JPH06186700A - Color photographic material containing 5-pyrazolone polymer coupler - Google Patents

Abstract

PURPOSE: To obtain a photographic material which can be selectively bleached in a retouching process by using a base substrate on which a specified polymer coupler is applied. CONSTITUTION: This photographic material has a base substrate on which a silver halide emulsion and a polymer coupler having a repeating unit expressed by the formula are applied. In the formula, R<1> , R<2> are independently selected from hydrogen and methyl groups, R<3> is selected from hydrogen, methyl and ethyl group, D is additional polymerizable monomers, (x), (y) represent about 20 to 80mol%, (z) represents 0 to about 50%, A is CONH, COO, etc., B is selected from unsubstd. or substd. straight-chain or branched alkylene groups, etc., Y is (O(CH2 )m )n , wherein (m) is 1 to 4 and (n) is 1 to 8, or OCOO, (q) is 0 or 1, (p) is same as (q), (r) is 1 to 8, Q is a coupler group derived from 5- pyrazolone, and E is O or NH.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to color photographic materials containing 5-pyrazolone polymeric couplers. More particularly, this invention relates to color photographic materials containing 5-pyrazolone polymeric couplers formed from at least one dye-forming monomer and at least one non-dye-forming monomer.

[0002]

BACKGROUND OF THE INVENTION Color photographic materials containing silver halide emulsions are well known in the art and are described in those materials including the reaction of oxidized aromatic primary amine color developing agents with dye-forming couplers. The same applies to development. Various yellow, cyan and magenta dye forming couplers are also known in the art. In particular, Ichi
U.S. Pat. Nos. 4,301,235 and 4,310,619 to Jima et al. and U.S. Pat. No. 4,584,226 to Hirose et al. disclose 2 equivalents for use in silver halide color photographic materials. Disclosed are 5-pyrazolone magenta dye forming couplers.

It is also known that couplers can be included in polymeric form to improve the ability of the dye to stay at the dye-forming sites in color photographic elements. For example, Monbaliu et al. (US Pat. No. 3,926,4)
No. 36), photographic elements containing polymeric couplers as latices which have a reduced tendency to foam and are highly miscible with hydrophilic colloids such as gelatin. Y
agihara et al. (US Pat. No. 4,474,870)
Discloses a photographic material containing a polymeric coupler latex that forms a magenta dye when coupled with an oxidized developing agent. Hirano et al. (US Pat. No. 4,
511,647) disclose color photographic materials containing a cyan color forming coupler latex. Yag
ihara et al. (British Patent No. 2,092,573B) disclose a silver halide photographic material containing a magenta color forming coupler latex. Cawse and Ha
rris (European Patent Application No. 0321399 A
3) discloses a method for producing a color coupler latex.

Generally, three methods have been used in the past to disperse polymeric couplers. These three methods can include: (1) Coupler in aqueous solution of surfactant and gelatin with high vapor pressure and / or low vapor pressure organic solvent by colloid milling or homogenization method. Dispersing method; (2) Direct mixing method of water-soluble polymer solution; (3) Latex forming method by emulsion polymerization or suspension polymerization.

Hirano (US Pat. No. 4,522,9
No. 16) discloses the preparation of polymeric magenta dye-forming coupler latexes capable of obtaining images with improved photostability. Hirano and Furutach
i (U.S. Pat. No. 4,576,910) discloses the preparation of polymeric magenta dye-forming coupler latices formed from triazole and tetrazole monomers. Helling et al. (US Pat. No. 4,756,
No. 998) discloses the preparation of polymeric couplers containing at least one urethane or urea group.
Yamanouchi et al. (US Pat. No. 4,874,68
No. 9) discloses the preparation of polymeric couplers using chain transfer agents of 8 or more carbon atoms. Hellin
g (U.S. Pat. No. 4,921,782) discloses the preparation of polymeric magenta dye-forming couplers in which the magenta coupler monomer contains a carboxyl group. Maekawa and Hirano (US Pat. No. 4,946,771) disclose the preparation of polymeric couplers incorporating certain advantageously incorporated coupling and non-coupling comonomers.

Polymeric couplers can be prepared by attaching a reactive coupler to a synthetic polymer. Such polymers include polyacrylic acid, poly-p-aminostyrene and other natural polymers. A method for producing such a polymer coupler is disclosed in US Pat. No. 2,698,
No. 797, No. 2,852,381, No. 2,852,3
No. 83 and No. 2,870,712 and Japanese Patent Publication No. 35
-16932 and 44-3661. A method of forming a polymeric coupler from an ethylenically unsaturated monomer or another polymerizable monomer is disclosed in British Patent No. 880,2.
06, 955, 197, 967, 503, 967, 504, 995, 363 and 1, 10
No. 4,658.

Jones (US Pat. No. 2,561,20
No. 5) discloses the formation of water-soluble polymeric couplers derived from β, γ-ethylenically unsaturated amides. Wi
lliams (U.S. Pat. No. 2,739,956)
Disclosed is the formation of water-soluble polymeric couplers derived from vinyl-substituted monomers such as 2-vinyl-1-naphthol. Firestone (US Pat. No. 2,976,29
No. 4) is 1- (m-methacryloylaminophenyl)
Disclosed are water soluble polymers derived from methacrylamide related monomers such as 2-carboxy-5-pyrazolone.

Umberger (US Pat. No. 3,45
1,820) disclose dispersions of lipophilic color-forming polymeric couplers. Van Passchen and Pri
em (U.S. Pat. No. 4,080,211) discloses a method for producing a color-coupling agent by emulsion polymerization. P
onticello et al. (US Pat. No. 4,215,195
No.) discloses the preparation of crosslinkable polymers containing color coupler residues. Hirano et al. (US Pat.
18,687) disclose photographic materials containing cyan dye-forming lipophilic polymeric couplers. Lau and T
ang (US Pat. No. 4,612,278) discloses a photographic material containing a polymeric coupler which is copolymerized with an alkoxyalkyl acrylate monomer.

Retouching color photographic images is well known in the art, especially in reversal film systems. Retouching occurs after development and processing of the photographic material. When retouching,
Magenta, yellow or cyan image dyes can be selectively removed using a suitable bleaching solution. The ability to selectively bleach color photographic image dyes is an important property of parent image couplers.

[0010]

Accordingly, there is provided a color photographic material comprising a silver halide emulsion and a polymeric coupler which can be selectively bleached, especially during retouching of the photographic material. Is desirable.

[0011]

The color photographic material of the present invention comprises a supporting substrate having a silver halide emulsion and a polymeric coupler coated on its surface. The polymeric coupler is of formula (I):

[0012]

[Chemical 2]

Wherein R ¹ and R ² are independently selected from the group consisting of hydrogen and methyl; R ³ is selected from the group consisting of hydrogen, methyl and ethyl; D is at least one species. Represents additional polymerized monomer; x is about 20-80 mol%
Y is about 20 to 80 mol%; z is 0 to about 5
0 mol%; A is -CONH-, -COO-, -O
-And a phenylene group; B is selected from unsubstituted and substituted, linear and branched alkylene groups, unsubstituted and substituted, linear and branched aralkylene groups, and unsubstituted and substituted phenylene groups. Y is-(O (C
H ₂ ) m) n- (wherein m is 1 to 4 and n is 1
~ OC), -OCOO-, -OCONH-, -CO.
NR'-, -NR'CONR'-, -NR'COO-,
-NR'CO-, -OCONR'-, -NR'-, -C
OO -, - OCO -, - CO -, - O -, - SO 2 -,
-NR'SO ₂ -, and -SO ₂ NR '- (wherein, R'
Is selected from the group consisting of hydrogen atom, substituted and unsubstituted alkyl groups, and substituted and unsubstituted aryl groups, and when two or more R'substituents are present in Y, the two or more The substituents may be the same or different), q is 0 or 1; p is the same as q; r is 1-8; Q is 5- Represents a coupler group derived from hirazolone; and E is -O-
Or -NH- is included.

The present inventors have found that the magenta dye-forming pyrazolone-containing polymeric coupler contained in the color photographic material of the present invention can be selectively bleached by using, for example, an aqueous stannous chloride solution. It has been found that the photographic materials of the invention are particularly suitable for use in reversal film systems. These objects and resulting advantages of the color photographic materials of this invention will be more fully apparent from the detailed description below.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The color photographic material of the present invention comprises a support substrate coated on its surface with a silver halide emulsion and a magenta dye-forming 5-pyrazolone polymeric coupler. An important feature of the present invention is the polymeric coupler, said polymeric coupler having the formula (I):

[0016]

[Chemical 3]

Wherein R ¹ and R ² are independently selected from the group consisting of hydrogen and methyl; R ³ is selected from the group consisting of hydrogen, methyl and ethyl; D is at least one species. Represents additional polymerized monomer; x is about 20-80 mol%
Y is about 20 to 80 mol%; z is 0 to about 5
0 mol%; A is -CONH-, -COO-, -O
-And a phenylene group; B is selected from unsubstituted and substituted, linear and branched alkylene groups, unsubstituted and substituted, linear and branched aralkylene groups, and unsubstituted and substituted phenylene groups. Y is-(O (C
H ₂ ) m) n- (wherein m is 1 to 4 and n is 1
~ OC), -OCOO-, -OCONH-, -CO.
NR'-, -NR'CONR'-, -NR'COO-,
-NR'CO-, -OCONR'-, -NR'-, -C
OO -, - OCO -, - CO -, - O -, - SO 2 -,
-NR'SO ₂ -, and -SO ₂ NR '- (wherein, R'
Is selected from the group consisting of hydrogen atom, substituted and unsubstituted alkyl groups, and substituted and unsubstituted aryl groups, and when two or more R'substituents are present in Y, the two or more The substituents may be the same or different), q is 0 or 1; p is the same as q; r is 1-8; Q is 5- Represents a coupler group derived from hirazolone; and E is -O-
Or -NH- is included.

The 5-pyrazolone coupler group is, for example, Ic
It is well known in the art as shown in U.S. Pat. Nos. 4,301,235 and 4,310,619 to hijima et al. In a preferred embodiment of polymeric coupler, Q is of formula (II)-(IV):

[0019]

[Chemical 4]

In the above formula, * represents a binding site to (Y) q; R ⁴ represents arylamino, carbonamido, ureido, sulfonamide, alkylamino,
And a heterocyclic amino group, all of which may be substituted or unsubstituted; R ⁵ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X is hydrogen,
And a group capable of leaving via a coupling reaction with an oxidized aromatic primary amine developing agent; and X '.
Is X having a pyrazolone ring and a binding site for (Y) q
Is a divalent group derived from In a preferred embodiment, R ⁵ in the coupling group Q comprises a substituted or unsubstituted aryl group. Suitable substituents for the aryl group include halogen atom, cyano, alkylsulfonyl, arylsulfonyl, sulfamoyl, sulfonamide, carbamoyl, carbonamido, alkoxy,
Examples include, but are not limited to, acyloxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, ureido, nitro, alkyl and trifluoromethyl groups. Halogen-substituted aryl groups are particularly preferred.

In a further preferred embodiment, the coupler group Q is of formula (II), wherein R ⁵ is selected from the group consisting of substituted and unsubstituted aryl groups and X is

[0022]

[Chemical 5]

## EQU3 ## where Za, Zb, Zc and Zd
Independently, a substituted or unsubstituted methine group and -N =
Selected from the group consisting of. Suitable substituents for the methine group include, but are not limited to, substituted and unsubstituted alkyl groups and substituted and unsubstituted aryl groups. Examples of the nitrogen-containing heterocyclic group formed by Za, Zb, Zc and Zd and the tertiary nitrogen atom include a pyrazolyl group, an imidazolyl group, a triazolyl group and a tetrazolyl group. Among these, a pyrazolyl group in which Za represents -N = and each of Zb, Zc and Zd represents a methine group or a substituted methine group is particularly preferable. In a further preferred embodiment all Zb, Zc and Zd are unsubstituted.

For the polymeric coupler repeat unit of formula (I)
In a preferred embodiment, A is-
CONH-, and p and q are 0. More preferable
In an embodiment, r is 1 and R³Is an ethyl group or
It is a methyl group. Further, x is in the range of about 20-80 mol%.
And y may be in the range of 20-80 mol%.
Damn z can be up to about 50 mol%, but more
In a preferred embodiment, x is about 30-60 mol%
, Y is 30 to 60 mol%, and z is 0 to about 25 mol%.
It is le%. z is greater than 0 and at least 1 additional
No additional polymerized monomer D is present in the polymeric coupler.
Recurring unit D can be any suitable ethylenically unsaturated mono
May be produced from Mar. With ethylenically unsaturated monomer
And the repeating unit D is polymerized from them.
Is an ester such as a lower alkyl ester, eg
For example, methyl acrylate, ethyl acrylate, pro
Pill acrylate, butyl acrylate, ethylhex
Acrylate, hexyl acrylate, methylmethac
Relate, octylmethacrylate, laurylmethacrylate
Rate, vinyl esters, eg vinyl acetate
G, vinyl propionate, vinyl laurate, acrylate
Ronitrile, methacrylonitrile, amides, for example,
Acrylamide and methacrylamide, vinyl aromatic
Classes such as styrene and vinyltoluene, divinyl vinyl
And its derivatives including vinyl ethers
But is not limited thereto. In one embodiment
Where D is R in the D repeating unit³Is the opposite of formula (I)
R during recovery unit³Except for the previous iteration unit of formula (I), except that
Position is the same, that is, variable (variable permutation
Group) R ², E and R³Is a repeating unit containing

The polymeric couplers of this invention can be made by any known polymerization method for the polymerization of ethylenically unsaturated monomers. The emulsion polymerization method is Yagihar
It is particularly suitable as disclosed in U.S. Pat. No. 4,367,282 to A. et al. The polymer coupler may be formed as homogeneous latex particles by a well-known polymerization method,
Or, for example, U.S. Pat. No. 4,44 to Hirano et al.
It may also be formed in the form of core-shell latex particles as taught in 4,870.

Alternatively, the polymer latex may be a coupler monomer, a comonomer, and an ionic comonomer containing sulfonic acid, sulfuric acid, sulfinic acid, carboxylic acid or phosphoric acid, such as acrylamido-2,2'-dimethyl-propane sulfonic acid, It is formed by solution polymerization of a monomer mixture consisting of 2-sulfoethyl methacrylate or sodium styrene sulfonate. The resulting polymer solution is then dispersed in an aqueous solution to form a latex.

A third method of forming polymer latices is by solution polymerization of a monomer mixture consisting of coupler monomers and comonomers. An organic solvent was used to dissolve the polymer coupler and then the solution was dispersed in an aqueous gelatin solution to obtain a solution of the method of US Pat. No. 4,668,613.
No. 4,874,689 and 4,946,771
To a latex as described in No.

Specific polymeric couplers for use in the color photographic materials of the present invention include, but are not limited to, couplers consisting of repeating units of the formula:

[0029]

[Chemical 6]

[0030]

[Chemical 7]

[0031]

[Chemical 8]

[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

The photographic materials of this invention can be single color elements or multilayer, multicolor elements. Multicolor elements contain dye image-forming units sensitive to each of the three primary regions of the visible spectrum. Each unit can consist of a single emulsion layer or multiple emulsion layers sensitive to the spectrum of a given area. The layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the photographic art.

A typical multicolor photographic element is a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer in combination with at least one cyan dye-forming coupler, at least one magenta dye. A magenta image-forming unit comprising at least one green-sensitive silver halide emulsion layer in combination with a forming coupler and at least one blue-sensitive silver halide emulsion layer in combination with at least one yellow dye-forming coupler. It comprises a support bearing a yellow dye-forming unit comprising. The elements of the invention may include additional layers such as filter layers, interlayers, overcoat layers and subbing layers. The total thickness of the element of the invention (excluding the support) is typically 5 to 30 microns. The support may be transparent or reflective.

Suitable materials for use in the elements of the present invention are Re
search Disclosure , 1978 12
Mon, Item 17643; January 1983, Item
22534; and December 1989, Item 30.
8119, Kenneth Mason Publica
tions, Ltd. , Dudley Annex, 1
2a North Street, Emsworth,
Hampshire P010 7DQ, England
Is disclosed in. This publication is referred to below as "Research
ch Disclosure ". The elements of the invention can include emulsions and addenda described in these publications and publications cited in these publications.

The silver halide emulsion used in the color photographic material of the present invention is silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide. Or it can be a mixture of these. These emulsions can contain silver halide grains of any conventional shape and size. Specifically, these emulsions can contain coarse silver halide grains, medium silver halide grains or fine silver halide grains. A useful tabular grain emulsion is Rese
arch Disclosure, Item 2253
4, and U.S. Pat. No. 4,748,106. High aspect ratio tabular grain emulsions are specifically contemplated and include, for example, Wilgus US Pat. No. 4,434,226, Daubendiek et al. 4,424,310, Wey 4 ,. 399,215
No. 4, Solberg et al., No. 4,433,048, Mi.
gnot ibid 4,386,145, Evans et al ibid 4,504,570, Maskasky ibid 4,40.
0,463, Wey et al., 4,414,306, M
Askasky Nos. 4,435,501 and 4,
4414,966 and Daubendiek et al., 4,672,027 and 4,693,964. Also specifically contemplated are silver bromoiodide grains having a higher molar ratio of iodide in the core of the grain than in the periphery of the grain, such as those described in British Patent 1,027,146.
No. 54,48,521, US Pat. No. 4,37.
9,837, 4,444,877, 4,66
5,012, 4,686,178, 4,56
5,778, 4,728,602, 4,66
No. 8,614, No. 4,636,461 and European Patent No. 264,954 or the specification thereof. These silver halide emulsions can be precipitated as either monodisperse or polydisperse. The grain size distribution of the emulsion can be adjusted by a silver halide grain separation method or by blending silver halide emulsions of various grain sizes.

Sensitizing compounds such as copper, thallium, lead, bismuth, cadmium and Group VIII noble metal compounds can be present during the precipitation of the silver halide emulsion. The silver halide emulsions of the present invention are surface sensitizable and can be used individually or in combination with noble metals (eg,
Gold), intermediate chalcogens (eg, sulfur, selenium or tellurium) and reduction sensitizers. Typical chemical sensitizers are
The above-mentioned Research Disclosure , I
tem 17643, section III.

Spectral sensitization of a silver halide emulsion with a sensitizing dye is carried out, for example, by the above-mentioned Research Disc
Closure , Item 17643, Chapter IV. Suitable vehicles for the emulsion layers and other layers of the element of the invention are Research Discl.
Osure , Item 17643, Section IX and publications cited therein.

[0041] In addition to the polymeric 5-pyrazolone magenta couplers described herein, these elements Resear
ch Disclosure , Section VII, paragraphs D, E, F and G and additional couplers as described in the references cited therein. The photographic elements of this invention are comprised of optical brighteners ( Research Di
Sclosure , Section V), Antifoggants and Stabilizers ( Research Disclosure , Section VI)
Section), antifouling agents and image dye stabilizers ( Rear
ch Disclosure , Section VII, paragraph I
And J), light absorbers and scattering materials ( Research
Disclosure , Section VIII), Hardener ( Res
search Disclosure , Section X), Application Aids ( Research Disclosure , Section XI)
Section), plasticizer and lubricant ( Research Disc)
Loss , Section XII), Antistatic agent ( Rearse
ch Disclosure , Section XIII), matting agents ( Research Disclosure , Sections XII and XVI), and development modifiers ( Research
Disclosure , Section XXI).

These photographic elements are Research D
It can be coated on a variety of supports as described in isclosure , Section XVII and references cited therein. These photographic elements are typically exposed to actinic radiation in the visible region of the spectrum, Research
A latent image as described in Disclosure , Item Section XVIII is formed and then processed to produce a Resea.
A visible dye image can be formed as described in rch Disclosure , Section XIX. Preferred color developing agents include p-phenylenediamines. Particularly preferred is 4-amino-3-
Methyl-N, N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-β- (methanesulfonamido) ethylaniline sulfate hydrate, 4-amino-3
-Methyl-N-ethyl-N-β-hydroxyethylaniline sulfate, 4-amino-3-β- (methanesulfonamido) ethyl-N, N-diethylaniline hydrochloride and 4-amino-N-ethyl-N , N-diethylaniline hydrochloride and 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine di-p-toluenesulfonic acid.

As is known in the art, the solution used to selectively bleach the magenta dye is typically a stannous chloride solution. The present inventor has found that the 5-pyrazolone polymer coupler of the present invention exhibits good selective bleaching property. This property is particularly important in reversal film systems, which makes the color photographic materials of the present invention suitable for use in such reversal film systems.

The advantages of the color photographic material of the present invention are demonstrated in the following examples. All parts and percentages throughout the specification are parts and percentages by weight unless otherwise specified. Examples In this example, color photographic materials containing the polymeric couplers of this invention were tested for bleachability. For comparison purposes, the bleachability of color photographic materials containing non-polymeric couplers and other polymeric couplers was also tested.

Couplers were prepared as described in the synthetic examples below. 1. Synthesis of polymer P-1 80 g deionized water and 10% sodium N-methyl-N
-Oleoyl taurate (Igepon T-77)
4.4 g were mixed in a 500 mL 4-neck round bottom flask equipped with mechanical stirrer, nitrogen inlet and condenser. The flask was immersed in a constant temperature bath at 80 ° C. and heated for 30 minutes while purging with nitrogen. 0.5 g of methoxyethyl acrylate and 1 mL of 5% ammonium persulfate were added to the flask and polymerized for 1 hour. An additional 1.3 mL of 5% ammonium persulfate was added. N- (4 ', 5'-dihydro-5'-oxo-1'-(2,4,6-trichlorophenyl) (1,4'-bi-1H-pyrazole) -3'-
Yl) -2-methyl-2-propenamide 4.0 g, methoxyethyl acrylate 5.5 g and ethanol 40
The monomer solution containing mL was then added to the reactor over 3 hours and then polymerized for an additional 3 hours. Cool the latex,
It was filtered and dialyzed against distilled water overnight. Next, this is an Amicon's Ultrafiltration unit.
solids 4.1 using the filtration unit.
Concentrated to 7%. Malvan Autosizer (Malv
The Z-average particle size measured by Ern's Autosizer) IIC was 120 nm. Elemental analysis results are C (52%), H (5.9%), N (6.92%)
And Cl (11.00%). The yield was 80%.

2. Synthesis of Polymer P-2 440 g deionized water and sodium N-methyl-N-oleoyl taurate (Igepon T-77) 1.5.
g and 40 mL of methanol were mixed in a 1 L 4-neck round bottom flask equipped with a mechanical stirrer, nitrogen inlet and condenser. The flask is immersed in a constant temperature bath at 80 ° C and 30
Heated while purging with nitrogen for minutes. 6 mL of 5% ammonium persulfate was added and then stirred for 3 minutes. N-
(4 ', 5'-dihydro-5'-oxo-1'-(2,
4,6-Trichlorophenyl) (1,4'-bi-1H-
A monomer solution containing 12 g of pyrazol) -3'-yl) -2-methyl-2-propenamide, 18 g of ethoxyethyl acrylate and 180 mL of methanol was then added to the reactor over 3 hours and then polymerized for a further 3 hours. The latex was cooled, filtered and dialyzed against distilled water overnight. Next, this is the Amicon ultrafiltration unit (Amico
n's Ultrafiltration unit)
Was used to concentrate to a solid content of 12.63%. Malvern's Autosize
r) Z-average particle size measured by IIC is 65.8.
was nm. The result of elemental analysis is C (51.8%), H
(6.0%), N (6.73%) and Cl (1.29)
%)Met. The yield was 77%.

Polymers P-3 to P-12 and comparative polymers C-1 to C-18 and C-20 to C-described below.
22 was prepared in a similar manner. 3. Synthesis of Comparative Polymer C-19 Pyrazotriazole coupler monomer 6.5 g, ethoxyethyl acrylate 1.75 g, acrylic acid 1.25
g, 0.5 g of 2-acylamido-2-methylpropanesulfonic acid and 100 mL of ethanol were mixed in a 250 mL three-necked flask equipped with a condenser, a nitrogen inlet and a magnetic stirrer. The solution was immersed in an oil bath and then heated to 85 ° C. until all the monomer had dissolved. 5 mL of ethanol
0.25 g of azo-bis-isobutyronitrile (AIBN), prepared by dissolving in, was added to the flask. The polymerization was continued for 5 hours and then 0.25 g of AIBN was added afterwards. The polymer solution was diluted with 50 mL of ethanol and then added to 300 mL of hot distilled water with vigorous stirring. The particle size of the polymer latex thus produced was 60 nm. The final% solids after ultrafiltration was 5.6%. The results of elemental analysis are C (61%), H (7.6%),
N (8.94%) and Cl (4.5%). The yield was 82%.

The comparative coupler is of the formula:

[0049]

[Chemical 12]

[0050]

[Chemical 13]

[0051]

[Chemical 14]

[0052]

[Chemical 15]

[0053]

[Chemical 16]

[0054]

[Chemical 17]

[0055]

[Chemical 18]

[0056]

[Chemical 19]

[0057]

[Chemical 20]

[0058]

[Chemical 21]

[0059]

[Chemical formula 22]

In the production of color photographic materials, gelatin, water, surfactant and TAI were mixed and then each coupler was added to the resulting solution. The polymeric coupler was added in the form of a polymer latex. The coupler-silver halide emulsion mixture was then coated on a support substrate. The exposure was performed for 0.02 seconds, and a 1B sensitometer, a 0 to 3 step tablet, a 0.9 neutral density filter and a DLV filter were used. The processing steps were performed at 98.4 ° F. as follows: Process Time Atmosphere MQ Development 6 min N ₂ Satisfaction Cleaning 2 min N ₂ Inversion Bath 2 min N ₂ Color Development Mitsuru be bleached to a 6 minute N ₂ fill to conditioner 2 minutes N ₂ in (Table I) of the continuous air Fixing 4 min continuous air wash 4 minutes continuous air bleaching measurements, use the following operations I was there. Status A density (1.0) was read on the treated strips. Square (1/4 inch) blanks were made on the treated strips using tape as an edge. A cotton swab was dipped in freshly prepared bleach and applied to the squares for 6 minutes, after which the strips were rinsed with water for 5 minutes. After drying, the Status A densities of the square areas of the film were reread and the% density loss calculated.

Two types of bleaching solutions were used: Bleaching solution A was stannous chloride (SnCl ₂ ) 5 g, 10% H 2.
_It consists of 30 mL of ₂ SO ₄ solution and 65 mL of water. Bleach B
Is stannous chloride (SnCl ₂ ) 5 g, 5% H ₂ SO
₄ consisting of 30 mL of solution and 65 mL of water. To demonstrate the effect of comonomers on the bleachability of polymeric couplers, a series of polymeric 5-pyrazolone couplers with various types of comonomers were prepared. Three separate bleaching experiments were performed and the results are shown in Tables I-III.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

From these results, it is clear that the 2-equivalent or 4-equivalent 5-pyrazolone couplers containing the comonomer of the present invention show significantly improved bleaching properties compared to the comparative examples. The 5-pyrazolone coupler component defined in the present invention is essential for selective bleaching. IV
As shown in the table, comparisons were made between polymeric couplers derived from 5-pyrazolone couplers and other magenta couplers, especially pyrazotriazole type magenta couplers. From Table IV, it is clear that the polymeric 5-pyrazolone couplers of the present invention have much higher bleaching properties than the comparative polymeric and non-polymeric magenta couplers.

[0066]

[Table 4]

The results shown in Tables I-IV demonstrate that the polymeric couplers of this invention exhibit significantly improved bleaching properties. Therefore, the color photographic material of the present invention is particularly useful for reversal film systems. The example above
It is for explaining a specific embodiment of the present invention,
It is not intended to limit the scope of the inventive material. Additional embodiments and advantages within the scope of the claimed invention will be apparent to those skilled in the art.

[0068]

The color photographic material of the present invention comprising a silver halide emulsion and a polymeric coupler can be selectively bleached when retouching the photographic material.

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[Procedure amendment]

[Submission date] November 16, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

The silver halide emulsion used in the color photographic material of the present invention is silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide. Or it can be a mixture of these. These emulsions can contain silver halide grains of any conventional shape and size. Specifically, these emulsions can contain coarse silver halide grains, medium silver halide grains or fine silver halide grains. A useful tabular grain emulsion is Rese
arch Disclosure, Item 2253
4, and U.S. Pat. No. 4,748,106. High aspect ratio tabular grain emulsions are specifically contemplated and include, for example, Wilgus US Pat. No. 4,434,226, Daubendiek et al. 4,424,310, Wey 4 ,. 399,215
No. 4, Solberg et al., No. 4,433,048, Mi.
gnot ibid 4,386,145, Evans et al ibid 4,504,570, Maskasky ibid 4,40.
0,463, Wey et al., 4,414,306, M
Askasky Nos. 4,435,501 and 4,
Described in 643, 966 and Daubendiek et al. Nos 4,672,027 and the 4,693,964 Pat. Also specifically contemplated are silver bromoiodide grains having a higher molar ratio of iodide in the core of the grain than in the periphery of the grain, such as those described in British Patent 1,027,146.
No. 54,48,521, US Pat. No. 4,37.
9,837, 4,444,877, 4,66
5,012, 4,686,178, 4,56
5,778, 4,728,602, 4,66
No. 8,614, No. 4,636,461 and European Patent No. 264,954 or the specification thereof. These silver halide emulsions can be precipitated as either monodisperse or polydisperse. The grain size distribution of the emulsion can be adjusted by a silver halide grain separation method or by blending silver halide emulsions of various grain sizes.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Michael Phillip Young Blood USA, New York 14625, Rochester, Heather Drive 42

Claims (1)

[Claims] 1. A color photographic material comprising a support substrate coated with a silver halide emulsion and a polymeric coupler on its surface, said polymeric coupler being of formula (I): Wherein R ¹ and R ² are independently selected from the group consisting of hydrogen and methyl; R ³ is selected from the group consisting of hydrogen, methyl and ethyl; D is at least one additional polymerization Represents about 20 to 80 mol%; y is about 20 to 8 mol%.
0 mol%; z is 0 to about 50 mol%; A is-
Selected from the group consisting of CONH-, -COO-, -O- and phenylene groups; B is an unsubstituted and substituted, linear and branched alkylene group, an unsubstituted and substituted, linear and branched aralkylene group, and selected from unsubstituted and substituted phenylene group; Y is _{- (O (CH 2) m} ) n- ( wherein, m is 1 to 4 and n is 1 to 8), - OCOO
-, -OCONH-, -CONR'-, -NR'CON
R'-, -NR'COO-, -NR'CO-, -OCO
NR'-, -NR'-, -COO-, -OCO-, -C
O -, - O -, - SO 2 -, - NR'SO 2 -, and -
SO ₂ NR ′-(wherein R ′ is selected from the group consisting of hydrogen atom, substituted and unsubstituted alkyl groups, and substituted and unsubstituted aryl groups, and two or more R ′ substituents are present in Y. Two or more substituents, if present, may be the same or different), q is 0 or 1; p is the same as q; r Is 1-8
Q represents a coupler group derived from 5-hirazolone; and E is -O- or -NH-.