JPH0486658A - Heatdevelopable color photosensitive material - Google Patents

Abstract

PURPOSE:To attain the reading of the information recorded by using longer wavelengths of light than 750 nm by using a compound for which at least one comp. of dye imparting supplying materials has an absorption maximum at 400-700 nm, and incorporating a specified compound. CONSTITUTION:This material is a heatdevelopable color photosensitive material having photosensitive silver halide, a reducing agent, and a dye imparting material is a compound forming a dye having an absorption maximum at 400-700 nm and further incorporates a compound forming a dye having an absorption maximum at longer wavelengths than 725 nm expressed with formula I. In formula I, R<1> and R<2> are electron attractive groups of sigmap>=0.50 and X is atomic groups forming an aromatic cyclic which may have substituted groups and Z is H atom or a coupling type releasing group. Thus by using the photosensitive material, it becomes easy to read the information recorded with longer wavelength light than 750 nm.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a heat-developable color photosensitive material, and more specifically,
This invention relates to a heat-developable color photosensitive material in which recorded information can be read with light having a wavelength longer than 750 nm.

[Background of the invention] In recent years, information records such as various ID cards (in A-uri,
Along with color image information, character information or signal information such as a bar code is provided on the same recording material. This record, in which character information or signal information is recorded, can be read mechanically using light with a wavelength longer than 750 nm, such as from a semiconductor laser or light emitting diode, to speed up information determination and prevent misidentification. is often the case.

On the other hand, silver halide color light-sensitive materials are the most superior in terms of the quality of color images obtained, and information recording materials using silver halide color light-sensitive materials are also being developed. However, in the case of ordinary silver halide color light-sensitive materials, the processing is wet, so the processing is simple and easy.
[Or many problems remain in terms of promptness.]

It is a material that shares the good image quality that is the characteristic of silver halide color photosensitive materials, and is superior in terms of ease and speed of processing. Photosensitive materials are known.

This diffusion transfer heat-developable color photosensitive material and its image forming method are described, for example, in JP-A-59-12431 and JP-A-59-12431;
No. 159159, No. 59-181345, No. 59-2
29556@, 60-2950@, 61-5264
No. 3, No. 61-61158, No. 61-61157,
No. 59-180550, No. 61-132952, No. 61-139842, U.S. Patent No. 4,595,6
No. 52, No. 4.590, 154 and No. 4584.26
It is stated in No. 7 etc.

However, in the above-mentioned diffusion transfer type heat-developable color light-sensitive materials, a dye-providing substance that forms or releases three color dyes, yellow, magenta, and cyan, is usually used. It is difficult to read the information displayed.

In order to improve these problems, we have developed a compound that forms a dye with an absorption maximum at a wavelength longer than 725r+m.
C1 The present inventors have already made a proposal.

By containing such a compound, a heat-developable color photosensitive material can be configured to enable the above-mentioned reading.

However, although the compound proposed by the present inventors for ir1 satisfies the condition that the absorption maximum is at a wavelength longer than 725 nm, it has problems such as a relatively short wavelength and being somewhat difficult to synthesize.

[Purpose of the invention] An object of the present invention is to solve such problems.

That is, an object of the present invention is to provide a dye-donating substance that forms a dye that has good color development and transferability, excellent thermal stability, and has favorable absorption in the infrared region, and which solves the above-mentioned problems in synthesis. J:su,7
It is an object of the present invention to provide a heat-developable color photosensitive material in which information recorded with light having a long wavelength of 50 nm J can be easily read.

[Structure of the Invention] As a result of intensive research in order to achieve the above object, the present inventor has developed a heat-developable color photosensitive material having at least a photosensitive silver halide, a reducing agent, and a dye-providing substance on a support. At least one of the donor substances has a wavelength of 400 nm to 700 nm.
mk: @ A compound that forms a dye having an absorption maximum, and further contains a compound that forms a dye that has an absorption maximum at a wavelength longer than 725 nm, represented by the following general formula (1). It has been found that a heat-developable color photosensitive material according to the present invention satisfies the above objects of the present invention.

General formula (1) In the formula, R+ and R2 are electron-withdrawing groups with σp≧0.50, X
represents an atomic group that forms an aromatic ring even if it has a substituent.

Z is a hydrogen atom or coupling t! L M JJI'
Represents the i group.

The present invention will be described in more detail below.

In the present invention, the expression that the dye formed by the compound represented by the general formula (1) "has an absorption maximum at a wavelength longer than 725nllll" means that when the compound is thermally developed to form a dye, the dye forms a dye. In the case of a transfer method, it means that the reflection density or transmission density applied to the dye image transferred to the transfer member has the absorption maximum (λmax). It is.

First, a compound represented by general formula (1), 725
A compound (hereinafter also referred to as an infrared coupler of general formula (1), etc.) that forms a dye having an absorption maximum at a wavelength longer than nm (hereinafter also referred to as an infrared dye of the present invention) will be described.

The infrared coupler of general formula (1) preferably has molecule 1 (Z
The molecular weight (excluding the molecular weight) of 700 or less, more preferably 500 or less is used. When the molecular group is within this range, the transferability of the produced infrared dye can be particularly improved.

In addition, in order to improve the immobility in the photosensitive layer and the solubility of the coupler in the solvent, the infrared coupler 1 of formula (1) has a ballast group (preferably a group having 8 or more carbon atoms). or a polymer residue), and the ballast group is preferably substituted by Z.

R+, R2 represent an electron-withdrawing group with σp≧0.50,
Specifically, sulfonyl groups, sulfonic acid esters, dicyanovinyl groups, carboxyvinyl groups, tetrazolyl groups,
Siam L phosphate ester star, sulfamoyl group, perfluoroalkyl group, ω hydroperfluoroalkyl group,
2) ~0 groups, etc.

Preferred are a cyano group, a fluorinated alkyl group, and an alkylsulfo group. When a dye having a small electron-withdrawing group substituted with σp of 05j is formed, the dye has the disadvantage that the maximum absorption of the dye is at a short wavelength.

x i, L represents an atomic group necessary to form a substituted or unsubstituted aromatic ring, and preferably forms a substituted J or unsubstituted benzene ring or aromatic heterocycle. X
The group to be substituted on the covering aromatic ring can be selected depending on the purpose, such as an alkyl group, an aryl group, a tro group, a halogen atom, an aryloxy group, etc., depending on physical properties such as absorption wavelength and solubility. You can choose.

Z represents hydrogen or a coupling predetermined U, preferably a coupling-off group. Preferred examples of the coupling group I2 include halogen atoms (eg, chlorine, bromine, iodine), sulfo groups, alkoxy groups, aryloxy groups, thiocyanyloxy groups, arylthio groups, nitrogen-containing heterocyclic residues, and the like.

Specific examples of the infrared coupler of general formula (1) are listed below, but the compounds used in the present invention are not limited thereto.

Below #100!・Σ IR-, 5 IR-10 Copolymer of IR-17 and butyl acrylate (11L composition ratio: 5:5 by weight) and BA copolymer (composition ratio: 6: IR by weight ratio) IR-14 IR-16 Next, a typical synthesis example of the infrared coupler of general formula (1) will be described.

Synthesis Example 1 (Synthesis of IR-6) 2-hydroxy-1,3-indanedione 5.67CI
, 800 g of 11-dodecyl bromide and 435 Q of potassium carbonate were dissolved in 70 iΩ of dry acetic acid, and 2
+R distance flowed. After cooling, the reaction solution was poured into 350 g of diluted hydrochloric acid water, and the precipitated crystals were filtered and dried to obtain 972 g of 2-dodecatoxy-1,3-indandione.

972 g of the 2-dodecatoxy 1,3-indanedione
What, malononitrile 693! ll, ethanol 50d
After stirring at room temperature for 15 minutes, sodium acetate (
trihydrate) 7.14 g were added.

The mixture was refluxed for 5 hours, and after cooling, the reaction solution was filtered to remove the monomer.The filtrate was diluted with 120 ml of water, and 1-2 times of 1)H was added with hydrochloric acid.

The precipitated crystals were washed with water and dried to give white crystals 9,99
I got 0.

The main reaction route is as shown in 2 below.

Synthesis Example 2 (Synthesis of IR-14) 29.22 g of 1,3-indanedione and 32.11 g of N-chlorosuccinimide were added to 200 g of chloro-1form.
112, stirred at room temperature for 30 minutes, and then left to stand for 2 days. 12.48 (l) of 2-chloro1-1,3-indandione was obtained by distilling off the chloro]form and fractionating it by column chromatography.

12.48 g of said 2-chloro-1,3-indanedione, Ju 13.35 (l
was suspended in 150 μm of acetone and centrifuged for 21 hours.

After distilling off the acetone, extract with ethyl acetate and wash with water.]
J Lamb Chroma] to 2-(p-nitrophenoxy)-1,3-indandione was purified by 6.050
(It's 1.

This was dissolved in ethanol 10 (he) and palladium PA
2-(+1- aminophenoxy)1
．． 3-Indansion is 5229 blue.

This solution was dissolved in 50 mg of acetate, 200 g of pyridine was added, and 2-. 12. /l-ditertiary-amylphenoxy)butanoylc[''ride 768g
was dripped.

After stirring for 1 hour, aretonitrile was distilled off under reduced pressure, and the mixture was extracted with ethyl acetate and washed with water. After distilling ethyl acetate under reduced pressure, it was purified by column chromatography to obtain 2-(1-(1-
(2,4-di-tert-amylph-1noxy)butanamide)pheno4nidiL-1,3indanedione 6,yg
I got it.

The above compound 5.6 (], Mamarouni 1 to Ril 2.0]
was dissolved in ethanol 30112, stirred at room temperature for 15 minutes, and then 21 g of sodium acetate (trihydrate) was added.

After stirring the mixture for 30 minutes, the reaction? The 8 solution was poured into diluted hydrochloric acid water, and the precipitated crystals were washed with water and filtered with oil to obtain 2-(4-(1-(2,5-di[-amylphenoxy)propionylamino)phenoxy)-5-acedel, which is compound lR14. −
1,3- and dicyanodivinyl indane, 1.95o
It's 11.

Main reaction route 11 below (7) & +3 S1 ° 1
C41H41N503 Calculated intermolecular value 5557 Measured molecular role value 555 The thermal image color photosensitive material of the present invention has the general formula (1
) The amount of infrared coupler added differs depending on the characteristics of the infrared coupler used and the characteristics of the photosensitive material, but the appropriate amount of R is determined by the infrared dye concentration of the obtained image due to light of 800 nm. The amount added is such that it becomes 03 or more, more preferably 05 or more in inverse 11) J m degrees when measured.

Specifically, the amount of infrared coupler used in general formula (1) is:
Preferably 0005 to 50 g per 1 v' of photosensitive material
, more preferably o, io-.10 (I).Furthermore, only one type of infrared coupler of the general formula (1) may be used, or two or more types may be used in combination.

The infrared coupler of general formula (1) is generally preferably added to a layer containing photosensitive silver halide, or a layer adjacent thereto, and is preferably added to a cyan coloring layer or a cyan dye-providing substance. added in the same layer. Although the addition method is arbitrary, it can be added alone or together with a dye-providing substance, for example, by the same method as for the dye-providing substance described below.

Next, the dye-providing substance contained in the heat-developable color photosensitive material of the present invention will be explained. In the present invention, one or more types of dye-providing substances are contained, and at least one of them is 4
It is a compound that forms a dye having an absorption maximum between 00 nm and 700 nm. It acts as a color coupler and 1
It's a good thing.

Various dye-donating substances can be used in the same layer as the layer containing the infrared coupler of general formula (1) and/or in a separate layer. For example, JP-A-6
Couplers that form non-diffusible dyes such as those described in US Pat. US Patent 4,23
Azo dyes used in the heat-developable dye bleaching method described in No. 5,957 and the like can also be used as the dye-providing substance.

More preferably, a diffusible dye-donor substance that forms or releases a diffusible dye is used together with the infrared coupler of general formula (1). It is preferable to use a compound that forms

Hereinafter, in the present invention, a diffusive dye-providing substance that can be used together with the infrared coupler of general formula (1) will be described. The diffusible dye-donor substance may be one that is capable of forming or releasing a diffusible dye as a function of the reduction reaction of the photosensitive silver halide and/or the organic silver salt used if necessary. Depending on their reaction form, they can be classified into negative-type dye-donating substances and positive-type dye-donating substances.

As the negative dye-donating substance, for example, Fr 4
, No. 463,079, No. 4,439,513, JP-A No. 59-60434, No. 59-65839, No. 59-
No. 71046, No. 59-87450, No. 59-887
No. 30, No. 59-123837, No. 59-12432
No. 9, No. 59-165054, No. 59-164055
Examples include reducible dye-releasing compounds described in specifications such as No.

Other negative dye-providing substances include, for example, U.S. Pat.
．． No. 474.867, JP-A-59-12431, JP-A No. 59-12431, No. 5
No. 9-48765, No. 59-174834, No. 59-
No. 776642, No. 59-159159, No. 59-2
Examples include coupling dye-forming compounds described in specifications such as No. 31040.

As yet another negative-tone dye-providing substance of the coupled dye-forming compound, there is one represented by the following general formula (a).

General formula (a) Cp-fJ+-+B) In the formula, Cp represents an organic group (coupler residue) that can react (coupling reaction) with the oxidized form of the reducing agent to form a diffusible dye, J represents a divalent bonding group bonded to an active position that reacts with the oxidized form of the reducing agent, and B represents a ballast group. Here, the ballast group is a group that substantially prevents the dye-providing substance from diffusing during heat development processing, and its effect is determined by the properties of the molecule.
The Kabra residue represented by cp, which is a group that exhibits its effect depending on its size (such as a group with a large number of carbon atoms), has a molecular weight of 700 to improve the diffusivity of the dye formed. It is preferably 500 or less, more preferably 500 or less.

The group represented by B preferably has 8 or more carbon atoms, more preferably 12 carbon atoms, and more preferably a group that is a polymer chain.

As the coupling dye-forming compound having a group which is a polymer chain, it is preferable to use a compound having a polymer button having a repeating unit derived from a monomer represented by the general formula (b) as the above group.

General formula (b) Cp-+J+-+YK → Z square → 1-) In the formula, 0ρ, J
is the same as defined in general formula (a), Y represents an alkylene group, arylene group or aralkylene group, y represents 0 or 1, 7 represents a divalent 41 group,
[ represents an ethylenically unsaturated group or a group corresponding to an ethylenically unsaturated group.

Specific examples of the coupling dye-forming compounds represented by general formulas (a) and (b) include JP-A-59124339, JP-A No. 59-181345, and JP-A No. 60-1989. 9,'+
Publications such as No. 0, No. 61-57943, No. 61-59336, U.S. Patent No. 4.631,251, No. 4.6
No. 50.748 and No. 4.656.124 of each Mei 11
111, etc., especially U.S. Patent No. 4.
．． Preferred are the polymeric dye-providing materials described in U.S. Pat. No. 656.124, U.S. Pat. No. 4,631,251, and U.S. Pat.

As a positive dye-donating substance, for example, JP-A-59-
No. 55430, No. 59-165054, No. 59-15
4445, No. 59-766954, No. 59-1
No. 16655, No. 59-424327, No. 59-1
Examples include compounds described in publications such as No. 52440.

These dye-providing substances may be used alone or in combination of two or more kinds. The amount used is not limited, and depends on the type of dye-providing substance, whether it is used alone or in combination of two or more, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer, a multilayer of two or more types, or a shade. It may be determined accordingly, but for example, the product used is 0.005 to 5 Q g per 112, preferably 0.1 Q to 1'O! ] Can be used.

The method of incorporating the dye-providing substance used in the present invention into the photographic constituent layer of a heat-developable photosensitive material is cumbersome, such as using a low boiling point solvent (methanol, ethanol, ethyl acetate, etc.)
Or, after dissolving in a high boiling point solution (dibutyl phthalate, dioctyl phthalate-1~, tricresyl phosphate, etc.), it is emulsified and dispersed, or it is dissolved in an alkaline aqueous solution (e.g., 10% aqueous solution of sodium hydroxide, etc.). After that, it can be used after being neutralized with an acid (e.g., citric acid or nitric acid), or after being solidly dispersed in an aqueous solution of an appropriate polymer (e.g., gelatin, polyvinyl butyral, polyvinylpyrrolidone, etc.). can.

Next, the photosensitive silver halide used in the present invention will be described. Any silver halide can be used, and examples thereof include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, and silver iodobromide. The photosensitive silver halide can be prepared by any method commonly used in the photographic art.

Further, it is possible to use an emulsion containing grains having a multilayer structure in which the halogen composition of the grains is different on the surface and inside. For example, a silver halide emulsion having core/shell type silver halide grains in which the halogen composition changes stepwise or continuously can be used.

In addition, the shape of photosensitive silver halide is cubic, spherical, 8
It can be used whether it has a clear crystal habit such as a hedron, dodecahedron, or tetradecahedron, or -b which does not have a crystal habit. The silver halide of this yuzu is JP-A-60=215948.
There are some listed in the issue.

Also, for example, JP-A-58-111933, JP-A No. 58-1
No. 11934, No. 58108526, Research Disclosure No. 22534, etc., it has two parallel crystal planes, and each of these crystal planes has a larger area than the other single crystal of this particle. It is also possible to use a silver halide emulsion containing tabular silver halide grains which are large grains and have an asbec of 1 to 1, and a ratio of diameter to thickness of straw grains of 5=1 or more.

In general, a silver halide emulsion containing internal latent image type silver halide grains whose surfaces have not been fogged in advance can be used in the present invention. For internal latent image type silver halide whose surface has not been fogged in advance, for example, U.S. Pat.
．． 592.250, 3.206, 313, 3.
317.322, 3,511,622, 3.4
No. 47,927, 3.7612 (No. i6, 3.70
It is described in each specification such as No. 3.584 and No. 3.736.440.

Internal latent image type silver halide grains whose surfaces are not fogged in advance are silver halide grains in which the sensitivity inside the grain is higher than the sensitivity on the surface of the silver halide grain, as described in Section 11 & above. be. Also, U.S. Patent No. 3,271,1
No. 57, No. 3.447.927 @ and No. 3.531
．． No. 291, silver halide emulsions having silver halide grains incorporating polyvalent metal ions, or silver halide emulsions containing dopants as described in U.S. Pat. A silver halide emulsion whose grain surface is weakly chemically sensitized or
-8!124 and 5O-384i25, etc., silver silver emulsion consisting of 7 grains having a laminated structure, and other publications +1jl 52-156614
Silver halide emulsions described in JP-A-55-127549 and the like can be used.

The silver halide in the above-mentioned photosensitive emulsion may be coarse grains or fine grains, but preferred grains have a diameter of about 0.05 μm to about 1.5 μm, which is more preferred. is about 0.01 μm to 0.5 μm.

In the present invention, as another method for preparing photosensitive silver halide, a photosensitive silver salt-forming component may be allowed to coexist with a covering organic silver salt, which will be described later, to form photosensitive silver halide in a part of the silver salt. can.

These photosensitive silver halides and photosensitive silver salt-forming components can be used in combination in various ways, and the usage range is from 1 g to 50 pieces per layer per 1112 pieces of support. is preferable, more preferably (j, 01-10g
It is.

The light-sensitive silver halide emulsion may be chemically sensitized by methods known in the photographic field.

Further, the photosensitive silver halide emulsion used can be spectral sensitized using a known spectral sensitizing dye to impart sensitivity to blue, green, red, and near-infrared light.

Typical spectral sensitizing dyes that can be used include, for example, cyanine, merocyanine, complex (that is, trinuclear or tetranuclear) cyanine, polobora-cyanine,
Examples include styryl, hemicyanine, oxonol, and the like.

The preferred addition can of these sensitizing dyes is lX10 per mole of photosensitive silver halide or cognate silver halide forming component.
-4 mol to 1 mol. More preferably, lXl0-
4 to 1×10 −1 mol.

The sensitizing dye may be added at any stage of the preparation of the silver halide emulsion. That is, it may be carried out at any time, such as when silver halide grains are formed, when soluble salts are removed, before the start of chemical sensitization, during chemical sensitization, or after the end of chemical sensitization.

In the heat-developable photosensitive material of the present invention, it is preferable to use various organic silver salts, if necessary, for the purpose of increasing sensitivity and improving developability.

Examples of organic silver salts that can be used in the heat-developable photosensitive material of the present invention include JP-A Nos. 53-4921 and 49"5262.
6 @, No. 52-141.222, No. 53-36224
No. 53-37626, No. 53-37610, etc., and specifications such as U.S. Patent No. 3.330.633, U.S. Patent No. 3,794,496, U.S. Patent No. 4105, and U.S. Patent No. 451, etc. Silver salts of carboxylic acids having a long-inclined aliphatic carboxylic acid ring, such as silver behenate, α(1-phenyltetrazoldiΔ) silver resistance, etc., as described in Special Publication No. 44-26582, No. 45
-12700, 45-18416, 15-2
No. 2185, JP-A-52-137321, JP-A No. 58-1
There are silver salts of imino groups described in the following publications: No. 18638, No. 58-118639, and U.S. Patent No. 4,123,274.

Among the above organic silver salts, imino group silver salts are preferred;
Particularly preferred are benzotriazole-derived silver salts, more preferably 5-methylbenzotriazole and its derivatives, sulfobenzo-1-lyazole and its derivatives, and N-alkylsulfamoylbenzo-I-lyazole and its derivatives.

The organic silver salts used in the present invention may be used alone or in combination of two or more. Alternatively, the silver salt may be prepared in a suitable binder and used as is without isolation.
The isolated product may be used after being dispersed in a binder by an appropriate means. Dispersion methods include, but are not limited to, ball mills, sand mills, colloid mills, vibration mills, and the like.

The amount of organic silver salt used is usually preferably 0.01 to 500 mol, more preferably 0.1-.100 mol per 1 mol of photosensitive silver halide. Roughly preferably 0
It is 3 to 30 moles.

As the reducing agent used in the heat-developable color photosensitive material of the present invention (herein included in the reducing agent brecasa and the like), those commonly used in the field of heat-developable color photosensitive materials may be used. I can do it.

Reducing agents that can be used in the present invention include, for example, U.S. Pat.
No. 0, No. 3.764.328, and RD (
Resurge Disclosure) No. 1214 (i
, No. 015108, No. 15127, No. 6-27132, U.S. Pat. No. ε'F No. 3
．． 342.59'1, 3.7H1,492 specifications, JP-A-53-135628, JP-A-57-7903
p-phenylenediamine-based and p-aminophenol-based developing agents described in various publications such as No. 5, )A Sfluoroamide! Phenol type, sulfonamide aniline type developing agents, hydrazone type color developing agents and their precursors,
Alternatively, phenols, sulfonamide phenols, polyhydroxybenzenes, naphthols, hydroxybinaphdyls, methylene bisonols, methylene bisonols, ascorbic acid, 3-pyrazolidones, and pyrazolones are used. be able to.

Further, the dye-donating substance may also serve as a reducing agent.

As a particularly preferable reducing agent, JP-A-56-146133
N-(p
-N.

N-dialkyl) phenylsulfamine 11 is mentioned.

Two or more reducing agents may be used simultaneously.

The reducing agent used in the heat-developable color photosensitive material of the present invention depends on the type of photosensitive silver halide used, the type of organic silver salt, and the type of other additives, and is not necessarily constant. However, it is usually preferably in the range of 0.01 to 1500 mol per 1 mol of photosensitive silver halide,
More preferably, it is 01 to 200 moles.

An appropriate binder can be used in the heat-developable photosensitive material of the present invention. Binders that can be used include polyvinyl butyral, polyvinyl acetate, ethylcellulose, polymethyl methacrylate, hirulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, gelatin derivatives such as phthalated gelatin, cellulose acetate, protein, starch, There are synthetic or natural polymer substances such as gum arabic,
These can be used alone or in combination of two or more. In particular, it is preferable to use gelatin or its In in combination with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably
Gelatin described in 1150-22'+556 publication,
It is to use a mixed binder with polyvinyl and lolidon.

Preferred use of binder? is usually O, osg to 50 (I) per v' of support, more preferably 02
It is 0-20CJ.

In addition, the binder is 01 to 1 g per 1 g of the dye-providing substance.
It is preferable to use 109, and J: more preferably 02 to
It is 5g.

The heat-developable color photosensitive material 11 of the present invention can be obtained by forming a photographic constituent layer on a support, and examples of supports that can be used here include polyethylene film, cellulose acetate-1-film, A paper support such as polyethylene terephthalate film, synthetic plus deck film such as polyvinyl chloride, photographic base paper, printing paper, baryta paper and Resinoco-1 paper, and an electron beam curable resin composition on these supports. Examples include q-cloth, hardened paper towels, etc.

In the heat-developable color photosensitive material of the present invention, and when the photosensitive material is of a transfer type and uses an image-receiving part, it is preferable that various heat solvents are added to the heat-developable color photo-sensitive material and/or the image-receiving member. The thermal solvent is a compound that is liquid during thermal imaging and promotes thermal development and/or thermal transfer. These compounds are described, for example, in U.S. Patent No. 3.347.67.
No. 5, cylinder No. 3.667959, (RD Research Disclosure) No. 17643 (X II)
, JP-A No. 59-229556, JP-A No. 59-68730, JP-A No. 59-84236, JP-A No. 60-191251, Go-232547, JP-A No. 60-14241, JP-A No. 61
-52643, 62-78554 father-in-law, 62-42
No. 153, No. 62-4213, etc., U.S. Patent No. 3
．． 438.776, 3.666, 477, 3.
667, 959 specifications, JP 51-19525, JP 53-24829, JP 53-60223, JP 5
Examples include organic compounds having polarity such as those described in No. 8-118640 and No. 53-19825,
Particularly useful in carrying out the present invention include, for example, urea derivatives such as dimethyl 1 crea, diethyl urea, phenyl urea@), amide Km forms (e.g. acetamide, benzamide, p-toluamide, etc.), sulfonamides, etc. derivatives (e.g. benzenesulfonamide, α-
toluenesulfonamide, etc.), polyhydric alcohols (e.g., 1,6-hexanediol, 1,2-cyclohexanediol, pentaerythritol, etc.), or polyJ
Examples include tyrene glycols.

Among the above thermal solvents, water-insoluble solid thermal solvents are particularly preferably used.

Specific examples of the above-mentioned water-soluble heat solvent include, for example, JP-A-62
-136645, 62-139549, 63-
53548 Specification Publication, Japanese Patent Application No. 63-39950, No. 6
There is one described in No. 3-54113.

Layers to which a heat solvent is added include a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, an image receiving layer of the image receiving area H, etc., and the heat solvent is added and used to obtain an effect depending on each layer. .

The preferred addition amount of the heat solvent is usually 10% to 500% by weight of the binder, more preferably 1% to 2% by weight of the binder.
+ (1% by weight.

The organic silver salt and the thermal solvent may be dispersed in the same dispersion. The same binder, dispersion medium, and dispersion device as those used for producing each dispersion can be used.

In addition to the above-mentioned components, the photothermographic material of the present invention may contain various additives, such as a development accelerator, an antifoggant, a base breaker, etc., if necessary.

Examples of development accelerators include compounds described in JP-A-59-177550, JP-A-59-111 [136], and JP-A-50-124333; It is also possible to use the image accelerator-releasing compounds described above, or metal ions having an electronegativity of 4 or more as described in 'Ft Application No. 104645/1983.

Examples of antifoggants include those described in US Pat. No. 3,645.
Higher fatty acids described in specification No. 739, Japanese Patent Publication No. 4
Second mercury salt described in Publication No. 7-11113, JP-A-51
N-halogen compound described in -47419 September Publication, U.S. Pat.
Mercapto compound releasing compounds described in Japanese Patent No. 50725, arylsulfonic acids described in Japanese Patent No. 49-125016, lithium carboxylic acid salts described in Japanese Patent No. 51-47419, British Patent No. 1,455,271
, the oxidizing agent described in JP-A No. 50-101019, the sulfinic acids or thiosulfonic acids described in JP-A No. 53-19825, the 2-
Thiouracils, simple sulfur described in No. 51-26019, No. 51-42529, No. 51-81124,
Disulfide and polysulfide compounds described in JP 55-93149, rosins or diterpenes described in JP 51-57435, polymer acids having free carboxyl groups or sulfonic acid groups described in JP JP 51-104338, U.S. Patent No. 4.138,265
Buazolinthione described in the specification of JP-A-54-51
1.2.4-1 to lyazole or 5-mercapto-1,2,4-triazole described in Publication No. 821 and US Pat. No. 4,137,079, JP-A-55-14
Thiosulfinate esters described in No. 0883, No. 5
1.2゜3.4-deatriazoles described in 5-142331 @ Publication No. 59-46641, No. 59-57
233, the dihalogen compounds or trihalogen compounds described in JP 59-57234, and JP 59-57234.
Thiol compound described in Publication No. 111636, 60-
198! Hydroquinone derivatives described in +40Q publication,
Examples include a combination of a hydroquinone derivative and a benzotriazole derivative described in JP 60-227255.

Still another particularly preferred antifoggant is disclosed in JP-A No. 6
The inhibitor having a hydrophilic group described in JP-A No. 2-78554, the polymer inhibitor described in JP-A-62-121452@, the inhibitor having a ballast group described in JP-A-62-123456 Can be mentioned.

Furthermore, colorless couplers described in Japanese Patent Application No. 62-320599 are also preferably used.

Examples of base breaker include compounds that release basic substances by decarboxylation upon heating (e.g., guanidinium trichloroazethi 1~), and compounds that decompose and release amines through reactions such as intramolecular nucleus substitution reactions. For example, Japanese Patent Application Publication No. 56-130745, Japanese Patent Application Publication No. 56-132332, British Patent No. 2.079.480, U.S. Patent No. 4,
060,420 specification, JP-A-59-157637, JP-A-59-166-43, JP-A-59i80537, JP-A-59-174830, JP-A-59-195237, JP-A-6
Examples include base releasing agents described in JP2-108249, JP62-174745, and the like.

Other -b Various additives used in heat-developable color photosensitive materials as necessary, such as antihalation dyes, optical brighteners, hardeners, antistatic agents, plasticizers, spreading agents, matting agents, and surfactants. Containing agents, anti-fading agents, etc., are specifically described in RD (Releach Disclosure) magazine V01.170. June 1978 NO, No. 17029, and JP-A-62-135825. It is described in etc.

These various additives can be added not only to the photosensitive layer but also to non-photosensitive layers such as an intermediate layer, a protective layer or a backing layer.

The heat-developable color photosensitive material of the present invention comprises (a) photosensitive silver halide, (b) reducing agent, (C) dye-providing substance, (d
) It contains a compound represented by the general formula (1), and (e) a binder can be used as appropriate. Furthermore, it is preferable to contain (f) organic silver as necessary. Basically, these may be contained in one heat-developable photosensitive layer, but they do not necessarily need to be contained in a single photographic constituent layer. For example, if the heat-developable photosensitive layer is divided into two layers, a)
(b >, (d), (e), <f)
Each component may be contained in one heat-developable photosensitive layer and the dye-providing substance (C) may be contained in the other layer adjacent to this photosensitive layer, as long as they are in a state where they can react with each other. It may be contained in two or more constituent layers.

Alternatively, the heat-developable photosensitive layer may be divided into two or more layers, a low-sensitivity layer and a high-sensitivity layer, a high-density layer and a low-density layer, or a number of layers may be formed.

The heat-developable color photosensitive material of the present invention has one or more heat-developable photosensitive layers. In the case of a full-color photosensitive material, it is generally provided with three heat-developable photosensitive layers having different color sensitivities, and in each photosensitive layer, dyes having different hues are formed or released by heat development.

Typically, a yellow dye is used in the blue-sensitive layer, a magenta dye is used in the green-sensitive layer, and a cyan dye is used in the red-sensitive layer, but the invention is not limited to this. It is also possible to combine a near-infrared sensitive layer.

The structure of each layer can be arbitrarily linked depending on the purpose. For example, a structure in which a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer, etc. are sequentially formed on a support, or a blue-sensitive layer is sequentially formed on a support. , a green-sensitive layer, and a red-sensitive layer, or a structure in which a green-sensitive layer, a red-sensitive layer, and a blue-sensitive layer are sequentially formed on the support.

In addition to the heat-developable photosensitive layer, the heat-developable color photosensitive material of the present invention includes an undercoat layer, an intermediate layer, a protective layer, a filter layer,
Non-photosensitive layers such as a backing layer and a peelable layer can optionally be provided. The heat-developable photosensitive layer and these non-photosensitive layers can be coated on the support using a method similar to that used for coating and preparing general silver halide photosensitive 4411. Can be applied by people.

The heat-developable color photosensitive material 1'l of the present invention is usually preferably 80°C to 200°C, more preferably 100°C after imagewise exposure.
℃ to 170℃, preferably for 1 second, 1
It can be developed by heating for 80 seconds, more preferably from 15 seconds to 120 seconds. Transfer of the diffusible dye to the image-receiving layer can be carried out simultaneously with thermal development by bringing the image-receiving member into close contact with the photosensitive surface of the photosensitive material and the image-receiving layer during thermal imaging, or by bringing the image-receiving member into close contact with the image-receiving member after thermal development. ,Also,
Transfer may be performed by supplying water and then applying heat if necessary. Also, before exposure, 70℃~
Preheating may be performed in a temperature range of 180°C. Also, JP-A-60-143338, JP-A No. 61-162041
As stated in the publication, in order to improve their mutual adhesion, the photosensitive material and image receiving member were heated to 80°C immediately before thermal development transfer.
Each may be preheated at a temperature of ~250°C.

Various heating means can be used for the heat-developable color photosensitive material of the present invention.

As the heating means, all methods applicable to ordinary photothermographic materials can be used. For example, contacting with a heated block or plate 1~, contacting with a heated roller or hot drum 18, or heating with a high) gate. By passing it through an atmosphere, or by using high-frequency heating, and furthermore, by providing a conductive layer containing a conductive phase substance such as carbon black on the back surface of the photosensitive material of the present invention or the back surface of the image receiving part H for thermal transfer. Joule heat generated by energization can also be used. There are no particular restrictions on the heating pattern, and it is possible to continuously maintain the temperature, such as by preheating and then reheating, or by heating at a high temperature for a short time or at a low temperature for about 1F. It is also possible to heat the heating layer (increasing the heating temperature, continuously) or repeating these steps, and discontinuous heating is also possible, but a simple pattern is preferable. Alternatively, a method in which exposure and heating proceed simultaneously may be used.

When the present invention is used as a transfer type heat-developable color photosensitive material,
An image receiving member is used as described above. In this case, the image-receiving layer that can be effectively used in the image-receiving member may be one that has the function of receiving the dye in the heat-developable photosensitive layer released or formed by heat development, such as tertiary amine or quaternary amine. Polymers Containing Ammonium Salts, U.S. Patent No. 3.709
．． Those described in No. 690 Mei 4I R1 are preferably used. A typical image-receiving layer for diffusion transfer is:
There are those obtained by mixing a polymer containing ammonium salt, tertiary amine, etc. with gelatin, polyvinyl alcohol, etc., and coating the mixture on a support. Another useful dye-receiving material is one made of a heat-resistant organic polymer material having a glass transition temperature of 40° C. or more and 250° C. or less, as described in Jikai wI57-207250 and the like.

These polymers may be supported on a support as an image-receiving layer, or may themselves be used as a support.

Regarding polymers, "Polymer Handbook, Second Edition" (edited by Joy Brandrup, E.H. Inmargala 1~) John Willian and Sands Publishing (Polymcr) l'and-book
2nd ed, (J, Brandrup, E
, l-1゜l mmergut ed.) John Wi
Also useful are synthetic polymers with glass transition temperatures of 40° C. or higher, such as those described by John Ley & 5ons). - For boat fishing, the molecular weight of the polymer substance is 2000 to 20.
0000 is useful. These polymeric substances may be used alone or in a blend of 2 seconds or more, or two or more of them may be used in combination as a copolymer.

A particularly preferable image-receiving layer is JP-A-59-22342
Examples include a layer made of polyvinyl chloride as described in Japanese Patent No. 5 and a layer made of polycarbonate and a plasticizer as described in JP-A-60-19138.

These polymers can also be used as a support and image-receiving layer (image-receiving member), in which case the support may be formed from a single layer or from multiple layers. good.

As the support for use in the image receiving section, any support such as a transparent support or an opaque support may be used, but for example, films of polyethylene terephthalate 1 to polycarbonate, polystyrene, polyvinyl chloride, polyethylene, polypropylene, etc. titanium oxide, barium sulfate,
A support containing pigments such as calcium carbonate and talc,
Baryta paper, resin-coated paper laminated with thermoplastic resin containing pigment on paper, cloth, glass, bottoms of aluminum ram, etc., and electron beam curable paper containing pigment on these supports. a support coated with a resin composition and cured;
and a support on which a coating layer containing a #ji diagonal is provided.
Various coated sets, such as the 4 Yast Coat paper described in No. 333, are also useful as supports.

In addition, there is a support on which an electron beam curable resin composition containing a pigment is coated and cured. Since the resin layer of the support coated with the composition and cured can be used as an image-receiving layer, it can be used as is as an image-receiving member.

The heat development color photosensitive monthly yield of the present invention is published in RD (Research Disclosure Magazine) No. 15108, JP-A-57-1
No. 98458, No. 57-207250, No. 61-80
It may be a so-called mono-sea mill type heat-developable photosensitive film in which a photosensitive layer and an image-receiving layer are formed on the same support, as described in Japanese Patent No. 148.

The heat-developable color photosensitive material of the present invention is preferably provided with a protective layer.

Various additives used in the photographic field can be used in the protective layer. Examples of such additives include various matting agents,
Colloidal silica, slipping agents, organic full delta compounds (especially fluorosurfactants), antistatic agents, ultraviolet absorbers, high-boiling organic solvents, antioxidants, hydroquinone derivatives, polymer latex, surfactants (high (including molecular surfactants), hardeners (including polymeric hardeners), 1M silver salt particles, non-photosensitive silver halide particles, antifoggants, image accelerators, and the like.

Regarding these additives, please refer to RD (S1 Norch Disclosure Magazine) VOl, 170. June 1978 N
O, 17029, JP-A No. 62-135825.

EXAMPLES] Specific examples of the present invention will be described below. However, as a matter of course, the present invention is not limited to the examples described below.

Example 1 In this example, a silver iodobromide emulsion, a dispersion of a thermal solvent such as a silver salt, a dispersion of dye 01 knob substance, and a dispersion of a reducing agent were prepared as follows, and these were used. A heat-developable color photosensitive material was prepared. Also, in ``2'' below, I created the image receiving part.

■ Preparation of silver iodobromide emulsion 50 'C NiJ3 IT, JP-A-57-92523H1
20 g of ossein gelatin, 1000 d of distilled water, and ammour were dissolved using the mixer shown in the specification of No. 57-92524.
At the same time, 500 g of solution (B), which is an aqueous solution containing g and 111 g of potassium bromide, and 500 g of solution (C), which is an aqueous solution containing 1 mol of silver nitrate and ammonia, were
1) A(I) was added while keeping it constant.

The shape and size of the emulsion grains to be prepared were adjusted by controlling pHlpAg and the addition rate of solutions (B) and (C). In this way, with a silver iodide content of 7 mol%,
A core emulsion containing grains having a face shape and an average grain size of 025 μm was prepared.

Next, by coating a shell of silver halide containing 1 mol % of silver iodide in the same manner as in the above 2 method, a regular octahedral, average grain (403 μm) 7' octahedral type silver halide emulsion was obtained. (Monodispersity was 9%).The 7L agent thus prepared was washed with water and subjected to 112 salt.

■ Preparation of photosensitive silver halide dispersion IN J: The following components were added to the silver iodobromide emulsion 700μ12 prepared in the above manner, and chemical sensitization and spectral sensitivity were applied to red sensitivity, green sensitivity, Blue-sensitive photosensitive silver halide emulsion dispersions were prepared.

(a) Preparation of red-sensitive silver iodobromide emulsion The above-mentioned silver iodobromide emulsion 70〇-4-hydroV-6-methyl-13,3a,7-tetra1findene 0.4 (1
Gelatin 32Ω Zutrium thiosulfate 10 Ing 1% by weight of the following sensitizing dye (a) Methanol solution 80d Distilled water
1200d g-enhancing dye (a
') (b) Green-sensitive silver iodobromide emulsion manufactured by W The above-mentioned silver iodobromide emulsion 4-hydroxy-6-methyl-1°3.3a, 7-tetrazaindengelatin mono-lium thiosulfate sensitized as follows: 11% methanol solution of dye (b) Distilled water sensitizing dye (b) 001g 0.4g 2 U 0mg 01g 12QO1fi (c) %J-sensitive silver iodobromide emulsion manufactured by wI 4-hydroxy -6-Methyl-1°3.3a, 7-chitrazaindengelatin sodium thiosulfate 1 mB% methanol solution of the following sensitizing dye (c) in distilled water sensitizing dye (C).

700 v (1 0,4 g 2 Q 10 mΩ 01 g 120 (hR) Dispersion of organic silver salt and hot solvent A dispersion of organic silver salt and hot solvent was prepared based on the following recipe.

Prescription 5-methylbenztriazole silver 605gp-1~
Rylamide 3460 Polyvinylpyrrolidone (10%) 4461112 in water
What about 2000fJ?

After dispersing in an alkanol mill, pl-1 was adjusted to 55 with a 10% aqueous citric acid solution to prepare a dispersion of an organic silver salt in a hot solvent.

■-(1) Preparation of dye-providing substance dispersion-1 The following polymeric dye-providing substance (1) 3! i 5 (1. Dissolve 50 g of the following hydroquinone compound in &l M Nibble 2001E! and add 124 v of Alkanol After mixing with 720d of gelatin aqueous solution containing .50 and dispersing with an ultrasonic homogenizer and distilling off m1II pull, pH 5,
5 and 795

Hydroquinone Compound ■-(2) Colored Water Donor Dispersion Liquid-2 Except that the dye-donating substance was changed to the following polymeric color-donating substance (2) and infrared dye-donating substance (comparative compound-1),
The same polymeric dye-donating substance as in Dye Adversary Trade Dispersion-1 - Polymer dye-donating substance! (3) CH.

CH.

Infrared dye-providing substance (comparison compound y = 40 jl amount %) Preparation of reducing agent solution 23.3 g of the following reducing agent, 14.60 g of poly(N-vinylpyrrolidone), 0.50 g of the following fluorinated surfactant
Dissolve 250112 in water, adjust the volume to 5.5, and add the reducing agent solution of 250112 to 1 V.

■-(3) Dye-providing substance dispersion-3 This 1.
This was obtained in the same manner as above, except that .

Surfactant NiO2S CHCOOCHz (CF 2 CF
2)n HCHz COOCl(-(CF-CF
-)n H (kasu, n-2* or 3) ■ Preparation of heat-developable color photosensitive material Dispersion of organic silver salt and thermal solvent prepared above, silver halide emulsion, dye-providing substance dispersion and reducing agent solution using,
Heat-developable color photosensitive material with multilayer structure as shown in Table 1 (1)
It was created.

Further, the infrared dye-providing substance (
In place of comparative compound-1), general formula (1) according to the present invention
Photosensitive materials (2) to (5) are the same as the above photosensitive material 1) except that an infrared coupler of
Create one (as shown in the table).

The absorption maximum of the infrared dye of the present invention formed by the infrared coupler of general formula (1) used in this example (measured by the fouling density in the image receiving member) is as follows.

Infrared dye formed by IR-1: Absorption maximum is 810 nm Infrared dye formed by IR-9: Absorption maximum is 816nii Infrared dye formed by 6: Infrared dye formed by 7: Absorption maximum is O2nm 10nm ';-'', , -- ■ Creation of image receiving member Polyvinyl chloride (n = 1,100, manufactured by Wako Pure Chemical Industries)
The following compounds (A) and (B) were added to a tetrahydrofuran solution of
) and melt this into polyvinyl chloride Murayama 15, OQ.
An image-receiving member was prepared by coating and drying it on photographic baryta paper so as to give a coating film of /1'.

Compound (A) Compound (B) HOCH, CH, SCH, CH, SCH, CH, OH phrase m600111(]/i+' For the above heat development color photosensitive 4,1$1l (1) and (5), step 8+IOcMs of blue light, green light, red mist light, and white light exposure were applied through the wedge, and each was combined with an image receiving member and thermally developed at 150°C for 70 seconds in a heat developing machine (Deibero Tuber Module 277.3M). The photosensitive materials (1) to (5) and the image-receiving member were quickly peeled off, and the anti-DJ density of the yellow (Y), magenta (M), and cyan (C) images on the obtained image-receiving member was And the reflection density for infrared light (850 nm) was measured using a densitometer (PDA-
65, manufactured by Konica ■). The maximum density obtained (Dmax) and the minimum density ([)min) (
Fog) is shown in Table 2.

In addition, infrared images are recognized in areas exposed to blue light and white light, but in Table 2, in the highest density area of the image (black), in the white exposed area, infrared light is observed. , H As can be seen from the results in Table 2, in the heat-developable color photosensitive material of the present invention, the density obtained with infrared light is greater than that in which the comparative compound is used in equimolar amounts.

According to this embodiment, it is possible to provide a heat-developable color photosensitive material that satisfies the basic requirements of being able to record high-quality color images, character information, signal information, etc., and to be capable of simple and quick processing. did it.

Moreover, the heat-developable color photosensitive material according to the present invention has a 750n
It is capable of recording text information, signal information, etc. that can be read with light with a wavelength longer than m at the same time as forming a color image, and moreover, it is more The use of the infrared coupler of general formula (1) has the advantage that a high density can be obtained with infrared light.

Furthermore, it was obtained as having excellent thermal stability and transferability.

[Effects of the Invention] As described above, according to the present invention, it is a heat-developable color photosensitive material that makes it easy to read information recorded with light with a wavelength longer than 750 r+m, and has low fog and high color development. It is possible to use heat-developable color photosensitive materials with certain advantages.

Claims (1)

[Scope of Claims] A heat-developable color photosensitive material having at least a photosensitive silver halide, a reducing agent, and a dye-providing substance on a support, wherein at least one of the dye-providing substances has a wavelength of 400 nm to 700 nm.
A compound that forms a dye that has an absorption maximum at m, and further contains a compound that forms a dye that has an absorption maximum at a wavelength longer than 725 nm and is represented by the following general formula (1). Heat-developable color photosensitive material. General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 represent an electron-withdrawing group with σp≧0.50, and (Z represents a hydrogen atom or a coupling-off group.)