JPH0612415B2 - Photographic material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photographic material having a flame-retardant support.

[Prior Art] Conventionally, a pattern material such as a printed plywood or a window curtain used for a wall layer is produced by a printing method. The production of the pattern material by the printing method is advantageous in terms of cost for replicating a large number of similar objects, but it cannot be said that it is advantageous for cost in the case of a small number of replicas according to the customer's order. Therefore, recently, a method of applying a photographic print image as a pattern material has been tried when a small number of similar patterns are duplicated.
That is, a photograph printed on a general photographic printing paper is used as a panel photograph or attached to a cloth surface. However, the conventional photographic printing paper easily burns because the support is paper, and it is not preferable for fire safety to use the photographic printing paper by converting it into a wall layer or a window curtain.

Various techniques have been proposed to overcome this drawback.
Japanese Utility Model Publication No. 61-42541 discloses a photographic printing material having a flexible cloth-like body woven using glass fibers as a support. In the same publication, a cloth woven using glass fibers is coated with a thin film of vinyl chloride, polyester or the like, and a photosensitive silver halide layer is coated. However, since a thin film made of vinyl chloride, polyester, or the like is difficult to adhere to a fabric woven using glass fibers, it has a drawback that it is easily peeled off.

Japanese Utility Model Publication No. 59-18446 discloses that a polyolefin resin is adhered to and coated on a fabric woven using glass fibers through an adhesive composed of an aqueous solution of polyvinyl alcohol and a hydrophobic solution of an isocyanate compound. Is listed.

Conventionally used glass fiber substrates are glass fibers spun with starch as a sizing agent, which are woven, and the sizing agent is incinerated and removed.

However, such a photographic material has a drawback that the processing liquid permeates from the cut surface in the processing step, and the permeated processing liquid is carried into the processing liquid of the next step and deteriorates the processing liquid of the next step. There is. Further, the treatment liquid that has penetrated into the cloth causes discoloration, fading, etc. of the finished photographic image. Also,
Such a glass fiber substrate also has the drawback of low tensile strength and tear strength.

[Problems to be Solved by the Invention] A first object of the present invention is a flame retardant, high tensile strength and tear strength, wall layer, window curtain, accordion.
To provide a photographic material suitable for a pattern material such as a curtain.

A second object of the present invention is to provide a photographic material which is less likely to undergo discoloration or fading and which is suitable for pattern materials such as wall layers, window curtains and accordion curtains.

[Constitution of the Invention] An object of the present invention is to provide a photographic material in which a photosensitive layer is coated on a support in which a glass fiber substrate is coated or filled with a polymer substance, and the glass fiber substrate is sized by a sizing agent for glass fibers. A glass fiber substrate obtained by weaving or paper-making glass fiber, wherein the sizing agent for glass fiber has a property of leaving a viscous liquid when water evaporates, and has a viscosity of 1 to 400 poises. This can be achieved by a photographic material which is a sizing agent for glass fibers in which a synthetic resin liquid that is non-curable at room temperature, a Gappling agent and a cationic lubricant are dispersed in water.

The synthetic resin liquid for the sizing agent used in the present invention, a non-curable unsaturated polyester resin containing no curing agent diallyl phthalate, a solution of styrene or the like,
Alternatively, a resol-type phenol / formaldehyde resin emulsion (cured when heated but not at room temperature) can be used. In particular, it has at least two epoxy groups in the molecule and has an epoxy equivalent of 10
A water-dispersed emulsion of a non-curable epoxy resin containing 0 to 400 and a viscosity of 1 to 400 poise and containing no curing agent is effective.

As the coupling agent, various silanes and methacrylate chromic chloride (borane) can be used.

As a cation lubricant, tetraethylenepentamine-pelargonic acid condensate solubilized with acetic acid (trade name: Arco 185A, manufactured by Arnold Hoffmann), 5 nitrogen atoms
-Tetraethylene pentamine fatty acid condensate substituted with allyl methallyl side chain (trade name Arco 220, manufactured by Arnold Hoffmann), acetic acid-solubilized tetraethylene pentamine stearic acid condensate (trade name Cationics X, Onyx oil) And Chemical Co., Ltd.) and the like can be used.

In the present invention, the polymer materials used for coating or filling the glass fiber substrate include the following.

(1) Polyvinyl chloride resin (emulsion type) (trade name: GE-576, manufactured by Nippon Zeon Co., Ltd.) (2) Polyvinyl chloride-vinyl acetate copolymer (emulsion type) (trade name: Vinyl Blanc 375, trade name VinylBran 625V, manufactured by Nissin Chemical Industry Co., Ltd. (3) Vinyl acetate resin (emulsion type) (trade name Ricabond AW-141, manufactured by Chuo Rika Co., Ltd.) (4) Ethylene-vinyl acetate copolymer resin ( Emulsion type (trade name: Ricabond BE800, Chuo Rika Kogyo Co., Ltd.)
Product name: Sumikaflex 400 Sumitomo Chemical Co., Ltd. (5) Ethylene-vinyl chloride copolymer resin (emulsion type) (Product name: Sumielite 1010, Sumitomo Chemical Co., Ltd.)
(6) Polyvinylidene chloride resin (emulsion type) (Parasol CA, Ohara Palladium Chemical Co., Ltd.)
(7) Polyester resin (aromatic type) (emulsion type) (Brand name Finetex ES-675, Finetex ES-525, manufactured by Dainippon Ink and Chemicals, Inc.) (8) Acrylic resin (aqueous) ( Emulsion type (trade name: Polysol F-361, Showa Highpolymer Co., Ltd.)
(9) Acrylic resin (oil-based) (solution type, solvent: toluene) (Brand name Toa Akron XE-1345, manufactured by Toa Paint Co., Ltd.) (10) Polyurethane resin (water-based) (emulsion type) (Brand name Merci -535, manufactured by Toyo Polymer Co., Ltd. (11) Polyurethane resin (oil-based) (solution type, one-component type,
(Solvent: MEK / DMF) (trade name: Rezamine ME-3705LP-2, manufactured by Dainichiseika Kogyo Co., Ltd.) In addition to the above, use of an oily type of vinyl acetate type, vinyl chloride type, polyester type resin You can

As the flame retardant used in the present invention, antimony trioxide,
Examples thereof include zircon oxide, aluminum hydroxide and the like.

In the present invention, the sharpness of the image and the whiteness of the background color are increased,
In addition, a white pigment can be filled in the polymer substance so as to have a light shielding property. Examples of white pigments include titanium dioxide, zinc oxide, barium sulfate, silicon dioxide, calcium sulfate, calcium carbonate, talc, clay, antimony trioxide and the like. Among them, titanium dioxide having an excellent hiding power is preferable. This titanium dioxide is produced by a sulfuric acid method or a chlorine method, and further hydrous aluminum and / or hydrous silicon dioxide is precipitated on the titanium dioxide for modification. The crystal form of titanium dioxide may be either a lithyl type or an anatase type, or a blend of both. The hydrated aluminum is used in an amount of 0.1 to 8% by weight, preferably 0.5 to 3% by weight, based on titanium dioxide. Hydrous silicon dioxide is used in an amount of 0.1 to 10% by weight, preferably 0.5 to 4% by weight, based on titanium dioxide. Further, in order to improve the dispersibility of titanium dioxide, titanium dioxide whose surface is coated with various surfactants may be used.
Various types of titanium dioxide are commercially available. For example, as anatase titanium dioxide, trade name TYPEK A-220, manufactured by Ishihara Sangyo Co., Ltd. can be used.

The glass fiber substrate used in the present invention may be a cloth-like woven fabric such as a plain weave, a twill weave, a lattice weave, or a one-way weave obtained by twisting glass fibers spun using the sizing agent of the present invention. It may be a paper-like material produced by using glass fibers sized by the sizing agent.

In the present invention, in order to improve the adhesion between the support and the photosensitive layer, halogenation is carried out on the support through the undercoat layer described in JP-B-38-5792 and 41-7311. You may coat a silver photosensitive layer. Gelatin is preferred as the binder for the undercoat layer. It is more preferable to include the resin emulsion in gelatin. Also,
In addition to the corona discharge treatment described in JP-B No. 31-9411, UV irradiation treatment, electron impact treatment, and other methods are used to hydrophilize the surface of the polymer material to form a silver halide photosensitive layer. May be. In addition, potassium permanganate,
The surface can be made hydrophilic by using an oxidizing agent such as concentrated sulfuric acid, and these methods can be used in combination.

As the photosensitive component used in the present invention, silver halide emulsions such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver iodochlorobromide can be used. Silver halide emulsion,
P. P.Glafkides, Chimie et Physique Phot
ographique, published by Paul Montel (19
67), Photographic emulsion (Photograp
hic Emulsion), Focal Press
Published by the company (1966), V.I. L. VL Zelikman,
Making and Coating Photographic E
mulsion), published by The Focal Press (1964), and the like. In the present invention, any of the acidic method, the neutral method, the ammonia method and the like may be used. As the method of reacting the soluble silver salt with the soluble halogen, any of a single jet method, a double jet method and a triple jet method may be used. A halogen conversion method may be used.

The crystal structure of the silver halide grains of the silver halide emulsion used in the present invention is a uniform silver halide grain, a so-called core-shell silver halide grain having a layered structure in which the inside and the outside are heterogeneous (for example, Japanese Patent Application No. 62-289993
No.), epitaxial silver halide grains (JP-A-59-
133540). Further, the latent image may be mainly formed on the surface of the silver halide grain or may be mainly formed inside the silver halide grain.

The grain size of silver halide grains of the silver halide emulsion used in the present invention is not limited, but is preferably 0.7 μm or less. The silver halide grains may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, a spherical or plate-like crystal form, or a mixture of these crystal forms. May consist of

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt thereof, rhodium salt or complex salt thereof, iron salt or iron complex salt may coexist.

The silver halide emulsion used in the present invention usually removes soluble salts after precipitation formation or physical ripening. As a means therefor, a Nudel washing method which is a gelation of gelatin known from old times is used. In addition, inorganic salts composed of polyanions (eg sodium sulfate), anionic surfactants, anionic polymers (eg polystyrene sulphonic acid), gelatin derivatives (eg aliphatic acylated gelatin, aromatics) A precipitation method (flow cholation) using acylated gelatin, aromatic carbamoyl pergelatin, etc. may be used.

For the silver halide emulsion and the non-photosensitive hydrophilic colloid used in the present invention, a hydrophilic colloid usually used for silver halide emulsions can be used as a binder. Examples thereof include gelatin, gelatin derivatives, colloidal albumin, casein, carboxymethyl cellulose derivatives, agar, sodium alginate, polyvinyl alcohol, poly-N-vinylpyrrolidone polymers and the like. You may use these in mixture of 2 or more types as needed. Particularly preferred hydrophilic colloids are gelatin and derivative gelatin. As for gelatin,
Examples thereof include lime-processed gelatin, acid-processed gelatin, gelatin hydrolyzate and gelatin enzyme hydrolyzate. Derivative gelatins are described in U.S. Pat. No. 2,614,928 and JP-A-46-5182.
Examples include reaction products of gelatin with acid anhydrides, isocyanates, and compounds having active halogen. Examples of acid anhydrides include maleic anhydride, phthalic anhydride, benzoic anhydride, acetic anhydride, succinic anhydride, and the like. Isocyanate compounds include phenyl isocyanate, p-tolyl isocyanate, naphthyl isocyanate, and the like, and compounds having active halogens. , Benzenesulfonyl chloride, p-toluenesulfonyl chloride, m-carboxybenzenesulfonyl chloride, 2,4-dichloro-6-hydroxy-s-triazine / sodium salt and the like.

The silver halide emulsion used in the present invention is preferably chemically sensitized. For chemical sensitization, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a noble metal sensitization method using a noble metal compound such as gold, or a reduction sensitization method using a reducing substance is used. , And can be used alone or in combination. Regarding this, P. It is described in Grafficides, Simi et Physic Photographic.

Examples of the sulfur sensitizer include thiosulfates (for example, sodium thiosulfate and potassium thiosulfate), isothiocyanates (for example, allyl isothiocyanate), thiocyanates (for example, potassium thiocyanate, ammonium thiocyanate), thioureas, and thiazoles. , Rhodanine and the like can be used. Noble metal sensitizers such as gold, platinum, iridium, palladium, etc.
Complex salts of Group VIII metals can be used. Among these noble metal sensitizers, the gold sensitizer is particularly effective. Examples of the gold sensitizer include chloroauric acid salts (eg, sodium chloroaurate, potassium chloroaurate). Examples of reduction sensitizers include stannous salts, amines, formamidinesulfinic acid, silane compounds and the like.

The silver halide emulsion used in the present invention may contain an antifoggant. Antifoggants are 1, 2, 3
-Triazole compound (for example, benzotriazole), 1,2,4-triazole compound substituted in 3-position, 2-mercaptobenzimidazole compound, 2-mercaptopyrimidine compound, 2-mercaptobenzothiazole compound, benzothiazolium Compound (for example, N-alkylbenzothiazolithium halide, N-allylbenzothiazolium halide), 2-mercapto-1,3,4-thiadiazole compound, 5-mercaptotetrazole compound (for example, 1-phenyl-
Examples thereof include 5-mercaptotetrazole), sulfinic acid compounds (for example, sodium benzenesulfinate), tetrazaindene compounds (for example, 4-hydroxy-6-methyl-1,3,3a, 7-teratotheindene), and the like.

The silver halide emulsion used in the present invention may be spectrally sensitized with a sensitizing dye. Examples of the sensitizing dye include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol. Particularly preferred dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. For these dyes, the nuclei usually used for cyanine dyes can be used as the basic heterocyclic nucleus. 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, a nucleus in which an aliphatic hydrocarbon ring nucleus is fused to these nuclei, and an aromatic hydrocarbon ring nucleus is fused to these nuclei. The above-mentioned nuclei, that is, indolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be used. These nuclei may have a substituent on a carbon atom. The merocyanine dye or the complex merocyanine dye contains pyrazoline-containing nuclei having a ketomethylene structure.
Use 5- to 6-membered heterocyclic nuclei such as 5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus be able to.

In the silver halide emulsion used in the present invention, a water-soluble dye can be used as a filter dye or an anti-irradiation dye for various other purposes. Examples of such dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes, cyanine dyes, and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are preferred.

The silver halide emulsion and the non-photosensitive hydrophilic colloid used in the present invention preferably contain an inorganic or organic hardener. As a hardening agent, a chromium salt (for example, chromium alum, chromium acetate), an aldehyde compound (for example, formaldehyde, glyogizal, glutaraldehyde), an N-methylol compound (for example, dimethylol urea, dimethylol hydantoin), a dioxane compound (for example, , 2,3-dihydroxydioxane), active vinyl compounds (eg 1,3,5-triacryloyl-
Hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether), active halogen compounds (2,4-
Di-chloro-6-hydroxy-s-triazine sodium salt), mucohalogen acid compound (mucochloric acid, mucophenoxycycloric acid), isoxazole compound, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin. Etc. can be used alone or in combination.

The silver halide emulsion and the non-photosensitive hydrophilic colloid used in the present invention include a coating aid, an antistatic agent, an improvement in smoothness,
Various surfactants can be used for the purposes of emulsification and dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration, hardening, and sensitization). As the surfactant, saponin (steroidal), alkylene oxide derivative (for example, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyeletin glycol alkyl or aryl ether, polyethylene glycol sorbitan ester, polyalkylene glycol alkylamine or amide, Polyalkylene oxide adduct of silicone), glycidol compound (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), alkyl ester compound such as fatty acid ester compound of polyhydric alcohol, nonionic surface active agent such as urethane compound or ether compound Agent,
Triterpenoid saponins, alkyl carboxylates,
Alkyl sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfate compound, N-acyl-N-alkyl taurine compound, sulfosuccinate compound, sulfoalkyl polyoxyethylene alkyl phenyl ether compound, polyoxyethylene alkyl Anionic surfactants containing amino groups such as carboxy groups such as phosphate ester compounds, sulfo groups, phospho groups, sulfate ester groups, ester ester phosphate groups, amino acid compounds, aminoalkyl sulfonic acid compounds, aminoalkyl sulfates or phosphoric acid Ester compound,
Amphoteric surfactants such as alkyl betaine compounds, alkyl imide compounds and amine oxide compounds, alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, salts of heterocyclic quaternary ammonium such as pyridinium and imidazolium, and aliphatic Alternatively, a cationic surfactant such as a phosphonium salt containing an aromatic ring can be used.

For the silver halide emulsion and the non-photosensitive hydrophilic colloid used in the present invention, use of a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving gloss, dimensional stability, and adhesion resistance. You can 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 with these (meth) alkulic acid, α , Β−
A polymer having a monomer component of a combination of unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid and the like can be used.

Besides the silver halide emulsion and the non-photosensitive hydrophilic colloid used in the present invention, a plasticizer (for example, glycerin), an ultraviolet absorber (for example, 2- (2'-hydroxyphenyl) benzotriazole compound, α-cyanocinnamic acid ester compound), fluorescent whitening agent (for example, stilbene-based water-soluble compound having a sulfonic acid group), mordant (for example, polyvinylpyrrolidone), thickener (for example, polystyrenesulfonic acid), antioxidant Agents and the like can be used.

The silver halide photographic material of the present invention can be developed by a conventional method. As the developer, a dihydroxybenzene compound (for example, hydroquinone), a 3-pyrazolidone compound (for example, 1-phenyl-3-pyrazolidone), an aminophenol compound (for example, N-methyl-4-aminophenol) or the like is used alone or in combination. To use. In addition to this, the developing solution includes an alkali agent (for example, sodium carbonate, potassium carbonate, sodium metaborate, sodium hydroxide, calcium hydroxide, alkanolamine), a preservative (for example, sodium sulfite, potassium sulfite, sodium bisulfite, Potassium pyrosulfite, sulfur disulfide adduct of alkanolamine), chelating agents (eg ethylenediaminetetraacetic acid, nitrilotriacetic acid, polyphosphoric acid), antifoggants (eg 5-nitroindazole, 5-nitrobenzimidazole, 6- Nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 1-phenyl-5-mercaptotetrazole), pH buffer, solubilizing agent, toning agent, development accelerator, surfactant, defoaming agent, Including water softener, hardener, viscosity enhancer, etc. It may be. PH of developer
Is usually 8 to 12 is suitable. The temperature of the developer is usually 18
Used at ~ 45 ° C.

As the fixer, a fixer having a commonly used composition can be used. As the fixing agent, an organic sulfur compound known as a fixing agent can be used in addition to thiosulfates and thiocyanates. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The light-sensitive material of the present invention may contain a color coupler.

As the yellow coupler, a benzoylacetanilide type coupler, a pivalylacetanilide type coupler, or a two-equivalent coupler in which a carbon atom at the coupling position is substituted with an atom or a substituent capable of leaving during the coupling reaction, for example, Examples of yellow couplers and magenta couplers described in JP-A Nos. 55-598 and 51-102636 include 5-pyrazolone type couplers, pyrazolotriazole type couplers, pyrazolinobenzimidazole type couplers, and indazolone type couplers. Couplers or 2-equivalent couplers, for example, magenta couplers described in JP-A-49-111631, JP-A-50-122935 and JP-A-57-35858, and phenol couplers as cyan couplers, Naft Le coupler or, 2 eq couplers, for example, U.S. Pat. No. 2,698,794,
Japanese Examined Patent Publication No. 49-11572 and Japanese Patent Laid-Open No. 59-1956.
The cyan coupler described in Japanese Patent No. 42 can be mentioned.

A developing agent may be included in the layers constituting the photographic material of the present invention to accelerate development. Examples of developing agents include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-3).
-Pyrazolidone), aminophenols (eg N-
Methyl-p-aminophenol), 1-phenyl-3-
Examples thereof include pyrazolines.

When the photographic material of the present invention is a color photographic material, the processing described in Japanese Patent Application No. 62-249045 can be carried out.

[Effects of the Invention] The present invention makes it possible to obtain a photographic material which is flame-retardant and has high tensile strength and tear strength and which is suitable for pattern materials such as wall layers, window curtains, accordion curtains and the like.

[Examples] Example 1 (Preparation of glass fiber substrate) Example 1-Propylene glycol 2 mol, ethylene glycol 1 mol, maleic anhydride 1.5 mol and phthalic anhydride 1.
5 mol was reacted in a carbon dioxide gas stream at 200 ° C. for 6 hours to obtain an unsaturated polyester resin having an acid value of 40. To 60 parts of this resin, 40 parts of a styrene monomer and 0.01 part of halodoquinone were added to obtain a resin liquid having a viscosity of 15 poises.
This resin liquid 4.0%, coupling agent (trade name: Silane Z6040, Dow Corning Co., Ltd.) 0.45%, amide lubricant (trade name: Arco 220, Arnold Hoffmann Co., Ltd.) 0.1% Was dispersed in 95.45% of water to prepare a sizing agent. In the spinning step, about 0.5% by weight of this sizing agent was applied to the glass fiber bundle as a solid component with respect to the glass fiber by a roller type application device. The yarn wound on the bobbin is twisted into a plain weave,
A cloth-like glass fiber substrate was obtained.

Example 1-3.0 mol of propylene glycol, maleic anhydride 2.
60 parts of an unsaturated polyester resin made from 0 mol and 1.0 mol of phthalic anhydride was dissolved in 40 parts of diallyl phthalate to obtain a resin liquid having a viscosity of 50 poise. A cloth-like glass fiber substrate was obtained in the same manner as in Example 1 by using 12% of this resin liquid.

Example 1-Using a phenol-formaldehyde resin emulsion having a viscosity of 130 poise (trade name: Fa Index PF20, manufactured by Dainippon Ink and Chemicals, Inc.) as a resin liquid Example 1-
A sizing agent was prepared with similar coupling agents and cationic lubricants. Using this sizing agent, a cloth-like glass fiber substrate was obtained in the same manner as in Example 1-.

Example 1-Epoxy resin (trade name: Epicoat 828, Shell Chemical Co., Ltd.) (epoxy equivalent 190, viscosity 100-160)
Poise) was dissolved in styrene monomer and an emulsifier was added to obtain a water-dispersed epoxy resin emulsion. This emulsion 1.2%, cationic lubricant (trade name: Cationics X, manufactured by Onyx Oil and Chemical Co., Ltd.)
0.1% and coupling agent (trade name: Silane Z-6
040, manufactured by Dow Corning Co., Ltd.) 0.45% with water 9
It was dispersed to 8.25% to obtain a sizing agent. Using this sizing agent, a cloth-like glass fiber substrate was obtained in the same manner as in Example 1-. Example 1-Epoxy resin (trade name: Epicoat 812, manufactured by Shell Chemical Co., Ltd.) (epoxy equivalent 140-160, viscosity 1-2)
A resin emulsion was prepared in the same manner as in Example 1 except that the poise was used. This emulsion 4.0%, cationic lubricant (trade name: Cationics X, Onyx.
Oil and Chemical Co., Ltd. 0.1% and coupling agent (trade name: Silane Z-6040, Dow Corning Co., Ltd. 0.45%) were dispersed in water 95.45% to obtain a sizing agent. . Example 1 using this sizing agent
A glass fiber substrate in the form of cloth was obtained in the same manner as in.

The physical properties of the raw yarn and the cloth-like glass fiber substrate obtained in Example 1 and the conventional product were compared.

Tensile strength of raw yarn Conventional product (starch-based) 67 g / tex Invention product 87 g / tex Fabric glass fiber substrate Tensile strength (kg / 25 mm) Normal state After incineration removal Conventional product (starch-based) 122 56 Inventive product 148 Tensile strength after bending (kg / 25mm) Normal state After incineration removal Conventional product (starch type) 107 31 Invention product 133 From the above results, it can be seen that the product of the present invention is extremely superior to the conventional product.

Further, when the twisted yarn obtained by the prior art and the twisted yarn obtained by the present invention were dipped in an alcal aqueous solution, the allied aqueous solution penetrated into the twisted yarn obtained by the conventional technique, but the twisted yarn obtained by the present invention was obtained. The twisted yarn had no penetration of the alkaline aqueous solution.

Example 2 (Resin Processing of Glass Fiber Substrate) The glass fiber substrate prepared in Example 1 was coated with the following two resin layers.

First layer (numerical values represent% by weight) Polyurethane resin emulsion liquid ^* 1 20 Antifoam liquid ^* 2 0.01 Water 79.99 * 1 Product name Mercy 535, manufactured by Toyo Polymer Co., Ltd. * 2 Product name Antifoam 544, manufactured by Dow Corning Co., Ltd. The above liquid was applied by a dip coating method on both surfaces of a glass fiber substrate so that the solid content was 10 g / m ₂ and dried.

As the second layer, the one shown in Table-1 was used. The numerical values represent parts by weight.

The second layer was uniformly applied to the entire surface at a solid content of 70 g / m ₂ by a dip coating method.

Example 3 (Preparation of color photographic material) On the back surfaces of the supports A, B and C prepared in Example 2, the following gelatin solution was uniformly applied so as to have a solid content of 1 g / m ₂ in order to prevent curling. Coated.

Gelatin 75 g Saponin 10% aqueous solution 20 m Hardener ^* 8 1.2 g Water 1000 m * 8 1,2-Bis- (α-vinylsulfonylacetamide) ethane The following first layer on the surface of the glass fiber support thus obtained. A color photographic material was prepared by simultaneously coating the (bottom layer) to the seventh layer (top layer).

Each emulsion layer contains 4-hydroxy-6- as a stabilizer.
Methyl-1,3,3a, 7-tetrazaindene was added in an amount of 50 mg per mol of silver halide, and 1,2-bis- (α-vinylsulfonylacetamide) ethane was added as a hardening agent to each layer per 1 g of gelatin. 15 mg was added. Further, as a sensitizing dye, an anhydro-
120 mg of 5,5'-di-chloro-3,3'-di- (3-sulfopropyl) -thiocyanine hydroxide sodium salt per mol of silver halide, anhydro-5,5 for a green light-sensitive emulsion. 320 mg of 1′-di-phenyl-9-ethyl-3,3′-di- (sulfoethyl) oxacarbocyanine hydroxide per mol of silver halide, and anhydro-2- (4,4) for red light-sensitive emulsion.
4-di-methyl-2- (5,6-di-methyl-3-phenethylbenzothiazoline-2-ylidene) methyl-1-
Cyclohexane-6-ylidene) methyl-3-sulfopropylnaphtho [2,1-d] thiazolium hydroxide was added at 350 mg per mol of silver halide.

A color image was magnified and exposed to the color photographic material thus produced through a color negative film using a photographic enlarger. After the exposure, it was developed with a large automatic processor under the following processing conditions and dried.

Processing step Processing temperature Processing time Color development 40 ° C 1 minute 40 seconds Bleach fixing 40 ° C 1 minute Washing stability 28-34 ° C 3 minutes Color developer 4-Amino-3-methyl-N-ethyl-N- (β-methylsulfone Amidoethyl) aniline sesquisulfate monohydrate 5.0 g Potassium sulfite (anhydrous) 2.0 g Potassium carbonate (anhydrous) 30.0 g Nitrilotriacetic acid 2.1 g 1-Hydroxyethylidene-1,1'-diphosphonic acid 1.7 g Benzyl alcohol 15.0 m Diethylene glycol 15.0 m Potassium bromide 0.7 g Hydroxylamine / sulfate 4.0 g Calium hydroxide 5.4 g Add water to adjust pH to 10.20 ± 0.10 Bleach fixer Thio Ammonium sulfate (54% aqueous solution) 150m Sodium sulfite (anhydrous) 15g Ethylenedia Ferric acid sodium ferric acid sodium monohydrate 55g Ethylenediaminetetraacetic acid disodium salt dihydrate 4.0g Add water to adjust pH to 7.10 ± 0.20 Stabilized water wash p-hydroxybenzoic acid-n-butyl ester 0.15 g thiabendazole 0.005 g ethylene glycol 2.0 m methanol 4.0 m Add water to adjust pH to 1.74 ± 0.20 After color development, a large color photograph was obtained. The surface of the obtained color photograph was sprayed with lacquer to impart water resistance, and then eyelets and edge sewing were applied to obtain a large-sized display canvas. The display canvas obtained using the supports A and B can be used for reflection viewing, and the display canvas obtained using the support C can be used for transmission viewing by illuminating from the back surface. Can be used.
In each of the color photographs, there was no contamination due to permeation of the development processing solution from the cut surface of the support.

When an attempt was made to ignite the color photographs of Supports A, B, and C using a gas lighter, the color photograph of A burned with a slight flame, but it did not spread to a large extent.
On the other hand, the color photographs of Supports B and C were slightly black, but did not burn at all.

Example 4 (Preparation of black-and-white photographic material) 1 kg of silver chlorobromide emulsion chemically sensitized with sodium thiosulfate and potassium chloroaurate (20 mol% of silver chloride, 80 mol% of silver bromide, average grain size of 0. 3 μm) (including 30 g of silver and 30 g of gelatin) in 10% of 1% aqueous solution of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 30 m of 10% aqueous solution of saponin and 1% aqueous solution of formaldehyde. 20 m was added to prepare a silver halide emulsion. In addition, 1% of 4% gelatin aqueous solution
5% of sodium p-dodecylbenzenesulfonate
Aqueous solution 15 m and 8% aqueous solution of 2,4-di-chloro-6-hydroxy-s-triazine sodium salt 10
m was added to prepare a non-photosensitive hydrophilic colloid solution for the protective layer.

Two layers were simultaneously coated on each of the supports A, B and C using a slide hopper type coating machine, and dried. The coating amount is 1. The silver amount per 1 m _{2 of the} silver halide emulsion layer is 1.
6 g of the non-photosensitive hydrophilic colloid layer was applied so that the amount of gelatin was 1.2 g per 1 m ₂ .

A black-and-white image was magnified and exposed to the black-and-white photographic materials of the supports A, B and C through a black-and-white negative film using a photographic enlarger. After exposure, develop at 20 ° C. with the following developer,
Fix with an acidic fixing solution containing sodium thiosulfate, and wash with water.
Dried.

Developer (D-72) Metol 3 g Anhydrous sodium sulfite 45 g Hydroquinone 12 g Sodium carbonate (monohydrate) 80 g Sodium bromide 2 g After black and white development with water added to give a large black and white photograph. Similar to Example 3, a reflective viewing canvas and a transparent viewing display canvas were obtained. In each of the black and white photographs of the supports A, B and C, there was no contamination due to permeation after the development processing from the cut surface of the support.

When black and white photographs of Supports A, B, and C were tried to ignite using a gas lighter, the same results as in Example 3 were obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hideya Suzuki 1-24-40 Minamihara, Hiratsuka-shi, Kanagawa Oriental Photography Industry Co., Ltd. (72) Inventor Masaomi Okamoto 1-24-24 Minamihara, Hiratsuka-shi, Kanagawa Within Oriental Photography Co., Ltd. (72) Iwamatsu Matsumoto 2-14-28 Miyahara, Yodogawa-ku, Osaka City, Osaka Prefecture Photocraft Co., Ltd. (72) Inventor Takeshi Okuda 4--7 Minamisenba, Minami-ku, Osaka City, Osaka Prefecture No. 23 Unitika Yu-M Glass Co., Ltd. (72) Inventor Yoshihito Tabuchi 4-7-23 Minamisenba, Minami-ku, Osaka-shi, Osaka Prefecture (72) In-Unit Yuka Glass Co., Ltd. 278 Murato 278 Shoei Special Dyeing Co., Ltd. (72) Inventor Hideki Date Date 278, Mori, Mori, Kumiyama-cho, Kuse-gun, Kyoto Prefecture Toshiyasu Kimura, Examiner, Sakae Special Dyeing Co., Ltd. (56) Reference JP-A-51-115291 (JP, A) JP-A-55-43528 (JP, A) JP-A-62-136643 (JP, A) Kai 62-178948 (JP, A) JP 62-232640 (JP, A) Actual 61-42541 (JP, U)

Claims (5)

[Claims] 1. A photographic material comprising a glass fiber substrate coated with or filled with a polymeric material and a photosensitive layer coated on the support, wherein the glass fiber substrate is woven with glass fibers sized by a sizing agent for glass fibers. Alternatively, it is a glass fiber substrate obtained by papermaking, the sizing agent for glass fibers has a property of leaving a viscous liquid when water evaporates, and has a viscosity of 1 to 400 poise and is non-curable at room temperature. A photographic material characterized by being a sizing agent for glass fibers in which a synthetic resin liquid, a coupling agent and a cationic lubricant are dispersed in water. 2. A sizing agent for glass fibers has the property of leaving a viscous liquid when water evaporates, and has at least two epoxy groups in the molecule without containing a curing agent, Epoxy equivalent of 100-400, viscosity of 1-400 poise, water-dispersed emulsion of non-curable epoxy resin (as resin content) 0.05-6.0%, surface treatment agent 0.
05-0.5% and cationic lubricant 0.05-0.5
%. The photographic material according to claim 1, wherein the photographic material comprises%. 3. The photographic material according to claim 1 or 2, wherein the cationic lubricant is an amide-based cationic lubricant. 4. The photographic material according to claim 1, wherein the polymer substance coated or filled in the glass fiber substrate contains a flame retardant. 5. The photographic material according to claim 1, wherein the polymer substance to be coated or filled has an affinity for gelatin.