JPH087425B2 - Color photosensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel infrared ray absorbing image-forming compound and a color light-sensitive material containing the same.

[Conventional technology]

Color diffusion transfer photography using a dye image-forming compound that provides a dye having a diffusivity different from that of the image-forming compound itself as a result of the development of silver halide under basic conditions is well known in the art. These systems are usually
A color image is formed by using dyes of three colors of yellow, magenta and cyan, and has almost no absorption in a wavelength region longer than the visible region, that is, in the infrared region. Generally, the absorption tail on the long wavelength side of a cyan dye extends to 700 nm or more, but no cyan dye having a large absorption in the infrared region is known at all. On the other hand, in recent years, an optical character reading device and a label bar code reading device have been developed, and the frequency of their use is increasing, and their importance is increasing. Many of these devices use a semiconductor laser or an emission die auto that emits light with a wavelength of 700 nm or more as a reading light source. In addition, a tungsten lamp is used as the light source, and the light receiving element has a light receiving sensitivity peak around 900 nm and
Those with a sensitivity range of 1200 nm are widely used. However, since images using the above-mentioned dyes hardly absorb light in the near-infrared region of 700 nm or more, it is impossible or extremely difficult to read image information with these reading devices. Therefore, development of a diffusion transfer type color image forming compound having a light absorption wavelength of 700 nm, preferably 750 nm or more has been strongly desired.

[Object of the Invention]

An object of the present invention is to provide a diffusion transfer type color image forming compound which has strong light absorption in the near infrared region (700 nm or more) and is excellent in photographic properties such as transferability and fastness.

Another object of the present invention is to provide a color light-sensitive material capable of reading image information by using an image reading device equipped with a light source such as a semiconductor laser that is easily available.

[Means for solving problems]

The above object of the present invention has been achieved by incorporating an infrared-absorbing image-forming compound represented by the following general formula (I) into a silver halide color photographic material.

(Dye-X) _q -Y (I) [In the formula, Dye represents an infrared light absorbing dye group represented by the following formula (II), X represents a simple bond or a linking group, and Y represents an image-like structure. Represents a group having the property of causing a difference in the diffusibility of the dye component before and after the reaction with the photosensitive silver salt having a latent image or corresponding to the photosensitive silver salt having a latent image.

In the formula, R ¹ and R ² may be the same or different, and represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, a sulfo group, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, and a heterocyclic group. Group, alkoxy group, aryloxy group, amino group, acylamino group, sulfonylamino group, acyl group, sulfonyl group, carbamoyl group,
It represents a substituent selected from a sulfamoyl group, a ureido group, a urethane group, an alkylthio group, an arylthio group, a nitro group and an alkoxycarbonyl group. Ar represents an aryl group or a heterocyclic group. Further, these substituents may be further substituted with other substituents. m and n represent an integer of 0 to 4, and when they are 2 to 4, they may be the same or different. Dye and X may be bonded from any position of the formula (II). q is 1 or 2, and when q is 2,
Dye-X may be the same or different. Hereinafter, the present invention will be described in more 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.), aryl group (eg phenyl group, p-tolyl group, p- Methoxyphenyl group, o
-Methoxyphenyl group, etc.), alkoxy group (C1-C1)
8 alkoxy groups such as methoxy group, ethoxy group, isopropoxy group, 2-methoxyethoxy group, 2-hydroxyethoxy group, etc., aryloxy groups (eg phenoxy group, p-methoxyphenoxy group, o-carboxyphenoxy group, etc.) ), Cyano group, acylamino group (for example, acetylamino group, propionylamino group, o-carboxybenzoylamino group, etc.), sulfonylamino group (for example, methanesulfonylamino group, benzenesulfonylamino group, p-methoxybenzenesulfonylamino group, etc.) ,
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 (methoxy Carbonyl 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-carboxyanilino) Group, p-hydroxyanilino group, etc.), hydroxyl group, carboxyl group, heterocyclic group (α-pyridyl group, γ-pyridyl group, 2-furyl group, etc.). Of these, particularly preferred are an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, a chlorine atom,
The following acylamino groups, sulfonylamino groups having 7 or less carbon atoms, aryloxy groups having 8 or less carbon atoms, hydroxyl groups, carboxyl groups, carbamoyl groups having 7 or less carbon atoms,
And a sulfamoyl group having 7 or less carbon atoms.

Ar represents an aryl group or a heterocyclic group. Examples of the aryl group include 2-carboxyphenyl group, 3-carboxyphenyl group, 3-hydroxyphenyl group, 3-methanesulfonamidophenyl group, 4-carboxymethylphenyl group, 4-methoxy-3-sulfemoylphenyl group, and the like. Can be mentioned. Examples of the heterocyclic group include a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-pyrimidyl group, a 2-thiazolyl group, and a 4-methyl-2-thiazolyl group.

It is necessary that the dye part does not have a hydrophobic group that suppresses the diffusion of the dye, and it is desirable that the dye part has a water-soluble group that promotes the diffusion.

X may be bonded to any part of the Dye moiety basically, and the linking group represented by X is (R ₅ represents a hydrogen atom, an alkyl group or a substituted alkyl group), —SO ₂ —, —CO—, an alkylene group, a substituted alkylene group, a phenylene group, a substituted phenylene group, a naphthylene group, a substituted naphthylene group , -O-, -SO-
A group obtained by combining two or more of these divalent residues is a typical example, and among them, preferred is -NR ₅ -SO
₂ -, - NR ₅ -CO- or _{-R 6 - (L) k -} (R 7) l - is a group represented by each alkylene groups R ₆ and R ₇ is a substituted alkylene group, a phenylene group substituted phenylene Group, naphthylene group, substituted naphthylene group, L is -O-, -CO
-, - SO -, - SO 2 -, - SO 2 NH -, - NHSO 2 -, - CONH
-, -NHCO-, k represents 0 or 1,
l represents k = 1 and represents 1 or 0 when k = 0.

In addition, -NR ₅ -SO ₂ -or -NR ₅ -CO- and -R _6- (L) _k- (R ₇ ) _l
A combination of-is also preferred.

Bonding mode of Dye portion and Y portion is particularly preferably of the form of Dye-SO ₂ NH-Y.

 Next, Y will be described in detail.

Y is first selected so that the compound represented by formula (I) is oxidized and self-cleaved as a result of the development treatment to be a non-diffusible image-forming compound which gives a diffusible dye.

An example of a useful Y for this type of compound is an N-substituted sulfamoyl group. For example, Y can be a group represented by the following formula (Y1).

In the formula, β represents a group of non-metallic atoms necessary for forming a benzene ring, and a carbon ring or a hetero ring is fused to the benzene ring, for example, a naphthalene ring, a quinoline ring, 5, 6, 7,
An 8-tetrahydronaphthalene ring, a chroman ring, or the like may be formed.

α represents a group represented by —OG ¹¹ or —NHG ¹² . Here G ¹¹ represents a group resulting hydrogen or hydrolyzed to the hydroxyl group, G ¹² represents a hydrogen atom, a group that allows hydrolyze 1-22 alkyl group or NHG ¹² carbon atoms. Ball represents a ballast base. b is 0.1 or 2.

Specific examples of this type of Y are described in JP-A-48-33826 and JP-A-53-50736.

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

In the formula, Ball, α, and b are synonymous with the formula (YI),
β ′ represents an atomic group necessary for forming a carbocycle, for example, a benzene ring, and a carbocycle or a heterocycle is further condensed with the benzene ring to form a naphthalene ring, a quinoline ring, 5,6,7,8-
It may form a tetrahydronaphthalene ring, a chroman ring or the like.

Specific examples of this kind of Y are described in JP-A-51-113624,
56-12642, 56-16130, 56-16131, 57-4
043, 57-650 and U.S. Pat. No. 4,053,312.

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

In the formula, Ball, α and b have the same meanings as in the formula (YI),
β ″ represents an atomic group necessary for forming a hetero ring such as a pyrazole ring or a pyridine ring, and a carbon ring or a hetero ring may be bonded to this hetero ring. No. 51-104343.

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

Wherein, gamma preferably represents an or unsubstituted alkyl group having a hydrogen atom or each substituent, an aryl group or a heterocyclic group, or -CO-G ^21,; G ²¹ is -O
G ^22, -S-G ²² or (G ²² represents hydrogen, an alkyl group, a cycloalkyl group or an aryl group, G ²³ represents the same group as the above G ²² , or G ²³ is derived from an aliphatic or aromatic carboxylic acid or sulfonic acid. Represents an acyl group represented by
²⁴ represents hydrogen or unsubstituted or substituted alkyl); δ represents the residue necessary to complete the fused benzene ring.

Specific examples of this kind of Y are described in JP-A-51-104343, JP-A-53-46730, JP-A-54-130122 and JP-A-57-85055.

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

In the formula, Ball has the same meaning as in formula (YI), ε is an oxygen atom or = NG ³² group (G ³² represents a hydroxyl group or an amino group which may have a substituent), H ₂ N-G ³²
Examples of the compound include hydroxylamine, hydrazines, semicarbazides, thiosemicarbazides and the like, where β ″ is a 5-membered, 6-membered or 7-membered saturated or unsaturated non-aromatic hydrocarbon ring. Is a group of atoms necessary to form.

G ³¹ represents a hydrogen atom, a halogen atom such as fluorine, chlorine, or bromine. A specific example of this kind of Y is disclosed in JP-A-53-3819.
And No. 54-48534.

Other examples of Y in this type of compound include, for example, Japanese Patent Publication
48-32129, 48-39165, JP-A-49-64436, U.S. Pat. No. 3,443,934 and the like.

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

In the formula, α is OR ⁴¹ or NHR ⁴² , R ⁴¹ is hydrogen or a hydrolyzable component, and R ₄₂ is hydrogen or an alkyl group having 1 to 50 carbon atoms or a group capable of hydrolyzing NHR ^42. A ₄₁ represents an atomic group necessary for forming an aromatic ring, Ball is an organic immobilizing group existing on the aromatic ring, and Balls may be the same or different, and m is 1
Alternatively, it is an integer of 2.

X 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. Nu represents a nucleophilic group. n is an integer of 1 or 2. α is the above formula (YI)
Is synonymous with. A specific example of this kind of Y is disclosed in
It is described in No. 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 it reacts with an oxidized product of a developer, the dye is not substantially released. There are various non-diffusible imaging compounds.

Examples of Y effective for this type of compound include compounds represented by the formula (YVI
The ones given in I) are given.

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,
α ″ is a dialkylamino group or any of the groups defined in α ′, G ⁵¹ is an alkylene group having 1 to 3 carbon atoms, a represents 0 or 1, and G ⁵² represents 1 carbon atom. A substituted or unsubstituted alkyl group containing up to 40,
Or a substituted or unsubstituted aryl group containing 6 to 40 carbon atoms, G ⁵³ is -CO -, - an electrophilic group CS- like, G ⁵⁴ represents 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 or a substituted alkyl group containing 1 to 10 carbon atoms,
It may be substituted with 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 containing 1 to 40 carbon atoms, or
It is of G ⁵² as defined, G ⁵⁵ and G ⁵⁶ may together form a 5- to 7-membered ring.

Also, G ⁵⁶ It may be. However, at least one of G ⁵² , G ⁵⁵ , G ⁵⁶ and G ⁵⁷ represents a ballast group. Specific examples of Y of this kind are described in JP-A-51-63618.

Further suitable Y for compounds of this type are formulas (YVII) and (YIX).

Nu ⁶¹ and Nu ^{62, which} may be the same or different, each represents a nucleophilic group or a precursor thereof, and 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. Represents each of 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 form a} fused ring with the rest of the molecule when they are at adjacent positions 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 may be the same or different and may represent hydrogen, a hydrocarbon group or a substituted hydrocarbon group. Represents the substituents R ⁶¹ , R ⁶² ,
A ballast group (Ball) of sufficient size in at least one of R ⁶³ , R ⁶⁴ or R ⁶⁵ is present to render the compound immobile. A specific example of Y of this type is disclosed in JP-A-53-6903.
3 and 54-130927.

Y suitable for compounds of this type further includes groups of formula (YX).

Where Ball and β ′ are the same as those in equation (YII),
G ⁷¹ represents an alkyl group (including a substituted alkyl group).
Specific examples of Y of this kind 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.

Examples of the effective Y for a compound of this type include, for example, a compound represented by the formula (YX
And groups represented by I).

Where Ball and β ′ are the same as those in equation (YII),
G ⁷¹ is an alkyl group (including a substituted alkyl group). Specific examples of this type of Y are described in JP-A-53-35533 and JP-A-5-35533.
It is described in 3-11082.

Y suitable for compounds of this type further includes the group represented by (YXII).

Specific examples of Y are described in JP-A-53-110827 and US4356.
There are descriptions in 249 and US4358525.

Further suitable Y for this type of compound is the formula (YXIIIA)
And (YXIIIB).

(However, (Nu ox) ¹ and (Nu ox) ² may be the same or different and each represents an oxidized nucleophilic group, and other symbols have the same meanings as in formulas (YVIII) and (YIX). The specific examples of Y of this type are described in JP-A-53-1309.
27 and 56-164342.

The patent specifications listed in YXI, YXII, YXIIIA and YXIIIB describe electron donors used in combination.

Further, as a more preferable one, European Patent No. 220,746A
No. 2, Open Technical Report 87-6199, Japanese Patent Application No. 62-34953, No. 62-34
N-X bond (X is oxygen,
A compound having an electron-withdrawing group (representing a sulfur or nitrogen atom) and SO ₂ − in one molecule described in Japanese Patent Application No. 62-106885.
A compound having X (X is as defined above) and an electron-withdrawing group,
A compound having a PO-X bond (X has the same meaning as above) and an electron-withdrawing group in one molecule described in Japanese Patent Application No. 62-106895, and one compound described in Japanese Patent Application No. 62-106887. Examples thereof include compounds having a C—X ′ bond (X ′ is synonymous with X or represents —SO ₂ —) and an electron withdrawing group.

Particularly preferred compounds of the formula (I) include those of the formula (YXIV). Specific examples of Y are described in JP-A-62-215,270, but in the present invention, a compound represented by the formula (YXV) is particularly preferably used.

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 is R ⁸²
May combine with each other to form a ring.

X is -O-, -S- or Is represented (R ⁵ has the same meaning as above). Particularly, -O- is preferable.

Time represents a group that releases Dye through a subsequent reaction using the cleavage of the nitrogen-oxygen-heavy bond in the formula as a scratch,
t represents 0 or 1. In the formula, a solid line indicates a bond, and a broken line indicates that at least one is bonded.

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

The ballast group in the general formulas (YI) to (YXV) is an organic ballast group capable of making the dye image-forming compound of the general formula (I) non-diffusible, which is a hydrophobic group having 8 to 32 carbon atoms. It is preferably a group containing a 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).

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

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

The synthesis method of the compound of the present invention varies depending on the structure of the dye moiety and the type of the substrate Y, but it is roughly classified into a method by condensation of a dye moiety having a chlorosulfonyl group and a substrate Y having an amino group and a dye precursor in advance. A method in which a coupler and a substrate Y are condensed beforehand and a dye skeleton is formed by a coupling reaction in the last step can be classified. When Y is an oxidizable substrate, the former method is mainly adopted, and when Y is a reducible substrate, any method is acceptable, but when the latter method synthesizes various derivatives, Is suitable. A specific synthesis example will be described below.

Synthesis Example Synthesis of image-forming compound (23) The following isoxazolone intermediate (A) was synthesized according to the method described in Japanese Patent Application No. 62-106,896.

To a mixture of 13.5 g of intermediate (A), 5.5 g of 1-hydroxy-5-methanesulfonamide-2-naphthoic acid and 100 ml of dry tetrahydrofuran was added 1.6 g of pyridine at room temperature, and then 6.1 g of dicyclohexylcarbodiimide was added little by little. It was After stirring at 40 ° C. for 1 hour and at 20 ° C. for 3 hours, the crystals were separated and the solution was evaporated under reduced pressure. The residue was purified by column chromatography (silica gel, eluent: ethyl acetate / hexane = 1/1) to give 9.2 g of white crystalline form of intermediate (B).

To a mixture of 5.5 g of intermediate (B), 30 ml of ethyl acetate and 30 ml of acetonitrile was added 5 ml of triethylamine at room temperature, and then 2,6-dichloroquinone-4-chloroimide 1.5.
2g was added in small portions.

After stirring at room temperature for 30 minutes, 1N-hydrochloric acid 100 ml was added, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure to precipitate black crystals.
The crystals were taken and recrystallized from acetonitrile / ethyl acetate to obtain 3.5 g of crystals of the image forming compound (23) having a melting point of 186 to 189 ° C.

It had an absorption maximum at 725 nm in dimethylformamide containing a small amount of triethylamine.

In the light-sensitive material of the present invention, the compound represented by the general formula (I) can be used alone, but is usually used together with an image forming compound of yellow, magenta, and cyan, and is provided to a system for forming a full-color image. . At that time, the image-forming compound of the present invention can be added together with any of the yellow, magenta, and cyan image-forming compounds, or can be added separately from them. Here, the image forming substances of yellow, magenta and cyan are the same as those of general formula (I) except that the dye part of the general formula (I) is a dye of yellow, magenta and cyan or a precursor thereof. They are known.

In general, the infrared light-absorbing image-forming compound of the present invention often has the short wavelength side of the absorption overlapped with the cyan dye region (600 to 700 nm). Above is advantageous.

The infrared ray absorbing image-forming compound of the present invention can be added to the light-sensitive material in the same manner as other image-forming compounds. In many cases, since the substrate Y in the general formula (I) contains a hydrophobic ballast group for making the image forming compound itself nondiffusible, an addition method of emulsifying and dispersing in a state of being dissolved in a non-volatile oil is often employed. Is done.

The addition amount of the infrared light absorbing image forming compound of the present invention varies depending on the type and purpose of the light-sensitive material or the physical properties of the compound itself, but is generally in the range of 0.05 to 1.0 g / m ² .

The image forming compound in the present invention can be used alone, but a reducing substance that reduces exposed silver halide and cross-oxidizes with the compound of the present invention can be used in combination. Although various substances can be used as the reducing substance, preferably, hydroquinones, 3-pyrazolidones, aminophenols, catechols, p-phenylenediamines, aminonaphthols, catechols,
Examples include p-phenylenediamines, aminonaphthols, reductones and the like.

Further, a precursor that can be hydrolyzed under alkaline conditions to form the above-described reducing compound can also be used.

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

Specific examples of the more preferable reducing compound 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,
-Phenyl-2-acetyl-3-pyrazolidone, 1-phenyl-3-acetoxypyrazolidone; hydroquinones such as hydroquinone, trihydroquinone, 2,6
-Dimethylhydroquinone, t-butylhydroquinone, 2,5-di-t-butyl-hydroquinone, t-octylhydroquinone, 2,5-di-t-octylhydroquinone, pentadecylhydroquinone, 5-pentadecylhydroquinone-2-sulfone Sodium acid, 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-dimethylaminophenol, p-dimethylaminophenol, p-
Dibutylaminophenol, p-piperidinoaminophenol, 4-dimethylamino-2,6-dimethoxyphenol, etc .; 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, pyridinohexose reductone and the like.

Research Disclosure No. 151, No. 1510
8, U.S. Pat.No. 4,021,240 includes 2,6-dichloro-4-
Substituted sulfonamidophenol, 2,6-dibromo-4-
Substituted sulfonamide phenols, p- (N, N-dialkylaminophenol) sulfamine and the like are described in JP-A-59-116740 and are useful. In addition to the phenol-based reducing agents described above, naphthol-based reducing agents such as 4-aminonaphthol derivatives and 4-substituted sulfonamide naphthol derivatives are also useful.

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

Silver halide that can be used in the present invention includes silver chloride, silver bromide, silver iodide, or silver chlorobromide, silver chloroiodide, silver iodobromide,
Any of silver chloroiodobromide may be used. The halogen composition inside the grains may be uniform, or the grains may have a multiple structure having different compositions on the surface and inside (Japanese Patent Laid-Open Nos. 57-154232 and 58-10).
8533, 59-48755, 59-52237, U.S. Pat.
433,048 and EP 100,984). Further, tabular grains having a grain thickness of 0.5 μm or less, a diameter of at least 0.6 μm and an average aspect ratio of 5 or more (US Pat. No. 4,414,31)
0, 4,435,499 and West German Published Patent (OLS) 3,24
1,646A1) or monodisperse emulsions having a nearly uniform particle size distribution (JP-A-57-178235, JP-A-58-100846, JP-A-58-100846).
-14829, WO 83 / 02338A1, EP 64,412A
3 and 83,377 A1) can also be used in the present invention. Two or more kinds of silver halides having different habits, halogen compositions, grain sizes, grain size distributions and the like may be used in combination. The gradation can be adjusted by mixing two or more kinds of monodisperse emulsions having different grain sizes.

The grain size of the silver halide used in the present invention is preferably one having an average grain size of 0.001 μm to 10 μm,
The thickness of 5 to 5 μm is more preferable. These silver halide emulsions may be prepared by any of the acidic method, the neutral method and the ammonia method, and the reaction form of the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination method thereof. Any combination of A back mixing method, in which grains are formed in the presence of excess silver ions, or a controlled double jet method, which keeps pAg constant, can also be employed. Further, in order to accelerate grain growth, the addition concentration, addition amount or addition rate of silver salt and halogen salt to be added may be increased (JP-A-55-142329, JP-A-55-158124, U.S. Pat.No. 3,650,757). etc).

Epitaxy-bonded silver halide grains can also be used (JP-A-56-16124, U.S. Pat. No. 4,094,6).
No. 84).

In the step of forming silver halide grains used in the present invention, ammonia as a silver halide solvent, JP-B-47-11
No. 386, organic thioether derivatives described in
The sulfur-containing compounds described in No. 144319 can be used.

Cadmium salt, zinc salt, lead salt, thallium salt and the like may be present together in the process of grain formation or physical ripening.

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

Soluble salts may be removed from the silver halide emulsion after the formation of a precipitate or after physical ripening, and thus the Nudell washing method or the precipitation method can be used.

The silver halide emulsion may be used as it is without ripening, but it is usually chemically sensitized before use. Well-known sulfur sensitizing methods, reduction sensitizing methods, noble metal sensitizing methods and the like can be used alone or in combination for the emulsions for conventional type light-sensitive materials. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-126526 and JP-A-58-215644).

The silver halide emulsion used in the present invention may be either a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside the 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.Nos. 2,592,250 and 3,761,2
No. 76, JP-B-58-3534 and JP-A-57-136641. Preferred nucleating agents to combine in the present invention are U.S. Patent Nos. 3,227,552 and 4,245,037.
No. 4,255,511, No. 4,266,031, No. 4,276,36
No. 4 and OLS No. 2,635,316. As for the optical fogging, Japanese Patent Publication No. 45-12710, Japanese Patent Laid-Open No. 61-15964
A known method according to No. 1 or the like can be used.

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

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus 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; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of, that is, an indolenine nucleus,
A benzindrenine nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole 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, 2-thiooxazolidine-
A 5- or 6-membered heterocyclic nucleus such as 2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, or 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 especially for the purpose of supersensitization.

Along with the sensitizing dye, a dye that does not have a spectral sensitizing effect itself or a substance that does not substantially absorb visible light and that shows a sensitizing dye may be included in the emulsion. For example, aminostyryl compounds substituted with a nitrogen-containing heterocyclic group (for example, those described in U.S. Pat.Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (for example, U.S. Pat. Listed)),
It may contain a cadmium salt, an azaindene compound or the like. U.S. Pat.Nos. 3,615,613, 3,615,641 and 3,
The combinations described in 617,295 and 3,635,721 are particularly useful.

Gelatin is advantageously used as a binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin may be lime-treated,
It may be either treated with an acid or not. Details of the method for producing gelatin are described in Arthur Weiss, 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.

Although they are used as coating aids, they are sometimes used for other purposes such as emulsion dispersion, improvement of sensitized photographic characteristics, antistatic, and adhesion prevention.
These surfactants are natural surfactants such as saponin,
Nonionic surfactants such as alkylene oxide type, glycerin type, glycidol type, higher alkyl amines,
Quaternary ammonium salts, pyridine and other heterocycles,
Cationic surfactants such as phosphonium or sulfoniums, anionic surfactants containing acidic groups such as carboxylic acid, sulfonic acid, phosphoric acid, sulfate group, phosphate group, amino acids, aminosulfonic acids, sulfuric acid or phosphoric acid of amino alcohol It is divided into amphoteric activators such as esters.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benztriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines Thioketo compounds such as oxazoline thiones; azaindenes; eg triazaindenes; tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7-tetraazaindenes), pentaazaindenes, etc .; Many compounds known as antifoggants or stabilizers such as benzenethiosulphones, benzenesulfinic acid, benzenesulphonic acid amide, etc. 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, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3 -Pyrazolidones may be included.

The photographic light-sensitive material used in the present invention includes a photographic emulsion layer and other hydrophilic colloid layers for the purpose of improving dimensional stability.
It may include a dispersion of water insoluble or sparingly soluble synthetic polymer. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with acrylic acid, Methacrylic acid, α-β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate,
A polymer having a combination of a sulfoalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used.

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, sliding agents, matting agents, development accelerators, mordants, ultraviolet absorbers, anti-fading agents, and color fog prevention Agents and the like.

About these additives, specifically, RESEARCH DISCLOSURE No. 176 No. 22-31
Those described on page (RD-17643) (Dec, 1978) and the like can be used.

The compounds of the general formula (I) of the present invention capable of releasing a diffusible dye are described, for example, in JP-A-58-149046, JP-A-59-154445,
No. 59-165054, No. 59-180548, No. 59-218443, No.
60-133449, U.S. Patents 4,503,137, 4,474,867
No. 4,483,914, No. 4,455,363, No. 4,500,62
No. 6, No. 4,740,445, Photothermographic materials utilizing silver halide in which a movable dye is formed by thermal development as described in JP-A-61-238056 and the like is transferred to a dye fixing layer. It is preferably used for In the following, the photothermographic material may be referred to as a photosensitive element.

When applied to a photothermographic element, an organic metal salt may be used as an oxide together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the above organic silver salt oxidizing agent include benzotriazoles, fatty acids and other compounds described in US Pat. No. 4,500,626, columns 52 to 53. Further, silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolic acid described in JP-A-60-113235 and acetylene silver described in JP-A-61-290444 are also useful. Two or more kinds of organic silver salts may be used in combination.

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

Various antifoggants or photographic stabilizers can be used in the present invention. For example, RD17643
(1978) pages 24 to 25, azoles and azaindenes, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercapto compounds and metals thereof described in JP-A-59-111636. Salts, acetylene compounds described in JP-A-62-87957 and the like are used.

As the binder for the constituent layers of the photosensitive element and the dye fixing element, hydrophilic binders are preferably used. Examples thereof include those described on pages (26) to (28) of JP-A-62-253159. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin or a protein or cellulose derivative such as a gelatin derivative, starch, gum arabic, dextran, a natural compound such as a polysaccharide such as pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Further, superabsorbent polymers described in JP-A-62-245260, that is, --COOM or --SO ₃ M (M
Is a homopolymer of a vinyl monomer having a hydrogen atom or an alkali metal or a copolymer of the vinyl monomers with each other or with another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L- manufactured by Sumitomo Chemical Co., Ltd.). 5H) is also used. These binders can be used in combination of two or more.

In the case of adopting a system in which a small amount of water is supplied for thermal development, it becomes possible to quickly absorb water by using the above superabsorbent polymer. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer.

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

In the constituent layers (including the back layer) of the light-sensitive element or the dye-fixing element, various polymers are used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, film crack prevention, and pressure increase / decrease prevention. A latex can be included. Specifically, JP-A Nos. 62-245258, 62-136648, 62
Any of the polymer latices described in No. 110066 and the like can be used. In particular, when a polymer latex having a low glass transition point (40 ° C or lower) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl-preventing effect is obtained. can get.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, an image-forming substance having a reducing property (a dye-donating compound) 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, in addition to those described above, U.S. Pat.No.4,500,626, columns 49 to 50, and column 4,48.
Columns 30-31 of 3,914, 4,330,617, 4,590,15
2, JP-A-60-140335, pages (17) to (18), ibid., 57.
-40245, 56-138736, 59-178458, 59-5
3831, 59-182449, 59-182450, 60-1195
55, 60-128436 to 60-128439, still 60-
198540, 60-181742, 61-259253, 62-24
4044, 62-131253 to 62-131256, there are reducing agents and reducing agent precursors described in European Patent 220,746A2, pages 78 to 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 added, if necessary, in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide. A combination of precursors can be used.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agent or its precursor.
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). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any one that does not substantially move in the layer of the photosensitive element among the reducing agents described above, and is preferably a hydroquinone, Examples thereof include sulfonamide phenols, sulfonamido naphthols, compounds described as electron donors in JP-A-53-110827, and non-diffusive and reducing dye-providing compounds described later.

In the present invention, the reducing agent is added in an amount of 1 mol of silver.
The amount is 0.001 to 20 mol, particularly preferably 0.01 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. For specific compounds preferably used, U.S. Pat.
No. 626, columns 51-52.

Dye-fixing elements are used with light-sensitive elements in systems that form images by diffusion transfer of dyes. The dye-fixing element may be applied separately on a support different from the photosensitive element, or may be applied 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 relationships described in column 57 of US 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, one known in the photographic field can be used, and specific examples thereof include U.S. Pat. No. 4,500,626, columns 58 to 59 and JP-A-61
-88256, mordanting agents described on pages (32) to (41), JP-A-6-26
2-244043, 62-244036, etc. can be mentioned. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 may be used.

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

The constituent layers of the photosensitive element and the dye fixing element include a plasticizer,
A high-boiling organic solvent can be used as a slipping agent or an agent for improving the peelability between the light-sensitive element and the dye-fixing element. Specific examples include those described in JP-A-62-253159, page (25), JP-A-62-245253, and the like.

Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. Examples include various modified silicone oils described in "Modified Silicone Oil" technical material P6-18B issued by Shin-Etsu Silicone Co., Ltd., especially carboxy-modified silicone (trade name X-22-37.
10) etc. are effective.

Further, the silicone oils described in JP-A No. 62-215953 and Japanese Patent Application No. 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, coumarane compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A No. 61-159644 are also effective.

Examples of UV absorbers include benzotriazole compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. No. 3,352,681), benzophenone compounds (JP-A No. 46-2784), and others. Akira 54
-48535, 62-136641, 61-88256 and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

As the metal complex, U.S. Pat. Nos. 4,241,155 and 4,2
45,018, columns 3 to 36, 4,254,195, columns 3 to 8, JP-A-62-174741, 61-88256 (27) to (29),
Japanese Patent Application Nos. 62-234103 and 62-31096, Japanese Patent Application No. 62-23059
There are compounds described in No. 6 and the like.

Examples of useful anti-fading agents are disclosed in JP-A-62-215272 (125).
~ (137) pages.

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. .

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

A fluorescent whitening agent may be used in the light-sensitive 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. An example is K. Veenkataraman's ed. “The Chemistry of Synt
hetic Dyes ", Volume V, Chapter 8, and compounds described in JP-A-61-143752 and the like. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned.

The optical brightener can be used in combination with a fading inhibitor.

Examples of the hardener used in the constituent layers of the photosensitive element and the dye-fixing element include U.S. Pat.
The hardeners described in No. 5, No. 62-245261, No. 61-18942 and the like can be mentioned. More specifically, aldehyde type hardener (formaldehyde etc.), aziridine type hardener, epoxy type hardener Vinyl sulfone type hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide) ethane, etc.), N-methylol type hardeners (dimethylol urea, etc.), or polymer hardeners (JP-A-62) -234157 and the like).

In the constituent layers of the photosensitive element and the dye fixing element, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, promoting development, and the like. Specific examples of the surfactant are described in JP-A-62-173463 and JP-A-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 slipperiness, preventing electrification, and improving releasability. As typical examples of organic fluoro compounds, JP-B-57-9053, columns 8 to 17, JP-A-61-20944 can be used.
Nos. 62-135826 and the like, and fluorine-based surfactants, or hydrophobic fluorine compounds such as oily fluorine-based compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin. To be

A matting agent can be used for the photosensitive element and the dye fixing element. As the matting agent, in addition to the compounds described in JP-A No. 61-88256 (page 29) such as silicon dioxide, polyolefin or polymethacrylate, there are also Japanese Patent Application No. 62-110064, such as benzoguanamine resin beads, polycarbonate resin beads and AS resin beads. No. 62-110065.

In addition, in the constituent layers of the light-sensitive element and the dye fixing element,
A hot solvent, an antifoaming agent, an antibacterial / antifungal agent, colloidal silica and the like may be included. Specific examples of these additives are disclosed in JP-A-61-
88256 (26)-(32).

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye fixing element. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. For more information on these, see U.S. Pat.
No. 9 columns 38-40.

Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. Specific examples thereof are U.S. Pat. No. 4,511,493 and JP-A-62.
-65038 and the like.

In a system in which heat development and transfer of a dye are simultaneously performed in the presence of a small amount of water, it is preferable to add a base and / or a base precursor to the dye-fixing element in order to enhance the storage stability of the light-sensitive element.

In addition to the above, a combination of a sparingly soluble metal compound described in European Patent Publication No. 210,660 and a compound capable of forming a complex with a metal ion constituting the sparingly soluble metal compound (referred to as a complex forming compound); Compounds that generate a base by electrolysis described in JP-A 61-232451 can also be used as the base precursor. The former method is particularly 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.

In the light-sensitive element and / or dye-fixing element of the present invention, various development terminators can be used for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development.

The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base after proper development to lower the concentration of the base in the film to stop the development or to inhibit development by interacting with silver and a silver salt. Compound. Specific examples thereof 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. More specifically, JP-A-62-253159 (31) to (32)
Page.

As the support of the light-sensitive element or dye fixing element of the present invention,
A material that can withstand the processing temperature is used. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, and further polypropylene etc. Film synthetic paper made from, synthetic paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryder paper, coated paper (especially cast coated paper), metal, cloth, glass etc. are used To be

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

In addition, the supports described in JP-A-62-253159, pages (29) to (31) can be used.

A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

The method of exposing and recording an image on a photosensitive element includes, for example, a method of directly photographing a landscape or a person using a camera, a method of exposing through a reversal film or a negative film using a printer or a enlarger, and a method of using a copier. Scanning and exposing the original image through slits using an exposure device, etc., exposing the image information by emitting light from a light emitting diode or various lasers via electrical signals, CRT, liquid crystal display, electroluminescence display And a method of outputting the image to an image display device such as a plasma display and exposing the image directly or via an optical system.

As a light source for recording an image on a photosensitive element, as described above, natural light, a tungsten lamp, a light emitting diode, a laser light source, a CRT light source, etc., U.S. Pat.
The light source described in the column can be used.

Further, the image information is an image signal obtained from a video camera, an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC), an image obtained by dividing an original image into many pixels such as a scanner. It is possible to use image signals created using a computer represented by Signal, CG, CAD.

The color light-sensitive material of the present invention may be designed to be processed by a so-called conventional wet color diffusion transfer method.
In this case, the above-mentioned light-sensitive material and dye-fixing material can be used except for additives (for example, organic silver salt) unique to heat development. The base and the electron transfer agent may be supplied from a processing solution contained in a breakable container. As is well known, a viscosity imparting agent or the like can be added to this treatment solution. Color diffusion transfer methods are well known in the art and the present invention can be applied to any of these known means.

(Effect of the Invention) According to the present invention, a color light-sensitive material which gives a color image readable by an infrared light reading device can be obtained because it contains the image-forming compound represented by the general formula (I). it can.

(Specific Examples of the Invention) Hereinafter, specific examples of the present invention will be shown to describe the effects of the present invention in more detail.

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

600 ml of an aqueous solution containing sodium chloride and potassium bromide in a well-stirred aqueous gelatin solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water and kept at 75 ° C.) and an aqueous solution of silver nitrate (600 ml of water and 0.59 of silver nitrate) Mols dissolved) were added simultaneously at equal flow rates over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol%) having an average grain size of 0.35 μ was prepared.

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

 Next, we will explain how to make the emulsion for the third layer.

600 ml of an aqueous solution containing sodium chloride and potassium bromide in a well-stirred aqueous gelatin solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water and kept at 75 ° C.) and an aqueous solution of silver nitrate (600 ml of water and 0.59 of silver nitrate) And a dye solution (I) described below at the same time.
It was added at an equal flow rate over 40 minutes. Thus, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol 5) having a dye having an average particle size of 0.35 μ adsorbed was prepared.

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

Next, the method for preparing the silver halide emulsion for the fifth layer will be described.

Well stirred gelatin aqueous solution (20g gelatin and ammonia dissolved in 1000ml water and kept at 50 ℃)
Aqueous solution containing potassium iodide and potassium bromide 10
00 ml and an aqueous solution of silver nitrate (one mol of silver nitrate dissolved in 1000 ml of water) were simultaneously added while keeping the pAg constant. Thus, a monodisperse silver iodobromide octahedral emulsion having an average grain size of 0.5 μm (iodine 5 mol%) was prepared.

After washing with water and desalting, 5 mg of chloroauric acid (tetrahydrate) and 2 mg of sodium thiosulfate were added, and gold and sulfur sensitization was performed at 60 ° C. The yield of the emulsion was 1.0 kg.

 How to make an organic silver salt is described.

Organic Silver Salt (1) A method for preparing a benzotriazole silver emulsion will be described.

28 g of gelatin and 13.2 g of benzotriazole 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 and allowed to settle to remove excess salt. Then adjust the pH to 6.30,
A yield of 400 g of benzotriazole silver emulsion was obtained.

Organic silver salt (2) 20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid were dissolved in 1000 ml of 0.1% sodium hydroxide aqueous solution and 200 ml of ethanol.

 The solution was kept at 40 ° C. and stirred.

A solution prepared by dissolving 4.5 g of silver nitrate in 200 ml of water was added to this solution over 5 minutes.

The pH of this dispersion was adjusted and allowed to settle to remove excess salt. Then, the pH was adjusted to 6.3 and a yield of 300 g was obtained as a dispersion of the organic silver salt (2).

Next, how to prepare a gelatin dispersion of the image forming compound will be described.

4 g of the image-forming compound (7) of the present invention and 4 g of the cyan image-forming compound described below, 0.2 g of an antifoggant having the following structure and 3.5 g of triisononyl phosphate were weighed, and ethyl acetate 40
ml was added and dissolved by heating at about 60 ° C. to obtain a uniform solution.
This solution, 0.5 g of sodium dodecylbenzenesulfonate and 100 g of a 10% solution of lime-processed gelatin were stirred and mixed, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes.
This dispersion is referred to as a cyan image forming compound dispersion.
A dispersion of the image forming compound was prepared in the same manner by using each of the following yellow image forming compound and magenta image forming compound.

Antifoggant From these, a color photosensitive material 101 having a multilayer structure as shown in Table 1 was prepared. For comparison, a color light-sensitive material 102 (Comparative 1) was prepared in the same manner except that the image-forming compound of the present invention was omitted.

Next, how to make the dye fixing material will be described.

63 g of gelatin, 130 g of a mordant having the structure shown below, and 80 g of guanidine picolinate were dissolved in 1300 ml of water and coated on a paper support laminated with polyethylene so as to have a wet film thickness of 45 μm, and then dried.

mordant Further, a solution prepared by dissolving 35 g of gelatin and 1.05 g of 1,2-bis (vinylsulfonylacetamidoethane) in 800 ml of water was coated and dried to a wet film thickness of 17 μm to prepare a dye fixing material D-1. .

A tungsten light bulb was used as a color light-sensitive material having the above-mentioned multilayer structure, and a character image pattern was exposed at 20 lux for 1 second through a transparent test chart for exposure. Water of 15 ml / m ² was supplied to the emulsion surface of the exposed light-sensitive material with a wire bar, and then the dye-fixing material and the film surface were superposed so as to be in contact with each other. It was heated for 20 seconds using a heat roller whose temperature was adjusted so that the temperature of the absorbed film became 95 ° C. Next, when the dye-fixing material was peeled off, a black character image with excellent contrast was obtained on the dye-fixing material.

The obtained image is displayed on a Sumitomo Electric optical character reader HS-OCR.
The following results were obtained when the reading test was conducted at.

OCR by containing the image forming compound of the present invention
It can be seen that readability can be imparted.

Comparative Example A photosensitive material was prepared in the same manner as in Example 1 except that the image forming compound of the present invention was omitted from Example 1 and the cyan image forming compound was replaced with C-2 and C-3 below.

Exposure and development were performed in the same manner as in Example 1, and the obtained image was subjected to an OCR reading test. The results are shown below.

Example 2 In the same manner as in Example 1 except that the image forming compound of the present invention in Example 1 was replaced with (7) to (2), (6), (10), (11) and (13). Multi-layered color light-sensitive materials 201, 202, 203, 204 and 205 were prepared.

A dye fixing material was prepared in the same manner as in Example 1, exposed and developed under the same conditions, and an OCR reading test of the obtained image was conducted. The results are shown below.

It can be seen that all the image-forming compounds of the present invention have excellent OCR reading ability.

Example 3 A method for preparing a silver halide emulsion for the fifth layer and the first layer will be described.

600 ml of an aqueous solution containing sodium chloride and potassium bromide in a well-stirred aqueous gelatin solution (containing 20 g of gelatin and 3 g of sodium chloride in 1,000 ml of water and kept at 75 ° C) and an aqueous solution of silver nitrate (600 ml of water and silver nitrate) 0.59 mol dissolved) was added simultaneously at an equal flow rate over 40 minutes. Thus, a monodisperse cubic silver chlorobromide emulsion (50 mol% of bromine) having an average grain size of 0.40 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, and chemical sensitization was performed at 60 ° C. Emulsion yield is 60
It was 0g.

Next, how to prepare a silver halide emulsion for the third layer will be described.

600 ml of an aqueous solution containing sodium chloride and potassium bromide in a well-stirred aqueous gelatin solution (containing 20 g of gelatin and 3 g of sodium chloride in 1,000 ml of water and kept at 75 ° C) and an aqueous solution of silver nitrate (600 ml of water and silver nitrate) 0.59 mol dissolved) was added simultaneously at an equal flow rate over 40 minutes. Thus, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol%) having an average grain size of 0.35 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, and chemical sensitization was performed at 60 ° C. Emulsion yield is 60
It was 0g.

Next, how to prepare a gelatin dispersion of the image forming compound will be described.

4 g of the infrared light absorbing image-forming compound (7) of the present invention, 4 g of the cyan image-forming compound, 0.3 g of the antifoggant of Example 1, and 2-ethylhexyl ester sulfonate succinate 0.5 g as a surfactant. Weigh 20 g of triisononyl phosphate, add 60 ml of ethyl acetate, and
It was heated to dissolve at 0 ° C. to obtain a uniform solution. This solution and 150 g of a 10% solution of lime-processed gelatin were stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a cyan image forming compound dispersion.

Dispersions of yellow and magenta imaging compounds were made in the same manner as above using the yellow and magenta imaging compounds.

The organic silver salts (1) and (2) used in Example 1 were used. From these, a color photosensitive material 301 having a multilayer structure as shown in Table 4 was prepared. For comparison, a color photosensitive material 302 (Comparative 4) was prepared in the same manner except that the image forming compound of the present invention was omitted.

A dye-fixing material having the same composition as that of Example 1 except that guanidine picolinate was removed from D-1 was used as a dye-fixing material D-2.

A tungsten light bulb was used for the color light-sensitive material having the above-mentioned multilayer structure.
It was exposed for 1 second with looks.

Thereafter, the mixture was uniformly heated on a heat block heated to 140 ° C. for 30 seconds.

Next, after supplying 20 ml of water per 1 m ² to the film surface side of the dye-fixing material, the photosensitive coating materials after the heat treatment were overlapped with the fixing material so that the film surfaces were in contact with each other.

After heating for 6 seconds on a heat block at 80 ° C., the dye fixing material was peeled off from the light-sensitive material, whereby a black character image with excellent contrast was obtained on the fixing material.

The OCR reading test of the obtained image was conducted and the following results were obtained.

It can be seen that the image forming compound of the present invention is effective even in a system developed at a high temperature of 100 ° C. or higher.

Claims (1)

[Claims] 1. A silver halide color light-sensitive material comprising at least a silver halide and an infrared light absorbing image forming compound represented by the following general formula (I) on a support. (Dye-X) _q -Y (I) [wherein, Dye represents an infrared light absorbing dye group represented by the following formula (II), X represents a simple bond or a linking group, and Y represents
Represents a group having the property of producing a difference in the diffusibility of the dye component before and after the reaction with a photosensitive silver salt having an imagewise latent image and correspondingly or inversely. In the formula, R ¹ and R ² may be the same or different, and represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, a sulfo group, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, and a heterocyclic group. Group, alkoxy group, aryloxy group, amino group, acylamino group, sulfonylamino group, acyl group, sulfonyl group, carbamoyl group,
It represents a substituent selected from a sulfamoyl group, a ureido group, a urethane group, an alkylthio group, an arylthio group, a nitro group and an alkoxycarbonyl group. Ar represents an aryl group or a heterocyclic group. Further, these substituents may be further substituted with other substituents. m and n represent an integer of 0 to 4, and when they are 2 to 4, they may be the same or different. Dye may be attached to X from any position of formula (II). q is 1 or 2, and when q is 2,
Dye-X may be the same or different. ]