JPH0588452B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION Technical Field The present invention relates to a silver halide photographic material containing an alkali-soluble matting agent in the outermost layer, and more specifically, the alkali-soluble matting agent consists essentially of ethyl methacrylate, methacrylate, etc. This invention relates to a silver halide photographic material comprising a copolymer of methyl acid and methacrylic acid. Prior Art and its Problems Generally, the outermost layer (uppermost layer or back layer) of a silver halide photographic light-sensitive material (hereinafter simply referred to as light-sensitive material) uses a hydrophilic colloid, typified by gelatin, as a binder. Therefore, when the surface of a photosensitive material is in a high-temperature, high-humidity atmosphere, its adhesion or tackiness increases, and when it comes into contact with another object, it easily adheres to it. This adhesion phenomenon occurs between photosensitive materials, or between photosensitive materials and other objects that come into contact with them, during manufacturing, storage, photographing, processing, projection, or storage after processing. ,
This often resulted in serious failures. In particular, in color photosensitive materials, adhesiveness has been a major problem since the photographic layer contains a large number of additives such as color couplers. To solve this problem, the top layer or back layer contains fine particles of inorganic substances such as silicon dioxide, magnesium oxide, titanium dioxide, calcium carbonate, and organic substances such as polymethyl methacrylate and cellulose acetate propionate. Methods have been proposed to increase the roughness of the surface of the material, resulting in so-called matting and reducing adhesion.
In color light-sensitive materials, it is necessary to use a large amount of matting agent for the above-mentioned reasons. However, the above-mentioned matting agents are insoluble in alkaline processing solutions and remain in the photosensitive material even after processing, so if a large amount of matting agents is used, it may deteriorate the transparency of the formed image or impair the image quality. It had some flaws. In order to avoid such problems, matting agents that are insoluble in neutral or acidic solutions and soluble in alkaline solutions have been proposed. For example, U.S. Pat.
No. 2992101 proposes the use of a copolymer of methyl methacrylate (hereinafter abbreviated as MMA)/methacrylic acid (hereinafter abbreviated as MAA) in a molar ratio of 1/1 as a matting agent. However, when a matting agent made of such a copolymer is used, a large amount of the matting agent is dissolved, especially in the coating process during the production of a photosensitive material in which a coating solution containing a matting agent is coated and dried.
To improve this drawback, US Pat. No. 3,767,448 discloses a technique of using demineralized gelatin or deionized gelatin when using a matting agent with a molar ratio of MMA/MAA of 1/1. Here, the reason why the matting agent made of a copolymer having free carboxyl groups dissolves during the coating process is because the calcium ions contained in gelatin and the matting agent form a salt, and therefore the gelatin is deionized or deionized. It is said that it is necessary to dispose of the ash. However, gelatin that has been treated in this way generally lacks coating suitability and may cause coagulum or so-called "repellency," and gelatin processing also increases costs, making it impractical. . On the other hand, in Special Publication No. 57-9054, MMA/
A matting agent comprising MAA in a molar ratio of about 6/4 to 9/1 is disclosed. When the ratio of MMA/MAA is within this range, the matting agent will not dissolve during the coating process and sufficient matting properties will be obtained. However, this large amount of butanol remains without being completely removed even after washing the dispersion, resulting in an undesirable odor. Furthermore, in JP-A No. 58-66937, a matting agent using a copolymer of ethyl methacrylate (hereinafter abbreviated as EMA) and MAA (containing 20 to 50% by weight of MAA) as a matting agent dissolved in ethyl acetate is disclosed. is proposed. However, EMA/
Compared to MMA/MAA copolymer, MAA copolymer has
Due to its low glass transition point (hereinafter abbreviated as Tg), it had the disadvantage that it was difficult to obtain sufficient matte properties. Furthermore, these matting agents have the disadvantage that solid matter such as dust and bubbles floating in the developing solution adhere to the surface of the photosensitive material, causing uneven development and deteriorating image quality. OBJECT OF THE INVENTION The object of the present invention is to solve the above-mentioned drawbacks, namely, to reduce the amount of butanol used without dissolving it in the coating process, and to eliminate the need to use deionized and demineralized gelatin, and to reduce the amount of butanol used. The object of the present invention is to provide a silver halide photographic material containing a novel matting agent in the outermost layer that has matting properties and does not cause uneven development. The above object of the present invention is to provide at least one
In a silver halide photographic material having a light-sensitive silver halide emulsion layer and at least one non-light-sensitive layer as the outermost layer, in the outermost layer,
This is achieved by a silver halide photographic light-sensitive material characterized in that it contains a matting agent consisting of a copolymer having a copolymer composition essentially of ethyl methacrylate, methyl methacrylate, and methacrylic acid. Detailed Description of the Invention The copolymer used as the matting agent of the present invention is a copolymer consisting essentially of three components: EMA, MMA, and MAA, and the molar composition ratio of these is as follows:
EMA and MMA/MAA=5/5 to 9/1 are preferred, particularly 6/4 to 8/2, and
EMA/MMA=9/1 to 1/9 is preferred, particularly 8/2 to 2/8. If MAA exceeds 50% in the former composition ratio, EMA and MMA/MAA, it is likely to dissolve during the coating process.
Further, if the amount is less than 10%, the matting agent is difficult to dissolve in the alkaline solution, which is not preferable. Also, in the composition ratio of EMA/MMA, MMA is 9
If the ratio is exceeded, a large amount of butanol will be used as a solvent, for example, EMA/MMA/MAA=
For a copolymer with a composition ratio (mole ratio) of 5/55/40, ethyl acetate/n-butanol = 8/2 (weight ratio)
It dissolves only up to 10% in mixed solvents. On the other hand, if the EMA exceeds 90%, the Tg will be low and sufficient mattability will be difficult to obtain, so the above range is preferred. Especially in light of such requests, EMA//
The ratio of MMA is preferably 8/2 to 2/8. The copolymer of the present invention can be easily synthesized by conventionally known methods such as solution polymerization, bulk polymerization, and suspension polymerization. For example, in solution polymerization, a mixture of three monomers at appropriate concentrations (usually 40% by weight or less, preferably 10 to 25% by weight based on the solvent) in a suitable solvent (e.g. ethanol, methanol, etc.) is generally used. A mixture of three monomers at different concentrations) in the presence of a polymerization initiator (e.g. benzoyl peroxide, azobisisobutyronitrile, etc.) at a suitable temperature (e.g. 40°C)
The copolymerization reaction is carried out by heating to 120°C to 100°C, preferably 50 to 100°C. Thereafter, the unreacted mixture is separated off by pouring the reaction mixture into a medium such as water, allowing the product to settle, and then drying. The molecular weight of the copolymer used as the matting agent of the present invention is 5,000 to 1,000,000, preferably 20,000 to 200,000. As used herein, "substantially" means EMA in the copolymer constituting the matting agent,
95% by weight composition consisting of MMA and MAA
That's all. The copolymer of the present invention includes EMA as described above,
Unsaturated vinyl monomers other than MMA and MAA,
For example, known monomers that can be copolymerized with the three types of monomers of the present invention, such as acrylonitrile, vinyl acetate, styrene, ethyl vinyl ether, and butyl vinyl ether, etc., may be used within the range that does not adversely affect the purpose of the present invention. A small amount (preferably 5% by weight or less) can be added. The structure of the copolymer of the present invention and its properties hardly change even if the above monomer is added. The matting agent of the present invention is finely dispersed and contained in the outermost layer of the photosensitive material. These matting agents are prepared by adding a solution of the copolymer dissolved in a low-boiling organic solvent such as ethyl acetate, ethyl acetate containing butanol (less than 50% by weight of butanol), methanol containing butanol (less than 50% by weight of butanol), etc. to an aqueous gelatin solution. The size of the matting agent of the present invention can be varied within a considerable range;
A range of 0.2 to 10 μm, particularly 0.5 to 5 μm is preferred. The aqueous gelatin solution containing the matting agent obtained above can be applied as the outermost layer of a light-sensitive material by any method known in the photographic field. Next, specific examples of preferable mole percentages of monomers in the copolymer used as the matting agent of the present invention are shown below, but the present invention is not limited thereto.

[Table] The outermost layer in the present invention refers to, for example, a surface protective layer, a back layer, a non-photosensitive intermediate layer of a final product in a multilayer photosensitive material coated in multiple layers, or all of them. In the present invention, it is particularly preferable that the surface protective layer contains a matting agent. The matting agent of the present invention has a
It is preferable to contain 50 mg to 500 mg, particularly 100 mg to 400 mg. In the present invention, examples of the hydrophilic colloid binder constituting the outermost layer include gelatin, gelatin derivatives (eg, acetylated gelatin, phthalated gelatin, etc.), albumin, collodion, and the like, with gelatin being particularly preferred. Furthermore, in the present invention, if necessary, a hardening agent is added to the outermost layer.
Various additives such as a smoothing agent, a surfactant, an antistatic agent, a thickener, and a polymer latex can be included. Examples of hardening agents include aldehyde compounds, 2-hydroxy-4,6-dichloro-1,
Compounds having active halogens such as 3,5-triazine, vinylsulfone compounds, N-methylol compounds, halogencarboxaldehyde compounds such as mucochloric acid, and the like can be used.
As the smoothing agent, for example, liquid paraffin, waxes, polyfluorinated hydrocarbons, silicones, etc. can be used. Examples of surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxides, cationic surfactants such as higher alkylamines and quaternary ammonium salts, and acidic groups such as carboxylic acids and sulfonic acids. Any of the anionic surfactants including the above can be used. Examples of antistatic agents include the above-mentioned surfactants, alkali metal salts such as styrene-maleic acid copolymers and acrylonitrile-acrylic acid copolymers, and US Pat.
The antistatic agent described in No. 3428451 may be contained. In the present invention, known matting agents such as silicon dioxide, polymethyl methacrylate, etc. can be used in combination. However, since such known matting agents remain in the photographic material after processing, they are preferably used in smaller amounts than the copolymers of the present invention, for example up to 50 mg per square meter. The silver halide emulsion used in the light-sensitive material of the present invention can be prepared by any method such as the usual single-jet method, double-jet method, acid method, ammonia method, or neutral method. There are no particular restrictions on shape, size and size distribution. As the silver halide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used. Hydrophilic colloid binders used in silver halide emulsions include gelatin, modified gelatin,
In addition to gelatin derivatives, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, poly-N-pyrrolidone, polyacrylic acid copolymers, polyacrylamide, etc.
These may be used alone or in combination of two or more. Further, the photographic constituent layer according to the present invention may contain a latex-like water-dispersed vinyl compound. As such a latex, homo- or copolymers of alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, glycidyl acrylate, styrene, vinyl chloride, vinylidene chloride, etc. are used. The silver halide emulsion used in the present invention can be chemically sensitized by conventional methods. For example, U.S. Pat.
Gold compounds as shown in specifications such as No. 2399083 and No. 2597856, as well as platinum, palladium, rhodium,
Salts of precious metals such as iridium, U.S. Pat.
Chemical sensitization can be performed using sulfur compounds shown in specifications such as No. 2410689 and No. 3501313, other stannous salts, amines, and the like. A stabilizer or an antifoggant can be added to the halogenated emulsion used in the present invention. For example, 4-hydroxy-6-methyl-1,3,3α,
Many compounds such as 7-tetrazaindene, 3-methyl-benzothiazole, 1-phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, metal salts, etc. can be used. Furthermore, the silver halide emulsion used in the present invention includes:
Various spectral sensitizing dyes such as merocyanine dyes, carbocyanine dyes, cyanine dyes, etc. can be used depending on the purpose. In the present invention, color couplers include a 4-equivalent methylene yellow coupler, a 2-equivalent diketomethylene yellow coupler, a 4-equivalent or 2-equivalent pyrazolone magenta coupler, an indazolone magenta coupler, an α-naphthol cyan coupler, and a phenol coupler. cyan couplers can be used. It is also possible to use so-called DIR couplers. Further, the photographic constituent layers of the present invention may contain dyes, ultraviolet absorbers, hardeners as described above, surfactants, polymer latex, and the like. As the support for the photosensitive material of the present invention, any support commonly used in the art, such as cellulose acetate film, polyethylene terephthalate film, baryta paper, or paper coated with α-olefin polymer, can be used. The photographic constituent layers of the light-sensitive material of the present invention can be formed using various methods such as dip coating, air knife coating, curtain coating, extrusion coating, etc.
It is possible to apply one layer at a time or multiple layers simultaneously. For information on various additives, vehicles, supports, coating methods, etc. used in the present invention, please refer to the Product Licensing Index.
You can refer to the description in vol. 92, pages 107-110 (December 1971) of Index). The exposure light source for the photosensitive material of the present invention is not particularly limited, and any light source can be used ranging from low to high illuminance, and the exposure time ranges from several tens of seconds to about 10 ^-6 seconds. I can do it. The photosensitive material applicable to the present invention may be a black-and-white photographic material, a color photographic material, or one for general use, for printing, for X-rays, for radiation, etc. Specifically, black and white negative film, paper, It can be applied to all kinds of photographic materials, such as reversal photographic materials, color negative films, papers, and so-called external color photographic materials containing color formers in reversal and processing solutions. When the light-sensitive material of the present invention is a color light-sensitive material, after exposure, it is developed to form a dye image. Here, the development process basically includes at least one color development process, and optionally includes a pre-hardening process, a neutralization process, a first development (black and white development) process, and the like. Said steps and the steps following them (e.g. selected combinations of bleaching, fixing, bleach-fixing, intensification, stabilization, washing, etc.) are carried out at temperatures above 30.degree. C., particularly preferably above 35.degree. A color developer is a compound whose oxidation product reacts with a color former (color coupler) to form a color product, i.e., a compound containing p-phenylene diamines (for example, N,N-diethyl-p-phenylene diamine) as a developing agent. Nylenediamine, N,N-diethyl-3-methyl-p
-phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline, N-ethyl-N -β-hydroxyethyl-p-phenylenediamine) or salts thereof (e.g. hydrochloride,
Alkaline aqueous solution (PH8) containing sulfate, sulfite)
Above, the pH is preferably 9 to 12). As the developing agent, U.S. Patent No. 2193015, U.S. Patent No. 2592364,
Compounds described in JP-A-48-64933 and other specifications can be used. The color developing solution also contains salts such as sodium sulfate, PH regulators such as sodium hydroxide, sodium carbonate, and sodium phosphate, buffers (e.g., acids such as acetic acid and boric acid, or their salts), and development accelerators. (For example, U.S. Patent No. 2648604
Various pyridinium compounds, cationic compounds, potassium nitrate, sodium nitrate, and U.S. patent no.
2533990, 2577127, 2950970, etc., and derivatives thereof, as typified by the compounds described in British Patent Nos. 1020032 and 1020033. nonionic compounds such as polythioethers, polymer compounds with sulfite esters as typified by the compound described in U.S. Patent No. 3,068,097, other organic amines such as pyridine and ethanolamine, benzyl alcohol, hydrazine, etc.) can be included. The color developer further contains antifoggants (for example, alkali bromide, alkali iodide, nitrobenzimidazoles, benztriazole compounds, mercaptotetrazole compounds, etc.), US Pat. No. 3,161,514,
Stain or sludge inhibitors described in specifications such as British Patent No. 1144481, interlayer effect promoters and preservatives known in specifications such as U.S. Patent No. 3536487 (e.g. sulfites, acid sulfites, hydroxylamine hydrochloride) , formaldehyde-alkanolamine sulfite adduct, etc.). The processing solution that precedes the development process is usually a pre-hardening bath, which contains aldehydes that have the effect of reacting with and hardening gelatin, which is a constituent factor in photographic emulsions, such as those described in US Pat. No. 3,232,761. aliphatic aldehydes, formaldehyde, glyoxal, succinaldehyde, glutaraldehyde, pyruvaldehyde, etc.) described in US Pat. An aqueous solution is used. This solution includes inorganic salts such as sodium sulfate, PH regulators and buffers such as borax, boric acid, acetic acid, sodium acetate, sodium hydroxide, and sulfuric acid, and developing agents such as alkali halides (e.g., potassium bromide). Contains antifoggant. Generally, a neutralization bath is provided for the purpose of preventing aldehydes used in the pre-hardening process from being carried into the development process. An aldehyde removing agent such as hydroxylamine and L-ascorbic acid is added to the neutralization bath, and inorganic salts, a PH regulator, and a buffering agent are also added. The first developer for the color reversal film is also a step prior to color development, and an alkaline aqueous solution containing one or more developing agents such as hydroquinone, 1-phenyl-3-pyrazolidone, and N-methyl-p-aminophenol is used. In addition, inorganic salts such as sodium sulfate, PH regulators and buffers such as borax, boric acid, sodium hydroxide, and sodium carbonate, alkali halides (e.g., potassium bromide), and other developer fog preventive agents. is included. The various additives and amounts added in the above processing steps are well known in color photographic processing methods. After color development, color photographic materials are usually bleached and fixed. Bleaching and fixing can also be combined into a bleach-fixing bath. Many compounds are used in bleaching agents, among them ferricyanates, dichromates, water-soluble iron () salts, water-soluble cobalt () salts, water-soluble copper () salts, water-soluble quinones, and nitrosates. Complex salts of polyvalent cations such as phenol, iron (), cobalt (), copper () and organic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, Metal complex salts such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid,
Copper 6-dipicolinate complex, peracids such as alkyl peracids, persulfates, permanganates, hydrogen peroxide, hypochlorite, chlorine, bromine, salicy powder, etc. alone or in appropriate combinations. Common. Other bleaching accelerators described in US Pat. No. 3,042,520, US Pat. Any conventionally known fixing solution can be used for fixing. That is, ammonium, sodium, and potassium salts of thiosulfate are used as fixing agents.
It is used in an amount of ~200g/, and may also contain stabilizers such as sulfites and isomeric bisulfites, hardeners such as potash alum, and PH buffers such as acetates and borates. . For bleach, fixatives and bleach-fix baths,
It is described in US Pat. No. 3,582,322, etc. As the intensification liquid, intensification liquids obtained by a method using Co() salt, a method using hydrogen peroxide, or a method using chlorous acid can be used. For image stabilizing baths, U.S. Patent No. 2,515,121;
The method described in the specification of the same No. 3140177 etc. can be used. Specific Examples of the Invention Hereinafter, the present invention will be specifically explained using Examples, but is not limited thereto. Synthesis Example 1 (Exemplary Compound No. 5) EMA34.2g (0.30mol), MMA30.0g (0.30mol), MAA34.4g (0.40mol), α,α′-Azobisisobutyronitrile (AIBN) 2.0g and 500 c.c. of ethanol were placed in a three-necked flask, and the mixture was refluxed for 10 hours. Thereafter, the reaction solution was poured into a large amount of water with vigorous stirring to precipitate the reaction product. Next, the precipitate was filtered, washed with water, and dried in air at 60°C to obtain a copolymer (1) according to the present invention. Yield: 92.7g (94% of theoretical yield)
It was hot. The molar composition ratio is EMA according to NMR:
MMA:MAA=30:30:40. This copolymer (1) was dissolved up to 25% in a mixed solvent of ethyl acetate/n-butanol=8/2 (weight ratio). Moreover, Tg=132°C, and the intrinsic viscosity in ethanol at 25°C was 0.14 ml/g. Synthesis Example 2 (Exemplary Compound No. 4) 22.8 g (0.20 mol) of EMA, 40.0 g (0.40 mol) of MMA, 34.4 g (0.40 mol) of MAA, and 2.0 g of AIBN were reacted and treated in the same manner as in Example 1. A copolymer (2) according to the invention was obtained. Yield: 91.4g (theoretical yield: 94g)
%), and the molar composition ratio is according to NMR.
EMA:MMA:MAA=22:39:39. This copolymer (2) is ethyl acid/n-butanol=
It was dissolved up to 23% in a mixed solvent of 8/2 (weight ratio).
Moreover, Tg=127°C, and the intrinsic viscosity in ethanol at 25°C was 0.15 ml/g. Synthesis Example 3 (Exemplified Compound No. 10) EMA45.7g (0.40mol), MMA30.0g (0.30mol), MAA25.8g (0.30mol), AIBN2.0g in ethyl acetate/n-butanol = 8/2 (weight) The copolymer (3) was dissolved in 400 c.c. of a mixed solvent (ratio), reacted under reflux for 8 hours, and then the solvent was distilled off under reduced pressure at 100 mmHg and 45°C to obtain copolymer (3). Yield: 97.8g (96% of theoretical yield)
According to NMR, the composition ratio (molar ratio) is
EMA:MMA:MAA=41:30:29. In addition, the intrinsic viscosity in ethanol at 25℃ and Tg=114℃ is
It was 0.17ml/g. This copolymer (3) can also be dispersed to form a matting agent without removing the solvent under reduced pressure after the reaction. Synthesis Example 4 (Illustrated Compound No. 12) 22.8 g (0.20 mol) of EMA, 60.0 g (0.60 mol) of MMA, 17.2 g (0.20 mol) of MAA, and 2.0 g of AIBN were copolymerized in the same manner as in Synthesis Example 1. We obtained combination (4).
The yield was 96.2g (96% of the theoretical yield), and the composition ratio (mole ratio) was determined by NMR to be EMA:MMA:
MAA = 22:57:21. Copolymer (4) was dissolved up to 30% in a mixed solvent of ethyl acetate/n-butanol=9/1 (weight ratio). Also, Tg=123℃, 25
The intrinsic viscosity in ethanol at °C was 0.16 ml/g. Example 1 80 g of copolymer (1) obtained in Synthesis Example 1 was added to a mixed solvent of 190 g of ethyl acetate and 60 g of n-butanol at 40°C.
It was dissolved in Further, 1.0 g of sodium dodecylbenzenesulfonate was dissolved in 40 g of water. moreover
40 g of gelatin was placed in a 500 ml beaker, 320 g of water was added, the gelatin was allowed to swell for 30 minutes, and then dissolved at 60°C.
Next, the dissolved gelatin solution and the aqueous sodium dodecylbenzenesulfonate solution were placed in a three-necked flask with an internal volume of 1, and the flask was heated to 35°C.
Add a solution of copolymer (1) dissolved in advance to it,
Stirring was carried out for 20 minutes at a speed of 1000 revolutions per minute. As a result of observing the obtained emulsion with an optical microscope,
Polymer oil droplets of 2-5 μm were observed. This emulsion was dried under reduced pressure at 100 mmHg and 45°C to remove the solvent. Thereafter, a matting agent (1) having a particle size of 2 to 5 μm was obtained by centrifugation. Example 2 The copolymer (2) obtained in Synthesis Example 2 was treated in the same manner as in Example 1 to obtain a matting agent (2) having a particle size of 2 to 4 μm. Example 3 The copolymer (3) obtained in Synthesis Example 3 was treated in the same manner as in Example 1 to obtain a matting agent (3) having a particle size of 2 to 4 μm. Example 4 The copolymer (4) obtained in Synthesis Example 4 was treated in the same manner as in Example 1 to obtain a matting agent (4) with a particle size of 2 to 4 μm. Example 5 Contains 300 g of gelatin per mole of silver halide and uses α-pivaloyl-α-(1-benzyl-2,4-dioxyimidazolin-3-yl)-2-chloro-5 as the yellow coupler. [γ-
Blue-sensitive iodobromide for color containing 2.5×10 ^-2 mol of (2,4-tert-aminophenoxy)butyramide]acetanilide and 0.02 g of 1,2-bis(vinylsulfonyl)ethane/1 g of gelatin as hardener. A silver (silver iodide 7 mol %) emulsion was prepared. Along with this emulsion, matting agent (1) of the present invention, matting agent (2) and EMA/
Particle size 2~ with composition MAA=6/4
A 4 μm matting agent (A) was applied from the support onto a cellulose triacetate film support having a subbing layer by the slide hopper method so that the gelatin solution containing the coating aid had the composition shown in Table 1 below. In order, the emulsion layer,
Apply a protective layer, matting agent (1), (2) and matting agent
(A) is the sample without dissolving during coating.
(1), sample (2) and sample (A) were obtained. The dry film thickness of the protective layer was 1.5 μm.

[Table] For each of the above samples, cut two pieces into 5cm square pieces, making sure that they do not touch each other.
After storing for 1 day at 23℃ and 80%RH,
Two protective layers of the same sample were brought into contact with each other, a load of 800 g was applied, and the sample was stored in an atmosphere of 40°C and 80% RH.Then, the sample was peeled off and the area of the bonded part was measured to measure adhesion. did. The evaluation criteria are as follows. Rank Area of adhesive part A 0-20% B 21-40% C 41-60% D 61% or more The above results are shown in Table 2.

[Table] From the results in Table 2, it can be seen that the adhesive resistance of the matting agent of the present invention is superior to that of the conventional matting agent. Example 6 In the same manner as in Example 3, a blue-sensitive silver iodobromide emulsion for color was prepared, and the matting agent (3) of the present invention, the matting agent (4), and EMA/MMA/MAA= for comparison were added to this emulsion.
A matting agent (B) having a particle size of 2 to 4 μm and having a composition (molar ratio) of 55/5/40 was coated on a cellulose triacetate film support to prepare sample (3), sample (4) and sample (B), respectively. ) was obtained. These samples (3), (4) and (B)
In both cases, matting agents (3), (4) are used during the application.
and (B) did not dissolve. The dry film thickness of the protective layer of each of these samples was 1.6 μm. The same evaluation as in Example 3 was performed for each of the above samples. The results are shown in Table 3.

[Table] Example 7 Samples (1), (2) and (A) prepared in Example 5 were developed in the following processing steps. Processing process Temperature Processing time (1) Developer...38℃ 3 minutes 15 seconds (2) Bleaching...38℃ 4 minutes 30 seconds (3) Fixing...38℃ 4 minutes 20 seconds (4) Washing... ...38°C 3 minutes 15 seconds (5) Stabilization...38°C 1 minute 5 seconds The compositions of the developer, bleaching solution, fixing bath and stabilizing bath are 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 Add water to make 1. Bleach bath (PH=5.70) Ammonium bromide 173g 80% acetic acid 20ml EDTA FeNH ₄ 103g EDTA 27g Add water to make 1. Nitrogen bath (PH=6.50) Ammonium thiosulfate 800ml Sodium sulfite 4.6g Sodium bisulfite 5.0g Add water to make 1. Stable bath (PH=7.30) 40% formalin 6.6ml 50% polyoxyethylated lauryl alcohol
Add 0.6ml water to make 1. These samples were evaluated for the presence or absence of dust on the surface of the sample after the development process, and for "development unevenness" caused by dust adhering in the developer. The results are shown in Table 4.

[Table] It was found that when the matting agent of the present invention was used, there was no adhesion of dust in the developer and uneven development due to dust did not occur. Also, after the development process,
Almost no matting agent (1), matting agent (2), and matting agent (A) remained, and there was no difference in their residual properties.

Claims (1)

[Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer as the outermost layer on a support, wherein the outermost layer contains substantially methacrylic acid. A silver halide photographic light-sensitive material characterized in that it contains a matting agent consisting of a copolymer having ethyl, methyl methacrylate, and methacrylic acid as a copolymer composition.