JPS6388549A - Silver halide color photosensitive material containing polymer coupler - Google Patents

Abstract

PURPOSE:To improve retention stability of a coating solution for the titled material by using a polymer coupler which has a repetitive unit composed of alkoxyalkyl acrylate monomer having a branched or substituted alkyl in the alkyl part as a non-coloring co-monomer. CONSTITUTION:The polymer coupler comprises the alkoxyalkyl acrylate type monomer as the non-coloring comonomer, and the repeating unit of the comonomer contains the branched or the substituted alkyl group. The comonomer is shown by the formula wherein R1 is hydrogen atom, chlorine atom or 1-4 C alkyl group, R2 is alkyl group, J is a brenched or a substituted alkyl group. The coupler monomer and the comonomer used for the polymer coupler may be jointly used two or more kinds thereof, respectively. The compounding ratio of the coupler monomer and the comonomer is preferably a range of (1:0.5)-(1:5). Thus, the stable photographic performance of the titled material and the good image are obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide color photosensitive material (hereinafter referred to as photosensitive material) containing a novel polymer coupler.

(Prior art) It is known that by polymerizing photographic couplers, it is possible to improve non-diffusibility, prevent precipitation, and further prevent sweating by removing high boiling point solvents, and make it possible to form thin films. In particular, U.S. Patent tjS4,61
No. 2,278 discloses that high color density can be obtained by using an alkoxyalkyl acrylate compound as a comonomer.

However, although these couplers can provide high color density, they are not satisfactory because they have poor coating solution stagnation stability and cannot provide stable light-sensitive materials during long-term coating.

(Object of the Invention) An object of the present invention is to provide a photosensitive material containing a polymer coupler having excellent coating solution stagnation stability.

(Structure of the Investigation) It has been discovered that the object of the present invention can be achieved by a photosensitive material having a quantitative structure.

That is, the silver halide color light-sensitive material of the present invention is a silver halide color light-sensitive material containing a polymer coupler.
The polymer coupler is characterized in that the non-color-forming co/mer is an alkoxyfurkyl acrylate type mo7mer, and the alkyl moiety has a repeating unit of the co/mer which is an alkyl moiety having a branch or a substituent. configured.

In a silver halide color light-sensitive material containing a polymer coupler, the polymer coupler is an alkoxyalkyl acrylate monomer as a non-color-forming comonomer, and the alkyl moiety is an alkyl moiety having a branched or substituent group. Repeat! It is characterized by having the 11th place.

In the polymer coupler according to the present invention, as long as the alkyl moiety of the alkyl acrylate monomer that is a non-color-forming co/mer is not linear and is branched or has an ra substituent, other moieties are not particularly limited. Preferred comonomers that can achieve the objects of the present invention are those represented by the following formula.

R6 represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms, R2 represents an alkyl group, and J represents a branched or substituted alkylene group.

The alkyl group represented by R2 includes those having a substituent (eg, hydroxy group, alkoxy group), and may be linear or branched, and is preferably 1. ( is an alkyl group having 1 to 20 carbon atoms. Examples of substituents for the alkylene group represented by J include an alkoxy group and a hydroxy group,
In addition, the branched part of the branched alkylene represented by J is a substituent (
For example, J preferably has 2 to 20 carbon atoms, including those having an alkoxy group.

Next, examples of preferred comonomers according to the present invention are 1, Cl
12=CI-COOCH, CHOCH.

薯CH1゜3、CH2=CH-C00CH2CHOC112
C112CI.

C) 120C2H6 4, CH = Cl-C00CII□Cll0CII□C
1l.

CH20C, lI.

5, c112=c11-coocl12cllo
cl+3C)I 20CH.

6, CH2=CH-C00C112CIOC11
゜CH3 8, CH2=CH 曾C211゜9, CH2=CH-COOCII2C)IOCL
Book C, L 10, CH2=CH-C00CH,C! 1OclI
2cH20H■ 11, C112=CH-COOCII2C1lC1
120C211512, CB, =C) 1-COOCH,
CHCH20C,ll.

14, C11z=CIl-COOCIIzC1lO
CII□C11□0110CII.

C1l, CH.

++3 Utl As the coupler monomer used in the polymer coupler according to the present invention, as long as it is a monomer having a coupler part,
Although not particularly limited, examples include those represented by the following formula.

(:H2=C-f Y ”pr-f A frr-X
-Q In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or chlorine h L , X1i-CONH-1
-NIICONII-1-N11C00-1-COO-
1-SO2-1-CO-1 or -0-, Y is -
CONIi or -COO-, where ^ has 1 or more carbon atoms
It represents 10 fullkylene groups, aralkylene groups, or arylene groups, and the fullkylene moiety in the fullkylene group and the 7-ralkylene group may be linear or branched.

q represents a cyan coupler residue, a magenta coupler residue or a yellow coupler residue.

Jll represents 0 or 1.

Two or more kinds of coupler monomers and comonomers according to the present invention used in the polymer coupler according to the present invention may be used. As for the monomer ratio, the ratio of coupler monomer to comonomer according to the present invention is 1:0.5 to 1:5.
A range of is preferred.

Moreover, the polymer coupler according to the present invention may further contain repeating units of other polymers, such as:
Acrylic acids and their esters (e.g. ethyl acrylate) and amides (e.g. methacrylamide), vinyl esters (e.g. vinyl acetate), 7-crylonitrile, metha-7-crylonitrile, aromatic vinyl compounds (e.g. styrene, divinylbenzene), itaconic acid, Citraconic acid, crotonic acid, vinylidene chloride, vinylfurkyl ether (e.g. vinyl ethyl ether), maleic acid ester, N-vinyl-2-pyrrolidone, N-
Examples include vinylpyridine, 2- and 4-vinylpyridine.

Specific examples of polymer couplers used in the present invention are shown below, but the present invention is not limited thereto.

Example of yellow polymer coupler X, Y, Z indicate mol% ゛Yu.

Example of a magenta polymer coupler Rr R4Rs Among them, it is preferable that it is added as latex.

To add the polymer coupler as a latex, the polymer coupler may be polymerized by a specific polymerization method, or a lipophilic polymer coupler obtained by another polymerization method is dissolved in a growth solvent and dispersed in the form of a latex in an aqueous gelatin solution. You can also make it by

Regarding the emulsion polymerization method, see US Pat. No. 4,080,211;
No. 3,370,952 and US Pat. No. 3,451,520, the method of dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution can be used.

Examples of initiators and their effects are given by F. Dovey [E.
mulsion polymerizaLionJ
Interscience Pu1)lishes
Inc. New York Publication 1 Issue 1 Hayabusa 55 listed.

As the emulsifier used in the specific polymerization, a compound having a surfactant is used, and preferred examples include soaps, sulfonates, sulfates, cationic compounds, amphoteric compounds, and polymeric protective colloids. Examples of these groups and their effects can be found in Be1g1scbe Chemis
che Industrie, Vol. 28, 116-20 (1963).

On the other hand, when a lipophilic polymeric coupler is dispersed in the form of a latex in an aqueous gelatin solution, the organic solvent used to dissolve the lipophilic polymer UV absorber may be used before or (less preferably) after coating the dispersion. It can be removed during vaporization during drying of the liquid.

The polymeric coupler contains from 0.0001 mole to 0.5 mole, preferably 0.0001 to 0.5 mole per mole of silver, based on coupler monomer.
．． It is preferable to add 0.001 to 0.5 mol.

Synthesis Example 1 Synthesis of polymer coupler PY-6 Dodecylbenzenesulfonic acid Sorg 1, Oig 800
11 Heat the aqueous solution to 80°C while deoxidizing it through a nitrogen stream. Add 20% of potassium persulfate 350B to this aqueous solution.
xl aqueous solution added 1 then Como/mer 1 according to the present invention
4.35 g (0.03 mol) of the following coupler monomer and 5.2 g (0.01 mol) of the following coupler monomer were added to 150 zff of ethanol.
It was heated and dissolved in i and added. After the addition, stirring was continued for 1 hour, 10 ml of an aqueous solution of potassium persulfate 250B was added, and the reaction was continued for another 1 hour. Ethanol and unreacted monomers were distilled off as an azeotrope of water, and 0. The pH was adjusted to 6.01 with IN sodium hydroxide and filtered.

The polymer concentration of latex PY-6 was 10% and the content of coupler monomer units was 25 mol%.

CH. =CH Synthesis Example 2 Synthesis of Polymer Coupler PC-2 1.5 g of sodium salt of oleyl methyl tauride
The N aqueous solution was passed through a nitrogen stream and heated to so'c while being deoxidized.

A 20zN aqueous solution of 2501 g of potassium persulfate was added to this water ig solution, and then Como/mer 16 according to the present invention was added to 4-
95 ri (0-0” A thousand ru) te drink 1-1 drunken music m
Comonomer 16 was added to the latex of 1.65, (0.0
1 mol) and the following coupler monomer 2.1y (0.01 mol) in ethanol 200++/! was added, then 20ml of an aqueous solution of 300mg of potassium persulfate was added, and after further reaction for 1 hour, 2001g of potassium persulfate was added.
0w1 aqueous solution was added. Subsequently, after reacting for 1 hour, ethanol and 1 unreacted monomer were distilled off as an azeotropic mixture of water, the pH was adjusted to 6.0 with 0.18 sodium hydroxide, and the mixture was filtered.

The polymer concentration of the latex pc-z was 10% and the content of coupler monomer units was 30 mol%.

y Synthesis Example 3 Synthesis of polymer coupler PH-3 5.25 g (0.03 mol) of comonomer 3 according to the present invention and 2.4 g (0.01 mol) of the following coupler monomer were dissolved in 450 ml of quaxane, and the mixture was dissolved under a nitrogen stream. 2,2' dissolved in Nooxane 5111 while heating and stirring at 70°C.
-Azobis(2,4-trimethylvaleronitrile) 270
i, l with jy added? After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was poured into 2N ice water, and the precipitated solid was collected by filtration. This solid was Polymer 118-3 containing 25 mole percent coupler monomer.

A latex was produced using this polymer as follows.

5 g of polymer was dissolved in 20 ml of methyl acetate at 38°C, and 0.5 ml of a 70% by weight solution of sodium dodecylbenzenesulfonate was added.Then, this was mixed with 7 ml of a 10% by weight aqueous gelatin solution, and double After dispersing with a cylindrical disperser, ethyl acetate and methanol were distilled off under reduced pressure to produce a latex.

CI(.

C1l□=CI According to Synthesis Example 1, PY-6, PH-7 to PH-11,
PC-4 to I'C-6 and PC-10 were converted to r'Y-1, PY-2, PH-4 to r'14-6 according to Synthesis Example 2.
, PC-1 and PC-3 were also synthesized with PY according to Synthesis Example 3.
-3゜PY-4, r'M-1, l'M-2, PC-7~
Latex of PC-9 was obtained and used in the photosensitive material of the present invention)
Silver 10denide? For L cutting and 17, ordinary silver halide'
Any of the JL agents can be used.

The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. It is preferable to use gelatin as the pineapple in the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

The polymer coupler according to the present invention has a coupler other than the present invention (
(Whether or not it is a polymeric coupler) may also be used in combination with a colored coupler, which also has a color correction effect, and is a development inhibitor by combing with an oxidized form of a competing coupler and a developing agent. Photographic agents such as development accelerators, bleaching agents, developing agents, toning agents, hardeners, fogging agents, antifogging agents, chemical sensitizers, spectral sensitizers, and desensitizers. Compounds that release a 7-ragment that is useful in clinical trials can be used.

The light-sensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an anti-yellow acid layer. These layers and/or the emulsion layer may contain dyes that flow out of the sensitive material or are bleached during development.

Sensitive materials include matting agents, lubricants, image stabilizers, surfactants,
A color antifoggant, a development accelerator, and a self-accelerating agent can be added before the development delay.

As a support, paper laminated with polyethylene, etc.
It can be applied to polyethylene pre-7 tallate film, baryta paper, cellulose triacetate, etc.

To obtain a dye image using the photosensitive material of the present invention, it is necessary to
; 山昂An, -h gloa, 79)
-Five blind additions, 2,000, 2-shi can do it.

(Example) The dispersion stability of polymer coupler latex was tested by the following method.

The polymer coupler latex liquids prepared by the methods of Synthesis Example-(1) and Synthesis Example-(2) were as follows: Synthesis Example=3(
The polymer coupler/gelatin/sodium totysylbenzene sulfonate ratio was adjusted accordingly. Next, the prepared polymer coupler latex liquid and the polymer coupler latex liquid prepared by the method of Synthesis Example (3) were each adjusted to have a gelatin concentration of 2%. The dispersion stability of these adjusted polymer coupler latex liquids was determined by heating at 40°C for 8 hours,
The turbidity of the acrobatic dispersion was measured and evaluated based on the rate of change in turbidity.

The results are shown in the table below.
Comparison 17 to the comparative polymer coupler with i alkyl,
The polymer coupler-Latenx separation solution of the present invention is
It has been found that the turbidity temperature is low when kept warm, there is little aggregation of latex particles, and it has excellent dispersion stability.

Dispersion stability is evaluated in the table below by comparing the amount of change in turbidity of the polymer coupler latex liquid of the present invention before and after being left to warm. It is expressed as a relative value when the amount of change in turbidity after 1 moth is set as 100.

In addition, sensitive materials produced using the yellow coupler, cyan coupler, and the polymer coupler according to the present invention exhibit stable photographic performance (in this case, unsubstituted alkaline material is used instead of COMO 77- according to the present invention). A good image with a density 1.3 to 3 times that of a polymer coupler using acrylate mo/mer was obtained.

Applicant: Konishiroku Photo Industry Co., Ltd. Procedure old man t1-positive 1! (: Showa 61! February 24th

Claims (1)

[Claims] In a silver halide color light-sensitive material containing a polymer coupler, the polymer coupler is a non-color-forming comonomer that is an alkoxyalkyl acrylate monomer, and the alkyl moiety is a branched or substituent-containing alkyl moiety. A silver halide color photosensitive material characterized by having: