JPH10268489A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material containing low cost yellow dye color image borming composition by incorporating at least one of specified image forming compounds in this photosensitive material. SOLUTION: This photosensitive material contains at least one of the image forming compounds represented by formula I in which dye is an azo dye group represented by formula II or the like; B is a simple bond or a bonding group to be cleft in response or reverse response to development; A is a group for giving difference in diffusivity of the dye in response or reverse response to development of photosensitive silver salts having an imagewise latent image; each of (m) and (n) is 1 or 2, and when (m) is 2, each dye may be same or different, and when (n) is 2, (dye)m -B- may be same or different; R is a substituent; X is a carbon atom or the like; Y is an oxygen atom or the like; Z is an alkyl group or the like; G is the auxochrome group of the dye; (p) is 1 or 2; and (r) is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material having an image forming compound containing a novel azo dye or a precursor of the azo dye.

[0002]

2. Description of the Related Art Color diffusion transfer photography using an azo dye image forming compound which gives an azo dye having a diffusivity different from that of the image forming compound itself as a result of development under basic conditions has been well known for a long time. ing. For example, as an image forming compound releasing a yellow dye, JP-A-52-7
727, 54-79031, JP-A-2-2350
No. 59 and U.S. Pat. No. 4,736,632.

[0003] However, these azo dyes have drawbacks such as insufficient absorption characteristics, inadequate color image fastness, and a long synthesis process up to production and high cost. Was. In addition, when this is used for a diffusion transfer photographic material because of its relatively large molecular weight, a long transfer time is required, which has been an obstacle to performing rapid processing.

[0004]

The azo dyes known so far have been found to have both a sufficient hue sharpness as a yellow dye and sufficient stability to light, heat, air, chemicals and the like. Absent. In addition, molecular design for solving these problems is not practical because the cost of the dye is greatly increased. Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material containing a low-cost yellow dye image-forming compound while improving both the sharpness of hue and the stability against light, heat, air, and chemicals. An object of the present invention is to provide a low-cost silver halide photographic material having improved sharpness of hue and stability to light, heat, air, chemicals and the like.

[0005]

The inventors of the present invention have conducted intensive studies and as a result, have found that a silver halide photographic material having at least one image forming compound represented by the following general formula (1) has the above-mentioned object. That can be achieved effectively and the disadvantages of the prior art can be sufficiently improved.

[0006]

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In the formula, Dye represents an azo dye or an azo dye precursor represented by the following general formula (2), and B represents a mere bond or linkage which is cleaved in correspondence with or in reverse correspondence with the development of silver halide. A represents a group having the property of causing a difference in the diffusibility of a dye portion corresponding to or opposite to the reaction of a photosensitive silver salt having an image-like latent image.
Dye and B are bonded in at least one of R, Y, and Z of the azo dye represented by the following general formula (2) or the azo dye precursor. m and n are 1 or 2, and when m is 2, Dye may be the same or different;
Is 2, (Dye) _m -B- may be the same or different.

[0008]

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In the formula, R represents a substituent. X is a carbon atom,
Y represents an oxygen atom, a sulfur atom or NR
Represents ² . Here, R ² represents a hydrogen atom, an alkyl group, or an aryl group. Z is an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heterocyclic arylthio group, an acylamino group, a sulfonylamino group, an alkoxycarbonylamino group, Represents an aminocarbonylamino group, a sulfamoylamino group, or an amino group.
Y and Z are not bonded to each other to form a ring. G represents an auxochrome of the dye, and represents a group selected from —NR ³ R ⁴ and —OH. Here, R ³ and R ⁴ represent a hydrogen atom, an alkyl group, or an aryl group, and R ³ and R ⁴ may be the same or different. R ³ and R ⁴ may form a 5- to 8-membered ring together with R. p is 1 or 2, and p is 2
In the case, Z may be the same or different. r is 0 to 4, and when r is 2 or more, Rs may be the same or different, and each may form a ring with each other.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the general formula (1) will be described below in detail. m and n are 1 or 2, and when m is 2, Dye may be the same or different, but is preferably 1. When n is 2, (Dye) _m −
B-, may be the same or different, but is preferably 1.

Dye and B are R and R in the general formula (2) described above.
It bonds at at least one of Y and Z, but preferably bonds at R or Z.

The precursor of the dye represented by Dye includes:
For example, dyes whose absorption is temporarily shifted and the like can be mentioned, and specific examples thereof are described in US Pat.
579334, and JP-A-57-15838.

Next, A will be described. A represents a group having a property that an AB bond is cleaved corresponding to or inversely corresponding to a 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 U.S. Pat.
No. 184852).

A will be described in detail. The formula was described including B. (1) A includes a negative-acting releaser that releases a photographically useful group in response to development.

As Y classified as a negative-acting releaser, a group of releasers that release a photographically useful group from an oxidized product is known. Preferred examples of this type A include the following formula (A-1). (A-1)

[0016]

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In the formula, β is necessary to form a benzene ring.
Represents a group of non-metallic atoms.
An unsaturated carbocycle or heterocycle may be condensed. α is-
OZ ^TwoOr -NHZ^ThreeWhere Z^TwoIs a hydrogen atom
Or a group which forms a hydroxyl group by hydrolysis;^Three
Represents a hydrogen atom, an alkyl group, an aryl group, or hydrolysis
Represents a group generating an amino group. Z¹Is a substituent
Alkyl group, aryl group, aralkyl
Group, alkoxy group, alkylthio group, aryloxy
Group, arylthio group, acyl group, sulfonyl group, acyl
Amino group, sulfonylamino group, carbamoyl group, sulfo
Famoyl, ureido, urethane, and heterocyclic groups
Or a cyano group or a halogen atom, and a represents a positive integer.
Shi Z¹Are different even if they are the same when
May be. For formula (Y-1), -X¹Is -NH
SO_TwoZ^FourA group represented by^FourRepresents a divalent group.

Preferred groups among the groups contained in (A-1) are (A-2) and (A-3). (A-2)

[0019]

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(A-3)

[0021]

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In the formula, Z ² and X ¹ have the same meanings as described in (A-1). Z ⁵ and Z ⁶ represent an alkyl group, an aryl group, or an aralkyl group, and these may have a substituent. Further Z ⁵
Is a secondary or tertiary alkyl group, and preferably has a sum of carbon numbers of Z ⁵ and Z ⁶ of 20 or more and 50 or less.

Examples of these are disclosed in US Pat.
No. 28, 4,336,322, JP-A-51-113
No. 624, No. 56-16131, No. 56-71061
No. 56-71060, No. 56-71072, No. 56-73057, No. 57-650, No. 57-40
No. 43, No. 59-60439, JP-B-56-1765
No. 6, No. 60-25780.

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

[0025]

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In the formula, α, X ¹ , Z ¹ and a have the same meanings as described in (A-1). β ¹ represents a group of nonmetallic atoms necessary for forming a benzene ring, and the benzene ring may be condensed with a saturated or unsaturated carbocyclic or heterocyclic ring.

In the group represented by (A-4), α is -OZ
² , wherein β ¹ forms a naphthalene skeleton. Specifically, US Pat. No. 3,928,312
No. 4,135,929.

Japanese Patent Application Laid-Open (JP-A) Nos. 51-104343, 53-46730 and 54-54 describe releasers which release a photographically useful group by the same reaction as (A-1) and (A-2).
-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.
The groups described in No. 4 can be mentioned.

Compounds which release a photographically useful group from an oxidized product by another reaction mechanism include those represented by formula (A-5) or (A-
The hydroquinone derivative represented by 6) is mentioned. (A-5)

[0030]

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(A-6)

[0032]

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Where β¹Is Z in the formula (A-4)^TwoIs the formula (A-
It has the same meaning as described in 1), and Z⁷Is Z ^TwoIs synonymous with Z
⁸Is Z¹Represents a substituent or a hydrogen atom described above. Z^TwoAnd Z⁷
May be the same or different. Specific examples of this kind
Are described in U.S. Pat. No. 3,725,062.

Hydroquinone derivative releasers of this type include those having a nucleophilic group in the molecule. Specifically, it is described in JP-A-4-97347.

Another example of A is disclosed in US Pat.
P-hydroxydiphenylamine derivatives described in U.S. Pat. No. 3,939, U.S. Pat. Nos. 3,844,785 and 4,684,604; D. And hydrazine derivatives described in Journal No. 128, p. 22.

The negative acting releaser is represented by the following formula (A-7). (A-7)

[0037]

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In the formula, Coup represents a group that couples with an oxidized product of p-phenylenediamines or p-aminophenols, that is, a group known as a photographic coupler. A specific example is described in British Patent 1,330,524.

(2) Next, A is a positive-acting releaser that releases a photographically useful group in reverse to development.

Examples of the positive-acting releaser include a releaser which exhibits a function when reduced at the time of treatment. Preferred examples of this type of A include the following formula (A-
8). (A-8)

[0041]

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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 each} represent a mere bond or a substituent other than a hydrogen atom. A solid line indicates a bond, and a broken line indicates that at least one of them is connected.

Among the groups represented by the formula (A-8), a preferred one is the formula (A-9). (A-9)

[0044]

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In the formula, O represents an oxygen atom (that is, (A-8)
W represents an oxygen atom), and Z ¹² represents an atomic group having the property of forming a heterocyclic ring containing an NO bond and breaking the Z ¹² -B bond following cleavage of the NO bond. Z ¹² may have a substituent or a saturated or unsaturated ring may be condensed. Z ¹³ represents —CO— or —SO ₂ —.

As a more preferred group of (A-9), (A-10) can be mentioned. (A-10)

[0047]

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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; and 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, or 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. Most preferably, 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 this type of A is disclosed in JP-A-62-2.
No. 15,270 and U.S. Pat. No. 4,783,396.

Other positive-acting releasers that exhibit functions by being reduced include BEND compounds described in US Pat. Nos. 4,139,379 and 4,139,389, and British Patent No. 11,445. Carq as listed in
uin compound, JP-A-54-126535, JP-A-57
-84453.

When these reducible releasers represented by A represented by (A-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 disclosed in US Pat. No. 4,551,4.
No. 23.

Some positive-acting releasers are contained in the light-sensitive material as reductants and deactivate when oxidized during processing. Japanese Patent Application Laid-Open No. 51-63618 and U.S. Pat.
Fields compound described in No. 79 and JP-A-49-11162
No. 8, No. 52-4819, U.S. Pat. No. 4,199,35
No. 4 Hinshaw compound.

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

[0054]

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Where Z¹⁷, Z¹⁹Is a hydrogen atom or
Or unsubstituted acyl group, alkoxycarbonyl group,
Z represents an oxycarbonyl group;¹⁸Is an alkyl group,
Reel group, aralkyl group, acyl group, alkoxycarbo
Nyl group, aryloxycarbonyl group, carbamoyl
A sulfonyl group, a sulfonyl group or a sulfamoyl group;²⁰, Z
^{twenty one}Is a hydrogen atom or a substituted or unsubstituted alkyl group,
Represents a reel group or an aralkyl group. Specifically, JP-A-62
-245270 and 63-46450.
You.

As a positive-acting releaser having another mechanism, there is a thiazolidine-type releaser. Specifically, it is described in U.S. Pat. No. 4,468,451.

Hereinafter, the general formula (2) will be described in detail. In the formula, R represents a substituent, and examples of the substituent include the following. Cyano group, carboxyl group, sulfo group, hydroxy group, nitro group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (having 30 or less carbon atoms, preferably 8 or less carbon atoms) Good alkyl groups, for example, methyl, trifluoromethyl, benzyl, dimethylaminomethyl, ethoxycarbonylmethyl, acetylaminomethyl, ethyl, carboxyethyl, allyl, n-propyl,
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 (optionally substituted aryl group having 30 or less carbon atoms, preferably 10 or less carbon atoms, for example, phenyl group, naphthyl group, 3- Hydroxyphenyl group, 3-
Chlorophenyl group, 4-acetylaminophenyl group, 2
A methanesulfonylphenyl group, a 4-methoxyphenyl group, a 4-methanesulfonylphenyl group, a 2,4-dimethylphenyl group, etc.), a heterocyclic residue (having 30 or less carbon atoms,
An optionally substituted heterocyclic residue having preferably 10 or less carbon atoms. 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-
A tetrazolyl group, a 2-benzothiazolyl group, a 2-benzimidazolyl group, a 2-benzoxazolyl group, a 2-oxazolin-2-yl group, a morpholino group, etc., an acyl group (having 20 or less carbon atoms, preferably 8 or less carbon atoms) Which may be substituted, for example, acetyl, propionyl, butyroyl, iso-butyroyl, 2,2-dimethylpropionyl, benzoyl, 3,4-dichlorobenzoyl, 3-acetylamino-4 -Methoxybenzoyl group, 4-methylbenzoyl group, etc.), sulfonyl group (optionally substituted sulfonyl group having 20 or less carbon atoms, preferably 8 or less carbon atoms, for example, methanesulfonyl group, ethanesulfonyl group, chloromethanesulfonyl group) ,
Propanesulfonyl group, butanesulfonyl group, n-octanesulfonyl group, n-dodecanesulfonyl group, benzenesulfonyl group, 4-methylphenylsulfonyl group, etc.),

An alkoxy group (optionally substituted alkoxy group having 20 or less carbon atoms, preferably 8 or less carbon atoms; for example, methoxy group, ethoxy group, n-propyloxy group,
iso-propyloxy group, cyclohexylmethoxy group and the like), aryloxy group, heteroaryloxy group (optionally substituted aryloxy group having 20 or less carbon atoms, preferably 10 or less carbon atoms, heteroaryloxy group. Phenoxy group, naphthyloxy group, 4-acetylaminophenoxy group, pyrimidin-2-yloxy group, 2-pyridyloxy group, etc., silyloxy group (having 10 or less carbon atoms, preferably 8 or less carbon atoms) Good silyloxy group, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group, etc., alkylthio group (C20 or less, preferably C8 or less, optionally substituted alkylthio group, for example, methylthio group, ethylthio group) , N-butylthio group,
an n-octylthio group, a t-octylthio group, an ethoxycarbonylmethylthio group, a benzylthio group, a 2-hydroxyethylthio group, an arylthio group, a heteroarylthio group (having 20 or less carbon atoms, preferably having 10 or less carbon atoms) Arylthio and heteroarylthio groups such as phenylthio, 4-chlorophenylthio, 2-n-butoxy-5-t-octylphenylthio, 4-nitrophenylthio, and 2-nitrophenylthio; Group, 4-acetylaminophenylthio group, 1-phenyl-5-tetrazolylthio group, 5-methanesulfonylbenzothiazol-2-yl group, etc., carbamoyl group (having 20 or less carbon atoms, preferably having 8 or less carbon atoms) Carbamoyl groups such as carbamoyl and methylcarbamoyl , Dimethylcarbamoyl group, a bis -
(2-methoxyethyl) carbamoyl group, diethylcarbamoyl group, cyclohexylcarbamoyl group, di-n-
An octylcarbamoyl group, a sulfamoyl group (an optionally substituted sulfamoyl group having 20 or less carbon atoms, preferably 8 or less carbon atoms, for example, a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, a bis- (2 -Methoxyethyl) sulfamoyl group, diethylsulfamoyl group, di-n-butylsulfamoyl group, methyl-n-octylsulfamoyl group, 3-ethoxypropylmethylsulfamoyl group, N-phenyl-
N-methylsulfamoyl group),

Acylamino group (optionally substituted acylamino group having 20 or less carbon atoms, preferably 8 or less carbon atoms;
For example, an acetylamino group, a 2-carboxybenzoylamino group, a 3-nitrobenzoylamino group, a 3-diethylaminopropanoylamino group, an acryloylamino group, etc., a sulfonylamino group (having 20 or less carbon atoms, preferably having 8 or less carbon atoms) A sulfonylamino group which may be substituted, for example, a methanesulfonylamino group, a benzenesulfonylamino group, a 2-methoxy-5-n-methylbenzenesulfonylamino group, an alkoxycarbonylamino group (having 20 or less carbon atoms, preferably An alkoxycarbonylamino group which may be substituted by the number 8 or less, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a 2-methoxyethoxycarbonylamino group,
iso-butoxycarbonylamino group, benzyloxycarbonylamino group, t-butoxycarbonylamino group, 2-cyanoethoxycarbonylamino group, etc., alkoxycarbonyloxy group (having 20 or less carbon atoms, preferably having 8 or less carbon atoms) An alkoxycarbonyloxy group such as a methoxycarbonyloxy group,
An ethoxycarbonyloxy group, a methoxyethoxycarbonyloxy group, etc., an aryloxycarbonylamino group (optionally substituted aryloxycarbonylamino group having 20 or less carbon atoms, preferably 8 or less carbon atoms, for example, phenoxycarbonylamino group, 2 , 4-nitrophenoxycarbolamino group, 4-t-butoxyphenoxycarbonylamino group, etc.), aminocarbonylamino group (optionally substituted aminocarbonylamino group having 20 or less carbon atoms, preferably 8 or less carbon atoms. , Methylaminocarbonylamino group, morpholinocarbonylamino group, diethylaminocarbonylamino group, N-ethyl-N-phenylaminocarbonylamino group, 4-cyanophenylaminocarbonylamino group, 4-methanesulfonylaminocarbonyl An aminocarbonyloxy group (an aminocarbonyloxy group having 20 or less carbon atoms, preferably 8 or less carbon atoms, which may be substituted, such as a dimethylaminocarbonyloxy group or a pyrrolidinocarbonyloxy group), aminosulfonyl An amino group (an optionally substituted aminosulfonylamino group having 20 or less carbon atoms, preferably 8 or less carbon atoms, such as a diethylaminosulfonylamino group, a di-n-butylaminosulfonylamino group, and a phenylaminosulfonylamino group);

Amino group (having 30 or less carbon atoms, preferably 8
The following optionally substituted amino groups. For example, an amino group,
Methylamino group, dimethylamino group, ethylamino group,
Ethyl-3-carboxypropylamino group, ethyl-2
-A sulfoethylamino group, a phenylamino group, a methylphenylamino group, a methyloctylamino group and the like, an alkoxycarbonyl group (an optionally substituted alkoxycarbonyl group having 20 or less carbon atoms, preferably 6 or less carbon atoms, for example, methoxycarbonyl Group, ethoxycarbonyl group,
A methoxyethoxycarbonyl group or the like), an aryloxycarbonyl group (an optionally substituted aryloxycarbonyl group having 20 or less carbon atoms, preferably 10 or less carbon atoms, such as a phenoxycarbonyl group or a p-methoxyphenoxycarbonyl group), or an acyloxy group (An optionally substituted acyloxy group having 20 or less carbon atoms, preferably 8 or less. For example, an acetoxy group, a benzoyloxy group, a 2-
Butenoyloxy group, 2-methylpropanoyloxy group, etc., aryloxycarbonyloxy group (C 2
0 or less, preferably 8 or less, optionally substituted aryloxycarbonyloxy groups. For example, a phenoxycarbonyloxy group, a 3-cyanophenoxycarbonyloxy group, a 4-acetoxyphenoxycarbonyloxy group,
-T-butoxycarbonylaminophenoxycarbonyloxy group, etc., sulfonyloxy group (optionally substituted sulfonyloxy group having 20 or less carbon atoms, preferably 8 or less, for example, phenylsulfonyloxy group, methanesulfonyloxy group, chloromethane Sulfonyloxy group, 4-chlorophenylsulfonyloxy group, dodecylsulfonyloxy group, etc.).

R is 0 to 4, and when r is 2 or more, Rs may be the same or different, and each may form a ring with each other. This ring may be a carbocycle or a heterocycle.

Particularly preferred as R is a cyano group,
Carboxyl group, nitro group, halogen atom (fluorine atom, chlorine atom), alkyl group, sulfonyl group, alkoxy group, carbamoyl group, sulfamoyl group, acylamino group, and sulfonylamino group.

X represents a carbon atom, a sulfur atom and a phosphorus atom, and Y represents an oxygen atom, a nitrogen atom and a sulfur atom. X is particularly preferably a carbon atom or a phosphorus atom, more preferably a carbon atom. Particularly preferred as Y is an oxygen atom.

P is 1 or 2, and when p is 2,
Z may be the same or different.

Z is an alkyl group, aryl group, heterocyclic residue, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heterocyclic arylthio group, acylamino group, sulfonylamino group, alkoxycarbonylamino Group, aminocarbonylamino group, sulfamoylamino group, represents an amino group,
The details are the same as those described for R.

Z is preferably an alkoxy group, an aryloxy group, a heteroaryloxy group or an amino group, more preferably an alkoxy group or an amino group.
Particularly preferred is an alkoxy group.

Y and Z are not bonded to each other to form a ring. G represents an auxochrome of the dye, and represents —NR ³ R ⁴ , —OH
Represents a group selected from Here, R ³ and R ⁴ represent a hydrogen atom, an alkyl group or an aryl group, and examples of the substituent are the same as those described for R. Here, R ³ and R ⁴ may be the same or different. R ³ and R ⁴ may form a 5- to 8-membered ring together with R.

When the dye of the present invention is used, it is preferable to use a dissociator in which a hydrogen atom is removed from a hydroxyl group of the general formula (1), and for this purpose, it is preferable to use a basic substance and / or a mordant in combination. As the basic substance, any of organic bases such as amines and inorganic bases such as sodium hydroxide may be used. The mordant will be described later.

Hereinafter, specific examples of the image forming compound represented by formula (1) used in the present invention will be shown, but the present invention is not limited thereto.

[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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Specific examples of the dye moiety in the image forming compound of the formula (1) used in the present invention are shown below, but the present invention is not limited to these. Here, the dye portion is obtained by removing any hydrogen atom from these exemplified dyes.

[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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Next, a method for synthesizing the image forming compound used in the present invention will be described.

The dye represented by the general formula (2) of the present invention is p
Hydrazide is obtained by the reaction of a hydrazine having an amino group, a hydroxyl group, or a hydroxyl group equivalent (a group that can be easily converted to a hydroxyl group later) with a corresponding acid halide, isocyanate, or other acid halide equivalent. It can be easily obtained by oxidation with various oxidizing agents. Further, the image forming compound of the present invention can be easily synthesized with reference to the method described in the patent cited in the description of formula (1).

Next, typical synthesis examples will be described. (1) Synthesis of Compound Example (13) 1) Synthesis of Intermediate (A) 11.0 g of 4-aminophenol and 9.0 g of 3-hydroxypropionic acid were combined with N, N-dimethylacetamide 10
0 ml, and a solution of 25.7 g of dicyclohexylcarbodiimide dissolved in 20 ml of N, N-dimethylacetamide was added dropwise at room temperature over 10 minutes. After dripping,
After further reacting for 2 hours, the reaction solution was poured into 300 ml of water, and the precipitated crystals were separated by filtration, washed with water and dried to obtain an intermediate (A) 1.
5.5 g were obtained.

[0092]

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2) Synthesis of Intermediate (B) The mixture was heated under reflux for 3 hours in 18.2 g of the intermediate (A), 57.8 g of the compound (C), 30 g of potassium carbonate and 500 ml of acetone. After the reaction, the reaction solution was poured into 1 liter of 1N hydrochloric acid, and the obtained crystals were separated by filtration, washed with water and dried, and 62.6 g of the intermediate (B) was obtained.
I got

[0094]

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3) Synthesis of Intermediate (E) 17.8 g of 4-amino-2,6-dichlorophenol was dissolved in 26.1 ml of concentrated hydrochloric acid and 50 ml of water, and the reaction temperature was kept at 5 ° C. or lower under ice-cooling. 7.6 g of sodium nitrite
Was added dropwise. After further reacting at 5 ° C or lower for 1 hour, 40 ml of concentrated hydrochloric acid was added, and 42 g of tin chloride was added.
A 00 ml methanol solution was added keeping the reaction temperature below 5 ° C. After the dropwise addition, the reaction temperature was raised to room temperature, and the reaction was further performed for 2 hours. After the reaction, the reaction solution was poured into 300 ml of methanol, and the precipitated crystals (intermediate (D)) were separated by filtration. Intermediate (D) was used in the next reaction without drying completely. Separately, 72.2 g of the intermediate (B) was dissolved in 500 ml of acetonitrile and heated under reflux. To this, 16.4 g of phenyl chloroformate was added dropwise over 20 minutes. After the dropwise addition, the mixture was refluxed for another 6 hours, and then the above-mentioned intermediate (D), 8.2 g of imidazole and 8 ml of pyridine were added.
The reaction was continued for another hour. After the completion of the reaction, the reaction solution was poured into 2 liters of 1N hydrochloric acid. The precipitated crystals were separated by filtration, washed with water, and dried to obtain 88.8 g of an intermediate (E).

[0096]

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4) Synthesis of Exemplified Compound (13) 47.1 g of the intermediate (E) was dissolved in 500 ml of ethyl acetate, and 21.8 g of manganese dioxide was separately added at room temperature in 5 portions. After the addition, the mixture was further reacted for 1 hour, insolubles were removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and hexane / ethyl acetate = 1/1.
From the eluate, 37.1 g of Compound Example (13) was obtained as an oil.

In the present invention, any of the layers on the support contains a silver halide color photographic light-sensitive material containing at least one image-forming compound represented by the above formula (1). The amount of the image forming compound used in the present invention can be varied within a wide range, but is usually 0.01 mol to 4 mol, preferably 0.05 mol to 0.1 mol, per mol of silver.
Used in the range of 5 moles.

The above-mentioned image-forming compounds and hydrophobic additives such as image-forming accelerators described below are described in US Pat.
It can be introduced into the layer of the photosensitive element by a known method such as the method described in JP-A No. 22,027. In this case, Japanese Patent Application Laid-Open Nos. 59-83154, 59-178451, 59-178452, 59-178453, and 5
Nos. 9-178454, 59-178455, 59
A high-boiling organic solvent as described in, for example, 178457 can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C, if necessary. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye image forming compound used. In addition, Japanese Patent Publication No. 51-39
No. 853 and JP-A-51-59943.

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

In the present invention, a dye-donating compound represented by the following general formula (3) can be used in combination. General formula (3) DYE-A

Here, DYE represents a dye or a precursor thereof, and A represents a component which gives a compound having a different diffusibility from the compound under alkaline conditions. According to the function of A, the compound is roughly classified into a negative type compound which becomes diffusible in a silver developed portion and a positive type compound which becomes diffusible in an undeveloped portion.

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

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

Among the Y's in the negative dye-releasing redox compound, a particularly preferred group is an N-substituted sulfamoyl group (an N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). Can be. Representative examples of A, positive-type compounds, and other types of compounds, etc. are described in JP-A-2-32335, page (16), upper left column to the publication (1).
7) The contents of the description up to the 7th line in the lower right column of the page apply.

When the dye-providing compound that can be used in combination in the present invention is a reducible dye-providing compound, a reducing agent (sometimes referred to as an electron donor) is used. The reducing agent may be supplied from the outside or may be previously contained in the photosensitive material. In addition, a reducing agent precursor which does not itself have a reducing property but develops a reducing property by the action of a nucleophilic reagent or heat during the development process can be used.

Examples of the electron donor used in the present invention are described in US Pat. No. 4,500,626, Nos. 49-50.
Column, column Nos. 30-31 of No. 4,483,914;
Nos. 330,617 and 4,590,152;
0-140335, pages (17) to (18), ibid.
No.-40245, No.56-138736, No.59-1
No. 78458, No. 59-53831, No. 59-182
No. 449, No. 59-182450, No. 60-1195
No. 55, 60-128436 to 60-1284
No. 39, No. 60-198540, No. 60-181
No. 742, No. 61-259253, No. 62-2440
No. 44, No. 62-131253 to No. 62-1312
No. 56, No. 78 of EP 220,746 A2.
And electron donor precursors described on pages 96 to 96 and the like. Various electron donor combinations, such as those disclosed in U.S. Pat. No. 3,039,869, can also be used.

When the dye-donating compound of the present invention has diffusion resistance, or when the reducing agent used in combination with the reducible dye-donating compound of the present invention has diffusion resistance, 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 higher mobility than 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 is not particularly limited as long as it does not substantially move in the layer of the light-sensitive material among the above-described reducing agents, and is preferably a hydroquinone or a sulfonamide phenol. And sulfonamide naphthols, and compounds described as electron donors in JP-A-53-110827. The electron transfer agent may be supplied from the outside or may be previously contained in the photosensitive material.

The dye-providing compounds that can be used in the present invention include:
It 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 via an electron transfer agent. For example, if a colored dye-providing compound is present in the lower layer of the silver halide emulsion layer, a decrease in sensitivity can be prevented.

The above-mentioned dye-providing compound can be used for a diffusion transfer type color photographic light-sensitive material. As a method for developing and forming an image, a method of developing a processing composition at around room temperature, supplying a small amount of water, or using a hot solvent It is possible to adopt a method in which the composition is contained and heat development is performed.

First, the color diffusion transfer method will be described. A typical form of the 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 removed. This is a form that does not need to be separated 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 light-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-donating substance, a magenta dye (Infrared light-sensitive emulsion layer means an emulsion layer having a sensitivity to light of 700 nm or more, particularly 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 layer containing the dye-providing substance 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 developing process can be completed in a light place. If desired, a release layer may be provided at an appropriate position so that all or a part of the photosensitive element can be peeled off from the image receiving element.
7840 and Canadian Patent 674,082).

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

In another mode in which peeling is unnecessary, the above-described photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. .
An image receiving element, a white reflective layer, a release layer, and a photosensitive element are laminated on the same support, and an embodiment in which the photosensitive element is intentionally peeled from the image receiving element is described in US Pat. No. 3,730,71.
No. 8 is described.

On the other hand, there are roughly two typical forms in which a photosensitive element and an image receiving element are separately coated on two supports, respectively, one of which is a peeling type, and the other is a peeling-free type. is there. More specifically, 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. Before the end of the exposure, the photosensitive layer-coated surface and the mordant layer-coated surface are not opposed to each other, but after the end of the exposure (for example, during the developing process), the photosensitive layer-coated surface is turned upside down and overlaps with the image-receiving layer-coated surface. .
After the transfer image is completed in the mordant layer, the photosensitive element is immediately separated from the image receiving element.

In a preferred embodiment of the peeling-free film unit, at least one mordant layer is provided on a transparent support, and a photosensitive element is provided on a support having a transparent or light-shielding layer. The surface on which the photosensitive layer is applied and the surface on which the mordant layer is applied face each other.

The above-described embodiment may be combined with a pressure-rupturable container (processing element) further containing an alkaline processing liquid. In particular, in a peeling-free 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. In the case where the photosensitive element and the image receiving element are separately coated on the two supports, it is preferable that the processing element is arranged between the photosensitive element and the image receiving element at the latest at the time of development processing. The processing element preferably contains a light-shielding agent (such as carbon black or a dye whose color changes depending on pH) and / or a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in the film unit of the color diffusion transfer system, 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.

Hereinafter, the image receiving element of the color diffusion transfer method will be described in more detail. The image receiving element of the color diffusion transfer method preferably has at least one layer containing a mordant (mordanting layer). As the mordant, those known in the field of photography can be used. A specific example is British Patent 2,011.
No. 1,912, No. 2,056,101, No. 2,09
No. 3,041, U.S. Pat. Nos. 4,115,124, 4,273,853, 4,282,305, JP-A-59-232340, JP-A-60-118834, and JP-A-60-128443. No. 60-122940, No. 6
Nos. 0-122921 and 60-235134.

In addition, various additives can be appropriately used in the image receiving element for the color diffusion transfer method, and these are described in the section of the dye fixing element (image receiving element) for the color diffusion transfer method for heat development. It is explained together.

Next, the photosensitive element of the color diffusion transfer method will be described. Japanese Patent Application Laid-Open No. 2-32335 discloses a processing composition such as a silver halide emulsion, a spectral sensitizing dye, an emulsion layer, and a full-color multilayer structure used in a color diffusion transfer method. 17) Bottom right column, line 8 to the same publication (20) Bottom right column 19
The contents described up to the line apply.

Next, the release layer of the color diffusion transfer method will be described. The release layer used in the present invention can be provided at any position on the photosensitive sheet in the unit after the treatment. Examples of the release material include JP-A-47-8237, JP-A-59-220727, JP-A-49-4653, U.S. Pat. Nos. 3,220,835, 4,359,518, and JP-A-49-49518. No.-4334, No.50-65133, No.45
-24075, U.S. Pat. Nos. 3,227,550, 2,759,825, 4,401,746, and 4,366,227 can be used. Specific examples include water-soluble (or alkali-soluble) cellulose derivatives. Examples include hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, and the like. In addition, there are various natural polymers such as alginic acid, pectin, and gum arabic. Also, various modified gelatins, for example, acetylated gelatin, phthalated gelatin and the like can be used. Further, polyvinyl alcohol, polyacrylate, polymethyl methacrylate or a copolymer thereof is used. Of these, a cellulose derivative is preferably used as the release material, and hydroxyethyl cellulose is particularly preferably used. Also,
In addition to the water-soluble cellulose derivative, a granular substance such as an organic polymer can be used as a material for peeling. The organic polymer used in the present invention has an average particle size of 0.01 μm.
m to 10 μm polyethylene, polystyrene, polymethyl methacrylate, polyvinylpyrrolidone, polymer latex such as butyl acrylate, and the like.Here, as described below, contains air inside,
It is preferable to use a light-reflective hollow polymer latex containing a material having an organic polymer on the outside. The light-reflective hollow polymer latex is disclosed in JP-A-61-151646.
Can be synthesized by the method described in the above item.

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

The silver halide which can be used 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 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 light fogging. Further, a so-called core-shell emulsion having a different phase between the inside of the grain and the grain surface layer may be used. The silver halide emulsion may be monodispersed or polydispersed, or a mixture of monodispersed emulsions may be used. The particle size is preferably from 0.1 to 2 μm, particularly preferably from 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 any other. Specifically, U.S. Pat. Nos. 4,500,626, column 50, 4,628,021, and Research Disclosure Magazine (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 and the like can be used.

The silver halide emulsion may be used as it is after unripe, but usually it is used after chemical sensitization. A known sulfur sensitization method, reduction sensitization method, noble metal sensitization method, selenium sensitization method, or the like can be used alone or in combination for an emulsion for a conventional light-sensitive material. These chemical sensitizations can also 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 can be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 0,626, columns 52 to 53 and the like. In addition, JP
Silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate described in JP-A-113235;
The acetylene silver described in 1-249944 is also useful.
Two or more organic silver salts may be used in combination. The above organic silver salts can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of the photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is suitably from 50 mg to 10 g / m ² in terms of silver.

In the present invention, various antifoggants or photographic stabilizers can be used. Examples thereof include azoles and azaindenes described in RD17643 (1978), pp. 24-25, and JP-A-59-1684.
No. 42 nitrogen-containing carboxylic acids and phosphoric acids,
Or JP-A-59-111636, JP-A-4-73
No. 649, mercapto compounds and metal salts thereof, and acetylene compounds described in JP-A-62-87957 and JP-A-4-255845.

The silver halide used in the present invention may be spectrally sensitized with methine dyes or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyan 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, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, a dye which has no spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. , 615, 641, and JP-A-61-23145). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

As the binder for the constituent layers of the photosensitive material and the dye fixing element, hydrophilic binders are preferably used. Examples thereof include pages (26) to (2) of JP-A-62-253159.
8) Those described on page 8 are mentioned. Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Further, a superabsorbent polymer described in JP-A-62-245260, that is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or those vinyl monomers or other vinyl monomers. (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) may also be used. These binders can be used in combination of two or more.

In the case of employing a system in which a small amount of water is supplied to carry out thermal development, the use of the above superabsorbent polymer makes it possible to rapidly absorb water. Further, when the superabsorbent polymer is used for the dye fixing layer and its protective layer, it is possible to prevent the dye from being re-transferred 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 preferably 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 film physical properties such as dimensional stability, curling prevention, adhesion prevention, film crack prevention and pressure increase / decrease sensation. Various polymer latexes can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, and 62-110066 can be used. Especially,
When a polymer latex having a low glass transition point (40 ° C. or less) is used for the mordant layer, it is possible to prevent cracking of the mordant layer, and when a polymer latex having a high glass transition point is used for the back layer, an anti-curl effect is obtained. Can be

In the present invention, a redox compound releasing a development inhibitor can be used. For example, JP-A-61-21
No. 3,847, No. 62-260, 153;
Nos. 68,547, 2-110,557, 253
Nos. 253 and 1-150, 135 can be used. A method for synthesizing the development inhibitor releasing redox compound used in the present invention is described in, for example, JP-A-61-21.
Nos. 3,847, 62-260,153, U.S. Pat. No. 4,684,604, JP-A-1-269936, U.S. Pat. Nos. 3,379,529 and 3,620,746.
No. 4,377,634, No. 4,332,878
JP-A-49-129,536 and JP-A-56-153,
336, 56-153, 342 and the like.

The development inhibitor-releasing redox compound of the present invention is used in an amount of from 1 × 10 ^{−6 to} 5 × 10 ⁻² per mol of silver halide.
Mole, more preferably in the range of 1 × 10 ^-5 to 1 × 10 ^-2 mole. The development inhibitor releasing redox compound used in the present invention may be any suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide. And methylcellosolve. In addition, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. Objects can also be created and used. Alternatively, by a method known as a solid dispersion method, a powder of a development inhibitor-releasing redox compound is placed in water with a ball mill, a colloid mill,
Alternatively, they can be used by being dispersed by ultrasonic waves.

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 which activates the development of the photosensitive material and simultaneously stabilizes the image can be used. Specific compounds preferably used are described in U.S. Pat.
No. 0,626, columns 51 to 52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a photosensitive material. The dye-fixing element may be in the form of being separately coated on a support separate from the light-sensitive material, or in the form of being coated on the same support as the light-sensitive material. The relationship between the photosensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer described in US Pat. No. 4,500,626, column 57, can be applied to the present invention. 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 field of photography can be used, and specific examples thereof are described in US Pat.
00,626, columns 58-59 and JP-A-61-8825.
No. 6, pages (32) to (41);
Nos. 2-244043 and 62-244036. Also, U.S. Pat.
A dye-accepting polymer compound as described in JP-A-63,079 may be used. The dye-fixing element may be provided with an auxiliary layer such as a protective layer, a release layer, and an anti-curl layer, if necessary. It is particularly useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing element, a plasticizer, a sliding agent, or a high-boiling organic solvent can be used as an agent for improving the releasability of the light-sensitive material and the dye-fixing element. Specifically, Japanese Patent Application Laid-Open No. 62-253159 (2)
5), pages 62-245253 and the like. Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. Examples thereof include various modified silicone oils described in Technical Data P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X).
-22-3710) are effective. In addition, JP
Silicone oils described in JP-A-2155953 and JP-A-63-46449 are also effective.

An anti-fading agent may be used in a light-sensitive material or a dye-fixing element. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.
Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, 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-based compounds (such as U.S. Pat. No. 3,533,794), 4-thiazolidone-based compounds (such as U.S. Pat. No. 3,352,681),
Benzophenone compounds (JP-A-46-2784, etc.), and JP-A-54-48535, 62-13
Nos. 6641 and 61-88256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are 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 27-29), JP-A-63-199248, JP-A-1-75568 and JP-A-1-74272.

Examples of useful discoloration inhibitors are described in JP-A-62-21.
No. 5272, pages (125) to (137). An anti-fading agent for preventing 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 photosensitive material. . The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other. A fluorescent whitening agent may be used for the light-sensitive material and the dye fixing element. In particular, whether the dye-fixing element contains a fluorescent whitening agent,
It is preferable to supply from the outside such as a photosensitive material. For example, K. Veenkataraman ed., “The Chemistry of Sy
nthetic Dyes ", Volume V, Chapter 8, JP-A-61-14375
Compounds described in No. 2 and the like can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds,
And carbostyryl compounds. The fluorescent whitening agent can be used in combination with an anti-fading agent.

Examples of the hardener used in the constituent layers of the light-sensitive material and the dye-fixing element include US Pat. No. 4,678,739, No. 4,
Column 1, JP-A-59-116655, JP-A-62-2452
No. 61, No. 61-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane, etc., N
-Methylol-based hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157). Particularly preferred is JP-A-Hei 3
A vinyl sulfone hardener described in JP-A-114043 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, improving releasability, improving slipperiness, preventing static charge, accelerating development and the like. Specific examples of the surfactant are described in JP-A-62-173463.
And No. 62-183457. 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 static charge, and improving releasability. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-61-20.
No. 944, No. 62-135826 or the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as ethylene tetrafluoride resin. No.

A matting agent can be used for the light-sensitive material and the dye fixing element. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
JP-A-63-274944 such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads in addition to the compounds described on page 1-88256 (29).
And No. 63-274952. In addition, the constituent layers of the light-sensitive material and the dye-fixing element may contain a heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica and the like. Specific examples of these additives are described 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. Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the generation of a dye from a dye-providing substance or the decomposition or release of a diffusible dye, and the use of a photosensitive material layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40. Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement, and the like. A specific example is disclosed in U.S. Pat. No. 4,511,493.
And JP-A-62-65038.

In a system in which thermal development and transfer of a dye 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 from the viewpoint of improving the storability of the light-sensitive material. In the present invention, EP 210,660, U.S. Pat.
Use is made of a combination of the hardly soluble metal compound described in No. 45 and a compound capable of forming a complex with a metal ion constituting the hardly soluble metal compound (referred to as a complex forming compound). Specifically, JP-A-2-269,338 (2)-
It is described on page (6). Particularly preferred compounds as poorly soluble metal compounds are zinc hydroxide, zinc oxide and mixtures thereof.

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 with respect to fluctuations in processing temperature and processing time during development. As used herein, the term "development terminator" refers to a compound that neutralizes a base or reacts with a base immediately after appropriate development to reduce the base concentration in the film and to stop development by interacting with a compound or silver and silver salt to suppress development. And specifically include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. Can be For further details, see JP-A-62-25
No. 3159, pages (31) to (32).

In the present invention, a support capable of withstanding the processing temperature is used as a support for the light-sensitive material and the dye-fixing element. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or a film containing pigment such as titanium oxide in these films, and polypropylene. For example, a mixed paper made from synthetic resin pulp such as polyethylene, a synthetic resin pulp such as polyethylene, and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass and the like are used. These can be used alone,
It can also be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, 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, or another antistatic agent may be applied to the surface of these supports.

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

As a light source for recording an image on a photosensitive material,
As described above, light sources described in U.S. 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. Also, image exposure can 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 express nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is given,
Lithium niobate, potassium dihydrogen phosphate (KDP),
Inorganic compounds represented by lithium iodate, BaB ₂ O _{4 and the} like, urea derivatives, nitroaniline derivatives, for example, 3-
Methyl-4-nitropyridine-N-oxide (POM)
Nitropyridine-N-oxide derivatives such as those described in JP-A-61-53462 and JP-A-62-210432 are preferably used. As a 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 image information includes an image signal obtained from a video camera, an electronic still camera, a television signal represented by the Nippon Television Signal Standards (NTSC), and an image obtained by dividing an original image into a number of pixels such as a scanner. Signals, image signals applied using a computer represented by CG and 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 diffusion transfer of the dye. The transparent or opaque heating element in this case is described in JP-A-61-1.
No. 45544 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., but development at about 80 ° C. to about 180 ° C. is particularly useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step. In the latter case, the heating temperature in the transfer step can be transferred within the range from the temperature in the heat development step to room temperature, but is more preferably from 50 ° C. or higher to about 10 ° C. lower than the temperature in the heat development step.

Although the transfer of the dye is caused only by heat,
Solvents may be used to promote dye transfer. Also,
As described in detail in JP-A-59-218443 and JP-A-61-238056, a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also useful. is there. In this method, the heating temperature is preferably not lower than 50 ° C. and not higher than the boiling point of the solvent. For example, when the solvent is water, the temperature is preferably 50 ° C. or more and 100 ° C. or less. Examples of the solvent used for promoting 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 (these bases include Those described in the section of formation accelerator are used)
Can be mentioned. In addition, a low-boiling solvent or a mixed solution of a low-boiling solvent and water or a basic aqueous solution can also 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 in a method of imparting them to the dye fixing element, the light-sensitive material, or both.
The amount used may be as small as not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (especially not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film). As a method for imparting a solvent to the photosensitive layer or the dye fixing layer, for example, JP-A-61-147244 (2)
6) There is a method described on page. Further, the solvent can be used by being incorporated in advance in the light-sensitive material or the dye-fixing element or both in the form of enclosing the solvent in microcapsules.

In order to promote dye transfer, a method in which a hydrophilic heat solvent which is solid at normal temperature and dissolves at high temperature is incorporated in the light-sensitive material or the dye-fixing element can be adopted. The hydrophilic thermal solvent may be incorporated in either the photosensitive 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 is preferably incorporated in the dye-fixing layer and / or an adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles. In order to promote dye transfer, a high-boiling organic solvent may be contained in the light-sensitive material and / or the dye-fixing element.

As a heating method in the developing and / or transferring step, a heating block or a plate is brought into contact, 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. Or passing through a high temperature atmosphere. A pressure condition and a method of applying pressure when the photosensitive element and the dye fixing element are overlapped and brought into close contact with each other are described in JP-A-61-1.
No. 47244, page 27, can be applied.

For processing the photographic element of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181
No. 353, No. 60-18951, Shokai 62-259
No. 44, JP-A-3-131856 and JP-A-3-13185
The device described in No. 1 or the like is preferably used.

[0155]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these.

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

19.0 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethylcellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of a 5% aqueous gelatin solution, and milled to give an average particle size of 0.75 mm. Grinding was performed using glass beads for 30 minutes. The glass beads were separated to obtain a dispersion of zinc hydroxide.

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

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

[0160]

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[0161]

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Next, a 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
While stirring this mixture, 600 ml of a 5% aqueous solution of the anionic surfactant (1) was added over 10 minutes. The dispersion thus prepared was concentrated and desalted to 500 ml using an ultrafiltration module. Then 1500ml
And the same operation was repeated once again to obtain 500 g of a dye trapping agent dispersion.

[0164]

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[0165]

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Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described. Cyan, magenta, and yellow dye-donor compounds and gelatin dispersions of electron donors were prepared according to the formulations shown in Table 1, respectively. That is, each oil phase component is
Heat and dissolve at 0 ° C to make a uniform solution.
The aqueous phase component heated to ° C. was added, and the mixture was stirred and mixed, and then dispersed with a homogenizer for 13 minutes at 12,000 rpm. Water was added thereto and stirred to obtain a uniform dispersion.

[0167]

[Table 1]

[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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[0175]

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[0176]

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[0177]

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[0178]

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[0179]

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[0180]

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[0181]

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Next, how to prepare a photosensitive silver halide emulsion will be described.

Photosensitive silver halide emulsion (1) [for red-sensitive emulsion layer] A 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 thereto, and the mixture was kept at 45 ° C.).
It was added at an equal flow rate for 0 minutes. After 6 minutes, (III) in Table 2
The solution and the solution (IV) were simultaneously added at an equal flow rate for 25 minutes. Also
10 minutes after the start of the addition of the liquids (III) and (IV), an aqueous solution of a gelatin dispersion of the pigment (1 g of gelatin in 105 ml of water, 70 mg of the following pigment (a), 139 mg of the following pigment (b), 139 mg of the following pigment ( c) 20 mg containing 5 mg)
It was added over a minute.

After washing with water and desalting in a conventional manner, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and the pAg to 7.8, and to adjust 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene is added, then sodium thiosulfate and chloroauric acid are added to optimize chemical sensitization at 68 ° C,
Then, the following antifoggant (2) was added, followed by cooling. Thus, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0185]

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[0186]

[Table 2]

[0187]

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[0188]

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[0189]

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Photosensitive silver halide emulsion (2) [for red-sensitive emulsion layer] A well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 6 g of sodium chloride in 800 ml of water)
g) and 30 mg of the following chemical (A) were added thereto, and the mixture was kept at 65 ° C.).
It was added at an equal flow rate for 0 minutes. After 5 minutes, (III) in Table 3
The solution and the solution (IV) were simultaneously added at an equal flow rate for 15 minutes. Also
Two minutes after the start of the addition of the solutions (III) and (IV), an aqueous solution of a gelatin dispersion of the pigment (1.1 g of gelatin in 95 ml of water, 76 mg of the pigment (a), 150 mg of the pigment (b), 18 mg of pigment (c) containing 5 mg of
It was added over a minute.

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

[0192]

[Table 3]

Photosensitive silver halide emulsion (3) [for green-sensitive emulsion layer] A well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 4 g of sodium chloride in 690 ml of water)
g) and 15 mg of the above-mentioned chemical (A) were added thereto, and the mixture was kept at 47 ° C.).
Add at an equal flow rate for minutes. After 10 minutes, (III) in Table 4
The solution and the solution (IV) were simultaneously added at an equal flow rate for 32 minutes. Also
One minute after the completion of the addition of the liquids (III) and (IV), an aqueous solution of a gelatin dispersion of the 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 collected at a time. Was added.

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

[0195]

[Table 4]

[0196]

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Photosensitive silver halide emulsion (4) [for green-sensitive emulsion layer] A well-stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide, 0.3 g of sodium chloride in 700 ml of water)
g) and 15 mg of the above-mentioned chemical (A) were added thereto, and the mixture was kept at 60 ° C.).
It was added at an equal flow rate for 0 minutes. After 10 minutes, (II) in Table 5
Solution I) and solution (IV) were simultaneously added at an equal flow rate for 20 minutes.
One minute after the completion of the addition of the solutions (III) and (IV), 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 above dye (d) and kept at 45 ° C.)
Was 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 the pH to 6.0 and the pAg to 7.6, and to adjust 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimal chemical sensitization at 68 ° C. Then, the following antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0199]

[Table 5]

Photosensitive silver halide emulsion (5) [for blue-sensitive emulsion layer] A well-stirred aqueous gelatin 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), and the mixture was kept at 51 ° C.).
Add at an equal flow rate for minutes. After 10 minutes, (III) in Table 6
The solution and the solution (IV) were simultaneously added at an equal flow rate for 32 minutes. Also
One minute after the completion of the addition of the solution (III) or (IV), an aqueous solution of the dye (the following dye (e) 235 was added to 95 ml of water and 5 ml of methanol)
mg and the following dye (f) containing 120 mg and kept at 45 ° C.) were added all at once.

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

[0202]

[Table 6]

[0203]

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[0204]

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Photosensitive silver halide emulsion (6) [for blue-sensitive emulsion layer] A 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 15 mg of the above-mentioned chemical (A) were added, and the mixture was kept at 63 ° C.).
It was added at an equal flow rate for 0 minutes. After 10 minutes, (II) in Table 7
Solution I) and solution (IV) were simultaneously added at an equal flow rate for 30 minutes.
One minute after the completion of the addition of the solutions (III) and (IV), the dye (e) 1 was added to an aqueous solution of the dye (66 ml of water and 4 ml of methanol).
55 mg and the above-mentioned dye (f) containing 78 mg 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 the pH to 6.0 and the pAg to 7.7, and to adjust 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimal chemical sensitization at 68 ° C. Then, the following antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.52 μm was obtained.

[0207]

[Table 7]

Using the above, photosensitive material 101 shown in Table 8 was prepared.

[0209]

[Table 8]

[0210]

[Table 9]

[0211]

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[0212]

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[0213]

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[0214]

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[0215]

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The light-sensitive material 10 was replaced with the light-sensitive material 101 except that the gelatin dispersion of the dye-donating compound in the fifth layer was changed to the gelatin dispersion of the dye-donating compound shown in Table 9 above.
The photosensitive materials 102 to 10 shown in Table 9 were prepared in exactly the same manner as in Example 1.
I made 6. The above photosensitive materials 101 to 106 and PS paper P manufactured by Fuji Photo Film Co., Ltd. as an image receiving material.
The processing was performed using S-SG using a Pictrostat 200 manufactured by Fuji Photo Film Co., Ltd. as an image recording apparatus. That is, the original image [Y, M, Cy.
The test chart in which a gray wedge is recorded] is scanned and exposed through a slit, and the exposed photosensitive material is exposed to 4
After immersion in water kept at 0 ° C. for about 2.5 seconds, it was squeezed with a roller and immediately superimposed so that the image-receiving material and the film surface were in contact with each other. When the photosensitive material was peeled off from the image receiving material by heating with a heat drum for 17 seconds, a clear color image corresponding to the original image was obtained on the image receiving material. The density measurement was performed by measuring the reflection density using a densitometer X-light 404 manufactured by X-Light, and measuring the maximum density (Dmax) and the minimum density (Dm) of yellow.
in) was measured and evaluated. The images obtained using the photosensitive materials 101 to 106 were irradiated with xenon light for one week, and the residual ratio of the portion having a yellow density of 1.0 was determined. Result 9
It is shown in the table.

From the results shown in Table 9, it was found that the compounds of the present invention had image densities equivalent to those of the comparative compounds and had relatively high light fastness.

[0218]

[Table 10]

Further, the cyan image obtained by using the compound of the present invention had a clear hue without smear.

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 liquids I and II having the composition shown in Table 11 were added over 10 minutes, and then the liquids III and IV having the composition shown in Table 11 were added. The liquid was added over 25 minutes.

[0222]

[Table 11]

[0223]

[Table 12]

The chemicals (A) in Table 10 are the same as those used in Example 1.

[0225] Immediately before chemical sensitization, 1% of the dye (g) was used.
50 cc of the solution (methanol: water = 1: 1 mixed solvent) was added.

Washing with water, desalting (pH = 4.
1), and then 22 g of gelatin was added, and pH = 6.
After adjusting to 0 and pAg = 7.9, it was chemically sensitized at 60 ° C. The compounds used for chemical sensitization are as shown in Table 12.

The yield of the obtained emulsion was 630 g, a monodisperse cubic emulsion having a coefficient of variation of 10.3%, and the average grain size was 0.2 μm.

[0228]

[Table 13]

[0229]

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[0230]

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[0231]

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[0232]

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[0233]

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The method of preparing the third layer emulsion (8) will be described.

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

[0236]

[Table 14]

[0237]

[Table 15]

Washing with water, desalting (pH = 3.
9), and 22 g of gelatin were added, and the pH = 5.
9. After adjusting the pAg to 7.8, it was chemically sensitized 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 chemical sensitization are as shown in Table 15.

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

[0240]

[Table 16]

[0241]

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[0242]

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The method of preparing the first layer emulsion (9) will be described.

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

[0245]

[Table 17]

[0246]

[Table 18]

Washing with water, desalting (pH = 4.
Then, 22 g of gelatin was added, and pH = 7.
4. After adjusting the pAg to 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 chemical sensitization are as shown in Table 18.

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

[0249]

[Table 19]

[0250]

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

A homogeneous 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 for 10 minutes at 10,000 rpm. This dispersion was treated with a dispersion of a magenta dye-donating substance (M-
5).

[0253]

[Table 20]

[0254]

[Table 21]

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

[0256]

[Table 22]

[0257]

[Table 23]

A homogeneous solution having the composition shown in Table 23 and a uniform solution having the 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 was treated with a dispersion of a yellow dye-providing substance (Y-
5).

[0259]

[Table 24]

[0260]

[Table 25]

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

A homogeneous solution having the composition shown in Table 25 and a homogeneous solution having the composition shown in Table 26 were prepared, mixed and stirred, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm. This dispersion is referred to as an electron donor dispersion.

[0263]

[Table 26]

[0264]

[Table 27]

Using these emulsions and dispersions of the dye-donating compounds, photosensitive materials 201 having the composition shown in Table 27 were prepared.

[0266]

[Table 28]

[0267]

[Table 29]

The support used here 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 the dispersion of the dye-donating compound and the dispersion of the electron donor.

[0270]

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[0271]

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[0272]

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[0273]

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[0274]

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[0275]

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[0276]

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[0277]

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[0278]

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[0279]

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[0280]

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[0281]

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Light-sensitive materials 202 to 206 were prepared in exactly the same manner except that the yellow dye-donating compound of the light-sensitive material 201 was changed to that shown in Table 29.

The photosensitive materials 201 to 206 and the image receiving material were processed using PS paper manufactured by Fuji Photo Film Co., Ltd., and the image recording apparatus was processed using Pictography 3000 manufactured by Fuji Photo Film Co., Ltd. That is, using a laser exposure apparatus described in Japanese Patent Application No. 2-129625, exposure was performed under the conditions shown in Table 28, and 11 cc / m ² of water was supplied to the emulsion surface of the exposed photosensitive material by a wire bar. The dye-fixing material and the film surface were overlaid so that they were in contact with each other. After heating for 30 seconds using a heat drum whose temperature was adjusted so that the temperature of the water-absorbing film became 83 ° C., the image receiving material was peeled off from the photosensitive material to obtain an image on the image receiving material. In the density measurement, the reflection density was measured using a densitometer X-light 404 manufactured by X-Light, and the maximum density (Dmax) and the minimum density (Dmin) of yellow were measured and evaluated. The above photosensitive material 201
To 206 were irradiated with xenon light for one week, and the residual ratio of a portion having a yellow density of 1.0 was determined.
The results are shown in Table 29.

From the results shown in Table 29, it was found that the compounds of the present invention had image densities equivalent to those of the comparative compounds, and had relatively high light fastness.

[0285]

[Table 30]

[0286]

[Table 31]

Further, the yellow image obtained by using the compound of the present invention had a clear hue without smear.

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

Photosensitive material 301 A photosensitive sheet was prepared by coating the following layers on a polyethylene terephthalate transparent support. Back layer: (a) carbon black 4.0 g / m ^2, a photosensitive layer having a gelatin 2.0 g / m ^2, the emulsion layer side: (1) the following cyan dye-releasing redox compound 0.44
g / m ² , 0.09 g of tricyclohexyl phosphate /
m ^2, 2,5- di -t- pentadecylhydroquinone 0.
Layer containing 008g / m ^2, and gelatin 0.8 g / m ^2.

[0290]

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(2) A layer containing 0.5 g / m ² of gelatin. (3) Red-sensitive internal latent type direct positive silver bromide emulsion (with a silver content of 0.
6 g / m ² ), gelatin 1.2 g / m ² , the following nucleating agent:
015mg / m ² and red-sensitive emulsion layer containing a 2-sulfo -5-n-pentadecylhydroquinone sodium salt 0.06 g / m ^2.

[0292]

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[0293] (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) The following magenta dye-releasing redox compound was added to 0.1.
29 g / m ² , tricyclohexyl phosphate (0.0
9g / m ^2), 2,5- di - pentadecylhydroquinone (0.009g / m ²⁾ and a layer containing gelatin (0.5g / m ^2).

[0294]

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(6) Green-sensitive internal latent type direct positive silver bromide emulsion (silver amount: 0.42 g / m ² ), gelatin (0.9 g / m
m ² ), the same nucleating agent as in layer (3) (0.013 g / m ² ) and 2-sulfo-5-n-pentadecylhydroquinone.
Red-sensitive emulsion layer containing sodium salt (0.07 g / m ² ). (7) Same layer as (4). (8) yellow dye-releasing redox compound having the following structure (0.54 g / m ^2), tri-cyclohexyl phosphate (0.14g / m ^2), 2,5- di -t- pentadecylhydroquinone (0.014 g / m ² ) And gelatin (0.7 g / m ² ).

[0296]

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(9) Blue-sensitive internal latent type direct positive silver bromide emulsion (0.6 g / m ^{2 in} silver), gelatin (1.1 g / m ² )
m ² ), the same nucleating agent as in layer (3) (0.019 g / m ² ) and 2-sulfo-5-n-pentadecylhydroquinone.
Blue-sensitive emulsion layer containing sodium salt (0.05 g / m ² ). (10) A layer containing 1.0 g / m ² of gelatin.

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

[0299]

[Table 32]

[0300]

Embedded image

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

Next, the composition of the processing solution will be 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) 200cc Benzyl alcohol 1.5cc Water 835cc

Further, photosensitive materials 302 to 306 were produced in exactly the same manner except that the yellow dye-donating compound of the photosensitive material 301 was changed to those shown in Table 31.

After exposing the photosensitive materials 301 to 306 through a color chart in which cyan, magenta, yellow, and gray wedges whose density is continuously changed are recorded, the photosensitive materials 301 to 306 are superimposed on a dye fixing material. The treatment liquid was spread between the sheets so as to have a thickness of 60 μm. (The development was performed with the help of a pressure roller.) The processing was performed at 25 ° C. 90 seconds after the processing, the light-sensitive material and the dye-fixing material were separated, air-dried, and the density was measured.

In the density measurement, the reflection density was measured using a densitometer X-light 404 manufactured by X-Light Corporation, and the maximum density (Dmax) and the minimum density (Dmin) of yellow were measured and evaluated.
The images obtained using the photosensitive materials 301 to 306 were irradiated with xenon light for one week, and the residual ratio of a portion having a yellow density of 1.0 was determined. The results are shown in Table 31.

From the results shown in Table 31, it was found that the compounds of the present invention had image densities equivalent to those of the comparative compounds, and had relatively high light fastness.

[0307]

[Table 33]

The yellow image obtained by using the compound of the present invention had a clear hue without smear.

[0309]

According to the dye and silver halide color photographic light-sensitive material of the present invention, a clear hue can be obtained,
Excellent stability against heat, air, chemicals, etc. It can be manufactured at lower cost.

Claims (1)

[Claims] 1. A silver halide photographic material having at least one image forming compound represented by the following general formula (1) on a support. Embedded image In the formula, Dye is an azo dye represented by the following general formula (2),
Alternatively, it represents an azo dye precursor, B represents a mere bond or linking group which is cleaved corresponding to or opposite to the development of silver halide, and A corresponds to a reaction of a photosensitive silver salt having an image-like latent image. Alternatively, it represents a group having a property that causes a difference in the diffusibility of the dye moiety in the opposite manner. Dye and B are bonded in at least one of R, Y, and Z of the azo dye represented by the general formula (2) or the azo dye precursor.
m and n are 1 or 2; when m is 2, Dye may be the same or different; when n is 2, (D
ye) _m- B- may be the same or different. Embedded image In the formula, R represents a substituent. X represents a carbon atom, a phosphorus atom, Y represents an oxygen atom, a sulfur atom or N-R ^2. Here, R ² represents a hydrogen atom, an alkyl group, or an aryl group.
Z is an alkyl group, aryl group, heterocyclic residue, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heterocyclic arylthio group, acylamino group, sulfonylamino group, alkoxycarbonylamino group , An aminocarbonylamino group, a sulfamoylamino group, or an amino group. Y and Z are not bonded to each other to form a ring. G represents an auxochrome of the dye, and represents a group selected from —NR ³ R ⁴ and —OH. Here, R ³ and R ⁴ represent a hydrogen atom, an alkyl group, or an aryl group, and R ³ and R ⁴ may be the same or different. R ³ and R ⁴ may form a 5- to 8-membered ring together with R. p is 1 or 2, and when p is 2, Z may be the same or different. r is 0 to 4, and when r is 2 or more, Rs may be the same or different, and each may form a ring with each other.