JPH02975A - Photosensitive body and image forming method - Google Patents

Abstract

PURPOSE:To allow the faster and stabler formation of a polymerized image having good contrast by incorporating a polymerizable polymer precursor having >=35 deg.C m.p. into the photosensitive body. CONSTITUTION:The photosensitive body contains the component to form the distribution of the component which is sensitized and is heat-developed by image exposing and heating and exerts influence on the polymn. characteristic of a photopolymerizable element according to said image exposing and the component which is polymerized by exposing of light in the same layer 1. Said body is exposed by light having 400-900nm wavelength region, is heated to 60-180 deg.C and is exposed by light having 250-700nm wavelength region. The photosensitive body which is polymerized in an unexposed part 4 by the light having 400-900nm wavelength to form a polymerized part 6 contains the polymerizable polymer precursor having >=35 deg.C m.p. as the photopolymerizable element. The polymerized image having the excellent contrast, resolution, etc., is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photoreceptor that forms a polymerized image using light or heat, and an image forming method using the photoreceptor.

[Prior Art] Energy used to form or record images includes light, sound, electricity, magnetism, heat, particle beams (electron beams, X-rays), and chemical energy, among which light,
Electricity, thermal energy, or a combination of these are commonly used.

For example, image forming methods using a combination of light energy and chemical energy include methods using silver salt photography, diazo copying paper, and the like. Further, as a method using a combination of light energy and electric energy, there is an electrophotographic system. Furthermore, methods that utilize thermal energy include methods that use thermal recording paper, transfer recording paper, etc., while methods that utilize electrical energy include electrostatic recording paper, current-carrying recording paper, discharge recording paper, etc. method is known.

Among the image forming methods described above, silver salt photography is one that allows high resolution images to be obtained. However, silver salt photography requires complex development and fixing processes using liquid agents, drying processes for images (prints), and the like.

Therefore, efforts are being made to develop image forming methods that can form images through simple processing.

For example, a method is known from JP-A-61-69062 and the like in which a dry (thermal) polymerization reaction is caused using a photosensitive reaction of silver halide as a trigger to form an image made of a polymer.

Although this method has the advantage of not requiring complicated wet processing, it has the disadvantage that the polymer formation rate (polymerization rate of the polymerizable compound) is slow and it takes time to form a polymer 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 difficult to proceed quickly due to the low

On the other hand, in order to speed up 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 the catalytic action of the silver nuclei is used to oxidize a reducing agent, which has a polymerization inhibiting ability different from that of the reducing agent, under heating. By converting the reducing agent into a polymerization inhibiting ability, a difference in polymerization inhibiting ability is created between the reducing agent and the generated oxidant, and a thermal polymerization reaction using a thermal polymerization initiator is caused, and the polymer latency is changed according to the polymerization inhibiting ability. This is a method of forming images.

However, this method has the disadvantage that it is difficult to obtain good contrast in the polymer image.

This drawback is that the redox reaction to generate the oxidant and the polymerization reaction to form the polymer image occur in the latent image area during the same heat treatment, so these reactions become competitive reactions, and each reaction This is thought to be because the process does not proceed efficiently.

Furthermore, image formation by this method is extremely unstable, for example, even if the amount of the reducing agent is changed by a small amount, the polymerized area may become an exposed area or an unexposed area of the image.

Furthermore, JP-A-61-75342 discloses that a reducing agent having polymerization inhibiting ability is consumed in an image form (image-exposed area) during the development process of silver halide to form an oxidized product, and the remaining reducing agent is After inhibiting the polymerization reaction in an image-wise manner (image-unexposed area), light energy is uniformly injected from the outside (full-surface exposure) to cause photopolymerization in the area where the reducing agent has been consumed (image-exposed area). A method of forming a polymerized image is disclosed.

The above method has advantages such as excellent sensitivity in latent image writing due to the use of silver halide, and efficient separation of each process from image formation writing to full-surface exposure, but it also has the advantage of having sufficient contrast. It is difficult to obtain a superimposed image of. The causes will be explained below.

The reducing agent used in the above method is a reducing agent that originally has an action as a polymerization inhibitor, and loses its action as a polymerization inhibitor after reducing silver halide. Therefore, sufficient polymerization will not occur unless the reducing agent in the image-exposed area is completely converted into an oxidant. However, if a sufficient amount of thermal energy is applied during development to convert the reducing agent in the exposed areas of the image into an oxidant, a redox reaction will occur even in the unexposed areas of the image. On the other hand, if the amount of thermal energy applied during development is reduced to prevent the oxidation-reduction reaction from occurring in the unexposed areas of the image, the conversion to an oxidant in the exposed areas of the image will not proceed sufficiently. In this case, the image-exposed areas of the redox image are difficult to polymerize, so the amount of light energy applied during full-surface exposure must be increased, and as the amount of applied light increases, unnecessary polymerization occurs in the unexposed areas. As a result, a superimposed image with sufficient contrast cannot be obtained.

The polymerized image formed by the above method is an image consisting of a polymerized portion and an unpolymerized portion.

For the purpose of visualizing this polymerized image and further converting it into a color image, Japanese Patent Application Laid-Open No. 61-75342 and other publications disclose various methods that utilize the difference in physical properties between the polymerized part and the unpolymerized part. ing. For example, a method of treating with a liquid that does not dissolve the polymerized portion but dissolves the layer of the unpolymerized portion to elute and remove the unpolymerized portion (etching treatment), or utilizing the difference in adhesiveness between the polymerized portion and the unpolymerized portion, A method of dryly separating polymerized and unpolymerized parts by attaching a sheet such as a plastic film and then peeling it off (beer-apart treatment), and furthermore, when converting a polymer image into a color image, the photopolymerized layer is coated with pigment in advance. A method is to color the image with a coloring agent or dye and then elute it (the etching process described above) or peel it off (the Beer Apart process described above) to create a color image, or to take advantage of the tackiness of the unpolymerized area to selectively create a color image using a colored powder. Methods have been disclosed in which the unpolymerized areas are selectively dyed by coloring (toning treatment and inking treatment) or by treatment with a dye solution by utilizing the difference in liquid permeability between the polymerized and unpolymerized areas. .

However, as mentioned above, in conventional polymerization image forming methods, polymerized images with sufficient contrast cannot be obtained. The contrast of visible images and color images is insufficient, and it has been particularly difficult to obtain high-definition visible images and color images.

Furthermore, JP-A-62-78552, JP-A-62-81
Publication No. 635 and the like discloses a method of obtaining a colored image by mainly controlling the breaking strength of the capsule in the polymerized portion and the unpolymerized portion. However, this method still has problems such as the generation of bad odors and the complexity of processing, and there is also the problem that the resolution deteriorates due to the spread of oil droplets on the image receptor side.

[Problems to be Solved by the Invention] The purpose of the present invention is to solve all of the various conventional problems mentioned above, and in particular, to provide a photoreceptor that can more quickly and stably form polymerized images with good contrast. and to provide an image forming method.

Another object of the present invention is to provide a photoreceptor and an image forming method that can provide visible images and color images with excellent resolution and no color cast.

Another object of the present invention is that no bad odor is generated during image formation;
Color imaging processing also aims to provide a simple photoreceptor and image forming method.

Another object of the present invention is to provide a photoreceptor with excellent shelf life.

[Means for Solving the Problems 1] The photoreceptor of the present invention contains a photosensitive and heat-developable element and a photopolymerizable element in the same layer, and
exposed to light in the wavelength range of , heated to 60-180°C,
A photoreceptor in which the unexposed areas of the photoreceptor are polymerized by exposure to light in the wavelength range of 250 to 700 nm, the photopolymerizable element having a melting point of 35° C. or higher. This is a photoreceptor characterized by containing a polymerizable polymer precursor having the following properties.

The photoreceptor of the present invention contains a polymerizable polymer precursor having a melting point of 35° C. or higher, and generates a bad odor compared to a photoreceptor containing a polymerizable polymer precursor having a lower melting point. It is easy to handle and process because it is less likely to cause blocking. Furthermore, resolution is also excellent due to less distortion of the photosensitive layer during heat treatment. Furthermore, storage stability is also improved.

Although it is unclear why storage stability is improved by using a polymerizable polymer precursor with a melting point of 35°C or higher,
(2) Low hygroscopicity during storage makes it difficult for the dark reaction between the silver salt and the reducing agent of the present invention to proceed. ■When using a polymerizable polymer precursor having a urethane group or an ester group and a reducing agent having a hydroxyl group, the reducing agent exists in a stable state in the photosensitive layer due to hydrogen bonds between both groups, and dark reactions occur. It is also speculated that the reason is that it is difficult to progress.

In addition, the reason why the resolution is greatly improved by using a polymerizable polymer precursor having a melting point of 35°C or higher is that the distortion of the photosensitive layer during heat treatment is reduced as described above. It is also presumed that the precursor has a favorable effect on the redox reaction of the reducing agent.

Hereinafter, the photoreceptor of the present invention will be explained in detail.

In the photoreceptor of the present invention, the term "melting point" refers to the temperature at which a crystalline or solid substance melts or softens, or the temperature at which a waxy substance melts and becomes transparent.

In the present invention, a photosensitive and heat-developable element is defined by imagewise exposure (400 nm to 900 nm) and heating (60°C to 18°C).
0°C) and is capable of producing a distribution of components that affects the polymerizability of the photopolymerizable element depending on its image exposure, and if it has such an effect, what kind of Any type of ingredient may be used. Particularly desirable are elements comprising a photosensitive silver halide, an organic silver salt, and a reducing agent. A photoreceptor containing this element has a wavelength of 400 nm to 90 nm.
When imagewise exposed to 0 nm light and further heated to 60°C-180°C, a redox image (an image consisting of a reducing agent and an oxidant produced by oxidation of the reducing agent) is formed.
This redox image influences the polymerizability of the photopolymerizable element.

In the present invention, the photopolymerizable element is 250 to 700n
It means an element that polymerizes upon exposure to light of m, and includes at least a polymerizable polymer precursor having a melting point of 35°C or higher as a polymerizable element. Furthermore, it is desirable to include a photopolymerization initiator sensitive to 250 to 700 nm as a polymerizable element. For example, when the photoreceptor on which the redox image is formed is irradiated with light, the polymerizable polymer precursor in the unexposed areas of the image is polymerized.

JP-A-61-75342 discloses that image-exposed areas of a photosensitive layer are polymerized by image-wise exposure, heating, and overall exposure. On the other hand, the photoreceptor of the present invention has a characteristic that polymerization occurs in the unexposed area of the image rather than in the exposed area of the image, and such a photoreceptor was discovered by the present inventors. The above characteristics can be imparted to the photoreceptor by, for example, selecting and containing a specific reducing agent. However, the above characteristics may be imparted by components other than the reducing agent.

The photoreceptor of the present invention has the property that polymerization occurs in the unexposed areas of the image, so it is possible to partially generate a polymerization inhibitor in the photosensitive layer, which originally does not have a polymerization inhibitor. Even if only a small amount occurs, a superimposed image with sufficient contrast can be formed.

Note that in the photoreceptor of the present invention, r is 400 nm to 900 nm.
"The unexposed area (unexposed area of the image) is polymerized by light in the nm wavelength range" means the property of polymerization to the extent described below. First, all or at least a portion of the photosensitive layer is dissolved or extracted by immersing or ultrasonicating an untreated photoreceptor (not subjected to imagewise exposure, heating, or full-surface exposure) for 30 seconds to 10 minutes. Select the type of solvent that will be used. Then, when the photoreceptor after imagewise exposure, heating, and full-surface exposure is immersed or subjected to ultrasonic treatment in the same manner as above using the above-mentioned solvent, the image-unexposed areas are less likely to be dissolved or extracted than the image-exposed areas, If it is confirmed by visual observation or spectroscopic measurement that an uneven pattern, a turbidity pattern, a colored pattern, etc. have been formed, the photoreceptor is the photoreceptor of the present invention, that is, a photoreceptor that has the property of polymerizing the unexposed areas of the image. be.

In addition, in the photoreceptor of the present invention, since the photosensitive and heat-developable element and the polymerizable element are contained in the same layer, compared to a photoreceptor with a multilayer structure, the photoreceptor has a higher viscosity during the conversion from image exposure to a polymerized image. There is no image blurring, and a high-resolution superimposed image can be obtained. Furthermore, when extracting a superimposed image,
It has advantages such as requiring fewer processing steps and low manufacturing cost due to fewer coating steps.

In one embodiment, the photoreceptor of the present invention preferably contains silver halide and a photopolymerization initiator. In that aspect,
Light up to 400nm if the silver halide is silver chloride and unsensitized, 450n if the silver halide is silver bromide and unsensitized.
If silver halide is unsensitized with silver iodobromide, light up to 480 nm; if silver halide is sensitized, light in the sensitized range (for example, infrared sensitized (with wavelengths up to approximately 900 nm), up to 1 mJ/
Optical density of mask part is 3.0 with energy up to cm2
Image exposure is carried out through a mask having a temperature of 60°C to 180°C.
, preferably at a temperature of 100° C. to 150° C., for 1 second to 5 minutes, preferably 3 seconds to 60 seconds, using a hot plate, a heat roller, or the like. At this stage, an optical image may or may not be formed in the image exposure area. After this, the light to which the photopolymerization initiator is sensitive is 250n
m to 700nm, preferably 300nm to 500n
The unexposed areas of the image are polymerized by full-surface exposure with light having a wavelength of m and an energy of up to 500 mJ/cm2.

In the present invention, the polymerizable polymer precursor having a melting point of 35° C. or higher is preferably a bifunctional or higher compound from the viewpoint of sensitivity, and one or more types of polymer precursors can be used. In the case where the capsule method is used, that is, when the polymerizable polymer precursor is contained in the capsule, the unpolymerized portion must be substantially melted or have sufficient tackiness to be transferred depending on the heating conditions during transfer. be. Also,
A polymerizable polymer precursor consisting of a monomer or a low degree of polymerization is preferable from the viewpoint of contrast, etc., than a polymerizable polymer precursor consisting of a relatively high molecular weight polymer having a polymerizable functional group in a side chain. In particular, when performing etching treatment, inking treatment, toning treatment, beer apart treatment, etc., the solvent solubility in polymerized/unpolymerized areas,
Differences in adhesiveness and tackiness are important, but from these points as well, it is preferable to use monomers or polymerizable polymer precursors with a low degree of polymerization. When forming an image by thermally transferring the unpolymerized portion to an image receptor, the melting point of the polymerizable polymer precursor is preferably 140° C. or lower.

In addition, since acrylamide-based polymerizable polymer precursors such as acrylamide, methylenebisacrylamide, ethylenebisacrylamide, etc. are dissolved in water, it is not possible to use them by mixing them into the image forming layer in the form of capsules or oil droplets. In that case, it is preferable to use other polymerizable polymer precursors.

The polymerizable polymer precursor used in the present invention includes 2
Examples include polyester acrylate, polyurethane acrylate, and the like having higher functionality. For example, ester condensates of hexamethylene glycol, octamethylene glycol, decamethylene glycol, dodecamethylene glycol, trimethylolpropane, etc., and acryloxyacetic acid, acryloxypropionic acid, etc.; cyclohexylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,4-cyclohexylene methylene diisocyanate, phenylene diisocyanate, etc., and hydroxyalkyl acrylate, hydroxyalkoxyalkyl acrylate, and the like.

Specific chemical names of the polymerizable polymer precursors used in the present invention are listed below, but the present invention is not limited thereto.

Bis(4-[2-(acryloxy)ethoxycarbamoylcocyclohexyl)methane (melting point 126-129°C)
, bis(4-[2-(acryloxy)ethoxycarbamoyl]phenyl)methane (melting point 75-786C), 1.
6-bis[2-(acryloxy)acetoxy]hexane (melting point 63-65°C), 1,12-bis[2-(acryloxy)acetoxy]dodecane (melting point 70-72°C),
1.4-bis[2-(acryloxyacetoxy)ethoxycarbamoylmethylcocyclohexane (melting point 104~
1066C), 1,3-bis[2-(acroxyacetoxy)ethoxyrubamoylcobenzene (melting point 67-7
0°C), bis(4-[2-(acroxyacetoxy)isopropoxycarbamoyl]phenyl)methane (melting point 7
1-74°C), 2,4-bis[2-(acryloxy)ethoxycarbamoyl]toluene (melting point 75-778°C)
, 2.4-bis[2-(acryloxyacetoxy)ethoxycarbamoyl]toluene (melting point 72-74°C), 1
．． 6-bis[2-(acryloxyacetoxy)ethoxycarbamoyl]hexane (melting point 125-127°C), bis(4-[(3-acryloxy)propoxycarbamoylcocyclohexyl)methane (melting point 51-55°C).

In the present invention, a polymerizable polymer precursor having a melting point of less than 35° C. can also be used as the polymerizable element within a range that does not depart from the object of the present invention. In other words, when a precursor with a melting point of 35°C or higher and another precursor are mixed and used, it is sufficient that the mixture does not melt or soften below 35°C.

Examples of the polymerizable polymer precursor include styrene, methylstyrene, chlorstyrene, bromostyrene,
Methoxystyrene, dimethylaminostyrene, cyanostyrene, aminostyrene, acrylic acid, methyl acrylate, ethyl acrylate, cyclohexyl acrylate, methacrylic acid, methyl methacrylate, ether methacrylate, propyl methacrylate, butyl methacrylate, phenyl methacrylate , cyclohexyl methacrylate, N-
Monovalent monovalent monomers such as vinylimidazole, N-methyl-2-vinylimidazole, propyl vinyl ether, butyl vinyl ether, inbutyl vinyl ether, β-tetraloethyl vinyl ether, phenyl vinyl ether, p-methylphenyl vinyl ether, p-chlorophenyl vinyl ether, etc. For example, divinylbenzene, di(ethyl acrylate) oxalate, di(methyl ethyl acrylate) dioxalate, di(ethyl acrylate) malonate;
, malonic acid di(methyl ethyl acrylate), succinic acid di(ethyl acrylate), glutaric acid di(ethyl acrylate), adipic acid di(ethyl acrylate), maleic acid di(diethyl acrylate), fumaric acid di(ethyl acrylate), β, β° -Dimethylglutaric acid di(ethyl acrylate), oxalic acid di(ethyl methacrylate), oxalic acid di(methyl ethyl methacrylate), malonic acid di(ethyl methacrylate), malonic acid di(methyl ethyl methacrylate), succinic acid Di(ethyl methacrylate), di(methyl ethyl methacrylate) succinate, di(ethyl methacrylate) glutarate, di(ethyl methacrylate) adipate, di(ethyl methacrylate) maleate,
ethyl methacrylate), fumaric acid di(ethyl methacrylate), fumaric acid di(methyl ethyl methacrylate)
, β, β°-dimethylglutarate di(ethyl methacrylate); e.g. pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tri(hydroxystyrene), cyanuric acid triacrylate, cyanuric acid Trimethacrylate, 1,1.1-trimethylolpropane triacrylate, 1,1.1-trimethylolpropane trimethacrylate, 1.1.1-1-trimethylolpropane tri(ethyl acrylate), cyanuric acid tri(ethyl vinyl ether) Trivalent monomers such as; tetravalent monomers such as tetra(acryloxymethyl)methane and tetra(methacryloxymethylmethane); hexavalent monomers such as dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate. In addition, examples include polymerizable polymer precursors with reactive vinyl groups left at the ends of oligomers or polymers, or polymerizable polymer precursors with reactive vinyl groups attached to the side chains of oligomers or polymers. I can do it.

Next, each component in the case where silver halide, organic silver salt, reducing agent, and polymerization initiator are used in the photoreceptor of the present invention will be illustrated.

Examples of silver halides include silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. The film may be subjected to sensitization or optical sensitization treatment. 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.

Examples of the organic silver salt include silver salts of aliphatic carboxylic acids, aromatic carboxylic acids, thiocarbonyl compounds having a mercapto group or α-hydrogen, and imino group-containing compounds.

Examples of aliphatic carboxylic acids include acetic acid, butyric acid, succinic acid, sebacic acid, adipic acid, oleic acid, linoleic acid, linoleic acid, tartaric acid, palmitic acid, stearic acid, behenic acid, and cephalic acid. The lower the number of carbon atoms,
Since silver salts are unstable, those having an appropriate number of carbon atoms are preferred.

Examples of aromatic carboxylic acids include benzoic acid derivatives, quinolinic acid derivatives, naphthalenecarboxylic acid derivatives, salicylic acid derivatives, gallic acid, tannic acid, phthalic acid, phenylacetic acid derivatives, and pyromellitic acid.

Compounds having a mercapto or thiocarbonyl group include 3-mercapto-4-phenyl-1゜2.4-triazole, 2-mercaptobenzimidazole, 2-mercapto-5-aminothiadiazole, 2-mercaptobenzthiazole, S-alkylthio Glycolic acid (alkyl group with 12 to 22 carbon atoms), dithiocarboxylic acids such as dithioacetic acid, thiamides such as thiostearamide, 5
-carboxy-1-methyl-2-phenyl-4-thiopyridine, mercaptotriazine, 2-mercaptobenzoxazole, mercaptooxadiazole or 3-amino-5-benzylthio-1,2,4-triazole, etc. US Patent No. 4123. Examples include mercapto compounds described in No. 274.

As a compound having an imino group, Japanese Patent Publication No. 44-302
70 or No. 45-18416, or derivatives thereof, such as alkyl-substituted benzotriazoles such as pensylitriazole and methylbenzotriazole, halogen-substituted benzotriazoles such as 5-chlorobenzotriazole, and carboxyl-substituted benzotriazoles such as butylcarboimidobenzotriazole. Imidobenzotriazoles, nitrobenzotriazoles described in JP-A-58-118639, sulfobenzotriazole, carboxybenzotriazole or a salt thereof, or hydroxybenzotriazole, etc. described in JP-A-58-118638, U.S. Pat. No. 4,220 1.2.4- described in No. .709
Representative examples include triazole, IH-tetrazole, carbazole, saccharin, imidazole and derivatives thereof. Among them, preferred organic silver salts include organic silver salts of aliphatic carboxylic acids.

As the reducing agent used in the present invention, the following general formula (I
), (II) or (r[I) are preferred. These compounds have the ability to inhibit polymerization when oxidized, and are very suitable for imparting the property of "polymerizing the unexposed areas of the image" to the photoreceptor.

[However, in the above general formulas (I) to (m), R1R2, R3
, R5R6 each independently represents a hydrogen atom, a halogen atom,
Represents 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, and R4 is a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group. group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted cycloalkyl group, carboxyl group, carboxylic acid ester group, A represents an oxygen atom or a sulfur atom, R represents a hydrogen atom, It represents a substituted alkyl group, a substituted or unsubstituted aralkyl group, n is O or 1, and Z is a divalent linking group and represents an alkylidene group, an aralkylidene group, or a sulfur atom. ] Below, R1- in -1lQ formulas (I) to (III)
The group represented by R6 will be exemplified in more detail.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The substituted or unsubstituted alkyl group has 1 to 1 carbon atoms.
Up to 8 straight-chain or branched alkyl groups, preferably for example methyl, ethyl, propyl, i-propyl, butyl, t-butyl, i-butyl, amyl, i-amyl, hexyl, thexyl, heptyl, octyl, Nonyl, dodecyl, stearyl, methoxyethyl, ethoxyethyl,
Ethoxypropyl, ethoxybutyl, propoxybutyl, i-propoxypentyl, t-butoxyethyl, hexyloxybutyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl,
aminomethyl, dimethylaminomethyl, aminoethyl,
These include dimethylaminoethyl, diethylaminoethyl, morpholinoethyl, bioveridinoethyl, aminopropyl, diethylaminopropyl, dipropylaminoethyl, aminobutyl, morpholinobutyl, and the like.

The substituted or unsubstituted aralkyl group has 7 to 19 carbon atoms, preferably, for example, benzyl, phenethyl, benzhydryl, trityl, phenylpropyl,
naphthylmethyl, chlorobenzyl, dichlorobenzyl,
These include methoxybenzyl and methylbenzyl.

The substituted or unsubstituted aryl group has 6 to 1 carbon atoms.
6, preferably, for example, phenyl, naphthyl, anthryl, phenanthryl, tolyl, xylyl, cumenyl, mesityl, chlorophenyl, methoxyphenyl, fluorophenyl and the like.

The alkoxyl group has 1 to 18 carbon atoms,
Preferred are methoxy, ethoxy, propoxy, i-propoxy, butoxy and the like.

The substituted or unsubstituted cycloalkyl group has 5 to 18 carbon atoms, preferably cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl and the like.

The carboxylic acid ester group has 2 to 10 carbon atoms, preferably methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, and the like.

The alkylidene group has 1 to 8 carbon atoms, preferably methylene, ethylidene, butylidene, hexylene, etc.

The aralkylidene group has 7 to 18 carbon atoms, and preferred examples include benzylidene, naphthylmethylene, p-dimethylaminophenylmethylene, p-hydroxyphenylmethylene, and p-tolylmethylene.

Specific examples of particularly preferred compounds (reducing agents) represented by the above general formulas (1) to (III) are listed below, but the reducing agents used in the present invention are not limited to these.

Specific examples of the compound represented by general formula (I) include 1,4-dihydroxynaphthalene, 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 5
-Methyl-4-methoxy-1-naphthol, ■, 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-benzyl-1-naphthol, 6-benzyl-1-naphthol, 6-benzyl-
4-methoxy-1-naphthol, 4-methyl-1,7-
Dihydroxynaphthalene, 4-methoxy-6-benzyl-1-naphthol, 4-methoxy-6-cyclohexyl-1-naphthol, 4-methylthio-6-cyclohexyl-1-naphthol, 34-dimethyl-1-naphthol , 4-benzyloxy-1-naphthol and the like.

Specific examples of the compound represented by the general formula (II) include 8-hydroxyquinoline, 4°8-dihydroxyquinoline-2-carboxylic acid, 4-hydroxyquinoline-2-carboxylic acid, 4-methyl-8- Hydroxyquinoline, 4-benzyl-8-hydroxyquinoline, 4,8
-dihydroxy-5-methylquinoline and the like.

Specific examples of the compound represented by the general formula (III) include 2,2'-methylenebis(6-t-butyl-
1,4-dihydroxybenzene), 2,2°-methylenebis(4-methoxyphenol), 2,2°-methylenebis(4,6-di-t-butylphenol), 2,2°
-methylenebis(4-methyl-6-t-butylphenol), 2.2°-butylidenebis(4-methoxyphenol), 2.2'-butylidenebis(6-t-butyl-
1,4-dihydroxybenzene), 2゜2'-thiobis(4-methoxyphenol), 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)-(5-methoxy-2 -hydroxyphenyl)methane and the like.

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

The present inventors have discovered for the first time that the object of the present invention can be achieved by using the above-mentioned reducing agent in combination with a polymerizable polymer precursor having a melting point of 35° C. or higher. That is, another photoreceptor of the present invention is: 2) A photoreceptor containing a photosensitive and heat-developable element and a polymerizable element, which is represented by the general formula (I), (II) or (III). The photoreceptor is characterized in that it contains at least one compound selected from the group of compounds, and a polymerizable polymer precursor having a melting point of 35° C. or higher.

In the above photoreceptor as well, it is preferable that the photosensitive and heat-developable element and the polymerizable element are contained in the same layer, and that the polymerizable polymer precursor is photopolymerized, but even if this is not the case, the present invention It is possible to fully achieve the purpose of the invention. For example, the heat-developable element and the polymerizable element may be contained in separate layers, or the polymerizable element may contain a thermal polymerization initiator instead of a photopolymerization initiator.

Examples of the photopolymerization initiator used in the present invention 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(dimethyl)aminobenzophenone, and 4,4'-dimethoxybenzophenone. Benzophenones such as; acetophenones such as acetophenone and 4'-methoxyacetophenone; benzoin alkyl ethers;
For example, 2-chlorothioxanthone, 2,5-diethylthioxanthone, thioxanthone-3-carboxylic acid-β-
Thioxanthone such as methoxyethyl ester; chalcone and styryl ketone having dialkylamino group; 3,3°-carbonylbis(7-medoxycoumarin), 3,3°carbonylbis(7-dinithylaminocoumarin), etc. Examples include coumarins.

Examples of useful compounds include disulfides such as dibenzothiazolyl sulfide and decylphenyl sulfide.

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.

Furthermore, among the photopolymerization initiators described above, two or more types can be combined to obtain a more efficient photopolymerization reaction.

Examples of such a combination of photopolymerization initiators include a combination of chalcone, styryl ketone, or coumarin having a dialkylamino group, and S-1 riazine or camphorquinone having a triheromethyl group.

In addition to the above, diazo compounds and peroxides having photoinitiation ability can also be used as photopolymerization initiators. These polymerization initiators may also be used in combination of two or more thereof or in combination with the above-mentioned compounds.

As the thermal polymerization initiator, known ones can be used, and are roughly divided into azo initiators and peroxide initiators.

First, an azo initiator is an organic compound having at least one nitrogen-nitrogen double bond in its molecule, such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylphenethylcarbonitrile, azobis5ec- Examples include amylontrile, azobisphenylethane, azobiscyclohexylpropylonitrile, azobismethylchloroethane, trityl azobenzene, phenylazoisobutyronitrile, 9-(p-nitrophenylazo)-9-phenylfluorene, and the like. .

The peroxide initiator includes almost all organic compounds having at least one oxygen-oxygen bond in the molecule.

For example, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3.5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1
．． 1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, n-butyl-4,4-bis(t-)゛thylperoxy) parerato, 2.2-bis(t-butylperoxy)butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropyl pembene hydroperoxide, p-menthane hydroperoxide, 2.5-dimethylhexane-2 -dihydroperoxide, 1,1,3.3-
Tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,α゛-bis(t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2 , 5-di(t-butylperoxy)hexane,
2.5-dimethyl-2゜5-di(t-butylperoxy)hexyne-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3
．． 5.5-1 Limethylhexanoyl peroxide, succinic peroxide, benzoyl peroxide, 2゜4-dichlorobenzoyl peroxide, m-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2
-Ethylhexyl peroxydicarbonate, Moro-propyl peroxydicarbonate, Di-2-ethoxyethyl peroxydicarbonate, Dimethoxyisopropyl peroxycarbonate, Di(3-methyl-3-methoxybutyl) peroxydicarbonate, t- Butyl peroxy acetate, t-butyl peroxy isobutyrate, t-butyl peroxy bivalate, t-butyl peroxy neodecanoate, t-butyl peroxy octanoate, t-butyl peroxy-3,5 , 5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, di-t-shiba-
Examples include oxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxide maleic acid, t-peroxyisopropyl carbonate, and the like.

Other known thermal polymerization initiators can also be used.

In the photoreceptor of the present invention, the preferred blending ratio when using the components detailed above is as follows.

Preferably 0 silver halide per mol of organic silver salt
．． 001 mol to 2 mol, more preferably 0.05 mol to
Contain 0.4 mol. Further, the reducing agent is preferably contained in a range of 0.2 mol to 3 mol, more preferably 0.4 mol to 1.3 mol, per 1 mol of the organic silver salt. Furthermore, the polymerization initiator is preferably 0.1 to 50 parts by weight, more preferably 0.5 parts by weight, based on 100 parts by weight of the polymerizable polymer precursor.
Parts by weight to 30 parts by weight are used. Further, the polymerization initiator is preferably contained in a range of 0.01 mol to 10 mol, more preferably 0.1 mol to 3 mol, per 1 mol of the reducing agent.

The photoreceptor described in detail above is produced by dissolving and dispersing the above components in a solvent together with appropriately used additives and binders.
It can be formed by coating and drying on the support 2 as shown in FIG. It is also possible not to use body 2. Further, as shown in FIG. 2(C), it is also preferable to provide an oxygen inhibiting layer 9 such as polyvinyl alcohol on the photosensitive layer 1 in order to prevent the influence of oxygen during polymerization. Moreover, as shown in FIG. 2(d),
An image receptor 7 such as art paper, coated paper, film, metal foil, etc. may be provided on the photosensitive layer 1 in advance. Further, as shown in FIG. 2(e), the above-mentioned components such as silver salt and polymerizable polymer precursor are microencapsulated, and the microcapsules 10 are scattered in a binder 11 to form a photosensitive layer l. Also good.

As the support 2, metals such as aluminum and copper, plastic films such as polyester films, boilimide films, aromatic polyamide films, polycarbonate films, polysulfone films, polyphenylene sulfide films, polyetherimide films, fluorine-based films, and coats can be used. Paper, synthetic paper, etc. can be used.

Suitable binders for use in the present invention can be selected from a wide variety of resins.

Specifically, cellulose esters such as nitrocellulose, cellulose phosphate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose myristate, cellulose palmitate, cellulose acetate/propionate, cellulose acetate/butyrate:
Cellulose ethers such as methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose; vinyl resins such as polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyvinylpyrrolidone; e.g. styrene-butadiene copolymers , styrene-acrylonitrile copolymer, styrene-
Copolymer resins such as butadiene-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer; for example, polymethyl methacrylate, polydimethylaminoethyl methacrylate, polymethyl acrylate, polybutyl acrylate, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyacrylonitrile Acrylic resins such as acrylic resins and their copolymers; polyesters such as polyethylene terephthalate;
-isopropylidene, diphenylene-2-1,4-cyclohexylene dimethylene carbonate), poly(ethylenedioxy-3,3°-phenylenethiocarbonate)
, poly(4,4°-isopropylidene diphenylene carbonate coate terephthalate), poly(4,4”
-isopropylidene diphenylene carbonate), poly(4,4'-5ec-butylidene diphenylene carbonate), poly(4,4°-isopropylidene diphenylene carbonate-block-oxyethylene), etc. Boarylate resins: Boryamides ; Polyimides,
Epoxy resins; phenolic resins; examples include polyolefins such as polyethylene, polypropylene, and chlorinated polyethylene.

In addition, coloring materials, antifoggants, photodiscoloration inhibitors, solid solvents, surfactants, antistatic agents, and the like can be added to the photosensitive layer as required.

The thickness of the photosensitive layer of the photoreceptor is 0.1 μm to 2 mm,
Preferably it is about 1-0.1 mm.

When a polymerizable polymer precursor containing a silver salt and a reducing agent is encapsulated, a method of heating and melting it for encapsulation or a method of dissolving it in a solvent and encapsulating it can be used. However, if the latter method is adopted, it is necessary to use a method that does not leave any solvent in the capsule, and for example, the method disclosed in Japanese Patent Application No. 61-224805 is preferable. As the capsule membrane, known membranes such as gelatin, polyurethane, polyurea, urea-formalin, and melamine-formalin can be used.

As a specific encapsulation method, the encapsulation method conventionally used for carbonless paper can be used, for example,
US Pat.
This is the method described in No. 0, No. 43-23909, etc. Furthermore, when performing etching treatment, beer apart treatment, or inking/toning treatment instead of the capsule method, the photosensitive silver salt, reducing agent, polymerization initiator, and polymerizable polymer precursor are contained in the same layer. I need to be there.

The layer structure may be a single layer or a multilayer structure, and in the case of a multilayer structure, the type and composition ratio of the composition may be different for each layer.

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

The image forming method of the present invention includes (a) a step of imagewise exposing the photoreceptor of the invention, (b) a step of heating the photoreceptor, and (
c) A step of exposing the entire surface of the photoreceptor to light.

In addition, general formula (I), (II) or (II
When using a photoreceptor containing the compound represented by I), the object of the present invention can also be achieved by polymerizing the polymerizable polymer precursor by heating in (b) above. Furthermore, (
A preferred embodiment includes the step of d) transferring the unpolymerized portion of the photoreceptor to an image receptor.

Furthermore, the aspects of each process of the image forming method are shown in FIGS.
This will be explained below with reference to (C).

FIG. 1 (a) step C in the image forming method of the present invention (
a)] is a process of writing an image using light, in which the photosensitive layer 1 on the support 2 is exposed by analog exposure using a mask or the like, or by digital exposure by exposing an image signal such as an external electrical signal or optical signal using a laser or the like. Expose the desired image.

As a result, silver nuclei 3 are generated on the photosensitive silver halide in the exposed area 1-a, forming a latent image.

The generated silver nuclei 3 serve as a catalyst for the thermal reaction between the organic silver salt contained in the photosensitive layer 1 and the reducing agent.

The exposure conditions for writing this latent image include the concentration and type of silver halide contained in the photosensitive layer, such that the desired characteristics such as sufficient contrast can be obtained in the resulting polymerized image. They may be selected and used as appropriate depending on the situation.

Since photosensitive silver halide is used in this process,
Highly sensitive writing is possible.

Next, step (b) of the method of the present invention [in FIG. 1(b) 1, when the photoreceptor 1 on which the latent image has been formed is heated, the silver nuclei 3 selectively act as a catalyst in the exposed area 1-a. As a result, the organic silver salt and the reducing agent react, and the organic silver salt is reduced to silver atoms, and at the same time, the reducing agent is oxidized to become the oxidant 5.

As a result, an exposed portion 1-a containing the oxidant 5 and an unexposed portion 1-b containing the reducing agent 4 are formed. When the reducing agent 4 used in the photosensitive layer 1 is oxidized, it becomes an oxidant having the ability to inhibit polymerization of the polymerizable polymer precursor. A latent image is formed from the difference between the two.

In addition, general formula (I), (II) or (I
When using a photoreceptor containing the compound represented by II), an excellent polymerized image can be obtained even if the latent image is thermally polymerized at the same time or after the formation of the latent image in step (b). In that case, it is heated at 70 to 180°C, preferably 80 to 150°C, for 1 to 100 seconds. This heating may be performed in place of the heat treatment described above, or may be performed anew.

The heating in step (b) is carried out by appropriately selecting conditions necessary for the progress of the redox reaction. Although it cannot be generalized depending on the composition of the photosensitive layer, heat treatment may be performed at 60°C to 180°C, more preferably 100°C to 150°C, for 1 second to 5 minutes, more preferably 3 seconds to 60 seconds. . −
Numerically speaking, high temperatures require a short amount of heating time, while low temperatures require long heating times. As a heating means, in addition to a method using a hot plate, a heat roll, a thermal head, etc., there is also a method of heating by supplying electricity to a heating element of the support, and a method of heating by laser beam irradiation. Note that the heating is usually substantially uniform.

Next, the process moves on to step (c). Before starting step (C), it is also possible to laminate a material to be transferred onto the surface to be exposed for the purpose of preventing oxygen inhibition of the polymerization reaction.

In the step (C) [Fig. 1 (C)], the entire photosensitive layer 1 is exposed to light to cleave the photopolymerization initiator contained in the layer,
Generates radical species, etc. A polymerization reaction occurs due to these radical species, and a polymerized portion 6 is formed in the photosensitive layer 1. In other words, since the concentration of the oxidant having the ability to inhibit polymerization is different between the exposed area 1-a and the unexposed area 1-b, there is a difference in the state of polymerization between the exposed area 1-a and the unexposed area 1-b. , a superimposed image is formed by the difference.

In the photoreceptor of the present invention, the oxidant 5 has the ability to inhibit polymerization, the unexposed portion becomes a polymerized portion, and a positive polymerized image is produced.

As the light source used in the above steps (a) and (C), for example, sunlight, tungsten lamp, mercury lamp, halogen lamp, xenon lamp, fluorescent lamp, LED, laser beam, etc. can be used, and the wavelength of the light used in these processes is the same. may be different. Note that even if light of the same wavelength is used, silver halide usually has a sufficiently higher photosensitivity than a photoinitiator, so in step (a), sufficient latent light can be obtained using light of an intensity that does not cause photopolymerization. Images can be written.

In order to further promote photopolymerization in the step (c) above, the photoreceptor may be heated anew, or residual heat from the step (b) above may be used.

The method of visualizing and converting the polymerized image formed through steps (a) to (c) [or (a) and (b)] of the method of the present invention into a color image as described above is as described above. ,
Various methods have been proposed in the past, and all of these conventionally known methods can be applied to the method of the present invention, and visible images and color images with sufficient contrast can be obtained.

For example, when the capsule method is used, it is possible to suppress the spread of the image area that occurs when unpolymerized areas are transferred to an image receptor, and at the same time, it is possible to suppress the spread of the image area that occurs when the unpolymerized area is transferred to the image receptor. can eliminate the problem of bad odors. Furthermore, the storage stability of the image once transferred to the image receptor is also good. That is, conventionally, Jikai II
When using the polymerizable polymer precursors described in No. 61-78552 and No. 62-81653, the colored images produced may suffer from fading problems due to reverse reactions to leuco dyes or polymerizable polymers in the image receptor during image storage. Image blur due to the spread of the precursor can also be improved.

Further, when inking processing or toning processing is used, the formed superimposed image is not sticky, so there is an advantage that it is easy to handle.

Furthermore, when Beer-Apart treatment is used, it is possible to improve cohesive failure in the photosensitive layer that has occurred due to differences in working environments, so that peeled images can be stably obtained.

The beer apart process will be described below with reference to the drawings. The photoconductor on which the polymerized image is formed and the image receptor are laminated.
FIG. 1(d) ] Then, the unpolymerized portion is transferred to the image receptor by heating and pressure treatment. The unpolymerized portion 1 is transferred to the image receptor, forming an image 8 on the image receptor [FIG. 1(e)]. At the time of this transfer, the present invention uses a polymerizable polymer precursor with a melting point of 35° C. or higher, so there is no image blurring and there is good correspondence between the unpolymerized area 1 and the image area 8, and a high-resolution image can be obtained. It can be taken out. The heating and pressing in this process must be carried out under conditions such that the polymerizable polymer precursor develops tackiness, and must be heated to a temperature of 60 to 150°C and pressurized at 20 to 300 kg/mm2. It is preferable.

〔Example〕

Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto. In addition, in the following description, "Part c"
"indicates weight part j.

Example 1 V of Microcapsules Polymerizable polymer precursor (melting point 75-7
7°C) and 3.1 parts of leuco dye [TG-11, Nippon Kayaku Co., Ltd.].
It was dissolved in a mixed solution of 45 parts of chloroform and 40 parts of methyl ethyl ketone. Subsequently, 0.8 part of behenic acid was added, followed by 1.0 part of silver behenate, and the mixture was dispersed for about 10 minutes using a homogenizer (5000 revolutions per minute).

Subsequently, AgBr0. 2 parts, 0.35 part of 4-methoxynaphthol, 0.1 part of phthalazinone, 1.3 part of 2-chlorothioxanthone, and 0.6 part of ethyl p-dimethylaminobenzoate were added, and the mixture was further stirred for 30 minutes.

The fraction liquid thus prepared was encapsulated by the following procedure. 2.0% by weight of isopane (manufactured by Kuraray ■), which is an isobutylene-maleic anhydride copolymer, and 0.3% by weight of pectin were dissolved in the above dispersion, the pH was adjusted to 4.5 with sulfuric acid, and 150 parts of an aqueous solution was prepared. This was added to the mixture and emulsified using a homogenizer at 7000 revolutions per minute. After stirring the mixture for about 3 hours while passing air through it, 2 parts of melamine, 5.5 parts of a 50% by weight urea aqueous solution, and 12 parts of a 37% formalin aqueous solution were added, and the mixture was reacted at 65° C. for 3 hours. Then 20% NaOH
Adjust the pH to 9.0 with water and add 0 sodium bisulfite.
．． 6 parts and 1.1 parts of sodium sulfite were added, and the mixture was allowed to cool. The average particle size of the resulting capsules was 8.6 μm. Image Formation To the above capsule dispersion of the sheet, 40 parts of a 5.0% by weight aqueous solution of polyvinyl alcohol was added, and 45 g/m2 of art It was applied uniformly to paper at a coating weight of 6 g/m2.

Add 11 g of 40% sodium hexametaphosphate aqueous solution to 125 g of water, and add salicylic acid derivative zinc salt (R-0
54, Sangen Kagaku), 60 g of 55% calcium carbonate slurry, and 20 g of activated clay were mixed and ground in a ball mill. 3 g of 50% SBR latex and 20 g of 3% polyvinyl alcohol were added to 100 g of the obtained liquid.

This was applied uniformly to 45 g/m2 art paper at a coating amount of Log/m2. Thereafter, a calendar treatment was performed to obtain an image-receiving paper.

A mask consisting of line images having intervals and widths of 20 μm, 30 μm, and 40 μm is closely attached to the photosensitive sheet,
A fluorescent lamp of 0 nm and power consumption of 20 W was irradiated for 1 second. After passing this through a heat developing machine whose temperature is adjusted to 120°C,
The entire surface was further irradiated for 30 seconds. Combine this with receiver paper,
When the paper was passed through a heat roll pressurized at 80° C. and 87 cm 2 , a black line image corresponding to the image-exposed area was formed on the image-receiving paper side.

Example 2 An image was formed in the same manner as in Example 1, except that the polymerizable polymer precursors were changed to 20 parts of the following structure having a melting point of 51 to 55°C and 5 parts of dipentaerythritol hexaacrylate.

Comparative Example 1 A photosensitive sheet was obtained in the same manner as in Example 1, except that the polymerizable polymer precursor was replaced with trimethylolpropane triacrylate (liquid). After image exposure, thermal development, and photopolymerization, it was matched with image receiving paper and passed through a roller pressurized at 250 Kg/am2 to obtain an image.

Example 3 Polymerizable polymer precursor was converted into 1,6-bis[2-(acryloxy)acetoxy]hexane (melting point 63-65°C) 20
Example 1 was repeated except that 5 parts of trimethylolpropane triacrylate was used. The mixture of the polymerizable polymer precursors melted from a wax state to a transparent state at 40°C.

Example 4 Polymerizable polymer precursor was converted into bis([2-(acryloxy)
The same procedure as in Example 1 was repeated except that 15 parts of ethoxycarbamoyl]cyclohexyl)methane (melting point 125-129°C) and 5 parts of trimethylolpropane triacrylate were used. Note that the mixture of the polymerizable polymer precursors changed from a wax state to a transparent liquid state at 36°C.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the polymerizable polymer precursors were changed to 1.2 parts of 1,6-bis[2-(acryloxy)acetoxy]hexane and 30 parts of trimethylolpropane triacrylate. Note that the mixture of the polymerizable polymer precursors was in a liquid state at room temperature (25° C.).

[Evaluation During transfer processing, Comparative Example 1.2 compared with Examples 1 to 4,
The odor was so strong that it was a practical problem.

The resolution of the images of Examples 1 to 4 and Comparative Examples 1.2 was measured using a microscope. The results are shown in Table 1.

Table 1 Comparative Example 3 A photosensitive sheet was obtained in the same manner as in Example 1 except that the polymerizable polymer precursor was replaced with NK-Ester 23G (manufactured by Shin Nakamura Chemical Industries) (melting point 30°C). After image exposure, thermal image, and photopolymerization, 250 Kg/cm2 according to image receiving paper
Images were obtained through a roller pressurized to .

At this time, the image density was 1.4 in Comparative Example 1, whereas it was as low as 0.9. When the transfer was performed under heat and pressure under the same conditions as in Example 1, the image density increased to 1.4, but the minimum resolvable line width was 20μ.
It spread from m to 40 μm.

Example 5 0.8 parts of polyvinyl butyral was added to 1 part of isoprono\nol
0 parts of AgBr, and furthermore, 0.1 parts of AgBr was added to this solution.
part and 0.6 part of silver behenate were dispersed. Subsequently, 0.29 4-methoxy-1-naphthol was added to this dispersion.
Part was dissolved to obtain Solution A.

Separately, 15 parts of methyl ethyl ketone, 0.15 part of 2-chlorothioxanthone, 0.18 part of ethyl p-dimethylaminobenzoate, and 0.1 part of polymethyl methacrylate.
6 parts, 2.5 parts of 1.6-bis[2-(acryloxy)acetoxy]hexane (melting point 63-65°C) were dissolved,
I asked for liquid B.

Next, mix the A solution and the B solution well, and mix each separately for 12 hours.
A dry film thickness of 2.0 μm on a polyethylene terephthalate (PET) film. A photoreceptor layer was provided by coating the photoreceptor to give JJIll, and a 2 μm polyvinyl alcohol (PVA) layer was further provided thereon to obtain a photoreceptor.

Next, a mask film was placed on the PVA layer on the photoreceptor, and a latent image was formed by imagewise exposure. This image exposure uses a light source with a light emission output of 5 mW with a fluorescence peak at 420 nm.
Using a fluorescent lamp, place the light source 5cm away from the photoconductor and set it at a distance of 10m.
This was done by exposing for 5 ec.

Thereafter, the mask film was removed, and the photoreceptor was passed through a heat developing machine adjusted to 105° C. for 20 seconds. Furthermore, the photoreceptor was placed on a photoreceptor plate heated to 60° C., and was irradiated with light from a fluorescent lamp of 390 nm and a luminous output of 10 mW for 1 osec at a distance of 5 cm.

Finally, the PVA layer was removed by washing with water, and then the photoreceptor was rinsed in ethanol, whereby the image-exposed areas were removed from the PET film, leaving a positive image consisting of clear polymerized areas on the PET film.

Note that all treatments in this example were performed under safe light.

Comparative Example 4 Same as Example 5 except that 2.5 parts of trimethylolpropane triacrylate was used instead of 2.5 parts of 1,6-bis[2-(acryloxy)acetoxy]hexane. A photoreceptor was produced in the same manner. After imagewise exposure of this photoreceptor, it was passed through a heat developing machine adjusted to 105° C., and a polymerized image was formed by exposing the entire surface to light, but the image after etching treatment did not have sharpness.

In addition, the photoreceptors produced in Example 5 and Comparative Example 4 were heated at 35°C.
When a storage durability test was carried out under safe light for 2000 hours at 70% RH, the photoreceptor of Comparative Example 4 suffered from soil burr, but the photoreceptor of Example 5 did not. It wasn't.

Example 6 AgBr 0.1 parts Silver behenate 0.7 parts Isopropyl alcohol/toluene (1/1) 15 parts 4-benzyloxy-1-naphthol 0.4 parts Polymethyl methacrylate 3.0 parts 1.12-bis[ 2-(acryloxy)acetoxy]dodecane 1.5 parts (melting point 70-72°C) 7-nodoxy-3-benzoylcoumarin 0.16 parts Ethyl-4-dimethylaminobenzoate 0.04 parts The above blended liquid was mixed with a dispersion machine. The mixture was sufficiently dispersed and mixed to prepare an emulsion. Next, the emulsion was coated on a 50 μm polyester film using a bar coater and dried to form a 5 μm thick photosensitive layer. A 12 μm thick polyester film was then laminated on top of that layer. Next, for the photosensitive layer,
Ultra-high pressure mercury lamp (manufactured by Ushio, VAH-500D) was used as a light source.
) using a cut filter (manufactured by Toshiba Glass, Y-42)
Imagewise exposure was carried out for 5 seconds with light of approximately 400 nm or more. Next, the silver halide latent image was thermally amplified by heating at 115° C. for 10 seconds. Next, the front filter was removed and irradiation was performed for 20 seconds. Then, separate the polyester film and
Layer plain paper and photosensitive layer, heat to 80℃, 25kg/c
It was passed between rollers pressurized to m2 and then peeled off. The unexposed portions of the photosensitive layer were transferred onto the plain paper, and almost no unexposed portions of the photosensitive layer remained on the polyester film.

Comparative Example 5 Example 6 except that 1.12-bis[2-(acryloxy)acetoxy]dodecane in Example 6 was replaced with a liquid polymerizable polymer precursor (Kayad TPA-320, manufactured by Nippon Kayaku). A photoreceptor was formed and evaluated in the same manner as described above. Although the unexposed areas of the photoreceptor were transferred onto plain paper, there were some areas where the unexposed areas of the photosensitive layer remained on the polyester film, and the residual rate was not constant.

Example 7 AgBr 0.1 part Silver behenate 0.7 part Isopropyl alcohol/toluene (1/1) lo part Methyl methacrylate butyl acrylate copolymer 2.0 parts 4.8-dihydroxyquinoline-2-carboxylic acid 0 .35 parts 1.3-bis[2-(acryloxyacetoxyethoxycarbamoyl]benzene (melting point 67-70°C) 1.8 parts dipentaerythritol hexaacrylate 0.2 parts 7-medoxy 3-benzoylcoumarin 0.16 parts Ethyl-4-dimethylaminobenzoate 0.04 parts The above-blended solution was sufficiently dispersed and mixed using a dispersion machine to prepare an emulsion.Then, the emulsion was coated on a 50μ nail polyester film with an applicator and dried. A photosensitive layer with a thickness of 5 μm was formed.A polyester film with a thickness of 12 μm was then laminated on top of that layer.Next, the photosensitive layer was exposed to an image for 5 seconds using a Tanksten daylight light source as a light source. The silver halide latent image was thermally amplified by heating at 120°C for 20 seconds.Then, at 340 nm
The entire surface was irradiated for 60 seconds using an ultraviolet fluorescent lamp. After that, when the polyester film on the photosensitive layer was peeled off and carbon black was developed using a Fabrush, carbon black adhered to the exposed areas (unpolymerized areas), and carbon black adhered to the unexposed areas (polymerized areas). A black pattern with excellent resolution could be formed without any black adhesion. Further, the resolution of the black pattern was possible up to a line width of 10 μm, and the image was well cut.

Comparative Example 6 Example 7 except that 1,3-bis[2-(acryloxyacetoxy)ethoxycarbamoyl]benzene was replaced with trimethylolpropane trimethacrylate.
The same procedure as in Example 7 was carried out. In the obtained black pattern image, the line width of the 10 lines was not constant. In addition, Example 7
The photoreceptor of Comparative Example 6 was subjected to a durability test at 35°C and 70% RH for 2000 hours under safe light. There was hardly any yellowtail.

Example 8 AgBr 0.1 part Silver behenate 0.7 part Isopropyl alcohol/toluene (1/1) 10 parts Polyvinyl butyral 2 parts 2.2゛-
Methylenebis(4-methoxyphenol) 0.4 parts 1.4-bis[2-(acryloxyacetoxy)ethoxycarbamoylmethylcocyclohexane 2.5 parts (melting point 104
~106°C) Azobisisobutyronitrile 0.5 part Phthalazinone 0.1 part The above-mentioned liquid was thoroughly dispersed and mixed using a disperser to prepare an emulsion. Next 50μ
The emulsion was coated on a polyester film of 5 µm using an applicator and dried to form a photosensitive layer with a thickness of 5 µm. A photosensitive layer having a thickness of 5 μm was then formed on the layer. Then, a 12 μm thick polyester film was laminated on top of that layer. The photosensitive layer was then imagewise irradiated for 10 seconds using a tungsten daylight light source as a light source.

Next, after heating for 40 seconds in a heat developing machine at 80°C,
It was heated for 10 seconds in a heat developing machine at ℃. After that, 12IJIt
When the polyester film of I was peeled off and immersed in an ethanol bath, the image-exposed areas were dissolved and a polymerized image remained on the film.

[Effects of the Invention] As described above in detail, by using the photoreceptor and image forming method of the present invention, polymerized images and color images with excellent contrast, resolution, etc. can be stably obtained. Furthermore, the photoreceptor of the present invention produces less bad odor during image formation and has good shelf life.

[Brief explanation of the drawing]

FIGS. 1(a) to (e) are partial sectional views schematically showing aspects of each process in the image forming method of the present invention, and FIG.
a) to (e) are partial cross-sectional views schematically showing aspects of the photoreceptor of the present invention. 1... Photosensitive H2... Support 3... Silver nucleus 4... Reducing agent 5... Oxidized product 6... Polymerization part 7... Image receptor
8... Image 9... Oxygen inhibition layer lO... Microcapsule 11... Binder patent applicant Oriental Photo Industry Co., Ltd. Canon Co., Ltd.

Claims (1)

[Claims] 1) A photosensitive and heat-developable element and a photopolymerizable element are contained in the same layer, exposed to light in the wavelength range of 400 nm to 900 nm, and heated to 60 to 180°C. , 250-700
By exposing to light in the wavelength range of 40 nm,
A photoreceptor whose unexposed area is polymerized by light in a wavelength range of 0 nm to 900 nm, wherein the photopolymerizable element is 35 nm.
A photoreceptor characterized by containing a polymerizable polymer precursor having a melting point of ℃ or higher. 2) In a photoreceptor containing a photosensitive and heat-developable element and a polymerizable element, at least one compound selected from the group of compounds represented by the following general formula (I), (II) or (III). and a polymerizable polymer precursor having a melting point of 35° C. or higher. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) [However, the above general formula (I) ) ~ (III) Medium, R^1, R^
2, R^3, R^5, and R^6 each independently represent 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, or an alkoxyl group. group, substituted or unsubstituted cycloalkyl group, R^4 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, a carboxylic acid ester group, A represents an oxygen atom or a sulfur atom, R represents a hydrogen atom, an unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, n is 0 or 1, and z is It is a divalent linking group and represents an alkylidene group, an aralkylidene group, or a sulfur atom. 3) (a) a step of imagewise exposing the photoreceptor according to claim 2;
(b) An image forming method characterized by comprising the step of heating the photoreceptor. 4) It is characterized by comprising (a) a step of imagewise exposing the photoreceptor according to claim 1 or 2, (b) a step of heating the photoreceptor, and (c) a step of exposing the entire surface of the photoreceptor to light. An image forming method. 5) (a) a step of imagewise exposing the photoreceptor according to claim 1 or 2; (b) a step of heating the photoreceptor; (c) a step of polymerizing an image-unexposed area of the photoreceptor; (d) An image forming method comprising the step of transferring the unpolymerized portion of the photoreceptor to an image receptor.