JPS63197947A - Full-color recording material - Google Patents

Abstract

PURPOSE:To improve the stability of IR spectral sensitization sensitivity by forming a titled material of photosensitive layers, of which at least one layer is a silver halide emulsion layer spectrally sensitized in the region of the max. wavelength of spectral sensitization longer than about 670nm and forms a color image of a direct positive type or negative type. CONSTITUTION:At least three kinds of the photosensitive layer units contg. a yellow coupler, magenta coupler and cyan coupler respectively corresponding to photosensitive silver halide emulsion layers having respectively different spectral sensitivity distributions are provided on a base. At least one of the photosensitive layers is the silver halide emulsion layer spectrally sensitized to the region of the max. wavelength of the spectral sensitivity longer than about 670nm and forms the color image of the direct positive or negative type. The stable spectral sensitization in the red and IR regions with the high sensitivity and high efficiency is thereby permitted.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color recording material used to print a color image with gradations from a color original or a soft information source, and in particular to a color recording material used for printing a color image with gradation from a color original or a soft information source, and in particular to The present invention relates to a color recording material that is suitable for laser light and has spectral sensitivity completely in the red to infrared region.

[Conventional technology]

Conventionally, color copying technology has mainly been binary information recording, such as copying machines using electrophotographic technology, laser printers, and thermal recording systems. In recent years, there has been a growing demand for full-color recording materials with excellent gradation. On the other hand, there has been remarkable progress in color development processing systems for color photosensitive materials that use ordinary color couplers, that is, couplers that satisfy the three primary colors of yellow coupler, magenta coupler, and cyan coupler. With a processing time of less than 3 minutes and 40 seconds, color images with extremely high gradation can now be obtained at a relatively low price.

Conventionally, a method is known in which a color television image signal is recorded using the modulated control output of a light emitting diode (LDE). For example, it is shown in Japanese Patent Application Laid-Open No. 13505/1983. This involves a technique for recording on a photosensitive layer containing a cyan coupler and an infrared spectrally sensitized silver halide emulsion using infrared light in a wavelength range longer than 700". 2443 or 3443 manufactured by K.O.D.A.A.
The type is also known. This was a negative-type photographic film that produced false color photographs, and was not necessarily a recording material that produced perfect gradation.

Heat-developable color photosensitive materials are also known as described in JP-A-59-180550 and JP-A-59-180553. In addition, heat-developable photosensitive materials are also known, which are provided with a photosensitive layer containing an organic silver salt and an image dye-providing compound and having spectral sensitivity in a wavelength range longer than 700''. This is a heat-developable photosensitive material that is different from photosensitive materials that use color couplers.

[Problems to be solved by the invention]

Furthermore, among the manufacturing technologies for silver halide light-sensitive materials, infrared spectral sensitization has drawbacks such as the sensitizing dyes used for this purpose are generally unstable, the exacerbation efficiency is low, and fogging is likely to occur. It is known that when they coexist, sensitivity stability tends to deteriorate.

The first object of the present invention is to create a color image with gradation from a color original or soft information source by utilizing a conventional three-primary color coupler that stably achieves excellent color reproduction and a method used for silver halide photosensitive materials. An object of the present invention is to provide a color recording material that can be printed.

Second, we need a color recording material that has at least one photosensitive layer that is highly sensitive, stable, and spectrally sensitized with high efficiency in the red or infrared region, making the LED light suitable for the output of a light control system such as a semiconductor laser. It is to provide. Thirdly, the same type of spectral enhancing agent as above is used, but a negative recording material is prepared using a conventional surface latent image type silver halide emulsion, preferably a multiple structure silver halide emulsion, and an internal latent image type preferably multiple structure silver halide emulsion. To provide a positive color recording material that directly produces a positive image by using a silver halide emulsion and a nucleating agent, or by adding a light fogging process to the color development process of a material using the emulsion. There is a particular thing. Fourthly, the same type of development process as that of ordinary color photographic paper, for example, the quick and simple color development process such as the minilab system, can be applied to both positive and negative types in substantially the same way.
The purpose of the present invention is to provide color recording materials that can be passed through. Various other objects will be understood from the description herein.

[Means for solving problems]

The present invention provides a color recording material for solving the above-mentioned problems, in which light-sensitive silver halide emulsions having different spectral sensitivity distributions and correspondingly yellow couplers, magenta couplers, and cyan couplers are used. A color recording material comprising at least three types of photosensitive layer units containing on a support, in which at least one of the photosensitive layers has spectral sensitivity in a region where the maximum spectral sensitivity wavelength is longer than about 670 nm. It is a color recording material characterized in that it is a silver halide emulsion layer formed by a silver halide emulsion, and directly forms a positive or negative color image.

At least one photosensitive silver halide emulsion layer of the color recording material of the present invention has a spectral absorption maximum of 700 to 1200 nm.
It is preferable to be spectrally sensitized in the wavelength region of m. In addition, the wavelength range of spectral sensitization is that the tail of the spectral absorption spectrum is approximately 650.
It is preferable that it is not less than nm.

The color recording material of the present invention is preferably subjected to color development treatment after light scanning exposure.

The first feature of the present invention lies in the aggravating dye used.

In general, enhancement dyes used for infrared enhancement are chemically unstable and have considerable reducing properties, so they tend to give capri. Compared to ordinary color light-sensitive materials, the color recording material of the present invention requires stability of the raw light-sensitive material because it can be used anywhere, anytime, and by anyone, and furthermore, it can be processed quickly and easily for color development. It must also be resistant to fogging. For this improvement,
It has been found that the methine chain can be stabilized by incorporating it into a fused ring, such as an isophorone ring, and supersensitizing it. We also found that by using an indolenine nucleus, the wavelength-absorbing dyes were equally stabilized. The sensitizing dye represented by general formula (1) is particularly useful in the present invention.

General formula (I) R+
Rz(X○)7-1 Here, R1 and R2 may each be the same or different, and each represents an alkyl group [preferably 1 carbon atom number]
~8, unsubstituted or substituted alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, heptyl (substituents include carboxy, sulfo, cyano, halogen atoms (e.g. fluorine, chlorine atom, bromine atom, etc.), hydroxy group, alkoxycarbonyl group (8 or less carbon atoms, e.g. methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy group (7 or less carbon atoms, e.g. methoxy group, ethoxy group, propoxy group, butoxy group, benzyloxy group, etc.), aryloxy group (e.g. phenoxy group, J)-tolyloxy group, etc.), acyloxy group (3 or less carbon atoms, e.g. acetyloxy group, propionyloxy group) ), acyl groups (with 8 or less carbon atoms, such as acetyl, propionyl, benzoyl, mesyl, etc.), carbamoyl groups (e.g. carbamoyl, N,N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl, etc.), carbamoyl group, etc.), sulfamoyl group (e.g., sulfamoyl group, N,N-dimethylsulfamoyl group, monophorinosulfonyl group, etc.)
, an alkyl group (preferably having 6 or less carbon atoms) substituted with an aryl group (eg, phenyl group, P-hydroxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group, α-naphthyl group, etc.).

However, two or more of these substituents may be substituted with an alkyl group in combination. )].

L and R2 represent a methine group, and the methine group is used to include a substituted methine group. Examples of such substituted methine groups include methine groups having lower alkyl groups such as methyl, ethyl and propyl groups, phenyl groups and benzyl groups.

D represents a group of nonmetallic atoms necessary to complete a 6-membered ring containing three methylene groups. This ring may have a substituent such as a lower alkyl group such as a methyl group.

Z and O each represent a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. Examples of these include, for example, thiazole nuclei [e.g. benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6
-Chlorbenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-7'romohenzothiazole, 6-bromobenzothiazole, 5-
Iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5
-Fluorobenzothiazole, 5-trifluoromethylhendithiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho(2,1-d) Thiazole, naphtho (1,
2-d) Thiazole, naphtho(2,3-d)thiazole, 5-methoxynaphtho(1,1-d)thiazole, 7-
nitoxynaphtho(2,1-d)thiazole, 8-methoxynaphtho(2,1-d)thiazole, 5-methoxynaphtho(2,3-d)thiazole, etc.], zelenazole nucleus [
For example, penzoselenazole, 5-chlorobenzothiazole nucleus, 5-methylbenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoxazole, naphtho[2,1-d)zelenazole, naphtho(1,2
-d) zelenazole, etc.], oxazole nucleus [benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5
-Trifluorobenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-ethoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole , 4,6-dimethylbenzoxazole,
5-ethoxybenzoxazole, naphtho(2,1-d
) oxazole, nut[1°2-d]oxazole,
naphtho(2,3-d)oxazole etc.], quinoline nucleus [e.g. 2-quinoline, 3-methyl-2-quinoline, 5
-ethyl-2, quinoline, 6-methyl-2, quinoline,
8-fluoro-2-quinoline, 6-medoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2
-quinoline, 8-fluoro-4-quinoline, etc.], 3.
3-Dialkylindolenine nucleus (e.g., 3,3-dimethylindolenine, 3°3-diethylindolenine, 3
, 3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-methylindolenine, 3,3-dimethyl-5-chlorindolenine, etc.), imidazole nucleus (e.g. l
-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5-chlorobenzimidazole,
1-Ethyl-5-chlorobenzimidazole, 1-methyl-5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, l-methyl- 5-
Cyanobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-methyl-5-fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-allyl -5゜6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-
Phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, l-methyl-5-trifluoromethylbenzimidazole, ■-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnaphtho(1
, 2-d) imidazole, etc.), pyridine nuclei (e.g. pyridine, 5-methyl-2-pyridine, 3-methyl-4-
pyridine, etc.). Among these, thiazole nuclei and oxazole nuclei are preferably used.

More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus, or a benzoxazole nucleus is advantageously used.

X represents an acid anion.

n represents 1 or 2; m represents 1. Represents 2 or 3. n is 1 if the compound forms betaine.

The sensitizing dye represented by the general formula (I) is used in the non-red region (spectral sensitivity maximum wavelength is 670 mm or more) and the infrared region (700 mm or more).
It has the effect of spectrally sensitizing silver halide to light of wavelengths of 740 nm or more, particularly 740 nm or more. Specific examples of the aggravating pigment represented by general formula (I) are shown below. However, the present invention is not limited to these exacerbating pigments.

+13 (+-4) (+-7) [In addition, the sensitizing dye represented by the general formula (■) is also useful in the present invention. These dyes have slightly better desensitization properties than the sensitizing dyes represented by general formula (1),
Although it is easy to form H aggregates, it is preferable to use, for example, the general formula (
It has been found that this defect can be overcome by combined use with a supersensitizer oxidized by II). Next, the general formula (■)
The sensitizing dye represented by is explained below.

General formula (■) In the formula, R1% and R3° may be the same or different, and each represents an alkyl group [preferably 1 carbon number]
~8, unsubstituted or substituted alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, heptyl, etc. (substituents include carboxy, sulfo, cyano, halogen atoms (e.g. fluorine) atom, chlorine atom, bromine atom, etc.), hydroxy group, alkoxycarbonyl group (8 or less carbon atoms, e.g. methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy group (7 or less carbon atoms, e.g. methoxy group, ethoxy group, propoxy group, butoxy group, benzyloxy group, etc.), aryloxy group (e.g. phenoxy group, P-tolyloxy group, etc.), acyloxy group (3 or less carbon atoms, e.g. acetyloxy group, propionyloxy group, etc.) , acyl group (8 or less carbon atoms, e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (e.g. carbamoyl group, N, N
-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.), aryl group (e.g. phenyl group, p-hydroxy phenyl group,
P-carboxyphenyl group, p-sulfophenyl group, α
- an alkyl group (having 6 or less carbon atoms) substituted with a naphthyl group, etc. However, two or more of these substituents may be substituted with an alkyl group in combination. )].

Preferably, both R2 and R3 are unsubstituted alkyl groups,
Alternatively, a substituted alkyl group in which both RZ9 and R3° are selected from an alkyl group containing a sulfo group or an alkyl group containing a carboxy group is advantageously used. R1l1 is a hydrogen atom, an alkyl group (including lower unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, substituted alkyl group such as benzyl group), or an aryl group (including unsubstituted and substituted aryl groups, such as phenyl R111 is preferably a lower alkyl group or a benzyl group. (2) represents a hydrogen atom, an alkyl group (preferably a lower alkyl group (e.g., methyl group, ethyl group, etc.), a substituted alkyl group (e.g., trifluoromethyl group, carboxymethyl group, etc.)), an alkoxy group (a substituted or unsubstituted alkoxy group). (e.g., methoxy group, ethoxy group, butoxy group, etc.), halogen atom (e.g., fluorine atom, chlorine atom, etc.).

Z represents a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, and the nitrogen-containing heterocycle may be further substituted. For example, a thiazole nucleus [e.g. benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole,
5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole,
6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-sylbenzothiazole Methylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho[2,1-d)thiazole, naphtho(1,2-d)thiazole, naphtho(2,3
-d) Thiazole, 5-methoxynaphtho(1,2-d)
Thiazole, 7-nitoxynaphtho(2,1-d)thiazole, 8-methoxynaphtho(2,1-d)thiazole,
5-methoxynaphtho(2,3-d)thiazole, etc.],
Zelenazole core [e.g., penzozelenazole, 5-chlorobenzimidazole, 5-methylbenzothiazole, 5-methylbenzimidazole, 5-hydroxybenzoxazole, naphtho(2,1-d)zelenazole,
naphtho (1,2-d]zelenazole etc.), oxazole nucleus [benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5
-Phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenzoxazole, 5
-Hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-
Chlorbenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5.6-
Dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, naphtho(2,1-d)oxazole, naphtho(1,2-d)
oxazole, naphtho[2,3-d]oxazole, etc.], quinoline nucleus [e.g. 2-quinoline, 3-methyl-2
-quinoline, 5-ethyl-2-quinoline, 6-methyl-
2-quinoline, 8-fluoro-2-quinoline, 6-medoxy-2-quinoline, 6-hydroxy-2-quinoline,
8-chloro-2-quinoline, etc.], 3,3-dialkylindolenine nuclei (e.g., 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3 .3-dimethyl-5-methoxyindolenine, 3.3-dimethyl-5-methylindolenine, 3゜3-dimethyl-5-chloroindolenine, etc.), imidazole core (for example, l-methylbenzimidazole, 1. -ethylbenzimidazole, 1-
Methyl-5-chlorobenzimidazole, 1-ethyl-
5-chlorobenzimidazole, 1-methyl-5,6-
Dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-methyl-5-cyanobenzimidazole, ■-ethyl-5-cyanobenzimidazole, 1-methyl -5-fluorobenzimidazole,
1-ethyl-5-fluorobenzimidazole, l-phenyl-5,6-dichlorobenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole 1-phenyl benzimidazole, l-phenyl-5-chlorobenzimidazole, 1-methyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnaphtho(1,2-d)imidazole, etc.) , pyridine nucleus (e.g. pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine, etc.)
etc. can be mentioned. Among these, thiazole nuclei, selenazole nuclei, and oxazole nuclei are preferably used. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoselenazole nucleus, a penzozelenazole nucleus, and a naphthoxazole nucleus are advantageously used.

X represents an acid anion.

2 and p represent 1, 2 or 3, j and n represent 1 or 2
represents. When the dye has a betaine structure, n is 1.

L2 and L3 are synonymous with Ll or L2.

Specific examples of the sensitizing dye included in the general formula (■) used in the present invention are listed below. However, the present invention is not limited only to these compounds.

■-1 ■-2 に 2 tla Ll 11 ■-3 ■-4 ■-5 ■-6 ■-7 ■-8 ■-9 ■-10 ■-11 ■-12 ■- ■-13 ■-14 ■ -15 "■-16 ■-17 ■-18 ■- ■-19 The sensitizing dye used in the present invention is 5X per mole of silver halide.
10-'mol-5X 10-'mol, preferably lX
It is contained in the silver halide photographic emulsion in a proportion of 10-' mol-1×104 mol or 2×10-6 mol-5×10-’ mol.

The compound represented by the general formula (1) and the compound represented by the general formula (■) may be used together.

The sensitizing dye used in the present invention can be directly dispersed into the emulsion. In addition, these can be prepared using a suitable solvent, such as evaporated methyl alcohol, ethyl alcohol, methyl cellosolve,
It can also be dissolved in acetone, water, pyridine, or a mixed solvent thereof, and added to the emulsion in the form of a solution. Ultrasonic waves can also be used for dissolution. Also, as a method of adding this infrared sensitizing dye, US Pat.
A method of dissolving a dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding this dispersion to an emulsion, as described in Japanese Patent Publication No. 469.987, etc.
A method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding this dispersion to an emulsion, as described in US Pat. No. 3,822,135, etc.
As described in the specification, the dye is dissolved in a surfactant,
Method of adding the solution into an emulsion: JP-A-51-7462
A method of dissolving a red-shifting compound and adding the solution to an emulsion as described in No. 4: VF Kaisho 5
A method such as that described in No. 0-80826, in which a dye is dissolved in an acid substantially free of water, and the solution is added to an emulsion, is used. In addition, U.S. Patent No. 2
, No. 912,343, No. 3.342,605, No. 2. The methods described in 996°287, 3,429,835, etc. can also be used. The above infrared sensitizing dyes may be uniformly dispersed in the halide emulsion before being coated on a suitable support, but of course they may not be dispersed during any step in the preparation of the silver halide emulsion. can.

Unlike ordinary cyanine dyes, the aggravating dye according to the present invention does not cause so-called coupler desensitization even if a substituent having an acidic group is not necessarily introduced into the molecule. In particular, the use of compounds of the general formula (II) or (III) in combination with supersensitization makes it possible to eliminate coupler desensitization effects. In addition, especially when a coupler represented by the general formula (IV) or (V) is dispersed in the coexistence of a water-insoluble polymer that is soluble in a solvent, it is preferable to use a sensitizing dye that does not have an acidic group. It may even be more advantageous. This fact was previously unknown.

The compound represented by the general formula (II) imparts a supersensitizing effect to specific cyanine dyes, merocyanine dyes, and logocyanine dyes that are often used in a monomolecular adsorbed state (rather than in an aggregated state).

However, for the aggravating pigment in the present invention, it is several times to 1
It has a special effect of suppressing the occurrence of fog in high-frequency development of more than 0 times and rapid development.

The compound represented by the general formula (III) also promotes the adsorption of the sensitizing dye and has a supersensitizing effect, and at the same time has the effect of suppressing the oxidative decomposition of the sensitizing dye over time. The former compound improves the efficiency of photoelectron transfer through interaction with the sensitizing dye, and the latter compound has a different mechanism.
It appears that strong supersensitization occurs by the combination of the three sensitizing dyes according to the present invention.

The compound represented by general formula (II) used in the present invention will be explained.

General formula (II) Here, A represents a divalent aromatic residue. R3゜R4,R
s and R are each a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an arylthio group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, It represents an aryl group or a mercapto group, and these groups may be substituted.

However, at least one of A, R3, R,, Rs and R6
One has a sulfo group.

X and Y represent husbands #-CH= and -N=, and at least one of the middle ones of X and Y represents -N=.

More specifically, in the general formula (II), -A- is 2
These are -303M groups, where M is a hydrogen atom or a cation imparting water solubility (eg, sodium, potassium, etc.). ] may be included.

For example, one selected from the following -A1- or -A2- is useful. However, R: l, R4, R3 or R
When 5 does not contain -3o or M group, -A- is -AI
- selected from the group.

\SO3M etc. Here, M represents a hydrogen atom or a cation that provides water solubility.

Az: R=, R4, Rs and R6 are each a hydrogen atom, a hydroxy group, an alkyl group (the number of carbon atoms is preferably 1 to 8. For example, a methyl group, an ethyl group, an n-probyl group, an n-
butyl group, etc.), alkoxy group (number of carbon atoms is 1
-8 is preferable. (e.g. methoxy group, ethoxy group, propoxy group, butoxy group, etc.), aryloxy group (e.g. phenoxy group, naphthoxy group, 0-)roxy group, p-sulfophenoxy group, etc.), halogen atom (e.g. chlorine atom, bromine atom, etc.) , heterocyclic nucleus (e.g., morpholinyl group, piperidyl group, etc.), alkylthio group (e.g., methylthio group, ethylthio group, etc.), heterocyclylthio group (e.g., benzothiazolylthio group, benzimidazolylthio group, phenyltetrazolylthio group, etc.), Arylthio groups (e.g. phenylthio group, tolylthio group), amino group, alkylamino group or substituted alkylamino group (e.g. methylamino group, ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group) , β-hydroxyethylamino group, di(β-hydroxyethyl)amino group, β-sulfoethylamino group), arylamino group, or substituted arylamino group (e.g. anilino group, O
-sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, 0-toluidino group, m-)luidino group,
p-toluidino group, 0-carboxyanilino group, m-
Carboxyanilino group, p-carboxyanilino group, 0
-Chloroanilino group, m-chloroanilino group, P-chloroanilino group, p-aminoanilino group, O-anisidino group, m-anisidino group, p-anisidino group, 0-acetaminoanilino group, hydroxyanilino group, disulfonanilino group phenylamino group, naphthylamino group, sulfonaphthylamino group), heterocyclylamino group (e.g. 2-benzothiazolylamino group, 2-pyridyl-amino group, etc.)
, a substituted or unsubstituted aralkylamino group (eg, benzylamino group, 0-anisylamino group, m-anisylamino group, p-anisylamino group, etc.), an aryl group (eg, phenyl group, etc.), and a mercapto group.

R3, R4, Rs, and Rh may be the same or different from each other. When -A- is selected from the group -A2-, at least one of R, , R, , R, , R & has one or more sulfo groups (which may be free acid groups or may form salts). good). X and Y are -CH=
or -N=, preferably X is -CH=Y is -N
− is used.

Next, specific examples of compounds included in general formula (II) used in the present invention will be given. However, the present invention is not limited only to these compounds.

(II-1) 4.4'-bis[2,6-di(2-naphthoxy)pyrimidin-4-ylaminocostilbene-2,2'-disulfonic acid disodium salt (II-2) 4.4'-bis[2,6-di(2-naphthotylamino)pyrimidin-4-ylaminocostilbene-2,2'-disulfonic acid disodium salt (I[-3)4,4'-bis(2,6 -dianilinopyrimidin-4-ylamino)stilbene-2,2'-disulfonic acid disodium salt (II-4) 4.4'-bis(2-(2-naphthylamino)-6-anilinopyrimidine-4- ylamino]stilbene-2,2'-disulfonic acid disodium salt (II-5) 4.4'-bis(2,6-diphenoxypyrimidin-4-ylamino)stilbene-2,2'-disulfonic acid triethylammonium salt (I[-6)4.4'-bis[2,6-di(benzimidazolyl-2-thio)pyrimin-4-ylaminocostilbene-2,2'-disulfonic acid disodium salt (If-7) 4 .4'-bis[4,6-di(benzothiazolyl-2-thio)pyrimidine-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt (II-8) 4.4'-bis[4 ,6-di(benzothiazolyl-2-amino)pyrimidin-2-ylaminocostilbene-2゜2'-disulfonic acid disodium salt (n-9)4,4'-bis[4,6-di(naphthyl- 2
-oxy)pyrimidin-2-ylamino]stilbene-2,2'-disulfonic acid disodium salt (II-10) 4. 4'-bis(4,6-diphenoxypyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (II-11) 4. 4'-bis(4,6-cyphenylthiopyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (II-12) 4. 4'-bis(4,6-dimethylcabutovirimidin-2-ylamino)biphenyl-2,2'-disulfonic acid disodium salt (II-13) 4. 4'-bis(4,6-dianilino-triazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (II-14) 4. 4'-bis(4-anilino-6
-Hytrochiratriazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (II-15) 4. 4'-bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylamino]bibenzyl-2,2'-disulfonic acid disodium salt (n-16) 4,4'-bis(4,6 -dianilinopyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (n-17) 4,4'-bis[4-chloro-6-(2-
Naphthyloxy)pyrimidin-2-ylamino)biphenyl-2,2'-disulfonic acid disodium salt (II-18) 4. 4'-bis[4,6-di(1-
Phenyltetrazolyl-5thio)pyrimidin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt (n-19) 4,4'-bis[4,6-di(benzimidazolyl-2-thio) ) Pyrimidine-2-ylamino]stilbene-2゜2'-disulfonic acid disodium salt (IF-20) 4. 4'-bis(4-naphthylamino-6-anisotutriazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt Among these specific examples, (I[-1) to (■ to 6 ) are preferred, especially (II-1), (II-2), (■-4)
, (I[-5), (II-9), (II-15), (I
I-20) is preferred.

The compound represented by the general formula (n) is used in an amount of 0.01 to 5 g per mole of silver halide, and the weight ratio to the sensitizing dye is 1/1 to 1/100, preferably 1/2.
There are advantageous usage amounts in the range 1150 to 1150. In addition, it is preferable to use a compound represented by the general formula CI[[) in combination.

Next, the compound represented by general formula (III) will be explained.

General Formula (III) Here, Z2 represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. This ring may be fused with a benzene ring or a naphthalene ring. For example, thiazoliums (e.g. thiazolium, 4-methylthiazolium,
Benzothiazolium, 5-methylbenzothiazolium,
5-chlorobenzothiazolium, 5-methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methoxybenzothiazolium, naphtho(1,2-d)thiazolium, naphtho(2,1-d) thiazolium, etc.), oxacilliums (e.g. oxacillium, 4-methyloxacillium, benzoxacillium, 5-chlorobenzoxacilium, 5-phenylbenzoxacilium, 5-methylbenzoxacilium, naphtho[1, 2-
d) oxacillium, etc.), imidazoliums (e.g. 1-methylbenzimidazolium, 1-propyl-5-
chlorobenzimidazolium, 1-ethyl-5゜6-cyclopenzimidazolium, 1-allyl-5-trifluoromethyl-6-chlorobenzimidazolium, etc.)
, selenazoliums [e.g. benzoselenazolium, 5
Examples include -chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazolium, naphtho (1°2-d]selenazolium, etc.).

R? is a hydrogen atom, an alkyl group (preferably a carbon atom number of 8
Hereinafter, it represents a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc.), an alkenyl group (such as an allyl group, etc.). R8 represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc.). R7 and R8 may be substituted alkyl groups. Xl is an acid anion (e.g.
Cll-1Br-1I-, Cff1O,-, etc.), Z2
Among them, thiazoliums are preferably used.

More preferably, substituted or unsubstituted benzothiazolium or naphthothiazolium is advantageously used.

Note that these groups include substituted groups even if not specifically mentioned.

Specific examples of the compound represented by general formula (III) are shown below. However, the present invention is not limited to only these compounds.

(I[l-1) (III-2) (III-3) (I[[-4) (I[[-5) (III-6) (I[[-7) CHz CH=CHz (III- 8) (I[l-9) (I[-10) (III-11) Cz H5 (III-12) (II[-13) tits (I[l-16) (III-17) (III- 18) The compound of general formula (I[[) used in the present invention is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion.

The ratio (weight ratio) of the infrared sensitizing dye of general formula (I) to the compound represented by general formula (I[I) is represented by the dye represented by general formula (T)/-general formula DI). Compound=1
A range of 1/1 to 1/300 is advantageously used, in particular 1/1 to 1/300.
A range of 2 to 1150 is advantageously used.

The compound represented by the general formula (II[) used in the present invention can be directly dispersed in an emulsion, or can be dispersed in a suitable solvent (for example, water, methyl alcohol, ethyl alcohol, propatool, methyl cellosolve, acetone, etc.). )
Alternatively, it can be dissolved in a mixed solvent using two or more of these solvents and added to the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid in accordance with the method for adding aggravating dyes.

The compound represented by the general formula (III) is a compound represented by the general formula (I)
It may be added to the emulsion before or after the addition of the sensitizing dye represented by the general formula (
(2) The compound and the sensitizing dye of general formula (I) may be dissolved separately and added to the emulsion separately and simultaneously, or they may be mixed and then added to the emulsion.

When the combination of the infrared sensitizing dye represented by the general formula (1) of the present invention and the compound represented by the general formula (II[) is preferably further combined with the compound represented by the following general formula (II), Used to advantage.

The color recording material in the present invention uses a subtractive three primary color method. Therefore, conventionally, cyan couplers used for color photographic paper, color positive film, color reversal film, etc.
Magenta coupler and yellow coupler are used. A silver halide photosensitive layer unit containing a cyan coupler (CL), a silver halide photosensitive layer unit containing a magenta coupler (ML), and a silver halide photosensitive layer unit containing a yellow coupler (YL) are respectively They have different spectral sensitivity distributions. Depending on the wavelength of the output light, CL, ML, and YL can be distinguished, and the spectral sensitivity can be selected and designed at will. However, in reality, the output light
With the use of ED or laser light, and in particular recent advances in semiconductor laser elements, small, stable light sources have become available at low cost. Utilizing these, it is best to distinguish between red to infrared light, red light, green light, and blue to ultraviolet light as the case may be. The color recording material according to the invention is designed to use red or infrared light in at least one of the photosensitive layer units. Preferably, the CL is spectrally enhanced in the red to infrared wavelength region.

Cyan couplers used for CL include oil-protected naphthol-based and phenol-based couplers.
The naphthol couplers described in U.S. Pat. No. 2,474,293, preferably U.S. Pat. No. 4,052,212, U.S. Pat. 146°396, same No. 4,228.23
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 3 and No. 4,296,200. Also, specific examples of phenolic couplers are:
U.S. Patent No. 2,369,929, U.S. Patent No. 2°801.1
No. 71, No. 2,772,162, No. 2,895.
It is described in No. 826, etc.

Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is a cyan coupler having an ethyl or higher alkyl group in the meta-position of the phenol nucleus described in U.S. Pat. No. 3,772,002. Phenolic Cyan Couplers Having Groups, U.S. Pat. No. 2,772,
No. 162, No. 3,758゜308, No. 4.126
, No. 396, No. 4゜334.011, No. 4,32
No. 7,173, West German Patent Publication No. 3,329,729, European Patent No. 121.365, etc. 2,
5-diacylcimino-substituted phenolic couplers and U.S. Pat. No. 3,446.622, U.S. Pat. No. 4,333.99
No. 9, No. 4,451,559 and No. 4,427
, No. 767, etc., which have a phenylureido group at the 2-position and an acylamino group at the 5-position. Particularly preferred are couplers represented by the following general formula (IV) or (V).

General formula (IV) Y.

General formula (V) R, 3CON' I HY.

The symbols in the formula will be collectively described later.

Magenta couplers used for ML are oil-protected indacylon or cyanoacetyl couplers,
Preferred are pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles.

The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include U.S. Pat. Same No. 2,343.
No. 703, No. 2.600,788, No. 2.908
．． No. 573, No. 3,062,653, No. 3,15
No. 2.896 and No. 3,936.015, etc. As a leaving group for the second-generation 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or U.S. Pat. No. 4,351,89
The arylthio group described in No. 7 is particularly preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 provides a high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
Pyrazolobenzimidazoles as described in US Pat. (1
Examples include pyrazolotetrazoles described in Research Disclosure 24230 (June 1984) and JP-A-60-33552, and pyrazolopyrazoles described in Research Disclosure 24230 (June 1984) and JP-A-60-43659.

Imidazo(
1,2-b) pyrazoles are preferred and are described in U.S. Pat.
Pyrazolo(1,5-b)(1
, 2, 4)) Riazoles are particularly preferred.

Particularly preferred are couplers represented by general formula (IX) or (X). In particular, the coupler represented by the general formula (X) is more preferable from the viewpoint of photographic properties since it has a property of suppressing the occurrence of fog in addition to its good coloring properties. Furthermore, 2-equivalent couplers are preferred.

General formula (IX) General formula (X) A typical example of the yellow coupler used in YL is an oil-protected type acylacetamide coupler. A specific example is U.S. Patent No. 2,407,21
No. 0, No. 2,875,057 and No. 3,265
．． 506, etc. The use of two-equivalent yellow couplers is preferred for the present invention, and U.S. Pat.
08゜194, No. 3,447,928, No. 3゜933.501, No. 4,022,620, etc., or the oxygen atom separation type yellow couplers, or Japanese Patent Publication No. 10739/1983. , U.S. Patent No. 4,401,
No. 752, No. 4,326°024, British Patent No. 1,
No. 425,020, West German Application No. 2,219,917
No. 2,261.361, No. 2,329,58
Typical examples include the nitrogen atom separation type yellow couplers described in Japanese Patent No. 7 and No. 2,433,812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness;
- Benzoylacetanilide couplers provide high color density.

Particularly preferred are couplers represented by general formula (XI).

General formula (XI) CH.

■ (General formula (IV), (V), (IX), (X), (XI
), R1, R, t and R11 each represent an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group; Each represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group, and Roll and R33 represent an aromatic group, which may be substituted.

R3□ is a hydrogen atom, an aliphatic or aromatic acyl group,
represents an aliphatic or aromatic sulfonyl group, R34 represents a hydrogen atom or a substituent, Q represents a substituted or unsubstituted N-phenylcarbamoyl group, Za and zb are methine (which may be substituted with W), Represents substituted methine, or =N-, and Y, Y, and Y4 represent a hydrogen atom, a halogen atom, or a group that can be separated during the coupling reaction between the oxidant and the developing agent (hereinafter abbreviated as a leaving group). where, Y represents a hydrogen atom or a leaving group, Y represents a leaving group, and in general formula (IV) and general formula (V), R1° and R
11 and R1, and 'R14 are respectively 5.6 or 7
It may form a member ring.

Furthermore, R,,R,. , Ro or YI + R2Zn
R13+R14 or Yz i R31, R4N+ R
31 or Y: R24+Za, Zb or Y4; Q or Y may form a dimer or more multimer.

The aliphatic group mentioned here represents a linear, branched or cyclic alkyl, alkenyl or alkynyl.

Note that these groups include substituted groups even if not specifically mentioned. ) The dye-forming couplers and the above-mentioned special couplers may form dimers or higher polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451.82.
No. 0 and No. 4,080°211. Specific examples of polymerized magenta couplers are described in British Patent No. 2. 102. No. 173 and U.S. Pat. No. 4,367
．． It is described in No. 282.

These couplers can be used in the form of coexistence and dispersion with at least one type of high boiling point organic solvent.

Preferably, a high boiling point organic solvent represented by the following general formula (A) or E) is used.

General formula (A) General formula (B) w, -coo-w.

General formula (C) General formula CD) General formula (E) W+ OWz , (wherein, W+ , Wz and W are each a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group , and W4 is w,,o
represents w or s-w, n is an integer from 0 to 5, and when n is 2 or more, W4 may be the same or different from each other, and in general formula (E), W and Wz may form a fused ring. Note that these groups include substituted groups even if not specifically mentioned. ). Further, it is preferable to use a water-insoluble organic solvent-soluble polymer, such as the polymer described in Japanese Patent Publication No. 48-30494, for dispersion.

This makes it possible to eliminate the desensitizing effect of the coupler on the sensitizing dye according to the invention over time.

In the present invention, the water-insoluble organic solvent-soluble polymer used in particular with the cyan coupler is preferably a water-insoluble and organic solvent-soluble polymer having 20% by weight or less of repeating units having an acid group in the main chain or side chain. , any polymer may be used.

Polymers whose repeating units have a carbonyl bond are preferred from the viewpoint of fading improvement effect. On the other hand, when a polymer made of a monomer containing an acid group is used, the fading-improving effect of the polymer is significantly reduced, although the reason is not clear.

Therefore, the proportion of repeating units having acid groups in the polymer is 20% or less by weight, preferably 5% or less, and more preferably 2% or less. Most preferably, it does not contain a repeating unit having an acid group. The polymer according to the present invention will be explained below using specific examples, but the present invention is not limited thereto.

Preferred polymers include vinyl polymers and their copolymers as described in Japanese Patent Application No. 189771/1982, and polyester resins obtained by condensing polyhydric alcohols and polybasic acids. Some specific examples of the polymer used in the present invention are shown below, but the present invention is not limited thereto.

P-1) Polyvinyl acetate P-2) Polymethyl methacrylate P-3) Polyethyl acrylate P-4) Poly n-butyl methacrylate P-5) Polycyclohexyl methacrylate P-6) Poly(N-ter)
(t-butyl methacrylamide) P-7) Vinyl acetate-vinyl alcohol copolymer (95
:5) P-8) n-butyl acrylate-acrylamide copolymer (95:5) P-9) 1,4-butanediol-adipic acid polyester P-10) n-butyl methacrylate-N-vinyl-2
-Pyrrolidone copolymer (90:10) P-11) Diacetone acrylamide-methyl methacrylate copolymer (55:45) P-12) Methyl methacrylate-acrylic acid copolymer (95:5) P-13) Poly (N-also crt-butylacrylamide) P-14) Poly(N-sec-butylacrylamide) P-15) Poly(N,N-dimethylacrylamide) Represented by general formula (IV) or (V) according to the present invention Specific examples of cyan couplers include
-175233 and Japanese Patent Application No. 61-162813, specific examples thereof are given below. However, it is not limited to this.

(IV-3) (IV-4) (IV-5) C! (V-1) (V-3) (V-4) (V-6) (V-7) (V-8) (V-9) (V-10) (V-11) (t)CsH+t book In the present invention, specific examples of magenta couplers represented by general formula (IX) or (X), particularly preferred 2-equivalent magenta couplers, are shown below. However, it is not limited to this.

(IX)-3 2 (IX)-5 (IX>6 Hx 2 (X)-1 CaH+, (t) (X)-2 (X>3 (X)-4 (X)-5 (X )-7 Typical usage amounts of color couplers range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.02 mole for yellow couplers.
5 moles, 0.003 to 0.00 for magenta couplers.
3 mol, and for cyan couplers 0.002 to 0.
It is 3 moles.

Further, the standard coating amounts of color couplers in color vapor range from 4 to 14 x 10-', 2 to 8 x 10-' and 2 to 9 x 10-' mof/rrf for yellow, magenta and cyan couplers, respectively.

In the present invention, the negative full-color recording material usually uses a silver halide emulsion that is used in color photographic paper, color positive film, reversal color photographic paper, etc.
For example, Japanese Patent Application No. 61-123072, Japanese Patent Application No. 61-13
No. 0736, Kaikai No. 61-13073'7, and Kaikai No. 61-13073'7
Those described in No. 131209 and the like are used. In general, silver halides used in the present invention include silver chloride, silver bromide, and mixed silver halides such as silver chlorobromide, silver chloroiodobromide, and silver iodobromide. It is true.

The silver halide preferably used in the present invention is silver chloroiodobromide, silver iodochloride, or silver iodobromide, which does not contain silver iodide or contains less than 3% by mole of silver iodide. The silver halide grains may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain.

Moreover, they may be mixed. For example, regarding silver chlorobromide grains having different phases, the grains may have a core or single or multiple layers that are richer in silver bromide than the average halogen composition. Further, the grains may have a core rich in silver chloride or a single or plural layers within the grains based on the average halogen composition. Therefore, the grain surface layer may be covered with a layer richer in silver bromide than the average halogen composition, or vice versa.

The average grain size of silver halide grains (in the case of spherical or nearly spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the ridge length is used as the grain size and the projected area is also calculated on average) is 2 μ or less is preferably 0.1μ or more,
Particularly preferred is 1μ or less and 0.15μ or more. The particle size distribution may be narrow or wide, but more than 90%, especially 95% of all particles are within ±40%, preferably within ±20%, of the average particle size in terms of particle number or weight.
It is preferable to use a so-called monodisperse silver halide emulsion having a narrow grain size distribution in which the above is included in the present invention.

In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in emulsion layers having substantially the same color sensitivity. It is preferable to apply multiple layers. 2 more
It is also possible to use more than one type of polydisperse silver halide emulsion or a combination of a monodisperse emulsion and a polydisperse emulsion by mixing or layering them.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), but those having regular crystals are preferred. Also, irregular shapes such as spherical (
It may have an irregular crystal form, or it may have a composite form of these crystal forms. Tabular grains may also be used, and in particular, tabular grains with a length/thickness ratio of 5 or more, particularly 8 or more account for 50% of the total projected area of the grain.
An emulsion having a concentration of more than 100% may be used. An emulsion consisting of a mixture of these types of crystal forms may also be used. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is described in "Chemistry and Physics of Photography J" by Grafkides, Chi.
mie etPhysique Photography
ique (Paul Mante 1, 1967)
], “Photographic Emulsion Chemistry” by Duffin (G, F, Duf
Written by fin Photographic En+ulsi
onChemistry (Focal Pres.
sfll, 1966)], Zelikman et al., "Production and Coating of Photographic Emulsions J"
Making and Coating by at al
Photographic Emulsion (F
ocal Press, 1964)]. That is,
Any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one form of the simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

In the process of silver halide grain formation or physical ripening,
Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, etc. can be used to prevent reciprocity law failure, increase sensitivity, and improve t [! f
They may coexist for purposes such as f.

After grain formation, silver halide emulsions are usually subjected to physical ripening, desalting and chemical ripening before being used for coating.

Well-known halogenation! ! Solvents (for example, ammonia, Rodankali, or When physical ripening is performed in the presence of thioethers and thione compounds (described in JP-A-54-155828, etc.), a monodisperse emulsion having a regular crystal shape and a nearly uniform particle size distribution can be obtained. . In order to remove soluble root salts from the emulsion before and after physical ripening, Nudel water washing, flocculation sedimentation method, ultrafiltration method, etc. are used.

The silver halide emulsion used in the present invention can be chemically sensitized by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization using gold salts or total complex salts, etc. alone or in combination.

That is, a sulfur sensitization method using sulfur-containing compounds that can react with active gelatin and silver (such as thiosulfates, thioureas, mercapto compounds, and rhodanines); reducing substances!
(e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); metal compounds (e.g., total complex salts, Pt,
Ir.

A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as Pd, Rh, and Fe can be used alone or in combination.

In the present invention, for the direct positive color recording material, an internal latent image type silver halide emulsion, which is usually used in direct positive (or autopositive) type color photographic paper or photosensitive material for instant photography, is used.

The aggravation technique represented by the general formula (1), (II), (I[) or (■) in the present invention can be applied to each silver halide emulsion used in a negative tone or a direct positive tone. , and the benefits found by the present invention are similarly expressed. Couplers represented by general formula (IV) or (V) can be similarly applied to negative type and direct positive type.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surfaces of silver halide grains are not fogged in advance and latent images are mainly formed inside the grains. However, more specifically, 0.5 to 3 g of silver halide emulsion is deposited on a transparent support.
/rrf, exposed to light for a fixed time of 0.01 to 10 seconds, and developed for 5 minutes at 18°C in the following developer A (internal type developer), using the usual photographic density measurement method. The maximum density measured by the following developer B (
Preferred are those having a density that is at least 5 times greater, more preferably at least 10 times greater than the maximum density obtained when developed for 6 minutes at 20° C. in a surface-type developer.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone
8g Soda carbonate (-water salt)
52.5gKBr
Add 5g KI O, 5g water 11゜Surface developer B Metol 2.5g! -Ascorbic acid LogNaBOz ・4Hz
0 35g KBr
Add 1g water
Specific examples of latent type emulsions include U.S. Patent No. 2,592,250, Japanese Patent Publication No. 58-54379,
No. 58-3536, No. 60-5582, Japanese Unexamined Patent Publication No. 1973
-156614, 57-79940, 5B-7
The conversion type silver halide emulsion described in the specification of No. 0221 and the emulsion with a shell attached thereto,
U.S. Patent No. 3,761.276, U.S. Patent No. 3,850.637
No. 3゜923.513, No. 4,035,185, No. 4.395,478, No. 4,431,730,
No. 4,504,570, JP-A-53-60222,
No. 56-22681, No. 59-208540, No. 6
No. 0-107641, No. 61-3137, Patent Application No. 1983
-3642, Research Disclosure Magazine No.
23510 (issued November 1983) P2S5, same N
o, 18155 (published in May 1979) P265-2
Mention may be made of the core/shell type silver halide emulsion in which a metal is doped inside, as described in the patent disclosed in No. 68.

Recording materials having a photosensitive layer using an internal latent image type silver halide emulsion undergo a photofogging process (fogging by uniform dusk), color development, bleaching and fixing, rinsing bath or stabilizing bath, etc. after image exposure. Color positive images can be created directly through the color development process. For example, the special public official public company Sho 58-693
No. 6, JP-A-58-60739, JP-A-58-702
No. 23 and Japanese Patent Application No. 136948/1984.

However, without using the photofogging step, a color positive image can be obtained directly by the color development step described above by using a so-called nucleating agent together with an internal latent image type silver halide emulsion.

The present invention includes, for example, research disclosure (Research Disclosure).
Search Disclosure) Magazine No. 22.
538 (Published January 1983, pages 50-54) Same magazine No.
, 15.162 (published in November 1976, pages 76-77) and the same magazine No. 23.510 (published in November 1983, pages 346-352). In particular, for example, Japanese Patent Application No. 61-136948,
A nucleation accelerator may be used in combination with a nucleating agent as described in JP-A-61-136949, JP-A-61-153481, JP-A-61-259799, and the like. As a result, a color image can be obtained by performing a quick and simple development process similar to the color development process for ordinary color photographic paper.

In the color photosensitive material according to the present invention, the photosensitive layer units other than the photosensitive layer units having spectral sensitivity to red light or infrared light can be spectral sensitive to red region, green region, and in some cases ultraviolet to blue region, by a conventional method. For example, specific examples are shown in Table 1.

Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dyes and a strong color enhancer may be used in combination. For detailed examples, see Research Disclosure Magazine No. 17643-
IV (issued December 1978), patents described in pages 23-24, etc., Japanese Patent Application No. 131583/1983, 61-1
31209, etc.

The photographic emulsion used in the present invention may contain an antifoggant or a stabilizer for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. For detailed examples, see Research Disclosure Magazine No. 17643-
Vl (published December 1978) pages 24-25 and E
, J. Birr, “5tabilization o
f Photographic 5ilver
Halide Emulsions” (Focal Pre
ss), published in 1974.

Table 1 However, PL: Protective layer G: Line sensitive AH: Anti-Halley scene layer R: Red R/IR,
Red to infrared sensitivity B: Blue sensitivity (): Although not essential, it means that it is preferable to have it.

An intermediate layer may be inserted between each photosensitive layer.

The dye for preventing irradiation or antihalation for the photosensitive layer having spectral sensitivity in the end red to infrared wavelength region used in the present invention has spectral absorption in the wavelength region longer than about 670 nm and up to 2000 nm. It is durable, has no photographic harmful side effects, and is chemically stable enough.
It is desirable to have a dye that has a decolorizing effect or dissolves out of the film during the color development process, but this has not been found so far.

Dyes represented by the following general formula (Vl) or general formula (■) are particularly preferably used for the present invention.

RR0! (XS'n-1 1'(:ku!+R111 where RISr R16, R+t+ R1+!+ RI
Q and Rto may be the same or different from each other, represent an alkyl group or an aryl group, and may have a substituent,
Z3° and Z4 each represent a group of nonmetallic atoms necessary to form a benzo-fused ring or a naphtho-fused ring, and may have a substituent. However, R,s,'R,6゜RI
Ql RIL RI9+ Rzo* L t
Of the groups represented by 24, at least one, preferably two or more, more preferably four to six, have an acid substituent (for example, a sulfonic acid group or a carboxylic acid group), and particularly preferably a dye molecule. represents a group that allows the group to have 4 to 6 sulfonic acid groups. In the present invention, a sulfonic acid group means a sulfo group or a salt thereof, and a carboxylic acid group means a carboxyl group or a salt thereof.

L represents a methine group, which may have a substituent, and
61 represents an anion. A specific example of an anion also represented by X is a halogen ion (C12-Br)
, p F luenesulfonate ion, ethyl sulfate ion, etc.

n represents 1 or 2, and is 1 when the dye forms an inner salt. l represents 3.4 or 5.

RISI R1&I R1? + RIL R1,
, the alkyl group represented by Rto preferably has 1 carbon number.
-5 lower alkyl groups (e.g. methyl, ethyl, n
-propyl group, n-butyl group, isopropyl group, n-pentyl group, etc.), and may have a substituent (e.g., sulfonic acid group, carboxylic oxygen, hydroxyl group, etc.), more preferably R+s+ and R1 ° represents a lower alkyl group having 1 to 5 carbon atoms (for example, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, etc.) having a sulfonic acid group.

23, Substituents of the benzo-fused ring or naphtho-fused ring formed by the nonmetallic atom group represented by Z4 include sulfonic acid group, carboxylic acid group, hydroxyl group, halogen atom (for example, F, Cj!, Br, etc.), cyano group, substituted amine group (e.g. dimethylamino group, diethylamino group, ethyl-4-sulfobutylamino group, di(3-sulfopropyl)amino group, etc.), or bonded to the ring directly or via a divalent linking group. Substituted or unsubstituted carbon number 1-5
represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc. (as a substituent, a sulfonic acid group, a carboxylic acid group, a hydroxyl group, etc. are preferable)), and a divalent linking group is, for example, -〇- 1NHCO, NH3(h
, NHCOO.

-NHCONH-, Coo-, -Co-, -3o□-2
etc. are preferable.

The substituent of the methine group represented by
Lower alkyl groups (for example, methyl group, ethyl group, etc.) and halogen atoms (for example, F, (1, Br, etc.) of 5 are preferable.The substituents of the methine group expressed as (e.g. 4,4
-dimethylcyclohexene ring).

Specific examples of the dye compound represented by the general formula (VI) used in the present invention are shown below, but the scope of the present invention is not limited thereto.

(Vl-1) (V[-2) (Vl-3) (Vl-4) (VT-5) (Vl-6) (Vl-7) ('/l-8) (Vl-7) (Vl -10) (Vl-11) (VT-12) (V'l-131 (Vl-141 (Vl-151 (VT-16) (Vl-17) (Vl-18) (Vl-19) (Vl- 20) General formula (■) R□′ゝR1゜In the formula, R2□ represents an alkyl group, an aryl group (e.g., a phenyl group, a naphthyl group, etc.), or a heterocyclic group, which may have a substituent, R2□ and R2S may be the same or different from each other and represent a hydrogen atom or a group capable of substituting it; RZ3 and R24 may be the same or different from each other and represent a halogen atom (for example, C2, Br
etc.), an alkoxy group having 1 to 5 carbon atoms (e.g., methoxy group, ethoxy group, 2-sulfoethoxy group, methoxyethoxy group, etc.), and an alkyl group, which may have a substituent, and RZb and RZ? may be the same or different, and may include substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups (e.g. phenyl group, naphthyl group, etc.), acyl groups (e.g. acetyl group, propionyl group, etc.), sulfonyl groups ( For example, methanesulfonyl group, ethanesulfonyl group, etc.) or Rzb and R
2, represents a group of nonmetallic atoms (eg, pyrrolidine ring, piperidine ring, morpholine ring, etc.) necessary for forming a 5- or 6-membered ring by linking. However, R21, R22, R21,
RZ4, R25, R26 and R2? At least one, preferably 2 to 5 of the groups represented by have a sulfo group or a salt thereof, or a carboxyl group or a salt thereof.

RZI, R23, R24, Rzb or RZ? The alkyl groups represented by may be the same or different, and include lower alkyl groups having 1 to 5 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, etc.)
is preferable, and may have a substituent (for example, a sulfo group, a carboxyl group, a hydroxyl group, etc.).

R□, RZb or R2? The aryl groups represented by may be the same or different, and may include a substituted or unsubstituted phenyl group (substituents include, for example, a sulfo group, a carboxyl group, a hydroxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a fluorine atom, etc.), Acyl groups having 1 to 5 carbon atoms (e.g. acetyl group, propionyl group, etc.), sulfonyl groups having 1 to 5 carbon atoms (e.g. methanesulfonyl group, ethanesulfonyl group, 2-sulfoethanesulfonyl group, 3-sulfopropa, sulfonyl group) ), a carbamoyl group having 1 to 5 carbon atoms (e.g., an unsubstituted carbamoyl group, a methylaminocarbamoyl group, a 2-sulfoethylcarbamoyl group,
2-carboxyethylcarbamoyl group, 2-hydroxycarbamoyl group), sulfamoyl group having 1 to 5 carbon atoms (for example, unsubstituted sulfamoyl group, methylsulfamoyl group, ethylsulfamoyl group, 2-sulfoethylsulfamoyl group) group, 2-carboxysulfamoyl group, etc.), alkoxycarbonyl group having 1 to 5 carbon atoms (e.g., methoxycarbonyl group, ethoxycarbonyl group, trichloroethoxycarbonyl group, trifluoroethoxycarbonyl group, etc.), Alkoxy group (e.g. methoxy group, ethoxy group, etc.), amino group (e.g. dimethylamino group, diethylamide group, etc.)) or substituted or unsubstituted naphthyl group (substituents are the same as those for phenyl group) ) is preferred.

The heterocycle represented by Rz+ represents a monocyclic heterocycle or a fused heterocycle, and may have a substituent, such as a 1,3-thiazole ring, a 1,3,4-) riazole ring, a benzothiazole ring, Benzimidazole ring, benzoxazole ring, 1. 3. A 4-thiadiazole ring and the like (as a substituent, for example, a lower alkyl group such as a methyl group or an ethyl group, a lower alkoxy group such as a methoxy or ethoxy group, a sulfo group, a hydroxyl group, a carboxyl group, etc.) are preferable.

Groups capable of substituting hydrogen atoms represented by R2□ and Rts include halogen atoms (for example, F, ClXBr, etc.), hydroxyl groups, sulfo groups, carboxyl groups, cyan groups, or substituents bonded directly or via divalent linking groups. or represents an unsubstituted alkyl group having 1 to 5 carbon atoms [for example, methyl group, ethyl group, etc. (substituents include sulfo group, carboxyl group, hydroxyl group, etc.)], and the divalent linking group is, for example, -〇-1
-NHCO-1-NH3O□-1-NHCOO-1-N
HCON H-1-COO-2-CO-1-3O□-
etc.

Specific examples of the dye compound represented by the general formula (■) used in the present invention are shown below, but the scope of the present invention is not limited thereto.

(■-2) (■-3) KO＠5(CH city/＼(CHRIl5OIK(■-4)( -6
) Na03S(CHJ4 (CHz)4So:+N
aNa03S(CHz)4 (CHzLSOtN
a(■-8) (■-9) HsCz (CHz)4sO3Na The above-mentioned dye in the present invention can be dissolved in water or a water-soluble solvent such as alcohol, methyl cellosolve, acetone, or a mixed solvent thereof, or A solution solubilized in the surfactant used is added to the photosensitive layer, intermediate layer, or protective layer, and is diffused and incorporated into the water-softening colloid layer. Further, it is mixed and dissolved or dispersed in a solution with a coupler, a color mixing inhibitor, an ultraviolet absorber, and an additive for silver halide emulsions to be used, and is incorporated into the hydrophilic colloid layer. The amount to be used can be selected from a preferable range, generally from 10-'g to 5g/po, preferably from 0.2g to 2g/y. It is also possible to use a mixture of two or more types of dyes.

In particular, the dye represented by the general formula (VI) has almost no harmful effects such as desensitization and fogging, and has sharp spectral absorption in the red to infrared region, so it is particularly sensitive to red to infrared light. When used in large amounts in the layer, irradiation prevention and altihalation effects can be effectively imparted. More preferably, anti-array ii (AH
).

In the present invention, in order to contain the dye substantially only in the non-photosensitive hydrophilic colloid layer, it is sufficient to prevent the dye from diffusing from the non-photosensitive hydrophilic colloid layer to the emulsion layer. For example, a method may be used in which a silver halide emulsion layer is coated and completely set, and then a non-photosensitive hydrophilic colloid layer containing a non-diffusible dye is coated on this emulsion layer.

Furthermore, when simultaneously coating an emulsion layer and a non-photosensitive hydrophilic colloid layer using a multilayer simultaneous coating method, it is most preferable to add a non-diffusible dye or a polymer mordant together with the dye to the non-photosensitive hydrophilic colloid layer. .

Polymer emulsions are disclosed, for example, in JP-A No. 57-202539, Zenshitsu No. 59-131931, Zenshitsu No. 59-219745.
No. 59-232340 fully open, No. 60-57836 fully closed, No. 61-42655 fully closed, No. 61-46948 fully open,
It can be selected from the compounds described in JP-A No. 60-95241, Zenshitsu No. 60-174734, Zenshitsu No. 61-87180, Zenshitsu No. 61-87181, and the like. These polymer mordants may be dispersed in a hydrophilic colloid such as gelatin to form a coating layer, and the dye of the present invention may be added to another layer and fixed by diffusion to form an AH layer.

As the support, those commonly used for photosensitive materials are used. For example, plastic films such as PET, TAC, DAC, and polycarbonate, paper, baryta paper, paper laminated with polyethine, paper laminated with metal, synthetic paper, metal plate, tinsel foil, etc. are used.

Furthermore, a vinyl chloride resin containing a white pigment can be used.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Although amine phenol compounds are also useful as color developing agents, p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, and 4-methyl. -4-amino-N-ethyl-N
-β-hydroxylethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride and P-)luenesulfonate. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or anti-capri agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Generally, it includes such things as Also, if necessary, preservatives such as hydroxylamine or sulfites, organic solvents such as triethanolamine, diethylene glycol,
Development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developers such as 1-phanyl-3-pyrazolidone. , viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, oxidation as described in West German Patent Application (OLS) No. 2,622,950. An inhibitor or the like may be added to the color developer.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-
3-pyrazolidones such as 3-pyrazolidone or N-
Known black and white developers such as aminophenols such as methyl-p-aminephenol can be used alone or in combination.

The color developing solution according to the present invention is suitable for color development processing, which is quick, easy, and has good processing stability. Among the above compositions, the following element A is particularly prepared at a pH of 11.
5 or less developer is preferred.

This color developing solution enables full-color recording according to the present invention.
Recording materials can be commonly subjected to color development processing.

Element A: Contains an aromatic primary amine color developing agent, a restoring agent for its oxidized form, and a capture agent for its oxidized form.

A "restoring agent" is a compound that restores the oxidized form of a color developing agent, and can be easily defined by certain tests. Next, as a representative example of a color developing agent, 3-methyl-4
A method for defining amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline is described. If the crude drug used changes, it is sufficient to measure the total number of moles.

The restoring agent is a hydroxylamino derivative, for example, Japanese Patent Application No. 1983.
Compounds described in Japanese Patent Application No. 170756-170756 and hydrazine derivatives such as Japanese Patent Application No. 170756-1982 and Japanese Patent Application No. 61-1-1
It can be selected from the compounds described in No. 71682, Kaifuku No. 61-173468, and the like.

<Test method for restoring agent> Prepare the following test solutions A, B, and C, mix equal amounts of test solutions A and B, and stir gently for 10 minutes at room temperature. After filtering the mixed solution, the mixed solution was designated as D, and the absorbance at 302 nm (C302 and D302) of the D solution and the C solution was measured.

° ' A Monopotassium phosphate 0.05 mol Sodium sulfite 0.2 g 3-methyl-4-
Amino-N-3.0g Ethyl-N-(β-methanesulfonamidoethyl)-aniline oxide Si 1.67g Add water and 1000 mj! H70 pH is prepared with hydrochloric acid or potassium hydroxide.

Formula 1 'B monopotassium phosphate 0.05 mole test compound 7X10-'' moles
1000 m4 pH 7.0 pH is adjusted with hydrochloric acid or potassium hydroxide.

"Eng." C Monopotassium phosphate 0.05 mol Sodium sulfite 0.1 g 3-methyl-4-
Amino-N-1,5g ethyl-N-(β-methanesulfonamidoethyl)aniline in 1000 ml pH 7, O The pH is adjusted with hydrochloric acid or potassium hydroxide.

Regulation of restoring agent> D302/C302 is 0.80 according to the above test method.
A test compound is defined as a "restorant" if:

The scavenger for the one-electron or two-electron oxidized form of the restoring agent can be determined experimentally as follows.

By coexisting with the restoring agent and the capture agent, the color developing agent can be prevented from being separated from the coupler and the coloring reaction due to secondary oxidation, and the coloring developing agent can be used extremely efficiently for the coloring reaction, and the coloring agent can be used extremely efficiently. Improves developer retention.

Capture agents are disclosed in, for example, Japanese Patent Application No. 61-259799 and Japanese Patent Application No. 1983.
It can be selected from the compounds described in No. 1-169789, aminocarboxylic acids, and the like.

<Test method for capture agent> The following test solutions E and F were prepared.

-E KzCOz 25g Restorer below 4.2g Test compound
Add 0.05 morph
1000ml pH 10,25 Restoration agent CH2CH, NCH, CH3 Test solution Standards for capture agent that does not contain test compounds in test solution E was measured. Compare the spectral intensity of liquid E and the spectral intensity of liquid F, and a test compound whose spectral intensity (SE) of liquid E is 90% or less compared to that of liquid F (SF) is defined as "capture agent J." .

The conditions for measuring the ESR spectrum were as follows.

(1) Central magnetic field 3376C; (Gauss) ±5
0G (2) Measurement temperature 25°C (3) Microwave output 4mW (4) Modulation 100 KHz modulation of 0.63G was applied to the liquid frequency.

(5) Response 0.1 (6) Width increase rate 1000 times After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Examples of bleaching agents include iron (■), cobalt (■), and chromium (■).
), compounds of polyvalent metals such as copper (It), peracids, quinones, nitrone compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (II), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propatol Complex salts of aminopolycarboxylic acids such as tetraacetic acid or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; manganates; nitrosophels, etc. can be used.

Among these, ethylenediaminetetraacetic acid iron (III) salt,
Iron diethylenetriaminepentaacetate ( I [ [ ) salt and persulfate are quick processing and! ! : is preferable from the viewpoint of environmental pollution.

Furthermore, the ethylenediaminetetraacetic acid iron(I[I) complex salt is particularly useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

A bleach accelerator may be used in combination with the bleaching solution, bleach-fixing solution, and their pre-bath, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3.893.858, German Pat.
, No. 290.812, 2. 059゜989, JP-A-53-32736, JP-A-53-57831, JP-A-53
-37418, 53-65732, 53-72
No. 623, No. 53-95630, No. 53-95631
Nos. 53-104232, 53-124424, 53-141623, 53-28426, Research Disclosure No. 17129 (19
Compounds having a mercapto group or disulfide group as described in JP-A No. 1978-140129; thiazolidine derivatives as described in JP-A No. 140129-1977:
No. 8506, JP-A-52-20832, JP-A No. 53-32
No. 735, thiourea derivatives described in US Pat. No. 3,706,561; iodized side described in West German Patent No. 1,127,715, JP-A-58-16235; West German Patent No. 96
Polyethylene oxides described in No. 6.410 and No. 2.748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others described in Japanese Patent Publication No. 49-42434,
No. 49-59644, No. 53-94927, No. 54
-35727, 55-26506 and 58-
The compounds described in No. 163940 and iodine and bromide ions can also be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect.
In particular, U.S. Patent No. 3,893,858, West German Patent No. 1,
Compounds described in No. 290,812 and JP-A-53-95630 are preferred. Furthermore, compounds described in US Pat. No. 4,552,834 are also preferred. These bleach accelerators may be added to the photosensitive material.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodides, but thiosulfates are generally used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the bleach-fixing treatment or the fixing treatment, washing treatment and stabilization treatment are usually performed. Various known compounds may be added to the water washing process and stabilization process for the purpose of preventing precipitation and saving water. For example, to prevent precipitation, use water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, fungicides and anti-piping agents that prevent the growth of various bacteria, algae, and mold. Agents, metal salts such as magnesium salts and aluminum salts and bismuth salts, surfactants for preventing drying load and unevenness, and various hardening agents can be added as necessary. Photographic Science and Engineering Magazine by Aiha West (L, E, West
, Phot, Sci, Eng,) + Volume 6, 34
Compounds described on pages 4 to 359 (1965) may be added, and addition of chelating agents and anti-piping agents is particularly effective.

In the washing process, two or more tanks are generally used for countercurrent washing to save water. Furthermore, instead of the water washing process,
A multi-stage countercurrent stabilization treatment process such as that described in No.-8543 may be implemented. In the case of this process, 2 to 9 countercurrent columns are required.In addition to the above-mentioned additives, various compounds are added to the stabilizing bath for the purpose of specifying images. For example, the membrane p
Various buffers for adjusting H (e.g. pH 3-9) (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, mono- Typical examples include (using a combination of carboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (benzisothiazolinone, isothiazolone, 4- Various additives such as thiazoline (benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardeners, etc. may be used, and two compounds for the same or different purposes may be used. The above may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

The washing and stabilization processing time of the present invention varies depending on the type of sensitive material and processing conditions, but is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. For this purpose, it is preferable to use various precursors of color developing agents.

For example, indoaniline compounds described in US Pat. No. 3,342,597, US Pat. No. 3,342,599, Research Disclosure No. 14850 and US Pat. No. 15159
In addition to the Schiff base-type compounds described in JP-A No. 13924, the metal salt complexes described in U.S. Pat. No. 56-6235, No. 56-16133, No. 56-59232, No. 5
No. 6-67842, No. 56-83734, No. 56-8
No. 3735, No. 56-83736, No. 56-8973
No. 5, No. 56-81837, No. 56-54430,
Examples include various salt-type precursors described in No. 56-106241, No. 56-107236, No. 57-97531, and No. 57-83565.

The silver halide color photosensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may also be incorporated. Typical compounds are JP-A Nos. 56-64339, 57-144547, 57-211147, 5B-50532, 58-50536, 58-50533, and 5B-
No. 50534, No. 58-50535 and No. 58-1
It is described in No. 15438, etc.

Various processing solutions in the present invention are used at temperatures of 10°C to 50°C. A temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in the various processing baths as necessary.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

〔Example〕

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Silver halide emulsion (1) used in the examples of the present invention was prepared as follows.

(1 liquid) (2 liquid) Sulfuric acid (IN) 24 cc (3 liquid) Silver halide bath agent below (1%) 3 cc Hs (4 liquid) (5 liquid) (6 liquid) (7 liquid) (1 liquid) was heated to 56°C, and (liquid 2) and (liquid 3) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 30 minutes. After another 10 minutes, (Liquid 6) and (Liquid 7) were added simultaneously over a period of 20 minutes. After 5 minutes of addition, the temperature was lowered and desalted. Add water and dispersed gelatin, adjust the pH to 6.2, average particle size (J) 0.45 μm, coefficient of variation (standard deviation S divided by average particle size: S/d) 0
．． 08, a monodispersed cubic silver chlorobromide emulsion containing 70 mol % of silver bromide was obtained. Sodium thiosulfate was added to this emulsion to perform optimal chemical sensitization.

Next, silver halide emulsions (2) (3) with different silver chloride contents
) (4) with the above 4 and 6 liquids of KBr, NaCj! Adjustments were made in the same manner by changing the amounts and addition times of 4 liquids and 5 keys as shown in Table 1.

Table 2 Average grain size of silver halide emulsions (1) to (4),
The coefficient of variation and halogen composition are shown in Table 3.

Table 3 Both sides of photographic white base paper were laminated using polyethylene. After the surface was subjected to a corona discharge treatment, an undercoat treatment was performed using gelatin, a hardening agent, and 1,4-bis(vinylsulfonylacetamido)ethane. On top of this
Each layer having the composition shown in Table 4 was coated in multiple layers by a conventional method.

Table-4 Mordant (A) Color image stabilizer (D) Shiri NH-(II [lu,) Solvent (F) l Consolidation inhibitor (G) H H Red-sensitive sensitizing dye (1-I) Color image stabilization Agent (J) Melt (K) Magenta coupler (1) E Ultraviolet absorber (L) Linear sensitizing dye (M) Yellow coupler (N) l Especially, the red unsensitized light layer of the third layer was prepared as follows. Using silver halide emulsion (4), using a 0.05% methanol solution of photosensitive dye for red rice sensitization, lX per mole of silver.
10-' moles were added and stirred. Immediately supersensitizer ■
-1 in 1% methanol solution, 5X1 per mole of silver
0-'mol added.

In addition, a coating liquid was prepared according to Table 3.

After coating, it was dried to obtain sample 101.

First, a light source of 2854 degrees is used, and a red-end light filter consisting of a Fujifilm dark five-color filter (SC-70) and an ultraviolet absorbing filter (SC-38) is used, and a special light source of 600 to 700 nm (mid-half value) is used. A red light filter made by layering 5C-38 on a vapor-deposited metal filter made to transmit wavelength light, or a special 540 nm wavelength light filter.
Exposure was carried out using a color separation machine using a green light filter obtained by laminating 5C-38 on a vapor-deposited metal filter made to transmit light having a wavelength of 590 nm to 590 nm (mid-half maximum). This sample was color recorded, bleached, fixed and further developed through a rinsing bath. As seen on color photographic paper, it produced gradated yellow, magenta, and cyan images with excellent color separation.

Also, JP-A-57-151933 and JP-A-59-18
The intensity distribution of each light as described in No. 0131 was measured using an optical scanning exposure machine using the semiconductor light source to measure green light (PC light emission), red light (PR light emission), and end-red light (PIR light emission). I did a separate gradation exposure. After color development, bleach-fixing, and rinsing bath, an image with excellent hue was obtained.

Development Prescription A 35”C 45 seconds bleach fixing
Prescription A Rinse at 35°C for 45 seconds Prescription A
28-35°C 1 minute 30 seconds Color developer formulation A Water 800cc
Diethylenetriaminepentaacetic acid 1.0g Sodium sulfite 0.2gN, N-diethylenehydroxylamine 4.2g Potassium bromide 0.6g Sodium chloride 1.5g Triethanolamine 8.0g Potassium carbonate
30gN-ethyl-N-(β-
Methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 4.5g4.4
'-Diaminostilbene-based fluorescent brightener (Sumitomo Chemical ■-hitex4) 2.
Add 0g water to 1000cc
At KOH pH 10,25 Bleach-fix solution formulation A Ammonium thiosulfate (54wt%) 150mf NazS03 158N
H4(Fe(III)(EDTA)) 55gED
TA・2Na 4 g Glacial acetic acid Add 8.61 g water and make the total amount LOOOMJ2 (pH 5,4) Rinse liquid prescription A EDTA・2Na・2Hz OO, Add 4 g water and make the total amount 1000 m4 (pH 7,0) Example-1 In place of magenta coupler (f), magenta coupler (X)-1°2 or 3 of the present invention is used.
A sample was made instead. Similarly, sesocytometry was performed and images with excellent hue were obtained.

Example-2 An anti-halation layer was provided on a polyethylene terephthalate film (undercoated) according to Example-1,
Thereon, a photosensitized silver halide emulsion (1) and a coupler dispersion in which cyan coupler V-3 was dispersed in the coexistence of a copolymer of acrylic acid and butyl acrylate (molar ratio of 15:85) were added. A coating solution containing the composition shown in Table 5 below was prepared and applied so that the amount of silver was 0.4 g/bore.
Samples 102 to 113, A, and B of 6 were obtained.

-5:/, -1 sensitized silver halide emulsion 1!0.4g/sensitizing dye supersensitizer gelatin...1.5g/rd cyan coupler V-3...0.65 〃Acrylic acid/butyl acrylate copolymer (15:85 molar ratio) (E)
...0. 2 o Four-color image stabilizer (D)...
・o, 3〃Solvent (F)...1.5〃Table-
6 Sample No., amount of sensitizing dye used Super sensitizer (XI
O-'u/silver 1t3) (XIO-'ac/silver 1t3) 103 (1-7) i (l[[-3) 0
．． 5104 u-7>i 1 105 u-7) i 3 106 (I-7) i (I[l-3) 1 <
■-1) 1107 u-7)i 〃13 108 (1-7)i 〃1 5109
(1-7) i (II-1) 3111
〃j (G1) 1 112 ・ 1 ・ (]I+2) 5113
・i (I[-2) 5A (comparison>
(I) i B (comparison) (1) i
5. The obtained samples 102 to 113, A, and B are exposed to light fi
The light at an angle of 2854° was passed through a color resolving filter 5C-70 and an ultraviolet absorbing filter SΩ-38 (SC-70 and 5C-38 are manufactured by Fuji Film), and exposed using a photomachine as a longer wavelength light from about 700 nm.

The exposure time was 1 second. Example 1 of this strip
Color development was carried out according to the method described in 2007, and cyan colored strips were obtained.

The fog and relative sensitivity at a red optical density of fog +0.2 were determined. The results obtained were as shown in Table-7. The raw sample was stored at 50° C. and 175% RH for 3 days, and the relative sensitivity was determined in the same manner.

Table-7 Sample No., Relative Sensitivity Fog 50″C×75%R
Relative sensitivity when stored for HX 3 days Fog 102 100 0.08 64 0.09
103 135 0.0B 120 0.0
9104 146 0.07 132 0.1
0105 140 0.0B 135 0.
10106 620 0.08 611 0.
07107 795 0.07 805 0.
07108 920 0.07 920 0.
07109 745 0.07 745 0.
07110 112 0.09 50 0.
09 Sample Nα Relative sensitivity Fog 50°C x 75°C
Relative sensitivity when RIIX is stored for 3 days Fog 111 135 0.09 65 0.10
112 525 0.08 525 0.08
113 495 0.08 495 0.07
A (comparison) 32 0.0B 14 0.
10B (comparison) 280 0.08 275 0.
09 The following values were obtained in the same manner.

Table-8 Sample No., sensitizing dye retained amount Supersensitizer Relative sensitivity Fog (×104 mol/i 1 moB) (XIO mol/1 mol of Rei) (■-9) 1. 5
100 0. 08(III-6) 1
145 0. 09〃〃(II-8)3 7
25 0. 08 〃 5 65
It will be understood from the measured value of 00.07 or more that the compounds and combinations thereof used in the present invention are compatible with the purpose of the present invention. The compounds shown in the specific examples were similarly tested and showed similar excellent properties and trends.

Example-3 Internal latent image type silver halide emulsion A was obtained in the following manner.

1■Δ An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added to an aqueous gelatin solution containing 0.3 g of 3,4-dimethyl-1°3-thiazoline-2-thione per mole of Ag at 75°C with vigorous stirring. It took about 20 minutes to add them simultaneously, and the average particle size was 0. A monodisperse silver bromide emulsion of 4 μm octahedrons was obtained. To this emulsion were added sodium thiosulfate and chloroauric acid (tetrahydrate) in an amount of 6 μm per mole of silver, and the emulsion was heated to 80°C at 75°C.
Chemical sensitization treatment was performed by heating for minutes. Using the thus obtained silver bromide particles as cores, they were further grown by further treatment for 40 minutes in the same precipitation environment as the first time, and finally octahedral monodisperse core/shell silver bromide particles with an average particle diameter of 0.7 μm were obtained. An emulsion was obtained.

After washing with water and desalting, this emulsion contains 1.5 m of silver per mole of silver.
Sodium thiosulfate and chloroauric acid (tetrahydrate) of g1 were added and heated at 60°C for 60 minutes to carry out chemical sensitization treatment to obtain internal latent image type silver halide emulsion A.

A full multilayer color photographic paper having the layer structure shown in Table 8 was prepared using core/shell type internal latent image emulsion A on a paper support laminated on both sides with polyethylene.

The coating solution was prepared as follows.

3rd layer coating solution prepared: 10 g of nitrogen coupler V-3 and 2.3 g of color image stabilizer (D)/10 m of ethyl acetate! and 4 ml of solvent (K) were added and dissolved, and this solution was emulsified and dispersed in 90 mff1 of a 10% gelatin aqueous solution containing 5 mff1 of 10% sodium dodecylbenzenesulfonate.

On the other hand, the silver halide emulsion A (Ag708/Kg
90, in which 2.0 x 10-4 mol of the red-sensitive dye shown below was added to the red-sensitive dye shown below per 1 mol of silver halide to make a red-sensitive emulsion.
I made g. The emulsified dispersion, emulsion and development accelerator (Q) are mixed and dissolved, the concentration is adjusted with gelatin as shown in Table 8, and a nucleating agent, 6-nitoxythiocarponylamino-2-methyl- 2.1-allylquinolinium trifluoromethane sulfonate per 4 moles of Ag. lXl0
-' moles and a nucleation accelerator 2-(3-dimethylaminopropylthio)-5-mercapto-1,3,4-thiadiazole hydrochloride was added to the coating solution for the first layer at 4.5 x 10-' moles per 1 mole of Ag. was prepared.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. 1-oxy-3 as gelatin hardening agent in each layer
, 5-dichloro-8-triazine sodium salt was used.

Table-9 Mordant (P) Sensitizing dye (R) Magenta coupler (S) Solvent (U) Using a light source of 2854°K according to Example-1, green, red, and luminous flux lights were used using a color separation filter. I disassembled them and performed stepwise exposure on each.

A color development process was performed using Process B shown below.

Yellow, magenta, as in regular color photographic paper
A positive type image with excellent cyan color gradation was obtained.

In Example 3, a sample was obtained by using the coupler (X)-1 of the present invention in place of the magenta coupler (S). Cennetometry was performed in the same manner, and images with high chroma were obtained.

Time Temperature color development B 1 minute 40 seconds 38°C bleach-fixing B 1 minute 35°C water washing (or stable) ■ 20 seconds 〃〃 ■ 20 seconds
[Drying] The composition of the treatment solution used at 70°C was as follows.

Color developer formulation B Diethylenetriaminepentaacetic acid 2.0g Diethyl hydroxylamine 2.67g Tetramethylethylenediamine 5.8g Sodium bromide
0.26 g sodium chloride
3.20 g3-methyl-4-amino-
6,OOg N-ethyl-N-(β-methanesulfonamidoethyl)-aniline potassium carbonate 30.0g Fluorescent brightener (stilbene type) Add 1.0g water 100100OH10,20 pH with potassium hydroxide or hydrochloric acid It was adjusted.

Bleach-fix solution formulation B Ammonium thiosulfate 110g Sodium bisulfite Log ethylenediaminetetraacetic acid Ferric 0.12mol Ammonium monohydrate Ethylenediaminetetraacetic acid disodium 5g Add thulium dihydrate 10100O! pH
6,5 pH was adjusted with aqueous ammonia or hydrochloric acid.

Stabilizing liquid formulation B: Add tap water to H-type strongly acidic cation exchange resin (Mitsubishi Kasei Corporation)
Water was passed through a mixed-bed column packed with Diaion 5K-IB) and an OH-type strong basic anion exchange resin (Diaion 5A-10A) to obtain the following water quality. Sodium nurate 20mg/
1 was added.

Calcium ion 1.1■/1 Magnesium ion 0. 5■/lpH6.9 [Effects of the Invention] The present invention is a color recording material capable of printing a color image with gradations from a color original or a soft information source.

Furthermore, the present invention has at least one photosensitive layer that increases and decreases spectrally in the red or infrared region with high sensitivity and stability, and is therefore suitable for outputting light control systems such as LED light and semiconductor lasers. be. Furthermore, positive and negative tones can be subjected to processing similar to that of conventional color photographic papers, such as rapid and simple color processing such as minilab systems, in substantially the same manner.

Representative Patent Attorney (8107) Kiyoyuki Sasaki Procedural correction divination September 1986 (i day)

Claims (2)

[Claims] (1) At least three types of photosensitive layer units each containing a light-sensitive silver halide emulsion having a different spectral sensitivity distribution and a corresponding yellow coupler, magenta coupler, and cyan coupler are provided on a support. In the color recording material, at least one of the photosensitive layers is a silver halide emulsion layer spectrally sensitized in a region with a maximum spectral sensitivity wavelength longer than about 670 nm, and the color recording material is directly positive-type or negative-type color image. A full-color recording material characterized by forming. (2) The color recording material according to claim 1, wherein a positive color image or a negative color image is directly formed by optical scanning exposure and subsequent color development processing.