JP2524523B2 - Image recording method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a step of imagewise exposing an image recording material containing silver halide to form a latent image of silver halide; It relates to an image recording method comprising a step of developing a latent image and a step of forming a polymer image by exposing the above image recording material substantially uniformly in the presence of a photopolymerization initiator and a polymerizable compound.

BACKGROUND OF THE INVENTION A method of forming a polymer image in an imagewise manner using a photopolymerization initiator composed of an organic compound is well known. However, the photopolymerization initiator has low sensitivity as compared with silver halide and requires long time or strong exposure. Therefore, the use of the image recording method using the photopolymerization initiator is limited due to the limitation of the sensitivity of the photopolymerization initiator.

On the other hand, a method of causing a polymerization reaction by using silver halide as an optical sensor is also well known. For example, a method of causing a polymerization reaction by radicals generated from a reducing agent oxidized in the development process of silver halide is disclosed in JP-B-45-11149.
45-30338, 46-6581, 46-21723, and
47-12638, 47-14667, 47-14668, 47-1
No. 4669, No. 46-16357, No. 47-18585, No. 47-20741
No. 49-1569, No. 49-1570, No. 49-10697, JP-A No. 57-13862, No. 57-142638, No. 57-176033,
No. 58-107529, No. 58-169143 and No. 58-174947. In addition, a method of generating radicals from a peroxide to cause a polymerization reaction by a redox method of developed silver and a peroxide (described in JP-B-41-18862), silver ions and peroxides remaining in unexposed areas A method of generating a radical from a peroxide by an oxidation-reduction reaction to cause a polymerization reaction (described in Japanese Patent Publication No. 39-2657), iron (I) which is developed by developing a silver halide with an iron (I) salt and remains in an unexposed area. A method in which a polymerization reaction is caused by radicals generated from a peroxide by a redox reaction between a salt and a peroxide (described in US Pat. No. 30,29,145), and a reducing agent remaining in an unexposed area directly after developing a silver halide. Method of causing polymerization reaction (Japanese Patent Laid-Open No. 55-14
9939 publication)) etc. In principle, these methods can form a polymer image with a sensitivity close to that of silver halide. However, each method requires a wet treatment in the process, which is a great limitation in designing equipment.

An image recording method which solves the problems of both the method using a photopolymerization initiator and the method using a silver halide as an optical sensor as described above is disclosed in JP-A-61-75342 (US Pat. No. 4349098). )It is described in. This method comprises the steps of imagewise exposing an image recording material containing silver halide to form a latent image of silver halide, developing a latent image of silver halide using a reducing agent and a photopolymerization initiator and It comprises a step of forming a polymer image by exposing the above image recording material substantially uniformly in the presence of a polymerizable compound.

The reducing agent used in the image recording method described in JP-A-61-75342 is (1) acting as a developing agent for silver halide, and (2) polymerizable vinyl monomer (ethylenically unsaturated polymerizable). The compound) acts as a polymerization inhibitor, and further has the property of (3) losing the action as a polymerization inhibitor after the silver halide is developed. By using such a reducing agent, in the above-described image recording method, the polymerizable compound in the portion without the reducing agent (the portion where the oxidized form of the reducing agent is formed) is photopolymerized to form a polymer image. That is, this image recording method is a system in which a polymer image is formed on the exposed portion in latent exposure.

[Summary of the Invention] The present inventors further studied the image forming method described in JP-A-61-75342, and found that a system in which a polymer image was formed in an unexposed portion in imagewise exposure was used. It became clear that is also possible.

In order to carry out a system in which a polymer image is formed on the unexposed area, it is necessary to use, as a reducing agent, a compound which forms an oxidant having a polymerization inhibiting effect on the polymerizable compound after development of silver halide. The reducing agent itself having such properties is known in the image recording method described in JP-A No. 61-243449, in which the silver halide and the thermal polymerization initiator are used in combination.

JP-A-61-243449 discloses, as specific examples of the reducing agent having the above-mentioned properties, 1-phenyl-3-pyrazolidone (phenidone), 4-methyl-1-phenyl-3-pyrazolidone, 4,4- Dimethyl-1-phenyl-3-pyrazolidone, 4-ethyl-1-phenyl-3-pyrazolidone, 5-methyl-1-phenyl-3-pyrazolidone, 5
-Phenyl-3-pyrazolidone, 5,5-dimethyl-1-
Phenyl-3-pyrazolidone, 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone, 4-methyl-4
-Hydroxymethyl-1-phenyl-3-pyrazolidone, 4,5-dimethyl-1-phenyl-3-pyrazolidone, 1-p-methoxyphenyl-3-pyrazolidone, 1
-P-tolyl-3-pyrazolidone, 2-hydroxymethyl-1-phenyl-3-pyrazolidone, p (m or o) -aminophenol, 2,6-dichloro-p-aminophenol, 2,6-dimethyl-p -Aminophenol,
3,5-Dimethyl-p-aminophenol, hydroquinone, methylhydroquinone, catechol, p-tert-butylcatechol, chlorohydroquinone, p-methoxyphenol, p-anisidine, o-anisidine, o (m
Or p) -phenylenediamine, 2,4-tolylenediamine and 3,4-tolylenediamine.

The image recording method using a silver halide and a thermal polymerization initiator in combination includes (1) imagewise exposing an image recording material containing a silver halide, a reducing agent having the above properties, a polymerizable compound and a thermal polymerization initiator. To form a latent image of silver halide, and (2) the image recording material is heated to develop the latent image of silver halide, and an oxidant of the reducing agent (having a polymerization inhibiting effect) is not formed. It consists of two steps of thermally polymerizing a part of the polymerizable compound to form a polymer image.

The image recording method using the silver halide and the photopolymerization initiator as described above has a more complicated processing step (comprising three steps) as compared with the image recording method using the silver halide and the thermal polymerization initiator in combination. Is. Therefore, the image recording method in which the silver halide and the photopolymerization initiator are used in combination is
It is required to use a compound having the above-mentioned action and excellent storage stability. However, the above-mentioned JP-A-61-1
The reducing agent of Japanese Patent No. 243449 did not satisfy this requirement. For the above reasons, no system has been attempted at all in the image recording method in which a silver halide and a photopolymerization initiator are used in combination, in which a polymer image is formed in the unexposed area.

An object of the present invention is to provide a system in which a polymer image is formed in an unexposed area in an image recording method using a silver halide and a photopolymerization initiator in combination.

The present inventors analyzed the chemical structure of the reducing agent and found that the compound represented by the formula [I] described later forms an oxidant having a strong polymerization inhibiting action after development of silver halide. . Further, this compound is disclosed in JP-A-61-24
Compared to the reducing agent described in Japanese Patent No. 3449, the storage stability is also excellent. By using this compound as a reducing agent, it has become possible to put a system in which a polymer image is formed in an unexposed area into practical use in an image recording method using both a silver halide and a photopolymerization initiator.

The present invention comprises (1) a step of imagewise exposing an image recording material containing silver halide to form a latent image of silver halide; An image recording method comprising the steps of developing a latent image; and forming a polymer image by exposing the above image recording material substantially uniformly in the presence of a photopolymerization initiator and an ethylenically unsaturated polymerizable compound. Then, as the reducing agent, a compound that forms an oxidant having a polymerization-inhibiting action of an ethylenically unsaturated polymerizable compound after development of silver halide is used, and thereby the polymerizable compound in a portion where the oxidant is not formed is It is intended to provide an image recording method characterized by forming a polymer image by photopolymerization.

(2) The reducing agent is preferably a compound represented by the following formula [I].

[In the above formula [I], R ¹ is a monovalent organic group bonded to the benzene ring through a hetero atom having a lone electron pair, and R ² is a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Is a monovalent group selected from the group consisting of (each group may have a substituent), m is 1, 2, 3 or 4, and n is the formula 0 ≦ n ≦ (4-m And an aromatic ring, an aliphatic ring, and / or a heterocycle may be condensed with the benzene ring.] The image recording method of the present invention may also be in the following embodiments. preferable.

(3) The image recording material at the time of imagewise exposure contains a reducing agent, a photopolymerization initiator and a polymerizable compound.

(4) The exposure dose in the imagewise exposure is 10 ^{-2 to} 10 ⁴ cms, and the exposure dose in the uniform exposure is 10 ^{3 to} 10 ⁸ erg / cm ^2.
Is.

(5) The development processing is performed by heating.

(6) The image recording material that has been subjected to the uniform exposure is pressed while being superimposed on the image receiving material, and the unpolymerized polymerizable compound is transferred to the image receiving material.

(2-2) R ¹ in the above formula [I] is a monovalent group represented by the following formula [II].

-(VI B) -R ³ [II] [In the above formula [II], (VI B) is a divalent group selected from the group consisting of an oxygen atom, a sulfur atom and a selenium atom, and R ³ Is a monovalent group selected from the group consisting of an alkyl group, an aryl group and a heterocyclic group (each group may have a substituent)] (2-3) R in the above formula [I] ¹ is the following formula [III]
It is a monovalent group represented by.

[In the above formula [III], (VB) is a trivalent group consisting of a nitrogen atom or a phosphorus atom, and R ⁴ is a group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and a heterocyclic group. A valent group (each group may have a substituent), and R ⁵ is an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group or It is a monovalent group selected from the group consisting of carbamoyl groups (each group may have a substituent)] (3-2) The above image recording material is a silver halide on a support and a reducing agent. A recording layer containing a photopolymerization initiator and a polymerizable compound is provided, and the silver halide, the reducing agent, the photopolymerization initiator and the polymerizable compound are contained in the recording layer in the form of microcapsules. .

[Advantages of the Invention] In recent years, along with the development of color hard copy, there is an increasing demand for image processing such as color tone conversion. In order to realize this, it is essential that the information to be copied is once converted into an electric signal (digitalized). In the case of the recording method by forming a polymer image, a method of obtaining a color image by transferring the unpolymerized portion to an image receiving material is general. Considering this together with the above-mentioned problem of electric signal formation, the method in which the unexposed portion is a polymer image (the present invention) is more advantageous than the method in which the exposed portion is a polymer image.

According to the research conducted by the present inventors, in the latter case, it is necessary to read a portion without information (a background portion such as a white background) and expose this portion, whereas in the former case (the present invention),
It is very efficient because it is sufficient to read the information part and give exposure corresponding to the information part. In particular, the effect of the present invention is remarkable when the copy target is a document containing many characters.

In addition, it is conceivable to use laser light as a light source for imagewise exposure in association with digitalization of information. When laser light is used as the light source, it is possible to perform imagewise exposure with high resolution even on a document having very fine lines. Of course, even if laser light is used as a light source, a polymer image having high sharpness cannot be formed if the resolution of the treatment after imagewise exposure is low.

According to the study by the present inventors, a system in which a polymer image is formed in an unexposed area in imagewise exposure has a higher resolution and a fine line image than a system in which a polymer image is formed in an exposed area. The expressiveness of is excellent. Therefore, the image recording method of the present invention can record a clear image with high sharpness. The effect of the present invention is particularly remarkable when laser light is used as a light source for imagewise exposure.

The compound represented by the formula [I] forms an oxidant having a strong polymerization inhibiting action, as described above. Therefore, by using this compound, the image recording method of the present invention can record a very clear image. Further, this compound is also superior in stability during storage as compared with the reducing agent described in JP-A No. 61-243449. Therefore,
The compound represented by the formula [I] can be contained as a reducing agent in the image recording material before imagewise exposure.

DETAILED DESCRIPTION OF THE INVENTION The image forming method of the present invention uses, as a reducing agent, a compound that forms an oxidant having a polymerization-inhibiting effect on a polymerizable compound after development of silver halide. As the reducing agent, the compounds described in JP-A No. 61-243449 described above can be used.

However, in the image forming method of the present invention, it is preferable to use the compound represented by the following formula [I] as the reducing agent. Some of the compounds represented by the following formula [I] are
It is known as a developing agent in the field of heat development type silver salt photography. However, it was not known at all to form an oxidant having a polymerization-inhibiting effect on a polymerizable compound after development of silver halide.

In the above formula [I], R ¹ is a monovalent organic group that bonds the benzene ring through a heteroatom having a lone electron pair.

R ² is a monovalent group selected from the group consisting of a halogen atom, an alkyl group, an aryl group and a heterocyclic group. In addition,
Each group may have one or more substituents.

 m is 1, 2, 3 or 4.

 n is an integer that satisfies the expression 0 ≦ n ≦ (4-m).

An aromatic ring, an aliphatic ring and / or a heterocycle may be condensed with the Hensen ring in the above formula [I]. The ring fused to the benzene ring may have one or more substituents. However, the above-mentioned benzene ring has the above-mentioned R ¹ and R ²
It does not have a substituent other than.

Incidentally, two or more compounds represented by the formula [I] may be condensed to form a multimer. When forming a multimer, it is preferable to bond via R ¹ or R ² in the formula [I].

Hereinafter, the compound represented by the formula [I] will be further described.

The hetero atom having a lone pair of electrons contained in R ¹ is preferably an oxygen group atom or a nitrogen group atom. Specific examples of the hetero atom include: and Can be mentioned. The above Means a lone pair of electrons.

R ¹ in the formula [I] is a monovalent group represented by the following formula [II] (when the hetero atom is an oxygen group atom) or the formula [III] (when the hetero atom is a nitrogen group atom). It is preferable.

-(VI B) -R ³ [II] In the above formula [II], (VI B) is a divalent group selected from the group consisting of an oxygen atom, a sulfur atom and a selenium atom. A sulfur atom is particularly preferred.

R ³ is a monovalent group selected from the group consisting of an alkyl group, an aryl group and a heterocyclic group. In addition, each group may have one or more substituents.

In the above formula [III], (VB) is a trivalent group composed of a nitrogen atom or a phosphorus atom. A nitrogen atom is particularly preferred.

R ⁴ is a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and a heterocyclic group. In addition, each group may have one or more substituents.

R ⁵ is a monovalent group selected from the group consisting of an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, a carbamoyl group and a sulfamoyl group. Acyl group, alkylsulfonyl group and arylsulfonyl group are particularly preferable. In addition, each group may have one or more substituents.

R ⁴ and R ⁵ may be the same.

The halogen atom constituting R ² in the formula [I] may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Chlorine and bromine atoms are preferred.

The number of carbon atoms of the alkyl group constituting R ² , R ³ , R ⁴ and R ⁵ is preferably 1 to 22. The alkyl group may have a linear structure or a branched structure. Further, the alkyl group may form a cyclic structure. That is, the “alkyl group” in the present specification includes a cycloalkyl group. The alkyl group may have a substituent such as a halogen atom, an aryl group (eg, a phenyl group), an alkoxy group, a hydroxyl group and a cyano group. The "alkyl group" in the present specification includes an aralkyl group (an alkyl group having an aryl group as a substituent).

Specific examples of the aryl group constituting R ² , R ³ , R ⁴ and R ⁵ include a phenyl group, a naphthyl group, an anthryl group and a phenanthryl group. Phenyl is particularly preferred. The aryl group is an alkyl group, an aryl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, an amide group, an alkylsulfonyl group, an arylsulfonyl group, a carboxyl group, an acyl group, a hydroxyl group, a cyano group, a nitro group, an amino group, Carbamoyl group,
It may have a substituent such as a sulfamoyl group.

Specific examples of the heterocyclic group constituting R ² , R ³ , R ⁴ and R ⁵ include a pyridyl group, a pyrimidyl group, an imidazoyl group, a thiazoyl group, an oxazolyl group, a succinimide group and a hydantoyl group. The heterocycle may be condensed with an aromatic ring such as a benzene ring or a naphthalene ring and / or another heterocycle. The heterocyclic group is a halogen atom or an alkyl group (preferably having 1 to 1 carbon atoms).
0), an alkoxy group (preferably having 1 to 1 carbon atoms)
0) and may have a substituent such as a nitro group.

m is 1, 2, 3 or 4. m is preferably 1
Or 2. When m is 2 or more, a plurality of R ¹ 's may be different from each other.

n is an integer that satisfies the expression 0 ≦ n ≦ (4-m). n
Is preferably 0 or 1. When n is 2 or more, a plurality of R ² may be different from each other.

The acyl group constituting R ⁵ in the formula [III] is represented by the following formula [III-a].

^{-CO-R 6 [III-a} ] formula [III-a], R ⁶ is an alkyl group, a monovalent group selected from the group consisting of aryl group and a heterocyclic group. In addition, each group may have one or more substituents.

The alkylsulfonyl group and arylsulfonyl group constituting R ⁵ in the formula [III] are represented by the following formula [III-b]
Is represented by

In ^{_{-SO 2 -R 8 [III-b}} ] formula [III-b], R ⁸ is an alkyl group or an aryl group. In addition, each group may have one or more substituents.

The alkoxycarbonyl group constituting R ⁵ in the formula [III] is represented by the following formula [III-c].

—CO—OR ⁹ [III-c] In the formula [III-c], R ⁹ is an alkyl group.
The alkyl group may have one or more substituents.

The carbamoyl group constituting R ⁵ in the formula [III] is
It is represented by the following formula [III-d].

—CO—NR ¹⁰ R ¹¹ [III-d] In the formula [III-d], R ¹⁰ and R ¹¹ are each a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and a heterocyclic group. It is a base. In addition, each group may have one or more substituents.

The sulfamoyl group constituting R ⁵ in the formula [III] is represented by the following formula [III-e].

—SO ₂ —NR ¹² R ¹³ [III-e] In the formula [III-e], R ¹² and R ¹³ are each a monovalent selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and a heterocyclic group. It is the basis of In addition, each group may have one or more substituents.

Regarding the alkyl group, aryl group, heterocyclic group and their substituents constituting R ^{6 to} R ¹³ in the above formulas [III-a] to [III-e], R ² , R ³ and R ⁴ described above can be used. And an alkyl group, an aryl group, a heterocyclic group and their substituents which compose R ⁵ .

Next, typical specific examples of the reducing agent that can be used in the present invention are shown.

The representative synthetic examples of the reducing agent used in the present invention are shown below. Other reducing agents can be synthesized by the same method.

[Synthesis Example 1] Synthesis of 1,4-dimethoxy-2-isopalmitoylaminobenzene 10.7 g of 2,5-dimethoxyaniline and 6.00 ml of pyridine
Was dissolved in 30 ml of acetonitrile, and 19.2 g of isopalmitoyl chloride was added dropwise over 10 minutes while stirring at room temperature. After stirring for a further 30 minutes, the reaction mixture was poured onto water and extracted with ethyl acetate. The organic layer was washed with water and dried over sodium sulfate. The desiccant was removed by filtration and the solvent was distilled off to obtain 27.0 g of a colorless oily substance.

Synthesis of Compound (1) 1,4-Dimethoxy-2-isopalmitoylaminobenzene (27.0 g) was dissolved in chlorobenzene (130 ml), and anhydrous aluminum chloride (21.3 g) was added little by little while stirring at room temperature. It heated up at 90 degreeC and stirred for 3 hours. After cooling down, water 135m
l was added in small portions. Chlorobenzene was removed by steam distillation, and the mixture was extracted with ethyl acetate. After washing the organic layer with water,
Dry over sodium sulfate. The desiccant was removed by filtration, and the solvent was distilled off to obtain a pale yellow oily substance. Crystallization was performed from a mixed solvent of methylene chloride-n-hexane to obtain 21.5 g of colorless crystals of compound (1). The melting point was 74-76 ° C.

[Synthesis Example 2] Synthesis of 4-acetoxy-2-n-hexadecyloxyacetophenone 2-n-hexadecyloxy-4-hydroxyacetophenone (50.0 g) and pyridine (1.30 ml) were dissolved in DMF (150 ml), and the mixture was stirred at room temperature with acetic anhydride. 15.0 ml was added dropwise over 10 minutes. The mixture was further stirred at room temperature for 2 hours. The reaction mixture was poured onto water, and the precipitated colorless crystals were collected by filtration, washed with water and dried to obtain 52.9 g of colorless crystals.

Synthesis of 1,4-diacetoxy-2-n-hexadecyloxybenzene 4-acetoxy-2-n-hexadecyloxyacetophenone 75.0 g, concentrated sulfuric acid 4.0 ml and glacial acetic acid 40 ml are dissolved in chloroform 350 ml and stirred at room temperature. While adding 80.0 g of m-chloroform benzoic acid little by little. The reaction mixture was poured onto water and extracted with ethyl acetate. The organic layer was washed with water and aqueous sodium hydrogen carbonate, and dried over sodium sulfate. The desiccant was filtered off by filtration and the solvent was distilled off to obtain 60.0 g of a pale yellow powder.

Synthesis of compound (14) 1,4-diacetoxy-2-n-hexadecyloxybenzene 60.0 g, hydroxylamine hydrochloride 38.7 g and sodium acetate 45.3 were dispersed in 300 ml of methanol and refluxed for 1 hour. The reaction mixture was poured onto water, and the precipitated crystals were collected by filtration and washed with water. Recrystallization from methanol gave 37.0 g of colorless crystals of compound (14). The melting point was 106-108 ° C.

[Synthesis Example 3] Synthesis of n-hexadecane-sulfenyl-p-benzoquinone 100 g of p-benzoquinone was dispersed in 500 ml of methanol, and 120 g of n-hexadecanethiol was added to the mixture while refluxing.
It was dripped over a period of minutes. Reflux for an additional 30 minutes. After cooling, the precipitated crystals were collected by filtration, washed with methanol and dried. 126 g of yellow crystals were obtained.

Synthesis of compound (15) n-hexadecane sulphenyl-p-benzoquinone 12
6 g was dissolved in 600 ml of ethyl acetate, and 43.7 g of an 85% aqueous solution of N, N-diethylhydroxylamine was added dropwise over 20 minutes while refluxing. Reflux for an additional 30 minutes. The reaction mixture was poured onto diluted hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with water and brine and then dried over sodium sulfate. The desiccant was removed by filtration and the solvent was distilled off to obtain pale yellow crystals. Recrystallization from acetonitrile gave 120 g of colorless crystals of compound (15). The melting point was 83-84 ° C.

[Synthesis Example 4] Synthesis of compound (23) n-palmitoylamino-p-hydroquinone 60.0 g,
Dodecyl aldehyde 22.8g and anhydrous calcium chloride 50.
0 g was dispersed in 500 ml of ethyl acetate, and 15.0 ml of concentrated hydrochloric acid was added with stirring at room temperature. The reaction concentration was adjusted to 27 to 30 ° C, and the mixture was stirred for 8.5 hours. The insoluble matter was filtered off, the organic layer was washed with water,
After washing with brine, it was dried over sodium sulfate. The desiccant was filtered off and the solvent was distilled off to give a yellow oil.
Crystallization was performed from a mixed solvent of ethyl acetate-n-hexane,
37.6 g of colorless crystals of compound (23) were obtained. Melting point 173-174
° C.

In the image recording method of the present invention, as the reducing agent, the compounds described above may be used alone or in combination of several kinds.

In the light-sensitive material, the above-mentioned reducing agent is 1 mol of silver (including the above-described silver halide and an organic silver salt as an optional component).
It is preferably used in the range of 0.1 to 1500 mol% based on the total amount. A more preferable range of use is 10 to 500 mol%.

In the image recording method of the present invention, the above formula (I)
The reducing agent represented by may be used in combination with the reducing agent described in JP-A-61-243449. Further, a reducing agent generally known as a developing agent in the field of silver salt photography may be used in combination. Known reducing agents as developing agents include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones,
3-aminopyrazoles, 4-amino-5-pyrazolones, 5-aminouracils, 4,5-dihydroxy-6-
Aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o-
Alternatively, p-sulfonamidonaphthols, 2-sulfonamidoindanones, 4-sulfonamido-5-pyrazolones, 3-sulfonamidoindoles, sulfonamidepyrazolobenzimidazoles, sulfonamidepyrazolotriazoles, α- There are sulfonamide ketones and the like.

Specific examples of the developer include pentadecylhydroquinone, 5-t-butylcatechol, p- (N, N-diethylamino) phenol, 1-phenyl-4-methyl-
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-heptadecylcarbonyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamino-4-hexadecyloxy-5-t-octylphenol, 2-phenyl Sulfonylamino-4-t-butyl-5-hexadecyloxyphenol, 2- (N-butylcarbamoyl) -4-phenylsulfonylaminonaphthol, 2- (N-methyl-N-octadecylcarbamoyl) -4-sulfonylaminonaphthol Etc. can be mentioned.

Regarding various reducing agents (developing agents) that can be used in combination with the reducing agent of the present invention, see “The Theory of” by T. James.
the Photographic Process "Fourth Edition, pp. 291-334 (1977
Year), Research Disclosure Magazine Vol. 170, No. 17029, June 1978 (pages 9-15), and the same magazine, Vol. 176, 197
It is also described in December 1976, No. 17643 (pages 22 to 31).

When two or more reducing agents are used in combination, the reducing agents may interact with each other by first promoting the reduction of silver halide (and / or organic silver salt) by so-called superadditivity. In addition, the polymerization of the polymerizable compound is suppressed via the redox reaction with the other reducing agent in which the oxidant of the first reducing agent produced by the reduction of silver halide (and / or organic silver salt) coexists. Things can be considered. However,
In the actual use, it is difficult to specify which action the reactions as described above can occur at the same time.

Hereinafter, in the image recording method of the present invention, (I) a step of imagewise exposing an image recording material containing silver halide to form a latent image of silver halide, (II) the above image recording material using a reducing agent To develop the latent image of silver halide contained in, and (III) exposing the above image recording material substantially uniformly in the presence of a photopolymerization initiator and an ethylenically unsaturated polymerizable compound, The process of forming an image will be sequentially described.

(I) In the imagewise exposure of the image recording material, various exposure means can be used. Examples of the light source include a tungsten lamp, a halogen lamp, a mercury lamp, a fluorescent lamp, a xenon lamp, a laser beam, an LED and a CRT. Then, a latent image of silver halide is obtained by imagewise exposure to radiation including visible light. The type of light source and the exposure amount can be selected according to the photosensitive wavelength of silver halide (in the case of dye sensitization, the sensitized wavelength) and the sensitivity.
The original image may be a black and white image or a color image. The exposure amount in imagewise exposure is generally 10 ^{-2 to} 10 ⁴ cms (Cd (candela) · m · sec).

In the embodiment in which the image recording material at the time of imagewise exposure contains a photopolymerization initiator and a polymerizable compound, the polymerizable compound in the exposed portion is photopolymerized by the action of the photopolymerization initiator in the imagewise exposure. There is a possibility. However, since the sensitivity of the photopolymerization initiator is significantly lower than that of silver halide, the action of the photopolymerization initiator in imagewise exposure can be substantially ignored.

The development treatment of the image recording material (II) may be performed using the developing solution containing the reducing agent. However, the heat development treatment performed by heating the image recording material is
Since it is a dry process, it has the advantages that it is easy to operate and can be processed in a short time. Therefore, the heat development process is particularly excellent as the development process for the photosensitive material.

As the heating method in the thermal development treatment, various conventionally known methods can be used. For example, a hot plate, heat roller, infrared heater or the like can be used. Further, a heating element layer may be provided on the image recording material to be used as a heating means. Further, the heat development treatment may be carried out while suppressing the amount of oxygen existing in the image recording material. As a specific means for suppressing the amount of oxygen present in the image recording material, it is preferable to carry out the heat development treatment in a state where a liquid (preferably water) is permeated into the image recording layer. The heating temperature is generally 80 ° C to 200 ° C, preferably 1
The temperature is 00 ° C to 160 ° C. The heating time is generally 1 second to 5 minutes, preferably 5 seconds to 1 minute.

(III) The light source used for uniform exposure of the image recording material is
It is the same as that used for the imagewise exposure described above. The exposure dose during uniform exposure is preferably 10 ^{3 to} 10 ⁸ erg / cm ² , and more preferably 10 ^{4 to} 10 ⁶ erg / cm ² .

The image forming method of the present invention has the following two modes depending on the form of the image recording material used.

The first mode is a case where a silver halide and a photopolymerization initiator are contained in the same image recording material. In this case, the silver halide and the photopolymerization initiator are preferably contained in the same layer. Furthermore, it is preferable that the reducing agent and the polymerizable compound are also contained in the same recording material.

A first aspect of the image forming method of the present invention is an image recording material having a recording layer containing a silver halide, a reducing agent, a photopolymerization initiator and an ethylenically unsaturated polymerizable compound on a support (I). Imagewise exposing to form a latent image of silver halide; (II) heating the image recording material to develop the latent image of silver halide; and (III) substantially uniformizing the image recording material. It preferably comprises the step of exposing to light and forming a polymer image.

The second mode is a case of using an image recording material in which a layer containing silver halide and a layer containing a photopolymerization initiator are provided on different supports. Hereinafter, the support provided with a layer containing silver halide is referred to as a silver halide element, and the support provided with a layer containing a photopolymerization initiator is referred to as a photopolymerization initiator element.

The second embodiment of the image forming method of the present invention comprises (I) a step of imagewise exposing a silver halide element to form a latent image of silver halide, and (II) a reducing agent contained in the silver halide element. The heat-development or water-development of the silver halide element, and the step of developing the silver halide element with an aqueous solution containing the reducing agent when the reducing agent is not contained, (III-
a) superposing the developed silver halide element and the photopolymerization initiator element, or superposing and then heating to transfer the reducing agent remaining in the silver halide element to the photopolymerization initiator element, and (III-b) leaving the silver halide element and the photopolymerization initiator element in a superposed state, or after separating the photopolymerization initiator element, exposing the photopolymerization initiator element substantially uniformly, The process comprises forming a polymer image.

However, it is particularly preferable to carry out the image forming method of the present invention according to the first aspect.

As described above, a polymer image can be obtained according to the image recording method of the present invention. The unpolymerized polymerizable compound can be removed by washing with a suitable solvent. Alternatively, a dye or pigment can be fixed to the polymer to obtain a dye image. Further, the dye may be bleached (bleached) using an unpolymerized ethylenically unsaturated polymerizable compound to form an image.

Further, an image can be formed on the image receiving material by using the image receiving material.

By pressing the image recording material on which the polymer image is obtained and the image receiving material in a superposed state, the unpolymerized polymerizable compound is transferred to the image receiving material, and an image can be obtained on the image receiving material. Various conventionally known methods can be used for the pressing means.

Further, in an embodiment in which the image recording material contains a color image forming substance, a polymer image is formed, thereby immobilizing the color image forming substance in the cured portion. Then, by pressing the image recording material and the image receiving material in a superposed state, the color image forming substance in the uncured portion is transferred to the image receiving material, and a color image can be obtained on the image receiving material.

After forming an image on the image receiving material as described above,
As in the image forming method described in Japanese Patent Application No. 61-55501, the image receiving material may be heated. The above method also has an advantage that the unpolymerized polymerizable compound transferred onto the image receiving material is polymerized, and the preservability of the obtained image is improved.

INDUSTRIAL APPLICABILITY The image recording method of the present invention has many applications such as black and white or color photographing and printing, printing, printing plate, X-ray photographing, medical photographing (for example, ultrasonic diagnostic machine CRT photographing), computer graphic hard copy, copying machine and the like. There is.

Next, the image recording material used in the image recording method of the present invention will be described. As described above, the image recording material preferably has a recording layer containing a silver halide, a reducing agent, a photopolymerization initiator and an ethylenically unsaturated polymerizable compound on the support. The image recording material of this aspect will be described below in particular.

The image recording material includes, as silver halide, silver chloride, silver bromide, silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide,
Any grains of silver chloroiodobromide can be used.

The halogen composition of the silver halide grains may be uniform or non-uniform on the surface and inside. Regarding silver halide grains having multiple structures having different compositions on the surface and in the interior, JP-A-57-154232, JP-A-58-108533, and JP-A-59-48
Nos. 755, 59-52237, U.S. Pat. No. 4,433,048 and European Patent No. 100984. Also,
As in the light-sensitive material described in JP-A-62-183453, silver halide grains having a high silver iodide ratio in the shell portion may be used.

There is no particular limitation on the crystal habit of the silver halide grains.
For example, tabular grains having an aspect ratio of 3 or more as in the light-sensitive material described in JP-A-62-210455 may be used.

Incidentally, the silver halide grains described in JP-A-63-68
It is preferable to use silver halide grains having a relatively low fog value as in the light-sensitive material described in JP-A-830-830.

The silver halide used in the image recording material may be used in combination with two or more kinds of silver halide grains having different halogen compositions, crystal habits, grain sizes and the like.

There is no particular limitation on the grain size distribution of the silver halide grains. For example, monodisperse silver halide grains having a substantially uniform grain size distribution may be used, such as a photosensitive material described in JP-A-62-210448.

In the image recording material, the average grain size of silver halide grains is preferably 0.001 to 5 μm,
More preferably, it is from 1 to 2 μm.

The amount of silver halide contained in the photosensitive layer is 0.1 mg to 10 g / m 2 in terms of silver containing an organic silver salt which is an optional component described later.
The range of ² is preferable. Further, in terms of silver equivalent of only silver halide, it is preferably 1 g / m ² or less, and 1 mg / m ² or less.
It is particularly preferred that the concentration be in the range of from 500 to 500 mg / m ² .

The reducing agent used in the image recording material has been described above.

In the present invention, as the photopolymerization initiator, a carbonyl compound (for example, acetophenone, benzoins, benzyl, diacetyl, ketones such as benzophenone, anthraquinones, naphthoquinones, quinones such as phenanthrenequinones), organic sulfur compounds, Peroxides, halogen compounds, photo-semiconductors (eg zinc oxide, titanium dioxide, etc.), metal ions (eg iron (I) ions, metal carbonyls, metal complexes, uranyl salts, etc.), azo and diazo compounds, photoreducible A dye or the like can be used.

Regarding the photopolymerization initiator that can be used in the present invention, see Oster et al., "Chemical Review", Vol. 68 (1968) 12
Pp. 5-151, "Light-Sensitive Systems" by Kosar (Joh
n Wiley & Sons, 1963) pp. 158-192, and Fine Chemicals Vol. 16, No. 9, (1987) pp. 5-19 (especially the second
Table) etc.

A photopolymerization initiator using a photoreducing agent dye is generally composed of a photoreducing dye and a hydrogen donating compound, and it is considered that a radical capable of initiating polymerization is generated by the reaction between the photoexcited dye and the hydrogen donating compound. There is. Examples of the photoreducing dye include methylene blue, thionine, rose bengal, erythrosin-B, eosin, rhodamine, phloxine-
B, safranine, acriflavine, riboflavin, fluorescein, uranine, benzoflavin, N, N, N ',
Carbonyl compounds such as N'-tetra-n-butylthionine, N, N, N ', N'-tetramethyl-4'-dedosylsafranine, acridine orange, acridine yellow, 9,10-phenanthrenequinone and benzanthrone Can be mentioned. As the hydrogen-donating compound, β-diketones such as dimedone and acetylacetone, amines such as triethanolamine, diethanolamine, monoethanolamine, dimethylamine, diethylamine, tetramethylethylenediamine, triethylamine, phenylhydrazine, and p-toluene. Sulfinic acids such as sulfinic acid, benzenesulfinic acid, p- (N-acetylamine) benzenesulfinic acid and salts thereof, N-
Examples include phenylglycine, L-ascorbic acid, thiourea, allylthiourea and the like.

The molar ratio of the photo-reducing dye to the hydrogen-donating compound is 0.005 to 3 mol, preferably 0.05 to 1 mol, based on 1 mol of the hydrogen-donating compound. When a carbonyl compound such as 9,10-phenanthrenequinone is used as a photoreducible dye, the binder acts as a hydrogen-donating compound, and therefore the hydrogen-donating compound is not necessarily used.

In the image recording method of the present invention, the photopolymerization initiator is preferably used in the range of 0.0001 mol to 0.1 mol, and more preferably 0.001 mol to 0.05 mol, per mol of the polymerizable compound.

The polymerizable compound that can be used in the image recording material is not particularly limited as long as it has an ethylenically unsaturated group, and a known polymerizable compound can be used. In the image recording method of the present invention, when a thermal development process is planned, it has a high boiling point (for example, a boiling point of 80 ° C. or higher) that hardly volatilizes during heating.
It is preferred to use the compounds of The mode in which the recording layer contains a color image-forming substance as an optional component described later is
The polymerizable compound is preferably a crosslinkable compound having a plurality of polymerizable functional groups in the molecule, because the color image forming substance is immobilized by polymerization and curing of the polymerizable compound. Further, as will be described later, when a transfer image is formed using an image receiving material, it is preferable to use a highly viscous substance as a polymerizable compound, as in the light-sensitive material described in Japanese Patent Application No. 62-162147. preferable.

Examples of the compound having an ethylenically unsaturated group that can be used in the image recording material include acrylic acid and its salts, acrylic acid esters, acrylamides, methacrylic acid and its salts, methacrylic acid esters, methacrylamides, and anhydrides. There are maleic acid, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters and their derivatives.

Specific examples of the polymerizable compound that can be used in the image recording material include acrylic acid esters, n-butyl acrylate, cyclohexyl acrylate, and 2-
Ethylhexyl acrylate, benzyl acrylate,
Furfuryl acrylate, ethoxyethoxyethyl acrylate, dicyclohexyloxyethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate, diacrylate of polyoxyethylenated bisphenol A, diacrylate of 2,2-dimethyl-3-hydroxypropionaldehyde and trimethylolpropane condensate, 2,2-dimethyl-3-hydroxypropion Triacrylate of aldehyde and pentaerythritol condensate, hydroxy poly Ether of polyacrylate,
Examples thereof include polyester acrylate and polyurethane acrylate.

As other specific examples, methacrylates, methyl methacrylate, butyl methacrylate,
Ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate,
Examples thereof include pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and dimethacrylate of polyoxyalkylenated bisphenol A.

The polymerizable compounds may be used alone or in combination of two or more. The image recording material containing two or more kinds of polymerizable compounds in combination is described in JP-A-62-210445. In addition, a substance in which a polymerizable functional group such as a vinyl group or a vinylidene group is introduced into the chemical structure of the above-mentioned reducing agent or a color image forming substance which is an optional component described later can also be used as the polymerizable compound. A reducing agent and a polymerizable compound, as described above.
Alternatively, it goes without saying that the use of a substance that serves as a color image forming substance and a polymerizable compound is also included in the embodiment of the image recording material.

In the image recording material, the polymerizable compound is preferably used in the range of 50 to 120,000 parts by weight with respect to 1 part by weight of silver halide. More preferred range of use is 12 to 1200
0 parts by weight.

The image recording material preferably has a mode in which a recording layer containing the components described above is provided on a support. The support is not particularly limited, but when heat development processing is planned in the image recording method, it is preferable to use a material that can withstand the processing temperature of the development processing.
Materials that can be used for the support include glass,
Paper, fine paper, coated paper, cast coated paper, synthetic paper, metal and its analogs, polyester, acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, and other films, and resin materials and polyethylene and other polymers. The laminated paper can be mentioned.

When the support is made of a porous material such as paper,
Like the support used in the light-sensitive material described in JP-A-62-209529, it is preferable that the support has a certain degree of smoothness according to a swelling regulation method. When a paper support is used, a paper support having a low water absorption such as a photosensitive material described in JP-A-63-38934 and a fixed material such as a photosensitive material described in JP-A-63-47754 can be used. Paper support having a Beck's smoothness of less, a paper support having a low shrinkage as in the light-sensitive material described in JP-A-63-81339, and an air-permeable material as in the light-sensitive material described in JP-A-63-81340. Paper support, low
A paper support having a pH value of 5 to 9 as in the light-sensitive material described in JP-A-63-97941 can also be used.

Hereinafter, various aspects of the image recording material, arbitrary components that can be contained in the recording layer, auxiliary layers that can be optionally provided in the image recording material, and the like will be sequentially described.

In the image recording material, the polymerizable compound is preferably dispersed in the recording layer in the form of oil droplets. An example of a photosensitive material in which a polymerizable compound is dispersed in the photosensitive layer in the form of oil droplets is described in JP-A-62-78552. In the oil drop,
Other components in the recording layer such as a silver halide, a reducing agent, a photopolymerization initiator, and a color image forming substance may be contained. Regarding the light-sensitive material containing silver halide in the oil droplet, JP-A-62-209450 and 62-164040 disclose the light-sensitive material further containing a reducing agent in the oil droplet. Each of them is described in JP-A-62-183453. When silver halide is included in oil droplets, it is disclosed in JP-A-63-1523.
As described in JP-B-9, it is preferable that the number of silver halide grains contained in the oil droplet is 5 or more.

More preferably, the oil droplets of the polymerizable compound are in a state of microcapsules. Various known techniques can be applied to the microcapsules without any particular limitation. For an example of a light-sensitive material in which oil droplets of a polymerizable compound are in a microcapsule state, see JP-A-61-27
It is described in Japanese Patent No. 8441.

There is no particular limitation on the wall material that constitutes the outer shell of the microcapsule. For a photosensitive material using a microcapsule having an outer shell made of a polyamide resin and / or a polyester resin, Japanese Patent Application Laid-Open No. 62-209437 discloses a microcapsule having an outer shell made of a polyurea resin and / or a polyurethane resin. Japanese Patent Application Laid-Open No. 62-209438 discloses a photosensitive material used, and Japanese Patent Application Laid-Open No. 62-209439 discloses a photosensitive material using a microcapsule having an outer shell made of an amino-aldehyde resin. Japanese Patent Application Laid-Open No. 62-209440 discloses a photosensitive material using microcapsules having epoxy resin, and Japanese Patent Application Laid-Open No. 62-209441 discloses a photosensitive material using microcapsules having an outer shell made of epoxy resin. For photosensitive materials using microcapsules having a composite resin shell containing urea resin and polyurea resin 094
Japanese Patent Application Laid-Open No. 62-209442 discloses a light-sensitive material using microcapsules having a composite resin outer shell containing a polyurethane resin and a polyester resin.

When aldehyde-based microcapsules are used, it is preferable that the amount of residual aldehyde is not more than a certain value, as in the light-sensitive material described in JP-A-63-32535.

When containing silver halide in microcapsules,
It is preferable that silver halide is present in the wall material constituting the outer shell of the microcapsule. Regarding a light-sensitive material containing silver halide in the wall material of microcapsules, JP-A-62-62
No. 169147.

Further, two or more microcapsules in which at least one of the components contained in the microcapsules such as silver halide, a reducing agent, a polymerizable compound, and a color image forming substance which is an optional component described later are different may be used in combination. Good. In particular, in the case of forming a full-color image, it is preferable to use together three or more types of microcapsules in which the color hue of the color image forming substance contained is different. A photosensitive material using two or more types of microcapsules in combination is described in JP-A-62-1988.
It is described in Japanese Patent Publication No. 50.

The average particle size of the microcapsules is preferably 3 to 20 μm. It is preferable that the distribution of the particle diameter of the microcapsules is uniformly distributed to a certain value or more as in the photosensitive material described in JP-A-63-5334. Also,
The thickness of the microcapsule is preferably within a certain range with respect to the particle size, as in the photosensitive material described in JP-A-63-81336.

When silver halide is contained in the microcapsules, the average grain size of the silver halide grains described above is preferably set to 1/5 or less of the average size of the microcapsules, and is set to 1/10 or less. Is more preferred. By setting the average grain size of the silver halide grains to 1/5 or less of the average size of the microcapsules,
A uniform and smooth image can be obtained.

Optional components that can be contained in the recording layer of the image recording material include color image-forming substances, sensitizing dyes, organic silver salts,
Radical generators, various image formation accelerators, thermal polymerization inhibitors,
Development stopper, fluorescent whitening agent, anti-fading agent, dye or pigment for preventing halation or irradiation, dye having a property of decolorizing by heating or light irradiation, matting agent, anti-smudge agent, plasticizer, water releasing agent, binder,
Examples include solvents for polymerizable compounds and water-soluble vinyl polymers.

With the image recording material, a polymer image can be obtained by the constitution of the recording layer described above, but a color image can be formed by including a color image forming substance as an arbitrary component in the recording layer.

The color image-forming substance that can be used as the image recording material is not particularly limited, and various types can be used. That is, the substance that is itself colored (dye or pigment)
Alternatively, a substance (color former) that is colorless or light-colored by itself but develops color by the contact of energy (heat, pressure, light irradiation, etc.) from the outside or another component (developing agent) is also a color image-forming substance. included. The general photosensitive material using a color image forming substance is described in the above-mentioned JP-A-61-73145. Further, a light-sensitive material using a dye or a pigment as a color image forming substance is described in JP-A-62-187346, and a light-sensitive material using a leuco dye is described in JP-A-62-187346.
209436, JP-A-62-251741 for a light-sensitive material using a triazene compound, and JP-A-62-288827 for a light-sensitive material using a yellow color-forming leuco dye.
JP-A No. 63-53542 and JP-A No. 62-288828 describe the light-sensitive materials using a cyan color-forming leuco dye.

Dyes and pigments, which are substances that themselves are colored, are commercially available, as well as various references (for example, "Dye Handbook" edited by the Society of Synthetic Organic Chemistry, published in 1970, "Latest Pigment Handbook" edited by the Japan Pigment Technical Association, Known ones described in (1977) can be used. These dyes or pigments are used after being dissolved or dispersed.

On the other hand, examples of a substance that develops a color by some energy such as heating, pressurizing, and light irradiation include thermochromic compounds, piezochromic compounds, photochromic compounds, and leuco such as triarylmethane dyes, quinone dyes, indigoid dyes, and azine dyes. The body is known. All of them develop color by heating, pressurizing, light irradiation or air oxidation.

Examples of substances that develop color by contact with another component include acid-base reaction between two or more components, redox reaction,
Various systems that develop color by a coupling reaction, a chelate forming reaction, and the like are included. For example, pressure-sensitive copying paper (pages 29 to 58) and azography (87 to 95) described in "Introduction to Special Paper Chemistry" written by Hiroyuki Moriga (published in 1975).
Page), known color development systems such as thermosensitive coloring (pages 118-120), etc., or a seminar organized by Kinki Chemical Industry Association "Latest Dye Chemistry-Attractive Use and New Development as Functional Dyes" The coloring system described on pages 26 to 32 (June 19, 1980) can be used. Specifically, lactone, lactam,
Coloring system consisting of a coloring agent having a partial structure such as spiropyran and an acidic substance (coloring agent) such as acidic clay and phenols; aromatic diazonium salts, diazotates, diazosulfonates and naphthols, anilines, active methylenes A chelation-forming reaction such as a reaction between hexamethylenetetramine and ferric ion or gallic acid, or a reaction between phenolphthalein-complexones and an alkaline earth metal ion; stearic acid A redox reaction such as a reaction between ferric iron and pyrogallol and a reaction between silver behenate and 4-methoxy-1-naphthol can be used.

The color image forming substance is based on 100 parts by weight of the polymerizable compound.
It is preferably used in a proportion of 0.5 to 20 parts by weight, more preferably in a proportion of 2 to 7 parts by weight. When a color developer is used, it is preferably used in a ratio of about 0.3 to 80 parts by weight with respect to 1 part by weight of the color former.

When two types of substances that cause a color reaction in a contact state are used as the above-mentioned color image forming substances, one of the substances that cause the color reaction and the polymerizable compound are contained in microcapsules. Then, a color image can be formed on the recording layer by allowing another substance out of the substances that cause the above-mentioned color development reaction to exist outside the microcapsules containing the polymerizable compound. The photosensitive material from which a color image can be obtained without using an image receiving material as described above is described in JP-A-62-209444.

The sensitizing dye that can be used in the image recording material is not particularly limited, and a silver halide sensitizing dye known in the photographic art and the like can be used. The above sensitizing dyes include
Examples include methine dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemin anine dyes, styryl dyes, and hemioxonol dyes. These sensitizing dyes may be used alone,
You may use these in combination. Particularly for the purpose of supersensitization, a method of using a sensitizing dye in combination is generally used. Further, together with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a substance which does not substantially absorb visible light but exhibits supersensitization may be used in combination. The addition amount of the sensitizing dye is generally 10 ^{-8 to} 10 ^-2 per mol of silver halide.
It is about molar.

The sensitizing dye is preferably added at the stage of preparing a silver halide emulsion described below. A photosensitive material obtained by adding a sensitizing dye in the stage of forming silver halide grains is described in JP-A-62-947, in which a sensitizing dye is added to a silver halide emulsion after forming silver halide grains. Regarding the photosensitive material obtained by adding in the preparation stage,
Each is described in JP-A-62-210449. Further, specific examples of sensitizing dyes that can be used in the image recording material are also described in JP-A Nos. 62-947 and 62-210449. Further, as in the light-sensitive material described in JP-A-63-184738, an infrared light-sensitive sensitizing dye may be used in combination.

The addition of an organic silver salt in the image recording material is particularly effective in the heat development processing. That is, when heated to a temperature of 80 ° C. or higher, it is considered that the organic silver salt participates in an oxidation-reduction reaction using a latent image of silver halide as a catalyst. In this case, the silver halide and the organic silver salt are preferably in a contact state or a close state. Examples of the organic compound constituting the organic silver salt include an aliphatic or aromatic carboxylic acid, a thiocarbonyl group-containing compound having a mercapto group or α-hydrogen, and an imino group-containing compound. Among them, benzotriazole is particularly preferred. The organic silver salt is generally used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of silver halide.
Use mol. The same effect can be obtained by adding an organic compound (for example, benzotriazole) constituting the organic silver salt to the recording layer instead of the organic silver salt. A photosensitive material using an organic silver salt is described in JP-A-62-3246.
The organic silver salt as described above is preferably used in the range of 0.1 to 10 mol per mol of silver halide,
More preferably, it is used in the range of 0.01 to 1 mol.

A radical generator that participates in the above-mentioned polymerization promoting (or polymerization suppressing) reaction of the reducing agent may be added to the recording layer. Japanese Patent Application Laid-Open No. 62-195369 discloses a light-sensitive material using silver triazene as the radical generator, and Japanese Patent Application Laid-open No. 62-195640 discloses a light-sensitive material using silver diazotate.
JP-A No. 62-195641 discloses the light-sensitive material using an azo compound.

Various image formation accelerators can be used in the image recording material. As the image forming accelerator, promotion of redox reaction between silver halide (and / or organic silver salt) and reducing agent and redox agent, from image recording material to image receiving material or image receiving layer (these will be described later) Has a function of promoting the movement of the image forming substance. From the viewpoint of physicochemical functions, the image formation accelerator is a base, a base precursor, an oil, a surfactant, a compound having an antifogging function and / or a development accelerating function, a thermal solvent, a compound having an oxygen removing function, and the like. It is further classified into However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Therefore, the above classification is a matter of convenience, and in practice, one compound often has a plurality of functions.

 Examples of various image formation accelerators are shown below.

Examples of preferable bases include hydroxides of alkali metals or alkaline earth metals as inorganic bases; tertiary phosphates, borates, carbonates, metaborates of alali metals or alkaline earth metals; water. Zinc oxide or a combination of zinc oxide and a chelating agent such as sodium picolinate; ammonium hydroxide; quaternary alkyl ammonium hydroxide; other metal hydroxides, etc. Group amines (trialkylamines, hydroxylamines, aliphatic polyamines); aromatic amines (N-alkyl substituted aromatic amines, N-
(Hydroxylalkyl-substituted aromatic amines and bis [p- (dialkylamino) phenyl] methanes), heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, and the like.
The above is preferable.

As base precursors, salts of organic acids and bases that are decarboxylated by heating, intramolecular nucleophilic substitution, Rossen rearrangement,
Compounds which release a base by causing some reaction by heating, such as compounds which release amines by a reaction such as Beckmann rearrangement, and compounds which generate a base by electrolysis or the like are preferably used. Specific examples of the base precursor include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, p-toluidine trichloroacetic acid, 2-picoline trichloroacetic acid, guanidine phenylsulfonyl acetate, guanidine 4-chlorophenylsulfonyl acetate, and 4-methyl- Guanidine sulfonylphenylsulfonyl acetate and guanidine 4-acetylaminomethylpropiolate can be exemplified.

The base or base precursor can be used in a wide range of amount in the image recording material. The base or base precursor is suitably used in an amount of 100% by weight or less in terms of the coating film of the recording layer, more preferably 0.1% by weight to 40% by weight. In the present invention, the base and / or the base precursor may be used alone or as a mixture of two or more.

The photosensitive material using a base or a base precursor is described in JP-A-62-264041. Further, photosensitive materials using a tertiary amine as a base are described in JP-A-62-170954, and photosensitive materials using a particulate dispersion of a hydrophobic organic basic compound having a melting point of 80 to 180 ° C. JP-A-62-209523 discloses that the solubility is 0.1%.
JP-A-62-215637 describes a photosensitive material using the following guanidine derivative, and JP-A-62-209448 describes a photosensitive material using a hydroxide or salt of an alkali metal or an alkaline earth metal. Is described in each.

Further, a photosensitive material using an acetylide compound as a base precursor is described in JP-A-63-24242.
For a photosensitive material containing propiolate as a base precursor and further containing silver, copper, a silver compound or a copper compound as a catalyst for the base formation reaction, JP-A-63-46446 discloses the above-mentioned propiolate and the above silver and copper. JP-A-63-81338 discloses a photosensitive material containing a silver compound or a silver compound or copper compound in a state of being isolated from each other in addition to the propiolate and the silver, copper, silver compound or copper compound. For photosensitive materials containing ligands, see
JP-A-63-97942 discloses a photosensitive material using a propiolate as a base precursor and further containing a heat-meltable compound as a reaction accelerator for a base formation reaction.
Japanese Patent No. 46447 discloses a photosensitive material containing a sulfonyl acetate salt as a base precursor and further containing a heat-meltable compound as a reaction accelerator for a base generation reaction.
In JP-A-63-24242, JP-A-63-24242 describes a light-sensitive material using a compound obtained by bonding an isocyanate or isothiocyanate to an organic base as a base precursor.

When a base or a base precursor is used for the image recording material, the above-mentioned microcapsule contains silver halide, a reducing agent, a photopolymerization initiator and a polymerizable compound, and the base or base is contained in the recording layer outside the microcapsule. It is preferred to have a precursor present. Alternatively,
A base or a base precursor may be contained in another microcapsule like the light-sensitive material described in JP-A-62-209521. In addition to the above specification, an image recording material using a microcapsule containing a base or a base precursor is a photosensitive material containing the base or the base precursor dissolved or dispersed in an aqueous solution of a water retention agent in the microcapsule. No. 62-209522 discloses a photosensitive material containing solid fine particles carrying a base or a base precursor in a microcapsule. JP-A No. 62-209526 discloses a microcapsule containing a base compound having a melting point of 70 ° C. to 210 ° C. Japanese Patent Application Laid-Open No. 63-65437 discloses a light-sensitive material using
Each of these is described in Japanese Patent Publication No. Also, instead of the microcapsules containing the base or base precursor,
As in the light-sensitive material described in JP-A-63-97943, particles containing a base or a base precursor and a hydrophobic substance in a compatible state may be used.

The base or base precursor is described in JP-A-62-25.
It may be added to an auxiliary layer (a layer containing a base or a base precursor described later) other than the recording layer as described in JP-A-3140. Further, as described in JP-A-63-32546, the above-mentioned support may be made porous, and a base or a base precursor may be contained in this porous support.

As the oil, a high boiling point organic solvent used as a solvent for emulsifying and dispersing a hydrophobic compound can be used.

Examples of the surfactant include pyridinium salts, ammonium salts, phosphonium salts described in JP-A-59-74547, and polyalkylene oxides described in JP-A-59-57231.

The compound having an antifogging function and / or a development accelerating function can be used for the purpose of obtaining a clear image having a high maximum density and a low minimum density (an image having a high S / N ratio). JP-A-62-151838 discloses a photosensitive material using an antifoggant as a compound having an antifogging function and / or a development accelerating function, and discloses a light-sensitive material using a compound having a cyclic amide structure. JP-A-61-151841 discloses a photosensitive material using a thioether compound in JP-A-62-151842, and a photosensitive material using a polyethylene glycol derivative is described in JP-A-62-151843. Japanese Patent Application Laid-Open No. Sho 62-151844 discloses a photosensitive material using a derivative, and Japanese Patent Application Laid-Open No. 62-17 / 1987 describes a photosensitive material using an acetylene compound.
No. 8232, a photosensitive material using a sulfonamide derivative is described in JP-A-62-183450, and a photosensitive material using a quaternary ammonium salt is described in JP-A-63-91653. .

As the thermal solvent, a compound which can be used as a solvent for a reducing agent, a compound which is a substance having a high dielectric constant and which is known to promote physical development of a silver salt, and the like are useful. Useful thermal solvents, polyethylene glycols U.S. Patent No. 3347675 Pat described derivatives such as oleic acid esters of polyethylene oxide, beeswax, glycerol monostearate, -SO ₂ -
And / or a high dielectric constant compound having a -CO- group, a polar substance described in U.S. Pat.
1,10 on pages 26-28 of the December 1976 Disclosure Magazine
-Decanediol, methyl anisate, biphenyl suberate and the like are preferably used. The photosensitive material using a thermal solvent is described in JP-A-62-86355.

The compound having an oxygen removing function can be used for the purpose of eliminating the influence of oxygen during development (oxygen has a polymerization inhibiting effect). Examples of the compound having an oxygen removing function include compounds having two or more mercapto groups. The photographic material using a compound having two or more mercapto groups is described in JP-A-62-209443.

The development terminator that can be used in the image recording material is
Proper development, a compound that neutralizes or rapidly reacts with a base to lower the concentration of the base in the film to stop development, or a compound that interacts with silver and a silver salt to suppress development.
Specifically, an acid precursor that releases an acid by heating,
An electrophilic compound that causes a substitution reaction with a coexisting base upon heating, a nitrogen-containing heterocyclic compound, a mercapto compound, or the like can be given. Examples of acid precursors include JP-A-60
Examples thereof include oxime esters described in JP-A-108837 and JP-A-60-192939, and compounds that release an acid by Rossen rearrangement described in JP-A-60-230133.
Examples of electrophilic compounds which undergo a substitution reaction with a base upon heating include compounds described in JP-A-60-230134.

A dye or a pigment may be added to the recording layer of the image recording material for the purpose of preventing halation or irradiation. JP-A-63-29748 discloses a photosensitive material in which a white pigment is added to a photosensitive layer for the purpose of preventing halation or irradiation.

In the case where the recording layer of the image recording material is a mode in which the above-mentioned microcapsules are used, the microcapsules may contain a dye having a property of being decolorized by heating or light irradiation. The dye having the property of being decolorized by heating or light irradiation can function as a yellow filter in a conventional silver salt photographic system. The image recording material using the dye having the property of being decolorized by heating or irradiation with light as described above is described in JP-A-63-97940.

As the anti-smudge agent used for the image recording material, a particulate matter which is solid at room temperature is preferable. Specific examples include starch particles described in British Patent No. 1232347, U.S. Pat.
Polymer fine powder described in 625736, etc., British Patent No. 1235
Coloring agent-free microcapsule particles described in 991 specification, cellulose fine powder described in US Pat. No. 2711375, talc, kaolin, bentonite, pyrophyllite, zinc oxide, titanium oxide, inorganic particles such as alumina, etc. Can be mentioned. The average particle size of the particles,
The volume average diameter is preferably in the range of 3 to 50 μm, and 5 to
The range of 40 μm is more preferable. As described above, when the oil droplets of the polymerizable compound are in the microcapsule state, it is more effective that the particles are larger than the microcapsules.

The binder that can be used in the image recording material can be contained in the recording layer alone or in combination. It is preferable to mainly use a hydrophilic binder. As the hydrophilic binder, a transparent or translucent hydrophilic binder is typical, and examples thereof include natural substances such as gelatin, gelatin derivatives, cellulose derivatives, starch, and arabic gum, and polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers and the like. Includes synthetic polymeric materials such as water soluble polyvinyl compounds. Other synthetic polymeric substances include dispersed vinyl compounds in the form of latex, in particular for increasing the dimensional stability of the photographic material.
For the photosensitive material using a binder, see
There is a description in 61-69062. A light-sensitive material using a binder together with microcapsules is described in JP-A-62-209525.

When using a solvent of a polymerizable compound for the image recording material,
It is preferable to use by encapsulating in a microcapsule different from the microcapsule containing the polymerizable compound. In addition,
For a light-sensitive material using an organic solvent miscible with a polymerizable compound encapsulated in microcapsules, see JP-A-62-2095.
It is described in Japanese Patent No. 24.

A water-soluble vinyl polymer may be adsorbed on the above-described silver halide grains for use. A light-sensitive material using a water-soluble vinyl polymer as described above is described in JP-A-63-91652.

In addition to the above, examples of optional components that can be contained in the recording layer and their use modes are also described in Research Disclosure Vol. 170, June 1978, No. 17029.
No. (pp. 9-15).

The recording layer of the image recording material comprising the components as described above preferably has a pH value of 7 or less as in the light-sensitive material described in JP-A-62-275235.

As the layer which can be optionally provided in the image recording material, an image receiving layer, a heating element layer, an antistatic layer, an anti-curl layer, a peeling layer, a cover sheet or a protective layer, a layer containing a base or a base precursor, and a base barrier layer. , An antihalation layer (colored layer), and the like.

Instead of using the image receiving material described later as a method of using the image recording material, the image receiving layer may be provided on the image recording material and an image may be formed on this layer. The image receiving layer provided on the image recording material can have the same structure as the image receiving layer provided on the image receiving material. Details of the image receiving layer will be described later.

For the photosensitive material using the heating element layer, see JP-A-61
-294434 discloses a photosensitive material provided with a cover sheet or a protective layer in JP-A-62-210447, and a photosensitive material provided with a layer containing a base or a base precursor in JP-A-62-253140. Japanese Patent Application Laid-Open No. 63-1018 discloses a light-sensitive material provided with a coloring layer as an antihalation layer.
No. 42, respectively. The image recording material provided with a base barrier layer is also described in the above-mentioned JP-A-62 / 62.
-253140 publication. Further, examples of other auxiliary layers and usage modes thereof are also described in the specification of the series of photosensitive materials described above.

 The method for producing the image recording material will be described below.

Although various methods can be used as a method for producing an image recording material, a general production method is to prepare a coating liquid by dissolving, emulsifying or dispersing the components of the recording layer in an appropriate solvent, and It comprises a step of obtaining an image recording material by coating the coating liquid on the support as described above and drying.

Generally, each coating solution is prepared by preparing a liquid composition containing each component for each component, and then mixing each liquid composition. The liquid composition may be prepared so as to contain a plurality of components. Some of the constituent components of the recording layer can also be used by adding them at the stage of preparing the liquid composition or the coating solution or after the preparation. Further, as described below, a method of preparing a secondary composition by further emulsifying an oily (or aqueous) composition containing one or more components in an aqueous (or oily) solvent may be used. .

With respect to the main components contained in the recording layer, a method for preparing a liquid composition and a coating liquid is shown below.

The preparation of the halogenated emulsion can be carried out by any of known methods such as an acidic method, a neutral method and an ammonia method.

The reaction between the soluble silver salt and the soluble halogen salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof. An inverse mixing method in which grains are formed under silver ion excess conditions and a controlled double jet method in which pAg is kept constant can also be employed. Further, in order to accelerate the grain growth, the addition concentration, the addition amount or the addition speed of the silver salt and the halogen salt to be added may be increased (JP-A-55-158124).
Nos. 55-158124 and U.S. Pat. No. 3,650,57).

The silver halide emulsion used for producing the image recording material may be a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside the grain.
A direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used. Internal latent emulsions suitable for this purpose are described in U.S. Pat. Nos. 2,592,250 and 3,761,276, Japanese Patent Publication No. 58-3534, and Japanese Patent Laid-Open No. 58-136641. Preferred nucleating agents to be combined with the above emulsions are U.S. Pat.Nos. 3,227,552, 4,245,037 and 4,425,551.
No. 1, No. 4266013, No. 4276364, and West German Published Patent (OLS) No. 2635316. In the preparation of a silver halide emulsion used for producing an image recording material, it is preferable to use a hydrophilic colloid as a protective colloid. Examples of hydrophilic colloids include gelatin, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates, and sodium alginate. , Starch derivatives and other sugar derivatives; and homo- or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. And various kinds of synthetic hydrophilic polymer substances. Of these, gelatin is preferred. As gelatin, in addition to coal-processed gelatin, acid-processed gelatin or enzyme-processed gelatin may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used.

In the silver halide emulsion, at the stage of forming silver halide grains, ammonia, an organic thioether derivative (see JP-B-47-386) and a sulfur-containing compound (see JP-A-53-144319) as a silver halide solvent. Etc. can be used. In the process of particle formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, and the like may coexist. Further, for the purpose of improving high illuminance failure and low illuminance failure, a water-soluble iridium salt such as iridium chloride (III or IV) and ammonium hexachloroiridium salt, or a water-soluble rhodium salt such as rhodium chloride can be used.

The soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening. In this case, it can be carried out according to the Noudel washing method or the sedimentation method. Although the silver halide emulsion may be used as it is after unripe, it is usually used after chemical sensitization. In the emulsion for a conventional type photosensitive material, known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method and the like can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 58-1983).
-126526 and 58-215644).

When a sensitizing dye is added to a silver halide emulsion, the above-mentioned JP-A-62-947 and JP-A-62-210 may be used.
It is preferably added at the stage of preparing a silver halide emulsion as in the light-sensitive material described in JP-A-449. When a nitrogen-containing heterocyclic compound is added as the compound having the fog-preventing function and / or the development-accelerating function, it should be added in the step of forming silver halide grains or the step of ripening in the preparation of a silver halide emulsion. You can A method for producing a light-sensitive material in which a nitrogen-containing heterocyclic compound is added at the stage of forming or ripening silver halide grains is described in JP-A-62-161144.

When the above-mentioned organic silver salt is included in the recording layer, the organic silver salt emulsion can be prepared by a method similar to the method for preparing the silver halide emulsion.

In the production of the image recording material, the polymerizable compound can be used as a medium for preparing the composition of other components in the recording layer. For example, a silver halide (including a silver halide emulsion), a reducing agent, a photopolymerization initiator, a color image forming substance, etc. may be dissolved, emulsified or dispersed in a polymerizable compound to be used for the production of an image recording material. it can. In particular, when a color image forming substance is added, it is preferable to include the compound in a polymerizable compound. Further, as described later, when oil droplets of the polymerizable compound are microencapsulated, components such as wall material necessary for microencapsulation may be included in the polymerizable compound.

A photosensitive composition containing a polymerizable compound containing silver halide can be prepared using a silver halide emulsion.
In addition, in addition to the silver halide emulsion, a silver halide powder prepared by freeze-drying or the like can be used for the preparation of the photosensitive composition. These photosensitive compositions containing silver halide can be obtained by stirring with a homogenizer, a blender, a mixer, or another commonly used stirrer.

The polymerizable compound used for preparing the photosensitive composition preferably has a copolymer of a hydrophilic repeating unit and a hydrophobic repeating unit dissolved therein. For a photosensitive composition containing the above copolymer, see JP-A-62-1
It is described in Japanese Patent No. 209449.

Further, instead of using the above copolymer, a photosensitive composition may be prepared by dispersing microcapsules having a silver halide emulsion as a core substance in a polymerizable compound. The photosensitive composition containing microcapsules containing the above silver halide emulsion as a core substance is described in JP-A-62-164041.

The polymerizable compound (including the one containing other components like the above-mentioned photosensitive composition) is preferably used as an emulsion emulsified in an aqueous solvent. In addition, JP-A-61
As in the image recording material described in JP-A-275742, when oil droplets of a polymerizable compound are microencapsulated, a wall material necessary for microencapsulation is added to this emulsion, and then the microcapsules are separated. The shell-forming treatment can also be carried out at this emulsion stage. Further, a reducing agent or other optional components may be added at the stage of the emulsion.

As an example of the microencapsulation method, a method utilizing coacervation of a hydrophilic wall forming material described in US Pat. Nos. 2,800,457 and 2,800,458; US Pat. No. 3,287,154 and British Patent No. 990,443. Each statement,
And JP-B-38-19574, 42-446 and 42-77
US Patent Nos. 3,418,250 and 3,660,304 by precipitation of polymer; US Patent No. 3,796,669, using isocyanate-polyol wall material; US Patent No. 391451
A method using the isocyanate wall material described in No. 1;
U.S. Pat.Nos. 4001140, 4087376 and 408980
No. 2, a method using a urea-formaldehyde-based or urea-formaldehyde-resylcinol-based wall-forming material; a method using a melamine-formaldehyde resin, hydroxypropylcellulose, or the like described in U.S. Pat. No. 4,025,455. An in situ method by polymerization of monomers described in JP-B-36-9168 and JP-A-51-9079; a polymerization dispersion cooling method described in British Patent Nos. 927807 and 965074; U.S. Pat. The spray drying method described in the specifications of 3111407 and British Patent No. 930422 can be exemplified. The method of microencapsulating the oil droplets of the polymerizable compound is not limited to the above, but a method of forming a polymer film as a microcapsule wall after emulsifying the core substance is particularly preferable.

The photosensitive microcapsules that can be used for producing the image recording material are described in JP-A-62-169147.
62-169148, 62-209437, 62-209438,
62-209439, 62-209440, 62-209441, 62
-209447 and 62-209442.

When the polymerizable compound is a photosensitive composition containing silver halide in the emulsion of the polymerizable compound (including the microcapsule solution subjected to the microencapsulation treatment) described above, the image recording material is directly applied. It can be used as a liquid. Emulsions other than those described above can be mixed with a composition of other components such as a silver halide emulsion and optionally an organic silver salt emulsion to prepare a coating solution. The addition of other components at the stage of this coating solution can be carried out in the same manner as in the above-mentioned emulsion.

An image recording material is manufactured by applying the coating liquid for the recording layer prepared as described above to a support and drying. The coating of the coating liquid on the support can be easily carried out according to known techniques.

The image receiving material will be described below. A general image recording method using an image receiving material or an image receiving layer is described in JP-A-61-278849.

As the support of the image receiving material, in addition to the support that can be used for the image recording material described above, baryta paper can be used. When a porous material such as paper is used as the support of the image receiving material, it is preferable that the image receiving material has a certain degree of smoothness like the image receiving material described in JP-A-62-209530. An image receiving material using a transparent support is described in JP-A-62-209531.

The image receiving material generally has an image receiving layer provided on a support. The image receiving layer is in accordance with the above-described color image forming material color forming system and the like.
It can be configured in any form using various compounds. When a polymer image is formed on an image receiving material, a dye or a pigment is used as a color image forming substance, the image receiving material may be composed of only the above support.

For example, when a color-developing system comprising a color-developing agent and a color-developing agent is used, the image-receiving layer may contain the color-developing agent.
Further, the image receiving layer may be configured as a layer containing at least one mordant. The mordant can be selected from compounds known in the photographic art and the like in consideration of conditions such as the type of color image forming substance and used. If necessary, two or more image receiving layers may be constituted by using a plurality of mordants having different mordant powers.

The image receiving layer preferably has a structure containing a polymer as a binder. The binder that can be used in the recording layer of the image recording material described above can be used as the binder. Further, as in the image receiving material described in JP-A-62-209454, a polymer having low oxygen permeability may be used as a binder.

The image receiving layer may contain a thermoplastic compound. When the image receiving layer contains a thermoplastic compound, it is preferable that the image receiving layer itself is formed as an aggregate of thermoplastic compound fine particles. The image-receiving layer having the above-described structure has an advantage that a transfer image can be easily formed and a glossy image can be obtained by heating after the image formation. The thermoplastic compound is not particularly limited and can be arbitrarily selected and used from known plastic resins (plastics) and waxes. However, the glass transition point of the thermoplastic resin and the melting point of the wax are preferably 200 ° C. or less. Regarding the image receiving material having the image receiving layer containing the above-mentioned thermoplastic compound fine particles, JP-A-62-280071 is used.
No. 62-280739.

The image receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator. In image formation using an image receiving material, a color image forming substance is transferred together with an unpolymerized polymerizable compound as described later. For this reason, a photopolymerization initiator or a thermal polymerization initiator can be added to the image receiving layer for the purpose of smoothly proceeding the curing treatment (fixing treatment) of the unpolymerized polymerizable compound. The image receiving material having an image receiving layer containing a photopolymerization initiator is described in JP-A-62-161149, and the image-receiving material having an image receiving layer containing a thermal polymerization initiator is described in JP-A-62-210444. There is a description.

The dye or pigment may be contained in the image receiving layer for the purpose of writing characters, symbols, frames, etc. on the image receiving layer or for the purpose of making the background of the image a specific color. A dye or pigment may be included in the image receiving layer for the purpose of facilitating the distinction between the front and back of the image receiving material. As the dye or the pigment, various known substances including a dye or a pigment that can be used in image formation can be used, but the dye or the pigment may impair an image formed in the image receiving layer. In some cases, it is preferable to lower the dyeing density of the dye or pigment (for example, to reduce the reflection density to 1 or less), or to use a dye or pigment having a property of decoloring by heating or light irradiation. For an image receiving material having an image receiving layer containing a dye or pigment having a property of decoloring by heating or light irradiation,
It is described in JP-A-62-251741.

Further, when a white pigment such as titanium dioxide or barium sulfate is added to the image receiving layer, the image receiving layer can function as a white reflective layer. When the image receiving layer functions as a white reflective layer, the white pigment is preferably used in an amount of 10 g to 100 g per 1 g of the thermoplastic compound.

When the dye or pigment described above is contained in the image receiving layer, it may be contained uniformly or partially localized. For example, by forming a support described later from a material having a light transmitting property and including the white pigment in a part of the image receiving layer, a part of the reflection image can be used as a projection image. By doing so, unnecessary image information in the projected image can be written as a reflection image in the image receiving layer portion containing the white pigment.

The image receiving layer may be configured as two or more layers according to the functions described above. The thickness of the image receiving layer is 1 to
It is preferably 100 μm, more preferably 1 to 20 μm.

Note that a protective layer may be further provided on the image receiving layer. Further, a layer composed of an aggregate of fine particles of a thermoplastic compound may be provided on the image receiving layer. Japanese Patent Application Laid-Open No. Sho 62-210460 discloses an image receiving material in which a layer comprising an aggregate of fine particles of a thermoplastic compound is further provided on the image receiving layer.

Further, a layer containing an adhesive or an adhesive and a release paper may be sequentially laminated on the surface of the support opposite to the surface on which the image receiving layer is provided. The sticker type image receiving material having the above constitution is described in JP-A-63-24647.

The following examples further illustrate the present invention. However, the present invention is not limited to these.

Example 1 Preparation of (Blue Sensitive) Silver Halide Emulsion (A-1) 16 g of gelatin and 0.5 g of sodium chloride were added to an aqueous solution of gelatin (1500 ml of water, and the pH was adjusted to 3.2 with 1N sulfuric acid, 300 ml of an aqueous solution containing 71 g of potassium bromide and an aqueous solution of silver nitrate (300 ml of water and 0.59 of silver nitrate).
Mols dissolved) were added simultaneously at equal flow rates over 50 minutes. One minute after completion of this addition, 43 ml of a 1% methanol solution of the sensitizing dye (1) shown below was added, and 15 minutes after the addition, an aqueous solution containing 2.9 g of potassium iodide was added.
0 ml and an aqueous solution of silver nitrate (0.018 mol of silver nitrate dissolved in 100 ml of water) were added at an equal flow rate over 5 minutes. To this emulsion was added 1.2 g of polyisobutylene-monosodium co-maleate) to cause precipitation, followed by washing with water and desalting.
Gelatin (12 g) was added and dissolved, and sodium thiosulfate (0.5 mg) was further added, followed by chemical sensitization for 15 minutes to obtain a monodisperse tetradecahedral silver iodobromide emulsion (A-1) having an average grain size of 0.22 μm.
1000 g was prepared.

(Green Sensitive) Preparation of Silver Halide Emulsion (A-2) Gelatin aqueous solution (20 g of gelatin and 0.5 g of sodium chloride were added to 1600 ml of water, adjusted to pH 3.2 with 1N sulfuric acid, and kept at 42 ° C. 200 ml of an aqueous solution containing 71 g of potassium bromide and an aqueous solution of silver nitrate (200 ml of water and 0.59 of silver nitrate).
Mols dissolved) were added simultaneously at equal flow rates over 30 minutes. One minute after this addition was completed, 48 ml of a 1% methanol solution of the sensitizing dye (2) shown below was added, and 10 minutes after the addition of the sensitizing dye, 100 ml of an aqueous solution containing 2.9 g of potassium iodide and an aqueous solution of silver nitrate ( 0.018 mol of silver nitrate dissolved in 100 ml of water) was added simultaneously over 5 minutes. To this emulsion, 1.2 g of poly (isobutylene-co-monomaleate monosodium) was added, allowed to settle, washed with water and desalted, then 18 g of gelatin was added and dissolved, and further 0.7 mg of sodium thiosulfate was added, Chemical sensitization was performed at 60 ° C. for 15 minutes to prepare 1000 g of a monodisperse tetradecahedral silver iodobromide emulsion (A-2) having an average grain size of 0.12 μm.

(Red-sensitive) Preparation of silver halide emulsion (A-3) Aqueous gelatin solution (20 g of gelatin and 0.5 g of sodium chloride were added to 1600 ml of water, adjusted to pH 3.5 with 1N sulfuric acid, and kept at 45 ° C).
To 200 ml) and 200 ml of an aqueous solution containing 71 g of potassium bromide and an aqueous solution of silver nitrate (0.59 mol of silver nitrate dissolved in 200 ml of water) were simultaneously added at an equal flow rate for 30 minutes. One minute after this addition was completed, 48 ml of a 0.5% methanol solution of the following sensitizing dye (3) was added, and 15 minutes after the addition of the sensitizing dye, 100 ml of an aqueous solution containing 3.65 g of potassium iodide and an aqueous solution of silver nitrate. (0.022 g of silver nitrate dissolved in 100 ml of water) was added at an equal flow rate over 5 minutes. To this emulsion, 1.2 g of poly (isobutylene-co-monomaleate monosodium) was added, precipitated, washed with water, desalted, and then dissolved by adding 10 g of gelatin, and further adding 0.45 mg of sodium thiosulfate. Chemical sensitization was carried out at 55 ° C. for 20 minutes to prepare 1000 g of a monodisperse tetradecahedral silver iodobromide emulsion (A-3) having an average grain size of 0.13 μm.

Preparation of Photosensitive Composition (B-1) 63 g of the following polymerizable compound (Kayarat R604, manufactured by Nippon Kayaku Co., Ltd.), 0.77 g of the following copolymer, 0.36 g of p-toluenesulfonamide, and the following yellow image formation Substance 1
2.5 g was dissolved. Add the following reducing agent (4) 6.
1 g, the following development inhibitor releasing precursor 0.09 g, the following photopolymerization initiator (Irgacure 651, manufactured by Ciba Geigy) 4.71
g, 0.01 g of the following antifoggants, 1.8 g of Emarex NP-8 (manufactured by Nippon Emulsion Co., Ltd.) and 20 g of methylene chloride
Was added to obtain a uniform solution.

To 15 g of the above silver halide emulsion (A-1) was added 1.5 ml of a 10% aqueous solution of potassium bromide, and 0.5 ml of a 0.08% by weight 1-methoxy-2-methylpropanol solution of the following development accelerator was added to give 5 ml. Stir for minutes. Further, 1.5 ml of a 1% aqueous solution of polyvinylpyrrolidone (K-15, manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred for 5 minutes. The mixed solution containing this silver halide emulsion was added to the above homogeneous solution and stirred at 15,000 rpm for 5 minutes using a homogenizer to obtain a photosensitive composition (B-1) consisting of a W / O emulsion. It was

Preparation of photosensitive microcapsule liquid (C-1) Sodium salt of polyvinylbenzenesulfonic acid (Vera
sa TL502, National Starch) 210% 10% aqueous solution
Was adjusted to pH 6.0 with a 10% aqueous sodium hydroxide solution.

On the other hand, a polyvalent isocyanate compound (Takenate D110N, Takeda Pharmaceutical Co., Ltd.) was added to the photosensitive composition (B-1).
Manufactured by K.K.) was added to the above aqueous solution.

This mixed solution was heated to 40 ° C. and stirred at 9000 rpm for 30 minutes using a homogenizer to obtain an emulsion in a W / O / W emulsion state.

Separately, 21.6 g of 37% aqueous solution of formaldehyde and 70 g of distilled water were added to 13.2 g of melamine, heated to 60 ° C., and stirred for 30 minutes to obtain a transparent aqueous solution of melamine-formaldehyde initial condensation product.

77 g of an aqueous solution of this initial condensate was added to the above W / O / W emulsion, and the pH was adjusted to 6.0 using a 20% aqueous solution of phosphoric acid. Then, this was heated to 60 ° C. and stirred for 120 minutes, 27 g of a 40% aqueous solution of urea was added, the pH was adjusted to 3.5 using a 20% aqueous solution of phosphoric acid, and stirring was continued for 40 minutes. Finally, the pH was adjusted to 6.5 and cooled to room temperature to prepare a photosensitive microcapsule dispersion (C-1).

Preparation of Photosensitive Compositions (B-2) and (B-3) The silver halide emulsion used in the preparation of Photosensitive Composition (B-1), the amount of the antifoggant, and the color image-forming substance are The photosensitive composition (B- was prepared in the same manner as in the preparation of the photosensitive composition (B-1) except that the composition was changed according to Table 1 below.
2) and (B-3) were prepared.

Preparation of Photosensitive Microcapsule Liquid (C-2) In the preparation of photosensitive microcapsule liquid (C-1), photosensitive composition (B-2) is used instead of photosensitive composition (B-1). A dispersion liquid (C-2) of photosensitive microcapsules was prepared in the same manner except that it was not used.

Preparation of Photosensitive Microcapsule Liquid (C-3) In the preparation of photosensitive microcapsule liquid (C-1), photosensitive composition (B-3) is used instead of photosensitive composition (B-1). A dispersion liquid (C-3) of photosensitive microcapsules was prepared in the same manner except that it was not used.

Preparation of base precursor dispersion 20 g of the following base precursor was added to 80 g of a 4% aqueous solution of polyvinyl alcohol (PVA205, Kuraray Co., Ltd.),
A Dynomill was used to disperse the base precursor at 20 ° C. until the average particle size became 2 μm to prepare a dispersion liquid of the base precursor.

Preparation of image recording material 16 g of photosensitive microcapsule liquid (C-1), (C-
2) 18.5 g, (C-3) 14.8 g, base precursor dispersion liquid 6.8 g, sorbitol 20% aqueous solution 9 ml and starch 10% aqueous solution 10 ml were mixed. Further, 4 ml of a 5% aqueous solution of the following surfactant and water were added to adjust the total amount to 74 g to prepare a coating liquid for the image recording material.

This coating solution was applied on a colored coated paper having a basis weight of 60 g at a rate of 50 g per m ² and dried at about 60 ° C. to prepare an image recording material (A).

[Example 2] In the preparation of the photosensitive composition of Example 1, the reducing agent (4)
Instead of using 5.52 g of the following reducing agent (3),
An image recording material (B) was prepared in the same manner as in Example 1.

Example 3 In the preparation of the photosensitive composition of Example 1, the reducing agent (4)
Instead of using 5.42 g of the following reducing agent (12),
An image recording material (C) was prepared in the same manner as in Example 1.

Example 4 In the preparation of the photosensitive composition of Example 1, the reducing agent (4)
Instead of using 6.59 g of the following reducing agent (16),
An image recording material (D) was prepared in the same manner as in Example 1.

Example 5 In the preparation of the photosensitive composition of Example 1, the reducing agent (4)
Instead of using 3.39 g of the following reducing agent (19),
An image recording material (E) was prepared in the same manner as in Example 1.

Example 6 In the preparation of the photosensitive composition of Example 1, the reducing agent (4)
Instead of using 5.13 g of the following reducing agent (21),
An image recording material (F) was prepared in the same manner as in Example 1.

Example 7 In the preparation of the photosensitive composition of Example 1, the reducing agent (4)
Instead of using 3.83 g of the following reducing agent (24),
An image recording material (G) was prepared in the same manner as in Example 1.

Example 8 In the preparation of the photosensitive composition of Example 1, the reducing agent (4)
Instead of using 1.11 g of the following reducing agent (101),
An image recording material (a) was prepared in the same manner as in Example 1.

[Example 9] In the preparation of the photosensitive composition of Example 1, the reducing agent (4)
Instead of using 1.47 g of the following reducing agent (102),
An image recording material (b) was prepared in the same manner as in Example 1.

Example 10 In the preparation of the photosensitive composition of Example 1, the reducing agent (4)
Instead of using 1.63 g of the following reducing agent (103),
An image recording material (c) was prepared in the same manner as in Example 1.

Example 11 In the preparation of the photosensitive composition of Example 1, the reducing agent (4)
Instead of using 1.10 g of the following reducing agent (104),
An image recording material (d) was prepared in the same manner as in Example 1.

Preparation of image receiving material 40% aqueous solution of sodium hexametaphosphate in 125 g of water
11 g was added, and further 34 g of 3,5-di-α-methylbenzylsalicylate zinc and 82 g of 55% calcium carbonate slurry were mixed and dispersed with a mixer. The liquid was dispersed with a Dynomill disperser, and to 200 g of the obtained liquid, 6 g of 50% SBR latex and 55 g of 8% polyvinyl alcohol were added and uniformly mixed. 30 μm of this mixed solution on a paper with a basis weight of 55 g / m ^2.
And then dried to obtain an image receiving material.

Image formation and evaluation thereof Image recording materials (A) to (G) and (a) to (d)
Was imagewise exposed at 2000 lux for 1 second through a gray continuous filter whose transmission density was continuously changed from 0 to 3.0 using a halogen lamp, and then heat-developed at 155 ° C. Then, using a halogen lamp, uniform exposure was carried out at 50,000 lux for 30 seconds, each image recording material was superposed on the image receiving material, and in this state, it was passed through a pressure roller of 500 kg / cm ² . The maximum density (Dmax) and the minimum density (Dmin) were measured with a Macbeth reflection densitometer for each hue (yellow, magenta and cyan) of the negative color image obtained on each image receiving material. The measurement results are shown in Table 2.

Separately, each image recording material was stored under conditions of 40 ° C. and 80% relative humidity for 8 days, and then image forming processing was performed in the same manner as above, and the obtained image was evaluated. The measurement results are shown in Table 3.

As is clear from the results shown in Table 2, the image recording method of the present invention gave a very clear image.

Furthermore, as is clear from the results shown in Table 3,
The image recording materials (A) to (G) containing the reducing agent represented by the above formula [I] give clear images even after storage under severe conditions.

Example 12 Preparation of Image Recording Material The photosensitive microcapsule liquids (C-1), (C-2) and (C-3) prepared in Example 1 were respectively prepared.
17 g, 5 g of a 10% aqueous gelatin solution, 6 ml of a 5% aqueous solution of the surfactant used in Example 1, 7.3 g of a 10% aqueous dispersion of zinc hydroxide and 28 g of water were mixed to prepare a coating solution for the image recording material. Prepared.

This coating liquid was applied onto a polyethylene terephthalate sheet having a thickness of 100 μm so that the wet film thickness was 50 μm, and dried to prepare an image recording material (H).

Example 13 In the preparation of the photosensitive composition of Example 12, reducing agent (4)
Instead of the reducing agent (3) 5.52 used in Example 2.
An image recording material (I) was prepared in the same manner as in Example 12 except that g was used.

Example 14 Reducing agent (4) in the preparation of the photosensitive composition of Example 12
Instead of the reducing agent (12) 5.42 used in Example 3.
An image recording material (J) was prepared in the same manner as in Example 12 except that g was used.

Example 15 In the preparation of the photosensitive composition of Example 12, the reducing agent (4)
Instead of the reducing agent (16) 6.59 used in Example 4.
An image recording material (K) was prepared in the same manner as in Example 12 except that g was used.

[Example 16] A reducing agent (4) in the preparation of the photosensitive composition of Example 12
Instead of the reducing agent (19) 3.39 used in Example 5.
An image recording material (L) was prepared in the same manner as in Example 12 except that g was used.

Example 17 In the preparation of the photosensitive composition of Example 12, the reducing agent (4)
Instead of the reducing agent (21) 5.13 used in Example 6.
An image recording material (M) was prepared in the same manner as in Example 12 except that g was used.

Example 18 In the preparation of the photosensitive composition of Example 12, the reducing agent (4)
Instead of the reducing agent (24) 3.83 used in Example 7.
An image recording material (N) was prepared in the same manner as in Example 12 except that g was used.

Example 19 Reducing agent (4) in the preparation of the photosensitive composition of Example 12
Instead of the reducing agent (101) 1.1 used in Example 8.
An image recording material (e) was prepared in the same manner as in Example 12 except that 1 g was used.

Example 20 In the preparation of the photosensitive composition of Example 12, the reducing agent (4)
Instead of the reducing agent (102) 1.4 used in Example 9.
An image recording material (f) was prepared in the same manner as in Example 12 except that 7 g was used.

[Example 21] In the preparation of the photosensitive composition of Example 12, a reducing agent (4)
Instead of the reducing agent (103) 1.6 used in Example 10.
An image recording material (g) was prepared in the same manner as in Example 12 except that 3 g was used.

Example 22 In preparation of the photosensitive composition of Example 12, reducing agent (4)
Instead of the reducing agent (104) 1.1 used in Example 11.
An image recording material (h) was prepared in the same manner as in Example 12 except that 0 g was used.

Preparation of base generation sheet 27% of 10% gelatin aqueous solution, guanidine picolinate 3.2
A solution was prepared by mixing 17 g of 5% aqueous dextran solution, 5 ml of 5% aqueous solution of the surfactant used in Example 1, 2 ml of 2% aqueous solution of 1,2-bis (vinylsulfonylacetamide) ethane, and 45 ml of water. This mixed solution
A base generation sheet was prepared by coating a polyethylene terephthalate sheet having a thickness of 100 μm so that the wet film thickness was 70 μm, and drying at about 40 ° C.

Image formation and evaluation thereof Image recording materials (H) to (N) and (e) to (h)
Was imagewise exposed for 1 second at 2000 lux through a continuous gray filter with a halogen lamp, the transmission density varying continuously from 0 to 3.0. Then, water was applied to the photosensitive layer in an amount of 10 g per 1 m ² , and then the base generating sheets were adhered to each other so that their film surfaces were in contact with each other. In this state, heating was performed using a belt transport roller type heating device (heating temperature 85 ° C., heating time 10 seconds).

After the base generating sheet was peeled from the photosensitive material, it was uniformly exposed for 30 seconds at 50,000 lux using a halogen lamp. Then, each image recording material was superposed on the image receiving material used in Example 1, and in this state, it was passed through a pressure roller of 500 kg / cm ² . The maximum density (Dmax) and the minimum density (Dmin) were measured with a Macbeth reflection densitometer for each hue (yellow, magenta and cyan) of the negative color image obtained on each image receiving material. Table 4 shows the measurement results.

Separately, each image recording material was stored under conditions of 40 ° C. and 80% relative humidity for 8 days, and then image forming processing was performed in the same manner as above, and the obtained image was evaluated. The measurement results are shown in Table 5.

As is clear from the results shown in Table 4, the image recording method of the present invention gave a very sharp image.

Furthermore, as is clear from the results shown in Table 5,
The image recording materials (H) to (N) containing the reducing agent represented by the above formula [I] give a clear image even after storage under severe conditions.

Claims (2)

(57) [Claims] 1. A step of imagewise exposing an image recording material containing silver halide to form a latent image of silver halide; a latent image of silver halide contained in the image recording material using a reducing agent. And a step of developing a polymer image by exposing the image recording material substantially uniformly in the presence of a photopolymerization initiator and an ethylenically unsaturated polymerizable compound. As the reducing agent, a compound that forms an oxidant having a polymerization-inhibiting effect on the ethylenically unsaturated polymerizable compound after the development of silver halide is used, whereby the polymerizable compound in a portion where the oxidant is not formed is photosensitized. An image recording method comprising polymerizing to form a polymer image. 2. The image recording method according to claim 1, wherein the reducing agent is a compound represented by the following formula [I]: [In the above formula [I], R ¹ is an organic group bonded to the benzene ring via a hetero atom having a lone electron pair, and R ² is a group consisting of a halogen atom, an alkyl group, an aryl group and a heterocyclic group. A monovalent group selected from the group (each group may have a substituent), m is 1, 2, 3 or 4, and n satisfies the formula 0 ≦ n ≦ (4-m) And an aromatic ring, an aliphatic ring and / or a heterocycle may be condensed with the benzene ring].