JPH06186701A - Color photographic material containing 5-pyrazolone polymer coupler and colvent - Google Patents

Abstract

PURPOSE: To obtain a color photographic material having improved selective bleaching property in a retouching process of the material by incorporating a specified polymer magenta dye forming coupler and a specified solvent into a coupler compsn. CONSTITUTION: The coupler compsn. contains a polymer magenta dye forming coupler containing a 5-pyrazolone coupler group and a solvent selected from compds. expressed by formulae I and II. In formulae I and II, R<1> and R<2> are independently selected form substd. or unsubstd. alkyl groups and substd. or unsubstd. alkenyl groups, or R<1> and R<2> form a cyclic structure, R<3> and R<4> are independently selected from substd. or unsubstd. alkyl groups and substd. or unsubstd. alkenyl groups, or R<3> and R<4> form a cyclic structure, R<5> is selected from hydrogen, substd. or unsubstd. alkyl groups and substd. or unsubstd. alkenyl groups, or R<4> and R<5> form a cyclic structure.

Description

Detailed Description of the Invention

[0001]

This invention relates to a color comprising a silver halide emulsion and a substrate coated on its surface with a coupler composition comprising a polymeric magenta dye-forming coupler and a sulfoxide or carbonamide solvent. Regarding photographic materials.

[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.

It is also possible to use the coupler in combination with solvents and other additives that facilitate the incorporation of the coupler into the photographic material and / or improve one or more of the properties of the dye formed from the coupler. It is well known in the photographic art. For example, Japanese Patent Application Laid-Open No. 62-1
No. 41554 discloses the use of polymeric couplers in combination with high boiling organic phosphate solvents. JP-A-58-224352 cited above also generally discloses the use of polymeric couplers in combination with various types of high boiling organic solvents. Because of the variety of effects obtained with solvents in combination with individual coupler compounds, there is a continuing need to provide coupler-solvent combinations that further improve the color forming properties of the coupler.

Retouching of 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.

[0011]

It is an object of the present invention to provide a color photographic material comprising a silver halide emulsion coated on a supporting substrate and a coupler composition. It is a further object to provide a color photographic material as described above having improved one or more properties useful in forming color images. It is a further aspect of the present invention to provide a color photographic material comprising a silver halide emulsion and a coupler composition comprising a polymeric dye-forming coupler having enhanced selective bleaching properties upon retouching the photographic material. Purpose.

[0012]

The above and further objects are as follows.
This is accomplished by a color photographic material comprising a support substrate coated with a silver halide emulsion and a coupler composition on its surface. The coupler composition is a polymeric magenta dye-forming coupler containing a 5-pyrazolone coupler group, and formulas (I) and (II):

[0013]

[Chemical 2]

R in the above formula containing a solvent selected from¹
And R²Are independently substituted and unsubstituted alkyl groups, substituted and
Unsubstituted alkenyl group, and substituted and unsubstituted aryl group
Selected from the group consisting of or R¹And R ²Is a ring structure
Formed; R³And R^FourAre independently substituted and unsubstituted alkyl
Group, substituted and unsubstituted alkenyl group, and substituted and non-substituted
Selected from the group consisting of substituted aryl groups, or R³When
R^FourForms a ring structure, and R^FiveIs hydrogen, substituted and non
Substituted alkyl groups, substituted and unsubstituted alkenyl groups and groups
Selected from the group consisting of substituted and unsubstituted aryl groups, or
Is R^FourAnd R^FiveForm a ring structure.

We have found that a coupler composition comprising a polymeric dye-forming coupler containing a 5-pyrazolone coupler group and the sulfoxide or carbonamide solvent described above can be selectively used, for example, with an aqueous stannous chloride solution. It has been found that the bleachability can be increased, whereby the photographic material of the invention is particularly suitable for use in reversal film systems.

These and further objects and resulting advantages of the color photographic materials of this invention will be more fully apparent from the detailed description below.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The color photographic material of the present invention comprises a support substrate coated with a silver halide emulsion and a coupler composition on its surface. The coupler composition comprises a polymeric magenta dye-forming coupler containing a 5-pyrazolone coupler group and a sulfoxide or carbonamide solvent. The combination of certain solvents with polymeric magenta dye-forming couplers results in couplers with enhanced selective bleaching properties, which makes the color photographic materials of the present invention particularly suitable for use in reversal film systems.

The polymeric coupler included in the coupler composition of the photographic material of the present invention contains a 5-pyrazolone coupler group. The 5-pyrazolone coupler group is described in US Pat. Nos. 4,301,235 and 4,310, Ichijima et al.
619, and Hirose et al., U.S. Pat. No. 4,58.
As shown in US Pat. No. 4,226, as well as their method of manufacture, they are well known in the art. In a preferred embodiment, the 5-pyrazolone coupler group has the formula (II
I)-(V):

[0019]

[Chemical 3]

In the above formula, * represents a linking site to the polymer chain; R ⁶ represents arylamino, carbonamido, ureido, sulfonamide, alkylamino, and heterocyclic amino groups (all of these). R ⁷ may be substituted or unsubstituted); R ⁷ is selected from the group consisting of substituted and unsubstituted alkyl groups and substituted and unsubstituted aryl groups; 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 binding site to a pyrazolone ring and a polymer chain.
Is a divalent group that is derivable from and can be released from the polymer chain during processing of the photographic material.

In a preferred embodiment, R ⁷ in the coupling group comprises a substituted or unsubstituted aryl group. Suitable substituents for R ⁷ include halogen atom, cyano, alkylsulfonyl, arylsulfonyl, sulfamoyl, sulfonamide, carbamoyl,
Examples include, but are not limited to, carbonamido, alkoxy, acyloxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, ureido, nitro, alkyl and trifluoromethyl groups. Halogen-substituted aryl groups are particularly preferred.

In a more preferred embodiment, the coupler group is of formula (III), wherein R ⁷ is selected from the group consisting of substituted and unsubstituted aryl groups and X is

[0023]

[Chemical 4]

## 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.

In a more preferred embodiment, the 5-pyrazolone coupler group has the formula (VII):

[0026]

[Chemical 5]

Is bonded to a polymer chain containing a repeating unit of the formula, wherein * represents a linking site to the 5-pyrazolone coupler group; R ⁸ is hydrogen, an alkyl group having 1 to 4 carbon atoms And selected from the group consisting of chlorine; A is -CONH
Selected from the group consisting of-, -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 groups; Y is -CONR'-, -NR'CONR'-, -N
R'COO-, -NR'CO-, -OCONR '-,-
NR'-, -COO-, -OCO-, -CO-, -O
_{-, - SO 2 -, -} NR'SO 2 -, and -SO ₂ N
R '-(wherein R'is selected from the group consisting of hydrogen atom, substituted and unsubstituted aliphatic groups, and substituted and unsubstituted aryl groups, and two or more R'substituents are present in Y. And the two or more substituents may be the same or different), q is 0 or 1; and p is the same as q.

Polymeric couplers of this type, and methods for making them, are disclosed, for example, in Yagihara et al., US Pat. No. 4,367,282. For polymer chains comprising recurring units of formula (VII) above, in a preferred embodiment, A is -CONH- and p and q are 0. In a further embodiment, the polymeric couplers of the present invention may contain non-dye forming repeat units derived from any suitable ethylenically-unsaturated monomer. Ethylenically unsaturated monomers that can be used to form the non-dye-forming repeat units in the polymeric coupler include esters such as lower alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl. Acrylate, ethylhexyl acrylate, hexyl acrylate, methyl methacrylate, octyl methacrylate, lauryl methacrylate, vinyl esters such as vinyl acetate, vinyl propionate, vinyl laurate,
Examples include, but are not limited to, acrylonitrile, methacrylonitrile, amides such as acrylamide and methacrylamide, vinyl aromatics such as styrene and vinyltoluene, divinylbenzene, and derivatives thereof including vinyl ethers.

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.

The amount of dye-forming repeat units in the polymeric coupler can be varied, but the polymeric coupler is about 2 parts.
0 to about 80% dye-forming repeat units and about 80 to about 20
It is preferred to contain% non-pigmenting repeat units.
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:

[0033]

[Chemical 6]

[0034]

[Chemical 7]

[0035]

[Chemical 8]

[0036]

[Chemical 9]

[0037]

[Chemical 10]

[0038]

[Chemical 11]

[0039]

[Chemical 12]

[0040]

[Chemical 13]

[0041]

[Chemical 14]

[0042]

[Chemical 15]

[0043]

[Chemical 16]

[0044]

[Chemical 17]

[0045]

[Chemical 18]

[0046]

[Chemical 19]

[0047]

[Chemical 20]

[0048]

[Chemical 21]

Polymeric 5-pyrazolone polymeric couplers are used in combination with sulfoxide or carbonamide solvents in the color photographic materials of the present invention. The sulfoxide solvent and the carbonamide solvent may be used individually or in combination, or may be used in combination with other usual solvent. It is an important feature that the sulfoxide and carbonamide solvents used in the coupler composition contain sufficient ballast groups to minimize their water solubility, volatility and diffusivity.

Suitable sulfoxide compounds for use in the coupler composition have the formula:

[0051]

[Chemical formula 22]

In the above formula, R ¹ and R
² is independently selected from the group consisting of substituted and unsubstituted alkyl groups, substituted and unsubstituted alkenyl groups and substituted and unsubstituted aryl groups, or R ¹ and R ² form a ring structure. Alkyl and alkenyl groups from which R
What forms ¹ and R ² may be linear or branched. Suitable substituents on alkyl, alkenyl and aryl groups include, but are not limited to, alkoxy, aryloxy, aryl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, carbonamido, carbamoyl groups and halogen atoms. In a preferred embodiment, R ¹ and R ² are individually selected from straight chain and branched chain alkyl groups and straight chain and branched chain alkenyl groups, or R ¹ and R ² form a ring structure. In order to reliably reduce the water solubility, volatility and diffusibility of the solvent, R
¹ and R ² total at least 12, more preferably about 16
It preferably contains from about 24 carbon atoms.

Suitable sulfoxides may include, but are not limited to, the following:

[0054]

[Chemical formula 23]

[0055]

[Chemical formula 24]

Suitable carbonamide compounds for use as a solvent in the coupler composition of the present invention are of formula (II):

[0057]

[Chemical 25]

Wherein R ³ and R ⁴ are independently selected from the group consisting of substituted and unsubstituted alkyl groups, substituted and unsubstituted alkenyl groups and substituted and unsubstituted aryl groups, or R ³ and R ⁴ form a ring structure, and R ⁵ is selected from the group consisting of hydrogen, substituted and unsubstituted alkyl groups, substituted and unsubstituted alkenyl groups, and substituted and unsubstituted aryl groups. The alkyl group and the alkenyl group which can form R ³ , R ⁴ and / or R ⁵ may be straight chain or branched chain, and may be substituted or unsubstituted. Good. Suitable substituents for R ³ , R ⁴ and R ⁵ include, but are not limited to, substituents selected from the group consisting of alkoxy, aryloxy, aryl, alkoxycarbonyl, aryloxycarbonyl and acyloxy groups.
In a preferred embodiment, R ³ is selected from straight-chain and branched-chain alkyl groups, straight-chain and branched-chain alkenyl groups and aryl-substituted alkyl groups, or R ³ and R ⁴ form a ring structure. In another preferred embodiment, R ⁴ and R ⁵ are individually selected from the group consisting of phenyl-substituted and unsubstituted, straight and branched chain alkyl groups. Water solubility of solvent,
In order to surely reduce volatility and diffusivity, R ³ , R ⁴
And R ⁵ preferably contain a total of at least 12, more preferably from about 15 to about 30 carbon atoms.

Suitable carbonamides include, but are not limited to:

[0060]

[Chemical formula 26]

[0061]

[Chemical 27]

[0062]

[Chemical 28]

[0063]

[Chemical 29]

Preferred carbonamides are N, N
-Diethyllauramide, N-n-butylacetanilide, Nn-amylphthalamide, N, N-di-n-butylcarbamate, N, N-dibutyllauramide,
N, N-diethylcaproamide, N, N, N ', N'-
Tetraethyl phthalamide, and Nn-amyl succinimide.

The solvent is combined with the polymeric coupler in an amount sufficient to enhance the selective bleachability of the polymeric coupler. In a preferred embodiment, the coupler composition comprises about 1: 0.
1 to about 1:10 weight ratio, more preferably about 1: 0.
It contains the polymeric coupler and solvent in a ratio of 1 to about 1: 2. The photographic materials of this invention can be single color elements or multilayer multicolor elements. 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 emulsion is a surface-sensitive emulsion, that is, an emulsion that forms a latent image mainly on the surface of a silver halide grain, or an internal latent image-forming emulsion, that is, a latent image that forms a latent image mainly inside a silver halide grain. Can be an emulsion. These emulsions are either negative-working emulsions, such as surface-sensitive emulsions or unfogged internal latent image-forming emulsions, or unfogged internal latent image-forming direct positive emulsions. Thus, they may act positively when exposed to uniform light or developed in the presence of a nucleating agent.

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. Is. Typical chemical sensitizers are the Research Disclosure mentioned above.
e , Item 17643, Section III.

Silver halide emulsions can be spectrally sensitized with various classes of dyes. Specific sensitizing dyes are described in Research Disclosure , cited above,
Item 17643, Chapter IV. Suitable vehicles for the emulsion layers and other layers of the element of the invention are Research Disclosure , It.
em 17643, Section IX and publications cited therein.

In addition to the polymeric 2-equivalent 5-pyrazolone magenta couplers described herein, these elements are Re
Additional couplers may be included as described in the search Disclosure , Section VII, paragraphs D, E, F and G and the references cited therein. These additional couplers are available in ResearchDi
sclosure , chapter VII paragraph C and references cited therein.

The photographic elements of this invention contain optical brighteners ( Rese
arch Disclosure , Section V), Antifoggants and Stabilizers ( Research Disclos
ure , Section VI), antifouling agents and image dye stabilizers ( Research Disclosure , Section VII).
Sections, paragraphs I and J), light absorbers and scattering materials ( Research Disclosure , VIII.
Section), Hardener ( Research Disclosur
e , Section X), coating aid ( Research Disc)
loss , Section XI), plasticizers and lubricants ( Rese
arch Disclosure , Section XII), Antistatic Agent ( Research Disclosure , Section XI)
Section II), matte agent ( Research Disclos
, Sections XII and XVI), and development modifiers ( Research Disclosure , Section XXI).
Section) can be included.

These photographic elements are ( Research
It can be coated on a variety of supports such as those described in Disclosure , Section XVII and references cited therein. Preferred color developing agents include p-phenylenediamines. Especially preferred is 4
-Amino-3-methyl-N, N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-β-
(Methanesulfonamide) ethylaniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate, 4-amino-3-β-
(Methanesulfonamide) 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 may be mentioned.

With negative-working silver halide emulsions this processing step provides a negative image. The elements are, for example, the British Journal of
Photographic Annual , 1988,
Known C-4 as described on pages 196-198.
It is preferable to perform the processing by the one-color development processing method. To obtain a hosi (or reversal) image, in this color development step the exposed silver halide is first developed with a non-color developing agent (no dye is formed) and then the element is uniformly fogged. Thus, the unexposed silver halide can be developed. Alternatively, a direct positive emulsion can be used to obtain a positive image. Preferably, the color photographic material of the present invention is of the color reversal type.

After development, conventional bleaching, fixing or bleach-fixing steps are carried out to remove silver or silver halide, washing and drying. 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 materials of the present invention are demonstrated in the examples below. All parts and percentages throughout the specification are significant parts and percentages by weight unless otherwise noted. Synthesis of Polymer P-1 This example illustrates the preparation of Polymer P-1 using the solution polymerization method. 550 g deionized water and sodium N-methyl-N-oleoyl taurate (Igepon T-7
7) 1.875 g and 50 mL methanol were mixed in a 1 L 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. 5
7.5 mL of% 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-pyrazol) -3'-yl) -2-methyl-2-propenamide 15 g, ethoxyethyl acrylate 20.62 g, acrylamidoundecanoic acid 1.8
A monomer solution containing 75 g and 225 mL of methanol was then added to the reactor over 3 hours and then polymerized for an additional 3 hours. The latex was cooled, filtered and dialyzed against distilled water overnight. Next, use this for Amicon ultrafiltration unit (Am
icon's Ultrafiltration uni
t) was used to concentrate to 15.4% solids. Malvern's Autosizer
er) Z-average particle size measured by IIC is 69 nm
Met. The result of elemental analysis is C (51.8%), H
(5.9%), N (7.06%) and Cl (10.36)
%)Met. The yield was 83.8%.

Other polymeric couplers of the present invention were prepared in a similar manner. Example 1 In this example, a color photographic material containing a coupler composition of the present invention was tested for bleachability. For comparison purposes, bleachability was also tested on color photographic materials containing solvent-free coupler compositions. In preparing a color photographic material, 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.

When a solvent was used, the solvent was added to the coupler-containing solution and the solution was stirred for at least 1 hour before adding the silver halide emulsion. If solvent is present,
The coupler: solvent weight ratio was 1: 0.5. The coupler-silver halide emulsion mixture was then coated on a support substrate. Exposure is 0.02 seconds, 1B sensitometer, 0
A ~ 3 step tablet, 0.9 neutral density filter and DLV filter were used. Treatment process is 98.4 ° F
In was carried out as follows: Engineering enough time between atmosphere MQ developing 6 minutes N ₂ the full to wash 2 min N ₂ the full to reversal bath 2 minutes N ₂ the full to color development 6 min N ₂ the full to Conditioner 2 minutes Bleaching with N ₂ (Table I) Continuous air settling 4 minutes Continuous air washing 4 minutes Continuous air The following procedure was used to measure bleachability. 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. Swabs were dipped into the freshly prepared bleaching solution and applied to the squares for the indicated times as shown in Table I, after which the strips were washed with water for 5 minutes. After drying, the Status A density of the square portion of the film was read again, and the density reduction rate% was calculated.

The results of the bleaching test are shown in Table I. In Table I, couplers (P-1), (P-2) and (P-8) are the polymeric couplers of the present invention described above in the specification. In Table I, the solvents are abbreviated as follows: S1: N, N-diethyllauramide S2: bisethylhexyl sulfoxide Further in Table I, the bleaching solution B1 is stannous chloride (S
nCl ₂ ) 5 g, 10% H ₂ SO ₄ solution 30 mL and water 65 mL. The bleaching solution B2 is stannous chloride (SnC
1 ₂ ) 5 g, 1N HCl solution 30 mL and water 65 mL. For each coupler and solvent, the bleaching time and bleaching solution used and the resulting percent density loss are shown in Table I.

[0080]

[Table 1]

The results shown in Table I demonstrate that the selective bleachability of coupler compositions used in photographic materials of the present invention containing polymeric couplers in combination with sulfoxide or carbonamide solvents was significantly enhanced. To do.
Therefore, the color photographic materials of this invention are particularly useful in reversal film systems. Example 2 In this example a further bleaching test was performed according to the procedure described in Example 1. The film strip used in this example contained a coupler composition consisting of the polymeric coupler (P-6) described above. A bleaching solution containing a stannous chloride aqueous solution and hydrochloric acid was used, and then bleaching treatment was performed for 2 minutes. The solvents S1 and S2 mentioned in Example 1 were used. For comparison purposes, photographic materials containing solvents outside the scope of the invention, namely S3 (p-dodecylphenol) and S4 (ethylhexyl hydroxybenzoate) were also prepared and tested. The coupler: solvent weight ratio was 1: 0.5. The concentration reduction rate% obtained for each solvent used is shown in Table II.

[0082]

[Table 2]

The results shown in Table II show that the polymer 5-
The color photographic material of the present invention containing a coupler composition comprising a pyrazolone magenta coupler and a sulfoxide or carbonamide solvent is a color photographic material formed from a 5-pyrazolone magenta coupler and another solvent, or in the absence of a solvent. It demonstrates that the selective bleaching property is enhanced as compared with.

Example 3 In this example, a color photographic film was prepared and processed according to the general procedure of Example 1. The polymeric couplers used in the photographic film coupler compositions are shown in Table III. % Coupler density was measured using a coupler: solvent weight ratio of 1: 0.5 in combination with a carboxamide solvent consisting of N, N-diethyllauramide. The bleaching solution was B1 as described in Example 1. For comparative purposes, a similar photographic film was prepared and processed in the absence of the carbonamide solvent. Table III shows the density reduction rate% for the photographic film containing various coupler compounds and the carbonamide solvent and the photographic film containing no various coupler compounds and the carbonamide solvent.

[0085]

[Table 3]

The results, shown in Table III, demonstrate that the photographic materials containing the carbonamide solvent had enhanced selective bleachability compared to films prepared without the carbonamide solvent. The examples given above are intended to illustrate specific embodiments of the invention and are not intended to limit the materials and compositions of the invention. Further embodiments and advantages within the scope of the claimed invention will be apparent to those skilled in the art.

[0087]

INDUSTRIAL APPLICABILITY The present invention is useful for forming a color image.
Provided are color photographic materials having improved one or more properties. Further, the present invention provides a color photographic material with enhanced selective bleaching upon retouching of the photographic material.

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

Claims (1)

[Claims] 1. A silver halide emulsion and a calender on its surface.
A color comprising a support substrate coated with a puller composition.
-A photographic material, wherein the coupler composition is 5-pyrazo
Polymeric magenta dye-forming dyes containing ron coupler groups
Puller and formulas (I) to (II):In the above formula, R¹And R²Are independently substituted and unsubstituted alkyl groups, substituted
And unsubstituted alkenyl groups, and substituted and unsubstituted aryl
Selected from the group consisting of¹And R ²Is a ring structure
Forming structure; R³And R^FourAre independently substituted and unsubstituted
Alkyl group, substituted and unsubstituted alkenyl group, and substituted and unsubstituted
And an unsubstituted aryl group, or R
³And R^FourForms a ring structure, and R^FiveIs hydrogen, substitution
And unsubstituted alkyl groups, substituted and unsubstituted alkenyl groups
Selected from the group consisting of substituted and unsubstituted aryl groups
Or R^FourAnd R^FiveIs selected from:
A color photographic material that comprises a solvent.