JPH0673006B2 - Photo elements - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to photographic elements, and more particularly to photographic elements used in the field of silver halide photographic light-sensitive materials containing polymeric matting agents.

Prior Art and its Problems In general, a photographic element has an outermost layer (surface layer) containing a hydrophilic organic colloid represented by gelatin as a binder. Therefore, the surface of the photographic element has increased adhesiveness and tackiness in an atmosphere of high temperature and high humidity, and is likely to cause an adhesive failure such as contact with another object.

Such adhesion phenomenon occurs between the photographic elements, between the photographic elements and an object in contact with the photographic elements, such as during production, storage, photography, processing, or storage after processing of the photographic elements, Frequently, there are significant disadvantages such as blocking of stacked photographic elements, coating damage, transfer of compounds in coating to other adhesive surfaces, discharge failure, and the like.

In addition, the writability with a pencil or the like is often required on the surface (especially the back surface) of the photographic element, but the plastic film support or the paper support laminated with polyethylene or the like can be used as it is without any binder such as gelatin. Even if it is painted, it is not writable.

In order to solve such problems, the uppermost layer is made of an inorganic substance such as silicon dioxide, magnesium oxide, titanium dioxide, calcium carbonate or an organic substance such as starches, polymethylmethacrylate or cellulose acetate propionate. It is well known in the art that fine particles (hereinafter referred to as “matting agent”) are added to increase the roughness of the surface of the photographic element, so-called matte, reduce the adhesiveness, and impart writability. ing.

However, the conventional matting agents as described above have various drawbacks. For example, some deteriorate the photographic property, some have too large a specific gravity in the manufacturing process and settle in the coating solution to cause troubles with coating, and some have a limited size due to the manufacturing method and the required size. It is a defect that things cannot be obtained.

It is known that a hard material is generally more effective as a matting agent used for imparting writability. As a result of various investigations by the present inventors as a matting agent for improving adhesion resistance, it has been found that a hard material is more effective for this purpose when compared in the same size.

An inorganic matting agent is known as a hard material.
However, although this one generally has high hardness and is effective in improving writing properties and adhesion resistance, it has a manufacturing problem that the dispersion liquid or the coating liquid tends to settle out due to its large specific gravity.

II Object of the Invention The object of the present invention is improved in terms of writability, adhesive failure, etc.
Another object of the present invention is to provide a photographic element which has excellent photographic properties, is easy to manufacture, and has good stability.

III DISCLOSURE OF THE INVENTION Such an object is achieved by the present invention described below.

That is, the present invention is a photographic element characterized by containing particles comprising a benzoguanamine / formaldehyde condensation polymer.

IV Specific Structure of the Invention Hereinafter, the specific structure of the present invention will be described in detail.

The photographic element of the present invention contains particles consisting of a benzoguanamine-formaldehyde condensation polymer.

Here, the benzoguanamine-formaldehyde condensation polymer is represented by the following formula.

In this case, n represents a positive integer, specifically 10 or more,
It is preferably 50 or more.

This is, for example, the existing chemical substance 7-31 marketed under the trade name Eposter (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.).

The particles of the benzoguanamine / formaldehyde condensation polymer (hereinafter abbreviated as polymer particles) in the present invention are white spherical fine particles.

The particle size is in the range of 0.1 to 70 μm, and the particle size can be appropriately selected according to the intended use.

Moreover, since it is white, it does not adversely affect the photographic properties.

The polymer particles in the present invention are hard. For example, the test method
JIS-K7215 / Durometer D hardness is 40 or more. Therefore, the effect of improving the adhesion resistance and the writability is extremely large, and since the specific gravity is relatively small, the sedimentation speed in the dispersion liquid or the coating liquid is slow, and there is no problem in manufacturing.

Such polymer particles can be contained in each layer of a light-sensitive material or an image-receiving material (dye fixing material) constituting the photographic element of the present invention.

In particular, the polymer particles of the present invention are useful when incorporated as a matting agent in the protective layer of a light-sensitive material, or as a matting agent in the protective layer or back layer of a dye-fixing material.

Thus, the average particle size when used as a matting agent is about 0.
1 to 10 μm is suitable, preferably 0.5 to 8 μm, and more preferably 1 to 6 μm.

When the polymer particles of the present invention are used as a matting agent, conventionally known matting agents may be used in combination.

Matting agents are well known in the photographic art and can be defined as discrete solid particles of an inorganic or organic material dispersible in a hydrophilic organic colloid binder. Examples of inorganic matting agents include oxides (eg, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.),
Alkaline earth metal salts (for example, sulfates and carbonates,
Specifically, barium sulphate, calcium carbonate, magnesium sulphate, etc.), silver halide grains that do not form an image (such as silver chloride or silver bromide, with a slight addition of iodine atoms as a halogen component), glass, etc. Is.

Examples of organic matting agents include starch, cellulose ester (eg, cellulose acetate pyropionate, etc.),
Examples thereof include cellulose ether (eg ethyl cellulose) and synthetic resin. Examples of synthetic resins are dispersions of water-insoluble or sparingly soluble synthetic polymers such as alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, glycidyl (meth) acrylates, (meth) acrylamides, vinyl esters (eg acetic acid). Vinyl), acrylonitrile, olefin, styrene, etc., alone or in combination, or with these, acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid. A polymer having a combination of the above and the like as a monomer component can be used.

The thickness of the protective layer containing the matting agent and the back layer is about 1/10 to 1/3 of the average particle size (average diameter) of the matting agent,
It is preferable in terms of adhesion resistance, blocking resistance, writing property, peelability improving property and the like.

The protective layer and the back layer may be multi-layered, in which case the matting agent is contained in the outermost layer, and, for example, in the case of a two-layer structure, oil droplets are dispersed in at least one of these layers. Is preferred.

About 0.01 to 10 μm is suitable for the size of oil droplets, and 0.05 to 5
μm is preferred.

As the substance that forms the oil droplets, a high-boiling organic compound used for dispersing a photographic coupler is usually useful,
As the high-boiling organic compound, those having a boiling point of 180 ° C. or higher under normal pressure are preferable, and examples thereof include those described in US Pat. No. 2,322,027, and specific examples include those described below.

The polymer particles in the present invention can be used in various conventional silver halide photographic light-sensitive materials.

The polymer particles in the present invention can be used, for example, in a coupler type color photographic material. As a color photosensitive material,
Examples include color negative films for photography (general use, professional use, movie use, etc.), color reversal films, color photographic papers, color reversal photographic papers, and cinema positives.

The polymer particles in the present invention are, for example, The Theory of th
e Photographic Process, Chapter 12, Principles and C
hemisty of Color Photography IV.Silve Dye Bleach P
rocess, 4th ed., THJames ed., Macmillan, New York, 19
77, p363-366. It can also be used in the silver dye bleaching method.

The polymer particles of the present invention can be further used in a black-and-white light-sensitive material. Examples of the black-and-white light-sensitive material include X-ray film for direct medical use, black-and-white film for general photography, lith film, scanner film and the like.

The polymer particles in the present invention are used in the emulsion layer, intermediate layer, surface protective layer and back layer of the color and black-and-white light-sensitive materials as described above, particularly preferably in the outermost layer.

In these multi-layered photographic elements, it is often difficult to coat all the layers at the same time, and they are coated in several portions. In that case, take it up once and apply it on top of it,
Until then, it is stored in a roll form, and the coating film tends to adhere to the back surface, causing a failure. Therefore, by using the polymer particles of the present invention in any layer, preferably the outermost layer during the first coating, the adhesion during storage in a roll state is significantly improved.

The silver halide that can be used in the present invention includes silver chloride, silver bromide,
It may be any of silver iodide, silver chlorobromide, silver chloroiodosilver, silver iodobromide and silver chloroiodobromide. The halogen composition in the grains may be uniform or may have a multiple structure in which the composition is different between the surface and the inside (JP-A-57-154232 and JP-A-58-108533).
No. 59-48755, 59-52237, U.S. Pat.
048 and European Patent No. 100,984). Further, tabular grains having a grain thickness of 0.5 μm or less, a diameter of at least 0.6 μm, and an average aspect ratio of 5 or more (US Pat. No. 4,414,310,
No. 4,435,499 and West German Open Patent (OLS) No. 3,241,64
6A1), or monodisperse emulsions having a nearly uniform grain size distribution (JP-A-57-178235, JP-A-58-100846, and JP-A-58-14).
829, WO83 / 02338A1, European Patents 64,412A3 and 83,377A1) may also be used in the present invention. Two or more kinds of silver halides having different crystal habits, halogen compositions, grain sizes, grain size distributions and the like may be used in combination. The gradation can be adjusted by mixing two or more kinds of monodisperse emulsions having different grain sizes.

The grain size of the silver halide used in the present invention is preferably 0.001 μm to 10 μm, more preferably 0.001 μm.
It is more preferably from m to 5 μm. These silver halide emulsions may be prepared by any of the acidic method, the neutral method and the ammonia method, and the reaction form of the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination method thereof. Any combination of A back mixing method, in which grains are formed in the presence of excess silver ions, or a controlled double jet method, which keeps pAg constant, can also be employed. Also,
In order to accelerate the grain growth, the addition concentration, the addition amount or the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329, JP-A-55-158124, U.S. Pat.
650, 757).

Epitaxial junction type silver halide grains can also be used (JP-A-56-16124, U.S. Pat. No. 4,094,684).
issue).

When the silver halide is used alone in the heat development method without using the organic silver salt oxidizing agent, silver chloroiodide, silver iodobromide, chloroiodo, which can recognize the X-ray pattern of the silver iodide crystal, can be used. Preference is given to using silver halide.

With respect to such a silver salt, for example, a silver nitrate solution is added to a potassium bromide solution to prepare silver bromide grains, and further potassium iodide is added to obtain silver iodobromide having the above-mentioned properties.

In the step of forming silver halide grains used in the present invention, ammonia as a silver halide solvent, JP-B-47-11
Organic thioether derivatives described in Japanese Patent No. 386 or JP-A-53-53
The sulfur-containing compounds described in No. 144319 can be used.

Cadmium salt, zinc salt, lead salt, thallium salt and the like may be present together in the process of grain formation or physical ripening.

Further, for the purpose of improving the high illuminance failure and the low illuminance failure, a water-soluble iridium salt such as iridium chloride (III, IV) or ammonium hexachloroiridate, or a water-soluble rhodium salt such as rhodium chloride can be used.

Soluble salts may be removed from the silver halide emulsion after the formation of a precipitate or after physical ripening, and thus the Nudell washing method or the precipitation method can be followed.

The silver halide emulsion may be used as it is without ripening, but it is usually chemically sensitized before use. Well-known sulfur sensitizing methods, reduction sensitizing methods, noble metal sensitizing methods and the like can be used alone or in combination for the emulsions for conventional light-sensitive materials. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A Nos. 58-12652 and 58-21544).

The silver halide emulsion used in the present invention may be either a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside the grain. A direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used. Internal latent image type emulsions suitable for this purpose are described in U.S. Pat.
No. 2,592,250, No. 3,761,276, JP-B-58-3534 and JP-A-57-136641. A preferred nucleating agent for combination in the present invention is US Pat.
No. 227,552, No. 4,245,037, No. 4,255,511, No. 4
4,266,031, 4,276,364 and OLS 2,635,316.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus,
Benzindolenin nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus,
A naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used particularly for the purpose of supersensitization.

A dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion. For example,
Aminostyryl compounds substituted with a synthetic nitrogen heterocyclic group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (for example, described in US Pat. No. 3,743,510, etc.) ), Cadmium salt, azaindene compound and the like. U.S. Pat.Nos. 3,615,613, 3,615,641 and 3,617,29
The combinations described in No. 5 and No. 3,635,721 are particularly useful.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated and may be either one treated with an acid or both. Details of the method for producing gelatin are described in Arthur Weiss, The Macromolecular Chemistry of Gelatin, (Academic Press, 1964).

Surfactants may be added to the photographic emulsion used in the present invention alone or in combination.

Although they are used as coating aids, they are sometimes used for other purposes such as emulsion dispersion, improvement of sensitized photographic characteristics, antistatic, and adhesion prevention. These surfactants include natural surfactants such as saponins, nonionic surfactants such as alkylene oxides, glycerin and glycidols, higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, phosphonium or Cationic surfactants such as sulfonium, anionic surfactants containing carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester group, acidic group such as phosphoric acid ester group, amino acids, aminosulfonic acids, sulfuric acid or phosphoric acid esters of aminoalcohol And amphoteric activator.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines Thioketo compounds such as oxazoline thiones; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7 tetraazaindenes), pentaazaindenes, etc .; benzene Many compounds known as antifoggants or stabilizers such as thiosulphonic acid, benzenesulfinic acid, benzenesulphonic acid amide and the like can be added.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3 -Pyrazolidones may be included.

The photographic light-sensitive material of the present invention includes a photographic emulsion layer and other hydrophilic colloid layers for the purpose of improving dimensional stability.
It may include a dispersion of water insoluble or sparingly soluble synthetic polymer. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or these and acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

When the present invention is applied to a coupler type color photographic light-sensitive material, the coupler used may be any conventionally known one. Examples of magenta couplers include 5-pyrazolone couplers, birazolobenzimidazole couplers, pyrazoloimidazole couplers, pyrazolopyrazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, and closed acylacetonitrile couplers. Examples of couplers include acylacetamide couplers (for example, benzoylacetanilides and pivaloylacetolinides), and examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule or polymerized ones. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ions. Further, it may be a colored coupler having a color correcting effect, or a coupler releasing a development inhibitor with development (so-called DIR coupler).

In addition to the DIR coupler, the coupling reaction product may be colorless and may contain a non-colored DIR coupling compound which releases a development inhibitor. In addition to the DIR coupler, the light-sensitive material may contain a compound which releases a development inhibitor upon development.

The above couplers and the like can be used in combination in two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound in two or more different layers.

To introduce the above-mentioned dye-donor substance or the above-mentioned coupler into a light-sensitive material, a known method, for example, US Pat.
The method described in No. 7 is used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate),
Citric acid ester (for example, tributyl acetyl citrate), benzoic acid ester (for example, octyl benzoate),
Alkyl amides (eg diethyl lauryl amide), fatty acid esters (eg dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg tributyl trimesate), etc., or a boiling point of about
After being dissolved in an organic solvent at 30 ° C. to 150 ° C., for example, ethyl acetate, lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., Dispersed in hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

Further, a dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The photographic light-sensitive material in the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-). Triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycyclolic acid, etc.), etc. can be used alone or in combination.

In the light-sensitive material constituting the photographic element of the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like.

The light-sensitive material that constitutes the photographic element of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

The light-sensitive material constituting the photographic element of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, U.S. Pat. Nos. 3,214,794, 3,352,6).
81), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., those described in U.S. Pat.Nos. 3,705,805 and 3,707,375), butadiene compounds ( For example, U.S. Pat.
No. 045,229) or a benzooxide compound (for example, those described in US Pat. No. 3,700,455) can be used. UV absorbing couplers (eg cyan dye forming couplers of α-naphthol)
Alternatively, an ultraviolet absorbing polymer or the like may be used. These UV absorbers may be mordanted in a specific layer.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers in the present invention may be used alone or in combination of two or more kinds. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives and bisphenols.

When mentioning a conventional silver halide photographic light-sensitive material as the photographic element of the present invention, there is no particular limitation on the developing method, for example, known methods such as those described in Reseach Disccloue 176, pages 28-30, and Any known processing liquid can be applied. This photographic processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose. The treatment temperature is usually chosen between 18 ° C and 50 ° C, but below 18 ° C or 50 ° C
The temperature may exceed.

The polymer particles of the present invention are further used for a light-sensitive material and / or a dye-fixing material as a photographic element used in a color image forming method in which a dye that is imagewise diffusible is formed or released and then the dye is fixed. can do.

The color image forming method described above involves developing using a developer (color diffusion transfer method) (see, for example, Belgian Patent No.
No. 757,959), one which makes a diffusible hydrophilic dye image by heat development in a substantially water-free state (heat development method) (for example, European Patent No. 76492A2 and JP-A-58-79247,
No. 58-58543) and various other forms, and any of them can be applied.

As described above, the polymer particles in the present invention are used for the protective layer and back layer of the photographic light-sensitive material described above, and various other layers such as a light-sensitive layer, an intermediate layer, a dye-donor-containing layer, an image-receiving layer, and a white layer. It can be used as a reflection layer, a neutralization layer, a neutralization timing layer, and the like.

V Specific Action and Effect of the Invention According to the present invention, a photographic element having excellent photographic properties can be obtained.
This is because the polymer particles in the present invention do not adversely affect the photographic properties and, for example, as a matting agent, improve adhesiveness, paper feedability, transportability and the like, or impart an effect such as antistatic.

Further, in the process of manufacturing a photographic element, when the coating liquid containing the polymer particles of the present invention is used for coating, the coating can be carried out without any trouble, which facilitates the manufacturing. This is because the specific gravity of the polymer particles in the present invention is close to the specific gravity of the coating solution of the hydrophilic colloid such as gelatin which is usually used for photography, and thus it is difficult to settle.

VI Specific Examples of the Invention Hereinafter, the present invention will be described in more detail by showing specific examples of the invention.

Example 1 As described in Table 1, a double-sided polyethylene laminated paper was coated with the first layer (bottom layer) to the seventh layer (top layer). At that time, the matting agent of the present invention was added to the seventh layer as shown in Table 2 to prepare color photographic light-sensitive materials, and samples 101 to 103 were prepared.

An adhesion test was carried out after these samples were developed with the following processing solutions.

Developer Benzyl alcohol 15ml Diethylenetriamine pentaacetic acid 5g KBr 0.4g Na ₂ SO ₃ 5g Na ₂ CO ₃ 30g Hydroxyamine sulphate 2g 4-Amino-3-methyl-N-β- (methanesulfonamide) ethylanine ・ 3 / 2H ₂ SO ₄ · H ₂ O 4.5 g Water to 100 ml pH 10.1 Bleach-fixer Ammonium thiosulfate (70 wt%) 150 ml Na ₂ SO ₃ 5 g Na [Fe (EDTA)] 40 g EDTA 4 g Water 1000 ml pH 6.8 Treatment process temperature Time Image developer 33 ℃ 3 minutes 30 seconds Bleach-fix solution 33 ℃ 1 minute 30 seconds Water wash 28-35 ℃ 3 minutes <Adhesion resistance test> After the developed sample was dried, it was cut into 4 cm x 8 cm and 2
Set the sheets as one set, and after conditioning the humidity at 35 ° C, 90% RH for 24 hours, contact the protective layers of the same set of samples and apply a load of 500 g.
It was left at 90 ° C and 90% RH for 24 hours. Next, the load was removed, the protective layer was peeled off between the protective layers, and the area of the bonded portion (change in gloss) was calculated. The adhesion resistance was evaluated according to the following criteria.

Rank A Adhesive area is 0 to 40% B Adhesive area is 41 to 80% C Adhesive area is 81% or more or the adhesive strength is strong, and when peeling off the emulsion layer or part of the support To be

The results are shown in Table 2.

As is clear from Table 2, the samples containing the matting agent of the present invention have improved adhesion resistance.

Example 2 A silver halide emulsion layer having the following composition was coated on both sides of an undercoated polyethylene terephthalate film support having a thickness of 180 µ, and a protective layer having the upper and lower compositions was further coated thereon. Further, a back layer of gelatin 4 g / m ² and its protective layer were coated on the opposite side of the support and dried to prepare a black and white silver halide light-sensitive material. These are designated as samples 201 to 203.

(Emulsion layer) Thickness: about 5μ Silver iodobromide gelatin emulsion containing 1.5 mol% of silver iodide (average grain size of silver halide: 1.3μ) 0.6 mg of chloroauric acid and 3.4 mol of silver halide per mol Sodium thiosulfate (mg) was added and the mixture was heated at 60 ° C for 50 minutes for aging.

To the resulting emulsion was added 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer.

(Protective layer) Thickness: about 1 μ The composition and the coating amount are as follows.

Gelatin 1.0 g / m ² C ₁₂ H ₂₅ —OCH ₂ CH ₂ O ₁₀ H 60 mg / m ² 2,6-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² <Back protective layer> Samples 201 to 203 were prepared by adding a matting agent as shown in Table 3 to the same formulation as the protective layer of the emulsion layer.

<Adhesion resistance test> Each sample was cut into 4 cm x 4 cm pieces, and two pieces were made into one set.
After conditioning the humidity in% RH (relative humidity) for 24 hours, contact the back layer and protective layer of the same set of samples and apply a load of 1 kg.
It was left for 18 hours at ℃ and 75% RH. Next, the load was removed, the layer was peeled off between the back layer and the protective layer, and the area of the bonded portion (in the protective layer, the portion colored with the dye transferred from the back layer) was calculated. The adhesion resistance was evaluated according to the following criteria.

Rank A Adhesive area% 0-25% Rank B Adhesive area% 26-50% Rank C Adhesive area% 51-75% Rank D Adhesive area% 76% or more or adhesive strength Can not be peeled off strongly.

From Table 3, it can be seen that Samples 202 and 203 containing the matting agent of the present invention have excellent adhesion resistance.

Example 3 A dye fixing material 301 for a heat development / transfer image forming method having the constitution shown in Table 4 was prepared.

Oil Drops Preparation and Addition Method Oil prepared by adding 5 ml of a 5% aqueous solution of sodium dodecylbenzene sulfonate to 100 g of 10% gelatin aqueous solution, 20 g of liquid paraffin, and emulsifying and dispersing for 6 minutes at 10,000 rpm in a homoblender. The dispersion of the drops is applied to the dye fixing layer (first
Layer).

* 5) Hardener A * 6) Surfactant C * 7) Silicone oil drop * 4) was prepared in the same manner except that the liquid paraffin was changed to silicone oil (dimethylpolysiloxane).

* 8) Made by Nippon Shokubai Chemical Co., Ltd. On the other hand, a dye fixing material 302 was prepared in the same manner except that the matting agent was removed from the back layer of the dye fixing material 301.

Fifty sheets of each of these samples 301 and 302 were placed in the tray shown in FIG. 1 of Japanese Patent Application No. 61-73714, left for 3 days at 30 ° C. and 70% RH, and then the paper feed roller was driven. In the sample 302, 2-3 sheets were fed at the same time 16 times, but all the samples of the present invention could be fed one by one.

Claims (1)

[Claims] 1. A photographic element containing particles comprising a benzoguanamine-formaldehyde condensation polymer.