JP2668294B2 - Color photosensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel magenta dye image forming compound and a color light-sensitive material containing the same.

[0002]

2. Description of the Related Art A color diffusion transfer method using a dye releasing redox compound which releases a diffusible magenta dye as a result of development under basic conditions is well known in the art. For example, as a dye-releasing redox compound that releases a magenta dye, JP-A-49-114424 can be used.
No. 50-115, 528, No. 55-4028, No. 6
1-273,542, U.S. Pat. No. 3,932,380
Nos. 3,931,144 and the like are known.

However, the compounds disclosed in these prior arts have a problem in color reproducibility due to insufficient spectral characteristics of the dye. In particular, it has been desired to reduce the side absorption of the dye in the blue region.

JP-A-61-55650 discloses 1,3,1.
Magenta azo dye-forming compounds containing 4-thiadiazolylazo groups are described. However, reduction of secondary absorption in the blue region is not yet sufficient.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color light-sensitive material containing a dye-releasing redox compound which releases a diffusible magenta dye having excellent spectral characteristics.

[0006]

The above objects of the present invention have been attained by a color light-sensitive material containing at least one image-forming compound represented by the following general formula (I) on a support. (Dye-X) q-Y (I)

In the formula, Dye represents a magenta dye group or a dye precursor group represented by the following general formula (II), X represents a simple bond or a linking group, and Y represents a photosensitive image having a latent image on an image. A substrate having the property that the XY bond is cleaved by a development reaction corresponding to or inversely corresponding to the distribution of the silver salt. General formula (II)

[0008]

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In the formula, R ₁ and R ₂ represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group,
Alkenyl, alkynyl, aryl, alkoxy, aryloxy, cyano, acylamino, sulfonylamino, ureido, alkylthio, arylthio, alkoxycarbonyl, carbamoyl, sulfamoyl, sulfonyl, acyl , Urethane group, amino group, hydroxyl group, carboxyl group,
Represents a sulfamoylamino group or a heterocyclic group;
Represents an integer of 0 to 4, and when n is 2, 3, or 4,
R ₂ may be the same or different. n is 2, 3, or 4
In this case, two R _{2 s} may combine with each other to form a saturated or unsaturated ring (however, excluding a naphthalene ring).

R ₃ represents a hydrogen atom, a monovalent cation or a group which can be hydrolyzed. q is 1 or 2, q
When is 2, Dye-X may be the same or different. Dye and X bind at R ₁ , R ₂ , and R ₃ in Chemical Formula 2. Further, the above substituent may be substituted with another substituent.

Hereinafter, the general formula (I) will be described in detail. R ₁ and R ₂ are hydrogen atom, halogen atom (chlorine atom, bromine atom, etc.), alkyl group (alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxyethyl group, Cyanoethyl group, trifluoromethyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), aralkyl group (benzyl group, 2-phenethyl group etc.), alkenyl group (vinyl group, allyl group, crotyl group etc.), Alkynyl group (eg, ethynyl group, 2-propynyl group, etc.), aryl group (eg, phenyl group, p-tolyl group, p-methoxyphenyl group, o-methoxyphenyl group, etc.), alkoxy group (C 1-8 alkoxy) Groups such as methoxy group, ethoxy group, isopropoxy group, 2-methoxyethoxy group, 2-hydroxyetho group Si group etc.), aryloxy group (eg phenoxy group, p-methoxyphenoxy group, o-carboxyphenoxy group etc.), cyano group, acylamino group (eg acetylamino group, propionylamino group, o-carboxybenzoylamino group etc.) A sulfonylamino group (for example, a methanesulfonylamino group, a benzenesulfonylamino group, a p-methoxybenzenesulfonyl group, etc.), a ureido group (3-methylureido group,
3,3-dimethylureido group etc.), alkylthio group (methylthio group, ethylthio group etc.), arylthio group (phenylthio group, o-carboxyphenylthio group etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group etc.), Carbamoyl group (methylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (methylsulfamoyl group, dimethylsulfamoyl group, etc.), sulfonyl group (methanesulfonyl group, ethanesulfonyl group, 2-methoxyethylsulfonyl group, etc.), Acyl group (acetyl group, propionyl group, cyanoacetyl group, acetoacetyl group, etc.), urethane group (methyl urethane group, ethyl urethane group, etc.), amino group (amino group, methylamino group, dimethylamino group, carboxymethylamino group) , O-carbo Shianirino group, p- hydroxyanilino group), a hydroxyl group, a carboxyl group, a sulfamoylamino group (sulfamoylamino group, 3,3
-Dimethylsulfamoylamino group), heterocyclic (α
-Pyridyl group, γ-pyridyl group, 2-furyl group, etc.). Particularly preferred among these are an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, a chlorine atom,
An acylamino group having 7 or less carbon atoms, a sulfonylamino group having 7 or less carbon atoms, an aryloxy group having 8 or less carbon atoms, a hydroxyl group, a carboxyl group, a carbamoyl group having 7 or less carbon atoms, a sulfamoyl group having 7 or less carbon atoms, and the like. .

R ₃ is a hydrogen atom, a monovalent cation (eg Na ⁺ , K ⁺ , NH ₄ ⁺ , N ⁺ (CH ₃ ) ₄ etc.) or a hydrolyzable group (eg acyl group, sulfonyl group, dialkylphosphoryl). A hydrogen atom is preferable.

[0013] X may be bonded to any site of essentially Dye part, the linking group X represents the -NR ₄ - is represented by (R ₄ represents a hydrogen atom, an alkyl group or a substituted alkyl group) group, -SO ₂ -, - CO-, an alkylene group,
Substituted alkylene group, phenylene group, substituted phenylene group,
Naphthylene group, a substituted naphthylene group, -O -, - SO- and a group representative example obtained by combining two or more of these divalent residues, of which preferred are -NR ₄ -SO
₂ -, - NR ₄ -CO- or _{-R 5 - (L) k -} (R 6) p
R ₅ and R ₆ each represent an alkylene group, a substituted alkylene group, a phenylene group, a substituted phenylene group, a naphthylene group, or a substituted naphthylene group, and L represents —O—, —CO—, or —SO. -, -SO ₂ -,-
_{SO 2 NH -, - NHSO 2} -, - CONH -, - NH
CO represents-, k represents 0 or 1, and p represents k
= 1, and 1 or 0 when k = 0.

Further, —NR ₄ —SO ₂ — and —NR ₄ —C
O- and _{-R 5 - (L) k -} (R 6) P - a combination of a also preferred. The connection between the Dye part and the Y part is Dye
Those in the form of -SO ₂ NH-Y are particularly preferred. Next, Y will be described in detail. Y is first selected such that the compound represented by formula (YI) is a non-diffusible image forming compound which is oxidized and self-cleaved to give a diffusible dye as a result of development processing.

An example of Y useful for this type of compound is an N-substituted sulfamoyl group. For example, as Y, the following equation (Y
The group represented by I) can be mentioned. Formula (YI)

[0016]

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In the formula, β represents a group of non-metal atoms necessary for forming a benzene ring, and a carbon ring or a hetero ring is condensed with this benzene ring to form, for example, a naphthalene ring, a quinoline ring, 5, 6, 7, It may form an 8-tetrahydronaphthalene ring, a chroman ring, or the like. α is -OG ¹¹ or -NH
It represents a group represented by G ^12. Here, G ¹¹ represents a hydrogen atom or a group which is hydrolyzed to form a hydroxyl group, and G ¹² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or NHG.
Represents a group capable of hydrolyzing ¹² Ball stands for ballast group. b is 0, 1 or 2. Specific examples of Y of this type are disclosed in JP-A-48-33826 and JP-A-53.
No. -50736. Another example of Y suitable for this type of compound is a group represented by the following formula (YII). Formula (YII)

[0018]

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In the formula, Ball, α, and b have the same meanings as in formula (YI), and β'represents an atomic group necessary to form a carbocycle, for example, a benzene ring. Alternatively, the heterocyclic ring may be condensed to form a naphthalene ring, a quinoline ring, a 5,6,7,8-tetrahydronaphthalene ring, a chroman ring, or the like.

A specific example of Y of this type is disclosed in JP-A-51-11.
No. 3624, JP-A-56-12624, JP-A-56-16
No. 130, No. 56-16131, No. 57-4043
No. 57-650 and U.S. Pat.
No. 2.

Another example of Y suitable for this type of compound is a group represented by the following formula (YIII). Formula (YIII)

[0022]

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In the formula, Ball, α, and b have the same meanings as in the formula (YI), and β ″ represents an atomic group necessary for forming a hetero ring such as a pyrazole ring or a pyridine ring. A specific example of this kind of Y is described in JP-A-51-10434.
No. 3.

Further, there is a compound represented by the formula (YIV) as an effective Y for the compound of this type. Formula (YIV)

[0025]

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In the formula, γ preferably represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group or heterocyclic group, or —CO—G ²¹ ; G ²¹ represents —OG ²² , -S-G ^22, or, -NG ²³
(G ²⁴⁾ represents, (G ²² represents hydrogen, an alkyl group, a cycloalkyl group or an aryl group, G ²³ is the G ²²
G ²³ represents an acyl group derived from an aliphatic or aromatic carboxylic acid or a sulfonic acid, G ²⁴ represents hydrogen or an unsubstituted or substituted alkyl group); Represents the residues required to complete the ring.

A specific example of this kind of Y is disclosed in JP-A-51-10.
4343 and Japanese Patent Laid-Open Nos. 53-46730 and 5
Nos. 4-130122 and 57-85055.

Further, Y suitable for this type of compound includes a group represented by the formula (YV). Formula (YV)

[0029]

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In the formula, Ball has the same meaning as in formula (YI), ε is an oxygen atom or a = NG ³² group (G ³² represents a hydroxyl group or an amino group which may have a substituent), In this case, the compound H ₂ N-G ³² includes, for example, hydroxylamine, hydrazines, semicarbazites, thiosemicarbazites and the like, and β ″ ″ in the formula is a 5-membered ring, 6-membered ring or 7-membered ring. A group of atoms necessary for forming a saturated or unsaturated non-aromatic hydrocarbon ring.

G ³¹ represents a hydrogen atom or a halogen atom such as fluorine, chlorine or bromine. Specific examples of this kind of Y are described in JP-A-53-3819 and JP-A-54-48534.

Other examples of Y of this type of compound include, for example, JP-B-48-32129 and JP-B-48-39165.
U.S. Pat. No. 3,644,436, U.S. Pat. No. 3,443,443.
Examples thereof include those described in No. 934 and the like.

Further, as Y in the present invention, a group represented by the formula (YVI) can be mentioned. Formula (YVI)

[0034]

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Where α is OR ⁴¹ or NHR ⁴² , and R is
⁴¹ is hydrogen or a hydrolyzable component, R ⁴² is hydrogen or an alkyl group having 1 to 50 carbon atoms or a group capable of hydrolyzing NHR ⁴² , and A ⁴¹ is necessary for forming an aromatic ring. Ball is a ballast group existing on the aromatic ring, and Ball may be the same or different, and m is an integer of 1 or 2.

X ₁ is a divalent organic group having ₁ to 8 atoms, and a nucleophilic group (Nu) and an electrophilic center (* carbon atom) generated by oxidation form a 5- to 12-membered ring. I do.
Nu represents a nucleophilic group. n is an integer of 1 or 2. α has the same meaning as in the above formula (YI). Specific examples of this kind of Y are described in JP-A-57-20735.

Further, as another type of compound represented by the formula (I), a diffusible dye is released by self-ring closure in the presence of a base, but when reacted with an oxidized product of a developing agent, the dye is substantially released. There are non-diffusible imaging compounds that do not occur. Examples of Y effective for compounds of this type include those shown in formula (YVII). Formula (YVII)

[0038]

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In the formula, α'is an oxidizable nucleophilic group such as a hydroxyl group, a primary or secondary amino group, a hydroxyamino group, a sulfonamide group or a precursor thereof, and α "is a dialkylamino group. Group or any of the groups defined for α ′, wherein G ⁵¹ is carbon atom 1-3
An alkylene group having a, a represents 0 or 1,
G ⁵² is a substituted or unsubstituted aryl group containing 6 to 40 carbon substituted or unsubstituted alkyl group or a carbon atom, containing 1 to 40 carbon atoms, G ⁵³ is -CO -, - C
G ⁵⁴ is an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom or the like, and when it is a nitrogen atom, a hydrogen atom, an alkyl group containing 1 to 10 carbon atoms or a substituent. It may be substituted with an alkyl group or an aromatic residue containing 6 to 20 carbon atoms.

G ⁵⁵ , G ⁵⁶ and G ⁵⁷ are each a hydrogen atom,
A halogen atom, a carbonyl group, a sulfamyl group, a sulfonamide group, an alkyloxy group having 1 to 40 carbon atoms or the same meaning as G ^52, and G ⁵⁵ and G ⁵⁶ together form a 5- to 7-membered ring. You may.

Further, G ⁵⁶ is _{^{- (G 51) a -NG 52}} (G 53
It may be a -G ^54). However, at least one of G ⁵² , G ⁵⁵ , G ⁵⁶ and G ⁵⁷ represents a ballast group. Specific examples of this kind of Y are described in JP-A-51-63618.

Further suitable Y for compounds of this type are the formulas (YVIII) and (YIX). Formula (YVIII)

[0043]

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Formula (YIX)

[0045]

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Nu ⁶¹ and Nu ^{62, which} may be the same or different, represent a nucleophilic group or its precursor,
Z ⁶¹ represents a divalent atomic group which is electronegative with respect to the carbon atom to which R ⁶⁴ and R ⁶⁵ are substituted, and R ⁶¹ , R ⁶² and R
⁶³ is hydrogen, halogen, an alkyl group, an alkoxy group or an acylamino group, or R ⁶¹ and R ⁶²
Forms a condensed ring with the rest of the molecule when adjacent on the ring, or R ⁶² and R ⁶³ form a condensed ring with the rest of the molecule, and each of R ⁶⁴ and R ⁶⁵ is the same or different And represents a hydrogen, a hydrocarbon group or a substituted hydrocarbon group, and a ballast group (Bal) having a sufficient size in at least one of the substituents R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ or R ^65.
l) is present to render the compound immobile. Specific examples of this kind of Y are described in JP-A-53-69033 and JP-A-54-69033.
No. 130927.

Further suitable Y for this type of compound is a group of formula (YX). Formula (YX)

[0048]

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In the formula, Ball and β 'are the same as those in formula (YII), and G ⁷¹ represents an alkyl group (including a substituted alkyl group). Specific examples of this kind of Y are described in JP-A-49-111628 and JP-A-52-4819.

Another type of compound of formula (I) is a non-diffusible imaging compound which does not itself release a dye but which upon reaction with a reducing agent releases a dye. In this case, it is preferable to use a compound that mediates a redox reaction (a so-called electron donor) in combination.

The effective Y for this type of compound is, for example, a group represented by the formula (YXI). Formula (YXI)

[0052]

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In the formula, Ball and β 'are the same as those of the formula (YII), and G ⁷¹ is an alkyl group (including a substituted alkyl group). Specific examples of this kind of Y are described in JP-A Nos. 53-35533 and 53-11082.

Further suitable Y for this type of compound is a group represented by (YXII). Formula (YXII)

[0055]

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(Wherein α ′ _ox and α ″ _ox are groups which give α ′ or α ″ respectively by reduction, and α ′,
α ″, G ⁵¹ , G ⁵² , G ⁵³ , G ⁵⁴ , G ⁵⁵ , G ⁵⁶ , G ⁵⁷ and a are the same as those in the case of YVII.

Specific examples of Y are described in JP-A-53-11.
0827, US4356249, US435852
No. 5 describes it.

Further suitable Y for compounds of this type are formulas (YXIIIA) and (YXIIIB). Formula (YXIIIA)

[0059]

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Formula (YXIIIB)

[0061]

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(However, (Nu _ox ) ¹ and (Nu _ox ) ²
May be the same or different and each is oxidized to represent a nucleophilic group, and the other symbols are as defined in the formulas (YVIII) and (YIX). Specific examples of this kind of Y are described in JP-A-54-130927 and JP-A-56-164342.

Formula (YXI), Formula (YXII), Formula (Y
XIIIA) and the patents cited in formula (YXIIIB) describe electron donors used in combination.

Further, as more preferable ones, European Patent No. 220,746A2, JP-A-87-6199, US Pat. No. 4,783,396, JP-A-62-21527 are preferable.
No. 0, etc., a compound having an N—X ₂ bond (X ₂ represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, US Pat. No. 4,840,887, and JP-A No. 64
No. 266842 describes SO ₂ -X ₂ (X
₂ has the same meaning as described above) and a compound having an electron-withdrawing group, and PO-X in one molecule described in JP-A-63-271344.
A compound having ₃ bonds (X ₃ has the same meaning as above) and an electron-withdrawing group, and a C—X ₄ bond (X ₄ has the same meaning as X ₂ or − in one molecule described in JP-A-63-271341. SO ₂ −
And a compound having an electron-withdrawing group.

Particularly preferred compounds of the formula (I) include those of the formula (YXIV). Specific examples of Y are described in U.S. Pat. No. 4,783,396 and JP-A-62-215,270, but the compound represented by formula (YXV) is particularly preferably used in the invention. Formula (YXIV)

[0066]

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In the formula, EAG represents a group that receives an electron from a reducing substance. N and O represent a nitrogen atom and an oxygen atom, respectively. R ⁸¹ and R ⁸² represent a substituent other than a hydrogen atom. When R ⁸¹ or R ⁸² is bonded _to- (Time) _t-, it represents a mere bond or a substituent other than a hydrogen atom. R ⁸¹ and R ⁸² may combine with each other to form a ring.

Time represents a group which releases Dye via a subsequent reaction by cleavage of the nitrogen-oxygen-bond in the formula, and t represents 0 or 1. In the formula,
A solid line indicates a bond, and a dashed line indicates that at least one is connected. Formula (YXV)

[0069]

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In the formula, R ⁸³ and R ⁸⁴ each represent a mere bond;
It is a hydrogen atom or a group capable of substituting it and may be bonded to each other to form a saturated or unsaturated carbocycle or heterocycle. The general formulas (YXIV) and (YXV) represent R ^{81 to} R ⁸⁴
Alternatively, it is preferable to have a ballast group at the position of EAG.

The ballast group in the general formulas (YI) to (YXV) is an organic ballast group capable of rendering the dye image-forming compound of the general formula (I) non-diffusible, and it has 8 to 32 carbon atoms. Is preferably a group containing a hydrophobic group. Such an organic ballast group is directly or directly connected to a dye image forming compound (for example, an imino bond, an ether bond, a thioether bond, a carbonamide bond, a sulfonamide bond, a ureido bond, an ester bond, a carbamoyl bond, a sulfamoyl bond, etc.) Combinations).

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

[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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Next, a method for synthesizing the image-forming compound of the present invention will be described. A structural feature of the image forming compound of the present invention is that a pigment bone nucleus is completed by coupling of a phenol and a diazonium salt of an aminothiadiazole.

The specific synthesis examples are shown below.

Synthesis Example, Synthesis of Image Forming Compound "Chemical Formula 19"

[0092] Croatica Chemica A
The following 2-amino-5-sulfonic acid-1,3,4 according to the method described in cta magazine, 1971, vol. 43, pp. 73-78.
-A thiadiazole "Chemical 35" was synthesized.

[0093]

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25 g of 2,6-dinitrophenol was added to 1
Using 0.5 g of 0% palladium-carbon, hydrogenation was performed in ethyl acetate at normal temperature and 50 atm. After 2 hours, the catalyst was filtered off, and 28.2 ml of acetic anhydride was added dropwise to the obtained reaction solution at room temperature, followed by stirring for 1 hour. After the reaction was completed, the solvent was distilled off under reduced pressure by half, and 100 ml of n-hexane was added to precipitate crystals. This was collected by filtration to obtain 22.8 (g) of 2,6-diacylaminophenol “formula 36”.

[0095]

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Compound “Chemical 35” 15 (g) was diazotized with nitrosylsulfuric acid according to a conventional method. Compound 3
6 "A mixture of 17.2 (g), 200 ml of methyl cellosolve and 200 ml of a saturated aqueous solution of sodium acetate was cooled to 5 ° C. in an ice-water bath, and the dizo solution was added dropwise. Stir for 2 hours and then at room temperature for 1 hour. Next, the reaction mixture was poured into a saturated saline solution heated to 40 ° C., and cooled to room temperature.
(G) obtained.

[0097]

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A mixture (30 g) of the compound “Formula 37” and sodium chloride, 150 ml of acetonitrile, N, N-
45 ml of phosphorus oxychloride was added to a suspension of 10 ml of dimethylacetamide, and the mixture was stirred at 70 ° C. for 3 hours. The reaction solution was cooled to 5 ° C. in an ice water bath, poured into 750 ml of ice water and stirred. The crystals were collected by filtration, washed with 50 ml of acetonitrile, and then dried to obtain 20 g of compound "Chemical Formula 38".

[0099]

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The following compound “Chemical Formula 39” was synthesized according to the method described in JP-A-59-60434.

[0101]

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The compound “Chemical 39” (30.3 g) was dried under nitrogen stream and dried with N, N-dimethylformamide 100.
The mixture was dissolved in ml, and 15.4 (g) of 2,6-lutidine was added. Next, under ice cooling, 20 (g) of the compound "Chemical 38" was added little by little. After stirring at the same temperature for 1 hour, the temperature was gradually raised to room temperature and stirring was continued for 2 hours. Thereafter, the reaction solution was poured into cold diluted hydrochloric acid and extracted with ethyl acetate. The extract was washed with water and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure.
The residue was purified by silica gel chromatography (eluent: chloroform / methanol = 9/1) to obtain 23.2 (g) of orange crystals of the image forming compound “Chemical Formula 19”.

The image-forming compound in the present invention can be used alone, but a reducing substance capable of reducing the exposed silver halide and a reducing substance capable of cross-oxidizing with the compound of the present invention can be used in combination. Various compounds can be used, but hydroquinones and 3-
Pyrazolidones, aminophenols, catechols,
Examples include p-phenylenediamines, aminonaphthols, reductones and the like.

Further, it is also possible to use a precursor which is hydrolyzed under alkaline conditions to form the above-mentioned reducing compound.

For example, it is disclosed in JP-A-55-52055, JP-B-54-39727, JP-A-57-135949, and the like.

Specific examples of more preferable reducing compounds include the following compounds.

3-Pyrazolidones, for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 1 -M-tolyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone,
1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4,4-bis- (hydroxymethyl) -3-pyrazolidone, 1,4-di-methyl-3-pyrazolidone,
4-methyl-3-pyrazolidone, 4,4-dimethyl-3
-Pyrazolidone, 1- (3-chlorophenyl) -4-methyl-3-pyrazolidone, 1- (4-chlorophenyl)
-4-methyl-3-pyrazolidone, 1- (4-tolyl)
-4-methyl-3-pyrazolidone, 1- (2-tolyl)
-4-methyl-3-pyrazolidone, 1- (4-tolyl)
-3-Pyrazolidone, 1- (3-Tolyl) -3-pyrazolidone, 1- (3-Tolyl) -4,4-dimethyl-3-
Pyrazolidone, 1- (2-trifluoroethyl) -4,
4-dimethyl-3-pyrazolidone, 5-methyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone,
1-phenyl-4-methyl-4-stearoyloxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-
4-lauroyloxymethyl-3-pyrazolidone, 1-
Phenyl-4,4-bis- (lauroyloxymethyl)
-3-pyrazolidone, 1-phenyl-2-acetyl-3
Pyrazolidone, 1-phenyl-3-acetoxypyrazolidone; hydroquinones such as hydroquinone, toluhydroquinone, 2,6-dimethylhydroquinone,
t-butyl hydroquinone, 2,5-di-t-butyl-
Hydroquinone, t-octylhydroquinone, 2,5
-Di-t-octylhydroquinone, pentadecylhydroquinone, sodium 5-pentadecylhydroquinone-2-sulfonate, p-benzoyloxyphenol, 2-methyl-4-benzoyloxyphenol, 2
-T-butyl-4- (4-chlorobenzoyloxy) phenol and the like; aminophenols such as 4-amino-2,6-dichlorophenol, 4-amino-2,6-
Dibromophenol, 4-amino-2-methylphenol sulfate, 4-amino-3-methylphenol sulfate, 4-amino-2,6-dichlorophenol hydrochloride, p-aminophenol, p-methylaminophenol, p-dimethyl Aminophenol,
p-Dimethylaminophenol, p-dibutylaminophenol, p-piperidinoaminophenol, 4-dimethylamino-2,6-dimethoxyphenol and the like; phenylenediamines such as N-methyl-p-phenylenediamine, N, N- Dimethyl-p-phenylenediamine,
N, N-diethyl-p-phenylenediamine, N, N,
N ', N'-tetramethyl-p-phenylenediamine,
4-diethylamino-2,6-dimethoxyaniline and the like; reductones such as piperidinohexose reductone and pyridinohexose reductone.

Further, Research Disclosure Magazine 15
No. 1 No. 15108 and U.S. Pat. No. 4,021,240 include 2,6-dichloro-4-substituted sulfonamide phenol, 2,6-dibromo-4-substituted sulfonamide phenol, JP-A-59-116740. The signal has p- (N,
N-dialkylaminophenol) sulfamine and the like are described and useful. In addition to the above phenol-based reducing agents, naphthol-based reducing agents such as 4-aminonaphthol derivatives and 4-substituted sulfonamidonaphthol derivatives are also useful.

These reducing substances or their precursors can be used alone or in combination of two or more.

The silver halide which can be used in the present invention may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide. . The halogen composition inside the grain may be uniform, or may have a multiple structure in which the composition is different between the surface and the inside (JP-A-57-1542).
No. 32, No. 58-108533, No. 59-48755
No. 59-52237, U.S. Pat.
48 and EP 100,984). The particle thickness is 0.5 μm or less, and the diameter is at least 0.6 μm.
m and tabular grains having an average aspect ratio of 5 or more (US Pat. Nos. 4,414,310 and 4,435,499 and West German Open Patent (OLS) No. 3,241,646A1).
Etc.) or monodisperse emulsions having a nearly uniform particle size distribution (JP-A-57-178235, JP-A-58-100846).
No. 58-14829, International Publication 83/02338
A1, European Patent Nos. 64,412A3 and 83,832.
377A1) can also be used in the present invention. Two or more silver halides having different crystal habits, halogen compositions, grain sizes, grain size distributions and the like may be used in combination. Two or more types of monodispersed emulsions having different grain sizes may be mixed to adjust the gradation.

The grain size of the silver halide used in the present invention is preferably from 0.001 μm to 10 μm, more preferably from 0.001 μm to 5 μm. These silver halide emulsions may be prepared by any of an acidic method, a neutral method, and an ammonia method. The reaction between the soluble silver salt and the soluble halide may be a one-sided mixing method, a simultaneous mixing method, May be used. A back-mixing method in which grains are formed under excess silver ions,
Alternatively, a controlled double jet method in which pAg is kept constant can also be employed. Further, in order to accelerate grain growth, the addition concentration, amount or rate of silver salt and halogen salt to be added may be increased (Japanese Patent Application Laid-Open No. 55-14232).
9, 55-158124, U.S. Pat. No. 3,65.
No. 0,757).

Epitaxial silver halide grains can also be used (JP-A-56-16124,
U.S. Pat. No. 4,094,684).

In the step of forming silver halide grains used in the present invention, ammonia is used as a silver halide solvent, an organic thioether derivative described in JP-B-47-11386, or an organic thioether derivative described in JP-A-53-144319. A sulfur compound or the like can be used.

In the course of particle formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt and the like may coexist.

Further, for the purpose of improving high-illuminance failure and low-illuminance failure, water-soluble iridium salts such as iridium chloride (III, IV) and ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used. .

The soluble salts may be removed from the silver halide emulsion after the formation of the precipitate or after the physical ripening. For this reason, the silver halide emulsion can be subjected to the Nudel washing method or the sedimentation method.

The silver halide emulsion may be used as it is after ripening, but it is usually chemically sensitized before use. A known sulfur sensitization method, reduction sensitization method, noble metal sensitization method, or the like can be used alone or in combination for an emulsion for a normal photosensitive material. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-126526 and JP-A-58-21).
No. 5644).

The silver halide emulsion used in the present invention may be a surface latent image type in which a latent image is mainly formed on the surface of a grain or an internal latent image type in which a latent image is formed inside a grain.
Direct reversal emulsions combining an internal latent image type emulsion with a nucleating agent and / or light fogging can also be used. Internal latent image type emulsions suitable for this purpose are described in U.S. Pat.
No. 50, No. 3,761,276, JP-B-58-35
No. 34 and JP-A-57-136641. Preferred nucleating agents for combination in the present invention are U.S. Patent Nos. 3,227,552 and 4,24.
No. 5,037, No. 4,255,511, No. 4,2
Nos. 66,031, 4,276,364 and OL
S No. 2,635,316 and the like. Japanese Patent Publication No. 45-12710 and Japanese Unexamined Patent Publication No. Sho 61
A known method can be used according to, for example, No. 159641.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Styryl dyes and hemioxonol dyes are included. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like;
A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic nucleus hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadol nucleus, and a naphtho An oxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, and a thiazolidine-2,4-
A 5- to 6-membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. For example, aminostyryl compounds substituted with a nitrogen-containing heterocyclic group (for example, US Pat. No. 2,933,390,
Those described in U.S. Pat. No. 3,635,721), aromatic organic acid formaldehyde condensates (for example, US Pat.
No. 743,510), a cadmium salt, an azaindene compound, and the like. U.S. Patent No. 3,
The combinations described in 615, 613, 3,615,641, 3,617,295, and 3,635,721 are particularly useful.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. Can be.

In the present invention, gelatin may be either lime-treated or acid-treated. For details on the gelatin manufacturing method, see Arthur Weiss,
It is described in The Macromolecular Chemistry of Gelatin, (Academic Press, 1964).

The photographic emulsion used in the present invention may contain a surfactant alone or as a mixture.

These are used as coating aids, but are sometimes applied for other purposes such as emulsification / dispersion, improvement of sensitized photographic characteristics, antistatic and adhesion prevention. These surfactants include natural surfactants such as saponins, nonionic surfactants such as alkylene oxides, glycerin and glycidols, higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, phosphonium or Cationic surfactants such as sulfonium, anionic surfactants containing carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester group, acidic group such as phosphoric acid ester group, amino acids, aminosulfonic acids, sulfuric acid or phosphoric acid esters of aminoalcohol And the like.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes; Dens; tetraazaindenes (especially 4-hydroxy-substituted (1,
3,3a, 7-tetraazaindenes), pentaazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfones, benzenesulfinic acid, benzenesulfonamide and the like. Can be added.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or promoting development,
For example, it may contain thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer in a photographic emulsion layer or other hydrophilic colloid layers for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination;
Alternatively, a polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, etc. may be used. it can. Various other additives may be used in the silver halide photographic light-sensitive material of the present invention. For example,
Hardeners, brighteners, dyes, desensitizers, coating aids, antistatic agents, plasticizers, slip agents, matting agents, development accelerators, mordants, ultraviolet absorbers, anti-fading agents, anti-foggants, etc. .

Regarding these additives, specifically, Research Disclosure 1
No. 76, pages 22 to 31 (RD-17643) (Dec, 19)
78) etc. can be used.

The compound of the general formula (I) of the present invention capable of releasing a diffusible dye is, for example, JP-A-58-149046.
Nos. 59-154445 and 59-16505
No. 59-180548 and No. 59-218443
No. 60-133449, U.S. Pat.
No. 137, No. 4,474,867, No. 4,48
No. 3,914, No. 4,455,363, No. 4,5
No. 00,626, Japanese Patent Application No. 60-79709, and the like. A movable dye is formed by thermal development, and the dye is preferably transferred to a dye fixing layer. Is done. In the following, the photothermographic material may be referred to as a photosensitive element.

In the case of application to a photothermographic element, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, an organic silver salt is particularly preferably used.

Organic compounds that can be used to form the above organic silver salt oxidizing agent include those described in US Pat. No. 4,500,6.
Benzotriazoles, fatty acids and other compounds described in No. 26, columns 52-53 and the like. Japanese Patent Application Laid-Open No. 60-1
Carboxylic acids and silver salts having an alkynyl group such as silver phenylpropiolate described in 13235;
The acetylene silver described in No. 249044 is also useful. Two or more organic silver salts may be used in combination.

The above-mentioned organic silver salts can be used as photosensitive silver halide 1
0.01 to 10 mol, preferably 0.1 to 10 mol, per mol.
01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is suitably from 50 mg to 10 g / m ² in terms of silver.

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

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

In the case of employing a system in which a small amount of water is supplied to carry out thermal development, the use of the above superabsorbent polymer makes it possible to rapidly absorb water. Further, when the superabsorbent polymer is used for the dye fixing layer and its protective layer, it is possible to prevent the dye from being re-transferred from the dye fixing element to another after transfer.

In the present invention, the coating amount of the binder is 1
It is preferably 20 g or less per m ² , particularly preferably 10 g or less, and more preferably 7 g or less.

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

As the reducing agent used in the present invention, 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 may be used in combination). In addition, a reducing agent precursor which does not itself have a reducing property but finds 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:
U.S. Pat. No. 4,500,626, columns 49 to 50; U.S. Pat. No. 4,483,914, columns 30 to 31;
30,617, 4,590,152, JP-A-6
0-140335, pages (17) to (18), ibid.
No.-40245, No.56-138736, No.59-1
No. 78458, No. 59-53831, No. 59-182
No. 449, No. 59-182450, No. 60-1195
No. 55, 60-128436 to 60-1284
No. 39, No. 60-198540, No. 60-181
No. 742, No. 61-259253, No. 62-2440
No. 44, No. 62-131253 to No. 62-1312
No. 56, No. 78 of EP 220,746 A2.
On page 96 and the like.

Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.

When a diffusion-resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent may be used, if necessary, in order 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.

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). A particularly useful electron transfer agent is 1-phenyl-3-
Pyrazolidones or aminophenols.

As the diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent, any one which does not substantially move in the layer of the photosensitive element among the above reducing agents may be used.
Preferred are hydroquinones, sulfonamidophenols, sulfonamidonaphthols, and JP-A-53-11.
Compounds described as electron donors in No. 0827 and dye-donating compounds having a diffusion-resistant and reducing property described later are exemplified.

In the present invention, the reducing agent is added in an amount of 0.01 to 20 mol, and particularly preferably 0.1 to 1 mol of silver.
10 to 10 mol.

In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive element. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52.

Dye-fixing elements are used in conjunction with the light-sensitive elements in systems that form images by diffusion transfer of dyes. The dye-fixing element may be coated separately on a support separate from the photosensitive element, or may be coated on the same support as the photosensitive element. As for the relationship between the photosensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of U.S. Pat. No. 4,500,626 can be applied to the present invention.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the field of photography can be used, and specific examples thereof are described in US Pat. No. 4,500,626.
No. 58-59 and JP-A-61-88256 (3)
Mordants described on pages 2) to (41), JP-A-62-244;
Nos. 043 and 62-244036. No. 4,463,073.
A dye-receiving polymer compound as described in No. 9 may be used.

If necessary, the dye fixing element can be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer. It is particularly useful to provide a protective layer.

In the constituent layers of the photosensitive element and the dye-fixing element, a plasticizer, a sliding agent, or a high-boiling organic solvent can be used as an agent for improving the releasability of the photosensitive element and the dye-fixing element. Specifically, Japanese Patent Application Laid-Open No. 62-253159 (2)
5), pages 62-245253 and the like.

Further, 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 for the above purpose. As an example thereof, various modified silicone oils described in “Modified Silicone Oil” Technical Data P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name: X-22-3710) are effective.

The silicone oils described in JP-A Nos. 62-215953 and 62-23687 are also effective.

An anti-fading agent may be used in the light-sensitive element and the dye-fixing element. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg hindered phenols), hydroquinone derivatives, hindered amine derivatives and spiroindane compounds. Further, the compounds described in JP-A-61-159644 are also effective.

As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794, etc.),
4-thiazolidone compounds (US Pat. No. 3,352,6)
No. 81), benzophenone-based compounds (JP-A-46-
2784, etc.), and JP-A-54-48535,
There are compounds described in JP-A-62-136641 and JP-A-61-88256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective.

As the metal complex, US Pat. No. 4,24
No. 1,155, No. 4,245,018 Nos. 3-36
No. 4,254,195, columns 3-8, JP-A-62
-174741 and 61-88256 (27)-
(29), Japanese Patent Application No. 62-234103, 62-3
No. 1096, and Japanese Patent Application No. 62-230596.

Examples of useful discoloration inhibitors are described in JP-A-62-21.
No. 5272, pages (125) to (137).

The anti-fading agent for preventing the fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or may be supplied to the dye-fixing element from the outside such as a light-sensitive element. You may.

The above-mentioned antioxidant, ultraviolet absorber and metal complex may be used in combination.

An optical brightener may be used in the light-sensitive element and the dye-fixing element. In particular, it is preferable to incorporate a fluorescent brightening agent in the dye fixing element or to supply it from outside such as a photosensitive element. For example, K. Veenkataraman, edited by The Chemi
stry of Synthetic Dyes, Vol. V, Chapter 8, JP-A-61-
No. 143752 and the like. 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.

A fluorescent whitening agent can be used in combination with a fading inhibitor.

As the hardener used in the constituent layers of the light-sensitive element and the dye-fixing element, US Pat. No. 4,678,739, No. 4 can be used.
Column 1, JP-A-59-116655, JP-A-62-2452
No. 61, No. 61-18942 and the like. More specifically, aldehyde-based hardeners (such as formaldehyde), aziridine-based hardeners, and epoxy-based hardeners (such as “Chemical 40”)

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A vinyl sulfone hardener (such as N, N'-ethylene-bis (vinylsulfonylacetamide) ethane), an N-methylol hardener (such as dimethylol urea), or a polymer hardener (such as 62-23415
No. 7, etc.).

In the constituent layers of the light-sensitive element and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, and promoting development. Specific examples of the surfactant are described in JP-A-62-173463.
And No. 62-183457.

The constituent layers of the light-sensitive element and the dye-fixing element may contain an organic fluoro compound for the purpose of improving sliding property, preventing static charge, improving releasability and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8 to 17,
JP-A-61-20944, JP-A-62-135826, etc., such as fluorine-based surfactants, or oil-like fluorine-based compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin, etc. And hydrophobic fluorine compounds.

A matting agent can be used for the photosensitive element and the dye fixing element. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
In addition to the compounds described on page 1-88256 (page 29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in Japanese Patent Application No. 62-110064.
Nos. 62-110065.

In addition, the constituent layers of the photosensitive element and the dye-fixing element may contain a heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye-fixing element. Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the generation of a dye from a dye-providing substance or the decomposition or release of a diffusible dye, and the use of a photosensitive material layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is disclosed in U.S. Pat.
493 and JP-A-62-65038.

In a system in which thermal development and transfer of a dye are carried out simultaneously in the presence of a small amount of water, it is preferable to include a base and / or a base precursor in the dye-fixing element from the viewpoint of improving the storage stability of the photosensitive element.

In addition to the above, European Patent Publication 210,660
And combinations of compounds which are capable of forming a complex with metal ions constituting these hardly soluble metal compounds (referred to as complex forming compounds) described in
Compounds that generate a base by electrolysis described in 232451 can also be used as the base precursor.
In particular, the former method is effective. The sparingly soluble metal compound and the complex forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element.

The light-sensitive element and / or the dye-fixing element of the present invention have the following properties:
Various development stoppers can be used for the purpose of always obtaining a constant image.

The term "development terminator" as used herein means that after appropriate development,
It is a compound that quickly neutralizes a base or reacts with a base to reduce the base concentration in the film and stop development, or a compound that interacts with silver and a silver salt to suppress development. In particular,
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 further details, see JP-A-62-25315.
No. 9, pages (31) to (32).

As the support for the light-sensitive element and the dye-fixing element of the present invention, those which can withstand the processing temperature are used. Generally, paper and synthetic polymers (films) are used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide, and polypropylene are used. Film synthetic paper, synthetic paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), metal, cloth, glass and the like are used.

These can be used alone,
It can also be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

In addition, JP-A-62-253159 (2)
The supports described on pages 9) to (31) can be used.

On the surface of these supports, a hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide,
Carbon black or another antistatic agent may be applied.

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

As a light source for recording an image on a photosensitive element,
As described above, light sources described in U.S. Pat. No. 4,500,626, column 56, such as natural light, tungsten lamps, light emitting diodes, laser light sources, and CRT light sources, can be used.

Further, the image information is a video camera,
Image signals obtained from electronic still cameras, television signals represented by the Nippon Television Signal Standards (NTSC),
An image signal obtained by dividing an original image into a large number of pixels such as a scanner, and an image signal created using a computer represented by CG and CAD can be used.

As the method, the method described in JP-A-61-147244 can be applied.

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According to the present invention, since it contains the image-forming compound represented by the general formula (I), it has a narrow absorption band in an appropriate magenta region by a simple method, It is possible to obtain a color light-sensitive material having a small absorption and giving an image with excellent color reproducibility.

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EXAMPLES Hereinafter, specific examples of the present invention will be described, and the effects of the present invention will be described in more detail.

Example 1 A method for preparing an emulsion for the first layer will be described.

A well stirred gelatin aqueous solution (water 10
An aqueous solution (600 ml and a silver nitrate aqueous solution (0.59 mol of silver nitrate dissolved in 600 ml of water) containing 20 g of gelatin and 3 g of sodium chloride in 00 ml and kept at 75 ° C. and containing sodium chloride and potassium bromide) thing)
And the following dye solution “Chemical 41” were added simultaneously at an equal flow rate over 40 minutes. Thus, a monodispersed cubic silver chlorobromide emulsion (80 mol% of bromine) having a dye having an average particle size of 0.35 μm adsorbed thereon was prepared.

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After washing with water and desalting, 5 mg of sodium thiosulfate and 4 mg
20 mg of -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added and chemical sensitization was performed at 60 ° C. The yield of the emulsion was 600 g.

The method for preparing the organic silver salt will be described. Organic silver salt (1)

A method for preparing a benzotriazole silver emulsion will be described.

28 g of gelatin and benzotriazole 1
3.2 g were dissolved in 300 ml of water. This solution was kept at 40 ° C. and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over 2 minutes.

The pH of this benzotriazole silver emulsion was adjusted, allowed to settle, and excess salt removed. Thereafter, the pH was adjusted to 6.30 to obtain a silver benzotriazole emulsion with a yield of 400 g.

Organic silver salt (2)

20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid were dissolved in 1000 ml of a 0.1% aqueous sodium hydroxide solution and 200 ml of ethanol.

The solution was kept at 40 ° C. and stirred. To this solution, a solution prepared by dissolving 4.5 g of silver nitrate in 200 ml of water was added over 5 minutes. The pH of the dispersion was adjusted and settled to remove excess salt. Thereafter, the pH was adjusted to 6.3 and the yield was 30.
0 g of a dispersion of the organic silver salt (2) was obtained.

Next, a method of preparing a gelatin dispersion of an image forming compound will be described.

The image forming compound "Formula 19" of the present invention was converted to 5
g, 0.2 g of the antifoggant shown in Chemical formula 42 and 2.5 g of triisononyl phosphate, and ethyl acetate 3
0 ml was added, and the mixture was dissolved by heating at about 60 ° C. to obtain a uniform solution. This solution and sodium dodecylbenzenesulfonate 0.1.
5 g and 100 g of a 10% solution of lime-processed gelatin were mixed by stirring, and then homogenized for 10 minutes at 1000 g.
Dispersed at 0 rpm. This dispersion is referred to as a dispersion of the magenta image forming compound.

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From these, a photosensitive element 101 having a two-layer structure as shown in "Table 1" was prepared.

[0202]

[Table 1]

[0203]

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[0204]

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[0205]

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[0206]

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[0207]

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[0208]

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Next, for the light-sensitive element 101, the magenta image-forming compound was changed from the compound of the present invention "Chemical formula 19" to "Chemical formula 4".
9 ”and“ Chemical Formula 50 ”, except that the compounds shown in“ Chemical Formula 9 ”and“ Chemical Formula 50 ”are used, and the two-layered photosensitive elements 102 and 103 have the same composition
made.

[0210]

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[0211]

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[0212] Next, how to make the dye fixing element will be described. 63 g of gelatin, 130 g of mordant shown in Chemical Formula 51
And 80 g of guanidine picolinate were dissolved in 1300 ml of water, and 45 μm was applied on a paper support laminated with polyethylene.
m and then dried.

[0213]

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Further on this, 35 g of gelatin and 1.05 of 1,2-bis (vinylsulfonylacetamidoethane) were added.
A solution prepared by dissolving g in 800 ml of water was applied and dried so as to give a wet film thickness of 17 μm to prepare Dye fixing element D-1.

The light-sensitive elements 101 to 101 thus prepared
Exposure was performed at 2,000 lux for 1 second through a G filter using a tungsten bulb for 103.

4 ml / ml of the emulsion surface of the exposed photosensitive element
m ² of water through a wire bar and then dye fixing element D
-1 and the film surface were in contact with each other.

In order that the temperature of the water-absorbed film becomes 95 ° C.,
Heating was performed for 30 seconds using a temperature-controlled heat roller. Next, when peeled off from the dye fixing element, a clear image of magenta was obtained on the dye fixing element corresponding to the G filter. The spectral absorption spectrum of the magenta color image obtained from the photosensitive element 101 was measured and compared with the spectra of the photosensitive elements 102 and 103 in "Table 2".

[0218]

[Table 2]

It can be seen that the compounds of the present invention have excellent spectral characteristics characterized by a narrow absorption band and small side absorption in the blue region of the visible spectrum.

It is also found that λmax is in an appropriate green range.

Example 2 Photosensitive elements 104 to 106 were prepared in the same manner as in Example 1 except that compounds [Chemical Formula 22], [Chemical Formula 30] and [Chemical Formula 31] were used instead of the chemical formula [Chemical Formula 19] of the present invention. Then, the same processing as in Example 1 was performed.

The results of measuring the spectral absorption spectra of the magenta color images obtained from the photosensitive elements 104 to 106 are shown in Table 3.

[0223]

[Table 3]

It can be seen that the compounds of the present invention give magenta images characterized by narrow absorption bands and small side absorptions in the blue region of the visible spectrum. It can also be seen that λmax can be adjusted to an appropriate green range.

Example 3 A photosensitive element having the structure shown in Table 4 was prepared and used as a photosensitive element 107.

Further, a dye-fixing element having the constitution shown in Table 5-A was prepared, and was referred to as a dye-fixing element D-2.

[0227]

[Table 4]

[0228]

[Table 5]

[0229]

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[0230]

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[0231]

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[0232]

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[0233]

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[0234]

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[0235]

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[0236]

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[0237]

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[0238]

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[0239]

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[0240]

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[0241]

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[0242]

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[0243]

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[0244]

[Table 6]

[0245]

[Table 7]

[0246]

[Table 8]

[0247]

[Table 9]

[0248]

[Table 10]

Water-soluble polymer (1) Sumikagel L5-H
(Manufactured by Sumitomo Chemical Co., Ltd.) Water-soluble polymer (2) Copper-carrageenan (manufactured by Taito Corporation) Water-soluble polymer (3) Dextran (molecular weight 70,000)

[0250]

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[0251]

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[0252]

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[0253]

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[0254]

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[0255]

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[0256]

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Fluorescent whitening agent (1) 2,5-bis (5-
t-benzoxazol (2)) thiophene High-boiling organic solvent (1) Empara 40 (manufactured by Ajinomoto Co., Inc.) Matting agent (1) Benzoguanamine resin (average particle size 15 μm)

[0258]

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[0259]

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Also, except that the magenta image forming compounds shown in “Formula 76” and “Formula 77” were used in place of the magenta image forming compound (2) of the present invention in the third layer of “Table 4”, Photosensitive elements 108 and 109 having the same composition were prepared.

[0261]

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[0262]

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The above photosensitive element and dye fixing element were processed using an image recording apparatus described in JP-A-2-84634. That is, an original image (a test chart in which yellow, magenta, cyan, and gray wedges having continuously changing density are recorded) is scanned and exposed to a photosensitive element through a slit, and the photosensitive element is kept in water at 40 ° C. After immersion for about 5 seconds, squeezed with a roller, and then immediately superimposed so that the dye-fixing element and the membrane surface are in contact,
It heated for 15 seconds using the heat roller adjusted so that the film surface which absorbed water might be set to 80 degreeC. Next, when the photosensitive element and the dye fixing element were peeled off, a clear color image corresponding to the original image was obtained on the dye fixing element. The results of measuring the spectral absorption of the obtained magenta color image are shown in Table 11.

[0264]

[Table 11]

It can be seen that the compounds of the invention give magenta images which are characterized by a narrow absorption band and a small side absorption in the blue region of the visible spectrum. In addition, λma
indicates that there is x.

Claims (1)

(57) [Claims] 1. A color light-sensitive material comprising a support and at least one image-forming compound represented by the following general formula (I). (Dye-X) q-Y (I) wherein Dye represents a magenta dye group or a dye precursor group represented by the following general formula (II), X represents a simple bond or a linking group, and Y represents an image. The development reaction corresponds to or inversely corresponds to the distribution of the photosensitive silver salt having a latent image thereon, whereby X-
Indicates a substrate having a property that a Y bond is cleaved. General formula (II) In the formula, R ₁ and R ₂ represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group,
Alkynyl group, aryl group, alkoxy group, aryloxy group, cyano group, acylamino group, sulfonylamino group, ureido group, alkylthio group, arylthio group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, urethane group , An amino group, a hydroxyl group, a carboxyl group, a sulfamoylamino group and a heterocyclic group, n represents an integer of 0 to 4, and when n is 2, 3 or 4, R ₂ is the same or different. You may. When n is 2, 3, or 4, two R
_{And 2} may combine with each other to form a saturated or unsaturated ring (however, excluding a naphthalene ring). R ³ represents a hydrogen atom, a monovalent cation or a hydrolyzable group.
q is 1 or 2, and when q is 2, Dye-X may be the same or different. Dye and X are R ₁ and R of the general formula (II)
₂ and R ₃ , and the above substituents may be substituted with other substituents.