JPH0358052A - Photosensitive material and photosensitive body and image forming method - Google Patents

Abstract

PURPOSE:To enhance lightness, saturation, and density gradation of a polymerized image by incorporating a specified compound in a photosensitive material. CONSTITUTION:This photosensitive material is formed by laminating on a support 2 a polymerizable layer 8 having a polymerizable element and a photo sensitive layer 7 having a photosensitive heat-developable element, and this layer 7 contains the compounds of formula I in which each of R1 and R2 is lower alkyl or optionally substituted aryl, and photosensitive silver salts, such as silver iodide, an organic silver salt, such as silver behenate, a reducing agent, such as 4, 4' -methylene-bis(2,6-di-t-butylphenol), and the compound of formula I, such as that of formula II, and the layer 8 can contain a polymerizable com pound, a reducing agent, and the like, and in addition, this material can be formed into the single layer structure.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention is characterized in that a latent image is formed by imagewise exposure, heated at the same time or after the formation, an oxidation-reduction reaction occurs in the latent image area, and then an image is formed by full-surface exposure. Concerning a photosensitive material, photoreceptor, and image formation or method for forming a polymerized image in unexposed areas, and a photosensitive material for obtaining a color image by transferring a heat-diffusible dye onto an image receptor after forming a polymerized image; The present invention relates to a photoreceptor and an image forming method.

[Prior Art] Currently, as photosensitive materials, there are materials that form a polymerized image upon irradiation with light, and various materials are known. for example,
It is applied to printing inks, IC materials, plate-making materials, recording materials, etc., but many of these photosensitive materials are
The drawbacks are that the sensitive wavelength range is short and the photosensitivity is poor. The fact that the sensitive wavelength range is short means that it is difficult to use lasers, which have made significant progress in recent years, and it is not compatible with digital processing.

Inferior photosensitivity means that the processing speed is slow, making it unsuitable for practical use.

Under these circumstances, attempts have been made to use silver salts to cause polymerization reactions; for example, US Pat. No. 3,019,
104 specification and Photographic Sci
ence and Engineering 1962, Vol. 6, p. 222, etc. However, these methods carry out the polymerization reaction in a solution, which poses the problem of complicated processing.

Research has been conducted to treat these polymerization reactions by dry processing. For example, in Japanese Patent Application Laid-open No. 61-69062, etc., a dry (thermal) polymerization reaction is caused using a photosensitive reaction of silver halide as a trigger. Methods of forming latent images consisting of polymerization are known.

This method has the advantage of not requiring complicated wet processing, but has the disadvantage that the polymerization rate (polymerization rate of the polymerizable compound) is slow and it takes time to form a polymerized latent image. This drawback is that during the heat treatment process, the reaction intermediate (which functions as a polymerization initiator) generated from the reaction between the silver produced from the silver halide by image exposure and the reducing agent is extremely stable and has no activity as a polymerization initiator. This is thought to be because the polymerization reaction is low, making it difficult for the polymerization reaction to proceed quickly. On the other hand, in order to accelerate the polymerization rate, JP-A-62-70836 discloses a method in which a thermal polymerization initiator is used in combination. In this method, a latent image is formed by silver nuclei generated from silver halide through image exposure, and by utilizing the catalytic action of the silver nuclei, a reducing agent is heated to have a polymerization inhibiting ability different from that of the reducing agent. By converting to an oxidant, a difference in polymerization inhibition ability is created between the reducing agent and the generated oxidant, and a thermal polymerization reaction using a thermal polymerization initiator is caused, resulting in a difference in the polymerization inhibition ability formed as a result. This method forms a polymerized latent image according to the difference. However, this method has the disadvantage that it is difficult to obtain good contrast in the polymerized latent image.

This drawback is that the redox reaction for producing oxidants and the polymerization reaction for forming a polymerized latent image occur in the same heat treatment process, which causes these reactions to become competitive reactions. This is thought to be because the reaction does not proceed efficiently.

In addition, image formation by this method is extremely unstable, for example, even by changing the amount of the reducing agent by a small amount, the area where the polymer is formed becomes an exposed area or an unexposed area.

Therefore, the present inventors caused a polymerization reaction in an image-forming medium using light, formed a polymerized image, and depending on the degree of polymerization, thermally transferred an internal heat-diffusible dye to an image receptor to form a color image. A recording method was proposed.

[Problems to be Solved by the Invention] An object of the present invention is to form a polymerized image with even better contrast, to have excellent brightness and chroma without being affected by the color of the silver image, and to have good density gradation. The object of the present invention is to provide a photosensitive material capable of forming a good image, a photoreceptor made of the photoreceptor, and a method for forming an image using the photoreceptor.

[Means to solve the problem]

As a result of intensive studies to solve the above problems, the present inventors have provided a photosensitive material containing a photosensitive and heat-developable element and a polymerizable element, which has the following general formula (I) 1 Rl [in the formula , R1 and R1 represent a lower alkyl group or a substituted or unsubstituted aryl group, and may be the same or different. ] It has been found that this can be achieved by using a photosensitive material characterized by containing at least one type of metal compound represented by the following.

The present invention will be explained in detail below.

In the present invention, the photosensitive and heat-developable element includes a photosensitive silver salt, an organic silver salt, and a reducing agent, and the polymerizable element includes a polymerizable compound and a photopolymerization initiator.

The compound represented by general formula (I) will be explained. In general formula CI), examples of the lower alkyl group include methyl, ethyl, proyl, n-butyl, t-butyl, and the like.

Examples of unsubstituted aryl groups include phenyl groups and naphthyl groups, and examples of substituted aryl groups include lower alkyl groups, lower alkoxy groups, acyl groups, halogen atoms such as chlorine and bromine, nitro groups, cyano groups, and carboxyl groups. , a phenyl group or a naphthyl group substituted with an amino group or the like.

Specific examples of the compound represented by the general formula (1) include the following. Compound no. CH3 CH3 CH3 CH3 GHz C21”I.jir These compounds prevent unintended redox reactions between the organic silver salt and the reducing agent in unexposed areas during heating, and
During the polymerization reaction, it acts as a chain transfer agent, making it possible to obtain a polymerized image with a high crosslinking density. Particularly, in an image forming method in which a heat-diffusible dye is diffused and transferred in accordance with the degree of polymerization, a good image with little color cast in highlight areas can be provided.

In the photosensitive material of the present invention, images are formed in the following two ways.

In Form 1, the reducing agent is converted into a polymerization inhibitor by image exposure and heating, and a polymerization inhibitor can be generated partially in places where there was originally no polymerization inhibitor, and a small amount of polymerization inhibitor is generated. A polymerized image with sufficient contrast can be formed just by doing this.

Form 2 is a photosensitive material that prevents radical cleavage by light itself by producing a compound (hereinafter referred to as a light-absorbing compound) that absorbs light in a wavelength range to which the photopolymerization initiator is sensitive.

Examples of the photosensitive silver halide used in the photosensitive material of the present invention include silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. It may be subjected to chemical sensitization or optical sensitization treatment similar to that applied to photographic emulsions. That is, as chemical sensitization, sulfur sensitization, noble metal sensitization, reduction sensitization, etc. can be used, and as optical sensitization, methods using conventionally well-known sensitizing dyes can be applied.

As the organic silver salt, organic silver salts such as organic acid silver and triazole silver salts described in "Fundamentals of Photographic Optics, Non-Silver Salt Edition, p. 247 J, JP-A-59-55429, etc. are used. It is preferable to use a silver salt which can be used as a silver salt and has low photosensitivity.

As the reducing agent used in the photosensitive material of the present invention, it is preferable to select and use the reducing agent from the two forms described above.

As the reducing agent for Form 1, the following general formula (n), (
Reducing agents represented by m) and (TV) are preferred.

[However, in the above general formulas (II) to (TV), Y1.
Y2. Y3, YS. Y8 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, an alkoxyl group, a substituted or unsubstituted cycloalkyl group Y4 represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a carboxyl group, or a carboxylic acid group. represents an ester group, A represents an oxygen atom or a sulfur atom, K represents a hydrogen atom, an unsubstituted alkyl group, a substituted or unsubstituted aralkyl group,
Z is a divalent linking group and represents an alkylidene group or a sulfur atom, and n represents O or 1. ] The reducing agents represented by the above general formulas (II), ``(III), and (IV) exhibit a polymerization inhibiting ability when oxidized, and in order to impart the property that the unexposed image area of the photoreceptor is polymerized, These are very suitable compounds.Specific examples of particularly preferred reducing agents are listed below, but the reducing agents used in the present invention are not limited to these.

Specific examples of the reducing agent represented by general formula 01) include 1,4-dihydroxynaphthalene, 4-methoxy-1-naphthol, 4-dithoxy-1-naphthol, 5
-Methyl-4-methoxy-1-naphthol, 1,5-dihydroxynaphthalene, 4-chloro-1-naphthol,
5-chloro-1-naphthol, 4-methylthio-1-naphthol, 4-ethylthio-1-naphthol, 6-phenyl-4-methyl-1-naphthol, 6-phenyl-4-methoxy-1-naphthol, 6-benzy-1-naphthol, 6-benzy-4-methoxy-1-naphthol, 4-methoxy-1,7-dihydroxynaphthalene,
4-methoxy-6-benzyl-l-naphthol, 4-mel-xy-6-cyclohexyl-l-naphthol, 3.
4-dimethyl-1-naphthol, 4-penzyloxy-1
-Naphthol etc.

Specific examples of the reducing agent represented by general formula (m) include 8-hydroxyquinoline, 4,8-dihydroxyquinoline-2-carboxylic acid, and 4-hydroxyquinoline-2-carboxylic acid.
2-carboxylic acid, 4-methyl-8-hydroxyquinoline, 4-benzyl-8-hydroxyquinoline, 4,8-dihydroxy-5-methylquinoline.

Specific examples of the reducing agent represented by general formula (IV) include:
For example, 2,2°-methylenebis(6-t-butyl-1
．． 4-dihydroxybenzene), 2,2°-methylenebis(4-methoxyphenol), 2,2°-methylenebis(4.6-di-t-butylphenol), 2,2
゜1 methylenebis(4-methyl-6-t-butylphenol), 2,2゜-butylidenebis(4-methoxyphenol) 2.2'-butylidenebis(6-t-butyl-1,4-dihydroxybenzene), 2. 2'-
Thiobis(6-methyl-1,4-dihydroxybenzene), 2,2゛-thiobis(4,6-di-t-butylphenol), bis(2-hydroxy-5-methylphenyl)phenylmethane, (3 -t-butyl-5-methyl-2
-hydroxyphenyl)methane and the like.

Note that two or more types of the above-mentioned reducing agents may be used in combination, and it is also possible to use these and conventionally known reducing agents in combination to the extent that the object of the present invention is not hindered.

As reducing agents for Form 2, the following general formula (V), (
Preference is given to reducing agents represented by Vl).

[In formula (V), Y7 and Y8 are each independently a hydrogen atom, a hydroxyl group, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aralkyl group, m represents an integer of 1 to 3, and A2 is a monovalent to trivalent linking group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkyl group, Indicates substituted alkyl, substituted amino group, divalent alkylidene group, aralkylidene group, and trivalent methine group. 1DH UN [In formula (VI), R and R' may be the same or different and represent a hydrogen atom, an alkyl group, or a cycloalkyl group, and r and r' may be the same or different. [R'' represents a hydrogen atom, a halogen atom, an alkyl group, an amino group, an aryl group, an aralkyl group, or an alkoxyl group; Preferred reducing agents include, for example, 2,6-di-t-butyl-4-(2-hydroxy-3-t-butylbenzyl)phenol, 2,6-di-t-butyl-4-(3.5-dichloro-4 -hydroxybenzyl)phenol, 2-t-butyl-4-(2-
Hydroxy-3,5-dimethylbenzyl)-5-methylphenol, 4,4゛-methylenebis(2-7-butynole-5-methynolephenol), 4,4゜-methylenebis(2-t-butyl-6-methyl phenol), 4,4
゜-Methylenebis(2,6-di-t-butylphenol), 4,4゛-butylidenebis(2,6-di-t-butylphenol), 4,4゜-methylenebis(2-cyclohexyl-6-t-butylphenol) ), screw (3.5
-di-t-butyl-4-hydroxyphenyl)phenylmethane, bis(3.5-di-t-butyl-4-hydroxyphenyl)(4-methoxyphenyl)methane, bis(
3.5-di-t-butyl-4-hydroxyphenyl) (
4-dimethylaminophenyl)methane, tris(3,5
-di-t-butyl-4-hydroxyphenyl)methane and the like.

Preferred reducing agents represented by general formula (VI) include:
For example, 4,4゛-methylenebis(2-methyl-1-naphthol), 4,4゛-methylenebis(2-ethyl-1-naphthol)
-naphthol), 4,4゜-methylenebis(2-t-butyl-1-naphthol), 4.4''-methylenebis(2
cyclohexyl-1-naphthol), 4,4°-methylenebis(2-t-butyl-6-methyl-1-naphthol), 4,4°-methylenebis(2,6-diethyl-1
-naphthol), 4,4°-methylenebis(2-benzy-1-naphthol), 4,4°-methylenebis(2-
t-butyl-8-methyl-1-naphthol), 4,4゜-methylenebis(2-methyl-8-dimethylamino-1)
-naphthol), 4-(3'-t-butyl-4'-hydroxynaphthyl)methyl-2-methyl-l-naphthol, 4-(3'-cyclohexyl-4°-hydroxynaphthyl)methyl-2-methyl-l-naphthol , 4.4
'-benzylidene bis(2-methyl-l-naphthol)
, 4,4°-benzylidenobis(2-7-butyl-1
-naphthol), 4.4゛-ethylidene bis(2-methyl-1-naphthol), 4.4゛-ethylidene bis(2-methyl-1-naphthol),
-t-butyl-l-naphthol), bis(4-hydroxy-3-methylnaphthyl)tolylmethane, and the like.

As the polymerizable compound contained in the material of the present invention, a compound having at least one reactive vinyl group in one molecule can be used.

The reactive vinyl groups of these compounds include styrene vinyl groups, vinyl acrylate groups, vinyl methacrylate groups, allyl vinyl groups, vinyl ethers, and ester vinyl groups such as vinyl acetate, which have polymerization reactivity. Examples include substituted or unsubstituted vinyl groups. Specific examples of polymerizable monomers that satisfy these conditions are as follows.

For example, styrene, methylstyrene, chlorstyrene,
Promostyrene, methoxystyrene, dimethylaminostyrene, cyanostyrene, nitrostyrene, hydroxystyrene, aminostyrene, carboxystyrene, acrylic acid, methyl acrylate, ethyl acrylate, cyclohexyl acrylate, acrylamide, methacrylic acid,
Methyl methacrylate, ethyl methacrylate, probyl methacrylate, butyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, vinylpyridine, N
-vinylpyrrolidone, N-vinylimidazole, 2-vinylimidazole, N-methyl-2-vinylimidazole, probyl vinyl ether, butyl vinyl ether,
Monovalent monomers such as isobutyl vinyl ether, β-chloroethyl vinyl ether, phenyl vinyl ether, p-methylphenyl vinyl ether, p-chlorophenyl vinyl ether; for example, divinylbenzene, distyryl oxalate, distyryl malonate, distyryl succinate, glutaric acid Distyryl, distyryl adibate, distyryl maleate, distyryl fumarate, β. β゜-distyryl dimethylglutarate, distyryl 2-promoglutarate, α, α゜-distyryl dichloroglutarate,
Distyryl terephthalate, dioxalate (ethyl acrylate), dioxalate (methyl ethyl acrylate), dimalonate (ethyl acrylate), dimalonate (methyl ethyl acrylate), disuccinate (ethyl acrylate), diglutarate ( (ethyl acrylate), adivic acid di(ethyl acrylate), maleic acid di(diethyl acrylate), fumaric acid di(ethyl acrylate),
β. β-dimethylglutaric acid di(ethyl acrylate), ethylene diacrylamide, brobylene diacrylamide, 1,4-phenylene diacrylamide, 1.4
-phenylene bis(oxyethyl acrylate), 1.
4-phenylenebis(oxymethylethyl acrylate), 1,4-bis(acryloyloxyethyloxy)cyclohexane, 1,4-bis(acryloyloxymethylethoxy)cyclohexane, 1,4-bis(acryloyloxyethoxy) carbamoyl) benzene, 1.
4-bis(acryloyloxymethylethoxycarbamoyl)benzene, 1,4-bis(acryloyloxyethoxycarbamoyl)cyclohexane, bis(acryloyloxyethoxycarbamoylcyclohexyl)methane, di(ethyl methacrylate) oxalate, di(methylethyl methacrylate) oxalate ), malonic acid di(ethyl methacrylate), malonic acid di(methyl ethyl methacrylate), succinic acid di(ethyl methacrylate), succinic acid di(methyl ethyl methacrylate), glutaric acid di(ethyl methacrylate), adivic acid di( ethyl methacrylate), maleic acid di(ethyl methacrylate)
, fumaric acid di(ethyl methacrylate), fumaric acid di(
methyl ethyl methacrylate), β,β゛-dimethylglutarate di(ethyl methacrylate), 1.4-phenylene bis(oxyethyl methacrylate), 1.4
- Bivalent monomers such as bis(methacryloyloxyethoxy)cyclohexane 7-cryloyloxyethoxyethyl vinyl ether; for example, bentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tri(hydroxystyrene),
Cyanuric acid triacrylate, cyanuric acid trimethacrylate, 1.1.1-h Rimethylolpropane triacrylate, 1, 1. 1-trimethylolbrobantrimethacrylate, cyanuric acid tri(ethyl acrylate), 1.1.1-trimethylolbrobantri(
ethyl acrylate), cyanuric acid tri(ethyl vinyl ether), 1,1.1-}condensate of dimethylolpropane tri(toluene diisocyanate) and hydroxyethyl acrylate, 1, 1. 1- Trimethylolbrobantri(hexane diisocyanate) and p
- trivalent monomers such as condensates with hydroxystyrene;
Examples include tetravalent monomers such as ethylenetetraacryl heptamide and brobylenetetraacrylamide. Note that, as described above, two or more of these polymerizable compounds may be used.

Examples of the photopolymerization initiator include carbonyl compounds, sulfur compounds, halogen compounds, redox photopolymerization initiators, and the like.

Specifically, carbonyl compounds include diketones such as benzyl, 4,4゜-dimethoxybenzyl, diacetyl, and camphorquinone; for example, 4,4゛-bis(diethylamino)penzophenone, 4,4゜-dimethoxybenzophenone, etc. Penzophenones; for example, acetophenones such as acetophenone and 4-methoxyacetophenone; benzoin alkyl ethers; for example, 2-cyclothioxanthone, 2,5-diethylthioxanthone, thioxanthone-3-carboxylic acid-β-methoxyethyl ester Thioxanthone such as; chalcone and styryl ketone having dialkylamino group; 3,3゜-carponylbis(7-methoxycoumarin)
, 3.3°-1carbonylbis(7-diethylaminocoumarin) and other coumarins.

Examples of the sulfur compound include dibenzothiazolyl sulfide, decylphenyl sulfide, and disulfides.

Examples of halogen compounds include carbon tetrabromide, quinolinesulfonyl chloride, and s-
Examples include triazines.

Redox-based photopolymerization initiators include those used in combination with trivalent iron ion compounds (e.g. ferric ammonium citrate) and peroxide, and those used in combination with photoreducible dyes such as riboflavin and methylene blue and triethanolamine. , those using a combination of reducing agents such as ascorbic acid, and the like.

Further, among the photopolymerization initiators described above, two or more types can be combined to perform photopolymerization with higher efficiency.

Examples of such a combination of photopolymerization initiators include a combination of chalcone, styryl ketones, or coumarins having a dialkylamino group, and s-triazine or camphorquinone having a trihalomethyl group.

The preferred blending ratio of the above components in the photosensitive polymer layer of the present invention is as follows. Preferably, the amount of photosensitive silver halide is 0.0% per mol of organic silver salt. 001 mol to 2 mol, more preferably 0.0
It is desirable to contain 5 mol to 0.4 mol.

In addition, the reducing agent is preferably added to 0.0% per mole of the organic silver salt.
It is desirable to contain 2 mol to 3 mol, more preferably 0.4 mol to 1.3 mol. Furthermore, polymerizable compound 100
It is desirable to use the photopolymerization initiator in an amount of preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight. In addition, the amount of photopolymerization initiator is preferably 0.0% per mole of reducing agent. It is desirable to contain Ol mol to 10 mol, more preferably 0.1 mol to 3 mol.

Further, the compounding ratio of the compound represented by the general formula (I) is 0.000. 0001 to 0.1 mol, preferably 0.0001 to 0.1 mol. 005 to 0.04 mole. In addition, when forming the photosensitive material of the present invention into a desired layered form or molding a photoreceptor, the above-mentioned essential components are dissolved in a solvent together with an appropriately used binder to form metal foil, plastic film, paper, or baryta. It can be shaped by coating it on a support such as paper or laminated paper and drying it.

Note that the shape of the photoreceptor of the present invention when molded into a desired shape is not particularly limited, such as a flat plate, a cylindrical shape, a roll shape, and the like. When formed into a layer, the layer thickness is preferably about 0.1 μm to 2 mm, preferably about 1 to 0.1 mm. Further, the photosensitive layer may be formed into a single layer or may be formed into multiple layers as necessary.

The binder that can be used in the present invention can be selected from a wide range of resins, and specifically includes, for example, nitrocellulose, cellulose phosphate, cellulose sulfate, cellulose acetate, cellulose probionate, cellulose butyrate, cellulose myristate. , cellulose valmitate,
Cellulose esters such as cellulose acetate/brobionate, cellulose acetate/butyrate; cellulose ethers such as methylcellulose, ethylcellulose, probylcellulose, butylcellulose; e.g. boristyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl butyrate, polyvinyl acetal Vinyl resins such as , polyvinyl alcohol, and polyvinylpyrrolidone; e.g., styrene-butadiene-copolymer, styrene-acrylonitrile-copolymer, styrene-butadiene-acrylonitrile-copolymer, vinyl chloride-vinyl acetate copolymer, etc. 'B: Acrylic resins such as polymethyl methacrylate, polymethyl acrylate, polybutyl acrylate, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyacrylonitrile; Polyesters such as polyethylene terephthalate; For example, poly(4.4 -isobropylidene,
Diphenylene-1,4-cyclohexylene dimethylene carbonate), poly(ethylenedioxy-3.3゛-phenylenethiocarbonate), poly(4.4゜-isobropylidene diphenylene carbonate-coterephthalate), poly(4.4゜-inpropylidene diphenylene carbonate), poly(4,4゜-sec-butylidene diphenylene carbonate), poly(4.4'-
polyacrylate resins such as isobropylidene diphenylene carbonate block oxyethylene); polyamides; polyimides; epoxy resins; phenolic resins; polyolefins such as polyethylene, polybropylene, and chlorinated polyethylene; Examples include molecules.

Incidentally, in the present invention, the binder is not an essential component, and there is no particular need to contain it if the film properties, sensitivity, etc. of the material are sufficient.

In addition, photodiscoloration inhibitors, solid solvents, surfactants, antistatic agents, and the like may be added as necessary.

When producing a photoreceptor using the above photosensitive material,
The layer structure of the photoreceptor may be either a single layer or a multilayer. In the case of a single layer, a photosensitive and heat-developable element and a polymerizable element, or a photosensitive and heat-developable element, a polymerizable element and a heat-diffusible dye are contained in the same layer. As a multilayer structure, a photosensitive layer consisting of a photosensitive and heat-developable element and a polymerization layer consisting of a polymerizable element may be formed separately, and a heat-diffusible dye may be contained in the polymerization layer. Alternatively, a three-layer structure may be used in which a dye layer containing a heat-diffusible dye is provided separately from the polymer layer. Alternatively, a dye layer may be provided separately from a photosensitive polymer layer containing a photosensitive and heat-developable element and a polymerizable element.

Each of the above layers is preferably provided on a support, and a protective layer is preferably provided on the layer in order to protect the layer or to advance the polymerization reaction efficiently.

The protective layer may be laminated with a film such as polyethylene terephthalate, or may be applied by dissolving a binder such as polyvinyl alcohol or cellulose in a solvent.

Next, the image forming method of the present invention will be described.

The photoreceptor of the present invention is subjected to imagewise exposure (a) and heating (b) to produce a light-absorbing compound, and is then subjected to full-surface exposure (c) to light at a wavelength to which the photopolymerization initiator is sensitive. Hereinafter, each of the above steps (a) to (C) will be explained in detail with reference to the drawings. First, a case where a photoreceptor consisting of a single layer is used will be explained.

Step (a) in the above method is a step of writing an image using light, and as shown in FIG.
Desired portions of the upper photosensitive polymer layer 1 are exposed by analog exposure using a mask or the like, or digital exposure by exposing an image signal such as an external electric signal or optical signal using a laser or the like. As a result, silver nuclei 3 grow from the photosensitive root salt in the image exposure area 1-a and form a latent image.

Note that the exposure conditions for writing this latent image include the concentration of the photosensitive silver salt contained in the photosensitive polymer layer, the conditions that allow desired characteristics such as sufficient contrast to be obtained in the resulting polymerized image, and the concentration of the photosensitive silver salt contained in the photosensitive polymer layer. They may be appropriately selected and used depending on the type, etc.

Since a photosensitive silver salt is used in this process, highly sensitive writing is possible.

Next, in the step (b3) of the above method, when the photosensitive polymer layer 1 on which the latent image has been formed is heated, the silver nuclei 3 selectively act as a catalyst in the image-exposed area 1-a, as shown in FIG. However, the organic silver salt and the reducing agent react, and the organic silver salt is reduced to silver atoms (metallic silver), and at the same time, the reducing agent 4 is oxidized to become the oxidant 5.

The heating in step (b) is carried out by appropriately selecting conditions necessary for the progress of the redox reaction and the production of the light-absorbing compound. Although it cannot be generalized depending on the composition of the photoreceptor, etc.
60°C to 200°C, more preferably 100°C to 15°C
Heat treatment may be performed at 0° C. for 1 second to 5 minutes, more preferably 3 seconds to 60 seconds. Generally, heating at a high temperature requires only a short time, while heating at a low temperature requires a long period of time. As a heating means, in addition to the method of using a hot tube notebook, a heat roll, a thermal head, etc., there are also methods of heating by supplying electricity to the heating element of the support, and heating by laser light irradiation.

Subsequently, in the step (c), the entire surface of the photosensitive polymer layer 1 is exposed. When the reducing agent of Form 2 is used, the light used for the exposure is the effective wavelength light described above (light at a wavelength to which the photopolymerization initiator has sensitivity and to which the light-absorbing compound has absorption). However, within the range in which a desired polymerized image can be obtained, light having a wavelength other than the effective wavelength light may be used in combination. Also,
If it is necessary to limit the wavelength range, exposure may be performed using, for example, a cut filter. When the reducing agent of Form 1 is used, the entire surface is exposed to light having a wavelength to which the photopolymerization initiator is sensitive.

When this entire surface is exposed, the polymerizable compound is polymerized in the unexposed portion 1-b of the image due to the action of the photopolymerization initiator.

On the other hand, in the image exposure area 1-a, since the oxidant is present, the effective wavelength light of the entire surface exposure is absorbed by the oxidant, or the radicals are quenched by the oxidant, and polymerization does not proceed. Therefore, there is a difference in the formation state of the polymer between the image-exposed area 1-a and the image-unexposed area 1-b, and polymerized portions 6 as shown in FIG. 3 are selectively formed. In other words, a superimposed image is formed.

Next, the case of using a photoconductor with a multilayer structure will be explained. As shown in FIG. 4, this photoreceptor has a polymerized layer 8 made of a polymerizable element formed on a support 2, and a photosensitive layer 7 made of a photosensitive and heat-developable element further laminated thereon. be.

Image formation can be performed on this photoreceptor in the same manner as with the single-layer structure photoreceptor described above, but in addition, a photosensitive element with only a photosensitive layer and a polymerized element with only a polymeric layer are formed separately, and the photosensitive element is first formed. It is also possible to form a polymerized image by exposing and thermally developing the material to produce a light-absorbing material, and then superimposing the material with a polymerization element and exposing the entire surface to light. In this case, the photosensitive element can be used multiple times by laminating it with an unexposed polymeric element, which is also economically advantageous.

After forming a polymerized image in this way, an image can be obtained by thermally diffusing a heat-diffusible dye, which has been contained in a photoreceptor in advance, onto the image receptor. A full-color image can be obtained by performing transfer for each color using a heat-diffusible dye.

[Example 1] Next, the present invention will be explained by giving examples. Add 0.8 parts of polyvinyl butyral to isobrobanol IO
Furthermore, silver bromide (0.1%) was dissolved in this solution.
part and 0.6 part of silver behenate were dispersed. Continuing,
In this dispersion, 0.29 4-methoxyl-naphthol
part and compound no. 7 exemplified compound Q. Q(15
Part was dissolved to obtain Solution A.

Separately, add 0.2-chlorothioxanthone to 15 parts of methyl ethyl ketone. 5 parts of ethyl p-dimethylaminobenzoate, 0.18 parts of ethyl p-dimethylaminobenzoate, 0.6 parts of polymethyl methacrylate, and 1.8 parts of pentaerythritol triacrylate were dissolved to obtain Solution B.

Next, a photosensitive layer was provided by thoroughly mixing liquid A and liquid B and coating it on a polyethylene terephthalate (PET) film to a dry film thickness of 4μ, and on top of this a 2μ polyvinyl 7 alcohol (P A) layer was provided to obtain a photoreceptor.

A mask film was placed on the PVA layer on this photoreceptor, and a latent image was formed by imagewise exposure. This image exposure was carried out by using a fluorescent lamp with a fluorescence peak of 420 nm and a light emission output of 5 mW as a light source, and by placing the light source 5 cm away from the photoreceptor and exposing for 10 msec.

Thereafter, the mask film was removed, the photoreceptor was passed through a heat developing machine adjusted to 105°C for 20 seconds, and the photoreceptor was placed on a hot plate heated to 60°C.
Light from a fluorescent lamp with a wavelength of 90 nm and a light output of 11) mW is 5c+n.
l! ! It was then irradiated for 10 seconds.

Finally, the PVA layer was removed by washing with water, and then the photoreceptor was rinsed in ethanol. As a result, the exposed image area was removed from the PET film, and a clear image consisting of a clear polymerized area was obtained on the PET film.

In addition, even when the entire surface exposure time was 5 seconds, a polymerized image was obtained by the etching process, but NO. When compound No. 7 was not used, no polymerized image was formed with an overall exposure time of 5 seconds.

When the heating temperature is increased from 105°C to 110°C,
No. When compound No. 7 was used, thermal fog did not occur in the unexposed area, but when compound No. When compound 7 was not used, thermal fogging occurred.

Ethyl p-dimethylaminobenzoate 0.4 parts2.
4-Diethylthioxanthone 1.2 parts MS
Magenta VP 2.0 parts Dipentaerythritol hexaacrylate 8.0 parts Polybutyl methacrylate 10 parts Methyl ethyl ketone 60 parts The above solution was applied onto a PET film to a dry film thickness of 3-. Furthermore, the following dispersion No. 0.06 part of compound No. 14 was added and applied to give a dry film thickness of 5 μm. A PET film was laminated thereon to obtain a photoreceptor.

Polyvinyl butyral IO part behenic acid 22 parts silver behenate
4.5 parts silver bromide
0.7 parts phthalazinone
0. 6 parts 4.4'-methylenebis(2.6-di-t-butylphenol) 2.6 parts 1 part % of sensitizing dye with the following structural formula Dimethylformamide solution 0.1 part C82COO
80 parts of H n-butanol toluene 20 parts This photoreceptor was imagewise exposed using a He-Ne laser, and then heated for 16 seconds in a heat developing machine adjusted to 125°C.
Subsequently, the entire surface was exposed for 40 seconds using a 380 nm fluorescent lamp. After peeling off the PET film for lamination, it was superimposed on the image receptor and placed on a heat roller heated to 130°C.
When the film was passed through at a speed of mm/sec, an image corresponding to the image exposure area was transferred to the image receptor side.

No. The average difference in fog in the image of the image receptor when compound No. 14 was not used and when it was used was 0.0 for magenta.
9, and the case where it was not used was inferior.

[Effect of the invention 1 As explained above, in the present invention, by using the compound represented by the general formula (I), a photosensitive material and a photoreceptor that have excellent sensitivity in full-surface exposure and are thermally stable can be obtained. As a result, it has become possible to obtain excellent images without fogging using the photoreceptor.

[Brief explanation of drawings]

1 to 3 are schematic cross-sectional views showing an example of the image forming method of the present invention, and FIG. 4 is a schematic cross-sectional view showing an example of the photoreceptor of the present invention. ...Photosensitive polymer layer...Silver nucleus...Oxidant...Photosensitive layer 2...Support 4...Reducing agent 6...Polymerization portion 8...Polymerization layer

Claims (1)

[Scope of Claims] 1. A photosensitive material containing a photosensitive and heat-developable element and a polymerizable element, characterized by containing at least one compound represented by the following general formula (I). photosensitive material. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R^1 and R^2 represent a lower alkyl group or a substituted or unsubstituted aryl group, and may be the same or different. . 2. A photoreceptor comprising the photosensitive material according to claim 1 formed in a layer on a support. 3. A photoreceptor comprising a photosensitive layer consisting of a photosensitive and heat-developable element and a polymer layer containing a polymerizable element formed in a layered manner on a support, comprising a compound represented by the general formula (I). A photoreceptor characterized by containing at least one type of photoreceptor. 4. An image forming method, which comprises polymerizing the unexposed areas of the photoreceptor according to claim 2 or 3 by subjecting the photoreceptor to imagewise exposure, heating, and exposing the entire surface thereof to light. 5. A photosensitive material containing a photosensitive and heat-developable element, a polymerizable element, and a heat-diffusible dye, which is characterized by containing at least one compound represented by general formula (I). . 6. A photoreceptor comprising the photosensitive material according to claim 5 formed in a layer on a support. 7. A photoreceptor formed by forming on a support a photosensitive polymer layer containing a photosensitive and heat-developable element and a polymerizable element, and a layer containing a heat-diffusible dye, which is represented by the general formula (I). A photoreceptor characterized by containing at least one of the compounds shown below. 8. A photoreceptor comprising a photosensitive polymer layer containing a photosensitive and heat-developable element and a polymerizable element and a layer containing a heat-diffusible dye formed on a support, the photosensitive polymer layer having a general formula(
A photoreceptor characterized by containing at least one of the compounds represented by I). 9. After the photoreceptor according to claim 6, 7 or 8 undergoes a process of imagewise exposure, a heating process, and a process of full-surface exposure, it is superimposed on an image receptor, and thermal diffusivity is applied on the image receptor according to the imagewise exposure. An image forming method characterized by transferring a dye to obtain an image on an image receptor.