JP3037853B2 - Thermal development color photosensitive material - Google Patents

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, no processing unevenness and low fog.

[0002]

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

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

On the other hand, a photographic method using silver halide photography is superior to other photographic methods, such as electrophotography and diazo photographic method, in terms of photographic characteristics such as sensitivity and gradation control, and thus has been used most widely. I have been.

In recent years, a technique for easily and rapidly obtaining an image by changing the image forming processing method of a photosensitive material using silver halide from a conventional wet processing using a developing solution or the like to a dry processing using heating or the like. Has been developed.

[0006] Photothermographic materials are known in the art and are described, for example, in "Basics of Photographic Engineering" (Corona, 1979), pp. 553-555, April 1978. Published video information 40
Section 7: 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. 04, No. 3301678, No. 3392020, No. 3457075, British Patent No. 1131108, No. 1
No. 167777 and Research. Disclosure Magazine, June 1978, pp. 9-15 (RD-17029)
It is described in.

[0007] In any of these methods, a dye is generated or released by heating to form an image-like distribution of the dye, and is characterized in that an 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 on such a photosensitive material using image information once converted into an electric signal, a color C signal is required.
It is common to use an RT (cathode ray tube) as an exposure light source, but a CRT is unsuitable for obtaining large-size prints.

A light emitting diode (LED) is used as a writing head capable of obtaining a large-sized print.
And semiconductor lasers (LDs) have been developed. But,
Those optical writing heads that efficiently emit blue light have not been developed.

Thus, for example, a light emitting diode (LED)
When using near infrared (800 nm), red (670 n
m) and a light source combining three light emitting diodes of yellow (570 nm) to expose a color photosensitive material having three layers spectrally sensitized to near infrared, red and yellow. Is a system that records images at "Nikkei New Materials", September 14, 1987, No. 47-
It is described on page 57 and partially used.

A system for recording on a color photosensitive material having three photosensitive layers having a spectral sensitivity at each wavelength with a light source combining three semiconductor lasers emitting at 880 nm, 820 nm and 760 nm is disclosed in Japanese Patent Application Laid-Open No. Sho 61-1986. 13714
No. 9 is described.

By the way, in a heat-developable color light-sensitive material having at least two or more infrared light-sensitive layers having a spectral sensitivity peak with respect to infrared light of 700 nm or more, how to maintain the storage stability Is an important point. Needless to say, the infrared sensitizing dye is LUMO
And the HOMO have a small energy difference, and are susceptible to thermal excitation of electrons, resulting in the formation of a latent image on silver halide and unnecessary fogging. On the other hand, infrared sensitizing dyes are known to be weakly adsorbed. If carelessly introducing an antifoggant, the dyes are desorbed and desensitized.

In the case of the thermal development transfer system as in the present invention, since heat is applied during the development and transfer processes, processing unevenness is likely to occur. As a result of investigations to prevent this, the acid-treated gelatin was used as the binder of the protective layer located on the photosensitive layer side of the photosensitive material, and the total amount of the binder in the protective layer was 6%.
It has been found that it is essential to use acid-treated gelatin at 0 wt% or more (Japanese Patent Application No. 4-87622). However, when acid-treated gelatin was used, the cause was not clearly understood, but it was also found that Dmin (fog) increased. Therefore, without causing desensitization and without processing unevenness, Dmin
(Fogging) must be suppressed.

[0014]

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

[0015]

This and other objects are attained by the present invention which is defined below as (1). (1) On one surface of a support, there is provided a photosensitive layer comprising at least a photosensitive layer containing a photosensitive silver halide emulsion and a binder and a protective layer containing at least a binder. In a heat-developable color light-sensitive material containing at least one layer containing a dye-donating compound, at least two of the photosensitive layers are infrared-sensitive layers having a peak in spectral sensitivity to infrared light of 700 nm or more,
In addition, at least 60% by weight of the total amount of the binder of the protective layer located on the uppermost layer of the protective layer is an acid-treated gelatin, and at least one non-photosensitive layer of the photosensitive material constituting layer is as follows. 2. A heat-developable color light-sensitive material containing the compound represented by 2.

[0016]

Embedded image

Wherein R ₁ , R ₂ , R ₃ and R ₄ each represent 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 —SO ₂ NRR ¹ or —CN (where R and R ¹ represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, respectively, and R ² represents an alkyl group, an aryl group or an aralkyl group). ]

[0018]

[Specific Configuration] Hereinafter, a specific configuration of the present invention will be described in detail.

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

Until now, 6 of the binder in the protective layer
It has been found that by using 0% by weight or more of acid-treated gelatin, the occurrence of processing unevenness during thermal development and transfer can be prevented, but fogging is liable to occur. In addition, fog tends to occur when an infrared sensitizing dye is used, and further, if an attempt is made to reduce fog with an antifoggant in the infrared-sensitive layer, there is a problem that the sensitivity is reduced. there were. In the present invention, this problem is solved by selecting and using the compound represented by Chemical Formula 2 from various compounds and adding this compound to the non-photosensitive layer. The effect of the present invention is as follows.
Is obtained for the first time by using the compound as described above, and is not obtained by using other kinds of compounds, for example, a mercapto compound or the like.

In the present invention, the acid-treated gelatin is used in the protective layer in an amount of 60% by weight or more for the purpose of preventing the occurrence of processing unevenness, preferably 80 to 100% by weight. Should be 100 wt%.
At this time, the amount of the acid-treated gelatin is based on the amount added at the time of preparing the coating solution for the protective layer.

The protective layer having the acid-treated gelatin amount in the above range may be at least the uppermost protective layer when a plurality of protective layers are present.

The non-photosensitive layer containing the compound of formula 2 may be any of layers called a protective layer, an intermediate layer and the like, and may be added to only one layer or two or more layers. It may be added separately to the non-photosensitive layer.

In the present invention, the addition of the compound of formula (2) to the photosensitive layer, particularly the infrared-sensitive layer, causes a decrease in sensitivity.

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

The compound represented by Chemical formula 2 used in the color photothermographic material of the present invention is described below.

In the 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, etc .; Substituted or unsubstituted aralkyl groups such as benzyl group, β-phenethyl group and α-methylbenzyl group; and the alkenyl group is a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms such as propenyl group and isopropenyl group. An alkoxy group is a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, such as a methoxy group, an ethoxy group or a methoxyethoxy group; an aryl group is a substituted or unsubstituted alkoxy group having 6 to 14 carbon atoms; Examples include a substituted aryl group such as a phenyl group and a tolyl group.

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

In the above, the substituent "substituted or unsubstituted" 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.

The following are specific examples of the benzotriazole compound of the formula (2).

[0033]

Embedded image

[0034]

Embedded image

The compound of formula 2 is a known compound, and can be synthesized with reference to the descriptions in JP-A-58-11838 and JP-A-58-11839.

The content of the compound of the formula (2) is preferably from 10 ^-1 to 10 ^-6 mol, more preferably from 10 ^-1 to 10 ^-6 mol, per mol of silver halide in each of the infrared-sensitive layers. 10
The amount is preferably ^-2 to 10 ^-5 mol.

The content is from 10 ^-4 to 1 mol per mol of the infrared sensitizing dye added to the silver halide emulsion of the infrared-sensitive layer.
This is a value corresponding to 10 ^-1 mol, preferably 10 ^-3 to 1 mol. Further, 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 formula 2 may be used alone or in combination of two or more. In the case of using together, the total amount may be within the above range.

The heat-developable color light-sensitive material of the present invention comprises two or more layers of a light-sensitive material such as an infrared light-sensitive layer and a protective layer on one surface of a support. Contains a photosensitive silver halide, a reducing agent, a binder, and a dye-providing compound (which may also serve as a reducing agent as described later), and further contains an organic metal salt oxidizing agent, if necessary. be able to. These components are often added to the same layer, but may be added separately to another layer if they can react. For example, if a coloring dye-providing compound is present in the lower layer of the silver halide emulsion, the sensitivity can be prevented from lowering. The reducing agent is incorporated in the photothermographic material. Alternatively, a method of externally supplying the reducing agent may be used, for example, by diffusing from a dye fixing element described later. As described above, by incorporating a reducing agent into the photosensitive material, an effect of promoting color image formation and the like 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, at least three silver halide emulsion layers sensitive to different spectral regions are used in combination. . For example, there is a combination of a first infrared photosensitive layer, a second infrared photosensitive layer, and a third infrared photosensitive layer, or a combination of a red sensitive layer, a first infrared photosensitive layer, and a second infrared photosensitive layer. Each photosensitive layer can have various arrangement orders known for a conventional type color photosensitive material. Each of these photosensitive layers may be divided into two or more layers as 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 formula 2 can be contained in the above layers except for the back layer and the like.

The silver halide which can be used 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 a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Also, a so-called core-shell emulsion having a different phase between the inside of the grain and the grain surface layer may be used. The silver halide emulsion may be monodispersed or polydispersed, or a mixture of monodispersed emulsions may be used. The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm.

The crystal habit of the silver halide grains may be any one of cubic, octahedral, tetradecahedral, high aspect ratio tabular, potato-like, and the like, but is preferably cubic. Specifically, U.S. Pat.
28021, Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (1978),
Any of the silver halide emulsions described in JP-A-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, as a means for this, a Nudel washing method carried out by gelling gelatin which has been known for a long time is carried out. And an inorganic salt comprising a polyvalent anion, such as sodium sulfate, an anionic surfactant, an anionic polymer (eg, polystyrene sulfonic acid), or a gelatin derivative (eg, aliphatic acylated gelatin, aromatic acyl A sedimentation method (flocculation) using hydrated gelatin, aromatic carbamoylated gelatin, etc.) may be used. Removal of excess salt may be omitted. Alternatively, US Pat.
No. 05, JP-A-62-113137, JP-B-59-4
No. 3,727, U.S. Pat. No. 4,334,012 may be used to remove excess salt using an ultrafiltration apparatus.

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, depending on an intended application, and is generally 0 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly contained in the particles, or may be localized on the surface or inside of the particles.

In the stage of forming the silver halide grains, a rhodan salt, NH ₃ or a solvent such as NH _{3 is used} as a silver halide solvent.
An organic thioether derivative described in 11386 or a sulfur-containing compound described in JP-A-53-144319 can be used.

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

The silver halide emulsion may be used as it is after unripe, but usually it is used after chemical sensitization. Known sulfur sensitization, reduction sensitization, noble metal sensitization, Se sensitization, and the like can be used singly or in combination for emulsions for conventional light-sensitive materials. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-25315).
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 a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.

More specifically, see US Pat. No. 4,617,257.
JP-A-59-180550 and JP-A-60-14033
No. 5, RD17029 (1978), pp. 12-13, and the like. In particular, Japanese Patent Application No. 2-100
No. 102, JP-A-5-45833 and 5-45834
And the sensitizing dyes described in JP-A-5-45828.

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

Along with the sensitizing dye, a dye which has 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 Pat. Patent No. 3615641, JP-A-6
3-23145).

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

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

Organic compounds which can be used to form the above-mentioned organic silver salt oxidizing agents include US Pat. No. 4,500,626.
No. 52-53, benzotriazoles, fatty acids and other compounds. Japanese Patent Application Laid-Open No. 60-1132
A silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolate described in JP-A No. 35;
The acetylene silver described in No. 044 is also useful. Two or more organic silver salts may be used in combination.

The above-mentioned organic silver salt is a photosensitive silver halide 1
0.01 to 10 mol, preferably 0.1 to 10 mol, per mol.
01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is suitably from 50 mg to 10 g / m ² in terms of silver.

In the present invention, various antifoggants or photographic stabilizers can be used. Examples thereof are disclosed in Japanese Patent Application No. 4-310895, Japanese Patent Application Laid-Open No. 59-1805.
No. 50, JP-A-59-191332, JP-A-59-1
No. 68442, nitrogen-containing carboxylic acids and phosphoric acids, or mercapto compounds and metal salts thereof described in JP-A-59-111636, JP-A-62-28795.
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-providing compound having a reducing property described later is also included (in this case, another reducing agent can be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can 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. 83914, columns 30-31, No. 4330617,
Nos. 4590152 and pp. 17-17 of JP-A-60-140335, pp. 57-40245 and pp. 56
138736, 59-178458, 59-
Nos. 53831, 59-182449 and 59-18
No. 2450, No. 60-119555, No. 60-128
From No. 436 to No. 60-128439, No. 60-1
No. 98540, No. 60-181742, No. 61-25
No. 9253, No. 62-244444, No. 62-131
From 253 to 62-131256, there are reducing agents and reducing agent precursors described in EP 220746A2, pages 78 to 96 and the like.

[0062] Combinations of various reducing agents may also be used, such as those disclosed in US Patent No. 3,039,869.

When a diffusion-resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent may be used, 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 mobility of the electron transfer agent or its precursor is 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 non-diffusible reducing agent (electron donor) used in combination with the electron transfer agent may be any one which does not substantially move in the layer of the photosensitive element among the above reducing agents, and is preferably used. Hydroquinones, sulfonamidophenols, sulfonamidonaphthols, JP-A-53-
Compounds described as electron donors in JP-A No. 110827, and dye-donor compounds having diffusion resistance and reducing property, which will be described later, are exemplified.

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

In the present invention, when silver ions are reduced to silver under high-temperature conditions, a compound that generates or releases a mobile dye in response to this reaction or in reverse correspondence, that is, a dye donor May be contained.

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

As another example of the dye donating compound,
Compounds having a function of releasing or diffusing a diffusible dye in an image form can be mentioned. 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 corresponds to a photosensitive silver salt having an image-like latent image. Alternatively, a difference is caused in the diffusivity of the compound represented by (Dye-Y) _n -Z, or D
ye, and the released Dye and (Dye-Y) _n −
Z represents a group having a property that causes a difference in diffusibility with Z, and n represents 1 or 2, and when n is 2, two Dye-Ys may be the same or different.

Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds. The following (1) to (4) are to form a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide, and "(1)" is to form a diffusible dye image (positive dye image) in correspondence to the development of silver halide. (A negative dye image).

US Pat. Nos. 3,134,764 and 336, US Pat.
No. 2819, No. 3597200, No. 3544545
No. 3,482,972, etc., a dye developing agent comprising a hydroquinone-based developing agent and a dye component linked to each other. The dye developer is diffusible in an alkaline environment, but becomes non-diffusible corresponding to silver halide.

As described in US Pat. No. 4,503,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can also be used. Examples of the compound include a compound capable of releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479, US Pat.
Compounds which release a diffusible dye by an intramolecular reversal reaction of an isoxazolone ring described in JP-A No. 354 or the like.

US Pat. No. 4,559,290, EP 220746A2, US Pat. No. 4,783,396,
As described in JP-A-87-6199, a non-diffusible compound that reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used.

For example, US Pat.
Nos. 9 and 4139379, JP-A-59-185333.
And compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction described in U.S. Pat. No. 4,232,107, and JP-A-59-84453.
-101649, 61-88257, RD240
No. 25 (1984) and the like, compounds which release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 308588A, JP-A-56-14.
No. 2530, U.S. Pat. Nos. 4,434,893 and 4,619.
No. 8450, etc., compounds which release a diffusible dye by cleavage of a single bond after reduction, US Pat.
For example, nitro compounds which release a diffusible dye after electron acceptance described in U.S. Pat. No. 223, and the like, compounds which release a diffusible dye after electron acceptance described in U.S. Pat. No. 4,609,610 and the like can be used.

Further, as more preferable examples, European Patent No. 220746A2, Japanese Patent Publication No. 87-6199, US Pat. No. 4,783,396, and Japanese Patent Application Laid-Open No. 63-201653.
Compounds having an NX bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule described in JP-A-63-201654 and JP-A-63-201654. SO ₂ -X (X is as defined above) in one molecule
And compounds having an electron-withdrawing group, JP-A-63-2713
No. 44, a compound having a PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule.
No. 271341 include compounds having a C—X ′ bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group in one molecule. Further, Japanese Patent Laid-Open No.
Nos. 161237 and 1-116142, compounds capable of releasing a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated to an electron accepting group can also be used.

Of these, compounds having an NX bond and an electron-withdrawing group in one molecule are particularly preferred. Specific examples thereof are described in European Patent No. 220746A2 or U.S. Pat.
No. 396, compounds (1) to (3), (7) to
(10), (12), (13), (15), (23)-
(26), (31), (32), (35), (36),
(40), (41), (44), (53)-(59),
(64), (70) and compounds (11) to (23) described in Published Technical Report 87-6199.

Compounds which have a diffusible dye as a leaving group and release a diffusible dye upon reaction with an oxidized reducing agent (DDR coupler). Specifically, British Patent No. 1,330,524, JP-B-48-39165, U.S. Patent Nos. 3,443,940, 4,474,867, and 448
No. 3914 and the like.

A compound (DDR compound) which is reducible to silver halide or an organic silver salt and releases a diffusible dye when the 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 oxidized decomposition products of the reducing agent. Representative examples are U.S. Pat. Nos. 3,923,312, 4,053,312 and 405.
Nos. 5428 and 4336322, JP-A-59-658.
No. 39, No. 59-69839, No. 53-3819,
Nos. 51-104343, RD17465, U.S. Pat. Nos. 3,725,062, 3,728,113 and 3,443.
No. 939, JP-A-58-11637 and JP-A-57-17.
No. 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, compounds (1) to (3) described in the aforementioned 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. The compounds described in U.S. Pat. No. 4,639,408 at columns 37 to 39 are also useful.

Other examples of the above-mentioned couplers and dye-donating compounds other than the general formula [LI] include dye silver compounds in which an organic silver salt is combined with a dye (Research Disclosure Magazine, May 1978, pp. 54-58). Azo dyes used in the heat-developed silver dye bleaching method (U.S. Pat.
957, Research Disclosure Magazine, April 1976, pp. 30-32, etc., leuco dyes (U.S. Pat.
Nos. 98565 and 40222617) can also be used.

A hydrophobic additive such as a dye-donating compound or a nondiffusible reducing agent can be introduced into a layer of a light-sensitive material by a known method 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
A high boiling organic solvent as described in JP-A Nos. 9-178455 and 59-178457 may be used, if necessary, with a boiling point of 50 ° C.
It can be used in combination with a low-boiling organic solvent of up to 160 ° C.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing 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 and JP-A-51-39853
A dispersion method using a polymer described in No. 59943 can also be used.

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

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

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

In the present invention, a non-diffusible dye can be contained for the purpose of improving sharpness and the like. If necessary, a filter dye having absorption in the infrared region can be used. Details of such a filter dye are described in Japanese Patent Application Nos. 2-137885, 4-217243, 4-276744, 5-45834, and the like.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a photosensitive material. The dye-fixing element may be in the form of being separately coated on a support coated separately from the light-sensitive material, or in the form of being coated on the same support as the light-sensitive material. As for the relationship between the photosensitive element and the dye-fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationships described in US Pat.

As described above, the light-sensitive material of the present invention will be described mainly for convenience in terms of the light-sensitive element in order to include a form in which the light-sensitive element and the dye-fixing element are coated on the same support. I 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 field of photography can be used, and specific examples thereof are described in U.S. Pat.
Mordant described in JP-A-62-244043, 6
Examples described in JP-A-2-244036 can be mentioned. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used.

The dye-fixing element may be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer, if necessary. It is particularly useful to provide a protective layer.

As the binder for the constituent layers of the photosensitive material and the dye fixing material, hydrophilic binders are preferably used. Examples thereof include pages (26) to (2) of JP-A-62-253159.
8) Those described on page 8 are 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 a gelatin derivative, starch,
Examples include natural compounds such as polysaccharides such as gum arabic, dextran and pullulan, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, and other synthetic high molecular compounds. Also, Japanese Patent Application Laid-Open No. Sho 62-24526
No. 0 etc., ie, -COOM
Or —SO ₃ M (M is a hydrogen atom or an alkali metal)
A homopolymer of a vinyl monomer having the following or a copolymer of the vinyl monomer or another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more kinds.

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

In the case of employing a system for performing thermal development by supplying a small amount of water, the use of the above superabsorbent polymer makes it possible to rapidly absorb water. When the superabsorbent polymer is used for the dye-fixing layer and its protective layer, it is possible to prevent the dye from being re-transferred from the dye-fixing material to another after transfer.

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

Examples of the hardening agent used for the constituent layers of the photosensitive element and the dye fixing element include US Pat. No. 4,678,739 No. 41.
Column, JP-A-59-116655 and JP-A-62-24526.
No. 1, No. 61-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), N-
Methylol-based hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157) can be mentioned.

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye-fixing element.
Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the generation of a dye from a dye-providing substance or the decomposition or release of a diffusible dye, and the use of a photosensitive material layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement. An example is described in US Pat.
93 and JP-A-62-65038.

In a system in which thermal development and transfer of a dye are carried out simultaneously in the presence of a small amount of water, it is preferable to add a base and / or a base precursor to the dye-fixing material from the viewpoint of improving the storability of the light-sensitive material.

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

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

The term "development terminator" as used herein means that after proper development,
It is a compound that quickly neutralizes a base or reacts with a base to reduce the base concentration in the film and stop development, or a compound that interacts with silver and a silver salt to suppress development. In particular,
Examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-2531.
59, pages 31 to 32.

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

In the constituent layers of the photosensitive element and the dye-fixing element, a plasticizer, a slipping agent, or a high-boiling organic solvent can be used as an agent for improving the releasability of the photosensitive element and the dye-fixing element. Specific examples include JP-A-62-253159, 25
Page, pp. 62-245253, and the like.

Further, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. As examples thereof, various modified silicone oils described in Technical Data P6-8B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective.

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

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

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

Examples of the ultraviolet absorber include benzotriazole compounds (US Pat. No. 3,533,794),
Thiazolidone-based compounds (US Pat. No. 3,352,681, etc.) and benzophenone-based compounds (JP-A-46-2784)
No. JP-A-54-48535 and JP-A-64-28535.
There are compounds described in JP-A-1366641, JP-A-61-8256 and the like. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective.

As the metal complex, US Pat.
No. 55, No. 4245018, Columns 3-36, No. 4254
No. 195, columns 3 to 8, JP-A Nos. 62-174741, 61-88256, pp. 27-29, and Japanese Patent Application No. 62-234.
No. 103, No. 62-31096, No. 62-23059
No. 5 and the like.

Examples of useful discoloration inhibitors are described in JP-A-62-21.
No. 5272, pages 125 to 137.

An anti-fading agent for preventing fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or supplied to the dye-fixing element from outside such as a photosensitive element. You may.

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

A fluorescent whitening agent may be used for the light-sensitive element and the dye-fixing element. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing element or to supply it from outside such as a photosensitive element. For example, K. Veenkataraman ed., “The Chemi
stry of Synthetic Dyes, Vol. V, Chapter 8, JP-A-61-
No. 143752 and the like. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given.

The fluorescent whitening agent can be used in combination with a fading inhibitor.

In the constituent layers of the light-sensitive element and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, and promoting development. Specific examples of the surfactant are described in JP-A-62-173463.
And No. 62-183457.

The constituent layers of the light-sensitive element and the dye-fixing element may contain an organic fluoro compound for the purpose of improving sliding property, preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8 to 17,
JP-A-61-20944, JP-A-62-135826, etc., such as fluorine-based surfactants, or oil-like fluorine-based compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin, etc. And hydrophobic fluorine compounds.

A matting agent can be used for the photosensitive element and the dye fixing element. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
In addition to the compounds described on page 29 of 1-88256, benzoguanamine resin beads, polycarbonate resin beads, A
Japanese Patent Application Nos. 62-110064, 6
There are compounds described in 2-110065. The matting agent can be used not only for the purpose of preventing adhesion, controlling slipperiness, and preventing Newton's ring, but also for the purpose of making the surface of the dye fixing element (image surface) non-glossy.

In addition, the constituent layers of the photosensitive element and the dye-fixing element may contain a heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256, pp. 26-32.

As the support of the light-sensitive element or the dye-fixing element of the present invention, a support that can withstand the processing temperature is used. Generally, paper and synthetic polymers (films) are used. Specifically, polyethylene terephthalate (P
ET), polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, and film-processed synthetic paper made from polypropylene, etc. Mixed paper, Yankee paper, baryta paper, coated paper (especially, cascoat paper), metal, cloth, glass, etc., made from synthetic resin pulp such as polyethylene and natural pulp are used.

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

On the surface of these supports, a hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide,
Carbon black or another antistatic agent may be applied.

Examples of a method of exposing and recording an image on a photosensitive element include a method of directly photographing a landscape or a person using a camera, a method of exposing through a reversal film or a negative film using a printer or a enlarger, and the like. A method of scanning and exposing an original image through a slit or the like by using an exposure device of a copying machine, a method of exposing and exposing image information by emitting light-emitting diodes and various lasers via electric signals, a method of exposing image information to a CRT, a liquid crystal display, There is a method of outputting an image to an image display device such as an electroluminescence display or a plasma display and exposing the image directly or via an optical system. Specifically, Japanese Patent Laid-Open No. 2-12
No. 9625, Japanese Patent Application No. 3-338182, 4-938
No. 8, No. 4-281442 and the like.

As a light source for recording an image on a photosensitive element,
As noted above, U.S. Pat. No. 4 for natural light, tungsten lamps, emitting diodes, laser light sources, CRT light sources, etc.
The light source described in 50626, column 56 can be used.

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

The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and particularly, about 80 ° C. to about 180 ° C.
C is useful. The dye diffusion transfer step may be performed simultaneously with the thermal development, or may be performed after the thermal development step. In the latter case, the heating temperature in the transfer step can be transferred within the range of the temperature in the heat development step to room temperature.
As described above, the temperature is more preferably about 10 ° C. lower than the temperature in the heat development step.

Although the transfer of the dye is caused only by heat,
Solvents may be used to promote dye transfer.

Further, JP-A-59-218443, 6
As described in detail in Japanese Patent Application Laid-Open No. 1-238056, a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also useful. In this scheme,
The heating temperature is preferably 50 ° C or higher and the boiling point of the solvent or lower. For example, when the solvent is water, the heating temperature is preferably 50 ° C or higher and 100 ° C or lower.

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

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

A method for imparting 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. Further, the solvent can be used by being incorporated in a photosensitive element or a dye-fixing element or both in advance in a form such as enclosing a solvent in a microcapsule.

In order to promote dye transfer, a system in which a hydrophilic thermal solvent which is solid at normal temperature and dissolves at high temperature is incorporated in the photosensitive element or the dye fixing element can be adopted. The hydrophilic 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 is preferably incorporated in the dye-fixing layer and / or an adjacent layer.

Examples of the hydrophilic heat solvent include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles.

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

As a heating method in the development and / or transfer step, a heated block or plate is brought into contact, or a hot plate, hot presser, heat roller, halogen lamp heater, infrared or far infrared lamp heater, or the like is contacted. Or passing through a high temperature atmosphere. Further, a resistive heating element layer may be provided on the photosensitive element or the dye fixing element, and the layer may be heated by being energized. As the heating element layer, those described in JP-A-61-145544 can be used.

A photosensitive element and a dye-fixing element are superimposed,
Japanese Patent Application Laid-Open No. Sho 6
The method described on page 27 of 1-1147244 can be applied.

In the processing of the light-sensitive element and the dye-fixing element of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-75247 and JP-A-59-17747.
No. 59-181353, No. 60-18951,
Apparatuses described in Japanese Utility Model Application Laid-Open No. 62-25944 and Japanese Patent Application No. 4-242053 are preferably used.

[0139]

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

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)] In a well-stirred aqueous solution having the composition shown in Table 1, the solution (I) having the composition shown in Table 2 and ( II) The solution was added simultaneously over 13 minutes, and 10 minutes later, (III) having the composition shown in Table 2
Liquid and liquid (IV) were added over 33 minutes.

[0142]

[Table 1]

[0143]

[Table 2]

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

After washing with water and desalting (using a precipitant b of formula 5 at pH 4.1), 22 g of lime-processed ossein gelatin was added thereto to adjust the pH to 6.0. After adjusting the pAg to 7.9, it was chemically sensitized at 60 ° C. The compounds used for chemical sensitization are as shown in Table 1C. The yield of the obtained emulsion was 630 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 10.2%, and an average grain size of 0.20 μm.
Met.

[0146]

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[0147]

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[0148]

[Table 3]

Photosensitive Silver Halide Emulsion (2) [Emulsion for Third Layer (750 nm Sensitive Layer)] A solution (I) of the composition shown in Table 5 was added to a well-stirred aqueous solution of the composition shown in Table 4. II) The solution was added simultaneously over 18 minutes, and 10 minutes later, (III) having the composition shown in Table 5
Liquid and liquid (IV) were added over 24 minutes.

[0150]

[Table 4]

[0151]

[Table 5]

Lime-treated ossein gelatin which has been washed with water and desalted (using a precipitant a of formula 5 at a pH of 3.9) and then decalcified by a conventional method (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-
0.39 g of tetrazaindene was added to adjust the pH to 5.9,
pAg was adjusted to 7.8. Thereafter, chemical sensitization was performed at 70 ° C. using the chemicals shown in Table 6. At the end of the chemical sensitization, a methanol solution represented by sensitizing dye D shown in Table 7 was added.
Further, after the chemical sensitization, the temperature was lowered to 40 ° C., and a gelatin dispersion 200 of the stabilizer (1) represented by the following chemical formula 10 described later was prepared.
g was added and stirred well before storage. The yield of the obtained emulsion was 938 g, 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 Sensitive Layer)] In a well-stirred aqueous solution having the composition shown in Table 8, the solution (I) having the composition shown in Table 9 and ( II) The solution was added simultaneously over 18 minutes, and 10 minutes later, (III) having the composition shown in Table 9
Liquid and liquid (IV) were added over 24 minutes.

[0156]

[Table 8]

[0157]

[Table 9]

After washing with water and desalting (using a precipitant b of the above formula (5) at a pH of 3.8) in a conventional manner, 22 g of lime-treated ossein gelatin was added to adjust the pH to 7.0. 4,
After adjusting pAg to 7.8, it was chemically sensitized at 60 ° C. The compounds used for chemical sensitization are as shown in Table 10.
The yield of the obtained emulsion was 680 g, a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 9.7%, and an average grain size of 0.32.
μm.

[0159]

[Table 10]

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

A solution having the composition shown in Table 12 was added to the well-stirred aqueous solution having the composition shown in Table 11 over 24 minutes. Thereafter, the precipitate was washed with the sedimenting agent b represented by Chemical Formula 5, and then the pH was adjusted to 6.3 by adding 43 g of lime-treated ossein gelatin. The average particle size was 0.02 μm and the yield was 512 g (dispersion containing 2% silver and 6.8% gelatin).

[0162]

[Table 11]

[0163]

[Table 12]

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

Gelatin dispersions of a yellow dye-donating compound, a magenta dye-donating compound, and a cyan dye-donating compound were prepared as shown in Table 13. That is,
Heating and dissolving each oil phase component at about 70 ° C to make a uniform solution,
The 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 thereto and stirred to obtain a uniform dispersion. Furthermore, an ultrafiltration module (Asahi Kasei ultrafiltration module: A)
Using CV-3050), dilution with water and concentration were repeated to reduce the amount of ethyl acetate to 1/7 of the amount of ethyl acetate in Table 13.

[0166]

[Table 13]

A gelatin dispersion of the reducing agent (2) was prepared as shown in Table 14. That is, each oil phase component is heated to about
After heating and dissolving in this solution, the aqueous phase component heated to about 60 ° C. was added thereto, followed by stirring and mixing.
The mixture was dispersed at 10,000 rpm to obtain a uniform dispersion. Further, ethyl acetate was removed from the obtained dispersion using an organic solvent removal device under reduced pressure.

[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, and the aqueous phase component heated to about 40 ° C. was added to this solution, followed by stirring and mixing.
Dispersed at rpm. This was added with water and diffused to obtain a uniform dispersion.

[0170]

[Table 15]

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

[0172]

[Table 16]

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

[0174]

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[0175]

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[0176]

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[0177]

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[0178]

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[0179]

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[0180]

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[0181]

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[0182]

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[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

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Next, a method for producing a gelatin dispersion of a matting agent added to the protective layer will be described. P in methylene chloride
The solution in which MMA was dissolved was added to gelatin together with a small amount of a surfactant, followed by high-speed stirring and dispersion. Subsequently, methylene chloride was removed using a vacuum desolvation apparatus 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 in Tables 17 and 18 are, in addition to those described above, those represented by Chemical Formulas 23 to 26.

[0192]

[Table 17]

[0193]

[Table 18]

[0194]

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[0195]

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[0196]

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[0197]

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

A dye-fixing material having the composition shown in Table 19 was prepared. The structure of the surface layer (1) is as shown in Table 20, and the structure of the back layer (1) is as shown in Table 21. The configuration of the support (1) is as shown in Table 22, and the physical properties 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]

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[0207]

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[0208]

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[0209]

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Next, evaluation was made by the following exposure and processing.

First, exposure was performed under the conditions shown in Table 24 using the optical system shown in FIG. 2 of Japanese Patent Application No. 4-281422. Apply 12 cc / m ² of water to the emulsion surface of the exposed photosensitive material,
Thereafter, the dye-fixing material (trade name: PG-SG, manufactured by Fuji Photo Film Co., Ltd.) was overlapped so that the film surface was in contact therewith. After heating for 35 seconds using a heat drum whose temperature was adjusted so that the temperature of the water-absorbed film became 83 ° C., 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 the sensitivity, Dmin (fog) +
A rating of 0.8 was evaluated.

Further, the processing unevenness is caused by the fact that the temperature of the film during processing is 8
The temperature was raised to 8 ° C., and the sample was visually observed and evaluated.

Further, the constitution of the light-sensitive material 100 is shown in Table 25,
The photosensitive materials 101 to 116 were produced by changing as shown in Table 26. These were also processed and evaluated in the same manner as described above.

Tables 27 and 28 show the results.

[0218]

[Table 25]

[0219]

[Table 26]

[0220]

[Table 27]

[0221]

[Table 28]

As can be seen from the above results, by having at least one non-photosensitive layer containing the compound represented by the formula (2) shown in the present invention, the processing unevenness was substantially suppressed without desensitization. It is clear that fog can be suppressed.

Further, in addition to those shown in Tables 25 and 26,
Various light-sensitive materials of the present invention were prepared by using two or more of the compounds of the present invention together in the same non-light-sensitive layer and divided into two or more non-light-sensitive layers and adding the compound of the present invention. As a result, good results equivalent to those of the photographic materials of the present invention shown in Tables 25 and 26 were obtained.

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

[0225]

According to the present invention, high sensitivity and low fog can be obtained, and processing unevenness can be prevented.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 8/40 505 G03C 8/52

Claims (1)

(57) [Claims] A photosensitive material comprising at least one photosensitive layer containing a photosensitive silver halide emulsion and a binder and a protective layer containing at least a binder on one surface of the support. Wherein at least one layer of the photothermographic color photosensitive material contains a dye-donating compound, wherein at least two of the photosensitive layers are infrared photosensitive layers having a peak in spectral sensitivity to infrared light of 700 nm or more. And at least 60 wt% of the total amount of the binder of the protective layer located at the uppermost layer of the protective layer is an 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 the formula (1) Embedded image [Wherein R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an alkoxy group, an aryl group, —NRR ¹ , and —COO, respectively.
R ² , -CONRR ¹ , -NHSO ₂ R, -SO ₂ NR
Represents R ¹ or —CN (where 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). ]