JPH02289853A - Image forming method and heat-developable color photosensitive material to be used for the same - Google Patents

Abstract

PURPOSE:To enhance diffusivity and stability against heat and light by using a heat- developable color photosensitive material containing photosensitive silver halide, a reducing agent, a binder, and a dyestuff donor having a specified dye stuff moiety. CONSTITUTION:The heat-developable color photosensitive material formed on a sub strate comprises the photosensitive silver halide, the reducing agent, the binder, and the dyestuff-donor having the dyestuff-moiety represented by formula I or II in which X is an atomic group necessary to form an N-containing aromatic hetero ring; R1 is halogen or a monovalent organic group; m is 0 or an integer of 1 - 3; Y is OH or the like; and each of R2 - R5 is H, halogen, or the like. After imagewise exposure or at the time of it, the photosensitive material is brought into close contact with an image-receiving material and heat developed. The diffusive dyestuff having the dyestuff moiety formed from the dyestuff donor as the function of development is transferred to the image-receiving material, and a dyestuff image chelated with a metal is formed in the image-receiving material at the time of transfer or after it, thus permitting an infrared dyestuff image superior in heat and light stability to be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for forming an image by thermal development, and more particularly, to a method for forming an infrared dye image that can be read by infrared light, and a method for forming an image using heat development. It relates to developing color photosensitive materials.

(Prior Art) In recent years, in various information recording materials such as IO cards, the 17i! is being issued. This recording material, on which character information or signal information is recorded, uses a 7500-meter sensor such as a semiconductor laser or light emitting diode to speed up the judgment of information and prevent misidentification.
(2) It is often read optically using longer wavelength light (hereinafter referred to as infrared light).

(Problems to be Solved by the Invention) However, among color image dyes obtained from known heat-developable color photosensitive materials, even cyan dyes having maximum absorption in the longest wavelength range hardly absorb light with wavelengths longer than 7500 liters. However, it has been difficult to record information that can be read with infrared light using heat-developable color photosensitive materials that form clear color images using only dyes.

In order to improve this problem, the present inventors have already proposed a heat-developable color photosensitive material containing a dye-donating substance that forms or releases an infrared dye (Japanese Patent Application No. 1184-1983).
No. 76), however, such heat-developable color photosensitive materials require further improvement in terms of the absorption wavelength, diffusivity, and stability against heat and light of the infrared dyes formed.

An object of the present invention is to improve the problems of the prior art.

That is, the object of the present invention is to provide a method for forming an infrared dye image that has excellent stability against heat and light and has an absorption wavelength that can be read even with longer wavelength infrared light, and a heat-developable color photosensitive material used in the method. It is about providing.

(Means for Solving the Problems) As a result of intensive research, the inventors of the present invention have found that the above-mentioned object of the present invention is to provide a heat-resistant silver halide solution containing at least a photosensitive silver halide, a reducing agent, a binder and a dye-donating substance on a support. A heat-developable color photosensitive material in which the dye-providing substance has at least one of a dye moiety represented by the following general formula (1) and a dye moiety represented by the following general formula (2) is image-formed. After exposure or simultaneously with imagewise exposure, heat development is performed in close contact with the image-receiving material, and all or part of the diffusible dye containing the dye portion formed as a function of development from the dye-providing substance is transferred to the image-receiving material. Along with transferring, during or after transfer,
-11 or all of the dye is chelated with a metal, and the metal chelated dye i' is contained in the image-receiving material. It has been found that this can be achieved by providing an image forming method characterized by forming an i-image.

Y General formula (2) In the formula, X represents a collection of atoms necessary to form an aromatic nitrogen-containing heterocycle. R1 represents a halogen atom or a monovalent organic group, the garden represents 0 or an integer of 1 to 3, and 1 is 2
Or in the case of 3, two or more R1s may be the same or different from each other.

R6/Y represents a hydroxyl group or a -N group (Rs and R7 each represent a hydrogen atom or an optionally substituted alkyl group), R2, Ra.R4 and R5 each represent a hydrogen atom, a halogen atom or a Represents a valent group.

The present invention will be explained in more detail below.

In the present invention, the dye represented by the above general formula (1) or <<2>> is usually a cyan dye, but when it forms a metal chelate forceps with a transition metal ion, the absorption wavelength range shifts to longer wavelengths by 100 ns or more and becomes infrared. Becomes a pigment. Therefore, in general,
A heat-developable color photosensitive material containing a dye-donating substance having a dye moiety represented by formula (1) or (2) (hereinafter referred to as the compound of the present invention) forms an infrared dye image and/or a cyan dye image. can do.

In addition, the dye portion may form a chelate with metal ions in advance (blechelate), but from the viewpoint of dye diffusivity, it is necessary to It is preferable to form a chelate (post-chelate 1.) on the uppermost layer of the photosensitive material, etc.

In each of the general formulas (1) and (2), X represents a group of atoms necessary to form an aromatic nitrogen-containing heterocycle, preferably a group of atoms forming a condensed pyridine ring.

In each of the above general formulas (1) and (2), R1 represents a hydrogen atom, a halogen atom, or a monovalent organic group,
The halogen atom is preferably a chlorine atom or a fluorine atom. In addition, monovalent organic groups include alkyl groups that may have substituents (for example, methyl groups, ethyl groups, etc.),
! Alkoxy group which may have a group (e.g. methoxy group, ethoxy group, etc.), -CONRs R7, -NH
CORa. -NHCO2 Re. -NHSO2R
a. -NHS02 NR6 R7. COORa,
-SO2 Ra. -NHCORs R? Or a cyano group is preferred. Here, R6 and R7 are each a hydrogen atom,
It represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and R8 represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, a heterocyclic group, or an amino group, and each group has a substituent. You may do so. Above R+. R6. As the substituent in the group which may have a substituent represented by each of Ry and R8,
For example, substituents that can be converted into alkyl groups, alkyl groups, aryl groups, and heterocyclic groups include, for example, halogen atoms (fluorine atoms, chlorine atoms, etc.), alkyl groups, aryl groups, heterocyclic groups, and nitro groups. , cyan group, alkoxy group, aryloxy group, alkylthio group, arylthio group, keto group, sulfonamide group, sulfamoyl group, acylamino group, carpamoyl group, sulfonyl group, sulfinyl group, hydroxy group, carboxy group, amino group, or - , a secondary amine group, and the like.

Further, when R1 represents a halogen atom or a monovalent organic group,
In the case of general formula (1), at least one R1 is c
- It is at the ortho position of the 0 group, and in the case of general formula (2),
Preferably, it is in the rose position of the C-O group.

R2. R3, R+ and R5 each represent a hydrogen atom, a halogen atom, or a monovalent I1 group, and the halogen atom is preferably a chlorine atom or a fluorine atom. Further, examples of the monovalent organic group include those defined for R1 above.

In particular, the alkyl group represented by each of R6 and R7 preferably has 1 to 4 carbon atoms (alkyl M of II (e.g., methyl group, ethyl group, n-propyl group, n-butyl group, etc.); Examples of substituents include alkoxy groups (for example, methoxy groups, ethoxy groups, etc.), alkylsulfamide!!! (for example, methanesulfamide, etc.), sulfo groups,
Carboxy group, sulfur? Preferred examples include moyl group and carbamoyl group.

In the present invention, the dye portion represented by general formula (1) or (2) preferably forms a metal chelate dye in the image receiving layer or in the vicinity of the receiver IIIFJl, but it is preferable that the dye portion represented by the general formula (1) or (2) forms a metal chelate dye in the image receiving layer or in the vicinity of the receiver IIIFJl. Compounds with functions〈
The metal source) may be an organic or inorganic salt of the metal ion (eg, carboxylate, sulfone m salt), or a complex such as chelate chemistry (5). It may also be Kim M Xankyu, which is written in Keihei Ueno's collection (Nankodo). The metal ion is a divalent transition metal (preferably divalent nickel,
Copper, zinc, cobalt, platinum and palladium) ions are preferred. The amount of the compound to be added is preferably 0.1 to 10 times the amount of the compound of the present invention added to the light-sensitive material. The addition method can be carried out in the same manner as the addition method of the compound of the present invention described below, for example, by dissolving or dispersing in a low-boiling point or high-boiling point solvent, and then dissolving or dispersing it together with the polymer that forms the image-receiving layer, and then coating. Can be added.

The compound of the present invention has a group (so-called carrier) that has the property of causing a difference in the diffusivity of a dye component having a dye portion before and after development as a number during silver development, and the carrier is R + , R2. R3. R4. The carrier bonded to at least one of R5 and Y will be described below.

There are two types of Ki V rears: one type (negative type) that corresponds to the development of silver (positive function) and makes the dye have diffusivity, and the other type that makes the dye have diffusivity (negative type) that corresponds inversely to the development of silver (a negative function). There is a type that causes it to occur (positive type).

An example of a negative type carrier is a carrier having a reducing property that releases a diffusible dye when oxidized, such as the following general formula (3).
General formula (4) General formula <5> Single-pronged formula (6) 7. U In the formula, A1 represents a collection of atoms necessary to form a benzene ring or a naphthalene ring, and A2 forms a fused benzene ring. represents the collection of atoms necessary for A.
The ring represented by 1 or A2 may have a substituent, and at least one of the substituents is a ballast group.

z1 and z2 are each water! ! group, amino group (including Im! substituted amino group) or hydroxyl group or amino W (
W-substituted amino group.

Specific examples of the above carriers are disclosed in Japanese Patent Application Laid-open Nos. 48-33826, 51-113624, and 57-179840.
No. 58-116537, No. 59-60434, No. 59-65839, No. 59-165055, No. 51-104343, No. 59-124329, etc.

When a compound having the above-mentioned V rear is used as the compound of the present invention, the dye-providing substance may also serve as a reducing agent.

Another negative type carrier is Kabler, who remains on base. The dye moiety is substituted at the active site of the coupler, and at least 1l1 of ballast groups are substituted on the coupler residue. Specific examples of this type of carrier are JP-A Nos. 57-122596, 57-186744, 59-159159, 59-174834,
No. 59-231540, each publication sls.

Still another type of negative-type clearer is a coupler in which the active site is substituted with a ballast group, and the dye moiety is substituted with a group other than the active site. A specific example of this type of carrier is described in Japanese Patent Application No. 63-257998.

A specific example of a body type carrier is disclosed in Japanese Patent Application Laid-Open No. 51-63618.
No. 53-69033, No. 54-130927,
No. 49-111628, No. 52-4819, No. 5
No. 3-35533, No. 53-110827, No. 5
No. 4,130,927, US Pat. No. 5B-164,342, and US Pat. No. 4,783,396.

Specific examples of the dye portion of the present invention are shown below.

N /\ C. H, C, H. OCH3 D-4 D-9 D-10 D-11 D-16 Furthermore, Specific examples of the compounds of the present invention are shown below.

(7》 し t′1 くしl”It (Jti (l2) /＼ C ! H * C t H 40 H / ＼ C * H s C * H , O H (1 day) Ryo L Ri N / \ C, H% c.Hs (C) Easy J1 The dye moiety of the compound of the Japanese invention can be obtained according to the method described in JP-A No. 63-227569, Japanese Patent Application No. 82-294600, etc. , an 8-hydroxyquinolinol derivative and a p-phenylenediamine derivative or a p-aminophenol derivative.

Furthermore, the functional group of the above dye moiety can be directly or acid chloride (
For example, the compound of the present invention can be obtained by converting it into a sulfonyl chloride) and then reacting it with a portion of the carrier, for example by a condensation reaction.

The compound of the present invention can also be synthesized by reacting 8-, droxyquinolinol, and a portion of the carrier, followed by oxidative coupling.

A specific synthesis method will be shown below, taking Compound (1) of the present invention as an example.

That is, compound (1) of the present invention is synthesized according to the following scheme.

(B) <<1>> Step compound (A>10g is dissolved in 1.SIl of ice, 2.6g of sodium carbonate and 2.5g of sodium hydroxide are added,
While stirring, add 200 g of an aqueous solution containing 3 g of 8-hydroxyquinoline and 1.5 g of sodium hydroxide.
62 ntr of 5% sodium hypochlorite was added dropwise at °C. The resulting precipitate was separated and purified using ram chromatography to obtain compound (B).

(2) Process compound (B) 7.79 in dimethylformamide 10
Dissolve phosphorus oxychloride 6112 in 0-15-20℃
After stirring at 40 to 45°C for 2 hours, the mixture was poured into ice water. The precipitated blue crystals were separated by filtration and air-dried to obtain Compound (C).

(3) Step Compound (c) 4.84y was added little by little to a mixture of 7.5g of compound (D), pyridine 7,5, ρ, and dimethylformamide 40112 while passing nitrogen gas. Stirred at room temperature for 1 hour. The reaction solution was poured into diluted hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was separated, dried, and concentrated, and the solid was purified by column chromatography to obtain the compound (1) of the present invention. The visible part of the compound (1) of the present invention in chloroform has a λ■aX of 625n* (ε:
18000) Te Akuta.

The above compounds of the present invention may be used alone or in combination of two or more. The amount used is not limited and is determined depending on the type of compound, whether it is used alone or in combination, and whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or a multilayer of two or more. However, for example, the usage amount is 0. (105-50g, preferably 0.
It can be used in 1Q to 10o.

The compound of the present invention may be incorporated into the photographic constituent layer of the heat-developable color light-sensitive material using any method. cresyl phosphate, etc.) and then emulsified and dispersed, or dissolved in an alkaline aqueous solution (e.g., 10% aqueous sodium hydroxide solution, etc.), and then dissolved in l(e.g.,
It can be used after being neutralized with citric acid, nitric acid, etc., or after being solidly dispersed in an aqueous solution of an appropriate polymer (eg, gelatin, polyvinylbutyral, polyvinylpyrrolidone, etc.).

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 made from W4 by any method commonly used in the photographic field.

Furthermore, it is possible to use an emulsion containing grains having a multilayer structure in which the halogen composition of the grains differs 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 one that does not. This type of silver halide is described in JP-A-60-215948. Also, for example, JP-A-58
-111933, 58-111934, 58-
No. 108526, Research Disclosure 225
As described in No. 34, etc., the particle has two parallel crystal planes, and each of these crystal planes has a larger area than other single crystals of this particle, and the aspect ratio, i.e. Silver halide emulsions containing tabular silver halide grains having a grain diameter to thickness ratio of 5=1 or more can also be used.

Furthermore, the present invention can include a silver halide emulsion containing internal latent image type silver halide grains whose surfaces have not been fogged in advance. For internal latent image type silver halide whose surface is not prefogged, for example, U.S. Pat.
, No. 592,250, No. 3,206,313, No. 3
, No. 317,322, No. 3,511,622, No. 3
, No. 447,927, No. 3,761,266, No. 447,927, No. 3,761,266, No.
It is described in each specification such as No. 3,703,584 and No. 3,736,140.

Internal latent image type silver halide grains whose surfaces have not been 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 each of the above-mentioned Sections III. be. Also, U.S. Patent No. 3,271,1
No. 57, No. 3,447,927 and No. 3,531
, 291, or silver halide emulsions having silver halide grains incorporating polyvalent metal ions, or halogenated emulsions containing dopants, as described in U.S. Pat. No. 3,761,276. Silver halide emulsion in which the surface of silver particles is weakly chemically sensitized, or JP-A-1985-1985
Silver halide emulsions comprising grains having a laminated structure described in publications such as No. 24 and No. 50-38525;
Other JP-A-52-156614 and JP-A-55-1
Silver halide emulsions such as those described in No. 27549 can be used.

The silver halide in the above-mentioned light-sensitive emulsion may be coarse grained or fine grained, but the preferred grain size is a diameter of about o. oosμ1 to about 1.5 μl, more preferably about 0.01 μl to 0.5 μl.

In the present invention, as another method for preparing photosensitive silver halide, it is also possible to allow a photosensitive silver salt-forming component to coexist with an organic silver salt described below to form photosensitive silver halide in a part of the organic silver salt. .

These photosensitive silver halides and photosensitive rM salt-forming components can be used in combination in various ways, and the amount used is 0.000 to 1f per layer. It is preferably 0.001 g to 50 g, and more preferably 0.1 to 10 g.

The light-sensitive silver halide emulsion may be chemically sensitized by any method in the photographic art.

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, holoboracyanine,
Examples include styryl, hemicyanine, oxonol, and the like.

The preferred addition m of these sensitizing dyes is 1 x 10 - per mole of photosensitive silver halide or silver halide forming component.
The amount is 6 mol to 1 mol. More preferably, 1X10-5
~IX10-' 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.

As the reducing agent used in the heat-developable color photosensitive material of the present invention (in this specification, reducing agent brecasa is also included in the term "reducing agent"), those commonly used in the field of heat-developable photosensitive materials can be used. can.

Examples of reducing agents that can be used in the present invention include those described in U.S. Pat. Nos. 3,531,286 and 3,761.
No. 270, No. 3, 764, 328, 1 [1
Book, RD (Research Disclosure') N0
．． 12146, same No. 15108, N0.
15127 and JP-A-56-27132, U.S. Pat. No. 3,342,599, U.S. Pat. No. 3,719,4
Specifications of No. 92, JP-A-53-135628, JP-A No. 57
p-phenylenediamine type and p-amine phenol type developing agents, phosphoroamide phenol type, sulfonamide aniline type developing agents, hydrazone type color developing agents and their breccasas described in various publications such as No. 79035, or Phenols, sulfonamide phenols, or polyhydroxybenzenes, naphthols, hydroxybinaphthyls and methylene bisnaphthols, methylene bisphenols, ascorbic acid,
3-Lazolidones and vilazolones can be used.

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

As a particularly preferable reducing agent, JP-A-56-146133
N-(1) described in No. 62-727141 and JP-A-62-727141
-N,N-dialkylamino) phenylsulfamate.

Two or more reducing agents may be used simultaneously.

The amount of 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, the type of other additives, etc., and is not necessarily constant. , usually preferably in the range of 0.01 to 1500 mol per 1 mol of photosensitive silver halide,
More preferably, it is 0.1 to 200 mol.

Binders that can be used in the heat-developable color photosensitive material of the present invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate,
Cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, gelatin derivatives such as phthalated gelatin, cellulose derivatives, proteins, starch, gum arabic, and other synthetic or natural polymeric substances. Alternatively, two or more can be used in combination. In particular, it is preferable to use gelatin or a derivative thereof together with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably gelatin and polyvinylpyrrolidone as described in JP-A-59-229556. Using a mixed binder.

The preferred amount of binder used is usually O. osg to 50g, more preferably 0. 2
g to 20 g.

In addition, the binder is 0.1% per 1g of the dye-providing substance.
It is preferable to use ~10g, more preferably 0.2
~5g.

The color light-sensitive material of the present invention may contain a dye-providing substance together with the compound of the present invention. Examples of such dye-donating substances include, for example, JP-A Nos. 62-44737 and 62-44737;
2-129852 and 62-169158; leuco dyes such as those described in U.S. Pat. No. 475,441; Although an azo dye used in the heat-developable dye bleaching method can be used as the dye-donating substance, it is more preferable to use a diffusible dye-donating substance that forms or releases a diffusible dye. It is preferable to use a compound that forms a more diffusible dye.

Diffusible dye-providing substances that can be used in the present invention will be explained below. 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.

Examples of negative dye-donating substances include, for example, U.S. Pat.
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 the specifications of No.

Other negative dye-providing substances include, for example, U.S. Pat.
, No. 474,867, JP-A-59-12431, No. 5
No. 9-48765, No. 59-174834, No. 59-
No. 776642, No. 59-159159, fi51
Examples thereof include coupled dye-releasing compounds described in specifications such as No. 59-231040.

Another particularly preferred negative-tone dye-providing substance of the coupled dye-forming compound is one represented by the following general formula (a).

General formula (a) C p-+ J -}-{- B ) In the formula, Cp is an organic group (coupler) that can react with the oxidized form of the reducing agent (coupling reaction) to form a diffusible dye. J represents a divalent bonding group bonded to the 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 includes groups that exhibit this effect depending on the nature of the molecule (such as a sulfo group),
Refers to groups that exhibit their effects depending on their size (such as groups with a large number of carbon atoms). The coupler residue represented by Cp preferably has a molecular weight of 700 or less, more preferably 500 or less, in order to improve the diffusibility of the dye formed.

The number of pallast groups is preferably 8 or more, more preferably 12l! A group having the above carbon atoms is preferable, and a group having a polymer chain is more preferable. The coupled dye-forming compound having a group as a polymer chain is preferably one having a polymer chain as the above-mentioned group having a repeating unit derived from a monomer represented by the general formula (2).

General formula (1) C p -f- J -}-{- Y +i-fZ7,000) In the formula, Cp and J have the same meaning as defined in general formula (a), and Y is an alkylene group. , represents an arylene group or an aralkylene group, 2 represents O or 1, 2 represents 21
i represents an organic group, and shi represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of coupling dye-forming compounds represented by general formulas (a) and (a) include JP-A-59-124339;
No. 59-181345, No. 60-2950, No. 61-57943, No. 61-59336, etc., U.S. Pat.
, No. 748, No. 4,656, and No. 124 of Mei II
There are those described in U.S. Patent Nos. 4 and 6, etc.
No. 56,124, U.S. Patent No. 4,631,251;
The polymeric dye-donating substances described in each specification of No. 4,650,748 are preferred.

As a positive type dye-donating substance, for example, JP-A-59-
No. 55430, No. 59-165054, No. 59-
No. 154445, No. 59-766954, No. 59-1
No. 16655, No. 59-124327, No. 59-15
Examples include compounds described in publications such as No. 2440.

These dye-providing substances may be used alone or in combination of two or more. The usage is not limited and depends on the type of dye-providing substance, whether it is used alone or in combination, and whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or a multilayer of two or more. However, for example, the employee should be given o.o. per 11 years old. oos to 50 (1, preferably 0.1 g to 10 g).

The dye-providing substance used in the present invention can be incorporated into the photographic constituent layer of the heat-developable light-sensitive material using any method. , tricresyl phosphate, etc.).
Either by emulsifying and dispersing it, or by dissolving it in an alkaline aqueous solution (e.g., 10% aqueous sodium hydroxide solution, etc.) and then neutralizing it with an acid (e.g., citric acid or nitric acid, etc.).
or an aqueous solution of a suitable polymer (e.g. gelatin,
It can be used after being solidly dispersed in polyvinyl butyral, polyvinyl pyrrolidone, etc.).

In the heat-developable color 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 color photosensitive material of the present invention include JP-A Nos. 53-4921 and 49-5.
No. 2626, No. 52-141222, No. 53-362
No. 24 and No. 53-37626, No. 53-37610
Publications such as No. 1 and U.S. Patent No. 3,330,633,
3,794,496, 4,105,45
Silver salts of monocyclic aliphatic carboxylic acids and silver salts of heterocyclic carboxylic acids, such as silver behenate, α-(1-phenyltetrazole), etc. thio) silver acetate, etc., Special Publication No. 44-26582,
No. 45-12700, No. 45-18416, No. 45
-22185, JP-A-52-137321, JP-A No. 58
There are silver salts of imino groups described in the following publications: No.-118638, No. 58-118639, and U.S. Pat.

Among the above-mentioned silver salts, imino group silver salts are preferred;
In particular, silver salts of penzotriazole derivatives, more preferably penzotriazole and its derivatives, 5-methylbenzotriazole and its derivatives, sulfobenzotriazole and its derivatives, N-alkyl sulfur? Moylbenzotriazole and its derivatives are preferred.

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 means 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 moles, more preferably 0.1 to 100 moles, per mole of photosensitive silver halide. More preferably 0.
It is 3 to 30 moles.

When the heat-developable color photosensitive material of the present invention is used as a transfer type image-receiving member, various heat solvents are preferably added to the heat-developable photo-sensitive material and/or the image-receiving member. Thermal solvent is liquid during heat development, and
or a compound that promotes thermal transfer. Examples of these compounds include, for example, U.S. Patent No. 3,347,675, U.S. Pat. No. 59
-84236, 60-191251, 60-
No. 232547, No. 60-14241, No. 61-52
No. 643, No. 62-78554, No. 62-42153
No. 62-44737, etc., U.S. Patent Nos. 3 and 4
No. 38,776, No. 3, 666, 477, No. 3.
667,959 specifications, JP-A No. 51-19525, JP-A No. 53-24829, JP-A No. 53-60223, JP-A No. 53-60223,
Examples include organic compounds having polarity such as those described in Japanese Patent No. 58-118640 and No. 58-198038. Particularly useful compounds in carrying out the present invention include, for example, urea derivatives (e.g., dimethylurea). , diethylurea, phenylurea, etc.), amide derivatives (e.g., acetamide, penzamide, p-toluamide, etc.),
Examples include sulfonamide derivatives (e.g. benzenesulfonamide, α-toluenesulfonamide, etc.), polyhydric alcohols (e.g. 1,6-hexanediol, 1,2-cyclohexanediol, pentaerythritol, etc.), or polyethylene 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-
Some of them are described in Japanese Patent Application No. 53548, Japanese Patent Application No. 63-205228, and Japanese Patent Application No. 63-54113.

Layers to which a thermal solvent is added include a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, an image receiving layer of an image receiving member, etc., and the effects vary depending on each layer. It is added and used so that it can be used.

The preferred addition time of the hot solvent is usually 10% to 500% by weight, more preferably 30% to 200% by weight of the binder.
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 used for producing each dispersion can be used.

The heat-developable color photosensitive material of the present invention may contain various additives, such as a development accelerator, an antifoggant, a base breaker, etc., if necessary, in addition to the above-mentioned components.

As development accelerators, compounds described in JP-A-59-177550, JP-A-59-111636, and JP-A-59-124333 are used, as well as compounds described in JP-A-61-159642 and JP-A-62-203908. The development accelerator-releasing compounds described above or metal ions having an electronegativity of 4 or more as described in Japanese Patent Application No. 104645/1988 can also be used.

Examples of antifoggants include those described in US Pat. No. 3,645.
Higher fatty acids described in the specification of No. 739, mercuric salts described in Japanese Patent Publication No. 11113/1983,
N-halogen compound described in Japanese Patent Publication No. 1-47419, US Pat.
Mercabuto compound-releasing compounds described in Japanese Patent No. 50725, arylsulfonic acids described in Japanese Patent No. 49-125016, lithium carboxylate salts described in Japanese Patent No. 51-47419, British Patent No. 1,455,271 Ii
ll oxidizing agent described in JP-A No. 50-101019,
Sulfinic acids or thiosulfonic acids' described in Publication No. 53-19825, 2-thiouracils described in Publication No. 51-3223, simple sulfur described in Publication No. 51-26019, No. 51-42529, No. 51-81124
Disulfide and polysulfide compounds described in Japanese Patent No. 55-93149, rosins or diterbenes described in Japanese Patent No. 51-57435, Japanese Patent No. 51-10433
Polymer acid having a free carboxyl group or sulfonic acid group described in Publication No. 8N, U.S. Pat. No. 4,138,2
Thiazolinthione described in No. 65 Mei III, JP-A-1988
-51821, U.S. Patent No. 4,137,07
1,2,4-triazole or 5-mercabuto-1,2,4-triazole described in JP-A No. 9, 1973
Thiosulfinic acid esters described in No. 5-140883, 1.2, 3. described in No. 55-142331.
4-thiatriazoles, No. 59-46641, No. 5
Dihalogen compounds or trihalogen compounds described in No. 9-57233 and No. 59-57234, thiol compounds described in Zarani No. 59-111636,
Examples include the hydroquinone derivatives described in JP-A No. 60-198540, and the combination of hydroquinone derivatives and penzotriazole derivatives described in JP-A No. 60-227255.

Still another particularly preferred antifoggant is disclosed in JP-A No. 6
Inhibitors having hydrophilic groups as described in JP-A No. 2-78554, polymeric inhibitors as described in JP-A-62-121452, and inhibitors having ballast groups as described in JP-A-62-123456. can be mentioned.

Further, a colorless coupler described in Japanese Patent Application No. 62-320599 is also preferably used.

Examples of base breaker include compounds that release basic substances by decarboxylation upon heating (e.g., guanidinium acetate), compounds that decompose by reactions such as intramolecular nucleation substitution reactions, and release amines. , for example, Japanese Patent Application Laid-open No. 56-130745, Japanese Patent Application Publication No. 56-132332, British Patent No. 2,079,480, and U.S. Patent No. 4.
, No. 060, 420, JP 59-1576
No. 37, No. 59-166943, No. 59-18053
No. 7, No. 59-174830, No. 59-19523
No. 7, No. 62-108249, No. 62-17474
Examples include base release agents described in Publication No. 5 and the like.

In addition, various additives used in heat-developable photosensitive materials as necessary include antihalation dyes, optical brighteners, hardeners, antistatic agents, plasticizers, spreading agents, matting agents, surfactants, It can contain anti-fading agents, etc., and these are specifically described in RD (Research Disclosure) magazine V01.170, June 1978, No. 17.
No. 029, JP-A-62-135825, etc.

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

The heat-developable color photosensitive material of the present invention contains (a) photosensitive silver halide, (b) a reducing agent, (C) a binder,
When used as a color light-sensitive material, it contains (d) a dye-providing substance. Furthermore, it is preferable to contain (e) nada 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 l/4 layer. For example, if the heat-developable photosensitive layer is divided into two layers, The above (a >. (b >, (c
>. The component (e) may be contained in one heat-developable photosensitive layer, and the dye-providing substance (d) may be contained in the other layer adjacent to this photosensitive layer, in a state where they can react with each other. If necessary, it may be contained in two or more constituent layers.

Further, the heat-developable photosensitive layer may be divided into 2111 or more layers including a low-sensitivity layer, a high-sensitivity layer, a high-density layer, and a low-density layer.

The heat-developable photosensitive material of the present invention has one or more heat-developable photosensitive layers. In the case of full-color photosensitive materials,
Generally, three heat-developable photosensitive layers having different color sensitivities are provided, and each photosensitive layer forms or releases a dye of a different hue upon heat development.

Normally, a yellow dye is coarsely mixed in the blue-sensitive layer, a magenta dye is in the green-sensitive layer, and a cyan dye is mixed 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 selected depending on the purpose. For example, a structure in which a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are sequentially formed on a support, or a blue-sensitive layer is sequentially formed on a support. , a green-sensitive layer, a red-sensitive layer, or a green-sensitive layer, a red-sensitive layer, and a blue-sensitive layer sequentially 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 packing layer and a release layer can be optionally provided. To coat the heat-developable photosensitive layer and these non-photosensitive layers on the support, a method similar to that used for coating and preparing general silver halide photosensitive materials can be applied.

The heat-developable color photosensitive material of the present invention can be obtained by forming a photographic constituent layer on a support, and examples of the support that can be used here include polyethylene film, cellulose acetate film, polyethylene terephthalate film, Synthetic plastic films such as polyvinyl chloride, paper supports such as photographic base paper, printing paper, art paper, cast coated paper, baryta paper, and resin coated abrasive paper, and electron beam curable resin compositions on these supports. Examples include supports coated with and cured. The heat-developable color photosensitive material of the present invention usually preferably has a
It can be developed by simply heating at a temperature range of 100 to 170°C, more preferably 1 to 180 seconds, more preferably 1.5 to 120 seconds. Transfer of the diffusible dye to the image-receiving layer may be carried out simultaneously with heat development by bringing the image-receiving member into close contact with the photosensitive surface of the photosensitive material and the image-receiving layer during heat development, or by bringing the image-receiving member into close contact with the image-receiving member after heat development. Alternatively, the transfer may be carried out by supplying water and then applying heat if necessary. Moreover, you may perform preheating in the temperature range of 70 degreeC - 180 degreeC before exposure. Also, JP-A-60-1433
As described in No. 38 and No. 61-162041, in order to improve their mutual adhesion, the photosensitive material and the image receiving member may be preheated at a temperature of 80°C to 250°C immediately before thermal development transfer. good.

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

As the heating means, any method that can be applied to ordinary heat-developable photosensitive materials can be used. For example, it can be brought into contact with a heated block or plate, brought into contact with a heated roller or drum, or passed through a high-temperature atmosphere. Alternatively, high-frequency heating may be used, or furthermore, carbon black or the like may be applied to the back surface of the photosensitive material of the present invention or the back surface of the image receiving member for thermal transfer.
! It is also possible to provide a conductive layer containing an electrically conductive substance and utilize Joule heat generated by energization. There are no particular restrictions on the heating pattern, such as preheating (breheating) and then reheating, or heating at a high temperature for a short time or at a low temperature for a long time, by continuously increasing the temperature, or by continuously increasing the temperature. It is also possible to lower the heating temperature or to repeat 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. Pat. No. 3,709
, No. 690, et al., are preferably used. Typical image-receiving layers for diffusion transfer include 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, corrugated polymeric material having a glass transition temperature of 40 DEG C. or more and 250 DEG C. or less, as described in Japanese Patent Application Laid-Open No. 57-207250.

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

Polymer Handbook 2nd Edition (Joy Brandrup, E.H. Inmargut) John Willi & Sons Publishing { Polymer Handbook 2nd
ed. (J, 3randrup, E
．． H. In+mergut I) John Wil
Synthetic polymers having a glass transition temperature of 40° C. or higher, such as those described in J. E. & 3 oz. Generally, the molecular weight of the polymer substance is 2000 to 200.
000 is useful. These polymeric substances may be used alone or in a blend of two or more types, or may be used in combination of two or more types 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 an 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 the image-receiving member, any material such as a transparent support or an opaque support may be used.
and supports containing pigments such as titanium oxide, barium sulfate, calcium carbonate, and talc, baryta paper, resin-coated paper in which thermoplastic resin containing pigments is laminated on paper, and cloth. , glasses, metals such as aluminum, etc., and supports on which electron beam curable resin compositions containing pigments are coated and cured; Examples include a support provided with a coating layer. Furthermore, various coated papers such as the cast coated paper described in JP-A-62-283333 are also useful as supports.

In addition, a support is prepared by coating and curing an electron beam curable resin composition containing a pigment on paper, or a support having a pigment coating layer on paper and an electron beam curable resin composition on the pigment coating layer. The resin layer of the support coated with and cured can be used as an image-receiving layer, so it can be used as is as an image-receiving member.

The heat-developable color photosensitive material of the present invention is published in RD (Research Disclosure Magazine) No. 15108, JP-A-57-
No. 198458, No. 57-2G7250, No. 61-
It can be a so-called monosheet-type photothermographic material in which a photosensitive layer and an image-receiving layer are formed on the same support, as described in Japanese Patent No. 80148.

It is preferable to provide a protective layer on the heat-developable color photosensitive material and image-receiving member of the present invention.

Various additives used in the photographic field can be used in the protective layer. The additives include various matting agents, colloidal silicate agents, slipping agents, organic fluoro compounds (especially fluorine surfactants), antistatic agents, ultraviolet absorbers,
High boiling point solvents, antioxidants, hydroquinone derivatives,
Polymer latex, surfactant (including polymeric surfactant), hardening agent (including polymeric li! film agent), organic silver salt particles, non-photosensitive silver halide particles, antifoggant, development accelerator agents, etc.

Regarding these additives, please refer to RD (Research Disclosure Magazine) Vol. 170. June 1978 N
o. No. 17029 and JP-A-62-135825.

(Example) Example 1 A photosensitive material 1 (1) having a multilayer structure having the composition shown in Table 1 was produced.

In addition, the polymeric dye-donating substances and reducing agents (CO
The structures of P), thermal solvent (A), inhibitor (A), and scavenger (A) are as follows.

Dye-donor trade-(1) Dye-donor substance-(3) Dye-donor substance-(2) Reducing agent (CDP) Heat solvent 1A Inhibitor 1A Scavenger-A Also, the 6th layer of photosensitive material-(1) Photosensitive material (2) was prepared in the same manner as photosensitive material (1) except that the composition of the blue sensitive layer (blue sensitive layer) was changed as shown below.

<Composition of the 6th layer of photosensitive material (2)> Penztriazole silver 2.59 Reducing agent (CDP) 1.60 Dibutyl phthalate 0.4 g Polymeric dye-donor (1) 0.81:1 Blue-sensitive halogenated Silver emulsion 0. 76! )A! ]gelatin
4.8g polyvinylpyrrolidone (K-30) 0.6 (+thermal solvent - A6. Photosensitive material 1 (3) and ( 4) was produced.

Comparative compound (A)? Each of the photosensitive materials (1) to (4) was exposed to white light, blue light, green light, and red light through a step wedge, and then overlapped with image receiving member 1 or 2 shown below. In total, heat development was performed at 145° C. for 90 seconds.

High-density and low-fog transferred images of black, cyan, magenta, and yellow were obtained on image-receiving member-2 in accordance with each exposure.

Table 2 shows the maximum density (■a+ax) and minimum density (fog, pmin) of the obtained black image, which was measured for reflection density against infrared light (850 nm).

Image receiving member-1 Polyvinyl chloride (n -1 10
0, manufactured by Wako Pure Chemical Industries, Ltd.) coated with a weight of 15.0 g/t'.

Image-receiving member-2 An image-receiving member in which nickel stearate (appended ml. 3Q/1') is further added to the polyvinyl chloride layer of image-receiving member-1.

Table 2 As shown in Table 2, a dye image having absorption in the infrared region could be formed by using a photosensitive material containing the compound of the present invention and by incorporating metal ions into the image receiving member.

Even when the metal ions in the image receiving member were changed to copper ions or cobalt ions, the effects of the present invention could be obtained.

Example-2 A photosensitive material 1 (5) having a multilayer structure shown in Table 3 was prepared.

Moreover, the compound (2) of the present invention in photosensitive material 1 (5)
A photosensitive material (6) was produced in the same manner except that compound (21) of the present invention was used.

Each of the obtained photosensitive materials 1 (5) and (6) was exposed to green light, red light and infrared light through a step wedge, and water was applied to the emulsion surface of the photosensitive material with a wire spar. , image receiving member -3, -4 or -5 shown below
The film was developed at 130° C. for 30 seconds. Cyan, magenta, and yellow transferred images were obtained on the image receiving member corresponding to each exposure.

The anti-tJJIl degree of the obtained cyan image with respect to infrared light (850n+g) was measured. Maximum concentration ([)WaX)
and the minimum life (fog, Dgiin >) are shown in Table 4.

Image receiving member-3 Lime-treated gelatin (Grade 2.3) on photographic baryta paper
o/f) I! ) and further coated with a dyed layer having the composition shown below to obtain image receiving member-3.

Composition of dye 1wlJ Polymer (I) below Polymer (II) Lime-treated gelatin polymer (4.25 g/f [4 Q/f 3a/f Receiver 9 member-5 Acetic acid applied to the dye layer of image-receiver member-3 Copper (0.6 (J/t)
) is the same image receiving member as image receiving member-3 except that it has been added.

Bolimar (I) x: 60! l! Y% y: 30 weight% Z: 10% by weight Image receiving member-4 Acetic acid nickel (o.eg/
The same image receiving member as image receiving member-3 except that t') was added.

*1) Book 2) Soft solvent 1 B: Benzene sulfone 7mide dye-donating substance - (4): Kyo 3 inhibitor 1 B: Kyo 4) Dye-donating substance - (5): Book 5) 6) Sensitization The following was used as the dye: Dye-donor substance 1 (6): In addition, the images obtained with the image-receiving members (3), (4), and (5) were irradiated 24 hours a day with a 6000 watt xenon lamp (on the surface of the image-receiving member). The illuminance is so, ooo lux), the maximum brightness before and after exposure (DO before exposure, D after exposure) is measured, and the value of (D / Do) x 100 is the residual rate (%), The light resistance was evaluated.Also, the heat resistance was evaluated by leaving it for 7 days at a relative humidity of 70% and a temperature of 60°C, and measuring the residual rate from the maximum concentration before and after exposure.These values were 90%. The above is considered to be sufficient for practical purposes.

Table 4 As shown in Table 4, by using a photosensitive material using the compound of the present invention and an image receiving member containing metal ions,
A dye image having absorption in the infrared region could be obtained. Furthermore, the light resistance and heat resistance were at a practically sufficient level.

In addition, when using the same photosensitive material as photosensitive material 1 (5) except that nickel stearate was added to the protective layer of photosensitive material 1 (5) (addition! fi 1.O Q/f ) L/ Even when member-3 was used, an image with infrared dye was obtained, and O*aX was 1.12.

Example 3 A photosensitive material (74) having a multilayer structure shown in Table 5 was produced. Moreover, the compound (1) of the present invention in photosensitive material 1 (7)
Photosensitive material 1 (8) was produced in the same manner except that 7) was replaced with the compound (24) of the present invention, and the obtained photosensitive material - (7)
and (8) were exposed in the same manner as in Example-2, and then overlapped with image receiving member-2 of Example-1 and processed in the same manner as in Example-1.

High-density, low-fog transfer images of cyan, magenta, and yellow were obtained on the image-receiving member-2 in response to each exposure, and an infrared dye image was also formed in the cyan image forming area.

(Effects of the Invention) As described above in detail, the present invention can provide an infrared dye image that has excellent stability against heat and light and has an absorption wavelength that can be read even with infrared light.

Claims (2)

[Claims] (1) A dye-donating substance containing at least a photosensitive silver halide, a reducing agent, a binder, and a dye moiety represented by the following general formula (1) and/or a dye moiety represented by the following general formula (2) on a support. A heat-developable color photosensitive material containing at least one is thermally developed in close contact with an image-receiving material after imagewise exposure or at the same time as imagewise exposure, and diffusion containing the dye part formed from the dye-providing substance as a function of development is performed. Transferring all or part of the coloring dye to the image-receiving material, and chelating part or all of the dye to a metal during or after the transfer, to form the metal-chelated dye image in the image-receiving material. An image forming method characterized by: General formula (1) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (2) ▲ Contains numerical formulas, chemical formulas, tables, etc. ▼ In the formula, X is a collection of atoms necessary to form an aromatic nitrogen-containing heterocycle represents. R_1 represents a halogen atom or a monovalent organic group, m represents 0 or an integer of 1 to 3, and when m is 2 or 3, R_1 may be the same or different from each other. Y is a hydroxyl group or a ▲mathematical formula, chemical formula, table, etc.▼ group (
R_6 and R_7 each represent a hydrogen atom or an optionally substituted alkyl group), and R_2, R_
3, R_4 and R_5 are each a hydrogen atom, a halogen atom,
Or represents a monovalent organic group. (2) In a heat-developable color photosensitive material containing at least a photosensitive silver halide, a reducing agent, a binder, and a dye-providing substance on a support, the dye-providing substance has the following general formula (
1. A heat-developable color photosensitive material having at least one dye moiety represented by the formula (1) and the following general formula (2). General formula (1) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (2) ▲ Contains numerical formulas, chemical formulas, tables, etc. ▼ In the formula, X is a collection of atoms necessary to form an aromatic nitrogen-containing heterocycle represents. R_1 represents a halogen atom or a monovalent organic group, m represents 0 or an integer of 1 to 3, and when m is 2 or 3, R_1 may be the same or different. Y is a hydroxyl group or a ▲mathematical formula, chemical formula, table, etc.▼ group (
R_6 and R_7 each represent a hydrogen atom or an optionally substituted alkyl group), and R_2, R_
3, R_4 and R_5 are each a hydrogen atom, a halogen atom,
Or represents a monovalent organic group.