JP2890199B2 - Color photosensitive material - Google Patents

Description

The present invention relates to a color light-sensitive material, and more particularly to a color light-sensitive material.
The present invention relates to a color light-sensitive material that can be used for different types of light sources.

(Background Art) Silver halide color light-sensitive materials have extremely high image quality,
It is used in many fields.

On the other hand, with the advancement of professional imaging equipment due to the recent advancement of office automation, the appearance of electronic still cameras, the spread of video and facsimile, the advancement of computer graphics, the development of image sensors and the advancement of digital processing technology for original images, etc. There is an increasing demand for obtaining a color hard copy from image information converted into an electric signal.

Conventional color light-sensitive materials usually have blue, green, and red spectral sensitivities. To obtain an image on such a color light-sensitive material by using image information once converted into an electric signal, a color is required.
It is common to use CRTs (cathode ray tubes), but CRTs are not suitable for obtaining large prints.

Also, light emitting diodes (LEDs) and semiconductor lasers have been developed as optical writing heads capable of obtaining large-sized prints. However, those optical writing heads that efficiently emit blue light have not been developed.

Therefore, for example, when a light emitting diode is used, a light source that combines three light emitting diodes of near infrared (800 nm), red (670 nm), and yellow (570 nm) is spectrally sensitized to near infrared, red, and yellow. It is necessary to expose a color light-sensitive material having two layers, and a system for recording an image with such a configuration is called "Nikkei New Materials", September 14, 1987.
It is described on pages 47-57 of the JP publication and is partially used.

Japanese Patent Application Laid-Open No. 61-137149 discloses a system for recording on a color photosensitive material having three photosensitive layers having a spectral sensitivity at each wavelength with a light source combining three semiconductor lasers emitting at 880 nm, 820 nm and 760 nm. Are listed.

However, the color photosensitive materials used in these conventional systems, for example, those having three photosensitive layers of blue, green, and red cannot be used for image reproduction using an optical writing head such as a light emitting diode or a semiconductor laser. And
In addition, color light-sensitive materials having three light-sensitive layers spectrally sensitized to near infrared, red, and yellow cannot be used for photographing landscapes or recording visible light such as ordinary color CRTs. It is limited to image reproduction by a specific light source.

(Problems to be Solved by the Invention) An object of the present invention is to provide a color light-sensitive material that can be used for at least two different light sources.

(Means for Solving the Problems) An object of the present invention is to provide at least three photosensitive layers having different color sensitivities on a support and containing at least a photosensitive silver halide, a binder and a dye-providing compound in combination. Wherein at least one of the layers has a spectral sensitivity peak at at least two wavelengths separated by 50 nm or more, and at least one of the spectral sensitivity peaks has a wavelength of 700 nm or more. Color photosensitive material.

The color light-sensitive material of the present invention basically has three light-sensitive layers having different color sensitivities on a support,
Each of the photosensitive layers contains a combination of a photosensitive silver halide, a binder and a dye-donating compound. Here, the term "containing in combination" means that not only the mode in which the photosensitive silver halide and the dye-donating compound are added together with the binder to the same layer, but also the state in which each of the photosensitive silver halide and the dye-donating compound can be reacted with a separate layer together with the binder. It is an expression including a certain aspect.

Each color-sensitive layer may also be divided into two or more layers having different sensitivities.

In the present invention, at least one of these color-sensitive layers has two or more spectral sensitivities separated from each other by 50 nm or more, and at least one of them has a spectral sensitization peak of 700 nm.
Set above.

Examples of the layer constitution of the color light-sensitive material of the present invention are shown below, but the present invention is not limited thereto.

(I) a color light-sensitive material having blue, green, and red color-sensitive layers, i) an embodiment in which the blue color-sensitive layer has a spectral sensitivity of 700 nm or more; (C) an embodiment in which the red color-sensitive layer has a spectral sensitivity even at 700 nm or more.

In each of the above embodiments a), b) and c), this 700 nm
The above spectral sensitization peak is the same as the spectral sensitization peak of the red color sensitive layer.
It must be at least 50 nm apart.

In each of the above embodiments, the yellow dye-donating compound is combined with the green color-sensitive layer, the magenta dye-donating compound is combined with the green color-sensitive layer, and the cyan dye-donating compound is combined with the red color-sensitive layer. Is preferred.

When a colored dye-providing compound is used, if the exposure is performed from the emulsion layer side, it is preferable from the standpoint of color separation that the layer farthest from the support contains a yellow dye-providing compound. Further, it is preferable that the layer closest to the support contains a cyan dye-donating compound. When exposure is performed from the support side using a transparent support, the reverse configuration is preferable.

When an uncolored dye-providing compound is used, a yellow filter layer is preferably provided to prevent the green and red color-sensitive layers from being exposed to blue light.

Among the above embodiments a), b) and c), the embodiment a) is particularly preferred.

(II) In a color light-sensitive material having green-yellow, red and infrared color-sensitive layers, d) an embodiment in which the green-yellow color-sensitive layer has a spectral sensitivity even at 700 nm or more; A) an embodiment in which the red color-sensitive layer has spectral sensitivity even at 700 nm or more; f) an embodiment in which the infrared color-sensitive layer has spectral sensitivity at 700 nm or more.

Note that, in each of the above embodiments d) e) and f), this 700 nm
It is necessary that the above-mentioned spectral sensitization peaks are at least 50 nm apart from the spectral sensitization peaks of the red and original infrared color-sensitive layers.

In each of the above embodiments (d), (e) and (f), a yellow dye-donating compound is applied to the green-yellow color-sensitive layer, a magenta dye-donating compound is applied to the red color-sensitive layer, and an infrared color-sensitive layer is applied to the infrared color-sensitive layer. It is preferable to combine cyan dye-donating compounds. Further, in each of the above embodiments, similarly to the above-mentioned embodiments a) and b), when a colored dye-providing compound is used,
It is preferable to provide an emulsion layer containing a yellow dye-donating compound on the side closest to the light source and provide an emulsion layer containing a cyan dye-donating compound on the farthest side. Further, when a non-colored dye-providing compound is used, it is preferable to provide a yellow filter layer on the emulsion layer closest to the exposure light source.

As a method of exposing and recording an image on a photosensitive material, for example, a layer containing a yellow dye-donating compound is blue, a layer containing a magenta dye-donating compound is green, and a layer containing a cyan dye-donating compound is red. If each is spectrally sensitized,
In the case of a light-sensitive material in which the infrared sensitizing dye having a wavelength of 700 nm or more of the present invention is further added to a layer containing a yellow dye-donating compound, the following applications can be considered.

In other words, using blue, green, and red spectral sensitization, a method of directly photographing landscapes and people using a normal camera, a method of exposing through a reversal film or a negative film using a printer or a enlarger, and copying. A method of scanning and exposing an original image through slits or the like using an exposure device of a machine, or outputting image information to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a pragma display, or directly or an optical system. And the like.

Further, image information can be recorded via electric signals using green, red and infrared light emitting diodes as light sources using green, red and infrared spectral sensitization using the same photosensitive material.

That is, this photosensitive material can be used for two kinds of uses with one photosensitive material.

As another example, the layer containing the yellow dye-donating compound is yellow, the layer containing the magenta dye-donating compound is red,
In the case where the layer containing the cyan dye-donating compound is spectrally sensitized to the near infrared of 810 nm, and in the case of a photosensitive material in which a 750 nm infrared sensitizing dye is further added to the layer containing the yellow dye-donating compound, The following applications are possible.

Using yellow and red and spectral sensitization of 810 nm to record an image via an electric signal with a light emitting diode, and using red and 750 nm and 810 nm spectral sensitization to record an image with a semiconductor laser via an electric signal Can also be used. Various other combinations are conceivable.

The image information is an image signal obtained from a video camera, an electronic still camera, or the like. A TV signal represented by the Nippon Television System (NTSC), an image signal obtained by dividing an original image into a number of images such as a scanner. It can use image signals produced using computers represented by CG, CG, and CAD.

As the light emitting diode of the light source used in the present invention,
GaAsP (red), GaP (red, green), GaAsP: N (red, yellow), GaAs
s (infrared), GaAlAs (infrared, red), GaP: N (red, green,
Yellow), GaAsiSi (infrared), GaN (blue), Sic (blue), etc.
Various types can be used.

Further, an infrared-visible conversion element that converts infrared light of the infrared light-emitting diode into visible light by a phosphor can be used. As such a phosphor, a phosphor activated with a rare earth is preferably used.
r ³⁺ , Tm ³⁺ , Yb ^{3+ and the} like can be used.

As a specific example of a semiconductor laser that can be used in the present invention, In _1-x G _ax P (x700 n
m), GaAs _1-x P _x (610-900 nm), Ga _1-x Al _x As (690-900 nm)
nm), InGaAsP (1100-1670 nm), AlGaAsSb (1250-140
0 nm). Irradiation of light to the color photosensitive material in the present invention, in addition to the above-described semiconductor laser, Nd: YAG crystal GaAs _x P _(1-x)
A YAG laser (1064 nm) excited by a light emitting diode may be used.

In the present invention, the second harmonic generation element (SHG element) converts the wavelength of laser light to half by applying a nonlinear optical effect. For example, a CD ^{* is used} as a nonlinear optical crystal ^. Examples using A and KD ^* P (Laser Handbook, edited by The Laser Society of Japan, December 15, 1982)
Jpn., Pp. 122-139). Also, LiNbO ₃ crystal contains Li
A LiNbO ₃ optical waveguide device having an optical waveguide formed by ion-exchanging ⁺ with H ⁺ can be used (NIKKEI ELECTRONICS 1
986.7.14. (No. 399) pp. 89-90.

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

The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. A so-called core shell emulsion in which the inside of the grains and the surface layer of the grains have different phases may be used. The silver halide emulsion may be monodispersed or polydispersed, or a mixture of monodispersed emulsions may be used. Particle size is 0.1 ~
2μ, especially 0.2-1.5μ, is preferred. The crystal habit of the silver halide grains may be any of cubic, octahedral, tetrahedral, high aspect ratio tabular, and the like.

Specifically, U.S. Patent No.
Any of the silver halide emulsions described in No. 28,021, Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (1978), and JP-A No. 62-253159 can be used.

The silver halide emulsion may be used as it is after unripe, but usually it is used after chemical sensitization. A known sulfur sensitization method, reduction sensitization method, noble metal sensitization method, or the like can be used alone or in combination for an emulsion for a normal photosensitive material. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-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.

When used in addition to the silver halide used in the heat-developable color light-sensitive material of the present invention, a sensitizing dye having a spectral sensitizing peak of 700 nm or more has the following structure, but is not limited thereto. Not something.

In the formula, Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ each represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring.

D ₁ and D ₁ ′ represent an atomic group necessary for forming an acidic nucleus, and 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 each represents a methine group.

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

l ₁ represents ₁ , 2 or 3.

However, when l ₁ is 1, Z ₁ and Z ₂ represent a 4-quinoline nucleus or a 4-pyridine nucleus.

When l ₂ is 2, at least one of Z ₁ and Z ₂ is 4-
Represents a quinoline nucleus and a 4-pyridine nucleus.

l ₂ represents 2 or 3.

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

l ₃ is 1, 2 or 3, l ₄ represents 0, 1 or 2.
However, l ₃ + l ₄ represents 2 or more.

M ₁ , M ₂ and M ₃ represent charge-balancing counterions, m ₁ , m ₂
And m ₃ is a number greater than or equal to 0 required to balance the charges.

The nucleus formed by Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ includes a thiazole nucleus and a thiazole nucleus (for example, thiazole,
4-methylthiazole, 4-phenylthiazole, 4,5
-Dimethylthiazole, 4,5-diphenylthiazole), benzothiazole nucleus (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzo) Thiazole, 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-methylbenzothial, tetrahydrobenzothiazole, 4-phenylbenzothiazole, a 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 A nucleus (e.g., oxazole, 4-methyloxazole, 4
-Nitrooxazole, 5-methyloxazole, 4-
Phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), 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)}, oxazoline nucleus (eg, 4,4-dimethyloxazoline), selenazole nucleus selenazole nucleus (eg, 4-methylselenazole, 4-nitroselenazole, 4-phenylselena) Benzo), benzoselenazole nucleus (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5
-Hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole), naphthoselenazole nucleus (for example, naphtho [2,1-d] selenazole , Naphtho [1,2-d] selenazole)}, selenazoline nucleus (for example, selenazoline, 4-methylselenazoline), tellurazole nucleus {tellurazole nucleus (for example, tellurazole, 4-methyltellurazole, 4-phenyltellurazole) A benzotellurazole nucleus (for example, benzotellurazole, 5-chlorobenzotellurazole, 5-methylbenzotellurazole, 5,6-dimethylbenzotellurazole, 6-methoxybenzotellurazole), a naphthotellurazole nucleus (for example, Naphtho [2,1-d] tellurazole, naphtho [1,2-d] tellurazole }, Terurazorin nucleus (e.g., Terurazorin, 4-methyl shine ethylbenzthiazoline), 3,3-dialkylindolenine nucleus (e.g., 3,3
Dimethylindolenine, 3,3-diethylindolenine,
3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-6-nitroindolenine, 3,3-dimethyl-5-nitroindolenin, 3,3-dimethyl-5-methoxyindolenine, 3,3 3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus ｛imidazole nucleus (for example, 1-alkylimidazole,
-Alkyl-4-phenylimidazole, 1-arylimidazole), benzimidazole nucleus (for example, 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 ), Said alkyl group having 1 to 8 carbon atoms,
For example, methyl, ethyl, propyl, isopropyl,
Preferred are an unsubstituted alkyl group such as butyl and a hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl). Particularly preferred are a methyl group and an ethyl group. The aforementioned aryl groups include phenyl, halogen (eg, chloro) substituted phenyl, alkyl (eg, methyl)
Substituted phenyl, alkoxy (eg methoxy) substituted phenyl; ｝, Pyridine nucleus (for example, 2-pyridine, 4-pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine), quinoline nucleus ｛quinoline nucleus (for example, 2-quinoline, 3-methyl-2-pyridine) 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 nucleus (for example, 6-nitro-1-isoquinoline, 3,
4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline)}, imidazo [4,5-d] quinoxaline nucleus (for example, 1,3-diethylimidazo [4,5-b] quinoxaline, 6-chloro- 1,3-diallylimidazo [4,5-b]
Quinoxalin), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus and pyrimidine nucleus.

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

D ₁ and D ₁ ′ represent a group of atoms necessary for forming an acidic nucleus, and 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, and D ₁ ′ represents the remaining group of atoms necessary to form an acidic nucleus.

When the acidic nucleus is acyclic, i.e. when D ₁ and D ₁ 'are independent groups, the terminus of the methine bond may be such as malononitrile, alkylsulfonylacetonitrile, cyanomethylbenzofuranyl ketone or cyanomethylphenyl ketone. Group.

D ₁ , D ₁ ′ together form carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium, and tellurium)
Form a 5- or 6-membered heterocyclic ring of atoms. Preferably, D ₁ and D ₁ ′ are joined together to complete the next nucleus.

2-pyrazolin-5-one, pyrazolidin-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-
4-one, 2-oxazoline-5-one, 2-thiooxazolidin, 2,4-dione, isoxazolin-5-one, 2-thiazolin-4-one, thiazolidine-4-one, thiazolidine-2,4- Dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indan-
1,3-dione, thiophen-3-one, thiophen-3
-One-1,1-dioxide, indoline-2-one, indoline-3-one, indazolin-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 -The core of dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazolin-2-one or pyrido [1,2-a] pyrimidin-1,3-dione.

More preferably, a 3-alkylrhodanine nucleus,
Alkyl-2-thiohydantoin nucleus, 3-alkyl-2
Thiooxazolidine-2,4-dione nucleus.

Assuming that the substituent bonded to the nitrogen atom contained in the nucleus is R ₇ , this substituent R ₇ is a hydrogen atom, an alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms ( For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, octadecyl group), substituted alkyl group {eg, aralkyl group (eg, benzyl group, 2-phenylethyl group) A hydroxyalkyl group (e.g., 2-hydroxyethyl group, 3-hydroxypropyl group), a carboxyalkyl group (e.g., 2-carboxyethyl group,
3-carboxypropyl group, 4-carboxybutyl group,
Carboxymethyl 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), sulfatoalkyl group (for example, 3-sulfatopropyl) Group,
4-sulfatobutyl group), heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-yne) ethyl group, tetrahydrofurfuryl group, 2-morpholinoethyl group), 2-acetoxyethyl group, carbomethoxymethyl Group, 2-methanesulfonylaminoethyl group, allyl group, aryl group (for example, phenyl group, 2-naphthyl group), substituted aryl group (for example, 4-carboxyphenyl group, 4-sulfophenyl group, 3-chlorophenyl group,
A 3-methylphenyl group) and a heterocyclic group (for example, a 2-pyridyl group, a 2-thiazolyl group) are preferred.

More preferably, they are an unsubstituted alkyl group (for example, methyl group, ethyl group, pentyl group) and a carboxyalkyl group (for example, carboxymethyl group, 2-carboxyethyl group).

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are preferably an unsubstituted alkyl group having 18 or less carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, decyl group, dodecyl A carboxy group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom,
It is a bromine atom. ), A hydroxy group, an alkoxycarbonyl group having 8 or less carbon atoms (for example, a methoxycarbonyl group,
Ethoxylbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group), alkoxy group having 8 or less carbon atoms (for example, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group), monocyclic aryl having 10 or less carbon atoms Oxy group (for example, phenoxy group, p-tolyloxy group), acyloxy group having 3 or less carbon atoms (for example, acetyloxy group, propionyloxy group), acyl group having 8 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl group, mesyl group) A) carbamoyl group (e.g., carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), sulfamoyl group (e.g., sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, Piperidinosulfonyl group), carbon number 10 or less Aryl groups (e.g., phenyl, 4-chlorophenyl, 4-methylphenyl,
an alkyl group 炭素 having 18 or less carbon atoms, which is substituted with an α-naphthyl group).

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

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

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 are methine groups ｛substituted or unsubstituted alkyl groups (eg, methyl group, ethyl group, 2-carboxyethyl group), substituted or unsubstituted aryl group (eg, phenyl group, o-carboxyphenyl group), halogen atom (eg, chlorine atom, bromine atom), alkoxy group (eg, methoxy group, ethoxy group), alkylthio Group (eg, methylthio group, ethylthio group), and the like. And may form a ring with another methine group, or may form a ring with an auxochrome.

M ₁ m ₁ , M ₂ m ₂ and M ₃ m ₃ are used in the formula to indicate the presence or absence of a cation or an anion when necessary to neutralize the ionic charge of the dye. Is included. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents.

Typical cations are ammonium and alkali metal ions, while the anion can be specifically an inorganic or organic anion, such as a halogen anion (eg, fluoride, chloride, bromine). Ion, iodine ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p
-Chlorobenzenesulfonic acid ion), aryldisulfonic acid ion (for example, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion) ), Sulfate, thiocyanate, perchlorate, tetrafluoroborate, picrate, acetate, and trifluoromethanesulfonate.

 Preferably, it is an iodine ion.

Specific examples of the dye used in the present invention are shown below, but the scope of the present invention is not limited only to these.

General formulas (I), (II) and (II) used in the present invention
The compound represented by I) is a known compound and can be synthesized based on a method described in a literature or the like.

Literature F.M.Hamer, Heterocyclic Compounds-Cyanine Dye and
Related Compounds-(Heterocyclic Compoun
ds-Cyaninedyes and related Compounds-) "Chapters IV, V, VI, VII, VIII, IX, pages 86 to 291 Chapter XIV, pages 511 to 611, Chapter XV, pages 612 to 684 (Jillon Willie And Sons John Wiley &
Sons, New York, London, 1964) Article DMStumer, Heterocyclic Compounds-Special Topics
In Heterocyclic Chemistry
clic Compounds-Special.topics in heterocyclic che
mistry-) ", Chapter 8, Section 4, pp. 482-515 (Jilln Wiley & Sons, Jnhn Wiley &
Sons, New York, London, 1977) Article DJFry, "Rods' Chemistry of Carbon Compounds (Rodd's Ch.)
emistry of Carbon Compounds) ”(2nd.Ed.vol.IV, partB, 1977) Chapter 15, pp. 369-422 (2nd.Ed.vol.IV, partB, 1985) Chapter 15, 267- 296 pages (ELSVIER SCIENCE PUBLISHING COMPANY, Inc.)
INC, New York) Known cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxo dyes that are used in the present invention and spectrally sensitize below 700 nm. Nol dyes are included.

Specifically, U.S. Pat.No. 4,617,257, JP-A-59-180
No. 550, No. 60-140335, RD17029 (1978), pp. 12-13, and the like.

These sensitizing dyes may be used alone, or a combination thereof may be used.
Often used for supersensitization.

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

These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or may be added to U.S. Pat.
No. 4,225,666 before and after the nucleation of silver halide grains. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

The color photographic material of the present invention can be constituted as a wet processing type color photographic material using a coupler as a dye-donating compound. The couplers and other additives used herein and the wet treatment method are known, and may be referred to, for example, the description in JP-A-62-215272.

Further, the color light-sensitive material of the present invention can be constituted as a color diffusion transfer light-sensitive material which is subjected to wet processing. This method is also known, for example, JP-B-46-16356 and JP-B-48-3.
No. 3697, JP-A-50-13040, JP-A-57-119345, JP-A-62-2
The description such as 26649 can be referred to.

The color light-sensitive material of the present invention is described in "The Theory of the Ph
otographic Process ”4th edition (by THJames, Macmilla
n, New York, 1977), pp. 363-366.

The present invention is particularly preferably configured as a heat-developable color photosensitive material from the viewpoint of simplicity of image forming processing. In the following, the additives used in constituting the present invention as a heat developable color light-sensitive material and the processing method thereof will be described in detail. Hereinafter, an element containing silver halide, a binder and a dye-donating compound is referred to as a photosensitive element, an element for receiving a diffusible dye released from the photosensitive element is referred to as a dye-fixing element, and both of them are referred to as a heat-developable color photosensitive material.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, an organic silver salt is particularly preferably used.

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include benzotriazoles, fatty acids and other compounds described in U.S. Pat. No. 4,500,626, columns 52-53. Also useful are silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A-60-113235 and acetylene silver described in JP-A-61-249044. Two or more organic silver salts may be used in combination.

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

In the present invention, various antifoggants or photographic stabilizers can be used. An example is RD17643
(1978) Azoles and azaindenes described on pages 24 to 25, carboxylic acids and phosphoric acids containing nitrogen described in JP-A-59-168442, or mercapto compounds and metals thereof described in JP-A-59-111636 Salts and acetylene compounds described in JP-A-62-87957 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, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -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 or other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-manufactured by Sumitomo Chemical Co., Ltd.) 5H) is also used. These binders can be used in combination of two or more kinds.

When a system for performing thermal development by supplying a small amount of water is used, it is possible to quickly absorb water by using the above superabsorbent polymer. Further, when the superabsorbent polymer is used for the dye fixing layer and its protective layer, it is possible to prevent the dye from being re-transferred from the dye fixing element to another after transfer.

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

Various polymers are used in the constituent layers (including the back layer) of the photosensitive element or the dye fixing element for the purpose of improving the physical properties of the film, such as stabilization of dimensions, prevention of curling, prevention of adhesion, prevention of cracking of the film, and prevention of pressure fluctuation. Latex can be included. Specifically, JP-A Nos. 62-245258, 62-136648, 62
Any of the polymer latexes described in JP-A-110066 can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or less) is used for the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, the curl prevention effect is reduced. can get.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-providing compound having a reducing property described later is also included (in this case, another reducing agent may be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can also be used.

Examples of reducing agents used in the present invention include U.S. Pat.
Columns 49-50 of 4,500,626, 30-31 of 4,483,914
No. 4,330,617, 4,590,152, JP-A-60-14
Nos. 17- (18), Nos. 57-40245 and 56-1 of No. 0335
38736, 59-178458, 59-53831, 59-1824
No. 49, No. 59-182450, No. 60-119555, No. 60-128436
No. to No. 60-128439, No. 60-60-198540, No. 60
-181742, 61-259253, 62-244044, 62-
131253 to 62-131256, EP 220,746A
No. 2, pp. 78-96, etc., there are reducing agents and reducing agent precursors.

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

When a diffusion-resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent are optionally added to promote electron transfer between the diffusion-resistant reduction agent and the developable silver halide. Precursors can be used in combination.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors.
It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). 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 amount of the reducing agent added is based on 1 mole of silver.
It is 0.001 to 20 mol, particularly preferably 0.01 to 10 mol.

First, examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Also,
A 2-equivalent coupler having a nondiffusible group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Specific examples of color developers and couplers are described in James, The Theory of the Photographic Process, 4th Edition.
Edition (THJames “The Theory of the Photographic Proc
ess ") pp. 291-334, and 354-361, JP-A-58-1235.
No. 33, No. 58-149046, No. 58-149047, No. 59-111148
Nos. 59-124399, 59-174835, 59-231539
No. 59-231540, No. 60-2950, No. 60-2951, No.
Nos. 60-14242, 60-23474, and 60-66249.

Further, as another example of the dye-donating compound, a compound having a function of releasing or diffusing a diffusible dye imagewise can be mentioned. This type of compound can be represented by the following general formula [LI].

(Dye-Y) nZ [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image-like latent image. (Dye-Y) n-Z to cause a difference in the diffusivity of the compound represented by (Dye-Y) nZ, or to release Dye and to release the released Dye and (Dye- Y) represents a group having a property that causes a difference in diffusivity with n-Z, n represents 1 or 2, and when n is 2, two Dye-Ys are the same but different. Is also good.

Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds.
The following items (1) to (2) form a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide.
Is to form a diffusible dye image (negative dye image) corresponding to the development of silver halide.

U.S. Pat.Nos. 3,134,764, 3,362,819, 3,591
7,200, 3,544,545 and 3,482,972. A dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide.

As described in U.S. Pat. No. 4,503,137, non-diffusible compounds which release a diffusible dye in an alkaline environment but lose their ability when reacted with silver halide can also be used. Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in U.S. Pat.No. 3,980,479 and the like, and an intramolecular reversion reaction of an isoxazolone ring described in U.S. Pat. Compounds that release diffusible dyes are included.

As described in U.S. Pat.No. 4,559,290, European Patent No. 220,746A2, U.S. Pat.No.4,783,396, Published Technical Report 87-6199, etc. Non-diffusible compounds that release

Examples are U.S. Pat.Nos. 4,139,389 and 4,13
No. 9,379, JP-A-59-185333, and compounds capable of releasing a diffusible dye by a nucleophilic substitution reaction in a molecule after reduction described in U.S. Pat.
No., JP-A-59-101649, JP-A-61-88257, RD24025 (19
1984), a compound that releases a diffusible dye by an electron transfer reaction in the molecule after being reduced.
No. 3,008,588A, JP-A-56-142530, U.S. Pat.
Nos. 893, 4,619,884, etc., compounds that release a diffusible dye by cleavage of a single bond after reduction, and release a diffusible dye after electron acceptance, as described in U.S. Pat. Nitro compounds, U.S. Pat.No. 4,609,61
Compounds which release a diffusible dye after electron acceptance described in No. 0 and the like are exemplified.

Also, as more preferred, EP 220,746A
No. 2, published technical report 87-6199, U.S. Pat. No. 4,783,396, JP-A-63-201653, JP-A-63-201654, and the like, in which NX bond (X is oxygen, sulfur or nitrogen) in one molecule. Represents an atom)
With a compound having an electron attractive group, compounds SO ₂ -X (X is as defined above) in one molecule described in Japanese Patent Application Sho 62-106885 having an electron attractive group, JP 63-271344 Compound having a PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule described in JP-A-63-271341, and a C-X 'bond (Min. X 'is the same as X or -SO
_2- )) and a compound having an electron-withdrawing group. Further, the compounds described in Japanese Patent Application Nos. 62-319989 and 62-320771, which release a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated to an electron accepting group can also be used.

Among them, a compound having an NX bond and an electron-withdrawing group in one molecule is particularly preferable. A specific example is European Patent No. 22
0,746A2 or compounds (1) to (3), (7) to (10), (12), (13) described in US Pat. No. 4,783,396.
(15), (23)-(26), (31), (32), (35),
(36), (40), (41), (44), (53)-(59),
(64), (70), Compounds (11) to of Published Technical Report 87-6199
(23).

Compounds that have a diffusible dye as a leaving group and release a diffusible dye upon reaction with an oxidized reducing agent (DD
R coupler). Specifically, U.S. Patent No. 1,330,524, JP-B-48-39,165, U.S. Patent No. 3,443,940, U.S. Pat.
Nos. 4,867 and 4,483,914.

Is reducible to silver halides or organic silver salts,
A compound that releases a diffusible dye when the partner is reduced (DRR
Compound). Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidized decomposition products of the reducing agent. A representative example is U.S. Pat.No. 3,928,312
No. 4,053,312, No. 4,055,428, No. 4,336,32
No. 2, JP-A-59-65839, JP-A-59-69839, JP-A-53-3819
No. 51-104,343, RD17465, U.S. Pat.
No. 2, 3,728,113, 3,443,939, JP-A-58-1
Nos. 16,537, 57-179840 and U.S. Pat. No. 4,500,626. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, the compounds (1) to (3) described in the above-mentioned U.S. Pat. (10)-(13), (16)-
(19), (28)-(30), (33)-(35), (38)-
(40), (42) to (64) are preferred. Also U.S. Pat.
The compounds described in 639,408, columns 37-39 are also useful.

Other examples of the above-mentioned couplers and dye-donating compounds other than the general formula [LI] include dye silver compounds in which an organic silver salt is combined with a dye (Research Disclosure Magazine, 1978, May 1978).
Monthly publications, pages 54 to 58), azo dyes used in the thermally developed silver dye bleaching method (US Pat. No. 4,235,957, Research Disclosure, April 1976, pages 30 to 32, etc.), leuco dyes (US Patent Nos. 3,985,565 and 4,022,617) can also be used.

Hydrophobic additives such as a dye-providing compound and a diffusion-resistant reducing agent can be introduced into a layer of a photosensitive element by a known method such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154, JP-A-59-178451, and JP-A-59-178451
-178452, 59-178453, 59-178454, 59-
High boiling organic solvents such as those described in JP-B-178455 and JP-B-59-178457 can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C, if necessary.

The amount of the high boiling organic solvent is 1 g of the dye-donating compound used.
10 g or less, preferably 5 g or less. In addition, 1 cc or less of binder 1 g, further 0.5 cc or less, especially 0.
3cc or less is appropriate.

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

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

When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59
The surfactants listed on pages (37) to (38) of No. 157636 can be used.

In the present invention, a compound for stabilizing an image simultaneously with activation of development can be used in the photosensitive element. Specific compounds preferably used are described in U.S. Pat.
No. 626, columns 51-52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a photosensitive element. The dye-fixing element may be coated separately on a support separate from the photosensitive element, or may be coated on the same support as the photosensitive element. As for the relationship between the photosensitive element and the dye-fixing element, the relationship with the support, and the relationship with the white reflective layer, those 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, those known in the field of photography can be used, and specific examples thereof include U.S. Pat.
-88256, mordants described on pages (32) to (41);
Nos. 2-244043 and 62-244036. Further, a dye-receiving polymer compound as described in US Pat. No. 4,463,079 may be used.

The dye-fixing element may be provided with an auxiliary layer such as a protective layer, a release layer, and an anti-curl layer, if necessary. It is particularly 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 releasability of the photosensitive element and the dye fixing element. Specific examples include those described in JP-A-62-253159, page (25) and JP-A-62-245253.

Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. Examples thereof include various modified silicone oils described in Technical Data “Modified Silicone Oil” published by Shin-Etsu Silicone Co., Ltd., page 6-18B, especially carboxy-modified silicone (trade name: X-22-37).
10) is effective.

Also, silicone oils described in JP-A-62-215953 and Japanese Patent Application No. 62-23687 are effective.

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

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

Examples of ultraviolet absorbers include benzotriazole-based compounds (US Pat. No. 3,533,794, etc.), 4-thiazolidone-based compounds (US Pat. No. 3,352,681), benzophenone-based compounds (JP-A-46-2784, etc.), and others. JP-A-54-
There are compounds described in JP-A-48535, JP-A-62-136641 and JP-A-61-88256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective.

As metal complexes, U.S. Pat.Nos. 4,241,155 and 4,2
Nos. 45,018, columns 3-36, 4,254,195, columns 3-8, JP-A-62-174741 and JP-A-61-88256, pages (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, etc.

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

An anti-fading agent for preventing 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 outside such as a photosensitive element. .

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other.

A fluorescent whitening agent may be used for the photosensitive element and the dye fixing element. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing element or to supply it from outside such as a photosensitive element. An example is K. Veenkataraman ed., "The Chemistry of Synthe
tic Dyes ", Vol. V, Chapter 8, JP-A-61-143752, and the like. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given.

The fluorescent whitening agent can be used in combination with an anti-fading agent.

Examples of the hardening agent used in the constituent layers of the photosensitive element and the dye fixing element include U.S. Pat.No. 4,678,739, column 41, and JP-A-59-11665.
No. 5, 62-245261, 61-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners Vinyl sulfone hardeners (such as N, N'-ethylene-bis (vinylsulfonylacetamide) ethane), N-methylol hardeners (such as dimethylol urea), or polymer hardeners (Japanese Patent Laid-Open No. Sho 62) -234157, etc.).

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 Nos. 62-173463 and 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 static charge, and improving releasability. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8 to 17, JP-A-61-20944.
No. 62-135826, and hydrophobic surfactants such as fluorine surfactants described in JP-A No. 62-135826, or oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as ethylene tetrafluoride resin. Can be

A matting agent can be used for the photosensitive element and the dye fixing element. Examples of the matting agent include compounds described on page 29 of JP-A-61-88256, such as silicon dioxide, polyolefin and polymethacrylate, as well as benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like. And No. 62-110065.

In addition, the constituent layers of the photosensitive element and the dye fixing element include:
A heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica and the like may be contained. Specific examples of these additives are disclosed in
No. 88256, pages (26) to (332).

In the present invention, an image formation accelerator can be used in the photosensitive element and / or the dye fixing element. Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the generation of a dye from a dye-providing substance or the decomposition or release of a diffusible dye, and the use of a photosensitive material layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. See U.S. Pat.
No. 9, columns 38-40.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement, and the like. Specific examples thereof are described in U.S. Pat.
-65038 and the like.

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

In addition to the above, 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. In particular, the former method is effective. The sparingly soluble metal compound and the complex forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element.

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 terminator" as used herein means that after appropriate development, the base is quickly neutralized or reacts with the base to reduce the base concentration in the film, and interact with a compound that stops development or silver and silver salts to suppress development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. More specifically, JP-A-62-253159 (31) to (32)
Page.

As the support of the photosensitive element or dye fixing element of the present invention,
Those that can withstand the processing temperature are used. Generally, paper and synthetic polymers (films) are used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (eg, triacetylcellulose), or films containing pigments such as titanium oxide, and polypropylene. Synthetic paper made from film, synthetic paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass, etc. Can 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, or another antistatic agent may be applied to 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. Using an exposure device to scan and expose the original image through slits, etc., a method of exposing image information by emitting light from a light emitting diode or various lasers via electrical signals, exposing image information to a CRT, liquid crystal display, or 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 the light source for recording an image on the photosensitive element, as described above, natural light, a tungsten lamp, a light emitting diode, a laser light source, a U.S. Pat.
The light sources described in the column can be used.

Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, a nonlinear optical material is a material that can exhibit nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, such as lithium niobate and potassium dihydrogen phosphate (KDP ), Inorganic compounds represented by lithium iodate, BaB ₂ O _{4 and the} like, urea derivatives, nitroaniline derivatives such as nitropyridine-N-oxide such as 3-methyl-4-nitropyridine-N-oxide (POM). Oxide derivatives, JP-A-61-53462, 6
The compounds described in 2-210432 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful.

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

The photosensitive element and / or the dye fixing element may have a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of the dye. In this case, as the transparent or opaque heating element, those described in JP-A-61-145544 can be used. Note that these conductive layers also function as antistatic layers.

The heating temperature in the thermal development step can be developed at about 50 ° C. to about 250 ° C., and particularly about 80 ° C. to about 180 ° C. is useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step. In the 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 particularly preferable that the temperature is 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

Dye transfer is caused only by heat, but a solvent may be used to promote dye transfer.

Further, as described in detail in JP-A-59-218443 and JP-A-61-238056, a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also available. Useful. In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower, for example, when the solvent is water, 50 ° C. or higher.
100 ° C or less is desirable.

Examples of the solvent used for promoting development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases include Those described in the section of the formation accelerator are used. In addition, a low-boiling solvent or a mixed solution of a low-boiling solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound may be contained in the solvent.

These solvents can be used in a method for imparting to the dye fixing element, the photosensitive element, or both. The amount used may be as small as not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (especially not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, a method described in JP-A-61-147244, page (26). Further, the solvent can be used by being previously incorporated in the photosensitive element or the dye fixing element or both in the form of enclosing the solvent in microcapsules.

In order to promote dye transfer, a method in which a hydrophilic thermal solvent which is solid at normal temperature and dissolves at high temperature is incorporated in the photosensitive element or the dye fixing element can be adopted. The hydrophilic heat solvent may be incorporated in any of the photosensitive element and the dye fixing element,
It may be built in both. Also, the layer to be incorporated is an emulsion layer,
Any of an intermediate layer, a protective layer, and a dye-fixing layer may be used, but it is preferable to be incorporated in the dye-fixing layer and / or a layer adjacent thereto.

Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alkenyls,
There are oximes and other heterocycles.

Further, in order to promote dye transfer, a high boiling organic solvent may be contained in the photosensitive element and / or the dye fixing element.

As a heating method in the development and / or transfer step, it is contacted with a heated block or plate, or in contact with a hot plate, hot presser, heat roller, halogen lamp heater, infrared and far infrared lamp heater, For example, passing through a high temperature atmosphere.

The method described in JP-A-61-147244, page 27, can be applied as a pressure condition and a method of applying pressure when the photosensitive element and the dye-fixing element are overlapped and brought into close contact with each other.

Any of a variety of thermal development equipment can be used to process the photographic elements of the present invention. For example, JP-A-59-75247, JP-A-59-75247
-17747, 59-181353, 60-18951, Shokai 6
An apparatus described in, for example, No. 2-25944 is preferably used.

Example 1 A photosensitive element 101 as shown in Table 1 was prepared.

High-boiling point organic solvent (1) Trinonyl phosphate Water-soluble polymer (Super-absorbent polymer) (1) Sumikagel L-5 (H) Water-soluble polymer (Super-absorbent polymer) manufactured by Sumitomo Chemical Co., Ltd. (2) A method for preparing an emulsion for the fifth layer will be described.

Emulsion (I) Well-stirred aqueous gelatin solution (20 g gelatin, 3 g sodium chloride and compound in 800 ml water) Were dissolved and kept at 65 ° C.), and the following solutions I and II were added over 70 minutes. Simultaneously with the start of addition of solution I and solution II A dye solution obtained by dissolving 0.24 g in a solution of (120 cc of methanol + 120 cc of water) was added over 60 minutes.

Solution I Solution II (600 ml in total) (600 ml in total) AgNO ₃ (g) 100-KBr (g) -56 NaCl (g) -7 Immediately after addition of solution I and solution II, 2 g of KBr are dissolved in 20 ml of water And added and left for 10 minutes.

After washing with water and desalting, 25 g of gelatin and 100 ml of water were added to adjust the pH to 6.4, p.
Ag was adjusted to 7.8. The resulting emulsion has a grain size of about 0.5
μ was a cubic monodispersed emulsion.

Keep this emulsion at 60 ° C, triethylthiourea 1.3mg; 4
-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (100 mg) was added simultaneously to optimize chemical sensitization. Yield 650
g

 The method of preparing the emulsion for the third layer will be described.

Emulsion (VI) Well-stirred aqueous gelatin solution (20 g gelatin, 2 g sodium chloride and compound in 800 ml water) And the following solutions I and II were added over 60 minutes.

Simultaneously with the start of addition of solution I and solution II A dye solution prepared by dissolving 0.16 g in methanol (80 ml) was added over 40 minutes.

Solution I Solution II (600 ml in total) (600 ml in total) AgNO ₃ (g) 100-KBr (g)-56 NaCl (g)-7 , Washing and desalting, then 25g gelatin and 100ml water
Was added to adjust the pH to 6.5 and the pAg to 7.8.

After adjusting the pH and pAg, triethylthiourea and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added and optimally sensitized at 60 ° C.

The resulting emulsion was a cubic monodispersed emulsion having a grain size of about 0.35 µm and the yield was 650 g.

 The method of preparing the first layer emulsion will be described.

Emulsion (VII) Well-stirred aqueous gelatin solution (20 g gelatin and 4 g sodium chloride in 1000 ml water) 600 ml of an aqueous solution containing 49 g of potassium bromide and 10.5 g of sodium chloride and an aqueous solution of silver nitrate (0.59 mol of silver nitrate dissolved in 600 ml of water) were simultaneously dissolved in the same solution and kept at 60 ° C. for 50 minutes. Was added. After washing and desalting, 25 g of gelatin and 200 ml of water were added to adjust the pH to 6.4, and triethylthiourea and 4-hydroxy-6-methyl-1,3,3a-7 were added.
Performing optimal chemical sensitization using tetrazaindene,
700 g of a cubic monodispersed emulsion (I) having an average particle size of 0.4 µ was obtained.

 How to make an organic silver salt is described.

Organic silver salt (1) A method for preparing a silver benzotriazole 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 the benzotriazole silver emulsion was adjusted, allowed to settle, and excess salts were removed. Then adjust the pH to 6.30,
A yield of 400 g of silver benzotriazole 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 a 0.1% aqueous sodium hydroxide solution and 200 ml of ethanol.

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

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

The pH of the dispersion was adjusted and settled to remove excess salts. Thereafter, the pH was adjusted to 6.3 to obtain a dispersion of the organic silver salt (2) in a yield of 300 g.

Next, a method of preparing a gelatin dispersion of a dye-providing substance will be described.

12 g of a yellow dye-donating substance (Y-1), (Y-
2) 3 g, high boiling organic solvent (1) 7.5 g, reducing agent (1) 0.3
g and mercapto compound (1) 0.3 g in ethyl acetate 45m
Then, 100 g of a 10% gelatin solution and 60 ml of a 2.5% aqueous solution of sodium dodecylbenzenesulfonate were mixed with stirring, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm. This dispersion is referred to as a yellow dye-providing substance dispersion.

15 g of a magenta dye-donating substance (M), 7.5 g of a high-boiling organic solvent (1), 0.3 g of a reducing agent (1) and 0.15 g of a mercapto compound (1) were added to 25 ml of ethyl acetate and dissolved, and 100 g of a 10% gelatin solution was dissolved. Of sodium dodecylbenzenesulfonate
After stirring and mixing with 60 ml of a 2.5% aqueous solution, the mixture was dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a magenta dye-providing substance dispersion.

15 g of a cyan dye-donating substance (C), 7.5 g of a high-boiling organic solvent (1), 0.4 g of a reducing agent (1), and 0.6 g of a mercapto compound (1) are added to 40 ml of ethyl acetate and dissolved. 2.100 g of sodium dodecylbenzenesulfonate
After stirring and mixing with 60 ml of a 5% aqueous solution, use a homogenizer to mix
Dispersed at 10,000 rpm for 0 minutes. This dispersion is referred to as a dispersion of a cyan dye-donating substance.

Next, a method of making the dye fixing material will be described.

The composition was coated on a paper support laminated with polyethylene according to the composition shown in the following table to prepare a dye fixing material.

Next, as shown in Table 2 below, a spectral sensitizing dye having a sensitizing wavelength of 700 nm or more was further added to the fifth layer after completion of Emulsion (I) to prepare a fifth layer. The addition amount of this spectral sensitizing dye is
5 × 10 ⁻⁵ g / m ² .

The layer constitution and other additives are the same as those of the photosensitive element 101.

These photosensitive materials were exposed using a color printer "Pictrograph" manufactured by Fuji Photo Film Co., Ltd. while changing the light amount of the LED. This printer is 3 types 570n
m, 670 nm and 810 nm light emitting diodes are used.

12 ml / m ² of water was supplied to the emulsion surface of the exposed photosensitive element with a wire bar, and then the dye fixing element and the film surface were superposed so that they were in contact with each other. After heating for 20 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbing film became 90 ° C., the dye-fixing element was peeled off from the photosensitive element, whereby an image was obtained on the dye-fixing material.

Next, using the apparatus described in Example 1 of Japanese Patent Application No. 62-147821, exposure was performed by using the following three types of semiconductor lasers (abbreviated as LD) while changing the amount of light.

Semiconductor laser AlGaInP (oscillation wavelength about 670 nm) GaAlAs (oscillation wavelength about 750 nm) GaAlAs (oscillation wavelength about 810 nm) Thereafter, development was performed under the same conditions as described above.

From this table, it can be seen that the photosensitive material of the present invention is effective for two exposure light sources.

In the light-sensitive material element 102, hue deterioration is practically inconspicuous because magenta and yellow are mixed.

 The following evaluation was performed as the evaluation of color separation.

The concentration was measured with a status A filter using X-RITE. From the value, the degree of color mixing was expressed as a percentage based on the density obtained by subtracting the density of the support.

The color mixture was evaluated when the reflection density of the original color was 1.5 to 1.7.

Example 2 A method of preparing a gelatin dispersion of a dye-providing compound will be described.

Yellow, magenta, and cyan were added to 50 ml of ethyl acetate as described above, and dissolved by heating at about 60 ° C. to form a uniform solution. 100 g of a 10% aqueous solution of this solution and lime-processed gelatin and 0.6 g of sodium dodecylbenzenesulfonate
And 50 ml of water were stirred and mixed, and then dispersed at 10,000 rpm for 10 minutes with a homogenizer. This dispersion is referred to as a gelatin dispersion of the dye-providing compound.

Next, a method for preparing a gelatin dispersion of an electron donor for the intermediate layer will be described.

The following electron donor 23.6 g and the above high boiling solvent 8.5 g
Was added to 30 ml of ethyl acetate to obtain a uniform solution. This solution, 100 g of a 10% aqueous solution of lime-processed gelatin, 0.3 g of sodium dodecylbenzenesulfonate and 30 ml of water were mixed with stirring, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm.
This dispersion is called a gelatin dispersion of an electron donor.

Next, how to prepare the photosensitive silver halide emulsion (I) will be described.

A well-stirred aqueous gelatin solution (20 g of gelatin, 3 g of potassium bromide and HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ O in 800 ml of water
H (added with 0.3 g) and kept at 60 ° C.], the following solutions (I) and (II) were added simultaneously over 30 minutes. Thereafter, the following solution (III) and solution (IV) were simultaneously added over 20 minutes. After the addition is completed, add 30 cc of a 1% aqueous solution of potassium iodide,
Next, the following dye solution was added. After washing with water and desalting, 20 g of lime-processed ossein gelatin was added to adjust the pH to 6.2 and pAg 8.5, then sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene, Optimally chemically sensitized by adding chloroauric acid. In this way the average particle size is 0.45
600 g of a monodisperse octahedral silver iodobromide emulsion of μm was obtained.

Dye solution 0.14 g of the following dye dissolved in 70 cc of methanol Next, how to prepare the photosensitive silver halide emulsion (II) will be described.

Well stirred aqueous solution (gelatin 20m in water 730ml)
g, potassium bromide 0.30 g, sodium chloride 6 g and the following chemical A 0.015 g, and the mixture was kept at 60.0 ° C.) and the following solutions (I) and (II) were added simultaneously at the same flow rate over 60 minutes. . After the addition of the solution (I), a methanol solution (III) of the following sensitizing dye was added. Thus, a monodispersed cubic emulsion adsorbing a dye having an average particle size of 0.45 μm was prepared.

After washing with water and desalting, add 20 g of gelatin, pH 6.4 and pAg.
After adjusting to 7.8, chemical sensitization was performed at 60.0 ° C. The chemicals used at this time were triethylthiourea 1.6 mg and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 100 m
In g, the aging time was 55 minutes. The yield of this emulsion was 635 g.

Next, how to prepare the photosensitive silver halide emulsion (III) will be described.

A well stirred gelatin solution (20 g gelatin, 1 g potassium bromide, and OH (CH ₂ ) ₂ S (CH ₂ ) ₂ OH in 800 ml water
Solution (I), solution (II) and solution (III) below were simultaneously added at an equal flow rate over a period of 30 minutes. Thus, a monodispersed silver bromide emulsion to which a dye having an average grain size of 0.35 μ was adsorbed was prepared.

After washing and desalting, add 20 g of lime-processed ossein gelatin, p
After adjusting H to 6.4 and pAg to 8.2, the mixture was kept at 60 ° C., and sodium thiosulfate (9 mg), chloroauric acid 0.01% aqueous solution (6 ml), 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 190m
g was added and chemically sensitized for 45 minutes. Emulsion yield 635g
It was.

Using the above, the following photosensitive material 105 was prepared.

Next, as shown in Table 5 below, in the fifth layer, a spectral sensitizing dye having a sensitizing wavelength of 700 nm or more was further dissolved. In the preparation of emulsion (I), 20 mg was dissolved in methanol after a ripening time of 55 minutes. The added emulsion was made. Otherwise, it is the same as the photosensitive element 105.

 Next, a method of making the dye fixing material will be described.

The composition was coated on a paper support laminated with polyethylene according to the composition shown in the following table to prepare a dye fixing material.

For these photosensitive elements, SP manufactured by Fuji Photo Film Co., Ltd.
-1 (blue), SP-2 (green), and SP-3 (red) were applied with a filter of three colors and an infrared cut filter.

The exposed photosensitive element is placed in water kept at 35 ° C.
After immersion for 2 seconds, it was squeezed by a roller, and immediately thereafter, the dye fixing element and the film surface were overlapped with each other so as to be in contact with each other. Using a heat drum temperature-controlled so that the temperature of the supplied water is about 80 ° C
Heated for 15 seconds. When the dye-fixing element was peeled off from the photosensitive element, an image was obtained thereon.

Next, as in Example 1, exposure was performed using a color printer "Pictrograph" manufactured by Fuji Photo Film Co., Ltd. Thereafter, the same water application and heat treatment as described above were performed.

 Table 6 shows the results.

Also in this example, it can be seen that the photosensitive material of the present invention can be used for two purposes and is excellent.

Continuation of front page (56) References JP-A-53-20926 (JP, A) JP-A-63-115160 (JP, A) JP-A-63-19652 (JP, A) JP-A-62-147451 (JP, A) , A) JP-A-59-2249 (JP, A)

Claims (1)

(57) [Claims] 1. A color light-sensitive material comprising at least three light-sensitive layers having different color sensitivities each containing at least a light-sensitive silver halide, a binder and a dye-donating compound in combination on a support. A color light-sensitive material, wherein at least one layer has a spectral sensitivity peak at at least two wavelengths separated by 50 nm or more, and at least one of the spectral sensitivity peaks has a wavelength of 700 nm or more.