JPH08160576A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE: To obtain the silver halide color photosensitive material containing a yellow dye forming coupler superior in color development performance by incorporating a specified yellow dye forming coupler in at least one layer on a support. CONSTITUTION: At least one layer on the support contains at least one kind of the yellow dye forming couplers represented by the formula in which R1 is an alkyl or cycloalkyl or aryl group or the like; R2 is an aliphatic group or a halogen atom or an aliphatic oxy group or the like; each of R3 and R4 is, independently, an H atom or an aliphatic or aryl group; R5 is an alkyl or alkenyl or aryl group; R6 is a substituent; each of R7 and R8 is, independently, an H atom, an alkyl or alkoxy group or the like; W is a -N(R9 )- group or an O or S atom; R9 is an H atom or an alkyl or aralkyl or aryl group; (m) is an integer of 2-20; (n) is 0-3, 1, 2, or 3; and when R9 is a benzyl group, both of R7 and R8 are not H atoms at the same time.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color light-sensitive material containing a novel photographic yellow dye-forming coupler.

[0002]

2. Description of the Related Art A silver halide color light-sensitive material reacts with a dye-forming coupler (hereinafter referred to as "coupler") which is oxidized with an aromatic primary amine developing agent which is oxidized by exposing the material to color and then developing the color. As a result, a color image is formed. Generally, in this method, a color reproduction method using a subtractive color method is used, and in order to reproduce blue, green, and red, color images of yellow, magenta, and cyan, which have complementary colors, respectively, are formed. Acylacetamide couplers and malondianilide couplers as yellow dye-forming couplers (hereinafter referred to as yellow couplers) for forming yellow color images, and 5-pyrazolone couplers and pyrazolotriazole couplers as magenta couplers for forming magenta color images, Phenol couplers and naphthol couplers are generally used as cyan couplers for forming cyan images.

Yellow dyes, magenta dyes and cyan dyes obtained from these couplers have a silver halide emulsion layer or a silver halide emulsion layer having a sensitivity to radiation which is complementary to the radiation absorbed by the dyes. It is generally formed in an adjacent layer. Incidentally, yellow couplers, particularly acylacetamide couplers such as benzoylacetoanilide couplers and pivaloylacetoanilide couplers, are generally used for image formation. The former generally has high coupling activity with an oxidized product of an aromatic primary amine developing agent at the time of development and has a large molecular extinction coefficient of a yellow dye to be formed, so that a high-sensitivity color photosensitive material for photographing, particularly a color photosensitive material is required. It is mainly used for negative films, and the latter is mainly used for color papers and color reversal films because of its excellent yellow dye spectral absorption characteristics and fastness. For example, JP-A-63-123047 and US Pat. No. 3,65
8,544, JP-A-52-86333, JP-A-1-
No. 209448, a pivaloyl acetanilide yellow coupler is disclosed in JP-A-2-193146 and JP-A-52-1439.
No. 86333 and U.S. Pat. No. 3,658,544 disclose benzoylacetanilide yellow couplers, respectively. The couplers described in these patents show color fastness to color images, light, heat and humidity. There were still many points that were insufficient in terms of stability of the emulsion during refrigeration.

Recently, it has been desired to provide a silver halide color light-sensitive material at low cost by using an inexpensive coupler. However, a coupler using an inexpensive raw material has a drawback that it is inferior in color developability and its solubility in a high boiling point organic solvent is low, so that it is inferior in stability of the emulsion during refrigeration and the like. Particularly, those having satisfactory color developability have low solubility in a high-boiling point organic solvent and are inferior in temporal stability of emulsions, while those having satisfactory solubility have low color developability. Moreover, the dyes obtained from these couplers have insufficient image fastness, and the development of couplers which give dyes with high fastness has been desired.

[0005]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide color light-sensitive material containing a yellow dye-forming coupler excellent in color forming property.
Another object of the present invention is to provide a yellow dye-forming coupler excellent in solubility in an organic solvent and excellent in stability of an emulsion during refrigeration, or a silver halide color light-sensitive material containing the same. The object of the present invention is
Another object of the present invention is to provide a yellow dye-forming coupler or a silver halide color light-sensitive material containing the yellow dye-forming coupler which gives a color image excellent in fastness to light, heat and temperature. A further object of the present invention is to provide a yellow dye-forming coupler which can be produced using inexpensive raw materials, or a silver halide color light-sensitive material containing the yellow dye-forming coupler.

[0006]

The objects of the present invention have been achieved by the following means. (1) A silver halide color light-sensitive material containing at least one yellow dye-forming coupler represented by the following general formula (I) (hereinafter simply referred to as a yellow coupler) in at least one layer on a support.

[0007]

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In the general formula (I), R ₁ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R 1
₂ represents an aliphatic group, a halogen atom, an aliphatic oxy group, an aryloxy group or an amino group, R ₃ and R ₄ each independently represent a hydrogen atom, an aliphatic group or an aryl group, and R
₅ represents an alkyl group, an alkenyl group or an aryl group. R ₆ represents a substituent, and R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group, an alkoxy group or an aryloxy group. W represents -N (R ₉ )-, an oxygen atom or a sulfur atom, and R ₉ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. m is an integer of 2 to 20, n is 0 to 3
Represents the integer. However, when R ₉ is a benzyl group, R ₇
Neither R ₈ nor R ₈ becomes a hydrogen atom.

(2) The silver halide color light-sensitive material described in (1) above, wherein in the general formula (I), R ₂ represents a chlorine atom. The yellow coupler of the present invention represented by formula (I) is described in detail below.

Unless otherwise specified, the aliphatic moiety in the aliphatic group and the aliphatic oxy group in the present invention may be linear, branched or cyclic, and may contain an unsaturated bond, It may be substituted with a known substituent in the yellow coupler. That is, the aliphatic group in the present invention contains alkyl, alkenyl, alkynyl, cycloalkyl and the like.

Unless otherwise specified, the alkyl group and alkenyl group in the present invention may be linear or branched, and may be substituted with a substituent known in the yellow coupler.

Further, the cycloalkyl group in the present invention may be substituted with a substituent known as a yellow coupler or may be condensed ring unless otherwise specified.

Further, the aryl moiety in the aryl group, heterocyclic group and aryloxy group in the present invention is
Unless otherwise specified, it may be substituted with a substituent known as a yellow coupler, or may be condensed.

Further, the amino group in the present invention may be substituted with a substituent known as a yellow coupler unless otherwise specified. When the compound of the present invention contains a geometric isomer such as an unsaturated bond, either one of the isomers may exist or a mixture thereof.

In the general formula (I), R ₁ is preferably an alkyl group having 1 to 30 carbon atoms (hereinafter referred to as C number) (for example, methyl, ethyl, i-propyl, t-butyl, t).
-Pentyl, octyl, benzyl), a C3-30 cycloalkyl group (eg, cyclopropyl, 1-methylcyclopropyl, 1-ethylcyclopropyl, 1-benzylcyclopropyl, cyclopentyl, 1-methylcyclohexyl, cyclohexyl) , A C 6-36 aryl group (eg, phenyl, 2-naphthyl, 4-methylphenyl, 4-methoxyphenyl, 3-acetylaminophenyl, 2-chlorophenyl), a C 1-30 heterocyclic group (eg, , Indolinyl, 3,5-dioxanyl,
1-methyl-3,5-dioxanyl), more preferably t-butyl, 1-methylcyclopropyl, 1-ethylcyclopropyl, 1-benzylcyclopropyl, 4
-Methoxyphenyl and indolinyl groups are particularly preferred, t-butyl, 1-ethylcyclopropyl and 4-methoxyphenyl groups are particularly preferred, and t-butyl group is most preferred.

In the general formula (I), R ₂ is preferably a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, iodine), an aliphatic oxy group having a C number of 1 to 30 (eg, methoxy, i-propoxy). , T-butoxy, benzyloxy,
Cyclohexyloxy), an aryloxy group having a C number of 6 to 36 (for example, phenoxy, 2,4-t-butylphenoxy, 2-naphthoxy, 4-methoxyphenoxy, 2-
Chlorphenoxy), an aliphatic group having a C number of 1 to 30 (for example, methyl, i-propyl, t-butyl, benzyl, trifluoromethyl, cyclohexyl), an amino group having a C number of 0 to 30 (for example, N, N- Dimethylamino, N-cyclohexylamino, N-butylamino), more preferably R ₂ is a halogen atom, an aliphatic oxy group or an aryloxy group, and more preferably a halogen atom or an alkoxy group having 1 to 20 C atoms. And more preferably a chlorine atom or a methoxy group, and most preferably a chlorine atom.

In the general formula (I), R ₃ and R ₄ are each preferably a hydrogen atom or an aliphatic group having a C number of 1 to 20 (eg,
Methyl, ethyl, i-propyl, t-butyl, octyl, dodecyl, hexadecyl, octadecyl, i-octadecyl, benzyl, cyclohexyl, allyl, oleyl), an aryl group having 6 to 26 C atoms (eg, phenyl, 2
-Naphthyl, 4-methoxyphenyl, 3-methylphenyl, 2-chlorophenyl), preferably a hydrogen atom or an aliphatic group having 1 to 20 C atoms. Particularly, R ₄ is preferably a hydrogen atom.

In the general formula (I), m represents an integer of 2 to 20, preferably 2 to 10, more preferably 2 to 8 and even more preferably 2 to 4. It represents an integer and is most preferably 2. R ₃ and R ₄ may be the same or different.

In the general formula (I), R ₅ is an alkyl group (preferably having a C number of 1 to 20, for example, methyl, t-butyl, octyl, 2-ethylhexyl, dodecyl, 3,5,5-.
Trimethylhexyl, i-tridecyl, hexadecyl,
2-hexyldecyl, 5,7,7-trimethyl-2-
(1,3,3-Trimethylbutyl) octyl, benzyl, 2-butoxyethyl, tetradecyl, octadecyl), alkenyl group (preferably having a C number of 2 to 20, for example, oleyl, vinyl, linole, ricinol, linolene, 10-decenyl). ), An aryl group (preferably having a C number of 6)
To 26, for example, phenyl, 2,4-di-t-pentylphenyl, 4-octyloxyphenyl, 3-methylphenyl), preferably a C 1-20 straight-chain or branched alkyl group or C 3 It is an alkenyl group having 20 to 20 carbon atoms, and more preferably an unsubstituted linear or branched alkyl group having 8 to 18 C atoms.

In the general formula (I), R ₆ represents a substituent, preferably an aliphatic group having a C number of 1 to 30 (eg, methyl, i
-Propyl, t-butyl), an aliphatic oxy group having 1 to 30 carbon atoms (eg, methoxy, i-propoxy, benzyloxy, 2-ethylhexyloxy, hexadecyloxy, cyclohexyloxy), an acylamino having 2 to 30 carbon atoms. A group (eg, acetylamino, benzylamino, pivaloylamino), a carbamoyl group having a C number of 1 to 30 (eg, N-methylcarbamoyl, N-phenylcarbamoyl, N, N-dibutylcarbamoyl, N-methyl-N)
-Phenylcarbamoyl), a C2-30 alkoxycarbonyl group (eg, methoxycarbonyl, hexyloxycarbonyl, octadecyloxycarbonyl),
Alkyl sulfonamide group having 1 to 30 C numbers (for example, methane sulfonamide, octane sulfonamide, hexadecane sulfonamide), aryl sulfonamide group having 6 to 36 C numbers (for example, benzene sulfonamide, p-
Chlorobenzenesulfonamide), a cyano group, a nitro group and a halogen atom (for example, chlorine and bromine), more preferably an aliphatic group, an aliphatic oxy group and a halogen atom.

In the general formula (I), n represents an integer of 0 to 3, preferably n represents 0 or 1, and more preferably n.
Is 0.

In the general formula (I), R ₇ and R ₈ are each preferably a hydrogen atom or an alkyl group having a C number of 1 to 10 (eg, methyl, ethyl, i-propyl, t-butyl, 2-
Methoxyethyl, n-butyl), C 1-10 alkoxy group (eg, methoxy, ethoxy, i-propoxy, t-butoxy), C 6-15 aryloxy group (eg, phenoxy, 4-methoxyphenoxy). , 3-
Methylphenoxy), preferably a hydrogen atom, an alkyl group having a C number of 1 to 4 or an alkoxy group having a C number of 1 to 4, more preferably a hydrogen atom, a methyl group, a methoxy group or an ethoxy group, and It preferably represents a hydrogen atom or a methyl group.

In the general formula (I), W represents -N (R ₉ )-, an oxygen atom or a sulfur atom, R ₉ is a hydrogen atom, an alkyl group (preferably having a C number of 1 to 20, for example, methyl, ethyl, i-propyl, t-butyl, 2-methoxyethyl), an aryl group (preferably having a C number of 6 to 20, for example, phenyl, 2-naphthyl, 3-methylphenyl, 4-methoxyphenyl,
2-chlorophenyl) and an aralkyl group (preferably having a C number of 7 to 20, for example, benzyl, phenethyl, 3-phenylpropyl). However, when R ₉ is a benzyl group, R _{9
Neither 7} nor R ₈ becomes a hydrogen atom. W is preferably -N (R ₉ )-or an oxygen atom, more preferably
-N (R ₉ )-, where R ₉ is preferably a hydrogen atom, C
It represents an alkyl group or a benzyl group of the formulas 1 to 4, more preferably a hydrogen atom, a methyl group or a benzyl group, and further preferably a hydrogen atom or a methyl group.

W is -N (R₉) -When R₇, R₈, R₉of
A preferred combination is R₉Is a hydrogen atom, and R₇Over
And R₈Is a methyl group (1), R₉Is a methyl group
R ₇And R₈Is a hydrogen atom (2), R₉Is meth
R group, R₇Is a methoxy group, R₈Is a hydrogen atom
Or (3), R₉Is a benzyl group, R₇Is Etoki
R group₈Is a hydrogen atom (4)
And more preferably a combination of (1), (2) and (4)
And more preferably a combination of (1) and (2),
Most preferred is the combination of (1).

The yellow coupler represented by the general formula (I) has substituents R ₁ , R ₂ , R ₅ , R ₆ , R ₇ and R _9.
Etc., they may be bonded to each other via a divalent or higher valent group to form a dimer or a multimer. In this case, the number of carbon atoms may be out of the specified range for each substituent.

Preferred combinations of each group in the general formula (I)
As a result, R₂Is a halogen atom or an C 1-20
Rukoxy group, R₃Is a hydrogen atom or a C number of 1 to 20
R is an aliphatic group_FourIs a hydrogen atom and m is 2 to 10.
R is an integer_FiveIs a straight-chain or branched al having a C number of 1 to 20.
A kill group or an alkenyl group having a C number of 3 to 20, wherein W is -N
(R₉)-Or an oxygen atom, R₇, R₈Is a hydrogen atom, C
An alkyl group having 1 to 4 or an alkoxy group having 1 to 4 C
Yes, R₉Is a hydrogen atom, an alkyl group having 1 to 4 C or a group
A combination representing an benzyl group (however, R₉Is a benzyl group
Come, R₇And R₈Are not hydrogen atoms at the same time)
Preferably R₁Is a t-butyl group, R₂
Is a chlorine atom or a methoxy group, m is 2, and R is
_FiveIs an unsubstituted linear or branched alkyl group having a C number of 8 to 18
, N is 0, and W is -N (R₉)-And R₇, R
₈, R₉Are each independently a hydrogen atom or a methyl group.
Is more preferable, R₂Is a chlorine atom
More preferably, in that case, R₉Is a methyl group and R₇as well as
R₈Are both hydrogen atoms, or R₉Is a hydrogen atom and R₇Over
And R₈It is particularly preferable that both are methyl groups, and R is₉But water
Elementary atom, R₇And R ₈Most preferred if both are methyl groups
New

Specific examples of the yellow coupler of the present invention represented by formula (I) are shown below, but the present invention is not limited thereto.

[0028]

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[0029]

[Chemical 4]

[0030]

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[0031]

[Chemical 6]

[0032]

[Chemical 7]

[0033]

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[0034]

[Chemical 9]

[0035]

[Chemical 10]

[0036]

[Chemical 11]

In the yellow coupler of the present invention represented by the general formula (I), a cyclic anhydride such as succinic anhydride and an alcohol are generally heated or reacted, or a dicarboxylic acid and an alcohol are half-esterified with an acid catalyst or the like. Etc.
Carboxylic acid HOOC- (C (R ₃ ) (R ₄ ))- _m C (= O) OR ₅ was synthesized, which was converted to an acid chloride with oxalyl chloride, thionyl chloride, phosphorus trichloride, etc. In the presence of a aniline having a nucleus and a deoxidizing agent such as triethylamine, pyridine and potassium carbonate, dimethylformamide, ethyl acetate,
It is synthesized through a step of performing an amidation reaction in a solvent such as acetonitrile.

The synthesis examples of the yellow coupler of the present invention represented by the general formula (I) are shown below, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Y-1

[0040]

[Chemical 12]

After 242 g (2.4 mol) of succinic anhydride and 428.8 g (2.0 mol) of tetradecanol were heated to 100 ° C. to dissolve them, the mixture was heated and stirred at 130 ° C. for 3 hours. After cooling to 80 ° C, add 500 ml of water,
The mixture was stirred at 0 ° C for 30 minutes. After adding 100 ml of ethyl acetate, the mixture was cooled to 40 ° C. and separated. The organic phase is saline 15
The extract was washed twice with 0 ml, dried over magnesium sulfate, concentrated and dried to obtain 625 g (yield 99.4%) of white crystals of carboxylic acid (1).

62.9 g (0.2 mol) of carboxylic acid (1),
Dissolve 1 ml of dimethylformamide in 100 ml of methylene chloride, stir and stir to dissolve oxalyl chloride ((COCl) ₂ ) 38.1.
g (0.3 mol) was added dropwise over 10 minutes, and the mixture was further stirred for 1 hour. Concentrated under reduced pressure with an assurator and acid chloride
I got (2).

Aniphosphoric acid (3) 53.8 g (0.2 mol),
Pyridine (17.4 g, 0.22 mol) was dissolved in dimethylformamide (100 ml) and stirred to give acid chloride (2).
Dissolve (0.2 mol) in dimethylformamide to give 30
It dripped over minutes. 300 ml water, 100 acetonitrile
ml was added to crystallize the amide (4), which was filtered off, washed with water and acetonitrile, and the amides (4) crystallized 100.
3 g (88.7%) were obtained.

Amides (4) 100.3 g (0.177 mo
l) was dissolved in 300 ml of methylene chloride, stirred, and bromine 29.
1 g (0.182 mol) was added dropwise over 30 minutes, and 1 more
Stir for 0 minutes. Water was added for liquid separation, and the organic phase was washed twice with water, dried over magnesium sulfate and then concentrated. Here, 45.4 g (0.354 mol) of hydantoins (5), 1,8-
Diazabicyclo [5,4,0] undecene (DBU) 5
4.8 g (0.36 mol) of dimethylformamide 10
A solution dissolved in 0 ml was added and stirred for 2 hours. After ethyl acetate and water were added and the layers were separated, the organic phase was washed with dilute hydrochloric acid, further washed with water, dried over magnesium sulfate and concentrated. Silica gel column chromatography (developing solvent:
Purification with ethyl acetate: hexane = 1: 2 → 1: 1.5), and the desired white crystals of Y-1 90.2 g (73.7%)
I got

Melting point 79 ° C., NMR spectrum (300 MHz,
COCl, δ: ppm) 0.88 (3H, t, CH ₃ CH _2- ), 1.26
(9H, S (CH ₃ ) ₃ C-, + 22H, m, -CH _2- ), 1.47 (3H, S, CH
_3- ), 1.53 (3H, S, CH _3- ), 1.62 (2H, m, OCH ₂ CH
_2- ), 2.70 (4H, m-NHCOCH ₂ CH ₂ COO-), 4.07 (2H,
t, -OCH _2- ), 5.69 (1H, S, CH), 6.68 (1H, S, CON
H), 7.20 (1H, d, aromatic), 7.72 (1H, d, aroma)
tic), 7.93 (1H, S, aromatic), 8.48 (1H, S, CON
H), 9.20 (1H, S, CONH).

MS spectrum M ⁺ 690

As the yellow coupler used in the present invention, one type of yellow coupler represented by the general formula (I) may be used, or two or more types may be used, and the yellow coupler may be used in combination with other known yellow couplers. Good.

The yellow coupler represented by formula (I) of the present invention (hereinafter referred to as the yellow coupler of the present invention).
In the silver halide color light-sensitive material (hereinafter sometimes referred to simply as light-sensitive material), the preferable amount is 0.01 to 1
The range is 0 mmol / m ² , and more preferably 0.05 to 5
range mmol / m ^2, and most preferably from 0.1 to 2 mmol / m ^2. Of course, two or more couplers represented by formula (I) may be used in combination. It can also be used in combination with a coupler other than the coupler represented by formula (I).

The light-sensitive material of the present invention may have at least one layer containing the yellow coupler of the present invention on the support, and the layer containing the yellow coupler of the present invention may be a hydrophilic colloid on the support. Any layer may be used, and a typical light-sensitive material is a blue-sensitive silver halide emulsion layer on a support,
The green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer can be formed by coating at least one layer at a time in this order, but the order may be different. An infrared-sensitive silver halide emulsion layer can also be used in place of at least one of the above-mentioned photosensitive emulsion layers. Color reproduction of the subtractive method is performed by incorporating a silver halide emulsion having sensitivity in each wavelength range and a color coupler forming a dye having a complementary color relationship with the light to be exposed in these light-sensitive emulsion layers. be able to. However, the photosensitive emulsion layer and the coloring hue of the color coupler may not have the above correspondence. In the present invention, the yellow coupler of the present invention is particularly preferably used in the blue-sensitive silver halide emulsion layer.

The yellow coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, is dissolved in a high-boiling organic solvent (if necessary, a low-boiling organic solvent is also used), and is emulsified and dispersed in a gelatin aqueous solution to be halogenated. The oil-in-water dispersion method of adding to a silver emulsion is preferred. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, steps of latex dispersion method as one of polymer dispersion methods, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) 2,541,274. , Ibid 2,54
No. 1,230, Japanese Patent Publication No. 53-41091, European Patent Publication No. 029104, and the like, and dispersion by an organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00723.

Examples of the high-boiling point organic solvent that can be used in the oil-in-water dispersion method described above include phthalates such as dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4). -Di-tert-amylphenyl) phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate], phosphoric acid or phosphonic acid esters (for example, tri- Phenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethyl Cyclohexyl phenyl phosphonate), benzoic acid esters (e.g., 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl -p- hydroxybenzoate), sulfonamides (e.g., N- butyl benzenesulfonamide),
Alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg, bis (2
-Ethylhexyl) sebacate, dioctyl azepate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (eg. , Paraffin, dodecylbenzene, diisopropylnaphthalene), and chlorinated paraffins. As the auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-Ethoxyethyl acetate and dimethylformamide can be mentioned.

The silver halide emulsion and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied in the present invention, and processing methods and processing additions applied to process the light-sensitive material. As the agent, JP-A-62-2
15272, JP-A-2-33144, European Patent EP
Those described in No. 0,355,660 A2 are preferably used. Further, JP-A-5-34889, 4-359249, 4-313753 and 4-2.
70344, 5-66527, 4-34548.
No. 4, No. 4-145433, No. 2-854, No. 1-1
58431, 2-90145, 3-19453.
No. 9, No. 2-93641, European Patent EP 0,520,
The silver halide color photographic light-sensitive materials described in No. 457A2 and the processing methods thereof are also preferable.

As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide and the like can be used, but especially for the purpose of rapid processing. Is a silver chlorobromide containing substantially no silver iodide and having a silver chloride content of 90 mol% or more and 100 mol% or less, further 95 mol% or more and 100 mol% or less, and particularly 98 mol% or more and 100 mol% or less. The use of pure silver chloride emulsion is preferred.

Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer is added to the photosensitive colloid layer for the purpose of improving the sharpness of an image, etc., in EP No. 0,337,490A2, Nos. 27-37.
Dyes which can be decolorized by treatment (among others, oxonol dyes) described on page 76 are added so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.70 or more, or the water-resistant resin layer of the support. 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a dihydric to tetrahydric alcohol (eg, trimethylolethane)
It is preferably contained.

In the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole-based magenta coupler.

That is, the compound (F) and // which chemically bond with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Or to use the compound (G), which forms a chemically inactive and substantially colorless compound, chemically or in combination with the oxidation product of the aromatic amine color developing agent remaining after the color developing treatment, simultaneously or alone. However, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or the oxidant thereof with the coupler during storage after processing.

Further, the light-sensitive material of the present invention has a mildewproofing agent as described in JP-A-63-271247 in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image. It is preferable to add an agent.

As a support used in the light-sensitive material of the present invention, a white polyester support for display or a layer containing a white pigment is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer-coated side or the back side of the support. Especially, the transmission density of the support is 0.35 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of 0.8.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, upon exposure, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved.

[0060]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these. Example 1 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated to form the layers shown below. A multilayer color photographic paper (101) having the constitution was produced. After the application, it was prepared as follows.

Preparation of coating solution for first layer Yellow coupler (RY-9) 122.0 g, color image stabilizer (Cpd-2) 7.5 g, color image stabilizer (Cpd-3)
16.7 g, color image stabilizer (Cpd-5) 8.0 g, solvent (Solv-3) 22 g, solvent (Solv-9) 22
g and 180 ml of ethyl acetate, and the solution is 10%
1 containing 86 ml of sodium dodecylbenzene sulfonate
Emulsified dispersion A was prepared by emulsifying and dispersing in 1000 g of 0% gelatin aqueous solution. On the other hand, silver chlorobromide emulsion A (cubic, large size emulsion A having an average grain size of 0.88 μm and 0.70
3: 7 mixture with μm small size emulsion A (silver molar ratio).
Coefficients of variation of particle size distribution are 0.08 and 0.1 respectively
0. For each size emulsion, 0.3 mol% of silver bromide was locally contained on a part of the surface of the grain based on silver chloride) was prepared. In this emulsion, the blue-sensitizing dyes A, B and C shown below were each 8.0 × 10 ^-5 moles per mole of silver for the large-sized emulsion A, and for the small-sized emulsion A. ,
1.0 × 10 ⁻⁴ mol of each is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the following composition. The emulsion coating amount indicates a coating amount equivalent to silver.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. In addition, Cpd-12 and Cp are added to each layer.
the total amount d-13, Cpd-14 and Cpd-15, respectively is ^{15.0mg / m 2, 60.0mg / m} 2, was added to a 5.0 mg / m ² and 10.0 mg / m ^2. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0063]

[Chemical 13]

(1.4 × 10 ⁻⁴ mol each for a large-sized emulsion and 1.7 × 10 ⁻⁴ mol for a small-sized emulsion, per mol of silver halide). ) Green-sensitive emulsion layer

[0065]

Embedded image

(Sensitizing dye D per mol of silver halide, 3.0 × 10 ^-4 mol for large size emulsion, 3.6 × 10 ^-4 mol for small size emulsion, and Sensitizing dye E per mol of silver halide is 4.0 × 10 ⁻⁵ mol for large-sized emulsion, 7.0 × 10 ⁻⁵ mol for small-sized emulsion, and sensitized. Dye F is 2.0 × 1 per mol of silver halide for a large-sized emulsion.
0 ^-4 mol, or 2.8 x 10 ^-4 for small size emulsions
Mole was added. ) Red-sensitive emulsion layer

[0067]

[Chemical 15]

(1 mol of silver halide was added to the large-sized emulsion at 5.0 × 10 ^-5 mol, and to the small-sized emulsion at 8.0 × 10 ^-5 mol. )

Further, the following compounds were added in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0070]

Embedded image

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)
-5-Methylcaptotetrazole was added in an amount of 3.3 x 10 ^-4 mol, 1.0 x 10 ^-3 mol and 5.9 x 10 ^-4 mol per mol of silver halide, respectively. In addition, the second layer,
0.2 mg / m ^{2 for} each of the fourth, sixth and seventh layers,
The amount added was 0.2 mg / m ² , 0.6 mg / m ² , and 0.1 mg / m ² . Further, 4-hydroxy-6-methyl-1,3,3a, 7- was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol per mol of silver halide, respectively. Also,
In order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer.

[0072]

[Chemical 17]

(Layer Structure) The layer structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [White pigment (TiO ₂ ; content 1 on polyethylene on the first layer side
5% by weight) and bluish dye (ultra-blue)]

First layer (blue-sensitive emulsion layer) The silver chlorobromide emulsion A 0.27 gelatin 1.60 yellow coupler (RY-9) 0.61 color image stabilizer (Cpd-2) 0.04 color image Stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-5) 0.04 Solvent (Solv-3) 0.11 Solvent (Solv-9) 0.11

Second Layer (Color Mixing Prevention Layer) Gelatin 0.99 Color mixing inhibitor (Cpd-4) 0.10 Solvent (Solv-1) 0.07 Solvent (Solv-2) 0.20 Solvent (Solv-3) 0.15 Solvent (Solv-7) 0.12

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion B having average grain size 0.55 μm and small size emulsion B having 0.39 μm (silver molar ratio) The coefficient of variation of the grain size distribution is 0.10 and 0.08, respectively. In each size emulsion, 0.8 mol% of silver bromide was locally contained in a part of the grain surface of which the substrate was silver chloride). .13 Gelatin 1.35 Magenta coupler (ExM-1) 0.12 UV absorber (UV-1) 0.12 Color image stabilizer (Cpd-2) 0.01 Color image stabilizer (Cpd-5) 0. 01 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-7) 0.08 Color image stabilizer (Cpd-8) 0.01 Solvent (Solv-4) 0.30 Solvent (Solv- 5) 0.15

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.72 Color mixing inhibitor (Cpd-4) 0.07 Solvent (Solv-1) 0.05 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.12 Solvent (Solv-7) 0.09

Fifth layer (red sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C of 0.41 μm (silver molar ratio) The coefficient of variation of the grain size distribution is 0.09 and 0.11, respectively. In each size emulsion, 0.8 mol% of silver bromide was locally contained in a part of the grain surface of which the substrate was silver chloride.) 0 .18 Gelatin 0.80 Cyan coupler (ExC-1) 0.28 Ultraviolet absorber (UV-3) 0.19 Color image stabilizer (Cpd-1) 0.24 Color image stabilizer (Cpd-6) 0. 01 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.01 Solvent (Solv-1) 0.01 Solvent (Solv- 6) 0.21

Sixth Layer (UV Absorbing Layer) Gelatin 0.64 UV Absorber (UV-2) 0.39 Color Image Stabilizer (Cpd-7) 0.05 Solvent (Solv-8) 0.05

Seventh Layer (Protective Layer) Gelatin 1.01 Acrylic Modified Copolymer of Polyvinyl Alcohol (Modification Degree 17%) 0.04 Liquid Paraffin 0.02 Surfactant (Cpd-11) 0.01

The compounds used below are shown below.

[0083]

Embedded image

[0084]

[Chemical 19]

[0085]

Embedded image

[0086]

[Chemical 21]

[0087]

[Chemical formula 22]

[0088]

[Chemical formula 23]

[0089]

[Chemical formula 24]

[0090]

[Chemical 25]

[0091]

[Chemical formula 26]

[0092]

[Chemical 27]

[0093]

[Chemical 28]

In the sample 101 prepared as described above, the yellow coupler (RY-9) in the first layer was replaced as shown in Table A, and the other samples were replaced by the samples 102 to 121 in the same manner as the sample 101. It was made. At this time, the yellow coupler was replaced so as to have an equimolar amount. further,
Samples 201 to 228 were prepared by using emulsions of 101 to 128 emulsion stored at 5 ° C. for 30 hours. Each sample was exposed by using a sensitometer (color temperature of FWH type light source manufactured by Fuji Photo Film Co., Ltd., 3200K) so that about 35% of the coated silver amount was developed to give gray. Each of the above samples was subjected to continuous treatment of 50 m ² using a paper processor in the following treatment steps.

Treatment process Temperature Time Replenishment amount * Color development 38.5 ° C. 45 seconds 73 ml Bleach fixing 35 ° C. 45 seconds 60 ml ** Rinse (1) 35 ° C. 30 seconds Rinse (2) 35 ° C. 30 seconds Rinse ( 3) 35 ℃ 30 seconds 360 ml Dry 80 ℃ 60 seconds * Replenishment amount per 1 m ^{2 of} light-sensitive material ** In addition to the above 60 ml, light-sensitive material 1 from rinse (1)
120 ml per m ² was poured. (Rinse was a three-tank countercurrent system from (3) to (1).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] water 800 ml 800 ml ethylenediaminetetraacetic acid 3.0 g 3.0 g 4,5-dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g 0.5 g triethanolamine 12.0 g 12.0 g Potassium chloride 6.5 g Potassium bromide 0.03 g Potassium carbonate 27.0 g 27.0 g Optical brightener (WHITEX 4 manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 3.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis (sulfonate ethyl) ) Hydroxylamine 5.0 g 10.0 g Triisopropyl naphthalene (β) sodium sulfonate 0.1 g 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid Monohydrate 5.0 g 11.5 g Add water 1000 ml 1000 ml pH (25 ° C / Adjusted with potassium oxide and sulfuric acid) 10.00 11.00

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Water 600 ml 150 ml Ammonium thiosulfate (750 g / liter) 93 ml 230 ml Ammonium sulfite 40 g 100 g Ethylenediaminetetraacetic acid (III) ammonium 55 g 135 g Ethylenediamine Tetraacetic acid 5 g 12.5 g Nitric acid (67%) 30 g 65 g Water added 1000 ml 1000 ml pH (25 ° C / adjusted with acetic acid and ammonia water) 5.8 5.6

[Rinse Solution] (tank solution and replenisher are the same) Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

Next, each sample was subjected to gradation exposure with blue light and treated with the running treatment liquid. The color density of the processed sample was measured with blue light and the maximum yellow color density Dmax
I asked. The results are shown in Table A.

[0100]

[Table 1]

As is clear from Table A, the yellow couplers of the present invention show high color-forming properties with respect to the known yellow couplers RY-1 to 10.

Further, since the known yellow couplers are poor in solubility, the color developability (Dmax) after the emulsion is refrigerated and stored at 5 ° C. for 30 days is remarkably lowered, but all of the yellow couplers of the present invention have the color developability. Almost no decrease was observed, indicating the good solubility of the yellow coupler of the present invention.

Example 2 Each sample of Example 1 was subjected to 1 under a fluorescent light source of 80,000 lux.
Light irradiation was carried out for 4 days, and the color image residual rate at an initial density of 1.5 was determined. Further, each sample was stored at 80 ° C.-70% RH for 20 days, and the color image residual rate at an initial density of 1.5 was obtained.

[0104]

[Table 2]

As is clear from Table B, the couplers of the present invention are superior in fastness to heat, humidity and light as compared with known yellow couplers.

[0106]

The yellow coupler of the present invention has excellent solubility, does not cause deterioration in color developability even when the emulsion is stored under refrigeration for a long time, and has excellent fastness.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 31, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

Embedded image In the general formula (I), R ₁ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₂ is a hydrogen atom, an aliphatic group, a halogen atom, an aliphatic oxy group, an aryloxy group or an amino group. Represents R ₃ and R ₄ each independently represent a hydrogen atom, an aliphatic group or an aryl group, and R 3
₅ represents an alkyl group, an alkenyl group or an aryl group. R ₆ represents a substituent, and R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group, an alkoxy group or an aryloxy group. W represents -N (R ₉ )-, an oxygen atom or a sulfur atom, and R ₉ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. m is an integer of 2 to 20, n is 0 to 3
Represents the integer. However, when R ₉ is a benzyl group, R ₇
Neither R ₈ nor R ₈ becomes a hydrogen atom.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

[0007]

Embedded image

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

In the general formula (I), R ₂ is preferably a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, iodine), an aliphatic oxy group having a C number of 1 to 30 (eg, methoxy, i-propoxy). , T-butoxy, benzyloxy,
Cyclohexyloxy), an aryloxy group having a C number of 6 to 36 (eg, phenoxy, 2-naphthoxy, 4-methoxyphenoxy, 2-chlorophenoxy), a C number of 1 to 3
An aliphatic group of 0 (for example, methyl, i-propyl, t-butyl, benzyl, trifluoromethyl, cyclohexyl), an amino group having a C number of 0 to 30 (for example, N, N-dimethylamino, N-cyclohexylamino, N-butylamino), more preferably R ₂ is a halogen atom, an aliphatic oxy group or an aryloxy group, more preferably a halogen atom or an alkoxy group having 1 to 20 C atoms, and further preferably a chlorine atom. Or a methoxy group,
Most preferably, it is a chlorine atom.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

62.9 g (0.2 mol) of carboxylic acid (1),
Dissolve 1 ml of dimethylformamide in 100 ml of methylene chloride, stir and stir to dissolve oxalyl chloride ((COCl) ₂ ) 38.1.
g (0.3 mol) was added dropwise over 10 minutes, and the mixture was further stirred for 1 hour. Concentrated under reduced pressure with an aspirator and acid chloride
I got (2).

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

Anilines (3) 53.8 g (0.2 mol),
Pyridine (17.4 g, 0.22 mol) was dissolved in dimethylformamide (100 ml) and stirred to give acid chloride (2).
Dissolve (0.2 mol) in dimethylformamide to give 30
It dripped over minutes. 300 ml water, 100 acetonitrile
ml was added to crystallize the amide (4), which was filtered off, washed with water and acetonitrile, and the amides (4) crystallized 100.
3 g (88.7%) were obtained.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

Melting point 79 ° C., NMR spectrum (300 MHz,
CDCl ₃ , δ: ppm) 0.88 (3H, t, CH ₃ CH _2- ), 1.26
(9H, S, (CH ₃ ) ₃ C-, + 22H, m, -CH _2- ), 1.47 (3H, S, CH
_3- ), 1.53 (3H, S, CH _3- ), 1.62 (2H, m, OCH ₂ CH
_2- ), 2.70 (4H, m, -NHCOCH ₂ CH ₂ COO-), 4.07 (2H,
t, -OCH _2- ), 5.69 (1H, S, CH), 6.68 (1H, S, CON
H), 7.20 (1H, d, aromatic), 7.72 (1H, d, aroma)
tic), 7.93 (1H, S, aromatic), 8.48 (1H, S, CON
H), 9.20 (1H, S, CONH).

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0094

[Correction method] Change

[Correction content]

In the sample 101 prepared as described above, the yellow coupler (RY-9) in the first layer was replaced as shown in Table A, and otherwise the samples 102 to 126 were prepared in the same manner as the sample 101. It was made. At this time, the yellow coupler was replaced so as to have an equimolar amount. further,
Samples 201 to 226 were prepared by using the emulsions of 101 to 126 stored at 5 ° C. for 30 hours. Each sample was exposed by using a sensitometer (color temperature of FWH type light source manufactured by Fuji Photo Film Co., Ltd., 3200K) so that about 35% of the coated silver amount was developed to give gray. Each of the above samples was subjected to continuous treatment of 50 m ² using a paper processor in the following treatment steps.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masakazu Morigaki 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (2)

[Claims] 1. A silver halide color light-sensitive material characterized in that at least one layer on a support contains at least one yellow dye-forming coupler represented by the following general formula (I). Embedded image In formula (I), R ₁ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₂ represents an aliphatic group, a halogen atom, an aliphatic oxy group, an aryloxy group or an amino group. R ₃ and R ₄ each independently represent a hydrogen atom, an aliphatic group or an aryl group, and R ₅ represents an alkyl group, an alkenyl group or an aryl group. R ₆ represents a substituent, R ₇ and R ₈ are each independently a hydrogen atom,
It represents an alkyl group, an alkoxy group or an aryloxy group. W represents -N (R ₉ )-, an oxygen atom or a sulfur atom, and R ₉
Represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. m represents an integer of 2 to 20, and n represents an integer of 0 to 3. However, when R ₉ is a benzyl group, R ₇ and R ₈ are not both hydrogen atoms. 2. The silver halide color photographic material according to claim 1, wherein in the general formula (I), R ₂ represents a chlorine atom.