JP2532934B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly, to a dye image which is stable to heat and light.
Moreover, the present invention relates to a silver halide color photographic light-sensitive material in which generation of stain is prevented.

[Prior Art] When a silver halide color photographic light-sensitive material is imagewise exposed and color-developed, an oxidized aromatic primary amine type color developing agent reacts with a coupler to give indophenol, indoaniline, indamine. It is well known that dyes, azomethines, phenoxazines, phenazines, and similar dyes are formed to form dye images.

Generally, the quality of these photographic images is not permanent and deteriorates over time. In particular, a color photograph having an image composed of an azomethine dye and X being an indoaniline dye, is subject to fading and discoloration of the dye image, and further to a white discoloration (yellow stain) when exposed to light for a long period of time or stored under high temperature and high humidity. ) Also causes image deterioration.

Such deterioration in image quality is a disadvantage that can be fatal to recording materials, and improvement is desired.

In general, cyan, magenta, and yellow dye images are used in color photographs, and studies have been conducted on making each dye image fast. Many studies have been done on magenta dye images, but many studies have been done on yellow dye images and cyan dye images because their dye images are not as fast as magenta dye images. I haven't been wiped. However, as a result of many studies on the fastness of the magenta dye image, the fastness thereof has become high, and the fading and discoloration of the yellow dye image and the cyan image have become conspicuous, and the fastening of these dye images has been desired.

As a method of using an anti-fading agent for improving light and wet heat fastness of a yellow dye image, for example, hindered amine derivatives and phenol derivatives are disclosed in British Patent 1,326,889,
1,354,313, 1,410,846, U.S. Patent 3,336,135,
No. 4,268,593, Japanese Patent Publication No. 48-31256, No. 51-1420, No. 52
-6623, JP-A-58-114036, 59-5426, 61-2151
, European Patent 246,766, phosphoric acid ester European Patent 265,196, hydrazine compounds European Patent 255,722
And JP-A-63-220,142.

Further, as a method of using an anti-fading agent for improving light and wet heat fastness of a cyan dye image, for example, hindered amine derivatives and phenol derivatives are used in U.S. Pat. Nos. 4,452,884 and 4,46,46.
5,765, JP-A-54-48535, 59-3433, 59-5246
No. 59-87456, No. 61-2151, No. 61-86750, the spirochroman derivative is JP-B-59-52825, amine compounds are JP-A-56-46224, 63-149642, Ibid 63-149643
No. 63-149645, No. 63-163347, and No. 63-220142.

Although these compounds have a slight effect of improving the light and wet heat fastness to the respective dyes, the effect is small, or the photographic property is deteriorated (for example, change in hue, occurrence of fog, and sensitivity of the photosensitive material). There was something that changed.

On the other hand, various anti-fading agents have been proposed for fastness to magenta color images, but these compounds certainly show an effect on fastening of magenta color images,
Many of the images showed little effect on yellow dye images and cyan dye images, and promoted fading.

[Problems to be Solved by the Invention] 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 yellow dye image or a cyan dye image is improved.

A second object of the present invention is to provide a stabilizer having a sufficient effect for improving the fastness of a yellow dye image or a cyan dye image without causing a change in hue or fog, and without causing poor dispersion or crystals. The purpose of the present invention is to provide a silver halide color photographic light-sensitive material in which a yellow dye image or a cyan color image is stabilized by being contained therein.

A third object of the present invention is to provide a silver halide color photographic light-sensitive material in which the color balance of the three fading colors is improved by improving the fastness of the yellow dye image or the cyan image to light and heat. It is in.

[Means for Solving Problems] As a result of various studies, the present inventors have made it possible to provide a cyan dye image by incorporating at least one compound represented by the following general formula [I] into the cyan dye image forming layer. It was found that the object of the present invention was achieved, and the first aspect of the present invention was completed.

The present inventor has conducted various studies and found that the object of the present invention relating to a yellow dye image can be achieved by incorporating at least one compound represented by the following general formula [I] into the yellow dye image forming layer. Heading Completed the second aspect of the invention.

General formula [I] In the formula, R ₁ is an acyl group, a sulfonyl group, a phosphonyl group,
A sulfinyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkyloxycarbonyl group or an aryloxycarbonyl group, R ₂ is a hydrogen atom,
Represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or a heterocyclic group, R ₃
Is a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, phosphonyl group, sulfinyl group, alkylsulfamoyl group, arylsulfamoyl group, It represents an alkyloxycarbonyl group or an aryloxycarbonyl group. However, R ₂ and R ₃ are not hydrogen atoms at the same time. R ₁ and R ₂ may be bonded to each other to form a 5- to 8-membered heterocycle with a nitrogen atom (provided that the nitrogen atom and a sulfonyl group or a sulfinyl group are bonded via an alkylene group. Except R), R ₁ , R ₂
And the total number of carbon atoms of R ₃ is 8 or more, and X represents an oxygen atom or a sulfur atom. Among the compounds represented by the above general formula [I], R ₁ , R ₂ and R ₃ each have a carbon number of 40 or less, and the sum of these carbon numbers is 8 to 50. preferable.

 Next, the present invention will be described in detail.

The cyan coupler contained in the cyan dye image forming layer includes the following general formulas [C-I], [C-II] and [C-III].
And [C-IV].

General formula [C-I] General formula [C-II] General formula [C-III] General formula [C-IV] In the formula, Z represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.

R ¹⁰ is -NHSO ₂ -R ¹⁴ , Or represents -SO ₂ -R ¹⁶ . Where R ¹³ , R ¹⁴ , R ¹⁵ and R
¹⁶ represents an aliphatic group, an aromatic group, a heterocyclic group, or an amino group which may have a substituent. R ¹³ and R ¹⁵ further represent an aliphatic oxy group, an aromatic oxy group, or a heterocyclic oxy group. R ¹¹
Represents a hydrogen atom, an aliphatic group or a group defined by R ¹⁰ . R ¹² represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic oxy group, or a group defined for R ¹⁰ . X ¹⁰ represents = CH- or = N-, R ¹¹ and
R ¹² may combine with each other to form a 5- to 7-membered ring. R ²¹ and
R ²² may be the same or different, and each is an aromatic group,
It represents a substituent which is a heterocyclic group or at least one of which is an electron-withdrawing group. Q ³⁰ represents a group of non-metallic atoms necessary for forming a nitrogen-containing heterocyclic ring. R ³¹ , R ³² and R ^{33, which} may be the same or different, each represents a hydrogen atom or a substituent. Further, at least one of R ³² and R ³³ represents a group defined by Z. n represents 1 or 2. When n is 2, two R ³² 's may be the same or different. However, R ³¹ , R
^At least one of ³² and R ³³ is an electron withdrawing group. Q ⁴⁰ represents a group of non-metal atoms necessary for forming a hetero ring or an aromatic group together with> = (X ⁴⁰ -Y ⁴⁰ ) _m = <residue. X ⁴⁰ and Y ^{40 each} represent a nitrogen atom or a methine group which may have a substituent, and m represents 1 or 2. R ⁴⁰ and R ⁴¹
Represents a substituent. However, at least one of R ⁴⁰ and R ⁴¹ represents an electron-withdrawing group. When m is 2, 2 x ⁴⁰
And the two Y ^{40 s} may be the same or different from each other.

The aliphatic group referred to in the present invention may be a linear or branched chain or cyclic, may be saturated or unsaturated, and may be an alkyl group which may be further substituted with a substituent. An alkenyl group and an alkynyl group. The aromatic group referred to in the present invention is a carbocyclic aromatic group.
Heterocycle, alicyclic ring, etc. may be condensed and may be further substituted with a substituent. The heterocyclic group referred to in the present invention is a 5- to 7-membered heterocycle having at least one oxygen atom, nitrogen atom, or sulfur atom in addition to a carbon atom as a ring-constituting atom. All may be hetero atoms. Further, the heterocyclic group may be a saturated ring or an unsaturated ring, and may be substituted with a substituent. General formulas [C-III] and [C-IV] of the present invention
The substituent referred to in, for example, an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, an aliphatic thio group, an aromatic thio group, a heterocyclic thio group,
Halogen atom, acyl group, ester group, carbamoyl group, sulfamoyl group, sulfonyl group, hydroxy group,
Cyano group, carboxy group, nitro group, sulfo group, acyloxy group, silyloxy group, sulfonyloxy group, carbamoyloxy group, optionally substituted amino group (for example, amino group, alkylamino group, amide group, sulfonamide) Group, urethane group, ureido group, anilino group, imide group) and the like.

The cyan couplers represented by the general formulas [CI] to [C-IV] will be described in more detail. Z represents a hydrogen atom or a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent, and examples thereof include a halogen atom (fluorine, chlorine, bromine, etc.), an alkoxy group (ethoxy, dodecyloxy, methoxy). Ethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, etc.), aryloxy group (4-chlorophenoxy, 4-
Methoxyphenoxy, 4-carboxyphenoxy, etc.), acyloxy group (acetoxy, tetradecanoyloxy, benzoyloxy, etc.), sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy, etc.), amide group (dichloroacetylamino, heptafluorobutyryl) Amino, methanesulfonylamino, toluenesulfonylamino, etc.), alkoxycarbonyloxy group (ethoxycarbonyloxy, benzyloxycarbonyloxy, etc.), aryloxycarbonyloxy group (phenoxycarbonyloxy, etc.), aliphatic or aromatic thio group (ethylthio, Phenylthio, tetrazolylthio, etc.), imide groups (succinimide, hydantoinyl, etc.), aromatic azo groups (phenylazo, etc.) and the like. These leaving groups may include photographically useful groups.

The electron-withdrawing group in the general formulas [C-III] and [C-IV] represents a substituent having a Hammett's substituent constant σ _p of a value larger than 0.

Preferred cyan couplers represented by the general formula [CI] can be represented by the following general formulas [C-Ia], [C-Ib], and [C-Ic].

General formula [C-Ia] General formula [C-Ib] General formula [C-Ic] In the formula, R ⁵⁰ represents an aliphatic group, an aromatic group, a heterocyclic group or an amino group which may have a substituent. R ⁵¹ represents an alkyl group or an acylamino group, and R ⁵² represents a hydrogen atom, a halogen atom, an aliphatic group or an alkoxy group. R
⁵¹ and R ⁵² may combine with each other to form a 5- to 7-membered ring.
Z has the same meaning as in general formula [C-I], R ⁵³ has the same meaning as R ^{10 in} general formula [C-I], and R ⁵⁴ , R ⁵⁵ , R ⁵⁶
And R ⁵⁷ represent a hydrogen atom or a substituent.

Among the cyan couplers represented by the general formula [C-III], more preferred are the following general formulas [C-IIIa] and [C
-IIIb], [C-IIIc], [C-IIId], [C-IIIe]
And [C-IIIf].

In the formula, R ³¹ , R ³² and Z have the same meaning as in formula [C-III], and R ³² ′ has the same meaning as R ³² . R ⁶⁰ and R ⁶¹ represent a hydrogen atom or a substituent. However, with R ⁶⁰
At least one of R ⁶¹ is an electron withdrawing group.

In the cyan couplers represented by the general formulas [C-IIIa] to [C-IIIe], R ³¹ is preferably an electron-withdrawing group. In the cyan coupler represented by the general formula [C-IIIf], R ⁶⁰ is an electron-withdrawing group. Is preferred.

Among the cyan couplers represented by the general formula [C-IV], it is preferable that m is 1 and Q ⁴⁰ is —O—, —S— or vinylene.

Among the cyan couplers represented by the general formulas [C-I] to [C-IV], particularly preferred are those represented by the general formula [C-I], among which the general formulas [C-Ia],
Those represented by [C-Ib] are preferred.

Specific examples of particularly preferred cyan couplers include the following compounds, but are not limited thereto.

These cyan couplers are US Patents 2,369,929,
4,511,647, 2,772,162, 4,500,653, 4,5
No. 64,586, European Patent Application Publication EPO.249,453A2,
It can be synthesized by the methods described in 1-390441, 61-153640, 62-257158, and the like, and methods analogous thereto.

The cyan couplers represented by the general formulas [C-I], [C-II], [C-III] and [C-IV] are 2 × 10 ^{−3 to} 5 × 10 ³ mol per mol of silver in the emulsion layer. ^-1 mol, preferably 1 × 10 ^-2 mol to 5 × 10 ^-1 mol.

Further, these cyan couplers may be used alone or in combination of two or more kinds.

As the yellow coupler used in the yellow dye image forming layer in the silver halide color photographic light-sensitive material of the present invention, any yellow coupler can be used. In particular, the compound represented by the general formula [Y-I] is preferably used. preferable.

General formula [Y-I]: [In the formula, R ¹ represents a substituted or unsubstituted N-phenylcarbamoyl group. R ² represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted phenyl group. X ¹ represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized developing agent. R ¹ , R ² or
X ¹ in it may form a dimer or higher polymer.

The yellow coupler represented by the general formula [Y-I] is described in more detail as follows: R ¹ (N-phenylcarbamoyl group)
As the substituent of the well-known substituent in the yellow coupler, for example, an alkyl group, an alkenyl group, an alkoxy group,
Alkoxycarbonyl group, halogen atom, alkoxycarbamoyl group, aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylureido group, alkyl-substituted succinimide group, aryloxy group,
It represents an aryloxycarbonyl group, an arylcarbamoyl group, an arylamide group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group and the like. Two or more substituents may be attached, and in this case, they may be the same or different from each other.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R ² include a methyl group, a t-butyl group, a t-amyl group,
-Octyl group, 1,1-diethylpropyl group, 1,1-dimethylhexyl group, 1,1,5,5-tetramethylhexyl group, 1
-Methyl-cyclohexyl group, adamantyl group and the like are mentioned as typical examples. As the substituent of the substituted phenyl group of R ^2, the substituent represented by R ¹ is exemplified.

The coupling-off group for X ¹ may be a hydrogen atom, but is preferably a coupling-off group for forming a 2-equivalent yellow coupler, for example, the following general formulas [Y-II] and [Y-
III], [Y-IV] or [YV].

R ¹⁶ represents an optionally substituted aryl group or heterocyclic group.

R ¹⁷ and R ¹⁸ each represent a hydrogen atom, a halogen atom, a carboxylic ester group, an amino group, an alkyl group, an alkylthio group,
It represents an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl group or a heterocycle, and these groups may be the same or different.

W ¹ in the formula Together with a non-metallic atom required to form a 4-, 5- or 6-membered ring.

More preferred yellow couplers used in the present invention are represented by the following general formula [Y-VI].

General formula [Y-VI] In the formula, R ³ represents a tertiary alkyl group having 4 to 12 carbon atoms, a phenyl group substituted with a halogen atom, an alkyl group, or an alkoxy group, or an unsubstituted phenyl group. R ⁴ represents a halogen atom or an alkoxy group. R ⁵
Represents a hydrogen atom, a halogen atom or an optionally substituted alkoxy group.

R ⁶ is an optionally substituted acylamino group, alkoxycarbonyl group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonamide group, arylsulfonamide group, alkylureido group, arylureido group, succinimide Represents a group, an alkoxy group, or an aryloxy group.

X ² has the following general formula [Y-VII] [Y-VIII] [Y-IX]
Alternatively, it represents a group represented by [Y—X].

In the formula, R ⁷ represents a substituted or unsubstituted alkylsulfonyl group, arylsulfonyl group, acyl group, hydroxy group or the substituent represented by R ¹ . l is 2, 3, 4
Or 5 and l is 3 or more, R ⁷ may be the same or different.

In the formula, R ⁸ and R ⁹ each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxy group. R ¹⁰ , R ¹¹ and R ¹² each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an acyl group. W ² represents an oxygen or sulfur atom.

Particularly preferred yellow couplers used in the present invention are represented by the following general formula [Y-XI].

General formula [Y-XI] In the formula, R ¹³ represents an optionally substituted acylamino group, alkoxycarbonyl group, alkylsulfamoyl group, or alkylsulfonamide group. X ³ represents the following general formula [Y-XII] or the above general formula [Y-VIII], [Y
-IX] or [Y-X] is represented.

In the formula, R ¹⁴ represents a hydrogen atom, a halogen atom, a cyano group, an optionally substituted acylamino group, an alkyl or arylsulfamoyl group, or an alkyl or arylsulfonyl group.

R ¹⁵ represents a hydrogen atom, a cyano group, an optionally substituted alkyl or aryl sulfonyl group, an alkyl or aryl sulfamoyl group, an alkyl or aryl sulfonamide group, an acyl group, an alkyl or aryloxycarbonyl group or a carboxy group, And R ¹⁴ , R ¹⁵
Of these, at least one may be substituted alkyl or aryl sulfonyl group, alkyl or aryl sulfamoyl group, alkyl or aryl sulfonamide group, alkyl or aryloxycarbonyl group,
Or a carboxy group.

Specific examples of the yellow coupler represented by the general formula [Y-I] used in the invention are shown below, but the invention is not limited thereto.

The following X and Y ratios are all weight ratios.

These yellow couplers are, for example, Japanese Patent Publication No. 51-10783.
No. 51-33410, No. 52-25733, JP-A-47-26133,
48-73147, 51-102636, 50-130442, 50-6
341, 50-123342, 51-21827, 50-87650,
52-82424, 52-115219, British Patent 1425020, West German Patent 1547868, West German Application Publication No. 2219917, 2261361.
No. 2414006, European Patent Nos. 272041 and 249473, and JP-A No. 63-43144.

In the present invention, the yellow coupler is a silver coupler in the emulsion layer.
2 × 10 ^-3 mole to 5 × 10 ^-1 mole, preferably 1
X 10 ^-2 mol to 5 x 10 ^-1 mol are added.

These yellow couplers may be used alone or in combination of two or more.

Next, the compound represented by the general formula [I] will be described in more detail. R ₁ , R ₂ and R ₃ are each a hydrogen atom, an alkyl group (eg, methyl, butyl, tertbutyl, hexadecyl, phenoxyethyl, methoxyethyl). , A cycloalkyl group (eg, cyclopentyl, cyclohexyl), an alkenyl group (eg, 2-propenyl, 1,3-butadienyl), a cycloalkenyl group (eg, cyclohexenyl, cyclooctenyl), an aryl group (eg, phenyl, naphthyl, methoxyphenyl) ), A heterocyclic group (eg, furyl, oxazolyl, thiazolyl), an acyl group (eg, acetyl, dodecanoyl, benzoyl), a sulfonyl group (eg, dodecylsulfonyl, hexadecylsulfonyl, benzenesulfonyl), a phosphonyl group (eg, butyloctyl). Phospho Group, octyloxyphosphonyl, aryloxyphosphonyl), sulfinyl group (eg, octylsulfinyl, benzenesulfinyl), alkylsulfamoyl group (eg, N-methylsulfamoyl, N, N-diethylsulfamoyl), Arylsulfamoyl group (for example, N-phenylsulfamoyl N-P-methoxyphenylsulfamoyl), alkoxycarbonyl group (for example, methoxycarbonyl, dodecyloxycarbonyl), and aryloxycarbonyl group (for example, phenyloxycarbonyl). , P-methoxyphenoxycarbonyl).
However, R ₁ is limited to the acyl group to the aryloxycarbonyl group among the above, and R ₂ is limited to the hydrogen atom to the heterocyclic group among the above. Further, R ₂ and R ₃ are not hydrogen atoms at the same time. R ₁ and R ₂ may be bonded to each other to form a 5- to 8-membered heterocycle (for example, piperidine ring piperazine ring) with a nitrogen atom, provided that the nitrogen atom and the sulfonyl group or sulfinyl group are alkylene. Excludes heterocycles attached through. Also, these alkyl groups,
A cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an acyl group, a heterocycle and the like are substituents (for example, alkyl, alkoxy, alkoxycarbonyl, alkylcarbamoyl, alkylsulfamoyl, acyl, sulfonyl, aryl). , Aryloxy,
Aryloxycarbonyl, arylcarbamoyl, arylsulfamoyl, acylamino, hydroxy, alkylureido, arylureido, alkoxycarbonylamino, aryloxycarbonylamino, alkylsulfonyl, arylsulfonyl, halogen). However, the total carbon number of R ₁ R ₂ and R ₃ is 8 or more, preferably 8 to 50. X represents an oxygen atom or a sulfur atom.

A more preferable compound in the general formula [I] is when X is an oxygen atom. It is also preferred that R ₁ and R ₂ together with the nitrogen atom form a 5- to 8-membered heterocycle.

Even more preferred compounds of general formula [I] include R ₃
Is not a hydrogen atom.

Specific examples of the compound of the present invention represented by the general formula [I] are shown below, but the invention is not limited thereto.

These compounds can be synthesized by a method described in JP-A-63-85548, Shin Jikken Kagaku Koza, Vol. 14, pages 1585 to 1594 (1977) Maruzen or the like or a method analogous thereto.

Some of the compounds represented by the general formula [I] are
It is similar to the compounds described in JP-A-63-85548 and known to be effective in preventing fading of magenta couplers. However, the compound effective for fixing the magenta color image is not always effective for fixing the cyan image or the yellow image.

When the compound of the present invention represented by the general formula [I] is applied to a dye image of a cyan coupler or a dye image of a yellow coupler, it shows a remarkable improving effect on the fastness to light and heat without deteriorating the photographic property. It was

The compound represented by the general formula [I] in the present invention is used in an amount of 5 to 400 mol%, preferably 10 to 200 mol%, based on the coupler, although it varies depending on the kind of couplers used in combination. Is. If it is less than this range, the anti-fading effect is so small that it is not suitable for practical use. On the other hand, if the amount is more than this range, the progress of development may be hindered and the color density may be lowered.

The compound represented by the general formula [I] used in the present invention may be used alone or in combination of two or more kinds.

The compound represented by the general formula [I] used in the present invention has an excellent anti-fading effect when used in a cyan dye image forming layer or a yellow dye image forming layer, and further in a high boiling organic solvent together with a cyan coupler or a yellow coupler. When it is present in, it has an excellent anti-fading effect.

The color light-sensitive material of the present invention is provided with a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support in this order or in any arrangement thereof. It is preferred that

The silver halide used in the present invention includes silver chloride,
Silver bromide, silver salt (iodo) bromide and silver iodobromide can be mentioned. Among them, silver chloride and silver chloro (iodo) bromide are preferable. Furthermore, the halogen composition of the silver halide grains in one emulsion layer is 9.0 times that of all the silver halide grains constituting the silver halide grains.
It is preferably composed of silver chlorobromide containing mol% or more of silver chloride and containing substantially no silver iodide. Here, "contains substantially no silver iodide" means that the silver iodide content is 1.0 mol% or less. A particularly preferred halogen composition of the silver halide grains is 95% of the total silver halide constituting the silver halide grains.
It is a silver chlorobromide containing substantially no silver iodide, wherein mol% or more is silver chloride.

Furthermore, the silver halide grains according to the present invention preferably have a silver bromide localized phase in a silver bromide content of at least 10 mol% and less than 70 mol%. Such an arrangement of the silver bromide localized phase can be freely selected according to the purpose, and may be inside the silver halide grain, on the surface or subsurface, or divided into the interior and the surface or subsurface. May be. The localized phase may have a layered structure surrounding silver halide grains inside or on the surface, or may have a discontinuous isolated structure. As one preferable specific example of the arrangement of the silver bromide localized phase, the silver bromide content on the surface of the silver halide grains (among others, at the corners of the grains) is at least 10 mol%, more preferably more than 20 mol%. The localized phase is locally epitaxially grown.

The content of silver bromide in the localized phase is preferably more than 20 mol%. However, if the content of silver bromide is too high, desensitization may occur when pressure is applied to the light-sensitive material, or the composition of the processing solution may be reduced. In some cases, characteristics unfavorable for a photographic light-sensitive material, such as a large change in sensitivity and gradation due to fluctuations in the light-sensitive material, may be imparted. Taking these points into consideration, the silver bromide content of the localized phase is preferably in the range of 20 to 60 mol%, and 30 to 50 mol%.
The range of mol% is most preferred. The other silver halide constituting the localized phase is preferably silver chloride. The silver bromide content of the localized phase is described by X-ray diffraction method (for example, described in “Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis” Maruzen).
Alternatively, it can be analyzed using the XPS method (for example, described in “Surface Analysis, —IMA, Application of Auger Electron / Photoelectron Spectroscopy—” Kodansha). The localized phase accounts for 0.1 to 20% of the total silver constituting the silver halide grains of the present invention.
Of silver, and more preferably 0.5 to 7% of silver.

The interface between such a silver bromide localized phase and another phase may have a clear phase boundary or may have a short transition region in which the halogen composition changes gradually. The position of the silver bromide localized phase can be confirmed by observation with an electron microscope or the method described in EP-A-273430A2.

Various methods can be used to form such a silver bromide localized phase. For example, a soluble silver salt and a soluble halogen salt can be reacted by a one-sided mixing method or a simultaneous mixing method to form a localized phase. Further, the localized phase can be formed also by using a so-called conversion method including a process of converting already formed silver halide into silver halide having a smaller solubility product. Alternatively, a localized phase can be formed by adding silver bromide fine particles and recrystallizing the surface of silver chloride particles. For these manufacturing methods,
For example, it is described in the aforementioned European Patent Application 273430A2.

In the localized phase of the silver halide grain of the present invention or its substrate, a metal ion different from silver ion (for example, VI
It is preferable to include a group II metal ion, a group II transition metal ion, a lead ion, a thallium ion) or a complex ion thereof, from the viewpoint of further improving the effects of the present invention.

Iridium ion, rhodium ion, iron ion, etc., mainly in the localized phase, osmium,
A metal ion selected from iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron and the like or a complex ion thereof can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate.

In order for the metal ion to be contained in the localized phase of silver halide grains and / or other grain portions (substrates),
The metal ion may be added to the preparation liquid before grain formation, during grain formation, or during physical ripening. For example, metal ions can be added to an aqueous gelatin solution, an aqueous halide solution, an aqueous silver salt solution, or other aqueous solution to form silver halide grains.

Alternatively, it is also possible to incorporate metal ions into silver halide fine grains in advance, add them to a desired silver halide emulsion, and dissolve the fine grain silver halide to introduce metal ions. This method is particularly effective for introducing metal ions into the silver bromide localized phase on the surface of silver halide grains. The addition method can be appropriately changed depending on where in the silver halide grain the metal ion is present.

In particular, the localized phase is preferably deposited together with at least 50% of the total iridium added during the preparation of the silver halide grains.

Here, the term “precipitating the localized phase together with iridium ions” means that the iridium compound is supplied simultaneously with, immediately before, or immediately after the supply of silver and / or halogen for forming the localized phase. Say.

The silver halide grains according to the present invention have (10
It is preferable that the substrate has a (0) plane, a (111) plane, or both, and further includes a higher-order plane. Used.

The shape of the silver halide grains used in the present invention has a regular crystal form such as a cube, a tetradecahedron and an octahedron, and an irregular shape such as a sphere and a plate. Some have a irregular crystal type, or have a complex form of these crystal forms. Further, it can be used even if it is composed of a mixture of particles of various crystal forms, but among them, 50% of the particles having the above-mentioned regular crystal form can be used.
The content is preferably 70% or more, more preferably 90% or more. Silver halide emulsion used in the present invention,
Tabular grains having an average aspect ratio (length / thickness ratio) of 5 or more, particularly preferably 8 or more, account for 50% of the total projected area of the grains.
An emulsion occupying the above may be used.

The size of the silver halide grains according to the present invention may be within the range generally used, but the average grain size is 0.1 μm to 1.5 μm.
m is preferred. The particle size distribution may be polydisperse or monodisperse, but monodisperse is preferable. The particle size distribution representing the degree of monodispersion has a statistical variation coefficient (a value S / d obtained by dividing the standard deviation S when the projected area is approximated by a circle and divided by the diameter d) of preferably 20% or less, and 15% or less. Is more preferred.

Further, two or more of such tabular grain emulsions and monodispersed emulsions may be mixed. When emulsions are mixed, at least one of them preferably has the above-mentioned coefficient of variation, and more preferably the coefficient of variation of the mixed emulsion satisfies the above range of values.

The so-called substrate portion other than the localized phase of the silver halide grains used in the present invention may have a different phase between the inside and the surface layer, or may have a uniform phase.

The silver halide emulsion used in the present invention is usually one subjected to physical ripening, chemical ripening and spectral sensitization. Regarding the chemical sensitizer used for chemical ripening, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column, and for the spectral sensitizer, Those described in the upper right column of page 22 to page 38 of the same publication are preferably used.

Further, as the antifoggant or stabilizer used during the production or storage of the silver halide emulsion used in the present invention, those described in the right-hand column on pages 39 to 72 of the same publication are preferably used.

Examples of the magenta coupler used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. 5-pyrazolone couplers are preferably couplers in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. Representative examples are U.S. Pat. Nos. 2,311,082 and 2,343,703.
No. 2,600,788, No. 2,908,573, No. 3,062,65
No. 3, No. 3,152,896 and No. 3,936,015. As a leaving group for a 2-equivalent 5-pyrazolone-based coupler, a nitrogen atom leaving group described in US Pat. No. 4,310,619 or US Pat. No. 4,351,897, International Publication No. W
The arylthio groups described in O88-0479 are preferred.
In addition, a compound having a ballast group described in European Patent No. 73,636.
-High color density can be obtained with pyrazolone couplers.

Pyrazoloazole-based couplers include U.S. Pat.
Pyrazolobenzimidazoles described in US Pat. No. 369,879, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3,725,067, Research Disclosure 24220 (June 1984). Pyrazolotetrazole described and Research Disclosure 24
The pyrazolopyrazoles described in 230 (June 1984) can be mentioned. Any of the couplers described above may be a polymer coupler.

These compounds are specifically represented by the following general formula (M-
1), (M-2) or (M-3).

Here, R ³¹ represents a diffusion-resistant group having a total carbon number of 8 to ³² , and R ³² represents a phenyl group or a substituted phenyl group. R ³³ represents a hydrogen atom or a substituent. z represents a group of non-metal atoms necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring).

X ² represents a hydrogen atom or a leaving group. Column 2, line 41 - column 8 of substituents and for more substituents azole ring, for example, US Patent 4,540,654 Pat of R ³³ 27
Are listed in a row.

Among the pyrazoloazole couplers, U.S. Pat.
The imidazo [1,2-b] pyrazoles described in 500,630 are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in U.S. Pat. No. 4,540,654 are particularly preferred.

In addition, a pyrazolotriazole coupler in which a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2,3 or 6-position of a pyrazolotriazole ring, JP-A-61-652.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A No. 46, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254, and European It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in Japanese Patent No. 226,849.

 Specific examples of these couplers are listed below.

These couplers can be contained in the emulsion layer dispersed together with at least one high boiling point organic solvent.
Preferably, a high boiling point organic solvent represented by the following formulas (A) to (E) is used.

Formula (A) Formula (B) W ¹ -COO-W ² Formula (C) Formula (D) Formula (E) W ¹ —O—W ² (wherein W ¹ , W ² and W ³ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group; W ⁴ represents W ^1, OW ¹ or S-W ^1, n is a number from 1 to 5, n is 2
In the above case, W ⁴ may be the same as or different from each other, and in the general formula (E), W ¹ and W ² may form a condensed ring). It can be impregnated with a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence or absence of a solvent, or dissolved in a water-insoluble and organic solvent-soluble polymer to be emulsified and dispersed in an aqueous hydrophilic colloid solution. . The homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO88 / 00723 are preferably used, and the use of an acrylamide polymer is particularly preferable in terms of color image stabilization and the like.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, as an organic anti-fading agent for cyan, magenta and / or yellow images, hydroquinones,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Typical examples are hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating and alkylating the phenolic hydroxyl groups of these compounds. Can be mentioned. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of organic anti-fading agents are described in the specifications of the following patents.

Hydroquinones are U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
728,659, 2,732,300, 2,735,765, and
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No. 2, U.S. Patent Nos. 2,710,801 and 2,816,028,
6-hydroxychromans, 5-hydroxycoumarans and spirochromans are described in U.S. Pat. No. 3,432,300
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP-A-52-152225 and the like, spiroindanes in U.S. Pat.No. 4,360,589, p-alkoxyphenols in U.S. Pat. British Patent No. 2,06
6,975, JP-A-59-10539, JP-B-57-19765, etc., hindered phenols are described in U.S. Pat.
No. 5, JP-A-52-72224, U.S. Pat.No. 4,228,235, Japanese Patent Publication No. 52-6623, etc., gallic acid derivatives, methylenedioxybenzenes, aminophenols U.S. Pat.Nos. 3,457,079 and 4,332,886, respectively. , Japanese Patent Publication No. 56-21144, hindered amines are U.S. Pat. No. 3,336,135,
No. 4,268,593, British Patent No. 1,326,889, No. 1,354,
No. 313, No. 1,410,846, Japanese Patent Publication No. 51-1420, Japanese Patent Laid-Open No. 58-
114036, 59-53846, 59-78344 and the like, the metal complex, U.S. Pat.Nos. 4,245,018, 4,684,603, 4,
050,938, 4,241,155, British Patent 2,027,731
(A) and the like, respectively. These compounds can achieve their purpose by adding 5 to 100% by weight, based on the corresponding color coupler, to the photosensitive layer, usually by co-emulsifying the coupler with the coupler. In order to prevent the cyan dye image from deteriorating due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into both layers adjacent to the cyan coloring layer.

The photosensitive material prepared using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat.No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat.Nos. 3,314,794 and 3,352,681), benzophenone compounds (for example, Kaisho
46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat.Nos. 3,705,805 and 3,707,375), bradiene compounds (for example, U.S. Pat. No. 4,045,
229) or a benzooxide compound (eg, as described in US Pat. No. 3,700,455)
Can be used. An ultraviolet absorbing coupler (for example, an α-naphthol-based cyan dye forming coupler), an ultraviolet absorbing polymer, or the like may be used. These ultraviolet absorbers may be mordanted to a specific layer.

The photosensitive material prepared according to the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As a binder or protective colloid which can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin may be lime-treated,
It may be either treated with an acid or not. Details of the method for producing gelatin are described in Arthur Weiss, The Macromolecular Chemistry of Gelatin, (Academic Press, 1964).

As the support used in the present invention, a transparent film such as a cellulose nightlace film or polyethylene terephthalate, which is generally used in a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of reflective supports is more preferred.

The "reflective support" used in the present invention means one which enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clear. Examples include those coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light-reflecting substance dispersed therein as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or in combination with a reflective material, such as a glass plate, polyethylene terephthalate, polyester film of cellulose triacetate or cellulose nitrate, polyamide There are films, polycarbonate films, polystyrene films, vinyl chloride resins, etc.
These supports can be appropriately selected depending on the purpose of use.

As the light-reflecting substance, a white pigment should be sufficiently kneaded in the presence of a surfactant, and the surface of the pigment particles should not be mixed.
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) per defined unit area of the white pigment fine particles is most typically obtained by dividing the observed area into adjacent 6 μm × 6 μm unit areas and projecting the unit area. It can be determined by measuring the occupied area ratio (%) (R _i ) of the fine particles. The coefficient of variation of the occupied area ratio (%) is the ratio of the standard deviation s of R _{i to} the average value of R _i () s /
Can be sought by. The number (n) of the target unit areas is preferably 6 or more. Therefore, the coefficient of variation s / is Can be sought by.

In the present invention, the occupied area ratio (%) of the fine particles of the pigment
Is preferably 0.15 or less, particularly preferably 0.12 or less. 0.08
In the following cases, the dispersibility of particles can be said to be “uniform”.

The color photographic light-sensitive material of the present invention is preferably subjected to a coloring phenomenon, bleach-fixing, and washing treatment (or stabilizing treatment). Bleaching and fixing may be performed separately instead of the one bath as described above.

In the case of continuous processing, it is desirable that the replenishment amount of the developer is small from the viewpoint of resource saving and low pollution.

The preferred amount of replenishing color developer is 1 m ^{2 of} light-sensitive material
200ml or less. More preferably, it is 120 ml or less.
More preferably, the volume is 100 ml or less. However, the replenishing amount here indicates the amount of replenishment of the so-called color developing replenisher, and the amount of an additive or the like for correcting deterioration with time or concentration is outside the replenishing amount. Here, the additive refers to, for example, water for diluting concentration, a preservative which is susceptible to deterioration with time, or an alkali agent for increasing pH.

The color developing solution applied to the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used.
-Methyl-4-amino-N, N-diethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p
-Toluenesulfonate and the like. Two or more of these compounds can be used in combination depending on the purpose.

Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazites, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Preservatives, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines, dye-forming couplers, competitive couplers, sodium boron hydride and the like. Fogging agent, auxiliary developing agent such as 1-phenyl-3-pyrazolidone, viscosity-imparting agent, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ,ethylene Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1
Representatives of diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof Examples can be given.

When the reversal process is performed, color development is usually performed after black-and-white development. This black-and-white developer contains dihydroxybenzenes such as hydroquinone and 1-phenyl-3.
Known black-and-white developing agents such as 3-pyrazolidones such as -pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 l or less per square meter of the light-sensitive material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the treatment layer with air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
Fixing before bleach-fixing or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Examples of the bleaching agent include iron (III) and cobalt (II
Compounds of polyvalent metals such as I), chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used.
Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. . Among them, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salt and persulfate are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually from 5.5 to 8, but the processing can be carried out at a lower pH to speed up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: U.S. Patent No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,
988, JP-A-53-32736, JP-A-53-57831, and JP-A-53-37418
No. 53, No. 53-72623, No. 53-95630, No. 53-95631, No. 53
-104232, 53-124424, 53-141623, 53-2842
No. 6, Research Disclosure No. 17,129 (1978
Compounds having a mercapto group or a disulfide group described in JP-A No. 50-140129; JP-B-45-8506; JP-A-52-20832;
No. 53-32735, thiourea derivatives described in U.S. Pat. Oxyethylene compounds; JP-B-45-8836
Polyamine compounds described in JP-A-49-42434,
No. 49-59644, No. 53-94927, No. 54-35727, No. 55-265
Compounds described in No. 06 and No. 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect,
Especially U.S. Patent No. 3,893,858, West German Patent No. 1,290,812,
The compounds described in JP-A-53-95630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodide salts, and the use of thiosulfates is common.
In particular, ammonium thiosulfate can be used most widely.
As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and
Television Engineers Vol. 64, pp. 248-253 (5 May 1955)
Month issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in Japanese Patent Application No. 131632/1986 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry and antifungal chemistry", It is also possible to use the bactericides described in "Microbial Sterilization, Sterilization, and Antifungal Techniques" edited by the Sanitary Technology Association and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to
9, preferably 5 to 9. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilizing process, the method disclosed in
All known methods described in Nos. 57-8543, 58-14834, and 60-220345 can be used.

Further, after the water washing treatment, a stabilization treatment may be further performed. As an example, a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photography, can be mentioned. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, U.S. Patent No. 3,342,597
No. 3,342,599, indoaniline compounds described in No.
Research Disclosure No. 14,850 and 15,159
Examples thereof include the Schiff base type compounds described in JP-A No. 13924/1983, the aldol compounds described in JP-A-13924, the metal salt complexes described in US Pat. No. 3,719,492, and the urethane compounds described in JP-A-53-135628.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.
No. etc.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality and improves the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

In order to fully exhibit the excellent characteristics of the silver halide photographic light-sensitive material of the present invention, 2 minutes and 30 seconds in a color developer containing substantially no benzyl alcohol and containing bromine ions in an amount of 0.002 mol / l or less. It is preferable to perform processing in the following developing time.

"Substantially free of benzyl alcohol" as described above
Means 2 ml or less, preferably 0.5 ml or less, and most preferably none at all per color developer.

EXAMPLES Hereinafter, the present invention will be described based on specific examples, but the present invention is not limited thereto.

[Example 1] Silver halide emulsion (1) of blue-sensitive silver halide emulsion layer
Was prepared as follows.

(1st solution) H ₂ O 1000ml NaCl 8.8 g Gelatin 25 g (2nd solution) Sulfuric acid (1N) 20 ml (3rd solution) The following compound (1%) 3 ml (4 solutions) KBr 14.01g NaCl 1.72g H ₂ O added 130 ml (5 solutions) AgNO ₃ 25 g H ₂ O added 130 ml (6 solutions) KBr 56.03g NaCl 6.88g K ₂ IrCl ₆ (0.001) %) 1.0 ml H ₂ O was added to 285 ml (7 solution) AgNO ₃ 100 g NH ₄ NO ₃ (50%) 2 ml H ₂ O was added to 285 ml (1 solution) to 75 ° C., and ( (Part 2) and (Part 3) were added. Then, (4 solution) and (5 solution) were added simultaneously spending 40 minutes. After a further 10 minutes, (6 solution) and (7 solution) were added simultaneously spending 25 minutes. Five minutes after the addition, the temperature was lowered and the mixture was desalted. Add water and dispersed gelatin, adjust pH to 6.2, average particle size 1.01 μm, coefficient of variation (standard deviation divided by average particle size; s / d) 0.08 Monodisperse cubic salt of 80 mol% silver bromide A silver bromide emulsion (1) was obtained. This emulsion was optimally chemically sensitized with triethylthiourea.

The silver halide emulsion (2) of the blue-sensitive silver halide emulsion layer, the silver halide emulsions (3) and (4) of the green-sensitive silver halide emulsion layer and the silver halide emulsion of the red-sensitive silver halide emulsion layer ( 5) and (6) were prepared in the same manner by changing the amount of chemicals, the temperature and the addition time.

The shapes, average grain sizes, halogen compositions and variation coefficients of the silver halide emulsions (1) to (6) are as shown below.

On a paper support laminated on both sides with polyethylene,
A multilayer color photographic light-sensitive material having the following layer structure was prepared. The coating liquid was prepared as follows.

Preparation of 1st layer coating solution 19.1 g of yellow coupler (Y-15) and 0.46 g of antifoggant (Cpd-2) were added to 27.2 cc of ethyl acetate and solvent (So.
lv-1) 3.8cc and solvent (Solv-2) 3.8cc are added and dissolved,
Add this solution to 10% sodium dodecylbenzene sulfonate.
It was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc.
On the other hand, silver halide emulsion (1) and silver halide emulsion (2)
A blue-sensitizing sensitizing dye shown below was added to the 6: 4 mixed emulsion of 5.0 × 10 ⁻⁴ mol per mol of silver to prepare a mixture. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating liquid for the first layer having the composition shown below.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a gelatin hardening agent for each layer, 1-oxy-3,5-
Dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dye in each layer.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1.2 × 10 ^-2 mol, 1.1 × 10
^-2 mol was added.

Further, to the green-sensitive emulsion layer, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added at 1.0 × 10 ⁻³ mol per mol of silver halide.

Further, to the red-sensitive emulsion layer, 2-amino-5-mercapto-1,3,4-thiadiazole was added in an amount of 3.0 × 10 ^-4 mol per mol of silver halide.

The following dyes were used as the anti-irradiation dye.

and The composition of each layer is shown below. The numbers indicate the application amount (g / m ² )
The silver halide emulsion represents the coating amount in terms of silver.

(Layer structure) Support Paper support laminated on both sides with polyethylene [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (blue-sensitive layer) Silver halide emulsion (1) + (2) 0.26 Gelatin 1.20 Yellow coupler (Y-15) 0.66 Antifoggant (Cpd-2) 0.02 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13 Second layer (color mixing prevention layer) Gelatin 1.34 Anti-color mixing agent (Cpd-3) 0.04 Solvent (Solv-3) 0.10 Solvent (Solv-4) 0.10 Third layer (green sensitive layer) Silver halide emulsion (3) + (4) 0.14 Gelatin 1.30 Magenta coupler (ExM ) 0.27 Color image stabilizer (Cpd-5) 0.16 Anti-stain agent (Cpd-8) 0.025 Anti-stain agent (Cpd-9) 0.032 Solvent (Solv-3) 0.21 Solvent (Solv-5) 0.33 Fourth layer (UV absorption) Layer) Gelatin 1.44 UV absorber (UV-1) 0.53 Color mixture inhibitor (Cpd-2) 0.05 Solvent (Solv-2) 0.26 Fifth layer (red sensitive layer) Silver halide emulsion (5) + (6) 0.20 Gelatin 0.89 Cyan coupler (C-5) 0.13 Cyan coupler (C-4) 0.16 Color image stabilizer ( Cpd-1) 0.27 Color image stabilizer (Cpd-6) 0.07 Antifoggant (Cpd-2) 0.01 Solvent (Solv-1) 0.19 Sixth layer (UV absorbing layer) Gelatin 0.47 UV absorber (UV-1) 0.17 Solvent (Solv-2) 0.08 Seventh layer (protective layer) Gelatin 1.25 Polyvinyl alcohol acrylic 0.05 Modified copolymer (Modification degree 17%) Liquid paraffin 0.02 (Solv-2) solvent _{O = PO-C 9 H 19} -iso) 3 The above photosensitive material was exposed through an optical wedge and processed in the following steps. Processing process temperature Time Color development 37 ° C 3 minutes 30 seconds Bleach fixing 33 ° C 1 minute 30 seconds Water washing 24-34 ° C 3 minutes Drying 70-80 ° C 1 minute The composition of each processing solution is as follows. Color developer Water 800 ml Diethylenetriaminepentaacetic acid 1.0 g Nitrilotriacetic acid 2.0 g Benzyl alcohol 15 ml Diethylene glycol 10 ml Sodium sulfite 2.0 g Potassium bromide 1.0 g Potassium carbonate 30 g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulphate 4.5g Hydroxylamine sulphate 3.0g Optical brightener (WHITEX4B, Sumitomo Chemical Co., Ltd.) 1.0g Add water to 1000 ml pH (25 ° C) 10.25 Bleach fixer Water 400 ml Thio Ammonium sulfate (70%) 150 ml Sodium sulfite 18 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Water was added to 1000 ml pH (25 ° C) 6.70 Sample 1A obtained in this way was designated as the yellow of the first layer. Other samples were prepared in the same manner as Sample 1A except that the coupler and the additives (50 mol% relative to the coupler) were combined as shown in Table 1.

Each sample on which a dye image was formed in this way was exposed to a xenon tester (illuminance: 200,000 lux) for 8 days, and the residual density of yellow at an initial density of 1.0 was shown as a percentage.

Further, in order to examine the heat resistance, the dye residual rate at an initial density of 1.0 at a yellow density of 400 hours at 100 ° C. is shown as a percentage.
The obtained results are shown in Table 1. Macbeth densitometer
Performed with RD-514 type (status, AA filter).

From these results, it is understood that the compound of the present invention is extremely effective in preventing the photobleaching of the color image as compared with the comparative compound.
Not only that, but it also has an excellent effect on preventing thermal fading.

[Example 2] Silver halide emulsion (1) of blue-sensitive silver halide emulsion layer
Was prepared as follows.

(1st solution) H ₂ O 1000cc NaCl 5.8 g Gelatin 25 g (2nd solution) Sulfuric acid (1N) 20cc (3rd solution) The following compound (1%) 3cc (4 solution) KBr 0.18g NaCl 8.51g H ₂ O added 130cc (5 solution) AgNO ₃ 25g H ₂ O added 130cc (6 solution) KBr 0.70g NaCl 34.05g K ₂ IrCl ₆ (0.001%) 2cc H ₂ O was added and 285 cc (7 liquid) AgNO ₃ 100 g H ₂ O was added and 285 cc (1 liquid) was heated to 60 ° C., and (2 liquid) and (3 liquid) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 60 minutes. 10 minutes after the addition of (liquid 4) and (liquid 5),
(Sixth solution) and (Sixth solution) were simultaneously added over 25 minutes. Five minutes after the addition, the temperature was lowered and the mixture was desalted. Add water and dispersed gelatin, adjust pH to 6.0, average particle size 1.0 μm, coefficient of variation (standard deviation divided by average particle size; s /)
A monodisperse cubic silver chlorobromide emulsion containing 0.11 and 1 mol% of silver bromide was obtained. Triethylthiourea was added to this emulsion to perform optimum chemical sensitization. After that, the following spectral sensitizing dye (Se
n-1) was added in an amount of ^{7.times.10.sup.-4} mol per mol of the silver halide emulsion.

Silver halide emulsion in green-sensitive silver halide emulsion layer (2)
Also, the silver halide emulsion (3) in the red-sensitive silver halide emulsion layer was prepared in the same manner by changing the chemical amount, temperature and addition time.

For the silver halide emulsion (2), a spectral sensitizing dye (Sen
-2) was added in an amount of 5 × 10 ^-4 mol per mol of the emulsion, and a spectral sensitizing dye (Sen-3) was added to the silver halide emulsion (3).
^Was added in an amount of 0.9 × 10 ^-4 mol per mol of the emulsion.

The shapes, average grain sizes, halogen compositions and variation coefficients of the silver halide emulsions (1) to (3) are as shown below.

Using the prepared silver halide emulsions (1) to (3),
A multilayer color photographic light-sensitive material having the following layer structure was prepared. The coating liquid was prepared as follows.

1st layer coating liquid preparation Yellow coupler (Y-15) 19.1g to ethyl acetate 27.2c
c and 3.8 cc of solvent (Solv-1) were added and dissolved, and this solution was emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, a blue-sensitive sensitizing dye (Sen-1) was added to the silver halide emulsion (1) in an amount of 5.0 × 10 ^-4 mol per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating liquid for the first layer having the composition shown below.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a gelatin hardening agent for each layer, 1-oxy-3,5-
Dichloro-s-triazine sodium salt was used.

The following compounds were added to the red-sensitive emulsion layer in an amount of 1.9 × 10 ⁻³ mol per mol of silver halide.

Further, to the blue-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1.0 × 10 ^-2 mol per mol of silver halide.

For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 1-
(5-methylureidophenyl) -5-mercaptotetrazole was added at 1.0 × 10 ⁻³ mol per mol of silver halide;
1.5 × 10 ⁻³ mol was added.

Further, to the red-sensitive emulsion layer, 2-amino-5-mercapto-1,3,4-thiadiazole was added in an amount of 2.5 × 10 ^-4 mol per mol of silver halide.

The composition of each layer is shown below. The abbreviations and structural formulas of the respective compounds are the same as in Example 1.

(Layer constitution) Support Paper support laminated on both sides with polyethylene [White pigment (TiO ₂ ) on the polyethylene of the first layer (2.7 g
/ m ² ) and bluish dye (ultraviolet)] First layer (blue sensitive layer) Silver halide emulsion (1) 0.26 Gelatin 1.13 Yellow coupler (Y-15) 0.66 Solvent (Solv-4) 0.28 Second layer (Anti-color mixing layer) Gelatin 0.89 Anti-color mixing agent (Cpd-3) 0.08 Solvent (Solv-4) 0.20 Solvent (Solv-3) 0.20 Dye (T-1) 0.005 Third layer (Green-sensitive layer) Silver halide emulsion ( 2) 0.15 Gelatin 0.51 Magenta coupler (ExM) 0.27 Color image stabilizer (Cpd-5) 0.10 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Solvent (Solv-3) 0.19 Solvent ( Solv-5) 0.15 Fourth layer (ultraviolet absorbing layer) Gelatin 1.42 Ultraviolet absorber (UV-1) 0.52 Color mixture inhibitor (Cpd-3) 0.06 Solvent (Solv-2) 0.26 Dye (T-2) 0.015 Fifth layer (Red-sensitive layer) Silver halide emulsion (3) 0.22 Gelatin 1.06 Cyan coupler (C-1) 0.37 Color image stabilizer (Cpd-1) 0.32 color Image stabilizer (Cpd-6) 0.18 Solvent (Solv-2) 0.10 Solvent (Solv-7) 0.10 Solvent (Solv-6) 0.11 Sixth layer (UV absorbing layer) Gelatin 0.48 UV absorber (UV-1) 0.18 Solvent (Solv-2) 0.08 Dye (T-2) 0.005 Seventh layer (protective layer) Gelatin 1.33 Polyvinyl alcohol acrylic 0.05 Modified copolymer (Modification degree 17%) Liquid paraffin 0.03 The above photosensitive material was exposed through an optical wedge and processed in the following steps. Treatment process temperature Time Color development 35 ℃ 45 seconds Bleach fixing 35 ℃ 45 seconds Water wash 35 ℃ 30 seconds Water wash 35 ℃ 30 seconds Water wash 35 ℃ 30 seconds Dry 75 ℃ 60 seconds Color developer water 800ml Ethylenediamine-N, N, N ', N'-Tetramethylenephosphonic acid 3.0g Triethanolamine 8.0g Sodium chloride 1.4g Potassium carbonate 25g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.0g N, N-bis (carboxymethyl) hydrazine 5.0g Optical brightener (WHITEX4, Sumitomo Chemical Co., Ltd.) 1.0g Water added 1000 ml pH (25 ° C) 10.05 Bleach-fixing solution Water 700 ml Ammonium thiosulfate solution (700 g / l) 100 ml Ammonium sulfite 18 g Ethylenediaminetetraacetic acid ferric ammonium dihydrate 55 g Ethylenediaminetetraacetic acid disodium salt 3 g Ammonium bromide 40 g Glacial acetic acid 8 g Water is added 1000 ml pH (25 5.5) Water washing solution Tap water was treated with ion exchange resin to reduce calcium and magnesium to 3 ppm or less, respectively (conductivity at 25 ° C was 5 µs / cm).

The sample thus obtained was designated as sample 2A, and was the same as sample 2A except that the yellow coupler and the additive [color image stabilizer] (100 mol% based on the coupler) of the first layer were combined as shown in Table 2. Then, another sample was prepared.

Each sample thus formed with a dye image was exposed to a fluorescent lamp fading device (illuminance: 15,000 lux) for 4 weeks to perform a fading test, and the density residual ratio at an initial yellow density of 1.0 was shown as a percentage.

Further, the maximum reflection density (Dmax) of the yellow density is measured, and the ratio to the value when the density of the color image stabilizer-free level is 100 is shown in Table 2 together with the results of the fading test.

From these results, it can be seen that the compound of the present invention does not deteriorate the coupler's color developing property as compared with the comparative compound and is extremely effective in preventing photofading.

[Example 3] Except that the cyan coupler and the additive [color image stabilizer] (100 mol% additional addition to the coupler) of the fifth layer of the sample 2A of Example 2 were combined as shown in Table 3. Another sample was prepared in the same manner as sample 2A.

The density residual ratio at the initial cyan density of 1.0 after 12 days of exposure of each sample thus formed with a dye image with a xenon tester (illuminance: 200,000 lux) is shown in percentage.

Further, in order to investigate the resistance to moist heat, the dye residual rate at an initial cyan density of 2.0 when stored at 60 ° C. and 70% RH for 6 weeks is shown as a percentage. The results obtained are shown in Table 3.

From these results, it can be seen that the compound of the present invention is extremely effective in preventing the photobleaching of a color image as compared with the comparative compound. It is also understood that not only that, but it also has an excellent effect on prevention of heat and heat discoloration.

[Example 4] The yellow couplers of the samples 2A, 2B, 2C, 2D, 2E, 2L, 2M, 2N, and 2Q of Example 2 were replaced with Y-5, Y-13, Y-14, and Y.
When the same bleaching test as in Example 2 was conducted in place of -20 and Y-27, the compound of the present invention showed an extremely excellent fading preventing effect.

[Example 5] 2A, 3C, 3D, 3G, 3I, 3P, 3R, and 3S of Example 3 were replaced with cyan couplers C-2, C-5, C-7, and C-18, respectively.
When C-22, C-25, C-26, C-32 and C-34 were used and the same treatment and fading test as in Example 3 were carried out, the compound of the present invention showed an extremely excellent fading prevention effect. .

[Effect of the Invention] In the silver halide color photographic light-sensitive material of the present invention, the compound represented by the general formula [I] is contained in at least one of the cyan dye image forming layer or the yellow dye image forming layer and its adjacent layer. Therefore, the quality preservation of photographic images is extremely excellent.

The silver halide color photographic light-sensitive material of the present invention does not exhibit color developability, and the obtained dye image exhibits extremely high fastness to light, heat or humidity.

Claims (2)

(57) [Claims] 1. A silver halide color photographic light-sensitive material characterized in that a cyan dye image-forming layer on a support contains at least one compound represented by the following general formula [I]. General formula [I] [In the formula, R ₁ represents an acyl group, a sulfonyl group, a phosphonyl group, a sulfinyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkyloxycarbonyl group or an aryloxycarbonyl group, and R ₂ represents a hydrogen atom. Represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or a heterocyclic group, R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group,
It represents an alkenyl group, cycloalkenyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, phosphonyl group, sulfinyl group, alkylsulfamoyl group, arylsulfamoyl group, alkyloxycarbonyl group or aryloxycarbonyl group. However, R ₂ and R ₃ are not hydrogen atoms at the same time. R ₁ and R ₂ are bonded to each other,
A 5- to 8-membered heterocycle may be formed with a nitrogen atom (provided that a heterocycle in which a nitrogen atom and a sulfonyl group or a sulfinyl group are bonded via an alkylene group is excluded), R ₁ and R ₂
And the total number of carbon atoms of R ₃ is 8 or more, and X represents an oxygen atom or a sulfur atom. ] 2. A silver halide color photographic light-sensitive material characterized in that a yellow dye image-forming layer on a support contains at least one compound represented by the following general formula [I]. General formula [I] [In the formula, R ₁ represents an acyl group, a sulfonyl group, a phosphonyl group, a sulfinyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkyloxycarbonyl group or an aryloxycarbonyl group, and R ₂ represents a hydrogen atom. Represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or a heterocyclic group, R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group,
It represents an alkenyl group, cycloalkenyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, phosphonyl group, sulfinyl group, alkylsulfamoyl group, arylsulfamoyl group, alkyloxycarbonyl group or aryloxycarbonyl group. However, R ₂ and R ₃ are not hydrogen atoms at the same time. R ₁ and R ₂ are bonded to each other,
A 5- to 8-membered heterocycle may be formed with a nitrogen atom (provided that a heterocycle in which a nitrogen atom and a sulfonyl group or a sulfinyl group are bonded via an alkylene group is excluded), R ₁ and R ₂
And the total number of carbon atoms of R ₃ is 8 or more, and X represents an oxygen atom or a sulfur atom. ]