JPH0667428A - Image forming medium and image forming method - Google Patents

Abstract

PURPOSE:To enable stripping development with satisfactory resolution and sharpness of lines and to form a clear image. CONSTITUTION:This image forming medium has a photosensitive layer 2 contg. at least a binder, a polymerizable compd. and a photopolymn. initiator on the transparent substrate 3 and the binder contains 100 pts.wt. linear satd. polyester resin and 300-0.1 pt.wt. chlorinated polyolefin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dry processable image forming medium used for producing a color proof for printing proofs, a color image for drawings, and a printing plate.

[0002]

2. Description of the Related Art Conventionally, as a method for forming an image by a dry process, a peelable and developable image forming medium having a photopolymerizable composition layer provided on a transparent support is known. That is,
In this type of medium, after the photopolymerizable composition layer side is laminated on the base material, light is irradiated from the transparent support side to bond the transparent support and the base material between the exposed and unexposed areas. Of the photopolymerizable composition corresponding to the exposed or unexposed area is left on the substrate to form an image by peeling the transparent support by making use of this difference. To do.

In the above image forming method, the photopolymerizable composition is usually irradiated with light through a so-called mask composed of a light transmitting portion and a light non-transmitting portion according to the image. The mask here needs to be prepared separately, and a squirrel mask, a Cr mask, or the like is used. Further, the adhesion between the mask and the transparent support is important in terms of resolution.

On the other hand, in the medium described in JP-A-55-50246, the heat-developable photosensitive composition layer is formed on the transparent support, and it is necessary to prepare a mask separately. It is possible to say that it is a preferable form without any problem in terms of adhesion, since a mask can be formed without a dry method, and a heat-developable photosensitive composition layer is formed by coating on a transparent support.

[0005]

However, since the medium described in JP-A-55-50246 receives heat of 80 to 160 ° C. during the thermal development process, the photopolymerizable composition is damaged by heat. Resolution deterioration is likely to occur. The chlorinated polyolefin, which is described as being particularly preferable in various proposals including JP-A-55-50246, is evaluated by the present inventors to include a chlorinated polyolefin in the photopolymerizable composition. However, when exposed to heat, the photopolymerizable composition (unpolymerized portion) in the unexposed area that should be peeled off onto the substrate becomes easy to transfer, and the deterioration of the formed image (resolution (Deterioration) occurs, and at the same time, a patchy pattern occurs in the coating film of the photopolymerizable composition layer. In JP-A-55-50246, a medium is used as a printing plate. In that case, even if a spot-like pattern is generated in the image on the printing plate, the printed matter may not be affected so much, but various proposals have been made. Even in the case of using a tenting resist, there are many cases where it does not cause a problem, but when the peeled and developed image itself is used as a product, a marked image defect occurs. By reducing the content of the chlorinated polyolefin, it is possible to reduce the above-mentioned resolution deterioration and mottled pattern, but it becomes necessary to add another binder to maintain the layered state. However, for example, the addition of acrylic resins described in various proposals also leads to the same deterioration in resolution as described above, and in JP-A-57-62046, in order to solve this point, the inorganic particles are replaced with a photopolymerizable composition. It is contained in the product layer. The addition of inorganic particles of this proposal is for the purpose of making the thickness of the photopolymerizable composition layer about 30 to 100 μm,
Although an image having an image distance of 100 μm or more gives a preferable result, higher resolution is naturally required in the formation of a color image or the like which is one of the objects of the present invention, and the photopolymerizable composition layer is required. Is required to be at least 30 μm or less, preferably 5 μm or less, and when inorganic particles are added, unevenness of the particles appears on the coating film surface, which is not preferable.

From the above, a satisfactory improvement has not yet been made in a medium in which an image is formed by peeling and developing after heat treatment, particularly when the peeled and developed image itself is used as a product.

The problem to be solved by the present invention is to solve the above-mentioned various problems, and even after the heat treatment,
An image forming medium in which mask-formable layers are laminated by a dry process is to provide an image forming medium capable of peeling and developing, which does not cause defects such as mottled patterns in an image and has good resolution and line breakage. To provide the medium.

[0008]

As a result of intensive studies to solve the above problems, the present inventors have found that in an image forming medium having a peelable and developable photosensitive layer, a specific resin is used as a binder contained in the photosensitive layer. By using at a specific ratio,
The present invention has been completed by finding that an excellent image can be obtained without causing a mottled pattern and deterioration in resolution when peeling and developing after heat treatment.

That is, the present invention provides an image forming medium containing at least a binder, a polymerizable compound and a photopolymerization initiator on a transparent support, wherein a linear saturated polyester resin and a chlorinated polyolefin are contained in the binder. The image forming medium is characterized by containing 300 parts by weight to 0.1 parts by weight of the chlorinated polyolefin with respect to 100 parts by weight of the linear saturated polyester resin.
Hereinafter, this is referred to as a first mode.

The present invention also provides at least a binder,
An image forming medium having a photosensitive layer containing a polymerizable compound and a photopolymerization initiator, and a photosensitive silver salt layer containing at least a photosensitive silver halide, an organic silver salt and a reducing agent,
In the binder, a linear saturated polyester resin and a chlorinated polyolefin are added, and 3 parts of the chlorinated polyolefin is added to 100 parts by weight of the linear saturated polyester resin.
The image forming medium is characterized in that it is from 00 parts by weight to 0.1 parts by weight. Hereinafter, this is referred to as a second mode.

The image forming medium of the first aspect of the present invention includes, for example, a structure in which a peelable and developable photosensitive layer 2 and a transparent support 3 are sequentially laminated on a substrate 1 as shown in FIG. You can

As the image forming medium of the second aspect, for example, as shown in FIG. 2, a structure in which a photosensitive layer 2, a photosensitive silver salt layer 4, and a protective layer 5 are sequentially laminated on a substrate 1, or As shown in FIG. 3, an intermediate layer 6 may be provided between the photosensitive layer 2 and the photosensitive silver salt layer 4.

First, the material of each layer constituting the image forming medium of the present invention will be described.

The transparent support used in the image forming medium of the present invention serves as a support for peeling and developing the photosensitive layer, and is a photoinitiator contained in the photosensitive wavelength region of the photosensitive layer, that is, in the photosensitive layer. Has good transmittance in the absorption wavelength region, and a film having a smooth surface can be preferably used. Specifically, for example, polyethylene terephthalate, polypropylene,
Cellulose diacetate, cellulose triacetate,
Cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate, cellophane, methyl cellulose, ethyl cellulose, polyvinyl chloride, vinyl chloride copolymers such as vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl acetate copolymer, polyvinylidene chloride, polystyrene, polyvinyl. alcohol,
Polycarbonate, gelatin, polyamide (eg 6
-Nylon, 6,6-nylon, 6,10-nylon, etc.) and the like. Furthermore, it is also possible to use a mixture of two or more of these materials, or a laminate.

The thickness of the transparent support is about 0.5 μm.
˜about 300 μm, more preferably about 2 μm to about 50 μm.

Among the above, polyethylene terephthalate is particularly preferable because of its chemical resistance, dimensional stability, strength, transparency,
It is preferable in terms of heat resistance, cost, and versatility.

The photosensitive layer contained in the image-forming medium of the present invention is a lower layer (base material) of the photosensitive layer in the exposed and unexposed areas after exposure and an upper layer of the photosensitive layer (transparent support or a photosensitive silver salt described later). By utilizing the difference in the adhesiveness (tackiness) to the layer), the upper layer of the photosensitive layer and the portion of the photosensitive layer having a large adhesive force to the upper layer are peeled and removed, whereby the base of the photosensitive layer on the substrate is removed. An image can be formed by leaving a portion having a large adhesive force on the material.

The photosensitive layer contains at least a binder,
It is composed of a polymerizable compound and a photopolymerization initiator.

The binder material, which is a feature of the present invention, is composed of chlorinated polyethylene, chlorinated polyolefin represented by chlorinated polypropylene, terephthalic acid, ethylene glycol, and other dibasic acid and / or dihydric alcohol. A linear saturated polyester having a basic skeleton and having a carboxyl group and / or a hydroxyl group at both terminals of the molecule is used, and even if the linear saturated polyester is used alone, a preferable image can be obtained in peel development after heat treatment. However, when the chlorinated polyolefin is mixed, the resolution and the sharpness of the line can be further improved, and an excellent image can be obtained. The mixing ratio of the linear saturated polyester and the chlorinated polyolefin is 300 parts by weight to 0.1 parts by weight of the chlorinated polyolefin, and further 100 parts by weight of the linear saturated polyester.
100 to 0.5 parts by weight, particularly 50 to 1 parts by weight are preferred. When a chlorinated polyolefin in an amount larger than 300 parts by weight is mixed, resolution deterioration due to transfer of the unpolymerized portion of the photosensitive layer to the substrate and spot-like patterns in the coating film of the photosensitive layer are generated, resulting in image defects. If the amount is less than 1 part by weight, the resolution and the sharpness of the line are inferior as compared with the case where the amount is more than 1 part by weight.

As the polymerizable compound, a compound having at least one reactive vinyl group in one molecule can be used, and examples thereof include a reactive vinyl group-containing monomer, a reactive vinyl group-containing oligomer and a reactive vinyl group-containing oligomer. One or more selected from the group consisting of vinyl group-containing polymers can be used. The reactive vinyl group of these compounds is a styrene-based vinyl group, (meth) acrylic acid-based vinyl group, allyl-based vinyl group, vinyl ether, or other ester-based vinyl group substituted with polymerization reactivity Group or an unsubstituted vinyl group. Here, (meth) acrylic acid means methacrylic acid and acrylic acid.

Specific examples of the polymerizable compound satisfying the above conditions include JP-A-55-50246 and JP-A-57.
Although it is described in detail in many proposals such as JP-A-62046, examples of the compound having one reactive vinyl group include acrylic acid, methacrylic acid; propyl acrylate, butyl acrylate, ethylhexyl acrylate and the like. Acrylic acid esters; Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate; (meth) acrylamide, N- (meth) methylacrylamide, N- (meth) ethylacrylamide, N- (meth) butyl Acrylamide, N- (meth)
(Meth) acrylamides such as ethylhexylacrylamide; allyl compounds such as allyl acetate, allyl caproate, allyl caprylate and allyl palmitate; vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, ethylhexyl vinyl ether; vinyl butyrate, vinyl trimethyl acetate And vinyl esters such as vinyl caproate; styrenes such as styrene, chloromethylated styrene, styrene benzoate, nitrostyrene, hydroxystyrene, aminostyrene; and crotonic acid esters.

Examples of the compound having two or more reactive vinyl groups include esters of polyhydric alcohol and (meth) acrylic acid, such as di (meth) acrylate and poly (meth).
An acrylate is mentioned.

Here, as the polyhydric alcohol, polyethylene glycol, polypropylene glycol, polypropylene oxide, glycerin, neopentyl glycol,
Trimethylolpropane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitan, sorbitol, 1.4-butanediol, 1.2
-4-butanetriol, 2-butene-1.4-diol, 1.3-propanediol, triethanolamine, decalindiol and the like. Other examples include oligoesters or polyesters having one or more hydroxyl groups in the molecule synthesized from a polyhydric alcohol and a polybasic acid, and esters obtained by reacting acrylic acid or methacrylic acid with the above hydroxyl groups. . Examples of this commercially available product include Aronix M-5500, -5700, -6100, -6400, manufactured by Toagosei Co., Ltd.
-6300, -8030, -8060, -400, etc. are mentioned. In addition to the above, an acrylated epoxy resin or the like may be used.

The above polymerizable compounds can be used in combination of two or more kinds. The total amount of polymerizable compounds is 10
10 parts by weight to 500 parts by weight, preferably 20 parts by weight to 300 parts by weight, more preferably 30 parts by weight, relative to 0 parts by weight.
It can be used in the range of parts by weight to 250 parts by weight.

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

Specifically, as the carbonyl compound,
For example, diketones such as benzyl, 4,4′-dimethoxybenzyl, diacetyl, camphorquinone; benzophenones such as 4,4-diethylaminobenzophenone and 4,4-dimethoxybenzophenone; acetophenones such as acetophenone and 4-methoxyacetophenone For example, benzoin alkyl ethers; for example, thioxanthones such as 2-cyclolothioxanthone, 2-5-diethylthioxanthone, thioxanthone-3-carboxylic acid-β-methoxyethyl ester; chalcones and styryl ketones having a dialkylamino group; Examples thereof include coumarins such as 3,3′-carbonylbis (7-methoxycoumarin) and 3,3′-carbonylbis ′ (7-diethylaminocoumarin).

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

Examples of the halogen compound include carbon tetrabromide, quinolinesulfonyl chloride and S-triazines having a trihalomethyl group.

The redox photopolymerization initiator is 3
A combination of a high-valent iron ion compound (for example, ferric ammonium citrate) and a peroxide, or a combination of a photoreducing substance such as riboflavin and methylene blue and a reducing agent such as triethanolamine and ascorbic acid Things are included.

In the photopolymerization initiator described above,
It is also possible to obtain a more efficient photopolymerization reaction by combining two or more kinds.

Examples of combinations of such photopolymerization initiators include chalcone and styrylstyryl ethones having a dialkylamino group, coumarins and S-triazines having a trihalomethyl group, and camphorquinone.

The amount of the polymerization initiator is 0.1 to 30 parts by weight, more preferably 0.3 to 100 parts by weight of the polymerizable compound.
Preference is given to parts by weight to 25 parts by weight.

The film thickness of the photosensitive layer of the present invention is not particularly limited as long as it is a thickness capable of performing good peeling development, and the range is 0.2 μm to 50 μm, preferably 0.3 μm.
˜20 μm, more preferably 0.3 μm to 10 μm, and particularly preferably 0.5 μm to 5 μm.

In addition to the above-mentioned binder, polymerizable compound and photopolymerization initiator, a thermal polymerization inhibitor for preventing a dark reaction during storage, a colorant for improving plate inspection property, a plasticizer and an anti-aging agent, etc. Various additives can be contained in the photosensitive layer.

As the thermal polymerization inhibitor, for example, p-methoxyphenol, hydroquinone, phenothiazine, pyrogallol, naphthylamine, β-naphthol, tertiary pentylcatechol and the like can be used.

As the colorant, for example, carbon black, iron oxide, phthalocyanine type, azo type, methylene blue, crystal violet, rhodamine B auramine and the like can be used.

Examples of the plasticizer that can be used include phthalic acid esters such as dicyclohexyl phthalate and dimethyl phthalate, glycol esters such as dimethyl glycol phthalate, and stearic acid phosphates such as triphenyl phosphate.

The photosensitive silver salt layer contained in the image forming medium of the present invention will be described.

In the photosensitive silver salt layer contained in the image forming medium of the present invention, light transmission and non-transmission portions are formed by image exposure and heat treatment, whereby light transmission can be controlled, that is, an optical mask. It is a layer capable of producing a function, and is a layer containing a so-called dry silver salt composition containing at least a photosensitive silver halide, an organic silver salt, and a reducing agent.

The photosensitive silver halide may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide, and has a multiple structure in which the halogen composition in the grain is uniform or different. May be taken. Further, two or more kinds of silver halides having different halogen compositions, grain sizes and grain size distributions may be used in combination. Further, it may be spectrally sensitized or chemically sensitized with these dyes or the like.

The organic silver salt is a silver salt with an aliphatic carboxylic acid, an aromatic carboxylic acid, a thiocarbonyl group compound having a mercapto group or α-hydrogen, and an imino group-containing compound.

As the aliphatic carboxylic acid, acetic acid, butyric acid,
There are succinic acid, sebacic acid, adipic acid, oleic acid, linoleic acid, linolenic acid, tartaric acid, palmitic acid, stearic acid, behenic acid, camphoric acid, etc. Therefore, those having an appropriate carbon number are preferable.

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

Examples of the thiocarbonyl group compound having a mercapto group or α-hydrogen include 3-mercapto-4-phenyl-1,2,4-triazole, 2-mercaptobenzimidazole, 2-mercapto-5-aminothiadiazole, 2 -Mercaptobenzothiazole, S-alkyl thioglycols (alkyl group having 12 to 22 carbon atoms),
Dithiocarboxylic acids such as dithioacetic acid, thioamides such as thiostearoamide, 5-carboxy-1-methyl-2
-Phenyl-4-thiopyridine, mercaptotriazine, 2-mercaptobenzoxazole, mercaptooxadiazole or 3-amino-5-benzylthio-
1,2,4-triazole and the like, U.S. Pat.
The mercapto compound described in No. 274 is mentioned.

Examples of the compound containing an imino group include benzotriazole or its derivatives described in JP-B-44-30270 or 45-18416, for example, alkyl-substituted benzotriazoles such as benzotriazole and methylbenzotriazole, 5- Chlorobenzotriazole, etc., halogen-substituted benzotriazoles, butylcarbimidobenzotriazole, etc., carboimide benzotriazoles, nitrobenzotriazoles described in JP-A-58-18639, JP-A-58-11.
Sulfobenzotriazole, carboxybenzotriazole or a salt thereof described in 5638, hydroxybenzotriazole and the like, US Pat. No. 4,220,7.
Representative examples thereof include 1,2,4-triazole described in No. 09, 1H-tetrazole, carbazole, saccharin, imidazole and derivatives thereof.

As the reducing agent, a compound which reduces an organic silver salt to produce silver and forms a blackened image by a silver image and / or an image of an oxidant changed by the reaction of the reducing agent itself with the organic silver salt. A compound that forms a compound is used, and these reducing agents can be appropriately selected and used according to the type of organic silver salt used. As reducing agents that can be used, monophenols, bisphenols, trisphenols,
Tetrakisphenols, mononaphthols, bisnaphthols, dihydroxynaphthalenes, trihydroxynaphthalenes, dihydroxybenzenes, trihydroxybenzenes, tetrahydroxybenzenes, hydroxyalkyl monoethers, ascorbic acids, 3-pyrazolidones, pyrazoline Examples thereof include pyrazolones, phenylenediamines, hydroxyamines, reductones, hydrooxamic acids, hydrazides, amidoximes, and N-hydroxyureas. 51-22431,
U.S. Pat. Nos. 3,615,533 and 3,679,4
No. 26, No. 3,672,904, No. 3,751,
No. 252, No. 3,751,255, No. 3,78
No. 2,949, No. 3,801,321, No. 3,7
No. 94,455, No. 3,893,863, No. 3,
887,376, Belgian Patent No. 786,086
U.S. Pat. Nos. 3,770,448 and 3,81
9,382, 3,773,512, and 3,9
28,686, 3,839,048, 3,
887,378, JP-B-51-35851, JP-A-50-36143, US Pat. No. 3,827,
889, 3,756,829, JP-A-50-3.
6110, JP-A-50-116023, JP-A-50-147711, JP-A-51-2372.
1, JP-A-50-99719, and JP-A-51
-32324 gazette, Unexamined-Japanese-Patent No. 51-51923 gazette,
JP-A-50-140113, JP-A-52-847
No. 27 gazette is described in each specification. Here, in order to increase the contrast of the light absorption amount (transmission amount) between the exposed portion and the unexposed portion, an oxidant having a large molar absorption coefficient is preferable, and as a reducing agent that forms such an oxidant, Aromatic hydroxy compounds are preferred. Hereinafter, the aromatic hydroxy compounds will be described in detail.

The compounds represented by the following general formulas (1) and (2) are polymerized by the fact that the oxidant produced by the redox reaction with the organic silver salt absorbs light in the absorption wavelength region of the photopolymerization initiator. It is an aromatic hydroxy compound that develops the ability to inhibit.

[0048]

[Outer 1] (However, in the general formulas (1) and (2), r ¹ , r ² and r ³
Each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, r and r ⁴ are each independently a hydrogen atom, Represents a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, or an alkoxy group, m is a positive number of 1 to 3, and Y is a monovalent to trivalent linkage. As the group, a substituted or unsubstituted aralkyl group, a substituted amino group,
An alkylidene group, a substituted or unsubstituted aralkylidene group and a methine group are shown, and Z is an alkylidene group and a substituted or unsubstituted aralkylidene group. )

In the above general formulas (1) and (2), the unsubstituted alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, i-propyl and butyl. , T-butyl, i-butyl,
Examples thereof include amine, i-amine, sec-amyl, texyl, hexyl, heptin, octyl, nonyl, dodecyl and stearyl.

The substituted alkyl group includes an alkoxyalkyl group having 2 to 18 carbon atoms, a halogenalkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms, and an aminoalkyl group having 1 to 18 carbon atoms. , For example, as an alkoxyalkyl group, methoxyethyl,
Ethoxymethyl, ethoxyethyl, ethoxypropyl,
Examples thereof include ethoxybutyl, propoxymethyl, propoxybutyl, i-propoxypentyl, t-butoxyethyl and hexyloxybutyl.

Examples of the halogenalkyl group include chloromethyl, chloroethyl, bromoethyl, chloropropyl, chlorobutyl, chlorohexyl and chlorooxyl.

Examples of the hydroxyalkyl group include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl and hydroxyheptyl.

The aminoalkyl group includes aminomethyl, acetylaminomethyl, dimethylaminomethyl, aminoethyl, acetylaminoethyl, dimethylaminoethyl, diethylaminoethyl, morpholinoethyl, piperidinoethyl, diethylaminopropyl, dipropylaminoethyl, acetylaminopropyl. , Aminobutyl,
Examples thereof include morpholinobutyl.

The cycloalkyl group is cyclopentyl, cyclohexyl or cycloheptyl. Examples of the aralkyl group include benzyl, chlorobenzyl, phenethyl and the like.

The aryl group has 6 to 16 carbon atoms, and is preferably phenyl, naphthyl, anthryl, phenanthryl, tolyl, xylyl, cumenyl, mesityl, chlorophenyl, methoxyphenyl, fluorophenyl and the like.

The alkoxyl group has 1 to 1 carbon atoms.
8 and preferably methoxy, ethoxy, propoxy, i-propoxy, ptooxy and the like.

Of these, preferred substituents for r ² and r ³ are chlorine atom, bromine atom, methyl, ethyl, i-propyl, t-butyl, sec-amyl, thexyl, ethoxymethyl, ethoxyethyl, chloromethyl, Hydroxymethyl, aminomethyl, dimethyl-aminomethyl, benzyl, and particularly preferred substituents are chlorine atom, t-butyl and thexyl. Preferred substituents for r ¹ are
Chlorine atom, methyl, ethyl, i-propyl, t-butyl, amyl, thexyl, hydroxyl, chloromethyl,
Hydroxymethyl, benzyl, cyclohexyl,
Particularly preferred substituents are chlorine atom, methyl, t-butyl and thexyl.

Examples of the substituted or unsubstituted aralkyl group of the monovalent linking group include benzyl, p-methoxybenzyl, p-N, N-dimethylaminobenzyl, p-pyrrolidinobenzyl, p-methylbenzyl and p. -Hydroxybenzyl, p-chlorobenzyl, 3,5-dichloro-
4-hydroxybenzyl, o, p-dimethylbenzyl,
2-hydroxy-3-t-butyl-5-methylbenzyl, naphthylmethyl and the like can be mentioned.

Examples of the substituted amino group of the monovalent linking group include methylaminodimethylamino, diethylamino, acetylamino, phenylamino, diphenylamino and triazylamino.

As the alkylidene group of the divalent linking group,
For example, methylene, ethylidene, propylidene, butylidene and the like can be mentioned.

As the aralkylene group of the divalent linking group,
For example, benzylene, p-methyl benzylene, p- dimethylamino benzylene etc. can be mentioned.

A preferable reducing agent in the general formula (1) is 2,6-di-t-butyl-4- (2-hydroxy-).
3-t-butyl-5-methylbenzyl) 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 (2,6
-Di-t-butylphenol), 4,4'-methylenebis (2-t-butyl-5-methylphenol), 4,
4'-methylidenebis (2-t-butyl-6-methylenephenol), 4,4'-ethyldenbis (2,6-di-t-butylphenol) 4,4'-ethylidenebis (2-t-butyl-6-) Methylphenol), 4,4 '
-Propylidene bis (2,6-di-t-butylphenol), 4,4-butylidene bis (2,6-di-t-butylphenol), 4,4'-butylidene bis (2-cyclohexyl-6-methylphenol), bis ( 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 (3,3
5-di-t-butyl-4-hydroxyphenyl) methane.

Preferred reducing agents in formula (2) are 4,4'-methylenebis (2-methyl-1-naphthol) and 4,4'-methylenebis (2-t-butyl-1).
-Naphthol), 4,4'-methylenebis (2-t-butyl-6-methyl-1-naphthol), 4,4'-ethylidenebis (2-methyl-1-naphthol), 4,4 '.
-Ethylene bis (2-t-butyl-1-naphthol),
Bis (4-hydroxy-3-methyl-naphthyl) phenylmethane.

The reducing agents represented by the general formulas (1) and (2) can form a polymerized image with good contrast by selecting a photopolymerization initiator.

For example, as the reducing agent, 4,4'-methylenebis (2-methyl-6-t-butylphenol), 4,
When 4'-methylenebis (2,6-di-t-butylphenol) or the like is used, a photopolymerization initiator having sensitivity in 380 nm to 390 nm, such as 2-chlorothioxanthone, 2-methylthioxanthone, 2,4- Dimethylthioxanthone, 2,4-diethylthioxanthone,
2,4,6-Trimethylbenzoyldiphenylphosphine oxide, benzyl and the like are preferable.

As a reducing agent, 4,4'-methylenebis (2-methyl-1-naphthol), 4,4'-methylenebis (2, -ethyl-1-naphthol), 4,4'-
When methylenebis (2-t-butyl-1-naphthol) or the like is used, a photopolymerization initiator having a sensitivity in the range of 400 nm to 500 nm, such as 2,4-dichlorothioxanthone, camphorquinone, 3,3-carbonylbis ( A combination of coumarins such as 7-diethylaminocoumarin) and tris (trichloromethyl) triazine,
A combination of 2- (p-dimethylaminostyryl) -4,5-diphenylthiazole and 3-phenyl-5-isoxazolone, a combination of a merocyanine dye and 3-phenyl-5-isoxazolo and the like are preferable.

The preferable compounding ratio of the above components of the photosensitive silver salt layer in the image forming medium of the present invention is as follows.

The photosensitive silver halide is preferably contained in an amount of 0.001 to 2 mol, more preferably 0.05 to 0.4 mol, per mol of the organic silver salt. Further, the reducing agent is preferably 0.2 mol to 3 mol, and more preferably 0.7 mol to 1. mol per mol of the organic silver salt.
It is desirable to contain 3 mol.

Further, it is preferable to further provide a layer on the photosensitive silver salt layer, which acts as a protective layer for the photosensitive silver salt layer and prevents the photosensitive silver salt layer from adhering or sticking to other substances. And functions such as preventing moisture in the atmosphere from penetrating.

The protective layer can be selected from a wide range of materials as long as it is transparent to the light in the photosensitive wavelength region of the photosensitive layer and the photosensitive silver salt layer, and specifically, for example, , Polyethylene terephthalate, polypropylene, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate, cellophane, methyl cellulose, ethyl cellulose, polymethyl methacrylate, polyvinyl chloride, vinyl chloride-vinylidene chloride copolymer, vinyl chloride -Vinyl chloride copolymers such as vinyl acetate copolymers, polyvinylidene chloride, polystyrene, polyvinyl alcohol, polycarbonate, gelatin, polyamides (eg 6-nylon,
6,6-nylon, 6,10-nylon, etc.) and the like. Furthermore, it is also possible to use a mixture of two or more of these materials, or a laminate.

The protective layer has a thickness of about 0.2 μm to about 300 μm, preferably about 0.5 μm to about 50 μm, more preferably about 0.5 μm to about 20 μm.

The protective layer may contain a light-absorbing dye so as to have an effect of filtering light in a designated wavelength region. In addition, an additive suitable for the purpose may be added as needed.

The base material used in the image forming medium of the present invention can be selected from a wide range of materials as long as it can be peeled and developed, depending on the combination with the photosensitive layer. Examples thereof include paper, corrad paper, synthetic paper, wood, metal plate, metal foil, glass plate and the like.

Particularly for the image forming medium of the present invention, a polyimide film, a film of polyvinyl alcohol (which may or may not be crosslinked) or a coated film, a copper plate, an aluminum plate, aluminum The vapor-deposited polyester film and the like are preferable.

In order to prevent halation from the substrate to the photosensitive layer, the substrate may contain an antihalation agent,
An antihalation layer may be provided between the base material and the photosensitive layer.

The intermediate layer contained in the second aspect of the present invention is
It is a layer that becomes a support when the photosensitive layer is peeled off and developed. Therefore, the same material as the transparent support can be used. Similar to the transparent support, the thickness of the intermediate layer is about 0.5.
μm to about 30 μm, more preferably about 2 μm to about 50 μm.

Further, an antihalation dye may be contained in the intermediate layer in order to prevent halation, or an antihalation layer may be provided between the intermediate layer and the photosensitive silver salt layer. Further, in the case of not using this intermediate layer as shown in FIG. 2, an antihalation layer may be provided between the photosensitive layer and the photosensitive silver salt layer.

The provision of the above intermediate layer prevents the mixture of the layer constituent components of both layers due to thermal diffusion, which may occur when the photosensitive layer and the photosensitive silver salt layer are directly laminated, and improves the storage stability. It has the effect of accelerating the mixing or preventing the mixture at the time of coating. Further, since the mixture can be prevented, the selection of materials for both layers can be facilitated and the selection range can be expanded.

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

The image forming method of the present invention means that the image forming medium of the first embodiment is heated at the same time as image exposure to polymerize the polymerizable compound contained in the photosensitive layer site-selectively. And an unpolymerized part to form a latent image for polymerization, and an image forming method characterized by comprising a peeling and developing process of peeling the polymerized part or unpolymerized part of the photosensitive layer together with the transparent support to form an image. In addition, for the image forming medium of the second aspect, an image exposing process of performing image exposure on the photosensitive silver salt layer, a heat developing process of heating the image forming medium, and a heat developed photosensitive silver salt layer. The entire surface is exposed from the side, and the polymerizable compound contained in the photosensitive layer is site-selectively polymerized to form a polymerization latent image composed of a polymerized portion and an unpolymerized portion. Part together with the photosensitive silver salt layer The image forming method characterized by having the a peeling development process to form an image.

Hereinafter, the image forming method of the present invention will be described in detail with reference to the drawings as an example of each mode.

First, an image forming method using the first mode will be described.

As shown in FIG. 1, the photosensitive layer 2 is coated on the transparent support 3, and the substrate 1 and the photosensitive layer 3 prepared separately are coated.
Are laminated so that they are in contact with each other to produce an image forming medium. When laminating, it is preferable to apply heat,
Heating at 15 ° C to 120 ° C, more preferably 40 ° C to 80 ° C is preferable.

Then, as shown in FIG. 4, a suitable mask 7 is formed.
The photosensitive layer 2 is exposed to and heated by the light having the absorption wavelength of the photopolymerization initiator contained in the photosensitive layer 2 to polymerize the polymerizable compound in the photosensitive layer 2 according to the pattern of the mask 7. A latent image composed of the overlapped portion 2-a and the non-overlapped portion 2-b is formed.

As the mask used above, a mask having a light transmitting portion and a light non-transmitting portion is used.

Further, analog exposure other than mask exposure, digital exposure, etc. may be used, and the exposure light source is, for example,
Examples thereof include sunlight, a tungsten lamp, a mercury lamp, a halogen lamp, a xenon lamp, and a fluorescent lamp. Further, examples of the exposure without using a mask include a liquid crystal shutter array, a CRT, an optical fiber tube and the like. Besides, laser beams, electron beams, X-rays and the like may be used.

In this exposure process, it is very preferable to perform heating at the same time as the exposure, which has the effect of increasing the polymerization rate of the polymerizable compound and shortens the exposure time.

The heating means is not particularly limited, but it is preferable to use a hot plate, a heat roll, a thermal head or the like.

The heating temperature depends on the composition of the photosensitive layer and the like, but is preferably 30 ° C to 150 ° C, more preferably 50 ° C to 120 ° C.

As described above, the above heat treatment is carried out by the conventional peelable photosensitive layer (photopolymerizable composition layer).
Then, it was difficult to obtain an image defect, but image deterioration did not occur in the image forming medium of the present invention. In other words, this heat treatment can be performed by using the image forming medium of the present invention. Therefore, it can be said that the exposure time can be shortened as described above.

After the above exposure process, the transparent support 3 is peeled and removed as shown in FIG. At this time, the unpolymerized portion 2-b of the photosensitive layer 2 is adhered to the transparent support 3, and the unpolymerized portion 2-b
b is also peeled off at the same time.

Through this process, the photosensitive layer polymerized portion 2-a remains on the substrate, and an image is formed on the substrate.

The above-mentioned image obtained by the image forming method of the present invention is preferably further subjected to a heat treatment using a hot plate, a heat roll or the like so that the durability can be further improved.

The heating temperature depends on the composition of the photosensitive layer, the glass transition temperature of the polymerized portion of the photosensitive layer, the softening temperature, etc., but is 50 ° C.
˜200 ° C., more preferably 80 ° C. to 180 ° C. Also,
It is also preferable to perform a pressure treatment using a press, a roll or the like, and the durability can be further improved.

The pressure to be applied is preferably such that the photosensitive layer polymerized layer is not crushed, and is 0.2 kg / cm ^{2 to} 15 kg.
/ Cm ^2, further 1kg / cm ² ~10kg / cm ² is desirable.

Further, it is also preferable to expose the image again with the light used in the exposure step, and the post exposure can improve the durability.

Although the reason for this is not clear, the photopolymerization initiator remaining in the polymerized portion of the photosensitive layer during the exposure process reacts by the subsequent exposure to polymerize the unreacted polymerizable compound in the polymerized portion of the photosensitive layer. , Combined with the unreacted polymerizable compound in the hydrophilic layer,
It is considered that this contributes to the improvement of printing durability. Further, similarly to the above, it is also very preferable to perform heating at the same time as exposure in the post-exposure step, which is effective in further improving printing durability. This post-exposure (and simultaneous heating) treatment and the heating and / or
Alternatively, both pressure treatments are preferably performed, but the order thereof is not particularly limited.

In the above-mentioned image forming method, the case where the polymerized portion is peeled from the transparent support and the base material is transferred has been described. However, depending on the selection of the photosensitive layer composition transparent support base material, the unpolymerized portion is transferred. May be transferred onto the substrate. In this case, after being transferred in an image form, the unpolymerized portion is exposed (and simultaneously heated) in the above-mentioned condition range, and preferably, thereafter, the heating and / or pressure treatment is performed as in the above.

A method for forming a multicolor image with the image forming medium of the first aspect will be described.

As this method, i) a method of repeating the above-mentioned image forming method on the same base material, ii) a method of superposing a transparent support having a polymerized portion or unpolymerized portion of a peeled photosensitive layer, and iii) a peeled photosensitive material. There is a method in which the remaining polymerized portion or unpolymerized portion is transferred onto a substrate from a transparent support in which the layer polymerized portion or unpolymerized portion remains, and this operation is repeated.

The method i) will be described. First, a cyan photosensitive layer containing a colorant showing a cyan color as a colorant,
A magenta photosensitive layer containing a colorant showing a magenta color and a photosensitive layer containing a colorant showing a yellow color are respectively coated on a transparent support. Then, a cyan photosensitive layer is laminated on the white base material, and a cyan image is formed according to the above image forming method. Then, a magenta photosensitive layer is laminated on this cyan image, and a magenta image is formed on the cyan image with good registration accuracy in the same manner as described above. obtain. If necessary, a black ink image may be added to the cyan, magenta, and yellow images by using a photosensitive layer containing a pigment showing the color tone of black ink.

The method ii) will be described. First, similarly to i), a cyan photosensitive layer, a magenta photosensitive layer, and a yellow photosensitive layer are each coated on a transparent support, and laminated on an arbitrary peelable and developable substrate. Then, the above-mentioned image forming method is performed for each photosensitive layer. Then, the peeled transparent supports having the remaining polymerized portions or unpolymerized portions of the photosensitive layers of the respective colors are superposed and laminated with good registration accuracy to obtain a multicolor image.
Similarly to i), a black image may be added if necessary. The multicolor image here can of course be formed by sequentially laminating it on a white base material, for example.

The method iii) will be described. First, ii)
In the same manner as in (2) above, a transparent support in which the separated or unpolymerized photosensitive layer of each color remains is prepared. Then, for example, the respective colors are sequentially thermally transferred onto a white base material to obtain a multicolor image. When the remaining portion of the peeled photosensitive layer of each color is an unpolymerized portion, it is also possible to perform exposure (and simultaneous heating) in the same manner as the above-mentioned image forming method depending on the substrate and transfer it onto the substrate. Further, instead of using a transparent support in which the peeled or unpolymerized photosensitive layer of each color remains, the reverse unpolymerized portion or polymerized portion of the transferred substrate is used, for example, on a white substrate. Thermal transfer or exposure of each color,
A multicolor image may be formed. However, in order to form an image of each color with high registration accuracy, it is preferable to use a transparent support in which the photosensitive portion or unpolymerized portion of each photosensitive layer remains.
Further, a black image may be added if necessary.

In the method (iii) (method of forming a multicolor image by thermal transfer), by using the image forming medium of the present invention, the image defect which is observed when the conventional image forming medium is used is eliminated.

A single-color or multi-color image can be completed by the above-described image forming method. However, a writing image can be directly obtained by including a layer capable of controlling light transmission in an image forming medium and directly obtaining a laser or the like. You can also Materials capable of controlling light transmission include wet silver salts, dry silver salts, and high-molecular liquid crystals. However, the dry silver salts are simple in dry processing and have high light transmittance contrast. Is preferably used. This is the second aspect of the present invention, and an image forming method using this aspect will be described.

The image forming medium of the second aspect has various manufacturing methods by combining coating and laminating of the respective layers, and there is no particular limitation. For example, a medium as shown in FIG. 3 can be manufactured. it can.

That is, the photosensitive layer 2 is coated and formed on a transparent support such as polyethylene terephthalate (which becomes the intermediate layer 6 in the image forming medium), and a film which can be peeled from the photosensitive layer 2, for example, is formed. Laminate a fluororesin film or a silicone-coated plastic film. The fluororesin system includes, for example, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer. Etc. Then, a photosensitive silver salt layer 4 is coated and formed on the surface of the polyethylene terephthalate film, which is the base material for forming the photosensitive layer, opposite to the photosensitive layer 2, and a protective layer 5 is further formed on the photosensitive silver salt layer.
Then, the releasable film laminated on the photosensitive layer 2 is peeled off from the layer on which the photosensitive layer 2 and the photosensitive silver salt layer 4 are formed, and the photosensitive layer 2 and the substrate 1 are laminated so as to be in contact with each other. As a result, the image forming medium as shown in FIG. 3 of the present invention can be obtained.

Further, after preparing the original plate as shown in FIG. 1, the transparent support (this is the intermediate layer 6 in the image forming medium) is used.
Of course, it is also possible to form the photosensitive silver salt layer 5 and the protective layer 6 on the above.

An image forming method using the image forming medium of the above-mentioned form (that is, the image forming medium of the second aspect having the intermediate layer) will be described below. Here, the manufacturing method is no different from the case where the image forming medium of the second aspect (FIG. 2) having no intermediate layer is used.

The image forming medium produced as described above is first subjected to an image exposure process. As shown in FIG. 6, a photosensitive material containing at least a photosensitive silver halide, an organic silver salt and a reducing agent is used. A desired image is exposed (hν ₁ ) on the silver salt layer 4 by image exposure or digital exposure. As a result, silver nuclei 8 are formed on the photosensitive silver halide in the exposed portion 4-a,
This forms a latent image. The generated silver nuclei 8 serve as a catalyst for the thermal reaction between the organic silver salt contained in the photosensitive silver salt layer 4 and the reducing agent.

In this process, since photosensitive silver halide is used, high-sensitivity writing can be performed, and direct writing can be performed by digital processing using a laser, an LED or the like.

Next, in the heat development step shown in FIG. 7, when the photosensitive silver salt layer 5 on which the latent image is formed is heated, the exposed portion 4 is exposed.
In -a, the silver nuclei 8 selectively act as a catalyst, the organic silver salt and the reducing agent react, the organic silver salt is reduced to the silver atom 9, and at the same time, the reducing agent becomes the oxidant 10.

The heating temperature in this process cannot be generally determined depending on the composition of the photosensitive layer 2 and the like, but is from 60 ° C. to 200 ° C.
C., more preferably 70.degree. C. to 150.degree. C., the time is 1 second to 5 minutes, more preferably 3 seconds to 60 seconds. Generally, a high temperature requires a short time, and a low temperature requires heating for a long time. As a heating means, a method of using a hot plate, a heat roll, a thermal head, or the like, a method of heating by energizing the heating element of the support, a heating method by laser light irradiation, or the like can be used.

Subsequently, as shown in FIG. 8, in the above process, that is, in the process of the whole surface exposure, the whole surface exposure (hν
₂ ) Then, the photopolymerization initiator contained in the photosensitive layer 2 is cleaved to generate radical species. The radical species causes a polymerization reaction of the polymerizable compound to form a polymerized portion in the photosensitive layer 3. At that time, in the photosensitive layer 2, the photosensitive silver salt layer 5
Since the black silver atom 9 and / or the oxidant 10 of (4) absorbs light, the polymerizable compound in the photosensitive layer 2 is not polymerized in the exposed portion 4-a (unpolymerized portion 2-b) and unexposed. Polymerization occurs in the part 4-b (polymerized part 2-a), and as a result, a latent image for polymerization is formed.

As the light source used in the image exposure process and the whole surface exposure process, for example, sunlight, a tungsten lamp, a mercury lamp, a halogen lamp, a xenon lamp, a fluorescent lamp, an LED, a laser beam or the like can be used, and a direct drawing or the same mask as described above can be used. Exposure through
Further, the wavelengths of light used in these processes may be the same or different. Even when light of the same wavelength is used in both processes, since silver halide usually has a sufficiently higher photosensitivity than a photoinitiator, light having an intensity that does not cause photopolymerization in the image exposure process is sufficient. You can write a latent image. A sensitizing dye may be added at the time of forming the photosensitive layer according to the color distribution of each light source.

Specifically, the wavelength of light during the overall exposure is preferably 300 to 600 nm, and the wavelength of the light during the image exposure is such that when the photosensitive silver salt layer contains a sensitizing dye,
500 to 1000 nm, particularly preferably 500 to 900 nm, and 300 to 500 nm when no sensitizing dye is contained.
Is preferred.

In both processes, of course, exposure through a mask as described above is possible. Further, it is preferable to heat the image forming medium at the time of exposure as described above in the whole surface exposure process, and it may be newly heated or residual heat may be utilized in the above heat development process, but the organic silver salt in the photosensitive layer may be used. It is necessary to heat under conditions where the redox reaction of the reducing agent does not occur, and the conditions vary depending on the combination of the organic silver salt and the reducing agent, but the heating temperature is approximately 120 ° C or less, preferably 90 ° C or less. And more preferably 60 ° C. or lower.

The above-mentioned peeling and developing process for the printing plate having the latent image for polymerization thus obtained is performed between the intermediate layer 6 and the photosensitive layer 2 in exactly the same manner as described above with reference to FIG. Peel off. At this time, the unpolymerized portion 2-b of the photosensitive layer 2 is adhered to the intermediate layer 6, and the unpolymerized portion 3-b is also peeled off at the same time.

Through the above process, as shown in FIG.
An image on which the superposed portions 2-a of the photosensitive layer 2 remain is obtained.

Further, similarly to the image forming method from the image forming medium of the first aspect, it is preferable to perform heating and / or pressure treatment, and the durability can be further improved.

It is also preferable to carry out post-exposure (and simultaneous heating) as in the case of the image forming method of the first aspect, so that the durability can be further improved. Both the post-exposure (and simultaneous heating) treatment and the heating and / or pressure treatment are preferably performed, but the order is not particularly limited.

In the image forming method using the second aspect, the case where the polymerized portion is peeled off from the intermediate layer and transferred to the substrate has been described.
The unpolymerized portion may be transferred onto the substrate depending on the selection of the substrate. In this case, the unpolymerized portion transferred in the image form is exposed (and simultaneously heated) in the above condition range, and preferably, thereafter, the heating and / or pressure treatment is performed in the same manner as described above.

A method for forming a multicolor image with the image forming medium of the second aspect will be described.

This method is the same as the method for forming a multicolor image by the image forming medium of the first aspect, iv) a method in which the above image forming method is repeated on the same substrate, v) a peeled photosensitive layer polymerized portion or unpolymerized portion. Part of the remaining transparent support, vi) transferring the remaining polymerized part or unpolymerized part from the remaining transparent support of the peeled photosensitive layer polymerized part or unpolymerized part onto a substrate, There is a method of repeating this operation.

In the method iv), as in the method i), for example, a cyan, magenta, and yellow (black ink if necessary) image is used on the same white base material using the image forming medium of the second aspect. By the image forming method described above, the images are sequentially formed with high registration accuracy to obtain a multicolor image.

In the method of v), first, the above ii)
In the same manner as in the method of 1., the image forming medium of the second aspect is one in which the polymerized portion or unpolymerized portion of each color photosensitive layer remains on the intermediate layer (this also has a protective layer and a photosensitive silver salt layer). Is prepared by the above-mentioned image forming method using, and the protective layer / photosensitive silver salt layer is peeled from the intermediate layer. Then, these are superposed and laminated with high registration accuracy to obtain a multicolor image.

In the method vi), first, in the same manner as in the method v), the polymerized portion or unpolymerized portion of each color photosensitive layer remains on the intermediate layer (protective layer / photosensitive silver salt layer is peeled off). It may or may not be removed) is prepared, and transferred in the same manner as in the method iii) above, for example, sequentially transferred onto a white base material to obtain a multicolor image.

By the various methods as described above, a monochrome or multicolor image can be formed.
For example, as a substrate, an aluminum plate, a zinc plate, or a support having a hydrophilic resin layer or a layer containing an inorganic pigment such as zinc oxide or titanium oxide on the support, the surface of which is hydrophilic, or an etching treatment. When a (monochromatic) image is formed using a substrate which becomes hydrophilic by the above method, it can be used as a lithographic printing plate.

[0129]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Further, "parts" in the following description are parts by weight.

(Example 1) 140 g / m ² basis weight of long fiber pulp with excellent sizing degree, water resistance and smoothness
A solution having the following composition was coated on one surface of the wood free paper using a wire bar so as to have a dry film thickness of 5 μm to obtain a base material.

Polyvinyl alcohol (trade name Gohsenol NH-18, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 10 parts Glyoxal 2 parts Ammonium chloride 0.1 part Water 115 parts

Next, a 9 μm thick polyethylene terephthalate film (trade name Lumirror T, manufactured by Toray Industries, Inc.), which is a transparent support, was coated with a solution having the following composition using a wire bar so that the dry film thickness was 1.5 μm. Coating was performed to obtain a cyan photosensitive layer.

Linear saturated polyester resin (trade name: Byron 200, manufactured by Toyobo Co., Ltd.) 4 parts Chlorine polyolefin (trade name: Supercron 510, manufactured by Sanyo Kokusaku Pulp Co., Ltd.) 1 part Oligoester acrylate (trade name: Aronix M) −
6300, manufactured by Toagosei Kagaku Kogyo Co., Ltd. 3.5 parts 2.4-Diethylthioxanthone (trade name KAYACU)
RE DETX, manufactured by Nippon Kayaku Co., Ltd. 0.75 parts Ethyl 4-dimethylaminobenzoate (trade name KAYAC)
URE EPA, manufactured by Nippon Kayaku Co., Ltd. 0.75 parts Hydroquinone monomethyl ether 0.01 parts Copper phthalocyanine pigment 0.1 parts Methyl ethyl ketone 15 parts Toluene 15 parts

Further, a laminate in which the above-mentioned base material and the photosensitive layer were brought into contact with each other and heated to 45 ° C. (nip-fe 5 kgf / cm ² ).
To obtain an image forming medium of the present invention.

A negative image was brought into close contact with this medium (on a polyethylene terephthalate film) using the negative image as a mask and exposed from the negative image side to form a latent image for polymerization. The exposure was carried out for 10 seconds by using an ultra-high pressure mercury lamp (Ushio's 500 W) with the medium separated from the light source by about 10 cm. At this time, the medium was simultaneously heated to 80 ° C. using a hot plate.

When the polyethylene terephthalate film, which is the transparent support, is peeled off, the unexposed portion of the photosensitive layer is also adhered to the polyethylene terephthalate film and simultaneously peeled off. As a result, the exposed portion of the photosensitive layer remains on the substrate. A cyan image (A) was obtained.

On the other hand, a cyan image (B) was obtained in the same manner as above except that heating was not performed during exposure.
The exposure required 45 seconds.

When the images (A) and (B) are compared, the image (A) shows the same resolution and line breakage as (B).
No mottled pattern was observed and the image was good. Also,
From this, it was possible to shorten the exposure time to obtain an image of the same quality.

The resolution was 1800 dpi when the Cr mask of the resolution chart was used.

Comparative Example 1 An image forming medium was formed in the same manner as in Example 1 except that the cyan photosensitive layer had the following composition.

Linear saturated polyester resin (trade name: Byron 200, manufactured by Toyobo Co., Ltd.) 1 part Chlorinated polyolefin (trade name: Supercron 510,
Sanyo Kokusaku Pulp Co., Ltd. 4 parts Oligoester acrylate (trade name Aronix M-
6300, manufactured by Toagosei Kagaku Kogyo Co., Ltd. 3.5 parts 2.4-Diethylthioxanthone (trade name KAYACU)
RE DETX, manufactured by Nippon Kayaku Co., Ltd. 0.75 parts Ethyl 4-dimethylaminobenzoate (trade name KAYAC)
URE EPA, manufactured by Nippon Kayaku Co., Ltd. 0.75 part Hydroquinone monomethyl ether 0.005 part Cyan dye (trade name MS-cyan-VP, manufactured by Mitsui Toatsu Chemicals, Inc.) 0.81 part Methyl ethyl ketone 15 parts 15 parts of toluene

When a cyan image was obtained on this medium in the same manner as in Example 1, a good image could not be obtained because a patchy pattern was formed on the image and an unpolymerized portion was transferred onto the substrate.

(Example 2) An image forming medium was formed in the same manner as in Example 1 except that the cyan photosensitive layer had the following composition.

Linear saturated polyester resin (trade name: Byron 200, manufactured by Toyobo Co., Ltd.) 4.5 parts Chlorinated polyolefin (trade name: Supercron 510,
Sanyo Kokusaku Pulp Co., Ltd. 0.5 part Oligoester acrylate (trade name Aronix M-
6300, manufactured by Toagosei Kagaku Kogyo Co., Ltd. 3.5 parts 2.4-Diethylthioxanthone (trade name KAYACU)
RE DETX, manufactured by Nippon Kayaku Co., Ltd. 0.75 parts Ethyl 4-dimethylaminobenzoate (trade name KAYAC)
URE EPA, manufactured by Nippon Kayaku Co., Ltd. 0.75 part Hydroquinone monomethyl ether 0.005 part Cyan dye (trade name MS-cyan-VP, manufactured by Mitsui Toatsu Chemicals, Inc.) 0.81 part Methyl ethyl ketone 15 parts 15 parts of toluene

Cyan images (C) and (D) were obtained on this medium in the same manner as in Example 1. It should be noted that (C) has been heated at the time of exposure, and (D) has not been heated.

When the images (C) and (D) are compared, the image (C) shows the same resolution and line breakage as (D).
No mottled pattern was observed and the image was good. Also,
From this, it was possible to shorten the exposure time to obtain an image of the same quality.

(Example 3) 9 μm thick polyethylene terephthalate film (trade name: Lumirror T, Toray Industries, Inc.)
Solution) having the following composition was coated on the above (manufactured) using a wire bar so as to have a dry film thickness of 1.5 μm, and a magenta photosensitive layer and a yellow photosensitive layer were respectively obtained.

Magenta photosensitive layer formulation Linear saturated polyester resin (trade name: Byron 200, manufactured by Toyobo Co., Ltd.) 4.5 parts Chlorinated polyolefin (trade name: Supercron 510,
Sanyo Kokusaku Pulp Co., Ltd. 0.5 part Oligoester acrylate (trade name Aronix M-
6300, manufactured by Toagosei Kagaku Kogyo Co., Ltd. 3.5 parts 2.4-Diethylthioxanthone (trade name KAYACU)
RE DETX, manufactured by Nippon Kayaku Co., Ltd. 0.75 parts Ethyl 4-dimethylaminobenzoate (trade name KAYAC)
URE EPA, manufactured by Nippon Kayaku Co., Ltd. 0.75 parts Hydroquinone monomethyl ether 0.005 parts Magenta dye (trade name MS-magenta-VP, manufactured by Mitsui Toatsu Chemicals, Inc.) 0.54 parts Methyl ethyl ketone 15 parts 15 parts of toluene

Yellow photosensitive layer formulation Linear saturated polyester resin (trade name: Byron 200, manufactured by Toyobo Co., Ltd.) 4.5 parts Chlorinated polyolefin (trade name: Supercron 510,
Sanyo Kokusaku Pulp Co., Ltd. 0.5 part Oligoester acrylate (trade name Aronix M-
6300, manufactured by Toagosei Kagaku Kogyo Co., Ltd. 3.5 parts 2.4-Diethylthioxanthone (trade name KAYACU)
RE DETX, manufactured by Nippon Kayaku Co., Ltd. 0.75 parts Ethyl 4-dimethylaminobenzoate (trade name KAYAC)
URE EPA, manufactured by Nippon Kayaku Co., Ltd. 0.75 parts Hydroquinone monomethyl ether 0.005 parts Yellow dye (trade name MS-yellow-VP, manufactured by Mitsui Toatsu Chemicals, Inc.) 0.19 parts Methyl ethyl ketone 15 parts 15 parts of toluene

On the cyan image obtained in Example 2, a magenta photosensitive layer was contacted and laminated, and a magenta image was formed on the cyan image in the same manner as in Example 1, and further on this magenta image. Similarly, form a yellow image,
A multicolor image (E) was obtained. The exposure time is 10
Seconds, 15 seconds, 20 seconds, and the heating temperature during exposure is all 8
Performed at 0 ° C. Also, the mask used for exposure is
Using a negative mask for each color corresponding to the color separation,
By aligning the registration marks, the respective colors were successively formed with high registration accuracy.

A multicolor image (F) was obtained in exactly the same manner as above except that heating was not performed during exposure. still,
The exposure time was 45 seconds, 55 seconds, and 65 seconds, respectively.

When the images (E) and (F) are compared, the image (E) shows the same resolution and line breakage as (F).
In addition, no speckled pattern was observed and the image was a good multicolor image. Further, from this, it was possible to shorten the exposure time in order to obtain a multicolor image of the same image quality.

(Embodiment 4) A 50 μm thick polyimide base material (trade name Upilex;
Example 1 by laminating with Ube Industries, Ltd.)
Image formation was performed in the same manner as in. The exposure time was 10 seconds, 15 seconds, and 20 seconds, respectively, and the heating temperature during exposure was 80 ° C. in all cases. As the mask at the time of exposure, a positive mask for each color corresponding to a three-color separated original image was used.

Then, in the above-mentioned image formation, the polyethylene terephthalate film in which the unpolymerized portion of the photosensitive layer peeled off for each color remains is used. First, on the polyethylene terephthalate film having a thickness of 100 μm, the polyethylene terephthalate in the unpolymerized portion of the cyan photosensitive layer remains. Film, 100
A polyethylene terephthalate film having a thickness of μm is laminated so that the unpolymerized portion of the cyan photosensitive layer is in contact with each other (45
℃, 5kgf / cm ²⁾ Then, the polyethylene terephthalate film remaining unpolymerized portions of the cyan photosensitive layer, in contact with unpolymerized portion is a pair of magenta photosensitive layer of polyethylene terephthalate film remaining unpolymerized portion of the magenta photosensitive layer In this way, a multi-color image was obtained by laminating in the same manner as above and further laminating a polyethylene terephthalate film in which the unpolymerized portion of the yellow photosensitive layer remained.

For the above multicolor image, in order to improve the storability, an ultrahigh pressure mercury lamp was used, and a distance of 10 cm from 4 cm was used.
The entire surface was exposed for 5 seconds. At this time, the medium was heated to 80 ° C. using a hot plate simultaneously with the exposure.

Image deterioration due to heating during exposure was not observed, and a good image was obtained.

(Example 5) Similarly to Example 4, a polyethylene terephthalate film in which the unpolymerized portion of the peeled photosensitive layer of each color remained was prepared. First, on the white coated paper, the polyethylene terephthalate in the unpolymerized portion of the cyan photosensitive layer remained. The film was laminated so that the white coated paper and the unpolymerized part of the cyan photosensitive layer were in contact with each other (100 ° C., 5 kgf / cm
² ) By peeling off the polyethylene terephthalate film, only the unpolymerized part of the cyan photosensitive layer was thermally transferred onto the coated paper. Then, laminating thermal transfer is performed in the same manner as above so that the unpolymerized portion of the magenta photosensitive layer of the remaining unpolymerized portion of the magenta photosensitive layer is in contact with the unpolymerized portion of the cyan photosensitive layer.
In the same manner, heat transfer the unpolymerized portion of the yellow photosensitive layer,
A multicolor image was obtained.

For the above multicolor image, in order to improve the storability, an ultra-high pressure mercury lamp was further used, and the distance from 10 cm to 4 cm.
The entire surface was exposed for 5 seconds. At this time, the medium was heated to 80 ° C. using a hot plate simultaneously with the exposure.

Image deterioration due to heating during thermal transfer and during exposure was not observed, and a good image was obtained.

(Example 6) From the polyethylene terephthalate remaining in the unpolymerized portion of the peeled cyan photosensitive layer, obtained in the same manner as in Example 4, in the same manner as in Example 5, a zinc oxide offset printing master ( Product name Elefax
Master Paper ML-6B4 (GM),
It was thermally transferred to Iwasaki Tsushinki Co., Ltd. to prepare a printing plate.

An offset printing machine (trade name PR
INTPIA BP-7200II, manufactured by Bunshodo Co., Ltd .; the etching process is carried out by attaching it to the plate cylinder of an etching solution (made by Iwasaki Tsushinki Co., Ltd., which is automatically performed in the printing machine) (after the etching process, automatic. Ink) (brand name BSD New Rubber Ink Silver Co., Ltd. Bunshodou), dampening water (6 times diluted above etch solution)
When printing was carried out using, a good printed matter was obtained.

Example 7 A polyethylene terephthalate film having a thickness of 6 μm (trade name: Lumirror T, Toray Industries, Inc.)
And the photosensitive layer of Example 2 is formed on the
A 5 μm thick release-coated silicone-coated polyethylene terephthalate film (trade name Lumirror Silicone coating, manufactured by Toray Industries, Inc.) is laminated, and then AgBr 0.9 part silver behenate 5.0 parts silver behenate 4.0 parts Phthalazinone 1.0 parts 2-Methyl-4- (3,5-di-tert-butyl-4)
-Hydroxybenzyl) -1-naphthol 2.6 parts Polyvinyl butyral (trade name S-REC BM-2, manufactured by Sekisui Chemical Co., Ltd.) 10 parts Methyl ethyl ketone 90 parts Xylene 50 parts n-Butanol 30 parts

A solution prepared by dissolving 0.003 part of a sensitizing dye compound represented by the following general formula in 1.0 part of N, N-dimethylformamide was added to the above composition in a dark room.

[0164]

[Outside 2] Using a paint shaker, thoroughly dissolve, disperse and mix,
An emulsion for a photosensitive silver salt layer was obtained and coated on the above-mentioned 6 μm thick polyethylene terephthalate with a wire bar so as to have a dry film thickness of 4 to 5 μm, and further as a protective layer on this photosensitive silver salt layer. A 10% aqueous solution of polyvinyl alcohol (trade name Gohsenol NH-17Q, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was used to apply a dry film thickness of 2 to 3 μm using a wire bar.

Then, the silicone-coated polyethylene terephthalate film laminated on the photosensitive layer is peeled off from the above-mentioned formed body of the photosensitive layer and the photosensitive silver salt layer, and separately formed in the same manner as in Example 1. The image forming medium of the present invention was obtained by laminating in the same manner as in Example 1 so that the coating layer on the substrate and the photosensitive layer were in contact with each other.

Then, using a polygon scan type laser beam printer, a semiconductor laser (oscillation wavelength 780
nm, output 10 mW) and then image exposure
C., heat development under the condition of 10 seconds, to form an oxidant image on the exposed portion of the photosensitive silver salt layer, and further, using a fluorescent lamp having a fluorescent peak at 380 nm, perform full exposure for 20 seconds from a distance of 1 cm, The photosensitive layer below the portion of the photosensitive silver salt layer where the oxidant image was not formed was polymerized to obtain a polymerization latent image, and then the 6 μm-thick polyethylene terephthalate film as the intermediate layer was peeled off. The photosensitive layer below the portion where the oxidized image of the silver salt layer is formed, that is, the photosensitive layer at the unpolymerized portion is also adhered to the polyethylene terephthalate film,
At the same time, peeling was performed, and as a result, a cyan image in which the polymerized portion of the photosensitive layer remained on the substrate was obtained.

No deterioration of the photosensitive layer due to heat development was observed,
A good multicolor image was obtained.

Comparative Example 2 A cyan image was formed in the same manner as in Example 7 except that Comparative Example 1 and the photosensitive layer were used. As a result, a marked mottled pattern and the transfer of the unpolymerized portion onto the substrate occurred. , A good image was not obtained.

Example 8 A polyethylene terephthalate film having a thickness of 6 μm (trade name: Lumirror T, Toray Industries, Inc.)
Formed on each of the photosensitive layers of Examples 2 and 3 and coated with a 25 μm-thick silicone-releasing silicone-coated polyethylene terephthalate film (trade name: Lumirror Silicone coating, manufactured by Toray Industries, Inc.) And then the photosensitive silver salt layer of Example 7 was formed on each.

Using the above-mentioned photosensitive layer and photosensitive silver salt layer forming bodies, a cyan image was first formed on a substrate in the same manner as in Example 7, and then a magenta photosensitive layer and photosensitive silver salt layer were formed. The release silicone-coated polyethylene terephthalate film laminated on the photosensitive layer was peeled from the body, and the magenta photosensitive layer and the cyan image were compared and laminated, and a magenta image was formed in the same manner as in Example 7. In the same manner, a yellow image was formed on the magenta image to obtain a multicolor image. No deterioration of the photosensitive layer due to heat development was observed, and a good multicolor image was obtained.

[0171]

As described above, according to the present invention,
By using a linear saturated polyester resin and a chlorinated polyolefin in a specific ratio as a binder contained in a peelable and developable photosensitive layer, even in an image forming method in which heat treatment is applied, a mottled pattern and resolution deterioration may occur. Without
It has an effect that an excellent image is formed.

Further, when the latent image for polymerization is formed on the photosensitive layer, the heat treatment can be carried out at the same time as the whole surface exposure, so that the exposure time can be shortened.

Further, since a photosensitive silver salt layer containing photosensitive silver halide can be laminated, it is possible to directly draw on the image forming medium with high sensitivity by using a laser.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an example of an image forming medium of the present invention.

FIG. 2 is a schematic cross-sectional view showing an example of the image forming medium of the present invention.

FIG. 3 is a schematic cross-sectional view showing an example of the image forming medium of the present invention.

FIG. 4 is a schematic cross-sectional view showing an example of a process of forming an image from the image forming medium of the present invention.

FIG. 5 is a schematic cross-sectional view showing an example of a process of forming an image from the image forming medium of the present invention.

FIG. 6 is a schematic cross-sectional view showing an example of the process of forming an image from the image forming medium of the present invention.

FIG. 7 is a schematic cross-sectional view showing an example of the process of forming an image from the image forming medium of the present invention.

FIG. 8 is a schematic cross-sectional view showing an example of a process of forming an image from the image forming medium of the present invention.

FIG. 9 is a schematic cross-sectional view showing an example of a process of forming an image from the image forming medium of the present invention.

[Explanation of symbols]

 1 Base Material 2 Photosensitive Layer 3 Peeling Support Layer 4 Photosensitive Silver Salt Layer 5 Protective Layer 6 Intermediate Layer 7 Mask 8 Silver Nucleus 9 Silver Atom 10 Oxide

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location G03F 7/028 7/033 7/06 7124-2H 7/26 521 7124-2H 7/34 7124- 2H

Claims (4)

[Claims] 1. A transparent support having at least a binder,
In an image forming medium containing a polymerizable compound and a photopolymerization initiator, a linear saturated polyester resin and a chlorinated polyolefin are added to the binder in an amount of 100 parts by weight of the linear saturated polyester resin. Is contained in an amount of 300 parts by weight to 0.1 parts by weight. 2. An image forming medium having a photosensitive layer containing at least a binder, a polymerizable compound and a photopolymerization initiator, and a photosensitive silver salt layer containing at least a photosensitive silver halide, an organic silver salt and a reducing agent. In the binder, a linear saturated polyester resin and a chlorinated polyolefin are added in an amount of 300 parts by weight of the chlorinated polyolefin to 100 parts by weight of the linear saturated polyester resin.
An image forming medium containing 0.1 part by weight. 3. The image forming medium according to claim 1,
An exposure process in which heating is performed at the same time as image exposure to polymerize the polymerizable compound site-selectively to form a polymerization latent image composed of a polymerized portion and an unpolymerized portion, and the polymerized portion or the unpolymerized portion is peeled off together with the transparent support. And a peeling developer process for forming an image. 4. The image forming medium according to claim 2,
An image exposure process in which the photosensitive silver salt layer is subjected to image exposure, a heat development process in which an image forming medium is heated, and a whole surface exposure is performed from the side of the photosensitive silver salt layer that has been heat developed, and a polymerizable compound contained in the photosensitive layer is added. Full exposure process to selectively polymerize to form a polymerized latent image consisting of polymerized and unpolymerized parts, peeling and development process to peel the polymerized or unpolymerized part of the photosensitive layer together with the photosensitive silver salt layer to form an image An image forming method comprising: