JPH0363730B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to photographic materials, and more particularly to photographic materials having a photographic layer consisting of a hydrophilic colloid on a support having a hydrophobic surface.
Conventionally, polyethylene terephthalate, cellulose triacetate, polystyrene, polycarbonate, polyolefin laminated paper, and the like have been widely used as photographic supports due to their excellent transparency and flexibility. However, when these polymeric substances are used as supports, since all of the supports have hydrophobic surfaces, it is difficult to firmly adhere a photographic layer made of hydrophilic colloids, mainly gelatin, onto these supports. is extremely difficult. Surface treatments of hydrophobic supports in conventional techniques attempted to overcome these difficulties include (1) chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, and glow treatment. (2) After surface activation treatment such as electrical discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., a photographic emulsion is directly applied to obtain adhesive strength. There are two methods, one is to provide an undercoat layer and then coat the photographic emulsion layer thereon. (For example, U.S. Patent Nos. 2,698,241, 2,764,520,
No. 2864755, No. 3143421, No. 3462335, No. 3475193,
No. 3615556, British Patent No. 788365, No. 804005,
No. 891469, etc.). Among these methods, method (2) is more effective and widely used. All of these surface treatments treat the originally hydrophobic surface of the support.
To some extent, surface adhesion is increased by creating polar groups, removing thin layers that are a negative factor for adhesion on the extreme surface, and increasing the crosslinking density on the surface to increase adhesion strength. It seems like something,
This is due to an increase in affinity with the polar groups of the components contained in the undercoat liquid, or
This may be due to an increase in the fastness of the adhesive surface. Various methods have also been used to apply the undercoat layer, such as providing a layer that adheres well to the support as the first layer, and coating a hydrophilic resin layer on top of it as the second layer. There is a gravimetric method and a single layer method in which only one resin layer containing both a hydrophobic group and a hydrophilic group is applied. All of these methods are well researched;
Examples include copolymers starting from monomers selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc., as well as polyethyleneimine and epoxy resin grafts. The suitability of many resins such as gelatin and nitrocellulose has been investigated. In particular, in order to perform the undercoating method entirely in an aqueous system to obtain sufficient adhesion between a hydrophobic support and a hydrophilic silver halide emulsion for practical use, vinylidene chloride copolymers, diene copolymers, etc. A merger is currently being considered. We have found that a copolymer containing a diene monomer as one component is effective as an undercoat component, either alone or in combination with an appropriate crosslinking agent, as a method for adhering the base and the emulsion layer. I came. (For example, JP-A-51-114120, JP-A No. 54-94025,
No. 55-65949) It is well known to apply a hydrophilic substance such as gelatin or a gelatin derivative to the primed base surface in order to obtain adhesive strength with the photographic emulsion layer. In this case, if the undercoated surfaces are left in contact with each other, a so-called blocking phenomenon tends to occur, and this tendency is particularly noticeable under high humidity and high pressure. To prevent this blocking, before applying the undercoat layer and rolling it up, apply a second undercoat liquid containing a so-called hardening agent such as formaldehyde or a matting agent in gelatin to apply a multilayer coating. There is a way to get it. A method that does not use the second undercoating liquid is the method described in JP-A-52-119919, in which the film thickness is limited to 0.25 to 1.0μ and the average particle size is 0.1 to 10.0μ. There is a method in which synthetic copolymer particles having a rearrangement temperature of 45° C. or higher are contained as a matting agent. However, these methods have many drawbacks. First of all, the disadvantages of using a matting agent are: (1) The transparency of the film is considerably reduced, resulting in defects in photographic quality. (2) Rolls that come into contact during the process from drying after undercoating to winding up, and then during the process of coating and winding up a photographic hydrophilic organic colloid layer such as a silver halide photographic emulsion layer. The matte agent transfers onto the surface. (3) During application and drying, these matting agents may form nuclei or cause non-uniformity in the physical properties of the undercoat such as surface tension, causing pinhole-like repellency or staining, making it difficult to use as a photographic film base. Loss of value (4) If the film is laminated under high humidity (60% RH or higher) and high pressure (1 Kg/cm ² or higher), it will not have a sufficient anti-blocking effect. These are harmful effects caused by the inclusion of a matting agent in either single-layer or two-layer coating. A method that does not use a matting agent is to include a hardener in the second layer, but these methods may have a large effect on photographic performance depending on the type and amount of the hardener contained, or may not meet the original mission of the undercoat. This method has the disadvantage of insufficient adhesion with the emulsion layer, and also has insufficient blocking prevention performance, so it cannot be said to be an effective method in practice. The present invention has been developed to overcome these drawbacks found in the prior art. The first object of the present invention is to prevent blocking without interfering with adhesion to the photographic emulsion layer or affecting photographic performance. Second, when a photographic hydrophilic organic colloid layer, such as a silver halide photographic emulsion and a back layer, is provided on the undercoat layer, it is effective in preventing blocking between these layers. The third object is to provide a blocking prevention method that does not involve coagulation or sedimentation in the undercoating solution and does not cause repelling or unevenness on the coated and dried base. Fourthly, it should form a uniform film and not adversely affect the transparency of the film. Fifth, the base coated with the base coat has an excellent anti-blocking effect even if it is left for a long time under adverse conditions such as high humidity and high pressure.
Sixthly, it is necessary to provide an undercoat surface with good coating properties for a photographic emulsion coating solution. The seventh object is to provide a blocking prevention method that does not stain the pass rolls in the undercoating process and emulsion coating process. A feature of the present invention is that an undercoat layer made of a polymer substance is provided on a hydrophobic support, and the undercoat layer has a degree of substitution of 0.5.
A second subbing layer containing ~2.5% water-soluble methylcellulose is provided. There are no particular structural restrictions on the polymer material placed on the hydrophobic support, but in the case of a polymer, the glass transition temperature is -
Preferably, the temperature is in the range of 20°C to 40°C. When this undercoat layer contains a dichloro-s-triazine derivative and/or an electrolyte,
The effect on the object of the present invention is even more significant. The present invention has made it possible to prevent blocking, which was conventionally impossible without the use of matting agents and hardeners, without impairing the properties of the undercoat or affecting the photographic performance. Conventionally, the use of matting agents has become mainstream as an effective means of preventing blocking, but as mentioned above, the use of matting agents impairs the transparency of the film and may damage the roll during the post-coating process. It inevitably has drawbacks such as getting dirty and not being able to sufficiently prevent blocking under adverse conditions of high humidity and high pressure. By not using a matting agent, the present invention not only solves the drawbacks associated with the use of a matting agent, but also prevents blocking. The present invention provides a photographic material characterized in that an undercoat layer made of a polymer substance is provided on a hydrophobic support, and a hydrophilic layer containing water-soluble methyl cellulose with a degree of substitution of 0.5 to 2.5 is provided on the undercoat layer. This is what we provide. Hereinafter, the constituent elements used in the present invention will be explained in detail. In the present invention, hydrophobic supports include, for example, cellulose ester (especially cellulose triacetate, cellulose diacetate, cellulose propionate), polyamide, polycarbonate, polyester (especially polyethylene terephthalate,
Films made of poly(1,4-cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate), polystyrene, polypropylene, polyethylene, etc., and these films on other supports such as paper. A composite film that is applied or laminated onto the body. Among them, polyethylene terephthalate film is most preferably used, especially biaxially stretched and heat-set polyethylene terephthalate film.
It is also advantageously used in terms of stability, toughness, etc. There is no particular limit to the thickness of the plastic film support, but a thickness of about 15 to 500 microns, especially about 40 to 200 microns, is advantageous in terms of ease of handling and versatility. Further, the support may be transparent, may contain a dye, may contain a pigment such as titanium dioxide, and may further include silicon dioxide, alumina sol,
It may contain chromium salt, zirconium salt, etc. In the present invention, a copolymer of diene monomers is preferably used as the polymer material provided on the hydrophobic support. Copolymers of diene monomers include butadiene,
A copolymer containing a diene monomer having 4 to about 8 carbon atoms, such as isoprene, as one component of the polymer. Copolymerization partners include, for example, styrene, acronitrile, acrylic esters, methacrylic esters (methyl, ethyl, butyl, propyl, etc.), vinyl ethers (methyl, ethyl, chloroethyl, butyl, etc.), vinyl esters (such as vinyl acetate, vinyl propionate, etc.), glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinylpyridine, tert-butylaminoethyl methacrylate, acrylic acid,
Methacrylic acid, crotonic acid, itaconic acid, itaconic acid half ester, maleic acid, maleic acid half ester, itaconic anhydride, maleic anhydride, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl Metal acrylate, 2-hydroxypropyl acrylate, monoallyl ether of polyhydric alcohol, acrylamide, methacrylamide, maleamide, N-methylol acrylamide, N-methylol methacrylamide and its ether, vinyl isocyanate, allyl isocyanate, etc. with 2 to about 2 carbon atoms 8 vinyl or vinylidene compounds. These are conveniently produced by emulsion polymerization techniques and are also available commercially. The amount of diene component in this copolymer is about 30 to 60% by weight, preferably 32 to 40% by weight. In addition, the copolymer contains amide, hydroxy,
A monomer having a hydrophilic moiety such as carboxy can be included in an amount of about 0.1 to 20% by weight. In addition, examples of the polymeric substance used in the present invention include copolymers or homopolymers having a glass transition temperature in the range of -20°C to 40°C. Examples of monomers used in the synthesis of such copolymers or pomopolymers include, for example, acrylic esters, acrylamides, methacrylic esters, methacrylic acids, allyl compounds, vinyl ethers, vinyl esters, vinyl Examples include heterocyclic compounds, N-vinyl compounds, styrenes, crotonic acids, itaconic acids, olefins, olefins, maleic anhydride, and the like. Specific examples of these include acrylic acids, such as acrylic acid, acrylates (such as ethyl acrylate, propyl acrylate, butyl acrylate, amine acrylate, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, -methoxyethyl acrylate, 2-
Butoxyethyl acrylate, 2-phenoxyethyl acrylate, chloroethyl acrylate,
Hydroxyethyl acrylate, cyanoethyl acrylate, hydroxypropyl acrylate,
Dimethylaminoethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, diethylene glycol monoacrylate, trimethylpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, 2-hydroxy-3-chloropropyl acrylate, benzyl acrylate , methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate): Methacrylic acids, such as methacrylic acid, methacrylates (such as methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, cyanoacetoxyethyl methacrylate, chlorbenzyl methacrylate, octyl methacrylate,
Sulfopropyl methacrylate, N-ethyl-N
-phenylaminoethyl methacrylate, ethylene glycol monomethacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate,
2,2-dimethyl-3-hydroxypropyl methacrylate, diethylene glycol monomethacrylate, trimethylolpropane monomethacrylate, pentaerythol monomethacrylate,
Glycidyl methacrylate, 2-methoxyethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc. ): Acrylamides, such as acrylamide, N
-Substituted acrylamide (e.g., methylacrylamide, ethylacrylamide, propylacrylamide, isopropylacrylamide, butylacrylamide, t-butylacrylamide, heptylacrylamide, t-octylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylamino Ethylacrylamide, hydroxyethylacrylamide, phenyl acrylamide, hydroxyphenylacrylamide, triacrylamide, naphthylacrylamide, dimethyl acrylamide, diethyl acrylamide, dibutylacrylamide, diisobutylacrylamide, diacetone acrylamide, methylbenzylacrylamide, benzyloxyethylacrylamide, β-cyanoethyl Acrylamide, acryloylmorpholine, N-methyl-N-acryloylpiperazine, N-acryloylpiperidine, acryloylglydine, N-(1,1-dimethyl-3
-hydroxybutyl)acrylamide, N-β-
Morpholinoethyl acrylamide, N-acryloylhexamethyleneimine, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide, etc.): Methacrylamides, such as methacrylamide,
N-substituted methacrylamide (e.g. methyl methacrylamide, t-butyl methacrylamide, t-substituted methacrylamide)
-Octylmethacrylamide, benzylmethacrylamide, cyclohexylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, dipropylmethacrylamide, hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide , N-ethyl-N-phenylmethacrylamide, etc.): Allyl compounds, such as allyl esters (such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate,
Allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyl exiethanol, allyl butyl ether, allyl glycidine ether, allyl phenyl ether, etc. Vinyl ethers, (such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl Vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-
Methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl Tolyl ether, vinyl chlorophenyl ether, vinyl-
2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthrani ether, etc.): Vinyl esters, such as vinyl acetate,
Vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl methyl propionate, vinyl ethyl butyrate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl menoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl acetoacetate,
Vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate,
Vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc.: Vinyl heterocyclic compounds, such as N-vinyloxazolidone, vinylpyridine, vinylpicoline, N
-vinylimidazole, N-vinylpyrrolidone,
N-vinylcarbazole, vinylthiophene, N
-Vinylethylacetamide, etc.: Styrenes (e.g. styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene,
Cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene,
Acetoxymethylstyrene, methoxystyrene,
4-methoxy-3-methylstyrene, dimethoxystyrene, chlorstyrene, dichlorostyrene,
Trichlorstyrene, tetrachlorstyrene, pentachlorstyrene, bromstyrene, dibrostyrene, iodostyrene, fluorostyrene,
Trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, vinylbenzoic acid, vinylbenzoic acid ethyl ester, etc.): Croton types,
For example, crotonic acid, crotonic acid amide, crotonic ester (e.g. butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.) Vinyl ketones (e.g. methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.) Olefins (For example, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene,
5-methyl-1-nonene, 5,5-dimethyl-1
-octene, 4-methyl-1-hexene, 4,4
-dimethyl-1-pentene, 5-methyl-1-hexene, 4-methyl-1-heptene, 5-methyl-1-heptene, 4,4-dimethyl-1-hexene, 5,6,6-trimethyl-1 -Heptene, 1
-dodecene and 1-octadecene), itaconic acids (such as itaconic acid, itaconic anhydride,
methyl itaconate, ethyl itaconate), crotonic acids (e.g. crotonic acid, methyl crotonate,
ethyl crotonate), sorbic acid, cinnamic acid, methyl sorbate, glycidyl sorbate, citraconic acid, chloroacrylic acid, mesaconic acid, maleic acid, fumaric acid, ethacrylic acid, halogenated olefins (e.g. vinyl chloride, vinylidene chloride, isoprene, etc.), unsaturated nitriles (for example, acrylonitrile, methacrylonitrile, etc.). The polymer may be a copolymer composed of two or more types of monomers. Examples of such copolymers include styrene/n-butyl acrylate/acrylic acid copolymers, styrene/n-butyl acrylate/glycidyl acrylate copolymers, and the like. In order to apply the aqueous dispersion of the polymer thus obtained as an undercoat, the aqueous dispersion is further diluted with water, and if necessary, a crosslinking agent, a surfactant, a swelling agent,
Hydrophilic polymers, matting agents, antistatic agents, electrolytes, etc. can be added. The content of the polymer according to the present invention in the undercoating liquid is 1 to
It is preferably 20% by weight, especially 2 to 13% by weight. As a crosslinking agent, for example, US Pat. No. 3,325,287;
No. 3288775, No. 3549377, Belgian patent no.
Triazine compounds described in US Pat. No. 3,291,624, US Pat. No. 3,232,764, French Patent No.
1543694, dialdehyde compounds described in British Patent No. 1270578; US Patent No. 3091537,
Epoxy compounds described in US Pat. No. 49-26580, etc.; vinyl compounds described in US Pat. No. 3,642,486; aziridine compounds described in US Pat. No. 3,392,024; ethyleneimine compounds described in US Pat. No. 3,549,378, etc.; and methylol compounds. Among these compounds, examples of dichlorotriazine derivatives include the following formula:

[expression] or/and

[A: alkyl group, cyclic alkyl group, aryl group, aralkyl group, metal, hydrogen atom R ₁ / R ₂ : hydrogen, alkyl group, cyclic alkyl group, aryl group, aralkyl group, -NHR ₃ (R ₃ alkyl , acyl group) R ₁ and R ₂ may be bonded to each other, or may form a 5- to 6-membered ring containing O, S, and N-R ₄ (R ₄ alkyl group). There is a dichloro-S-triazine derivative represented by These amounts can range from 0.01% to 200% by weight based on the weight of the polymer. Specific examples of these dichloro-S-triazine derivatives include those shown below. Among these crosslinking agents, 2,4-dichloro-6-hydroxy-S-triazine sodium salt is preferably used. There is no particular need to add a swelling agent, for example, phenol, resorcinol, etc. may be added, and the amount added is 1 to 10 g per 1 base coating liquid. Hydrophilic polymer compounds include natural polymer compounds such as gelatin, polyvinyl alcohol, vinyl acetate-maleic anhydride copolymer, acrylic acid-acrylamide copolymer, styrene-maleic anhydride copolymer, etc. Examples include polymers. As the antistatic agent, anionic or cationic surfactants, inion-based polymers, maleic acid-based copolymers described in JP-A No. 49-3972, etc., colloidal silica (for example, Snotex manufactured by Nissan Chemical Co., Ltd.), etc. are used. I can do it. Examples of electrolytes include HCl, HBr, HClO ₄ , LiCl, LiBr, LiI, LiCl ₄ , NaCl, NaBr, NaI, NaClO ₄ , NaNO ₃ , NaOH, KCl, KBr, KI, KNO ₃ , NH ₄ Cl, RbCl, RbBr, RbI, _MgCl2 , _MgBr2 , _MgI2 , _CaCl2 , _CaBr2 , _CaI2 , Ca( _ClO4 ) ₂ , _SrCl2 , Sr( _ClO4 ) ₂ , _BaCl2 , _BaBr2 , _BaI2 , _AlCl3 , LaCl ₃ , Zn(ClO ₄ ) ₂ , etc. These electrolytes can exhibit an antistatic effect, and the amount added is 0.001 mg to 100 mg, preferably 0.1 mg to 10 mg per m ² . In addition, in the present invention, it is possible to prevent blocking without using a matting agent.The first undercoat layer and/or the second undercoat layer containing a copolymer is used for purposes other than preventing blocking (improving slipperiness, etc.). It is also possible to use a matting agent in the undercoat layer. The first and second undercoat liquids according to the present invention can be applied by a generally well-known coating method, such as a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or It can be coated by the extrusion coating method using a hopper as described in US Pat. No. 2,681,294. If necessary, the method described in U.S. Pat. Layers can be applied simultaneously. The coating amount of the first undercoat polymer according to the present invention is preferably from 0.01 to 10 g, particularly from 0.2 to 3 g, as a solid content, per square meter of the plastic support. Next, the second undercoat liquid, which is an important part of the present invention, will be described. The second undercoat liquid in the present invention preferably contains a hydrophilic polymer compound as a binder, which makes both the first undercoat layer described above and the photographic emulsion layer described below adhere to each other. When a binder is contained, the weight ratio of methyl cellulose per binder is about 1% to 99%, preferably about 2% to 50%, more preferably about 3% to 30%. The degree of substitution of methylcellulose used is from 0.5 to 2.5, but more preferably from 1.0 to 2.5, which provides an excellent anti-blocking effect, but if it exceeds 2.5, the object of the present invention will not be achieved. (The degree of substitution is explained in "Encyclopedia of polymer science and technology" Volume 3, page 460 (published in 1965), and the method for its analysis is described on page 509 mentioned above.) Degree of polymerization of methylcellulose can be appropriately selected depending on the coating method and its relationship with viscosity. However, the degree of polymerization is preferably 70 to 800. A remarkable feature of the present invention is the discovery that the object of the present invention can be efficiently achieved by using methylcellulose, which has a degree of substitution within a specific range of 0.5 to 2.5, among cellulose derivatives as water-soluble polymer compounds. It is at the point. In particular, when the methylcellulose of the present invention is used, it is significantly effective against blocking when the first undercoat layer contains an electrolyte. The methylcellulose used here may be etherified or esterified with other than methoxy groups, such as hydroxyprokyl groups, carboxybenzoyl groups, etc., without any problem. Such methylcellulose is commercially available from Shin-Etsu Chemical Co., Ltd. under the following name and can be easily obtained. Metrose SM-15, Metrose 60SH-50, Metrose 60SH-4000, Metrose 65SH-50, Metrose 90SH-100 For their synthesis methods and properties, please refer to Shin-Etsu Chemical's product catalog "Metrose" and Cellulose and Cellulose Derivatives No. 1. ~5, detailed in Ott.E et al. Methylcellulose can be produced by methylating cellulose with a 18-35% NaOH solution and dimethyl sulfate, and then repeating this methylation procedure to obtain a highly methylated sample, or by combining alkali cellulose and methyl chloride in an autoclave. There are ways to react. Examples of the hydrophilic polymer compound in the present invention include gelatin, acylated Zlatin such as phthalated gelatin and maleated gelatin, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, and gelatin grafted with acrylic acid, methacrylic acid or amide. Grafted gelatin, polyvinyl alcohol, polyhydroxyalkyl acrylate, polyvinylpyrrolidone, copolyvinylpyrrolidone-vinyl acetate, casein, agarose, albumin, sodium alginate, polysaccharide, agar, starch, grafted starch, polyacrylamide, polyethyleneimine acylated product Alternatively, a synthetic or natural hydrophilic polymer compound such as acrylic acid, methacrylic acid acrylamide, N-substituted acrylamide, N-substituted methacrylamide, etc. alone or a copolymer, or a partial hydrolyzate thereof may be used. These materials can be used alone or in combination. A preferred hydrophilic polymer compound is seratin or a gelatin derivative. As long as the above-mentioned hydrophilic polymer compound is used as a binder and water-soluble methylcellulose with a degree of substitution of 0.5 to 2.5 is contained, it is not important to the present invention what is added therein, and if necessary, it can be charged. An inhibitor, a crosslinking agent, etc. can be used. Next, the photographic layer used in the present invention will be briefly described. Binder for the photographic layer (hydrophilic organic protective colloids include gelatin, acylated gelatin such as phthalated gelatin and maleated gelatin, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, acrylic acid, methacrylic acid, or amide) to gelatin. Grafted gelatin, polyvinyl alcohol, polyhydroxyalkylarylate, polyvinylpyrrolidone, copolyvinylpyrrolidone-vinyl acetate, casein, agarose, albumin, sodium alginate, polysaccharide, agar, starch, grafted starch, polyacrylamide, Synthetic or natural hydrophilic polymer compounds such as polyethyleneimine acylation, single or copolymers of acrylic acid, methacrylic acid acrylamide, N-substituted acrylamide, N-substituted methacrylamide, or partial hydrolysates thereof These compounds can be used alone or in combination.As long as the binder is a hydrophilic polymer compound as described above, what is added therein is not particularly important in the present invention. However, these hydrophilic binders include physical development nuclei such as silver halide or silver sulfide used in diffusion transfer photography, as well as sensitive materials such as diazo compounds, various additives, couplers, emulsion polymerization, and latex polymers. Although not necessarily required for the present invention, surface treatment such as corona discharge treatment is carried out on the hydrophobic substrate and/or the subbing layer made of a polymeric substance and/or on the second layer. It may be applied from above the undercoat layer, and in that case, the adhesive strength of the layer before and after the treatment is improved.The present invention will be explained in more detail with reference to Examples below, which will explain the embodiments of the present invention. However, the present invention is not limited to this. Before describing the examples, various test methods will be explained. [Evaluation method of blocking]

After leaving the primer film in an atmosphere of 23°C ± 3°C and 80 ± 5% RH for 3 hours, remove the film to 35mm.
Cut the pieces into 35mm x 35mm pieces, stack 5 sets of 2 pieces on top of each other, and leave them for 21 hours under the same atmosphere under a load of 84kg. Take it out, peel off the film, and measure the blocking area. 3.5mm×3.5mm
is regarded as one frame, and ranks are set from A to E depending on how many blocks are blocked out of the total 100 frames. Values are shown as the average of 5 sets. Number of frames 0-5
If it is less than 5, it is class A, if it is between 5 and 10, it is class B, if it is between 10 and less than 20, it is class C, if it is between 20 and less than 30, it is class D, and if it is 30 or more, it is class E. As long as the product is within class B, it is sufficient to withstand use. For those in classes C to D, blocking may occur depending on the drying conditions at the time of coating, winding conditions of the film base, storage conditions, etc. E
class produces significant blocking. [Method for evaluating adhesion between film support and emulsion layer] Emulsion coating method and processing (development, fixing, washing)
For the subsequent adhesion test, use a knife to make 6 vertical and horizontal cuts at 3-5 mm intervals, making 5 x 5 squares.
Apply tape to this area, peel it off, and count the number of squares in the peeled emulsion layer. Those with 0 squares are classified as A class, those with 1 to 2 squares are classified as A' class, and 3 to 4.
Those below are classified as B class, and those below this are classified as C class. For the adhesion test in the processing solution, the end of the emulsion coating base was rubbed 15 times with a finger, and the length peeled from the end was 0 mm as class A, 1 to 2 mm as class A', 2 to 4 mm as class B. Anything below this is class C. The test was carried out using a plate development method using LDS-715 (manufactured by Fuji Photo Film Co., Ltd.) as a developing solution and LF-308 (manufactured by Fuji Photo Film Co., Ltd.) as a fixing solution. In these evaluation methods, materials that can be used as photographic materials are in classes A to A'. Example 1 A biaxially stretched polyethylene terephthalate film with a thickness of 100 μm was subjected to a corona discharge treatment, and a first undercoating liquid having the composition shown below was coated with a wire bar so that the coating amount was approximately 6 c.c./m ² . It was applied using a coater and dried at 140°C for 1 minute. Next, a first undercoat layer was provided on the opposite side in the same manner. Butadiene-styrene copolymer Latetex (solid content 43% butadiene/styrene weight ratio = 32/68
13c.c. 8% solution of 2,4-dichloro-6-hydroxy-S-triazine sodium salt 7c.c. 1% aqueous solution of sodium laurylbenzenesulfonate 1.6cc Distilled water 80c.c. First undercoat on both sides of the above The second undercoating liquids 1 to 7 having the compositions shown below are applied to each side of the layer at a coating amount of about 9 c.c./m ² and dried to form 7 types of coated films (undercoated). A support body) was prepared. Second undercoat composition 1 Gelatin 0.7g Methylcellulose (Metrose SM15 Substitution degree
1.79-1.83) 0.3g Acetic acid (concentration 99%) 0.02ml Distillates 99ml Second undercoat composition 2 Gelatin 0.9g Methylcellulose (Metrose SM15 Degree of substitution
1.79-1.83) 0.1g Acetic acid (concentration 99%) 0.02ml Distilled water 99ml Second undercoat composition 3 Gelatin 0.9g Methyl cellulose (degree of substitution 2.6) 0.1g Acetic acid (concentration 99%) 0.02ml Methanol 30ml Distilled water 69ml 2nd undercoat composition 4 Gelatin 0.7g Methylcellulose (degree of substitution 2.6) 0.3g Acetic acid (concentration 99%) 0.02ml Methanol 30ml Distilled water 69ml 2nd undercoat composition 5 Gelatin 0.9g Methylcellulose (degree of substitution 0.8) 1.0g NAOH 0.2g Distilled water 99ml Second undercoat composition 6 Gelatin 0.7g Methyl cellulose (degree of substitution 0.8) 0.3g NaOH 0.2g Distilled water 99ml Second undercoat composition 7 Gelatin 1g Acetic acid (concentration 99%) 0.02ml Distilled water 99ml First undercoat on both sides Seven types of coated films provided with a coating layer and a second undercoat layer were evaluated for blocking. The results obtained are shown in Table-1. Next, a silver halide emulsion layer having the following formulation (1) was coated on one side of the seven types of coated films so that the dry thickness was 6.0 μm and the coated silver amount was 5.0 g/m ² . Further, on the silver halide emulsion layer, a protective layer with the following formulation (2) was applied, and on the opposite side, a gelatin back layer was applied according to the following formulation (3) to a dry thickness of 5 μm.
Various types of photographic materials were produced. Prescription - (1) Silver halide emulsion prescription Gelatin 5g/m ² Silver chloroiodobromide (Cl: 80 mol% Br: 19.5 mol%
I: 0.5 mol%) Chloroauric acid 0.1 mg/m ² Polyethyl acrylate latex (same as used in Example 3 of US Pat. No. 3,525,620) 1.59 g/m ² Sensitizing dye 3-allyl -5-[2-(1-ethyl)
-4Methyl-2tetrazoline-5ylidene-ethylidene rhodanine 6mg/ ^m2 Antifoggant 4-hydroxy-6-methyl-
1,3,3a-7-sotrazaindene 30mg/m ² polyoxyethylene compound 20mg/m ² Gelatin hardening agent 2-hydroxy-4,6-dichloro-S-triazine sodium salt 60mg/m ² Surfactant Sodium p-dodecylbenzenesulfonate 40mg/m ² Prescription - (2) Protective layer formulation gelatin 1g/m ² Matting agent Polymethyl methacrylate with average particle size 3.0-4.0μ 0.05/m ² Surfactant Sodium p-dodecylbenzenesulfonate 0.03g/m ² Seratin hardening agent 2-hydroxy-4.6-dichloro-S- Triazine Sodium Salt 0.01g/m ² Formulation-3 Back Layer Formulation Gelatin Gelatin Hardener Matting Agent ^* 0.03g/m Shown in Table 1. Polymer latex ^** 50/100g gelatin Dye ^*** 0.3g/m ² * Same as the protective layer ** Same as the silver halide emulsion layer *** The following dyes (1): (2): (3 )=1:1:1 mixture The seven types of photographic materials obtained were evaluated for adhesion between the film support and the photographic emulsion layer. The results are shown in Table-1.

[Table] The results of the blocking evaluation show that the coated film using methylcellulose of the present invention has excellent blocking resistance. This base with good blocking properties also had good blocking resistance between these surfaces after a photographic emulsion layer and a back layer were coated thereon. The coated film obtained according to the present invention has excellent adhesion with the photographic emulsion layer, photographic properties,
It had no effect on Hayes. Example 2 A biaxially stretched polyethylene terephthalate film with a thickness of 100 μm was subjected to corona discharge treatment, and a first undercoating liquid having the composition shown below was applied so that the coating area was approximately 6 c.c./m ² . Dry, base coat thickness approx.
A first subbing layer of 0.2-0.4μ was obtained. Similarly, a first undercoat layer was provided on the opposite side. Butadiene-styrene copolymer latex (solid content 43% butadiene/styrene weight ratio = 32/
68) 13c.c. Vinyl sulfone compounds 0.5 g 1% aqueous solution of sodium laurylbenzenesulfonate 1.6 cc 1% aqueous solution of NaCl 5 ml Apply the second undercoating liquids 1 to 7 used in Example 1 on each side of the first undercoat layer on both sides and dry. did. 7 with a first undercoat layer and a second undercoat layer on both sides
Blocking tests were conducted on various coated films. Further, an emulsion layer, a protective layer and a back layer were provided on the coated film in the same manner as in Example 1 to prepare a photographic material, and the adhesion between the film support and the photographic emulsion layer was evaluated. These results are shown in Table-2.

[Table] The results of the blocking evaluation show that the coated film using methylcellulose of the present invention has excellent blocking resistance. The coated film obtained according to the present invention had no adverse effect on adhesion with the photographic emulsion layer, photographic properties, or haze. Example 3 A first undercoat layer and a second undercoat layer were applied on both sides in the same manner as in Example 2.
An undercoat layer was applied and dried to obtain a coated film. However, at this time, NaCl was removed from the first undercoating solution. A photographic material was produced in the same manner as in Example 1 using the obtained coated film. Next, a blocking test of the coated film and an evaluation of the adhesion of the photographic material were conducted. The results are shown in Table-3.

【table】

[Table] The results of the blocking evaluation show that the coated film using methylcellulose of the present invention has excellent blocking properties. The coated film obtained according to the present invention had no adverse effect on adhesion with the photographic emulsion layer, photographic properties, or haze.

Claims (1)

[Claims] 1. A first undercoat layer made of a polymeric substance is provided on a hydrophobic support, and a hydrophilic layer containing water-soluble methylcellulose with a degree of substitution of 0.5 to 2.5 is provided on the undercoat layer as a second undercoat layer. A photographic material characterized by providing.