JP3365680B2 - Method for producing silver halide photographic light-sensitive material - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photographic light-sensitive material having a silver halide emulsion layer on a glass support, and more specifically, a silver halide light-sensitive material having improved adhesion between the glass support and the emulsion layer. It is about.

[0002]

2. Description of the Related Art Since a silver halide photographic light-sensitive material having a glass support is excellent in dimensional stability, photomasks for ICs, shadow masks for CRTs, leadframes, and various display-related photomasks, which require high precision. It is used as a mask. Such a silver halide photographic light-sensitive material is formed by coating a silver halide emulsion layer on a sufficiently washed glass support, but when the silver halide emulsion layer is directly coated on the glass support, the emulsion layer and the support are supported. Adhesion to the body is poor and the emulsion layer peels off from the support during development or after drying. Therefore, practically, before coating the emulsion layer, an undercoat layer containing an inorganic chromium compound or an organic silane compound is provided, or these compounds are contained in the silver halide emulsion layer. However, even if these compounds are used, sufficient adhesiveness is not always obtained, and a part of the silver halide emulsion layer may peel off from the support during development processing. Further, the adhesiveness with the glass support is also influenced by the humidity conditions of seasoning of the light-sensitive material after coating the silver halide emulsion layer.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material in which the silver halide emulsion layer on the glass support does not peel off during development processing.

[0004]

An object of the present invention, in order to solve the problem] is the tetraalkoxysilane (hereinafter on a glass support, the
Tetraa contained as an essential constituent element in the light-sensitive material of the invention
It was achieved by a photographic light-sensitive material characterized by having an undercoat layer containing lithium oxide and lucoxysilane) . The present invention will be described in detail below.

The alkoxysilane used in the present invention preferably has an alkoxyl group having 10 or less carbon atoms. The preferred specific examples are shown below, but the invention is not limited thereto.

[0006]

[Chemical 1]

The weight ratio of alkoxysilane and lithium oxide contained in the undercoat layer of the present invention is alkoxysilane 9
The range of 5% to 99.9% and the range of 5% to 0.1% of lithium oxide are preferable, and the alkoxysilane is particularly preferably 9%.
It is in the range of 8% to 99.5% and lithium oxide in the range of 2% to 0.5%. The coating amount of alkoxysilane is 10 to 1000
The range of mg / m ² is preferred. The range of 50 to 500 mg / m ² is more preferable.

Gelatin is useful as a binder for the undercoat layer used in the present invention. The weight ratio of alkoxysilane to gelatin is 40% to 90% of alkoxysilane,
Gelatin is preferably in the range of 60% to 10%, alkoxysilane is 60% to 80%, and gelatin is 40% to 20%.
Is more preferable. The gelatin coating amount of the undercoat layer is 5
To 500 mg / m ² is preferred, 10 to 200 mg / m ²
Is more preferable.

The silver halide emulsion of the silver halide emulsion layer of the present invention includes silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any silver halide emulsion can be used, and the grain size and grain size distribution of silver halide grains are not limited. However, among these, an emulsion of silver chlorobromide or silver chloroiodobromide having a silver halide composition of 50 mol% or more of silver chloride and 10 mol% or less of silver iodide and having a grain size of 0.1 to 1.0 μm, And silver iodobromide having a silver iodide content of 8 mol% or less and a grain size of 0.1 μm.
An emulsion of m or less can be preferably used. The silver coating amount of the present invention is preferably in the range of 1 to 10 g / m ² , and 3 to 6 g.
The range of / m ² is more preferable. The thickness of the silver halide emulsion layer of the present invention is preferably in the range of 1 to 10 μm and 3 to
Range of 6 [mu m is more preferred.

The glass support used in the present invention is not particularly limited in 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 organic silicon compound and the application of the coating solution for the hydrophilic colloid layer, and a pretreatment for improving hydrophilicity is preferably performed.
Further, it is preferable in terms of handling that the end surface of the support is polished.

The light-sensitive material of the present invention has at least one undercoat layer on a glass support and at least one silver halide emulsion layer, and optionally a protective layer on the emulsion layer, Can be provided. Further, an antihalation layer may be provided between the undercoat layer and the emulsion layer.

The silver halide grains used in the silver halide emulsion layer of the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex acid) in the process of forming and / or growing the grains. Metal ion is added to the inside of the particle by adding at least one selected from the group consisting of rhodium salt (including complex salt) and iron salt (including complex salt).
Alternatively, these metal elements can be contained on the grain surface, and reduction sensitizing nuclei can be imparted to the inside of the grain and / or the grain surface by placing in a suitable reducing atmosphere. In the silver halide emulsion of the silver halide emulsion layer of the present invention, unnecessary soluble salts may be removed after the completion of the growth of silver halide grains, or may remain contained.

The silver halide emulsion of the present invention can be used alone or in combination with a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using a gold or other noble metal compound. 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 contains
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, during chemical ripening, at the end of chemical ripening, and / or after the completion of chemical ripening, before coating a silver halide emulsion, Compounds known in the art as antifoggants or stabilizers can be added.
It is also possible to add a hardening agent to the processing liquid. 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 light-sensitive material of the present invention comprises a polyalkylene oxide or a derivative thereof such as an ether, ester or amine, a thioether compound, a thiomorpholine compound, a quaternary ammonium compound or a urethane for the purpose of increasing sensitivity, increasing contrast or promoting development. A derivative, a urea derivative, an imidazole derivative, etc. may be included.

The silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material of the present invention has a grain size of 0.5-10.
Matting agents such as μm silica or polymethylmethacrylate particles can be used. In the light-sensitive material of the present invention,
An antistatic agent for the purpose of antistatic can be added. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and a protective colloid layer other than the emulsion layer on the side where the emulsion layer is laminated on the emulsion layer and / or the support. May be used for.

Gelatin is advantageously used as a binder for the subbing layer and emulsion layer used in the present invention, but other hydrophilic colloids can also be used.
For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric substances such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used. In addition to lime-processed gelatin as gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Gelatin enzymatic degradation products can also be used. The subbing layer used in the present invention may contain a dye for the purpose of preventing halation. Examples of the method of adding the dye include a method of adsorbing to a colloidal silica as an adhesion improving agent, a method of solid-dispersing in a binder, and a method of fixing with a mordant.
It is also possible to make the undercoat layer into two layers and to contain an adhesion improving agent in the lower layer and an antihalation dye in the upper layer.

The subbing layer or other hydrophilic colloid layer used in the present invention may contain various surfactants.
For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Nonionic surfactants such as alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents: alkyl carboxylates, alkyl sulfonates, alkyl benzene sulfonates Acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphorus A carboxy group, such as acid esters,
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfates, and phosphates; amino acids,
Amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkylbetaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, complex such as pyridinium and imidazolium Cationic surfactants such as ring quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

The undercoat layer or other hydrophilic colloid layer of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium yoban, chromium acetate, etc.),
Aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, mediloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxyoxane, etc.), active vinyl compounds (1,3,3) 5-triacryloyl-hexahydro-s-triazine, 1,3-virnisulfonyl-2-propanol, etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochlor) Acid, mucophenoxycyclo acid, etc.) can be used alone or in combination. Further, it is preferable that any one of the layers of the light-sensitive material of the present invention contains colloidal silica having an average particle diameter of 30 μm or less. Furthermore, it is preferable to add an antihalation dye during the backing.

The present invention will be further described below with reference to examples.

[0020]

【Example】

Example 1 Preparation of Coating Solution and Processing Solution (Preparation of Emulsion A) A Lippmann type silver halide emulsion containing 2 mol% of silver iodide and 98 mol% of silver bromide and having an average particle size of 0.06 μm was physically ripened according to a conventional method. , Desalted, and chemically ripened by adding sodium thiosulfate and gold chloride [III] acid. The following compounds A-1 as sensitizing dyes and the following compounds A-2, A-3, A-4, A as anti-irradiation agents
-5, 1,2-bis (vinylsulfonylacetamide) ethane as a hardening agent, 4-hydroxy-6 as a stabilizer
-Methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercaptotetrazole as an antifoggant, the following compound A-6 as a surfactant, and the following compound A-7 as a thickener Emulsion A was prepared.

[0021]

[Chemical 2]

[0022]

[Chemical 3]

(Preparation of Emulsion B) By a double jet method, 30 mol% of silver bromide and 70 mol% of silver chloride were used, and 2 × 10 ⁻⁶ g of hexabromorhodate potassium salt per mol of silver and 3 × 10 ⁻ A monodisperse cubic silver halide emulsion having an average particle size of 0.25 μm and containing ⁵ g of hexachloroiridate potassium salt was physically ripened and desalted according to a conventional method, and sodium thiosulfate and gold chloride [III] acid were added. Chemically aged. The following compound B-1 as a sensitizing dye, the above compound A-3 as an anti-irradiation agent, 1,3-divinylsulfonyl-2-propanol as a hardening agent, 4-hydroxy-6-methyl-1, as a stabilizer, 3,3a,
Emulsion B was prepared by adding 7-tetrazaindene, hydroquinone, 1-phenyl-5-mercaptotetrazole as an antifoggant, and colloidal silica.

[0024]

[Chemical 4]

(Preparation of coating liquid for undercoat layer) Gelatin as a binder, alkoxysilane, colloidal silica and lithium oxide as an adhesion improving agent are mixed with methanol and water in an amount of 1:
An undercoat liquid was prepared by dissolving it in the mixed liquid of 2. gelatin,
The amounts of colloidal silica, alkoxysilane and lithium oxide are shown in Table-1. (Preparation of backing liquid) Binder (compound C-1 below) 30 g Dye (compound C-2 below) 5 g (〃C-3) 5 g (〃C-4) 6 g (〃C-5) 1.2 g Ethanol 420 ml Methanol 550 ml

[0026]

[Chemical 5]

[0027]

[Chemical 6]

(Preparation of Protective Layer Solution) A protective layer solution having the following composition was prepared. Gelatin 65 g Polymethylmethacrylate fine particles 3 g Surfactant (the compound A-6) 3 g Thickener (〃 A-7) 0.5 g Spot inhibitor (compound D-1) 1.2 g Antifoggant (compound D below) -2) 0.6 g 〃 (Compound D-3 below) 0.8 g Water 900 ml

[0029]

[Chemical 7]

(Preparation of processing liquid) Developer 1 having the following composition,
Developer 2 and fixer were prepared. <Developer-1> Hydroquinone 5 g N-methyl-p-aminophenol 1/2 sulfate 1 g Anhydrous sodium sulfite 50 g Potassium hydroxide 20 g Potassium bromide 0.5 g Water was made up to 1000 ml. <Developer-2> Hydroquinone 20 g Potassium sulfite 5 g Sodium ethylenediaminetetraacetate 1 g Potassium carbonate 35 g Sodium carbonate 15 g Potassium bromide 3 g 5-Nitroindazole 4 mg Triethylene glycol 30 g Diethanolamine 20 g Formalin sodium bisulfite adduct 50 g Polyethylene glycol (average molecular weight 1500 ) 0.2 g made up to 1 liter with water and adjusted to pH 10 with sodium hydroxide.
Adjusted to 2.

<Fixer Formulation> (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 200 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2 g Acetic acid (90 % W / V aqueous solution) 13.6 g (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulfate (Al ₂ O ₃ conversion content is 8.1% W / V) Aqueous solution) 26.5 g When the fixing solution was used, the above composition A and composition B were dissolved in this order in 500 ml of water to make 1 liter. The pH of this fixer was about 4.3.

The processing conditions for Developer 1 and Developer 2 were as follows. Developer-1 20 ° C 5 minutes settled 20 ° C 2 minutes washed 20 ° C 5 minutes dried naturally dried Developer-2 20 ° C 3 minutes settled 20 ° C 2 minutes water washed 20 ° C 5 minutes dried naturally dried

Preparation of Photosensitive Material (Coating of Backing Layer) A backing liquid was coated on a glass support with a bar coater so that the coating amount was 15 ml / m ² to form backing layers of Photosensitive Materials A to H. (Application of Undercoat Layer) The amount of the additive shown in Table 1 was added to the above coating solution for the undercoat layer, and the coating amount was 10 ml / on the opposite side of the backing layer of the glass support provided with the backing layer. The undercoat layer was coated with a napkin coater so as to have m ^2, and the undercoat layers of the light-sensitive materials A to H were provided.

(Coating of Silver Halide Emulsion Layer and Protective Layer) Gelatin was added to Emulsion A to prepare a solution of JP-A-3-186377.
In the solid curtain coating method described in No. 2, the amount of silver is 2.8 g /
Photosensitive materials A to D were prepared by coating so that the amount of m ² and the amount of binder (the amount of gelatin) were 4.7 g / m ² . Gelatin, polyacrylamide derivative and polyethyl acrylate latex were added to emulsion B to give a silver content of 4.6 g /
Photosensitive materials E to H were prepared by coating so that the amount of m ² and the amount of binder (sum of gelatin, polyacrylamide derivative and polyethyl acrylate latex) was 5.8 g / m ² . The weight ratio of gelatin to polyacrylamide derivative and polyethyl acrylate latex was such that the ratio of gelatin to polyacrylamide derivative 3 and polyethyl acrylate latex 1 to gelatin was 16.

Evaluation of Photosensitive Materials After the photosensitive materials A to H thus obtained were seasoned at 25 ° C., relative humidity of 30%, 60% and 75% for 10 days, the photosensitive materials A to D were treated with a developer-1. At 20 ° C for 5 minutes,
The photosensitive materials E to H are immersed in the developer-2 at 20 ° C. for 3 minutes,
After the emulsion film was wet with the developing solution, the emulsion film was scratched with the tip of tweezers, and then the surface was rubbed with a finger to evaluate the adhesion to glass. The results are summarized in Table-1.

[0036]

[Table 1]

As is clear from Table 1, the photosensitive materials C, D, G and H containing alkoxysilane and lithium oxide had good adhesion to glass.

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Claims (4)

(57) [Claims] 1. A tetraalkoxysilane on a glass support.
For applying a coating solution containing orchid and lithium oxide
Forming at least one undercoat layer, and
Coating a silver halide emulsion on top of at least one layer
And a step of forming a silver halide emulsion layer.
To method of a silver halide photographic material have a least one silver halide emulsion layer thereon at least on a glass support and further undercoat layer. 2. The silver chloride content of the silver halide emulsion is 50 mol% or more.
A method for producing a silver halide photographic light-sensitive material. 3. The silver halide emulsion is a silver iodobromide emulsion having a silver iodide content of 8 mol% or less and an average grain size of 0.1 μm or less. 1. A method for producing a silver halide photographic light-sensitive material as described in 1. 4. The manufacturing method according to claim 1.
A silver halide photographic light-sensitive material produced by the manufacturing method.