JPH0685066B2 - Photographic material - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

TECHNICAL FIELD The present invention relates to a photographic light-sensitive material, and more particularly to a photographic light-sensitive material having improved adhesion resistance and antistatic property due to matting of the surface with a matting agent.

[Prior art]

Generally, the outermost layer of a silver halide photographic light-sensitive material uses a hydrophilic colloid represented by gelatin as a hinder. Therefore, the adhesiveness or tackiness of the surface of the light-sensitive material increases under an atmosphere of high temperature and high humidity, and when it comes into contact with another object, it easily adheres to it. This adhesion phenomenon occurs between the light-sensitive materials, or between the light-sensitive materials and other objects that come into contact with the light-sensitive materials during manufacturing, storage, photographing, etc. of the light-sensitive materials, and often causes a serious failure. In particular, in a color light-sensitive material, since a photographic layer contains a large number of additives such as color couplers, the adhesiveness has been a serious problem. In order to solve this problem, the outermost layer contains fine particles of inorganic substances such as silicon dioxide, magnesium oxide, titanium dioxide, calcium carbonate, etc. and fine particles of organic substances such as polymethylmethacrylate, cellulose acetate propionate, etc. A method has been proposed in which the surface is turned into a so-called mat to reduce the adhesiveness. However, in order to sufficiently improve the adhesion resistance with these matting agents, a large amount of matting agent is required (especially for color light-sensitive materials, it is necessary to use a large amount of matting agent) and cooling. The matting agent may aggregate in the liquid, or the transparency of the obtained image may be deteriorated. On the other hand, a photographic light-sensitive material is generally constructed by coating an insulating plastic film support with an insulating photographic constituent layer, for example, a photosensitive layer. Therefore, when handling photographic light-sensitive materials, it is known that they are easily charged due to, for example, friction or peeling, and cause various phenomena such as suction of dust, electric shock, and ignition, thereby impairing the commercial value. As an example thereof, the silver halide photographic light-sensitive material has a high-sensitivity photographic light-sensitive layer coated on an insulating plastic film support as described above.
That is, the coating layer surface of the photosensitive material receives friction or peeling from other substances during winding of the photosensitive material, rewinding, or coating of various constituent layers including the photosensitive layer, and the transporting step during drying. In some cases, the photosensitive material is exposed to electric charges during discharge, and after development, uneven photosensitization due to irregular static electricity called so-called static marks may occur after development. Further, the photographic light-sensitive material generates static electricity not only at the time of its production but also at the time of processing for obtaining an image, and is charged, dust is attached, or static marks as described above are generated. It will cause a failure. Various techniques for solving the problem due to such electrification are also known, and matting of the surface of the photosensitive material with the matting agent is described in U.S. Pat.No. 2,322,037 for preventing electrification of the photosensitive material. It is known to be somewhat effective. The antistatic effect of the matting agent is to minimize the contact surface with the other surface of the photographic light-sensitive material in contact with each other or the contact surface with the surface of the transport roll during the manufacturing process.
It is considered to reduce the generation of static electricity caused by contact separation between the surfaces. However, most of the conventionally known matting agents are
Although it tends to slightly reduce the electrostatic charge by itself, it cannot be said that it is so effective in view of the amount of static electricity generated. Under circumstances such as increasing opportunities for severe mechanical handling due to high-speed automatic processing, the contribution of these matting agents to the prevention of static electricity is very small and the problem cannot be solved. Therefore, conventionally, a method of improving the conductivity of a support of a light-sensitive material or various coated surface layers has been considered, and various hygroscopic substances, water-soluble inorganic salts, surfactants and polymers have been tried to be used. For example, U.S. Patent Nos. 2,982,651 and 3,42
8,456, 3,457,076, 3,454,625, JP-A-55-77
No. 62, No. 56-43636, No. 56-114944 and the like surfactants, for example, U.S. Pat.No. 2,882,157,
3,062,785, 3,938,999, JP-A-56-78834,
Polymers described in 57-204540, 57-179837, 58-82242 and the like are known. However, it is very difficult to prevent the hydrophilic colloid layer from being electrostatically charged, and the surface resistance is not sufficiently lowered at low humidity, or adhesion failure of the photosensitive material often occurs at high temperature and high humidity. Moreover, if a large amount of antistatic agent is added to the hydrophilic colloid in order to obtain a sufficient antistatic effect, the physical properties of the film are adversely affected. Even if the matting agent can improve the adhesion resistance, it cannot improve the antistatic property, so that it was necessary to use a large amount of the antistatic agent. U.S. Pat. No. 2,731,347 has a matte surface using polytetrafluoroethylene, polychlorotrifluoroethylene and poly (ethylene / tetrafluoroethylene) microparticles as a polymer obtained from fluorine substituted ethylene monomers. A light sensitive material is disclosed. A light-sensitive material using these polymer fine particles has a certain level of adhesion resistance and antistatic property. However, we have found that the antistatic property and the like are still insufficient and that the photographic performance, especially the sharpness is deteriorated.

[Object of the Invention]

An object of the present invention is to provide a light-sensitive material having a matting agent suitable for improving adhesion resistance and antistatic property without adversely affecting photographic performance and physical properties of film.

[Constitution of the invention]

As a result of various studies on the matting agent in terms of material, structure, etc., the present invention has been accomplished. That is, the photographic light-sensitive material of the present invention is a photographic light-sensitive material having at least one surface roughened with a matting agent,
The matting agent is a particle containing a polymer having a fluorine atom and an alkali solubilizing group. Hereinafter, the present invention will be described in more detail. The polymer having a fluorine atom and an alkali solubilizing group in the present invention includes a polymer having a monomer unit having a fluorine atom and an alkali solubilizing group, and a monomer unit having a fluorine atom and a monomer unit having an alkali solubilizing group. Polymers having are included. Examples of the monomer unit having a fluorine atom include alkyl vinyl ethers, alkyl isopropenyl ethers, alkylcarbonyloxyethylenes, styrenes, alkylstyrenes each having a fluorine atom,
Included are monomer units derived from acrylates, acrylamides and olefins. Preferred examples of the monomer unit derived from an alkyl vinyl ether having a fluorine atom and an alkyl isopropenyl ether having a fluorine atom include the following A.
The following group B is mentioned as a preferable example of the monomer unit derived from the alkylcarbonyloxyethylenes having a fluorine atom. Preferred examples of the monomer unit derived from a styrene having a fluorine atom include the following group C, and preferred examples of the monomer unit derived from an alkylstyrene having a fluorine atom include the following group D: Preferred examples of the monomer unit derived from an acrylate ester having an atom include the following group E, and preferred examples of the monomer unit derived from an acrylamide having a fluorine atom include the following group F: Preferable examples of the olefin having atoms include those having 2 to 3 carbon atoms. Where R ₁ , R ₂ , R ₅ , R ₆ , R ₇ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R
₁₅ , R ₁₈ , R ₁₉ and R ₂₀ are each a hydrogen atom or a fluorine atom, and R ₃ and R ₁₆ are each a hydrogen atom, a fluorine atom or a methyl group (this methyl group may be substituted with a fluorine atom or the like). .), And R ₄ and R ₁₇ each represent an alkyl group (this alkyl group may be substituted with a fluorine atom or the like),
R ₈ , R ₉ and R ₁₀ are each a hydrogen atom or a chlorine atom, and R ₂₁ , R
₂₂ is a hydrogen atom, an alkyl group or an aryl group, Each represents an alkyl group substituted with at least one fluorine atom, m represents an integer of 0 to 5, n represents an integer of 1 to 5, and when n is an integer of 2 to 5, May be the same or different. Also, R ₁ , R ₂ , R ₃ and
At least one of R ₄ and at least one of R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ is a fluorine atom or a group having a fluorine atom, and when m is 0, at least one of R ₈ , R ₉ and R ₁₀ One is a fluorine atom. Next, the monomer unit of group A will be described in more detail. The alkyl group represented by R ₄ may be linear or branched and is preferably one having 1 to 15 carbon atoms. The alkyl group may have a substituent other than a fluorine atom (including a substituent atom, the same applies hereinafter), and examples of the substituent include an alkyloxy group (preferably having 1 to 10 carbon atoms), Alkyloxycarbonyl group (preferably 2-11)
Etc. R ₄ is preferably-(CH ₂ ) p (CF ₂ ).
qX (where p is an integer of 1 to 10, q is an integer of 0 to 2, X is a hydrogen atom, a fluorine atom or Represents a group). Specific examples of the monomer unit of group A are listed below. Next, the monomer unit of group B will be described in more detail. The alkyl group substituted with a fluorine atom represented by ▲ R ¹ _f ▼ may be linear or branched, and preferably has 1 to 10 carbon atoms.
And may have a substituent other than a fluorine atom (for example, a phenyl group). Specific examples of the monomer unit of group B will be given below. Specific examples of the monomer unit of group C will be given below. Next, the monomer unit of group D will be described. The alkyl group substituted by a fluorine atom represented by ▲ R ² _f ▼ may be linear or branched, and preferably has 1 to 3 carbon atoms.
And may have a substituent other than a fluorine atom (for example, a hydroxyl group). Specific examples of the monomer unit of group D will be given below. The group represented by R ₁₇ in group E has the same meaning as described above for R _{4 in} group A. Specific examples of the monomer unit of group E will be given below. Specific examples of the monomer unit K of the F group include the following. Examples of the olefin monomer unit having a fluorine atom include the following. _{G-1 -CF 2 -CF 2 -} G-2 -CF 2 -CFH- G-3 -CF 2 -CFCl- G-4 -CF 2 -CH 2 - G-5 -CF 2 -CHCl- G-6 −CFH−CH ₂ − G-13 -CH ₂ -CFCl- Examples of other monomer units having a fluorine atom include the following. The alkali-solubilizing group in the present invention is a group that can be easily dissolved in an alkali by introducing it into the polymer, and is preferably a carboxyl group. Examples of the monomer unit having an alkali solubilizing group include those having an ethylene bond and a carboxyl group, and specific examples include the following. Examples of the monomer unit having a fluorine atom and an alkali solubilizing group include the followings. Examples of the polymer having a fluorine atom and an alkali solubilizing group include a polymer having at least one monomer unit having a fluorine atom and an alkali solubilizing group, and at least one monomer unit having a fluorine atom and an alkali solubilizing group. Examples thereof include a polymer having at least one monomer unit, and the polymer may further have another monomer unit. Examples of the other monomer include a unit formed of a monomer having at least one ethylenic double bond. Examples of the monomer include ethylene,
Olefins such as propylene, 1-butene, isobutene, vinyl chloride, vinylidene chloride and 2-methylbutene;
Diolefins such as 1,1,4,4-tetramethylbutadiene; Olefin alcohol esters such as vinyl acetate and allyl acetate; Methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, methyl acrylate, butyl acrylate, ethyl acrylate, etc. Esters of olefin carboxylic acids; olefin ethers such as methyl vinyl ether and ethyl vinyl ether; acrylonitrile; vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone; divinylbenzene,
Allyl acrylate, allyl methacrylate, 1,3-butylene diacrylate, 1,3-butylene dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, vinyl acrylate, vinyl methacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, ethylene di Acrylate, ethylene dimethacrylate, 1,
Examples thereof include those having two or more ethylenically unsaturated double bonds such as 6-hexanediacrylate and 1,6-hexanedimethacrylate. Among the above polymers, those having a fluorine atom-containing monomer unit (including a fluorine atom and an alkali-solubilizing group-containing monomer unit) occupying 10% by weight or more are preferable, and those occupying 30% by weight or more are more preferable. . Also,
Monomer unit having an alkali solubilizing group (including a monomer unit having a fluorine atom and an alkali solubilizing group)
Is preferably 20 to 90 mol%, 20 to 70 mol%
Those which occupy are more preferable. Further, the above-mentioned other monomer unit is preferably 70 mol% or less. Specific examples of the above polymers are given below (the ratio of monomer units is expressed in mol%). Any of the above-mentioned polymers can be easily synthesized by conventionally known methods such as solution polymerization, bulk polymerization, suspension polymerization and the like. For example, in solution polymerization, a mixture of two or three types of monomers in an appropriate solvent (eg, ethanol, methanol, etc.) at an appropriate concentration (usually 40
A mixture of two or three monomers in a concentration of up to wt%, preferably 10-25 wt%) in the presence of a polymerization initiator (eg benzoyl peroxide, azobisisobutyronitrile etc.). Temperature (for example 40 to 120 ° C, preferably 50 to 1
The copolymerization reaction is carried out by heating to (00 ° C).
The reaction mixture is then poured into a medium such as water, the product is allowed to settle and then dried to separate off the unreacted mixture. Further, in synthesizing the above-mentioned polymer, it is not always essential to polymerize using a monomer having an alkali-solubilizing group in advance, and after obtaining a polymer having no such group, it is possible to carry out alkali reaction by polymer reaction. Solubilizing groups may be generated. For example, in the specific examples P-1 to P-4, according to JP-B-45-26303, a polymer is obtained by using an alkoxycarbonylfluoroalkylfluorovinyl ether as a monomer, and then a carboxyl group is generated by hydrolysis. can do. Further, P-5 to P-8, P-11 and the like can be obtained by hydrolyzing a perfluoroallyl fluorosulfate polymer as described in JP-B-58-5908, or Journal.
of the American Chemical Society, Vol.100, 1948 (197
8 years), a polyolefin may be fluorinated in the presence of oxygen to obtain a -COF group and then converted to a -COOH group. P-12 can be obtained by reducing a polymer having a sulfamoyl group with HNO ₂ as described in JP-A-53-141188, and P-13 can be obtained as described in JP-A-54-83982. It is obtained by oxidizing the chlorosulfonyl group in the polymer.
P-13 can be obtained by adding an olefincarboxylic acid to the chlorosulfonyl group in the polymer as described in JP-A-54-32189. In the present invention, “particles containing the above polymer” means
The entire particles may be composed of the polymer,
This means that a part of the particles may be composed of the above polymer. In the latter case, it is preferable that the particle surface is coated with the polymer, and examples of the nuclear material coated with the polymer include silica, titanium oxide, barium sulfate, magnesium oxide, zinc carbonate and carbonic acid. Known as a matting agent for inorganic compounds such as calcium, glass, talc and organic compounds such as polymethylmethacrylate, polystyrene, polyvinyl acetate, polyvinyl alcohol, cellulose acetate propionate, ethyl cellulose, starch, and benzoguanamine-formaldehyde condensate. Substances constituting the grains can be cited, and substances other than those mentioned above can be freely used as long as the photographic characteristics are not adversely affected. Various methods can be used for producing particles of a matting agent using the above-mentioned polymer according to the present invention. For example, in order to produce particles in which the surface of particles made of the above-mentioned nuclear material is coated with the polymer, the particles of the nuclear material are immersed in a solution of the above-mentioned polymer in which the nuclear material is not dissolved, and dried, Alternatively, the above polymer can be present on the surface of the nuclear material by a method of grafting a monomer having a fluorine atom and a monomer having an alkali solubilizing group onto the surface of the nuclear material by plasma polymerization. When no nuclear substance is used, for example, an organic solvent solution of the above polymer is poured into a surfactant aqueous solution (which may contain a hydrophilic colloid such as gelatin) with stirring to obtain an emulsion. From the solvent under reduced pressure,
The polymer particles may be collected by centrifugation. Further, fine particles may be formed by pulverizing means. Alternatively, particles can be immediately obtained from the emulsion obtained by the polymerization reaction by centrifugation. The photographic light-sensitive material referred to in the present invention is a support used in the photographic light-sensitive material which is subjected to an undercoating treatment, and one or more photographic constituent layers (including a backing layer) are coated on the support. A photographic light-sensitive material as an intermediate product and a support on which a silver halide emulsion layer, an undercoat layer, an intermediate layer, a filter layer,
The present invention includes all of photographic light-sensitive materials as finished products coated with photographic constituent layers such as antihalation layer, protective layer, packing layer, etc. The effect is particularly remarkable when it is applied to a photographic light-sensitive material (including intermediate products) that is used for a photo, a special black and white, a color, a printing, and an X-ray. To roughen at least one surface of the above photographic light-sensitive material with a matting agent, for example, a matting agent is mixed with a coating composition for a layer (photographic constituent layer) to be coated on a support, and the coating is carried out by a usual coating means. It may be applied and dried. When two or more photographic constituent layers are coated and dried at one time, it is preferable to add a matting agent to the uppermost layer. As another method of roughening the surface with a matting agent, the matting agent may be sprayed or supercoated with the matting agent alone or mixed with a binder such as gelatin, and then dried. The matting agent that does not use the nuclear substance is not necessarily in the form of particles in advance, for example, the polymer of the present invention is a low boiling organic solvent such as ethyl acetate, butanol-containing ethyl acetate (butanol less than 50% by weight). , Particles containing butanol-containing methanol (butanol less than 50% by weight) are dispersed in a hydrophilic colloid solution, for example, an aqueous gelatin solution under rapid stirring to form particles, and the dispersion is applied and dried. Can be roughened by. In the present invention, at least one surface of the photographic light-sensitive material is “roughened by a matting agent” means that the outermost layer surface is roughened due to the presence of the matting agent. means. That is, not only when the protrusions on the outermost layer surface are formed of the matting agent material and the matting agent is exposed on the surface of the protrusions, the outermost layer material (outermost layer composition other than the matting agent) will come around the matting agent surface. It also includes a case where the surface of the protrusion is formed of the outermost layer material by the protrusion of the particulate matter on the surface of the outermost layer. In the present invention, the average particle size of the matting agent is preferably 0.1
It is ˜10 μ, more preferably 0.5 to 8 μ, but when mixed with the binder of the outermost layer, it is preferably larger than the dry film thickness (the film thickness of the portion having no protrusion due to the matting agent), From the viewpoint of antistatic effect, it is particularly preferable that the particle size of the matting agent of the present invention is 2 times or more, further 2.5 times or more larger than the dry film thickness. Further, the coating amount of the matting agent of the present invention is more effective for the purpose of improving the matting effect, and is preferably 10 mg / m ² or more, more preferably 20 mg / m ² or more, particularly preferably 50 mg / m ² or more, and Considering the effect on the transparency and the sharpness of the image, it is preferably 500 mg / m ² or less, and particularly 400 mg / m ²
The following is preferable. The matting agent according to the present invention can be used as a mixture with other matting agents, but it is preferable to use a smaller amount than the matting agent according to the present invention from the viewpoint of the effect. When the photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material, the silver halide emulsion includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride and the like. Any of the conventional silver halide emulsions can be used. The silver halide grains used in the silver halide emulsion may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different. In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or the other may be mixed in a liquid containing either one. Alternatively, it may be produced by sequentially adding halide ions and silver ions simultaneously while controlling the pH and pAg in the mixing vessel while considering the critical growth rate of silver halide crystals. By this method, silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained. After the growth, the conversion method may be used to change the halogen composition of the grains. Silver halide grains include cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including salt salt), rhodium salt (including salt salt) and iron during the process of forming grains and / or growing grains. Metal ions are added using at least one selected from salts (including barley salt), and
Alternatively, these metal elements can be contained on the grain surface, and reduction sensitizing nuclei can be imparted to the inside of the grain and / or the grain surface by placing in a suitable reducing atmosphere. In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained. When removing the salts, Research. Disclosure (Rerearch Disclosure D below)
It can be carried out based on the method described in Item 17643, Item II. The silver halide grain may be one having a uniform silver halide composition distribution within the grain, or may be a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer. The silver halide grain may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain. The silver halide grains may have a regular crystal form such as a cube, octahedron or tetradecahedron, or may have an irregular crystal form such as a spherical plate. In these grains, any ratio of {110} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed. The silver halide emulsion may have any grain size distribution. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion. The monodisperse emulsion referred to here is the standard deviation of the grain size distribution. When divided by the average grain size, the value is 0.20 or less, where the grain size is the diameter in the case of spherical silver halide and the projected image in the case of grains other than spherical. The diameter when converted to a circular image of the same area is shown).
Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used. As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used. The silver halide emulsion can be chemically sensitized by a conventional method. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
The noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination. The silver halide emulsion can be optically sensitized to a desired wavelength range by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Good. Silver halide emulsion, during the manufacturing process of the light-sensitive material, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, during chemical ripening, at the end of chemical ripening, and / or after the completion of chemical ripening, before coating a silver halide emulsion, Compounds known in the art as antifoggants or stabilizers can be added. As the binder (or protective colloid) of the silver halide emulsion, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other macromolecules, further proteins, sugar derivatives, cellulose derivatives, single Alternatively, a hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a copolymer can also be used. The photographic emulsion layer and other hydrophilic colloid layers used in the photographic light-sensitive material of the present invention are hardened by using one or two or more hardeners which crosslink binder (or protective colloid) molecules and enhance film strength. Can be membrane. The hardener can be added in an amount capable of hardening the photographic light-sensitive material to the extent that it is not necessary to add the hardener to the processing liquid, but it is also possible to add the hardener to the processing liquid. A plasticizer may be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the photographic light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in A of RD17643, section XII. The photographic emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. In the color development processing, the emulsion layer of the color photographic light-sensitive material is subjected to a coupling reaction with an oxidation product of an aromatic primary amine developer (for example, a p-phenylenediamine derivative or an aminophenol derivative) to form a dye. A dye-forming coupler that forms is used. The dye-forming couplers are usually selected for each emulsion layer so that a dye that absorbs the light in the light-sensitive spectrum of the emulsion layer is formed, and in the blue-sensitive emulsion layer, the yellow dye-forming coupler is green. A magenta dye forming coupler is used in the sensitive emulsion layer and a cyan dye forming coupler is used in the red sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose. It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible. Further, these dye-forming couplers are required to reduce 4 molecules of silver ions in order to form 1 molecule of dye, but even if they are 4 equivalents, only 2 molecules of silver ions are reduced. It may be either good dichotomic. The dye-forming coupler has a color-correcting effect and is coupled with a colored coupler and an oxidant of a developing agent to develop a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener. Compounds that release photographically useful fragments such as fog agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be included. A colorless coupler (also referred to as a competing coupler) which undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can also be used in combination with the dye-forming coupler. As the yellow dye-forming coupler, a known acylacetanilide type coupler can be preferably used.
Among these, benzoylacetanilide compounds and bivaloylacetanilide compounds are advantageous. As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indazolone couplers and the like can be used. As the cyan dye-forming coupler, a commonly used phenol or naphthol type coupler can be used. Of the dye-forming couplers, colored couplers, image stabilizers, antifoggants, UV absorbers, optical brighteners, etc. that do not need to be adsorbed on the surface of silver halide crystals, hydrophobic compounds are solid dispersion methods and latex dispersion methods. Various methods such as oil-in-water emulsion dispersion method can be used, which can be appropriately selected according to the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water emulsion dispersion method can be applied by a conventionally known method of dispersing a hydrophobic additive such as a coupler,
Usually, a low boiling point as needed in a high boiling point organic solvent having a boiling point of about 150 ° C. or higher, and / or a water-soluble organic solvent is dissolved in combination,
Stirrer, homogenizer, colloidal mill, using a surfactant in a new aqueous binder such as gelatin aqueous solution.
The dispersion may be emulsified and dispersed using a dispersing means such as a flowgit mixer or an ultrasonic device, and then added to the target hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion. As a high-boiling point oil agent, a phenol derivative, a phthalic acid alkyl ester, a phosphoric acid ester, a citric acid ester, a benzoic acid ester, an alkylamide, a fatty acid ester, a trimesic acid ester, etc. having a boiling point of 150 ° C or higher that does not react with the oxidized product of the developing agent. A solvent is used. A low boiling or water soluble organic solvent can be used with or in place of the high boiling solvent. The low boiling point substantially water-insoluble organic solvent includes ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, etc., and the water-soluble organic solvent includes acetone, Methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol,
Acetonitrile, dioxane, dimethylformamide,
Examples include dimethyl sulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, and phenoxyethanol. When a dye-forming coupler, a colored coupler, an image stabilizer, an antifoggant, a UV absorber, an optical brightener, etc. has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an aqueous alkaline solution. You can also do it. Dissolving a hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant, a nonionic surfactant, Cationic and amphoteric surfactants can be used. Between the emulsion layers of the photographic light-sensitive material (same color-sensitive layers and / or different color-sensitive layers), the oxidant of the developing agent or the electron transfer agent moves to cause color turbidity or deterioration of sharpness,
An antifoggant can be used to prevent the graininess from being noticeable. The color antifoggant may be contained in the emulsion layer itself,
An intermediate layer may be provided between adjacent emulsion layers and contained in the intermediate layer. A hydrophilic colloid layer such as a protective layer or an intermediate layer of the photographic light-sensitive material may contain an ultraviolet absorber. A formalin scavenger can be used in the light-sensitive material in order to prevent deterioration of the magenta dye-forming coupler and the like due to formalin during storage of the photographic light-sensitive material. When the hydrophilic colloid layer of the photographic light-sensitive material contains a dye, an ultraviolet absorber or the like, they may be mordanted with a mordant such as a cationic polymer. To the silver halide emulsion layer and / or other hydrophilic colloid layer of the photographic light-sensitive material, a compound such as a development accelerator or a development retarder which changes the developability and a bleaching accelerator can be added. The compound that can be preferably used as the development accelerator is RD17.
The compound described in Item XXI, B to D of 463, and the development retarder is the compound described in Item XXI, E of 17643. A black and white developing agent and / or its precursor may be used for the purpose of promoting development and other purposes. The photographic emulsion layer of a photographic light-sensitive material contains polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomolarolin, quaternary ammonium compound, urethane derivative, urea for the purpose of increasing sensitivity, increasing contrast, or promoting development. Derivatives, imidazole derivatives and the like may be included. A fluorescent brightening agent can be used in the photographic light-sensitive material for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background inconspicuous. Compounds which can be preferably used as the optical brightening agent are described in RD17643, item V. The photographic light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development process may be contained. Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, methocyanine dyes, cyanine dyes, and azo dyes. A lubricant may be added to the photographic light-sensitive material 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. The support used in the photographic light-sensitive material of the present invention includes paper laminated with α-olefin polymer (eg, polyethylene, polypropylene, ethylene / butene copolymer), a flexible reflective support such as synthetic paper, and cellulose acetate. , Films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide, and flexible supports provided with these film reflective layers, glass, metal, pottery, etc. included. For photographic light-sensitive materials, corona discharge on the surface of the support, if necessary,
After UV irradiation, flame treatment, etc., the adhesiveness, antistatic property, dimensional stability, abrasion resistance, hardness, antihalation property, friction property, and / or other properties of the support surface are directly or The hydrophilic colloid layer may be applied via one or more subbing layers for enhancement. At the time of coating the photographic light-sensitive material, a thickener may be used in order to improve coatability. Further, for a hardener such as a hardener that causes gelation before coating when it is added to the coating solution in advance because of its high reactivity, it is mixed with a static mixer or the like immediately before coating. Is preferred. As the coating method, extrusion coating and curtain coating, which allow simultaneous coating of two or more layers, are particularly useful, but bucket coating is also used depending on the purpose. Further, the coating speed can be arbitrarily selected. Any known method can be used for the development processing of the photographic light-sensitive material of the present invention. This developing process may be either a process for forming a silver image (black and white developing process) or a developing process for forming a color image depending on the purpose. If you want to draw by the reversal method, first perform the black and white negative development process,
Then, color development processing is performed by applying white exposure or by processing in a bath containing a fog agent. (Alternatively, a silver dye bleach may be used in which a dye is contained in the light-sensitive material, a black and white development processing step is performed after exposure to form a silver image, and this is used as a bleach catalyst to bleach the dye.) , Development process, fixing process,
A water washing process step is performed. When the stop processing step is performed after the development processing step or the stabilization processing step is performed after the fixing processing step, the water washing processing step may be omitted. Further, the developing agent or its precursor may be incorporated in the photographic light-sensitive material, and the developing treatment step may be carried out only with the alkaline solution. A development process using a lith developer as a developer may be performed. Color development processing includes color development processing step, bleaching processing step,
A fixing treatment step, a water washing treatment step, and a stabilization treatment step are carried out if necessary. Instead of the treatment step using a bleaching solution and the treatment step using a fixing solution, a bleach-fixing treatment using a one-bath bleach-fixing solution is performed. The process may be carried out, or a monobath processing process using a one-bath development bleach-fixing processing solution capable of performing color development bleaching and fixing in one bath may be carried out. In combination with these treatment steps, a pre-hardening treatment step, a neutralizing step thereof, a stop fixing treatment step, a post-hardening treatment step and the like may be performed. In these processes, instead of the color development processing step, the color developing agent or its precursor may be contained in the photographic light-sensitive material and the development processing may be carried out by an activator solution. Beta processing can be applied. Typical processing is shown below among these processings. (These steps include any one of a washing step, a washing step and a stabilizing step as a final step.) ・ Color development processing step-bleach processing step, fixing processing step-Color development processing step-bleach-fix processing Process-Pre-hardening process-Color development process-Stop fixing process-Water washing process-Bleaching process-Fixing process-Water washing process-Post-hardening process-Color development process-Water washing process-Supplement Color development processing step-Stop processing step-Bleaching processing step-Fixing processing step-Activator processing step-Bleaching fixing processing step-Activator processing step-Bleaching processing step-Fixing processing step-Mono bath processing step The processing temperature is usually 10 ° C. ~ 65 ℃, but 65 ℃
The temperature may be higher than that. It is preferably treated at 25 ° C to 45 ° C. The black-and-white developing solution used in the black-and-white developing process is a so-called black-and-white first developing solution which is usually used in the processing of color photographic light-sensitive materials, or the one used in the processing of black-and-white photographic photosensitive materials, Various additives to be added to the liquid can be contained. Typical additives include 1-phenyl-3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfite, accelerators composed of alkali such as sodium hydroxide, sodium carbonate, potassium carbonate, Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole, hard water softeners such as polyphosphoric acid hydrochloric acid, surface overdevelopment inhibitors consisting of trace amounts of iodides and mercapto compounds, etc. Can be mentioned. The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol-based and p-phenylenediamine-based derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, for example, salt acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate and the like. it can. These compounds generally have a concentration of about 0.1 to 30 g, preferably about 0.1 to 30 g, more preferably about color developing solution 1 for color developing solution 1.
Is used at a concentration of about 1 to 15 g. Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-
2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene and the like are included. Particularly useful primary aromatic amine-based color developing agents are N, N-dialkyl-p-phenylenediamine-based compounds, in which the alkyl and phenyl groups may or may not be substituted. Among them, particularly useful compound examples are NN-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N, N-dimethyl-p-phenylenediamine hydrochloride,
2-amino-5- (N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N
-Ethyl-N-β-hydroxyethylaminoaniline,
4-amino-3-methyl-N, N-diethylaniline, 4
-Amino-N- (2-methoxyethyl) -N-ethyl-
Examples thereof include 3-methylaniline-p-toluenesulfonate. The color developing agents may be used alone or in combination of two or more kinds. Furthermore, the color developing agent may be incorporated in a color photographic material. In this case, the silver halide color photographic light-sensitive material can be treated with an alkaline solution (activator solution) instead of the color developing solution. The color developing solution may contain an alkaline agent usually used in the developing solution, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax, and various other agents. Additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or a development modifier such as citrazinic acid, and a preservative such as hydroxylamine or sulfite. . Further, various antifoaming agents and surfactants, and an organic solvent such as methanol, dimethylformamide or dimethylsulfoxide, etc. may be appropriately contained. The pH of the color developer is usually 7 or more, preferably about 9 to
It is 13. Further, in the color developer, if necessary, diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, as an antioxidant,
An aromatic secondary alcohol, hydroxamic acid, bentose or hexose, pyrogallol-1,3-dimethyl ether and the like may be contained. In the color developing solution, various chelating agents can be used together as a sequestering agent. For example, as the chelating agent, ethylenediaminetetraacetic acid, amine polycarboxylic acid such as diethylenetriaminopentaacetic acid, organic phosphonic acid such as 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid Aminopolyphosphonic acid, oxycarboxylic acid such as citric acid or gluconic acid, phosphonocarboxylic acid such as 2-phosphonobutane 1,2,4-tricarboxylic acid, polyphosphoric acid 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 individually. As the bleaching agent, a metal complex salt of an organic acid is used, and for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid, citric acid, etc., in which metal ions such as iron, cobalt, copper are coordinated are used. . Among the above-mentioned organic acids, the most preferable organic acid is polycarboxylic acid or aminopolycarboxylic acid. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N,
N'N'-triacetic acid, propylenediaminetetraacetic acid,
Nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyl ether terdiamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, phenylenediamine tetraacetic acid, etc. can be mentioned. . These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaching agents are 5-450 g / l, more preferably 20-250 g
Use with / l. As the bleaching solution, in addition to the above-mentioned bleaching agent, a tissue solution containing sulfite as a preservative is applied if necessary.
Further, it may be a bleaching solution having a composition containing an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and adding a large amount of a halide such as ammonium bromide. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can. The bleaching solution includes JP-A-46-280, JP-B-45-8506 and 46-
556, Belgian Patent 770,910, Japanese Patent Publication No. 45-8836,
Various bleaching accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added. The bleaching solution is used at a pH of 2.0 or higher, but generally 4.0 to 9.
Used in 5, preferably used in 4.5-8.0, most preferably 5.0-7.0. The fixer may have a commonly used composition. As the fixing agent, a compound which reacts with silver halide to form a water-soluble complex salt as used in a usual fixing process, for example, thiosulfate such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, potassium thiocyanate. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea and thioether. These fixatives
5g / l or more, used in an amount that can be dissolved, but generally
Use at 70-250g / l. A part of the fixing agent can be contained in the bleaching tank, and conversely, a part of the bleaching agent can be contained in the fixing tank. The bleaching solution and / or the fixing solution include various pH 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. The agents can be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents or surfactants may be contained. In addition, preservatives such as hydroxyamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrates, hardening agents such as water-soluble aluminum salts, methanol,
An organic solvent such as dimethyl sulfamide or dimethyl sulfoxide can be appropriately contained. A fixer with a pH of 3.0 or higher can be used, but it is generally 4,5-
It is used at 10, preferably at 5-9,5 and most preferably at 6-9. Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the bleaching treatment step, and preferable compounds and concentrations in the processing solution are the same as in the bleaching treatment step. As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent other than the bleaching agent as described above and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition containing a small amount of an ethylenediaminetetraacetic acid iron (III) complex bleach and a halide such as ammonium bromide other than the above silver halide fixing agent, or conversely, a halide such as ammonium bromide. A bleach-fix solution composed of a large amount of iron, and further ethylenediaminetetraacetate iron (II
I) A special bleach-fixing solution having a composition comprising a combination of a complex salt bleaching agent and a large amount of a halide such as ammonium bromide can also be used. As the halide,
Hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can be used in addition to ammonium bromide. Examples of the silver halide fixing agent that can be contained in the bleach-fixing solution include the fixing agents described in the fixing processing step. The concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution are the same as those in the fixing processing step. The pH of the bleach-fix solution is 4.0 or higher, but it is generally 5.0.
It is used at ~ 9.5, preferably 6.0-8.5.

【Example】

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to this. Example 1. Titanium oxide matting agent (matting agent-1) 10 having an average particle size of 5μ
g was immersed in 500 ml of a 10 wt% acetone solution of Exemplified Polymer P-21 and dispersed for 30 minutes with an ultrasonic disperser, and the obtained dispersion was suspended in a spray gun at 70 ° C to 90 ° C. Was sprayed in hot air to obtain a titanium oxide matting agent whose surface was coated with the polymer of the present invention. This matting agent-
Set to 2. Next, a silver iodobromide gelatin high-sensitivity X-ray emulsion containing 35 g of gelatin per 1 kg of emulsion and 100 g of silver iodobromide (containing 3 mol% of silver iodide) was used during the second ripening.
After sulfur sensitization, 4-hydroxy-6 was used as a stabilizer.
-Methyl-1,3,3,7-tetrazaindene, glyoxal as a hardener, and saponin as a coating aid were added, and a dry film thickness was obtained on a polyethylene terephthalate film support having a thickness of 175 μ and subjected to an undercoating treatment. The coating was dried to a thickness of 7 μm, and then a protective layer having the following composition was coated and dried to a dry film thickness of about 1.0 μm to obtain Sample-1. (Protective film composition) (g / m ² ) Gelatin 1.0 g Di-2-ethylhexyl sodium sulfosuccinate 0.01 g Glyoxal 0.01 g The above matte agent-1 was added to the above protective film composition so that the ratio was 100 mg / m ^2. The sample additionally obtained was referred to as Sample-2, and the sample obtained by adding the matting agent-2 according to the present invention to the above protective film composition so as to have a ratio of 100 g / m ² was referred to as Sample-2.
Set to 3. Next, each sample was conditioned at 23 ° C. and 20% RH for 4 hours, the triboelectrification property of neoprene rubber was measured, and the static mark generation test was conducted. The results shown in Table 1 below were obtained. The above charge amount is the friction charge amount between the neoprene rubber and the sample, and is measured in an atmosphere of 23 ° C. and 20% RH.
The static mark was evaluated by rubbing it with a neoprene rubber rod for 4 hours in an atmosphere of 23 ° C. and 20% RH, rubbing it with a neoprene rubber rod, and developing the sample. Grade 1: No occurrence, 〃: Slight occurrence, 〃: Moderate occurrence, 〃: Occurrence on the entire surface, As shown in the above table, both the sample-1 in which the matting agent was not added to the protective layer and the sample-2 in which the titanium oxide matting agent was added were both positively highly charged and the generation of static marks was strong. . On the other hand, a sample to which the matting agent-2 according to the present invention is added-
In No. 3, the charge amount was small and static marks were hardly generated. Further, the samples of the present invention did not show a decrease in sensitivity or the occurrence of fog. Example 2 In place of the matting agent of Sample-2 of Example 1 was replaced with particles (matting agent-3) having an average particle diameter of 3 μm made of Exemplified Polymer P-29 and the amount of the matting agent was 200 mg / m ^2. Sample 4 was prepared in the same manner as Sample 2 above. Sample-5 was prepared in the same manner as in Sample-4, except that the exemplified polymer P-29 in Sample-4 was replaced with P-34. Sample-6 was prepared in the same manner as in Sample-4, except that the exemplified polymer P-29 in Sample-4 was replaced with P-35. On the other hand, Sample 7 was prepared in the same manner as Sample 4 except that PMMA having an average particle diameter of 3 μm was used as a matting agent for comparison. The samples were subjected to triboelectric charge measurement and static mark generation test in the same manner as in Example 1 to obtain the results shown in Table 2 below. As shown in Table 2, Sample 7 having the protective layer containing the comparative matting agent was positively and significantly charged, and the generation of static marks was also strong. However, in the samples 4, 5 and 6 to which the matting agent according to the present invention was added, the charge amount was small,
Moreover, the generation of static marks was hardly observed. Example 3 The same silver halide emulsion layer coating solution as in Example 1 was coated on a 100 μm-thick polyethylene terephthalate support which had been subjected to an undercoating treatment so as to have a dry film thickness of 3.5 μm, and the following composition was applied thereon. Was provided with a protective layer. Protective layer composition-1 (g / m ² ) Gelatin 0.5 Di-2-ethylhexyl sodium sulfosuccinate 0.01 Glyoxal 0.01 Matting agent-3 0.1 Furthermore, a back layer of the following composition having a dry film thickness of 3.5μ is provided on the back surface of the support. , Sample 8 was prepared. Back surface layer composition-2 (g / m ² ) Gelatin 4 Di-2-ethylhexyl sodium sulfosuccinate 0.04 Glyoxal 0.06 Exemplified polymer p-6 particles having an average particle size of 7 μ 0.15 From protective layer composition-1 in sample-8 Sample-8 ′ was prepared in the same manner as Sample-8 except that Matting Agent-3 was omitted. In addition, Sample-8 ″ was prepared in the same manner as in Sample-8, except that the particles of Exemplified Polymer P-6 were removed from the back surface layer composition-2 in Sample-8. Sample 8 was prepared in the same manner as Sample 8 except that the matting agent was removed from 1 and the back layer composition-2.The above samples were cut into 70 mm width and left at 23 ° C and 20% RH for one day. After humidity control, a camera-through test was carried out with a Canon mirror camera (LXM-70-M400, the rollers contacted on both sides of the film) After the development process, the occurrence of static marks was observed and Table 3 The results shown in are obtained. As is apparent from the third surface, the one using the matting agent according to the present invention on both sides has a very good effect of preventing the generation of static marks, and a little when the matting agent according to the present invention is used on only one side. A static mark was generated on the surface, but it was practical. On the other hand, in the case where the matting agent was not used, the generation of static marks was so great that it was not practical. Example 4. 300 g of gelatin per mol of silver halide and α-pivaloyl-α- (1 as a yellow coupler.
-Benzylimidazolidin-2,4-dione-3-yl)
Preparation of color-sensitive blue-sensitive silver iodobromide (7 mol% silver iodide) emulsion containing 2.5 × 10 ^-2 mol of 2-chloro-5 [γ- (2,4-tert-aminophenoxy) butyramide] acetanilide did. Along with this emulsion, particles (matting agent) shown in Table 4 below for the protective layer and di-2-
Prepare a gelatin solution containing sodium ethylhexyl sulfosuccinate and a hardener (0.02 g per 1 g of gelatin), and slide hopper method on a cellulose triacetate film support having an undercoat layer to support the emulsion layer in order from the support side and protect it. The layers were applied to obtain Samples 9-16. A paint 17 containing no matting agent was also prepared. The coating amount of the protective layer was 100 mg / m ^{2 of} matting agent and 0.5 g / m ² of gelatin. The antistatic property of each sample was examined by the following method. After conditioning the unexposed sample for 2 hours at 25 ° C and 25% RH, rub both sides of the sample emulsion with neon prene rubber rollers in the dark room under the same air-conditioning conditions, and then develop, bleach and fix with the processing solution below. Then, the degree of occurrence of static marks was examined by washing with water and stabilizing. Treatment process Humidity Treatment time (1) Current image liquid …… 38 ℃ 3 minutes 15 seconds (2) Bleaching …… 38 ℃ 4 minutes 30 seconds (3) Settling …… 38 ℃ 4 minutes 20 seconds (4) Washing with water ...... 38 ℃ 3 minutes 15 seconds (5) Stabilization …… 38 ℃ 1 minute 5 seconds The composition of the developer, bleach, fixing bath and stabilizing bath is as follows. Developer (pH = 10.05) Hydroxylamine sulfate 2.5g 4-Amino-3-methyl-N- (β-hydroxyethyl) -aniline sulfate 4.56g Diethylenetriaminohexaacetic acid 4.75g K ₂ CO ₃ 30.3g Sodium sulfite 4g Water Is added to make 1. Bleaching bath (pH = 5.70) Ammonium bromide 173 g 80% acetic acid 20 ml EDTA FeNH ₄ 103 g EDTA 27 g Add water to make 1. Fixing bath (pH = 6.50) Ammonium thiosulfate 800 ml Sodium sulfite 4.6 g Sodium bisulfite 5.0 g Add water to make 1. Stabilization bath (pH = 7.30) 40% formalin 6.6 ml 50% polyoxyethylated lauryl alcohol 0.6 ml Add water to make 1. The test results of the antistatic properties of these samples are shown in Table 4. In the table, the evaluation of the degree of occurrence of static marks is the same as in Example 1. As is clear from Table 4, the sample using the matting agent of the present invention has an excellent antistatic effect in which static marks are not generated. Example 5. Samples 3, 4, 6, 9 to 16 and 18 of the above example were cut into two pieces each having a size of 5 cm square, and were cut in an atmosphere of 23 ° C. and 80% RH so as not to contact each other. After storing for 2 days, contact two protective layers of the same sample,
A load of 800 g was applied, and the sample was stored in an atmosphere of 40 ° C. and 80% RH, and then the sample was peeled off to measure the area of the bonded portion and measure the adhesiveness. The evaluation criteria are as follows. Rank Area of bonded part A 1 to 20% B 21 to 40% C 41 to 60% D 61% or more The above results are shown in Table 5. From the results shown in Table 5, it can be seen that the matting agent of the present invention is superior in adhesion resistance to the conventional one. Example 6. The sharpness of each of Samples 6 to 15 and Sample 19 below was examined by the following method. That is, the unexposed sample was exposed to a normal wedge with a tungsten lamp and then subjected to the developing treatment of Example 4 to measure the MTF. MTF at spatial frequency of 30 lines / mm
The values were compared. Sample 19 is MMA / MAA = 60/40 (molar ratio) of Sample 15 instead of
It was prepared in the same manner as Sample 15 except that the homopolymer of MMA was used. The results are shown in Table 6. As is clear from Table 6, the use of the matting agent of the present invention does not deteriorate the sharpness.

【The invention's effect】

By using the matting agent of the present invention as a matting agent for matting the surface of a photographic light-sensitive material, adhesion resistance and antistatic property are improved without adversely affecting photographic performance and film physical properties.

Continuation of front page (56) Reference JP 58-66937 (JP, A) JP 58-210613 (JP, A) JP 57-179837 (JP, A) JP 60-210613 (JP , A) JP-A-60-189742 (JP, A) US Patent 2731347 (US, A)

Claims (1)

[Claims] 1. A photographic light-sensitive material having at least one surface roughened with a matting agent, wherein the matting agent is particles containing a polymer having a fluorine atom and an alkali solubilizing group. Photosensitive material.