JPS592016B2 - Syashinkankouzairiyo - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polymer compound that changes the properties of a monosilver halide photographic material.

1. It is well known that silver halide photographic materials undergo characteristic changes after production, such as a decrease in sensitivity, image density, change in color tone, and increase in fog. To prevent this, various stabilizers and additives are used. agent is used. Among these changes in characteristics,
A silver halide image created by exposure and development changes from black to brown or other colors, resulting in a change in image tone and a decrease in density, which is called bronzing. It is known as In photographic paper, this bronzing occurs particularly at the stage of high temperature press drying (ferrotype drying) to produce gloss. Various compounds are known as anti-pronization agents, but many have low inhibiting ability or impair photographic properties.

The aim of the present invention is to provide new anti-bronzing agents which have sufficient anti-bronzing effect and are harmless to the properties of photographic materials.

The present inventors have discovered that a polymer composition containing a vinylimidazole compound as a repeating monomer component is extremely effective as a pronzation inhibitor.

The present invention prevents bronzing of a polymer composition consisting of repeating units of monomer components (a) and (b) or monomer components (a), (b), and (c) represented by the following general formula. The present invention relates to a photographic material containing the present invention as an agent. (a) (b) In the formulas, R1 and R2 represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, or a hydroxyalkyl group having 2 or less carbon atoms, and R1 and R2 are the same or They can be different.

In the formula, R3 is a hydrogen atom or a methyl group, 'R4, R5
represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

KL, R4, and R5 are never hydrogen atoms at the same time. m is an integer of 1 to 3, and p is O or 1. (c) (
a), (b) Ethylenically unsaturated monomer copolymerizable with the monomer component.

The monomer component represented by general formula (a) is vinylimidazole, such as 1-vinylimidazole, 1-
Vinyl-2-methylimidazole, 1-vinyl-2-ethylimidazole, 1-vinyl-2-phenylimidazole, 1-vinyl-2.4(5)-dimethylimidazole, 1-vinyl-2-ethyl-4. (5)-methylimidazole, 1-vinyl-4(5)-betahydroxyethylimidazole, 1-vinyl-2-betahydroxyethylimidazole, and the like.

The monomer component represented by general formula (b) is N・N-
dialkylaminoalkyl acrylates, e.g. 2
-(N-N-dimethylamino)ethyl acrylate, 2
-(N-N-diethylamino)ethyl acrylate, 2
-(N-N-dibutylamino)ethyl acrylate, 3
-(N-N-dibutylamino)propyl acrylate,
N-N-dialkylaminoalkyl methacrylates,
For example, 2-(N-N-dimethylamino)ethyl methacrylate, 2-(N-N-diethylamino)ethyl methacrylate, 2-(N-N-dibutylamino)ethyl methacrylate, 3-(N-N-dibutylamino)propyl methacrylate or N-monosubstituted acrylamides,
Methacrylamides, such as N-methylacrylamide, N-ethylacrylamide, N-n-butylacrylamide, N-phenylacrylamide, N-N-dimethylacrylamide, N-N-diethylacrylamide, N-N-di-n -butylacrylamide, N-N-
Examples include diphenyl acrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-phenylmethacrylamide, and N-N diphenylmethacrylamide.

(c) Various monomer components can be used, but
Preferred are ethylenically unsaturated monomers having hydrophilic groups, such as SO3N groups (M is, for example, H.Na, K.Ca.M
etc.), such as vinyl sulfonic acid or its salt, allyl sulfonate, methacryl sulfonate, para-styrene sulfonic acid or its salt, sodium 3-sulfopropyl acrylate, vinyl pyrrolidone compounds, such as N- Vinyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2- Hydroxypropyl methacrylate, unsaturated ethylene compounds having a carboxyl group, such as acrylic acid, methacrylic acid, α-chloroacrylic acid, α-bromoacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, etc. Examples include acid anhydrides.

The polymer composition of the present invention (hereinafter referred to as polymer composition) is (
a), (b) When consisting of repeating units of monomer components,
The ratio of (a) and (b) can vary widely, but preferably (a) is 50 to 99.9 mol% and (b) is 0.1 to 50 mol%.
It is mole%.

When the polymer composition consists of repeating units of monomer components (a), (b), and (c), the ratios of (a), (b), and (c) vary widely, but preferably (a) ) is 50-99.9
(b) is 0.05 to 49.5 mol%, and (c) is 0.05 to 49.5 mol%. The silver halide photographic light-sensitive material contains a polymer consisting of repeating units of monomer components (a) and (b), or a polymer consisting of repeating units of unit components (a), (b), and (c). When used, it has an effect of preventing bronzing on silver images obtained by exposure and development.

Furthermore, if a polymer consisting of repeating units of the monomer components (a) and (b) is contained in the silver halide photographic light-sensitive material, the resulting silver image will generally have a cool tone (blue-black tone), and (a),
The color tone of a polymer composed of repeating units of the monomer components (b) and (c) changes depending on its composition.

The polymer composition is prepared by dissolving monomer components in a solvent such as water or alcohol, adding a polymerization initiator, and polymerizing the composition by heating and stirring, but it can also be polymerized by ultraviolet irradiation or the like. The polymerization time and temperature vary depending on the composition, degree of polymerization, polymerization initiator, solvent, etc., but are usually at 40 to 90°C for 5 to 20 hours.
During polymerization, it is desirable to replace air by introducing an inert gas such as nitrogen gas or carbon dioxide gas at the initial stage or during the entire polymerization period from the viewpoint of preventing discoloration and preventing residual polymerized monomer components.

Various polymerization initiators are used, such as benzoyl peroxide, acetyl peroxide, α・α1-azobisisobutyronitrile, tert-butyl hydroperoxide, cumene hydroperoxide, tertiary-butyl peroxide-azodicyclohexycarbonitrile. , α・α1-dimethyl azodiisobutyrate, co-citric acid peroxide, digtan peroxide, dichlorobenzoyl peroxide, ammonium peroxide, potassium peroxide, sodium peroxide, hydrogen peroxide, sodium perborate, etc. Can be used.

Further, a redox system consisting of a combination of these with ferrous ammonium sulfate, acidic sodium sulfite, etc. can also be used. The average degree of polymerization of the polymerization composition can be changed by using various polymerization degree regulators (chain transfer agents), such as mercabutanes, disulfides, diazothioethers, aliphatic halogen compounds, alcohols, etc., but preferably by adjusting the reduction ratio. The viscosity (Ns, /C.C=11/100m1, .0.1 mol NaCl water at 30°C) is 0.1 to 0.5, and if the degree of polymerization is too high, the bronzing prevention effect will be reduced, and gelatin etc. The compatibility with hydrophilic colloids also deteriorates, which is undesirable.

The polymer composition is used as it is or after being purified by a dialysis method, a reprecipitation method, or the like.

The polymer composition is compatible with water-soluble colloids such as gelatin, polyvinyl alcohol, and polyvinylpyrrolidone, and is stable over a wide pH range, and can be adjusted to pH with acid or alkali as necessary.
It can be used by changing it, or it can be used by dispersing it.

When incorporated into photographic materials, there are almost no adverse effects such as fogging or decreased sensitivity. It can also be used in combination with additives used in silver halide photographic emulsions, such as sensitizing dyes, chemical sensitizers, antifoggants, stabilizers, and hardeners, without impairing their properties. The polymer composition also has secondary effects such as improving the covering power of silver images, the antistatic properties of photosensitive materials, and the coating properties. The polymer composition can also be used in the emulsion layer, top layer, intermediate layer, anti-aging layer, undercoat layer, etc. of black-and-white light-sensitive materials and color light-sensitive materials, and can also be used in developing solutions, fixing solutions, stabilizers, and ferromagnetic materials. It is also possible to use it by incorporating it into a photographic processing solution such as a finishing solution.

When used in an emulsion, the amount of the polymerization composition used is 0.01 to 307, preferably 2 to 10 per mole of silver halide.
It is f. When added to the protective layer, 1f7 to 100% per kg of gelatin or other layer-constituting polymer
7, preferably 10f to 507. Examples of the polymerization composition include vinylimidazole-N-N-diethylamino methacrylate copolymer, vinylimidazole-N-N-dimethylaminoethyl methacrylate copolymer-1-vinyl-2-methylimidazole-N-
N-diethylaminoethyl methacrylate copolymer 1
-Vinyl-2-methylimidazole-N-N-dimethylaminoethyl methacrylate copolymer -1-vinyl-2-methylimidazole-N-N-dimethylacrylamide copolymer-1-vinyl-2-methylimidazole-N-N diethylamino Ethyl methacrylate-acrylic acid copolymer 1-vinyl-2-methylimidazole-N-N-diethylaminoethyl methacrylate-memethacrylic acid copolymer 1-vinyl-2-methylimidazole-N-N-diethylaminoethyl methacrylate-sodium 3 -Sulfopropyl acrylate copolymer -1,1-vinyl 2-methylimidazole-N-N
-diethylaminoethyl methacrylate-methallylsulfonic acid soda copolymer 1-vinyl-2-methylimidazole-N-N-diethylaminoethyl methacrylate-N-vinyl-2-pyrrolidone copolymer 1-
Vinyl-2-methylimidazole N-N-dimethylacrylamide-2-hydroxyethyl methacrylate copolymers may be mentioned.

Hereinafter, it will be specifically explained using synthesis examples and examples.

Synthesis Example 1 1-vinyl-2-methylimidazole 8.6y (80 mol%), N-N-diethylaminoethyl methacrylate 3.77 (20 mol%), methanol 55ml11 ion-exchanged water 45ml11α・α7-azobisisobutyro Fifty tons of nitrile was placed in a 200 ml four-bottle flask, heated in a water bath and stirred while introducing nitrogen gas.

Polymerization was carried out at 63-65°C for 8 hours to obtain a pale yellow viscous liquid.

Synthesis Example 2 1-vinyl-2-methylimidazole 8,6y (80 mol%), N-N-dimethylaminoethyl methacrylate 3.1y (20 mol%), methanol 50ml 11 ion-exchanged water 40ml 11 α・α1-Azobisisobutylene Fifty tons of ronitrile were placed in four 200 ml flasks, and heated and stirred in a water bath while introducing nitrogen gas.

Polymerization was carried out at 60-63°C for 7 hours to obtain a colorless viscous liquid.

Synthesis Example 3 1-vinyl-2-methylimidazole 8.6y (80 mol%), N-N-diethylaminoethyl methacrylate 2,87 (15 mol%), sodium-3-sulfopropyl acrylate 1.17 (5 mol%) Methanol 30m
11 Ion-exchanged water 20WLI1α・α5-Azobisisobutyronitrile 50~ were placed in a 200ml four-bottle flask, heated in a water bath and stirred while introducing nitrogen gas.

Polymerization was carried out at 60-65°C for 7 hours to obtain a colorless viscous liquid.

Synthesis example 4 1-vinyl-2-methylimidazole 14.07 (80
mol %), N-N-dimethylacrylamide 3.27 (
20 mol %), 9.7 y of isopropyl alcohol, and 60 ml of ion-exchanged water were placed in a 200 ml four-necked flask, heated in a water bath, and stirred while introducing nitrogen gas.

Polymerization was carried out at 80° C. for 7 hours to obtain a slightly cloudy yellow viscous liquid.

Synthesis example 5 1-vinyl-2-methylimidazole 15.447 (8
0 mol% 8N-N-diethylaminoethyl methacrylate 3.30y (10 mol%), acrylic acid 1.287y (
10 mol%), isopropanol denatured alcohol 802
, α・α1-azobisisobutyronitrile 50 to 20
The mixture was placed in a 0 ml four-bottle flask, heated in a water bath and stirred while introducing nitrogen gas.

Polymerization was carried out at 70-75°C for 6.5 hours to obtain a yellow transparent viscous liquid.

Synthesis Example 6 1-vinyl-2-methylimidazole 14.617 (8
0 mol%), N-N-diethylaminoethyl methacrylate 4.69y (15 mol% 8 methacrylic acid 0.73
7 (5 mol% octaisopropanol denatured alcohol 80y
was placed in a 200 ml four-loaf flask, heated in a water bath and stirred while introducing nitrogen gas.

Four hours after the temperature reached 70-73°C, 50~ of α·α5-azobisisobutyronitrile was added and polymerized for another 4 hours to obtain a yellow transparent liquid with a slight viscosity.

Example 1 Silver chlorobromide gelatin emulsion (AgCl6O mol%, AgBr
This emulsion was divided into eight equal parts, the polymer composition of the synthesis example described above was added to each part, and the emulsion was coated on a baryta coated paper support and dried.

The photographic material thus obtained was exposed and developed in a sensitometer customary in the art.

Temperature 20 with developer D-72 (Eastman Kodak Co.)
C. for 90 seconds, the sample was fixed in an aqueous solution of sodium thiosulfate for 10 minutes, and then washed with water. The moisture-containing material is air-dried naturally and then heated to 90° C. in a photometric polishing press. The maximum concentration (DM) of each sample was measured using a densitometer, Table 1
The results were obtained. Example 2 The same emulsion as in Example 1 was prepared without adding the polymer composition to the emulsion.
I tried adding it to the top protective layer.

Claims (1)

[Scope of Claims] 1 A polymer composition consisting of monomer components (a), (b) or repeating units of monomer components (a), (b), (c) represented by the following general formula: A photographic material characterized by containing: (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R_1
, R_2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, or a hydroxyalkyl group having 2 or less carbon atoms, and R_1 and R_2 may be the same or different. (b) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_3 is a hydrogen atom or a methyl group, R_4, R_
5 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. However, R_4 and R_5 are never hydrogen atoms at the same time. m is an integer of 1 to 3, and p is 0.1. (c) (a
), (b) an ethylenically unsaturated monomer copolymerizable with the monomer component.