US3907572A

US3907572A - Color photographic photosensitive emulsion and color photographic material

Info

Publication number: US3907572A
Application number: US436790A
Authority: US
Inventors: Bunzo Ueda; Sigeru Iguchi; Tetsuo Yano; Tamotu Iwata
Original assignee: Mitsubishi Paper Mills Ltd
Current assignee: Mitsubishi Paper Mills Ltd
Priority date: 1973-01-30
Filing date: 1974-01-25
Publication date: 1975-09-23
Anticipated expiration: 1992-09-23
Also published as: DE2404193A1; JPS49102339A; GB1456278A

Abstract

In color photographic photosensitive materials, coupler can be stably and finely dispersed in a silver halide color photographic emulsion by addition of a polymer which contains, as side chains in one molecule, carboxyl group, imidazole group and amide group or N-(1,1-dimethyl-3-oxobutyl)aminocarbonyl group beside said three groups.

Description

United States Patent Ueda et al. 1 Sept. 23, 1975 15 COLOR PHOTOGRAPHIC 3,598.600 8/1971 Tuites et ,11, 96/114 PHOTOSENSITIVE EMULSION AND g i 96/114 ague e a COLOR PHOTOGRAPH: MATERIAL 3.764.327 l0/l973 Nagae et a] 96/l I4 [75] Inventors: Bunzo Ueda; Sigeru lguchi; Tetsuo 3.813.251 5/1974 Hollister et al. 96/114 Yano; Tamotu Iwata, all of Nagaokakyo' Japan Primary E.raminer-J. Travis Brown [73] Assignee: Mitsubishi Paper Mills, Ltd., Japan An Agent, or Fi .c h D rby & 221 Filed: Jan. 25, 1974 Cushma [21] App]. No.: 436,790

[57] ABSTRACT [30] Foreign Application Priority Data in color photographic photosensitive materials, coum dpdn pler can be stably and finely dispersed in a silver hal- 152 US. Cl. 96/100- 96/84 96/1 14 ide Phomgmphic emulsion by addition of Poly 151 lm. c1. oosc 1/40- oosc 1/72 which Side chains in one [58] Field of Search 96/1 14 100 carboxyl group imidazo'e group and amide gmuP N-(1,l-dimethyl-3-oxobutyl)aminocarbonyl group be- [56] References Cited side said three groups.

UNITED STATES PATENTS 6/1969 Kondo et al. 96/114 10 Claims, No Drawings COLOR PHOTOGRAPHIC PHOTOSENSITIVE EMULSION AND COLOR PHOTOGRAPHIC MATERIAL BACKGROUND OF THE INVENTION The present invention relates to a color photographic photosensitive material. More particularly, it relates to an inner type color photographic photosensitive material in which a color coupler which couples an oxidation product of N,N-dialkyl-para-phenylenediamine developing agent to form a dye image is stably dispersed in a silver halide photographic emulsion layer.

Generally, there are two methods for introducing a coupler into a silver halide photographic emulsion, namely, one method which comprises introducing it by adding water soluble or alkali soluble group thereto and the other method which comprises mechanically dispersing a solution of an oil soluble coupler in solvent of high boiling point in gelatin with a surface active agent and redispersing thus obtained dispersed solution in a silver halide emulsion. However, both of these methods have various defects. According to the former method, when the coupler which carries carboxyl group and (or) sulfon group is incorporated into silver halide gelatin emulsion, generally, said coupler is dissolved in a solution of alkali metal hydroxide such as aqueous sodium hydroxide, alcoholic potassium hydroxide, etc. and then is added to the silver halide gelatin emulsion. In this case, coagulation may occur. Moreover, addition of a coupler which is soluble in only a highly alkaline solution causes excessive increase in pH of the photographic emulsion and therefore, it must be made acidic again, due to which coagulation may also be caused. Furthermore, there are other difficulties caused due to alcohol used in a large amount for making the dissolving of coupler easier. In addition, there is the problem that viscosity of the photographic emulsion changes with lapse of time, which appears to be attributable to the reaction of such type of coupler and gelatin. According to the latter method 4 comprising dispersing an oil soluble coupler, there is a difficulty in solubility of the coupler in the solvents of high boiling point such as dibutyl phthalate, tricresyl phosphate, etc. and a large amount of solvent is required. Furthermore, when the coupler is dissolved in only the solvent of high boiling point, particles of the dispersed coupler become coarse to result in reduction in density of colored image and obscuration due to irradiation. Therefore, generally, solvents of low boiling point such as ethyl acetate, methylethyl ketone, toluene, benzene, cyclohexane, etc. are jointly used as assistant solvent, but unless the coupler is such one as substantially improved in solubility, recrystallization occurs and coloration often becomes insufficient. On the other hand, dispersed particles of such coupler are preferably as fine as possible. As disclosed in The Theory of Photographic Process (Third edition, page 386) published from New York Macmillan Company,

in coating (tail-like stripes) occurs due to fine crystals of the coupler. Furthermore, clogging of filter is caused at filtration before coating. Thus, couplers suitable for production of color photographic photosensitive materials have been extremely limited.

SUMMARY OF THE INVENTION It has now been found that when a synthetic resin which contains, as side chains, imidazole group, amide group and carboxylic acid group in a same molecule and which is produced by copolymerization of three vinyl monomers, namely, vinylimidazole, acrylamide and acrylic acid or derivatives thereof or by hydrolyzing a copolymer of the two among said three vinyl monomers or a water soluble synthetic resin produced by introducing N-( l l -dimethyl-3- oxobutyl)aminocarbonyl group is incorporated into a color photographic emulsion of an inner type color photographic photosensitive materials, especially which contains an oil soluble coupler and a solvent of high boiling point, the coupler can be extremely finely dispersed in the emulsion and recrystallization of the coupler can be restrained.

Introduction of N-( l, 1 -dimethyl-3- oxobutyl)aminocarbonyl group can be accomplished by adding N-( l,l-dimethyl-3-oxobutyl)acrylamide (the so-called diacetone acrylamide) to the monomers before polymerization and copolymerizing them in accordance with usual method.

DESCRIPTION OF THE PREFERRED EMBODIMENT Optimum proportion of the monomers in the synthetic resin, namely, vinylimidazole derivative, acrylic acid, acrylamide and diacetone acrylamide varies depending upon kinds of coupler to be dispersed, solvent for the coupler and surface active agent.

The stability of the dispersed particles depends on various complicated factors and optimum conditions must be obtained in each case, but usually vinylimidazole is 1-20 mol acrylic acid is 1-20 mol acrylamide is 10-98 mol and diacetone acrylamide 0-50 mol Furthermore, isoelectric point of the polymer used in the present invention may be freely controlled within the range of 3-8.5 by proportion of each monomer.

The polymer used in the present invention may be applied to any kind of couplers. Furthermore, it is also effective for dispersing the agents usually employed in the color photographic photosensitive materials such as ultraviolet absorbing agents, e.g., Tinuvin ps, Tinuvin 320 and Tinuvin 328 (Tradenames for the products of Ciba-Geigy Co., Switzerland); stain-inhibitors, e.g., 2,5- di-tert-butylhydroquinone, 2,o-di-tert-butyl-p-cresol, etc.; and scavenger, e.g., 2,5-di-tert-octylhydroquinone. Furthermore, the layer to which the polymer is added is not limited to the photosensitive emulsion layer.

The vinylimidazole derivative used in the present invention is such as having the following general formula:

(wherein one of R, R, R" and R' is vinyl group and others are hydrogen, alkyl or hydroxyalkyl). Examples of such vinylimidazole are l-vinylimidazole, vinylimidazole, l-vinyl-2-methyl-imidazole, l-vinyl-2- ethyl-imidazole, l-vinyl-2,4-dimethyl-imidazole, lvinyl-2-ethyl-4-methyl-imidazole, l-vinyl-4(or 5)-62 -hydroxyethyl-imidazole, l-vinyl-2-B-hydroxyethylimidazole, etc.

The polymer used in the present invention can be added to the emulsion at any stage of dispersing the coupler, blending the emulsion and coating of the emulsion and most preferably it can be added at dispersing of the coupler.

Since the dispersing conditions are improved by addition of the polymer, amount of solvent used can be reduced and so the film thickness can be decreased to result in increase in sharpness of image.

There are substantially no differences in effects of the polymer used in the present invention depending upon its polymerization degree, but a polymerization degree of 500-2000 is suitable in view of easy formation of an aqueous solution and compatibility with gelatin.

Regarding the amount of the polymer added to the photosensitive emulsion, addition of about 50-60 by weight of gelatin can provide the maximum effect, but it may be added in an amount of less than said range. Furthermore, the polymer may also be added to a silver halide emulsion containing no gelatin as disclosed in Japanese Patent Publication No. 756/68. The preferable weight ratio of silver halide/polymer is l/0.ll/l0.

The polymer used in the present invention is effective for any couplers used in the inner type color photographic photosensitive materials. Furthermore, the polymer has no troubles such as dye absorption, etc. when the photosensitive materials contain halation inhibiting dyes and irradiation inhibiting dyes (such as food red dye No. 2 or food blue dye No. 2 as disclosed in US. Pat. No. 2,956,879 or those disclosed in Japanese Patent Publication No. 13,168/68) and has no adverse effects on photographic characteristics such as sensitivity, fog, preservability, etc.

Any supports to be coated with emulsion such as films, baryta paper, etc. may be used and have no limitation.

Another effect of the present invention is that as shown in the following Examples the coupler dispersion may be prepared from only the polymer used in the present invention without using gelatin to inhibit deviation in quality caused by lot of gelatin and to always obtain coupler dispersions of a constant quality. Furthermore, since there occur no deteriorations such as putrefaction and change of quality caused by bacteria, a large amount of coupler dispersion can be produced at one time it can be stored in a form of solution. Therefore, a necessary amount of thus stored coupler dispersion can be doled out and incorporated into silver halide photographic emulsion. This is markedly advantageous for producing color photographic photosensitive materials.

The following are examples of preparation of the representative copolymers used in the present invention.

PREPARATION EXAMPLE 1 Liquid (1) 99% Acrylamide 1-Vinyl-2-methylimidazole Nitric acid lsopropyl alcohol Water Liquid 2 Water To the liquid (2) through which nitrogen was previously and sufficiently passed and which was kept at 70C was added the liquid (1) dropwise in minutes and thereafter this was kept at 70C for another 30 minutes. Then, this was treated with 4 ml of 30 methanolic solution of N-dihydroxyethylaniline at 70C for 30 minutes to decompose the remaining potassium pe'rsulfate. Seventy-four grams of water containing 5.8 g of sodium hydroxide was added thereto and this was heated at 70C for 30 minutes to hydrolyze a part of amide group and was neutralized with 17 g of 70% nitric acid and then cooled. The resultant resin solution was added to methanol or acetone in an amount of 5 times that of the solution while stirring to precipitate the resin, which was filtered off and vacuum dried.

About 9 mol of side chains of thus obtained polymer was 2-methylimidazole, about 10 mol was carboxyl group and the remainder was acrylamide group.

PREPARATION EXAMPLE 2 99% Acrylamide V l-Vinyl-2-B.hydroxyethylimidazole Acrylic acid lsopropyl alcohol Water 2 Potassium persulfate The above monomer mixed liquid was subjected to polymerization reaction at 70C for 2 hours while passing nitrogen therethrough and stirring. After completion of the reaction, 4 ml of 3 methanolic solution of N-dihydroxyethylaniline was added thereto and this was heated at 70C for further 30 minutes and then cooled. The resin in the resultant resin solution was precipitated with methanol or acetone and the precipitate was vacuum dried.

About 15 mol of side chains of thus obtained polymer was 2-B.hydroxyethylimidazole, about 8 mol was carboxyl group and the remainder was acrylamide group.

PREPARATION EXAMPLE 3 Liquid (1) Liquid 2 Potassium persulfate Water Polymerization was carried out under the same conditions as in Preparation Example 1. To the product was added 4.5 g of sodium hydroxide and 100 ml of water and this was heated at 70C for 30 minutes to hydrolyze a part of amide group and then was neutralized by adding 14 g of 7O 7( nitric acid and 130 g of water and cooled.

The resultant polymer had the compositions of about 8 mol of 2methylimidazole group, about 7 mol of carboxyl group, about 20 mol of diacetone acrylamide and about 65 mol (remainder) of acrylamide group.

PREPARATlON EXAMPLE 4 99: Acrylamide LVinyl-Z-ethylimidazole Diacetone acrylamide Acrylic acid lsopropyl alcohol Water Potassium pcrsulfate EXAMPLE 1 Synthetic resin of Preparation Example I 6 kg Water 5% Aqueous solution of di-Z-ethyl-hexyl sulfo succinate l Magenta c0up|er* 4.

Liquid A Liquid 8 Tricresyl phosphate Ethyl acetate 2 l-( 2-4.6-trichluruphenyl)3-l A (3-n-pcniadecylphcnoxy )butyl Iamide-SpyraZolOne The above liquid A was kept at 50C and the liquid B was at 60C to sufficiently dissolve the coupler and then they were mixed and the coupler was dispersed with a homoblender for 1 hour. For comparison, a coupler dispersion was prepared under the same conditions as mentioned above except that 6 kg of photographic inert bone gelatin was substituted for the synthetic resin of Preparation Example 1. One-tenth of each of said dispersions was added to and redispersed in gelatin silver halide photographic emulsion containing 450 g of silver chlorobromide containing the usual green sensitive sensitizing dye and 1 kg of gelatin to prepare color photographic emulsions for magenta layer. 100 l of 3 gelatin solution was separately prepared. After lapse of 8 hours, two layers of the emulsion and the gelatin solution were simultaneously coated on a baryta paper at 30 m/min by an extrusion type coaterv State of the tail-like stripes formed after coating of 300 m were as follows:

Number of the tail-like stripes per in Emulsion of the present invention [0 The comparative emulsion 540 0. lO t 0.45;.1.

Emulsion of the present invention The comparative emulsion l l of each emulsion was left at 40C for 3 days and then was filtered with a filter fabric of Amilan. in case of the comparative emulsion, the filter fabric was clogged because the coupler was recrystallized and the filtration was impossible while in case of the present emulsion no such troubles were caused. Thus obtained photosensitive materials were exposed and subjected to the usual color development treatment comprising color developing, water washing, bleaching with potassium ferricyanide-bromide, fixation, etc. As the result, the photosensitive material having the present emulsion produced a brighter magenta image than the photosensitive material having the comparative emulsion.

EXAMPLE 2 Example 1 was repeated except that 6 kg of the synthetic resin of Preparation Example 1 was replaced by combination of4 kg of inert gelatin and 2 kg of the synthetic resin of Preparation Example 2 and by combina tion of 5 kg of inert gelatin and 1 kg of synthetic resin of Preparation Example 4. Thus obtained two photosensitive materials yielded the same results as in Example l.

EXAMPLE 3 Synthetic resin of Preparation Liquid A was kept at 50C and liquid B was at C to sufficiently dissolve the ultraviolet ray absorbing agent and then the absorbing agent was dispersed for 1 hour by a homoblender. For comparison, a dispersion was prepared in the same manner as mentioned above except that the synthetic resin of Preparation Example 2 was replaced with 86 g of a photographic bone gelatin and the solvent of high boiling point was increased to 2 times. After these dispersions were kept at 40C for 24 hours, the state of the dispersions was observed with a microscope to find that in the comparative dispersion, innumerable crystals of the ultraviolet ray absorbing agent were produced while in the present dispersion the dispersed particles of about 0.1 ,u. were stably maintained. Thus obtained ultraviolet ray absorbing agent dispersion may be coated on a coupler containing emulsion layer and this can be applied to a color photographic photosensitive material.

What is claimed is:

l. [n a color photographic silver halide emulsion which comprises silver halide and a coupler, the improvement of additionally including in said emulsion a polymer which contains as side chain groups (a) carboxyl groups, (b) imidazole groups, and (c) amide groups or side chain groups (a), (b) and (c) and also ((1) N-(1,1-dimethyl-3-oxobutyl) aminocarbonyl groups, the proportions of said groups being (a) 1-20 mo] (b) 1-20 mol (c) lO-98 mol and ((1) -50 mol said polymer being a terpolymer of l) acrylic acid, (2) acrylamide and (3) a vinyl imidazole or being a tetrapolymer of l (2), (3) and also (4) diacetone acrylamide.

2. A color photographic silver halide emulsion according to claim 1, wherein the polymer has a polymerization degree of 500-2000.

3. A color photographic silver halide emulsion according to claim 2, wherein the weight ratio of silver halide/polymer is l/0.ll/l0.

4. A color photographic material which comprises a support and the emulsion as defined in claim 2 coated thereon.

5. An emulsion according to claim 1 wherein the vinyl imidazole has the formula where one of R, R, R and R is the vinyl group and the other members of R, R, R" and R are hydrogen, alkyl or hydroxyalkyl.

6. An emulsion according to claim 1 wherein the polymer is a terpolymer of acrylamide, l-vinyl-2-,B- hydroxyethyl-imidazole and acrylic acid.

7. An emulsion according to claim 1 wherein the polymer is a terpolymer prepared by hydrolyzing a copolymer of acrylamide and l-vinyl-2-methylimidazole to form a terpolymer of l-vinyl-2- methylimidazole and acrylic acid.

8. An emulsion according to claim 1 wherein the polymer is a tetrapolymer prepared by hydrolyzing a terpolymer of acrylamide, 1-vinyl-2-methylimidazole and diacetone acrylamide.

9. An emulsion according to claim 1 wherein the polymer is a tetrapolymer of acrylamide, l-vinyl-2- ethylimidazole, diacetone acrylamide and acrylic acid.

10. A coupler dispersion which comprises a coupler and the polymer as defined in claim I.

ac rylamide

Claims

1. IN A COLOR PHOTOGRAPHIC SILVER HALIDE EMULSION WHICH COMPRISES SILVER HALIDE AND A COUPLER, THE IMPROVEMENT OF ADDITIONALLY INCLUDING IN SAID EMULSION A POLYMER WHICH CONTAINS AS SIDE CHAIN GROUPS (A) CARBOXYL GROUPS, (B) IMIDAZOLE GROUPS, AND (C) AMIDE GROUPS OR SIDE CHAIN GROUPS (A), (B) AND (C) AND ALSO (D) N-(1,1-DIMETHYL-3-OXOBUTYL) AMINOCARBONYL GROUPS, THE PROPORTIONS OF SAID GROUPS BEING (A) 1-20 MOL % (B) 1-20 MOL %, (C) 10-98 MOL % AND (D) 0-50 MOL %, SAID POLYMER BEING A TERPOLYMER OF (1) ACRYLIC ACID, (2) ACRYLAMIDE AND (3) A VINYL IMIDAZOLE OR BEING A TETRAPOLYMER OF (1), (2), (3) AND ALSO (4) DIACETONE ACRYLAMIDE.

3. A color photographic silver halide emulsion according to claim 2, wherein the weight ratio of silver halide/polymer is 1/0.1-1/10.

5. An emulsion according to claim 1 wherein the vinyl imidazole has the formula

6. An emulsion according to claim 1 wherein the polymer is a terpolymer of acrylamide, 1-vinyl-2- Beta -hydroxyethyl-imidazole and acrylic acid.

7. An emulsion according to claim 1 wherein the polymer is a terpolymer prepared by hydrolyzing a copolymer of acrylamide and 1-vinyl-2-methylimidazole to form a terpolymer of acrylamide, 1-vinyl-2-methylimidazole and acrylic acid.

9. An emulsion according to claim 1 wherein the polymer is a tetrapolymer of acrylamide, 1-vinyl-2-ethylimidazole, diacetone acrylamide and acrylic acid.

10. A coupler dispersion which comprises a coupler and the polymer as defined in claim 1.