JPH06266076A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the spectral absorption characteristics of a formed dye image and its lightfastness and to enhance color development performance by incorporating a specified polyhydric alcohol. CONSTITUTION:The silver halide color photographic sensitive material contains one of the polyhydric alcohols represented by formula I in which R1 is an alkyl, alkenyl, or cycloalkyl, or cycloalkenyl; R2 is same as R1 or the like, but each of R1 and R2 does not combine with each other to form a ring. This polyhydric alcohol is incorporated in an amount of >=50 weight % in fine lipohilic particles containing an image-forming coupler.

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 excellent in color image fastness to light and color development.

[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, the fastness of these dye images mainly to ultraviolet rays or visible rays is not satisfactory, and it is known that the dye images are easily discolored when exposed to these 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.

However, in order to give a satisfactory light resistance to a dye image using, for example, an ultraviolet absorber, a relatively large amount of the ultraviolet absorber is required, and in this case, the dye image is colored due to the coloring of the ultraviolet absorber itself. Could be significantly contaminated. 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), these complexes are not very effective in fading prevention itself and their solubility in organic solvents is not high, so it is not possible to add an amount sufficient to exert a fading prevention 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.

[0008]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a silver halide color photograph in which a dye image to be formed has good spectral absorption characteristics and the fastness of the dye image to light is remarkably improved. To provide a light-sensitive material.

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

[0010]

The above object of the present invention can be achieved by any of the following constitutions.

A silver halide color photographic light-sensitive material containing at least one polyhydric alcohol represented by the general formula [I] "Chemical Formula 1".

The silver halide color photographic light-sensitive material as described above, wherein the structure of the polyhydric alcohol is represented by the general formula [II] "Chemical formula 2" to the general formula [V] "Chemical formula 5".

At least one polyhydric alcohol represented by the general formula [I] “Chemical Formula 1” is present in the lipophilic fine particles containing the coupler for image formation in an amount of 50% or more by weight relative to the coupler. And a silver halide color photographic light-sensitive material.

A silver halide color photographic light-sensitive material containing at least one polyhydric alcohol represented by the general formula [VI] "Chemical formula 6" and / or the general formula [VII] "Chemical formula 7". material.

In the lipophilic fine particles containing the coupler for image formation, the general formula [VI] “Chemical formula 6” and / or the general formula [VII]
A silver halide color photographic light-sensitive material comprising at least one polyhydric alcohol represented by "Chemical Formula 7" in an amount of 50% or more based on the weight of the coupler.

A silver halide color photographic light-sensitive material containing at least one polyhydric alcohol represented by the general formula [VIII] “Chemical formula 8”.

At least one polyhydric alcohol represented by the general formula [VIII] “Chemical Formula 8” is present in the lipophilic fine particles containing the coupler for image formation in an amount of 50% by weight or more based on the coupler. And a silver halide color photographic light-sensitive material.

The present invention will be specifically described below.

First, the polyhydric alcohol compounds represented by the general formulas [I] to [VIII] of the present invention will be described.

In the general formulas [I] to [V], R ₁ ,
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ ,
R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ , R ₃₃ , R
₃₄ , R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ , R ₄₆ , R ₅₂ ,
R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ , R ₇₁ , R ₇₂ , R ₇₃ , R ₇₄ , R
_The alkyl group represented by ₈₁ , R ₈₂ and R ₈₃ (hereinafter abbreviated as R _{1 to} R ₈₃ ) may be linear or branched, and preferably has 1 to 32 carbon atoms, for example, a methyl group, an ethyl group, Isopropyl group, t-butyl group, dodecyl group, heptadecyl group, 2-
A typical example thereof is an ethylhexyl group.

The alkenyl group represented by R _{1 to} R ₈₃ may be linear or branched and preferably has 2 to 32 carbon atoms, for example, vinyl group, propenyl group, 1,1-undecenyl group, 1-methyl group. A typical example thereof is a propenyl group.

The cycloalkyl group represented by R _{1 to} R ₈₃ is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms,
It may have a branched structure, and typical examples thereof include a cyclohexyl group, a cyclopentyl group, a cyclopropyl group and a 2-methylcyclopropyl group.

The cycloalkenyl group represented by R _{1 to} R ₈₃ is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, which may have a branched structure, for example, a 1-cyclohexenyl group, A typical example thereof is a 2-cyclopentenyl group.

R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R
₁₀ , R ₁₁ , R ₁₂ , R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ , R ₇₁ ,
The aryl group represented by R ₇₂ , R ₇₃ , R ₇₄ , R ₈₁ , R ₈₂ and ₈₃ preferably has 6 to 14 carbon atoms, and typical examples thereof include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. Groups and the like.

The above-mentioned alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group and aryl group may be further substituted with a substituent, and the substituent may be alkyl, alkenyl, cycloalkenyl, alkynyl, aryl, Heterocycle, alkylthio, arylthio, heterocyclethio, sulfonyl, sulfinyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, anilino, acylamino, sulfonamide , Imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl groups,
And a spiro compound residue, a bridged hydrocarbon compound residue,
Halogen atom, hydroxyl group, etc. (however, in the case of R ₈₁ , R ₈₂ , R ₈₃ , alkyl, alkenyl, cycloalkenyl, alkynyl, aryl, alkylthio, arylthio, sulfonyl, sulfinyl, acyl, carbamoyl, sulfamoyl, cyano, amino, Alkylamino, anilino, acylamino, sulfonamide, imide, ureido, sulfamoylamino groups, halogen atoms, hydroxyl groups and the like, and among these, preferably alkyl, aryl,
Acylamino, sulfonyl groups, halogen atoms, hydroxyl groups, etc.).

The substituted alkyl group or substituted alkenyl group having two or more hydroxyl groups represented by R ₅₁ is the above R ₁ to
Represents a group in which any two or more hydrogen atoms of the alkyl group and alkenyl group of R ₅₂ (including those further substituted by a substituent group) are replaced by a hydroxyl group, and its representative example is 1,2-dihydroxy. Examples thereof include a propyl group and a 1,1-dihydroxymethylethyl group.

R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ , R ₃₃ , R
₃₄ , R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ , R ₄₆ , R ₆₁ ,
R ₆₂ , R ₆₃ , R ₆₄ , R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ (hereinafter R
_{21 to} R ₇₄ ) and the acyl group represented by Y,
C (= O) -R ₃ (R ₃ is as described above) is preferred, and R ₂₁
The sulfonyl group represented by ~R _74, -SO ₂ -R ₄
(R ₄ is as described above) is preferable, and the phosphonyl group represented by R _{21 to} R ₇₄ is-(O =) P <(OR ₅ ) (OR
₆ ) (R ₅ and R ₆ are as described above) are preferred, and R ₂₁ to
The carbamoyl group represented by R ₇₄ , R ₈₁ , R ₈₂ , R ₈₃ and Y includes —C (═O) —N <(R ₉ ) (R ₁₀ ) (R ₉ , R ₁₀
Is as described above), and the sulfamoyl group represented by R _{21 to} R ₇₄ and Y is —SO ₂ N <(R ₁₁ ) (R
₁₂ ) (R ₁₁ and R ₁₂ are as described above) are preferred.

In the general formulas [I] and [VIII], R ₁ and R
₂ , R ₈₁ and R ₈₂ , R ₈₂ and R ₈₃ , R ₈₁ and Y, R ₈₂ and Y, and R ₈₃ and Y do not fuse with each other to form a ring.

R ₅ and R ₆ , R ₇ and R ₈ , R ₉ and R ₁₀ and R ₁₁
And R ₁₂ may be condensed with each other to form a ring.

In the general formula [II], R ₂₁ , R ₂₂ and R
₂₃ (when m is 2 or more, each is regarded as an independent substituent), any two substituents are condensed with each other,
You may form a ring.

In the general formula [III], R ₃₁ , R ₃₂ , R
₃₃ and R ₃₄ (when n is 2 or more, plural R ₃₃ and plural R ₃₄ are regarded as independent substituents), any two substituents are condensed with each other to form a ring. May be.

In the general formula [IV], R ₄₁ , R ₄₂ ,
Any two substituents of R ₄₃ , R ₄₄ , R ₄₅ and R ₄₆ may be condensed with each other to form a ring.

In the general formulas [VI] and [VII], R ₆₁
And R ₆₂ and / or R ₆₂ and R ₆₃ and / or R ₆₃ and R ₆₄ may be condensed with each other to form a ring.

The alkylene group represented by L may be linear or branched, and examples thereof include an ethylene group, a 1-methylethyl group and a propylene group.

Examples of the arylene group represented by L include p-phenylene group, o-phenylene, and 1,4-naphthylene group. The alkylene group and arylene group represented by L may be substituted with other substituents, and the substituent has the same meaning as the substituents in R _{1 to} R ₃ .

The polyhydric alcohol of the present invention preferably has a total carbon number of 6 (provided that it is 10 in the general formulas [VI] and [VII]).

The polyhydric alcohol of the present invention preferably has a molecular weight of 5000 or less, and is preferably liquid at room temperature.

The polyhydric alcohol of the present invention preferably has a hydroxyl value of 50 or more.

The polyhydric alcohol of the present invention is preferably log
The P value is 3 or more.

Typical examples of the polyhydric alcohol of the present invention are shown below, but the present invention is not limited thereto.

[0041]

[Chemical 9]

[0042]

[Chemical 10]

[0043]

[Chemical 11]

[0044]

[Chemical 12]

[0045]

[Chemical 13]

[0046]

[Chemical 14]

[0047]

[Chemical 15]

[0048]

[Chemical 16]

[0049]

[Chemical 17]

[0050]

[Chemical 18]

[0051]

[Chemical 19]

[0052]

[Chemical 20]

[0053]

[Chemical 21]

[0054]

[Chemical formula 22]

[0055]

[Chemical formula 23]

[0056]

[Chemical formula 24]

[0057]

[Chemical 25]

[0058]

[Chemical formula 26]

[0059]

[Chemical 27]

[0060]

[Chemical 28]

[0061]

[Chemical 29]

In the present invention, preferred yellow couplers which can be used in combination with the polyhydric alcohol of the present invention include benzoylacetanilide type and pivaloylacetanilide type couplers, and magenta couplers include 5-pyrazolone type and pyrazolotype couplers. There are triazole type and indazolone type couplers, and cyan dye forming couplers include phenol type, naphthol type, pyrazoloquinazolone type, pyrazolopyrimidine type, pyrazolotriazole type and imidazole type couplers.

Next, typical examples of the yellow couplers that 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.

Next, 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.

[0066]

[Chemical 30]

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.

Typical examples of cyan couplers that can be used in combination are, 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 polyhydric alcohol of the present invention, the magenta couplers are preferable, and 1H-pyrazolo [5,1-c] [1,2,
4] Triazole and 1H-pyrazolo [1,5-b] [1,2,4] triazole magenta couplers.

In order to incorporate the polyhydric alcohol and the image forming coupler in the silver halide emulsion layer, a conventionally known method, for example, a high boiling point solvent such as known dibutyl phthalate, tricresyl phosphate and the like, butyl acetate and acetic acid are used. The image-forming coupler and the polyhydric alcohol are dissolved alone or in combination in a mixed solution of a low boiling point solvent such as ethyl or the like, or a solvent having only a low boiling point solvent, and then mixed with an aqueous gelatin solution containing a surfactant, Then, a method of emulsifying and dispersing using a high-speed rotary mixer, a colloid mill or an ultrasonic disperser, and then directly adding to the emulsion can be adopted. 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 polyhydric alcohol and the coupler may be separately dispersed by the above dispersion method and added to the silver halide emulsion, but both compounds are dissolved at the same time, dispersed and added to the emulsion. Is preferred.

The addition amount of the polyhydric alcohol of the present invention is preferably 0.01 g to 20 g, more preferably 0.5 g to 8.0 g per 1 g of the coupler, and two or more polyhydric alcohols are used in combination. It doesn't matter.

As the silver halide emulsion used in the light-sensitive material of the present invention, any ordinary silver halide emulsion 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 may be hardened and may 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, a competing coupler and an oxidized product of a developing agent, which has an effect of color correction, 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, fogging agents, 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 bleached or bleached from the light-sensitive material during the development process. Photosensitive materials include formalin scavenger, optical brightener, matting agent, lubricant, image stabilizer, surfactant, color fog inhibitor, development accelerator,
Development retarders and bleaching accelerators 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 using the light-sensitive material of the present invention, a color photographic process generally known can be carried out after exposure.

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

[0082]

[Chemical 31]

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

[0084]

[Chemical 32]

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. ]

[0086]

[Chemical 33]

[Wherein, R ₁₃₁ represents an aliphatic group or an aromatic group, and Y represents a group of non-metal atoms necessary for forming a 5- to 7-membered ring with a nitrogen atom. In the general formula [AO-I], _examples of the alkyl group, aryl group and heterocyclic group represented by R ₁₂₁ include the alkyl group and aryl represented by R ₃ in the general formulas [I] to [V]. Examples of the heterocyclic group described as the group include a pyrazole group, a 2-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. R _{122 to} R ₁₂₆
The group capable of substituting on the benzene ring represented by is a substituent when the alkyl group, aryl group or the like represented by R ₃ or the like in the above general formulas [I] to [V] is further substituted. The groups described above may be mentioned. R ₁₂₂ , R ₁₂₃ , R
₁₂₅ and R ₁₂₆ are preferably hydrogen atom, hydroxy group, alkyl group, aryl group, alkoxy group, aryloxy group and acylamino group, and R ₁₂₄ is preferably alkyl group, hydroxy group, aryl group, alkoxy group and aryloxy group. . Further, R ₁₂₁ and R ₁₂₂ may be ring-closed to each other to form a 5- or 6-membered ring, and R ₁₂₄ at that time is preferably a hydroxy group, an alkoxy group or an aryloxy group. R ₁₂₁ and R ₁₂₂ may be ring-closed to form a methylenedioxy ring. Furthermore, R ₁₂₃ and R ₁₂₄ may be ring-closed to form a 5-membered hydrocarbon ring, and at that time, R ₁₂₁ is preferably an alkyl group, an aryl group or a heterocyclic group.

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

[0089]

[Chemical 34]

[0090]

[Chemical 35]

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. 3-39956
Exemplified compounds II-1 to II-33 described on pages 0 to 11 may be mentioned.

Next, in the 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.

[0094]

[Chemical 36]

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 polyhydric alcohol of the present invention is added to the green light-sensitive layer, the silver halide emulsion layer is added to JP-A-61-1.
You may use the metal chelate compound described in 58329, 62-183459, etc.

[0098]

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 polyethylene laminated on one side of a paper support and polyethylene containing titanium oxide on the other side, titanium oxide was applied to each layer having the constitution 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.
To 67 g, stain inhibitor (HQ-1) 0.67 g and high boiling organic solvent (DNP) 6.67 g, 60 ml of ethyl acetate was added and dissolved. 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.

[0103]

[Table 1]

[0104]

[Table 2]

The structural formulas of the compounds used in each layer are shown below.

[0106]

[Chemical 37]

[0107]

[Chemical 38]

[0108]

[Chemical Formula 39]

[0109]

[Chemical 40]

Blue-Sensitive Silver Halide Emulsion (Em-B) Monodisperse cubic emulsion with average grain size 0.85 μm, coefficient of variation = 0.07, silver chloride content 99.5 mol% 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 / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX green-sensitive Silver halide emulsion (Em-G) Monodisperse cubic emulsion with average grain size 0.43 μm, coefficient of variation = 0.08, silver chloride content 99.5 mol% Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stability Agent STAB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX Red-sensitive silver halide emulsion (Em-R) Average grain size 0.50 μm, coefficient of variation = 0.08, Monodisperse cubic emulsion with a silver chloride content of 99.5 mol% Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer The structural formula of the TAB-1 6 × 10 ^-4 mol / mol AgX Sensitizing dye RS-1 1 × 10 ^-4 mol / compound used in the monodispersed cubic emulsion in mol AgX below.

[0111]

[Chemical 41]

Next, the high boiling point organic solvent D of the third layer of Sample 101 was used.
Replacing NP with the comparative HBS and the polyhydric alcohol of the present invention shown in Tables 3, 4 and 5 below, Samples 102-120 and 105'-1
20 ', 105 "-120" were made.

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 ℃ 45 seconds Bleach-fixing 35.0 ± 0.5 ℃ 45 seconds Stabilization 30-34 ℃ 90 seconds Dry 60-80 ℃ 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 set to 1000 ml, and the pH 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 Add water 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 Fluorescent brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Add water to bring the total volume to 1000 ml, and add pH 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 to determine the residual ratio (%) of the dye image at an initial density of 1.0.

Λmax: The maximum absorption wavelength of the wedge at a reflection optical density of 1.0.

Full width at half maximum; measured from a spectral absorption spectrum of a wedge at a reflection optical density of 1.0.

Dmax: represents the maximum color density.

The results are shown in Tables 3, 4 and 5.

[0125]

[Table 3]

[0126]

[Table 4]

[0127]

[Table 5]

[0128]

[Chemical 42]

As is apparent from Tables 3, 4, and 5, samples 104 to 110, 104 'to 110', 104 "to 110" in which the compound of the present invention was used as the high boiling point organic solvent (HBS) were compared. sample
Compared with 101, light resistance is greatly improved and color development is also improved. Further, the effect of sharpening the absorption without changing the maximum absorption wavelength was also recognized. In Sample 102 using HBS-1, which is a phenol derivative, although some light resistance improving effect is recognized, the effect cannot be said to be sufficient, and the absorption wavelength is further deep-color shifted to broaden the absorption waveform. It was confirmed that the undesired effect of expressing the color is also exhibited. Further, in the sample 103 using HBS-2 which is a monohydric alcohol,
Although the color reproducibility was not deteriorated as in 02, the effect of improving the light fastness was hardly recognized. Further, in the case of HBS-3 that does not fall within the scope of the present invention, although a slight light resistance improving effect was observed, the color development deteriorated and the absorption waveform became broad.

Samples 111 to 120, 115 'to 120', 115 "to 12
At 0 ″, the high boiling point organic solvent was used in an amount of 3 times, but it was found that in such a system, the compound of the present invention acts more effectively, the light resistance is significantly improved, and the absorption waveform is further sharpened. .

Example 2 Samples 200 and 201 to 220 were prepared by replacing the magenta coupler, high boiling point organic solvent and dye image stabilizer of the third layer of Sample 101 of Example 1 with the combinations shown in Table 6 below.

The same evaluation as in Example 1 was performed using the obtained sample. The results are shown in Table 6.

[0133]

[Table 6]

As is clear from Table 6, by using the polyhydric alcohol of the present invention as the high boiling point organic solvent in the magenta coupler (M-8) in which the secondary alkyl group is substituted at the 6-position, the light resistance is significantly increased. Could be improved. Samples 202, 204, 20 with increased amount of polyhydric alcohol of the present invention
It was found that 6, 208, 210, 212, 214, 216 and the like have further improved light resistance.

Example 3 Samples 101, 201'-21 were prepared by replacing the high boiling point organic solvents in the third layer of Sample 101 of Example 1 with the combinations shown in Table 7 below.
6'was produced.

The same evaluation as in Example 1 was performed using the obtained sample. The results are shown in Table 7.

[0137]

[Table 7]

As is apparent from Table 7, the amount of the polyhydric alcohol of the present invention added was 50% with respect to the magenta coupler.
Sufficient effect cannot be obtained below (weight ratio) (Sample 20
1 ', 202', 205 ', 206'209', 210 ', 213', 21
4 '), the added amount is 50% or more to the coupler,
In particular, it was found that when the total amount of DNP was replaced with the polyhydric alcohol of the present invention (Samples 204 ', 208', 212 ', 216'), a large light resistance improving effect was observed.

Example 4 The high boiling point organic solvent (DN) of the first layer of the sample 101 of Example 1 was used.
Samples 302 to 317 were prepared by replacing P) with comparative HBS shown in Table 8 below and the polyhydric alcohol of the present invention.

The sample thus produced was wedge-exposed with blue light according to a conventional method and then treated in the same manner as in Example 1 (the sample 101 thus treated is referred to as sample 301,
It was used as a comparative sample. ). The same evaluation as in Example 1 was performed using the obtained sample. The results are shown in Table 8.

[0141]

[Table 8]

As is clear from Table 8, samples 303 to 317 in which the compound of the present invention was used as a high boiling organic solvent (HBS).
Compared with the comparative sample 301, both the light resistance and the color developability are significantly improved. In Sample 302 using HBS-2, which is a monohydric alcohol, a slight improvement in color development was observed, but the light resistance was rather deteriorated.

Example 5 The high boiling point organic solvent (DO) of the fifth layer of the sample 101 of Example 1 was used.
Samples 402 to 417 were prepared by replacing P) with the comparative HBS shown in Table 9 below and the polyhydric alcohol of the present invention.

The sample thus prepared was wedge-exposed with red light according to a conventional method and then treated in the same manner as in Example 1 (the sample 101 thus treated was referred to as sample 401,
Used as a comparative sample). The same evaluation as in Example 1 was performed using the obtained sample. The results are shown in Table 9.

[0145]

[Table 9]

As is apparent from Table 9, samples 403-417 using the compound of the present invention as a high boiling organic solvent (HBS).
In comparison with Comparative Sample 401, both the light fastness and the color developability are significantly improved. In Sample 402 using HBS-2, which is a monohydric alcohol, a slight improvement in light resistance was observed, but the color development was rather deteriorated.

[0147]

According to the present invention, firstly, there is provided a silver halide color photographic light-sensitive material in which a dye image to be formed has good spectral absorption characteristics, and the fastness of the dye image to light is remarkably improved. Can be provided.

Secondly, it is possible to provide a silver halide color photographic light-sensitive material excellent in color developability.

Claims (7)

[Claims] 1. A silver halide color photographic light-sensitive material containing at least one polyhydric alcohol represented by the following general formula [I]. [Chemical 1] [In the formula, R ₁ represents an alkyl group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group, and R ₂ represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, —C (═O) —R ₃ , _{-SO 2 -R 4, - (O} =) P <
(OR ₅ ) (OR ₆ ),-(O =) P <(R ₇ ) (R ₈ ), -C (= O)
-N represents a _{<(R 9) (R 10} ) or _{-SO 2 N <(R 11)} (R 12). Here, R _{3 to} R ₉ and R ₁₁ each represent an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group or an aryl group, R ₁₀ and R ₁₂ represent a hydrogen atom,
It represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group or an aryl group. However, an alkyl group represented by R ₁ , an alkenyl group, a cycloalkyl group, a cycloalkenyl group and / or an alkyl group represented by R ₂ , an alkenyl group, a cycloalkyl group, a cycloalkenyl group and / or an alkyl represented by R _{3 to} R ₁₂ . At least one position on the carbon atom of the group, alkenyl group, cycloalkyl group, or cycloalkenyl group is substituted with a hydroxyl group, and the total sum of alcoholic hydroxyl groups in the molecule is 2 or more. Further, R ₁ and R ₂ do not fuse with each other to form a ring. ] 2. The structure of polyhydric alcohol is represented by the following general formula [I
The silver halide color photographic light-sensitive material according to claim 1, which is represented by formula [I] to general formula [V]. [Chemical 2] [Wherein R ₂₁ , R ₂₂ and R ₂₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group or a sulfamoyl group, and m is From 1
Represents an integer of 20. When m is 2 or more, a plurality of R ₂₃ may be the same or different. However, when m represents 1, any two of R ₂₁ , R ₂₂ and R ₂₃ are hydrogen atoms, and when m is 2 or more, at least 2 of R ₂₁ , R ₂₂ and a plurality of R ₂₃ are One is a hydrogen atom, and not all are hydrogen atoms. ] [Chemical 3] [In the formula, R _{31 to} R ₃₄ are each a hydrogen atom, an alkyl group,
An alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group or a sulfamoyl group, n represents an integer of 1 to 20, and when n is 2 or more, a plurality of R ₃₃ , R ₃₄ may be the same or different. However, when n represents 1, at least two of R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are hydrogen atoms and not all are hydrogen atoms, and when n is 2 or more, R is _At least two of ₃₁ , R ₃₂ , a plurality of R ₃₃ and a plurality of R ₃₄ are hydrogen atoms, and all are not hydrogen atoms. ] [Chemical 4] [In the formula, R _{41 to} R ₄₆ are each a hydrogen atom, an alkyl group,
It represents an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group or a sulfamoyl group. However, R _{41 to} R
_At least two of ₄₆ are hydrogen atoms, and not all are hydrogen atoms. ] [Chemical 5] [In the formula, R ₅₁ represents a substituted alkyl group or a substituted alkenyl group containing two or more hydroxyl groups, R ₅₂ represents an alkyl group,
It represents an alkenyl group, a cycloalkyl group or a cycloalkenyl group, and R ₅₁ and R ₅₂ may be condensed with each other to form a lactone ring. ] 3. A lipophilic fine particle containing an image forming coupler, wherein at least one polyhydric alcohol represented by the general formula [I] is present in an amount of 50% by weight or more based on the coupler. Silver halide color photographic light-sensitive material. 4. The following general formula [VI] and / or general formula [VI
A silver halide color photographic light-sensitive material containing at least one polyhydric alcohol represented by the formula I). [Chemical 6] [Chemical 7] [In the general formula [VI] and general formula [VII], R ₆₁ , R
₆₂ , R ₆₃ , R ₆₄ , R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ are each a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an acyl group, a sulfonyl group, a phosphonyl group, It represents a carbamoyl group or a sulfamoyl group. However, R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ , R
_At least two of ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ are hydrogen atoms, and not all are hydrogen atoms. ] 5. A lipophilic fine particle containing an image forming coupler contains at least one polyhydric alcohol represented by the general formula [VI] and / or the general formula [VII] in a weight ratio of 50% with respect to the coupler. A silver halide color photographic light-sensitive material characterized by being present as above. 6. A silver halide color photographic light-sensitive material containing at least one polyhydric alcohol represented by the following general formula [VIII]. [Chemical 8] [In the formula, R ₈₁ , R _82, and R ₈₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, or a carbamoyl group;
Represents an alkylene group or an arylene group, Y represents a hydrogen atom, a carbamoyl group, a sulfamoyl group or an acyl group, and n represents 0 or 1. ] 7. A lipophilic fine particle containing an image forming coupler, characterized in that at least one polyhydric alcohol represented by the general formula [VIII] is present in an amount of 50% or more based on the weight of the coupler. Silver halide color photographic light-sensitive material.