JPS59817B2 - Syashinkankouzairiyou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention uses a copolymer as an anti-bronzing agent to effectively contact a photographic silver halide emulsion with mechanical drying at high temperature on a high-gloss press. Photographs characterized by...Relating to silver halide photosensitive materials.

Photosensitive - Silver images obtained from silver halide emulsion layers are often altered by high gloss drying or mechanical drying at elevated temperatures.

This results in a decrease in density, or the tone of an all-blue image changes to a brownish tone, or the brown tone changes to a black tone with a greenish tone. Such changes can cause tanning or bronzing of the silver image (
Bron2ing). E., Weyde and E. on the causes of freon sink. Klein (
MiffelungenAgfaBd, 2, 117-1
20) is due to a change in the light dispersion of the gelatin layer containing silver particles, and the essential factor is said to be due to a change in the shape of silver aggregates. It is known to incorporate small amounts of certain compounds known as antibronzing agents into silver halide emulsion layers.

However, the effectiveness of known anti-bronzing compounds is limited because they do not have sufficient anti-bronzing effects or they impair photographic properties. It is an object of the present invention to provide new anti-bronzing agents which have a sufficient anti-bronzing effect and are harmless to the photographic properties of photographic materials. The present inventors have discovered that the object can be achieved by incorporating the following copolymer composition into a photographic light-sensitive material.

The copolymer composition used in the present invention comprises (a), (b) monomer components represented by the following general formula, or (a), (b), (
This is a copolymer composition consisting of repeating units of the monomer component c).

However, R1 and R2 are hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, aryl groups, or (CH2)NOH (n is 1, 2
).

However, R7 represents a hydrogen atom or a methyl group, R5 represents a divalent alkylene group having 1 to 6 carbon atoms,
R3 and R4 represent an alkyl group having 1 to 8 carbon atoms, R6 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, and XO represents an anion.
(P is O or 1) However, when Pi)'-0, the monomer is an inner salt and R6 represents an anion. (c) (
a), (b) Ethylenically unsaturated monomer copolymerizable with the monomer component. The monomer component represented by general formula (a) is a vinyl imidazole compound, for example, 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)-beta-hydroxyethylimidazole, 1-vinyl-2-beta-hydroxyethylimidazole, and the like.

The monomer component represented by general b) is N-N-dialkylaminoalkyl acrylates, N-N-dialkylaminoalkyl methacrylates, or, for example, 2-(
N-N-dimethylamino)ethyl acrylate, 2-(
N-N-diethylamino)ethyl acrylate, 2-(
N-N-dibutylamino)ethyl acrylate, 3-(
N-N-dibutylamino)propyl acrylate, 2-
(N・N-dimethylamino)ethyl methacrylate, 2
-(N-N-diethylamino)ethyl methacrylate,
It is synthesized by reacting 2-(N-N-dibutylamino)ethyl methacrylate, 3-(N-N-dibutylamino)propyl methacrylate, etc. with a quaternization reagent. General formula (c
A variety of ethylenically unsaturated monomer components can be used as the ethylenically unsaturated monomer component copolymerizable with the monomer components (a) and (b) of (a) and (b), all of which have effects, but particularly preferred ones are relatively hydrophilic monomer components. It is an ethylenically unsaturated monomer.

Preferably an acrylamide compound, such as acrylamide, N-methylacrylamide, N-ethylacrylamide, N-phenylacrylamide, N-N-dimethylacrylamide, N·N-diethylacrylamide,
N-N-dibutylacrylamide, N-N-diphenylacrylamide, N-methylolacrylamide, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-phenylmethacrylamide,
Examples include N-N-diphenyl methacrylamide. Also,
Vinyl monomers containing SO3M groups (M is H.Na.K.Ca, Mg) are also preferred, such as vinylsulfonic acid or its salts, allylsulfonates, methallylsulfonates, p-styrenesulfonic acid or its salts, sodium 3-sulfopropyl acrylate, etc.

Also, N-vinyl-2-pyrrolidone, N-vinyl-5-
Methyl-2-pyrrolidone, N-vinyl 3-methyl-2-
Vinylpyrrolidone compounds such as pyrrolidone, hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate are also preferred monomer components. When the copolymer composition used in the present invention is composed of repeating units of single components (a) and (b), the copolymer composition (a) and (
The ratio of b) can vary widely, but preferably (a) is 5
0 to 99 mol%, and (b) 1 to 50 mol%.

Although the copolymer composition consisting of (a) and (b) also has the anti-pronging effect, which is the object of the present invention, the monomer component (c) is used to change the color tone.

Although the ratio of each monomer component in the copolymer composition consisting of (a), (b), and (c) can vary widely, it is preferable that (a) be 50 to 95 mol % and (b) be 1 mol %. -50 mol%, and (c) is 1-50 mol%. The copolymer composition of the present invention is (a)
, (b) or (a), (b), and (c), or by copolymerizing the non-quaternized tertiary component of (b).
It is synthesized by quaternizing a copolymer containing an amine monomer. Various solvents can be used as the polymerization medium, but water and alcohol are preferred. Usually, monomer components are dissolved in these solvents, a polymerization initiator is added, and polymerization is carried out by heating, but polymerization can also be carried out by irradiation with ultraviolet rays or the like. The polymerization time and temperature vary depending on the composition, degree of polymerization, polymerization initiator, solvent, etc., but are usually 40 to 90'C and 5 to 20 hours. During polymerization, it is desirable to perform nitrogen substitution at the beginning or during the entire polymerization period. Various polymerization initiators can be used, such as benzoyl peroxide, acetyl peroxide, α・d-azobisisobutyronitrile, tert-butyl hydroperoxide, cumene hydroperoxide, tertiary-butyl peroxide azodicyclohexyl carbonitrile, α・α
Dimethyl 5-azodiisobutyrate, succinic 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. It is preferable to use the copolymer composition after purifying it by a dialysis method, a reprecipitation method, or the like.

The copolymer composition of the present invention has good compatibility with gelatin, polyvinyl alcohol, polyvinylpyrrolidone, and water-soluble colloids, and is stable over a wide pH range, and when contained in a photographic light-sensitive material, it causes fogging and decreases in photosensitivity. Almost no negative effects are observed.

In addition, they can 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. Furthermore, the copolymer composition of the present invention can be used in the emulsion layer, top layer, intermediate layer, anti-ratio layer, subbing layer, etc. of black-and-white light-sensitive materials and color light-sensitive materials.

The copolymer composition of the present invention includes, for example, 1-vinyl-2-methyimidazole-2-(methacryloyloxy)ethyl-N-N-diethyl-N-γ-sulfopropylammonium betaine copolymer, 1-vinyl-
2-ethylimidazole-2-(methacryloyloxy)ethyltrimethylammonium methosulfate copolymer 1-vinyl-2-methylimidazole-2-(methacryloyloxy)ethyl-N-N-dimethyl-N-β
Monocarboxyethyl ammonium betaine copolymer 1-
Vinyl-2-methylimidazole-3-(methacryloyloxy)propyl-N-N-dibutyl-N-γ-sulfopropylammonium betaine copolymer 1-vinyl-
2-ethylimidazole-2 (methacryloyloxy)
Ethyl-N-N-diethyl-N-γ-sulfopropylammonium betaine-acrylamide copolymer 1-vinyl-2-methylimidazole-2-(methacryloyloxy)ethyl-N-N-diethyl-N-β- Carboxyethylammonium betaine-sodium-3-sulfopropyl acrylate copolymer 1-vinyl-2-betahydroxyethylimidazole-2-(acryloyloxy)ethyl-trimethylammonium methosulfate-N-methylacrylamide copolymer 1 -vinyl-2
-Phenylimidazole-2-(methacryloyloxy)ethyltrimethylammonium methosulfate-sodium-3-sulfopropyl acrylate copolymer 1
-vinyl-2-methylimidazole-2-(methacryloyloxy)ethyltriethyl ammonium ethyl sulfate copolymer 1-vinyl-2-methylimidazole-2-(methacryloyloxy)ethyl-N-N-diethyl-N-carboxy Methylammonium chloride copolymer 1-vinyl-2-methylimidazole-2-(
methacryloyloxy)ethyl-N-N-diethyl-N
- Methylammonium tosylate copolymer and the like.

The amount of the above copolymer to be used is 10 to 5000 m9, preferably 1000 Tf1 per emulsion 1k9 (silver sulfate 33f).
9-1500Tf19 is optimal.

Also, when adding to the protective layer, 2% gelatin solution 100%
01, 100T19~10007f1f, preferably 300η~600~ is optimal. Any of silver chloride, silver chlorobromide, silver bromide, and silver iodochlorobromide may be used as the light-sensitive material.
Hereinafter, it will be specifically explained using synthesis examples and examples.

Synthesis Example 1 2-(methacryloyloxy)ethyl-N-N-diethyl-N-γ-sulfopropylammonium bentaine 1
2.07 (20 mol%), 1-vinyl-2-methylimidazole 17.0f (80 mol%), potassium persulfate 0.3
y, 0.1 f of sodium metabisulfite was dissolved in 300 ml of distilled water, and heated and stirred at 60 to 65° C. for 6 hours while blowing nitrogen into a 500 ml four-necked flask.

A pale yellow viscous liquid was obtained. After concentrating this to about half its volume, it was precipitated with 2.0 g of acetone and filtered and dried to obtain 21 tons of white powder. Synthesis Example 2 2-(methacryloyloxy)ethyl-N-N-diethyl-N-γ-sulfopropylammonium betaine6.
1f (10 mol%), 1-vinyl-2-methylimidazole 13.0t (60 mol%), acrylamide 4.3
f (30 mol%) A solution of 0.27 potassium persulfate and 0.17 sodium metabisulfite dissolved in 150 WL2 of distilled water was
The mixture was placed in a 00ml four-bottle flask, and heated and stirred in a water bath for 60-6 hours while nitrogen gas was introduced into the liquid to obtain a pale yellow viscous solution.

This was poured into 2.5 liters of acetone, and the resulting white precipitate was filtered and dried under reduced pressure to obtain hygroscopic white-yellow powder 207. Synthesis Example 3 2-(methacryloyloxy)ethyl-N-N-diethyl-N-γ-sulfopropylammonium betaine6.
1y (20 mol%), 1-vinyl-2-methylimidazole 5.4y (50 mol%), sodium 3-sulfopropyl acrylate 6.5y (30 mol%), potassium persulfate 0.2t, metabisulfite 0.17ml of sodium was dissolved in 120ml of distilled water, placed in a 300ml four-bottle flask, and heated and stirred for 60-6C5 hours while blowing nitrogen gas.

A pale yellow viscous liquid was obtained, which was mixed with ethanol:water (1:
1 volume ratio) The mixed solution was precipitated, filtered, and dried to obtain a hygroscopic white-yellow powder 15y. Synthesis Examples 1 to 3-1
Even when copolymerization is carried out using the same mol% of 1-vinyl-2-ethylimidazole in place of vinyl-2-methylimidazole, substantially the same copolymer is obtained.

Example 1 Silver chlorobromide gelatin emulsion (AgCl68 mol%AgBr3
This emulsion was divided into four equal parts, the copolymer composition used in the present invention was added to each part, and the emulsion was coated on a baryta coated paper support and dried.

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

Add D-72 (Eastman Kodak Co.) to the developer at a temperature of 2.
A sample developed at 0° C. for 90 seconds is 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 material was measured using a densitometer, and the results shown in Table 1 below were obtained. Example 21 Using the emulsion of Example 1 above, the amount of the copolymer composition of Synthesis Example 1 added was investigated.

The results were as shown in Table 2 below. Example 3 In the same emulsion as in Example 1, the copolymer composition was not added to the emulsion, but was added to the top protective layer.

Claims (1)

[Scope of Claims] 1 A copolymer consisting of repeating units of monomer components (a) and (b) or monomer components (a), (b), and (c) represented by the following general formula: A photographic material comprising a composition. (a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, R_1 and R_2 are hydrogen atoms, alkyl groups with 1 to 6 carbon atoms, aryl groups, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, R_7 is Represents a hydrogen atom or a methyl group, R_
5 represents a divalent alkylene group having 1 to 6 carbon atoms, R_3 and R_4 represent an alkyl group having 1 to 8 carbon atoms, R_6 is an unsubstituted or substituted alkyl group,
It represents an unsubstituted or substituted aryl group, and X^■ represents an anion. (P is 0 or 1) However, when P is 0, the monomer is an inner salt and R_6 represents an anion. (c)(a),
(b) Ethylenically unsaturated monomer copolymerizable with the monomer component.