JPH06347970A - Heat-developable color photosensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and to reduce fog and to prevent uneven processing in the heat-developable color photosensitive material having >=2 infrared sensitive layers. CONSTITUTION:The heat-developable color photosensitive material has a protective layer containing an acid-treated gelatin in an amount of >=60weight% of the total binder, and at least one of nonphotosensitive layers contains the general formula in which each of R1-R4 is H, alkyl, aralkyl, alkenyl, alkoxy, aryl, -NRR<1>, -COOR<2>, -CONRR<1>, -NHSO2R, -SO2NRR<1>, or -CN: each of R and R<1> is H, alkyl, aryl, or aralkyl: and R<2> is alkyl, aryl, or aralkyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable color light-sensitive material, and more particularly to a heat-developable color light-sensitive material having high sensitivity, uniform processing and low fog.

[0002]

2. Description of the Related Art Recent advances in office automation have led to advances in commercial imaging equipment, the advent of electronic still cameras, the spread of video and facsimile, advances in computer graphics, advances in image sensors and advances in digital processing technology for original images. Along with this, there is an increasing demand for obtaining a color hard copy from image information once converted into an electric signal.

Various methods such as electrophotography, ink jet, thermal transfer, and silver salt photography are known as methods for obtaining a color hard copy. However, the inkjet and thermal transfer methods are still insufficient in terms of image quality, and the development of a system capable of high image quality and simple and quick processing has been awaited.

On the other hand, the photographic method using silver halide photography is superior to other photographic methods such as electrophotography and diazo photographic method in photographic characteristics such as sensitivity and gradation control. Has been.

In recent years, a technique capable of easily and rapidly obtaining an image by changing the image forming method of a light-sensitive material using silver halide from a conventional wet process using a developing solution or the like to a dry process using heat or the like. Has been developed.

Photothermographic materials are well known in the art, and the photothermographic materials and their processes are described, for example, in "Basics of Photographic Engineering" (Published by Corona Publishing Co., Ltd., 1979), pages 553 to 555, April 1978. Issued video information 40
Nebletts, Handbook of Photog
raphy and Reprography 7th Ed.) Van. Nostrand. Line hold. Company (Van Nostrand Reinh
Old Company) pages 32-33, U.S. Pat. No. 31529.
No. 04, No. 3301678, No. 3392020, No. 3457075, British Patent No. 1131108, No. 1
167777 and Research. Disclosure, June 1978, pp. 9-15 (RD-17029)
It is described in.

All of these generate or release a dye by heating to form an image-like distribution of the dye, and are characterized in that the image-like distribution of the dye can be obtained in a short time.

Conventional photosensitive materials usually have spectral sensitivities of blue, green, and red. To obtain an image by using image information once converted into an electric signal in such a photosensitive material, color C is used.
It is common to use RT (cathode ray tube) as an exposure light source, but CRT is not suitable for obtaining a large size print.

Further, as a writing head capable of obtaining a large-sized print, a light emitting diode (LED) is used.
Semiconductor lasers (LD) have been developed. But,
These optical writing heads have not yet been developed to efficiently emit blue light.

Thus, for example, a light emitting diode (LED)
When using, near infrared (800nm), red (670n
There is a method of exposing a color light-sensitive material having three layers spectrally sensitized to near infrared, red and yellow by a light source combining three light emitting diodes of m) and yellow (570 nm). "Nikkei New Material" September 14, 1987 issue 47-
It is described on page 57 and is partly in practical use.

Further, a system for recording on a color light-sensitive material having three light-sensitive layers having spectral sensitivity at each wavelength by a light source combining three semiconductor lasers emitting light of 880 nm, 820 nm and 760 nm is disclosed in JP-A-61-161. 13714
No. 9.

By the way, in a heat-developable color light-sensitive material having at least two infrared light-sensitive layers having a peak of spectral sensitivity to infrared light having a wavelength of 700 nm or more, how to maintain its storage stability is as follows. Is an important point. Needless to say, the infrared sensitizing dye is LUMO.
Has a small energy difference between HOMO and HOMO, is easily subjected to thermal excitation of electrons, and thus forms a latent image on silver halide and is apt to cause unnecessary fog. On the other hand, it is known that the infrared sensitizing dye has weak adsorption, and if the antifoggant is carelessly introduced, the dye is desorbed and desensitized.

Further, in the case of the heat development transfer system as in the present invention, heat is applied during the development / transfer process, so that process unevenness is likely to occur. As a result of studies to prevent this, acid-treated gelatin was used as the binder for the protective layer located on the photosensitive layer side of the photosensitive material, and the total amount of binder in the protective layer was 6%.
It has been found that it is essential to use 0 wt% or more of acid-treated gelatin (Japanese Patent Application No. 4-87622). However, it was also found that the use of acid-treated gelatin increased Dmin (fog) although the cause was not clear. Therefore, Dmin does not occur without causing desensitization.
The problem of having to suppress (fog) occurred.

[0014]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a heat-developable color light-sensitive material having particularly high sensitivity, low fog and no processing unevenness.

[0015]

The above object is achieved by the present invention described in (1) below. (1) A photosensitive material layer containing a photosensitive layer containing at least a photosensitive silver halide emulsion and a binder and a protective layer containing at least a binder is provided on one surface of a support. In a heat-developable color light-sensitive material in which at least one layer contains a dye-donating compound, at least two of the light-sensitive layers are infrared light-sensitive layers having a peak of spectral sensitivity to infrared light of 700 nm or more,
At least 60 wt% or more of the total amount of the binder in the protective layer located at the uppermost layer of the protective layer is acid-treated gelatin, and at least one non-photosensitive layer of the photosensitive material constituting layer is A heat-developable color light-sensitive material containing the compound represented by 2.

[0016]

[Chemical 2]

[In the formula ₂ , R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, an alkyl group, an aralkyl group,
Alkenyl group, alkoxy group, aryl group, -NRR
^{1, -COOR 2, -CONRR 1,} -NHSO 2 R,
Represents a -SO ₂ NRR ¹ or -CN (wherein each R and R ¹ are a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, R ² represents an alkyl group, an aryl group or an aralkyl group). ]

[0018]

Specific Structure The specific structure of the present invention will be described in detail below.

The heat-developable color light-sensitive material of the present invention is 700
It has two or more infrared photosensitive layers having a peak of spectral sensitivity to infrared light of nm or more. Then, 60% by weight or more of the binder of the protective layer provided on the infrared-sensitive layer is acid-treated gelatin to form at least one non-photosensitive layer of the photosensitive material constituting layer provided on the support. The compound represented by Chemical formula 2 is contained. For this reason, it is possible to eliminate processing unevenness and to realize high sensitivity and low fog.

Up to now, 6 of the binder in the protective layer
It has been found that by using acid-treated gelatin in an amount of 0 wt% or more, it is possible to prevent the occurrence of processing unevenness at the time of thermal development and transfer, but there has been a problem that fog is likely to occur. Further, fog is liable to occur when an infrared sensitizing dye is used, and further, in an infrared photosensitive layer, if it is attempted to reduce fog by an antifoggant, then there is a problem that sensitivity is lowered. there were. In the present invention, this is solved by selecting and using the compound represented by Chemical formula 2 from among various compounds and adding this compound to the non-photosensitive layer. The effect of the present invention is
The compound can be obtained for the first time by using the compound as described above, and cannot be obtained even if another type of compound such as a mercapto compound is used in the same manner.

In the present invention, 60% by weight or more of acid-treated gelatin is used in the protective layer for the purpose of preventing the occurrence of uneven processing, but it is preferably 80 to 100% by weight, and it is particularly preferable in view of manufacturing advantages and the like. Should be 100 wt%.
The amount of acid-treated gelatin at this time is based on the amount added at the time of preparing the coating liquid for forming the protective layer.

The protective layer having the acid-processed gelatin amount within the above range may be the protective layer located at least at the top when a plurality of protective layers are present.

The non-photosensitive layer containing the compound of Chemical formula 2 may be any of layers called a protective layer and an intermediate layer, and may be added to only one layer to form two or more layers. You may divide and add to a non-photosensitive layer.

Further, in the present invention, addition of the compound of Chemical formula 2 to the photosensitive layer, particularly the infrared photosensitive layer causes a decrease in sensitivity, so that it is preferable that the addition amount is substantially 0.

Here, "substantially 0" means that the compound of Chemical formula 2 is added only to the coating liquid for the non-photosensitive layer and not added to the coating liquid for the photosensitive layer at the time of preparing the coating liquid. Therefore,
After the layer is formed, it may be contained in the photosensitive layer by being partially diffused into the photosensitive layer, especially when it is added to the intermediate layer adjacent to the photosensitive layer, but this case is also included.

The compound represented by Chemical formula 2 used in the color photothermographic material of the invention will be described.

In formula 2, R ₁ , R ₂ , R ₃ and R
Each hydrogen atom _4, a substituted or unsubstituted alkyl group, an aralkyl group, an alkenyl group, an alkoxy group or an aryl group, -NRR ^1, -COOR ^2, -CONR
R ¹ , -NHSO ₂ R, -SO ₂ NRR ¹ or -CN
(Wherein R and R ¹ are each a hydrogen atom,
Represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group, and R ₂ represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group).

More specifically, R ₁ , R ₂ , R
_The alkyl group represented by ₃ and R ₄ has 1 carbon atom.
To 18 substituted or unsubstituted alkyl groups such as methyl group, ethyl group, butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, 2-methoxybutyl group and the like; aralkyl group having 7 to 20 carbon atoms A substituted or unsubstituted aralkyl group, for example, a benzyl group, a β-phenethyl group, an α-methylbenzyl group and the like; an alkenyl group having a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, for example, a propenyl group, an isopropenyl group. A styryl group or the like; an alkoxy group having a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, for example, a methoxy group, an ethoxy group, a methoxyethoxy group or the like; an aryl group having a substituted or unsubstituted carbon number of 6 to 14 Substituted aryl groups such as a phenyl group and a tolyl group can be mentioned.

The alkyl group represented by R and R ¹ is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, such as a methyl group, a butyl group, an isobutyl group, a dodecyl group; and an aryl group. A substituted or unsubstituted aryl group having 6 to 14 carbon atoms, for example, a phenyl group, a tolyl group or the like; an aralkyl group, for example, a substituted or unsubstituted aralkyl group having 7 to 14 carbon atoms, such as a benzyl group,
β-phenethyl group and the like;

The alkyl group represented by R ₂ is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, for example, a methyl group, a butyl group, a dodecyl group, etc .; An aryl group having 6 to 14 carbon atoms A substituted or unsubstituted aryl group, for example, a phenyl group, a tolyl group, a naphthyl group, etc .; as an aralkyl group, a substituted or unsubstituted aralkyl group having 7 to 14 carbon atoms, for example, a benzyl group, a β-phenethyl group, α-methyl A benzyl group and the like.

In the above, the "substituted or unsubstituted" substituent is a group other than a hydrophilic group, such as a halogen atom, an alkoxy group, an aryloxy group, an alkyl group, an aryl group, an ester group, an alkylsulfonyl group,
Arylsulfonyl group, alkylsulfonylamino group,
Examples include an arylsulfonylamino group, an alkylcarbonylamino group, and an arylcarbonylamino group.

Specific examples of the benzotriazole compound of Chemical formula 2 are shown below.

[0033]

[Chemical 3]

[0034]

[Chemical 4]

The compound of Chemical formula 2 is a known compound and can be synthesized with reference to the descriptions in JP-A-58-118638 and JP-A-58-18639.

The content of the compound of formula 2 is 10 ^-1 to 10 ^-6 mol, preferably ^{1 -1} to 10 ^-6 mol, per mol of silver halide in each infrared-sensitive layer, with respect to any infrared-sensitive layer having two or more layers. 10
^{It is} preferable to set it to ^-2 to 10 ^-5 mol.

This content is from 10 ⁻⁴ to 1 mol per 1 mol of the infrared sensitizing dye added to the silver halide emulsion of the infrared sensitive layer.
It is a value corresponding to 10 ^-1 mol, and a preferable range of 10 ^-3 to 1 mol. The coating amount per 1 m ^{2 of} the photosensitive material is 0.1 to 1000 mg, preferably about 1 to 100 mg.

The compounds of Chemical formula 2 may be used alone or in combination of two or more kinds, and when they are used in combination, the total amount may be within the above range.

The heat-developable color light-sensitive material of the present invention has, on one surface of the support, two or more infrared light-sensitive layers and a light-sensitive material constituting layer such as a protective layer. Contains a photosensitive silver halide, a reducing agent, a binder, and a dye-donor compound (the reducing agent may also serve as described below), and further contains an organometallic hydrochloric acid agent and the like, if necessary. be able to. These components are often added to the same layer, but if they are in a reactive state, they can be divided and added to separate layers. For example, when a colored dye-donor compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented. Although the reducing agent is incorporated in the photothermographic material, it may be used in combination with a method of supplying it from the outside, for example, by a method of diffusing from a dye fixing element described later. Thus, by incorporating the reducing agent in the light-sensitive material, the effect of promoting color image formation can be obtained.

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

The photothermographic material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer. The compound of Chemical formula 2 can be contained in the above layers except the back layer and the like.

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

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

The crystal habit of the silver halide grains may be any of cubic, octahedral, tetradecahedral, high aspect ratio tabular, potato-like and the like, but cubic is preferred. Specifically, U.S. Pat. No. 4,500,626, column 50, column 46.
28021, Research Disclosure (hereinafter abbreviated as RD) 17029 (1978), JP-A-6
Any of the silver halide emulsions described in No. 2-25159 and the like can be used.

In the process of preparing the silver halide emulsion of the present invention, when a desalting step for removing excess salts is carried out, the Nudel water washing method, which is known as a means for this, is performed by gelling gelatin. In addition, inorganic salts composed of polyvalent anions such as sodium sulfate, anionic surfactants, anionic polymers (eg polystyrene sulfonic acid), or gelatin derivatives (eg aliphatic acylated gelatin, aromatic acyl). The precipitation method (flocculation) using a modified gelatin, an aromatic carbamoylated gelatin, etc. may be used. Removal of excess salt may be omitted. Alternatively, US Pat. No. 47585
05, JP-A-62-113137, JP-B-59-4
Excess salt removal may be accomplished using the ultrafiltration system shown in 3727, U.S. Pat. No. 4,334,012.

The silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron, chromium, ruthenium and rhenium for various purposes. These compounds are
They may be used alone or in combination of two or more. The addition amount depends on the purpose of use, but is generally about 0 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly added to the particles, or may be localized on the surface or inside of the particles.

In the step of forming silver halide grains, as a silver halide solvent, rhodan salt, NH ₃ or JP-B-47-
The organic thioether derivative described in 11386 or the sulfur-containing compound described in JP-A No. 53-144319 can be used.

In the step of forming silver halide grains, JP-B-46-7781, JP-A-60-222842,
Nitrogen-containing compounds such as those described in JP-A-60-122935 can be added.

The silver halide emulsion may be used in an unripened state, but it is usually chemically sensitized before use. Conventionally known emulsion sensitizing materials for sulfur sensitization, reduction sensitization, noble metal sensitization and Se sensitization can be used alone or in combination. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-25315).
No. 9).

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

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, US Pat. No. 4,617,257
No. 59-180550, 60-14033.
No. 5, RD17029 (1978), pages 12 to 13 and the like. In particular, Japanese Patent Application No. 2-100
102, JP-A-5-45833, and JP-A-5-45834.
No. 5 and No. 5-45828 sensitizing dyes are preferred.

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

Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Japanese Patent No. 3615641, JP-A-6
3-23145 etc.).

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

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

Organic compounds that can be used to form the above organic silver salt oxidizing agent include US Pat. No. 4,500,626.
There are benzotriazoles, fatty acids and other compounds described in Nos. 52 to 53 and the like. In addition, JP-A-60-1132
No. 35, a silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolate, and JP-A-61-249.
Acetylene silver described in No. 044 is also useful. Two or more kinds of organic silver salts may be used in combination.

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

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include Japanese Patent Application No. 4-310985 and Japanese Patent Laid-Open No. 59-1805.
50, JP-A-59-191032, JP-A-59-1
Nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-68442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, JP-A-62-8795.
The acetylene compounds described in No. 7 are used.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property by itself but exhibits a reducing property by the action of a nucleophile or heat during the development process can also be used.

Examples of the reducing agent used in the present invention include:
U.S. Pat. No. 4,500,626, columns 49-50, 44
No. 83, col. 31, columns 31-43;
No. 4,590,152, JP-A No. 60-140335, pages (17) to (18), Nos. 57-40245, 56.
-138736, 59-178458, 59-
No. 53831, No. 59-182449, No. 59-18
No. 2450, No. 60-119555, No. 60-128
436 to 60-128439, 60-1
No. 98540, No. 60-181742, No. 61-25.
9253, 624244044, 62-131
From 253 to 62-131256, there are reducing agents and reducing agent precursors described on pages 78 to 96 of EP 220746A2.

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

When a diffusion resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent may be added, if necessary, in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion resistant reducing agent (electron donor). A particularly useful electron transfer agent is 1-phenyl-3
-Pyrazolidones or aminophenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any one of the above-mentioned reducing agents which does not substantially move in the layer of the photosensitive element, and is preferable. Hydroquinones, sulfonamide phenols, sulfonamide naphthols, JP-A-53-
Examples thereof include compounds described as electron donors in No. 110827, and dye-donating compounds having diffusion resistance and reducing properties described below.

In the present invention, the reducing agent is added in an amount of 0.001 to 20 mol, and particularly preferably 0.1 to 20 mol, based on 1 mol of silver.
It is from 01 to 10 mol.

In the present invention, when a silver ion is reduced to silver under a high temperature condition, a compound that produces or releases a mobile dye in response to this reaction or in the opposite reaction, that is, a dye-donor is provided. It may contain a sex compound.

Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) which forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Specific examples of color developing agents and couplers can be found in T.W. H. J
by Ames, “The Theory of the P”
photographic Process "Fourth Edition 29
Pages 1-334 and 354-361, JP-A-58-1
No. 23533, No. 58-149046, No. 58-14
No. 9047, No. 59-111148, No. 59-124
No. 399, No. 59-174835, No. 59-2315.
No. 39, No. 59-231540, No. 60-2950.
No. 60, No. 60-2951, No. 60-14242, No. 6
0-23474, 60-66249 and the like.

As another example of the dye-donating compound,
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye in an image form. This type of compound can be represented by the following general formula [LI].

(Dye-Y) _n -Z [LI]

Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents a photosensitive silver salt having an imagewise latent image. Or, conversely, causes a difference in the diffusivity of the compound represented by (Dye-Y) _n -Z, or
ye is released, and the released Dye and (Dye-Y) _n-
Z represents a group having a property of causing a difference in diffusibility with Z, n represents 1 or 2, and when n is 2, two Dye-Y may be the same or different.

Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds. In addition, the following items (1) to (4) are for forming a diffusible dye image (positive dye image) in the opposite manner to the development of silver halide, and the terms and are the diffusible dye image (corresponding to the development of silver halide ( To form a negative dye image).

US Pat. Nos. 3,134,764 and 336.
2819, 3597200, 3544545.
No. 3,482,972 and the like, a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible corresponding to silver halide.

As described in US Pat. No. 4,053,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can be used. Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479, and US Pat. No. 4,199.
Compounds that release a diffusible dye by the intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354 and the like.

US Pat. No. 4,559,290, EP 220746A2, US Pat. No. 4,783,396,
As described in Published Technical Report 87-6199, a non-diffusible compound which reacts with a reducing agent remaining unoxidized by development to release a diffusible dye can also be used.

As an example, US Pat. No. 4,133,938
No. 9, 4139379, JP-A-59-185333.
Nos. 57-84453 and the like, which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, U.S. Pat.
No. 101649, No. 61-88257, RD240
25 (1984) and the like, which release a diffusible dye by intramolecular electron transfer reaction after reduction, West German Patent No. 3008588A, JP-A-56-14.
2530, U.S. Pat. Nos. 4,343,893 and 4619.
Compounds that release a diffusible dye by cleavage of a single bond after reduction, as described in U.S. Pat.
Examples thereof include nitro compounds described in U.S. Pat. No. 223, which release a diffusible dye after electron acceptance, compounds described in U.S. Pat. No. 4,609,610, which release a diffusible dye after electron acceptance, and the like.

Further, as more preferable ones, European Patent No. 220746A2, Kokai Giho No. 87-6199, US Pat. No. 4,783,396, and Japanese Patent Laid-Open No. 63-201653.
Nos. 63-201665 and the like, compounds having an N—X bond (X represents oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, described in Japanese Patent Application No. 1-26842. SO ₂ -X (X is as defined above)
And a compound having an electron-withdrawing group, JP-A-63-2713
No. 44, a compound having a PO—X bond (where X is as defined above) and an electron-withdrawing group in one molecule, JP-A-63-
No. 271341 and compounds having a C—X ′ bond (where X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group in one molecule. In addition, JP-A-1-
Compounds that release a diffusible dye by cleaving a single bond after reduction by a π bond conjugated with an electron-accepting group described in Nos. 161237 and 1-161342 can also be used.

Of these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof include European Patent No. 220746A2 or US Patent No. 4783.
Nos. 396, compounds (1) to (3) and (7) to
(10), (12), (13), (15), (23)-
(26), (31), (32), (35), (36),
(40), (41), (44), (53) to (59),
(64) and (70), and compounds (11) to (23) described in Kokai Giho 6-6199.

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and releases the diffusible dye by a reaction with an oxidant of a reducing agent. Specifically, British Patent No. 1330524, Japanese Patent Publication No. 48-39165, U.S. Patent Nos. 3443940, 4474867, 448.
3914 and the like.

A compound (DDR compound) which is reducible to a silver halide or an organic silver salt and releases a diffusible dye when its partner is reduced. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. Typical examples thereof are U.S. Pat. Nos. 3,928,312, 4,053,312 and 405.
No. 5428, No. 4336322, JP-A-59-658.
No. 39, No. 59-69839, No. 53-3819,
51-104343, RD17465, U.S. Pat. Nos. 3,725,062, 3,728,113 and 3,443.
939, JP-A-58-116537, 57-17.
9840, U.S. Pat. No. 4,500,626 and the like. Specific examples of the DDR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, the compounds (1) to (3) described in the above-mentioned U.S. Pat. (10) to (13), (1
6) to (19), (28) to (30), (33) to (3
5), (38) to (40) and (42) to (64) are preferable. Further, the compounds described in US Pat. No. 4,639,408, columns 37 to 39 are also useful.

Other than the above-mentioned couplers and dye-providing compounds other than the general formula [LI], dye silver compounds in which an organic silver salt and a dye are bound (Research Disclosure, May 1978, pages 54 to 58). , Etc., azo dyes used in the heat developable silver dye bleaching method (US Pat.
957, Research Disclosure, April 1976, pages 30-32, etc.), Leuco dyes (US Pat. No. 3).
985565, No. 4022617, etc.) can also be used.

Hydrophobic additives such as dye-donor compounds and diffusion-resistant reducing agents can be incorporated into the layers of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154,
59-178451, 59-178452, 59-178453, 59-178454, 5
9-178455, 59-178457 and the like, a high boiling point organic solvent, if necessary, a boiling point of 50 ° C.
It can be used in combination with an organic solvent having a low boiling point of up to 160 ° C.

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

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

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

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

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

In the present invention, a non-diffusible dye may be contained for the purpose of improving sharpness. If necessary, a filter dye having absorption in the infrared region can be used. Details of such filter dyes are described in Japanese Patent Application No. 2-137885, JP-A Nos. 4-217243, 4-276744, and 5-45834.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a light-sensitive material. The dye fixing element may be applied separately on a support which is coated separately from the light-sensitive material, or may be applied on the same support as the light-sensitive material. Regarding the relationship between the light-sensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application.

In order to include the form in which the light-sensitive element and the dye-fixing element are coated on the same support as described above, the light-sensitive material of the present invention will be described below mainly using the terms of the light-sensitive element for the sake of convenience. To do. The dye fixing element is also called a dye fixing material.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat. No. 4,500,626, columns 58 to 59 and JP-A No. 61-88256, 32-41.
The mordant described in the above pages, JP-A Nos. 62-244043 and 6
Examples thereof include those described in No. 2-244036. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 may be used.

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

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive material and the dye-fixing material. As an example thereof, pages (26) to (2) of JP-A No. 62-253159.
8) The thing described in page is mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, for example, lime-processed gelatin, acid-processed gelatin, or a protein or cellulose derivative such as gelatin derivative, starch,
Examples include natural compounds such as gum arabic, dextran, and pullulan, and other polysaccharides, and polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Also, JP-A-62-24526
Superabsorbent polymer described in No. 0, that is, -COOM
Or --SO ₃ M (M is hydrogen atom or alkali metal)
Homopolymers of vinyl monomers having the above or copolymers of the vinyl monomers with each other or with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd.) are also used. These binders can be used in combination of two or more.

The acid-treated gelatin used in the present invention is arbitrarily selected from "950 gelatin" manufactured by Nitta Gelatin, "ABA gelatin" manufactured by Nippi Gelatin, "Croda-A148" manufactured by Kuroda Gelatin, and the like. Can be used.

When a system in which a small amount of water is supplied for thermal development is adopted, it is possible to quickly absorb water by using the above superabsorbent polymer. Further, when the super absorbent polymer is used in the dye fixing layer or its protective layer, the dye can be prevented from being retransferred from the dye fixing material to another after the transfer.

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

As the hardener used in the constituent layers of the light-sensitive element and the dye fixing element, US Pat. No. 4,678,739, No. 41
Column, JP-A-59-116655 and JP-A-62-24526.
The hardeners described in No. 1 and No. 61-18942 are listed. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-
Examples thereof include methylol type hardeners (dimethylolurea etc.) and polymer hardeners (compounds described in JP-A-62-234157).

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye-fixing element.
The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. These details are described in US Pat. No. 4,678,739, columns 38 to 40.

Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is US Pat. No. 45114.
93, JP-A-62-65038 and the like.

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

In addition to the above, European Patent Publication 210660
No. 4,740,445, and combinations of sparingly soluble metal compounds and compounds capable of complex-forming reaction with metal ions constituting the sparingly soluble metal compounds (referred to as complex-forming compounds), and JP-A-61-232451. Compounds that generate a base by electrolysis as described in No. 1 can also be used as the base precursor. The former method is particularly effective. The sparingly soluble metal compound and the complex-forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element.

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

The term "development stopping agent" as used herein means, after proper development,
It is a compound that rapidly neutralizes or reacts with a base to lower the concentration of the base in the film to stop development, or a compound that interacts with silver and a silver salt to suppress development. In particular,
Examples thereof include acid precursors that release an acid upon heating, electrophilic compounds that undergo a substitution reaction with a coexisting base upon heating, or nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof. For more details, see JP-A-62-2531.
No. 59, pp. 31-32.

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

In the constituent layers of the light-sensitive element and the dye-fixing element, a high-boiling organic solvent can be used as a plasticizer, a slipping agent, or an agent for improving the releasability of the light-sensitive element and the dye-fixing element. Specific examples include 25 of JP-A-62-253159.
Page, No. 62-245253 and the like.

Further, various silicone oils (all silicone oils from dimethylsilicone oil to modified silicone oils obtained by introducing various organic groups into dimethylsiloxane) can be used for the above purpose. For example, various modified silicone oils described in “Modified Silicone Oil” technical data P6-8B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective.

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

An anti-fading agent may be used in the dye fixing element. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex.

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

As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794, etc.), 4-
Thiazolidone compounds (US Pat. No. 3,352,681, etc.), benzophenone compounds (JP-A-46-2784)
Etc.) and others, JP-A Nos. 54-48535 and 62-
There are compounds described in Nos. 136641 and 61-8256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

Examples of the metal complex include US Pat.
No. 55, No. 4245018, Columns 3 to 36, No. 4254.
195, columns 3 to 8, JP-A-62-174741, JP-A-61-88256, pages 27 to 29, Japanese Patent Application No. 62-234.
No. 103, No. 62-31096, No. 62-23059
There are compounds described in No. 5 and the like.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272, pages 125-137.

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

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

A fluorescent whitening agent may be used in the light-sensitive element and the dye-fixing element. In particular, it is preferable that the dye-fixing element contains a fluorescent whitening agent or is supplied from the outside of the light-sensitive element. For example, see “The Chemi” edited by K. Veenkataraman.
stry of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-
The compound described in 143752 etc. can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned.

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

In the constituent layers of the light-sensitive element and the dye-fixing element, various surfactants can be used for the purposes of coating aid, improvement of releasability, improvement of sliding property, prevention of electrostatic charge, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like.

The constituent layers of the light-sensitive element and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving releasability and the like. Typical examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17,
Fluorine-based surfactants described in JP-A-61-29444, JP-A-62-135826 and the like, oil-like fluorinated compounds such as fluorinated oil, or solid fluorinated compound resins such as tetrafluoroethylene resin Hydrophobic fluorine compounds may be mentioned.

A matting agent can be used in the light-sensitive element and the dye fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
1-88256, page 29, benzoguanamine resin beads, polycarbonate resin beads, A
Japanese Patent Application Nos. 62-110064 and 6 for S resin beads
There are compounds described in No. 2-110065. The matting agent can be used not only for the purpose of preventing adhesion, controlling slipperiness and preventing Newton's rings but also for making the surface of the dye fixing element (image surface) non-glossy.

In addition, the constituent layers of the light-sensitive element and the dye-fixing element may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A No. 61-88256, pages 26 to 32.

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

These can be used alone or
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition to these, the supports described in JP-A-62-253159, pages (29) to (31) can be used.

On the surface of these supports, a hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide,
You may apply carbon black and other antistatic agents.

As a method for exposing and recording an image on a photosensitive element, for example, a method of directly photographing a landscape or a person using a camera or the like, a method of exposing through a reversal film or a negative film using a printer or an enlarger, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting a light emitting diode, various lasers, etc. via an electric signal, a CRT, a liquid crystal display, There is a method of outputting to an image display device such as an electroluminescence display and a plasma display, and exposing directly or through an optical system. Specifically, JP-A 2-12
9625, Japanese Patent Application Nos. 3-338182 and 4-938.
The exposure method described in No. 8, No. 4-281442, etc. can be used.

As the light source for recording an image on the photosensitive element,
As mentioned above, US Patent No. 4 of natural light, tungsten lamp, emitting diode, laser light source, CRT light source, etc.
The light source described in 500626, column 56 can be used.

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

The heating temperature in the heat development step is from about 50 ° C. to about 250 ° C., and development is possible, but especially from about 80 ° C. to about 180 ° C.
C is useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the heat development process is completed. In the latter case, the heating temperature in the transfer step can be set within the range from the temperature in the heat development step to room temperature, but especially 50 ° C.
Above all, it is more preferable that the temperature is lower by about 10 ° C. than the temperature in the heat development step.

Although the migration of the dye occurs only by heat,
Solvents may be used to facilitate dye transfer.

Further, JP-A-59-218443 and JP-A-6-218443.
As described in detail in No. 1-238056 and the like, a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. In this method,
The heating temperature is preferably 50 ° C. or higher and not higher than the boiling point of the solvent. For example, when the solvent is water, it is preferably 50 ° C. or higher and 100 ° C. or lower.

Examples of the solvent used to accelerate development and / or transfer the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases). Examples thereof include those described in the section of the image formation accelerator). Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt, a complex-forming compound or the like may be contained in the solvent.

These solvents can be used by a method of applying them to a dye fixing element, a light sensitive element or both.
The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the total coating film).

A method for applying a solvent to the photosensitive layer or the dye fixing layer is described in, for example, JP-A-61-147244.
There is a method described on page 6. Alternatively, the solvent may be contained in a microcapsule in advance and incorporated in the light-sensitive element or the dye-fixing element or both.

In order to promote dye transfer, a system in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated in the light-sensitive element or the dye-fixing element can also be adopted. The hydrophilic thermal solvent may be incorporated in either the photosensitive element or the dye fixing element, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and / or its adjacent layer.

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

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

As a heating method in the developing and / or transferring step, a heated block or plate is contacted, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater, etc. is contacted. And passing through a high temperature atmosphere. Further, a resistance heating element layer may be provided on the photosensitive element or the dye fixing element, and the resistance heating element layer may be energized for heating. As the heating element layer, those described in JP-A-61-145544 can be used.

Superimposing the light-sensitive element and the dye-fixing element,
The pressure condition and the method for applying the pressure when closely contacting each other are disclosed in Japanese Patent Laid-Open Publication No.
The method described on page 27 of No. 1-147244 can be applied.

Any of a variety of heat developing apparatus can be used for processing the light-sensitive element and the dye fixing element of the present invention. For example, JP-A-59-75247 and JP-A-59-177547.
No. 59-181353, No. 60-18951,
The devices described in Japanese Utility Model Publication No. 62-25944 and Japanese Patent Application No. 4-242053 are preferably used.

[0139]

EXAMPLES The present invention will be described below with reference to examples.
The invention is not limited to this example.

Example 1 A method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive Silver Halide Emulsion (1) [Emulsion for Fifth Layer (680 nm Photosensitive Layer)] An aqueous solution having a composition shown in Table 1 and a solution (I) having a composition shown in Table 2 and ( Solution II) was added simultaneously over 13 minutes, and 10 minutes later, the composition (III) of the composition shown in Table 2 was added.
Solution and Solution (IV) were added over 33 minutes.

[0142]

[Table 1]

[0143]

[Table 2]

Also, 13 minutes after the start of addition of the solution III, 27
Over a period of 150 minutes, 150 cc of a 0.35% aqueous solution of the sensitizing dye A represented by Chemical Formula 6 was added.

After washing with water and desalting (pH was adjusted to 4.1 using the precipitating agent b represented by Chemical formula 5) by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0. After adjusting the pAg to 7.9, chemical sensitization was performed at 60 ° C. The compounds used for the chemical sensitization are as shown in Table 1C. The yield of the obtained emulsion was 630 g and was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 10.2% and an average grain size of 0.20 μm.
Met.

[0146]

[Chemical 5]

[0147]

[Chemical 6]

[0148]

[Table 3]

Photosensitive Silver Halide Emulsion (2) [Emulsion for Third Layer (750 nm Photosensitive Layer)] An aqueous solution having a composition shown in Table 4 and a solution (I) having a composition shown in Table 5 and ( Solution (II) was added simultaneously over 18 minutes, and 10 minutes after that, (III) having the composition shown in Table 5 was added.
Solution and solution (IV) were added over 24 minutes.

[0150]

[Table 4]

[0151]

[Table 5]

After rinsing with water and desalting (pH was set to 3.9 using the precipitating agent a represented by Chemical formula 5) by a conventional method, decalcified lime-treated ossein gelatin (calcium content 150 ppm or less) 22 g was added and redispersed at 40 ° C. to give 4-hydroxy-6-methyl-1,3,3a, 7-
Add 0.39 g of tetrazaindene to bring the pH to 5.9,
The pAg was adjusted to 7.8. Then, chemical sensitization was performed at 70 ° C. using the chemicals shown in Table 6. At the end of the chemical sensitization, the methanol solution shown in the sensitizing dye D shown in Table 7 was added.
Furthermore, after the chemical sensitization, the temperature was lowered to 40 ° C., and the gelatin dispersion 200 of the stabilizer (1) represented by the following chemical formula 10 described later was used.
g was added, stirred well and stored. The yield of the obtained emulsion was 938 g, which was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.25 μm.

[0153]

[Table 6]

[0154]

[Table 7]

Photosensitive Silver Halide Emulsion (3) [Emulsion for First Layer (810 nm Photosensitive Layer)] A solution (I) having the composition shown in Table 9 and ( Solution II) was added simultaneously over 18 minutes, and 10 minutes later, the composition (III) having the composition shown in Table 9 was added.
Solution and solution (IV) were added over 24 minutes.

[0156]

[Table 8]

[0157]

[Table 9]

After washing with water and desalting (pH was set to 3.8 using the precipitating agent b represented by the above chemical formula 5) by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 7. 4,
After adjusting pAg to 7.8, chemical sensitization was performed at 60 ° C. The compounds used for the chemical sensitization are as shown in Table 10.
The obtained emulsion had a yield of 680 g and was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 9.7% and an average grain size of 0.32.
It was μm.

[0159]

[Table 10]

A method for preparing a gelatin dispersion of colloidal silver will be described.

To the well-stirred aqueous solution having the composition shown in Table 11, the solution having the composition shown in Table 12 was added over 24 minutes. After washing with water using the precipitating agent b represented by Chemical Formula 5, 43 g of lime-treated ossein gelatin was added to adjust the pH to 6.3. The average particle size was 0.02 μm and the yield was 512 g (dispersion containing 2% silver, 6.8% gelatin).

[0162]

[Table 11]

[0163]

[Table 12]

Next, a method for preparing a gelatin dispersion of the hydrophobic additive will be described.

Gelatin dispersions of the yellow dye-donor compound, the magenta dye-donor compound and the cyan dye-donor compound were prepared according to the formulations shown in Table 13. That is,
Each oil phase component is heated and dissolved at about 70 ° C to form a uniform solution,
An aqueous phase component heated to about 60 ° C. was added to this solution, and the mixture was stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. Water was added to this and stirred to obtain a uniform dispersion. Further, a gelatin dispersion of a cyan dye-donating compound was added to the ultrafiltration module (Asahi Kasei ultrafiltration module: A
CV-3050), dilution with water and concentration were repeated, and the amount of ethyl acetate was reduced to 17.6 times the amount of ethyl acetate in Table 13.

[0166]

[Table 13]

A gelatin dispersion of reducing agent (2) was prepared according to the prescription in Table 14. That is, each oil phase component is about 60 ℃
The solution was heated to dissolve in, and the aqueous phase component heated to about 60 ° C. was added to the solution with stirring and mixing, followed by 10 minutes with a homogenizer.
Dispersion was performed at 10,000 rpm to obtain a uniform dispersion. Further, ethyl acetate was removed from the obtained dispersion using a vacuum deorganization solvent apparatus.

[0168]

[Table 14]

A gelatin dispersion of stabilizer (1) was prepared according to the formulation in Table 15. That is, each oil phase component was dissolved at room temperature, the water phase component heated to about 40 ° C. was added to this solution, and the mixture was stirred and mixed, and then was mixed with a homogenizer for 10 minutes at 10,000
Dispersed at rpm. This was hydrated and dispersed to obtain a uniform dispersion.

[0170]

[Table 15]

A gelatin dispersion of zinc hydroxide was prepared according to the formulation in Table 16. That is, each component was mixed and dissolved, and then dispersed in a mill for 30 minutes using glass beads having an average particle size of 0.75 nm. Further remove the glass beads,
A uniform dispersion was obtained (zinc hydroxide having an average particle size of 0.25 μm was used).

[0172]

[Table 16]

The compounds in Table 1, Table 3, Table 4, Table 6 to Table 8, Table 10, and Tables 13 to 16 are compounds represented by Chemical formulas 7 to 22.

[0174]

[Chemical 7]

[0175]

[Chemical 8]

[0176]

[Chemical 9]

[0177]

[Chemical 10]

[0178]

[Chemical 11]

[0179]

[Chemical 12]

[0180]

[Chemical 13]

[0181]

[Chemical 14]

[0182]

[Chemical 15]

[0183]

[Chemical 16]

[0184]

[Chemical 17]

[0185]

[Chemical 18]

[0186]

[Chemical 19]

[0187]

[Chemical 20]

[0188]

[Chemical 21]

[0189]

[Chemical formula 22]

Next, a method for producing a gelatin dispersion of a matting agent added to the protective layer will be described. P to methylene chloride
The liquid in which MMA was dissolved was added to gelatin together with a small amount of a surfactant, and the mixture was stirred and dispersed at high speed. Subsequently, methylene chloride was removed using a vacuum desolventizer to obtain a uniform dispersion having an average particle size of 4.3 μm.

Using the above materials, photothermographic materials 100 shown in Tables 17 and 18 were prepared. The compounds shown in Tables 17 and 18 are those shown in Chemical formulas 23 to 26 in addition to those mentioned above.

[0192]

[Table 17]

[0193]

[Table 18]

[0194]

[Chemical formula 23]

[0195]

[Chemical formula 24]

[0196]

[Chemical 25]

[0197]

[Chemical formula 26]

Next, a method for preparing the dye fixing material will be described.

Dye fixing materials having the constitution shown in Table 19 were prepared. The constitution of the surface layer (1) is shown in Table 20, and the constitution of the back layer (1) is shown in Table 21. Further, the constitution of the support (1) is as shown in Table 22, and the physical property values are as shown in Table 23.

[0200]

[Table 19]

[0201]

[Table 20]

[0202]

[Table 21]

[0203]

[Table 22]

[0204]

[Table 23]

The compounds in Tables 20 and 21 are those represented by Chemical formulas 27 to 30.

[0206]

[Chemical 27]

[0207]

[Chemical 28]

[0208]

[Chemical 29]

[0209]

[Chemical 30]

Next, evaluation was carried out by the following exposure and processing.

First, using the optical system shown in FIG. 2 of Japanese Patent Application No. 4-281422, exposure was performed under the conditions shown in Table 24. Apply 12 cc / m ² of water to the emulsion surface of the exposed light-sensitive material,
Then, the dye fixing material (trade name: PG-SG manufactured by Fuji Photo Film Co., Ltd.) was overlaid so that the film surface was in contact. Using a heat drum whose temperature was adjusted so that the temperature of the absorbed film was 83 ° C., after heating for 35 seconds, the dye fixing material was peeled off from the photosensitive material to obtain an image on the dye fixing material.

[0212]

[Table 24]

Next, the density was measured under the status A condition of X-RITE, and Dmin (fog) was evaluated.

Regarding sensitivity, Dmin (fog) +
It was evaluated for a concentration of 0.8.

The unevenness of the treatment depends on the temperature of the film during the treatment being 8
The sample was heated to 8 ° C., treated, and visually observed and evaluated.

Further, the constitution of the light-sensitive material 100 is shown in Table 25,
The light-sensitive materials 101 to 116 were manufactured by changing the conditions as shown in Table 26. For these, the same treatment and evaluation as above were performed.

The results are shown in Tables 27 and 28.

[0218]

[Table 25]

[0219]

[Table 26]

[0220]

[Table 27]

[0221]

[Table 28]

As shown in the above results, by having at least one non-photosensitive layer containing the compound represented by Chemical formula 2 in the present invention, desensitization is not substantially caused and processing unevenness is caused. It turns out that fogging can be suppressed.

Further, in addition to those shown in Tables 25 and 26,
Various photosensitive materials of the present invention in which two or more kinds of the compounds of the present invention were used in combination in the same non-photosensitive layer and various photosensitive materials of the present invention in which the compound of the present invention was divided into two or more non-photosensitive layers were prepared. When similarly evaluated, the same good results as those of the light-sensitive materials of the present invention shown in Tables 25 and 26 were obtained.

In the photosensitive materials of the present invention shown in Tables 25 and 26, when a photosensitive material using a mercapto compound instead of the compound of Chemical formula 2 was prepared, the sensitivity was lowered,
The effect of the present invention was not obtained.

[0225]

EFFECTS OF THE INVENTION According to the present invention, the sensitivity is high and the fog is low, and uneven processing is prevented.

Claims (1)

[Claims] 1. A photosensitive material constituting layer comprising, on one surface of a support, a photosensitive layer containing at least a photosensitive silver halide emulsion and a binder, and a protective layer containing at least a binder. At least one layer of the photothermographic color light-sensitive material contains a dye-donating compound, and at least two layers of the light-sensitive layers are infrared light-sensitive layers having a peak of spectral sensitivity to infrared light of 700 nm or more. Further, at least 60 wt% or more of the total amount of binders in the protective layer located at the uppermost layer of the protective layer is acid-treated gelatin, and at least one non-photosensitive layer of the photosensitive material constituting layer is as follows. A heat-developable color light-sensitive material containing the compound represented by Chemical formula 1. [Chemical 1] [In Chemical Formula 1, R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an alkoxy group, an aryl group, —NRR ¹ , —COO.
_{^{R 2, -CONRR 1, -NHSO 2}} R, -SO 2 NR
R ¹ or —CN (wherein R and R ¹ each represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and R ² represents an alkyl group, an aryl group or an aralkyl group). ]