JPH0240648A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a magenta picture having an excellent light resistance, and to reduce the generation of the color fog of the title material by incorporating a specified 5-pyrazolone type magenta coupler in a silver halide emulsion layer. CONSTITUTION:In the color photographic sensitive material comprising one or more layers of the silver halide emulsion layers, the 5-pyrazolone type magenta coupler shown by formula I is incorporated in at least one layer of the silver halide emulsion layers. Thus, the photosensitive material which is capable of forming the magenta picture and has the excellent light resistance and a less tendency for generating the color fog, is obtd. In the formula, R1 is aryl group, R2 is anilino, acylamino, ureido or carbamoyl group, R3 is -NHSO2R4, -NHSO2N (R5)2, -SO2NHR4 or -SO2N(R5)2 group, R4, R5 and R6 are each a straight chain or a branched chain alkyl, cycloalkyl or aryl group, Y is hydrogen atom or a monovalent group, (n) is an integer of 0-4. When (n) is 2-4, the group Y may be the same or the different with each other.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material containing a novel magenta dye-forming coupler.

[Background of the invention]

In silver halide color photographic materials, pyrazolone derivatives are widely used as couplers that form magenta dyes. In particular, as a method for improving color development, a coupler in which an arylthio group is introduced at the 4-position of a pyrazolone has been proposed. Such couplers are disclosed in, for example, Japanese Patent Publication No. 53-34044 and Japanese Patent Publication No. 60-57837.
No., W 088-4795, etc.

These couplers do not have sufficient coupling activity,
There is a difference in the storage stability of the magenta dye produced.

Furthermore, JP-A No. 55-62454 describes a pyrazolone coupler in which the 4-position of a pyrazolone derivative is substituted with R'-5- (R' represents a linear or branched alkyl group or an aralkyl group). There is.

These also had drawbacks such as low coupler coupling activity and poor image storage stability, particularly light resistance.

Furthermore, the above-mentioned pyrazolone couplers in which an arylthio group, an alkylthio group, or an aralkylthio group is substituted at the 4-position have the serious problem of causing significant color fog during development.

[Purpose of the invention]

The present invention has been made to solve the above-mentioned drawbacks, and a first object of the present invention is to provide a silver halide color photographic light-sensitive material that forms magenta images with excellent light resistance.

A second object of the present invention is to provide a silver halide color photographic material with low color fog.

[Structure of the invention]

The above object of the present invention is to provide a silver halide color photographic material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers is represented by the following general formula [I]. This was achieved by including a 5-pyrazolone magenta coupler.

General formula (1) In the formula, R1 represents an aryl group, R2 represents an anilino group, an acylamino group, a ureido group, or a carbamoyl group, and R1 represents -NH3O2R-NHSOzN(Rs)2.
5o2N[(Ra or -3OzN(Rs)z,
R6 and R2 are linear or branched alkyl groups,
represents a cycloalkyl group or an aryl group, and two R5
may be the same or different, Y represents a hydrogen atom or a monovalent group, n represents an integer of 0 to 4, and when n is 2 to 4, each Y may be the same or different.

More specifically, R1 represents an aryl group, preferably a phenyl group. Examples of substituents introduced into the phenyl group include halogen atoms (e.g., fluorine, chlorine, bromine, etc.), alkyl groups (e.g., methyl, ethyl, etc.)
, alkoxy groups (e.g., me-1-xy, ethoxy, etc.),
Aryloxy groups (e.g., ', phenyloxy, naphthyloxy, etc.), acylamino groups (e.g., benzamide, α-(2,4-di-monoaminophenoxy)butyramide, etc.), sulfonylamino groups (e.g., benzenesulfonamide, hexadecanesulfonamide, etc.), sulfamoyl groups (e.g., methylsulfamoyl, phenylsulfamoyl, etc.), carbamoyl groups (e.g., butylcarbamoyl, phenylcarbamoyl, etc.), sulfonyl groups (e.g., methylsulfonyl, dodecylsulfonyl,
(benzenesulfonyl, etc.), acyloxy group, ester group, carboxyl group, sulfo group, cyano group, nitro group, etc.

Furthermore, specific examples of R□ include phenyl, 2.4゜6
-1-! J chlorophenyl, pentachlorophenyl, pentafluorophenyl, 2.4.6-dolimethylphenyl, 2I'rolo-4,6-dimethylphenyl, 2.6-
Cycloro-4-methylphenyl, 2,4-dichloro-6
-methylphenyl, 2,4-cyclo-6-methylphenyl, 2.6-'; chloro-4-methoxyphenyl, 2
．． 6-dichloro-4-[α-(2,4-di-t-amylphenoxy)acetamido]phenyl and the like.

R2 is an anilino group (e.g., anilino, 2-chloroanilino, 2,4-dichloroanilino, 2,4-cyclo-5-methoxyanilino, 4-cyanoanilino, 2-chloro-5-(α-(2,4- di-t-amylphenoxy)
butyramide]anilino, 2-chloro-5-(3-octadecenylsuccinimide)anilino, 2-chloro-5
-tetradecanamide anilino, 2-chloro-5-[α
-(3-t-butyl-4-hydroxyphenoxy)tetradecanamide anilino, 2-chloro-5-[α-(4
-t-octylphenoxy)butyramide]anilino,
2-chloro-5-hexadecanesulfonamide anilino), acylamino groups (e.g. tetradecaneamide, g
-(3-pentadecylphenoxy)butyramide, 3-
[α-(2,4-di-t-amylphenoxy)acetamidobenzamide, benzamide, 3-acetamidobenzamide, 3-(3-dodecylsuccinamido)benzamide, 3-(4-dodecyloxybenzenesulfonamide)benzamide, etc.) , ureido groups (e.g. methylureido, phenylureido, 3-(α-(2,4-
di-t-amylphenoxy)butyramide] phenylureido, etc.) or carbamoyl groups (e.g., tetradecylcarbamoyl, phenylcarbamoyl, 3-[α-(
2,4-di-t-amylphenoxy)acetamido]phenylcarbamoyl, etc.).

Examples of the alkyl group represented by R3 and R6 include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, 5ec-butyl, t-butyl, [-octyl, 2-ethylhexyl, decyl, etc. Examples of the cycloalkyl group include cyclopentyl and cyclohexyl, and examples of the aryl group include phenyl, p-tolyl, and m-chlorophenyl.

Monovalent groups represented by Y include halogen atoms (e.g. fluorine, chlorine, bromine, iodine), alkyl, nitro,
cyano, hydroxyl, alkoxy, aryloxy,
Acyloxy, urethane, carboxyl, ester, carbamoyl, acyl, acylamino, sulfonamide,
Examples include multiple groups such as ureido, sulfonyloxy, oxysulfonyl, sulfo, sulfamoyl, thio, sulfinyl, and sulfonyl. The monovalent group represented by Y is preferably a halogen atom or an alkyl group.

Representative examples of the magenta coupler of the present invention represented by the general formula CI) (hereinafter referred to as the magenta coupler of the present invention) are shown below, but are not limited to these. Magenta couplers can be synthesized by conventionally known methods. In particular, the following synthetic methods are available for introducing a thio group as a leaving group into the 4-position of a pyrazolone derivative. That is, U.S. Patent Nos. 3,227.554 and 3,701.
A method of reacting a sulfenyl chloride with a 4-equivalent pyrazolone coupler having an active methylene group according to the method for synthesizing a DIR magenta coupler having an arylthio group or a heterocyclic thio group as a leaving group described in No. 783; As described in Japanese Patent Publication No. 49-62464, the 4-position of pyrazolone magenta coupler is dibrominated and reacted with about 3 times the molar amount of mercaptan, Research Disclosure (Research D).
13806 (1975), a method in which bromine is added dropwise in the presence of a 4-equivalent pyrazolone magenta coupler and a mercaptan, C.
hew, Pharm, Bull, 20.1862
1868 (1972), a method of reacting a 4-equivalent pyrazolone magenta coupler with S-alkylthioisothiourea.

Typical synthesis examples of the couplers of the present invention are shown below. O Synthesis Example (Exemplary Coupler 2) Exemplary Coupler 2 Compound (1) 14.7g and Compound (2) 11.4g
A solution of 1.7 g of bromine dissolved in 20 mα of dimethylformamide was added to a solution of 120 m(l) of dimethylformamide, and the mixture was reacted at 80°C for 2 hours. Ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 5.1 g of Exemplary Coupler 2. Production was confirmed by NMR and IR% MASS spectra.

The methods and techniques used for conventional magenta dye-forming couplers are similarly applicable to the magenta couplers of the present invention. Typically, the magenta coupler of the present invention is blended into a silver halide emulsion, and this emulsion is coated on a support to form the color light-sensitive material of the present invention.

The color photosensitive materials of the present invention include, for example, color negative and positive films, and color photographic paper.

The photosensitive materials of the present invention, including this color photographic paper,
It may be for a single color or for multiple colors.

In a multicolor light-sensitive material, the magenta coupler of the present invention is contained in a green-sensitive silver halide emulsion layer.

Multicolor light-sensitive materials have dye image-forming constituent units that are sensitive to each of the three primary color regions of the spectrum. Each building block can consist of a single or multiple emulsion layer sensitive to a certain region of the spectrum. The constituent layers of the photosensitive material, including the layers of image-forming units, can be arranged in various orders as is known in the art. A typical multicolor photographic material comprises a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler, at least one green emulsion layer containing at least one magenta coupler. A magenta dye image forming unit consisting of a light-sensitive silver halide emulsion layer (at least one magenta coupler)
one is a magenta coupler of the present invention), at least one
It consists of a yellow dye image-forming structural unit consisting of at least one blue-sensitive silver halide emulsion layer containing two yellow couplers supported on a support.

The photosensitive material may contain additional layers such as filter layers, interlayers,
It can have a protective layer, an undercoat layer, etc.

In order to incorporate the magenta coupler of the present invention into an emulsion,
A conventionally known method may be followed. For example, the magenta of the present invention can be applied to a high boiling point organic solvent having a boiling point of 175°C or higher such as tricresyl phosphate or dibutyl phthalate, or a low boiling point solvent such as ethyl acetate or butyl propionate, or a mixture thereof as necessary. After dissolving the coupler-- alone or in combination, it is mixed with an aqueous gelatin solution containing a surfactant, and then mixed with a high-speed rotary mixer or colo-
After emulsifying with Idomil, it can be added to silver halide to prepare the silver halide emulsion used in the present invention.

The couplers of this invention typically contain 7X per mole of silver halide.
10-" to 7 X 10-'% le, preferably l
It can be used in the range of Xl0-' to 4X10-' moles.

The couplers of the present invention can also be used in combination with other types of magenta couplers.

Silver halide compositions preferably used in the present invention include silver chloride, silver chlorobromide, and silver chloroiodobromide. Furthermore, a combination mixture such as a mixture of silver chloride and silver bromide may be used.

The silver halide emulsion is chemically sensitized by conventional methods. Furthermore, it can be optically sensitized to a desired wavelength range.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, compounds known in the photographic industry as anti-capri agents or stabilizers can be added for the purpose of preventing fog during photographic processing and/or keeping photographic performance stable.

The color photosensitive material of the present invention includes a color antifoggant, a dye image stabilizer, an ultraviolet inhibitor, which are commonly used in photosensitive materials,
Antistatic agents, matting agents, surfactants, etc. can be used.

Regarding these, for example, Research Disclosure
176, pages 22-31 (December 1978) can be referred to.

An image can be formed on the color photosensitive material of the present invention by subjecting it to a color development process known in the art.

The color light-sensitive material according to the present invention may contain a color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor, and may be processed in an alkaline activation bath.

After color development, the color photosensitive material of the present invention is subjected to a bleaching process and a fixing process. Bleaching treatment may be performed simultaneously with fixing treatment.

After the fixing process, a washing process is usually performed.

Further, a stabilization treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.

The magenta coupler of the present invention is used in combination with a yellow coupler and a cyan coupler to form a multicolor light-sensitive material.

Open-chain or heterocyclic ketomethylene compounds are used as yellow couplers, but α-benzoylacetanilide compounds provide high coloring density, while α-pivalo has a high color fastness, especially light resistance. Ilylacetanilide compounds are preferred.

Cyan couplers include phenol or naphthol derivatives.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto.

(Preparation of silver halide emulsion) By neutral method and simultaneous mixing method, 3 types shown in Table 1 Table 1 (SD-1) 2 mg per 1 mol of silver halide added 5xto-' mol per 1 mol of silver halide 0.9 mmol per mol of added silver halide 0.7 mmol per mol of added silver halide 0.2 per mol of added silver halide
mmol addition (SD-2) Each silver halide emulsion was added with 5TB-1 shown below as an emulsion stabilizer after chemical sensitization.
3) Iθ CSTB-1) (Preparation of silver halide color photographic light-sensitive material sample) Silver halide color photographic light-sensitive material was produced by sequentially coating each of the following layers on polyethylene resin coated paper containing anatase-type titanium oxide. Materials were prepared. In the following examples, the amount added to the photosensitive material is per 100 cs*''.

(1) 20ag of gelatin, silver content of 5119 (Evl-1), and Y of 8-9.
- A layer containing 3119 dioctyl phthalate coupler solvent in which coupler* and 0.1 ms of 2,5-di-t-octylhydroquinone were dissolved.

(2) 12119 gelatin, 0.5119 2.
Interlayer comprising 2IIg dibutyl phthalate UV absorber solvent in which 5-di-t-octylhydroquinone and 4119 UV absorber* were dissolved.

(3) 181119 gelatin, 4II as silver content
g of green-sensitive silver chlorobromide emulsion (Em-2), and 511 g
M-coupler* and 2+19 antioxidant* and 0.
A layer containing 2,5119 dioctyl phthalate coupler solvent in which 2,5119 2,5-di-t-octylhydroquinone was dissolved.

(4) An intermediate layer containing the same composition as (2).

(5) 16a+9 gelatin, silver content 4119
red-sensitive silver chlorobromide emulsion (Em-3), and 3.5 mg
of C-coupler* and 0.11119 of 2.5-di-
A layer containing 2.0 mg of tricresyl phos7ate coupler solvent in which t-octylhydroquinone was dissolved.

(6) Gelatin protective layer containing 9+ag gelatin.

Coating aids are added to each layer (1) to (6), and (
A gelatin crosslinking agent was added to layers 4) and (6).

(2) and (4”) UV absorbers include U-1 and U
-2 equimolar mixtures were used.

Di-t-pentylhydroquinone di-octyl ether was used as the antioxidant in (3).

CBH++
After wedge exposure with green light using a microprocessor, the film was processed according to the following color development process, and then fogging was measured with green light using an optical densitometer (Model PDA-65, manufactured by Konica Corporation).

In addition, the obtained sample was placed in a xenon fade meter for 15 minutes.
The light resistance was evaluated by irradiating for one day and determining the residual rate (%) of the dye image at an initial density of 1.0.

Table 2 shows the Y-coupler, M coupler and C-coupler used in each layer and the results.

[Processing process] Color development 34.7±0.3°O 45 seconds bleach fixing
34.7±0.5℃ Stabilized for 45 seconds 30~
Dry for 90 seconds at 34℃ 60-80℃ 60
Seconds [Color developer] Pure water
800+n2 triethanolamine
89N,N-diethylhydroxylamine
5g Potassium chloride 29N ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amylianiline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate
309 Potassium sulfite
0.2g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 19 Add pure water to bring the total amount to 112, and adjust the pH to 10.2.

[Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 100+++Q ammonium sulfite (40% solution) 27.5nQ Add water to make a total volume of 1Q, and add potassium carbonate or pH 5 with glacial acetic acid
, 7.

[Stabilizing liquid] 5-chloro-2-methyl-4-inthiazolin-3-one 191-hydroxyethylidene-1゜1-diphosphonic acid Add 2 g of water to make lI2, and add sulfuric acid or potassium hydroxide −
Compound described in No. 62454) (Japanese Patent Publication No. 53-34044
(Compound described in No. W 088-4795) As is clear from Table 2, Samples 4 to 9 using the magenta coupler of the present invention had excellent fogging and light resistance.

Also, instead of example coupler 4 of sample 5, 13.15.
The effects of the present invention were also observed when 17.19.23 was used.

Claims (1)

[Scope of Claims] In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formula [I].
A silver halide color photographic material containing a 5-pyrazolone magenta coupler represented by: General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents an aryl group, R_2 represents an anilino group, acylamino group, ureido group, or carbamoyl group, and R_3 represents -NHSO_2R_4, -NHSO_
2N(R_5)_2, -SO_2NHR_6 or -S
O_2N(R_5)_2, R_4, R_5 and R_6 represent a linear or branched alkyl group, cycloalkyl group or aryl group, two R_5 may be the same or different, and Y is a hydrogen atom or a monovalent represents a group, n
represents an integer of 0 to 4, and when n is 2 to 4, each Y may be the same or different. ]