographic material with improved antistatic properties and adhesion resistance, and in particular, the coating composition has excellent storage stability, and the antistatic properties and adhesion resistance are improved without impairing the sharpness of images after processing. This invention relates to an improved photographic material.

[Conventional technology]

Generally, photographic light-sensitive materials are formed by coating a similarly insulating photographic constituent layer, such as a photosensitive layer, on an insulating plastic film support. Therefore, when handling photographic materials, it is known that they are easily charged with electricity due to friction or peeling, and various phenomena such as absorption of dust, electric shock, and ignition occur, which impairs commercial value. For example, the /X silver lodenide photographic light-sensitive material has a highly sensitive photographic light-sensitive layer on the above-mentioned insulating plastic film support. There are 11 establishments, of which *
During the step a, that is, the winding and rewinding of the photosensitive material, the application of various H7 layers including the photosensitive layer, and the conveyance process during drying, the surface of the coating layer of the photosensitive material is exposed to friction due to the opening with other substances. The photosensitive material becomes electrostatically charged upon discharge or peeling, and the photosensitive material is exposed to light during discharge, and after development, uneven exposure due to irregular static electricity called so-called static marks may occur. Furthermore, photographic materials generate e-electricity not only when they are manufactured, but also when they are processed to obtain images, and they can become charged or Jl! This may cause dirt or static marks to form, causing malfunctions. The above-mentioned static marks are more likely to occur as the sensitivity of the photographic light-sensitive material increases, and in addition to the recent increase in the sensitivity of photographic light-sensitive materials, there are many opportunities for them to be subjected to harsh mechanical handling due to high-speed automatic processing. As a result, it is thought that there is a tendency for the above-mentioned failures to occur more frequently. Generally, photographic materials, such as silver halide photographic materials, are stacked in the form of rolls or sheets.
Furthermore, if the photosensitive material is stored under relatively high temperature and high humidity conditions, the front and back surfaces of the photosensitive material may adhere to each other. The constituent layers may peel off,
Static electricity may be generated. In order to solve such adhesion problems, the outermost layer contains fine particles of inorganic substances such as silicon dioxide, magnesium oxide, titanium dioxide, and calcium carbonate, and organic substances such as polymethyl methacrylate and cellulose acetate bionate. A method has been proposed in which the surface of a photosensitive material is roughened to make it so-called matte to reduce adhesiveness. However, depending on the matting agent ζ), it is difficult to obtain sufficient adhesion resistance without impairing other properties such as the transparency of the resulting image. In addition, various techniques for solving problems caused by charging are known, and as described in U.S. Pat. It is known to be effective in preventing static electricity. The antistatic effect of the matting agent can be achieved by minimizing the surface that comes into contact with other surfaces of the adjacent photosensitive material or the surface of the conveyor roll during the manufacturing process.
It is thought that the purpose of this method is to reduce the generation of static electricity caused by contact separation between the facing tiles. However, although most of the conventionally known matting agents tend to reduce static electricity by themselves, they cannot be said to be very effective in terms of the amount of static electricity generated. The contribution of these matting agents to prevention of static electricity is extremely small under conditions such as increased opportunities for harsh mechanical handling due to increased sensitivity, significantly increased coating speeds during manufacturing, and high-speed automatic processing, etc., making it a problem. cannot be resolved. Therefore, methods of improving the conductivity of supports and various coated surface layers of photosensitive materials have been considered, and attempts have been made to utilize various hygroscopic substances, water-soluble inorganic salts, surfactants, and polymers. For example, U.S. Patent Nos. 2.982.651, 3,428,456, 3,457,076,
Surfactants such as those described in U.S. Pat.
No. 82.157, No. 3,062,785, No. 3,93
No. 8,999, JP-A-58-78834, JP-A No. 57-2
No. 04540, No. 57-179837, No. 58-82
Polymers described in No. 242 and the like are known. However, it is very difficult to prevent static electricity on the hydrophilic colloid layer of photographic light-sensitive materials because it is limited by the influence on other properties (for example, film properties). Adhesion failure of photosensitive materials often occurs at high humidity. US Pat. No. 2,731,347 discloses a photographic material whose surface is roughened with particles of a fluorine-containing polymer such as polytetrafluoroethylene or polychlorotrifluoroethylene. Our studies have revealed that this photographic material has good charging properties and adhesion resistance. However, in the production of photographic light-sensitive materials, if a coating composition containing heptadon-containing polymer particles is applied after storage, the charging characteristics may deteriorate and the sharpness of the resulting image may also be significantly reduced. It became clear. Furthermore, it has been found that this tendency becomes stronger as the layer containing the particles becomes an RG film.

[Purpose of the invention]

An object of the present invention is to provide a photographic material which has excellent charging characteristics and adhesion resistance and can produce images with good sharpness.

[Structure of the invention]

As a result of intensive research to achieve the above object, we have found that the object of the present invention can be achieved by a photographic material having the following structure. That is, the photographic light-sensitive material of the present invention is a photographic light-sensitive material in which at least one surface is roughened with a matting agent.
The matting agent contains 20 units derived from at least one monomer excluded from olefins having a fluorine atom.
The particles are characterized in that they contain a polymer having a content of ~60% by weight. The present invention will be explained in detail below. Among the olefins having 7 atoms in 1- above, those having 3 or more 7 atoms are preferred, and those having 2 or 3 carbon atoms are preferred. Examples of monomer units derived from olefin monomers having 77 atoms include the following. The following margins are 11, -' -C11, -CF- -CF2-CI+, -CF. Monomers forming the 1tl -C2-CFCQ polymer include, for example, olefins such as ethylene, propylene, 1-butene, isobutyne, 2-methylbutene, vinyl chloride, vinylidene chloride, butanoene, 1,1,4 .Diolefins such as 4-tetramethylbutadiene, styrene, styrene M such as α-methylstyrene, olefin alcohol esters such as vinyl acetate and allyl acetate, methyl methacrylate,
Esters of olefin carboxylic acids such as ethyl methacrylate, cyclohexyl methacrylate, methyl 7-acrylate, butyl 7-acrylate, ethyl acrylate,
Examples include olefin ethers such as methyl vinyl ether and ethyl vinyl ether, acrylonitrile, and maleic esters. Next, polymers according to the present invention will be illustrated, but the present invention is not limited thereto. The following margin is も--~ Exemplary polymer 9 fcF2-CF+ (CH2-C
H=C)I-CH2S (40:60) CF. 10 PeCF2-CF2+ (CL ('
) I'f (56:44) 1! IC2ItS 13 (CF2-CI++-(C)I, -CH+
(55:45) CF, QC,) 1. . 16 -fcF2CF report (CII2C)I
-)-(43:57)CLOCOCl)1. . 17 (CF2CFH-)--(C)I2-01
) (35:65) ■ C) 120cOc, HI I9 -ecF2CFz+ -+C) 12c
)l) (35:65)0COC2H
5 20-+CF2CFH+--+C112CH
(35:65 OCOCH) 21 -fCF2CFCQi fc112C
I+? (45:55) = OCOCH. 23 -fCF2-CF2-) -+C)1
2-C)I (33:67)N 27 -fCF2-CFCQ)--+CH2-C)
I-) (25 Near 5) C00C)l. All of the polymers listed in item I- can be easily synthesized by known methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization. For example, solution polymerization generally involves the presence of a polymerization initiator (e.g. perfluorocarbon oxide or an azo compound) in a suitable solvent (e.g. a perfluorinated hydrocarbon solvent such as purple omethylcyclohexane, purple odimethylcyclobutane, perfluorooctane, etc.). The monomers are polymerized at a temperature of 0 to 200° C. and a pressure of 1 to 200 atmospheres or more. In suspension polymerization, monomers are forced into water containing a polymerization initiator. For example, it is pressure-injected into weakly alkaline water containing about 0.1% ammonium persulfate at 80°C and 20 to 200 atmospheres to polymerize. The polymer of the present invention is a copolymer having 20 to 60% by weight of monomer units derived from at least one monomer unit derived from olefins having a fluorine atom, wherein the monomer units are more than 20% by weight. If the amount is too small, an insufficient antistatic effect will be obtained, and if it exceeds 60% by weight, the sharpness will be reduced, probably due to poor compatibility with the hydrophilic colloid layer. There are no particular restrictions on the mixed state (block, graft, etc.) of the above monomer units and other monomer units in the copolymer molecule. In the present invention, "particles containing a polymer" means that the entire particle may be composed of the polymer, or a part of the particle may be composed of the polymer. In the latter case, it is preferable that the particle surface is coated with the polymer, and examples of the core covered with the polymer include silica, titanium oxide, barium sulfate, magnesium oxide, zinc carbonate, and calcium carbonate. , glass, talc, and other organic compounds such as polymethyl methacrylate, polystyrene, polyvinyl acetate, polyvinyl alcohol, cellulose acetate propionate, ethyl cellulose, starch, and benzoguanamine-formaldehyde condensate. In addition, particles other than those mentioned above can be freely used within the range that does not adversely affect photographic properties. ] Various methods can be used to produce the matting agent particles of the present invention using the polymers described in 2. For example, to manufacture a ladle by coating the surface of the core with the polymer, the core particles are immersed in a solution of the polymer that does not dissolve the substance constituting the particle; Dry or brush with heptafluorine monomer.

[The above polymer can be present on the surface of the core particle by grafting it onto the surface of the core particle by polymerization. In addition, in the case where a core is not used, for example, a solution of the above polymer in an organic solvent is poured into an aqueous surfactant solution (which may contain a hydrophilic colloid such as gelatin) under stirring,
After removing the solvent from the obtained emulsion under reduced pressure, the particles made of the above polymer may be fractionated by centrifugation. Furthermore, it may be made into fine particles by pulverization means. Particles can also be obtained directly from an emulsion obtained by a polymerization reaction by centrifugation. The photographic light-sensitive material referred to in the present invention is a support used in a photographic light-sensitive material subjected to subbing processing, and one or more photographic constituent layers (including a backing layer) coated on the support. A silver halide emulsion layer, a subbing layer, an intermediate layer, a filter layer,
The present invention includes all photographic light-sensitive materials as finished products coated with photographic constituent layers such as a halide prevention layer, a protective layer, and a backing layer. The effect is particularly remarkable when applied to photographic materials (including intermediate products) that are used for commercial purposes, special black-and-white materials, color materials, printing materials, and X-ray materials. The present invention is effective not only for silver halide photographic materials, but also for photographic materials in which a hydrophilic colloid is used as a binder in the outermost layer. In order to roughen at least one surface of the photographic light-sensitive material using a matting agent, for example, a coating composition of Jt<i.e. Alternatively, the matting agent of the present invention may be mixed alone or with a binder such as gelatin, sprayed or super coated, and then dried. It is not essential that the core-free particles be made into particles in advance; for example, the polymer of the present invention may be mixed with a low-boiling, α-organic solvent such as ethyl acetate, butanol-containing ethyl acetate (butanol). 50% by weight), butanol-containing methanol (butanol 50% by weight, not E4) dissolved in an equal amount of 8J in a hydrophilic colloid liquid, e.g. gelatin aqueous solution.
1! particles are formed by dispersing them under agitation,
The surface can be roughened by applying and drying this dispersion. Examples of the outermost layer include a surface protective layer, a back layer, and a non-photosensitive intermediate layer of an intermediate product in a multilayer photosensitive material coated in multiple layers. Preferably one. When gelatin is used as a binder for the outermost layer, the outermost layer on the side having the silver halide emulsion layer has a thickness of 0.
1 to 5 μm diameter, particularly preferably 0.5 to 3 μm diameter, and the outermost layer on the side not having a silver halide emulsion layer has a 0.1 to 10 μm diameter.
In particular, a ring of 3 to 6 μm is preferable, and when a polymer compound such as cellulose diacetate is used as the binder for the outermost layer on the back layer side, the ring is preferably 0.01 to 3 μm, particularly 0.03 to 1 μm.
Pus, especially 0.03 to 1 μm, is preferred. In the present invention, at least one surface of the photographic material is [
"The surface is roughened by a matting agent" means that the surface of the outermost layer is roughened due to the presence of a matting agent. That is, if the protrusion on the outermost N surface is made of a matting agent material and particles of the matting agent are exposed on the protrusion surface, the surface of the mantle agent may be covered with the outermost layer material (outermost layer composition other than the matting agent). ) Wrapped particulate matter protrudes from the surface of the outermost layer, so that the surface of the protrusion is constituted by the material of the outermost layer. In the present invention, the average particle size of the matting agent is preferably 0.
The thickness is 1 to 10 μm, more preferably 0.5 to 8 μm, but when it is mixed with the outermost layer, the dry film thickness (the film thickness of the area without protrusions caused by the matting agent)
It is preferable that the particle diameter of the matting agent of the present invention is larger than the dry film thickness, and it is particularly preferable that the particle size of the matting agent of the present invention is larger than the dry film thickness from the viewpoint of antistatic effect. The amount of the matting agent applied in the present invention is preferably 10 wg/m2 or more, more preferably 20-g/m2 or more, especially 50 mg/m2 for the purpose of improving the cloak effect.
The matting agent according to the present invention is preferably 2゛ or more, and considering the influence on transparency and image sharpness, it is preferably 500 B/m" or less, and particularly preferably 200 mg/brass 2 or less. The matting agent according to the present invention is Although it can be used in combination with the matting agent of Ike, it is preferable to use it in a smaller amount than the matting agent according to the present invention from the viewpoint of effectiveness.When the photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material The silver halide emulsion to be used includes any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. The silver halide grains used in the silver halide emulsion may be those obtained by any of the acidic method, neutral method, and seven-molecular method.The grains may be grown all at once, or The seed particles may be grown after they are created.The method of creating the seed particles and the method of growing the seeds may be the same or different.
＼Silver halide emulsions can be made by mixing halide ions and silver ions at the same time, or by mixing one in a solution in which the other is present, and considering the critical growth rate of silver halide crystals. Alternatively, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the pH and/or pAg in the mixing pot. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, the halogen composition of the particles may be changed using the compartstan method (). Silver halide grains are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), ronium salts (including complex salts), and iron salts ( (including complex salts) to add metal ions to the inside of the particles and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere. Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disc
It can be carried out based on the method described in Section 2 of No. 17643 (hereinafter referred to as losure). The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer. The silver halide grains may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain. Silver halide grains may have regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or may have irregular crystal shapes such as spherical or plate shapes. In the above, any ratio of the +1101 plane and the (1111 plane) can be used.Also, it may have a composite form of these crystal forms, or grains of various crystal forms may be mixed.The silver halide emulsion is Emulsions with any grain size distribution may be used. Emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions). A monodisperse emulsion is one in which the standard deviation of the grain size distribution divided by the average grain size is 0.20 or less, where the grain size is 0.20 or less in the case of spherical silver halide. In the case of particles having a shape other than spherical, the diameter is the diameter when the projected image is converted into a circular image of the same area. The silver halide emulsion may be used by mixing two or more types of silver halide emulsions formed separately. A silver halide emulsion of 211 or more formed in sense method,
A transmetallic sensitization method using a noble metal compound such as Kinsonike can be used alone or in combination. Silver halide emulsions can be pre-sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. Sensitizing dyes may be used alone, but 2fI1
You may use one or more in combination. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too. Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, to prevent capri during photographic processing, or to maintain stable photographic properties (for example, during chemical ripening, at the end of chemical ripening, and/or after chemical ripening, silver halide emulsion Compounds known in the printing industry as anti-capri agents or stabilizers can be added before coating the silver halide emulsion. Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion. However, hydrophilic fluids such as gelatin derivatives, graft polymers of gelatin and other polymers, higher proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymeric substances such as single or copolymers may also be used. The photographic emulsion layer and other hydrophilic colloid layers of silver halide photographic light-sensitive materials can be formed by using one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. A hardening agent can be added in an amount that can harden the photosensitive material to the extent that there is no need to add a hardening agent to the processing solution. A plasticizer can be added to the halogenated emulsion layer and/or other hydrophilic colloid layer for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in A of item 1 of RDI No. 7643. The photographic emulsion layer and other hydrophilic colloid layers of light-sensitive materials can contain a dispersion (latex) of water-insoluble or poorly soluble synthetic polymers for the purpose of improving dimensional stability.Color photography The emulsion layer of the light-sensitive material contains a dye that undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) to form a dye during color development processing. Dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the emulsion layer's light-sensitive spectrum, with a yellow dye for the blue-sensitive emulsion layer. A dye-forming coupler is used in the green-sensitive emulsion layer, a magenta dye-forming coupler is used in the red-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. It can be either tetra-isoelectric, which requires four molecules of silver ions to be reduced, or di-isoelectric, which requires only two molecules of silver ions to be reduced. The dye-forming coupler has a color correction effect, and by coupling with the oxidized form of the developing agent, it can be used as a development accelerator, bleach accelerator, developer, 7% silver lodenide solvent, toning agent, and hardener. Photographically useful agents such as film agents, capri agents, anti-capri agents, chemical sensitizers, spectral sensitizers, and desensitizers
Compounds that release fragments can be included. Colorless couplers (also referred to as competitive couplers) which undergo coupling reactions with oxidized aromatic primary amine developers but do not form dyes can also be used in combination with dye-forming couplers. As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. As the magenta dye-forming coupler, known 5-pyrazolone couplers, virazolobenlimigzole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, ingzolone couplers, and the like can be used. As a cyan dye-forming coupler, phenol or su7
Tall couplers are commonly used. Hydrophobic compounds, such as dye-forming couplers, colored couplers, image stabilizers, color capping inhibitors, ultraviolet absorbers, optical brighteners, etc. that do not need to be adsorbed on the silver halide crystal surface, can be used using the solid dispersion method or latex dispersion method. Various methods can be used, such as , oil-in-water emulsion dispersion method, etc., and can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. For the oil-in-water emulsion dispersion method, a conventionally known method for dissolving hydrophobic additives such as couplers can be applied, and usually a high boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low boiling point and/or Dissolve using a water-soluble organic '/8 medium and disperse using a stirrer, homogenizer, colloid mill, 70-knot mixer, ultrasonic device, etc. in a new aqueous binder such as an aqueous gelatin solution using a surfactant. After emulsifying and dispersing it using a suitable means, it may be added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion. Examples of high-boiling point solvents include phenol derivatives that do not react with the oxidized form of the developing agent, heptataral acid alkyl esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, etc. with boiling points of 150°C or higher. Organic solvents are used. Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butyl acetate, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene, and examples of water-soluble organic solvents include , 7setone, methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile, dioxane, trimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide,
Examples include diethylene glycol monophenyl ether, 7ethyl ether, and the like. When dye-forming couplers, colored couplers, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they are introduced into hydrophilic colloids as an alkaline aqueous solution. You can also. Anionic surfactant, 7 as a dispersion aid when a hydrophobic compound is dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using mechanical or ultrasonic waves.
Ionic surfactants, cationic surfactants and amphoteric surfactants can be used. The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color anticapri agent can be used to prevent graininess from becoming noticeable. The color antifoggant may be contained in the emulsion layer itself, or
An intermediate layer may be provided between adjacent milk M layers and contained in the intermediate layer. Hydrophilic colloid layers such as the protective Tl1 layer and the intermediate layer of the photographic light-sensitive material may contain an ultraviolet absorber. In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of photographic materials, a formalin scavenger can be used in the photographic material. When dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer of a photographic light-sensitive material, they may be mordanted with a mordant such as a cationic polymer; Developed on the sex colloid layer
Compounds that change the developability, such as reversing agents and development retardants, and bleaching accelerators can be added. Compounds that can be preferably used as development accelerators are listed in Section XXI B of RD17643.
-[Compound described in item 1, development retardant is 17643
It is a compound described in Section XXI, Section E of No. A black and white developing agent and/or its precursor may be used for the purpose of accelerating development or for other purposes. The emulsion layer of a photographic light-sensitive material is made of polyfulkylene oxide or its derivatives such as ethers, esters, and amines, 1,000-onythyl compounds, thiomol-7-olins, quaternary ammonium compounds, and urethane derivatives for the purpose of increasing sensitivity, increasing contrast, or accelerating development. , urea derivatives, imiguzol derivatives, etc. A fluorescent whitening agent can be used in photographic light-sensitive materials for the purpose of emphasizing the whiteness of the white background and (6) making the coloring of the white background less noticeable. Compounds which are preferably used as optical brighteners are described in section \1 of RD 17643. The photographic light-sensitive material can be provided with auxiliary layers such as a filter layer, anti-halesian dust, and anti-irradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. A lubricant can be added to photographic materials to reduce sliding friction. A surfactant can be used in the photographic emulsion layer and/or other hydrophilic colloid layer of the photographic light-sensitive material. Supports used in the photographic material of the present invention include paper laminated with a-olefin polymers (e.g., polyethylene, polypropylene, ethylene/butene copolymer), flexible reflective supports such as synthetic paper, and cellulose acetate. , films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, bonoethylene tere-7-thalerate, polycarbonate, polyamide, flexible supports with reflective layers on these films, plastics, metals, etc. , pottery, etc. After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface.
It may be applied through one or more subbing layers to improve anti-halation properties, friction properties, and/or other properties. When coating photosensitive materials, thickeners may be used to improve coating properties.Also, thickeners, such as hardeners, have quick reactivity and can be added to the coating solution in advance to prevent delamination before coating. 1. For materials that may cause such problems, it is preferable to mix them using a static mixer or the like immediately before application. As for the application method, 21! Extra root coatings and curtain coatings, which allow the simultaneous application of the above layers, are particularly useful, although packet coatings may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected. Any known method can be used for the development treatment of the photographic light-sensitive material of the present invention. This development process may be either a process to form a silver image (black and white development process I!f) or a process to form a color image depending on the purpose. The black-and-white material undergoes a development process, and then it is exposed to white light or processed in a bath containing a capriagent to perform color development (also, dyes are contained in the light-sensitive material, and a black-and-white development process is performed after exposure). Silver dye bleaching may also be used, in which a silver image is created by applying a silver image, and this is used as a bleaching catalyst to bleach the dye.) The black-and-white development process includes a development process, a fixing process, and a water washing process.Development process The washing process may be omitted if a stopping process is performed after the fixing process or a stabilizing process is performed after the fixing process.Furthermore, the developing agent or its precursor is incorporated into the photosensitive material and the developing agent or its precursor is incorporated into the photosensitive material. may be carried out using only an alkaline solution, or may be carried out using a Lith developer as the developing solution.Color development processing includes a color development processing step, a bleaching processing step,
The fixing treatment process, the water washing treatment process and the necessary 1-bath stabilization treatment -L culm are performed, but instead of the treatment process using a bleaching solution and the treatment process using a fixing solution, 1-bath bleaching is used. The bleach-fixing process can be carried out using a vacuum cleaner, or the more pass process can be carried out using a one-bath development, bleach-fixing solution that allows color development, bleaching, and fixing to be carried out in one bath. In combination with the treated culm, the culm treatment process, the neutralization process, the stop-fixing process, and the post-dural treatment are carried out.
1 is good. In these treatments, instead of the color development process, an activator treatment process may be performed in which a color developing agent or its precursor is contained in the material and the development process FP is performed using an activator solution, or a seven-activator process may be performed in the more bath process. can be applied. Among these processes 3+e, the representative music processes are shown below. (These treatments are treated as the final -L culm, and any one of the water washing process, water washing process, and stabilization process is performed.)・Color development process - bleaching process constant fixation Processing -
Culm/Color development processing process - Bleach fixing processing process/Moe hardening process ■
- Culm - Color development treatment I + 1 ton Culm - Stop 1 fixed treatment - [Culm - Water washing treatment [Culm - Bleaching treatment - Culm - Fixed 1 treatment Culm - Water washing treatment I - Process - Post-hardening treatment JY L process Color development process [Culm - Water washing process 1 - Culm - Supplementary color development process - Stop process Fl!Culm - Bleaching process J'li process Constant fixation process/activator process Culm - White fixing process I- Culm / Activator Process J￥L Culm - Bleaching Process J"f, , 11 Culm constant fixation treatment] r', Process / Monopass treatment process The treatment temperature is usually selected in the range of 10°C to 65°C, The temperature may exceed 65°C. Preferably 2
Store at 5°C-45°C. The black-and-white developer used in the black-and-white development process is commonly known as the black-and-white first developer used in the processing of color photographic light-sensitive materials, or the one used in the processing of black-and-white photographic materials. Various additives added to the black and white developer can be included. . Typical additives include 1-phenyl-3-virapritone, notol, and hydroquinone, drugs, preservatives such as sulfites, and alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. accelerator,
Inorganic or organic inhibitors such as potassium bromide, 2-methylbenlimigsol, and methylbenzthiazole, water softeners such as polyphosphoric acid, and surface overdevelopment inhibitors consisting of trace amounts of iodides and mercapto compounds. etc. can be mentioned. The color developing solution generally consists of an alkaline aqueous IP# solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, including ami/phenol and p-
Contains phenylenenoamine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids; for example, salts of salts, sulfates, 1)-toluenesulfonates, sulfites, sholates, benzenesulfonates, etc. can be used. I can do it. These compounds are generally used at a concentration of preferably from about 0.1 to 0 for color developer IQ, and preferably from about 1 to 15 for color developer IQ. Examples of the -al system developers include 0-amino7el/-l, p-amino/7el/-l, 5-amino7el/-
Included are 2-oxy-toluene, 2-7-7-3-oxy-toluene, 2-oxy-3-ami-7-1,4-tumethyl-benzene, and the like. Particularly useful primary 77 aromatic amine color development abrasions are N, N
-Noalkyl-I)-phenylenenoamide/based compounds, in which the alkyl group and phenyl JI (may be substituted or unsubstituted. Among them, a particularly useful example is N-N-tumethyl -1) -Phenylenenoamine mR salt, N-methyl-,
-phenylenenoamine hydrochloride, N,N-tumethyl-1)
-phenylenenoamine hydrochloride, 2-amine-5-(N-
Ethyl-N-dodecylamine/)-toluene, N-ethyl-N-β-methanesulfone 7 midethyl-3-methyl-4-ami7 aniline sulfate m, N-ethyl-N-β-hydrokine ethylamine/7 niline, 4 -7 minnow 3-methyl-N. N-diethylaniline, 4-ami/-N-(2-me)4
diethyl)-N-ethyl-3-methylaniline-p-)
Examples include luenesulfonate. Further, in the above color developing solution, L may be used alone or in combination of two or more types. Furthermore, the above color developing agents may be incorporated into color photographic materials. In this case, it is also possible to process the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution. The color developing solution may contain alkaline additives commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax, and various other additives. may contain additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or development regulators such as citranonic acid, hydroxylamine or sulfite macerates as preservatives. Furthermore, various antifoaming agents, surfactants, and organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide can be appropriately contained. The color developer usually has a pt+ of 7 or more, preferably about 9 to 13. In addition, the color developing solution may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-7nilinoethanol, nohydroxyacetone, aromatic! 52 alcohol, human mixamic acid, pentose or hexose, pyrogallol-1,3-dimethyl ether, etc. may be contained. In the color developing solution, various chelating agents can be used in combination as metal ion sequestering agents. organic phosphonic acids such as hydroxyethylidene-1,1-nophosphonic acid;
7-polyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenenoaminetitralic acid, oxycarboxylic acids such as citric acid or glufunic acid, phosphonocarboxylic acids such as 2-phosphonobutane 1,2,4-)licarboxylic acid , polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds. The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately. As a bleaching agent, a metal complex salt of an organic acid is used, for example, a polycarboxylic acid, an aminopolycarboxylic acid, or an monic acid such as oxalic acid or citric acid, coordinated with a metal ion such as iron, cobalt, or copper. It will be done. Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid iron hentaacetic acid, ethylenedi7mine-N-(β-oxyethyl)-N,N',N'-) diacetic acid, propylenenoaminetitraacetic acid, nitrilotriacetic acid, and cyclohexanediaminetetraacetic acid. , imi-7noacetic acid, dihydroxyethylglycinecitric acid (or tartaric PIl), ethyl etherno7minetetraacetic acid, glyfur etherlenoaminetetraacetic acid, ethylenenoaminetitrapropionic acid, phenylenediaminetetraacetic acid, etc. can. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaches contain 5 to 450 g/Q, more preferably 2
Use at 0 to 250g/Q. In addition to the above bleaching agent, the bleaching solution may contain a sulfite as a preservative, if necessary. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetate iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may also be used. I can do it. Bleaching solutions include JP-A No. 46-280 and JP-A No. 45-85.
No. 06, No. 46-556, Belgian patent tjS770
．． No. 910, Tokko Sho +5-8836, No. 53-985
No. 4, JP-A-54-71634 and No. 49-42:1
Various bleaching accelerators such as those described in No. 49 can be added. The pH of the bleaching solution used is 2° or higher, generally 4.0 to 9.5, preferably 4.5 to 8.0, most preferably 5.0 to 7.
．． It is 0. A fixer having a commonly used composition can be used. As fixing agents, compounds which react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes, are used. Typical examples include thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, and thioethers. These fixatives are 5
It is used in an amount of 8/Q or more, within a range that can dissolve it, but generally it is used in an amount of 70 to 250 g/Q. Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank. The bleaching solution and/or fixing solution may contain various pH 41 buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. It is possible to contain shavings singly or in combination of two or more kinds. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxyamine, hydranone, bisulfite adducts of aldehyde compounds, and W1 containing ami-7 polycarboxylic acids, etc.
Chelating agents or stabilizers such as nitroalcohols and nitrates, hardeners such as water-soluble aluminum salts, organic solvents such as methanol, trimethylsulfamide, trimethylsulfoxide, and the like can be contained as appropriate. The pH of the fixer is used at 3.0 or higher, but generally it is 4.
．． 5 to 10, preferably 5 to 9.5, most preferably 6 to 9. Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic enzymes described in the bleaching process described above, and the preferred compounds and concentrations in the processing solution are the same as in the bleaching process. The bleach-fixing solution contains a silver halide fixing agent other than the bleaching agent as mentioned above, and if necessary, a solution containing sulfite as a preservative is applied. In addition, a bleach-fix solution consisting of an ethylenedi7mine-iron acetate (Ill) complex salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer, or conversely, Bleach-fix solutions containing a large amount of halides, and even ethylenedi7mine-iron acetate (
Ifl) A special bleach-fix solution having a composition consisting of a combination of a complex salt bleach and a large amount of a halide such as ammonium bromide can also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can. As a silver halide fixing agent that can be included in the bleach-fixing solution, the silver halide fixing agent described in the above fixing treatment step is 3! Agents can be mentioned. The concentration of the fixing agent, pH 41, and other additives that can be contained in the bleach-fixing solution are the same as in the fixing process described above. The pH of the bleach-fix solution used is 4.0 or higher, generally 5.0 to 9.5, preferably 6.5 to 8.
It is 5. Examples Example 1 300 g of gelatin per mole of silver halide and a-bivalyl-〇-(1-pencyl-2,4-cyoxyimigzolin-3-yl-2) as a coupler. -Chloro-5[α-(2,4-tert-7-milphenoxy)butyramide]7cetanilide 2.5 x 10-2 mol Blue-sensitive silver iodobromide emulsion for colors containing glyoxal as a hardening agent (iodine) Together with the above emulsion, a coating solution consisting of the protective layer composition shown below and the matting agent listed in Table 1 was added to the slide hopper method. Two layers, a silver halide emulsion layer and a protective layer, were coated on the unprocessed cellulose triacetate film support in order from the support side, and dried to obtain Materials 1 to 6. (Preservative 5i layer composition) g/import 2) Gelatin 2.0g Sodium 2-ethylhexylsulfosuccinate 0.01g Glyoxal o, oig Each sample was measured for antistatic properties and sharpness of the image obtained. Antistatic properties were measured for unexposed samples. in an atmosphere at 50℃! (1
After being left to stand, the humidity was adjusted for 1 hour at 23°C in an atmosphere of 20% R11, and then the emulsion side was rubbed with a neoprene rubber roller and Delrin (
After rubbing with a DuPont formaldehyde polymer) roller, it is developed, bleached, fixed, and processed using the following processing steps and processing solution.
After washing with water and stabilizing, the occurrence of static marks was examined. Processing process Temperature Processing time (1) Development 38℃ 3 minutes 1
5 seconds (2) Bleach 38°C 4 minutes 30
Seconds (3) Fixing... 38°C 4 minutes 20 seconds (4) Washing... 38°C 3 minutes 15 seconds (5
) Stabilization: 38℃ for 1 minute and 5 seconds.
The compositions of the bleaching solution, fixing solution and stabilizing solution are as follows. Developer (pH=10.05) Hydroxylamine sulfate 2.5°4-7
Mi/-3-Methyl-N-(β-hydroxyethyl)-aniline sulfate 4.56g Noethylenetri7minehexaacetic acid 4.758-
CO330,38 Sodium sulfite Add 4g water to make IQ. Bleach solution (pH near 5.70) Ammonium bromide 173g80%
Acetic acid 2O-QEDTA
FeN11- 103g1
Mi DT ^
Add 27g of water to make 1 cup. Constant y/I B (++lI= 6.50) Ammonium thiosulfate 800mQ Sodium sulfite 4.6g Sodium bisulfite
Add 5.0 g of water to obtain IQ. Stabilizer (pH=7.30) 40% formalin 6.6IlI
Q50% polyoxyethylated diuryl alcohol 0.6mQ Add water to make IQ. The antistatic agent was judged by the following grade based on the degree of blackening of the static mark. Grade 1: No occurrence Grade 2: Slight occurrence Grade 3: Occurrence Grade 4: Slight occurrence Grade 5: Occurrence on the entire surface As for sharpness, the conventional MTF (Modulat)
ion Transfer Function) method. The determination of sharpness by the MTF method was well known in the field of evaluation at the time, but the 'Tbe Theory of PI
+oLograbic Process″T, H, J
amesW Vol, 4 p612-614. The results are shown in Table 1. From the results in the margins below, Samples 1 to 3 of the present invention are excellent in antistatic properties and sharpness, whereas Comparative Samples 4 to 6 have low antistatic properties depending on the material being rubbed, and are matte. It can be seen that when the agent-containing coating liquid is applied after stagnation, the sharpness is severely degraded. Example 2 Silver iodobromide gelatin high-sensitivity After sensitization and sulfur sensitization, 4-hydroxy-6-methyl 1.3.3a7-titrazaindene compound as a stabilizer, glyoxal as a hardening agent, and saponin as a coating aid were added, and subbing treatment was performed. Dry film thickness is 7μ on a polyethylene terephthalate film support with a thickness of 175μ
Samples 7 to 11 I got it. (Protective layer composition) (g/m') Gelatin 0.5g No 2
- Sodium ethylhexyl sulfosuccinate 0.01 g Glyoxal 0.01 g Each sample was treated in the same manner as in Example 1, and antistatic properties and adhesive properties were measured. Adhesion was measured as follows. For each sample, cut two pieces into 5 cm square pieces and store them at 23°C 180% so that they do not touch each other.
After storage for 1 day under the atmosphere of old 1, two samples of the same sample were each stored. ! The scraps were brought into contact with each other, a load of 800 g was applied, and the samples were stored in an atmosphere of 40°C and 80% RH.The samples were then peeled off and the area of the bonded portion was measured to measure adhesiveness. The results are shown in Table 2. The evaluation criteria are as follows. Rank Area of adhesive part A 0-20% 8 21-40% C'41-60% D 61% or more Also, even when the protective layer coating solution was applied after the pain had stopped for one day, the samples of the present invention had good sharpness. However, Sample 16 showed a marked decrease in sharpness. Example 3 The following composition solution was coated on the back side of a cellulose triacetate film support at a rate of about 20 mQ/m2 by roll coating, dried at 90°C for 3 minutes, and coated with the above support. After subjecting the surface of the Nt body to a subbing treatment by a conventional method, the same high-sensitivity X-ray emulsion and protective layer as Sample 7 prepared in Example 2 were coated and dried to obtain Sample-17. (Composition liquid) Cellulose diacetate 2.0ε, Ivy 7
-Le 700 Theory Q Acetone
300 theory 9 exemplified small coalescence-1 (average particle size 0.5μ) 30mg Example 1 for this sample
When the charging characteristics were examined in the same manner as above, no static occurred. Furthermore, the storage stability of the coated product was also good. (Effect of the invention 1) The photographic light-sensitive material of the present invention has excellent antistatic properties and adhesion resistance, and the images obtained are excellent regardless of the length of storage period of the coating composition containing matte scraping in the manufacturing process. It has sharpness.

Claims (1)

[Claims] In a photographic light-sensitive material in which at least one surface is roughened with a matting agent, the matting agent has 20 to 60% by weight of monomer units derived from at least one monomer derived from olefins having a fluorine atom. A photographic material characterized by comprising particles containing a polymer.