JP2001183786A - Image forming element and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color diffusion transfer image forming element excellent in the fastness of an image. SOLUTION: The image forming element contains a compound of formula I (where X is halogen, alkyl, aryl, a heterocyclic group, alkylthio, arylthio, heterocyclic thio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl or sulfamoyl; and Z is carbamoyl, acyl, alkoxycarbonyl, aryloxycarbonyl, sulfonyl or sulfamoyl), a compound which forms a diffusible dye by reaction with the oxidized body of the compound of the formula I, and at least one fading inhibitor contained in a binder and having a nitrogen-containing heterocycle substituted by a group which attains covalent bonding by reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an image forming element used in a color diffusion transfer image forming method.

[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 the methods 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 p-phenylenediamine reducing agent and a 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 transferred to the diffusible 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 more details, see U.S. Pat.
No. 25, No. 4,483,914, No. 4,503,13
7, 4,559,290, JP-A-58-149,
No. 046, No. 60-133, 449, No. 59-21
No. 8,443, No. 61-238,056, European Patent Publication No. 220,746A2, Published Technical Report 87-6199, European Patent Publication No. 210660A2, and the like. There is a problem in that the sensitivity of the light-sensitive material is reduced because it is fixed to a substance. Therefore, it is preferable that a system in which a colorless coupler reacts with a base agent at first to diffuse a target dye can be realized.

As a method of forming an image by the above-mentioned coupling method, Japanese Patent Publication No. 63-48787,
JP-A-59-1224 and JP-A-6-83005 disclose photothermographic materials containing a color developing agent precursor releasing p-phenylenediamine and a coupler.
No. 11,148 discloses a combination of a ureidoaniline-based reducing agent and an active methylene type coupler.
No. 9047 discloses a light-sensitive material using a coupler having a polymer chain as a leaving group and releasing a diffusible dye in color development. However, the color developing agent or the precursor of the color developing agent used in these documents has a problem that, in addition to the insufficient color image density after transfer, the light image fastness during storage is poor. Also, there has been a demand for the emergence of a technique for achieving both fastness and transfer density.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a color diffusion transfer imaging element having excellent image fastness. In particular, in an image forming method in which a dye is formed by a coupling reaction and a color image is obtained by diffusion transfer,
An object of the present invention is to provide an image forming element and an image forming method which are excellent in light fastness.

[0006]

The object of the present invention has been found to be solved by the following method. 1) Forming or releasing a diffusible dye on a support by reacting with a photosensitive silver halide, a binder, a color developing agent represented by the following general formula (I) and an oxidized form of the color developing agent. A photosensitive material having a compound is developed after exposure, and an image forming element used in a color diffusion transfer image forming method for transferring a generated diffusible dye to a dye fixing layer, wherein the dye fixing layer has a mordant polymer and the following general formula A color diffusion transfer image-forming element comprising the compound represented by (II). General formula (I)

[0007]

Embedded image

In the formula, X is a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, or a sulfamoyl group. General formula (II)

[0009]

Embedded image

In the formula, the ring structure containing N represents an atomic group capable of forming a nitrogen-containing non-aromatic ring having three or more members. X represents a hydrogen atom, an alkoxy group, an aryloxy group, an oxy radical group, a hydroxyl group, or a group that forms an imino group or a hydroxyimino group by hydrolysis. Y
Represents a group capable of forming a covalent bond by a chemical reaction with a reactive group contained in the binder. 2) The image forming element according to item 1, wherein a reactive group capable of reacting with Y in the general formula (II) is contained in the mordant polymer. 3) The image forming element according to item 1 or 2, wherein the mordant polymer contains a tertiary nitrogen atom. 4) The first, second, or third, wherein the N-containing cyclic structure of the general formula (II) is a pyrrolidine ring or a piperidine ring.
Or an image forming element according to item 3.

[0011]

Next, the compound represented by formula (I) used in the present invention will be described in detail.

The compound represented by formula (I) of the present invention will be described in detail. In the general formula (I), X is 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 32 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl,
-Octyl, tridecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), an aryl group (preferably an aryl group having 6 to 32 carbon atoms, for example, phenyl, 1-naphthyl, 2-
Naphthyl), a heterocyclic group (preferably having 1 to 32 carbon atoms)
A 5- to 8-membered heterocyclic group such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl,
-Pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-2-yl), an alkylthio group (preferably an alkylthio group having 1 to 32 carbon atoms, for example, methylthio, ethylthio, octylthio, benzylthio, cyclohexylthio) ), An arylthio group (preferably an arylthio group having 6 to 32 carbon atoms, for example, phenylthio, 1-naphthylthio),
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 having 1 to 32 carbon atoms) 32 alkylsulfinyl groups, for example, methylsulfinyl, benzylsulfonyl, dodecanesulfinyl), arylsulfinyl (preferably an arylsulfinyl group having 6 to 32 carbon atoms, for example, phenylsulfinyl), and alkylsulfonyl group (preferably 1 carbon atom) And alkylsulfonyl groups of, for example, methylsulfonyl, octylsulfonyl, benzylsulfonyl, cyclohexylsulfonyl) and arylsulfonyl groups (preferably arylsulfonyl groups having 6 to 32 carbon atoms, such as phenylsulfonyl, In naphthylsulfonyl), or a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, for example, represent sulfamoyl, N, N- dipropyl sulfamoyl, a N- ethyl -N- dodecyl sulfamoyl).

The group represented by X may further have a substituent. In this case, preferred substituents include a halogen atom (for example, a fluorine atom, a chlorine atom and a bromine atom) and an alkyl group (preferably a carbon atom). A linear, branched, or cyclic alkyl group of the formulas 1 to 32, 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-butene-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 having 1 to 32 carbon atoms)
A 5- to 8-membered heterocyclic group such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl,
-Pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-2-yl), cyano group, silyl group (preferably having 3 to 32 carbon atoms)
A silyl group such as trimethylsilyl, triethylsilyl, toshibutylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), a hydroxyl group,
Nitro group, alkoxy group (preferably an alkoxy group having 1 to 32 carbon atoms, for example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cyclopentyloxy, cyclohexyloxy), aryl An oxy group (preferably an aryloxy group having 6 to 32 carbon atoms, for example, phenoxy,
2-naphthoxy),

A heterocyclic oxy group (preferably having 1 to 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), acyloxy group (preferably an acyloxy group having 2 to 32 carbon atoms, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), alkoxycarbonyloxy group (preferably Is an alkoxycarbonyloxy group having 2 to 32 carbon atoms, for example, ethoxycarbonyloxy, t-butoxycarbonyloxy, cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably having 7 to 3 carbon atoms) An aryloxycarbonyloxy group such as phenoxycarbonyloxy), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 32 carbon atoms such as N, N-dimethylcarbamoyloxy and N-butylcarbamoyloxy), sulfo A famoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, for example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy),
Alkylsulfonyloxy group (preferably having 1 to 3 carbon atoms)
2 alkylsulfonyloxy groups, for example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), arylsulfonyloxy (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, for example, phenylsulfonyloxy), acyl A 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),

An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms such as phenoxycarbonyl), a carbamoyl group (preferably a carbamoyl group having 1 to 32 carbon atoms such as carbamoyl, N, N -Dibutylcarbamoyl, N-ethyl-N-octylcarbamoyl, N-propylcarbamoyl, N, N-dicyclohexylcarbamoyl), an amino group (preferably an amino group having 32 or less carbon atoms, for example,
Amino, methylamino, N, N-dioctylamino, tetradecylamino, octadecylamino, cyclohexylamino), anilino group (preferably anilino group having 6 to 32 carbon atoms, for example, anilino, N-methylanilino), heterocycle An 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 4 to 32 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 having 1 to 3 carbon atoms)
And two heterocyclic thio groups, for example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), and an alkylsulfinyl group (preferably having 1 to 1 carbon atoms)
32 alkylsulfinyl groups, for example, dodecanesulfinyl), arylsulfinyl (preferably 6 to 32 carbon atoms, for example, phenylsulfinyl), alkylsulfonyl groups (preferably 1 to 32 carbon atoms, alkylsulfonyl groups) So, for example,
Methylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl group (preferably an arylsulfonyl group having 6 to 32 carbon atoms, for example, phenylsulfonyl, 1-naphthylsulfonyl), 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 having 1 to carbon atoms)
The 32 phosphonyl groups include, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), and phosphinoylamino groups (diethoxyphosphinoylamino, dioctyloxyphosphinoylamino groups).

In the general formula (I), Z is a carbamoyl group (a carbamoyl group having 1 to 50 carbon atoms, preferably 6 to 40 carbon atoms, 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), an acyl group (1 carbon atom)
To 50, preferably 6 to 40 carbon atoms, such as formyl, acetyl, 2-methylpropanoyl, cyclohexylcarbonyl, octanoyl, 2-hexyldecanoyl, dodecanoyl, chloroacetyl, trifluoroacetyl, benzoyl, -Dodecyloxybenzoyl, 2-hydroxymethylbenzoyl), alkoxycarbonyl group (2 to 50 carbon atoms, preferably 6 to 6 carbon atoms)
40 alkoxycarbonyl groups, for example, methoxycarbonyl, ethoxycarbonyl, isobutyloxycarbonyl, cyclohexyloxycarbonyl, dodecyloxycarbonyl, benzyloxycarbonyl), aryloxycarbonyl group (C6-50, preferably C6-40) Aryloxycarbonyl groups such as phenoxycarbonyl, 4-octyloxyphenoxycarbonyl, 2-hydroxymethylphenoxycarbonyl, 4-dodecyloxyphenoxycarbonyl),
Sulfonyl group (1 to 50 carbon atoms, preferably 6 to 6 carbon atoms)
40 sulfonyl groups, for example, methylsulfonyl, butylsulfonyl, octylsulfonyl, 2-hexadecylsulfonyl, 3-dodecyloxypropylsulfonyl, 2-octyloxy-5-t-octylphenylsulfonyl, 4-dodecyloxyphenylsulfonyl) ,
Or a sulfamoyl group (a sulfamoyl group having 1 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 Z may further have a substituent. In this case, preferred substituents are the same as those described above as the preferred substituents of the group represented by X.

Next, preferred ranges of the compound represented by the formula (I) will be described. X is a halogen atom, an aryl group, a heterocyclic group, an alkylthio group, an arylthio group,
An alkylsulfonyl group, an arylsulfonyl group, and an arylsulfinyl group are preferred, a chlorine atom, an aryl group, an alkylthio group, and an arylthio group are more preferred, and an aryl group is most preferred. Z is preferably a carbamoyl group, particularly preferably a carbamoyl group having a hydrogen atom on a nitrogen atom.

The compound represented by the general formula (I) has X and
And at least one of the groups represented by Z_TwoH,-
NHSO_TwoR_a, -SO_TwoNHR_b, -CONHSO_TwoR_b,
-SO_TwoNHCOR_bOr one group represented by -OH
It is preferable that R_aIs an alkyl group, aryl
A heterocyclic group or a heterocyclic group;_bIs a hydrogen atom, al
Represents a kill group, an aryl group, or a heterocyclic group. these
Preferred alkyl, aryl and heterocyclic groups
The number of carbon atoms and specific examples are as follows.
It is the same as that mentioned in Ming. Represented by the general formula (I)
The compound is represented by a group represented by X_TwoH, -NHSO_Two
R_a, -SO_TwoNHR_b, -CONHSO_TwoR _b, -SO_TwoN
HCOR_bOr one or more groups represented by -OH
More preferably,

Specific examples of the color developing agent represented by formula (I) are shown below, but the scope of the present invention is not limited to these specific examples.

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

Next, a method for synthesizing the compound represented by the general formula (I) of the present invention will be described. For example, Exemplified Compound D-32 of the present invention can be synthesized by the following synthesis route in accordance with Synthesis Example 2 described on page 15 of JP-A-9-152702.

[0028]

Embedded image

Further, specific synthetic examples of the compound represented by the general formula (I) of the present invention are shown below, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Exemplified Compound (D-19) The synthesis method of Exemplified Compound (D-19) is described in JP-A-9-1527.
The synthesis was carried out by the following synthesis route according to the method described in No. 02. Compound (T-
4) was synthesized by the synthesis method described in Japanese Patent No. 2,845,331.

[0031]

Embedded image

Synthesis of Compound (T-3) 110.5 g of Compound (T-1) was suspended in 1.0 liter of methylene chloride, and perchloromethyl mercaptan 10
0 g was added. The reaction system was cooled to 0 to 5 ° C., and a solution of 200 g of sodium hydroxide dissolved in 600 ml of water was added dropwise so that the reaction temperature became 15 ° C. or lower. After the reaction, the aqueous layer was removed, and 50 g of hydrazine hydrate was added dropwise at 15 ° C. or lower. After the reaction, 1.0 liter of water was added to perform an extraction operation. The organic layer was concentrated under reduced pressure, and intermediate (T-3) 14
1.1 g (57% yield) were obtained.

Synthesis of Compound (T-5) Triphosgene (100.5 g) was dissolved in tetrahydrofuran (2 L), and while cooling, Compound (T-4) 300
g, and 150 ml of triethylamine was further added dropwise. After the dropwise addition, the mixture was reacted at room temperature for 1 hour, and then the compound (T
-3) 237.5 g was separately added in five batches. After the addition, the mixture was further reacted for 2 hours. Then, 2 liters of ethyl acetate and 2 liters of water were added, and an extraction operation was performed.
After washing twice with liter, the organic layer was dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was recrystallized from acetonitrile to give Compound (T-5) 33
0.2 g (yield 55%) was obtained as white crystals.

Synthesis of Exemplified Compound (D-19) 28.0 g of the intermediate (T-5) was mixed with 500 ml of ethyl acetate,
It was dissolved in 400 ml of water and 100 ml of ethanol, and 87 g of sodium hydrosulfite was further added. 2
After reacting for an hour, an extraction operation was performed. After washing twice with 500 ml of water, the organic points were dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was dissolved in 100 ml of N, N-dimethylacetamide and 7 ml of triethylamine, and 4.0 ml of methanesulfonyl chloride was added dropwise under cooling with water so that the internal temperature did not exceed 15 ° C.
After the addition, the reaction was continued for another hour.
Poured into 00 ml. The precipitated crystals were collected by filtration, washed with water and dried to obtain crude crystals. The crude crystals were recrystallized from acetonitrile to give 24.7 g of Exemplified Compound (D-19) (yield: 83).
%) As white crystals.

The color developing agent of the present invention is used together with a compound (coupler) which forms a dye by an oxidative coupling reaction. In the present invention, among couplers used in conventional silver salt photography using a paraphenylenediamine developing agent as a developing agent, a so-called "2-equivalent coupler" in which the coupling position is substituted with a coupling-off group other than a hydrogen atom. Is preferred. For two-equivalent couplers, see Theory of the Photographic
Process (4th.Ed., edited by THJames, MaCmillan, 1977)
Pages 354 to 361, Basics of Photographic Engineering-Silver halide photography (edited by the Photographic Society of Japan, Corona, 1998), pages 244 to 258.
It is described on the page.

The couplers that can be used in the present invention are described below. Examples of the coupler that can be used in the present invention include compounds described in JP-A No. 9-152705, 20 to
Couplers represented by general formulas (1) to (12) described on page 23 are mentioned. In these couplers, the total number of carbon atoms except for Y is preferably 1 or more and 30 or less, more preferably 1 or more and 24 or less, and 1 or more and 1 or less.
Most preferred is 8 or less.

Specific examples of the coupler which can be preferably used in the present invention are shown below, but the present invention is not limited by these.

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

In addition to the above couplers, JP-A-9-1527
Exemplary compounds (C-1) to (C-50) described on pages 24 to 37 of JP-A No. 05 are also preferred as the coupler used in the present invention.

The couplers that can be used in the present invention are cited in the description of couplers represented by formulas (1) to (12) described on pages 20 to 24 of JP-A-9-152705. Can be synthesized according to the methods described in patents and literatures. Hereinafter, specific synthesis examples of the coupler that can be used in the present invention will be described, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Exemplified Compound C-13 Synthesis was performed according to the following synthesis route.

[0047]

Embedded image

Synthesis of Compound C-13A 49.7 g of 2-aminophenyl disulfide and 2-aminophenyl disulfide
150 g of (2,4-di-t-amylphenoxy) butanoic acid chloride was added to 800 ml of acetonitrile, and the mixture was heated under reflux for 1 hour. After the reaction, the mixture was cooled to room temperature, the crystals were collected by filtration, washed with 200 ml of acetonitrile, and dried. Thus, 156 g (91.4%) of compound C-13A was obtained as white crystals.

Synthesis of Exemplified Compound C-13 28.2 g of Compound C-13A was converted to methylene chloride (300 m).
and sulfuryl chloride (3.6 ml) was further added. After reacting for 2 hours, the solvent was distilled off under reduced pressure. Thereafter, the residue was dissolved in 50 ml of methylene chloride to obtain a solution of compound C-13B. Separately, 10.45 g of compound C-13C was converted to N, N-dimethylformamide (hereinafter referred to as D
A solution dissolved in 100 ml of MF) was prepared, and a methylene chloride solution of the compound C-13B previously synthesized was added dropwise at room temperature so that the internal temperature did not exceed 30 ° C. After the dropwise addition, the mixture was further reacted for 1 hour, and the reaction mixture was poured into 500 ml of 1N hydrochloric acid. After performing an extraction operation with methylene chloride, the compound was recrystallized with acetonitrile to give Exemplified Compound C-13,
9.96 g (82.0%) were obtained as pale yellow crystals.

Synthesis Example 2 Synthesis of Exemplified Compound C-31 Synthesis was performed according to the following synthesis route.

[0051]

Embedded image

Synthesis of Compound C-31A Hydroquinone monobenzyl ether (200 g) was dissolved in a mixed solvent of acetonitrile (500 ml) and DMF (500 ml), and triethylamine (167 ml) was added. While dripping. After the completion of the dropwise addition, the mixture was reacted for 1 hour, and then the reaction solution was carefully poured into 3 liters of 1N hydrochloric acid. The precipitated crystals were collected by filtration and acetonitrile 300 m
and then dried. Thus, Compounds C-31A, 4
35 g (93% yield) were obtained as white crystals.

Synthesis of Compound C-31B 47 g of Compound C-31A, 1 g of 10% Pd-C, and 22 g of ammonium formate were dissolved in 500 ml of methanol, and heated under reflux for 4 hours. After the reaction, the catalyst was filtered off using celite while hot, and 2 liters of water was poured into the filtrate. The precipitated crystals were collected by filtration and washed with 100 ml of methanol.
After drying, compound C-31B, 36.3 g (98% yield)
Was obtained as white crystals.

Synthesis of Compound C-31C 37.8 g of Compound C-31B was added to 500 ml of methylene chloride.
And 8 ml of nitric acid having a specific gravity of 1.38 was added dropwise at room temperature. The reaction was further performed for 1 hour, and 1 liter of hexane was poured into the reaction solution. The precipitated crystals were collected by filtration and washed with 100 ml of isopropyl alcohol. After drying, compound C-
34.7 g (yield 82%) of 31C was obtained as yellow crystals.

Synthesis of Compound C-31D 42.3 g of Compound C-31C was added to 200 ml of methanol.
And 85 ml of an aqueous solution of sodium hypochlorite having an effective chlorine concentration of 5% was added dropwise at room temperature. After reacting for 2 hours, 500 ml of ethyl acetate and 800 m of 1N hydrochloric acid were added to the reaction solution.
1 was poured and an extraction operation was performed. After washing twice with 500 ml of water, the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give Compound C-31D, 35.
2 g (yield 77%) were obtained as pale red crystals.

Synthesis of Exemplified Compound C-31 45.7 g of Compound C-31D was added to 500 m of ethyl acetate.
1, dissolved in 400 ml of water and 100 ml of ethanol,
Further, 87 g of sodium hydrosulfite was added and stirred. After reacting for 2 hours, after washing twice with 500 ml of water, the organic layer was dried over anhydrous magnesium sulfate,
The solvent was distilled off under reduced pressure. The residue was dissolved in 100 ml of N, N-dimethylacetamide, and 8 ml of acetyl chloride was added dropwise at room temperature so that the internal temperature did not exceed 35 ° C. After the dropwise addition, the mixture was further reacted for 1 hour, and the reaction mixture was poured into 500 ml of 1N hydrochloric acid. The precipitated crystals were collected by filtration, washed with water and dried to obtain crude crystals. The crude crystals were recrystallized from acetonitrile to give 31.9 g of Exemplified Compound C-31 (yield 68).
%) As white crystals.

The amount of the coupler used in the present invention depends on the molar extinction coefficient (ε) of the dye to be formed. Ε of the dye is 5,000 to 500,000
In the case of a coupler of a degree, 0.001 to 10
0 mmol / m ² , preferably 0.01 to 10 mmol / m ² , more preferably 0.05 to 5.0 mmol / m ²
m ² is appropriate. Further, the amount of the color developing agent represented by the general formula (I) of the present invention has a wide range, but is preferably 0.01 to 100 times, more preferably 0.1 to 10 times, based on the coupler. Double is appropriate.

As a method for adding the coupler and the developing agent represented by the general formula (I), first, the coupler, the developing agent and a high-boiling organic solvent (for example, alkyl phosphate,
Phthalic acid alkyl ester, etc.), dissolve in a low boiling point organic solvent (eg, ethyl acetate, methyl ethyl ketone, etc.), disperse in water using an emulsification dispersion method known in the art, and then add. Also, JP-A-63-271
Addition by the solid dispersion method described in No. 339 is also possible.

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 development process of silver halide development,
It is an electron-emitting compound according to the Kendall-Peltz rule. 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 JP-A-52705 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.

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

In the present invention, Japanese Patent Application Laid-Open No. 9-15270
A blocked photographic reagent which releases a photographically useful group upon processing as represented by the general formula (A) described in paragraph No. 0074 on page 41 to paragraph 0077 on page 41 of the specification No. 5 is used. Can be used.

Next, the compound represented by formula (II) will be described. In the formula, the ring structure containing N represents a group of atoms capable of forming a nitrogen-containing non-aromatic ring having three or more members (eg, an aziridine ring, a pyrrolidine ring, a piperidine ring, etc.). This non-aromatic ring may contain a substituent and may have an unsaturated bond as long as it does not form an aromatic π-electron system. Of these, a pyrrolidine ring and a piperidine ring are preferable, and a piperidine ring is particularly preferable. Especially N
A derivative of tetramethylpyrrolidine or tetramethylpiperidine in which a carbon atom adjacent to the atom is substituted by a methyl group is preferably used.

X represents a hydrogen atom, an alkoxy group (eg, methoxy group, ethoxy group, butoxy group, octyloxy group, etc.), an aryloxy group (eg, phenoxy group, tolyloxy group, etc.), an oxy radical group, a hydroxyl group, or a hydrolyzate. Represents a group that forms a group that forms an imino group or a hydroxyimino group. Examples of the group that forms an imino group or a hydroxyimino group by hydrolysis include, for example, -QR, -QOR, -QNR (R
`), -OQR, -OQOR, -OQN-
The group represented by R (R ') can be mentioned. Here, Q represents a carbonyl group, an imino group, an α-diketo group, a sulfonyl group, —PO (R ′ ′)-(R ′ ′ represents an alkyl group, an aryl group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group. A divalent linking group selected from any of the above groups. R represents any of an alkyl group, an aryl group and a heterocyclic group, and when Q is an imino group, R and Q may be linked to each other to form a ring. R
`Represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Examples of such groups include, for example, an alkylcarbonyl group (eg, acetyl group, propionyl group, butyroyl group), an arylcarbonyl group (eg, benzoyl group, alkylbenzoyl group), an alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group) Group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidinocarbamoyl group, morpholinocarbamoyl group), arylcarbamoyl group (for example, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), Carbamoyl group, alkoxycarbamoyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (eg Phenoxycarbonyl group), acyloxy group (eg, acetyloxy group, propionyloxy group, butyroyloxy group), alkylcarbonyloxy group (eg, acetoxy group, propionyloxy group), arylcarbonyloxy group (eg, benzoyloxy group, alkylbenzoyloxy group) Group), alkoxycarbonyloxy group (eg, methoxycarbonyloxy group, ethoxycarbonyloxy group), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy group), alkyl carbamate group (eg, dimethylcarbamoyloxy group), aryl carbamate group (eg, ethyl Phenylcarbamoyloxy group), alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (eg, Phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkylsulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutyl) Sulfamoyl group, piperidinosulfamoyl group, morpholinosulfamoyl group), arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group) A moyl group), a sulfamoyl group, an alkyloxalyl group (eg, an ethyloxalyl group), and the like.

Y represents a group capable of forming a covalent bond by chemically reacting with a reactive group contained in the binder.
The reaction of Y with the binder enables the compound represented by formula (I) to be fixed in the image element of the present invention. Any organic chemical reaction capable of forming a covalent bond suitable for this purpose can be used. Examples include nucleophilic substitution reactions typified by S _N1 and S _N2 reactions, addition reactions typified by Michael reactions, and Diels
There are pericyclic reactions typified by -Alder reaction and the like, coupling reactions with redox widely used in photographic chemistry, and any of them can be used. As the binder to be used for the immobilization reaction, a polymer compound is generally used. For the purpose of the present invention, any of an oil-soluble polymer, a water-soluble polymer, and a polymer latex can be used. Above all, a mordant polymer capable of mordanting a diffusible dye to be released and transferred by a diffusion transfer type color photosensitive material by ionic interaction is preferable. Examples of such a polymer include a polymer having a secondary and / or tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, and a polymer having a quaternary cation group and having a molecular weight of 5,000 to 100,000.
0, especially 10,000 to 500,000. Among them, a polymer having a secondary or tertiary nitrogen atom is particularly preferable, and a polymer having a tertiary nitrogen atom is more preferable. Specifically, US Pat. No. 2,548,564
Nos. 2,484,430 and 3,148,061
Nos. 3,756,841 and 3,625,694
Nos. 3,859,096 and 4,128,538
No. 3,958,995, No. 2,721,852
No. 2,798,063, 4,168,976
Nos. 3,709,690 and 3,788,855
No. 3,642,482, No.3,488,706
No. 3,557,066, No. 3,271,147
No. 3,271,148, 2,675,316
No. 2,882,156, British Patent 1277453
No. JP-A-54-115228 and JP-A-54-14552.
No. 9, No. 54-126027, No. 50-71332
No. 53-30328, No. 52-155528,
Nos. 53-125, 53-1024, and the like.

Such a mordant polymer and a compound represented by the general formula (II)
Considering that a covalent bond is formed by the reaction with the compound represented by the general formula (II), the most preferably usable organic chemical reaction is represented by the general formula (II) by the nucleophilic nitrogen atom contained in the mordant polymer. Of the nucleophilic reaction of the compound to Y. For this reason, usable groups include a halogenated alkyl group, a halogenomethylene aryl group, a halogenomethylenecarbonyl group, a halogenomethylenecarbonyloxy group, a halogenomethylenecarbonamide group, a halogenomethylenesulfonyl group, a halogenomethylenesulfonamide group, and an alkylsulfonyloxy group. Alkyl group, alkylsulfonyloxymethylenearyl group, alkylsulfonyloxymethylenecarbonyl group, alkylsulfonyloxymethylenecarbonyloxy group, alkylsulfonyloxymethylenecarboxamide group, arylsulfonyloxyalkyl group, arylsulfonyloxymethylenearyl group, arylsulfonyloxymethylene Carbonyl group, arylsulfonyloxymethylenecarbonyloxy group, arylsulfonyl Oxymethylene carbonamido group, a vinyl group, a vinyl carbonyl group, a vinyl carboxylic amide group, vinylsulfonyl group, a vinyl sulfonamide group, an epoxy group, an episulfide group, and a formyl group.

Hereinafter, specific examples of the compound represented by formula (II) will be described, but the present invention is not limited to the compound.

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

The compounds described above can be synthesized by combining stepwise synthetic reactions widely known in organic chemistry. The synthesis scheme is shown below.

[0079]

Embedded image

The image forming element of the present invention refers to a photosensitive element, a dye fixing element, a processing element such as a processing sheet, and the like. The addition position of the compound represented by the general formula (II) will be described. The compound represented by the general formula (II) may be present together with the image element according to the present invention when an image is finally formed, and the compound may be added at the time of image formation or after the image formation. The compound represented by the formula (2) may be added anywhere as long as it can move to the dye fixing layer. Further, it may be added to a single place or may be added to a plurality of places. That is, it can be added to any place of the processing solution or image element, and specifically, it can be added to any layer of the dye fixing element, or any layer in the photosensitive element, or any of the processing elements. . In the photosensitive microcapsule method, the capsule may be added to a capsule or a binder in which the capsule is dispersed and fixed. Further, it can be added to the dye fixing element after image formation. That is, a method of applying a solution of the compound represented by the general formula (II) to the dye fixing element, immersing the solution in the solution, transferring the solution from the treatment sheet to be contained, spraying the solution like ink of an inkjet printer, and the like. Can also be added. However, preferably, when the purpose of the present invention is to fix the compound by reaction with the binder, it is preferable to add the desired binder, particularly to the same layer as the mordant polymer, and as a more preferable method, A method in which a compound represented by the general formula (II) is added in advance to the mordant polymer solution to cause a chemical reaction, followed by coating.

The compound represented by the general formula (II) may be added by dissolving it in water, or adding an organic solvent such as alcohols and ketones if it is not separated when added to the coating solution. Alternatively, they may be dissolved in a mixed solvent of water and added.
Further, it can be added by dissolving in an acid or a base. Also,
It can also be added by being included in an inclusion compound.

The amount of the compound represented by the general formula (II) may be set at 0.0 in the image element after the image is finally formed.
It is preferably present at 1 mmol / m ² or more. More preferably in the range of 0.1 mmol / m ² of 10 mmol / m ^2. Further, the addition mole of the compound represented by the general formula (II) is 0.1 to the reaction site of the binder to be reacted.
0001-1000 mole times, preferably 0.001-1
The molar ratio is 00 molar times, more preferably 0.01 to 10 molar times.

These compounds can be used in combination with other anti-fading agents. Further, it can be used in combination with other fading prevention methods such as addition of an ultraviolet absorber and lamination. The compound represented by the general formula (II) can be used in combination with a compound that generates active oxygen. Examples of the active oxygen generator include certain image forming dyes, titanium oxide, optical brighteners, and transition metal salts. Ultraviolet absorbers are also used as active oxygen generators.

Next, a technique desirably used in combination with the present invention will be described. The heat-developable color light-sensitive material used in the present invention basically has a light-sensitive silver halide emulsion and a binder on a support. In some cases, the reducing agent may also serve as a reducing agent.). These components are often added to the same layer, but can also be added separately to separate layers. For example, if a coloring dye-providing compound is present in the lower layer of a silver halide emulsion, the sensitivity can be prevented from lowering. 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, 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 et Phisique Photographique, Paul Montel,
1967), Duffin's "Photographic Emulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Chemistry,
Focal Press, 1966), `` Manufacture and coating of photographic emulsions '' by Zelikman et al., Published by Focal Press (VLZelikman et a
l., Making and Coating Photographic Emulsion, Focal
Press, 1964) and the like can be used.

The photosensitive 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 and JP-A-4-126629 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-47-1
Organic thioether derivatives described in 1,386 or sulfur-containing compounds described in JP-A-53-144,319 can be used.

For other conditions, see Physics and Chemistry of Photography by Grafkid, supra, 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 Chemis)
try, Focal Press, 1966), Zerikman et al., "Manufacture and Coating of Photographic Emulsions," Focal Press (VLZelikman
et al., Making and Coating Photographic Emulsion, F
ocal 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, a so-called controlled double jet method in which the pAg in a liquid phase in which silver halide is formed is kept constant can 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 (Japanese Patent Application Laid-Open Nos. 55-142,329 and 55-158; 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 carry out so-called desalting for removing excess salt. As a means for this, a Nudel water washing method in which gelatin is gelled 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.) may be used. The sedimentation method is preferably used.

The photosensitive 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 chalcogen sensitization method such as a tellurium sensitization method, or a gold or 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, Japanese Patent Application No. 4-75,798). 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, a fogging inhibitor 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,
More preferably, it is 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 sensitivity, red sensitivity, 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 these steps 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 RD No.
No. 18, 716 and No. 307, 105, and the corresponding 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, page 648, right column 3. Spectral sensitizer, page 23 to page 648, right column, page 866 to 868 Strong Color sensitizer ~ page 649 4. Optical brightener page 24 page 648 right column page 868 5. Antifoggant, page 24-25 page 649 right column page 868-870 Stabilizer 6. Light absorber, 25- Page 26 649 Right column Page 873 Filter dye, Page 650 Left column UV absorber 7. Dye image 25 Page 650 Left column 872 Stabilizer 8. Hardener Page 26 651 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 26-27 650 Right column 875-876 Surfactant 12. Static 27 Page 650 Right column Page 876-877 Inhibitor 13. Matting agent Page 878-879

As the binder for the constituent layers of the photothermographic material and the dye fixing material, hydrophilic binders are preferably used. Examples thereof include those described in the aforementioned Research Disclosure and JP-A-64-13546, pages (71) to (75). 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 and polyvinyl alcohol, Synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymer are exemplified. No. 4,960,681.
No. superabsorbent polymers described in JP-A-62-245,260, etc., i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer each other vinyl monomers having Alternatively, a copolymer with another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more kinds. In particular, a combination of gelatin and the above binder is preferable.The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes. Is also preferred.

In the case of employing a system in which thermal development is performed by supplying a small amount of water, the use of the above superabsorbent polymer makes it possible to rapidly absorb water. When a superabsorbent polymer is used in the dye-fixing layer or its protective layer separately from the present invention, 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 0.2 to 0.2 m ^2.
It is preferably 20 g, particularly 0.2 to 10 g or less,
Further, the amount is suitably 0.5 g to 7 g.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide emulsion. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include US Pat.
Bensotriazoles, fatty acids and other compounds described in, for example, columns 52 to 53 of 00,626. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above organic silver salt is used in an amount of 0.01 per mole of the photosensitive silver halide.
10 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. Total coating amount of light-sensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ² in terms of silver, and preferably from 0.1-4 g / m ^2.

In addition to the present invention, a reducing agent may be used. As the reducing agent to be used, those known in the field of photothermographic materials can be used. Further, a dye-providing compound having a reducing property described later is also included (in this case, another reducing agent can be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can be used. Examples of the reducing agent used in the present invention include columns 49 to 50 of U.S. Pat. No. 4,500,626, 4,839,272, 4,330,617, and 4,590,152. Nos. 5,017,454 and 5,139,919, and JP-A-60-140,335, pages (17) to (18), 57-40,245, and 56-.
138,736, 59-178,458, 59
Nos. 53,831 and 59-182,449, 59
-182,450, 60-119,555, 6
Nos. 0-128,436, 60-128,439, 60-198,540, 60-181,742,
Nos. 61-259,253 and 62-201,434
Nos. 62-244,044 and 62-131,25
No. 3, 62-131, 256, 63-10, 15
Nos. 1 and 64-13 and 546, pages (40) to (57), JP-A-1-120,553, JP-A-2-32,338 and JP-A-2,338.
-35,451, 2-234,158 and 3-1
No. 60,443, No. 78 of EP 220,746.
On page 96 and the like. Combinations of various reducing agents can also be used, such as those disclosed in U.S. Pat. No. 3,039,869.

When a diffusion-resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent may be used, if necessary, to promote electron transfer between the diffusion-resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination. Particularly preferably, said US Patent No. 5,139,
919, European Patent Publication No. 418,743,
Nos. 138,556 and 3-102,345 are used. Further, a method of stably introducing the compound into the layer as described in JP-A-2-230143 or JP-A-2-23504 is preferably used. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). The diffusion-resistant reducing agent (electron donor) to be used in combination with the electron transfer agent may be any one which does not substantially move in the layer of the light-sensitive material among the aforementioned reducing agents, and is preferably a hydroquinone, Sulfonamidophenols, sulfonamidonaphthols, JP-A-53-110827, U.S. Pat.
2,487, 5,026,634 and 4,83
Compounds described as electron donors in JP-A No. 9,272 and dye-donating compounds having diffusion resistance and reducibility described below are mentioned. Also, an electron donor precursor described in JP-A-3-160,443 is preferably used. Furthermore, color mixing prevention, color reproduction improvement,
The reducing agent can be used for various purposes such as improvement of the white background and prevention of silver transfer to the dye fixing material. Specifically, EP-A-524,649, EP-A-357,040, JP-A-4-249,245, JP-A-2-64,633, JP-A-2-46,450 and JP-A-63-450. 186,240 are preferably used. In addition, 3-6
3,733, JP-A-1-150,135, 2-1
Nos. 10,557, 2-64,634, 3-43,
735 and EP-A-451,833. In the present invention, the total amount of the reducing agent is 0.01 to 1 mol of silver.
-20 mol, particularly preferably 0.1-10 mol.

A hydrophobic additive such as a dye-donating compound or a nondiffusible reducing agent can be introduced into a layer of a photothermographic material by a known method such as the method described in US Pat. No. 2,322,027. it can. In this case, US Pat.
Nos. 55,470, 4,536,466, 4,53
6,467, 4,587,206, 4,55
5,476, 4,599,296, 3-6
A high-boiling organic solvent as described in JP-A-2,256 or the like can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C, if necessary. Two or more of these dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents, and the like can be used in combination. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, per 1 g of the dye-providing compound used. In addition, 1 cc or less per gram of the binder, further 0.5 cc
Below, especially 0.3cc or less is suitable. In addition, Tokiko Sho 51
-39,853, JP-A-51-59,943, and a dispersion method using a polymer described in JP-A-62-30,287.
No. 42 or the like and a method of adding it as a fine particle dispersion can also be used. 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 dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, Japanese Unexamined Patent Publication No. 59-157,636 (37)-
On page (38), those mentioned as the surfactants described in the aforementioned Research Disclosure can be used. In the photothermographic material of the present invention, a compound which activates development and stabilizes an image at the same time can be used. Specific compounds preferably used are described in US Pat. No. 4,500,
No. 626, columns 51 to 52.

In a system for forming an image by diffusion transfer of a dye, an unnecessary dye or coloring matter is fixed or made colorless in the constituent layers of the photothermographic material of the present invention to improve the white background of the obtained image. Various compounds can be added. Specifically, European Patent Publication No. 353,74
Nos. 1, 461, 416 and JP-A-63-163,34.
No. 5, 62-203, 158 can be used.

Various pigments and dyes can be used in the constituent layers of the photothermographic material of the present invention for the purpose of improving color separation and increasing sensitivity. Specifically, the compounds described in Research Disclosure and EP-A-479,1 are disclosed.
Nos. 67 and 502,508, and JP-A-1-167,83.
No. 8, 4-343, 355, 2-168, 252
No., JP-A-61-20,943, and EP-A-47.
Compounds and layer configurations described in JP-A Nos. 9,167 and 502,508 can be used.

In the present invention, a dye fixing material is used together with the photothermographic material to form an image by diffusion transfer of the dye. The dye-fixing material may be in a form separately coated on a support different from the photosensitive material, or in a form 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 are described in U.S. Pat. No. 4,500,626.
The relationships described in column 7 are also applicable 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, and
Nos. 1-88, 256, 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, 4,619,883, 4,594,308 and the like. be able to. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used. Binder used in the dye fixing material of the present invention,
The aforementioned hydrophilic binders are preferred. Further, it is preferable to use a combination of carrageenans as described in EP-A-443,529 and a latex having a glass transition temperature of 40 ° C. or lower as described in JP-B-3-74,820. Protective layer if necessary for dye fixing material,
Auxiliary layers such as a release layer, an undercoat layer, an intermediate layer, a back layer, and an anti-curl layer can be provided. It is particularly useful to provide a protective layer.

In the constituent layers of the photothermographic material and the dye fixing material, a high-boiling organic solvent can be used as a plasticizer, a slipping agent or an agent for improving the releasability of the photosensitive material from the dye fixing material. Specifically, there are those described in the above-mentioned Research Disclosure and JP-A-62-245253. 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. As examples thereof, various modified silicone oils described in "Modified Silicone Oil" Technical Document P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name: X-22-3710) are effective. Also, silicone oils described in JP-A Nos. 62-215,953 and 63-46,449 are effective.

A fluorescent whitening agent may be used for the photothermographic material and the dye fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing material or to supply it from outside such as a photothermographic material or a transfer solvent. For example, K. Veenka
Compounds described in Taraman, "The Chemistry of Synthetic Dyes", Vol. V, Chapter 8, JP-A-61-143752, etc. can be mentioned. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given. The fluorescent whitening agent can be used in combination with a fading inhibitor or an ultraviolet absorber. Specific examples of these anti-fading agents, ultraviolet absorbers, and fluorescent whitening agents include:
It is described in JP-A-62-215,272, pages (125) to (137), and JP-A-1-161,236, pages (17) to (43).

Examples of the hardening agent used for the constituent layers of the photothermographic material and the dye fixing material include the above-mentioned Research Disclosure, US Pat. No. 4,678,739, column 41, 4,791,042, 1984-116,655
No. 62-245,261, No. 61-18,942
And hardening agents described in JP-A-4-218,044. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetaamide)) Ethane, etc.), N-methylol hardeners (dimethylol urea, etc.), or polymer hardeners (JP-A-62-234,1).
No. 57 etc.). These hardeners are used in an amount of 0.001 to 1 per gram of gelatin applied.
g, preferably 0.005 to 0.5 g. The layer to be added may be any of the constituent layers of the light-sensitive material and the dye-fixing material, or may be added in two or more layers.

In the constituent layers of the photothermographic material or the dye fixing material, various antifoggants or photographic stabilizers and precursors thereof can be used. Specific examples thereof include azoles and azaindenes described in RD17643 (1978), pp. 24-25, and JP-A-59-168.4.
Examples thereof include nitrogen-containing carboxylic acids and phosphoric acids described in No. 42, mercapto compounds and metal salts thereof described in JP-A-59-111636, and acetylene compounds described in JP-A-62-87957. When a precursor is used in the present invention, it is particularly preferably used for the photosensitive silver halide emulsion layer as described above, but it can also be used for a dye fixing material. When these compounds are not precursors, 5 × 10 ⁻⁶ to 1 mol of silver
1 × 10 ^-1 mol is preferable, and 1 × 10 ^-5 to 1 × 1 is more preferable.
0 ^-2 mol is preferably used. More preferred amounts of the precursor are as described above.

The constituent layers of the photothermographic material and the dye fixing material may have coating aids, improved releasability, improved slipperiness, antistatic properties,
Various surfactants can be used for the purpose of accelerating development and the like. Specific examples of the surfactant are described in Research Disclosure, JP-A-62-173463, and JP-A-62-173463.
183,457. The constituent layers of the photothermographic material and the dye fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-61-209.
No. 44, 62-135826 and 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 described in, for example, JP-A-62-135826. No.

A matting agent can be used in the photothermographic material or the dye fixing material for the purpose of preventing adhesion and improving slipperiness. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
JP-A Nos. 63-274944 and 63-2 other than the compounds described on page 256 (29), such as benzoguanamine resin beads, polycarbonate resin beads and ABS resin beads.
No. 74952. Other compounds described in Research Disclosure can be used. These matting agents may be added not only to the uppermost layer (protective layer) but also to a lower layer as needed. In addition, the constituent layers of the photothermographic material and the dye-fixing material may contain a thermal solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256 (26).
~ (32), JP-A-3-11,338, Tokuhei 2-5
1,496 and the like.

In the present invention, an image formation accelerator can be used in the photothermographic material and / or the dye fixing material. Examples of the image formation accelerator include a redox reaction between a silver salt oxidizing agent and a reducing agent, promotion of a reaction such as formation of a dye from a dye-providing substance or decomposition of the dye or release of a diffusible dye, and photothermographic exposure. It has the function of promoting the transfer of the dye from the material layer to the dye fixing layer, and from the physicochemical function, a base or base precursor, a nucleophilic compound, a high-boiling organic solvent (oil), a thermal solvent, a surfactant , Silver, or compounds that interact with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. For details of these, see U.S. Pat. No. 4,678,739, 38-40.
Column. 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, Lossen rearrangement or Beckmann rearrangement, and the like. Specific examples thereof are described in U.S. Patent Nos. 4,514,493 and 4,657,848.

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, a method in which a base and / or a base precursor is contained in the dye-fixing material is preferable from the viewpoint of enhancing the storage stability of the photothermographic material. . In addition to the above,
EP 210,660, U.S. Pat. No. 4,74
No. 0,445, and combinations of compounds which can form a complex with metal ions constituting the hardly soluble metal compound (referred to as complex forming compounds); Compounds that generate a base by electrolysis described in (1) can also be used as the base precursor. In particular, the former method is effective. It is advantageous to separately add the hardly soluble metal compound and the complex forming compound to the photothermographic material and the dye fixing material as described in the above-mentioned patent.

In the present invention, various development stopping agents can be used in the photothermographic material and / or the dye fixing material 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. Compound. Specific examples 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. For more details, see
2-253, 159, pages (31) to (32).

In the present invention, as the support of the photothermographic material or the dye fixing material, those which can withstand the processing temperature are used. In general, papers and synthetic polymers (films) described in The Photographic Society of Japan, "Basics of Photonic Engineering-Silver Halide Photography", Corona Co., Ltd. (1979), pp. 223-240. And other photographic supports. In particular,
Polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (eg, triacetylcellulose), or films containing pigments such as titanium oxide, and polypropylene. Film-processed synthetic paper, 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 and the like are used. These can be used alone,
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene. The laminate layer may contain pigments and dyes such as titanium oxide, ultramarine blue and carbon black as necessary. In addition, Japanese Patent Application Laid-Open No. 62-253,159 (29)
Page (31), JP-A-1-61,236 (14)-(17), JP-A-63-316,848, JP-A-2-22,651
No. 3,56,955, U.S. Pat. No. 5,001,0.
The support described in No. 33 or the like 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-63-220,246 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 method of exposing and recording an image on a photothermographic material is, for example, a method of directly photographing a landscape or a person using a camera or the like, or a method of exposing through a reversal film or a negative film using a printer or a enlarger. Method, a method of scanning and exposing the original image through slits and the like using a copier exposure device, etc., and scanning exposure by emitting light from light emitting diodes and various lasers (laser diodes, gas lasers, etc.) to image information via electric signals. (Japanese Patent Application Laid-Open No. 2-129625, Japanese Patent Application No. 3-33)
8,182, 4-9,388, 4-281,4
No. 42 etc.), a method of outputting image information to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display, etc., and exposing directly or via an optical system.

As a light source for recording an image on the photothermographic material, as described above, natural light, a tungsten lamp, a light emitting diode, a laser light source, a CRT light source and the like, US Pat. No. 4,500,626, column 56, Kaihei 2-53,
No. 378 and 2-54, 672 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 non-linear optical material is a material that can exhibit nonlinearity between polarization and electric field that appears when a strong optical electric field such as a laser beam is applied, and includes lithium niobate and potassium dihydrogen phosphate (KDP). ), Inorganic compounds represented by lithium iodate, BaB ₂ O _{4 and the} like, and urea derivatives, nitroaniline derivatives, for example, nitropyridine-N- Oxide derivatives, JP-A Nos. 61-53462 and 62-210432
The compounds described in (1) 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. In addition, the image information includes an image signal obtained from a video camera, an electronic still camera, and the like, and the Nippon Television Signal Standard (NTS
A television signal represented by C), an image signal obtained by dividing an original image into a large number of pixels such as a scanner, and an image signal created by using a computer represented by CG and CAD can be used.

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-61-14.
No. 5,544 and the like can be used. The heating temperature in the heat development step is about 50 ° C. to 250 ° C., and particularly about 60 ° C. to 180 ° C. is 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 case of the latter, the heating temperature in the transfer step can be transferred within the range of the temperature in the heat development step to room temperature.
Up to lower temperatures are preferred.

The transfer 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 No. 61-238,056, 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 the boiling point of the solvent or lower. For example, when the solvent is water, the temperature is preferably from 50C to 100C. 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 complex-forming compound with a poorly soluble metal salt, a fungicide and a bactericide may be contained in the solvent. Water is preferably used as a solvent used in the steps of thermal development and diffusion transfer, and any water may be used as long as it is water generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. In the heat developing apparatus using the photothermographic material and the dye fixing material of the present invention, the water may be used up, or the water may be circulated and used repeatedly. In the latter case, water containing components eluted from the material will be used. JP-A-63-144,354 and JP-A-63-144,355.
No. 62-38,460, JP-A-3-210,55.
The device described in the item or water may be used.

These solvents can be applied to the photothermographic material, the dye fixing material, or both. The amount used may be not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film. As a method of applying this water,
For example, Japanese Patent Application Laid-Open No. 62-253,159, p.
The methods described in JP-A-3-85,544 and Japanese Patent Application No. 8-181,045 are preferably used. In addition, the solvent can be used by being encapsulated in a microcapsule or incorporated in advance in the photothermographic material and / or the dye fixing element in the form of a hydrate. The temperature of the water to be applied is from 30 ° to 60 ° C. as described in JP-A-63-85,544.
Is fine. In particular, it is useful to raise the temperature to 45 ° C. or higher for the purpose of preventing the propagation of various bacteria in water.

In order to promote dye transfer, a system in which a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature is incorporated in the photothermographic material and / or the dye fixing material may be employed. The layer to be incorporated may be any of a light-sensitive silver halide emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, but is preferably a dye fixing layer and / or a layer adjacent thereto. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles.

As a heating method in the developing and / or transferring step, a heating block, a plate, a hot plate, a hot presser, a hot roller, a hot drum, a halogen lamp heater, an infrared and far infrared lamp heater may be used. For example, or by passing through a high-temperature atmosphere. The method described in JP-A-62-253,159 and JP-A-61-147,244, page 27, can be applied to the method of superposing the photothermographic material and the dye fixing material.

For processing the photographic element of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-7
Nos. 5,247, 59-177,547, 59-1
81,353, 60-18,951, Shokai 62
-25,944, Japanese Patent Application No. 4-277,517, 4
Devices described in JP-A-243,072 and JP-A-4-244,693 are preferably used. Further, as a commercially available device, a Pictrostat 100, a Pictrostat 200, a Pictography 3000, a Pictography 2000, or the like manufactured by Fuji Photo Film Co., Ltd. can be used.

When the image obtained from the photothermographic material and the dye fixing element is used as a color proof for printing, the method of expressing the density is to use a continuous tone control or a portion having a discontinuous density. Either of the above-described area gradation control and the gradation control combining the two may be used. By using an LD or LED as an exposure light source, a digital signal can be output. As a result, it is possible to use a method (DDCP) of controlling an image such as the design and color of a printed matter on a CRT and outputting a color proof as a final output. That is, DDCP is an effective means for efficiently outputting proofs in the field of color proofs. This is because a color printer has a relatively simple configuration and is inexpensive, and a color printer does not require the production of a plate making film or a printing plate (PS plate) for a color printing machine, as is well known. Yes, a hard copy having an image formed on a sheet can be easily created a plurality of times in a short time. When an LD or LED is used as an exposure light source, two or more kinds of yellow, magenta and cyan spectral sensitivities or four spectral sensitivities of yellow, magenta, cyan and black, and a desired hue are obtained. The spectral sensitivities of the respective colors obtained by mixing the color materials preferably have peaks of the spectral sensitivities at different wavelengths separated by 20 nm or more. As a further alternative, if the spectral sensitivities of two or more different colors have a sensitivity difference of 10 times or more, 1
There is also a method of obtaining images of two or more colors at one exposure wavelength.

Next, a method of reproducing a moire or the like on a printed matter by a color printer will be described. In order to create a printing color proof that faithfully reproduces moire and the like appearing on high-resolution printing by a low-resolution color printer, a threshold matrix is used for each of the CMYK4 halftone dot area data aj. With reference to 24, each is converted into bitmap data b'j of 48800 DPI. Next, the area ratio ci for each color is counted by simultaneously referring to the bit map data b'j in a certain range. Next, the first tristimulus value data X, Y, Z of 1600 DPI, which is the colorimetric value data for each color, which is obtained in advance, is calculated. The first tristimulus value data X, Y, and Z are subjected to anti-aliasing filter processing to obtain 400 DPI.
Of the second tristimulus value data X ′, Y ′, Z ′.
This calculation data is used as input data for the color printer.
(The above is described in detail in Japanese Patent Application No. 7-5257.)

When a color image is recorded using an output device such as a color printer, a color image having a desired color can be realized by manipulating color signals for yellow, magenta, and cyan, for example. However, since the color signal depends on the output characteristics of the output device, color signals supplied from external devices having different characteristics need to be subjected to color conversion processing in consideration of the output characteristics. Therefore, a plurality of known color patches having different colors are created using the output device, and the color patches are measured, so that, for example, a known color signal CMY of the color patch is stimulated independent of the output device. A conversion relationship for converting into a value signal XYZ (hereinafter, this conversion relationship is referred to as a “forward conversion relationship”) is obtained,
Next, a conversion relationship for converting the stimulus value signal XYZ into a color signal CMY (hereinafter, this conversion relationship is referred to as an “inverse conversion relationship”) is determined from the forward conversion relationship, and the color conversion process is performed using the inverse conversion relationship. There is a way to do it. Here, as a method of obtaining the color signal CMY from the stimulus value signal XYZ,
The following three examples are given, but the examples of the present invention are not limited thereto. 1. A tetrahedron having the stimulus signal XYZ at four points as vertices is set, and the space of the stimulus value signal XYZ is divided by the tetrahedron, and the space of the color signal CMY is similarly divided by the tetrahedron. A color signal CMY for an arbitrary stimulus value signal XYZ in a tetrahedron to be obtained by a linear operation. 2. A method of repeatedly calculating a color signal CMY corresponding to an arbitrary stimulus value signal XYZ using the Newton method. (PHOTOGRAPHIC SCIENCE AND ENGINEERING Volume 1
6, Number 2. March-April 1972 pp136-pp143 "Metamer
ic color matching in subtractive color photograph
y "). 3. In a color conversion method for converting a color signal from a first color system to a second color system, the color conversion method of the first color system obtained from a known real color signal of the second color system. A first step of obtaining a relationship between real color signals as a first forward conversion relationship, and a second step of approximating the first forward conversion relationship with a monotonic function and setting a virtual color signal outside an area consisting of the real color signals And a third step of obtaining a relationship between the color signals of the first color system obtained from the color signals composed of the real color signals and the virtual color signals in the second color system as a second forward conversion relationship. From the second conversion relation, using the iterative operation method,
A fourth step of obtaining a relationship between color signals of a color system as an inverse conversion relationship, wherein the color signal is converted from a first color system to a second color system using the inverse conversion relationship. That is, this conversion method is a color conversion method for converting a color signal from a first color system to a second color system, and a first color signal corresponding to a known real color signal (for example, a CMY color signal) of the second color system. After obtaining real color signals (for example, XYZ color signals) of the color system, the first forward conversion relationship between these real color signals is approximated by a monotonic function, and the virtual relationship is set outside the region constituted by the real color signals. Set the color signal.
Then, based on the second forward conversion relationship between the second color system and the first color system consisting of the real color signal and the virtual color signal, the first color system is repeatedly calculated by the Newton method. For example, a method of obtaining an inverse conversion relationship for conversion into a system and the second color system and performing color conversion using the inverse conversion relationship can be given as an example.

Regarding the size of the image obtained by the above-described photothermographic material and the dye fixing element, any one of the A-format, A1-A6, chrysanthemum, B-format, B1-B6, and 46-format can be used. good. Further, the size of the photothermographic material and the dye-fixing element can be any size in the range of 100 mm to 2000 mm depending on the size. The photothermographic material and the dye-fixing element may be supplied in a roll or sheet form, and it is also possible to use one of them in a roll form and one in a sheet form.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

[0127]

EXAMPLES Examples Dye-fixing elements (image receiving sheets) R- having the constitutions shown in Tables 1 and 2
1 was produced.

[0128]

[Table 1]

[0129]

[Table 2]

[0130]

Embedded image

[0131]

Embedded image

Next, as shown in Table 3, except that the comparative compound and the compound of the present invention were added to the fourth layer, image receiving sheets R-2 to R- having exactly the same composition as R-1.
15 were prepared respectively.

[0133]

[Table 3]

[0134]

Embedded image

Next, how to make a photosensitive element will be described. First, a method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive silver halide emulsion (1) [fifth layer (6
Emulsion for 80 nm photosensitive layer) Solution (I) and solution (II) having the composition shown in Table 5 were simultaneously added to the well-stirred aqueous solution having the composition shown in Table 4 over 13 minutes, and 10 minutes later. And solution (III) and solution (IV) having the compositions shown in Table 5 were added over 33 minutes.

[0137]

[Table 4]

[0138]

[Table 5]

[0139]

Embedded image

An aqueous solution containing 0.350% of a sensitizing dye was added over a period of 27 minutes from 13 minutes after the start of addition of the solution III.
0 cc was added.

After washing with water and desalting (using a precipitant a at a pH of 4.1) in the usual manner, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and the pAg to 7.9. After adjustment, chemical sensitization was performed at 60 ° C. The compounds used for chemical sensitization are as shown in Table 6. The yield of the obtained emulsion was 6
A monodisperse cubic silver chlorobromide emulsion of 30 g having a coefficient of variation of 10.2% had an average grain size of 0.20 µm.

[0142]

Embedded image

[0143]

[Table 6]

[0144]

Embedded image

[0145]

Embedded image

Photosensitive silver halide emulsion (2) [Third layer (7
Emulsion for 50 nm photosensitive layer) Solution (I) and solution (II) having the composition shown in Table 8 were simultaneously added to an aqueous solution having the composition shown in Table 7 which was well stirred over 18 minutes, and 10 minutes later (III) solution having the composition shown in Table 8 and (I)
V) The solution was added over 24 minutes.

[0147]

[Table 7]

[0148]

[Table 8]

Lime-treated ossein gelatin (calcium content: 150 PPM) which was washed with water and desalted (performed at pH 3.9 using sedimentation agent b) and decalcified 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. Thereafter, using the chemicals shown in Table 9 at 70 ° C.
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 10). 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. 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.

[0150]

[Table 9]

[0151]

[Table 10]

[0152]

Embedded image

Photosensitive silver halide emulsion (3) [First layer (8
Emulsion for 10 nm photosensitive layer) Solution (I) and solution (II) having the composition shown in Table 12 were simultaneously added to the well-stirred aqueous solution having the composition shown in Table 11 over 18 minutes. Solutions (III) and (IV) having the compositions shown in Table 12 were added over 24 minutes.

[0154]

[Table 11]

[0155]

[Table 12]

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 13. At the end of the chemical sensitization, the spectral sensitizing dye was added as a methanol solution. The yield of the obtained emulsion was 680 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.32 μm.

[0157]

[Table 13]

A method of preparing a gelatin dispersion of colloidal silver will be described.

A solution having a composition shown in Table 15 was added to a well-stirred aqueous solution having a composition shown in Table 14 over 24 minutes. Thereafter, the precipitate was washed with water using a precipitant a, and 43 g of lime-treated ossein gelatin was added to adjust the pH to 6.3. The average particle size is 0.02 μm and the yield is 512 g
Met. (Dispersion containing 2% silver and 6.8% gelatin)

[0160]

[Table 14]

[0161]

[Table 15]

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

A yellow coupler, a magenta coupler, a cyan coupler, and a gelatin dispersion of a developing agent were prepared according to the formulations shown in Table 16, respectively. That is, each oil phase component is heated and dissolved at about 70 ° C. to form a uniform solution.
The aqueous phase component heated to 0 ° C. was added, and the mixture was stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. Water was added thereto and stirred to obtain a uniform dispersion.

[0164]

[Table 16]

Gelatin dispersions of antifoggants and reducing agents were prepared according to the recipe in Table 17. 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.
For 1 minute at 10,000 rpm to obtain a uniform dispersion.

[0166]

[Table 17]

A gelatin dispersion of the reducing agent was prepared according to the formulation in Table 18. 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.

[0168]

[Table 18]

The dispersion of the polymer latex (a) is shown in Table 1.
Prepared according to Formulation No. 9. 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 31 to obtain a uniform dispersion. Further, the obtained dispersion was treated with an ultra-loca module (Asahi Kasei ultra-loca 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.

[0170]

[Table 19]

A gelatin dispersion of the stabilizer was prepared as per the formulation in Table 20. 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.

[0172]

[Table 20]

A gelatin dispersion of zinc hydroxide was prepared according to the recipe in Table 21. 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.

[0174]

[Table 21]

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.

[0176]

Embedded image

[0177]

Embedded image

[0178]

Embedded image

[0179]

Embedded image

[0180]

Embedded image

[0181]

Embedded image

[0182]

Embedded image

[0183]

Embedded image

[0184]

Embedded image

[0185]

Embedded image

[0186]

Embedded image

[0187]

Embedded image

[0188]

Embedded image

Using the above, photosensitive elements 101 shown in Tables 22 and 23 were produced.

[0190]

[Table 22]

[0191]

[Table 23]

Next, as a comparative example, for yellow, magenta, and cyan, photosensitive element 1 was prepared in the same manner as photosensitive element 101 except that the developing agent and the coupler were changed as shown in Table 24.
02 was made.

[0193]

[Table 24]

Then, as shown in Table 25, the photosensitive elements 101 to 102 and the image receiving element containing the compound (II) of the present invention were used in combination with Fuji Photo Film Co., Ltd. 30
At 00, a gray image was output at a heating condition of 83 degrees 35 seconds. The output image was a clear color image. After this treatment, a transparent film having an ultraviolet absorbing layer was superimposed on the film surface of the sample, and a color image was irradiated with xenon (100,000 lux) for 7 days using an Atlas CI 65 weatherometer. The measurement was performed, and the percentage of the ratio to the density immediately after the treatment was shown as a fading rate, and the light fading was evaluated. (For the density measurement, a reflection densitometer X-rite manufactured by X-rite is used.
304 was used. ) Fading rate = (density after standing for 7 days) / (density immediately after treatment) × 1
Table 25 shows the results. As is evident from Table 25, when the compound of the present invention was used, the image fastness was excellent.

[0195]

[Table 25]

[0196]

According to the present invention, a transferred image having excellent light fastness can be obtained.

Claims (4)

[Claims] 1. A diffusible dye is formed on a support by reacting with a photosensitive silver halide, a binder, a color developing agent represented by the following general formula (I) and an oxidized form of the developing agent. A light-sensitive material having a compound to be released is developed after exposure, and in an image forming element used in a color diffusion transfer image forming method of transferring a generated diffusible dye to a dye fixing layer, the dye fixing layer comprises a mordant polymer and The following general formula (I
A color diffusion transfer image-forming element comprising the compound represented by I). General formula (I) In the formula, X is a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group,
Or a sulfamoyl group, Z is a carbamoyl group,
Represents an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, or a sulfamoyl group. General formula (II) In the formula, the ring structure containing N represents an atom group capable of forming a nitrogen-containing non-aromatic ring having three or more members. X represents a hydrogen atom, an alkoxy group, an aryloxy group, an oxy radical group, a hydroxyl group, or a group that forms an imino group or a hydroxyimino group by hydrolysis. Y represents a group capable of forming a covalent bond by chemically reacting with a reactive group contained in the binder. 2. A mordant polymer comprising a reactive group capable of reacting with Y of the general formula (II),
The image forming element according to claim 1. 3. The image forming element according to claim 1, wherein the mordant polymer contains a tertiary nitrogen atom. 4. The image forming element according to claim 1, wherein the N-containing cyclic structure of the formula (II) is a pyrrolidine ring or a piperidine ring.