JP2001147510A - Dye diffusion transfer heat developable silver halide color photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye diffusion transfer color photosensitive material which exhibits high color forming property, attains the shortening of processing time and ensures superior discrimination (S/N). SOLUTION: The dye diffusion transfer heat developable silver halide color photosensitive material contains a coupler of the formula Cp-A-E-(L)n-Dye (1), e.g. formula 4 and a developing agent of formula 2 or the formula Q-NHNH-R5 (3), e.g. formula 5 or 6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color light-sensitive material, and more particularly to a dye diffusion transfer heat-developable color light-sensitive material capable of obtaining an image having excellent color developability.

[0002]

2. Description of the Related Art It is known to form an image by thermally developing a silver halide photographic light-sensitive material. For example, 242 to 252 of "Basics of Photographic Engineering" Non-Silver Salt Photo Edition (1982, Corona Co., Ltd.). 255, US Pat. No. 4,500,626 and the like. In addition, a photothermographic material using silver halide is a photographic method that has been widely practiced since it is superior in photographic properties such as sensitivity and gradation as compared with methods such as electrophotography and diazo photography. . A number of methods for obtaining a color image by thermal development using a silver halide photosensitive material have been proposed, one of which is a color development method in which a dye image is formed by a coupling reaction between an oxidized developing agent and a coupler. . Regarding developing agents and couplers that can be used in this color development system, see US Pat.
No. 1,256, a combination of a reducing agent of p-phenylenediamines and phenol or an active methylene coupler; and 3,761,270, a p-aminophenol-based reducing agent; , A combination of a sulfonamide phenol-based reducing agent and a 4-equivalent coupler, and the like have been proposed. However, this method has drawbacks such as printout of undeveloped silver halide remaining after processing, color development of undeveloped portions over time, and color smearing due to the simultaneous presence of reduced silver and a color image in exposed portions. In order to solve this drawback, a dye transfer system has been proposed in which a diffusible dye is formed by thermal development and transferred to an image receiving layer. In such a diffusion transfer type photothermographic material, there are a case where the photosensitive material has an image receiving layer capable of receiving a dye on the same support, and a case where the photosensitive material has an image receiving layer on a support different from the photosensitive material. is there. Particularly when used as a heat-developable color photosensitive material, in order to obtain a dye image with high color purity,
It is desirable to use an image receiving material in which the dye image receiving layer is on another support, and to diffuse and transfer the dye simultaneously with or after the formation of the diffusible dye by color development.

A method has been proposed in which a diffusible dye is released or formed imagewise by thermal development, and the diffusible dye is transferred to a dye-fixing element. In this method, a negative dye image and a positive dye image can be obtained by changing the type of the dye-providing compound used or the type of the silver halide used. For further details see U.S. Pat.
0,625, 4,483,914, 4,50
3,137,4,559,290, JP-A-58-
No. 149,046, No. 60-133,449, No. 59
Nos. 218,443 and 61-238,056, European Patent Publication 220,746A2, and Published Technical Report 87-619.
9, European Patent Publication No. 210660A2. U.S. Pat. No. 4,483,194 discloses a method in which a dye linked to a coupler is released by reaction with an oxidized aminophenol-type main drug. However, these preformed coloring materials have a problem that the coloring activity is relatively low and a sufficient S / N cannot be obtained for short-time processing. In addition, the resulting dye is not fast enough.

On the other hand, as a method of forming an image by forming a diffusible dye by a coupling method, Japanese Patent Publication No. 63-3 / 1988
6487, JP-A-5-224381, 6-830
JP-A No. 05-111,148 discloses a photothermographic material containing a color developing agent precursor and a coupler which release p-phenylenediamine, and JP-A-59-111148 discloses a urea-aniline-based reducing agent and an active methylene type coupler. JP-A-58-149047 discloses a photosensitive material using a coupler having a polymer chain as a leaving group and releasing a diffusible dye in color development. JP-A-09-152705 discloses carbamoylhydrazine. In a combination of an active methylene type coupler and a base compound, a technique is disclosed in which a diffusible dye is formed by the reaction of a coupler mother nucleus of the coupler with an oxidized product of a carbamoylhydrazine base compound, and the dye is released.

However, the method of forming an image by forming a diffusible dye by the coupling method used in these documents has problems such as a large dependence on the development processing time. Improvement from the viewpoint of speeding up the process has been desired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dye-diffusion transfer color photosensitive material which exhibits high color-forming properties, achieves a short processing time, and provides excellent discrimination (S / N). It is to provide materials.

[0007]

The object of the present invention has been attained by the following means. (1) Dye diffusion transfer heat characterized by containing a coupler represented by the following general formula (1) and at least one developing agent represented by the following general formula (2) or (3) Developed silver halide color photosensitive material. Formula (1) Cp-AE- (L) _n -Dye In the formula, Cp represents a coupler residue capable of coupling with an oxidized developing agent, E represents an electrophilic site, and A represents C
In the coupling product between p and the oxidized developing agent, a nitrogen atom derived directly from the developing agent and directly bonded to the coupling position and the electrophilic site E undergo an intramolecular nucleophilic substitution reaction to form a 4- to 8-membered ring. -Represents a divalent linking group or a single bond capable of releasing (L) _n -Dye, and may be bonded to Cp at the coupling position of Cp, or to Cp at a position other than the coupling position of Cp. They may be combined. L is 2
And n represents 0 or 1, and Dye represents a diffusible dye residue.

[0008]

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In the formula, R _{1 to} R ₄ represent a hydrogen atom or a substituent, and D represents —CO—, —SO—, —SO ₂ —, and —P
(= O) represents at least one kind of divalent or higher linking group selected from <, and T represents a divalent linking group. M is a nucleophilic group and represents a group capable of attacking D when the compound is oxidized. R ₁ and R ₂ , and R ₃ and R ₄ may be bonded to each other to form a ring. General formula (3) Q-NHNH-R _{5 In the} formula, Q is bonded to -NHNH-R _{5 by a} carbon atom.
R ₅ represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, or a sulfamoyl group. (2) In a dye diffusion transfer heat-developable color light-sensitive material having at least three silver halide emulsion layers having color sensitivity in mutually different wavelength regions, one of the layers has-in the molecule.
General formula (1) wherein Dye is a diffusible yellow dye residue
And the other layer contains -Dy
e contains a coupler represented by the general formula (1) in which a magenta dye residue is a diffusible magenta dye, and -Dye is contained in another layer.
Wherein the dye is a diffusible cyan dye residue and comprises a coupler represented by the general formula (1).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The coupler represented by the general formula (1) will be described in detail below. The coupler residue represented by Cp may be a yellow coupler residue generally known as a photographic coupler (for example, open-chain ketomethine type coupler residue such as acylacetanilide or malondianilide) or a magenta coupler residue (for example, 5 Coupler residues such as pyrazolone type or pyrazolotriazole type), cyan coupler residues (e.g., phenol type, naphthol type or pyrrolotriazole type coupler residues), US Pat. No. 5,681,689, and JP-A-7-128.
No. 824, No. 7-128823, No. 6-222526
No. 9-258400, No. 9-258401, No. 9-269573, No. 6-27612, etc. having a novel skeleton and a yellow, magenta or cyan dye-forming coupler residue. Or other coupler residues (eg, US Pat. No. 3,632,345).
And coupler residues which react with oxidized aromatic amine-based developing agents to form colorless substances described in U.S. Pat. Nos. 1,939,231 and 21,819.
A coupler residue which reacts with an oxidized aromatic amine-based developing agent described in No. 44 or the like to form a black or intermediate color substance. The coupler residue represented by Cp may be a monomer or a part of a dimer coupler, an oligomer or a polymer coupler, and in this case, more than one Dye may be contained in the coupler. . Preferred examples of Cp of the present invention are shown below, but the invention is not limited thereto.

[0011]

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[0012]

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In the formula, * represents a bonding position to A. X represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), R ₃₁ —, R ₃₁ O—, and R _{31
S-, R 31 OCOO-, R 32} COO-, R 32 (R 33) N
_{COO-, R 32 CON (R 33} ) - represents, Y represents an oxygen atom, a sulfur atom, R ₃₂ N =, or R ₃₂ ON =. Here, R ₃₁ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. The alkyl group represented by R ₃₁ is preferably a substituted or unsubstituted alkyl group having 1 to 32 carbon atoms, more preferably 1 to 22 carbon atoms,
Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, t-amyl,
Hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,1,3,3-tetramethylbutyl, decyl,
Dodecyl, hexadecyl, and octadecyl. The alkenyl group and alkynyl group represented by R ₃₁ preferably have 2 to 32 carbon atoms, more preferably 2 carbon atoms.
To 22 substituted or unsubstituted alkenyl groups and alkynyl groups, including cyclic ones. As a specific example,
Vinyl, 2-propenyl, ethynyl, 2-propynyl. Here, when the alkyl group, the alkenyl group, and the alkynyl group have a substituent, the “carbon number” means the total carbon number including the carbon number of the substituent. Similarly, for groups other than an alkyl group, an alkenyl group, and an alkynyl group,
It means the total number of carbon atoms including the number of carbon atoms of the substituent.

The aryl group represented by R ₃₁ is preferably a substituted or unsubstituted aryl group having 6 to 32 carbon atoms, more preferably 6 to 22 carbon atoms, and specific examples include phenyl, tolyl and naphthyl. . The heterocyclic group represented by R ₃₁ is preferably a substituted or unsubstituted 3 to 8 membered (preferably 5 or 6 membered) heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 22 carbon atoms. Examples include 2-furyl, 2-pyrrolyl, 2-thienyl, 3
-Tetrahydrofuranyl, 4-pyridyl, 2-pyrimidinyl, 2- (1,3,4-thiadiazolyl), 2-benzothiazolyl, 2-benzoxazolyl, 2-benzimidazolyl, 2-benzoselenazolyl, 2-quinolyl,
Examples thereof include 2-oxazolyl, 2-thiazolyl, 2-selenazolyl, 5-tetrazolyl, 2- (1,3,4-oxadiazolyl), and 2-imidazolyl. R ₃₂
And R ₃₃ are each independently a hydrogen atom, an alkyl group,
Represents an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by R ₃₂ and R ₃₃ have the same meaning as R ₃₁ . Preferably, X is a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, or R ₃₂ CO
N represents an N (R ₃₃ ) —, Y represents an oxygen atom, R ₃₁ represents an alkyl group or an aryl group, R ₃₂ and R
₃₃ each independently represents a hydrogen atom, an alkyl group or an aryl group.

The substituents suitable for the groups described above and below and the "substituents" described below include, for example, halogen atom, hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, alkyl group, fluoroalkyl Group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, amino group, acyl group, alkyl or arylsulfonyl group, acylamino group, alkyl or arylsulfonylamino group, carbamoyl group, sulfamoyl group, Alkoxycarbonyl group, aryloxycarbonyl group,
Examples include an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an aminocarbonyloxy group, and an aminocarbonylamino group. R ₁₁ and R ₁₂ are each independently R ₃₂ CO—,
_{R 31 OCO-, R 32 (R} 33) NCO-, R 31 SO m -,
R ₃₂ (R ₃₃ ) represents NSO ₂ —, a cyano group or a group represented by the following formula. Here, R ₃₁ , R ₃₂ and R ₃₃ are as defined above, and m represents 1 or 2.

[0016]

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Y ₁ is an oxygen atom, a sulfur atom, or —N
Represents a group represented by (R ₃₂ ) —, and Z is necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring (which may be condensed with a benzene ring, a naphthalene ring or a heterocyclic ring) together with N and Y _1. Non-metallic atoms (preferably carbon atoms which may have a substituent). R ₁₃ represents the same group as R ₃₁ described above. R ₁₄ is _{R 32 -, R 32 CON (} R 33) -, R
_{32 (R 33) N-, R} 31 SO 2 N (R 3 2) -, R 31 S-,
_{R 31 O-, R 31 OCON (} R 32) -, R 32 (R 33) NC
_{ON (R 34) -, R} 31 OCO-, R 32 (R 33) NCO-
Or a cyano group. Where R ₃₁ , R ₃₂ and R ₃₃
Has the same meaning as described above, and R ₃₄ represents a group having the same meaning as R ₃₂ .

[0018] R ₁₅ and R ₁₆ each independently represent a hydrogen atom or a substituent, preferably R ₃₁ -, R ₃₂ CON
_{(R 33) -, R 31} SO 2 N (R 32) -, R 31 S-, R 31
_{O-, R 31 OCON (R 32} ) -, R 32 (R 33) NCON
_{(R 34) -, R 31} OCO-, R 32 (R 33) NCO-, a halogen atom or a cyano group, more preferably R
It is a group represented by ₃₁ . Here, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are as defined above. R ₁₇ represents a substituent,
p represents an integer of 0 to 4, and q represents an integer of 0 to 3. Preferred examples of the substituent represented by R ₁₇ include:
_{R 31 -, R 32 CON (} R 33) -, R 31 OCON (R 32)
_{-, R 31 SO 2 N (} R 32) -, R 32 (R 33) NCON
_{(R 34) -, R 31} S-, R 31 O-, and a halogen atom. Here, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are as defined above. When p and q are 2 or more, each R ₁₇ may be the same or different, or adjacent R ₁₇ may be bonded to each other to form a ring. In a preferred embodiment of the general formulas (I-1E) and (I-2E), at least one of the ortho positions of the hydroxyl group is R ₃₂ CONH— or R ₃₁ O
CONH- or R ₃₂ (R ₃₃ ) substituted with NCONH-.

R₁₈Represents a substituent, and r is an integer of 0 to 6.
Represents a number, and s represents an integer of 0 to 5. R₁₈Represented by
Preferred examples of the substituent represented by₃₂CON
(R₃₃)-, R₃₁OCON (R₃₂)-, R₃₁SO_TwoN
(R₃₂)-, R₃₂(R₃₃) NCON (R₃₄)-, R₃₁S
-, R₃₁O-, R₃₂(R₃₃) NCO-, R₃₂(R₃₃) N
SO_Two-, R₃₁OCO-, a cyano group or a halogen atom
No. Where R₃₁, R ₃₂, R₃₃And R₃₄Is above
Synonymous with When r and s are 2 or more, respectively
R₁₈May be the same or different, and
R₁₈They may combine with each other to form a ring. The general formula (I
Preferred embodiments of (-1F), (I-2F) and (I-3F)
Means that the ortho position of the hydroxyl group is R₃₂CONH-, R₃₂HNCO
NH-, R₃₂(R ₃₃) NSO_Two-Or R₃₂With NHCO-
It has been replaced.

R ₁₉ represents a hydrogen atom or a substituent, preferably R ₃₂ —, R ₃₂ CON (R ₃₃ ) —, R ₃₁ SO ₂ N
_{(R 33) -, R 31} S-, R 31 O-, R 31 OCON
_{(R 32) -, R 32} (R 33) NCON (R 34) -, R 31 O
_{CO-, R 32 (R 33)} NSO 2 -, R 32 (R 33) NCO
- represents a halogen atom or a cyano group, more preferably a group represented by R _31. Where R ₃₁ , R ₃₂ ,
R ₃₃ and R ₃₄ are as defined above.

R₂₀And R_{twenty one}Are each independently a hydrogen atom or
Represents a substituent, preferably R₃₂-, R₃₂CON
(R₃₃)-, R₃₁SO_TwoN (R₃₂)-, R₃₁S-, R₃₁
O-, R₃₁OCON (R₃₂)-, R₃₂(R₃₃) NCON
(R₃₄)-, R₃₂(R₃₃) NCO-, R₃₂(R₃₃) NS
O_Two-, R₃₁OCO-, a halogen atom and a cyano group
And more preferably R₃₂(R₃₃) NCO-, R₃₂
(R₃₃) NSO_Two-, Trifluoromethyl group, R₃₁OC
Represents O- and cyano groups. Where R₃₁, R₃₂, R
₃₃And R₃₄Is as defined above. E is -CO-, -C
S-, -COCO-, -SO-, -SO_Two-, -P (=
O) (R₅₁)-, -P (= S) (R₅₁)-｛R₅₁Is al
Kill, alkenyl, alkynyl, aryl,
Alkoxy group, alkenyloxy group, alkynyloxy
Group, aryloxy group, alkylthio group, alkenylthio
O represents an alkynylthio group or an arylthio group. ｝
Or an electrophilic group such as -C (R₅₂) (R₅₃)-(R ₅₂, R₅₃
Represents a hydrogen atom, an alkyl group, an alkenyl group,
Represents a quinyl group, an aryl group, or a heterocyclic group. each
Alkyl group, alkenyl group, alkynyl group, aryl
Group, heterocyclic group is R₃₁Has the same meaning as described in )
And preferably -CO-.

A is obtained by an intramolecular nucleophilic substitution reaction between a nitrogen atom derived from the developing agent in the coupling product of Cp and the oxidized developing agent and directly bonded to the coupling position with the electrophilic site E (preferably 4). Represents a divalent linking group or a single bond capable of releasing-(L) _n -Dye with a ring formation of from 1 to 8 members, more preferably from 5 to 7 members, and still more preferably from 6 members.

Examples of the linking group represented by A include the following. *-(CO) _n1- (Y ') _n2- {C (R ₄₁ ) (R ₄₂ )}
_n4 -** *-(CO) _n1- ｛N (R ₄₃ )｝ _n3- ｛C (R ₄₁ ) (R
₄₂ ) { _n4 -** *-(Y ') _n2- (CO) _n1- {C (R ₄₁ ) (R ₄₂ )}
_n4 -** *-{N (R ₄₃ )} _n3- (CO) _n1- ｛C (R ₄₁ ) (R
₄₂ )｝ _n4 -** *-(CO) _n1- ｛C (R ₄₁ ) (R ₄₂ )｝ _n4- (Y ′)
_n2 -** *-(CO) _n1- {C (R ₄₁ ) (R ₄₂ )} _n4- ｛N (R
₄₃ )｝ _n3 -** *-(Y ') _n2 -**, *-{N (R ₄₃ )} _n3 -**

In the formula, * represents a site binding to Cp;
* Represents a site bonded to E, Y ′ represents an oxygen atom or a sulfur atom, and R ₄₁ , R ₄₂ and R ₄₃ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. (these alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group has the same meaning as described in R _31.) represent, each of R _41,
R ₄₂ and R ₄₃ may combine with each other or Cp to form a ring. R ₄₁ and R ₄₂ are preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. R ₄₃ is preferably a hydrogen atom or an alkyl group.

N1 and n3 each represent an integer of 0 to 2, n2 represents 0 or 1, n4 represents an integer of 1 to 5 (when n3 and n4 represent an integer of 2 or more,
Each of N (R ₄₃ ) and C (R ₄₁ ) (R ₄₂ ) may be the same or different. And a 4- to 8-membered ring formed by an intramolecular nucleophilic substitution reaction between a nitrogen atom derived from the developing agent and directly bonded to the coupling position and an electrophilic site E in the coupling product of Cp and the oxidized developing agent. To form n1 + n2 + n4, n1 + n3 + n4, n
The values of 2 and n3 are chosen. However, -N (R ₄₃ )-
When R is directly bonded to E, R ₄₃ is preferably not a hydrogen atom. When the linking group A is linked at the coupling position of Cp, the portion directly linked to Cp is not -Y'-.

The linking position between Cp and the linking group A is determined by the intramolecular nucleophilic reaction between the nitrogen atom derived from the developing agent and the electrophilic site E in the coupling product after the coupling reaction between the coupler and the oxidized developing agent. Any one capable of releasing-(L) _n -Dye with a ring formation (preferably 4 to 8 member, more preferably 5 to 7 member, even more preferably 6 member) by a substitution reaction However, it is preferably at or near the coupling position of Cp (the atom next to the coupling position or the atom next to it), and the atom next to the coupling position or the atom next to the coupling position is preferable. Coupler and book according to the present invention when the linking group A is bonded to 1) the coupling position, 2) the atom next to the coupling position and 3) the adjacent atom next to the coupling position of the coupler residue represented by Cp. Inventive coupler and general formula (2) or (3)
The reaction of the developing agent with the oxidized form represented by the formula can be represented by the following formula.

[0027]

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Next, L, n and Dye in the compound represented by the general formula (1) will be described in detail. L represents a divalent linking group, and any group can be used as long as the bond on the left side of L in the general formula (1) is cleaved during the development processing, and then the group bonded on the right side can be cleaved. For example, U.S. Patent Nos. 4,146,396 and 4,652,
Nos. 516 and 4,698,297, which use a hemiacetal cleavage reaction, and US Pat. Nos. 4,248,962, 4,847,185, and 4,857,440. Or a group capable of causing a cleavage reaction using an intramolecular nucleophilic substitution reaction described in US Pat. No. 5,262,291, and US Pat. No. 4,409,323 or US Pat. No. 4,421,845. A group that causes a cleavage reaction by utilizing an electron transfer reaction, US Pat. No. 4,54
U.S. Patent No. 6,073, U.S. Pat.
No. 5,311,927, a group which causes a cleavage reaction by utilizing an ester hydrolysis reaction, or a cleavage reaction utilizing a reaction with a sulfite ion described in EP-A-0572984 or EP-A-0668412. And groups that cause it. Preferable L includes a group represented by the following formula (T-1), (T-2) or (T-3).

General formula (T-1) * -W- (Y_Three= Y_Four) j-C
(R_{twenty one}) (R_{twenty two})-** General formula (T-2) * -W-CO-** General formula (T-3) * -W-LINK-E₁-** In these formulas, * represents the position where the bond to E of the coupler is made.
And ** is the position bonded to -Dye in general formula (1).
Represents W is an oxygen atom, a sulfur atom or> N-
(R_{twenty three}) And Y_ThreeAnd Y_FourAre replaced or omitted
J represents 0, 1, or
Represents 2. Y_ThreeAnd Y_FourRepresents a substituted methylene group.
Mushroom substituent, R_{twenty one}, R_{twenty two}And R _{twenty three}Any two of each
Are connected to each other to form a cyclic structure (eg, benzene
Or a pyrazole ring). R_{twenty one}And R
_{twenty two}Is independently a hydrogen atom, an alkyl group, an aryl group,
Or a heterocyclic group, such an alkyl group, an aryl
And heterocyclic groups are represented by R₃₁Has the same meaning as described in
R_{twenty three}Represents an alkyl group, an aryl group, an acyl group, or a sulf group.
Represents a honyl group. R _{twenty three}An alkyl group represented by
Is R₃₁Has the same meaning as that described in
Is preferably an acyl group having 1 to 32 carbon atoms, for example,
For example, formyl, acetyl, pivaloyl, benzoyl,
Represents trdecanoyl, cyclohexylcarbonyl,
The sulfonyl group is preferably an alkyl having 1 to 32 carbon atoms.
Or an arylsulfonyl group such as methylsulfone
Honyl, octylsulfonyl, cyclohexylsulfoni
Phenylsulfonyl, p-tolylsulfonyl
You. In the general formula (T-3),₁Represents an electrophilic group
LINK is W and E₁And nucleophilic substitution reaction
Represents a linking group that relates sterically so that

Specific examples of the general formula (T-1), the general formula (T-2) and the general formula (T-3) are disclosed in
TIME described in JP-A No. 0-62923. n is preferably 0. Next, the group represented by Dye in the general formula (1) will be described in detail. Dye is a yellow dye residue, a magenta dye residue, a cyan dye residue,
Or, it represents a black dye residue, and examples thereof include an azo dye, an azomethine dye, an azine dye, a quinophthalone dye, and a phthalocyanine dye. As a preferred dye residue, a yellow dye residue is described in JP-A-52-7727,
No. 54-79031, U.S. Pat. No. 4,473,632
JP-A-9-244199, JP-A-61-2707
No. 57, Japanese Patent Publication No. 62-15851, U.S. Pat.
30,957, 4,837,142;
No. 275187, JP-A-2-235059, JP-A-6
And yellow dye residues described in JP-A-301179. Magenta dye residues are described in U.S. Pat. No. 3,453,1.
07, 3,544,545, 3,932,38
0, 3,931,114, 3,932,308
No. 3,954,476, No.4,233,237
Nos. 4,255,509 and 4,250,246
Nos. 4,142,891, 4,207,104
No. 4,287,292, JP-A-52-10672.
No. 7, No. 53-23628, No. 55-36, 804
Nos. 56-73057, 56-71060, 55-134, JP-A-49-114424, 50
-115528, 55-4028, 60-14
No. 0240, No. 60-14243, No. 61-5565
No. 0, No. 62-71951, No. 61-273542
And the dye residues described in JP-A Nos. 4-331954 and 9-127666. Examples of cyan dye residues include U.S. Patent Nos. 3,482,972 and 3,29.
2,760, 3,942,987, 4,26
8,625, 4,171,220, 4,24
2,435, 4,142,891, 4,19
5,994, 4,147,544, 4,14
8,642, 4,013,635, 4,273
No. 708, British Patent No. 1,551,138, European Patents (EPC) 53,037, 53-040, Res.
ear Disclosure 17,630 (1
987) and 16,475 (1977), JP-A-53-66227, JP-A-54-99431, and JP-A-52-662.
No. 8827, No. 53-47823, No. 53-1433
No. 23, 54-99431, 56-71061
No. 60-93434, No. 60-87134, No. 60-257579, No. 60-14243, No. 60
-140240, 62-257151, 61-
No. 44301, Japanese Unexamined Patent Publication No. Hei 3-11402, 7-21
9180 and JP-A-11-125888. A more preferred yellow dye residue is represented by the following formula (Y-1).

[0031]

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(Wherein, R ¹ and R ² represent a hydrogen atom or a substituent, and R ³ represents a substituted or unsubstituted aromatic or heterocyclic group. R ¹ , R ² , R ³ binds to Cp-AE- (L) _n -in the general formula (1).) For details of the above dye residue, see JP-A-1-2751.
No. 87 and No. 2-35059, and can be applied as it is. A more preferred magenta dye residue is represented by the following formula (M-1).

[0033]

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(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a cyano group, a carboxyl group, a sulfo group,
Nitro group, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, alkoxy group,
Aryloxy group, heterocyclic oxy group, silyloxy group, alkylthio group, arylthio group, heterocyclic thio group, carbamoyl group, sulfamoyl group, acylamino group, sulfonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyloxy A ureido group, a carbamoyloxy group, a sulfamoylamino group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an aryloxycarbonyloxy group, and a sulfonyloxy group. R ³ and R ⁴ may combine to form a ring structure. R ⁵ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R ⁶ represents a group defined as R ⁵ , a cyano group, or an alkylthio group. R ⁷ represents a cyano group, a nitro group, an alkoxycarbonyl group, or a carbamoyl group. Any one of R ^{1 to} R ^{6 is selected from} the group consisting of Cp-A-
Binds to E- (L) _n- . For details of the above dye residues, see JP-A-9-1276.
No. 66, which can be applied as it is. A more preferred cyan dye residue is represented by the following formula (C-1) or (C-2).

[0035]

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(In the formulas (C-1) and (C-2), R¹Is water
Represents an atom, a monovalent cation or a hydrolyzable group,
R^TwoIs acylamino, carbamoyl, sulfamoi
Group, ureido group or alkoxycarbonylamino group
And R^ThreeRepresents an alkyl group or an aryl group;^Four,
R^FiveRepresents a hydrogen atom or a substituent, and m and m_TwoAre each 0
Represents an integer of from 4 to 4. m_TwoIs 2 to 4, two R^FiveBut
May combine with each other to form a saturated or unsaturated ring
(However, excluding the case of a naphthalene ring). W ₁Is 5
Represents an atom group necessary for forming a 6-membered ring. R^Two~ R^Fiveor
Is W₁In at least one of the formulas (1)
-A-E- (L)_nCombine with-. For details of the above dye residue, see JP-A-11-125.
No. 888, and can be applied as it is.

The preferred embodiment of the coupler represented by formula (1) of the present invention is represented by formula (I-2) or (I-
3) wherein (I-3) is more preferable (in the general formulas (I-2) and (I-3), A, E,
L, n, Dye and their preferred ranges are the same as those described above. ). A more preferred embodiment of the general formula (I-3) is represented by the following general formula (I-3a), more preferably the following general formula (I-3b), and particularly preferably the general formula (I-3c) Is represented by

[0038]

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In the formula, each of Q ₁ and Q ₂ forms a 5- or 6-membered ring, and is a nonmetallic atom (ring) necessary for causing a coupling reaction with an oxidized developing agent at an atom at the base of X. Are preferably a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, and those which can be substituted may have a substituent, and more preferably may have a substituent. X, L,
n, Dye, R ₁₈ and R ₃₂ are as defined above. s' is 0
Represents an integer from to 4. R ₄₄ is a hydrogen atom, an alkyl group,
Represents an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, preferably represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and more preferably represents an alkyl group (these alkyl groups, alkenyl groups) , An alkynyl group, an aryl group and a heterocyclic group are represented by R ₃₁
Has the same meaning as described in ). The general formula (1) below
Specific examples of the coupler represented by are shown below, but are not limited thereto.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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Hereinafter, specific examples of the synthesis of the coupler represented by formula (1) will be described. Synthesis of Coupler of Compound Example (32) A coupler of Compound Example (32) was synthesized according to the following scheme.

[0054]

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Synthesis of Compound 32b Compound 32a (50 g) and bromotetradecane (78.
6 g) of 1-methylpyrrolidone (150 mL)
After stirring at 20 ° C for 5 hours, the mixture was cooled to 25 ° C and poured into ethyl acetate (600 mL) / water (600 mL). The organic layer was washed with water and concentrated under reduced pressure. Compound 32b was obtained by recrystallizing the concentrated residue from an ethyl acetate / hexane system.
(48 g) was obtained.

Synthesis of Compound 32c Compound 32b (6.5 g) was added to a solution of bis (trichloromethyl) carbonate (1.9 g) in tetrahydrofuran (5 mL).
And a solution of N, N-dimethylaniline (3.1 g) in tetrahydrofuran (20 ml) was added dropwise at 10 ° C.
After the reaction solution was stirred at 25 ° C. for 1 hour, ethyl acetate (1
(00 mL) / 1N aqueous hydrochloric acid (100 mL). The organic layer was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The concentrated residue was recrystallized from an ethyl acetate / hexane system to obtain compound 32c (5.4 g).

Synthesis of Compound 32d Compound 32c (4.5 g), p-hydroxybenzaldehyde (5.0 g) and N, N-diisopropyl-N
-Toluene (100 mL) of ethylamine (4.8 g)
The solution was refluxed for 5 hours with stirring. After cooling the reaction solution to 30 ° C., ethyl acetate (500 mL) / aqueous sodium bicarbonate (500
mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by a column (developing solvent: ethyl acetate / hexane = 1/3) to obtain compound 32d (3.8 g).

Synthesis of Compound 32e Methanol (100 mL) of Compound 32d (3.8 g)
Sodium borohydride (0.48 g) was added to a solution of
Stirred for hours. Ethyl acetate (100 mL) / 1
The mixture was poured into aqueous N hydrochloric acid (100 mL). Wash the organic layer with water,
After drying over magnesium sulfate, the mixture was concentrated under reduced pressure. The concentrated residue is applied to a column (developing solvent: ethyl acetate / hexane = 1).
/ 2) The compound 32e (3.7 g) was obtained by purification.

Synthesis of Compound 32f Compound 32e (3.5 g) in dichloromethane (20 m
L) Phosphorus tribromide (0.7 g) was added to the solution at 10 ° C and stirred for 1 hour. The reaction solution was treated with ethyl acetate (100 m
L) / 1N aqueous hydrochloric acid (100 mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by a column (developing solvent: ethyl acetate / hexane = 1/4) to give Compound 32f (2.
8 g) were obtained.

Synthesis of Compound 32 Compound 32 g (2.0 g) and DBU (0.71 g)
Compound 32f (2.8 g) was slowly added to a N, N-dimethylacetamide (20 mL) solution of
Stirred for hours. The reaction solution was poured into ethyl acetate (200 mL) / dilute hydrochloric acid solution (100 mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The concentrated residue was recrystallized from ethyl acetate / methanol to obtain 1.2 g of the exemplary compound (32) (the compound was identified by elemental analysis, NMR and Mass spectrum).

Synthesis of Coupler of Compound Example (33) The coupler of Compound Example (33) was synthesized according to the following scheme.

[0062]

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Synthesis of Compound 33 Compound 33a (6.4 g) and pyridine (0.97 m
Compound 33b (5.4 g) was slowly added to a solution of 1) in dimethylacetamide (30 ml), and the mixture was stirred at 25 ° C for 4 hours. To this solution, 7.8 ml of 25% aqueous ammonia was added dropwise, and the mixture was further stirred at 25 ° C. for 1 hour, and then 1N aqueous hydrochloric acid was added.
The mixture was poured into 0 ml, and the precipitated crystals were collected by filtration. The obtained crude crystals were purified by column chromatography (eluent: chloroform / ethyl acetate = 1/1), and further recrystallized from ethyl acetate / methanol to obtain 4.3 g of Exemplified Compound (33). (Compound identification is elemental analysis, N
MR and Mass spectra).

Next, the developing agent represented by the formula (2) will be described in detail. The compound represented by the general formula (2) is
Represents a derivative of a developing agent collectively referred to as aminophenol. In the formula, R _{1 to} R ₄ represent a hydrogen atom or a substituent.
R _{1 to} R ₄ are a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 48 carbon atoms, for example, methyl , Ethyl, propyl, isopropyl, butyl, t-butyl, 1-octyl, tridecyl,
Cyclopropyl, cyclopentyl, cyclohexyl, 1
-Norbornyl, 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 32 carbon atoms, for example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably an aryl group having 6 to 32 carbon atoms) For example, phenyl, 1-naphthyl, 2-naphthyl), a heterocyclic group (preferably a 5- to 8-membered heterocyclic group having 1 to 32 carbon atoms, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 2-pyridyl, 2
-Benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-2-yl), cyano group, silyl group (preferably a silyl group having 3 to 32 carbon atoms, for example, trimethylsilyl, triethylsilyl, tributylsilyl, t-butyl) Dimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, carboxyl group, nitro group, alkoxy group (preferably alkoxy group having 1 to 32 carbon atoms, for example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy) , T-butoxy, dodecyloxy, cyclopentyloxy, cyclohexyloxy), aryloxy group (preferably having 6 to 3 carbon atoms)
Two aryloxy groups, for example, phenoxy, 2-naphthoxy), a heterocyclic oxy group (preferably having 1 to 1 carbon atoms);
32 heterocyclic oxy groups, for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy, 2-furyloxy), silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, for example, trimethylsilyl Oxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably an acyloxy group having 2 to 32 carbon atoms, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy),

An alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 32 carbon atoms,
For example, ethoxycarbonyloxy, t-butoxycarbonyloxy, cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, for example, phenoxycarbonyloxy), a carbamoyloxy group ( It is preferably a carbamoyloxy group having 1 to 32 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms). For example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), alkylsulfonyloxy group (preferably having 1 to 32 carbon atoms)
Alkylsulfonyloxy groups, for example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), arylsulfonyloxy (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, for example, phenylsulfonyloxy), acyl group (Preferably an acyl group having 1 to 32 carbon atoms, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexylcarbonyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 32 carbon atoms, for example, Methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl), aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, If, phenoxycarbonyl), carbamoyl groups (preferably carbamoyl group having 1 to 32 carbon atoms, e.g., carbamoyl, N, N- dibutylcarbamoyl, N- ethyl -N- octylcarbamoyl, N
-Propylcarbamoyl, N, N-dicyclohexylcarbamoyl, N-phenylcarbamoyl), amino group (preferably an amino group having 32 or less carbon atoms, for example, amino, methylamino, N, N-dioctylamino, tetradecylamino, octadecyl) Amino, cyclohexylamino),

An anilino group (preferably an anilino group having 6 to 32 carbon atoms, for example, anilino, N-methylanilino); a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, for example, 4- Pyridylamino),
A carbonamide group (preferably a carbonamide group having 2 to 32 carbon atoms, for example, acetamido, benzamido,
Tetradecanamide), a ureido group (preferably a ureido group having 1 to 32 carbon atoms, for example, ureido, N, N-
Dimethylureido, N-phenylureido), imide group (preferably an imide group having 32 or less carbon atoms, for example, N
-Succinimide, N-phthalimide), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 32 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxy Carbonylamino), aryloxycarbonylamino group (preferably having 7 to 3 carbon atoms)
2 aryloxycarbonylamino groups, for example, phenoxycarbonylamino), sulfonamide group (preferably a sulfonamide group having 1 to 32 carbon atoms, for example,
Methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexylsulfonylamino), sulfamoylamino group (preferably a sulfamoylamino group having 1 to 32 carbon atoms, for example, N, N-dipropyls) Rufamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably an azo group having 1 to 32 carbon atoms,
For example, phenylazo), an alkylthio group (preferably an alkylthio group having 1 to 32 carbon atoms, for example, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably an arylthio group having 6 to 32 carbon atoms)
For example, phenylthio), a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 32 carbon atoms, for example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably Is an alkylsulfinyl group having 1 to 32 carbon atoms, for example, dodecanesulfinyl),

Arylsulfinyl (preferably an arylsulfinyl group having 6 to 32 carbon atoms, for example, phenylsulfinyl), alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 32 carbon atoms, for example, methylsulfonyl, octylsulfonyl, A cyclohexylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 32 carbon atoms, for example, phenylsulfonyl, 1-naphthylsulfonyl), an alkylsulfonylcarbamoyl group (preferably an alkylsulfonylcarbamoyl group having 2 to 36 carbon atoms) For example, methylsulfonylcarbamoyl, butylsulfonylcarbamoyl), an arylsulfonylcarbamoyl group (preferably an arylsulfonylcarbamoyl group having 7 to 32 carbon atoms, for example, phenyl Sulfonylcarbamoyl, p-toluenesulfonylcarbamoyl), sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, for example, sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl), sulfo Group, phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), phosphinoylamino group (diethoxyphosphinoylamino, dioctyloxyphosphino) Ylamino group).

When these groups are substitutable groups,
May further have the above group as a substituent,
When there are two or more groups, those groups are the same.
Or different. R₁And R_TwoAnd / or R_Three
And R_FourMay combine with each other to form a ring. R₁~
R_FourR in_TwoAnd / or R_FourIs preferably a hydrogen atom,
R ₁~ R_FourThe sum of Hammett's substituent constant σp values is 0 or more
Preferably,

[0069] D is -CO -, - SO -, - SO 2 -, and -P (= O) represents a divalent or more linking group selected from <, preferably -SO ₂ - include. When D is larger than divalent, the third or higher bond is a hydrogen atom or a substituent, and examples of the substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylamino group, and an arylamino group. Can be M represents a nucleophilic group, and an oxidant generated after the compound represented by the general formula (2) reduces silver halide is coupled with a coupler; Represents a group having a function of forming a ring and releasing-(L) _n -Dye by nucleophilic attack on a carbon atom, a sulfur atom or a phosphorus atom, and specific examples are described in JP-A-10-186564 and the like. Has been described.

T represents a divalent linking group, and links the nucleophilic group M to a position at which the nucleophilic group M can attack D via an intramolecular nucleophilic substitution via the linking group T. Represents a divalent group.
The atoms are preferably connected so that the transition state when the nucleophilic group M makes a nucleophilic attack on D can form a 5- to 6-membered ring by the number of atoms. For example, a 1,2- or 1,3-alkylene group, a 1,2-cycloalkylene group, a Z-vinylene group, a 1,2-arylene group, a 1,8-naphthalene group and the like can be mentioned.

Specific examples of the compound represented by the general formula (2) include compounds Nos. D-1 to D-38 described in JP-A-10-186564 and compounds described in JP-A-11-149146. Nos. D-1 to D-56. Particularly, compounds described in JP-A-11-149146 are preferred. The compound represented by the general formula (2) can be synthesized according to the method described in the above patent.

Next, the hydrazine-based developing agent represented by the formula (3) will be described in detail. Wherein, Q represents a 5- to 7-membered unsaturated ring that binds to -NHNH-R ₅ carbon atoms, R ₅ is a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group or a sulfamoyl, Represents a group.

Further, Q and R ₅ will be described in detail. Q represents a 5- to 7-membered unsaturated ring that binds to -NHNH-R ₅ carbon atoms, a benzene ring Examples of unsaturated ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring,
1,2,4-triazine ring, 1,3,5-triazine ring, pyrrole ring, imidazole ring, pyrazole ring,
2,3-triazole ring, 1,2,4-triazole ring, tetrazole ring, 1,3,4-thiadiazole ring,
1,2,4-thiadiazole ring, 1,2,5-thiadiazole ring, 1,3,4-oxadiazole ring, 1,2,2
A 4-oxadiazole ring, a 1,2,5-oxadiazole ring, a thiazole ring, an oxazole ring, an isothiazole ring, an isoxazole ring, a thiophene ring, and the like are preferable, and a condensed ring in which these rings are fused to each other is also preferable. . These rings may have a substituent, and when substituted with two or more substituents, those substituents may be the same or different.

R ₅ represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, or a sulfamoyl group. The carbamoyl group for R ₅ has 1 to 50 carbon atoms, preferably 6 carbon atoms.
And carbamoyl groups, for example, unsubstituted carbamoyl, methylcarbamoyl, N-ethylcarbamoyl, N
-Propylcarbamoyl, N-sec-butylcarbamoyl, N-octylcarbamoyl, N-cyclohexylcarbamoyl, N-tert-butylcarbamoyl, N
-Dodecylcarbamoyl, N- (3-dodecyloxypropyl) carbamoyl, N-octadecylcarbamoyl, N- {3- (2,4-tert-pentylphenoxy) propyl} carbamoyl, N- (2-hexyldecyl) carbamoyl, N -Phenylcarbamoyl, N-
(4-dodecyloxyphenyl) carbamoyl, N-
(2-chloro-5-dodecyloxycarbonylphenyl) carbamoyl, N-naphthylcarbamoyl, N-3
-Pyridylcarbamoyl, N-benzylcarbamoyl)
Is mentioned.

The acyl group represented by R _{5 is} an acyl group having 1 to 50 carbon atoms, preferably 6 to 40 carbon atoms, such as formyl, acetyl, 2-methylpropanoyl, cyclohexylcarbonyl, octanoyl, and 2-hexyldecanoyl. , Dodecanoyl, chloroacetyl, trifluoroacetyl, benzoyl, 4-dodecyloxybenzoyl,
-Hydroxymethylbenzoyl. The alkoxycarbonyl group for R _{5 is} an alkoxycarbonyl group having 2 to 50 carbon atoms, preferably 6 to 40 carbon atoms, for example,
Methoxycarbonyl, ethoxycarbonyl, isobutyloxycarbonyl, cyclohexyloxycarbonyl,
Dodecyloxycarbonyl and benzyloxycarbonyl. The aryloxycarbonyl group for R ₅ is
An aryloxycarbonyl group having 6 to 50 carbon atoms, preferably 6 to 40 carbon atoms, such as phenoxycarbonyl, 4-octyloxyphenoxycarbonyl, 2-hydroxymethylphenoxycarbonyl, and 4-dodecyloxyphenoxycarbonyl. The sulfonyl group for R ₅ has 1 to 50 carbon atoms, preferably 6 to 40 carbon atoms.
And for example, methylsulfonyl, butylsulfonyl, octylsulfonyl, 2-hexadecylsulfonyl, 3-dodecyloxypropylsulfonyl, 2
-Octyloxy-5-t-octylphenylsulfonyl, 4-dodecyloxyphenylsulfonyl. The sulfamoyl group for R _{5 is} a sulfamoyl group having 0 to 50 carbon atoms, preferably 6 to 40 carbon atoms, for example,
Unsubstituted sulfamoyl, N-ethylsulfamoyl group,
N- (2-ethylhexyl) sulfamoyl, N-decylsulfamoyl, N-hexadecylsulfamoyl,
N- {3- (2-ethylhexyloxy) propyl} sulfamoyl, N- (2-chloro-5-dodecyloxycarbonylphenyl) sulfamoyl, N- (2-tetradecyloxyphenyl) sulfamoyl.

The group represented by R ₅ may further have a substituent at a substitutable position. When the group is substituted with two or more substituents, those substituents are the same. Or different.

Next, the preferred range of the compound represented by the formula (3) will be described. R ₅ is preferably a carbamoyl group, particularly preferably a carbamoyl group having a hydrogen atom on a nitrogen atom. The unsaturated ring represented by Q is preferably a 5- to 6-membered ring, such as a benzene ring, a pyrimidine ring, 1,2,3.
-Triazole ring, 1,2,4-triazole ring, tetrazole ring, 1,3,4-thiadiazole ring, 1,2,2
4-thiadiazole ring, 1,3,4-oxadiazole ring, 1,2,4-oxadiazole ring, thiazole ring,
Oxazole rings, isothiazole rings, isoxazole rings, and rings obtained by condensing these rings with a benzene ring or an unsaturated hetero ring are more preferred.

The synthesis of the compound represented by formula (3) is described in JP-A-9-152702 and JP-A-8-286340.
No. 9-152700, No. 9-152701, No. 9-152703, and No. 9-152704.

The specific examples of the compounds represented by formula (3) are shown below, but the compounds of the present invention are not limited thereto.

[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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[0089]

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Dye released by a coupling reaction between the coupler of the present invention represented by the general formula (1) and an oxidized form of the developing agent represented by the general formula (2) or (3)
Is a diffusible dye, and the cyclic compound formed by the coupling reaction between the coupler and the oxidized developing agent and the subsequent intramolecular ring closure reaction is preferably non-diffusible. It is preferable not to transfer to a layer and not to use it substantially for image formation. For this purpose, Cp, A or / and a developing agent (in the phenol ring in the general formula (2) or Q in the general formula (3) in the general formula (2))
It is preferable that at least one of the above groups contains at least one group having diffusion resistance. Here, the diffusion-resistant group means an oil-solubilizing group, and has a carbon number of 8 or more and 80 or less, preferably 10 or more and 40 or less.
It is a group containing the following oil-soluble partial structure. Dye released by the reaction of the coupler represented by the general formula (1) with the oxidized form of the developing agent is a diffusible dye,
Those having a hydrophilic group in the partial structure of e are preferable. The hydrophilic group referred to herein is a partial structure such as -O
-, -CON <,>NCOO-,> NCON <, -SO
_{-, - SO 2 -, -} SO 2 N <, - OH, -COOH, -
_{P (O) (OH) 2} , -SO 3 H and the like. Preferably, -O-, -CON <,>NCOO-,> NCON
_{<, - SO 2 -, SO} 2 N <, - OH, and -COOH, and the like. In the present invention, it is preferable to use an auxiliary developing agent. Here, the auxiliary developing agent means a substance having an action of promoting the transfer of electrons from the color developing agent to the silver halide in the developing process of silver halide development, and is an electron-emitting compound according to the Kendall-Peltz rule. is there. The auxiliary developer used in the present invention is disclosed in
Compounds represented by general formulas (B-1) and (B-2) described on pages 37 to 38 of 152705, and pages 3 to 6 of JP-A-9-146248. And a sulfonamide phenol compound represented by the general formula [1]. Specific examples of these auxiliary developing compounds include compounds described in JP-A-9-152705, pp. 39-41 (ETA-
1) to (ETA-36) and JP-A-9-146248
D-1 described on pages 9 to 15 of the specification
D-35. Particularly preferred compounds as the auxiliary developer used in the present invention are shown below, but the present invention is not limited thereto.

[0091]

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[0092]

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[0093]

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[0094]

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The amount of the coupler of the present invention represented by the general formula (1) depends on the molar extinction coefficient (ε) of the dye represented by the Dye of the general formula (1), but the reflection density is 1.0 or more. In order to obtain the image density of
In the case of a coupler of about 500 to 500,000, about 0.001 to 100 mmol / m ² , preferably 0.01 to 10 mmol / m ² , more preferably 0.1 to 100 mmol / m ² as a coated product.
From 05 to 5.0 mmol / m ² are suitable. The addition amount of the color developing agent represented by the formula (2) or (3) has a wide range, but is preferably 0.01 to 100 times, more preferably 0.1 to 100 times the coupler. ~
10 molar times is appropriate. Total amount of auxiliary developing agent is 1 silver
0.01 to 20 mol, particularly preferably 0.1 to 20 mol, per mol.
1 to 10 mol.

The method of adding the coupler represented by the general formula (1) and the developing agent represented by the general formula (2) or (3) and the auxiliary developing agent according to the present invention include: A developing agent and a high boiling point organic solvent (eg, alkyl phosphate, alkyl phthalate, etc.) are mixed and dissolved in a low boiling point organic solvent (eg, ethyl acetate, methyl ethyl ketone, etc.), and an emulsification dispersion method known in the art is used. After dispersing in water, it can be added.
Further, addition by the solid dispersion method described in JP-A-63-271339 is also possible.

The heat-developable color light-sensitive material used in the present invention basically comprises a support having a light-sensitive silver halide emulsion and a binder, if necessary, an organic metal salt oxidizing agent, and a dye described later. A donor compound or the like can be contained. These components are often added to the same layer, but can also be added separately to separate layers. For example, when a colored coupler represented by the general formula (1) and a dye-donor compound are present in a lower layer of a silver halide emulsion, a decrease in sensitivity can be prevented. Further, the reducing agent is preferably incorporated in the photothermographic material, but may be supplied from the outside by, for example, a method of diffusing from a dye fixing element described later.

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 having photosensitivity in different spectral regions are used in combination. . For example, JP-A-59-180,550, JP-A-64-13,546,
No. 62-253,159, European Patent Publication No. 479, 1
No. 67, etc., a combination of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer, a red-sensitive layer, an infrared-sensitive layer (1), an infrared ray There is a combination of the photosensitive layer (2) and the like. Each photosensitive layer can have various arrangement orders known for a conventional type color photosensitive material. Each of these photosensitive layers may be divided into two or more layers as necessary, as described in JP-A-1-252954. In the photothermographic material, various non-photosensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer may be provided between the silver halide emulsion layers and the uppermost layer and the lowermost layer. Often, various auxiliary layers such as a back layer can be provided on the opposite side of the support. Specifically, the layer constitution described in the above patent, an undercoat layer as described in US Pat. No. 5,051,335, JP-A-1-167,838, JP-A-61
Intermediate layer having a solid pigment as described in JP-A-20-943, JP-A-1-129553, and JP-A-5-34,884.
And DIR as described in JP-A-2-64,634.
Interlayer with compound, US Pat. No. 5,017,454
No. 5,139,919 and JP-A-2-23504.
4, an intermediate layer having an electron transfer agent as described in
It is possible to provide a protective layer having a reducing agent or a layer obtained by combining them as described in JP-A-249,245. The support has an antistatic function and a surface resistivity of 10 ¹² Ω
-It is preferable to design so as to be not more than cm.

Next, the silver halide emulsion used in the photothermographic material will be described in detail. The silver halide emulsion that 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. When the silver halide grains contained in the silver halide emulsion of the present invention are composed of mixed crystals of different silver halides, grains having a uniform composition can be used within the grains. It is also preferable to provide a so-called laminated structure having the above layers. An example of the latter is a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different compositions. In addition to the above-described layered structure, a structure having a localized phase having a different halogen composition inside the grain can also be preferably used. Preferable examples of such grains include grains in which silver halides having different compositions are bonded on a surface, a ridge or a vertex of a base silver halide grain by epitaxial bonding.
Further, it is also preferable to form these localized phases inside the particles. The silver halide grains constituting the silver halide emulsion may have a monodisperse or polydisperse grain size distribution, as disclosed in JP-A-1-167,743 and JP-A-4-22.
As described in US Pat. No. 3,463, a method of mixing monodisperse emulsions having different grain sizes and sensitivities and adjusting the gradation is preferably used. The particle size is between 0.1 and 2 μm, especially between 0.
2 to 1.5 μm is preferred. The crystal habits of silver halide grains include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal systems such as spheroids, and high aspect ratio flat plates, and those having twin planes. It may be one having such a crystal defect, or a composite system thereof or any other. Specifically, US Pat. No. 4,500,626 No. 50
No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17, 029 (1
No. 17, 643 (December 1978)
Nos. 18, 716 (November 11, 1979)
Mon.), p. 648, No. 307, 105 (1989, January 1).
January) pages 863 to 865, JP-A-62-253,159.
No. 64-13,546, JP-A-2-236,54
No. 6, No. 3-110, 555, "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glafkide)
s, Chemie etPhisique Photographique, Paul Montel, 1
967), Duffin, Photographic Emulsion Chemistry, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry, F
ocalPress, 1966), `` Production and coating of photographic emulsions '' by Zerikman et al., published by Focal Press (VLZelikman et al., M.
aking and Coating Photographic Emulsion, FocalPres
s, 1964) and the like, any of which can be used.

The light-sensitive silver halide emulsion used in the present invention contains titanium or titanium for various purposes such as sensitization, high contrast, improvement of reciprocity failure, improvement of latent image stability, and improvement of pressure resistance. It is preferable to contain a transition metal ion such as iron, cobalt, ruthenium, rhodium, osmium, iridium, and platinum, or a typical metal ion such as zinc, cadmium, thallium, and lead. These metal ions are introduced in the form of a salt or a complex salt. Particularly when a transition metal ion is contained, as a complex having ammonia, halogen, cyan, thiocyan, nitrosyl or the like as a ligand, or a complex having an organic ligand such as imidazole, triazole, pyridine or bipyridine as a ligand Preferably, it is used. These ligands are used singly or in combination. These compounds may be used alone or in combination of two or more. The addition amount depends on the purpose of use, but is generally 10 ^-9 to 10 per mol of silver halide.
It is about ^-3 mol. When it is contained, it may be uniformly contained in the particles, or may be localized inside or on the surface of the particles. Specifically, emulsions described in JP-A-2-236542, JP-A-1-116637, JP-A-5-181246 and the like are preferably used.

In the step of forming the grains of the photosensitive silver halide emulsion of the present invention, as a silver halide solvent, a rhodan salt, ammonia, a tetra-substituted thioether compound or JP-B-477-1 is used.
Organic thioether derivatives described in 1,386 or sulfur-containing compounds described in JP-A-53-144,319 can be used.

Other conditions are described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glaf).
kides, Chemie et Phisique Photographique, Paul Mont
el, 1967), Duffin's "Photographic Emulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Chemistr)
y, Focal Press, 1966), Zerikman et al., "Manufacture and Coating of Photographic Emulsions," Focal Press (VLZelikman et.
al., Making and Coating Photographic Emulsion, Foc
al Press, 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-sided mixing method, and a combination thereof. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. An inverse mixing method in which grains are formed in the presence of excess silver ions can also be used. As one type of the double jet method, the pAg in the liquid phase in which silver halide is formed is kept constant, so-called controlled
The double jet method can also be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition speed of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329 and JP-A-55-158, JP-A-55-142329). No. 124, U.S. Pat. No. 3,650,75
No. 7). Further, the stirring method of the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner depending on the purpose. The preferred pH range is between 2.3 and 8.5, more preferably between 2.5 and 7.5.

In the process of preparing the photosensitive silver halide emulsion of the present invention, it is preferable to perform so-called desalting for removing excess salt. As a means for this, a Nudel water washing method in which gelatin is gelatinized may be used, and inorganic salts composed of polyvalent anions (for example, sodium sulfate), an anionic surfactant, and an anionic polymer (for example, polystyrene sulfonic acid) Sodium) or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.). The sedimentation method is preferably used.

The light-sensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. The chemical sensitization of the photosensitive silver halide emulsion of the present invention may be carried out by a known method such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method such as a chalcogen sensitization method, a gold sensitization method, a gold sensitization method and a platinum sensitization method. Metal sensitization method and reduction sensitization method using palladium or the like can be used alone or in combination (for example, see JP-A-3-11).
0,555, JP-A-5-241,267). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Laid-Open No. 62-253,159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, the methods described in JP-A-5-45,833 and JP-A-62-40,446 can be used. The pH at the time of chemical sensitization is preferably 5.3 to 10.5,
It is more preferably 5.5 to 8.5, and the pAg is preferably 6.0 to 10.5, more preferably 6.8 to 9.0.
It is. The coating amount of the photosensitive silver halide emulsions used in the present invention is in the range of terms of silver 1 mg to 10 g / m ^2, preferably a 10mg~10g / m ^2.

In order to give the photosensitive silver halide used in the present invention green, red, and infrared sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat.
And sensitizing dyes described in JP-A-617-257, JP-A-59-180,550, JP-A-64-13,546, JP-A-5-45,828 and JP-A-5-45,834. These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used particularly for the purpose of supersensitization or wavelength adjustment of spectral sensitivity. Along with the sensitizing dye, a dye which does not itself have a 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, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion at or before chemical ripening, or before or after nucleation of silver halide grains according to U.S. Pat. Nos. 4,183,756 and 4,225,666. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant. The addition amount is generally from 10 ^-8 to 10 per mol of silver halide.
^-2 moles.

The additives used in such a step and known photographic additives which can be used in the photothermographic material and the dye fixing material of the present invention are described in RD Nos. 17, 643 and N.
o.18, 716 and Nos. 307, 105, and the relevant portions are summarized in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer 648, right column 3. Spectral sensitizer page 23-24, page 648, right column 866-868, strong Color sensitizer 頁 Page 649 4. Fluorescent brightener Page 24 Page 648 Right column Page 868 5. Antifoggant, Page 24-25 Page 649 Right column 868-870 Stabilizer 6. Light absorber, 25- Page 26 649 page right column 873 filter dye, page 650 left column UV absorber 7. Dye image 25 page 650 page left column 872 stabilizer 8. Hardener 26 page 651 left column 874-875 9. Binder Page 26 651 Left column 873-874 10. Plasticizer, Page 27 650 Right column 876 Lubricant 11. Coating aid, Page 26-27 Page 650 Right column 875-876 Surfactant 12. Static 27 Page 650 Page right column pages 876-877 Inhibitor 13. Matting agent pages 878-879

In a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with the photothermographic material. The dye-fixing material may be in the form of being separately coated on a support separate from the photosensitive material, or may be in the form of being coated on the same support as the photosensitive material. The relationship between the photosensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer described in column 57 of US Pat. No. 4,500,626 can be applied to the present invention. The dye fixing material 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 U.S. Pat. No. 4,500,626, columns 58 to 59;
No. 88256, pages (32) to (41) and JP-A-1-16
No. 1,236, pages (4) to (7), mordants described in U.S. Pat. Nos. 4,774,162 and 4,619,883;
Nos. 4,594,308 and the like can be mentioned. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used.

In the present invention, as a support for the photothermographic material or the dye fixing material, a support that can withstand the processing temperature is used. In general, papers and synthetic polymers (films) described in the Photographic Society of Japan, "Basics of photographic engineering-silver halide photography-", pages 223 to 240, published by Corona Co., Ltd. (1979). And photographic supports. Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, and further, Film-processed synthetic paper made from polypropylene, etc., mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass, etc. Is used. These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. The laminate layer may contain pigments and dyes such as titanium oxide, ultramarine blue, and carbon black as necessary. In addition, JP-A-62-253159, pages (29) to (31), and JP-A-1-161236 (1)
The supports described in pages 4) to (17), JP-A-63-316848, JP-A-2-22651, JP-A-3-56955, and U.S. Pat. No. 5,001,033 can be used. The back surface of these supports may be coated with a hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black, or another antistatic agent.
Specifically, a support described in JP-A-63-220246 can be used. The surface of the support is preferably subjected to various surface treatments or undercoating for the purpose of improving the adhesion to the hydrophilic binder.

The photothermographic material and / or dye fixing material of the present invention may have a form having a conductive heating element layer as a heating means for heat development and diffusion transfer of dye. The heat generating element in this case is described in JP-A-61-145.
No. 544 can be used. The heating temperature in the thermal development step is about 50 ° C. to 250 ° C., and especially about 60 ° C.
C. to 180 C. is useful. The dye diffusion transfer step may be performed simultaneously with the thermal development, or may be performed after the thermal development step. In the latter case, the transfer temperature can be in the range of from the temperature in the heat development step to room temperature in the transfer step, but it is particularly preferably at least 50 ° C. and up to about 10 ° C. lower than the temperature in the heat development step.

Although the movement of the dye is caused only by heat,
Solvents may be used to promote dye transfer. Also,
U.S. Pat. Nos. 4,704,345 and 4,740,44
No. 5, JP-A-61-238056, etc., 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. In this method, the heating temperature is preferably 50 ° C. or higher and lower than the boiling point of the solvent. For example, when the solvent is water, the temperature is preferably 50 ° C. to 100 ° C. Examples of the solvent used for accelerating the development and / or diffusing and transferring the dye include water, a basic aqueous solution containing an inorganic alkali metal salt and an organic base (these bases are described in the section of the image formation accelerator). Described are used), a low-boiling solvent or a mixed solution of a low-boiling solvent and water or the basic aqueous solution. Further, a surfactant, an antifoggant, a compound forming a complex with a hardly soluble metal salt, a fungicide, and a bactericide may be contained in the solvent. Water is preferably used as a solvent used in these steps of thermal development and diffusion transfer, and any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the heat developing apparatus using the photothermographic material and the dye fixing material of the present invention, water may be used up or circulated and used repeatedly. In the latter case, water containing components eluted from the material will be used. JP-A-63-144354 and JP-A-63-144355,
The apparatus and water described in JP-A-62-38460 and JP-A-3-210555 may be used.

As a heating method in the development and / or transfer step, a heated block or plate is brought into contact, a hot plate, a hot presser, a hot roller, a hot drum, a halogen lamp heater, an infrared and far infrared lamp heater are used. For example, or by passing through a high-temperature atmosphere. The method described in JP-A-62-253159 and JP-A-61-147244, page 27, can be applied to the method of superposing the photothermographic material and the dye fixing material.

[0113]

Next, the present invention will be described in more detail with reference to examples. Example 1 A dye fixing material (image receiving element R101) was prepared by the following method. Support with pulp as core material (152μm thickness)
A surface PE layer (thickness: 36.0 μm) and a surface undercoat layer (thickness: 0.1 μm) are sequentially provided from the support side on the front surface, and a back surface PE layer (thickness: 27.0 μm) and a back surface undercoat layer (thickness: (Thickness: 0.1 μm) was sequentially formed from the support side. Table 1 shows the components of each layer.

[0114]

[Table 1]

Next, six layers of coating liquids for forming a layer were applied in layers on the surface of the surface undercoat layer, and six layers were formed on a support to prepare an image receiving element R101. Table 2 shows the constituent components of each layer.

[0116]

[Table 2]

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

Next, a light-sensitive material for thermal development was prepared by the following method. First, a method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive Silver Halide Emulsion (1) [Emulsion for Fifth Layer (680 nm Photosensitive Layer)] A well-stirred aqueous solution having the composition shown in Table 3 was mixed with the solution (I) having the composition shown in Table 4 and (II). ) Solution was added simultaneously over 19 minutes, and 5 minutes later, 3 parts of solution (III) having the composition shown in Table 4 were added.
Solution (IV) was added over 33 minutes and 30 seconds for 3 minutes.

[0122]

[Table 3]

[0123]

[Table 4]

[0124]

Embedded image

Further, 15 minutes after the start of the addition of the solution III,
Over a period of 7 minutes, 150 cc of an aqueous solution containing 0.350% of a sensitizing dye was added.

[0126]

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After washing with water and desalting (using a precipitant a at a pH of 3.7 to 4.1) according to a conventional method, 22 g of lime-treated ossein gelatin was added, and the pH and pAg were adjusted to 6.0 and pAg, respectively. 7.
After adjusting to 9, it was chemically sensitized at 60 ° C. The compounds used for chemical sensitization are as shown in Table 5. The yield of the obtained emulsion was 630 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 10.2%, and the average grain size was 0.20 μm.

[0128]

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[0129]

[Table 5]

[0130]

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Photosensitive Silver Halide Emulsion (2) [Emulsion for Third Layer (750 nm Photosensitive Layer)] A well-stirred aqueous solution having the composition shown in Table 6 was mixed with the solution (I) having the composition shown in Table 7 and (II). ) Solution was added simultaneously over 18 minutes, and 5 minutes later, solution (III) having the composition shown in Table 7 was added over 24 minutes, and solution (IV) was added over 24 minutes and 30 seconds.

[0132]

[Table 6]

[0133]

[Table 7]

Lime-treated ossein gelatin (calcium content: 150 PPM) after washing with water and desalting (performed at pH 3.9 using sedimentation agent b) in a conventional manner
22 g), redisperse at 40 ° C., add 0.39 g of 4-hydroxy-6-methyl-1,3,3a, -7-tetrazaindene, adjust the pH to 5.9 and the pAg to 7 .
Adjusted to 8. Then, at 70 ° C. using the chemicals shown in Table 8.
With chemical sensitization. At the end of the chemical sensitization, the sensitizing dye was added as a methanol solution (solution having the composition shown in Table 9). Further, after the chemical sensitization, the temperature was lowered to 40 ° C., and 200 g of a gelatin dispersion of a stabilizer described later was added thereto. The yield of the obtained emulsion was 938 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.25 μm. The emulsion for the 750 nm photosensitive layer had a J-band type spectral sensitivity.

[0135]

Embedded image

[0136]

[Table 8]

[0137]

[Table 9]

[0138]

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Photosensitive Silver Halide Emulsion (3) [Emulsion for First Layer (810 nm Photosensitive Layer)] A well-stirred aqueous solution having the composition shown in Table 10 was mixed with the solution (I) having the composition shown in Table 11 and (II). ) Solution was added simultaneously over 18 minutes, and 5 minutes later, solution (III) 24 having the composition shown in Table 11 was added.
Minutes and solution (IV) was added over 24 minutes and 30 seconds.

[0140]

[Table 10]

[0141]

[Table 11]

After washing with water and desalting (using a precipitant a at a pH of 3.8) according to a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 7.4 and the pAg to 7.8. After adjustment, chemical sensitization was performed at 60 ° C. The compounds used for chemical sensitization are as shown in Table 12. The yield of the obtained emulsion was 683 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.32 μm.

[0143]

[Table 12]

Preparation of silver chloride fine grain emulsion [First layer (810)
to the aqueous solution having the composition shown in Table 13 that is well stirred.
Solution (I) and Solution (II) having the composition shown in Table 14 were simultaneously added over 4 minutes, and 3 minutes later, the solution (II) having the composition shown in Table 14 was obtained.
Solution I) and solution (IV) were added over 8 minutes.

[0145]

[Table 13]

[0146]

[Table 14]

After washing with water and desalting (using a precipitant a represented by the above structural formula at a pH of 3.9) in the usual manner, 132 g of lime-treated gelatin was added, and the mixture was redispersed at 35 ° C.
0.39 g of -hydroxy-6-methyl-1,3,3a, -7-tetrazaindene was added to adjust the pH to 5.7 to obtain a silver chloride fine grain emulsion. The yield of the obtained silver chloride fine grain emulsion was 3,200 g, and the average grain size was 0.10 μm.

Next, a method for preparing a dispersion of a colloidal silver emulsion will be described. The solution having the composition shown in Table 16 was added to the sufficiently stirred aqueous solution having the composition shown in Table 15 over 24 minutes. Then, after washing with the sedimentation agent a represented by the above structural formula, 43 g of lime-treated ossein gelatin was added, and p
H was adjusted to 6.3. Average particle size is 0.02 μm
And the yield was 512 g. (2% silver, gelatin 6.
Dispersion containing 8%)

[0149]

[Table 15]

[0150]

[Table 16]

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described.

Gelatin dispersions of a yellow dye-donating compound, a magenta dye-donating compound, and a cyan dye-donating compound (each of which also serves as a developing agent) were prepared as prescribed in Table 17, respectively. That is, each oil phase component was heated and dissolved at about 70 ° C. to form a uniform solution. The aqueous phase component heated to about 60 ° C. was added to this solution, mixed with stirring, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm. Water was added thereto and stirred to obtain a uniform dispersion. Further, the gelatin dispersion of the cyan dye-donating compound was subjected to ultrafiltration using an ultrafiltration module (Asahi Kasei ultrafiltration module: ACV-3050) so that the amount of ethyl acetate in Table 17 became 1/76 of the amount of ethyl acetate. Was.

[0153]

[Table 17]

The gelatin dispersion of the antifoggant is shown in Table 1.
8 was prepared according to the formula. That is, the oil phase component is heated and dissolved at about 60 ° C., the aqueous phase component heated to about 60 ° C. is added to the solution, and the mixture is stirred and mixed.
The dispersion was performed at 00 rpm to obtain a uniform dispersion.

[0155]

[Table 18]

A gelatin dispersion of the reducing agent was prepared according to the recipe in Table 19. That is, the oil phase component is heated and dissolved at about 60 ° C., and the aqueous phase component heated to about 60 ° C. is added to the solution,
After stirring and mixing, use a homogenizer for 10 minutes, 10,000
Dispersed at rpm to obtain a uniform dispersion. Further, ethyl acetate was removed from the obtained dispersion using an organic solvent removal device under reduced pressure.

[0157]

[Table 19]

The dispersion of the polymer latex (a) is shown in Table 2
0 as prepared. That is, an anionic surfactant was added over 10 minutes while stirring a mixture of the polymer latex (a), surfactant and water in the amounts shown in Table 21, to obtain a uniform dispersion. Further, the obtained dispersion is subjected to an ultrafiltration module (Asahi Kasei ultrafiltration module: ACV-30).
Using 50), dilution with water and concentration were repeated so that the salt concentration in the dispersion was adjusted to 1/9.

[0159]

[Table 20]

A gelatin dispersion of the stabilizer was prepared according to the recipe in Table 21. That is, the oil phase component is dissolved at room temperature,
An aqueous phase component heated to about 40 ° C. is added to this solution, and the mixture is stirred and mixed. Then, the mixture is homogenized for 10 minutes at 10,000 rpm.
Was dispersed. Water was added thereto and stirred to obtain a uniform dispersion.

[0161]

[Table 21]

A gelatin dispersion of zinc hydroxide was prepared according to the recipe in Table 22. That is, after mixing and dissolving each component, the mixture was dispersed in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. Further, the glass beads were separated and removed to obtain a uniform dispersion (zinc hydroxide had a particle size of 0.25 μm).
Was used.)

[0163]

[Table 22]

Next, a method for preparing a gelatin dispersion of a matting agent added to the protective layer will be described. A solution obtained by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant, followed by high-speed stirring and dispersion. Subsequently, methylene chloride was removed using a vacuum desolvation apparatus to obtain a uniform dispersion having an average particle size of 4.3 μm.

[0165]

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[0166]

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[0167]

Embedded image

[0168]

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[0169]

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[0170]

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Using the above, a photosensitive element 101 shown in Table 23 was prepared.

[0172]

[Table 23]

[0173]

[Table 24]

Next, the dye-providing compounds in the fifth layer, the third layer and the first layer were changed in equimolar amounts as shown in Table 25, and the compound (D-21) of the present invention was replaced with the coupler of each coupler. The same light-sensitive materials 103 to 118 except for the molar amount and further addition.
It was created. Furthermore, except that the compound (D-21) of the present invention was changed as shown in Table 26 in the light-sensitive material 113 in an equimolar amount of each coupler, the same light-sensitive materials 119 to 119 were used.
126 was created. Further, a comparative photosensitive material (102) was prepared using a compound described in U.S. Pat. No. 4,483,194 and a developing agent (2,6 dichloro-4-aminophenol) as a dye-providing compound.

[0175]

Embedded image

These light-sensitive elements were replaced with the image receiving element R101.
An image was output at a heating condition of 83 ° C. using a Pictography 4000 manufactured by Fuji Photo Film Co., Ltd. to evaluate photographic properties and color turbidity. Photography is
Dmin (minimum density) and Dmax (highest density) for a development time of 10 seconds.

[0177]

[Table 25]

[0178]

[Table 26]

As is clear from Tables 25 and 26, when the compound of the present invention was used, good color development was exhibited even in a short development process.

[0180]

The silver halide color light-sensitive material of the present invention has a small dependence on the development processing time, exhibits high color development,
Enables faster processing time. Furthermore, discrimination (S
/ N) can form an excellent image.

Claims (2)

[Claims] 1. A dye diffusion comprising a coupler represented by the following general formula (1) and at least one developing agent represented by the following general formula (2) or (3): Transfer heat developed silver halide color photosensitive material. Formula (1) Cp-AE- (L) _n -Dye In the formula, Cp represents a coupler residue capable of coupling with an oxidized developing agent, E represents an electrophilic site, and A represents C
In the coupling product between p and the oxidized developing agent, a nitrogen atom derived directly from the developing agent and directly bonded to the coupling position and the electrophilic site E undergo an intramolecular nucleophilic substitution reaction to form a 4- to 8-membered ring. -Represents a divalent linking group or a single bond capable of releasing (L) _n -Dye, and may be bonded to Cp at the coupling position of Cp, or to Cp at a position other than the coupling position of Cp. They may be combined. L is 2
And n represents 0 or 1, and Dye represents a diffusible dye residue. Embedded image In the formula, R _{1 to} R ₄ represent a hydrogen atom or a substituent, and D is -C
O -, - SO -, - SO 2 -, and -P (= O) represents at least one divalent or more linking groups selected from <,
T represents a divalent linking group. M is a nucleophilic group and represents a group capable of attacking D when the compound is oxidized.
R ₁ and R ₂ , and R ₃ and R ₄ may be bonded to each other to form a ring. General formula (3) Q-NHNH-R _{5 In the} formula, Q is bonded to -NHNH-R _{5 by a} carbon atom.
R ₅ represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, or a sulfamoyl group. 2. A dye-diffusion transfer heat-developable color light-sensitive material having at least three silver halide emulsion layers having color sensitivity in mutually different wavelength ranges, wherein -Dye in the molecule has diffusivity in one of the layers. Another layer contains a coupler represented by the general formula (1) in which -Dye is a diffusible magenta dye residue, and contains a coupler represented by the general formula (1) which is a yellow dye residue. The dye-development transfer heat developing halogen according to claim 1, wherein the further layer contains a coupler represented by the general formula (1), wherein -Dye is a diffusible cyan dye residue. Silver color photosensitive material.