JPS6391660A - Silver halide color photosensitive material containing polymer coupler - Google Patents

Abstract

PURPOSE:To increase the color development density of a polymer coupler by incorporating a specified alkyloxystyrene, alkyloxymethylstyrene, alkylcarbonyloxyvinyl or alkylcarbamoylvinyl monomer as a comonomer developing no color into the polymer coupler. CONSTITUTION:A silver halide color photosensitive material contg. a polymer coupler is produced. The polymer coupler has repeating units of an alkyloxystyrene, alkyloxymethylstyrene, alkylcarbonyloxyvinyl or alkylcarbamoylvinyl monomer as a comonomer developing no color, and the alkyl moiety of the monomer has at least one group selected among oxy, oxycarbonyl, carbonyloxy, amino, carbamoyl, carbonylamino and cyclic ether as a substituent. The polymer coupler is preferably present as latex in the photosensitive material and ensures increased color development density.

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 has been disclosed in a patent publication that by polymerizing photographic couplers, it is possible to improve non-diffusibility, prevent precipitation, prevent sweating by removing high boiling point solvents, and make it possible to form a WI film. This is known from Publication No. 59-65844. However, polymer couplers still have the drawback of insufficient color density, and improvements are desired.

(Object of the Invention) The object of the present invention is to provide a photosensitive material containing a polymer coupler with excellent coloring density. I found it.

That is, the light-sensitive material of the present invention is a silver halide color light-sensitive material containing a polymer coupler, in which the polymer coupler is a non-color-forming co-7mer, such as an alkyloxystyrene type, an alkyloxymethylstyrene type, or an alkylcarbonyloxyvinyl type. or an alkylcarbamoyl vinyl monomer in which the alkyl moiety has at least one of an oxy group, an oxycarbonyl group, a carbonyloxy group, an amino group, a carbamoyl group, a carbonylamino group, or a cyclic ether group as a substituent. It is characterized by having a repeating unit.

In the comonomer according to the present invention, the oxy group that the alkyl moiety has as a substituent includes, for example, a hydroxy group and a hydrocarbon oxy group (for example, alkyloxy, cycloalkyloxy, aryloxy, and aryloxy groups). Examples of the oxycarbonyl group include hydrocarbon oxycarbonyl groups (e.g., furkyloxycarbonyl, cycloalkyloxycarbonyl,
Examples of the carbonyloxy group include hydrocarbon carbonyloxy groups (e.g., alkylcarbonyloxy, cyclonalkylcarbonyloxy, alkenylcarbonyloxy, and arylcarbonyloxy groups). Carbamoyl groups include, for example, hydrocarbon carbamoyl groups (e.g., alkylcarbamoyl, cycloalkylcarbamoyl, alkenylcarbamoyl, and arylcarbamoyl groups), and carbonylamino groups include, for example, hydrocarbon carbonylamino (e.g., alkylcarbonyl) groups. amihacyclofurkylcarbonylamino, octaalkenylcarbonylamino, and arylcarbonylamino groups).

Amino, carbamoyl and carbonylamino groups include those in which the nitrogen atom has a substituent (for example, alkyl, cycloalkyl, fulkenyl and aryl groups).

Substituents on the nitrogen atom of the above amino group and carbamoyl group are also included in the above amino group and carbamoyl group when they are bonded to each other to form a ring. The cyclic ether group may be a saturated ring or an unsaturated ring.

The comonomer according to the present invention only needs to have at least one of the above-mentioned substituents on its alkyl moiety, and may further have other substituents (for example, a flukoxy group).

7 Styrenes, which are classified into alkyloxystyrene and alkyloxymethylstyrene, include a-halodenostyrene and α-furkylstyrene, and vinyls, which are classified into alkylcarbonyloxyvinyl and alkylcarbamoylvinyl, includes a-halodenovinyl, a-furkylvinyl, and the like.

The comonomer used in the present invention is preferably represented by the following general formula.

General formula % Formula % In the formula, R1 represents a hydrogen atom, a furkyl group having 1 to 4 carbon atoms, or a chlorine atom, R2 represents a carbon number R, R4, and RIO represents an alkyl group, a cycloalkyl group, or an alkenyl group. , or represents an aryl group, R, -R,, R11
and RI2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. Z represents a carbon atom necessary to form a 4- to 7-membered ring together with an oxygen atom.

The alkylene group represented by R2 and the alkyl group represented by R1-R12 may be linear or branched.

It also includes those having a p-Shishishiro pattern 17 creation expression, ↓ + l, and a doroxy group).

The comonomer used in the present invention is described in "Polymer Data, Handpfuku Group I1 Edition J" (editor: Japan Society of Polymer Science, Japan).
Published by Baifukan Co., Ltd., published on January 30, 1986).

Next, preferred comonomers according to the present invention will be illustrated.

9) CH2= CHOCOCI12CH20C,
ll510) CH2= CHOCOCH2CH20
C4H911) C1l□= CHOCOCII20
C1l.

12) CH2=CHC0NHCH20CH.

CH.

■ 14) CH2=CC0NHCH2CH201(CH
3 15) CH2=CHC0NHCC)120H ■ L 17) CH2=CC0NHCH2Cl2CH20H
20) CH2=CHC0NHCH2CONH221
) CH2=CHC0NHCHzCHzCONHCH
a22) CI(2=CHCONHCH, N1(CO
C) l.

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.

CH2=C-f Y f■ "-[18'yr x-Q In the formula, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
or represents chlorine, and X is -CONH-1-NIICO
NI+-5-)IHCOO-1-COO-1-592-
1-〇〇-1 or -〇-, Y is -CONH-1
or -C00-, and ^ represents a fullkylene group, an aralkylene group, or an arylene group having 1 to 10 carbon atoms, and the alkylene group and the alkylene moiety in the aralkylene group may be linear or branched.

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

Kasumi, n 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 como/mer 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 can be further used in other como/
May contain repeating units of mer, for example:
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, vinylal-IF ether (e.g., ts! vinyl ethyl ether), maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and V4-vinylpyridine, etc. There is.

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, and Z indicate mol%.

Example of magenta polymer coupler R.

■ x, y, and z indicate mol%.

Below is Yuaki Examples of cyan polymer couplers R1 shell X, Y, and Z indicate mol%.

・\Hereinafter, 'margin' The polymer coupler of the present invention is preferably added to the sensitive material as a latex.

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

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

Examples of initiators and their action are given in F. A. Bovey, “E++ulsion polymerization”.
nJ Interscience Publishing
es Inc. New York Published 1955 No. 59
- described on page 93.

As the emulsifier used during emulsion polymerization, a compound having a surfactant is used, preferably soap, sulfonate, sulfate, cationic compounds, etc.
z car -n no shi ko r tobisu 2 gichireru.

Examples of these groups and their effects are Be1g1sch
e Chemische Industrie, Vol. 28, pp. 16-20 (1963).

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

The polymeric coupler contains 0.001 to 0.5 mole per mole of silver based on coupler monomer, preferably 0.001 to 0.5 mole, based on coupler monomer.
Shimogane, ρ ~ Synthesis Example I Synthesis of PY-7 rθ Coupler monomer (1) Comonomer 9-> TY-7 Sodium dodecylbenzenesulfonate 1.03 5001
The aqueous solution was heated to 80° C. while passing through a nitrogen stream to remove II. Add 350xg of potassium persulfate to this aqueous solution.
Oxi aqueous solution was added. Comonomer 9 of the invention was then added to 5.0. and 5.0 y of coupler monomer (1) were heated and dissolved in 150 ml of ethanol and added. After addition, stirring was continued for 1 hour, and potassium persulfate 25011? 10!
After adding 1 aqueous solution and reacting for another 1 hour, ethanol and unreacted monomers were distilled off as an azeotrope of water,
0. After adjusting the pH to 6.0 with IN sodium hydroxide a! passed. The polymer concentration of the latex was 12.0% and the coupler unit content was 21 mol%.

Synthesis Example 2 Synthesis of PM-1 1, :y Coupler monomer (n) Comonomer 4->
PM-1 Co/mer 4 of the present invention with 6.79 and coupler monomer
(II) 6.2y was dissolved in Nooxane 15011, and while heating and stirring at 70°C under a nitrogen stream, Nooxane 51 was dissolved.
/! After adding 270zy of IM 2,2'-azobis(2,4-dimethylvaleronitrile) to the mixture, the mixture was reacted for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature, poured into ice water 21, and the precipitated solid was collected by filtration.

This solid was a polymer containing 31 mol% of coupler Uni 7).

A latex was produced using this polymer as follows. Polymer 52 was dissolved in 20 ml of ethyl acetate at 38°C.
7 of sodium dodecylbenzenesulfonate dissolved in
Add 0.51% of 0 wt% methanol solution. Next, this was mixed with 70 g of a 10% by weight aqueous solution of gelatin and dispersed using a double cylindrical disperser, and then ethyl acetate and methanol were distilled off under reduced pressure to prepare a latex.

Synthesis Example 3 Synthesis of PC-2 Coupler monomer (I[[] Comonomer 1
2+ PC-2 Sodium salt of oleyl methyl tauride 1.52 I
The Il aqueous solution was heated to 80'1' while deoxidizing it through a nitrogen stream.
LL, 1, 2, 2011 aqueous solution of 250 zy potassium persulfate was added to the aqueous solution, and then 3.82 ml of comonomer 12 of the present invention was added and reacted for 1 hour. To this latex was added 200 ml of ethanol in which 3.89 g of comonomer 12 and 3.5 g of coupler monomer (III) were dissolved, and then 300 g of potassium persulfate was added.
2011 aqueous solution was added, and after further reaction for 1 hour, potassium persulfate 200311? A 20×fl aqueous solution of was added. Subsequently, after reacting for 1 hour, ethanol and unreacted monomers were distilled off as an azeotrope of water, and the mixture was filtered after adjusting the PM to 6.0 with O,IN sodium hydroxide.

The polymer concentration of the latex was 10.5%, and the coupler unit content was 22.8 mol%.

Synthesis Example 4 PY-4, PY-5, PM-7~P according to Synthesis Example 1
M-11, PC-4 to PC-6 and PC-10.

P Y -1, P Y -2, P Y according to Synthesis Example 2
-8, PM-4 to PM-6, PC-1 and PC-3, and PY-3, PY-6, PM-2 according to Synthesis Example 3.
, PM-3, PC-7 to PC-9, and PC-11 latexes were obtained.

As the silver halide emulsion used in the photosensitive material of the present invention, any conventional silver halide emulsion 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.

Anticapri agents, stabilizers, etc. can be added to the silver halide emulsion.6 Gelatin is advantageously used as a binder for 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 polymer coupler) may also be used in combination with a colored coupler having a color correction effect, a competitive coupler, and a development inhibitor or development accelerator by coupling with an oxidized form of a developing agent. agent, bleach, developer,
Using compounds that release photographically useful 7-ragments such as silver halide solvents, toning agents, hardeners, capri agents, anticapri agents, chemical sensitizers, spectral sensitizers, and desensitizers. be able to.

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

The sensitive material includes a matting agent, a lubricant, an image stabilizing M1 surfactant,
Color antifoggants, development accelerators, development retardants and bleach accelerators can be added.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

To obtain a dye image using the photosensitive material of the present invention, after exposure, commonly known color photographic processing is performed. -' [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

Example 1 In the following examples, the amounts added in silver halide photographic materials are expressed per 112 unless otherwise specified, and silver halide and colloidal silver are expressed in terms of silver.

A multilayer color photographic element was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Sample-1 (comparison) First layer: Halicon prevention layer (HC-1) Gelatin layer containing black colloidal silver.

2nd Layer; Intermediate Layer (1,L) Gelatin layer containing an emulsified dispersion of 2.5-octylhydroquinone.

3rd layer; low sensitivity red-sensitive silver halide emulsion layer (RL-1)
Average grain size (r) 0.30/7 Monodisperse emulsion (emulsion I) consisting of 8 gBrl containing 16 mol% to 8 mt... Silver coating amount 1.8 g/m2 Muzzling dye I... - 6X10-S mol sensitizing dye per 1 mol of silver 1. OX 10-'Morsian coupler (CPC-1)...0.0 per mole of silver
6 mol Colored cyan coupler (CC-1)...0.003 mol per mol of silver DIR compound (D-1) 0.0015 mol per mol of silver DIR compound (D-2>...0.002 mol per mol of silver 4th layer; High sensitivity red-sensitive silver halide emulsion N (RH-1)
Average particle size (r) 0.5μ111. Monodispersed emulsion (emulsion ■) consisting of 8 g Br I containing +7.0 mol% of silver...silver coating amount 1.3 g/+2 sensitizing dye I...3 x 10 per mole of silver −'Molar sensitizing dye■・・
... 1 mole of silver. OX 10" Morcian coupler (c-i)...0.03 mol per 1 mol of silver Colored cyan coupler (CC-1)... 1 silver
0.0015 mol to mole DIR compound (D -2)...0.001 mol to 1 mole of silver 5th layer; middle ff1 (1, L) Same gelatin layer as 271i.

6th layer; low-sensitivity green-sensitive halogenated plate emulsion layer (L-1)
Milk M-1... Coated silver amount 1.5 g/l 112 sensitizing dye ■... 2.5 x 10 moles of sensitizing dye per mole of silver ■... Silver 1.2X 10-' mole magenta coupler (M-1) per mole of silver...0.04 per mole of silver
5 mol colored magenta coupler (CM-1)... 0.009 mol per mol of silver DIR compound (D-1)... 0.0010 mol per mol of silver 1) IR compound CD-3) 7th layer: 0.0030 mol per mol of silver; high-sensitivity green-sensitive silver halide emulsion layer (GH-1
) Emulsion - ■... Coated silver amount 1.4 g/+2 sensitizing dye ■... 1.5X 10-' mol sensitizing dye ■... per 1 mole of silver
... 1 mole of silver. OX 10-'molar magenta coupler (M-1)...Q, 03 per mole of silver
0 mol Colored magenta coupler (CM-1)...0.002 mol per mol of silver DIR compound (D-3)...0.0010 mol per mol of silver 8NI; Yellow filter layer (YC-1) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-1-octylhydroquinone.

9th layer; low sensitivity blue-sensitive silver halide emulsion layer (BL-1)
Average particle size 0.48μm, 8gBr containing 16mol% Heg
Monodispersed emulsion (emulsion ■) consisting of 1 silver coated amount 0.9 g/m2 multiplication color code ■... 1.3X 10-5 mol yellow coupler (Y- 1) 0.29 per mole of silver
Mole 10th layer: Highly sensitive blue-sensitive emulsion layer (B11-1) Monodisperse emulsion consisting of 8 gBrl containing 115 mol% of average grain size 0.8 μm^g (emulsion ■)... Silver coating amount 0.5 g/+a2
Sensitizing dye V: 1.0% per mole of silver. OX 10-5 mol Yellow coupler (Y-1)...0.08 per mol of silver
Mol DIR compound (D-2)...0.0015 mol per mol of silver 11th layer; 1st layer: 11th layer (Pro 1) Silver iodobromide (Hg 11 mol% average grains) diameter 0.07 μm) silver coating amount 0.
5g/m2 Gelatin layer containing UV absorbers UV-1 and UV-2.

12th. Il; PIS2-protected HWI (Pro-2) polymethyl methacrylate particles (diameter 1.5 μ-) and formalin scavenger (Hs-i
) containing a gelatin layer.

In addition to the above composition, each layer contains gelatin. A hardening agent (H-1) and a surfactant were added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I; anhydro-5,5'-dichloro-9-
Ethyl-3,3'-no(3-sulfopropyl)thiacarbocyanine hydroxide sensitized color im; anhydro-9-ethyl-3,3'-
Di(3-sulfopropyl)-4,5,4'.

5'-7penzothi7carpocyanine hydroxide color-am; anhydro-5,5'-diphenyl-9-ethyl-3,3'-di(3-sulfopropyl)
Oxacarbocyanine hydroxide sensitizing dye ■; Anhydro-9-ethyl-3,3'-di(3-sulfopropyl)-5,6,5'6'-nobenzoxacarbocyanine hydroxide sensitizing dye IV ; Anhydro-3,3'-di(3-sulfopropyltoxythiacyanine CPC-1: Comparative polymer coupler C-1 in which monomer M-1 of PC-1 is replaced with butyl acrylate. I II M-1 I I v- i IV-2 S-1 Next, the couplers of the 6th layer and the 9th layer of 31. Table 1 In the table, comparative polymer couplers CPY-1 to CPY
-4, CPY-7, CPY-8, CPM-1 to CPM-
3.

CPM-5, CPH-7, CPM-IQ, CPM-11
, CPC-2, CPC-6, CPC-7 and 1/CPC-
9-CPC-11, PY-1 to PY-4, PY-7, PY-8, which are polymer couplers of the present invention,
PH-1 to PH-3, PI3-5 to PM-7, PH-1
0, PH-11, PC-2, PC-6, PC-7 and P
These are polymer couplers in which monomer M-1 in C-9 to PC-11 is replaced with butyl acrylate.

The amount of polymer coupler added is expressed as the number of moles per mole of silver when the number average molecular weight is divided by the number of functional groups that react with the oxidized form of the color developing agent present in one molecule to form a dye. Ta.

After each sample was exposed to wedge light, the following development treatment was performed.

Processing process (38℃) Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing with water
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer]

4-7mi/-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75
g Anhydrous sodium sulfite 4.25 g Hydroxylamine salt/disulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g DiF lyrotriacetic acid.
Trisodium salt (monohydrate) 2.5g Potassium hydroxide t, add og water and 1! shall be.

[i vote white liquor] (BL-1) Ethylenediaminetetraacetic acid iron ammonium salt 1008 Ethylenediaminetetraacetic acid W12 Ammonium salt 10. Of + ammonium bromide 150.0g glacial acetic acid
Add 10.0 ml of water to bring the pH to 11, and adjust the pH to 6.0 using aqueous ammonia.
4! ! do.

[Fixer]

Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 11, and adjust to pH=6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5 theory! Koniguthchus (
(manufactured by Konishiroku Photo Industry Co., Ltd.) + 7.5 mN' Add water to make 11.

The results are shown in Table 2.

In Table 2 DE! is the maximum density of blue light in an image obtained by exposure to blue light, DC is the maximum density of an image obtained by exposure to green light, and DR is the maximum density of an image obtained by exposure to red light. The maximum concentration is shown as a relative value when the maximum concentration of a sample using a comparative polymer coupler is set as 100. Here, the maximum density refers to the difference between the maximum density and the minimum density of the wedge image.1. -1, Hereinafter - Gold and Metal Table 2 As is clear from Table 2, it can be seen that the samples using the polymer coupler of the present invention have higher color density than those using the comparative polymer coupler.

Also, PY-5, PY-6, PM-4, PM-8, PM-
Good color density was also obtained for 9, PC-3 to PC-s and PC-8.

Applicant: Konishiroku Photo Industry Co., Ltd. Procedural amendment December 24, 1986

Claims (1)

[Claims] In a silver halide color light-sensitive material containing a polymer coupler, the polymer coupler is an alkyloxystyrene-based, alkyloxymethylstyrene-based, alkylcarbonyloxyvinyl-based, or alkylcarbamoylvinyl-based monomer as a non-color-forming comonomer, Halogenation characterized in that the alkyl moiety has a repeating unit of a monomer having as a substituent at least one of an oxy group, an oxycarbonyl group, a carbonyloxy group, an amino group, a carbamoyl group, a carbonylamino group, or a cyclic ether group. Silver color photosensitive material.