JPH02207254A - Image recording method - Google Patents

Abstract

PURPOSE:To allow a polymer image to be formed in an unexposed part in imagewise exposing by using a compd. forming an oxidant having the effect of inhibiting the polymn. of a polymerizable compd. after development of silver halide as a reducing agent. CONSTITUTION:An image recording material contg. the silver halide is formed with the latent image of the silver halide by imagewise exposing and this latent image is developed by using the compd. forming the oxidant having the effect of inhibiting the polymn. of the ethylenic unsatd. polymerizable compd. after the development of the silver halide as the reducing agent. The image recording material is substantially uniformly exposed in the presence of a photopolymn. initiator and the ethylenic unsatd. polymerizable compd. to photopolymerize the polymerizable compd. in the part where the oxidant is not formed, by which the polymer image is formed. The formation of the polymer image in the unexposed part is possible in this way.

Description

Detailed Description of the Invention [Field of the Invention] The present invention relates to a process of imagewise exposing an image recording material containing silver halide to form a latent image of silver halide, and a process of forming a latent image of silver halide using a reducing agent. The present invention relates to an image recording method comprising the steps of developing a latent image and substantially uniformly exposing the image recording material to light in the presence of a photopolymerization initiator and a polymerizable compound to form a polymer image.

[Background of the Invention] A method of imagewise forming a polymer image using a photopolymerization initiator made of an organic compound is well known. but,
Photoinitiators have lower sensitivity compared to silver halide,
Requires long or intense exposure. Therefore, the applications of image recording methods using photopolymerization initiators are limited due to limitations in the sensitivity of photopolymerization initiators.

On the other hand, a method of causing a polymerization reaction using silver halide as a photosensor is also well known. For example, a method of causing a polymerization reaction using radicals generated from a reducing agent oxidized during the development process of silver halide was published in Japanese Patent Publication No. 45-11149.
No. 45-30338, No. 46-6581, No. 4
No. 6-21723, No. 47-12638, No. 47-1
No. 4667, No. 47-14668, No. 47-1466
No. 9, No. 46-16357, No. 47-18585,
No. 47-20741, No. 49-1569, No. 49-
No. 1570, No. 49-10697, JP-A-57-13
No. 862, No. 57-142638, No. 57-1760
No. 33, No. 58-107529, No. 58-16914
No. 3 and No. 58-174947.

In addition, there is a method in which radicals are generated from the peroxide through an oxidation-reduction method between the developed silver and the peroxide (described in Japanese Patent Publication No. 18862/1986), and a method in which the silver ions remaining in the unexposed area and the peroxide are A method of generating radicals from peroxide through redox reaction of
-2657 publication), silver halide is developed with iron (I) salt, and the iron (I) salt remaining in the unexposed area undergoes an oxidation-reduction reaction with the peroxide, causing a polymerization reaction with radicals generated from the peroxide. Method (described in US Pat. No. 3,029,145)
, a method of causing a direct polymerization reaction using a reducing agent remaining in the unexposed area after developing silver halide (Japanese Patent Laid-Open No. 55-14993)
(described in Publication No. 9). These methods, in principle, can form polymer images with a sensitivity close to that of silver halide. However, both methods require wet processing in the process, which is a major constraint on equipment design.

An image recording method that solves the problems of both the method using a photopolymerization initiator and the method using silver halide as a photosensor as described above is disclosed in JP-A-61-75342 (U.S. Pat. No. 4,649,098). )It is described in. This method includes a step of imagewise exposing an image recording material containing silver halide to form a latent image of silver halide, a step of developing the latent image of silver halide using a reducing agent, and a step of developing a latent image of silver halide using a photopolymerization initiator and It consists of a step of substantially uniformly exposing the image recording material to light in the presence of a polymerizable compound to form a polymer image.

The reducing agent used in the image recording method described in JP-A-61-75342 has (1) an action as a developer for silver halide, and (2) a polymerizable vinyl monomer (
It has an action as a polymerization inhibitor for ethylenically unsaturated polymerizable metal compounds), and also has the property (3) of losing its action as a polymerization inhibitor after silver halide is developed. By using such a reducing agent, in the above image recording method, the polymerizable compound in the area where there is no reducing agent (the area where the oxidized product 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 in an exposed area in imagewise exposure.

[Summary of the Invention] When the present inventors further researched the image forming method described in JP-A-61-75342, they discovered a system in which a polymer image is formed in the unexposed area during imagewise exposure. It has become clear that this is also possible.

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

JP-A-61-243449 describes 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 dichlorop-
Aminophenol, 2,6-dimethyl-p-aminophenol, 3,5-dimethylp-aminophenol, hydroquinone, methylhydroquinone, catechol, p
-tert-butylcatechol, chlorohydroquinone, p-methoxyphenol, p-anisidine, 0-anisidine, o(m or p)-phenylenediamine, 2.
4-tolylene diamine and 3,4-)lylene diamine are mentioned.

An image recording method using a combination of silver halide and a thermal polymerization initiator consists of (1) imagewise exposing an image recording material containing silver halide, a reducing agent having the above-mentioned properties, a polymerizable compound, and a thermal polymerization initiator; forming a silver halide latent image;
and (2) heating the image recording material to develop the silver halide latent image, and thermally polymerizing the polymerizable compound in the portion where the oxidized product of the reducing agent (having a polymerization inhibiting effect) is not formed to form a polymer image. It consists of two steps: forming.

The image recording method using a combination of silver halide and a photopolymerization initiator as described above has fewer processing steps (consisting of three steps) than the image recording method using a combination of silver halide and a thermal polymerization initiator. It is complicated. For this reason, an image recording method using a combination of silver halide and a photopolymerization initiator requires the use of a compound having the above-mentioned effects and excellent storage stability as a reducing agent. However, the aforementioned JP-A-61-
The reducing agent described in Publication No. 243449 did not satisfy this requirement. For the above reasons, in an image recording method that uses silver halide and a photopolymerization initiator in combination, a system in which a polymer image is formed in an unexposed area has never been attempted.

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

The present inventors analyzed the chemical structure of the reducing agent and found that the compound represented by the formula [I] described below forms an oxidized product having a strong polymerization inhibiting effect after silver halide development. . Furthermore, this compound is disclosed in JP-A-61-2
It also has superior stability during storage compared to the reducing agent described in JP-A No. 43449. By using this compound as a reducing agent, it has become possible to put into practical use a system in which a polymer image is formed in an unexposed area in an image recording method that uses a combination of silver halide and a photopolymerization initiator.

The present invention includes (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 substantially uniformly exposing the image recording material to light in the presence of a photopolymerization initiator and an ethylenically unsaturated polymerizable compound to form a polymer image. As the reducing agent, a compound that forms an oxidant having a polymerization inhibiting effect on the ethylenically unsaturated polymerizable compound after development of the silver halide is used, thereby reducing the polymerizable compound in the portion where the oxidant is not formed. The present invention provides an image recording method characterized by forming a polymer image through photopolymerization.

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

[In the above formula [I], R1 is a monovalent organic group bonded to the benzene ring via a petro atom having a lone pair of electrons, and R2 is a halogen atom, an alkyl group, an aryl group, and a heterocyclic group. A monovalent group selected from the group (multigroup may have a substituent), m is 1.2.3 or 4, and n has the formula 0≦n≦(4-m). and an aromatic ring, an aliphatic ring, and/or a heterocyclic ring may be condensed with the benzene ring.] The image recording method of the present invention is also preferably in the following embodiment.

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

(4) The exposure amount during the above imagewise exposure is 10-2 to 10'c
ms, and the exposure amount during the uniform exposure is 103 to 1108 er/cm2.

(5) Perform the above development treatment by heating.

(6) The image recording material subjected to the above uniform exposure is pressed while superimposed on the image receiving material to transfer the unpolymerized polymerizable compound to the image receiving material.

(2-2) R1 in the above formula [I] is the following formula [n]
It is a monovalent group represented by

(VIB) -R3 [11] [In the above formula [11], (VIB) is a divalent group selected from the group consisting of an oxygen atom, a sulfur atom and a selenium atom, and R3 is an alkyl group, It is a monovalent group selected from the group consisting of an aryl group and a heterocyclic group (the polygroup may have a substituent)] (2-3) R1 in the above formula [I] is represented by the following formula [ m]
It is a monovalent group represented by

[In the above formula [m], (VB) is a trivalent group consisting of a nitrogen atom or a phosphorus atom, and R4 is a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group. (the multiple groups may have substituents), and R5 is an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, and a carbamoyl group. A monovalent group selected from the group consisting of (multigroups may have a substituent)] (3-2) The above image recording material is a monovalent group selected from the group consisting of silver halide, a reducing agent, and a light source on a support. A recording layer containing a polymerization initiator and a polymerizable compound is provided, and silver halide, a reducing agent, a photopolymerization initiator, and a polymerizable compound are contained in microcapsules in the recording layer.

[Effects of the Invention] In recent years, with the development of color hard copies, the demand for image processing such as color tone conversion has increased. In order to achieve this, the information to be copied must first be converted into an electrical signal (
It is essential to convert the data into digital signals. In the case of a recording method using polymer image formation, a color image is generally obtained by transferring a portion where no polymer is formed to an image receiving material. Considering this and the above-mentioned problem of converting into electrical signals, the system in which the unexposed area becomes a polymer image (the present invention) is more advantageous than the system in which the exposed area becomes a polymer image.

According to the research of the present inventors, in the latter case, it is necessary to read the area without information (background area such as a white background) and expose this area, whereas in the former case (the present invention), the information It is very efficient because all you have to do is read the area and apply the exposure corresponding to the information area. The effects of the present invention are particularly significant when the object to be copied is a document containing many characters.

Further, along with the conversion of information into digital signals, it is conceivable to use laser light as a light source for imagewise exposure. When laser light is used as a light source, imagewise exposure can be performed with high resolution even on originals with very fine lines. Of course, even if laser light is used as a light source, polymer images with high sharpness will not be formed if the resolution of imagewise post-exposure processing is low.

According to research by the present inventors, systems in which polymer images are formed in unexposed areas during imagewise exposure have higher resolution and fine line images compared to systems in which polymer images are formed in exposed areas. has excellent expressive power. Therefore, the image recording method of the present invention can record clear images with high sharpness. The effects of the present invention are particularly remarkable when laser light is used as a light source for imagewise exposure.

Note that, as described above, the compound represented by formula [I] forms an oxidant having a strong polymerization inhibiting effect. Therefore, by using this compound, the image recording method of the present invention can record very clear images. Also,
This compound also has superior stability during storage compared to the reducing agent described in JP-A-61-243449. Therefore, the compound represented by formula [I] can be included 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 an action of inhibiting the polymerization of a polymerizable compound after development of silver halide. As the reducing agent, the compounds described in JP-A-61-243449 mentioned above can be used.

However, in the image forming method of the present invention, it is preferable to use a compound represented by the following formula [I] as the reducing agent. Some of the compounds represented by the following formula [I] are known as developers in the field of heat-developable silver salt photography. However, it was completely unknown that an oxidized product having a polymerization inhibiting effect of a polymerizable compound is formed after development of silver halide.

In the above formula [I], R1 is a monovalent organic group bonded to the benzene ring via a petero atom having a lone pair of electrons.

R2 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,
Multiple groups may have one or more substituents.

m is 1.2.3 or 4.

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

An aromatic ring, an aliphatic ring and/or a heterocycle may be fused to the benzene ring in the above formula [I]. The ring fused to the benzene ring may have one or more substituents. However, the above benzene ring is the above R1 and R
It has no substituents other than 2.

Note that two or more compounds represented by formula [I] may be combined to form a multimer. When forming a multimer, it is preferable to bond via R1 or R2 in formula [I].

The compound represented by formula [I] will be further explained below.

The petro atom having a lone pair of electrons contained in R1 is preferably an oxygen group atom or a nitrogen group atom. As a specific example of a petro atom, (...) in an acid symbol means a lone pair of electrons.

R1 in formula [I] is a monovalent group represented by the following formula [■] (when the Peter atom is an oxygen atom) or formula [m] (when the Peter atom is a nitrogen group atom) is preferred.

-(VIB)-R3 [11] In the above formula [11], (VIB) is a divalent group selected from the group consisting of an oxygen atom, a sulfur atom, and a selenium atom. Sulfur atoms are particularly preferred.

R3 is a monovalent group selected from the group consisting of an alkyl group, an aryl group, and a heterocyclic group. Note that the polygroup may have one or more substituents.

In the above formula [111], (VB) is a trivalent group consisting of a nitrogen atom or a phosphorus atom. A nitrogen atom is particularly preferred.

R4 is a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group. Note that the polygroup may have one or more substituents.

R5 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. Particularly preferred are acyl, alkylsulfonyl and arylsulfonyl groups. Note that the polygroup may have one or more substituents.

R4 and R5 may be the same.

The halogen atom constituting R2 in 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 in the alkyl group constituting R2, R3R4 and R5 is preferably 1 to 22. The alkyl group may have a linear structure or may have a branch. Further, the alkyl group may form a cyclic structure. That is,
In this specification, "alkyl group 1" includes a cycloalkyl group. The alkyl group may have a substituent such as a halogen atom, an aryl group (e.g., phenyl group), an alkoxy group, a hydroxyl group, or a cyano group. Good. The r-alkyl group 1 in this specification includes an aralkyl group (an alkyl group having an aryl group as a substituent).

Specific examples of the aryl group constituting R2R3, R4 and R5 include phenyl group, naphthyl group, anthryl group,
Examples include phenanthryl group. A phenyl group is particularly preferred. Aryl groups include alkyl groups, aryl groups, halogen atoms, alkoxy groups, alkoxycarbonyl groups, amido groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, acyl groups, hydroxyl groups, cyan groups, nitro groups, amino groups, It may have a substituent such as a carbamoyl group or a sulfamoyl group.

Specific examples of the heterocyclic group constituting R2R3, R4 and R5 include a pyridyl group, a pyrimidyl group, an imidazolyl group, a thiazolyl group, an oxacylyl group, a succinimide group,
Mention may be made of hydantoyl groups. The heterocycle may be fused with an aromatic ring such as a benzene ring or a naphthalene ring and/or another heterocycle. The heterocyclic group includes a halogen atom, an alkyl group (preferably having 1 to 1 carbon atoms)
0), an alkoxy group (preferably having 1 to 10 carbon atoms), and a nitro group.

m is 1.2.3 or 4. m is preferably 1 or 2. When m is 2 or more, the plural R1's may be different from each other.

n is an integer that satisfies the formula 0≦n≦(4-m). n is preferably 0 or 1. If n is 2 or more,
The plurality of R2s may be different from each other.

The acyl group constituting R5 in formula [m] is represented by the following formula [
m-a].

-Co-R6[111-a] In formula [IIr-a], R6 is a monovalent group selected from the group consisting of an alkyl group, an aryl group, and a heterocyclic group. Note that the polygroup may have one or more substituents.

The alkylsulfonyl group and arylsulfonyl group constituting R5 in formula [I11] are represented by the following formula % formula % [ ] In formula [m-b], R8 is an alkyl group or an aryl group. Note that the polygroup may have one or more substituents.

The alkoxycarbonyl group constituting R5 in formula [m] is represented by the following formula [m-c].

Co-0R9[II[-c] In the formula [I[1-c], R9 is an alkyl group. Note that the alkyl group may have one or more substituents.

The carbamoyl group constituting R5 in formula [m] is represented by the following formula [I[[-d].

Co-NR"R" [m-d] In the formula [m-d], R" and R-th are respectively,
m groups selected from the group consisting of hydrogen atoms, alkyl groups, aryl groups, and heterocyclic groups. Note that the polygroup may have one or more substituents.

The sulfamoyl group constituting R5 in formula [II[] is represented by the following formula [■-e].

-3o2-NR12R13[III-e] Formula [I[I-
e], R12 and R13 are each m groups selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group. Note that the polygroup may have one or more substituents.

R6-R13 of the above formula [I[[-a] to [me]
The alkyl groups, aryl groups, heterocyclic groups and their substituents constituting are the same as the alkyl groups, aryl groups, heterocyclic groups and their substituents constituting R2H3R4 and R5 described above.

Next, typical examples of reducing agents that can be used in the present invention will be shown.

6H13 (n) ti 33L; l5S CH3 Typical synthesis examples of the reducing agent used in the present invention are shown below.

Other reducing agents can also be synthesized in a similar manner.

[Synthesis Example 1 10.7 gi of 1,4-dimethoxy-2 sobalmitoylaminobenzene and 6.00 mJZ of pyridine were added to 30 mJl of acetonitrile! 19. Inbalmitoyl chloride was dissolved in the solution and stirred at room temperature.
2 g was added dropwise over 10 minutes.

After stirring for an additional 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 oil.

Him 1 of 4 1.27.0 g of 4-dimethoxy-2-isobalmitoylaminobenzene was dissolved in 130 ml of chlorobenzene, and while stirring at room temperature, 21.3 g of anhydrous aluminum chloride was dissolved.
g was added little by little. The temperature was raised to 90°C and stirred for 3 hours. After cooling, 135 ml of water was added little by little. Chlorbenzene was removed by steam distillation and extracted with ethyl acetate. The organic layer was washed with water and then dried over sodium sulfate.

The desiccant was removed by filtration, and the solvent was distilled off to give a pale yellow oil. Crystallization from a methylene chloride-〇-hexane mixed solvent yielded 21.5 g of colorless crystals of compound (1).
I got it. The melting point was 74-76°C.

[Synthesis Example 2] 4-acetoxy-2-n hexadecyloxyacetophenone 42-n-hexadecyloxy-4-hydroxyacetophenone 50.0
g and 1.30 mJ2 of pyridine were dissolved in 150 mu DMF, and 15.0 ml of acetic anhydride was added dropwise over 10 minutes while stirring at room temperature. 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.

1.4-Diacetoxy-2-n-hexadecyloxybenzene 75.0 g 4-acetoxy-2-n-hexadecyloxyacetophenone, 4.0 ml concentrated sulfuric acid and 4 glacial acetic acid
0mI! , was dissolved in chloroform at 350 m°C, stirred at room temperature, and then m-chloroformbenzoic acid was dissolved at 80 mC. Og was added 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 bicarbonate, and then dried over sodium sulfate. The desiccant is removed by filtration,
When the solvent was distilled off, 60.0 g of pale yellow powder was obtained.

Δ 14 of 4 1,4-diacetoxy-2-n-hexadecyloxybenzene 60.0 g, hydroxylamine hydrochloride 38.7
g and 45.3 grams of sodium acetate were dispersed in JZ for methanol 300 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 yielded 37.0 g of colorless crystals of compound (14).
I got it. The melting point was 106-108°C.

[Synthesis Example 3] 100 g of n-hexadecane-sulfenyl-benzoquinone was dispersed in 500 mR of methanol, and while refluxing, n-hexadecanethiol 1
20g was added dropwise over 20 minutes.

The mixture was refluxed for an additional 30 minutes. After cooling, the precipitated crystals were collected by filtration, washed with methanol, and then dried. 126 g of yellow crystals were obtained.

Hum 15 n-hexadecanesulfenyl-p-benzoquinone 12
6 g was dissolved in 600 mj2 of ethyl acetate, and while refluxing, an 85% aqueous solution of N,N-diethylhydroxylamine was added.
3.7 g was added dropwise over 20 minutes. The mixture was refluxed for an additional 30 minutes. The reaction mixture was poured onto dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with water and brine, and then dried over sodium sulfate. The drying agent was removed by filtration, and the solvent was distilled off to obtain pale yellow crystals. Recrystallization was performed from acetonitrile to obtain 120 g of colorless crystals of compound (15). The melting point was 83-84°C.

[Synthesis Example 4] Him 23 mun-valmitoylamino-p-hydroquinone 60.0 g
, 22.8 g of dodecyl aldehyde and 50.0 g of anhydrous calcium chloride were dispersed in 500 mfi of ethyl acetate, and 15.0 ml of concentrated hydrochloric acid was added while stirring at room temperature. The reaction concentration was set at 27 to 30°C, and the mixture was stirred for 8.5 hours. Insoluble matters were removed by filtration, and the organic layer was washed with water and brine, and then dried over sodium sulfate. The drying agent 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 to obtain 37.6 g of colorless crystals of compound (23). The melting point was 173-174°C.

Margins Below In the image recording method of the present invention, the above-mentioned reducing agents may be used alone or in combination of several kinds.

In the light-sensitive material, the reducing agent is preferably used in an amount of 0.1 to 1,500 mol % based on 1 mol of silver (including the aforementioned silver halide and optional organic silver salt). A more preferable usage range is 10 to 500 mol%.

Further, in the image recording method of the present invention, the reducing agent represented by the above formula (I) may be
It may be used in combination with the reducing agent described in Publication No. 9. Furthermore, a reducing agent generally known as a developing agent in the field of silver salt photography may be used in combination. Reducing agents known as developing agents include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, and 5-aminopyrazoles. aminouracils, 4゜5-dihydroxy-6-aminopyrimidines, reductones, amylreductones, 0- or p-sulfonamidophenols, 0- or p-sulfonamidonaphthols, 2-sulfonamidoindanones, Examples include 4-sulfonamide-5-pyrazolones, 3-sulfonamide indoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α-sulfonamide ketones, and the like.

Specific examples of the above developer include pentadecylhydroquinone, 5-t-butylcatechol, p(N,N-diethylamino)phenol, 1-phenyl-4-methyl-4
-Hydroxymethyl-3-virazolidone, 1-phenyl-4-methyl-4-heptadecylcarbonyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamino-4-hexadecyloxy-5-t-octylphenol, 2-phenylsulfonyl Amino-4-t-butyl-
Examples include 5-hexadecyloxyphenol, 2(N-butylcarbamoyl)-4-phenylsulfonylaminonaphthol, and 2-(N-methyl-N-octadecylcarbamoyl)-4-sulfonylaminonaphthol.

Regarding various reducing agents (developing agents) that can be used in combination with the reducing agent of the present invention, see "The
Theory of the Photography
ic Process” 4th edition, pp. 291-334 (1
977), Research Disclosure Magazine Vol.
1.70.No. 17029 of June 1978 (9-15
176, December 1978, No. 17643 (pages 22-31).

When using more than one type of reducing agent in combination, the interaction of the reducing agents is, firstly, to promote the reduction of silver halide (and/or organic silver salt) by so-called superadditivity, and secondly, to promote the reduction of silver halide (and/or organic silver salt). , suppressing the polymerization of a polymerizable compound via a redox reaction with another reducing agent in which the oxidized form of the first reducing agent generated by reduction of silver halide (and/or organic silver salt) coexists. etc. are possible. However, in actual use, the reactions described above can occur simultaneously, so it is difficult to specify which effect is occurring.

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) a step of forming a latent image of silver halide using a reducing agent; (III) substantially uniformly exposing the image-recording material in the presence of a photopolymerization initiator and an ethylenically unsaturated polymerizable compound; The steps of forming an image will be sequentially explained.

(I) Various exposure means can be used for imagewise exposure of the image recording material. Examples of light sources include tungsten lamps, halogen lamps, mercury lamps, fluorescent lamps, xenon lamps, laser light, and LED%CRT. A latent image of the silver halide is then obtained by imagewise exposure to radiation, including visible light. The type of light source and the amount of exposure can be selected depending on the wavelength to which silver halide is sensitive (in the case of dye sensitization, the sensitized wavelength) and sensitivity. Further, 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
' cms (Cd (candela) m-sec).

In addition, in an embodiment in which the image recording material during imagewise exposure contains a photopolymerization initiator and a polymerizable compound, the polymerizable compound in the exposed area is photopolymerized by the action of the photopolymerization initiator during imagewise exposure. Possible. However, since the sensitivity of the photoinitiator is significantly lower than that of silver halide, the effect of the photoinitiator on imagewise exposure is virtually negligible.

(II) The image recording material may be developed using a developer containing the above-mentioned reducing agent. but,
Thermal development treatment performed by heating the image recording material is a dry treatment, so it has the advantage of being simple to operate and capable of being processed in a short time. Therefore, thermal development is particularly excellent as a development process for photosensitive materials.

As the heating power method in the above heat development treatment, various conventionally known methods can be used. For example, a hot plate, heat roller, infrared heater, etc. can be used. Further, a heating element layer may be provided on the image recording material and used as a heating means. Further, the heat development process may be performed while suppressing the amount of oxygen present 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 with a liquid (preferably water) permeated into the image recording layer.

The heating temperature is generally 80°C to 200°C, preferably 10°C.
The heating time is generally 1 second to 5 minutes, preferably 5 seconds to 1 minute.

(I[I) The light source used for uniform exposure of the image recording material is similar to that used for imagewise exposure described above. The exposure amount during uniform exposure is 103 to 1108er/crr
+' is preferable, and 104 to 106e r
More preferably, it is g/c.

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

The first embodiment is a case where silver octogenide 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 comprises (I) an image recording material having a recording layer containing silver halide, a reducing agent, a photopolymerization initiator and an ethylenically unsaturated polymerizable compound on a support; (II) heating the image-recording material to develop the latent silver halide image; and (III) exposing the image-recording material to a substantially uniform surface. Preferably, the method comprises a step of exposing to light to form a polymer image.

The second embodiment is a case where an image recording material is used 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 710 silver germide will be referred to as a silver halide element, and the support provided with a layer containing a photopolymerization initiator will be referred to as a photopolymerization initiator element.

A second aspect of the image forming method of the present invention includes (I) imagewise exposing a silver halide element to form a latent image of silver halide; (II) a reducing agent is included in the silver halide element. (m-a) developing the silver halide element with heat or water if the silver halide element contains a reducing agent, or with an aqueous solution containing a reducing agent if the silver halide element does not contain a reducing agent
superimposing the developed silver halide element and the photoinitiator element or heating after superposition to transfer the reducing agent remaining in the silver halide element to the photoinitiator element; -b) The photoinitiator element is substantially uniformly exposed to light, either while the silver halide element and the photoinitiator element remain superimposed or after the photoinitiator element has been peeled off, to form a polymer image. It consists of the process of forming.

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 is
It can be removed by washing using a suitable solvent. Also,
Dye images can also be obtained by fixing dyes or pigments to the polymer. Furthermore, an image may be formed by bleaching (decolorizing) the dye using an unpolymerized ethylenically unsaturated polymerizable compound.

The image-receiving material can also be used to form an image on the image-receiving material.

By pressing the image recording material and image receiving material in which a polymer image has been obtained in a superimposed state, the unpolymerized polymerizable compound can be transferred to the image receiving material and an image can be obtained on the image receiving material. Regarding the above-mentioned pressurizing means, various conventionally known methods can be used.

Additionally, in embodiments where the image-recording material includes a color image-forming substance, the formation of a polymeric image thereby immobilizes the color image-forming substance in the cured portions. Then, by pressing the image recording material and the image-receiving material in a superimposed state, the uncured portion of the color image forming substance 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, the image-receiving material may be heated as in the image forming method described in Japanese Patent Application No. 61-55501. The above method also has the advantage that the unpolymerized polymerizable compound transferred onto the image-receiving material is polymerized and the storage stability of the obtained image is improved.

The image recording method of the present invention can be used in many applications such as black and white or color photography and printing, printing, printing plates, X-ray photography, medical photography (for example, ultrasonic diagnostic CRT photography), computer graphics hard copies, copying machines, etc. There is.

Margins Below Next, the image recording material used in the image recording method of the present invention will be described. As mentioned above, the image recording material preferably has a recording layer on the support, which contains silver halide, a reducing agent, a photopolymerization initiator, and an ethylenically unsaturated polymerizable compound. The image recording material of this embodiment will be particularly described below.

In the image recording material, grains of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used as silver halide. can.

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 with different compositions on the surface and inside, Japanese Patent Application Laid-open Nos. 57-154232 and 58-10853 disclose
No. 3, No. 59-48755, No. 59-52237, U.S. Patent No. 4433048 and European Patent No. 1
It is described in the 00984 specification. Also, JP-A-62
Silver halide grains having a high proportion of silver iodide in the shell portion may be used, as in the photosensitive material described in Japanese Patent No. 183453.

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

In addition, as the silver halide grains mentioned above, Japanese Patent Application Laid-Open No. 63-6
It is preferable to use silver halide grains having a relatively low fog value, such as the light-sensitive material described in Japanese Patent No. 8830.

For the silver halide used in the image recording material, two or more types of silver halide grains different in halogen composition, crystal habit, grain size, etc. can also be used in combination.

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

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

The amount of silver halide contained in the photosensitive layer is 0.1 mg to 1 mg in terms of silver, including organic silver salt, which is an optional component described below.
The range is preferably 0 g/rn'. Further, in terms of silver equivalent of only silver halide, it is preferably 1 g/d or less, and particularly preferably 1 mg to 500 mg/rn''.

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

In the present invention, photopolymerization initiators include carbonyl compounds (e.g., acetophenone, benzoins, benzyl, diacetyl, ketones such as benzophenone, quinones such as anthraquinones, naphthoquinones, and phenanthrenequinones), organic sulfur compounds, Peroxides, halogen compounds, optical semiconductors (e.g. zinc oxide, titanium dioxide, etc.), metal ions (e.g. iron(I) ions, metal carbonyls, metal complexes, uranyl salts, etc.), azo and diazo compounds, photoreducibility A dye or the like can be used.

Regarding the photopolymerization initiator that can be used in the present invention,
'Chemical Review 4, Vol. 68 (1968), pp. 125-151, by Kosar, 'Light-5-sensitive Systems' by Oster et al.
(John Wiley & 5ons.

1963) pp. 158-192, and Fine Chemicals Vol. 1.16. No, 9. (1987) 5-19
There are also descriptions on pages (especially Table 2).

Photoinitiators using photoreducible dyes generally consist of a photoreducible dye and a hydrogen-donating compound, and it is believed that the reaction between the photoexcited dye and the hydrogen-donating compound generates radicals capable of initiating polymerization. There is. Photoreducible dyes include methylene blue, thionin, rose bengal, erythrosin B1 eosin, rhodamine, phloxine-B1
Safranin, acriflavin, riboflavin, fluorescein, uranine, benzoflavin, N, N, N'
, N'-tetra-n-butylthionine, N, N, N"
, No-tetramethyl-4'dodecylsafranine, acridine orange, acridine yellow, 9,10-phenanthrenequinone, penzanthrone, and other carbonyl compounds. In addition, examples of hydrogen-donating compounds include β-diketones such as dimedone and acetylacetone, triethanolamine, jetanolamine, monoethanolamine, dimethylamine, diethylamine,
Amines such as tetramethylethylenediamine, triethylamine, phenylhydrazine, sulfinic acids such as p-toluenesulfinic acid, benzenesulfinic acid, p-(N-acetylamino)benzenesulfinic acid and their salts, N-phenylglycine, L- Examples include ascorbic acid, thiourea, allylthiourea, and the like.

The molar ratio of the photoreducible dye to the hydrogen donating compound is such that the photoreducible dye is in the range of 0.005 to 3 moles, preferably 0.05 to 1 mole, per 1 mole of the hydrogen donating compound. . In addition, when using a carbonyl compound such as 9゜10-phenanthrenequinone as a photoreducible dye,
Since the binder acts as a hydrogen donating compound, it is not always necessary to use a hydrogen donating compound.

In the image recording method of the present invention, the photopolymerization initiator is preferably used in an amount of o,ooot mol to 0.1 mol, and preferably in a range of 0.001 mol to 0.05 mol, per mol of the polymerizable compound. It is more preferable to use it.

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 any known polymerizable compound can be used.

In addition, in the image recording method of the present invention, when thermal development treatment is planned, it is preferable to use a compound with a high boiling point (for example, a boiling point of 80° C. or higher) that is difficult to volatilize during heating. In addition, in the embodiment in which the recording layer contains a color image forming substance as an optional component described later, the color image forming substance is immobilized by polymerization and curing of the polymerizable compound. A crosslinkable compound having a polymerizable functional group is preferable. In addition, as will be described later, when forming a transferred image using an image-receiving material, Japanese Patent Application No. 62
It is preferable to use a highly viscous substance as the polymerizable compound, as in the photosensitive material described in Japanese Patent No. 162,147.

Compounds with ethylenically unsaturated groups that can be used in image recording materials include acrylic acid and its salts, acrylic esters, acrylamides, methacrylic acid and its salts, methacrylic esters, methacrylamide, anhydrous Examples include maleic acid, maleic esters, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters, and derivatives thereof.

Specific examples of polymerizable compounds that can be used in image recording materials include n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, and ethoxyethoxy. Ethyl acrylate, dicyclohexyloxyethyl acrylate,
Nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxyethylene Diacrylate to bisphenol, diacrylate of 2,2-dimethyl-3-hydroxypropionaldehyde and trimethylolpropane condensate, triacrylate of 2,2-dimethyl-3-hydroxypropionaldehyde and pentaerythritol condensate, hydroxy polyether polyacrylate,
Examples include polyester acrylate and polyurethane acrylate.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neobentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol Examples include tetramethacrylate and polyoxyalkylenated bisphenol A dimethacrylate.

The above polymerizable compounds may be used alone or in combination of two or more. An image recording material using a combination of two or more types of polymerizable compounds is described in JP-A-62210445. Note that 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. As mentioned above, it goes without saying that the use of a reducing agent and a polymerizable compound, or a substance that functions as both 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 an amount of 5 to 120,000 parts by weight per 1 part by weight of silver halide. A more preferable usage range is 12 to 1
It is 2000 parts by weight.

The image recording material preferably has an embodiment in which a recording layer containing the above-mentioned components is provided on a support. There are no particular restrictions on this support, but if thermal development is planned in the image recording method, it is preferable to use a material that can withstand the processing temperature of the development. Materials that can be used for the support include glass, paper,
High quality paper, coated paper, cast coated paper, synthetic paper, metals and their analogues, polyester, acetyl cellulose,
Examples include films of cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, etc., and papers laminated with resin materials and polymers such as polyethylene.

In addition, when the support is made of a porous material such as paper, it is necessary to obtain a certain level of smoothness according to the waviness-based method, as in the case of the support used in the photosensitive material described in JP-A No. 62-209529. It is preferable to have. In addition, when using a paper support, a paper support with low water absorption such as the photosensitive material described in JP-A No. 63-38934, and a paper support with a constant water absorption rate such as the photosensitive material described in JP-A No. 63-47754 can be used. Paper support having Bekk smoothness of JP-A-63-8133
A paper support with a low shrinkage rate such as the photosensitive material described in JP-A No. 9, a paper support with low air permeability such as the photosensitive material described in JP-A-63-81340, and a paper support as described in JP-A-63-97941. A paper support having a pH value of 5 to 9, such as the photosensitive material described above, can also be used.

Various aspects of the image recording material, arbitrary components that can be included in the recording layer, auxiliary layers that can be optionally provided in the image recording material, etc. will be sequentially explained below.

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 form of oil droplets in a photosensitive layer is described in JP-A-62-78552. The oil droplets may contain other components in the recording layer, such as silver halide, a reducing agent, a photopolymerization initiator, and a color image forming substance. Regarding photosensitive materials containing silver halide in oil droplets, JP-A-62-209450 and JP-A No. 62-1640
No. 40 JP-A-62-183453 describes photosensitive materials in which a reducing agent is further contained in the aromatic oil droplets. In addition, when silver halide is contained in the oil droplet, the number of silver halide particles contained in the oil droplet is 5 or more, as described in JP-A-63-15239. It is preferable.

More preferably, the oil droplets of the polymerizable compound are in the form of microcapsules. Various known techniques can be applied to the microcapsules without particular limitations. Note that an example of a photosensitive material in which oil droplets of a polymerizable compound are in the form of microcapsules is disclosed in JP-A-61-2.
There is a description in Publication No. 78441.

There are no particular restrictions on the wall material that constitutes the outer shell of the microcapsules. For photosensitive materials using microcapsules having outer shells made of polyamide resin and/or polyester resin, see JP-A-62-209437. A photosensitive material using microcapsules having an outer shell made of amino aldehyde resin is described in JP-A No. 62-209438, and a photosensitive material using microcapsules having an outer shell made of amino aldehyde resin is described in JP-A No. 62-209.
No. 439 describes a photosensitive material using microcapsules having an outer shell made of gelatin.
No. 440 discloses a photosensitive material using microcapsules having an outer shell made of epoxy resin, as described in Japanese Patent Laid-Open No. 62
JP-A-209441 discloses a photographic material using a microcapsule having a composite resin shell containing a polyamide resin and a polyurea resin; Photosensitive materials using microcapsules having the above-mentioned properties are described in JP-A-62-209442.

In addition, when using aldehyde-based microcapsules, it is preferable to keep the amount of residual aldehyde below a certain value, as in the photosensitive material described in JP-A-63-32535.

When silver halide is contained in microcapsules, it is preferable that silver halide be present in the wall material constituting the outer shell of the microcapsules. Regarding photosensitive materials containing silver halide in the wall material of microcapsules, JP-A-62
There is a description in the publication No.-169147.

Furthermore, two or more microcapsules containing at least one different component may be used in combination, such as silver halide, a reducing agent, a polymerizable compound, and a color image forming substance which is an optional component described below. good. In particular, when forming a full-color image, it is preferable to use three or more types of microcapsules containing different color image-forming substances in different hues. For photosensitive materials containing two or more types of microcapsules, please refer to JP-A-62198.
There is a description in Publication No. 850.

The average particle diameter of the microcapsules is preferably 3 to 20 μm. It is preferable that the particle size distribution of the microcapsules is uniformly distributed over a certain value, as in the photosensitive material described in JP-A No. 63-5334. In addition, the film thickness of the microcapsule is
As in the photosensitive material described in Publication No. 6, it is preferable that the particle diameter is within a certain range.

In addition, when storing silver halide in microcapsules, the average particle size of the silver halide grains mentioned above is preferably one-fifth or less, and preferably one-tenth or less, of the average size of the microcapsules. is even more preferable. A uniform and smooth image can be obtained by setting the average particle size of the silver halide grains to one-fifth or less of the average size of the microcapsules.

Optional components that can be included 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 stoppers, Fluorescent whitening agents, anti-fading agents, dyes or pigments for preventing halation or irradiation, pigments that can be decolored by heating or light irradiation, matting agents,
Examples include anti-smudge agents, plasticizers, water release agents, solvents for binder polymerizable compounds, and water-soluble vinyl polymers.

Although a polymer image can be obtained from the image recording material by the above-described structure of the recording layer, a color image can also be formed by including a color image forming substance as an optional component in the recording layer.

There are no particular restrictions on the color image forming substance that can be used in the image recording material, and various types of substances can be used. In other words, substances that are themselves colored (dyes and pigments),
Color image-forming substances also include substances (color formers) that are colorless or light-colored themselves but develop color when exposed to external energy (heating, pressure, light irradiation, etc.) or when they come into contact with another component (color developer). . Incidentally, general photosensitive materials using color image-forming substances are described in the above-mentioned Japanese Patent Laid-Open No. 73145/1983. Regarding photosensitive materials using dyes or pigments as color image forming substances, Japanese Patent Application Laid-Open No. 62-18734
6, JP-A-62-209436 for photosensitive materials using leuco dyes, and JP-A-62-251741 for photosensitive materials using triazene compounds using yellow coloring leuco dyes. Regarding photosensitive materials, see JP-A-62-288827 and JP-A No. 6228.
Regarding photosensitive materials using cyan color-forming leuco dyes, see Japanese Patent Application Laid-Open No. 63-53542.
There is a description for each.

Dyes and pigments, which are substances that color themselves, are available commercially as well as in various literature (for example, "Dye Handbook" edited by the Organic Synthetic Chemistry Association, published in 1970; "Latest Pigment Handbook" edited by the Japan Pigment Technology Association; The publicly known one described in ``Published in 1972'' can be used. These dyes or pigments are used after being dissolved or dispersed.

On the other hand, examples of substances that develop color due to some kind of energy such as heating, pressure, or light irradiation include thermochromic compounds, piezochromic compounds, photochromic compounds, and leuco compounds such as triarylmethane dyes, quinone dyes, indigoid dyes, and azine dyes. The body is known. All of these develop color upon heating, pressurization, light irradiation, or air oxidation.

Examples of substances that develop color upon contact with another component include various systems that develop color due to acid-base reactions, redox reactions, coupling reactions, chelate formation reactions, etc. between two or more components. For example, pressure-sensitive copying paper (pages 29-58) and Azography (pages 87-58) described in Hiroyuki Moriga's Introduction to Special Paper Chemistry 1 (published in 1975)
95 pages), known coloring systems such as heat-sensitive coloring by chemical changes (pages 118-120), or a preview of the seminar sponsored by the Kinki Chemical Industry Association - Latest Pigment Chemistry - Attractive Uses and New Developments as Functional Dyes - 1 Collection, pp. 26-32, (198
It is possible to use the coloring system described in June 19, 2013).

Specifically, a coloring system consisting of a coloring agent with a partial structure such as lactone, lactam, or spiropyran, which is used in pressure-sensitive paper, and an acidic substance (coloring agent) such as acid clay or phenols: an aromatic diazonium salt or Systems that utilize azo coupling reactions between diazotate, diazosulfonates, naphthols, anilines, active methylenes, etc.; reactions between hexamethylenetetramine and ferric ions and gallic acid; and reactions between phenolphthalein and combreculanes. Chelate-forming reactions such as reactions with alkaline earth metal ions; redox reactions such as reactions between ferric stearate and pyrogallol and reactions between silver behenate and 4-methoxy-1-naphthol can be used.

The color image forming substance is preferably used in a proportion of 0.5 to 20 parts by weight per 100 parts by weight of the polymerizable compound,
More preferably, it is used in a proportion of 2 to 7 parts by weight.

Further, when a color developer is used, it is preferably used in a proportion of about 0.3 to 80 parts by weight per 1 part by weight of the color former.

In addition, when using two types of substances that cause a color-forming reaction when in contact as the solid color image-forming substances described above, one of the substances that cause the above-mentioned color-forming reaction and a polymerizable compound are contained in microcapsules. However, a color image can be formed on the recording layer by allowing other substances among the substances that cause the color-forming reaction to exist outside the microcapsules containing the polymerizable compound. Regarding photosensitive materials that can obtain color images without using an image-receiving material as mentioned above,
There is a description in JP-A-62-209444.

The sensitizing dye that can be used in the image recording material is not particularly limited, and silver halide sensitizing dyes known in the photographic technology can be used.

The sensitizing dyes include methine dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, and the like.

These sensitizing dyes may be used alone or in combination. Particularly when the purpose is supersensitization, it is common to use a combination of sensitizing dyes. In addition, a dye that itself does not have a spectral sensitizing effect, or a substance that does not substantially absorb visible light but exhibits supersensitization may be used in combination with the sensitizing dye. The amount of sensitizing dye added is generally 10-8 to 10-2 per mole of silver halide.
It is on the order of moles.

The above-mentioned sensitizing dye is preferably added at the stage of preparing a silver halide emulsion, which will be described later. Regarding a light-sensitive material obtained by adding a sensitizing dye at the stage of forming silver halide grains, JP-A-62947 discloses that the sensitizing dye is added at the stage of preparing a silver halide emulsion after forming silver halide grains. The photosensitive materials obtained by adding the above are described in JP-A-62210449. Also,
Specific examples of sensitizing dyes that can be used in image recording materials are also described in the above-mentioned JP-A-62-947 and JP-A-62-947.
It is described in the publication No.-210449. Further, as in the photosensitive material described in JP-A-63-184738, a sensitizing dye sensitive to infrared light may be used in combination.

Addition of organic silver salts to image recording materials is particularly effective in thermal development processing. That is, when heated to a temperature of 80° C. or higher, the organic silver salt is considered to participate in an oxidation-reduction reaction using the latent image of silver halide as a catalyst. In this case, the silver halide and the organic silver salt are preferably in contact or in close proximity. Examples of the organic compound constituting the organic silver salt include aliphatic or aromatic carboxylic acids, thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and imino group-containing compounds. Among them, benzotriazole is particularly preferred. The above organic silver salt is generally 0.01 to 10 mol per mol of silver halide, preferably 0.01 to 10 mol, preferably 0.01 to 10 mol per mol of silver halide.
01 to 1 mole is used. Note that the same effect can be obtained by adding an organic compound (for example, hensitriazole) 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 an amount of 0.1 to 10 mol, more preferably 0.01 to 1 mol, per 1 mol of silver halide.

A radical generator that participates in the above-mentioned polymerization promotion (or polymerization inhibition) reaction of the reducing agent may be added to the recording layer.

A photosensitive material using silver triazene as the radical generator is described in JP-A No. 62195639, and a photosensitive material using silver diazotate is described in JP-A No. 62-1.
95640, and Japanese Patent Application Laid-open No. 195641/1983 describes a photosensitive material using an azo compound.

Various image formation accelerators can be used in the image recording material. Image formation accelerators include silver halide (and/or
Promotion of the redox reaction between the redox agent and the reducing agent (or organic silver salt) and the reducing agent, from the image recording material to the image receiving material or image receiving layer (
These functions include promoting the transfer of image forming substances to (described later). From the viewpoint of physicochemical functions, image formation accelerators include bases, base precursors, oils, surfactants, compounds with anti-fogging functions and/or development accelerating functions, thermal solvents, compounds with oxygen removal functions, etc. It is further classified into However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Therefore, the above classification is for convenience, and in reality, one compound often has multiple functions.

Examples of various image formation accelerators are shown below.

Examples of preferred bases include, as inorganic bases, alkali metal or alkaline earth metal hydroxides; alkali metal or alkaline earth metal phosphates, borates, carbonates, metaborates: hydroxides; Combinations of zinc or zinc oxide with chelating agents such as sodium picolinate; ammonium hydroxide; hydroxides of quaternary alkyl ammonium; hydroxides of other metals, etc. Examples of organic bases include aliphatic bases. 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,
Examples include cyclic guanidines, and those having a pKa of 7 or more are particularly preferred.

Examples of base precursors include salts of organic acids and bases that decarboxylate when heated, compounds that release amines through reactions such as intramolecular nucleophilic substitution, Rossen rearrangement, and Beckmann rearrangement. Compounds that emit bases and compounds that generate bases by electrolysis or the like are preferably used. Specific examples of base precursors include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, p-)luidine trichloroacetic acid, 2-picoline trichloroacetic acid, guanidine phenylsulfonylacetate, 4-chlorophenylsulfonylacetate guanidine, and 4-chlorophenylsulfonylacetate. Examples include guanidine methyl-sulfonylphenylsulfonylacetate and guanidine 4-acetylaminomethylpropiolate.

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

Incidentally, a photosensitive material using a base or a base precursor is described in JP-A-62-264041. Regarding photosensitive materials using tertiary amines as bases, JP-A-62-170954 discloses that the melting point is 8.
Regarding a photosensitive material using a fine particle dispersion of a hydrophobic organic base compound at a temperature of 0 to 180°C, Japanese Patent Application Laid-Open No. 62-209523
Regarding photosensitive materials using guanidine derivatives with solubility of 0.1% or less, JP-A-62-215637 describes photosensitive materials using hydroxides or salts of alkali metals or alkaline earth metals. For details, see JP-A-62-
Each of these is described in JP-A No. 209448.

Furthermore, regarding a photosensitive material using an acetylide compound as a base precursor, JP-A-63-24242 discloses a photosensitive material using a propiolate as a base precursor.
Furthermore, regarding photosensitive materials containing silver, copper, silver compounds, or copper compounds as catalysts for base-forming reactions, JP-A-63-46
No. 446 discloses the above propiolic acid salt and the above silver, copper,
Regarding a photosensitive material containing a silver compound or a copper compound in a state separated from each other, JP-A-63-81338 discloses that in addition to the above-mentioned propiolic acid salt and the above-mentioned silver, copper, silver compound, or copper compound, coordination in a free state JP-A-63-97942 describes a photosensitive material containing a base precursor, and JP-A-63-9794 describes a photosensitive material that uses a propiol salt as a base precursor and further contains a heat-melting compound as a reaction accelerator for the base production reaction. No. 46447 discloses a photosensitive material using a sulfonylacetate as a base precursor and further containing a heat-melting compound as a reaction promoter for the base production reaction, as described in JP-A-63-48543. A photosensitive material using a compound to which isothiocyanate is bonded is described in JP-A-63-24242.

When a base or a base precursor is used in the image recording material, silver halide, a reducing agent, a photopolymerization initiator, and a polymerizable compound are contained in the aforementioned microcapsules, and the base or base precursor is contained in the recording layer outside the microcapsules. Preferably, a precursor is present. Alternatively, the base or base precursor may be contained in a separate microcapsule, as in the photosensitive material described in JP-A-62-209521. Image recording materials using microcapsules containing bases or base precursors include, in addition to the above-mentioned specifications, photosensitive materials containing bases or base precursors dissolved or dispersed in an aqueous water retention agent solution in microcapsules, as described in Japanese Patent Application Laid-open No. No. 62-209522 discloses a photosensitive material in which solid fine particles carrying a base or a base precursor are housed in microcapsules.
A photosensitive material using microcapsules containing a basic compound having a melting point of 70 DEG C. to 210 DEG C. is described in Japanese Patent Application Laid-open No. 63-65437, respectively. In addition, instead of the microcapsules containing the base or base precursor, JP-A No. 63-9794
Particles containing a base or a base precursor and a hydrophobic substance in a compatible state may be used, as in the photosensitive material described in Publication No. 3.

The base or base precursor is described in Japanese Patent Application Laid-Open No. 62-2
As described in Japanese Patent No. 53140, it may be added to an auxiliary layer other than the recording layer (a layer containing a base or a base precursor, which will be described later). Furthermore, JP-A-63-32
As described in Japanese Patent Application No. 546, the above-mentioned support may be made porous and a base or a base precursor may be contained in the porous support.

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

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

A compound having an antifogging function and/or a development accelerating function can be used for the purpose of obtaining a clear image (an image with a high S/N ratio) having a high maximum density and a low minimum density. Note that a photosensitive material using an antifoggant as a compound having an antifogging function and/or a development accelerating function is described in JP-A-62-151838, and a photosensitive material using a compound having a cyclic amide structure is described in JP-A-62-151838. For photosensitive materials using thioether compounds, see JP-A-61-151841, and JP-A-62-151841.
No. 151842 describes photosensitive materials using polyethylene glycol derivatives, and Japanese Patent Application Laid-Open No. 151843/1983
For photosensitive materials using thiol derivatives, see JP-A-62-151844, and for photosensitive materials using acetylene compounds, see JP-A-62-17823.
For photosensitive materials using sulfonamide derivatives, see JP-A-62-183450, and for photosensitive materials using quaternary ammonium salts, see JP-A No. 63-9.
Publication No. 1653 has a description of each.

Useful examples of the thermal solvent include compounds that can serve as solvents for reducing agents, and compounds with high dielectric constants that are known to accelerate the physical development of silver salts. Useful thermal solvents include:
Polyethylene glycols described in U.S. Patent No. 3,347,675, derivatives such as oleic esters of polyethylene oxide, beeswax, monostearin, -80
Compounds with high dielectric constant having 2- and/or -C〇- groups, polar substances described in U.S. Pat. No. 3,667,959, 1,10-decane described in Research Disclosure magazine, December 1976 issue, pages 26-28 Diol, methyl anisate, biphenyl perate, etc. are preferably used. Incidentally, a photosensitive material using a heat solvent is described in JP-A-62-86355.

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

Development stoppers that can be used in margin image recording materials are compounds that neutralize bases or react with bases to reduce the base concentration in the film and stop development immediately after proper development, or silver and silver salts. It is a compound that interacts to inhibit development. Specific examples include acid precursors that release acids when heated, electrophilic compounds that cause a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and the like. Examples of acid precursors include JP-A-60
Oxime esters described in No.-108837 and No. 60-192939, JP-A-60-230133
Examples include compounds that release an acid through Rossen rearrangement as described in the above publication. In addition, as an example of an electrophilic compound that causes a substitution reaction with a base when heated, JP-A No. 60-2
Compounds described in Japanese Patent No. 30134 can be mentioned.

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

When the recording layer of the image recording material uses the above-mentioned microcapsules, the microcapsules may contain a dye having the property of being decolored by heating or light irradiation. The dye having the property of being decolored by heating or light irradiation can function as a yellow filter in conventional silver salt photography. Regarding image recording materials using dyes that have the property of decolorizing by heating or light irradiation as described above,
There is a description in JP-A-63-97940.

The anti-smudge agent used in the image recording material is preferably a particulate material that is solid at room temperature. Specific examples include starch particles described in British Patent No. 1,232,347, polymer fine powder described in U.S. Pat. Psel particles, US Pat. No. 2,711,375
cellulose fine powder, talc, kaolin,
Examples include inorganic particles such as bentonite, waxite, zinc oxide, titanium oxide, and alumina. The average particle size of the above particles is 3 to 50 μm in volume average diameter.
A range of m is preferred, and a range of 5 to 40 μm is more preferred. As mentioned above, when the oil droplets of the polymerizable compound are in the form of microcapsules, it is more effective if the particles are larger than the microcapsules.

Binders that can be used in the image recording material can be contained in the recording layer alone or in combination.

It is preferable to use a mainly hydrophilic binder. Hydrophilic binders are typically transparent or translucent, such as natural substances such as gelatin, gelatin derivatives, cellulose derivatives, starch, gum arabic, etc., and polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, etc. Contains synthetic polymeric materials such as water-soluble polyvinyl compounds. Other synthetic polymeric substances include dispersed vinyl compounds in the form of latexes, which increase the dimensional stability of photographic materials, among others. Regarding photosensitive materials using binders, JP-A-61
There is a description in Publication No. -69062. Regarding photosensitive materials that use binders together with microcapsules,
There is a description in JP-A-62-209525.

When a solvent for a polymerizable compound is used in an image recording material, it is preferable to encapsulate it in a microcapsule separate from the microcapsule containing the polymerizable compound. Regarding photosensitive materials using organic solvents that are miscible with polymerizable compounds encapsulated in microcapsules, Japanese Patent Application Laid-Open No. 62-20
There is a description in Publication No. 9524.

A water-soluble vinyl polymer may be adsorbed onto the silver halide grains described above. Regarding photosensitive materials using water-soluble vinyl polymers as mentioned above, Japanese Patent Application Laid-Open No. 63-9165
There is a description in Publication No. 2.

In addition to the above, examples of arbitrary components that can be included in the recording layer and their usage are also available through research.
Disclosure magazine Vow, 170° June 1978
It is described in Monthly issue No. 17029 (pages 9-15).

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

Layers that can be optionally provided on the image recording material include:
Examples include an image receiving layer, a heating element layer, an antistatic layer, an anticurl layer, a peeling layer, a cover sheet or a protective layer, a layer containing a base or a base precursor, a base barrier layer, an antihalation layer (colored layer), etc. .

Instead of using the image-receiving material described below 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.

Regarding photosensitive materials using a heat generating layer, Japanese Patent Application Laid-open No. 1983
For photosensitive materials provided with a cover sheet or a protective layer, see JP-A No. 62-210447, and for photosensitive materials provided with a layer containing a base or base precursor, see JP-A No. 62-253140. A photosensitive material provided with a colored layer as an antihalation layer is described in JP-A-63-101842. Further, an image recording material provided with a base barrier layer is also described in the above-mentioned Japanese Patent Application Laid-Open No. 62-253140. Furthermore, examples of other auxiliary layers and their usage are also described in the applications relating to the above-mentioned series of light-sensitive materials.

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

Various methods can be used to produce the image recording material, but the numerical method is to prepare a coating solution in which the constituent components of the recording layer are dissolved, emulsified, or dispersed in a suitable solvent; The process then comprises the steps of applying the coating liquid to the support as described above and drying it to obtain an image recording material.

Generally, each of the above-mentioned coating liquids is prepared by preparing a liquid composition containing each component and then mixing the respective liquid compositions. The liquid composition may be prepared to contain multiple components. Some of the constituent components of the recording layer can also be added during or after the preparation of the liquid composition or coating solution. Furthermore, as described below, a method of preparing a secondary composition by further emulsifying an oil-based (or aqueous) composition containing one or more components in an aqueous (or oil-based) solvent can also be used. .

Regarding the main components contained in the recording layer, methods for preparing the liquid composition and coating liquid are shown below.

Preparation of the halogenated emulsion can be carried out using any known method such as an acid method, a neutral method or an ammonia method.

The reaction format between soluble silver salt and soluble halogen salt is as follows:
Either one side mixing method, simultaneous mixing method or a combination thereof may be used. A back-mixing method in which particles are formed under conditions in excess of silver ions and a Chondrold double-jet method in which PAg is kept constant can also be employed. In addition, to accelerate particle growth,
The concentration, amount, or rate of addition of silver salts and halogen salts may be increased (Japanese Patent Application Laid-Open No. 1581-1581).
No. 24, No. 55-158124, and U.S. Pat. No. 3,650,757).

The silver halide emulsion used for producing the image recording material may be of the surface latent image type, in which the latent image is mainly formed on the surface of the grains, or may be of the internal latent image type, in which the latent image is formed inside the grains. Direct reversal emulsions combining internal latent image type emulsions and nucleating agents can also be used.

An internal latent image emulsion suitable for this purpose is disclosed in U.S. Pat.
No. 2250, No. 3761276, Japanese Patent Publication No. 5B-3534, Japanese Unexamined Patent Publication No. 136641/1984, and the like. Preferred nucleating agents for combination with the above emulsions are U.S. Pat.
No. 5037, No. 4255511, No. 426601
No. 3, No. 4276364 and West German published patent (O
LS) No. 2635316.

In the preparation of silver halide emulsions used in the production of image recording materials, it is preferred to use hydrophilic colloids as protective colloids. Examples of hydrophilic colloids include:
Gelatin, gelatin derivatives, graft polymers of gelatin and other polymers Proteins such as albumin and casein; Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc.; Sugar derivatives such as sodium alginate and starch derivatives; Various synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be mentioned. Among these, gelatin is preferred. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and gelatin hydrolysates or enzymatically decomposed products may also be used.

Silver halide emulsions contain ammonia, organic thioether derivatives (see Japanese Patent Publication No. 47-386), sulfur-containing compounds (see Japanese Patent Application Laid-Open No. 53144319), etc. as silver halide solvents in the stage of forming silver halide grains. Can be used. Further, in the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be allowed to coexist. Further, for the purpose of improving high illumination failure and low illumination failure, water-soluble iridium salts such as iridium chloride (■ or ■) and ammonium hexachloroiridium salt, or water-soluble rhodium salts 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 Tardel water washing method or the sedimentation method. The silver halide emulsion may be used as it is after ripening, but it is usually used after being chemically sensitized. In emulsions for conventional sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of nitrogen-containing heterocyclic compounds (Japanese Patent Application Laid-open No. 58
-126526, No. 58-215644).

In addition, when adding a sensitizing dye to a silver halide emulsion,
The aforementioned Japanese Patent Application Laid-open No. 62-947 and Japanese Patent Application Laid-open No. 62-
It is preferable to add it at the stage of preparing a silver halide emulsion as in the light-sensitive material described in Japanese Patent No. 210449. In addition, when adding a nitrogen-containing heterocyclic compound as a compound having the above-mentioned antifogging function and/or development accelerating function, it should be added during the formation stage or ripening stage of silver halide grains in the preparation of a silver halide emulsion. is preferred. 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-described 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 described above.

In the production of image recording materials, the polymerizable compound can be used as a medium in forming the composition of the other components in the recording layer. For example, silver halide (including silver halide emulsions), reducing agents, photopolymerization initiators, color image forming substances, etc. can be dissolved, emulsified or dispersed in a polymerizable compound and used in the production of image recording materials. can. Particularly when a color image forming substance is added, it is preferable to include a polymerizable compound therein. Furthermore, as will be described later, when the oil droplets of the polymerizable compound are microencapsulated, components such as a wall material necessary for microencapsulation may be included in the polymerizable compound.

A photosensitive composition containing silver halide in a polymerizable compound can be prepared using a silver halide emulsion. In addition to the silver halide emulsion, silver halide powder prepared by freeze-drying or the like can also be used to prepare the photosensitive composition.

Photosensitive compositions containing these silver halides can be obtained by stirring with a homogenizer, blender, mixer, or other commonly used stirrers.

In addition, it is preferable that a copolymer consisting of a hydrophilic repeating unit and a hydrophobic repeating unit is dissolved in the polymerizable compound used for preparing the photosensitive composition. Regarding photosensitive compositions containing the above-mentioned copolymers, JP-A-62-
There is a description in 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 material in a polymerizable compound. A photosensitive composition containing microcapsules having the above-mentioned silver halide emulsion as a core material is described in JP-A-62-164041.

It is preferable to use the polymerizable compound (including those containing other constituent components like the above photosensitive composition) in the form of an emulsion in an aqueous solvent. Also, JP-A-61
When microcapsulating a polymerizable compound into oil droplets as in the image recording material described in Japanese Patent No. 275742,
It is also possible to add a wall material necessary for microcapsulation to this emulsion and further perform a treatment to form the outer shell of the microcapsules at the stage of this emulsion. Further, a reducing agent or other optional components may be added at the stage of the emulsion.

Examples of the above-mentioned microencapsulation method include a method using coacervation of a wood-philic wall-forming material described in U.S. Pat. No. 2,800,457 and U.S. Pat. No. 2,800,458; U.S. Pat. Specification of contents and Special Publication No. 38-1957
4, No. 42446, and No. 42-771; interfacial polymerization methods described in US Pat. No. 3,418,250 and US Pat. No. 3,660,304; methods by polymer precipitation described in US Pat. Method using incyanate-polyol wall materials: Method using isocyanate wall materials described in U.S. Pat. No. 3,914,511; U.S. Pat. Nos. 4,001,140 and 40
A method using a urea-formaldehyde-based or urea-formaldehyde-resircinol-based wall forming material described in US Pat. No. 87376 and US Pat. Method using a forming material; in 5 in-itu method by polymerization of 1,000 yen as described in Japanese Patent Publication No. 36-9168 and Japanese Patent Publication No. 51-9079; British Patent No. 927807 and British Patent No. 965074; Polymerization dispersion cooling method:
US Patent No. 3,111,407 and British Patent No. 9304
Examples include the spray drying method described in the specification of No. 22 Yoyo. Although the method for microcapsulating oil droplets of a polymerizable compound is not limited to the above, a method in which a core substance is emulsified and then a polymer film is formed as a microcapsule wall is particularly preferred.

Note that photosensitive microcapsules that can be used in the production of image recording materials are disclosed in Japanese Patent Application Laid-Open No. 16914/1983.
No. 7, No. 62-169148, No. 62-209437
No. 62-209438, No. 62-209439, No. 62-209440, No. 62-209441,
There is a description in each of the publications No. 62-209447 and No. 62-209437.

Among the above-mentioned emulsions of polymerizable compounds (including microcapsule liquids subjected to microencapsulation treatment), if the polymerizable compound is a photosensitive composition containing silver halide, the image recording material can be applied as is. Can be used as a liquid. Emulsions other than the above include silver halide emulsions,
A coating solution can be prepared by optionally mixing with a composition of other components such as an organic silver salt emulsion. It is also possible to add other components at the stage of this coating solution in the same manner as in the case of the emulsion described above.

An image recording material is produced by applying the recording layer coating liquid prepared as described above onto a support and drying it. The coating liquid can be easily applied to the support according to known techniques.

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

As a support for the image-receiving material, baryta paper can be used in addition to the supports that can be used for the image-recording material described above. In addition, when using a porous material such as paper as a support for the image-receiving material, Japanese Patent Application Laid-Open No. 62-2095
It is preferable that the image-receiving material has a certain level of smoothness like the image-receiving material described in Japanese Patent No. 30. Further, an image receiving material using a transparent support is described in JP-A-62-209531.

Image-receiving materials generally have an image-receiving layer provided on a support.

The image-receiving layer can be constructed in any desired form using various compounds according to the coloring system of the color image-forming substance described above. In addition, when forming a polymer image on an image-receiving material, when a dye or a pigment is used as a color image-forming substance, the image-receiving material may be composed only of the above-mentioned support.

For example, when using a coloring system consisting of a color former and a color developer, the image receiving layer can contain the color developer. Furthermore, the image-receiving layer can also be configured as a layer containing at least one mordant. The mordant can be selected from compounds known in the photographic technology, taking into consideration conditions such as the type of color image forming substance, and used. Note that, if necessary, a plurality of mordants having different mordant powers may be used to form two or more image-receiving layers.

The image-receiving layer preferably contains a polymer as a binder. As the binder, a binder that can be used in the recording layer of the image recording material described above can be used. Furthermore, a polymer with low oxygen permeability may be used as the binder, as in the image-receiving material described in JP-A-62-209454.

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 constituted as an aggregate of thermoplastic compound fine particles. The image-receiving layer having the above structure has the advantage that it is easy to form a transferred image, and that a glossy image can be obtained by heating after image formation. The above thermoplastic compound is not particularly limited and can be arbitrarily selected from known plastic resins (plastics), waxes, and the like. However, the glass transition point of the thermoplastic resin and the melting point of the wax are preferably 200° C. or lower. An image receiving material having an image receiving layer containing thermoplastic compound fine particles as described above is disclosed in Japanese Patent Application Laid-Open No. 62-2800.
There is a description in No. 71 and 62280739 Hoyo Publication.

The image-receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator. In image formation using an image receiving material,
The color image forming material is transferred together with the unpolymerized polymerizable compound as described below. Therefore, a photopolymerization initiator or a thermal polymerization initiator can be added to the image-receiving layer for the purpose of smoothly proceeding with the curing process (fixing process) of the unpolymerized polymerizable compound. Regarding an image receiving material having an image receiving layer containing a photopolymerization initiator, see JP-A-62-161149,
Image-receiving materials having an image-receiving layer containing a thermal polymerization initiator are described in JP-A-62-210444.

A dye or pigment can be included 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 an image a specific color. Further, a dye or a pigment may be included in the image-receiving layer for the purpose of making it easier to distinguish between the front and back sides of the image-receiving material. As the dye or pigment, various known substances including dyes or pigments that can be used in image formation can be used, but there is a risk that the dye or pigment may damage the 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, make the reflection density 1 or less), or to use a dye or pigment that has the property of being decolored by heating or light irradiation.

An image-receiving material having an image-receiving layer containing a dye or pigment that has the property of being decolored by heating or light irradiation is described in JP-A-62-251741.

Furthermore, 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 amount of white pigment is 10 g per 1 g of the thermoplastic compound.
It is preferable to use the amount in the range of 100 g to 100 g.

When the dye or pigment described above is contained in the image-receiving layer, it may be contained uniformly or unevenly distributed in a portion. For example, a part of the reflected image can be made into a projected image by forming the support described later from a material having light transmittance and including the white pigment in a part of the image-receiving layer.

By doing so, image information that is unnecessary in the projected image can also be written as a reflected image in the image-receiving layer portion containing the white pigment.

The image-receiving layer may be configured as a layer on the tool depending on the functions described above. Further, the layer thickness of the image-receiving layer is 1 to 1
It is preferably 00 μm, and more preferably 1 to 20 μm.

Note that it is also possible to further provide a protective layer on the image-receiving layer. Furthermore, a layer made of aggregates of fine particles of a thermoplastic compound may be further provided on the image-receiving layer. An image-receiving material in which a layer made of aggregates of fine particles of a thermoplastic compound is further provided on the image-receiving layer is described in JP-A-62-210460.

Furthermore, a pressure-sensitive adhesive or a layer containing an adhesive and a release paper may be laminated in this order on the surface of the support opposite to the surface on which the image-receiving layer is provided. The sticker-like image-receiving material having the above structure is described in Japanese Patent Application Laid-Open No. 63-24647.

The present invention will be explained in more detail with reference to Examples below. However, the present invention is not limited to these.

[Example 1] A gelatin aqueous solution of halogen A-1 (16 g of gelatin in 1500 mJ2 of water)
and 0.5 g of sodium chloride, adjusted to pH 3.2 with IN sulfuric acid, and kept at 50°C), 300 rnJZ of an aqueous solution containing 71 g of potassium bromide and an aqueous solution of silver nitrate (0.5 g of silver nitrate in 300 ml of water). 59 mol dissolved) were simultaneously added at equal flow rates over 50 minutes. One minute after this addition is complete, add the following sensitizing dye (1 minute).
) was added, and from 15 minutes after the addition, 100 ml of an aqueous solution containing 2.9 g of potassium iodide and a silver nitrate aqueous solution (100 ml of water containing 0.0 g of silver nitrate) were added.
．． 018 mol dissolved) was added at equal flow rates over a period of 5 minutes. To this emulsion, 1.2 g of polyisobutylene-monosodium co-maleate was added and precipitated, washed with water and desalted, 12 g of gelatin was added and dissolved, and 0.5 mg of sodium thiosulfate was added to the colander. 1
Chemical sensitization was carried out for 5 minutes to prepare 1000 g of a monodisperse tetradecahedral silver iodobromide emulsion (A-1) having an average grain size of 0.22 μm.

(Sensitizing dye (1)) SO3SO3H・NH(C2H5)3 Halogen A-2 gelatin aqueous solution (20 g of gelatin in 1600 mJZ of water)
and 0.5 g of sodium chloride, adjusted to pH 3.2 with IN sulfuric acid, and kept at 42°C), 200rnJZ of an aqueous solution containing 71g of potassium bromide and an aqueous solution of silver nitrate (0.5g of silver nitrate in 200mJ2 of water). 59 mol dissolved) was simultaneously added at an equal flow rate over a period of 30 minutes. One minute after this addition is complete, add the following sensitizing dye (
Add 48 mk of the 1% methanol solution of 2), and then add 100 mλ of an aqueous solution containing 2.9 g of potassium iodide and an aqueous silver nitrate solution (0.018 mol of silver nitrate dissolved in 100 ml of water) from 10 minutes after adding the sensitizing dye. Added simultaneously over 5 minutes. Poly(isobutylene-
Add 1.2 g of co-malate monosodium),
After sedimentation, washing with water and desalting, 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, and the average particle size was 0.
．． 12 μm monodispersed tetradecahedral silver iodobromide emulsion (A-2) 1
000g was prepared.

(Sensitizing dye (2)) Aqueous gelatin solution of Halogen A-3 (20 gelatin in 1600 ml of water)
g and 0.5 g of sodium chloride, and pH was adjusted with IN sulfuric acid.
3.5 and kept at 45°C), 200 mf1. and a silver nitrate aqueous solution (0.59 mol of silver nitrate dissolved in water at 200 m°C) were simultaneously added at equal flow rates over 30 minutes.

One minute after this addition is complete, use the following sensitizing dye (3).
48ml of 0°5% methanol solution! , and then 15 minutes after adding the sensitizing dye, 100 ml of an aqueous solution containing 3.65 g of potassium iodide and an aqueous silver nitrate solution (100 mJ of water) were added.
(0.022 g of silver nitrate dissolved in Z) was added at an equal flow rate over 5 minutes. To this emulsion, 1.2 g of poly(imbutylene-monosodium co-maleate) was added, sedimented, washed with water, desalted, and gelatin 1.2 g was added.
Add 0g and dissolve, add 0.4g of sodium thiosulfate to the colander.
5 mg was added and chemical sensitization was carried out at 55 DEG C. for 20 minutes to prepare 1000 g of a monodisperse 14-hedral silver iodobromide emulsion (A-3) having an average grain size of 0.13 .mu.m.

(Sensitizing dye (3)) The following polymerizable compounds (Kayarat R604, Nippon Kayaku ■
0.36 g of the following copolymer (0.77 g% p-toluenesulfonamide) and 12.5 g of the following yellow image-forming substance were dissolved in 63 g of the following copolymer (0.77 g% p-toluenesulfonamide). To the above solution, 6.1 g of the reducing agent (4) shown below, 0.09 g of the development inhibitor release precursor shown below, and the photopolymerization initiator (Irgacur) shown below were added.
e 651 (manufactured by Ciba Geigy), 0.01 g of the following antifoggant, 1.8 g of Emmalex NP-8 (manufactured by Nippon Emulsion ■), and 20 g of methylene chloride were added to form a homogeneous solution.

To 15 g of the silver halide emulsion (A-1) above was added 1.5 mR of a 10% aqueous solution of potassium bromide, and then a 0.08% by weight solution of 1-methoxy-2-methylpropanol of the following development accelerator was added. .5mf1. was added and stirred for 5 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. This mixed solution containing the silver halide emulsion was added to the above homogeneous solution, and the mixture was heated at 15,000 m/min using a homogenizer.
The mixture was stirred by rotation for 5 minutes to obtain a photosensitive composition (B-1) consisting of a W10 emulsion.

(Polymerizable compound) (Copolymer) CH3 (Yellow image forming substance) CH3 CH30-CI-12CO20(:0GH-OH2 (Photopolymerization initiator) CH3 (Development inhibitor release precursor) CH3 (Antifoggant) (Development accelerator ) CH2CH2SH Sodium salt of polyvinylbenzenesulfonic acid of microcapsule c-i (Ver
asa Tl2O3, manufactured by National Starch Co., Ltd.) 10
% aqueous solution was adjusted to pH 6.0 using a 10% aqueous sodium hydroxide solution.

- On the other hand, a polyvalent isocyanate compound (Takenate DIION, Takeda Pharmaceutical Co., Ltd.) was added to the photosensitive composition (B-1).
4.5 g of the above-mentioned product) were added to the above aqueous solution.

This mixed solution was heated to 40° C. and stirred for 30 minutes at 9000 rpm using a homogenizer to obtain an emulsion in the form of a W10/W emulsion.

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

77 g of an aqueous solution of this initial condensate was added to the above W10/W emulsion, and the pH was adjusted to 6 using a 20% aqueous solution of phosphoric acid.
．． Adjusted to 0. Next, this was heated to 60°C and 12
After stirring for 0 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, cooled to room temperature, and the photosensitive microcapsule dispersion (
C-1) was prepared.

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

Table 1 Photosensitivity Heterogenization Antifoggant Color Image 11 Strengthening Composition Silver Emulsion Amount Used Hue Amount Used (Magenta Image Forming Substance) (Cyan Image Forming Substance) (B-1) (A-1) 0.01
g Yellow 12.5g (B-2)
(A-2) 0.015 g
v+! 20 g (B-3) (
A-3) 0.0075g cyan
In the preparation of photosensitive microcapsule liquid (C-1) of 16 g microcapsule C-2,
Instead of photosensitive composition (B-1), photosensitive composition (B-
A dispersion liquid (C-2) of photosensitive microcapsules was prepared in the same manner except that 2) was used.

In the preparation of photosensitive microcapsule liquid (C-1) of microcapsule C-3,
Instead of photosensitive composition (B-1), photosensitive composition (B-
A dispersion liquid (C-3) of photosensitive microcapsules was prepared in the same manner except that 3) was used.

Add 20g of the following base precursor to 80g of a 4% aqueous solution of polyvinyl alcohol (PVA205, manufactured by Kuraray ■), and use a Dynomill at 20°C to prepare a powder with an average particle size of 2μ.
A base precursor dispersion was prepared by dispersing the base precursor to m.

16g of photosensitive microcapsule liquid (C-1), (C-
2), 14.8 g of (C-3), 6.8 g of base precursor dispersion, and 9 ml of a 20% aqueous solution of sorbitol1. and 10 ml of a 10% aqueous solution of starch were mixed. Furthermore, 4ml of a 5% aqueous solution of the following surfactant
1 and water to make a total amount of 74 g to prepare a coating solution for an image recording material.

Apply this coating solution on colored coated paper with a basis weight of 60 g at a rate of 50% per coat.
The image recording material (
A) was created.

[Example 2] Image recording was carried out in the same manner as in Example 1, except that 5.52 g of the following reducing agent (3) was used in place of reducing agent (4) in the preparation of the photosensitive composition of Example 1. Material (B) was prepared.

[Example 4] Image recording was carried out in the same manner as in Example 1, except that 6.59 g of the following reducing agent (16) was used in place of reducing agent (4) in the preparation of the photosensitive composition of Example 1. Material (D) was prepared.

[Example 3] Image recording was performed in the same manner as in Example 1, except that 5.42 g of the following reducing agent (12) was used in place of reducing agent (4) in the preparation of the photosensitive composition of Example 1. Material (C) was prepared.

[Example 5] Image recording was carried out in the same manner as in Example 1, except that 3.39 g of the following reducing agent (19) was used in place of reducing agent (4) in the preparation of the photosensitive composition of Example 1. Material (E) was prepared.

(Reducing agent (19)) 2 H5 [Example 6] In the preparation of the photosensitive composition of Example 1, the following was used, except that 5.13 g of the following reducing agent (21) was used instead of reducing agent (4). An image recording material (F) was prepared in the same manner as in Example 1.

(Reducing agent (21)) (Reducing agent (24)) [Example 8] In the preparation of the photosensitive composition of Example 1, the following reducing agent (101) 1゜fig was used instead of reducing agent (4). Image recording material (a) was prepared in the same manner as in Example 1 except that the following was used.

[Example 7] Image recording was carried out in the same manner as in Example 1, except that 3.83 g of the following reducing agent (24) was used in place of reducing agent (4) in the preparation of the photosensitive composition of Example 1. Material (G) was prepared.

[Example 9] Image recording was carried out in the same manner as in Example 1, except that 1°47 g of the following reducing agent (102) was used in place of reducing agent (4) in the preparation of the photosensitive composition of Example 1. Material (b) was prepared.

(Reducing agent (102)) [Example 10] Example 10 except that 1.63 g of the following reducing agent (103) was used in place of the reducing agent (4) in the preparation of the photosensitive composition of Example 1. Image recording material (c) was prepared in the same manner as in Example 1.

(Reducing agent (103)) [Example 11] Example 11 except that 1°10 g of the following reducing agent (104) was used in place of the reducing agent (4) in the preparation of the photosensitive composition of Example 1. Image recording material (d) was prepared in the same manner as in Example 1.

(Reducing agent (104)) 40% aqueous solution fig of sodium hexametaphosphate was added to 125 g of water, and further mixed with 34 g of zinc 3.5-diα-methylbenzylsalicylate and 82 g of 55% calcium carbonate slurry, and mixed with a mixer. Dispersed. Disperse the liquid with a Dyno Mill disperser, and 200 g of the obtained liquid
6 g of 50% SBR latex and 55 g of 8% polyvinyl alcohol were added to the mixture and mixed uniformly. This mixed solution was uniformly applied onto paper having a basis weight of 55 g/rn'' to a wet film thickness of 30 μm, and then dried to prepare an image-receiving material.

and Part 1 Each of the image recording materials (A) to (G) and (a) to (d) was heated using a halogen lamp to produce a gray color whose transmission density was continuously changing from 0 to 3.0. 155°C after imagewise exposure for 1 second at 2000 lux through a continuous filter.
It was developed by heating.

Next, after uniform exposure for 30 seconds at 50,000 lux using a halogen lamp, each image recording material was overlapped with the image receiving material, and in this state was passed through a pressure roller of 500 kg/cm'. For each hue (yellow, magenta, and cyan) of the negative color image obtained on each image-receiving material, the maximum density (Dmax) and minimum density (Dmin) were measured using a Macbeth reflection densitometer. The measurement results are shown in Table 2.

Margin Table 2 below (immediately after manufacturing) Material Dmax Dmin Dmax Dmin D
max Dmin(A) (B) (C) (D) (E) (F) (G) 1.23 1.22 1.21 1.22 1.21 1.23 1.21 0.12 0, I3 0.12 0.11 0.12 0.13 0.12 1.25 1.23 1.24 1.22 1.24 1.21 1.25 0.10 0.11 0.09 0.09 0. 09 0.10 0.10 1.19 1.20 1.21 1.19 1.19 1.20 1.19 0.11 0.12 0.11 0.10 0.11 0.09 0.09 ( a) (b) (C) (d) 1.05 1.10 1.10 1.07 0.10 0.12 0.11 0.11 1.03 1.05 1.06 1.09 0.11 0.10 0.09 0.09 ■, 02 1.08 1.06 1.05 0.09 0.09 0.10 0.11 Separately, each image recording material was tested at 40" C1 under the condition of 80% relative humidity. After storing it for 8 days, the image formation process was performed in the same manner as above, and the obtained image was evaluated.The measurement results were
Shown in the table.

Table 3 (after storage for 8 days) Material Dmax Dmin Dmax Dmin
Dmax Dmin(A) (B) (C) (D) (E) (F) (G) 1.15 1.16 1.17 1.19 1.20 1.15 1.20 0.11 0.12 0.10 0.12 0.12 0.10 0.11 1.20 1.13 1.17 1.16 1.11 1.14 1.14 0.10 0.09 0.09 0.10 0. 11 0.09 0.10 1.19 1.12 1.11 1.14 1.15 1.19 1.19 0.09 0.11 0.12 0.09 0.16 0.12 0.09 ( a) (b) (C) (d) 0.43 0.42 0.50 0.51 0.10 0.12 0.13 0.11 0.35 0.29 0.40 0.42 0.12 0.10 0.10 0.09 0.51 0.39 0.41 0.45 0.10 0.12 0.09 0.11 As is clear from the results shown in Table 2, the images of the present invention The recording method gave very clear images.

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 formula [I] described above remain clear even after storage under harsh conditions. give an image.

[Example 12] Photosensitive microcapsule liquid prepared in Example 1 (1)
C-1), (C-2) and (C-3), 1 each
7 g, 5 g of 10% aqueous gelatin solution, 6 ml of 5% aqueous solution of the surfactant used in Example 1, 1 ml of zinc hydroxide
A coating solution for an image recording material was prepared by mixing 7.3 g of a 0% aqueous dispersion and 28 g of water.

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

[Example 13] Reducing agent (4) in the preparation of the photosensitive composition of Example 12
Reducing agent (3) used in Example 2 in place of 5.
Image recording material (I) was prepared in the same manner as in Example 12, except that 52 g was used.

[Example 14] Reducing agent (4) in the preparation of the photosensitive composition of Example 12
Reducing agent (12) 5 used in Example 3 instead of
．． An image recording material (J) was prepared in the same manner as in Example 12, except that 42 g was used.

[Example 15] Reducing agent (4) in the preparation of the photosensitive composition of Example 12
Reducing agent (16) 6 used in Example 4 instead of
．． An image recording material (K) was prepared in the same manner as in Example 12, except that 59 g was used.

[Example 16] Reducing agent (4) in the preparation of the photosensitive composition of Example 12
Reducing agent (19) 3 used in Example 5 instead of
．． An image recording material (L) was prepared in the same manner as in Example 12, except that 39 g was used.

[Example 17] Reducing agent (4) in the preparation of the photosensitive composition of Example 12
Reducing agent (21) 5 used in Example 6 instead of
．． An image recording material (M) was prepared in the same manner as in Example 12, except that 13 g was used.

[Example 18] Reducing agent (4) in the preparation of the photosensitive composition of Example 12
Reducing agent (24) 3 used in Example 7 instead of
．． An image recording material (N) was prepared in the same manner as in Example 12, except that 83 g was used.

[Example 19] Reducing agent (4) in the preparation of the photosensitive composition of Example 12
In place of, the reducing agent (101) used in Example 8
1. Image recording material (e) was prepared in the same manner as in Example 12 except that fig was used.

[Example 20] In preparing the photosensitive composition of Example 12, reducing agent (4
) used in Example 9, the reducing agent (102
) Image recording material (f) was prepared in the same manner as in Example 12, except that 1.47 g was used.

[Example 21] Reducing agent (4) in the preparation of the photosensitive composition of Example 12
In place of the reducing agent (10
3) An image recording material (g) was prepared in the same manner as in Example 12, except that 1.63 g was used.

[Example 22] In the preparation of the photosensitive composition of Example 12, reducing agent (4
) in place of the reducing agent (1) used in Example 11.
04) An image recording material (h) was prepared in the same manner as in Example 12, except that 1.10 g was used.

Salt: 27 g of 10% gelatin aqueous solution of sheet, 3.2 g of guanidine picolinate, 17 mR of 5% dextran aqueous solution, 5 mfL of 5% aqueous solution of surfactant used in Example 1,
1.2-bis(vinylsulfonylacetamido)ethane 2% aqueous solution 2ml1. , and 45 mJZ of water were mixed to prepare a solution. This mixed solution was applied to a 100 μm thick polyethylene terephthalate sheet to a wet film thickness of 7.
It was coated to a thickness of 0 μm and dried at about 40° C. to prepare a base generating sheet.

ㅅ　and its.

Each image recording material () () to (N) and (e) to (h)
Using a halogen lamp, the transmission density is between 0 and 3.0.
Imagewise exposure was performed for 1 second at 2000 lux through a continuous gray filter continuously varying to . Then,
After applying water to the photosensitive layer in an amount of 10 g per layer, base generating sheets were brought into close contact with each other so that the film surfaces were in contact with each other.

In this state, it was heated using a belt conveyance roller type heating device (heating temperature: 85° C., heating time: 10 seconds).

After the base generating sheet was peeled off from the photosensitive material, it was uniformly exposed to light for 30 seconds at 50,000 lux using a halogen lamp. Next, each image recording material was superimposed on the image receiving material used in Example 1, and in this state, 500 kg /
crn' pressure roller. For each hue (yellow, magenta and cyan) of the negative color image obtained on each image-receiving material, the maximum density (Dmax) and the minimum density (
Dmin) was measured with a Macbeth reflection densitometer. The measurement results are shown in Table 4.

Margin Table 4 below (immediately after manufacturing) Material Dmax Dmin Dmax Dmin D
max Dmin(H) (I) (J) (K) (L) (M) (N) ■, 23 1.22 1.25 1.24 1.23 1.26 1.24 0.10 0.12 0.11 0.12 0.11 O2O3 0,12 1,26 1,25 1,27 1,24 1,26 1,23 1,25 0,09 0,08 0,09 0,10 0,■1 0.10 0.09 1.21 1.19 1.20 1.24 1.20 1.21 1.19 0.09 0.09 0.09 0.10 0.11 O2O3 0.09 (e) ( f) (g) (h) ■, 04 1.03 1.05 1.07 0.08 0, IO 0,11 0,11 1,01 0,99 1,02 1,05 0,10 0,09 0,08 0,09 1,02 1,03 1,07 1,Ol 0.10 0.09 0.09 0.08 Each image recording material was separately stored at 40°C and 80% relative humidity for 8 days. After storage, image formation processing was performed in the same manner as above, and the resulting images were evaluated. The measurement results are shown in Table 5.

Table 5 (After storage for 8 days) Material max min max min min rnax min As is clear from the results shown in Table 4, the image recording method of the present invention provided very clear images.

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-mentioned formula [I] remain clear even after storage under harsh conditions. give an image.

(H) (I) (J) (K) (L) (M) (N) 1.19 1.18 1.17 1.18 1.19 1.19 1.20 0.10 0.11 0.10 0.11 o,i.

0.11 1.21 1.22 1.20 1.22 1.23 1.21 1°21 0.09 0.09 0.08 0.10 0.10 0.09 0.09 ■、20 1.17 1.19 1.20 1.18 1.19 1.16 0.09 0.09 0.09 0.09 0.09 0.10 0.10

Claims (1)

[Claims] 1. a step of imagewise exposing an image recording material containing silver halide to form a latent image of silver halide; a step of developing the latent image of silver halide contained in the image recording material using a reducing agent; and an image recording method comprising the step of substantially uniformly exposing the image recording material to light in the presence of a photopolymerization initiator and an ethylenically unsaturated polymerizable compound to form a polymer image, wherein the reducing agent is After development of the silver halide, a compound that forms an oxidant having a polymerization inhibiting effect on the ethylenically unsaturated polymerizable compound is used to photopolymerize the polymerizable compound in the areas where the oxidant is not formed, thereby creating a polymer image. An image recording method characterized by forming. 2. The image recording method according to claim 1, wherein the reducing agent is a compound represented by the following formula [I]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [The above formula In [I], R^1 is an organic group bonded to the benzene ring via a heteroatom having a lone pair of electrons, and R^2 is from the group consisting of a halogen atom, an alkyl group, an aryl group, and a heterocyclic group. is a selected monovalent group (each group may have a substituent), m is 1, 2, 3 or 4, and n satisfies the formula 0≦n≦(4-m) is an integer, and an aromatic ring, an aliphatic ring, and/or a heterocycle may be fused to the benzene ring].