JPH06130607A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a multilayer heat-developable color photosensitive material having excellent color separation for exposure of light in near infrared to infrared region, and high sensitivity and raw preservation stability. CONSTITUTION:At least one emulsion layer contains thiadicarbocyanine dye stuff and is sensitized in a manner that the max. spectral sensitivity is obtd. in 700-900nm wavelength region and the spectral sensitivity for light longer by 20nm wavelength of the max. sensitivity wavelength is <=1/3 of the max. sensitivity. The emulsion layer contains 0.1-10.0g high boiling point org. solvent to one mol of the silver halide emulsion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable multilayer color light-sensitive material, which is exposed in the near infrared to infrared region.
In particular, the present invention relates to a heat-developable color light-sensitive material capable of obtaining an image excellent in color separation with respect to a semiconductor laser, having high sensitivity and excellent raw storage stability.

[0002]

2. Description of the Related Art Photothermographic materials are known in this technical field, and the photothermographic material and its process are described, for example, in "Basics of Photographic Engineering", Non-Silver Photographs, 1982, Corona Publishing, page 242. ~ 255, U.S. Pat. No. 450
No. 0626 and the like.

In addition, for example, a method of forming a dye image by a coupling reaction between an oxidized product of a developing agent and a coupler is described in US Pat. Nos. 3,761,270 and 4,021,240. Further, a method of forming a positive color image by a photosensitive silver dye bleaching method is described in US Pat. No. 4,235,957.

Recently, a method of releasing or forming a diffusible dye imagewise by heat development and transferring the diffusible dye to a dye fixing element has been proposed. In this method, a negative dye image or a positive dye image can be obtained by changing the kind of dye-donor compound used or the kind of silver halide used. More specifically, U.S. Pat. Nos. 4,500,626, 4,483,914, 4,503,137, and 4,559,290, JP-A-58-58.
149046, 60-133449, 59-2
No. 18443, No. 61-238056, European Patent Publication 220746A2, Open Technical Report 87-6199, European Patent Publication 210660A2, and the like.

Many methods have been proposed for obtaining a positive color image by heat development. For example, in U.S. Pat. No. 4,559,290, a so-called DRR compound, which is an oxidized type compound having no color image releasing ability, is allowed to coexist with a reducing agent or a precursor thereof, and the reducing agent is added according to the exposure amount of silver halide by heat development. A method has been proposed in which the diffusible dye is released by being oxidized and reduced by the reducing agent remaining without being oxidized. Further, European Patent Publication No. 220746 and Kokai Giho No. 87-6199 (Vol. 12, No. 22) disclose that a compound that releases a diffusible dye by a similar mechanism is an N—X bond (X is an oxygen atom, a nitrogen atom or Photothermographic color light-sensitive materials using compounds which release diffusible dyes by reductive cleavage of (representing sulfur atoms) are described.

Conventional color light-sensitive materials are usually blue, green,
The color CRT (cathode ray tube) is used as an exposure light source to obtain an image by using image information that has been converted into an electric signal on such a color light-sensitive material because it has red spectral sensitization. Although common, CRTs are unsuitable for obtaining large prints.

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

Thus, for example, a light emitting diode (LED)
When using, near infrared (800nm), red (670n
It is necessary to expose 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," a system for recording images in Japan, September 14, 1987, Issue 4
It is described on pages 7 to 57 and is partially used.

Further, there is disclosed a system for recording on a color light-sensitive material having three light-sensitive layers having spectral sensitivity at each wavelength with a light source combining three semiconductor lasers which emit light of 880 nm, 820 nm and 760 nm. 137149.

Generally, in a multi-layer color light-sensitive material, when the respective colors of yellow, magenta and cyan are exposed to three different spectral regions to develop colors, it is possible to reproduce the colors without mixing. Has become an important technology on. In particular, when a light emitting diode (LED) or a semiconductor laser (LD) is used as an exposure light source, there is no choice but to design three spectral sensitivities in a narrow spectral range (from the red end to the infrared region).
The key to improving color separation is how to reduce the overlap of spectral sensitivities.

Conventionally used sensitizing dyes in the near infrared to infrared regions have a very broad spectral sensitivity, so that there is a problem that spectral sensitivities easily overlap and color separation is poor.

To ensure color separation, US Pat. No. 46
As described in 19892, there is known a technique of sequentially increasing the sensitivity on the short wavelength side or providing a filter layer. However, sequentially increasing the sensitivity on the short wavelength side has the drawback of causing an increase in fog and deteriorating the raw storage stability. Moreover, it is known that the infrared sensitization originally has poor raw storage stability. Further, it has been difficult to achieve high sensitivity in infrared sensitization.

As described above, it has been particularly desired to develop a light-sensitive material having high sensitivity, excellent raw storage stability, and good color separation.

[0014]

The object of the present invention is 70
It is an object of the present invention to provide a heat-developable color light-sensitive material which is excellent in color separation property with respect to exposure of a semiconductor laser having a long wavelength of 0 nm or more, high sensitivity, and excellent raw storage stability.

[0015]

It has been found that this object can be achieved by the method described below. That is, when a silver halide emulsion having different spectral sensitivity from each other on a support and silver ions are reduced to silver under high temperature conditions, dyes having different hues are released or produced corresponding to or opposite to this reaction. In a heat-developable color light-sensitive material having at least three layers containing a dye-donor compound in combination, at least one of the three layers has a maximum spectral sensitivity wavelength of 700 nm or more and 900 nm or less due to the thiadicarbocyanine dye. And containing at least one silver halide emulsion spectrally sensitized such that the spectral sensitivity to light having a wavelength longer by 20 nm than the wavelength of the maximum spectral sensitivity is 1/3 or less of the maximum spectral sensitivity. Thermal development characterized in that the layer contains a high boiling point organic solvent in an amount of 0.1 g or more and 10.0 g or less with respect to 1 mol of a silver halide emulsion. It was achieved by color photosensitive material.

[0016]

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 has at least three silver halide emulsion layers having different spectral sensitivities on a support. At least one of the silver halide emulsion layers contains at least one thiadicarbocyanine dye and has a wavelength of maximum spectral sensitivity (λma).
x) is 700 to 900 nm, and the spectral sensitivity (S ₁ ) to light having a wavelength 20 nm longer than the wavelength of this maximum spectral sensitivity is 1/3 or less of this maximum spectral sensitivity (S ₀ ). It contains at least one sensitive silver halide emulsion. This can improve the color separability when using a semiconductor laser or the like for exposure in the near infrared to infrared region, and may eliminate the need for providing a filter layer.

Further, it is generally known that the infrared-sensitized light-sensitive material has poor raw storage stability, but in order to improve the color separation property, a method of sequentially increasing the sensitivity on the short wavelength side. (US Pat. No. 4,619,892) leads to an increase in fog and further deteriorates the raw storage stability, which has been a problem. However, in the present invention, the color separation property can be improved without causing such a problem. Further, there is a problem that high sensitivity cannot be obtained with a light-sensitive material subjected to infrared sensitization, but the present invention can solve this problem.

In the present invention, a thiazylcarbocyanine dye is used, λmax is 700 to 900 nm, and the S ₁ / S ₀ ratio is 1/3 or less, and the high-boiling organic solvent is silver halide 1. 0.1 or more per mole 10.0
It is an essential condition that the silver halide emulsion layer is contained in an amount of g or less. If any one of these conditions is missing, the effect of the present invention cannot be obtained. For example, λmax, S ₁ / S ₀
Even if the ratio is satisfied, dyes other than the thiadicarbocyanine dye have drawbacks such as insufficient color separation property but insufficient raw storage stability. The amount of high boiling point solvent is 10.
If the amount exceeds 0 g, the sensitivity or color separation is insufficient, and if the amount is less than 0.1 g, the raw storage stability tends to be poor.

In the present invention, the lower limit of the S ₁ / S ₀ ratio is not limited, and the smaller this value, the better the color separation property.

In the present invention, at least three silver halide emulsion layers having different spectral sensitivities are used in combination with a dye-donor compound which releases or produces dyes having different hues. Here, "combined" means
Such a dye-donating compound may be contained in the silver halide emulsion layer, in a non-light-sensitive layer adjacent to the silver halide emulsion layer, or both in the silver halide emulsion layer and a non-light-sensitive layer adjacent thereto. Means that it may be contained in The dye-providing compound will be described later.

Next, the thiadicarbocyanine dye will be described in detail. In the present invention, those represented by Chemical Formula 1 or Chemical Formula 2 are preferably used.

[0023]

[Chemical 1]

[0024]

[Chemical 2]

In Chemical Formula 1, Q ₁ and Q ₂ each represent a methylene group, and R ₁ and R ₂ each represent an alkyl group. R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₃ and R ₄ are not hydrogen atoms at the same time. L ₁ , L ₂ and L ₃ each represent a methine group. A ₁ and A ₂ each represent an atomic group necessary for forming a benzene ring or a naphthalene ring.
R ₁ and L ₁ , and R ₂ and L ₃ may be bonded to each other to form a ring. M ₁ represents a charge balancing counter ion, and m ₁ represents a value required to neutralize the charge.

The alkyl group represented by R ₁ and R ₂ may be unsubstituted or may have a substituent, and preferably has 1 to 18 carbon atoms, for example, a methyl group or an ethyl group. , Propyl group, butyl group, pentyl group, octyl group, decyl group, dodecyl group and octadecyl group. Further, when it has a substituent, a preferable substituent is a sulfonic acid group, a carboxy group, a cyano group, or the like.

The alkyl group represented by R ₃ and R ₄ may be unsubstituted or may have a substituent, and preferably has 1 to 10 carbon atoms, for example, a methyl group, An ethyl group may be mentioned.

R ₁ and L ₁ and R ₂ and L ₃ may form a ring with each other. It is preferably a carbon atom forming an unsubstituted 5, 6 or 7 membered ring, and particularly preferably 6
It forms a carbon atom that forms a member ring.

R ₁ and R ₂ are preferably unsubstituted alkyl groups (eg methyl group, ethyl group, n-propyl group, n-butyl group) and sulfoalkyl groups (eg 2-
Sulfoethyl group, 3-sulfopropyl group, 4-sulfobobutyl group, 3-sulfobutyl group), R ₁ and L ₁ , R ₂
It is also preferable that L ₃ and L ₃ are bonded to each other to form a 5-membered ring or a 6-membered ring.

The aryl group represented by R ₃ and R ₄ may be unsubstituted or may have a substituent, and examples thereof include a phenyl group. Examples of the heterocyclic group represented by R ₃ and R ₄ include 2-pyridyl group and 2
Examples thereof include a thiazoyl group, a 2-furyl group, and a 2-quinolyl group. R ₃ and R ₄ are preferably a hydrogen atom, a methyl group, an ethyl group, a phenyl group or the like.

The benzene ring or naphthalene ring completed by A ₁ or A ₂ may be unsubstituted or may have a substituent, and the substituent at this time is a halogen atom such as chlorine atom. Hydroxyl group; alkyl group such as methyl group;
Alkoxy groups such as methoxy and ethoxy groups; aryl groups such as phenyl groups; carboxy groups; cyano groups; amino groups;
Examples thereof include a sulfonic acid group.

Examples of M ₁ include halide ions (bromide ion, iodide ion, etc.), perchlorate ion, anion such as paratoluenesulfonate ion, and cations such as triethylammonium ion and sodium ion.

When the dye molecule itself forms an intramolecular salt to maintain the charge balance, m ₁ is 0.

In Chemical formula 2, R ₁ and R ₂ each represent an alkyl group, and specific examples thereof are the same as those in Chemical formula 1. R ₅ represents an alkyl group, an aryl group or a heterocyclic group, and specific examples thereof are the same as those listed for R ₃ and R ₄ in Chemical formula 1. Among these, a methyl group, an ethyl group, a benzyl group and the like are preferable.

The benzene ring or naphthalene ring completed by A ₁ and A ₂ , and the ring formed by R ₁ and a methine group and R ₂ and a methine group are the same as those in Chemical formula 1.

Specific examples of the thiadicarbocyanine dyes preferably used in the present invention are shown in Chemical formulas 3 to 16 but are not limited thereto. Note that R in Chemical formula 3
The combinations of ₁ , R _{2 and the} like are shown in Chemical formula 4, Chemical formula 5 and Chemical formula 6, and the combination of R ₁ , R _{2 and the} like in Chemical formula 13 are shown in Chemical formula 14.

[0037]

[Chemical 3]

[0038]

[Chemical 4]

[0039]

[Chemical 5]

[0040]

[Chemical 6]

[0041]

[Chemical 7]

[0042]

[Chemical 8]

[0043]

[Chemical 9]

[0044]

[Chemical 10]

[0045]

[Chemical 11]

[0046]

[Chemical 12]

[0047]

[Chemical 13]

[0048]

[Chemical 14]

[0049]

[Chemical 15]

[0050]

[Chemical 16]

Among these, an anionic sensitizing dye is preferably used because the adsorption property is good, the spectral sensitivity is likely to be sharpened, and the stability of the coating solution over time is good. Further, anionic dyes are preferable because they have excellent raw storage stability.

The above-mentioned sensitizing dyes may be used alone, or may be used in combination, and other known sensitizing dyes (for example, US Pat. No. 4,617,257, JP-A-59-180550). Issue No. 60-140335, R
D17029 (1978) pages 12 to 13 and the like). Especially, those combinations are often used for the purpose of supersensitization. A dye that does not itself have a spectral sensitizing effect together with a sensitizing dye or a compound that does not substantially absorb visible light and that exhibits supersensitization may be contained in the emulsion (see, for example, US Pat. 3615641, JP-A-63-23145, etc.).

The sensitizing dye in the present invention can be synthesized with reference to the following documents. a) FM Hamer, "Heterocyclic Compounds-Cyanine Die and Related Compounds- (Heterocyclic Compounds)
-Cyanine dyes and related compounds) "(John ・
Willie & Sons John Wiley & Sons-New York, London-, 1964)

B) D. M. Starmer (DMSturme)
r) -Heterocyclic Compounds-Special topics
in heterocyclic chemistry-) "(John Wiley & Sons, Inc.-New York, London, 1977)

The silver halide emulsion of the present invention is spectrally sensitized with the above-mentioned sensitizing dye, but in the present invention, it is combined with such a silver halide emulsion and spectrally sensitized with another sensitizing dye. Sensitive silver halide emulsions can be used. As another spectral sensitizing dye, a known cyanine dye,
Merocyanine dyes and composite merocyanine dyes are used. In addition to these, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are used.

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

These sensitizing dyes, including those of the present invention, are 5 × 10 ⁻⁷ to 8 × 10 5 mol per mol of silver halide.
^-3 mol, preferably 1 x 10 ^-7 mol to 5 x 10 ^-3 mol, and particularly preferably 2 x 10 ^-7 mol to 2 x 10 ^-3 mol in the silver halide emulsion.

Next, the high boiling point organic solvent used in the present invention will be described. It is a known technique to use various organic solvents for the purpose of adding a hydrophobic compound to the silver halide emulsion layer, but in the present invention, the following high boiling point organic compounds belonging to a limited range of physical properties are used. It was found that by using a solvent, an unexpectedly good effect can be obtained for sharpening or sensitizing the spectral sensitivity and improving the raw storage stability. The boiling point of the high-boiling point organic solvent in the present invention is 100 ° C. or higher and 350 ° C. or lower in a conventional method.
The solubility range in water at 20 ° C. is 1% by weight or more and 25% by weight or less.

When the boiling point of the organic solvent is less than 100 ° C., the amount of the solvent remaining in the light-sensitive material after the coating layer is reduced or does not remain at all, and the effect of the present invention cannot be obtained. On the other hand, if the temperature exceeds 350 ° C., the physical properties at room temperature become highly viscous, and there is a drawback that it is difficult to put into practical use when added to a coating solution. The preferred boiling point range of the organic solvent used in the present invention is 120 ° C. or higher and 300 ° C. or lower, more preferably 140 ° C. or higher and 260 ° C. or lower.

If the solubility in water at 20 ° C. is 1% by weight or less, phase separation will occur in the coating liquid, and surface defects will occur in the photosensitive material after coating and drying. If the solubility is 25% by weight or more, the effect of the present invention, in particular, the sharpening of the spectral sensitivity is deteriorated. The preferred range of the solubility of the organic solvent used in the present invention in water at 20 ° C. is 1% or more and 20% or less, more preferably 1.5% or more and 15% or less, and most preferably 2%.
% Or more and 10% or less.

As the high boiling point organic solvent used in the present invention, a known solvent can be applied as long as the above physical properties are satisfied. For example, hydrocarbons, halogenated hydrocarbons, alcohols, ethers, acetals, ketones, esters, and so on, which are classified and published in “Solvent Pocket Book” edited by the Society of Synthetic Organic Chemistry (Ohm Co., Ltd.) It can be selected from polyhydric alcohols and their derivatives, fatty acids and phenols, nitrogen compounds, sulfur / phosphorus / other compounds.

In the present invention, the types of organic solvents preferably used are polyhydric alcohols and their derivatives. Specific examples of preferable organic solvents are shown below, but the present invention is not limited thereto. 1. Ethylene glycol diethyl ether 2. Ethylene glycol monoethyl ether acetate 3. Ethylene glycol monobutyl ether acetate 4. Ethylene glycol monophenyl ether 5. Ethylene glycol monohexyl ether 6. Ethylene glycol diacetate 7. Diethylene glycol monobutyl ether acetate 8. Triglycol dichloride 9. Propylene glycol monobutyl ether 10. Octyl glycol 11. Glyceryl triacetate 12. Glycerin-α, γ-dichlorohydrin 13. Phenol 14. Benzyl alcohol

The effective use amount of the high boiling point solvent in the present invention must be 0.1 g or more and 10.0 g or less per mol of the silver halide emulsion in the silver halide emulsion layer. If the amount of solvent exceeds 10.0 g, the sensitivity or color separation is insufficient, and if it is less than 0.1 g, the raw storage stability is poor. A more preferable amount of use is 0.2 g or more and 5.0 g or less, and most preferably 0.5 g or more and 3.0 g or less, per mol of silver halide emulsion.

The method for preparing the silver halide emulsion layer of the present invention will be described in detail below. The silver halide emulsion used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver iodochloride and silver chloroiodobromide, but preferably 10 mol% or less. Silver iodobromide, silver chloride and silver chlorobromide.

The silver halide emulsion used in the present invention may be either a surface latent image type or an internal latent image type. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging. Further, so-called multi-structured particles having different halogen compositions inside the particle and on the particle surface may be used. Of the multi-structure grains, those having a double structure are sometimes called a core-shell emulsion.

The silver halide emulsion of the present invention is preferably a monodisperse emulsion, and the coefficient of variation described in JP-A-3-110555 is preferably 20% or less. It is more preferably 16% or less, still more preferably 10% or less. However, the present invention is not limited to this monodisperse emulsion.

The average grain size of the silver halide grains used in the present invention is 0.1 μm to 2.2 μm, preferably 0.1 μm to 1.2 μm. More preferably, it is 0.1 μm to 0.8 μm.

The crystal habit of the silver halide grains may be any of a cube, an octahedron, a flat plate having a high aspect ratio, a potato, and the like, but the cube is preferable. Specifically, US Pat. No. 4,500,626, column 50, US Pat. No. 4,628,02.
No. 1, Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (1978), JP-A-62-251.
Any of the silver halide emulsions described in No. 59, etc. 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, a Nudel washing method is known as a means for this purpose, in which gelatin is gelatinized for a long time. In addition, inorganic salts consisting of polyvalent anions such as sodium sulfate, anionic surfactants, anionic polymers (eg polystyrene sulfonic acid), or gelatin derivatives (eg aliphatic acylated gelatin, aromatic Acylated gelatin,
A precipitation method (flocculation) using an aromatic carbamoylated gelatin or the like may be used. Preferably,
The precipitation method using a compound represented by Chemical formula 17
The present invention is not limited to this. Removal of excess salt may be omitted. Alternatively, US Pat.
758,505, JP-A-62-113137, JP-B-59-43727, and U.S. Pat. No. 4,334,012.
The excess salt may be removed using the ultrafiltration device shown in No.

[0070]

[Chemical 17]

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 10 ^-9 to 10 ^-3 mol per mol of silver halide. Further, 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, a rhodan salt, NH ₃ and a compound represented by Chemical formula 18 as a silver halide solvent, an organic thioether derivative described in JP-B-47-11386, or JP-A-53-1443.
The sulfur-containing compounds described in No. 19 can be used.

[0073]

[Chemical 18]

A nitrogen-containing compound as described in JP-B-46-7781, JP-A-60-222842, JP-A-60-122935 and the like can be added in the step of forming silver halide grains. .

As the protective colloid used in the preparation of the emulsion of the present invention and as the binder of other hydrophilic colloid, it is advantageous to use gelatin, but hydrophilic colloid can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, cellulose sulfates; sodium alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetals, poly -N-vinylpyrrolidone, polyacrylic acid,
Various synthetic hydrophilic polymer substances such as single or copolymers such as polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, britain and society of gelatin.
The Scientific, Photography of Japan (Bull.Soc.Sci.Phot., Japan), Number (No.)
16, enzyme-treated gelatin as described in 16, p. (P) 30 (1966) may be used, and a hydrolyzate or enzymatic hydrolyzate of gelatin may also be used.

For other conditions, see the graph
(P.Glafkides), "Chemie et Physique Photographique"
[Published by Paul Montel, 1967),
GFDfin, `` Photographic Emulsion Chemistry (PhotographicEmu
lsion Chemistry) "(The Focal Press The F
ocal Press, 1966), VL Zelikman et al, "Making and Coating Photographic Emulsion".
(Making and Coating Photographic Emulsion) "(The
Focal Press Published by The Focal Press, 1964
You can refer to the description such as (year). That is, any of the acidic method, the neutral method, and the ammonia method may be used, and as the method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used.

It is also possible to use a method of forming grains in the presence of excess silver ions (so-called reverse mixing method). As one type of simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled or double jet method can be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount or the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329, JP-A-55-158124, US Pat. No. 3650757).

During or after grain formation, the surface of the silver halide grain may be replaced with a halogen which forms a hardly soluble silver halide grain.

The reaction solution may be stirred by any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set arbitrarily.

The silver halide emulsion used in the present invention is
Although it can be used without being chemically sensitized, it is preferable to use one that has been chemically sensitized to increase the sensitivity. The chemical sensitization may be sulfur sensitization, gold sensitization, reduction sensitization, or a combination thereof.

In addition, chemical sensitization with a compound containing a chalcogen element other than sulfur such as selenium and tellurium, or chemical sensitization with a noble metal such as palladium and iridium may be combined with the above chemical sensitization.

Further, 4-hydroxy-6-methyl-
At the beginning of chemical sensitization, an inhibitor such as a nitrogen-containing heterocyclic compound represented by (1,3,3a, 7) -tetraazaindene is added.
A method of being added midway or after completion is also preferably used.

The sulfur sensitizer is a compound containing sulfur obtained by reacting with active gelatin or silver, and examples thereof include thiosulfate, allylthiocarbamide, thiourea, allylisothiacyanate, cystine and p-toluenethiosulfone. acid,
Rhodan, mercapto compounds and the like are used. In addition, US Pat. Nos. 1,574,944 and 2,41
No. 0,689, No. 2,278,947, No. 2,7
Those described in No. 28,668, No. 3,656,955 and the like can also be used.

The sensitizing dye used in the light-sensitive material can be directly dispersed in the emulsion. In addition, these are first a suitable solvent, for example, an organic solvent or water (which may be alkaline or acidic) that is compatible with water, such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, fluorinated alcohol, dimethylformamide, propyl alcohol and the like. It may be added after being dissolved in
You may use together more than one kind. It may also be added in the form of dispersion in a water / gelatin dispersion system or in the form of freeze-dried powder. Further, it may be added in the form of a powder dispersed with a surfactant or a solution.

If the emulsion can be stirred at 50 ° C. or higher and 85 ° C. or lower for 15 minutes or longer (preferably 30 minutes or longer) while the sensitizing dye is present in the silver halide emulsion, the timing for adding the sensitizing dye is basically Is always good for you. That is, at the beginning of silver halide emulsion grain formation (may be added before nucleation), during or after formation, or at the beginning, during or after the desalting step, during gelatin redispersion, and It is before, during or after chemical sensitization, or at the time of preparing a coating solution. Preferably, during or after the formation of silver halide grains, or
It is to add before, during, and after chemical sensitization. The addition after the chemical sensitization is to add the sensitizing dye after all the chemicals necessary for the chemical sensitization are added.

The method of addition may be generally, or may be divided into several times and added in the same step or different steps. The addition may be done gradually over time.

The addition amount is 30% or more of the adsorption saturation coating amount 1
It is preferable to add 50% or less. More preferably, the added amount is 50% or more and 100% or less. here,
The adsorption saturation coating amount is the amount necessary for the sensitizing dye to cover the entire surface of the silver halide emulsion grain, and can be determined from the area occupied by the sensitizing dye on the surface of the silver halide emulsion grain.

Even when the sensitizing dye is added before and after the formation of the silver halide grains and during the formation, even if the grain formation cannot be prevented at a low temperature of 50 ° C. or less, the subsequent step (for example, chemical sensitization) The emulsion may be stirred for 15 minutes or longer at a temperature of 50 ° C. or higher and 85 ° C. or lower.
It is preferable to heat the emulsion to 15% or less and stir the emulsion for 15 minutes or more. The sensitizing dye may be added and the emulsion may be stirred at a temperature of 50 ° C. or higher and 85 ° C. or lower. In the addition of sensitizing dye at the time of silver halide grain formation, if the sensitizing dye is added all at once, the amount of sensitizing dye added is close to the saturated coating amount. Since it may cause a problem, the sensitizing dye may be added continuously or in several times.

In addition, before and after the addition of the sensitizing dye,
Soluble Ca compound, soluble I compound, soluble Br
The compound, the soluble Cl compound and the soluble SCN compound may be added together. Preferably KI, CaC
It is preferable to use l ₂ , KCl, KBr, KSCN or the like.

Next, the method of adding the high boiling point solvent of the present invention to the silver halide emulsion layer will be described. In the process of preparing a silver halide emulsion, the high boiling point solvent may be basically added at any time. In other words, at the beginning of silver halide emulsion grain formation (may be added before nucleation), during the
After formation, or at the beginning, in the middle, or after the desalting step, when the gelatin is redispersed, before or after the chemical sensitization, during the middle, or when the coating solution is prepared. Preferably, it is added before, during, or after the chemical sensitization and before or after the addition of the sensitizing dye.
The addition method may be added at once, or divided into several times,
It may be added over the same step or different steps. The addition may be done gradually over time.

Further, in the step of adding the sensitizing dye of the present invention and the high boiling point solvent to the silver halide emulsion,
The compound of the present invention, which does not substantially absorb visible light and exhibits supersensitization, is added to the emulsion to obtain the effect of the present invention, namely increase in sensitivity, sharpening of spectral sensitivity or raw storage stability. It is preferable in that it can be further improved. Examples of such compounds include, for example, U.S. Pat. No. 3,615,641 and JP-A-63-2.
No. 3145 and the like.

[0094]

[Chemical 19]

The supersensitizer is preferably added in the silver halide emulsion preparation step after the sensitizing dye is added, and more preferably after the sensitizing dye is sufficiently adsorbed. Specifically, it is preferable to add the sensitizing dye to the emulsion at 50 ° C. or higher and 85 ° C. or lower, maintain the time required for adsorption for 15 minutes or longer, and then add at 30 ° C. or higher and 50 ° C. or lower. It is not preferable to store the emulsion to which the sensitizing dye has been added for a long period of time and to add the supersensitizer described above after 1 to several tens of days, for example. It is most preferable to add the high-boiling-point solvent at the same time as the supersensitizer is added.

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

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

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

The above organic silver salts are photosensitive silver halides.
0.01 to 10 mol, preferably 0.01 per mol
-1 mol can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 50 mg / m ^{2 to} 10 g in terms of silver.
/ M ² is suitable.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, the mercapto compound and its metal salt described in JP-A-59-111636, the acetylene compounds described in JP-A-62-87957, etc. may be used.

A hydrophilic binder is preferably used for the binder of the constituent layers of the light-sensitive material and the dye-fixing element. Examples thereof include those described on pages (26) to (28) of JP-A-62-253159. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, a protein such as gelatin derivative, or a cellulose derivative,
Natural compounds such as polysaccharides such as starch, gum arabic, dextran, pullulan and polyvinyl alcohol,
Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. In addition, JP-A-62-1
No. 245260 and the like, a superabsorbent polymer, that is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or a copolymerization of the vinyl monomers with each other or with other vinyl monomers. Combined (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L- manufactured by Sumitomo Chemical Co., Ltd.)
5H) is also used. These binders can be used in combination of two or more.

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.
Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer.

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

The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing element are used for the purpose of improving physical properties of the film such as dimensional stabilization, 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. .

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 itself but exhibits 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-60-140335
(17)-(18), ibid. 57-40245, ibid. 56-138.
No. 736, No. 59-178458, No. 59-5383.
No. 1, 59-182449, 59-182450.
Nos. 60-119555, 60-128436 to 60-128439, 60-19854.
No. 0, No. 60-181742, No. 61-259253.
Nos. 62-244044, 62-131253 to 62-131256, European Patent No. 2207.
There are reducing agents and reducing agent precursors described on pages 78 to 96 of No. 46A2.

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

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

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the 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 of those reducing agents which do not substantially move in the layer of the photographic material.
Hydroquinones, sulfonamide phenols, sulfonamide naphthols, JP-A-53-11 are preferred.
Examples thereof include compounds described as electron donors in No. 0827, and dye-donating compounds having diffusion resistance and reducing properties described below.

In the present invention, the addition amount of the reducing agent is 0.01 to 20 mol, and particularly preferably 0.1 to 1 mol of silver.
10 to 10 mol.

The dye-providing compound (also referred to as a dye-providing substance) used in the present invention, when reduced to silver ions under high temperature conditions, has a diffusibility (corresponding to this reaction or vice versa) ( A compound that produces or releases a (mobile) dye.

As an example of the dye-donating compound which can be used in the present invention, first, a compound (coupler) which forms a dye by an oxidative coupling reaction can be mentioned. 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 developers and couplers are TH James
"The Theory of the Photographic Process" Fourth Edition 2
91-334 pages, and 354-361 pages, JP-A-58
-123533, 58-149046, 58-
No. 149047, No. 59-111148, No. 59-1
24399, 59-174835, and 59-23.
1539, 59-231540, 60-295.
No. 0, No. 60-2951, No. 60-14242, No. 60-23474, No. 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 corresponds to a photosensitive silver salt having an imagewise latent image. Or, conversely, a difference is caused in the diffusivity of the compound represented by (Dye-Y) _n -Z, or Dye is released, and the released Dye and (Dye-Y) _n -Z Represents a group having a property of causing a difference in diffusibility between them, 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 (1) to (4). 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 when it reacts with 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 also be used. For example, US Pat.
Compounds releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 4,980,399.
Examples of the compounds described in No. 45, etc. release a diffusible dye by an intramolecular rewinding reaction of an isoxazolone ring.

US Pat. No. 4,559,290, European Patent No. 220746A2, US Pat. No. 4,783,396,
As described in Japanese Unexamined Patent Publication No. 87-6199, a non-diffusible compound that releases a diffusible dye by reacting with a reducing agent remaining unoxidized by development can also be used.

As an example thereof, 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), which releases a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 8808588A, 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.
No. 63, 2016-654, etc.
-X bond (X represents an oxygen, sulfur or nitrogen atom) and a compound having an electron-withdrawing group, Japanese Patent Application No. 62-106885.
No. ₂ within one molecule of 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-
The compound having a C—X ′ bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group in one molecule described in No. 271341. Also, Japanese Patent Application Sho 62
Compounds described in JP-A-319989 and JP-A-62-320771, in which a single bond is cleaved after reduction by a π bond conjugated with an electron-accepting group to release a diffusible dye, 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. 47833.
Compounds (1) to (3), (7) to (10), (1
2), (13), (15), (23) to (26), (31), (32), (35), (4
0), (41), (44), (53) to (59), (64), (70), open technical report 8
And compounds (11) to (23) of 7-6199.

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 (DRR 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 DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44, among which the compounds (1) to (3) described in the U.S. patents, (10) ~ (13), (16) ~ (19), (28)
To (30), (33) to (35), (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, 1976.
, April issue, pages 30 to 32), leuco dyes (US Pat. Nos. 3,985,565 and 4,022,617), and the like can also be used.

Hydrophobic additives such as dye-donating compounds and antidiffusive reducing agents can be incorporated into the layer 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 point organic solvent is 10 g or less, preferably 5 g or less, relative to 1 g of the dye-donor compound used. Further, 1 cc or less, more preferably 0.5 cc or less, and 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, 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 development and stabilizing an image at the same time can be used in the light-sensitive material. Specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52.

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 different 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 material 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.

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. Specific examples thereof include US Pat. No. 4,500,626, columns 58 to 59 and JP-A-61-88256, (32) to (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 can 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.

In the constituent layers of the light-sensitive material and the dye-fixing element, a plasticizer, a slipping agent, or a high boiling point organic solvent can be used as an agent for improving the releasability between the light-sensitive material and the dye-fixing element. A specific example is (25) of JP-A-62-253159.
Page, No. 62-245243 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. As examples thereof, various modified silicone oils described in "Modified Silicone Oil" technical materials p.6 to 18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy modified silicone (trade name X-22-3710) are effective. .

Further, JP-A-62-215953 and 63
The silicone oil described in No. 46449 is also effective.

An anti-fading agent may be used in the light-sensitive material and 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 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

Examples of metal complexes include US Pat. No. 4,2411,
No. 55, No. 4245018, Columns 3 to 36, No. 4254.
195, columns 3 to 8, JP-A Nos. 62-174741, 61-88256, pages (27) to (29), 63-19924.
No. 8, JP-A-1-75568, and JP-A-1-74272.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137). An anti-fading agent for preventing fading of the dye transferred to the dye fixing element may be contained in the dye fixing element in advance,
The dye fixing element may be supplied from the outside such as a light-sensitive material.

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 material and the dye fixing element. In particular, it is preferable to incorporate a fluorescent whitening agent in the dye fixing element or supply it from the outside such as a light-sensitive material. For example, see “The Chemis” edited by K. Veenkataraman.
try 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.

As the hardener used in the constituent layers of the light-sensitive material and the dye fixing element, US Pat. No. 4,678,739, No. 41 is used.
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 constituent layers of the light-sensitive material and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of slipperiness, prevention of electrification, 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 material and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification and improving releasability. 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 material and the dye fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
In addition to the compounds described on page 1-88256 (29), benzoguanamine resin beads, polycarbonate resin beads, A
Japanese Patent Laid-Open Nos. 63-274944 and 6-96, such as S resin beads.
There are compounds described in 3-274952.

In addition, the constituent layers of the light-sensitive material 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).

In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the dye fixing element.
The image forming accelerator includes a silver salt oxidizing agent and a reducing agent, which promotes oxidation-reduction reaction, formation of dye from dye-donor substance, decomposition of dye or release of diffusible dye, and light-sensitive material layer. It has functions such as promoting the migration of dyes to the dye-fixing layer. From the physicochemical functions, bases or base precursors, nucleophilic compounds, high boiling organic solvents (oils), thermal solvents, surfactants, silver or It is 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 a base precursor to the dye-fixing element in order to improve 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 material and the dye fixing element.

In the present invention, various development terminators can be used in the light-sensitive material and / or the dye-fixing element for the purpose of always obtaining a constant image against 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 (31) to (32).

In the present invention, as the support for the light-sensitive material and the dye fixing element, those which can withstand the processing temperature are used. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide, and polypropylene are used. The film method synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated 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 this, JP-A-62-253159 (2
The supports described on pages 9 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 of exposing and recording an image on a light-sensitive material, for example, a method of directly photographing a landscape or a person with a camera or the like, a method of exposing through a reversal film or a negative film with a printer 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 light from a light emitting diode or various lasers through an electric signal, a CRT, a liquid crystal display of image information, 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.

As a light source for recording an image on a photosensitive material,
As described above, the natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
The light source described in 500626, column 56 can be used.

Image exposure can also be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of exhibiting non-linearity between polarization and an electric field that appears when a strong optical electric field such as laser light is applied, and includes lithium niobate and potassium dihydrogen phosphate (KD).
P), lithium iodate, BaB ₂ O _{4 and} other inorganic compounds, urea derivatives, nitroaniline derivatives, for example, nitropyridine-N such as 3-methyl-4-nitropyridine-N-oxide (POM). -Oxide derivatives, JP-A-61-53462 and JP-A-62-210432
The compounds described in No. 10 are preferably used. As the form of the wavelength conversion element, a single crystal high waveguide type, a fiber type and the like are known, and any of them is useful.

Further, the above-mentioned 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 light-sensitive material and / or the dye fixing element are
It may have a form having a conductive heating element layer as a heating means for heat development or dye diffusion transfer. In this case, the transparent or opaque heating element is disclosed in
Those described in, for example, the specification of 145544 can be used.
Note that these conductive layers also function as antistatic layers.

The heating temperature in the heat development step is about 50 ° C. to about 2 ° C.
It can be developed at 50 ° C, but especially from about 80 ° C to about 180 ° C.
Is useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the end of the heat development process.
In the latter case, the heating temperature in the transfer step can be 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. Also,
As described in detail in JP-A-59-218443 and JP-A-61-238056, 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. is there. In this method, the heating temperature is 50 ° C.
As described above, the boiling point of the solvent or less is preferable.

Examples of the solvent used for promoting 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 (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 and a complex-forming compound, etc. may be contained in the solvent.

These solvents can be used by a method of applying them to the dye fixing element, the light-sensitive material 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 of applying a solvent to the photosensitive layer or the dye fixing layer is described in, for example, JP-A-61-147244 (2).
There is a method described on page 6). Alternatively, the solvent may be contained in microcapsules, and may be incorporated in the light-sensitive material or the dye-fixing element or both in advance.

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 material or the dye fixing element can also be adopted. The hydrophilic thermal solvent may be incorporated in either the light-sensitive material 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, in order to promote dye transfer, a high boiling point organic solvent may be contained in the light-sensitive material and / or the dye-fixing element.

The heating method in the developing and / or transferring step is as follows: contact with a heated block or plate, contact with a heat plate, hot presser, heat roller, halogen lamp heater, infrared or far infrared lamp heater, etc. And passing through a high temperature atmosphere.

The pressure conditions and the method for applying pressure when the light-sensitive element and the dye-fixing element are superposed and brought into close contact with each other are described in JP-A-6-61.
The method described in page 1-147244 (27) can be applied.

Any of a variety of thermal development equipment can be used in processing the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259.
The device described in No. 44 is preferably used.

[0175]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example A method for preparing the emulsion (1) for the fifth layer will be described.

To the well-stirred aqueous solution having the composition shown in Table 1, the solutions I and II having the compositions shown in Table 2 were added over 10 minutes, and then the solutions III and IV having the compositions shown in Table 2 were added to the solution 25 times. Added over minutes.

[0178]

[Table 1]

[0179]

[Table 2]

Compound-1 shown in Table 1 is shown in Chemical formula 20.

Immediately before the chemical sensitization, 50 cc of a 1% solution of the sensitizing dye shown in Chemical formula 21 (mixed solvent of methanol: water = 1: 1) was added.

After washing with water and desalting (performed at pH = 4.1 using the precipitating agent a shown in Chemical formula 22), 22 g of gelatin was added to adjust pH = 6.0 and pAg = 7.9. 60 ° C
I chemically sensitized. The compounds used for the chemical sensitization are as shown in Table 3.

The obtained emulsion had a yield of 630 g, was a unit cubic emulsion having a coefficient of variation of 10.3%, and had an average grain size of 0.21 μm.

[0184]

[Table 3]

[0185]

[Chemical 20]

[0186]

[Chemical 21]

[0187]

[Chemical formula 22]

[0188]

[Chemical formula 23]

[0189]

[Chemical formula 24]

[0190]

[Chemical 25]

A method for preparing the emulsion (2) for the third layer will be described.

To the well-stirred aqueous solution having the composition shown in Table 4, the solutions I and II having the compositions shown in Table 5 were added over 18 minutes, and then the solutions III and IV having the compositions shown in Table 5 were added to the solution 24 times. Added over minutes.

[0193]

[Table 4]

[0194]

[Chemical formula 26]

Compound-1 shown in Table 4 is shown in Chemical formula 20.

[0196]

[Table 5]

After washing with water and desalting (performed at pH = 3.9 using the precipitating agent b shown in Chemical formula 22), 22 g of gelatin was added to adjust pH = 6.0 and pAg = 7.8. 70 ° C
I chemically sensitized. In addition, in the middle of the chemical sensitization, the following Table 2
No. 0 sensitizing dye, supersensitizer and various high boiling organic solvents were added. The compounds used for the chemical sensitization are shown in Table 6. The addition amount of the sensitizing dye is 7.0 in all cases.
× 10 ^-4 g / m, addition amount of supersensitizer is 0.01 g
/ M ² .

The obtained emulsion had a yield of 645 g, was a monodisperse cubic emulsion having a coefficient of variation of 9.7%, and had an average grain size of 0.24 μm.

[0199]

[Table 6]

A method for preparing the emulsion (3) for the first layer will be described.

To a well-stirred aqueous solution having the composition shown in Table 7, the solutions I and II having the compositions shown in Table 8 were added over 18 minutes, and then the solutions III and IV having the compositions shown in Table 8 were added to the solution 25 times. Added over minutes.

[0202]

[Table 7]

[0203]

[Table 8]

Compound-1 shown in Table 7 is shown in Chemical formula 20.

After washing with water and desalting (performed at pH = 4.1 using the precipitating agent a shown in Chemical formula 22), 22 g of gelatin was added to adjust pH = 7.4 and pAg = 7.6. 60 ° C
I chemically sensitized. During the chemical sensitization, 7.5 cc of a 0.2% methanol solution of a sensitizing dye represented by Chemical formula 23 (p-toluenesulfonic acid 0.1N) was added. The compounds used for the chemical sensitization are shown in Table 9.

The yield of the obtained emulsion was 650 g, which was a monodisperse cubic emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.25 μm.

[0207]

[Table 9]

[0208]

[Chemical 27]

Next, a method for preparing a gelatin dispersion of a dye-donor compound will be described.

A uniform solution having the composition shown in Table 10 and a uniform solution having the composition shown in Table 11 were prepared, mixed and stirred, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a dispersion of a magenta dye-donor substance.

[0211]

[Table 10]

[0212]

[Table 11]

A uniform solution having the composition shown in Table 12 and a uniform solution having the composition shown in Table 13 were prepared, mixed and stirred, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a cyan dye-donor dispersion.

[0214]

[Table 12]

[0215]

[Table 13]

A uniform solution having the composition shown in Table 14 and a uniform solution having the composition shown in Table 12 were prepared, mixed and stirred, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a yellow dye-donor substance dispersion.

[0217]

[Table 14]

[0218]

[Table 15]

Next, a method for preparing a gelatin dispersion of a reducing agent will be described.

A uniform solution having the composition shown in Table 16 and a uniform solution having the composition shown in Table 17 were prepared, mixed and stirred, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a reducing agent dispersion.

[0221]

[Table 16]

[0222]

[Table 17]

Photosensitive materials having the constitutions shown in Tables 18 and 19 were prepared using these emulsions and dispersions of dye-donor compounds.

[0224]

[Table 18]

[0225]

[Table 19]

The support used at this time was a 135 μm thick paper support laminated with polyethylene.

The compounds shown in Tables 18 and 19 include the compounds shown in the formulas (see Tables 10 to 17) described in the preparation of dispersions of dye-donor compounds and reducing agents (see Tables 10 to 17).
4 shows. That is, the dye donating compound is
The high boiling organic solvents (1) and (2) are chemical compounds 32 and 33, the filter dye (F) is chemical compound 34, and the reducing agent (1) is chemical compound 35.
The mercapto compound (1) was converted to the compound 36 and the surfactant (2)
To (4) are chemical formulas 37 to 39, and water-soluble polymer (1) is chemical formula 4
0, reducing agent (2) is chemical formula 41, antifoggant (1) is chemical formula 4
2, the stabilizer is shown in Chemical formula 43, and the hardening agent is shown in Chemical formula 44. The surfactant (1) is an aerosol OT.
Is.

[0228]

[Chemical 28]

[0229]

[Chemical 29]

[0230]

[Chemical 30]

[0231]

[Chemical 31]

[0232]

[Chemical 32]

[0233]

[Chemical 33]

[0234]

[Chemical 34]

[0235]

[Chemical 35]

[0236]

[Chemical 36]

[0237]

[Chemical 37]

[0238]

[Chemical 38]

[0239]

[Chemical Formula 39]

[0240]

[Chemical 40]

[0241]

[Chemical 41]

[0242]

[Chemical 42]

[0243]

[Chemical 43]

[0244]

[Chemical 44]

Regarding the coating of the third layer (near-infrared photosensitive layer) of the light-sensitive material having the constitution of Tables 18 and 19, the types and addition amounts of the sensitizing dye and the high boiling point solvent are as shown in Table 20. did.
In this way, the photosensitive materials 101 to 115 were prepared.

[0246]

[Table 20]

Next, a method for producing the dye fixing material will be described. Table 21 on paper support laminated with polyethylene
A dye fixing material was prepared by applying the composition.

[0248]

[Table 21]

The compounds used in Table 21 are shown in Chemical formula 45 as silicone oil, those shown in Chemical formula 46 as surfactant, those shown in Chemical formula 47 as mordant, and those shown in Chemical formula 48 as hardener. It is what is done.

[0250]

[Chemical formula 45]

[0251]

[Chemical formula 46]

[0252]

[Chemical 47]

[0253]

[Chemical 48]

The polymer, high boiling point organic solvent and matting agent are shown below. Polymer * 5 Sodium vinyl alcohol acrylate copolymer (75/25 molar ratio) Polymer * 7 Dextran (molecular weight 7000) High boiling organic solvent * 8 Reofos 95 (Ajinomoto Co., Inc.)
Matting agent * 10 Benzoanamin resin (18 vol% of particles exceeding 10 μm)

Next, evaluation was carried out by the following exposure and processing. Using the laser exposure device described in Japanese Patent Application No. Hei 2-129625, exposure was carried out under the conditions shown in Table 22, and 11 cc / m ² of water was supplied to the emulsion surface of the exposed light-sensitive material with a wire bar.
After that, they were superposed so that the dye fixing material and the film surface were in contact with each other. Using a heat drum whose temperature was adjusted so that the temperature of the absorbed film was 83 ° C., after heating for 30 seconds, the dye fixing material was peeled off from the photosensitive material to obtain an image on the dye fixing material. The spectral sensitivity was measured by exposing each light-sensitive material to a series of monochromatic light through a wedge for 1 second and performing the same processing as above.

[0256]

[Table 22]

The transfer density was measured with a self-recording densitometer to determine fog and sensitivity (reciprocal of exposure amount giving fog + 1.0).

The raw storage stability was evaluated for storage at room temperature for 3 days and storage at 60 ° C. and relative humidity of 60% for 3 days.

Further, the evaluation of the color separation degree is carried out by the exposure amount logE1 which gives the density of yellow (Dmax-0.1) by the exposure of 810 nm, and (Dmin +
0.1) difference from the exposure dose logE2 that gives the density, logE = lo
It was evaluated by gE1-logE2. The smaller the value (negative value), the better the color separation property.

By the above method, the photographic materials 101 to 11
5, the spectral sensitivity of the cyan color developing layer, sensitivity, fog,
The degree of color separation was measured and summarized in Table 20 above. The following are the comparative sensitizing dyes (A).

[0261]

[Chemical 49]

From the results of Table 20, the light-sensitive material of the present invention is
It can be seen that it has high sensitivity, excellent raw storage stability, and excellent color dispersibility.

[0263]

According to the present invention, the sensitivity is high and the color separation property is excellent. Moreover, it has excellent raw storage stability.

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

[Procedure amendment]

[Submission date] May 25, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0084

[Correction method] Change

[Correction content]

Further, 4-hydroxy-6-methyl-
An inhibitor such as a nitrogen-containing heterocyclic compound typified by (1,3,3a, 7) -tetraazaindene, or a nucleic acid or a decomposition product thereof is added at the beginning, middle, or end of the chemical sensitization. The method is also preferably used. Examples of preferable nucleic acids include deoxyribonucleic acid (DNA) and ribonucleic acid (RNA), and the nucleic acid degradation products include those in the middle of degradation and monomers such as adenine, guanine, uracil, cytonin and thymine. .

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0199

[Correction method] Change

[Correction content]

[0199]

[Table 6]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0246

[Correction method] Change

[Correction content]

[0246]

[Table 20]

Claims (1)

[Claims] 1. A silver halide emulsion having at least three layers on a support and having different spectral sensitivities, and when silver ions are reduced to silver under a high temperature condition, they are different from each other in response to this reaction or inversely corresponding thereto. In a heat-developable color light-sensitive material having a layer containing a dye-donating compound that releases or produces a hue dye, at least one of the three layers has a wavelength of maximum spectral sensitivity due to a thiadicarbocyanine dye. Contains at least one silver halide emulsion spectrally sensitized to have a spectral sensitivity of 700 nm or more and 900 nm or less and having a wavelength 20 nm longer than the wavelength of this maximum spectral sensitivity is 1/3 or less of this maximum spectral sensitivity. In addition, the high-boiling organic solvent is contained in the emulsion layer in an amount of 0.1 g or more and 10.0 g or less with respect to 1 mol of the silver halide emulsion. Thermal development color photosensitive material.