JPH0440447A - Silver halide color photographic sensitive material having glass support - Google Patents

Abstract

PURPOSE:To enhance adhesion between the glass support and an emulsion layer by incorporating a silane coupling agent and colloidal silica having a specified average particle diameter in the silver halide emulsion layer formed on the support. CONSTITUTION:The emulsion layer formed on the glass support contains the silver halide emulsion, the silane coupling agent, and the colloidal silica having an average particle diameter of <= 30 mum, preferably, <= 10 mum. The silane coupling agent is a compound, preferably, represented by formula I in which X is -O- or -OCO-; each of n, n', and n'' is 0 or 1; and each of R11 - R14 is halogen or a hydrocarbon group. As the silver halide emulsion, optional ones used for usual silver halide emulsion layers, such as silver bromide or silver iodobromide, can be used, thus permitting the silver halide emulsion layer formed on the glass support not to be peeled at the time of development processing.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a photographic light-sensitive material having a silver halide emulsion layer on a glass support, and more specifically relates to a photographic material having a silver halide emulsion layer on a glass support. This invention relates to silver halide photosensitive materials.

[Background of prior art and invention]

Silver halide photographic materials with glass supports have excellent dimensional stability, so they can be used for IC photomasks that require precision, CRT shadow masks, hard frames, etc.
It is used as a photomask for various displays. Such silver halide photographic light-sensitive materials are formed by coating a silver halide emulsion layer on a glass support that has been thoroughly washed. However, if the silver halide emulsion layer is coated directly on the glass support, the emulsion layer and the support are separated. Adhesion to the substrate is poor, and the emulsion layer peels off from the support during development or after drying.

Therefore, in practice, it is necessary to provide a subbing layer containing an inorganic chromium compound, an organic silane compound, or an organic titanium compound before coating the emulsion layer, or to incorporate these compounds into the silver halide emulsion layer. It is. However, even when these compounds are used, sufficient adhesion cannot always be obtained, and a portion of the silver halide emulsion layer may peel off from the support during development.

[Purpose of the invention]

An object of the present invention is to provide a silver halide photographic material in which a silver halide emulsion layer on a glass support does not peel off during development.

[Disclosure of the invention]

The object of the present invention is to prepare a silver halide emulsion on a glass support.
This is achieved by a photographic material characterized by containing a silane coupling agent and colloidal silica with an average particle size of 30 mμ or less.

The present invention will be explained in detail below.

The silane coupling agent used in the present invention is preferably a compound represented by the following general formula.

\ ゝ(χ)n　-R+a In the formula, X does not represent an oxygen atom or -0-CO-.

R+, +, R'+□, R13 and RI4 each represent a halogen atom or a hydrocarbon group, and at least one of R11 to R14 is a double bond, halogen atom, epoxy group, acid anhydride residue, alkoxycarbonyl or amine groups. n, n' and n'' each represent 0 or 1, and n+n'+n'' is at least 1.

In the general formula [1], examples of the halogen atoms represented by RII to R14 include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., and the hydrocarbon groups are saturated and unsaturated chains, respectively. Examples include alkyl groups (eg, methyl, ethyl, propyl, etc.), alkenyl groups (eg, vinyl, allyl, etc.), aryl groups (eg, phenyl, tolyl, etc.), and the like.

The double bond that at least one of RI I to RI4 has is a C-C bond, such as an alkenyl group, an acryloyl group,
Acid anhydride residues include, for example, methylcarbonyloxycarbonylethyl groups, and halogen atoms include, for example, haloacylamino groups. It may be introduced in the form of

Preferred specific examples of the compound represented by the general formula (1) are shown below, but the invention is not limited to these.

Ctl:+ CI+2=CCOC+116Si (OCHz):+\
1 C! (2=CH5tCj23 C)1z=cH3i(OCzl140CH:+)+CL
=CtlSi (OCzHs) 3C112=CH3
i (OCH3) 31(JCJbSi (OC211
+, ) 3C6H5NHC3H6 (OCH3) 3tl
s03t14Si (OCH3) 3Ctl3 (12) HJCJJIIC:+116Si
(OCth) 3H3 HzNCztlJHC3116Si(OCH3)3 The compound represented by the general formula [I] can be synthesized by the method described in Japanese Patent Publication No. 483565. You can also get it.

The silane coupling agent may be added to any hydrophilic colloid layer such as the silver halide emulsion layer, subbing layer, or protective layer. Preferably, the silane coupling agent is contained in the silver halide emulsion and coated, or the silane coupling agent is contained in the undercoat layer. More preferably, the silane coupling agent is contained in the sublayer. This is an embodiment in which the compound is contained in and applied.

When the compound is added to a hydrophilic colloid layer such as a silver halide emulsion layer, it is preferably added after being dissolved in water, lower alcohol, acetone, or the like.

The coating amount of the compound is preferably in the range of I to 50 mg/rd, more preferably in the range of 10 to ]-00 mg/rrr.

The colloidal silica used in the present invention has an average particle size of 30
mμ or less, preferably 10 mμ or less. These colloidal silicas are easily available as commercial products from Kuchihiro Kagaku 01, for example. Colloidal silica may be added to any of the hydrophilic colloid layers, including the silver halide emulsion layer, the subbing layer, and the protective layer. A preferable embodiment is one in which colloidal silica is contained in a silver halide emulsion layer or a subbing layer, and a more preferable embodiment is a coating in which colloidal silica is contained in a subbing layer. When contained in the undercoat layer, gelatin is preferably used as the hydrophilic colloid in the undercoat layer, and the weight ratio of gelatin and colloidal silica is 1:1 to 1:1.
A range of 6 is preferable. The amount of colloidal silica applied is 5 to 100 mg/bo, preferably 10 to 50 mg.
/rrf. The ratio of colloidal silica to silane coupling agent used is preferably in the range of 1:10 to 10:1, more preferably in the range of 13 to 3:1. Further, the thickness of the undercoat layer is preferably in the range of 0.05 μm to 1 μm in terms of dry film thickness.

The silver halide emulsion of the silver halide emulsion layer of the present invention includes:
Any silver halide used in ordinary silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride can be used as the silver halide; There are no restrictions on the particle size and particle size distribution of silver particles, and the silver halide composition is 50 mol% or more of silver chloride - 10 mol% of silver iodide.
The following silver chlorobromide or silver chloroiodobromide, with a particle size of 0.1 to 1
It is also possible to use emulsions having a grain size of 0.1 μm or less and silver iodobromide containing 8 mol % or less of silver iodide.

The glass support used in the present invention is not particularly limited in its glass composition, but soda lime glass, soda lime aluminum glass, and the like are preferable.

The surface of the support is preferably degreased in advance before the surface treatment with the organosilicon compound and application of the hydrophilic colloid layer coating solution, and a pretreatment to improve hydrophilicity is performed. In addition, it is preferable for the end surface of the support to be polished in terms of handling.

The light-sensitive material of the present invention has at least one silver halide emulsion layer on a glass support, and contains colloidal silica and a compound represented by general formula CI), which is necessary in addition to the core layer. Depending on the requirements, a protective layer may be provided below the emulsion layer, and a subbing layer may be provided below the emulsion layer. Further, an antihalation layer may be provided between the subbing layer and the emulsion layer.

The silver halide grains used in the silver halide emulsion layer of the present invention are prepared in the process of grain formation and/or growth, including cadmium salt, zinc chloride, lead salt, thallium salt, and iridium salt (including complex salts). By adding metal ions using at least one selected from rhodium salts (including complex salts) and iron salts (including complex salts), these metal elements can be contained inside the particles and/or on the particle surfaces. Further, by placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

In the silver halide emulsion of the silver halide emulsion layer of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained.

The silver halide emulsion of the present invention can be produced by a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc., either alone or in combination.

The silver halide emulsion of the present invention can be spectrally sensitized. The sensitizing dyes may be used alone or in combination of two or more.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening, at the end of chemical ripening, and/or after chemical ripening, until silver halide emulsion is applied, for the purpose of preventing fog during storage or photographic processing, or to maintain stable photographic performance. In addition, compounds known in the photographic industry as antifoggants or stabilizers can be added.

It is also possible to add a hardening agent to the processing solution.

A plasticizer may be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of increasing flexibility.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

The photographic emulsion layer of the photosensitive material 1'4 of the present invention contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, It may also contain thiomorpholines, quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, and the like.

A capping agent such as silica or polymethyl methacrylate particles having a particle size of 0.5 to 10 .mu.m may be used in the silver halide emulsion layer and/or other hydrophilic colloid layer of the photosensitive material A of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to the photosensitive material of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used in the protective coating layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for.

Although it is advantageous to use gelatin as the binder for the subbing layer, emulsion layer, etc. used in the present invention, other hydrophilic colloids 1- can also be used. For example, gelatin derivatives, graft polymers of seratin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as alginate soap and starch derivatives; polyvinyl alcohol. , polyvinyl alcohol partial acetal, BoIJ
-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl alcohol,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers such as polyhinylviradur.

As the gelatin, in addition to lime-treated gelatin, acid-treated seratin may be used, and gelatin hydrolysates and gelatin hydrolysates may also be used.

The subbing layer used in the present invention may contain a dye for the purpose of preventing halation. Methods for adding the dye include adsorbing it on colloidal silica as an adhesion improver, dispersing it as a solid in a binder, and fixing it with a mordant. It is also possible to have two undercoat layers, with the F layer containing an adhesion improver and the upper layer containing an antihalation dye.

The subbing layer or other hydrophilic colloid layer used in the present invention may contain various surfactants.

For example, zabonin (steroid type), alkylene oxite derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl-1-nocor--yl 41 or polyethylene glycol alkyl aryl ethers, polyethylene Getacol - [sters, polyalkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicone], glycidol derivatives (e.g. alkenylsuccinic acid polyglyceride 1ζ, alkylphenol polyglyceride) , fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and other nonionic surfactants; alkyl carboxylates, alkyl sulfonates, alkyl hensens sulfonates, alkylnafucrene sulfmenates, alkyl sulfates. Esters, alkyl phosphates, N-acyl-N~alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphorus, etc., carboxy groups, sulfo groups, phosphorus anionic surfactants containing acidic groups such as sulfuric acid esters, sulfuric acid esters, phosphoric acid ester groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine oxides, etc. agents; cationic interfaces such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings; Activators can be used.

The subbing layer or other hydrophilic colloid layer of the present invention may contain an inorganic or organic hardening agent.

For example, chromium salts (chromium alum, chloroacetate J1, etc.), altehyde, i (porno, aldehyde, glyoxal, geltar aldehyde, etc.), N-methylol compounds (dimethylol urea, methylol simethylhydan I-yne, etc.) , dioxane derivatives (2,3-dihydroxyoxane, etc.), active vinyl compounds (], 3.
5-1-lyacryloylhekizahi (Inia-s-1-
riazine, 13-vinylsulfonyl-2-propatol, etc.), active halokene compounds (2,4-dichloro-6-
Hydroxy 5-1-riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

The present invention will be further explained below with reference to Examples.

(Example) Preparation of coating solution (preparation of silver halide emulsion) Average grain size 0 consisting of 2 mol% silver iodide and 98 mol% silver bromide
．． A Tubmann type halogenated emulsion having a thickness of 0.06 μm was physically ripened and desalted in accordance with a conventional method, and chemically prepared by adding I-lium thiosulfate and chloroauric (III) acid. The following compound A-1 is used as a sensitizing dye, the following compound A-2 is used as an irradiation inhibitor, 1,2-his(vinylsulfonylaceI-amido)ethane is used as a hardening agent, and / is used as a stabilizer.
IL, F waxy 6-methyl-1,3,3a,7
A silver halide emulsion was prepared by adding razaindene, 1-phenyl-5-mercaptotetrazole as an antifoggant, and colloidal silica. The silver concentration of this emulsion was 5% and the gelatin concentration was 8%.

Compound A-1 Compound 13-1 Compound A-2 Compound-2 OOH OOCth m:n=4:6 (molar ratio) (Preparation of backing liquid) A backing liquid having the following composition was prepared.

Compound-3 C1(3 (Preparation of subtraction liquid) Subtracting liquids Δ to F having the following compositions were prepared.

(This invention) (〃) (〃) Colloidal Sorikaniguchihiro Kagaku Stotex-XS Surfactant C, -1 CII2COOCII□CH (C2H5) C4119C
II COOC11□C11(C2+15)C4H10
aNa (Preparation of processing solution) A developing solution and a fixing solution having the following compositions were prepared.

<Developer> Hydroquinone monomethyl-p-aminophenozalphe-1 ~ Anhydrous sodium sulfite potassium hydroxide Potassium bromide 1000% water <Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% W/V Aqueous solution) Sodium sulfite sodium acetate, trihydrate boric acid, sodium citrate, dihydrate acetic acid (90% W/V aqueous solution) (Composition) Pure water (ion exchange water) Sulfuric acid (50% W/V aqueous solution) g g 0 g 0 g o, 5g 0ml 7g 6, 5g g g 13.6g 7ml 4, 7g Aluminum sulfate (W/V aqueous solution with A e 203 equivalent content of 8.1) 26.5g Use of fixer The above composition A was then dissolved in 500 ml of water to form 1P, which was then used.

The pH of this fixer was about 4.3.

The processing conditions for development, fixing, and washing were as follows.

Develop, fix, soak in water, wash and dry □Apply 10 cc of backing liquid to A Tsukuda (1) Glass support (2)
n? A backing layer of a photosensitive material was provided by coating with bar caulk so as to provide a backing layer of a photosensitive material. Next, subbing liquids A to F were applied to the opposite side of the banking layer using a napkin coater in an amount of 5 cc/rd. Furthermore, after the undercoat layer has dried, a silver halide emulsion is applied using a spin coater until the amount of silver reaches 2.
8g/n (.In this way, natural drying optical materials A-F corresponding to subbing liquids A-F were prepared. .

After seasoning the photosensitive materials A to F thus obtained at 50°C and 60% relative humidity for 6 hours, they were immersed in the developer described above at 20°C for 15 minutes to form an emulsion film. After scratching the emulsion film with the tip of a bottle set in a leaking state, the surface was rubbed with a finger to evaluate adhesion to glass.

In the photosensitive material A and the photosensitive material B containing a silane coupling agent, significant film peeling occurred. Photosensitive material C containing colloidal silica also suffered from film peeling with a width of 1 to 2 mm, but photosensitive materials E and F, which used a combination of a silane coupling agent and colloidal silica, were good with no film peeling at all.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 4. Subject of amendment: Specification "Detailed description of the invention" column Display of incidents name of invention 3. Person making the amendment Relationship with the incident 1990 Patent Application No. 147985 Silver halide with glass support photographic material

Claims (1)

[Claims] At least one silver halide emulsion layer, a silane coupling agent, and an average particle size of 30 mμ on a glass support.
A silver halide photographic material characterized by containing the following colloidal silica.