JPH08202000A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain the color photographic sensitive material improved in the lightfastness of a dye stuff image by incorporating at least one kind of specified compound in at least one of a layer formed on a support. CONSTITUTION: This photosensitive material contains, in at least one layer formed on a support, at least one kind of compound represented by the formula in which R1 is an alkoxy, aryloxy, amino, or anilino group; R2 is an H atom or an alkyl group; each of L1 and L2 is an alkylene group; and each of R3 and R4 is a hydroxy, acyloxy, acylamino, sulfonamudo group. As a silver halide emulsion to be used for this photosensitive material, an optional usual silver halide emulsion can be used, and this emulsion can be chemically sensitized by the usual method and optically sensitized in a desired wavelength region by using a sensitizing dye stuff.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material which is excellent in color image fastness to light and which is excellent in color development of a coupler.

[0002]

2. Description of the Related Art In the field of silver halide color photographic light-sensitive materials, it is desired that a dye image obtained from a coupler does not fade even when exposed to light for a long time or stored under high temperature and high humidity. .

However, it is known that these dye images are not in a state of fastness mainly to ultraviolet rays or visible rays, and that they are easily discolored when irradiated with active rays. In order to eliminate such defects, conventionally, various couplers having low fading properties are selected and used, an ultraviolet absorber is used to protect a dye image from ultraviolet rays, or light resistance is imparted to the coupler. A method of introducing a group to be introduced has been proposed.

[0004]

However, for example, in order to provide a dye image with satisfactory light fastness by using an ultraviolet absorber, a relatively large amount of the ultraviolet absorber is required. In this case, the ultraviolet absorber itself is required. In some cases, the dye image was significantly contaminated due to coloring. Further, even if an ultraviolet absorber is used, it does not show any effect in preventing fading of a dye image due to visible light, and there is a limit to improvement of light resistance by the ultraviolet absorber.

Further, there is known a method of using a dye image anti-fading agent having a phenolic hydroxyl group or a group which is hydrolyzed to form a phenolic hydroxyl group.
48-31256, 48-31625, 51-30462, JP-A-49-1
34326 and 49-134327 have phenols and bisphenols, U.S. Pat.No. 3,069,262 has pyrogallol, gallic acid and its esters, and U.S. Pat.Nos. 2,360,290 and 4,015,990 have α-tocopherols and acyl derivatives, and JP-A-52-27534, JP-A-52-14751 and US Pat. No. 2,735,765 include hydroquinone derivatives and US patents.
3,432,300 and 3,574,627 have 6-hydroxychromans, U.S. Pat.No. 3,573,050 has 5-hydroxychroman derivatives, and Japanese Patent Publication No. 49-20977 has 6,6'-dihydroxy-2,
It has been proposed to use 2'-spirobichromans and the like. However, these compounds have some effects as a discoloration preventing agent and a discoloration preventing agent for the dye, but they are not sufficient.

It is also described in British Patent 1,451,000 that the stability of dye images to light is improved by using azomethine quenching compounds whose absorption peak is bathochromic than the dye image peak. However, since the azomethine quenching compound itself is colored, it has a great adverse effect on the hue of the dye image.

A method for stabilizing a dye with light by a metal complex is disclosed in Japanese Patent Laid-Open No. 50-87649 and Research Disclosure No. 15162 (197).
As described in 6), since these complexes do not have a large fading-preventing effect themselves and do not have high solubility in an organic solvent, they cannot be added in an amount sufficient to exhibit the fading-preventing effect. Further, since these complexes have a large coloring themselves, when added in a large amount, they adversely affect the hue and purity of the dye image produced by the color development processing.

Therefore, a first object of the present invention is to provide a silver halide color photographic light-sensitive material in which the fastness of a dye image to light is remarkably improved.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in color developability.

A third object of the present invention is to provide a silver halide color photographic light-sensitive material in which the maximum concentration of the coupler changes little even when the amount of the high boiling point solvent is reduced.

[0011]

The above object of the present invention is characterized in that at least one layer on a support contains at least one compound represented by the following general formula [1]. Achieved with color photographic light-sensitive materials.

[0012]

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In the formula, R ₁ represents an alkoxy group, an aryloxy group, an amino group, or an anilino group, R ₂ represents a hydrogen atom or an alkyl group, L ₁ and L ₂ each represent an alkylene group, and R ₃ , R ₄ each represent a hydroxyl group, an acyloxy group, an acylamino group or a sulfonamide group.

The present invention will be specifically described below.

In the above general formula [1], the alkoxy group represented by R ₁ represents a linear or branched alkoxy group, which may have a substituent, and preferably has 1 to 20 carbon atoms in total. Specific examples include a methoxy group, an ethoxy group, a propyloxy group, an i-propyloxy group, a butyloxy group, a pentyloxy group, a decyloxy group and a 2-ethylhexyloxy group. When the alkoxy group represented by R ₁ has a substituent, specific examples of the substituent include an alkoxy group, an acylamino group, a sulfonamide group, an alkoxycarbonylamino, and an ureido group.

The aryloxy group represented by R ₁ is preferably a phenoxy group which may have a substituent. Specific examples of the substituent include an alkyl group (methyl group, ethyl group, dodecyl group, etc.), alkoxy group (methoxy group, ethoxy group, decyloxy group, etc.), acyloxy group (propanoyloxy group, octanoyloxy group, etc.), alkoxy Carbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.), acylamino group (acetylamino group, propanoylamino group, etc.) sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), halogen atom (fluorine atom, chlorine atom) Etc.) A cyano group, a nitro group and the like can be mentioned.

The amino group represented by R ₁ is preferably an alkylamino group which may have a substituent or a dialkylamino group having a total carbon number of 1 to 25. Specifically, methylamino group, ethylamino group, propylamino group, i-
Examples thereof include a butylamino group, a dodecylamino group, a benzylamino group, a dimethylamino group, a diethylamino group and a dibutylamino group. When the amino group represented by R ₁ is an alkylamino group or a dialkylamino, specific examples of the substituent include an alkoxy group, an aryloxy group (phenyloxy group, methoxyphenyloxy group, etc.), an acylamino group, Sulfonamide group, alkoxycarbonylamino group (methoxycarbonylamino group,
Ethoxycarbonylamino group, etc.) and ureido group, etc., and these have the same meanings as the case of the substituent on the benzene ring when R ₁ is an anilino group.

The anilino group represented by R ₁ may have a substituent on the benzene ring, and specific examples of the substituent in that case include an alkyl group (methyl group, ethyl group, dodecyl group, etc.), Alkoxy group (methoxy group, ethoxy group, decyloxy group, etc.) Acyloxy group (propanoyloxy group, octanoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.), acylamino group (acetylamino group, propanyl group, etc.) Examples thereof include noylamino group), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), halogen atom (fluorine atom, chlorine atom, etc.), cyano group and nitro group.

The alkyl group represented by R ₂ may be linear or branched, may have a substituent, and has a total carbon number of 1
Those of -20 are preferred. An unsubstituted linear alkyl group is particularly preferable as the alkyl group represented by R ₂ . Preferred specific examples of the alkyl group represented by R ₂ include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, a dodecyl group and a tetradecyl group.

The alkylene group represented by L ₁ and L ₂ is preferably an alkylene group having 2 to 5 carbon atoms, specifically,
CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ CH ₂ −, −CH ₂ CH
₂ CH ₂ CH ₂ CH ₂ −, − (CH ₃ ) CHCH ₂ −, − (C ₂ H ₅ ) CHCH ₂ −, −
Examples of the alkylene group include (CH ₃ ) CHCH ₂ CH ₂ — and the like, with an ethylene group and a propylene group being particularly preferable.

Specific examples of the acyloxy group represented by R ₃ and R ₄ include an acetyloxy group, a propanoyloxy group, a butanoyloxy group and a benzoyloxy group, which may have a substituent. Frequently in-situ substituents include alkyl groups, alkoxy groups, acyloxy groups, amino groups, acylamino groups, sulfonamide groups, halogen atoms, cyano groups, etc. These are benzenes when R ₁ is an anilino group. It is synonymous with the case of the substituent on the ring.

Specific examples of the acylamino group represented by R ₃ and R ₄ include an acetylamino group, a propanoylamino group, a benzoylamino group and the like, which may further have a substituent and are substituted in situ. As the group, an alkyl group, an alkoxy group, an acyloxy group, an amino group, an acylamino group,
Examples thereof include a sulfonamide group, a halogen atom, and a cyano group, which have the same meanings as those in the case where R ₁ is an anilino group and are a substituent on the benzene ring.

Specific examples of the sulfonamide group represented by R ₃ and R ₄ include a methanesulfonamide group, an ethanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, and the like. Alternatively, the in-situ substituent may, for example, be an alkyl group, an alkoxy group, an acyloxy group, an amino group, an acylamino group, a sulfonamide group, a halogen atom or a cyano group, in which R ₁ is an anilino group. It is synonymous with the case of the substituent on the benzene ring.

More preferred substituents for R ₃ and R ₄ are a hydroxyl group and an alkylsulfonamide group, most preferably a hydroxyl group.

Specific examples of the compound represented by the general formula [1] of the present invention are described below.

[0026]

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[0027]

[Chemical 4]

[0028]

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Next, synthetic examples of the compound represented by the general formula [1] of the present invention will be described.

Synthesis Example 1 (Synthesis of Exemplified Compound 1)

[0031]

[Chemical 6]

Compound a (15.3 g), compound b (5.7 g) and potassium carbonate (7.6 g) were stirred in 100 ml of dimethylformamide at room temperature for 9 hours. The reaction mixture was poured into 500 ml of water and extracted with ethyl acetate. The ethyl acetate solution was dried over magnesium sulfate, and then the solvent was distilled off to obtain a residue. The residue was purified by column chromatography to obtain 11 g of oily Exemplified Compound 1.

Synthesis Example 2 (Synthesis of Exemplified Compound 26)

[0034]

[Chemical 7]

11.2 g of Exemplified Compound 26 was obtained in the same manner as in Synthesis Example 1 using 19.1 g of compound c and 5.7 g of compound b.

Synthesis Example 3 (Synthesis of Exemplified Compound 44)

[0037]

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Compound d synthesized in the same manner as in Synthesis Example 2
Dissolve 37.8 g in 600 ml of tetrahydrofuran, add 47 g of pyridine, and add 23.8 g of thionyl chloride.
Was dripped. After the dropping, the mixture was stirred at room temperature for 2 hours, and then the solvent was distilled off under reduced pressure. Ice water was added to this residue, the mixture was neutralized with sodium hydrogen carbonate, and extracted with ethyl acetate. After the ethyl acetate solution was dried over magnesium sulfate, the solvent was distilled off to obtain a residue containing compound e. This residue was used in the next reaction without purification.

The total amount of this residue and potassium phthalimide
37 g was heated and refluxed in 200 ml of dimethylformamide for 2 hours. After allowing to cool, the reaction mixture was poured into 1200 ml of water, and a solid precipitated was obtained by filtration. After washing with water and drying, a residue containing compound f was obtained. This residue was used in the next reaction without purification.

The total amount of this residue was dispersed in 250 ml of ethanol, 12.0 g of hydrazine hydrate was added thereto, and the mixture was heated under reflux for 3 hours. After cooling, the precipitated solid was removed by filtration, and the solvent was distilled off from the filtrate under reduced pressure to obtain a residue containing compound g. The residue was purified by column chromatography to obtain 25g of compound g.

Next, 3.7 g of the compound g was dissolved in 20 ml of pyridine, and 2.6 g of methanesulfonyl chloride was added dropwise thereto. After reacting for 2 hours after dropping, the reaction mixture was poured into dilute hydrochloric acid, extracted with ethyl acetate, dried over magnesium sulfate, and the solvent was distilled off to obtain a residue. The residue was purified by column chromatography to obtain 4.2 g of Exemplified Compound 44.

In the present invention, preferable yellow couplers which can be used in combination with the compound represented by the general formula [1] of the present invention include benzoylacetanilide type and pivaloylacetanilide type couplers, and magenta couplers include There are 5-pyrazolone, pyrazolotriazole, and indazolone couplers, and cyan dye forming couplers include phenol, naphthol, pyrazoloquinazolone, pyrazolopyrimidine, pyrazolotriazole, and imidazole couplers. .

Next, typical examples of the yellow couplers which can be used in combination are, for example, JP-A-4-31.
Examples thereof include Y-1 to Y-15 described in No. 3751, pages 49 to 51.

In addition to these, yellow couplers that can be used in combination include, for example, OLS 2,163,812, JP-A-47-26133,
48-29432, 50-65321, 51-3631, 51-5073
No. 4, No. 51-102636, No. 48-66835, No. 48-94432, No.
49-1229, 49-10736, Japanese Examined Sho 51-33410, 52-25
Compounds described in No. 733 and the like can be mentioned, and the compounds can be synthesized according to the methods described therein.

Typical examples of magenta couplers that can be used in combination are, for example, JP-A-4-313751, No. 52.
M-1 to M-28 described on pages 58 to 58 and M-29 to M described below.
-33 etc. are mentioned.

[0046]

[Chemical 9]

In addition to these, magenta couplers that can be used in combination include, for example, US Pat. No. 3,684,514 and British Patent 1,18.
No. 3,515, Japanese Patent Publication No. 40-6031, No. 40-6035, No. 44-15754
No. 45-40757, No. 46-19032, JP-A No. 50-13041,
53-129035, 51-37646, 55-62454, U.S. Patent 3,725,067, British Patent 1,252,418, 1,334,515.
No. 59-195195, No. 59-162548, No. 60-43659
No. 2, No. 60-33552, Research Disclosure No. 2
4626 (1984), Japanese Patent Application Nos. 59-243007 and 59-243008,
59-243009, 59-243012, 60-70197, 60-701
The compounds described in No. 98 and the like can be mentioned, and the compounds can be synthesized according to the methods described therein.

Next, typical examples of cyan couplers that can be used in combination include, for example, JP-A-4-313751, No. 59.
C-1 to C-24 described on pages 61 to 61 are mentioned.

In addition to these, cyan couplers that can be used in combination include, for example, US Pat. Nos. 2,423,730 and 2,801,171,
JP-A-50-112038, 50-134644, 53-109630,
54-55380, 56-65134, 56-80045, 57-155
The compounds described in No. 538, No. 57-204545, No. 58-98731, No. 59-31953 and the like can be mentioned, and the compounds can be synthesized according to the methods described therein.

Of the above-mentioned couplers which can be used in combination with the compound represented by the general formula [1] of the present invention, a magenta coupler is preferable, and 1H-pyrazolo [5,1] is particularly preferable.
-c] [1,2,4] triazole and 1H-pyrazolo [1,5-b]
It is a [1,2,4] triazole magenta coupler.

In order to incorporate the compound represented by the general formula [1] of the present invention and the image-forming coupler into the silver halide emulsion layer, a conventionally known method such as known dibutyl phthalate or tricresyl phosphate can be used. Such as butyl acetate, ethyl acetate, etc., or a mixture of a low boiling point solvent such as butyl acetate, ethyl acetate, etc., or a solvent containing only a low boiling point solvent. It is possible to employ a method in which it is mixed with an aqueous gelatin solution containing an agent, then emulsified and dispersed using a high-speed rotary mixer, a colloid mill or an ultrasonic disperser, and then directly added to the emulsion. Further, after the above emulsified dispersion is set, it may be shredded, washed with water, and then added to the emulsion.

In the present invention, the general formula [1] of the present invention is used.
The compound represented by and the coupler may be separately dispersed by the above dispersion method and added to the silver halide emulsion, but a method in which both compounds are dissolved at the same time, dispersed and added to the emulsion is preferable.

The addition amount of the compound represented by the general formula [1] of the present invention is preferably 0.01 g to 1 g of the coupler.
The amount is 20 g, more preferably 0.5 g to 8.0 g, and two or more compounds represented by the general formula [1] of the present invention may be used in combination.

As the silver halide emulsion used in the light-sensitive material of the present invention, any of ordinary silver halide emulsions can be used. The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder of the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer. A coupler is used in the emulsion layer of the color photographic light-sensitive material.

Further, by coupling with a colored coupler having a color correcting effect, a competing coupler and an oxidized product of a developing agent, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener and a hardener. Compounds that release photographically useful fragments such as film agents, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an anti-irradiation layer. In these layers and / or emulsion layers,
Dyes may be included which are either bleached or bleached from the light-sensitive material during the development process. For light-sensitive materials, formalin scavenger, optical brightener, matting agent, lubricant,
An image stabilizer, a surfactant, an antifoggant, a development accelerator, a development retarder and a bleaching accelerator can be added.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

In order to obtain a dye image by using the light-sensitive material of the present invention, a commonly known color photographic process can be carried out after exposure.

Further, when the compound represented by the general formula [1] of the present invention is added to the green-sensitive layer, the compound represented by the general formula [A] is added to the silver halide emulsion layer containing a magenta coupler in the layer.
It is preferable that at least one of the dye image stabilizers represented by [O-I] or [AO-II] is contained.

[0062]

[Chemical 10]

In the formula, R ₁₂₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or the following residue.

[0064]

[Chemical 11]

Here, R ₁₂₁ a, R ₁₂₁ b and R ₁₂₁ c each represent a monovalent organic group. R ₁₂₂ , R ₁₂₃ , R ₁₂₄ , R
₁₂₅ and R ₁₂₆ each represent a hydrogen atom, a halogen atom, or a group capable of substituting for a benzene ring. Also R ₁₂₁ ~ R
₁₂₆ may combine with each other to form a 5- or 6-membered ring.

[0066]

[Chemical 12]

In the formula, R ₁₃₁ represents an aliphatic group or an aromatic group, and Y represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring with a nitrogen atom.

In the above general formula [AO-I], R ₁₂₁
Of the alkyl group, aryl group and heterocyclic group represented by, the alkyl group is preferably a linear or branched one having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, a t-butyl group and a dodecyl group. . Examples of the aryl group include a phenyl group which may have a substituent or a naphthyl group.
Examples of the substituent in this case include the groups described as the substituent for the aryloxy group represented by R ₁ in the general formula [1]. As the heterocyclic group, for example, a pyrazole group, 2-
Examples thereof include an imidazolyl group, a 3-pyridyl group and a 2-furyl group.

Examples of the monovalent organic group represented by R ₁₂₁ a, R ₁₂₁ b and R ₁₂₁ c include an alkyl group, an aryl group, an alkoxy group, an aryloxy group and a halogen atom. R ₁₂₁ is preferably a hydrogen atom or an alkyl group. Examples of the group capable of substituting on the benzene ring represented by R _{122 to} R ₁₂₆ include the groups described as the substituent of the aryloxy group represented by R ₁ in the general formula [I]. R ₁₂₂ , R ₁₂₃ , R ₁₂₅ and R ₁₂₆ are preferably a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group and an acylamino group, and R
₁₂₄ is preferably an alkyl group, a hydroxyl group, an aryl group, an alkoxy group, or an aryloxy group. R ₁₂₁ and R ₁₂₂ may be ring-closed to each other to form a 5-membered or 6-membered ring, in which case R ₁₂₄ is a hydroxyl group, an alkoxy group,
Aryloxy groups are preferred. R ₁₂₁ and R ₁₂₂ may be ring-closed to form a methylenedioxy ring. Further, R ₁₂₃ and R ₁₂₄ may be closed to form a 5-membered hydrocarbon ring, in which case R ₁₂₁ is an alkyl group, an aryl group,
Heterocyclic groups are preferred.

Specific examples of the compound represented by the general formula [AO-I] are shown below.

[0071]

[Chemical 13]

[0072]

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In addition to the above specific examples, the above general formula [AO-
Specific examples of the compound represented by the formula [I] are disclosed in JP-A-60-262.
Exemplified Compound A-described on pages 11 to 13 of Japanese Patent No. 159
1-A-28, the exemplified compounds PH-1 to PH-29 described on pages 8 to 10 of JP-A 61-145552, JP-A-1-306846.
Exemplified Compounds B-1 to 1 described on pages 6 to 7 of the publication
B-21, Exemplified compounds I-1 to I-13, I'-1 to I'-8, II-1 described on pages 10 to 18 of JP-A 2-958.
To II-12, II'-1 to II'-21, III-8 to III-14, IV
-1 to IV-24, V-13 to V-17, No. 10 of JP-A 3-39956
Exemplified compounds II-1 to II-33 described on pages 11 to 11 and the like can be mentioned.

Next, in the above general formula [AO-II],
R ₁₃₁ represents an aliphatic group or an aromatic group, preferably an alkyl group, an aryl group or a heterocyclic group, and most preferably an aryl group. Examples of the heterocycle formed by Y together with the nitrogen atom include a piperidine ring, a piperazine ring, a morpholine ring, a thiomorpholine ring, a thiomorpholine-1,1-dione ring, and a pyrrolidine ring.

Specific examples of the compound represented by the general formula [AO-II] are shown below.

[0076]

[Chemical 15]

In addition to the above specific examples, the above general formula [AO-
II], specific examples of the compound represented by
Exemplified Compound B-1 Described on Pages 8 to 11 of Japanese Patent Publication No. 43
To B-65, exemplified compounds (1) to (120) described on pages 4 to 7 of JP-A-63-95439, and the like.

The above general formula [AO-I] or [AO-I]
The addition amount of the compound represented by I] is preferably 5 to 500 mol% with respect to the coupler of the present invention, and more preferably 20 to 2
It is 00 mol%.

When the compound represented by the general formula [1] of the present invention is added to the green light-sensitive layer, the silver halide emulsion layer is described in JP-A Nos. 61-158329 and 62-183459. The metal chelate compounds described may also be used.

[0080]

EXAMPLES The present invention will now be described based on examples, but the embodiments of the present invention are not limited thereto.

Example 1 On a support having a polyethylene support laminated on one side of a paper support and polyethylene containing titanium oxide on the other side, titanium oxide was applied to each of the layers shown in Tables 1 and 2 below. By coating on the side of the contained polyethylene layer, a multilayer silver halide color photographic light-sensitive material sample 101 was prepared. The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (Y-9, JP-A-4-313751
(Yellow coupler described on page 51) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.
67 g, stain-preventing agent (HQ-1) 0.67 g and high boiling point organic solvent (DNP) 6.67 g were added and dissolved with 60 ml of ethyl acetate, and this solution was added with 10% of 20% surfactant (SU-2) 10%. 220 ml of an aqueous gelatin solution was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.67 g of silver) shown below, and an anti-irradiation dye (AIY-1) was further added to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Also, as a hardener, the second layer and the fourth layer
(HH-1) was added to the layer and (HH-2) was added to the seventh layer. As the coating aid, surfactants (SU-1), (S
U-3) was added to adjust the surface tension.

[0085]

[Table 1]

[0086]

[Table 2]

The structural formulas of the compounds used in the above layers are shown below.

[0088]

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[0089]

[Chemical 17]

[0090]

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[0091]

[Chemical 19]

Blue-sensitive silver halide emulsion (Em-B) Average grain size 0.85 μm, coefficient of variation = 0.07, silver chloride content 99.5
Mol% monodisperse cubic emulsion sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / Molar AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX green-sensitive silver halide emulsion (Em-G) average grain size 0.43 μm, coefficient of variation = 0.08, silver chloride content 99.5
Mol% monodisperse cubic emulsion sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / Molar AgX Red-sensitive silver halide emulsion (Em-R) Average grain size 0.50μm, coefficient of variation = 0.08, silver chloride content 99.5
Mol% monodisperse cubic emulsion sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / Molar AgX The structural formulas of the compounds used in each monodisperse cubic emulsion are shown below.

[0093]

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Next, the high boiling point organic solvent DNP of the third layer of Sample 101 was used.
Was replaced with the comparative HBS shown in Table 3 below and the compound represented by the general formula [1] of the present invention to prepare Samples 102 to 114.

The sample thus prepared was wedge-exposed with green light according to a conventional method and then processed according to the following processing steps.

Processing process Temperature Time Color development 35.0 ± 0.3 ° C 45 seconds Bleach fixing 35.0 ± 0.5 ° C 45 seconds Stabilization 30-34 ° C 90 seconds Dry 60-80 ° C 60 seconds Composition of each processing solution is as follows. Show.

The replenishing amount of each processing solution is 80 ml per 1 m ^{2 of} silver halide color photographic light-sensitive material.

Color developing solution tank solution Replenishing solution Pure water 800 ml 800 ml Triethanolamine 10 g 18 g N, N-diethylhydroxylamine 5 g 9 g Potassium chloride 2.4 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g 1.8 g N-ethyl -N-β-Methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4g 8.2g Optical brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.0g 1.8g Potassium carbonate 27g 27g Water In addition, the total volume is 1000 ml, and the pH of the tank liquid is
Is adjusted to 10.10 and the pH of the replenisher is adjusted to 10.60.

Bleach-fixing solution (tank solution and replenisher are the same) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added. Adjust the total volume to 1000 ml and adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution (tank solution and replenisher are the same) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediamine Tetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Add water to bring the total volume to 1000 ml and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide. Adjust to.

The following evaluations were performed using the sample after the continuous treatment.

<Light resistance> The obtained sample was irradiated with a xenon fade meter for 14 days, and the residual ratio (%) of the dye image at an initial density of 1.0 was determined.

<Dmax> represents the maximum color density.

The results are shown in Table 3.

[0105]

[Table 3]

[0106]

[Chemical 21]

As is clear from Table 3, Samples 105 to 114 using the compound represented by the general formula [1] of the present invention as the high boiling point organic solvent (HBS) have significantly higher light resistance than Comparative Sample 101. It has been improved and the color development is also improved. In Sample 102 using HBS-1, which is a phenol derivative, a slight light resistance improving effect is recognized, but the effect cannot be said to be sufficient. HBS-2, which is a monohydric alcohol
In Sample 103 using S., although the effect of improving the color developability was recognized, the effect of improving the light fastness was hardly recognized. Further, in the case of HBS-3 which does not fall within the scope of the present invention, although a slight light resistance improving effect was observed, the color developability deteriorated.

Example 2 As shown in Table 4, 0.1 mol of the coupler was taken with respect to 1 mol of silver, the high boiling point solvent shown in Table 4 and 3 times the amount of ethyl acetate of the coupler were added, and the mixture was heated to 60 ° C. It was completely dissolved.

120 ml of a 5% aqueous solution of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) was added to this solution.
It was mixed with 1200 ml of a 5% gelatin aqueous solution containing 1 and emulsified and dispersed by an ultrasonic disperser to obtain an emulsion. Next, this dispersion was added to 3.8 kg of a green-sensitive silver iodobromide emulsion (containing 6 mol% of silver iodide), and a 2% solution of 1,2-bis (vinylsulfonyl) ethane as a hardening agent (water: methanol = 1: 1) 120 ml was added, and it was coated on the undercoated transparent polyester base and dried.
Samples 201 to 215 were prepared. (Amount of coated silver 20 mg / 100 cm ² ) The sample thus obtained was subjected to wedge exposure according to a conventional method and then subjected to the following development processing.

<Specific Maximum Color Density> It is shown as a relative value with the maximum color density of the reference sample being 100.

The results are shown in Tables 4, 5 and 6.

[Development processing step] Color development 38 ° C 3 minutes 15 seconds Bleach 38 ° C 4 minutes 20 seconds Water wash 38 ° C 3 minutes 15 seconds Fixation 38 ° C 4 minutes 20 seconds Water wash 38 ° C 3 minutes 15 seconds Stability Chemical temperature 38 ° C 1 minute 30 seconds Dry 47 ° C ± 5 ° C 16 minutes 30 seconds The composition of the processing solution used in each processing step is as follows.

(Color developer composition) Potassium carbonate 30.0 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 5.0 g Potassium bromide 1.3 g Potassium iodide 2.0 g Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g Sodium diethylenetriaminepentaacetate 2.5 g 3- Methyl-4-amino-N-ethyl-N- (β-hydroxyethyl) aniline sulphate 4.8g Potassium hydroxide 1.2g Water was added to bring the total volume to 1 liter and potassium hydroxide or 20% sulfuric acid was added to obtain pH 10.06. Adjust to.

(Composition of Bleach) Ethylenediaminetetraacetic acid ferric ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 40.0 ml Sodium bromide 10.0 g Water was added to make a total amount of 1 l, and ammonia was added. Adjust to pH 3.5 with water or glacial acetic acid.

(Fixing Solution Composition) Ammonium thiosulfate 180.0 g Anhydrous sodium sulfite 12.0 g Sodium metabisulfite 2.5 g Ethylenediaminetetraacetic acid disodium 0.5 g Sodium carbonate 10.0 g Water is added to make 1 liter.

(Composition of Stabilizing Solution) Formalin (37% aqueous solution) 2.0 g Conidax (manufactured by Konica) 5.0 g Water is added to make 1 liter.

[0117]

[Table 4]

Amount of HBS: (weight of HBS / weight of coupler) TCP: tricresyl phosphate Specific maximum density: relative value of maximum density of color development relative to a comparative sample. Samples 202 to 207 are relative values when sample 201 is 100.

[0119]

[Table 5]

Amount of HBS: (weight of HBS / weight of coupler) TCP: tricresyl phosphate Specific maximum concentration: relative value of maximum concentration of color development relative to a comparative sample. Samples 209 to 211 are relative values when sample 208 is 100.

[0121]

[Table 6]

HBS amount: (HBS weight / coupler weight) DOP: Dioctyl phthalate Specific maximum density: relative value of color development maximum density with respect to a comparative sample. Samples 213 to 215 are relative values when sample 212 is 100.

[0123]

[Chemical formula 22]

As is clear from Tables 4, 5 and 6, by using the compound represented by the general formula [1] of the present invention,
It can be seen that the color developing property is improved, and even when the addition amount is reduced, the excellent performance is exhibited in that the decrease in concentration as in the comparative compound is not observed.

[0125]

According to the present invention, the first is a silver halide color photographic light-sensitive material in which the fastness of a dye image to light is remarkably improved, and the second is a silver halide color photographic light-sensitive material excellent in color developability. As a material, thirdly, it was possible to provide a silver halide color photographic light-sensitive material in which the maximum concentration of the coupler was little changed even when the amount of the high boiling point solvent was reduced.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material characterized in that at least one layer on a support contains at least one compound represented by the following general formula [1]. Embedded image [In the formula, R ₁ represents an alkoxy group, an aryloxy group, an amino group, or an anilino group, R ₂ represents a hydrogen atom or an alkyl group, L ₁ and L ₂ each represent an alkylene group, and R ₃ and R _{3 4} is a hydroxyl group, an acyloxy group,
It represents an acylamino group or a sulfonamide group. ]