JP2711340B2 - Image receiving material for thermal development - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image receiving material for thermal development, that is, an image receiving member that transfers an image or the like from a photothermographic material and receives the image. The present invention relates to a heat-developable image receiving material capable of obtaining a high density when a dye or the like formed in the material is transferred to the image receiving material.

[Background of the Invention]

Photosensitive materials (heat-developable light-sensitive materials) for obtaining an image simply and quickly by performing a developing process by heat dry processing are known, and the heat-developable light-sensitive materials and image forming methods are described, for example, in JP-B-43-4921, No. 43-4924, “Basics of photographic engineering”, silver halide photography (1879, published by Corona Co., Ltd.), pages 553 to 555
And Research Disclosure Magazine, June 1978, pages 9 to 15 (RD-17029).

There are two types of photothermographic materials: one that obtains a black-and-white image and one that obtains a color image. In particular, in recent years, development of a heat-developable color photographic material that obtains a color image using various dye-providing substances has been attempted.

There are various types of heat-developable color light-sensitive materials. For example, a method in which a diffusible dye is released or formed by thermal development and then the dye is transferred to obtain a color image (hereinafter referred to as a transfer method). Requires an image receiving member for transfer, but is excellent in terms of image stability, sharpness, simplicity and speed of processing, and the like. The heat-developable color photosensitive material of this transfer system and the image forming system are described in, for example, JP-A-50-12431, JP-A-59-159159, JP-A-59-181345,
No. 59-229556, No. 60-2950, No. 61-526430, No. 61
-61158, 61-61157, 59-180550, 61-13
Nos. 2952, 61-139842 and U.S. Pat.
Nos. 2, 4,590,154 and 4,584,267 are described in each specification and the like.

In a photothermographic material, a thermal solvent is often added to the photothermographic material for the purpose of activating thermal development. In particular, a diffusive transfer type photothermographic material increases the efficiency of forming a diffusible dye. Various thermal solvents or solvents are added to the photosensitive layer and / or the non-photosensitive layer of the photothermographic material for the purpose of improving the transfer efficiency of the dye.

Conventionally known thermal solvents are in a liquid state at around room temperature and in a solid state at around room temperature. However, they are liquefied at the time of heating and developing to exhibit various functions of the thermal solvent. Examples of the former include alcohols, polyols, phenols and relatively low molecular weight ureas,
Many typical amides can be found in amides, etc. However, this kind of thermal solvent which is liquid at normal temperature is often hygroscopic by itself or liquid in photosensitive material. In many cases, the light-sensitive material sticks or sticks to the back surface of the light-sensitive material or another substance, which is hardly practical.

On the other hand, a thermal solvent which is solid at room temperature remarkably reduces the above-mentioned disadvantages. Examples of this type of thermal solvent which is solid at room temperature include, for example, JP-A Nos. 62-136645 and 60-232547, and
-198528 can be mentioned.

By the way, the water-insoluble solid thermal solvent generally improves heat developability and transferability of dyes and the like in proportion to the amount added to the photothermographic material. In order to perform the transfer, it is preferable to add the thermal solvent as much as possible to the photothermographic material.
In order to obtain a particularly high-density image such as a dye, about 50% by weight or more, preferably about 80% by weight or more, particularly preferably about 100% by weight or more based on the total binder amount of the photothermographic material, Is preferably added.

However, in order to obtain images such as high-density dyes,
When a large amount of a solid thermal solvent is added to a photothermographic material, the following various disadvantages are caused.

(1) The flexibility of the hydrophilic binder layer such as gelatin is lowered, and cracks and peeling of the film are easily caused.

(2) Hardening of the binder layer is easily inhibited.

(3) The curl characteristics of the photothermographic material are significantly deteriorated.

(4) Sharpness deteriorates.

(5) In the production of a photothermographic material, when a coating solution containing the above-mentioned thermal solvent is applied, coating failures increase rapidly.

On the other hand, it has been conventionally known that a part of a thermal solvent is added to an image receiving material in advance. However, in the conventionally known technology of adding a thermal solvent to an image receiving layer of an image receiving material, it is difficult to add the thermal solvent to the image receiving layer in a good physical state, or the image receiving material is stored. During the heating, the thermal solvent precipitates on the surface of the image receiving layer, or volatilizes from the surface, and even when the thermal solvent is added to the image receiving material, the image density of the transfer dye and the like does not increase so much. There was a disadvantage.

[Object of the invention]

Accordingly, the present invention has been made in view of the above circumstances, and a first object of the present invention is to provide an image-receiving material for thermal development which can provide a high density of a dye image or the like during thermal development.

A second object of the present invention is to provide an image-receiving material for thermal development which has good storage stability and which does not adversely affect various additives added to the image-receiving material and its functions.

A third object of the present invention is to provide a heat-developable image-receiving material which causes less trouble during production even when a thermal solvent is added to the image-receiving material.

[Configuration of the invention]

The present inventors have conducted intensive studies to achieve the above object,
The following objects of the present invention have been found to be achieved by the present invention.

That is, the above object is achieved by an image receiving material for thermal development, which comprises at least one compound represented by the following general formula (I).

 Hereinafter, the present invention will be further described.

First, the compound represented by formula (I) contained in the image receiving material for thermal development of the present invention will be described.

 The general formula (I) is as follows.

General formula (I) In the formula, R ¹ represents a hydrogen atom or an alkyl group, and R ² represents an alkyl group, an alkenyl group, or an aryl group.
The above groups represented by R ¹ and R ² include those having a substituent. R ³ represents an alkylene group. R ⁴ is an alkyl group, an aryl group, an alkoxy group, an aryloxy group (each of the above groups includes those having a substituent), a halogen atom, or CONH
R ⁵ (R ⁵ represents an alkyl group or a hydrogen atom). k
Represents 0 or 1, l represents 0 or 1, and m represents 0 or 1. n represents 0 or 1, and p represents 0 or an integer of 1 to 4. However, when R ¹ is a hydrogen atom, 1 represents 1. Also, k, l, m, and n are not all 0, and l and m are not both 0, and k and n are not both 1. When n = 0, 1 represents 1.

In the above, the alkyl group represented by R ¹ is preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms (particularly preferably a methyl group or an ethyl group).

R ² represents an alkyl group, an alkenyl group or an aryl group which may have a substituent, and the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms.
Specific examples of the alkyl group of R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
Examples thereof include an i-butyl group, a t-butyl group, a sec-butyl group, and an n-hexyl group.

The alkenyl group for R ² is preferably an alkenyl group having 2 to 6 carbon atoms. Specific examples of the alkenyl group include a vinyl group, an allyl group, and a 2-butenyl group.

As the aryl group for R ² , a phenyl group is preferable.

As the substituent for R ² , an alkyl group (for example, a methyl group,
Ethyl group), phenyl group, alkoxy group (for example, methoxy group, ethoxy group, n-butoxy group), phenoxy group or halogen atom (for example, fluorine atom, chloro atom)
Can be mentioned.

R ³ represents an alkylene group, and the alkylene group is preferably an alkylene group having 2 to 4 carbon atoms. Specific examples of R ³ include, for example, -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH _2- , − (C
H ₂ ) ₄ −, And the like.

R ⁴ represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom (preferably a fluorine atom or a chloro atom) or a CONH
⁵ groups (R ⁵ represents an alkyl group or a hydrogen atom), wherein the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms (eg, a methyl group, an ethyl group, or an n-butyl group); Is preferably a phenyl group, and as the alkoxy group, an alkoxy group having 1 to 5 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group is preferable,
A phenoxy group is preferred as the aryloxy group. Examples of the substituent include an alkyl group (for example, a methyl group and an ethyl group), a phenyl group, an alkoxy group (for example, a methoxy group and an ethoxy group), a phenoxy group, and a halogen atom (for example, a fluorine atom and a chloro atom). it can.

When R ⁴ represents a CONR ⁵ group, R ⁵ is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or the like.

p represents 0 or an integer of 1 to 4, preferably 0,
1 or 2, and when p is 2 or more, two or more R ⁴
May be the same or different.

 m is preferably 1.

Next, specific compounds represented by the general formula (I) which can be preferably used in the present invention will be exemplified. However, it goes without saying that the compounds that can be used in the present invention are not limited to the following examples.

Examples of each compound are as follows: k = 0, l = 1, n = 1, R ¹ = H
, Ie, the case of the following general formula (I) -1 and k =
1, l = 1, m = 0, n = 0, R ¹ = H, that is, the case of the following general formula (I) -2, and k = 1, l = 1, n =
1. The case where R ¹ = H, that is, the case of the following general formula (I) -3, and the other cases are shown separately. Formula (I)-
In the case of 1-3, the substitution position and substituents R ² , R ³ , R ⁴ and m, p
Is indicated by specifying In other cases, it is indicated by specifying the substitution position and the substituents R ¹ , R ² , R ³ , R ⁴ and k, l, m, n, p.

General formula (I) -1 General formula (I) -2 General formula (I) -3 Next, synthesis examples of some examples of the above compounds will be described.

Synthesis example: (1) Synthesis of TS-15 36.2 g of p-2-hydroxyethyloxybenzamide
Was dissolved in 200 ml of N, N-dimethylformamide, and
35 g was added, and after heating and stirring for 1 hour, the reaction solution was poured into water,
The precipitated solid was separated by filtration. The solid was recrystallized from ethanol to obtain 52 g of the desired product (mp 102.5 ° C.).

(2) Synthesis of TS-43 p-Cyanobenzoic acid and 2-ethoxyethanol were subjected to an esterification reaction in benzene using p-toluenesulfonic acid as a catalyst to obtain p-cyanobenzoic acid 2-ethoxyethyl ester. To 50 g of this ester were added 10 g of 30% potassium hydroxide and 50 ml of aqueous hydrogen peroxide, reacted at 30 ° C. and hydrolyzed to obtain the desired product (mp 109 ° C.).

(3) Synthesis of TS-65 13.7 g of p-hydroxybenzamide was dissolved in 100 ml of pyridine, and 14 g of 2-methoxyethyl chloroformate was added dropwise to the pyridine solution at room temperature. After the dropwise addition, the mixture was stirred for a while, poured into ice water, and the precipitated crystals were filtered, washed with water, dried, and recrystallized with ethanol to obtain 19.8 g of the desired product (mp 120.5 ° C).

(4) Synthesis of TS-91 250 ml of acetonitrile and methylamine (40% aqueous solution) 3
3 ml were mixed, and 20 ml of pn-butoxybenzoic acid chloride was added dropwise while stirring at room temperature. After stirring for 1 hour after the addition, the reaction solution was poured into 500 ml of water, the pH was adjusted to about 4.0 with 0.5 N hydrochloric acid, and the solid was separated by filtration. This solid was recrystallized from acetonitrile to obtain 18.5 g of the desired product (mp156
° C).

(5) Synthesis of TS-97 27.6 g of p-hydroxybenzoic acid and acetyl chloride 1
6g, and after acylation, it is reacted with thionyl chloride to give p-acetyloxybenzoic acid chloride 3
2.2 g were obtained. This acid chloride was reacted with methylamine (40% aqueous solution) in acetonitrile to obtain 22.3 g of p-hydroxy-N-methylbenzamide. This intermediate 2
After hydroxyethylation of 0 g with ethylene oxide, the resultant was reacted with propionic anhydride, and the obtained crystals were recrystallized from ethanol to obtain 18.2 g of the desired product (mp134 to mp134).
135 ° C).

Among the compounds represented by the general formula (I) (hereinafter also appropriately referred to as “the solid thermal solvent of the present invention” or “the thermal solvent of the present invention”), particularly those having a melting point of 80 ° C. or more and 200 ° C. or less And more preferably those having a temperature of 100 ° C. or more and 180 ° C. or less.

The image receiving material for thermal development of the present invention (hereinafter, also referred to simply as the image receiving material of the present invention as appropriate) preferably has at least one image receiving layer capable of receiving a dye or the like on a support. The image receiving layer can also serve as the support itself. Further, the image receiving layer can be composed of two or more layers. Further, the image receiving material can be provided with layers such as an undercoat layer and a protective layer in addition to the support and the image receiving layer.

When the solid thermal solvent of the present invention is added to the image-receiving material of the present invention, the thermal solvent can be added to any part of the image-receiving material, but is preferably added to the image-receiving layer and / or a layer adjacent thereto. You.

The amount of the thermal solvent of the present invention depends on the layer to be added, the kind of binder of the additional layer, the presence or absence and amount of various additives to be added to the same layer as the thermal solvent, and the photothermographic material. Although it can vary widely depending on the composition of the binder, the amount is generally preferably 1 to 50% by weight, more preferably 2 to 30% by weight, based on the binder of the additional layer.

The thermal solvent of the present invention can be used in combination of two or more kinds. Further, a thermal solvent other than the present invention can be used in combination. In this case, the thermal solvent of the present invention is preferably 50% by weight or more, more preferably 70% by weight of the total thermal solvent contained in the image receiving material. %.

As a method of adding the thermal solvent of the present invention to the image receiving material,
Any method can be appropriately selected and used.

The thermal solvent of the present invention is generally poorly soluble in water, and preferably when the additive layer is made of a hydrophilic binder,
It is added as a finely pulverized dispersion in an aqueous colloid medium by a method such as a ball mill or a sand mill. When the additional layer is made of a hydrophilic binder, it is preferably dissolved in a suitable organic solvent capable of dissolving the hydrophobic binder and added to the coating solution for the additional layer.

When the present invention is carried out, the image receiving layer formed on the image receiving material of the present invention may be any of a hydrophobic one and a hydrophilic one, and is a photothermographic material released or formed by heat development. Any material may be used as long as it has a function of receiving a dye or the like in the photosensitive layer. For example, in polymers containing tertiary amine or quaternary ammonium salts, US Pat. No. 3,709,690
Those described in the specification are preferably used.
For example, as a polymer containing a quaternary ammonium salt, the ratio of polystyrene-co-N, N, N-tri-n-hexyl-N-vinyl-benzylammonium chloride is 1: 4 to
4: 1, preferably 1: 1. Examples of the polymer containing a tertiary amine include polyvinylpyridine. As the image receiving layer, there is a layer obtained by mixing a polymer containing an ammonium salt, a tertiary amine or the like with gelatin or polyvinyl alcohol and coating the mixture on a support.

The image-receiving layer particularly preferably used in the invention is preferably a heat-resistant organic polymer having a glass transition temperature of 40 ° C. or more and 250 ° C. or less described in JP-A-57-207250, for example, from the viewpoint of water resistance. These polymers may be supported on a support as an image receiving layer, or may be themselves used as a support.

Examples of the heat-resistant polymer substance, polystyrene,
A polystyrene derivative having a substituent having 4 or less carbon atoms,
Polyacetals such as polyvinylcyclohexane, polyvinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinylalcohol, polyvinylformal and polyvinylbutyral, polyvinyl chloride, chlorinated polyethylene, polytrifluoroethylene, polyacrylonitrile, poly-N , N−
Dimethylallylamide, polyacrylate having p-cyanophenyl group, pentachlorophenyl group and 2,4-dichlorophenyl group, polyacrylchloroacrylate,
Polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, poly-
Polyesters such as tert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate, polyethylene terephthalate, polycarbonates such as polysulfone and bisphenol A polycarbonate, polyanhydrides, polyamides and cellulose acetates Is mentioned. Also, "Polymer Handbook, 2nd Edition" (Joy Brand Wrap, EH Inmargat Edition), John Williand Sands Publishing (Polymer Handbook 2nd
ed. (edited by J. Brandrup, EHImmergut) John Wiley & Son
The synthetic polymer having a glass transition temperature of 540 ° C. or higher described in s] is also useful. Generally, 2,000 to 200,000 is useful as the molecular weight of the polymer substance. These polymer substances may be used alone or as a blend of two or more kinds, or two or more kinds may be used in combination as a copolymer.

Useful polymers include cellulose acetates such as triacetate, diacetate, heptamethylenediamine and terephthalic acid, fluorenedipropylpropylamine and adipic acid, polyamides by a combination of hexamethylenediamine and diphenic acid, hexamethylenediamine and isophthalic acid, and diethylene glycol. Polyester, polyethylene terephthalate, polycarbonate, and the like, in combination with diphenylcarboxylic acid, bis-p-carboxyphenoxybutane and ethylene glycol. These polymers may be modified. For example, cyclohexanedimethanol, isophthalic acid, methoxypolyethylene-glycol, 1,2
Polyethylene terephthalate using dicarbomethoxy-4-benzenesulfonic acid or the like as a modifier is also effective.

Particularly preferred image receiving layers include a layer composed of polyvinyl chloride described in JP-A-59-223425 and a layer composed of polyvinyl chloride described in JP-A-60-19223.
No. 138, a layer composed of a polycarbonate and a plasticizer.

When the image receiving layer is provided on the support, stability of performance,
The solution coating method is preferably used from the viewpoint of production cost and the like.

In this case, various solvents can be selected according to the support of the image receiving material, and commonly used organic solvents such as methylene chloride, methyl ethyl ketone, and tetrahydrofuran can be appropriately selected and used.

In the image receiving layer, an ultraviolet absorber (for example, a benzophenol compound and a benzotriazole compound),
Dye image stabilizers (for example, phenolic compounds, bisphenol compounds, hydroquinone compounds, gallic acid derivatives, hydroxychroman compounds, polyalkylpiperidine compounds, dialkoxybenzene compounds, hydroxyindane compounds, etc.), plasticizers (for example, Dibutyl phthalate, di- (2-ethylhexyl) phthalate,
Tricresyl phosphate, etc.), a development accelerator, a reducing agent, a thermal solvent and the like can be added as necessary.

As the support for the image receiving material, any material such as a transparent support and an opaque support may be used.For example, films such as polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, polyethylene, and polypropylene,
And a support in which pigments such as titanium oxide, barium sulfate, calcium carbonate, and talc are contained in the support, pure baryta paper, and RC (resin coat) in which a thermoplastic resin containing the pigment is laminated on paper. Paper, metal such as aluminum, etc., or a support obtained by applying and curing an electron beam-curable resinous tissue containing pigment on these supports, and a coating layer containing pigment on these supports And the like. Further, cast coated paper described in Japanese Patent Application No. 61-129672 is also useful as a support.

The photothermographic material and the image receiving material may be configured so that all of the dye image or the like formed by the photothermographic material is transferred to the entire surface or a part of the image receiving material. It is also possible to adopt a configuration in which a part of the dye image thus obtained is transferred onto the entire surface or a part of the image receiving material.

The photothermographic material and the image receiving material may be of any size, and may be substantially the same size. In order to improve the releasability of the image receiving material, for example, both are used. Different sizes are possible. Furthermore, they need not necessarily be similar.

The image-receiving material of the present invention receives an image or the like from the photothermographic material, and can be used in combination with the image-receiving material of the present invention (hereinafter referred to as “the photothermographic material of the present invention” as appropriate). May be abbreviated).

Generally, such a photothermographic material preferably has at least one photographic component layer containing a photosensitive silver halide, a reducing agent, a binder and, if necessary, a dye-providing substance on a support. In such a photothermographic material, an image is formed in the photothermographic material simply by performing a heat treatment after imagewise exposure. By superimposing the photothermographic material and the image receiving material simultaneously with or after the heating, a transferable compound such as a dye image is transferred into the image receiving layer of the image receiving material.

The photosensitive silver halide used in the photothermographic material is
Any material can be used, for example, silver chloride, silver bromide,
Silver iodide, silver chlorobromide, silver chloroiodobromide, silver iodobromide and the like can be used.

The silver halide may be in any shape (for example, cubic sphere, octahedron, dodecahedron, etc.), and the average grain size is preferably about 0.05 μm to 2 μm, more preferably. Is in the range of about 0.08 μm to 0.5 μm, and the particle size distribution may be monodisperse or polydisperse.

The photosensitive silver halide grains can be subjected to any chemical sensitization such as noble metal sensitization, sulfur sensitization, and reduction sensitization in order to enhance sensitivity, and optional sensitization if necessary. Spectral sensitization can be performed with a dye.

As the reducing agent used in the photothermographic material of the present invention (the reducing agent precursor is also included in the reducing agent in the present specification), those usually used in the field of photothermographic materials can be used. .

Examples of the reducing agent that can be used include, for example, U.S. Patent Nos. 3,531,286, 3,761,270, and 3,764,328, and RD (Research Disclosure) No. 121.
46, No. 15108, No. 15127 and JP-A-56-27132, U.S. Pat.Nos. 3,342,599, 3,719,492, JP-A-53-135628, and JP-A-57-79035. P-phenylenediamine-based and p-aminophenol-based developing agents, phosphoramidophenol-based, sulfonamidoaniline-based developing agents, hydrazone-based color developing agents and their precursors, phenols, and sulfonamides described in each publication Phenols or polyhydroxybenzenes, naphthols, hydroxybisnaphthyls and methylenebisnaphthols, methylenebisphenols, ascorbic acid, 3-pyrazolidones, pyrazolones can be used, and these can be used arbitrarily. .

Particularly preferred reducing agents include N- (pN, N-dialkyl-amino) phenyl sulfamate described in JP-A-56-146133 and Japanese Patent Application No. 61-71683.

Specific examples of particularly preferably used reducing agents are shown below.

These reducing agents are added in an amount of preferably about 0.01 mol to 10 mol, more preferably 0.1 mol to 5 mol, per 1 mol of the light-sensitive silver halide.

When the photothermographic material is a color photographic material, a dye-providing substance is generally used. Examples of the dye-donor include JP-A-62-44737, Japanese Patent Application No. 60-271117, and Japanese Patent Application No.
Non-diffusible dye-forming couplers described in 1-1115630, for example, leuco dyes described in U.S. Pat.No. 475,441, or azo dyes used in the thermal developing dye bleaching method described in U.S. Pat. Can be used as the dye-providing substance, but it is more preferable to use a diffusion-type dye-providing substance that forms or emits a diffusible dye, and particularly uses a compound that forms a diffusible dye by a coupling reaction. Is preferred.

Hereinafter, the diffusion type dye-providing substance that can be used will be described. As the diffusion type dye-providing substance, any substance which participates in the reduction reaction of the photosensitive silver halide and / or the organic silver salt used as necessary and can form or release a diffusible dye as a function of the reaction is provided. Well, depending on the mode of reaction, a negative dye-donating substance that acts on a positive function (that is, one that forms a negative dye image when a negative silver halide is used) and acts on a negative function (That is, those which form a positive dye image when a negative silver halide is used).

As negative dye-donating substances, for example, U.S. Pat.
Nos. 3,079 and 4,439,513, JP-A-59-60434, and 59-6
No. 5839, No. 59-71046, No. 59-87450, No. 59-88730
Nos. 59-123837, 59-124329, 59-165054
And reducing dye-releasing compounds described in the specifications such as JP-A Nos.

As another negative type dye-providing substance, for example, U.S. Pat.
4,474,867, JP-A-59-12431, JP-A-59-48765, and
9-174834, 59-776642, 59-159159, 59
And coupling dye-releasing compounds described in the specification such as US Pat. No. 213540.

Still another particularly preferred negative dye-donor substance of the coupling dye-forming compound is represented by the following general formula (A).

General formula (A) CpJB) In the formula, Cp represents an organic group capable of forming a diffusible dye by reacting (coupling reaction) with an oxidized form of a reducing agent, and B represents a ballast group. Here, the ballast group is
A substance that does not substantially diffuse a dye-donor substance during thermal development processing, and has a function (such as a sulfo group) depending on the nature of the molecule or a function (such as a large number of carbon atoms) having the function depending on the size. Group). 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 formed dye.

The ballast group is preferably a group having 8 or more, more preferably 12 or more carbon atoms. Also,
When the image receiving layer of the image receiving member is made of a hydrophobic binder, the ballast group may be a sulfo group. In this case, the alkyl group having 8 or more (preferably 12 or more) carbon atoms and the sulfo group The group containing the group is more preferable, and particularly preferably contains a polymer chain.

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

Formula (b) CpJY _a Z ′ _l L) In the formula, Cp and J have the same meanings as defined in Formula (A), Y represents an alkylene group, an arylene group or an aralkylene group, and a represents 0 Or 1; Z ′ has a divalent organic group; and L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of the coupling dye-forming compounds represented by formulas (a) and (b) are described in JP-A-59-124339,
59-181345, 60-2950, JP-A-61-57943, 6
Nos. 1-59336, U.S. Pat.Nos. 4,631,251, 4,650,748,
There are those described in each specification of 4,656,124, especially U.S. Pat.No.4,656,124, U.S. Pat.No.4,631,251,
The polymer type dye-providing substances described in the specifications of the above-mentioned 4,650,748 are preferred.

Examples of the positive dye-donating substance include, for example, JP-A-59-1984.
Nos. 55430, 59-165054, and the like, and dye developing compounds described in JP-A-59-165054, for example, JP-A-59-154445, and diffusible dyes by an intramolecular nucleophilic reaction described in JP-A-59-766954. A compound to be released, for example, a cobalt complex compound described in JP-A-59-116655 or a compound disclosed in JP-A-59-124327.
And compounds which lose their ability to release dye when oxidized as described in JP-A-59-152440 and the like.

The residue of the diffusible dye in the dye-providing substance preferably has a molecular weight of 800 to improve the diffusibility of the dye.
Below, more preferably those which are 600 or less, azo dye, azomethine dye, anthraquinone dye, naphthoquinone dye, styryl dye, nitro dye, quinoline dye,
Residues such as a carbonyl dye and a phthalocyanine dye are exemplified. These dye residues may be in a temporarily shortened form that can be recolored during thermal development or transfer. Further, these dye residues are preferably chelateable dye residues described in JP-A-59-48765 and JP-A-50-124337, for the purpose of increasing the light fastness of an image. It is.

These dye donating materials may be used alone or in combination of two or more. The amount used is not limited and depends on the kind of the dye-donating substance, whether it is used alone or in combination of two or more, or whether the photographic structure layer of the photographic material of the present invention is a single layer or two or more layers. The amount may be determined depending on the case. For example, the amount of use may be 0.005 to 50 g, preferably 0.1 g to 10 g per 1 m ² .

Examples of the binder that can be used for the photothermographic material 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, Protein, starch,
There are synthetic or natural polymer substances such as gum arabic, and these can be used alone or in combination of two or more. In the present invention, gelatin is preferably used as a main component of the binder.

Gelatin preferably used for the binder of the photothermographic material may be either alkali-processed gelatin or acid-processed gelatin. In the photothermographic material of the invention, in particular, gelatin or a derivative thereof and a hydrophilic polymer such as polyvinyl virolidone and polyvinyl alcohol can be used in combination.

The preferred amount of the binder to be used is generally 0.3 g to 30 g, more preferably 0.5 g to ²⁰ g, per 1 m ^{2 of the} support.

The binder is used in an amount of 0.1 to 1 with respect to 1 g of the dye-providing substance.
It is preferable to use 0 g, more preferably 0.25 to 4 g.

In the photothermographic material, various organic silver salts can be used for the purpose of increasing the sensitivity and improving the developability, if necessary.

Organic silver salts which can be used in the photothermographic material include JP-B-53-4921, JP-A-49-52626 and JP-A-52-141.
Nos. 222, 53-36224 and 53-37610 and U.S. Pat.Nos. 3,330,633, 3,794,496 and 4,
Silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocyclic ring as described in each specification such as No. 105,451, such as silver laurate, silver myristate, silver palmitate, and stearin Silver aromatic carboxylate, for example, silver benzoate, silver phthalate, etc., such as silver acid, silver arachidonic acid, silver behenate, silver α- (1-phenyltetrazolethio) acetate; No. 12700, 45-18
No. 416, No. 45-22185, JP-A-52-137321, JP-A-58
And silver salts of imino groups described in JP-A-1-118638, JP-A-58-118639 and U.S. Pat. No. 4,123,274.

In addition, a silver complex compound having a stability constant of 4.5 to 10.0 as described in JP-A-52-31728, a silver salt of imizolinthion as described in U.S. Pat. No. 4,168,980, and the like are used.

Among the above organic silver salts, a silver salt of an imino group is preferable, particularly a silver salt of a benzotriazole derivative, more preferably 5-methylbenzotriazole and its derivative, sulfobenzotriazole and its derivative, and N-alkylsulfamoylbenzo. Triazole and its derivatives are preferred.

The organic silver salts may be used alone or in combination of two or more. Further, a silver salt may be prepared in a suitable binder and used as it is without isolation, or the isolated silver salt may be dispersed in a binder by an appropriate means and used.

The photothermographic material used in combination with the image-receiving material of the present invention preferably contains the heat solvent of the present invention or other various heat solvents. In particular, it is preferable to contain the thermal solvent of the present invention.

The photothermographic material may contain various additives as necessary in addition to the above components.

Inorganic salts such as inorganic halides (eg, sodium chloride, potassium bromide, potassium chloride, potassium iodide, etc.) can be added and used, for example, in a manner in which an aqueous solution of sodium chloride is added to the dispersion (emulsion). can do.

What is known as a toning agent in the photothermographic material may be added to the photothermographic material of the present invention as a development accelerator. Examples of color toning agents include, for example, JP-A-46-4928
Nos. 46-6077, 49-5019, 49-5020, 49
-91215, 49-107727, 50-2524, 50-671
No. 32, No. 50-67641, No. 50-114217, No. 52-33722
No. 52-99813, No. 53-1020, No. 53-55115, No.
53-76020, 53-125014, 54-156523, 54
-1565324, 54-156525, 54-156526, 55
Nos. -4060, 55-4061, and 55-32015, and West German Patent Nos. 2,140,406, 2,141,063, and 2,22.
No. 0,618, U.S. Pat.Nos. 3,847,612, 3,782,941;
Nos. 4,201,582 and the like, and JP-A-57-207.
No. 244, No. 57-207245, No. 58-1896328, No. 58-1935
There are compounds described in each gazette such as No. 41.

As another development accelerator, JP-A-59-177550, JP-A-59-177550,
-111636. Further, a development accelerator releasing compound described in Japanese Patent Application No. 59-288081 can also be used.

Antifoggants include, for example, U.S. Patent No. 3,645,739
Higher fatty acids described in Japanese Patent Publication No. 47-1111
No. 3 mercury salt, N-halogen compound described in JP-A-51-47419, and mercapto compound release described in U.S. Pat. No. 3,700,457 and JP-A-51-50725. Compound, arylsulfonic acid described in JP-A-49-125016, lithium carboxylate described in JP-A-51-47419, British Patent No. 1,455,271, JP-A-50-1
Oxidizing agents described in JP-A-01019, sulfinic acids or thiosulfonic acids described in JP-A-53-19825, 51-32
2-thiouracils described in No. 23, sulfur alone described in 51-26019, 51-42529, 51-81124, 55
-93149, disulfide and polysulfide compounds described in JP-A-51-57435, rosin or diterpenes described in JP-A-51-57435, polymer acids having a free carboxyl group or sulfonic acid group described in JP-A-51-104338, U.S. Pat. Thiazoline thione described in No. 4,138,265,
JP-A-54-51821, 1,2,4-triazole or 5-mercapto-1,2,4-triazole described in U.S. Pat.No. 4,137,079, and thiol described in JP-A-55-140883. Sulfinic esters, 1,2,3,4-thiatriazoles described in JP-A-55-142331, JP-A-59-46641, and
59-57233, dihalogen compounds or trihalogen compounds described in 59-57234, and further 59-111636
And the hydroquinone derivative described in JP-A-60-198540, and a combination of a hydroquinone derivative and a benzotriazole derivative described in JP-A-60-227255.

Still another particularly preferred antifoggant is described in
No. 60-218169, a polymer inhibitor described in Japanese Patent Application No. 60-262177, and an inhibitor compound having a ballast group described in Japanese Patent Application No. 60-263564. Is raised.

In addition, inorganic or organic bases or base precursors can be added. Examples of the base precursor include compounds that release a basic substance by decarbonizing by heating (for example, guanidinium trichloroacetate), and compounds that release amines by being decomposed by a reaction such as an intramolecular nucleophilic substitution reaction. For example, JP-A-56-130745 and JP-A-56-130745
132332, British Patent 2,079,480, U.S. Patent 4,06
No. 0,420, JP-A-59-157637, JP-A-59-166943.
And base releasing agents described in JP-A Nos. 59-180537, 59-174830, and 59-195237.

In addition, various additives used in the photothermographic material as needed, such as antihalation dyes, optical brighteners, antistatic agents, plasticizers, spreading agents, hardeners, matting agents,
Surfactants, anti-fading agents, etc., specifically, RD
(Research Disclosure) Magazine, Vol. 170, No. 17029, June 1978, and Japanese Patent Application No. 60-276615.

The photothermographic material can be obtained by forming a photographic structure layer on a support. Examples of the support that can be used here include a polyethylene film, a cellulose acetate film, a polyethylene terephthalate film, and a polyvinyl chloride. Synthetic plastic films, photographic base paper, printing paper, paper supports such as baryta paper and resin-coated paper, and further, a support obtained by applying and curing an electron beam-curable resin composition on these supports. No.

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

Usually, a yellow dye is combined with the blue-sensitive layer, a magenta dye is combined with the green-sensitive layer, and a cyan dye is combined with the red-sensitive layer. However, the present invention is not limited to this. For example, when a cyan dye is combined with a blue photosensitive layer, a magenta dye is combined with a green photosensitive layer and a yellow dye is combined with a red photosensitive layer, and a cyan dye is combined with a blue photosensitive layer, a yellow dye is combined with a green photosensitive layer, and a red photosensitive layer is combined. A configuration in which a magenta dye is combined in the layer can also be adopted. Also,
It is also possible to combine near-infrared photosensitive layers.

The configuration of each layer can be arbitrarily selected according to the purpose. For example, a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are sequentially formed on a support, and a blue-sensitive layer is sequentially formed on a support. , A green photosensitive layer and a red photosensitive layer, or a green photosensitive layer, a red photosensitive layer, and a blue photosensitive layer on a support in this order.

The photothermographic material can have a non-photosensitive layer such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer, and a release layer, in addition to the photothermographic layer.

Hereinafter, a method for forming a dye image in the case where a heat-developable color light-sensitive material is used as a color light-sensitive material will be described.

Various exposure means can be used for the heat-developable color light-sensitive material. Preferably, imagewise exposure to radiation containing visible light is used. Light sources for image exposure preferably used include, for example, a tungsten lamp, a halogen lamp, a xenon lamp, a mercury lamp, a laser light source, a CRT light source, a fluorescent tube, and a light emitting diode.

Original images for recording images on heat-developable color light-sensitive materials include natural subjects, reflection-type and transmission-type documents, linear images such as drawings and bar codes, color films having continuous gradation, color paper, etc. There are various types of image information such as photographic images and print images, image information captured by a video camera, image information sent from a television station, and image information obtained by computer graphics, and these can be used as original images.

These originals can be exposed simultaneously or separately on the same photosensitive material using two or more.

When exposing the heat-developable color light-sensitive material from the various originals described above, the blue, green, and red image information of the original are usually performed as in the case of contact printing or stretching printing from a color negative film to color paper, It is possible to convert the image information into the corresponding complementary colors (that is, yellow, magenta, and cyan) (in this case, the negative / positive conversion may be performed simultaneously). Can be converted into dye image information different from each complementary color.

The photothermographic material to be used in the invention is usually preferably at 80 ° C to 200 ° C, more preferably at 100 ° C to 170 ° C, preferably for 1 second to after imagewise exposure.
The development is carried out only by heating for 180 seconds, more preferably for 1.5 seconds to 120 seconds. The transfer of the diffusible dye to the image receiving layer may be performed simultaneously with the 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 development, or may be brought into close contact with the image receiving member after thermal development. Alternatively, the transfer may be performed by closely contacting after supplying water and further heating if necessary. Further, pre-heating may be performed in a temperature range of 70 ° C. to 180 ° C. before exposure.

As the heating means, all methods applicable to ordinary photothermographic materials can be used.For example, the heating means can be brought into contact with a heated block or plate, or a heat roller or a heat drum, or can be passed through a high-temperature atmosphere. Or using high-frequency heating, or providing a conductive material containing a conductive 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 member for thermal transfer, and utilizing Joule heat generated by energization. Can also. The heating pattern is not particularly limited. For example, a method of preheating (preheating) and then heating again, a high temperature for a short time, or a low temperature for a long time, a continuous increase, a continuous decrease, or a repetition thereof. Although a discontinuous heating is also possible, a simple pattern is preferable.

 The heating may be a method that proceeds simultaneously with the exposure.

The time from exposure to heating (thermal development) is 1 second to
It is preferably 24 hours, more preferably 5 seconds to 12 hours. However, when exposure and heat development are performed by the same device,
1 second to 10 minutes, preferably 2 seconds to 5 minutes, particularly preferably 5 seconds
Seconds to 2 minutes.

〔Example〕

Hereinafter, specific examples and comparative examples of the present invention will be described.
However, it is needless to say that the present invention is not limited by the embodiments described below.

Example 1 (Preparation of Image Receiving Material) A gelatin layer containing barium sulfate was provided on one side of a paper support of 160 g / m ² , and an image receiving layer having the following composition was further applied thereon. 1-21 were created. In addition, the amount of addition was shown per 1 m ^{2 of the} image receiving material unless otherwise specified.

(Preparation of Photothermographic Material) A photothermographic material having the layer constitution shown in Table 1 was prepared. The amount of each material used is the amount per 1 m ^{2 of the} photothermographic material, and the photosensitive silver halide emulsion and silver 5-methylbenztriazole are each expressed in terms of silver.

(Image transfer etc. and evaluation) The obtained photothermographic material is subjected to imagewise exposure, and the above-mentioned image receiving materials 1 to 21 are overlapped so that the image receiving layer overlaps the protective layer of the photosensitive material. Heat development treatment was performed for 1 minute and 20 seconds (at this time, 20 seconds after the start of development, lamination was performed with a pressure roller of 10 kg / cm ² ). After the development, when the photosensitive material was peeled off, cyan, yellow, and magenta dye images were obtained on the image receiving layer of the image receiving material.

The obtained dye image was subjected to reflection density measurement using a PDA-65 type reflection densitometer (manufactured by Konica Corporation), and the results shown in Table 2 were obtained. In the table, B, G, and R represent yellow dye image, magenta dye image, and cyan dye image, respectively.
This indicates that the reflection density measurement was performed using blue, green, and red monochromatic lights, respectively.

Further, the above-mentioned image-receiving material was treated under the conditions of 50 ° C. and 80% relative humidity.
After storage for days, the same processing was performed as described above, and a storage stability test of the image receiving material was performed. Table 2 shows the results.

From the results shown in Table-2, the image receiving materials 8 to 21 which were the samples in which the thermal solvent of the present invention was added to the image receiving layer could obtain dye images having high maximum densities, while the comparative thermal solvent 1 The image receiving materials 2 to 4, which are samples using the samples No. 2 and No. 2, can obtain a relatively high maximum density before storage.
When stored at 80% for 3 days, it can be seen that the maximum concentration obtained is reduced. Further, it can be seen that, in the image receiving materials 6 and 7 which are the samples using the comparative thermal solvent-3, even when the thermal solvent is added to the image receiving layer, almost no increase in the maximum density is obtained. Table 2 shows that the image receiving materials 8 to which are the samples according to the present invention.
It is clear that Sample No. 21 has a higher maximum density than that of the image receiving materials 1 to 6 which are the comparative samples, and that the reduction in the maximum density is small even after storage.

Example-2 The sample obtained as a result of the heat development in Example-1 was irradiated with light for 240 hours using a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) to examine the photobleaching property. 1.0
Of the dye [= 100 × (1.0−density after light irradiation at an initial density of 1.0)] and the increased density of stain on a white background.

 The results are shown in Table-3.

From the results shown in Table 3, the sample using the thermal solvent according to the present invention has a higher dye fading ratio than Sample-1 using no thermal solvent in the image receiving layer and Samples-2 to 7 using the comparative thermal solvent. Is small. At this time, the stain is not increased.

Example 3 (Preparation of Image Receiving Material) On the paper support coated with the barium sulfate layer used in Example 1, two polyvinyl chloride layers having the following constitutions were applied, and the image receiving materials 22 to 29 were used. Created.

The obtained image receiving materials 22 to 29 were mixed at 50 ° C. and a relative humidity of 80% for 3 hours.
After storage for days, the photothermographic material used in Example 1 was subjected to a heat development treatment in the same manner as in Example 1 to obtain yellow, magenta and cyan dye images on the image receiving material. When the highest concentration and the lowest concentration were determined for this material in the same manner as in Example 1, the results shown in Table 4 were obtained.

Further, for each image-receiving material, after heat development, an exposure was applied to the heat-developable photosensitive material so as to give a substantially neutral gray having a reflection density of about 0.4, and then each of the image-receiving materials was used. The development was performed under the conditions. At this time, each image receiving material
Each of the image receiving materials was processed into 20 sheets each having a size of 18 cm × 12 cm. With respect to the obtained sample, occurrence of black spot-like coating failure was visually judged, and the result was converted into the number per 1 m ^{2 of} the image receiving material, and the results are shown in Table 4.

From the results shown in Table-4, even when the image receiving material was made to have the two-layered image receiving layer made of polyvinyl chloride as described above, the sample using the thermal solvent of the present invention (image receiving material 25) was used. ~ 28) is found to give a high maximum concentration.

Further, when the comparative thermal solvent was used, the coating failure increased considerably as compared with the case where the thermal solvent was not used, but it was found that the coating failure hardly increased in the sample of the present invention.

[Effects of the Invention] As described above, the image-receiving material of the present invention has a high maximum density of the obtained image and a small decrease in the maximum density obtained even when used after storage over time. It can be obtained without causing inconveniences such as a decrease in photobleaching rate and coating failure.

 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Hidenobu Oya 1 Sakuracho, Hino-shi, Tokyo Konica Corporation (56) References JP-A-61-210352 (JP, A) JP-A-62-136645 ( JP, A) JP-A-62-138852 (JP, A) JP-A-63-53548 (JP, A) JP-A-2-863 (JP, A)

Claims (1)

(57) [Claims] 1. An image-receiving material for thermal development comprising at least one compound represented by the following general formula (I). General formula (I) In the formula, R ¹ represents a hydrogen atom or an alkyl group, and R ² represents an alkyl group, an alkenyl group, or an aryl group. R ¹ , R
Each of the above groups represented by ² includes those having a substituent. R
³ represents an alkylene group. R ⁴ represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group (each of the above groups includes those having a substituent), a halogen atom, or CONHR ⁵
(R ⁵ represents an alkyl group or a hydrogen atom). k represents 0 or 1, l represents 0 or 1, and m represents 0 or 1.
n represents 0 or 1, and p represents 0 or an integer of 1 to 4. However, when R ¹ is a hydrogen atom, 1 represents 1. K,
l, m, n are not all 0, and both l, m are 0
Thus, k and n are not both 1. When n = 0,
l represents 1.