JPH05107711A - Heat development transfer type color photosensitive material - Google Patents

Abstract

PURPOSE:To lessen the degradation in the sensitivity of a coating liquid contg. IR photosensitive silver halides and dye donative compds. with lapse of time in a IR region by specifying the concn. of the anionic compds. in the coating liquid to a specific value or below. CONSTITUTION:This heat developable diffusion transfer type color photosensitive material is constituted by having at least one kind of the photosensitive silver halides spectrally sensitized to an IR region, binders and the non-diffusive dye donative compds. which release diffusive dyes in correspondence to the reaction by which the silver halides are reduced to silver on a base and adding the non-diffusive dye donative compds. together with a high boiling solvent by emulsion dispersion using anionic surfactants to the coating liquid. The concn. of the anionic compds. in the coating liquid contg. the IR photosensitive silver halides and the dye donative compds. is confined to <=1wt.% in such a case. The silver halide emulsions may be surface latent image type emulsions or internal latent image type emulsions.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat development diffusion transfer type color light-sensitive material, and particularly to a heat development diffusion transfer type color light-sensitive material which is excellent in image discrimination and can be manufactured with a constant and stable performance. It is about materials.

[0002]

2. Description of the Related Art The photographic method using silver halide is superior to other photographic methods such as electrophotography and diazo photography in photographic characteristics such as sensitivity and gradation control. Has been. In particular, since the best image quality is obtained for color hard copy, it has been studied more vigorously these days.

Recently, with the progress of office automation, commercial image equipment, electronic still cameras, video,
With the spread of facsimiles, etc.,
Graphics needs have also increased. In particular, along with the development of computer graphics and the development of image sensor technology and digital processing technology, there is an increasing demand for obtaining a color hard copy from image information once converted into an electric signal.

Conventional color light-sensitive materials usually have spectral sensitivities of blue, green and red. To obtain an image by using image information once converted into an electric signal in such a color light-sensitive material, a color image is obtained. It is common to use a CRT (cathode ray tube) as an exposure light source, but the CRT is unsuitable for obtaining a large size print.

Further, as a writing head capable of obtaining a large size print, a light emitting diode (LED) is used.
And semiconductor lasers have been developed. However, none of these optical writing heads that efficiently emit blue light has been developed.

Therefore, for example, a light emitting diode (LE
When using D), near infrared (800 nm), red (6
70 nm) and a yellow (570 nm) light emitting diode combination, it is necessary to expose a color light-sensitive material having three layers spectrally sensitized to near infrared, red, and yellow. "Nikkei New Material," a system for recording images with various configurations, September 14, 1987
It is described on pages 47 to 57 of the Japanese issue and is partly in practical use.

Also, 880 nm, 820 nm, 760 n
A system for recording on a color light-sensitive material having three light-sensitive layers having spectral sensitivities at respective wavelengths by a light source combining three semiconductor lasers each emitting m light is disclosed in Japanese Patent Laid-Open No. 61-
137149.

Due to the need for color hard copy as described above, in recent years, an image forming method for a light-sensitive material using silver halide has been changed from a conventional wet process to an inst photographic system containing a developing solution, and further. A system capable of simply and quickly obtaining an image has been developed by a dry heat development process such as heating. The simple and rapid processing method described above often employs a method of forming an image by a diffusion transfer method in order to prevent the image from being contaminated by a printout of silver halide after the image is formed.

The diffusion transfer method is a method of forming or releasing a diffusible dye imagewise and transferring the diffusible dye to an image-receiving material having a mordant with a solvent such as water. Angew.Chem.Int.Ed.Engl. 22 (19
83) 191. The present inventors have continued to study diffusion transfer type color photosensitive materials, particularly heat development diffusion transfer type color photosensitive materials, but the design of the color photosensitive material corresponding to the writing head (semiconductor laser, LED) described above was I need it.

Photothermographic materials are known in the art, and the photothermographic materials and their processes are described, for example, in "Basics of Photographic Engineering", Non-silver Salt Photographs (1982, Corona Publishing Co., pp.242-255). It is described in. Regarding the heat-developable color photosensitive material using the diffusion transfer method, U.S. Pat. Nos. 4,500,626 and 4,483,914,
4,503,137, 4,559,920; JP-A-59-165054, JP-A-59-231539,
No. 60-2950, No. 59-116643 and the like describe negative type systems.

According to the above method, the developing temperature is high and the stability of the photosensitive material with time cannot be said to be sufficient. Therefore, there is a method of promoting development, lowering the development temperature, and simplifying the processing by heat-developing in the presence of a base or a base precursor and a small amount of water to transfer the dye, and JP-A-59-21844.
No. 3, 61-238056, European Patent 210, 66.
0A2 and the like.

[0012]

The present inventors have been developing a heat development diffusion transfer type color light-sensitive material having a spectral sensitivity in the infrared region, but in order to have a spectral sensitivity in the infrared region, In color light-sensitive materials that use silver halide spectrally sensitized with a sensitizing dye that has spectral absorption in the infrared, desorption of the infrared sensitizing dye from silver halide in the coating solution is likely to occur and It has been found that when a light-sensitive material is applied while the solution is dissolved for a long time, the photographic performance is changed such that the sensitivity is greatly reduced several hours after the application is started.

[Object of the Invention] An object of the present invention is to provide a heat-development diffusion transfer type color light-sensitive material which is excellent in image discrimination and can be produced with a constant and stable performance.

[0014]

The objects of the present invention have been achieved by the heat development diffusion transfer type color light-sensitive material described in the following item (2).

(1) At least one photosensitive silver halide spectrally sensitized in the infrared region on a support, a binder,
And a non-diffusible dye-donor compound which releases a diffusible dye in response to a reaction in which the silver halide is reduced to silver, and the non-diffusible dye-donor compound is added by using an anionic surfactant. In a heat development diffusion transfer type color light-sensitive material added by emulsifying and dispersing with a high boiling point solvent, the concentration of the anionic compound in the coating liquid containing the infrared-sensitive silver halide and the dye-donor compound is 1% by weight or less. A heat-development diffusion transfer type color light-sensitive material.

(2) The heat-development diffusion transfer type color light-sensitive material as described in the item (1), wherein the anionic surfactant used for emulsifying and dispersing is a compound represented by the following general formula [I]. .. General formula [I]

[0017]

[Chemical 2]

In the formula, R represents an aliphatic hydrocarbon group having 4 to 22 carbon atoms. m ₁ and m ₂ each represent 0 or 1. B represents -O- or -NH-. A represents an aliphatic divalent group having 1 to 50 carbon atoms. X
Represents —SO ₃ — or —CO ₂ —. M represents a cation capable of forming a salt with X or a cationic root. The present invention will be described in detail below.

The silver halide emulsion used in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or a light fogging. Further, it may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.1 to 2 µ, and particularly preferably 0.2 to 1.5 µ. The crystal habit of the silver halide grains may be cubic, octahedral, tetrahedral, tabular with a high aspect ratio, or the like.

Specifically, US Pat. No. 4,500,62
No. 6, Column 50, No. 4,628,021, Research
Disclosure magazine (hereinafter abbreviated as RD) 1702
9 (1978) and any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

The silver halide emulsion may be used as it is after 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 light-sensitive materials. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

The sensitizing dye which can be spectrally sensitized to 700 nm or more by adding it to the silver halide used in the heat development diffusion transfer type color light-sensitive material of the present invention has the following structure. It is not limited. General formula (II)

[0024]

[Chemical 3]

General formula [III]

[0026]

[Chemical 4]

General formula [IV]

[0028]

[Chemical 5]

Where Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅
Represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle.

D ₁ and D ₁ 'represent an atomic group necessary for forming an acidic nucleus, which may be acyclic or cyclic.

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent an alkyl group.

R ₆ represents an alkyl group, an aryl group or a heterocyclic group. L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L ₇ , L ₈ , L
₉ , L ₁₀ , L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ , L ₁₅ , L ₁₆ ,
L ₁₇ , L ₁₈ , L ₁₉ , L ₂₀ , L ₂₁ , and L ₂₂ represent a methine group.

N ₁ , n ₂ , n ₃ , n ₄ , n ₅ and n ₆
Represents 0 or 1.

R ₁ represents 1, 2 or 3. However, when r ₁ is 1, Z ₁ and Z ₂ represent a 4-quinoline nucleus or a 4-pyridine nucleus.

When r ₂ is 2, at least one of Z ₁ and Z ₂ represents a 4-quinoline nucleus or a 4-pyridine nucleus.

R ₂ represents 2 or 3.

When r ₂ is 2, Z ₃ represents a 4-quinoline nucleus or a 4-pyridine nucleus.

R ₃ represents 1, 2 or 3, r ₄ represents 0, 1 or 2. However, r ₃ + r ₄ represents 2 or more.

K ₁ , K ₂ and K ₃ represent charge-balancing counterions, k ₁ , k ₂ and k ₃ being a number greater than or equal to 0 required to balance the charge.

The nuclei formed by Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ include thiazole nuclei {thiazole nuclei (eg thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole. , 4, 5
-Diphenylthiazole, benzothiazole nuclei (e.g. benzothiazole, 4-chlorobenzothiazole,
5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-
Bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-
Phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole,
5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole), naphthothiazole nucleus (for example, naphtho [2,1-d ] Thiazole, naphtho [1,2
-D] thiazole, naphtho [2,3-d] thiazole,
5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] Thiazole)}, thiazoline nucleus (for example, thiazoline, 4-methylthiazoline, 4-nitrothiazoline), oxazole nucleus {oxazole nucleus (for example, oxazole, 4-methyloxazole, 4-nitroxazole, 5-methyloxazole, 4-phenyl) Oxazole, 4,5-diphenyloxazole, 4
-Ethyloxazole), a benzoxazole nucleus (for example, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-
Phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole,
6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-
Dimethylbenzoxazole, 5-ethoxybenzoxazole), naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5-
Nitronaphtho [2,1-d] oxazole)}, an oxazoline nucleus (eg, 4,4-dimethyloxazoline),
Selenazole nucleus (selenazole nucleus (for example, 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzoselenazole nucleus (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-
Nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole), naphthoselenazole Nuclear (eg naphtho [2,1
-D] selenazole, naphtho [1,2-d] selenazole)}, selenazoline nucleus (eg, selenazoline, 4-
Methyl selenazoline), tellurazole nucleus {terrazole nucleus (eg, tellurazole, 4-methylterrazole,
4-phenylterrazole), a benzoterrazole nucleus (for example, benzoterrazole, 5-chlorobenzoterrazole, 5-methylbenzoterrazole, 5,6-dimethylbenzotelrazole, 6-methoxybenzoterrazole), naphtho Tellurazole nucleus (for example, naphtho [2,1-d] telrazole, naphtho [1,2-d] telrazole)}, tellrazoline nucleus (for example, tellrazoline, 4-methylterrazoline), 3,3-dialkylindolenine nucleus (For example, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-6-nitroindolenine, 3,3-dimethyl-5. -Nitroindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3,5-trimethyl Indolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus (imidazole nucleus (e.g., 1-alkylimidazole, 1-alkyl-4-phenylimidazole, 1-arylimidazole), benzimidazole nucleus (e.g., 1-alkylbenzimidazole, 1-alkyl-
5-chlorobenzimidazole, 1-alkyl-5,6
-Dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl -6-chloro-5
-Cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-
Allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1- Aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole), naphthoimidazole nucleus (for example, -alkylnaphtho [1,2-d] imidazole, 1-arylnaphtho [1,2-d] imidazole) The above-mentioned alkyl groups are those having 1 to 8 carbon atoms, for example, unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl, and hydroxyalkyl groups (eg 2-hydroxyethyl, 3-hydroxypropyl). preferable. Particularly preferred are methyl group and ethyl group. The above aryl group is
Represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. }, A pyridine nucleus (eg, 2-pyridine, 4-pyridine, 5-methyl-
2-pyridine, 3-methyl-4-pyridine), quinoline nucleus {quinoline nucleus (eg, 2-quinoline, 3-methyl-
2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6
-Hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline, 6-ethoxy-4-quinoline, 6-
Nitro-4-quinoline, 8-chloro-4-quinoline, 8
-Fluoro-4-quinoline, 8-methyl-4-quinoline, 8-methoxy-4-quinoline, 6-methyl-4-quinoline, 6-methoxy-4-quinoline, 6-chloro-4
-Quinoline), isoquinoline nuclei (eg 6-nitro-
1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline)}, imidazo [4,5-b] quinoxaline nucleus (eg 1,3-diethylimidazo [4,5-b]) Examples thereof include quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, and pyrimidine nucleus.

More preferred are benzothiazole nucleus, naphthothiazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, 4-quinoline nucleus and benzimidazole nucleus.

D ₁ and D ₁ 'represent an atomic group necessary for forming an acidic nucleus, but can take the form of an acidic nucleus of any general merocyanine dye. In a preferred form D ₁ is a cyano, sulfo or carbonyl group, D _1
1 'represents an atomic group necessary for forming an acidic nucleus.

When the acidic nucleus is acyclic, ie D ₁
And when D ₁ ′ is an independent group, the end of the methine bond is malononitrile, alkylsulfonylacetonitrile,
A group such as cyanomethyl benzofuranyl ketone or cyanomethyl phenyl ketone.

D ₁ and D ₁ ', taken together, are carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium,
And a tellurium) atom to form a 5- or 6-membered heterocycle. Preferably D ₁ and D ₁ ′ combine to complete the next nucleus.

2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazolin-5-one ,
2-thiooxazolidine-2,4-dione, isoxazoline-5-one, 2-thiazolin-4-one, thiazolidin-4-one, thiazolidine-2,4-dione, rhodamine, thiazolidine-2,4-dithione, Isorhodanine, indane-1,3-dione, thiophen-3-
On, thiophen-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, indazoline-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7- Dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbi Tool acid, 2-thiobarbituric acid, chroman-
Nuclei of 2,4-dione, indazoline-2-one, or pyrido [1,2-a] pyrimidine-1,3-dione.

More preferred are 3-alkylrhodonine nucleus, 3-alkyl-2-thiohydantoin nucleus and 3-alkyl-2-thiooxazolidine-2,4-dione nucleus.

When the substituent bonded to the nitrogen atom contained in the nucleus is R ₇ , the substituent R ₇ is a hydrogen atom and has 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms. Alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, octadecyl group), substituted alkyl {for example aralkyl group (for example, benzyl group,
2-phenylethyl group), hydroxyalkyl group (for example, 2-hydroxyethyl group, 3-hydroxypropyl group), carboxyalkyl (for example, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, carboxy) Methyl group), alkoxyalkyl group (eg, 2-methoxyethyl group, 2- (2-′methoxyethoxy) ethyl group), sulfoalkyl group (eg,
2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2- [3-sulfopropoxy) ethyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfopropoxyethoxyethyl group) , A sulfatoalkyl group (eg, 3-sulfatopropyl group, 4-sulfatobutyl group), a heterocyclic-substituted alkyl group (eg, 2- (pyrrolidin-2-one-1-yl) ethyl group, a tetrahydrofurfuryl group , 2-morpholinoethyl group), 2-acetoxyethyl group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group}, allyl group, aryl group (eg, phenyl group, 2-naphthyl group), substituted aryl group (eg, 4-carboxyphenyl group, 4-sulfophenyl group, 3-chlorophenyl group,
A 3-methylphenyl group) and a heterocyclic group (eg, 2-pyridyl group, 2-thiazolyl group) are preferable.

More preferred are unsubstituted alkyl groups (eg, methyl group, ethyl group, pentyl group) and carboxyalkyl groups (eg, carboxymethyl group, 2-carboxyethyl group).

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are preferably unsubstituted alkyl groups having 18 or less carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, Decyl group, dodecyl group, octadecyl group), or substituted alkyl group (as a substituent, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom)), a hydroxy group, carbon. An alkoxycarbonyl group having a number of 8 or less (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group),
An alkoxy group having 8 or less carbon atoms (for example, a methoxy group, an ethoxy group, a benzyloxy group, a phenethyloxy group),
A monocyclic aryloxy group having 10 or less carbon atoms (for example, phenoxy group, p-tolyloxy group), an acyloxy group having 3 or less carbon atoms (for example, acetyloxy group, propionyloxy group), an acyl group having 8 or less carbon atoms (for example, Acetyl group, propionyl group, benzoyl group, mesyl group), carbamoyl group (eg carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), sulfamoyl group (eg sulfamoyl group, N, N -Dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group), carbon number 1
And an alkyl group having 18 or less carbon atoms, which is substituted with an aryl group having 0 or less (for example, a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, an α-naphthyl group).

More preferably, an unsubstituted alkyl group (eg, methyl group, ethyl group, pentyl group), sulfoalkyl group (eg, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group), carboxyalkyl group ( (For example, carboxymethyl group, 2-carboxyethyl group)
Is.

Further, R ₁ , R ₂ , R ₃ , R ₄ and R ₅
The metal atom capable of forming a salt with is particularly preferably an alkali metal, and the organic compound capable of forming a salt is preferably pyridines, amines and the like.

R ₆ is preferably the same as R ₇ described above.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
₇ , L ₈ , L ₉ , L ₁₀ , L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ ,
L ₁₅ , L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ , L ₂₀ , L ₂₁ and L ₂₂
Is a methine group (substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, 2-carboxyethyl group), substituted or unsubstituted aryl group (eg, phenyl group, o
-Carboxyphenyl group), a halogen atom (eg chlorine atom, bromine atom), an alkoxy group (eg methoxy group, ethoxy group), an alkylthio group (eg methylthio group, ethylthio group), and the like. }
And may form a ring with another methine group,
Alternatively, a ring can be formed with the auxiliary chromophore.

K ₁ k ₁ , K ₂ k ₂ and K ₃ k ₃ are of the formula to indicate the presence or absence of a cation or anion when required to neutralize the ionic charge of the dye. It is included in. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents.

Typical cations are ammonium ions and alkali metal ions, while the anions can be either inorganic or organic anions, for example halogen anions (eg fluoride ions,
(Chlorine ion, bromine ion, iodine ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion (for example, 1,3-benzene disulfonate ion, 1, 5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkylsulfate ion (eg methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetic acid Ions and trifluoromethanesulfonate ion.

Iodine ions are preferred.

Preferred dyes used in the present invention are JP-A-2-239246 (Japanese Patent Application No. 1-60).
(526) page (10) to page (13).
Examples of the dyes include -1) to (III-2). The compounds represented by the general formulas [II], [III] and [IV] used in the present invention are known compounds and can be synthesized according to the methods described in literatures and the like.

Literature

FM Hamer, "Heterocyclic Compounds-Cyanine Die and Related Compounds- (Heterocycl
ic Compounds-Cyanine dyes and related compounds
-) "IV, V, VI, VII, VIII, IV Chapters 86-29
Page 1 chapter XIV, pages 511-611 chapter XV, 61
Pages 2-684 (John Wheelie and Sons Joh
n Wiley & Sons-New York, London-196
(4 years)

Literature

Day M Starmer (DMSturmer)
Written "Heterocyclic Compounds-Special-
Heterocyclic Compounds-Special topics in hete
rocyclic chemistry-) ", Chapter 8, Section 4, 482-5
Page 15 (John Wile and Sons
y & Sons-New York, London-, 1977)

Literature

DJ Fry, "Rodd's Chemistry of Carbon Compounds" (2nd Ed.
vol.IV, part B, 1977) Chapter 15, Chapter 369-
Page 422 (2nd.Ed.vol.IV, part B, 1985) 1st
Chapter 5, pp. 267-296 (ELSVIER SCI ELSVIER SCIENCE PUBLISHING COMPANY INC.
ENCE PUBLISHING COMPANY INC Company-New York-)

As the silver halide used in the present invention,
In addition to the above-mentioned dye sensitizing 700 nm or more, a dye spectrally sensitized with a methine dye or the like may be used in combination as a dye sensitizing wavelengths shorter than this. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, US Pat. No. 4,617,25
7, JP-A-59-180550 and JP-A-60-1403.
No. 35, RD17029 (1978) pages 12 to 13 and the like.

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

Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US (Patent No. 3,615,641 and Japanese Patent Application No. 61-226294).

These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or according to US Pat. Nos. 4,183,756 and 4,225,666, the core of silver halide grains may be added. It may be before or after formation. It may also be the case when other additives are added before coating. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

In the present invention, an organic metal salt may be used as an oxidizing agent 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 those described in US Pat. No. 4,500,6.
There are benzotriazoles, fatty acids and other compounds described in No. 26, columns 52 to 53. In addition, JP-A-60-1
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in 13235, and JP-A-61-161
The acetylene silver described in No. 249044 is also useful. Two or more kinds of organic silver salts may be used in combination.

The above organic silver salts are photosensitive silver halides.
0.01 to 10 moles per mole, preferably 0.1.
01 to 1 mol can be used in combination. 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. Examples thereof include azoles and azaindenes described on pages 24 to 25 of RD17643 (1978), JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, the mercapto compound and its metal salt described in JP-A-59-111636, the acetylene compounds described in JP-A-62-87957 and the like can be used.

A method of emulsifying and dispersing a non-diffusible dye-donating compound with a high boiling point solvent using a surfactant is a method known in the art, and is described in US Pat. No. 2,322,0.
No. 27 and the like show specific examples thereof. High boiling solvents used at this time include those disclosed in JP-A-59-83154 and JP-A-59-83154.
9-178451, 59-178452, 59
-178453, 59-178454, 59-
No. 178455, No. 59-178457, etc.,
Phosphoric acid esters, phthalic acid esters, benzoic acid esters, carboxylic acid esters, carboxylic acid amides and the like can be used. At this time, if necessary, boiling point 5
You may use together the low boiling point organic solvent of 0 degreeC-160 degreeC. The amount of the high boiling point solvent used is 10 g or less, preferably 5 g or less, relative to 1 g of the hydrophobic additive such as the dye-donating compound used. Also, 1 cc or less, particularly 0.3 cc or less is suitable for 1 g of the binder. Anionic, cationic, nonionic, and betaine-based surfactants are known as surfactants used for emulsification and dispersion, but in the present invention, anionic ones are used. Examples of such surfactants include alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyls. Tauric acid, sulfosuccinic acid esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl eicosic acid esters and the like can be mentioned.

The coating solution of the light-sensitive material of the present invention is a mixture of an emulsion of an organic material emulsified and dispersed by the above-mentioned surfactant and a silver halide emulsion having a sensitizing dye having a spectral absorption in infrared adsorbed thereon. It is a liquid and, if necessary, contains a coating aid for improving the coating property. The silver halide emulsion to which a sensitizing dye having a spectral absorption in the infrared is adsorbed, which is used in the light-sensitive material of the present invention, has a high concentration of the above surfactant contained in the emulsified dispersion in the coating liquid. Since the desorption of the sensitizing dye from the silver halide easily occurs, in the present invention, the concentration of the anionic compound including the surfactant in the coating solution needs to be 1% or less.

Among these surfactants, in the present invention, it is particularly preferable to use a surfactant polymer represented by the following general formula. The reason is that the surface active polymer has low solubility in water. Therefore, it is difficult to interact with the silver halide emulsion in the aqueous phase, and desorption of the sensitizing dye from the silver halide is unlikely to occur.

[0076]

[Chemical 6]

In the formula, R is an aliphatic hydrocarbon group having 4 to 22 carbon atoms, which may be linear or branched,
Further, it may have an unsaturated bond. The number of carbon atoms of R is preferably 6 to 18.

Examples of R include alkyl groups such as butyl, octyl, nonyl, dodecyl and octadecyl, and alkenyl groups such as cis-9-octadecenyl group.

A represents an aliphatic divalent group having 1 to 50 carbon atoms, preferably 2 such as an alkylene group, an alkyleneoxy group, a polyacrylyleneoxy group, or an alkyleneoxy-alkylene group. A valent group is included.
Examples thereof include ethylene, trimethylene, octamethylene, ethyleneoxy, polyethyleneoxy, polypropyleneoxy and ethyleneoxy-trimethylene groups.

Examples of the cation or cationic root represented by M include hydrogen, sodium, potassium, lithium, calcium, barium, ammonium, and carbon number 1.
~ 4 alkylammonium and the like.

The above-mentioned surface-active polymer contains at least 5 mol% and preferably at least 10 mol% of the unit represented by the general formula.

The above surface active polymer may be a copolymer or a homopolymer. In the case of a copolymer, the unit represented by the general formula is at least 5 mol% to 95%.
It is particularly preferable that the content of the above units is about 10 to 95 mol%. The unit represented by the general formula and the unit copolymerized may be one type, or two or more types may be used. The unit to be copolymerized has a methylene group. It is a divalent unit composed of a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring may be substituted with various substituents. It is preferred that at least one substituent is substituted.

Examples of the units to be copolymerized include the compound units shown below. However, R ₀ has 4 to 2 carbon atoms
Represents two aliphatic hydrocarbon groups.

[0084]

[Chemical 7]

[0085]

[Chemical 8]

[0086]

[Chemical 9]

[0087]

[Chemical 10]

[0088]

[Chemical 11]

[0089]

[Chemical 12]

[0090]

[Chemical 13]

The molecular weight of the above surface active polymer is not particularly limited, but is preferably 600 to 10,000, particularly preferably 900 to 5,000.

Specific examples of typical surface active polymers represented by the general formula are shown below. (The exemplified compounds are surface active polymers each containing the following structural units in the following proportions.)

[0093]

[Chemical 14]

[0094]

[Chemical 15]

[0095]

[Chemical 16]

[0096]

[Chemical 17]

[0097]

[Chemical 18]

[0098]

[Chemical 19]

Examples of the dye-donating compound used in the present invention include the following two compounds.

(1) A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and releases the diffusible dye by a reaction with an oxidant of a reducing agent. Specifically, British Patent No. 1,330,524, Japanese Patent Publication No. 48-39165,
U.S. Patents 3,443,940 and 4,474,867
No. 4,483,914 and the like.

(2) A compound (DRR compound) which is reducing to a silver halide or an organic silver salt and releases a diffusible dye when the other is reduced. Since this compound does not need to use any other reducing agent, it is preferable because it does not contaminate an image due to oxidative decomposition of the reducing agent. A typical example thereof is US Pat.
28,312, 4,053,312, 4,05
5,428, 4,336,322, JP-A-59-
No. 65839, No. 59-69839, No. 53-381.
9, No. 51-104343, RD17465, U.S. Pat. Nos. 3,725,062, 3,728,113.
No. 3,443,939, JP-A-58-11653.
7, 57-179840, U.S. Pat. No. 4,500,
No. 626, etc.

Among the above-mentioned two kinds of dye-donor compounds, the DRR compound described in (2) is particularly preferable in the present invention.

The color light-sensitive material of the present invention basically has a photosensitive silver halide, a dye-donating compound and a binder on a support. These components are often added to the same layer, but if they are in a reactive state, they can be added separately to separate layers. For example, when a colored dye-donating compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented.

In order to obtain a wide range of colors on the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers having photosensitivity in different spectral regions is used. .. For example, there are combinations of three layers of blue-sensitive layer, green-sensitive layer and red-sensitive layer, green-sensitive layer, red-sensitive layer and infrared-sensitive layer. Each of the light-sensitive layers can take various arrangement orders known in a normal color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary.

The photosensitive material may be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer and a back layer. Further, various filter dyes can be added to improve the color separation property.

These compounds used in the present invention can be synthesized by a conventional method. For example, the synthesis of a formalin polycondensate of alkylphenol is described in Industrial Chemistry Magazine, Vol. 66, 3
91 (1963), Oil Chemistry Vol. 12, 625 (19)
It can be easily synthesized according to the method described in (1988). The introduction of X in the general formula [I] is described, for example, in Industrial Chemistry, Vol. 73, page 563 (1970), Vol. 59, page 221 (1956) and J. Am. Chem. Soc.
77, 2496 (1955), U.S. Pat.
933, 431, 1,968,793, 2,0
It can be synthesized according to the method described in No. 05,619.

The surface-active polymer used in the present invention is either an oil-soluble photographic reagent solution or a colloid aqueous solution (or an aqueous solution containing no hydrophilic colloid), or both, as long as the solubility permits. It can be added.

When a hydrophobic additive containing a dye-donor compound is emulsified and dispersed by the anionic surfactant used in the present invention, an interface between the emulsion and the infrared-sensitive silver halide emulsion in a coating solution. The concentration of the anionic compound including the activator is 1% by weight or less, particularly preferably 0.
3% or less to 0.01% or more.

In the present invention, when the dye-donating compound is co-emulsified with a high boiling point solvent, a method known in the art can be adopted. Examples of the emulsification / dispersion method include the method described in US Pat. No. 2,322,027.

The coating solution containing the infrared-sensitive silver halide emulsion and the dye-donor compound, which is referred to in the present invention, is prepared as follows. A gelatin dispersion of a silver halide emulsion sensitized in the infrared region and an emulsion dispersion of a dye-donor compound are mixed, and various water-soluble additives are added to the mixture. In the present invention, the amount of the anionic surfactant from the emulsified dispersion in the coating liquid thus prepared is 1% by weight or less.

The light source used for exposing the color light-sensitive material of the present invention is a light emitting diode or a semiconductor laser. As the light emitting diode in the present invention, GaAs
P (red), GaP (red, green), GaAsP: N (red,
Yellow), GaAs (infrared), GaAlAs (infrared, red),
GaP: N (red, green, yellow), GaAsSi (infrared), G
Various materials such as aN (blue) and SiC (blue) can be used.

Further, as described above, an infrared-visible conversion element for converting infrared light of the infrared light emitting diode into visible light by using a phosphor can be used. As such a phosphor, a phosphor activated with a rare earth is preferably used, and as the rare earth, Er ³⁺ , Tm ³⁺ , Yb ³⁺ or the like can be used.

Specific examples of the semiconductor laser which can be used in the present invention include In _1-x as a light emitting material.
Ga _x P (up to 700 nm), GaAs _1-x P _x (610
900 nm), Ga _1-x Al _x As (690 to 900 n)
m), InGaAsP (1100 to 1670 nm), Al
A semiconductor laser using a material such as GaAsSb (1250 to 1400 nm) can be given. The color light-sensitive material in the present invention is irradiated with light by the YAG laser (1064n _{) which} excites the Nd: YAG crystal by the GaAs _x P _(1-x) light emitting diode, in addition to the above semiconductor laser.
m).

Further, in the present invention, the second harmonic wave generating element (SHG element) is for converting the wavelength of the laser light into one half by applying the non-linear optical effect. For example, the non-linear optical crystal. Examples include those using CD ^* A and KD ^* P (Laser Handbook, edited by Laser Society, published December 15, 1982, pages 122 to 1).
(See page 39). In addition, Li ⁺ is added to H in the LiNbO ₃ crystal.
A LiNbO ₃ optical waveguide device having an optical waveguide ion-exchanged with ⁺ can be used [NIKKEI ELECTRONICS
1986. 7, 14 (No. 399), pages 89-90].

As the other light source, a light source such as natural light, a tungsten lamp or a CRT light source can be used.

Each component of the light-sensitive material and the dye-fixing material used in the present invention, the layer constitution, the composition in each layer, the additive in the composition, the image used in combination with the light-sensitive material and the dye-fixing material Regarding the forming system, the material for forming the image, the image forming conditions, etc., JP-A-3-1604
The description from page 44, lower right column, line 18 to page (23) upper right column, line 7 can be applied.

In the present invention, the light emitting diode or the semiconductor laser is preferably used as the exposure light source as described above.

However, depending on the case, for example, a method of directly photographing a landscape or a person with a camera or the like, a method of exposing through a reversal film or a negative film with a printer, an enlarger or the like may be used.

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

When the present invention is used as a heat-developable color light-sensitive material and is subjected to heat-development, the heating temperature in the heat-development step is from about 50 ° C to about 250 ° C.
~ 180 ° C is useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the end of the heat development process. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is more preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

In such a heat-developable color light-sensitive material, the total film thickness of each layer coated on the support is 15 in terms of dry film thickness.
It is less than or equal to μ.

In the present invention, a solvent may be used to promote dye transfer. Hereinafter, JP-A-2-16044
The description from page 4, upper left column, line 6 to page 4, lower right column, line 4 of Publication No. 4 can be applied.

Further, a silver halide emulsion layer, a coloring material layer, an intermediate layer, a protective layer and the like can be selected as the addition layer of the emulsion dispersion, but in the present invention, it is added to the silver halide emulsion layer. Is preferred. There are two reasons.
First, the reaction between the silver halide and the dye-donor compound during development occurs most efficiently. The other is that sharpness is improved by the anti-irradiation effect of the filter dye. The latter effect is particularly remarkable in the false color light-sensitive material. The higher the extinction coefficient of the filter dye, the more preferable. The addition amount can be widely selected, but the molar extinction coefficient (ε) of 10,000 to
In the case of dyes in the range of 500000, 0.1 mg / m ² ~
It is 10 g, preferably 5 mg to 500 mg. The weight ratio of the filter dye to the dye donating compound is 0.01 to 100, preferably 0.1 to 10.

The color light-sensitive material of the present invention is of a diffusion transfer type and is used in an image forming method in which a diffusible dye formed imagewise is transferred to a dye fixing material which is an image receiving material. The color light-sensitive material may be either an instant photographic system containing a developing solution or a dry heat development processing system by heating, and the system is not particularly limited. However, it is preferable to use the heat development method.

The color light-sensitive material of the present invention basically has a photosensitive silver halide, a dye-donating compound (which may also serve as a reducing agent as described later) and a binder on a support. Further, if necessary, an organic metal salt oxidizing agent or the like can be added. These components are often added to the same layer, but if they are in a reactive state, they can be added separately to separate layers. For example, when a colored dye-donating compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented. Although the reducing agent is preferably incorporated in the light-sensitive material, it may be supplied from the outside by, for example, a method of diffusing from a dye-fixing material described later.

In order to obtain a wide range of colors on the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers sensitive to different spectral regions is used. .. For example, there are combinations of three layers of blue-sensitive layer, green-sensitive layer and red-sensitive layer, green-sensitive layer, red-sensitive layer and infrared-sensitive layer. Each of the light-sensitive layers can take various arrangement orders known in a normal color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary.

For the color light-sensitive material, a protective layer, an undercoat layer,
It can be provided in various auxiliary layers such as an intermediate layer, an antihalation layer and a back layer. Further, in the present invention, at least one layer containing the co-emulsified dispersion of the filter dye and the dye-providing compound is provided, which is for the following reason.

For example, layer A spectrally sensitized to 810 nm
When the layer B spectrally sensitized to 750 nm is provided on the top,
When exposure is performed from the layer B side with 0 nm light, the color of the layer A is mixed in a highly exposed portion, that is, a portion having a large amount of light, resulting in insufficient color separation. This tendency becomes remarkable especially when the sensitivity of the layer A spectrally sensitized to 810 nm is high.

Therefore, in the layer A or in the layer between the layer A and the layer B, there is no substantial absorption in the vicinity of the spectral sensitization peak of the layer A. Shortwave and layer B
By incorporating a dye having an absorption maximum wavelength (λmax) at a position capable of absorbing the light emitted from the light source used for the exposure, the spectral sensitized portion on the short wave side of layer A is cut to improve color separation.

The silver halide usable in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide.

The silver halide emulsion used in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging. Further, it may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.1 to 2 µ, and particularly preferably 0.2 to 1.5 µ. The crystal habit of the silver halide grains may be cubic, octahedral, tetrahedral, tabular with a high aspect ratio, or the like.

Specifically, US Pat. No. 4,500,626, column 50, US Pat. No. 4,628,012, Research Disclosure (hereinafter abbreviated as RD) 17029 (19).
1978), any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

The silver halide emulsion may be used as it is after ripening, but it is usually chemically sensitized before use. The known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method and the like can be used alone or in combination for the emulsion for a conventional type light-sensitive material.
These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

The silver halide used in the present invention may be spectrally sensitized with a methine dye or the like in addition to the infrared sensitization. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, US Pat. No. 4,617,257
No. 59-180550, 60-14033.
No. 5, RD17029 (1978) pages 12 to 13 and the like.

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

Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Patent No. 3615641, Japanese Patent Application No. 6
No. 1-222694, etc.).

These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or before or after the nucleation of silver halide grains according to US Pat. Nos. 4,183,756 and 4,225,666. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide. The use of an organic metal salt is particularly preferable in the photothermographic element. 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 US Pat. No. 4,500,626.
There are benzotriazoles, fatty acids and other compounds described in Nos. 52 to 53 and the like. In addition, JP-A-60-1132
No. 35, a silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolate, and JP-A-61-249.
Acetylene silver described in No. 044 is also useful. Two or more kinds of organic silver salts may be used in combination.

The above organic silver salts are photosensitive silver halides.
0.01 to 10 moles per mole, preferably 0.1.
01 to 1 mol can be used in combination. 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.
As an example, RD17643 (1978) 24-
Azoles and azaindenes described on page 25, JP-A-5
Nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-9-168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, JP-A-62-8.
The acetylene compounds described in 7957 are used.

As the reducing agent used in the present invention, those known in the field of diffusion transfer type color light-sensitive materials can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property by itself but exhibits a reducing property by the action of a nucleophile, an alkali 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 49-50, 44
No. 83, col. 30, columns 31-43617;
No. 4,590,152, JP-A No. 60-140335, pages (17) to (18), Nos. 57-40245, 56.
-138736, 59-178458, 59-
No. 53831, No. 60-182449, No. 59-18
No. 2450, No. 60-119555, No. 60-128
436 to 60-128439, 60-1
No. 98540, No. 60-181742, No. 61-25.
9253, 624244044, 62-131
From 253 to 62-131256, there are reducing agents and reducing agent precursors described in EP 220746A2, 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, if necessary, an electron transfer agent and / or an electron transfer agent may be added 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.

In addition, as a dye-donor compound, a dye silver compound in which an organic silver salt and a dye are bound (Research Disclosure, May 1978, p. 54-58, etc.), an azo used in a heat-developable silver dye bleaching method Dye (US Patent No. 4
No. 235957, Research Disclosure, 1
(April 976, pages 30 to 32, etc.), leuco dyes (US Pat. Nos. 3,985,565 and 4,022,617, etc.) can also be used.

Hydrophobic additives such as dye-donor compounds, filter dyes, water-insoluble dyes and diffusion-resistant reducing agents should be incorporated into the layers of the light-sensitive material by known methods such as the method described in US Pat. No. 2,322,027. You can In this case, JP-A-59-83154 and JP-A-59-178451.
No. 59-178452 and No. 59-178453.
Issue 59-178454, Issue 59-178455.
No. 59-178457 and the like, a high boiling point organic solvent can be used in combination with a low boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary.

The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less based on 1 g of the dye-donor compound used. Also, 1 cc or less, more preferably 0.5 cc or less, especially 0.3 cc or less is suitable for 1 g of the binder.

JP-B-51-39853, JP-A-51-
A dispersion method using a polymer described in 59943 can also be used.

In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method.

When dispersing the hydrophobic compound in the hydrophilic colloid as the binder, various surfactants can be used. For example, the surfactants listed on pages (37) to (38) of JP-A-59-157636 can be used.

[0153]

EXAMPLE A method for preparing the silver halide emulsion (I) for the third and first layers will be described.

A well stirred gelatin aqueous solution (water 10
600 ml of an aqueous solution 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, and an aqueous solution of silver nitrate (600 ml of water in which 0.59 mol of silver nitrate is dissolved). )
Were added simultaneously at equal flow rates over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 50 mol%) 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 carried out at 60 ° C. The yield of emulsion was 600 g.

Next, a silver halide emulsion (II) for the fifth layer
Describe how to make.

A well stirred gelatin aqueous solution (water 10
600 ml of an aqueous solution 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, and an aqueous solution of silver nitrate (600 ml of water in which 0.59 mol of silver nitrate is dissolved). )
Were added simultaneously at equal flow rates 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 carried out at 60 ° C. The yield of emulsion was 600 g.

Next, a method for preparing a gelatin dispersion of zinc hydroxide will be described.

12.55 g of zinc hydroxide having an average particle size of 0.25 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 cc of a 4% gelatin aqueous solution, and the average particle size was 0.75 mm with a mill.
The glass beads were crushed for 30 minutes. The glass beads were separated to obtain a gelatin dispersion of zinc hydroxide.

Next, a method for preparing a gelatin dispersion of the hydrophobic additive will be described. The oil phase components shown in the table below were each dissolved in 250 cc of ethyl acetate to obtain a uniform solution at 60 ° C.
To this, add the water phase component heated to 60 ℃, and use a disperser with a diameter of 8 cm for 30 minutes at 5000 rp.
dispersed at m. To this was added post-hydration and stirred to form a uniform dispersion. This is referred to as the hydrophobic additive gelatin dispersion.

[0162]

[Table 1]

Using these materials and the following materials, a heat developable color light-sensitive material 101 having a multilayer structure shown in Table 1 and a dye fixing material R-1 having a structure shown in Table 2 were prepared.

[0164]

[Table 2]

[0165]

[Table 3]

[0166]

[Table 4]

[0167]

[Table 5]

[0168]

[Table 6]

[0169]

[Chemical 20]

[0170]

[Chemical 21]

[0171]

[Chemical formula 22]

[0172]

[Chemical formula 23]

[0173]

[Chemical formula 24]

[0174]

[Chemical 25]

[0175]

[Chemical formula 26]

[0176]

[Chemical 27]

Next, with respect to the light-sensitive material 101, the same light-sensitive material 102 as in 101 except that the kind and concentration of the surfactant of the emulsion of each light-sensitive layer were changed as shown in Table 3. 110 were created respectively. Further, photosensitive materials 201-210 were prepared by coating the coating solutions for the photosensitive layers of the photosensitive materials 101 to 110 at 40 ° C. for 6 hours and then applying the solutions.

[0178]

[Table 7]

The above-mentioned multilayer color photosensitive material 101-1.
10 and 201-210 were exposed using a semiconductor laser exposure machine having the following specifications.

[0180]

[Table 8]

This exposed light-sensitive material was drawn at a linear velocity of 20 mm / sec.
While feeding, the emulsion surface was fed with 15 ml / m ² of water by a wire bar, and immediately thereafter, the emulsion was superposed so that the image receiving material and the film surface were in contact with each other.

Using a heat roller whose temperature was adjusted so that the water-absorbed film had a temperature of 83 ° C., it was heated for 25 seconds.

Next, when peeled off from the image receiving material, a clear transferred image was uniformly obtained on the image receiving material. About this transferred image, 20 times for each of the photosensitive materials 101-110.
Table 4 shows the sensitometric results of how much the sensitivity of 1-210 changed at a concentration of 0.5.

[0184]

[Table 9]

From Table 4, it can be seen that in the sample of the present invention, the sensitivity deterioration in the infrared region was suppressed even in the sample in which the coating solution was left in a dissolved state for 6 hours.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 1, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

[Correction method] Change

[Correction content]

[Chemical 1] In the formula, R represents an aliphatic hydrocarbon group having 4 to 22 carbon atoms. m ₁ and m ₂ each represent 0 or 1. B represents -O- or -NH-. A is 1 carbon atom
Represents an aliphatic divalent group having -50. X is -SO ₃
- or -CO ₂ - represents a. M represents a cation capable of forming a salt with X or a cationic root.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

Due to the need for color hard copy as described above, in recent years, an image forming method of a light-sensitive material using silver halide has been changed from a conventional wet process to an instant photographic system containing a developing solution, and further. A system capable of simply and quickly obtaining an image has been developed by a dry heat development process such as heating. The simple and rapid processing method described above often employs a method of forming an image by a diffusion transfer method in order to prevent the image from being contaminated by a printout of silver halide after the image is formed.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

According to the above method, the developing temperature is high and the stability of the photosensitive material with time cannot be said to be sufficient. Therefore, a method of accelerating the development, lowering the development temperature and simplifying the processing by heating and developing a base or a base precursor in the presence of a trace amount of water to transfer the dye is disclosed in JP-A-59-21844.
No. 3, 61-238056, European Patent 210, 66.
0A2 and the like.

[Procedure amendment 4]

[Document name to be amended] Statement

[Item name to be corrected] 0040

[Correction method] Change

[Correction content]

The nucleus formed by Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ is a thiazole nucleus {thiazole nucleus (eg thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole , 4, 5
-Diphenylthiazole), a benzothiazole nucleus (for example, benzothiazole, 4-chlorobenzothiazole,
5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-
Bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-
Phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole,
5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole), naphthothiazole nucleus (for example, naphtho [2,1-d ] Thiazole, naphtho [1,2
-D] thiazole, naphtho [2,3-d] thiazole,
5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] Thiazole)}, thiazoline nucleus (for example, thiazoline, 4-methylthiazoline, 4-nitrothiazoline), oxazole nucleus {oxazole nucleus (for example, oxazole, 4-methyloxazole, 4-nitroxazole, 5-methyloxazole, 4-phenyl) Oxazole, 4,5-diphenyloxazole, 4
-Ethyloxazole), a benzoxazole nucleus (for example, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-
Phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole,
6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-
Dimethylbenzoxazole, 5-ethoxybenzoxazole), naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5-
Nitronaphtho [2,1-d] oxazole)}, an oxazoline nucleus (eg, 4,4-dimethyloxazoline),
Selenazole nucleus (selenazole nucleus (for example, 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzoselenazole nucleus (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-
Nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole), naphthoselenazole Nuclear (eg naphtho [2,1
-D] selenazole, naphtho [1,2-d] selenazole)}, selenazoline nucleus (eg, selenazoline, 4-
Methyl selenazoline), tellurazole nucleus {terrazole nucleus (eg, tellurazole, 4-methylterrazole,
4-phenylterrazole), a benzoterrazole nucleus (for example, benzoterrazole, 5-chlorobenzoterrazole, 5-methylbenzoterrazole, 5,6-dimethylbenzotelrazole, 6-methoxybenzoterrazole), naphtho Tellurazole nucleus (for example, naphtho [2,1-d] telrazole, naphtho [1,2-d] telrazole)}, tellrazoline nucleus (for example, tellrazoline, 4-methylterrazoline), 3,3-dialkylindolenine nucleus (For example, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-6-nitroindolenine, 3,3-dimethyl-5. -Nitroindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3,5-trimethyl Indolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus (imidazole nucleus (e.g., 1-alkylimidazole, 1-alkyl-4-phenylimidazole, 1-arylimidazole), benzimidazole nucleus (e.g., 1-alkylbenzimidazole, 1-alkyl-
5-chlorobenzimidazole, 1-alkyl-5,6
-Dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl -6-chloro-5
-Cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-
Allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1- Aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole), naphthoimidazole nucleus (for example, -alkylnaphtho [1,2-d] imidazole, 1-arylnaphtho [1,2-d] imidazole) The above-mentioned alkyl groups are those having 1 to 8 carbon atoms, for example, unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl, and hydroxyalkyl groups (eg 2-hydroxyethyl, 3-hydroxypropyl). preferable. Particularly preferred are methyl group and ethyl group. The above aryl group is
Represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. }, A pyridine nucleus (eg, 2-pyridine, 4-pyridine, 5-methyl-
2-pyridine, 3-methyl-4-pyridine), quinoline nucleus {quinoline nucleus (eg, 2-quinoline, 3-methyl-
2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6
-Hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline, 6-ethoxy-4-quinoline, 6-
Nitro-4-quinoline, 8-chloro-4-quinoline, 8
-Fluoro-4-quinoline, 8-methyl-4-quinoline, 8-methoxy-4-quinoline, 6-methyl-4-quinoline, 6-methoxy-4-quinoline, 6-chloro-4
-Quinoline), isoquinoline nuclei (eg 6-nitro-
1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline)}, imidazo [4,5-b] quinoxaline nucleus (eg 1,3-diethylimidazo [4,5-b]) Examples thereof include quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, and pyrimidine nucleus.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

Iodine ion, aryldisulfonate ion, alkylsulfate ion and perchlorate ion are preferred.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0075

[Correction method] Change

[Correction content]

Among these surfactants, in the present invention, it is particularly preferable to use a surfactant polymer containing a repeating unit represented by the following general formula. The reason is that the surface active polymer has low solubility in water. Therefore, it is difficult to interact with the silver halide emulsion in the aqueous phase, and desorption of the sensitizing dye from the silver halide is unlikely to occur.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0079

[Correction method] Change

[Correction content]

A represents an aliphatic divalent group having 1 to 50 carbon atoms, preferably 2 such as an alkylene group, an alkyleneoxy group, a polyacrylyleneoxy group, or an alkyleneoxy-alkylene group. A valent group is included.
For example, ethylene, trimethylene, octamethylene, ethyleneoxy, polyethyleneoxy, polypropyleneoxy, ethyleneoxy-trimethylene group and the like can be mentioned. B represents -O- or -NH-. m ₁ and m ₂ each represent 0 or 1.

Claims (2)

[Claims] 1. A support comprising at least one photosensitive silver halide spectrally sensitized in the infrared region, a binder, and a diffusible dye corresponding to the reaction in which the silver halide is reduced to silver. Has a non-diffusible dye-donor compound that releases,
In a heat-development diffusion transfer type color light-sensitive material in which the non-diffusible dye-donor compound is emulsified and dispersed together with a high boiling point solvent using an anionic surfactant, the infrared-sensitive silver halide and the dye-donor compound A heat-development diffusion transfer type color light-sensitive material, characterized in that the concentration of the anionic compound in the coating liquid containing is 1% by weight or less. 2. The heat-development diffusion transfer type color according to claim 1, wherein the anionic surfactant used for emulsification and dispersion is a compound represented by the following general formula [I]. Photosensitive material. General formula [I] In the formula, R represents an aliphatic hydrocarbon group having 4 to 22 carbon atoms. m ₁ and m ₂ each represent 0 or 1. B represents -O- or -NH-. A is 1 carbon atom
Represents an aliphatic divalent group having -50. X is -SO ₃
- or -CO ₂ - represents a. M represents a cation capable of forming a salt with X or a cationic root.