JPS60107032A - Color photographic sensitive silver halide material - Google Patents

Abstract

PURPOSE:To improve the density of developed color and the shelf stability by incorporating a specified magenta coupler. CONSTITUTION:A magenta coupler represented by formula I (where R1 is alkyl or aryl; R2 is a univalent group; R3 is alkylene, arylene or a bivalent org. group prepd. by bonding at least one alkylene group and at least one arylene group to each other; R4 is alkyl, alkenyl, aryl, a heterocyclic group or a group which can be eliminated by a coupling reaction with the oxidized product of a color de- veloping agent: (l) is an integer of 1-5; and (m) is an integer of 0-4) is incorporated into a color photographic material. The preferred positon of -NHCOR3 SO2R4 is p-position with respect to -(CH2)l-. The density is hardly reduced even after contact with formaldehyde.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background Technical Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material that exhibits high sensitivity and high color density and provides magenta dye images with improved storage stability.

Prior art and its problems Usually, in silver halide color photographic light-sensitive materials, exposed silver halide grains are reduced with an aromatic M primary amine color developing agent, and the oxidized product of the color developing agent produced at this time is reduced. A dye image can be obtained by coupling the dye with a coupler that forms yellow, magenta, and cyan dyes.

The coupler that has conventionally been used in practice for forming the magenta dye is a pyrazolone type magenta coupler, but this coupler has a low maximum color density and low sensitivity.
Furthermore, it has disadvantages in that it has undesirable side absorption, has poor storage stability, particularly formalin resistance, and has significant changes in color tone and decreased color development.

Many proposals have been made in the past to improve these drawbacks. For example, Japanese Patent Publication No. 48-30895 describes IH-pyrazolone (
Although 3,2-Cal-8-) lyazole-type magenta couplers have been disclosed, there is little improvement in maximum color density and sensitivity, and formalin resistance.

Further, Japanese Patent Publication No. 16058/1983 discloses a screw type pyrazolone type magenta coupler.

Although the sensitivity and formalin resistance of this coupler are somewhat improved, the maximum color density is insufficient. In addition, JP-A-56-135841 discloses an IH in which the 1st position is substituted with the active site of a compound having an active methylene group. -pyrazolo(3,2-C)-8-) lyazole type magenta couplers are disclosed. Although this coupler has somewhat improved formalin resistance, maximum color density and sensitivity are inadequate.

Furthermore, JP-A-58-42045 discloses a ballast group containing hydroxyphenylenesulfonyl & as a coupler ballast group for the purpose of improving the maximum color density, but it is difficult to improve the maximum color density and sensitivity. It is still insufficient.

(2) Purpose of the Invention The first object of the present invention is to provide a silver halide color photographic material that exhibits high maximum color density and sensitivity in the magenta color layer and excellent formalin resistance. A second object of the present invention is to provide a silver halide color photographic material that does not exhibit undesirable side absorption in the magenta coloring layer. A third object of the present invention is to provide a silver halide color photographic light-sensitive material in which a photographic magenta coupler has excellent dispersion stability. A fourth object of the present invention is to provide a silver halide color photographic light-sensitive material that provides excellent dye images using a photographic magenta coupler having these excellent properties.

(2) Structure of the Invention The object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has the following general formula [ (2) This is achieved by a silver halide color photographic light-sensitive material characterized by containing at least one magenta coupler represented by [2].

General formula [I] [wherein R1 represents an alkyl group or an alkyl group,
R2 represents a monovalent group, R3 represents an alkylene group, an arylene group, or a divalent organic group in which at least one alkylene and at least one arylene are bonded;
4 represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group; 2 represents a group that can be separated by a coupling reaction with an oxidized color developing agent; t is 1 to 5;
represents an integer from m iiO to 4, respectively. [Detailed Description of the Invention] In the above general formula, R1 represents an argyl group or an aryl group, preferably an alkyl group.

The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 alkyl groups, such as methyl group, ethyl group, ethoxyethyl group,
A t-butyl group is mentioned.

These alkyl groups may have a substituent.

The aryl group represented by R1 is preferably a phenyl group, and this phenyl group may have a substituent, for example, p-methoxyphenyl group, m-chlorophenyl group, p-(L)- Butylphenyl group, etc.

R2 ha A monovalent group such as a halogen atom (chloro group, etc.), an alkoxy group (methoxy group, t-butoxy group, etc.), an alkyl group (methyl group, ethyl group, methoxyethyl group, benzyl group, etc.), nitro group, cyano group, etc. represents a group.

R3 is an alkylene group, an arylene group, or at least one
It represents a divalent organic group in which two alkylenes and at least one (1') arylene are bonded, preferably an alkylene group. The alkylene group preferably has 1 to 20 carbon atoms, such as methylene group, 1,1-ethylene group, 1,3-propylene group, 1.1-dodecylene group, 1.1) ly7silene group. and alkylene groups such as 1-methyl-2-ethylene group.

The arylene group represented by R8 is preferably a phenylene group, and this phenylene group may have a substituent, such as 4-methyl-〇-phenylene, 3-chloro-m-phenylene, 3- j toxic p-phenylene etc. is JH'j' larel.

Further, the divalent organic group represented by R3 in which at least one alkylene and at least one arylene are bonded includes an alkylene arylene group, an arylene alkylene group, an alkylene arylene alkyl group, and an arylene alkylene arylene in which the arylene has a substituent. It may have. Specifically, the divalent organic group is -C
H2-(II%R is an alkyl group, an alkenyl group,
represents an alkyl group or a heterocyclic group, preferably an alkyl group or an aryl group. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, a 18°-propyl group,
n-butyl group, n-hexyl group, cyclohexyl group, n
-nonyl i, n-)"f syl group, n-octadecyl group,
Examples include benzyl group and 7enethyl group.

The aryl group is preferably a phenyl group, and the phenyl group may have a substituent. Examples of the substituent include a norogen atom, an alkyl group, an alkoxy group, a carboxyne group, and an alkylamino group. , a sulfonamide group, an alkyloxycarbonyl group, and the like. Specifically, m-chlorophenyl i, p-carboxyphenyl group, p-dimethylaminosulfonamidophenyl group, p-tolyl a, 3. s-dimethylphenyl group, p-tert-butylphenyl group, p-n-dodecylphenyl group, p-methoxyphenyl group, p-ta
rt-butoxyphenyl group, pn-dodecyloxyphenyl group, pn-tetradecyloxyphenyl group,
2 tert 7” thyl-5-dodecylphenyl group.

2-n-butyloxy-5-tert-octylphenyl group, m-)'decyloxycarbonylphenyl group, 0
-ethoxycarbonylphenyl group and the like.

Examples of the alkenyl group represented by R4 include a propenyl group and a butenyl group.

Examples of the heterocyclic group represented by R4 include a thiazole group, a thiadiazole group, a pentzoxazole group, a tetrazole group, etc., and these -2-yl groups,
5-methylthiadiazol-2-yl group, benzoxazol-2-yl group, 1-methyl 7torazol-5-
Examples include yl group.

The group which can be separated by the coupling reaction of the oxidized color developing agent represented by 2 means a group conventionally known as a so-called tin-lit-off group of a double-loading coupler.
Contains no hydrogen atoms. Specifically, halogen atoms (e.g., chlorine atoms, etc.), aryloxy groups (e.g., phenoxy groups, p-methoxyphenoxy groups,
p-butanesrunone amidone enoxy group, pteyj
-butylcarboamidophenoxy group, etc.), arylthio group (e.g., phenylthio group), peterocyclic thio group (e.g., 1-ethyltetrazole-5-thioyl group), etc., but preferably a halogen atom, particularly preferably chloro It is an atom.

t represents an integer from 1 to 5, particularly preferably an integer from 1 to 3.

m5' represents an integer of 4, with O being particularly preferred. In this case, -NHCOR in the general formula CI)
The 3So2R, group is preferably a ballast group sufficient to provide diffusion resistance to the photographic magenta coupler represented by the general formula.

It can be bonded to any position of the phenyl group with respect to the bonding position of , but it is preferably bonded to the p-position.

In addition, in this -NHCOR3So2R4 group, when R3 is an alkylene group, R4 is an alkyl group, an alkenyl group,
It may be either an aryl group or a heterocyclic group, but the total number of carbon atoms including substituents is preferably 8 to 30, particularly preferably 12 to 25. Also R
When 3 is phenylene, R is preferably an alkyl group or a phenyl group, and the substituent for the phenyl group is preferably selected from an alkyl group, an alkoxy group, an alkoxycarbonyl group, etc., and this alkyl group or The number of carbon atoms shown in the alkyl group, alkoxy group, and alkoxycarbonyl group as a substituent of the phenyl group is preferable, and s< is from 8 to 30, particularly preferably from 8 to 20.

Typical specific examples of magenta couplers in the present invention will be described below, but the present invention is not limited thereto.

A representative method for synthesizing the magenta coupler of the present invention will be described below in the margins.

A specific synthesis example of the magenta coupler of the present invention will be described below.

Synthesis Example 1 (Synthesis of Exemplary Coupler 3) Dissolve 4.52 kg of anhydrous sodium acetate in 150 CH of acetic acid and prepare 6-methyl-3-[:3-(p-aminophenyl)-propyl]-IH-pyrazole [ 3,2-C)-S
-) Add 127v of lyazole, then under stirring, α-
Benzylsulfonyltetradecanoyl chloride 221
2 was added little by little.

After reacting for 5 hours, the reaction solution was added to water to produce an oil. This oil was then extracted with ethyl acetate, washed with water, separated from the oil layer, dried over anhydrous magnesium sulfate,
The solvent was removed under reduced pressure. The residue was purified using silica gel column chromatography and crystallized using ethyl acetate and n-hexane to obtain 16.7 f of white powder.

Obtained white powder 15. Of chloroform 150ω
Add 3.69% of sulfuryl chloride to 5% of chloroform to dissolve uniformly, and cool to 10°C ± 5°C using ice water.
001. The solution was slowly added dropwise. After dropping for 1 hour, the reaction was continued for another 1 hour at the same temperature. The reaction solution was added to water, washed with water, and the chloroform layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography and then recrystallized from acetonitrile.

5.52 of a white powder with a melting point of 75-79°C was obtained. The structure is N
Determined using MR and MASS.

Synthesis Example 2 (Synthesis of Exemplary Coupler 9) Dissolve 4.51 ml of anhydrous sodium acetate in 150 cc of acetic acid to prepare 6-methyl-3-(3-(p-aminophenyl)) at room temperature.
-propyl)-IH-pyrazole[3,2-C:]-8
-:) Add lyazole 127f, then add α- under stirring.
23.6 f of (p-dodecyloxyphenylsulfonyl)butanoyl chloride was added in 9 g portions. After reacting for 5 hours, the reaction solution was added to water to obtain an oily product. This oily product was extracted using ethyl acetate, washed with water, the oil layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography to obtain an oily substance 20. I got Of.

Obtained oil 15. Add 3.4 f of sulfuryl chloride and 50 f of chloroform to dissolve uniformly in 150Ω of chloroform and cool to 10°C ± 3°C using ice water.
The CC solution was added dropwise over a period of 1 hour. After further reaction for 1 hour at the same temperature, the reaction solution was added to water, washed with water, the chloroform layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. After purifying the residue using silica gel column chromatography, 4.42 of a colorless caramel was obtained. The structure is NMR
and determined using MASS.

A silver halide color photographic light-sensitive material prepared using the coupler according to the present invention (hereinafter referred to as the coupler of the present invention) may contain a conventionally used dye-forming coupler.

As the yellow dye-forming coupler, a known open-chain ketomethylene coupler can be used. Among these, pivaloylacetanilide couplers or benzoylacetanilide couplers are useful. Specific examples of yellow dye-forming couplers that can be used are U.S. Pat. No. 2,875,057 and British Patent No. 1.
．． No. 077.874, U.S. Patent No. 3.408.194;
JP-A-50-123342, JP-A-50-876
50, JP 54-133329, JP 46-19031, JP 48-29432, JP 48-66834, JP 48-66
835, JP 48-94432, JP 50-28834, JP 54-99433, JP 55-70841, JP 111556
-74249 Publication, Special Publication No. 19956-1974,
JP-A-51-102636, JP-A-56-870
It is described in Publication No. 41, etc. .

As cyan dye-forming couplers, phenolic compounds,
Naphthol compounds and the like can be used. Specific examples of these compounds include U.S. Pat.
No. 9, No. 2.474.293, No. 2, 772.162
No. 2.895.826, British Patent No. 1.038.3
No. 31, Japanese Patent Publication No. 4B-36894, Japanese Patent Publication No. 47-21
No. 139, U.S. Patent No. 3,737, 316, JP-A-48-74844, U.S. Patent No. 3,880,661
No. 4.124.396, No. 4.333.999, JP-A-55-21094, No. 50-11203
No. 8, No. 50-117422, No. 52-1831
Publication No. 5, Publication No. 54-115230, Publication No. 55-16
Publication No. 3537, Publication No. 57-136650, Publication No. 57
-155538 publication, 57-204545 publication,
No. 55-32071, No. 55-108662, No. 56-1938, No. 56-27147, No. 56-80045, No. 56-104333
Examples include those described in the No. 1 gazette.

Further, as the magenta dye-forming coupler, the caprani of the present invention may be used alone or in combination of two or more. Furthermore, conventionally known pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, pyrazolinobenzimidazole compounds, pyrazolotriazole compounds, etc. may be used in combination as appropriate. However, at least one coupler of the invention is used.

To use the magenta couplers of the present invention, the methods used for conventional magenta dye-forming couplers are similarly applicable. Typically, a magenta coupler is incorporated into a silver halide emulsion, and this emulsion is coated onto a paste to form a silver halide color photographic light-sensitive material. This silver chloride color photographic light-sensitive material may be monochromatic or multicolored. In multicolor silver halide color photographic materials,
The magenta coupler of the present invention is usually contained in a green-sensitive emulsion, but it may also be contained in a non-sensitized emulsion or an emulsion sensitive to the three primary colors of the spectrum other than green. Each structural unit forming a dye image in the present invention consists of a single pore agent layer or a multilayer emulsion layer that is sensitive to a certain region of the spectrum.

The layers necessary for the silver halide color photographic light-sensitive material, including the layers of the image-forming structural units described above, can be arranged in various orders as known in the art. A typical multicolor silver halide color photographic light-sensitive material contains a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion containing at least one cyan dye-forming coupler, and at least one magenta dye-forming coupler. a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer containing at least one yellow dye-forming coupler, provided that at least one of the magenta dye-forming couplers is a magenta coupler of the present invention; A yellow dye image-forming structural unit consisting of at least one blue-sensitive silver halide emulsion layer is supported on a support.

The silver halide color photographic light-sensitive material of the present invention may have additional layers other than the above layers, such as a filter layer, an intermediate layer, a protective layer, an undercoat layer, etc. In order to incorporate each such coupler into a silver halide light-sensitive material, a conventionally known method may be followed. For example, the magenta coupler of the present invention or the coupler according to the present invention is dissolved in a mixture of a known high-boiling point solvent and a low-boiling point solvent such as butyl acetate or butyl propionate, and then mixed with an aqueous gelatin solution containing a surfactant. The emulsifier may be emulsified using a high-speed rotary mixer, colloid mill or ultrasonic disperser, and then added to the silver halide emulsion.

Known high-boiling point solvents include phthalate esters (e.g. dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (trictosyl phosphate, trioctyl phosphate, etc.), N-substituted acid amides (N, N-
diethyllaurinamide, etc.).

In the heat-retaining silver halide color photographic light-sensitive material of the present invention, a non-color-forming, diffusion-resistant phenolic compound C is hereinafter referred to as the phenolic compound of the present invention. ) is preferably used in combination. In that case, the phenolic compound of the present invention is preferably contained in the same layer as the silver halide emulsion layer containing the magenta coupler of the present invention.

The 7-Nol compound of the present invention may be non-color-forming and preferably diffusion-resistant; for example, conventional 7-Nol-based high-boiling organic solvents used for coupler dispersion may be used. can do.

In the present invention, the phenolic compound of the present invention has a melting point of 50°C or less and is solid at room temperature (25°C), or a liquid at room temperature and a boiling point of 200°C at normal pressure (1 atm).
Contains phenolic compounds whose temperature is higher than ℃.

Furthermore, it is preferable that the heptadyl compound of the present invention has a group that imparts diffusion resistance.

The phenol compound of the present invention is preferably a phenol compound represented by the following general formula [■].

General formula (II) [In the formula, bird and R6 are respectively] ・Rogen atom,
represents an alkyl group, cycloalkyl group or alkoxy group, k represents an integer from O to 4, and when k is 2 or more, two or more R6 may be the same group or different groups,
Further, R3 and R6 may be bonded to each other to form a 5- or 6-membered ring. ] In the general formula (n), the halogen atoms represented by R6 and R6 are preferably chlorine atoms. The alkyl group represented by R5 and R6 has 1 to 20 carbon atoms.
are preferable, such as methyl group, ethyl group, phenethyl group, 2 (p-human tetraxyphenyl) propane-2
-yl group, 1-(p-hydroxyZenyl)butane-1
-yl group, is.

-propyl chrysanthemum, butyl group, tart-butyl group, amyl group, tert-amyl group, tert-amyl group, hexyl group,
It represents a substituted or unsubstituted linear or branched alkyl group such as an octyl group, a tert-octyl group, a decyl group, a dodecyl group, or an 8-hexadecenyl group, and the cycloalkyl group represented by R5 and R6 is, for example, a cyclohexyl group. etc., and the alkoxy group represented by R and R6 preferably has 1 to 20 carbon atoms, such as methoxy group, ethoxy group, 1so-propoxy group, t
Examples include ert-butoxy group, phenethyloxy group, ethoxyethyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group and the like.

In the general formula [■], k represents an integer from 0 to 4, preferably from 0 to 3, and particularly preferably from 0 or 1.

In the general formula CI [), the alkyl group, cycloalkyl group, or alkoxy group represented by R5 and R6 is preferably a group that can make the phenolic compound of the present invention diffusion resistant, each singly or jointly, and the number of carbon atoms is The total sum is preferably from 6 to 30, particularly preferably from 8 to 25.
It is.

In the general formula [■], when bird and R6 are bonded to each other to form a ring, preferably hydroxyindan (e.g. 2,2-dimethyl-4-tert-octyl-6-indanol), hydroxychroman (e.g. ,
2,2-dimethyl-4-tart-phthyl-7-octyl-6-chromanol), dihydroxyspirochroman (e.g., t haspiro[7-tert-butyl-6-hydroxy-4,4-dimethyl-2,2'- /Roman]),
Hydroxyindanes (e.g. 2-butyl-6-octyl-5-chromanol), hydroxybenzdioxane (
For example 2,3-dimethyl-6-tart-octyl-7
-hydroxybenzoxane), hydroxybenzdioxolane (e.g. 2,2-dimethyl-4-dodecyl-5
-hydroxybenzdioxolane). Particularly preferred is a hydroxychroman ring.

Typical specific examples of the heptanoyl compounds of the present invention are described below, but the present invention is not limited thereto.

Below are specific examples of margins (1) (2) (3) (4) (5) (6) (7) (s) (9) (1o) (lt) (12) (13) (14) (15) ( 16) (17) (18) (19) (20) (21) (22) (23) (24) (25) The phenolic compound of the present invention can be easily synthesized by a conventionally known method. For example, U.S. Patent No. 2.8
．． It can be synthesized by the method described in 35.5-9, etc. In addition, there are many compounds that are generally commercially available, such as the above-mentioned specific examples (3), (5), and (6).
), (21), etc.

In order to incorporate the magenta coupler of the present invention and the phenolic compound of the present invention into a silver halide light-sensitive material, conventionally known methods may be followed. For example, after dissolving the magenta coupler and phenol compound of the present invention alone or in combination in a mixture of a known high boiling point solvent and a low boiling point solvent such as butyl acetate or butyl propionate, a gelatin aqueous solution containing a surfactant is prepared. The silver halide emulsion used in the present invention can be prepared by mixing with silver halide and then emulsifying it with a high-speed rotary mixer, a colloid mill, or an ultrasonic dispersion, and then adding it to silver halide.

Known high-boiling point solvents include phthalate esters (e.g. dibutyl heptatarate, dioctyl phthalate, etc.), phosphoric acid esters (tricresyl phosphate, trioctyl phosphate, etc.), N-substituted acid amides (N,N-
Typical examples include diethyllaurinamide, etc.).

Furthermore, some of the phenolic compounds of the present invention can themselves be used as high-boiling point solvents, for example, specific examples of compounds (2), (3), (6), (10), (21
) etc. fall under this category. In this case, there is no need to use other high boiling point solvents such as phthalate esters. Although the phenolic compound of the present invention and the magenta coupler of the present invention may be dispersed separately and each added to the same silver halide emulsion, it is preferable to dissolve and add both at the same time. When the magenta coupler of the present invention is added to a silver halide emulsion, it is usually about 0.01 to 2 mol per mol of silver halide, preferably 0.
．． It is added in a range of 0.03 to 0.5 mol.

In addition, the effect of the present invention will be greater as the amount of the phenolic compound of the present invention is added to the magenta coupler of the present invention, but specifically, the amount of the phenol compound of the present invention is 0.1 to 1. 10v1 preferably 0.25
It is added in the range of ~3v.

The silver halide used in the silver halide emulsion used in the present invention may include ordinary silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Includes anything used.

The silver halide emulsion constituting the silver halide emulsion layer according to the present invention can be manufactured by various manufacturing methods, including the usual manufacturing method, for example, the method described in Japanese Patent Publication No. 7772/1983, i.e., the solubility is low. A method for producing a so-called conversion emulsion, which involves forming an emulsion of silver salt grains consisting of at least a portion of silver salts that are thicker than silver oxide, and then converting at least a portion of the grains into silver bromide or silver iodobromide; Or 0.
It can be prepared by any manufacturing method such as the method of manufacturing a Lippmann emulsion consisting of fine-grained silver halide having an average grain size of 1 μm or less. Furthermore, the silver halide emulsion of the present invention is
Sulfur sensitizers, such as arylthiocarbamide, thiourea, cystine, etc., also selenium sensitizers, active or inactive, and reduction sensitizers, such as stannous salts, polyamines, etc., and noble metal sensitizers, such as gold sensitizers. Sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2
- sensitizers such as aurosulfopenzthiazole methyl chloride, or water-soluble salts such as ruthenium, rhodium, and iridium, specifically ammonium chlorovaladate, potassium chloroaurate, and sodium chloroparadite alone; Alternatively, chemical sensitization can be achieved by using appropriate combinations.

Further, the silver halide emulsion used in the present invention can contain various known photographic additives. for example[
It is a photographic additive as described in Research Disclosure, December 1978, Ugly 17643.

The silver halide used in the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the wavelength range necessary for green-sensitive emulsions.

Various spectral sensitizing dyes are used, and these may be used alone or in combination of two or more.

Spectral sensitizing dyes usefully used in the present invention include 11, for example, U.S. Pat.
．． Cyanine dyes, merocyanine dyes or composite cyanine dyes as described in the specifications of No. 270.378, No. 2,442,710, No. 2.454.520, and No. 2.776.280. can be cited as a representative example.

The support according to the present invention may be appropriately selected from conventionally known supports such as plastic film, plastic laminated paper, baryta paper, synthetic paper, etc. depending on the intended use of the photographic material. These supports are generally subjected to a subbing process to enhance adhesion with the photographic emulsion layer.

(2) Specific Utilization of the Invention The silver halide color photographic material of the present invention thus constructed can be subjected to various photographic processing methods for color development treatment after exposure. A preferred color developing solution used in the present invention is one containing an aromatic primary amine color developing agent as a main component.

As a specific example of this color developing agent, a p-phenylene diamine type is representative.
-Phenylenediamine! Acid salt, mo/mef-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride% 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino )-toluene, 2-amino-5-(N-ethyl-
N-β-methanesulfonamidoethyl)amine toluene sulfur 1HfL, 4-(N-ethyl-N-β-methanesulfonamidoethylamino)anili 7.4-(N-ethyl-
β-hydroxyethylamino)aniline, 2-amino-
Examples include 5-(N-ethyl-β-methoxyethyl)aminotoluene. These color developing agents may be used alone or in combination of two or more, and if necessary, in combination with a black and white developing agent such as hydroquinone. Furthermore, the color developing solution generally contains an alkaline agent (e.g. hydroxide).
Including IJum, ammonium hydroxide, sodium carbonate, sodium sulfite, etc., and various additives such as
It may also contain an alkali metal halogenide, such as potassium bromide, or a development regulator, such as hydrazine.

The silver halide color photographic light-sensitive material of the present invention may contain the above color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor. A color developing agent precursor is a compound that can form a color developing agent under alkaline conditions;
Examples include a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, a skaramine reactant precursor, and a urethane type precursor. Precursors for these aromatic primary amine color developing agents are described, for example, in U.S. Pat.
No. 42.599, No. 2,507, 114, No. 2.
No. 695.234, No. 3,719,492, British Patent No. 803.783, JP-A-53-135,6
No. 28, No. 54-79,035, research
Disclosure Magazine No. 15.159, No. 12,146
No. 13.924.

These aromatic primary amine color developing agents or their precursors need to be added in amounts that will provide sufficient color development during development. This amount varies considerably depending on the type of photosensitive material, but it is generally 1
Between 90.1 and 5 mol per mol, preferably 0.5 mol
It is used in a range of mol to 3 mol. These color developing agents or their precursors can be used alone or in combination. In order to incorporate the above compound into a photographic light-sensitive material, it can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc., and added. It can be added as an emulsified dispersion using a high-boiling organic solvent or by impregnating a latex polymer as described in Research Disclosure No. 14850.

The silver halide color photographic light-sensitive material of the present invention usually includes:
After color development processing, bleaching and fixing, bleach-fixing, and water washing are performed.

Many compounds are used as bleaching agents, among them polyvalent gold maple compounds such as iron (■), cobal) (m), and tin (II); complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylenediaminediacetic acid, metal complexes of malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, or hepterythyanates. , dichromate, etc. may be used alone or in appropriate combinations.

(2) Specific Examples of the Invention The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Magenta Cub 2 of the present invention and a comparative coupler as shown in Table 1 were each taken in an amount of 0.1 mol per mol of silver, and tricresyl phosphate was added in an amount of 1 times the weight of the coupler and tricresyl phosphate was added in an amount of 3 times the weight of the coupler. of ethyl acetate was added and heated to 60°C to completely dissolve. This solution was mixed with 120% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
The mixture was mixed with 1.200% of an aqueous solution of 5tisgelatin containing -, and emulsified and dispersed using an ultrasonic dispersion machine to obtain an emulsion. Afterwards,
This dispersion was added to a green-sensitive silver iodobromide emulsion (containing 5 moles of silver iodide), and as a hardening agent, a solution of 1,2-bis(vinylsulfonyl)ethane (water:methanol = 1:1) was added. )
120- was added, coated on a subbed transparent polyester base, and dried to prepare samples 1 to 7. (Coated silver amount 2
0.0cm/100cJ) Each sample thus obtained was subjected to wedge exposure 9 in accordance with a conventional method, and then subjected to the following development treatment. Table 1 shows the results.

[Processing process] (35℃) Processing time Color development 4 minutes 00 seconds Bleach 1 minute 30 seconds Washing with water 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds Used in the processing process The composition of the treatment solution was as follows.

[Color developer composition]

4-Azuno 3-Methyl-N-ethyl-N-(β-hydroxyethyl)-aniline (idltJit7sy Anhydrous Sodium Sulfite 425F Hydroxyamine + Sulfate 2.02 Anhydrous Potassium Carbonate 37.!M' Sodium Bromide 1 .32 Nitrilotriacetic acid trisodium salt (monohydrate) 25f Potassium hydroxide 1.02 [Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt 10G
, (1 ethylenediaminetetraacetic acid diammonium salt
10. Of ammonium bromide 150. Of glacial acetic acid 10. Otag [Fixer composition] Ammonium thiosulfate (SO@aqueous solution) 16”2t,
lt Anhydrous sodium sulfite 124t [Stabilizing liquid composition] Formalin (37% aqueous solution) 5.0m Conidax (
(manufactured by Konishiroku Photo Industry Co., Ltd.) Add 7.5 m of water to 1 t
shall be.

*(1) Specific sensitivity is the reciprocal of the exposure amount that gives a density of fog density + 0.1, and Sample 1 using Comparative Coupler 1 was set as 100.

! 11 (2) Temperature and humidity controlled to 30℃, 62℃RH
After the sample is placed in a sealed container containing 6 CC of 9-thiformin aqueous solution for 3 days, color development is performed.

For comparison, a sample not treated with formalin is also developed.

Comparative coupler 1 Comparative coupler 2 2H5 Comparative coupler 3 Comparative coupler 4 As shown in Table 1, comparative coupler 1 has a structure similar to the coupler of the present invention, and gave good results in terms of sensitivity, maximum concentration, and formalin resistance. However, it was still insufficient to the extent desired by the inventors. Comparative coupler 2 has a structure more similar to the coupler of the present invention than comparative coupler 1, and is a coupler in which the 6-position of the pyrazolotriazole mother nucleus is hydrogen, but the specific sensitivity, maximum concentration,
Both formalin resistance was at an extremely low level. Comparative coupler 3 is a compound in which the 1st position of comparative coupler 2 is substituted with the active site of a compound having an active methylene group, and is a compound with improved formalin resistance.

However, although this comparative coupler 3 shows slight improvements in both specific sensitivity and maximum density, both are at low levels.
Although an improvement was observed in formalin resistance, it was still insufficient. Comparison coupler 4 is comparison coupler 3-6
This is a compound in which the chloro atom is substituted at the υ position, and the specific sensitivity, maximum concentration, and formalin resistance are improved, but all of these are still unsatisfactory. In contrast, Samples 5.6 and 7 containing the magenta coupler of the present invention were fully satisfactory in terms of specific sensitivity, maximum concentration, and formalin resistance.

According to the results in Table 1, the sensitivity, maximum concentration,
In order to satisfy all formalin resistance requirements, the 1st position of the pyrazolotriazole mother nucleus must be hydrogen, sb, and the 6th position must be:
A necessary condition is that it is substituted with a group capable of coupling with an oxidized form of a color developing agent, such as a chlorine atom. Furthermore, although Comparative Coupler 1 satisfied the above requirements, the results obtained were still unsatisfactory. It is understood from this that the effects of the present invention are completely surprising.

Example 2 A magenta coupler of the present invention and a comparative coupler were prepared in the same manner as in Example 1, and Samples 8 to 14 were prepared.
processed in the same way.

The results are shown in Table 2.

Table 2 Mine (3) Specific sensitivity has the same meaning as the specific sensitivity in Table 1, and shows the value ° when the sensitivity of sample 8 using comparative coupler 5 ° is taken as 100.

Comparative coupler 5 Comparative coupler 6 (Compound described in JP-B-49-16058) Comparative coupler 7 (Compound described in JP-A-58-42045) Comparative coupler 8 As shown in Table 2, Comparative coupler 5 has been used in practical use for a long time. However, this coupler has low sensitivity and maximum density, and also has poor storage stability, especially formalin resistance. Comparative coupler 6 had improved sensitivity but poor maximum density and formalin resistance. Although the comparative coupler showed improvement in maximum concentration and formalin resistance, it was still unsatisfactory in terms of sensitivity.

Comparative coupler 8 is a coupler developed by the present inventors, and although it shows improvements in sensitivity, maximum density, and formalin resistance, it is not satisfactory to the present inventors.

As shown in Table 2, the magenta coupler of the present invention was superior to both the conventionally known magenta coupler and Comparative Coupler 8 in sensitivity and maximum density, and also exhibited high formalin resistance. It will be appreciated that the effects of the present invention are completely unexpected and surprising.

As shown in Examples 1 and 2, the magenta coupler of the present invention is a material that exhibits high sensitivity and high color density, and also exhibits stable color development even when stored, especially in the presence of formalin. Therefore, by conventionally known methods, the open-chain active methylene yellow coupler was converted into a blue-sensitive silver halide emulsion, the magenta coupler of the present invention was converted into a green-sensitive silver halide emulsion, and the phenol or naphthol-based cyan coupler was converted into a red-sensitive silver halide emulsion. By adding each of these materials to a silver halide emulsion and coating them on a transparent support using various additives as appropriate, we succeeded in obtaining a completely new silver halide color photographic light-sensitive material having stable color balance.

Example 3 A magenta coupler of the present invention as shown in Table 3 and a comparative coupler below were each taken in an amount of 0.1 mole per mole of silver, and the same weight of tricresyl phosphate as the coupler and the phenol compound of the present invention were added. An appropriate amount of ethyl acetate was added to the coupler in an amount three times the weight of the coupler, and the mixture was heated to 60° C. to completely dissolve the coupler.

This solution was mixed with 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by Devon).
% gelatin aqueous solution and emulsified and dispersed using an ultrasonic dispersion liquid to obtain an emulsion.

Thereafter, this dispersion was added to green-sensitive silver iodobromide emulsion (containing 5 mol of silver iodide) 4 and 9, and a 2% solution of 1,2-bis(vinylsulfonyl)ethane (water: methanol, ,=1:1)120fn1. Sample 15~
37 was created. (Coated silver amount 20η/1o o a/
l) The samples thus obtained were subjected to wedge exposure according to a conventional method and then developed, and the results are shown in Table 3. The processing steps, color developing solution composition, bleaching solution composition, fixing solution composition, and stabilizing solution composition were the same as in Example 1.

*(1) Tricresyl phosphate was used as HBS, and in the table, non-use is indicated by (c), and use is indicated by O.

111(2) The amount of the heptanols-based compound of the present invention added is expressed as follows.

Hata (3) Same as Example 1.

*(4) Same as Example 1.

*(5) Maximum spectral absorption was measured by measuring the spectral absorption when the density of the sample subjected to color development processing was 1.0, and the wavelength of the maximum value was shown. (nm) Comparative couplers 5, 6, 7 and 8 are the same as those described in Example 2.

As is clear from Table 3, Comparative Coupler 5 is a coupler that has been in practical use for a long time, but the sensitivity, maximum density,
Both formalin resistance showed poor results. Furthermore, 7 of the present invention
Although some improvement is seen even when used together with a ethanol-based compound, it is not to the extent expected by the inventors. on the other hand,
Comparative coupler 6 has improved sensitivity, but both maximum color density and formalin resistance are low, and even when the phenol compound of the present invention is added, little effect is observed.

Comparative coupler 7 showed significant improvements in both maximum color density and formalin resistance, but had low sensitivity and little effect even when used in combination with the heptol-based compound of the present invention. Furthermore, Comparative Coupler 8 showed improvements in sensitivity, maximum color density, and formalin resistance, but was ultimately insufficient to the extent expected by the inventors.

On the other hand, the magenta coupler of the present invention has 7
By appropriately using ethanol-based compounds in combination, it is possible to achieve maximum color density and formalin resistance equivalent to or better than that shown by Comparative Couplers 7 and 8, and to achieve significant improvements in sensitivity.In addition, spectral absorption We have succeeded in developing a silver halide color photographic material that forms a magenta dye with good properties.

Example 4 0.1 mole of each of the magenta couplers of the present invention as shown in Table 4 was taken per mole of silver, and the same weight of 2,4-di-tert-amylphenol and Kirisler weight as Turnip 2- were added. Three times the amount of ethyl acetate was added and heated to 60°C to completely dissolve. This solution contains 5% of Kanol B (alkylnaphthalene sulfonate, manufactured by Devon).
1,200m of 5tisgelatin aqueous solution containing 120m of aqueous solution
g and emulsified and dispersed using an ultrasonic dispersion machine to obtain an emulsion. Thereafter, this dispersion was added to 4 kf of a green-sensitive silver iodobromide emulsion (containing 5 mol of silver iodide), and 1,
2% solution of 2-bis(vinylsulfonyl)ethane (water:
Methanol = 1:1) 120- was added, coated and dried on the undercoated transparent polyester base, and the amount of coated silver was 1.
I adjusted it so that it was 0km/100m.

For comparison, sample 15.17°2 used in Example 3
1.19 was used.

The sample thus obtained was subjected to wedge exposure according to a conventional method, and then developed in the same manner as in Example 3.

Table 4 *a TOP represents tricresyl phosphate and DAP represents 2,4-di-tart-amylphenol.

As shown in Table 4, in the system using the coupler of the present invention and the heptadol compound of the present invention, the amount of silver is halved.
Despite this, it shows sensitivity and maximum color density equivalent to or higher than that of the comparative couplers. This suggests that the combination of the coupler of the present invention and the phenolic compound of the present invention has a high utilization efficiency for halide complexes, resulting in a reduction in silver content, thinning, silicification, and It is understood that the material can fully satisfy the purpose of the present invention by improving the sharpness of other layers.

As shown in Examples 3 and 4, the combined use of the magenta coupler of the present invention and the phenolic compound of the present invention exhibits high sensitivity and high color density,
Furthermore, since it exhibits stable color development even when stored, especially in the presence of formalin, the magenta of the present invention can be prepared by adding an open-chain active methylene yellow coupler to a blue-sensitive silver halide emulsion using a conventionally known method. By adding a coupler and a heptol-based compound to a green-sensitive silver halide emulsion, and adding a phenol or a heptol-based cyan coupler to a red-sensitive silver halide emulsion, they are coated on a transparent support using various additives as appropriate. We succeeded in obtaining a completely new silver halide color photographic material with stable color balance.

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 CI]
A silver halide color photographic material containing at least one magenta coupler represented by: General formula CI) [wherein R1 represents an alkyl group or an aryl group,
R2 represents a monovalent group, R3 represents an alkylene group, an arylene group, or a divalent organic group in which at least one alkylene and at least one arylene are bonded;
4 represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group; Z represents a group that can be separated by a coupling reaction with an oxidized color developing agent; t is 1 to 5;
m ld represents an integer from O to 4, respectively. ]