JPH07219180A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a photosensitive material containing an image forming compound releasing a novel dye and capable of forming an image improved in stability against light and sharpness of hue. CONSTITUTION:The photosensitive material put on a support contains one of the compounds represented by formula I in which Dye is a dye group or its precursor group represented by formula II or the like; X is a simple bond or a bonding group; Y is a group causing difference between the diffusivities of the dye components in accordance or reversal accordance with the reaction of photosensitive silver salt having a latent image; q is 1 or 2; R is cyano or carboxyl or the like; A is acetyl or benzoyl or the like; each of X an Y is H or cyano or the like; Q is a heterocyclic group combining with the 1- or 3-position to the azo group; n is an integer of 0 to 4; m is an integer of 0 to 3; and r is 1 or 2.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel azonaphthol dye image-forming compound and a silver halide color photographic light-sensitive material containing the same.

[0002]

Background of the Invention Color diffusion transfer photography using azo dye image-forming compounds is well known in the art, providing as a result of development under basic conditions an azo dye having a diffusivity different from the image-forming compound itself. ing. For example, as an image-forming compound that releases a cyan dye, US Pat. 3,94
2,987, US. 4,013,635, US.
4,273,708, US. No. 4,268,625.

However, the compounds shown in these prior art documents all have a nitro group at the para position of the azo group,
It has become clear that this has the drawback of being reduced and discolored during the development process. Further, generally, an azo dye having a nitro group has a photo-reducing property, so that the light fastness of an image is not good. Furthermore, when these image forming compounds are contained in the same layer as the photosensitive silver halide emulsion,
A phenomenon in which development of silver halide is suppressed may be observed, and it is presumed that the cause is probably due to a nitro group.

JP-A-53-66227 describes a cyanazo dye image forming compound having a trifluoromethanesulfonyl group at the para position of the azo group. However, in addition to the synthetic and pollution problems that the compound contains fluorine, further improvement is desired in terms of sharpness of hue and diffusibility of released dye. British Patent 1,49
No. 0,248 and JP-A-55-40402 disclose magenta azo dye image-forming compounds using a diazo component having a plurality of alkylsulfonyl groups.
In all of these, the 2-position of naphthol is unsubstituted or an electron-withdrawing group is introduced, and the hue thereof is too shortwave to be used as a cyan dye image forming compound.

Recently, a novel cyanazo image forming compound obtained by azo coupling of a diazo component having no nitro group or trifluoromethanesulfonyl group with 2-acylamino-1-naphthols has been disclosed.
-93434, JP-A-60-87134, 60-
No. 257579. The image-forming compounds described in these documents are useful as cyan dyes as compared with conventional compounds, but they have a light hue and poor color reproducibility. In addition, since the hue is light, an image forming compound has to be additionally used in order to obtain a good gray balance.

The 8-sulfamoyl-1-naphtholazo dye disclosed in Japanese Patent Laid-Open No. 3-114042 is known to overcome the above drawbacks, but further improvement in light fastness is desired. ing.

[0007]

The conventionally known azo dyes have not been found to have sufficient hue sharpness as a cyan dye and sufficient stability to light. Accordingly, an object of the present invention is to provide a cyan image forming compound having improved hue sharpness and stability to light, and to provide a silver halide color photographic light sensitive material having improved hue and stability to light. It is to be.

[0008]

DISCLOSURE OF THE INVENTION As a result of intensive studies, the present inventors have found that a silver halide color photographic light-sensitive material containing at least one azonaphthol dye image-forming compound represented by the following general formula (I). It has been found that the material effectively achieves the above-mentioned objectives and is fully capable of satisfying the drawbacks of the prior art. General formula (I)

[0009]

[Chemical 4]

In the formula, Dye represents a dye group represented by the following general formula (II) or general formula (III), or a dye precursor group, X represents a simple bond or linking group, and Y represents a latent image. It represents a group having a property of causing a difference in diffusibility of the dye component in response to or in reverse response to the reaction of the photosensitive silver salt having an image.

[0011]

[Chemical 5]

In the general formula (II) or the general formula (III), R is a cyano group, a carboxyl group, a sulfo group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (having 12 or less carbon atoms). And preferably an optionally substituted alkyl group having 8 or less carbon atoms, for example, methyl group, trifluoromethyl group, benzyl group, dimethylaminomethyl group, ethoxycarbonylmethyl group, acetylaminomethyl group, ethyl group, carboxyethyl group. , Allyl group, n-propyl group, iso-propyl group, n-butyl group, t-butyl group, t-pentyl group, cyclopentyl group, n-hexyl group, t-hexyl group, cyclohexyl group, t-octyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc.), aryl group (having 18 carbon atoms)
Hereinafter, an aryl group having preferably 10 or less carbon atoms and which may be substituted. For example, phenyl group, naphthyl group, 3-hydroxyphenyl group, 3-chlorophenyl group, 4-acetylaminophenyl group, 2-methanesulfonylphenyl group, 4-methoxyphenyl group, 4-methanesulfonylphenyl group, 2,4- Dimethylphenyl group, etc.), heterocyclic residue (heterocyclic residue having 18 or less carbon atoms, preferably 10 or less carbon atoms, which may be substituted. For example, 1-imidazolyl group, 2-furyl group, 2-pyridyl group , 3-pyridyl group, 3,5-dicyano-2-pyridyl group, 5-tetrazolyl group, 5-phenyl-1-tetrazolyl group, 2-benzthiazolyl group, 2-benzimidazolyl group, 2-benzoxazolyl group, 2-oxazolin-2-yl group, morpholino group, etc., acyl group (having 12 or less carbon atoms, preferably 8 or less carbon atoms) There acyl group. For example, an acetyl group, a propionyl group, butyloyl, is
o-butyroyl group, 2,2-dimethylpropionyl group,
Benzoyl group, 3,4-dichlorobenzoyl group, 3-acetylamino-4-methoxybenzoyl group, 4-methylbenzoyl group, etc., sulfonyl group (having 12 or less carbon atoms,
A sulfonyl group having preferably 8 or less carbon atoms and which may be substituted. For example, methanesulfonyl group, ethanesulfonyl group, chloromethanesulfonyl group, propanesulfonyl group, butanesulfonyl group, n-octanesulfonyl group,
n-dodecanesulfonyl group, benzenesulfonyl group, 4
-Methylphenylsulfonyl group etc.), alkoxy group (C 12 or less, preferably C 8 or less alkoxy group which may be substituted. For example, methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group. , A cyclohexylmethoxy group, etc.), an aryloxy group, a heteroaryloxy group (C18 or less, preferably C10 or less, optionally substituted aryloxy or heteroaryloxy group. For example, a phenoxy group,
Naphthyloxy group, 4-acetylaminophenoxy group,
Pyrimidin-2-yloxy group, 2-pyridyloxy group, etc., alkylthio group (C12 or less, preferably C8 or less, optionally substituted alkylthio group. For example, methylthio group, ethylthio group, n-butylthio group. ,
n-octylthio group, t-octylthio group, ethoxycarbonylmethylthio group, benzylthio group, 2-hydroxyethylthio group, etc.), arylthio group, heteroarylthio group (having 18 or less carbon atoms, preferably 10 or less carbon atoms, substituted) And an arylthio group or heteroarylthio group, for example, phenylthio group, 4-chlorophenylthio group, 2-n-butoxy-5-t-octylphenylthio group, 4-nitrophenylthio group, 2-nitrophenylthio group, 4-acetylaminophenylthio group, 1-phenyl-5-tetrazolylthio group, 5-methanesulfonylbenzothiazol-2-yl group, etc., carbamoyl group (having 12 or less carbon atoms, preferably 8 or less carbon atoms even if substituted) Good carbamoyl group, eg carbamoyl group, methylcarbamoyl , Dimethylcarbamoyl group, a bis -
(2-Methoxyethyl) carbamoyl group, diethylcarbamoyl group, cyclohexylcarbamoyl group, di-n-
Octylcarbamoyl group, etc.), sulfamoyl group (having 12 or less carbon atoms, preferably 8 or less carbon atoms, optionally substituted sulfamoyl group, for example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, bis- (2 -Methoxyethyl) sulfamoyl group, diethylsulfamoyl group, di-n-butylsulfamoyl group, methyl-n-octylsulfamoyl group, 3-ethoxypropylmethylsulfamoyl group, N-phenyl-
N-methylsulfamoyl group, etc., acylamino group (C 12 or less, preferably C 8 or less, optionally substituted acylamino group. For example, acetylamino group,
2-carboxybenzoylamino group, 3-nitrobenzoylamino group, 3-diethylaminopropanoylamino group, acryloylamino group, etc., sulfonylamino group (having 12 or less carbon atoms, preferably 8 or less carbon atoms, optionally substituted sulfonyl) An amino group, for example, a methanesulfonylamino group, a benzenesulfonylamino group, a 2-methoxy-5-n-methylbenzenesulfonylamino group, etc., an alkoxycarbonylamino group (having 12 or less carbon atoms, preferably 8 or less carbon atoms, substituted) Optionally alkoxycarbonylamino group, for example, methoxycarbonylamino group, ethoxycarbonylamino group, 2-methoxyethoxycarbonylamino group, iso-butoxycarbonylamino group, benzyloxycarbonylamino group, t
-Butoxycarbonylamino group, 2-cyanoethoxycarbonylamino group, etc., aryloxycarbonylamino group (C12 or less, preferably C8 or less aryloxycarbonylamino group which may be substituted. For example, phenoxycarbonylamino. Group, 2,4-nitrophenoxycarbonylamino group, 4-t-butoxyphenoxycarbonylamino group, etc., aminocarbonylamino group (C12 or less, preferably C8 or less, optionally substituted aminocarbonylamino group For example, methylaminocarbonylamino group, morpholinocarbonylamino group, diethylaminocarbonylamino group, N-ethyl-N-phenylaminocarbonylamino group, 4-cyanophenylaminocarbonylamino group, 4-methanesulfonylaminocarbonyl group. Etc. Boniruamino group), aminocarbonyl group (having 12 or less carbon atoms, preferably 8 carbon atoms
The following optionally substituted aminocarbonyloxy groups. For example, a dimethylaminocarbonyloxy group, a pyrrolidinocarbonyloxy group, and the like, an aminosulfonylamino group (having 12 or less carbon atoms, and preferably having 8 or less carbon atoms, which may be substituted. For example, a diethylaminosulfonylamino group, Di-n-butylaminosulfonylamino group, phenylaminosulfonylamino group, etc.). In formula (II) or (III), n represents an integer of 0 to 4, and when n is 2 or more, R may be different.

In the general formula (II) or the general formula (III), A represents a hydrogen atom or a group which gives a hydroxyl group under basic conditions, examples of which include an acyl group (eg, acetyl group,
Benzoyl group), G-CH ₂ CH ₂ -group (G is an electron-attracting group such as cyano group and sulfonyl group) and G-CH = CH- group (G is an electron-attracting group such as cyano group and sulfonyl group) Is.

In the general formula (II), X and Y are each a hydrogen atom, a cyano group, a carboxyl group, a sulfo group, a hydroxy group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group or an aryl group. , Heterocyclic residue, acyl group, sulfonyl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, carbamoyl group, sulfamoyl group, acylamino group, sulfonylamino group, alkoxycarbonyl Amino group, aryloxycarbonylamino group, alkoxycarbonyloxy group, aminocarbonylamino group, aminocarbonyloxy group, aminosulfonylamino group, amino group (C 12 or less, preferably 8 or less amino group which may be substituted. For example, amino group , Methylamino group, dimethylamino group, ethylamino group, ethyl-3-carboxypropylamino group, ethyl-2-sulfoethylamino group, phenylamino group, methylphenylamino group, methyloctylamino group, etc.), acyloxy group ( C12 or less,
Preferably 8 or less optionally substituted acyloxy groups.
For example, acetoxy group, benzoyloxy group, 2-butenoyloxy group, 2-methylpropanoyloxy group, etc., aryloxycarbonyloxy group (having 12 carbon atoms).
The following, preferably 8 or less, optionally substituted aryloxycarbonyloxy groups. For example, phenoxycarbonyloxy group, 3-cyanophenoxycarbonyloxy group, 4-acetoxyphenoxycarbonyloxy group, 4
-T-butoxycarbonylaminophenoxycarbonyloxy group, etc., sulfonyloxy group (having 12 or less carbon atoms, preferably 8 or less sulfonyloxy group which may be substituted. For example, phenylsulfonyloxy group, methanesulfonyloxy group, chloromethane Sulfonyloxy group, 4-chlorophenylsulfonyloxy group, dodecylsulfonyloxy group and the like). Respect R ^2, R ^3, R ⁴ and R ^5, when there is no description of examples and preferred number of carbon atoms contained in the group indicates that it is the same as in R ^1. R ² and R ³ and R ⁴ and R ⁵ may combine with each other to form a 5- to 7-membered ring. This ring may be a carbocycle or a heterocycle. X is preferably an acylamino group, and Y is preferably one having a Hammett sigma para value of 0.3 or more.

In the general formula (II), Q is a heterocyclic residue bonded to the 1- or 3-position with respect to the azo group, and examples thereof include a 1,2,3-benzotriazol-2-yl group and a benzo group. Thiazol-2-yl group, benzoxazol-2-yl group, 5-methanesulfonylaminobenzothiazol-2-yl group, 1-methylimidazol-2-
Yl group, 1-ethylbenzimidazol-2-yl group,
3-pyrazolyl group, benzimidazol-2-yl group,
Examples thereof include a 6-methylsulfonylaminobenzothiazol-2-yl group.

In the general formula (III), Ar represents an aryl group or a heteroaryl group which is not substituted with a nitro group, examples of which include 4-methanesulfonyl-2-
Cyanophenyl group, 2-chloro-4,5-dicyanophenyl group, 3,4-dicyanophenyl group, 2,4-dicyanophenyl group, 2-methanesulfonyl-4-cyanophenyl group, 2,4,5-trisia Nophenyl group, 2-chloro-4-cyanophenyl group, 2-cyano-4-phenylsulfonylphenyl group, 5-cyanopyridin-2-yl group, 3,5-dicyanopyridin-2-yl group, 5-methane Examples thereof include a sulfonylpyridin-2-yl group, a 3,5-bis (methoxycarbonyl) pyridin-2-yl group, and a 4,5-dicyano-1-methylimidazol-2-yl group.

In the general formula (III), Q represents a saturated or unsaturated heterocyclic residue bonded to a naphthalene ring at a carbon atom, and examples thereof include benzothiazol-2-yl group and benzoxazol-2-yl group. Group, 4,5-dimethylthiazol-2-yl group, 2-pyridyl group, 1-methylimidazol-2-yl group, 1-ethylbenzimidazol-2-yl group, 3-pyrazolyl group, benzimidazol-2- And a 6-methylsulfonylaminobenzothiazol-2-yl group.

In the general formula (II), m represents an integer of 0 to 3 and r represents 1 or 2. However, m + r is 4 or less. When m is 2 or more or r is 2, Y and Q may be the same or different.

In the general formula (I), q is 1 or 2, and when q is 2, Dye-X may be the same or different. The bonding position of X with respect to Dye is R in the general formula (II), X, Y or Q, R in the general formula (III),
It binds to at least one of A, Ar or Q.

In the general formula (I), X is basically D
may be bonded to any site of ye portion, the linking group is -N X represents (R ₅₎ - (R ₅ represents a hydrogen atom, an alkyl group or a substituted alkyl group) groups represented by, -SO
_2- , -CO-, an alkylene group, a substituted alkylene group, a phenylene group, a substituted phenylene group, a naphthylene group, a substituted naphthylene group, -O-, -SO- and a divalent residue of two or more thereof are obtained in combination. group is a typical example of which preferred are _{-NR 5 -SO 2 -, - NR} 5 -CO
- or _{-R 6 - (L) k -} (R 7) q - and a group represented by each alkylene group R ₆ and R _7, substituted alkylene group, a phenylene group, substituted phenylene group, a naphthylene group, a substituted naphthylene Represents a group, L is -O-, -CO
-, - SO -, - SO 2 -, - SO 2 NH -, - NHS
_{O 2 -, - CONH -,} - NHCO- represent, k represents 0 or 1, l represents 1 or 0. The -NR ₅ -SO ₂ - and -NR ₅ -CO- and -R ₆ -
_{(L) k - (R 7} ) q - a combination of a also preferred. In the general formula (I), the binding mode of Dye portion and Y portion is particularly preferably of the form of Dye-SO ₂ NH-Y.

Next, Y in the general formula (I) will be described.
Y represents a group having a property of cleaving the Y-G bond corresponding to or inversely corresponding to the photosensitive silver halide having a latent image. Such groups are known in the field of photographic chemistry utilizing diffusion transfer of dyes, and are described, for example, in US Pat. No. 5,021,334 (JP-A-2-184852).

The Y will be described in detail. The expression was described including G. (1) Examples of Y include a negative-acting releaser that releases a photographically useful group in response to development.

As Y classified into the negative-acting releaser, a releaser group releasing a photographically useful group from an oxidant is known. The following formula (Y-1) is mentioned as a preferable example of Y of this type. (Y-1)

[0024]

[Chemical 6]

In the formula, β represents a group of non-metal atoms necessary to form a benzene ring, and this benzene ring may be condensed with a saturated or unsaturated carbocycle or heterocycle. α is −
Represents OZ ² or —NHZ ³ , wherein Z ² represents a hydrogen atom or a group capable of generating a hydroxyl group by hydrolysis, Z ^2
3 represents a hydrogen atom, an alkyl group, an aryl group, or a group capable of generating an amino group by hydrolysis. Z ¹ is an optionally substituted alkyl group, aryl group, aralkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, acyl group, sulfonyl group, acylamino group, sulfonylamino group, carbamoyl group, It represents a sulfamoyl group, a ureido group, a urethane group, a heterocyclic group or a cyano group, a halogen atom, a represents a positive integer, and when Z ¹ is 2 or more, they may be the same or different. For formula (Y-1), -G is -NHS.
O ₂ Z ⁴ Z ⁴ is a group represented by represents a divalent group.

Among the groups contained in (Y-1), preferable groups include (Y-2) and (Y-3). (Y-2)

[0027]

[Chemical 7]

(Y-3)

[0029]

[Chemical 8]

In the formula, Z ² and G have the same meanings as described in (Y-1). Z ⁵ and Z ⁶ represent an alkyl group, an aryl group or an aralkyl group, and these may have a substituent. Furthermore Z
⁵ is a secondary or tertiary alkyl group, Z ⁵ and Z ⁶
It is preferable that the sum of the number of carbon atoms is 20 or more and 50 or less.

Specific examples of these are shown in US Pat. No. 4,055,4.
28, 4,336,322, JP-A-51-113.
No. 624, No. 56-16131, No. 56-71061
No. 56, No. 56-71060, No. 56-71072, No. 56-73057, No. 57-650, and No. 57-40.
No. 43, No. 59-60, 439, Japanese Patent Publication No. 56-176
56 and 60-25780.

Another example of Y is (Y-4). (Y-4)

[0033]

[Chemical 9]

In the formula, α, G, Z ¹ and a have the same meanings as described in (Y-1). β ′ represents a group of non-metal atoms necessary for forming a benzene ring, and a saturated or unsaturated carbocycle or heterocycle may be condensed to this benzene ring.

Of the groups represented by (Y-4), α is -OZ
^{It is 2} that β ′ forms a naphthalene skeleton. Specifically, US Pat. No. 3,928,312
No. 4,135,929.

Further, as releasers releasing a photographically useful group by the same reaction as in (Y-1) and (Y-2), JP-A-51-104343, JP-A-53-46730, and JP-A-53-46730.
-130122, 57-85055, 53-3
No. 819, No. 54-48534, No. 49-64436.
No. 57-20735, JP-B-48-32129
No. 48-39165, U.S. Pat. No. 3,443,93.
The groups described in No. 4 are mentioned.

The compound releasing the photographically useful group from the oxidant by another reaction mechanism is represented by the formula (Y-5) or (Y-
Examples include hydroquinone derivatives represented by 6). (Y-5)

[0038]

[Chemical 10]

(Y-6)

[0040]

[Chemical 11]

In the formula, β'is the formula (Y-4) and Z ² is the formula (Y-).
1), and Z ⁷ is the same as Z ² .
Z ⁸ represents a substituent described in Z ¹ or a hydrogen atom. Z ²
And Z ⁷ may be the same or different. Specific examples of this type are described in US Pat. No. 3,725,062.

Examples of this type of hydroquinone derivative releaser having a nucleophilic group in the molecule are also included. Specifically, it is described in JP-A-4-97347.

Another example of Y is US Pat. No. 3,44.
P-hydroxydiphenylamine derivatives described in U.S. Pat. No. 3,939, U.S. Pat. No. 3,844,785, U.S. Pat. D. The hydrazine derivative described in No. 128, page 22 may be mentioned.

Further, examples of the negative acting releaser include the following formula (Y-7). (Y-7)

[0045]

[Chemical 12]

In the formula, Coup represents a group capable of coupling with an oxidized product of p-phenylenediamines and p-aminophenols, that is, a group known as a photographic coupler. Specific examples are described in British Patent 1,330,524.

(2) Next, as Y, there can be mentioned a positive-working releaser which releases a photographically useful group in the opposite manner to development.

The positive-acting releaser may be a releaser that exhibits a function when reduced during treatment. As a preferable example of Y of this type, the following formula (Y-
8). (Y-8)

[0049]

[Chemical 13]

In the formula, EAG represents a group that receives an electron from a reducing substance. N represents a nitrogen atom, W is an oxygen atom, a sulfur atom or -NZ ¹¹ - represents the EAG is the N-W bond is cleaved after receiving electrons. Z ¹¹ represents an alkyl group or an aryl group. Z ⁹ and Z ¹⁰ represent a mere bond or a substituent other than a hydrogen atom. A solid line represents a bond, and a broken line represents that at least one of them is bonded.

Preferred among the groups represented by (Y-8) is the formula (Y-9). (Y-9)

[0052]

[Chemical 14]

In the formula, O represents an oxygen atom (that is, (Y-8)).
W is an oxygen atom), and Z ¹² represents an atomic group having a property of forming a heterocycle containing an N—O bond and being cleaved by the Z ¹² —G bond following the cleavage of the N—O bond. Z ¹² may have a substituent and a saturated or unsaturated ring may be condensed. Z ¹³ represents -CO- or -SO ₂ - represents a.

(Y-9) is a more preferable group of (Y-9). (Y-10)

[0055]

[Chemical 15]

In the formula, Z ¹⁴ represents an alkyl group, an aryl group or an aralkyl group, Z ¹⁵ represents a carbamoyl group or a sulfamoyl group, Z ¹⁶ represents an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkylthio group or an aryloxy group. Represents a group, an arylthio group, a halogen atom, a cyano group, and a nitro group, and b represents an integer of 0 to 3. The substitution position of the nitro group in the formula is ortho or para to the nitrogen atom. It is most preferable that Z ¹⁵ is a carbamoyl group or a sulfamoyl group substituted with an alkyl group having 12 to 30 carbon atoms.

A specific example of Y of this type is disclosed in JP-A-62-2.
15,270, U.S. Pat. No. 4,783,396.

As another positive-acting releaser which exhibits a function by being reduced, BEND compounds described in US Pat. Nos. 4,139,379 and 4,139,389, and British Patent 11,445. Listed in Car
quin compound, JP-A-54-126535, JP-A-57.
The releaser of No. 84453 is mentioned.

When these reducible releasers represented by Y represented by (Y-8) are used, a reducing agent is used in combination, but an LD containing a reducing group in the same molecule is used.
A compound is also mentioned. This is US Pat. No. 4,551,4
No. 23 describes.

There is also a type of positive-working releaser that is incorporated as a reductant in a light-sensitive material and deactivates when oxidized during processing. As this type of releaser, Japanese Patent Laid-Open No. 51-63618 and US Pat.
Fields compounds described in Japanese Patent No. 79 and JP-A-49-1116
28, 52-4819, U.S. Pat. No. 4,199,3.
Hinshaw compounds described in No. 54 are mentioned.

An example of this type of Y is (Y-11). (Y-11)

[0062]

[Chemical 16]

In the formula, Z ¹⁷ and Z ¹⁹ represent a hydrogen atom or a substituted or unsubstituted acyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and Z ¹⁸ represents an alkyl group, an aryl group, an aralkyl group, an acyl group or an alkoxycarbonyl group. Group, aryloxycarbonyl group, carbamoyl group, sulfonyl group, sulfamoyl group, Z ²⁰ , Z
²¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, or aralkyl group. Specifically, JP-A-62
-245,270 and 63-46450.

A thiazolidine type releaser may be mentioned as a positive-acting releaser having another mechanism. Specifically, it is described in U.S. Pat. No. 4,468,451.

Specific examples of the compound of formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

[0066]

[Chemical 17]

[0067]

[Chemical 18]

[0068]

[Chemical 19]

[0069]

[Chemical 20]

[0070]

[Chemical 21]

[0071]

[Chemical formula 22]

[0072]

[Chemical formula 23]

[0073]

[Chemical formula 24]

[0074]

[Chemical 25]

[0075]

[Chemical formula 26]

Next, the synthetic method of the compound used in the present invention will be described. A specific synthesis example will be shown. Exemplified compounds I-II- (2) and I-II- (9) were synthesized by the following routes.

[0077]

[Chemical 27]

[0078]

[Chemical 28]

[0079]

[Chemical 29]

Imaging Compounds I-II- (2) and I-II-
Synthesis of (9) Synthesis of intermediate (b) 350 g of intermediate (a) was added to 700 ml of chlorosulfonic acid with stirring at room temperature over 30 minutes. The reaction mixture was stirred at 120 ° C. for 1 hour and 180 ° C. for 3 hours and then allowed to cool. After standing overnight, the reaction mixture was poured into 3 liters of ice water with stirring. After stirring at the same temperature for 2 hours, the precipitated crystals were collected by filtration, washed with water, and dried to obtain 360 g of intermediate (b).

Synthesis of Intermediate (c) Anhydrous aqueous sodium sulfite solution (Na ₂ SO ₃ 307 g /
Intermediate in water (1160 ml) over 1 hour with stirring
(b) 310 g was added. After the addition was completed, the reaction mixture was immediately added to an aqueous solution of sodium hydroxide (NaOH: 146 g).
/ 365 ml of water) was added dropwise over 30 minutes. After stirring the reaction mixture at 40 ° C. for 30 minutes, 354 g of sodium chloroacetate and 25.3 g of potassium iodide were added and 3
The mixture was heated under reflux with stirring for hours. The reaction mixture was cooled with water, and 240 ml of concentrated hydrochloric acid was added dropwise at room temperature or below. The precipitated crystals were collected by filtration, washed with water and dried to obtain 238 g of intermediate (c).

Synthesis of intermediate (d) 300 g of intermediate (c), p-toluenesulfonamide 26
To the suspension containing 2 g and 320 ml of sulfolane, 473 ml of phosphorus oxychloride was added dropwise over 30 minutes while stirring.
The reaction mixture was stirred at 120 ° C. for 3 hours and allowed to cool.
The reaction mixture cooled to room temperature was poured into 5 liters of ice water, and the precipitated crystals were collected by filtration and washed with water. To the crude crystals, 1 liter of acetone and 2 liter of isopropanol were added, heated and completely dissolved. Then, 1.5 liter of the solvent was concentrated, and the mixture was allowed to cool and stir. The precipitated crystals were collected by filtration, washed with isopropanol and dried to obtain 210 g of intermediate (d).

Synthesis of intermediate (e) Intermediate (d) 70 g, p-toluenesulfonamide 85.
A suspension containing 7 g, 69 g of potassium carbonate and 200 ml of N, N-dimethylacetamide was heated and stirred at 120 ° C. for 3 hours. After cooling to room temperature, 4 liters of water was added to the reaction mixture and the precipitated crystals were removed by filtration. Concentrated hydrochloric acid was added dropwise while stirring so that the pH of the filtrate became 4-5, and the precipitated oil was washed with ethyl acetate. The ethyl acetate layer was concentrated to dryness and the precipitated crystals were added with ethyl acetate, collected by filtration, washed with ethyl acetate and dried. 50 of the intermediate (e)
g was obtained.

Synthesis of intermediate (f) Intermediate (e) at 0 ° C. or below with stirring in 100 ml of concentrated sulfuric acid.
50 g was added. After stirring at the same temperature for 1 hour, ice water 5
The mixture was poured into 00 ml with stirring, and the precipitated crystals were collected by filtration, washed with water and dried. 22 g of intermediate (f) was obtained.

Synthesis of Intermediate (g) A suspension containing 5 g of Intermediate (f), 4.3 g of o-aminothiophenol and 50 g of polyphosphoric acid was heated and stirred at 150 ° C. for 3 hours. 500 ml of water to the reaction mixture cooled to room temperature
And the pH of the suspension was adjusted to 5 with sodium hydroxide.
Adjusted to ~ 6, the precipitated crystals were collected by filtration and washed with water. The obtained crude crystals were recrystallized from an acetone / ethyl acetate system to obtain 2.1 g of intermediate (g).

Synthesis of Intermediate (i) A solution containing 7 g of Intermediate (h), 70 ml of methyl cellosolve and 70 ml of water was stirred with ice-cooling and the intermediate (g) 7
The diazonium salt diazotized by the nitrosylsulfuric acid method from g was added at 10 ° C or lower. After stirring at the same temperature for 1 hour and further under water cooling for 1 hour, 1 liter of warm water at 40 ° C. was added, and the precipitated crystals were collected by filtration, washed with methanol and dried. The obtained crude crystals were washed with acetonitrile by heat to give the intermediate (i) as 3.2
g was obtained.

Synthesis of intermediate (j) 23 g of intermediate (j), 200 ml of acetonitrile / and N,
While stirring, 24 ml of phosphorus oxychloride was added dropwise to a suspension containing 2 ml of N-dimethylacetamide. 50-60 ° C
After stirring for 3 hours, the mixture was cooled with water. The reaction mixture was added to 1 liter of ice water with stirring. The precipitated crystals were collected by filtration, washed with water and dried to obtain 16 g of intermediate (j).

Synthesis of image forming compound I-II- (2) Intermediate (l) 9.5 g, N, N-dimethylacetamide 5
To a solution containing 0 ml and 4.1 ml of α-picoline, 10 g of intermediate (j) was added in 5 portions at 5 ° C or lower with stirring under ice cooling, and the reaction was continued for 1 hour under ice cooling. To the reaction mixture was added 115 ml of acetone and 115 ml of methanol, and 50 to 50
80 ml of water was added dropwise at 60 ° C., the mixture was stirred at the same temperature for 2 hours, and the precipitated crystals were collected by filtration, washed with water and dried. 12 g of this crude crystal was subjected to flash column chromatography (silica gel: chloroform / methanol / triethylamine =
25/2/4 (v / v)) to obtain 4.3 g of the image forming compound I-II- (2).

Synthesis of image-forming compound I-II- (9) Intermediate (l) 9 g, N, N-dimethylacetamide 50 ml
To a solution containing α-picoline (5 ml), 10 g of intermediate (j) was added in 5 portions at 5 ° C or lower while stirring with ice cooling under a nitrogen stream, and the reaction was continued for 1 hour under ice cooling. To the reaction mixture was added 130 ml of acetone and 150 ml of methanol, to which 50-
100 ml of water was added dropwise at 60 ° C., the mixture was stirred at the same temperature for 2 hours, and the precipitated crystals were collected by filtration, washed with methanol and dried. Flash column chromatography of 10 g of the crude crystals (silica gel: chloroform / methanol = 50/1
(V / v)) and image-forming compound I-II- (9)
5 g was obtained.

Next, a method for synthesizing the compound used in the present invention will be described. The compound of the present invention can be synthesized by a known method. For example, J. Amer. Chem.
Soc., 81, 2452 (1959), ibid, 81.
Issue, 12456 (1959) and Heterocycles.,
No. 27, page 2301, (1988), etc., the literature cited therein, or a similar method. Regarding the starting materials and intermediates in the synthesis, those described above or those can be referred to.

Exemplified Compound I-III-
(1) and I-III- (9) were synthesized.

[0092]

[Chemical 30]

[0093]

[Chemical 31]

Exemplified Compounds I-III- (1) and I-III-
Synthesis of (9) Synthesis of intermediate (b) A suspension containing 20.3 g of 5-amino-naphthoic acid (a) and 100 ml of N, N-dimethylacetamide was stirred under water cooling while stirring 25 g of trifluoroacetic anhydride. It dripped over 30 minutes. After stirring at the same temperature for 1.5 hours, 300 ml of water was added, and the precipitated crystals were collected by filtration and washed with water. The crude crystals were recrystallized from acetonitrile-acetone to obtain 20 g of compound (b).

Synthesis of intermediate (c) 150 g of intermediate (b), 56.5 g of phenol, N, N-
A suspension containing 1 ml of dimethylacetamide and 1 liter of acetonitrile was heated to reflux with stirring, and 69 ml of phosphorus oxychloride was added dropwise thereto over 30 minutes. After heating and refluxing for another 3 hours, the mixture was allowed to cool and stir for 3 hours, and the precipitated crystals were collected by filtration, washed with acetonitrile and dried to obtain 154 g of Intermediate (c).

Synthesis of intermediate (d) 100 g of intermediate (c) and o-phenylenediamine 86.3
The mixture of g was stirred at 160 to 170 ° C. for 2 hours and then left to cool. When the internal temperature became 100 ° C. or lower, 200 ml of acetonitrile was added dropwise, and the mixture was allowed to stand for cooling for 3 hours, and the precipitated crystals were collected by filtration, washed with acetonitoluri and dried to obtain 67.7 g of intermediate (d).

Synthesis of Intermediate (e) Sodium hydroxide aqueous solution (NaOH 8
Intermediate (d) 67.7 with stirring in 8 g / 880 ml of water
g was added. After 2 hours, 880 ml of ice water and 130 ml of acetic acid were added, and the precipitated crystals were collected by filtration, washed with water and dried to obtain 49.7 g of intermediate (e).

Synthesis of intermediate (f) To a solution containing 45 g of intermediate (e), 84 g of m-benzenedisulfonyl chloride and 1.8 liter of methanol, 61 ml of pyridine was added dropwise over 30 minutes while stirring under ice cooling. . After stirring at the same temperature for 1 hour and further stirring at 50 ° C. for 2 hours, 500 ml of warm water at 40 ° C. was added, the deposited precipitate was allowed to stand, and the supernatant was decanted and removed. 2.5 liters of warm water at 40 ° C. was added to the residue, and the mixture was stirred under water cooling for 3 hours. The precipitated crystals were collected by filtration, washed with water, dried, and the intermediate (f) was added to 3 times.
2.4 g was obtained.

Synthesis of intermediate (h) 20 g of intermediate (f), 800 ml of methyl cellosolve, 20 of water
A solution containing 0 ml and 1 liter of N, N-dimethylacetamide was stirred under ice cooling, and the intermediate (g) 1
From 1.8 g, a diazonium salt diazotized by the nitrosyl sulfuric acid method was added at 5 ° C or lower. The mixture was stirred at the same temperature for 1 hour and further under water cooling for 1 hour, 5% of 10% saline solution at 50 ° C was added thereto, and the mixture was stirred at 40 to 50 ° C for 2 hours. The precipitated crystals were collected by filtration, washed with 10% saline solution, dried, and the intermediate (h)
23 g was obtained.

Synthesis of intermediate (j) 23 g of intermediate (h), 200 ml of acetonitrile and N, N
24 ml of phosphorus oxychloride were added dropwise with stirring to a suspension containing 2 ml of dimethylacetamide. The mixture was stirred at 50-60 ° C. for 3 hours and then cooled with water. The reaction mixture was added to 1 liter of ice water with stirring. The precipitated crystals were collected by filtration, washed with water and dried to obtain 16 g of intermediate (j).

Synthesis of Exemplified Compound I-III- (1) Intermediate (j) 9 g, N, N-dimethylacetamide 50 ml
And to a solution containing 5 ml of α-picoline, 10 g of the intermediate (j) was added in 5 portions at 5 ° C or lower while stirring under ice cooling under a nitrogen stream,
The reaction was continued under ice cooling for 1 hour. Acetone 13 to the reaction mixture
Add 0 ml and 150 ml of methanol and add 50 to 60 to it.
Add 100 ml of water at ℃ and stir at the same temperature for 2 hours.
The precipitated crystals were collected by filtration, washed with methanol and dried. 10 g of crude crystals were subjected to flash column chromatography (silica gel; chloroform / methanol = 50/1 (v /
v)) to obtain Exemplified Compound I-III- (1) g.

Synthesis of Exemplified Compound I-III- (9) Intermediate (k) 9.5 g, N, N-dimethylacetamide 5
To a solution containing 0 ml and 4.1 ml of α-picoline, 10 g of intermediate (j) was added in 5 portions at 5 ° C or lower with stirring under ice cooling, and the reaction was continued for 1 hour under ice cooling. To the reaction mixture was added 115 ml of acetone and 115 ml of methanol, and 50 to 50
80 ml of water was added dropwise at 60 ° C., the mixture was stirred at the same temperature for 2 hours, and the precipitated crystals were collected by filtration, washed with water and dried. 12 g of this crude crystal was purified by flash column chromatography (silica gel: chloroform / methanol / acetonitrile / triethylamine = 26/4/6/4 (v / v)) to obtain 4.3 g of Exemplified Compound I-III- (9). It was

The amount of the dye image-forming compound used in the present invention can be varied within a wide range, but it is usually 0.
It is used in the range of 01 mol to 4 mol.

Hydrophobic additives such as the above image forming compounds and image forming accelerators described below are described in US Pat.
It can be incorporated into the layer of the light-sensitive element by a known method such as the method described in No. 22,027. In this case, JP-A-59-83154, JP-A-59-178451, JP-A-59-178452, JP-A-59-178453 and JP-A-5-78453.
9-178454, 59-178455, 59
A high-boiling point organic solvent such as described in No. 178457 can be used in combination with a low-boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. The amount of the high boiling point organic solvent is 10 g per 1 g of the dye image forming compound used.
The following is preferably 5 g or less. Also, Japanese Patent Publication Sho 51-3
The dispersion method using a polymer described in JP-A-9853 and JP-A-51-59943 can also be used.

In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing the hydrophobic substance in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157636, (37) to (3)
8) The surfactants listed on page 8 can be used.

The dye-providing compound used in combination is represented by the following general formula [I
V] can be used. General formula [IV] DYE-Y

Here, DYE represents a dye or its precursor, and Y represents a component that gives a compound having a different diffusibility from the compound under alkaline conditions. According to the function of Y, it is roughly classified into a negative type compound which becomes diffusive in the silver developed area and a positive type compound which becomes diffusible in the undeveloped area.

Specific examples of the negative type Y include those which are oxidized as a result of development and cleaved to release a diffusible dye.

A specific example of Y is described in JP-A-2-32335, page (15), upper right column, line 18 to the same, page (15), lower left column, 2.
It is described in U.S. Pat. No. 3,928,312 described in the 0th line.

Among Y of the negative dye-releasing redox compound, a particularly preferable group is an N-substituted sulfamoyl group (wherein the N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). it can. For representative examples of Y, positive compounds, compounds of other types, etc., JP-A-2-32335, page (16), upper left column to the same (1)
7) The information up to the 7th line in the lower right column of the page applies.

When the dye-donor compound used in the present invention and the dye used in combination are reducible dye-donor compounds, a reducing agent (sometimes referred to as an electron donor) is used. The reducing agent may be supplied from the outside or may be contained in the light-sensitive material in advance. Further, a reducing agent precursor which has no reducing property itself but exhibits a reducing property by the action of a nucleophile or heat in the developing process can also be used.

Examples of the electron donor used in the present invention include 49-50 of US Pat. No. 4,500,626.
Column, Nos. 4,483,914, columns 30-31, No. 4,
330,617, 4,590,152, JP-A-6
0-140335, pages (17) to (18), ibid. 57.
-40245, 56-138736, 59-1
78458, 59-53831, 59-182.
No. 449, No. 59-182450, No. 60-1195.
55, 60-128436 to 60-1284
39, 60-198540, 60-181
No. 742, No. 61-259253, No. 64-2440.
No. 44, No. 62-131253 to No. 62-1312
Up to 56, 78 of EP 220,746A2
To page 96 and the like, there are electron donors and electron donor precursors. Combinations of various electron donors such as those disclosed in US Pat. No. 3,039,869 can also be used.

When the dye-donor compound of the present invention is diffusion resistant, or when the reducing agent used in combination with the dye-donor compound of the present invention which is reducible is diffusion resistant, an electron transfer agent may be used. .

The electron transfer agent or its precursor can be selected from the above-mentioned electron donors or its precursors. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion-resistant electron donor. Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant electron donor used in combination with the electron transfer agent may be one that does not substantially move in the layer of the light-sensitive material among the above-mentioned reducing agents, and preferably hydroquinones and sulfonamidephenols. , Sulfonamide naphthols, and compounds described as electron donors in JP-A No. 53-110827. The electron transfer agent may be supplied from the outside or may be contained in the light-sensitive material in advance.

The dye-donor compound of the present invention is preferably contained in the same layer as the photosensitive silver halide emulsion, but may be contained in any layer as long as it can react directly or through an electron transfer agent. good. For example, when a colored dye-providing compound is present in the lower layer of the silver halide emulsion layer, the reduction in sensitivity can be prevented.

The dye-donating compound of the present invention can be used in a diffusion transfer type color photographic light-sensitive material, and the developing / image-forming method is to develop the processing composition at around room temperature or supply a trace amount of water or heat. A method of incorporating a solvent and performing heat development can be adopted.

First, the color diffusion transfer method will be described. A typical form of a film unit used in the color diffusion transfer method is that an image receiving element (dye fixing element) and a photosensitive element are laminated on one transparent support, and after the transfer image is completed, the photosensitive element is It is a form that does not need to be peeled from the image receiving element. More specifically, the image-receiving element comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive element, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer. A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a yellow dye-donor substance for each emulsion layer, A combination of a magenta dye-donating substance and a cyan dye-donating substance (herein, "infrared light-sensitive emulsion layer" means an emulsion layer sensitive to light of 700 nm or more, especially 740 nm or more). ). A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the dye-donating substance-containing layer so that the transferred image can be viewed through the transparent support.

A light shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the development processing can be completed in a bright place. If desired, a peeling layer may be provided at an appropriate position so that all or part of the light-sensitive element can be peeled off from the image-receiving element (for example, such an embodiment is disclosed in JP-A-56-6
7840 and Canadian Patent 674,082).

In another embodiment of the laminate type which is peeled off, at least (a) a layer having a neutralizing function, (b) a dye image receiving layer, and ((a) on a white support described in JP-A-63-226649. c) a release layer, (d) a light-sensitive element sequentially having at least one silver halide emulsion layer combined with a dye image-forming substance, an alkali processing composition containing a light-shielding agent, and a transparent cover sheet. There is a color diffusion transfer photographic film unit characterized by having a layer having a light shielding function on the side opposite to the side where the processing composition is developed.

In another embodiment in which peeling is not required, the above-mentioned photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. .
U.S. Pat. No. 3,730,71 describes a mode in which an image receiving element, a white reflective layer, a peeling layer and a photosensitive element are laminated on the same support and the photosensitive element is intentionally peeled from the image receiving element.
No. 8.

On the other hand, there are roughly two typical forms in which a light-sensitive element and an image-receiving element are separately coated on two supports, one is a peeling type and the other is a peeling-free type. is there. Explaining these in detail, in a preferred embodiment of the peelable film unit, at least one image receiving layer is coated on one support, and the photosensitive element is coated on a support having a light shielding layer. , The photosensitive layer coated surface and the mordant layer coated surface do not face each other before the exposure is completed, but after the exposure is completed (for example, during the development process), the photosensitive layer coated surface is turned over and overlapped with the image receiving layer coated surface. .
After the transfer image is completed on the mordant layer, the light-sensitive element is rapidly separated from the image-receiving element.

In a preferred embodiment of the peel-free type film unit, at least one mordant layer is coated on a transparent support, and a photosensitive element is coated on a support having a transparent or light-shielding layer. However, the photosensitive layer coated surface and the mordant layer coated surface face each other and are superposed.

A pressure-rupturable container (processing element) containing an alkaline processing liquid may be combined with the above-mentioned form. Among others, in a peel-free type film unit in which an image receiving element and a photosensitive element are laminated on one support, the processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon. Further, in the form in which the light-sensitive element and the image-receiving element are separately coated on the two supports, it is preferable that the processing element is disposed between the light-sensitive element and the image-receiving element at the latest during the development processing. The processing element preferably contains a light-shielding agent (such as carbon black or a dye whose color changes with pH) and / or a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in the color diffusion transfer type film unit, it is preferable that a neutralization timing mechanism comprising a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet, the image receiving element, or the photosensitive element.

The image receiving element of the color diffusion transfer method will be described in more detail below. The image receiving element of the color diffusion transfer method preferably has at least one layer containing a mordant (mordant layer). As the mordant, those known in the photographic field can be used. As a specific example thereof, British Patent 2,01
1,912, 2,056,101, 2,09
3,041, U.S. Pat. Nos. 4,115,124, 4,273,853, 4,282,305, JP-A-59-232340, 60-118834, and 60-128443. , Ibid. 60-122940, ibid. 6
It is described in gazettes such as 0-122921 and 60-235134.

In addition to the above, various additives may be appropriately used in the image receiving element for the color diffusion transfer method, which is described in the section of the dye fixing element (image receiving element) for the color diffusion transfer method for heat development. Will be explained together.

Next, the photosensitive element of the color diffusion transfer method will be described. JP-A-2-32335 discloses a processing composition such as a silver halide emulsion, a spectral sensitizing dye, an emulsion layer, a full-color multi-layered structure used in a color diffusion transfer method, a color diffusion transfer method film unit and its constituent layers. 17) Lower right column, page 8 to the same publication, lower right column, page 19 (20)
The contents up to the first line apply.

Next, the peeling layer of the color diffusion transfer method will be described. The release layer used in the present invention can be provided at any place on the photosensitive sheet in the unit after processing. Examples of the peeling material include, for example, JP-A-47-8237, JP-A-59-220727, JP-A-49-4653, US Pat. Nos. 3,220,835, 4,359,518, and JP-A-49. -4334, 56-65133, 45
-24075, U.S. Pat. Nos. 3,227,550, 2,759,825, 4,401,746, 4,366,227 and the like can be used. Specific examples include water-soluble (or alkali-soluble) cellulose derivatives. For example, hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, and the like. There are also various natural polymers such as alginic acid, pectin, and gum arabic. Also, various modified gelatins such as acetylated gelatin and phthalated gelatin can be used. Further, it is polyvinyl alcohol, polyacrylate, polymethylmethacrylate or a copolymer thereof. Of these, a cellulose derivative is preferably used as the peeling material, and hydroxyethyl cellulose is particularly preferably used. In addition to the water-soluble cellulose derivative, a granular substance such as an organic polymer can be used as a peeling material. The organic polymer used in the present invention has an average particle size of 0.0
Examples of the polymer latex include polyethylene, polystyrene, polymethylmethacrylate, polyvinylpyrrolidone, and butylacrylate having a size of 1 μm to 10 μm. Here, as described below, air is contained inside and the outside is made of an organic polymer. It is preferred to use a light-reflecting hollow polymer latex containing material. The above light-reflective hollow polymer latex is disclosed in JP-A-61-1516.
It can be synthesized by the method described in No. 46.

Next, the heat development color diffusion transfer method will be described. In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta, and cyan, a combination of at least three silver halide emulsion layers having photosensitivity in different spectral regions is used. For example, there are combinations of three layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, a combination of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer. Each of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary. For the photothermographic material, a protective layer,
Various auxiliary layers such as an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer can be provided.

The silver halide usable in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. The silver halide emulsion used in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging. Further, it may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.1 to 2 μm, particularly preferably 0.2 to 1.5 μm. The crystal habit of silver halide grains is cubic, octahedral,
It may be a tetrahedron, a flat plate having a high aspect ratio, or the like. Specifically, US Pat. No. 4,500,626, column 50, U.S. Pat. No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 17029 (19).
1978), JP-A-62-253159, JP-A-3-1.
No. 10555, No. 2-236546, No. 1-1677
Any of the silver halide emulsions described in No. 43, etc. can be used.

The silver halide emulsion may be used as it is after ripening, but it is usually chemically sensitized before use. The known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method, selenium sensitizing method and the like can be used alone or in combination for the emulsion for a conventional type light-sensitive material. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-25315).
No. 9). The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include those described in US Pat.
There are benzotriazoles, fatty acids and other compounds described in Nos. 0,626, columns 52 to 53. In addition, JP-A-60
No. 113235, a silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolic acid, and JP-A-6-63.
The acetylene silver described in No. 1-249044 is also useful.
Two or more kinds of organic silver salts may be used in combination. The above organic silver salt may be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver.

Various antifoggants or photographic stabilizers can be used in the invention. Examples thereof include azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, JP-A-59-111636 and JP-A-4-73
The mercapto compound and its metal salt described in JP-A No. 649, the acetylene compounds described in JP-A-62-87957 and JP-A-4-255845 are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257 and JP-A-59-180550.
No. 60-140335, RD17029 (197).
8 years) sensitizing dyes described on pages 12 to 13 and the like.
These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3). , 615, 641, JP-A 61-23145, etc.). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after the nucleation of silver halide grains. Good. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

A hydrophilic binder is preferably used for the binder of the constituent layers of the light-sensitive material and the dye fixing element. As an example thereof, pages (26) to (2) of JP-A No. 62-253159.
8) The thing described in page is mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl monomers with A copolymer with a vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more.

When a system in which a small amount of water is supplied for thermal development is adopted, it becomes possible to quickly absorb water by using the above superabsorbent polymer. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer. In the present invention,
The coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g or less, and more preferably 7 g or less.

The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing element are used for the purpose of improving physical properties of the film such as dimensional stability, curl prevention, adhesion prevention, film cracking prevention and pressure increase / decrease prevention. Various polymer latices can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, 62-110066 and the like can be used. In particular,
When a polymer latex having a low glass transition point (40 ° C. or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl preventing effect can be obtained. .

In the present invention, a development inhibitor releasing redox compound can be used. For example, JP-A-61-21
3,847, 62-260,153, JP-A-2-
68,547, 2-110,557, 2-25
Those described in Nos. 3,253 and 1-150,135 can be used. The synthesis method of the development inhibitor releasing redox compound used in the present invention is described in, for example, JP-A-61-161.
213,847, 62-260,153, U.S. Pat. No. 4,684,604, JP-A-1-269936.
U.S. Pat. Nos. 3,379,529 and 3,620,
No. 746, No. 4,377, 634, No. 4,332, 8
78, JP-A-49-129,536 and JP-A-56-15.
3, 336, 56-153, 342, etc.

The development inhibitor releasing redox compound of the present invention contains 1 × 10 ^{−6 to} 5 × 10 ⁻² per mol of silver halide.
It is used in an amount of 1 mole, more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mole. The development inhibitor releasing redox compound used in the present invention is a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide. , Dissolved in methyl cellosolve, etc. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, by a method known as a solid dispersion method, a powder of a development inhibitor-releasing redox compound is ball milled in water, a colloid mill,
Alternatively, they can be dispersed by ultrasonic waves and used.

Further, the development inhibitor releasing redox compound may be used in combination with a releasing aid. For example, those described in JP-A-3-293666 can be used.

When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157636, (37) to (38)
The surfactants listed on the page can be used.
In the present invention, a compound that activates the development of the light-sensitive material and stabilizes the image at the same time can be used. Specific compounds preferably used are described in US Pat. No. 4,50.
0,626, columns 51-52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a light-sensitive material. The dye fixing element may be applied separately on a support different from the light-sensitive material, or may be applied on the same support as the light-sensitive material. Regarding the relationship between the light-sensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application. The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat.
00,626, columns 58 to 59 and JP-A-61-8825.
No. 6, pages (32) to (41), mordants described in JP-A-6-61
Examples thereof include those described in Nos. 2-244043 and 62-244036. Also, US Pat.
A dye-accepting high molecular compound as described in No. 63,079 may be used. If necessary, the dye fixing element can be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer. In particular, it is useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing element, a plasticizer, a slipping agent, or a high boiling point organic solvent can be used as an agent for improving the releasability of the light-sensitive material and the dye-fixing element. Specifically, JP-A-62-253159 (2
5), No. 62-245253 and the like. Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. Examples thereof include various modified silicone oils described in "Modified Silicone Oil" technical material P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X
-22-3710) is effective. In addition, JP-A-62
Silicone oils described in JP-A-215953 and JP-A-63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive material and the dye fixing element. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex.
Examples of the antioxidant include chroman compounds, coumarans compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. No. 3,352,681),
Benzophenone compounds (JP-A-46-2784 and the like), JP-A-54-48535 and JP-A-62-13
There are compounds described in Nos. 6641 and 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155, 4,245,018, columns 3 to 36, and 4,254,195, columns 3 to 8,
There are compounds described in JP-A-62-174741, JP-A-61-88256, pages (27) to (29), JP-A-63-199248, JP-A-1-75568 and JP-A-1-74272.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137). The anti-fading agent for preventing the fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or may be supplied to the dye-fixing element from the outside such as a light-sensitive material. . The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination. A fluorescent whitening agent may be used in the light-sensitive material and the dye fixing element. In particular, whether to incorporate a fluorescent whitening agent in the dye fixing element,
It is preferably supplied from the outside such as a photosensitive material. As an example, K. Veenkataraman edition `` The Chemistry of
Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-143
Examples thereof include the compounds described in No. 752. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

As the hardener used in the constituent layers of the light-sensitive material and the dye fixing element, US Pat. No. 4,678,739 No.
Column 1, JP-A-59-116655 and JP-A-64-2452.
No. 61, No. 61-18942, etc. are mentioned. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners, vinyl sulfone type hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane etc.), N
-Methylol type hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157). Particularly preferably, JP-A-3
The vinyl sulfone type hardener described in -114,043 is used.

In the constituent layers of the light-sensitive material and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of slipperiness, prevention of electrification, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like. The constituent layers of the light-sensitive material and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving peelability and the like. As typical examples of organic fluoro compounds, JP-B-57-9053, columns 8 to 17, JP-A-61-20
No. 944, No. 62-135826, or the like, or a fluorochemical surfactant such as a fluorochemical compound such as a fluorocarbon oil or a solid fluorochemical resin such as a tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used in the light-sensitive material and the dye fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
In addition to the compounds described on page 1-88256 (29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-274944.
No. 63-274952. In addition, the constituent layers of the light-sensitive material and the dye fixing element may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are disclosed in JP-A-61-8.
No. 8256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the dye fixing element. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Details thereof are described in US Pat. No. 4,678,739, columns 38 to 40. Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is U.S. Pat. No. 4,511,493.
And JP-A-62-65038.

In a system in which heat development and dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferable to add a base and / or a base precursor to the dye fixing element in order to enhance the storage stability of the light-sensitive material. In the present invention, European Patent Publication No. 210,660 and US Pat. No. 4,740,4
A combination of a sparingly soluble metal compound described in No. 45 and a compound capable of undergoing a complex forming reaction with a metal ion constituting the sparingly soluble metal compound (referred to as a complex forming compound) is used. Specifically, JP-A-2-269,338 (2) to
It is described on page (6). Particularly preferred compounds as the sparingly soluble metal compound are zinc hydroxide, zinc oxide and a mixture of both.

In the present invention, various development stoppers can be used in the light-sensitive material and / or the dye-fixing element for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or to inhibit development by interacting with silver and a silver salt. Specific examples of the compound include an acid precursor that releases an acid by heating, an electrophilic compound that causes a substitution reaction with a coexisting base by heating, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. . For more details, see JP-A-62-25
No. 3159, pages (31) to (32).

In the present invention, the support for the light-sensitive material and the dye-fixing element is one that can withstand the processing temperature. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide, and polypropylene are used. Film-processed synthetic papers, mixed papers made of synthetic resin pulp such as polyethylene and natural pulp, Yankee papers, baryta papers, coated papers (particularly cast coated papers), metals, cloths and glasses are used. These can be used alone,
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition to these, the supports described in JP-A-62-253159, pages (29) to (31) can be used. A hydrophilic binder, a semiconductor metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

As a method for exposing and recording an image on a light-sensitive material, for example, a method of directly photographing a landscape or a person with a camera, a method of exposing through a reversal film or a negative film with a printer or a stretcher, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting light from a light emitting diode or various lasers through an electric signal, a CRT, a liquid crystal display of image information, There is a method of outputting to an image display device such as an electroluminescence display and a plasma display, and exposing directly or through an optical system.

As a light source for recording an image on a photosensitive material,
As described above, the light sources described in US Pat. No. 4,500,626, column 56, such as natural light, tungsten lamps, light emitting diodes, laser light sources, and CRT light sources can be used. Image exposure can also be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the nonlinear optical material is
It is a material that can develop the nonlinearity between the electric field and the polarization that appears when a strong optical electric field such as laser light is applied.
Lithium niobate, potassium dihydrogen phosphate (KDP),
Inorganic compounds represented by lithium iodate, BaB ₂ O _4, etc., urea derivatives, nitroaniline derivatives such as 3
-Methyl-4-nitropyridine-N-oxide (PO
Nitropyridine-N-oxide derivatives such as M) and the compounds described in JP-A Nos. 61-53462 and 62-210432 are preferably used. As the form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. The above-mentioned image information is an image signal obtained from a video camera, an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC), an image obtained by dividing an original image into many pixels such as a scanner. An image signal operated by using a computer represented by Signal, CG, CAD can be used.

The light-sensitive material and / or the dye fixing element may have a form having a conductive heating element layer as a heating means for heat development or dye diffusion transfer. The transparent or opaque heating element in this case is disclosed in JP-A-61-1.
Those described in No. 45544 and the like can be used. Note that these conductive layers also function as antistatic layers. The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and development is possible, but about 80 ° C. to about 180 ° C. is particularly useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the heat development process is completed. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is more preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

The migration of the dye occurs only by heat,
Solvents may be used to facilitate dye transfer. Also,
As described in detail in JP-A-59-218443 and JP-A-61-238056, a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. is there. In this method, the heating temperature is preferably 50 ° C. or higher and not higher than the boiling point of the solvent. For example, when the solvent is water, the temperature is preferably 50 ° C or higher and 100 ° C or lower. Examples of the solvent used for accelerating the development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (for these bases, an image). The one described in the section of the formation accelerator is used)
Can be mentioned. Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound may be contained in the solvent.

These solvents can be used by a method of applying them to the dye fixing element, the light-sensitive material or both.
The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the total coating film). Examples of the method for applying a solvent to the photosensitive layer or the dye fixing layer include, for example, JP-A-61-147244 (2).
6) There is a method described on page. Alternatively, the solvent may be contained in a microcapsule, and may be incorporated in the light-sensitive material or the dye-fixing element or both in advance.

In order to promote dye transfer, a method of incorporating a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature into the light-sensitive material or the dye-fixing element can also be adopted. The hydrophilic thermal solvent may be incorporated in either the light-sensitive material or the dye fixing element, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and / or its adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles. Further, a high-boiling organic solvent may be contained in the light-sensitive material and / or the dye fixing element in order to promote dye transfer.

As a heating method in the developing and / or transferring step, a heated block or plate is contacted, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater or the like is contacted. And passing through a high temperature atmosphere. JP-A-61-1 is a method for applying a pressure condition or pressure when the light-sensitive element and the dye fixing element are superposed and closely contacted with each other.
The method described on page 27 of No. 47244 can be applied.

Any of a variety of heat developing apparatus can be used to process the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259.
44, JP-A-3-131856, and JP-A-3-13185.
The device described in No. 1 etc. is preferably used.

[0160]

The present invention will be described with reference to the following examples.
The present invention is not limited to these.

Example 1 A method for preparing a zinc hydroxide dispersion will be described.

19.0 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of a 5% gelatin aqueous solution, and the average particle size was 0.75 mm with a mill. It was ground for 30 minutes using glass beads. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, a method for preparing a dispersion of the electron transfer agent will be described.

11 g of the following electron transfer agent, 0.5 g of polyethylene glycol nonyl phenyl ether as a dispersant
g, 0.5% of the following anionic surfactant (1) 5%
Add 100 ml of gelatin aqueous solution and mill to get an average particle size of 0.7
Milled for 60 minutes with 5 mm glass beads. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.35 μm.

[0165]

[Chemical 32]

[0166]

[Chemical 33]

Next, the method for preparing the dye trapping agent dispersion will be described.

The following polymer latex (solid content 13
%) 108 ml, the following surfactant 20 g, water 1232 ml
600 ml of a 5% aqueous solution of the above-mentioned anionic surfactant (1) was added over 10 minutes while stirring the mixed solution of. The dispersion thus prepared was concentrated and desalted to 500 ml using an ultrafiltration module. Next 1500 ml
Water was added and the same operation was repeated once again to obtain 500 g of a dye trapping agent dispersion.

[0169]

[Chemical 34]

[0170]

[Chemical 35]

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described. Cyan, magenta, and yellow dye-donor compounds and electron-donor gelatin dispersions were prepared according to the formulations shown in Table 1. That is, each oil phase component is about 6
Dissolve by heating to 0 ℃ to make a uniform solution,
The aqueous phase component heated to ℃ was added, and the mixture was stirred and mixed, and then dispersed by a homogenizer for 13 minutes at 12000 rpm. Water was added to this and stirred to obtain a uniform dispersion.

[0172]

[Table 1]

[0173]

[Chemical 36]

[0174]

[Chemical 37]

[0175]

[Chemical 38]

[0176]

[Chemical Formula 39]

[0177]

[Chemical 40]

[0178]

[Chemical 41]

[0179]

[Chemical 42]

[0180]

[Chemical 43]

[0181]

[Chemical 44]

[0182]

[Chemical formula 45]

[0183]

[Chemical formula 46]

[0184]

[Chemical 47]

[0185]

[Chemical 48]

[0186]

[Chemical 49]

Next, a method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive silver halide emulsion (1) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 3 g of sodium chloride in 500 ml of water).
g and 30 mg of the following chemical (A) were added and kept at 45 ° C.), and 20 parts of solution (I) and solution (II) in Table 2 were simultaneously added.
Added at equal flow rate for 1 minute. After 6 minutes, solution (III) and solution (IV) shown in Table 2 were added simultaneously at an equal flow rate for 25 minutes. Also (II
10 minutes after the addition of the solutions (I) and (IV) was started, an aqueous solution of a gelatin dispersion of a dye (1 g of gelatin in 105 ml of water, 70 mg of the following dye (a), 139 mg of the following dye (b), and the following dye (c) ) Containing 5 mg and kept at 45 ° C.) was added over 20 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.8, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimum chemical sensitization at 68 ° C.,
Next, the following antifoggant (2) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0190]

[Chemical 50]

[0191]

[Table 2]

[0192]

[Chemical 51]

[0193]

[Chemical 52]

[0194]

[Chemical 53]

Photosensitive silver halide emulsion (2) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide and 6 g of sodium chloride in 800 ml of water).
g and 30 mg of the following chemical (A) were added and kept at 65 ° C.), 30 parts of solution (I) and solution (II) in Table 3 were simultaneously added.
Added at equal flow rate for 1 minute. After 5 minutes, solution (III) and solution (IV) shown in Table 3 were added simultaneously at the same flow rate for 15 minutes. Also (II
2 minutes after the start of the addition of the solutions (I) and (IV), an aqueous solution of a gelatin dispersion of a dye (1.1 g of gelatin in 95 ml of water, 76 mg of the above dye (a), 150 mg of the above dye (b), and the above dye) (C) 5 mg and kept at 50 ° C.) was added over 18 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.8, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimum chemical sensitization at 68 ° C.,
Next, the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.50 μm was obtained.

[0197]

[Table 3]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (gelatin 20 g, potassium bromide 0.5 g, sodium chloride 4 in 690 ml of water).
g and 15 mg of the above-mentioned chemical (A) were added and kept at 47 ° C.), the solutions (I) and (II) in Table 4 were simultaneously added at an equal flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) in Table 4 were further added simultaneously at an equal flow rate for 32 minutes. Also (II
I), 1 minute after the end of the addition of the (IV) solution, an aqueous solution of a gelatin dispersion of a dye (2.5 g of gelatin in 100 ml of water and 250 mg of the following dye (d) and kept at 45 ° C.) was put together. Was added.

After washing with water and desalting by a conventional method, 32 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.27 μm was obtained.

[0200]

[Table 4]

[0201]

[Chemical 54]

Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide and 6 g of sodium chloride in 700 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 60 ° C.), the liquids (I) and (II) shown in Table 5 are simultaneously added to 20 parts.
Added at equal flow rate for 1 minute. 10 minutes later (III) in Table 5
Solution and Solution (IV) were added simultaneously at the same flow rate for 20 minutes. Also (I
II), 1 minute after the end of the addition of the (IV) solution, an aqueous solution of a gelatin dispersion of the dye (1.8 g of gelatin in 75 ml of water and 180 mg of the dye (d) and kept at 45 ° C.) was put together. Was added.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0204]

[Table 5]

Light-Sensitive Silver Halide Emulsion (5) [For Blue-Sensitive Emulsion Layer] Well-stirred gelatin aqueous solution (20 g of gelatin, 0.5 g of potassium bromide, 5 g of sodium chloride in 690 ml of water).
g and 15 mg of the above-mentioned chemical (A) were added and kept at 51 ° C.), the solutions (I) and (II) in Table 6 were simultaneously added at an equal flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) shown in Table 6 were added simultaneously at the same flow rate for 32 minutes. Also (II
One minute after the addition of the solutions (I) and (IV) was completed, an aqueous solution of the dye (water 9
235 mg of the following dye (e) in 5 ml and 5 ml of methanol
And 120 mg of the following dye (f) and kept at 45 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.7, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0207]

[Table 6]

[0208]

[Chemical 55]

[0209]

[Chemical 56]

Photosensitive silver halide emulsion (6) [For blue-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 695 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 63 ° C.), the liquids (I) and (II) shown in Table 7 were simultaneously added to 10
Added at equal flow rate for 1 minute. After 10 minutes (Table III) (III)
Solution and solution (IV) were added simultaneously at the same flow rate for 30 minutes. Also (I
II), 1 minute after the addition of the solution (IV), an aqueous solution of the dye (water 6
155 mg of the above dye (e) in 6 ml and 4 ml of methanol
And 78 mg of the above-mentioned dye (f) and kept at 60 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.7, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.52 μm was obtained.

[0212]

[Table 7]

A photosensitive material 101 shown in Table 8 was prepared using the above.

[0214]

[Table 8]

[0215]

[Table 9]

[0216]

[Chemical 57]

[0217]

[Chemical 58]

[0218]

[Chemical 59]

[0219]

[Chemical 60]

[0220]

[Chemical formula 61]

Light-sensitive material 10 except that the gelatin dispersion of the dye-donor compound in the first layer was changed from the light-sensitive material 101 to the gelatin dispersion of the dye-donor compound shown in Table 9 above.
The light-sensitive materials 102 to 10 shown in Table 9 in exactly the same manner as in 1.
I made 7. The above-mentioned photosensitive materials 101 to 107 and PS paper PS-SG manufactured by Fuji Photo Film Co., Ltd. were used as the image receiving material, and Pictrostat 200 manufactured by Fuji Photo Film Co., Ltd. was used as the image recording apparatus. That is, the original image [Y, M,
Cy. Gray wedge is recorded on the test chart] through a slit, and the exposed photosensitive material is dipped in water kept at 40 ° C for about 2.5 seconds, squeezed with a roller, and immediately exposed as an image receiving material. When the heat drum was heated for 17 seconds and the photosensitive material was peeled off from the image-receiving material, the original image was formed on the image-receiving material. A clear color image corresponding to was obtained. Concentration measurement
The reflection density was measured using a density measuring device X Light 404 manufactured by X-Light Co., Ltd., and the maximum density (Dmax) and the minimum density (Dmin) of cyan were measured and evaluated. The photosensitive materials 101 to 1
The image obtained by using No. 07 was irradiated with xenon light for one week, and the residual rate of the portion where the cyan density was 1.0 was obtained. The results are shown in Table 9.

From the results shown in Table 9, it can be seen that the compounds of the present invention provide image densities equivalent to those of the comparative compounds and have improved fastness to light.

[0223]

[Table 10]

It was also found that the cyan image formed by the image forming agent of the present invention has a clear hue without any turbidity.

Example 2 A method for preparing the emulsion (7) for the fifth layer will be described.

To the well-stirred aqueous solution having the composition shown in Table 10, the solutions I and II having the composition shown in Table 2 were added over 10 minutes, and then the solutions III and IV having the composition shown in Table 11 were added. The solution was added over 25 minutes.

[0227]

[Table 11]

[0228]

[Table 12]

The chemical (A) in Table 10 is the same as that used in Example 1.

Immediately before chemical sensitization, 1% of the dye (g) was added.
50 cc of solution (mixed solvent of methanol: water = 1: 1) was added.

Washing with water, desalting (pH = 4.
Then, 22 g of gelatin was added, and the pH = 6.
After adjusting to 0 and pAg = 7.9, chemical sensitization was performed at 60 ° C. The compounds used for the chemical sensitization are shown in Table 12.

The yield of the obtained emulsion was 630 g, and it was a monodisperse cubic emulsion having a coefficient of variation of 10.3%, and the average grain size was 0.21 μm.

[0233]

[Table 13]

[0234]

[Chemical formula 62]

[0235]

[Chemical formula 63]

[0236]

[Chemical 64]

[0237]

[Chemical 65]

[0238]

[Chemical formula 66]

A method for preparing the emulsion (8) for the third layer will be described.

To a well-stirred aqueous solution having the composition shown in Table 13, the solutions I and II having the composition shown in Table 14 were added over 18 minutes, and then the solutions III and IV having the composition shown in Table 14 were added. The liquid was added over 24 minutes.

[0241]

[Table 14]

[0242]

[Table 15]

Washing with water, desalting (pH = 3.
Then, 22 g of gelatin was added, and pH = 5.
9. After adjusting pAg to 7.8, chemical sensitization was performed at 70 ° C. During the chemical sensitization, 6.7 cc of a 1% methanol solution of the dye (h) was added. The compounds used for the chemical sensitization are shown in Table 15.

The yield of the obtained emulsion was 645 g, which was a monodisperse cubic emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.24 μm.

[0245]

[Table 16]

[0246]

[Chemical formula 67]

[0247]

[Chemical 68]

A method for preparing the emulsion (9) for the first layer will be described.

To a well-stirred aqueous solution having the composition shown in Table 16, the solutions I and II having the composition shown in Table 17 were added over 18 minutes, and then the solutions III and IV having the composition shown in Table 17 were added. The solution was added over 25 minutes.

[0250]

[Table 17]

[0251]

[Table 18]

Washing with water, desalting (pH = 4.
Then, 22 g of gelatin was added and pH = 7.
4, after adjusting to pAg = 7.6, it was chemically sensitized at 60 ° C. During the chemical sensitization, 7.5 cc of a 0.2% methanol solution of dye (i) (p-toluenesulfonic acid 0.1N) was added.
Was added. The compounds used for the chemical sensitization are shown in Table 18.

The yield of the obtained emulsion was 650 g, which was a monodisperse cubic emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.25 μm.

[0254]

[Table 19]

[0255]

[Chemical 69]

The zinc hydroxide dispersion was prepared in the same manner as in Example 1. Next, a method for preparing a gelatin dispersion of a dye-donor compound will be described.

A uniform solution having the composition shown in Table 19 and a uniform solution having the composition shown in Table 20 were prepared, mixed and stirred, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. A dispersion of the magenta dye-donor substance (M-
5).

[0258]

[Table 20]

[0259]

[Table 21]

A uniform solution having the composition shown in Table 21 and a uniform solution having the composition shown in Table 22 were prepared, mixed and stirred, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is a dispersion of a cyan dye-donor substance (Cy-
5).

[0261]

[Table 22]

[0262]

[Table 23]

A uniform solution having a composition shown in Table 23 and a uniform solution having a composition shown in Table 24 were prepared, mixed and stirred, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is used as a yellow dye-donor dispersion (Y-
5).

[0264]

[Table 24]

[0265]

[Table 25]

Next, a method for preparing a gelatin dispersion of an electron donor will be described.

A uniform solution having the composition shown in Table 25 and a uniform solution having the composition shown in Table 26 were prepared, mixed and stirred, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a dispersion of electron donors.

[0268]

[Table 26]

[0269]

[Table 27]

A light-sensitive material 201 having the constitution shown in Table 27 was prepared using these emulsions and dispersions of dye-donor compounds.

[0271]

[Table 28]

[0272]

[Table 29]

The support used at this time was a 135 μm thick paper support laminated with polyethylene.

The compounds in Table 27 are shown below, including the compounds (see Tables 19 to 26) shown in the preparation of dispersions of dye-donor compounds and electron donors.

[0275]

[Chemical 70]

[0276]

[Chemical 71]

[0277]

[Chemical 72]

[0278]

[Chemical formula 73]

[0279]

[Chemical 74]

[0280]

[Chemical 75]

[0281]

[Chemical 76]

[0282]

[Chemical 77]

[0283]

[Chemical 78]

[0284]

[Chemical 79]

[0285]

[Chemical 80]

[0286]

[Chemical 81]

Photosensitive materials 202 to 207 were prepared in exactly the same manner except that the cyan dye-donating compound of photosensitive material 201 was changed to those shown in Table 29.

Photosensitive materials 201 to 207 and PS paper manufactured by Fuji Photo Film Co., Ltd. were used as the image receiving materials, and Pictrography 3000 manufactured by Fuji Photo Film Co., Ltd. was used as an image recording apparatus. That is, using the laser exposure apparatus described in Japanese Patent Application No. 2-129625,
After exposure under the conditions shown in Table 28, 11 cc / m ² of water was supplied to the emulsion surface of the exposed light-sensitive material with a wire bar, and then,
The dye-fixing material and the film surface were superposed so that the film surface was in contact.
Using a heat drum whose temperature was adjusted so that the temperature of the absorbed film was 83 ° C., after heating for 30 seconds, the image receiving material was peeled off from the photosensitive material to obtain an image on the image receiving material. For the density measurement, the reflection density was measured using a density measuring instrument X-Light 404 manufactured by X-Light Co., Ltd., and the maximum density (Dmax) and the minimum density (Dmin) of cyan were measured and evaluated. The photosensitive material 201
The image obtained by using ˜207 was irradiated with xenon light for 1 week, and the residual rate of the portion where the cyan density was 1.0 was obtained. The results are shown in Table 29.

From the results shown in Table 29, it can be seen that the compounds of the present invention gave image densities equivalent to those of the comparative compounds and had improved fastness to light.

[0290]

[Table 30]

[0291]

[Table 31]

It was also found that the cyan image produced by the image forming agent of the present invention has a clear hue without any turbidity.

Example 3 The following photosensitive material 301 was prepared as a color diffusion transfer photosensitive material.

Photosensitive Material 501 A polyethylene terephthalate transparent support was coated with the following layers to prepare a photosensitive sheet. Back layer: (a) carbon black 4.0 g / m ^2, the light-shielding layer having a gelatin 2.0 g / m ^2, the emulsion layer side: (1) cyan dye-releasing redox compound of the following 0.44g
/ M ² , tricyclohexyl phosphate 0.09 g /
m ^2, 2,5- di -t- pentadecylhydroquinone 0.
Layer containing 008g / m ^2, and gelatin 0.8 g / m ^2.

[0295]

[Chemical formula 82]

(2) A layer containing 0.5 g / m ² of gelatin. (3) Red-sensitive inner latent direct positive silver bromide emulsion (0.6
g / m ² ), gelatin 1.2 g / m ² , the following nucleating agent 0.0
A red sensitive emulsion layer containing 15 mg / m ² and 0.06 g / m ² of 2-sulfo-5-n-pentadecylhydroquinone sodium salt.

[0297]

[Chemical 83]

[0298] (4) 2,5-di -t- pentadecylhydroquinone 0.43 g / m ^2, trihexyl phosphate 0.1 g / m ² and a layer containing gelatin 0.4 g / m ^2. (5) 0.3% of the following magenta dye releasing redox compound
g / m ² , tricyclohexyl phosphate (0.08 g
/ M ^2), 2,5- di -tert- pentadecylhydroquinone (0.009g / m ²⁾ and gelatin (0.5g / m ²⁾
Containing layers.

[0299]

[Chemical 84]

(6) Green-sensitive inner latent direct positive silver bromide emulsion (0.42 g / m ^{2 in} terms of silver amount), gelatin (0.9 g / m ² ),
A green-sensitive emulsion layer containing the same nucleating agent (0.013 g / m ² ) and 2-sulfo-5-n-pentadecylhydroquinone sodium salt (0.07 g / m ² ) as in layer (3). (7) Same layer as (4). (8) yellow dye-releasing redox compound having the following structure (0.53 g / m ^2), tri-cyclohexyl phosphate (0.13 / m ^2), 2,5- di -t- pentadecylhydroquinone (0.014 g / m ² ) And gelatin (0.
Layer containing 7 g / m ² ).

[0301]

[Chemical 85]

(9) Blue-sensitive inner latent type direct positive silver bromide emulsion (silver amount: 0.6 g / m ² ), gelatin (1.1 g / m ² ), layer
(3) the same nucleating agent (0.019 g / m ²⁾ and 2-sulfo -5-n-pentadecylhydroquinone sodium salt (0.05 g / m ²⁾ blue-sensitive emulsion layer containing a. (10) A layer containing 1.0 g / m ² of gelatin.

Next, a dye fixing material having the constitution shown in Table 30 was prepared.

[0304]

[Table 32]

[0305]

[Chemical 86]

Polymer latex (1): Polymer latex obtained by emulsion polymerization of styrene / butyl acrylate / acrylic acid / N-methylol acrylamide at a weight ratio of 49.7 / 42.3 / 4/4 Polymer latex (2) : Methyl methacrylate /
Acrylic acid / N-methylol acrylamide weight ratio 9
Polymer latex emulsion-polymerized by 3/4

Next, the composition of the treatment liquid is shown. Treatment liquid 1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 6.9 g Methylhydroquinone 0.3 g 5-Methylbenzotriazole 3.5 g Sodium sulfite (anhydrous) 0.2 g Carboxymethylcellulose Na salt 58 g Potassium hydroxide (28% aqueous solution) 200 cc Benzyl alcohol 1.5 cc Water 835 cc

Photosensitive materials 302 to 307 were prepared in exactly the same manner except that the cyan dye-donating compound of photosensitive material 301 was changed to those shown in Table 31.

The light-sensitive materials 301 to 307 were exposed through a color chart in which cyan, magenta, yellow, and gray wedges whose densities were continuously changed were recorded. The treatment liquid was spread between the sheets to a thickness of 60 μm. (Deployment was done with the help of pressure rollers.)
The treatment was carried out at 25 ° C., and 90 seconds after the treatment, the light-sensitive material and the dye-fixing material were peeled off and naturally dried, and the density was measured.

For the density measurement, the reflection density was measured using a density measuring instrument X Light 404 manufactured by X-Light Co., Ltd., and the maximum density (Dmax) and the minimum density (Dmin) of cyan were measured and evaluated.
The image obtained by using the above-mentioned photosensitive materials 301 to 307 was irradiated with xenon light for one week, and the residual rate of the portion where the cyan density was 1.0 was determined. The results are shown in Table 31.

From the results shown in Table 31, it can be seen that the compounds of the present invention gave image densities equivalent to those of the comparative compounds and had improved fastness to light.

Further, it was also revealed that the cyan color image produced by the compound of the present invention had a clear hue with no turbidity.

[0313]

[Table 33]

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one image-forming compound represented by the following general formula (I) on a support. General formula (I) In the formula, Dye represents a dye group or dye precursor group represented by the following general formula (II) or general formula (III), X represents a simple bond or linking group, and Y has a latent image in an image form. It represents a group having a property of causing a difference in diffusibility of dye components in response to or in reverse response to a reaction of a photosensitive silver salt. General formula (II) In the formula, R represents a cyano group, a carboxyl group, a sulfo group, a halogen atom, an alkyl group, an aryl group, a heterocyclic residue, an acyl group, a sulfonyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group. Group, heteroarylthio group, carbamoyl group, sulfamoyl group, acylamino group, sulfonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, aminocarbonylamino group, aminocarbonyloxy group, aminosulfonylamino group, alkoxycarbonyl group Represent. X and Y are each a hydrogen atom, cyano group, carboxyl group, sulfo group, hydroxy group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group, aryl group, heterocyclic residue, acyl group, Sulfonyl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group,
Arylthio group, heteroarylthio group, carbamoyl group, sulfamoyl group, acylamino group, sulfonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyloxy group, aminocarbonylamino group, aminocarbonyloxy group, aminosulfonylamino Represents a group, amino group, alkoxycarbonyl group, acyloxy group, aryloxycarbonyloxy group, sulfonyloxy group. Q represents a heterocyclic residue bonded at the 1- or 3-position to the azo group. q is 1 or 2, and when q is 2, Dye-X may be the same or different. n represents an integer from 0 to 4, and when n is 2 or more, R may be the same or different. A represents a hydrogen atom or a group which gives a hydroxyl group under basic conditions. m represents an integer from 0 to 3, and r represents 1 or 2. However, m + r
≦ 4. When m is 2 or more, or when r is 2, Y
And Q may be the same or different. General formula (III): In the formula, R represents a cyano group, a carboxyl group, a sulfo group, a halogen atom, an alkyl group, an aryl group, a heterocyclic residue, an acyl group, a sulfonyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group. Group, heteroarylthio group, carbamoyl group, sulfamoyl group, acylamino group, sulfonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, aminocarbonylamino group, aminocarbonyloxy group, aminosulfonylamino group, alkoxycarbonyl group In the formula, n represents an integer of 0 to 4, and when n is 2 or more, R may be different. A represents a hydrogen atom or a group which gives a hydroxyl group under basic conditions. Q represents a heterocyclic residue bonded at a carbon atom. Ar represents an aryl group which is not substituted with a nitro group, or a heteroaryl group.