JPH0792666A - Colored image forming material and its production and transferred image forming method - Google Patents

Abstract

PURPOSE:To provide a colored image forming material which suppresses blocking (missing) of a colored photosensitive layer in particular and a process for production thereof and a transferred image forming method, relating to a colored image forming material adequate for forming a color proof, etc., for color correction in color printing and a process for production thereof and a transferred image forming method. CONSTITUTION:This colored image forming material has a thermally softened layer, a colored photosensitive layer contg. a photosensitive compsn. and coloring agents, a protective layer and a cover sheet on a substrate in this order. The transferred image forming method comprises subjecting the colored image forming material described above to imagewise exposing and peeling the cover sheet, then developing the material to form an image and transferring the image to a material to be transferred. This process for production of the colored image forming material comprises forming the thermally softened layer on the substrate, then applying the colored photosensitive layer on the thermally softened layer and drying the coating, then laminating the sheet having the protective layer on the cover sheet consisting of the transparent substrate on the colored photosensitive layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored image forming material suitable for producing a color proof for color proofing in color printing, a method for producing the same, and a transfer image forming method. The present invention relates to a colored image forming material that suppresses blocking (missing), a method for producing the same, and a transfer image forming method.

[0002]

BACKGROUND OF THE INVENTION It is well known in the art that color sheets (also called color proofs) for color proofing are used to save the labor and time required for proof printing as a pre-step of main printing in multi-color printing. . As a method for producing a multicolor transfer image using a color sheet for color proofing, for example, a direct transfer method described in JP-A-47-41830, in which a colored image is directly transferred and laminated on a final image receiving paper,
An indirect transfer method described in JP-A-59-97140, in which a colored image is temporarily transferred onto a temporary image-receiving sheet, and
A method of repeating the process of forming an image after transferring the colored photosensitive layer to an image receiving paper and the like described in JP-A-56-50127 can be mentioned.

In all of these methods, the surface of the material to be transferred on which an image is formed is covered with an organic polymer layer, so that the glossiness of the obtained image surface is too high, which is different from the image quality at the time of actual printing. It had a problem of giving an impression. Therefore, in order to solve this problem, an image-only transfer method has been considered in which only a colored image is transferred and laminated on a material to be transferred to form a multicolor image. In this method, since the material to be transferred is not covered with the organic polymer layer, it is possible in principle to obtain an image that is extremely close to the image quality at the time of actual printing.

[0004]

A colored image-forming material used in a transfer method for transferring only an image portion can easily transfer only an image from a heat-softening layer to a material to be transferred during a heat lamination process. It is necessary to lower the Tg of the photosensitive layer in order to lower the adhesiveness between the heat-softening layer and the heat-softening layer (increase the releasability) and to give the colored photosensitive layer adhesiveness or thermal adhesiveness. Therefore, when a colored photosensitive layer is applied on the heat-softening layer, a protective layer is provided after drying, and laminated with a sheet, the back surface (PET surface) and the protective layer are stacked, and even if there is a protective layer, the Tg is low. The colored photosensitive layer, particularly the photopolymerizable photosensitive layer, causes blocking during storage with time.

When a colored image-forming material is produced, a colored photosensitive layer-coated sheet is wound up in a usual manner after the colored photosensitive layer is applied onto the heat-softening layer and dried. The back side of the coated sheet is superposed on the colored photosensitive layer coated on the softening layer and pressed against winding, so that the colored photosensitive layer is transferred to the PET surface even if there is a slight residual solvent.
The blocking (loss) of the colored photosensitive layer occurs.

The present invention solves the above problems of the prior art,
An object of the present invention is to provide a colored image forming material which prevents blocking of the colored photosensitive layer, a method for producing the same, and a transfer image forming method. In particular, it is an object of the present invention to provide a colored image forming material, a method for producing the same, and a transfer image forming method that prevent blocking during product packaging and prevent blocking that occurs when the colored photosensitive layer is coated and then wound up. .

[0007]

In order to achieve the above object, the present invention 1 comprises a heat-softening layer, a colored photosensitive layer containing a photosensitive composition and a colorant, a protective layer and a cover sheet on a support. Colored image-forming material having in order: The present invention 2 is imagewise exposed to a color image-forming material having a heat-softening layer, a colored photosensitive layer comprising a photosensitive composition and a colorant, a protective layer and a cover sheet on a support in this order. The transfer image forming method is characterized in that the cover sheet is peeled off and developed to form an image, and then the image is transferred to a material to be transferred; the present invention 3 comprises forming a heat softening layer on a support, A colored image-forming material characterized in that a colored photosensitive layer is coated on a softening layer and dried, and then a sheet having a protective layer on a cover sheet composed of a transparent support is laminated on the colored photosensitive layer. Manufacturing method: The present invention 4 is the transfer of claim 2. In the image forming method, the transfer image forming method is characterized in that the cover sheet is peeled off before imagewise exposing the colored image forming material; the present invention 5 is a coloring method in which an o-quinonediazide-containing colored photosensitive layer is provided on a support. In the image forming material, a colored image forming material having a protective layer on the o-quinonediazide-containing colored photosensitive layer; the present invention 6 contains a heat-softening layer, an o-quinonediazide and a colorant on a support. Transfer image formation characterized in that a colored image forming material having a colored photosensitive layer and a protective layer is imagewise exposed and then developed to form a colored image, which is transferred to a material to be transferred to form a transferred image. Method: The present invention 7 is the colored image forming material, the method for producing the same, and the transfer image forming method according to any one of claims 1 to 6, wherein the support is a transparent support.

The most preferred embodiments of the present inventions 1 to 7, particularly 1 to 4, are: transparent support; PET, polypropylene film 50 to 1
About 100 μm, protective layer; water-soluble polymer (PVA, cellulose, etc.) 0.5
˜1 μm, thermal softening layer: ethylene-vinyl acetate copolymer, ionomer resin 5 to 50 μm, cover sheet; PET 10 to 50 μm, and a specific example is a water-soluble polymer. The melted aqueous solution is applied onto 25 μm PET so as to have a dry film thickness of 0.5 μm to prepare a cover sheet. A colored photosensitive layer is coated on a transparent support (for example, PET having a thickness of 50 to 100 μm) having a heat-softening layer made of an ethylene-vinyl acetate resin having a thickness of 30 μm, and after drying, the cover sheet is heated and pressed (20 to 80 ° C., ^{2 to 5} Kg / cm ² ) and imagewise exposure of a colored image-forming material comprising transparent support / water or alkali-soluble resin layer / colored photosensitive layer / thermosoftening layer / transparent support. → Peeling the cover sheet → Development → Transfer to the material to be transferred to form a transferred image.

The most preferred embodiments of the present inventions 1 to 7, particularly 5 to 7, are a colored photosensitive layer; o-quinonediazide + novolak resin, acrylic resin or vinyl acetate resin; protective layer; water-soluble polymer (cellulose, poly Acrylic acid,
Modified vinyl acetate resin), the protective layer used in the conventional photopolymerization system has poor gas permeability, cannot be used in o-quinonediazide system, and needs a polymer having good gas permeability because it is used in o-quinonediazide. is there. And the protective layer is
It is particularly preferable to include a matting agent; silicon dioxide (including colloidal silica), aluminum oxide, aluminum silicate, titanium dioxide, calcium carbonate and the like.

[0010]

According to the present inventions 1 to 4, the interface between the protective layer and the cover sheet is good, and the peelability is good. According to the present invention 4, there is an advantage that the sharpness is further improved. According to the present invention 5 to 7, the o-quinonediazide-containing photosensitive layer does not have polymerization inhibition by oxygen unlike the photopolymerizable photosensitive layer, has a high softening point (Tg) of the photosensitive layer, and nitrogen gas is generated during exposure, In the past, no protective layer was used. However, a protective layer is required to prevent blocking when the blocking performance is improved during storage in product packaging and the adhesion to the support is weak for colored image transfer materials such as color proof, and for photosensitive materials having a low Tg of the photosensitive layer. Is. However, the gas permeability of the protective layer conventionally used for the photopolymerizable photosensitive layer is poor, and when this protective layer is used for the o-quinonediazide photosensitive layer, bubbles are generated in the photosensitive layer. Therefore, by using a water-soluble polymer with good gas permeability, we achieved both bubble prevention and blocking performance during exposure.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The present invention is described in detail below. The photoconductor that can be used to impart photosensitivity to the photosensitive colored recording layer will be described. Various photosensitive substances can be used as the photoconductor. For such a photoreceptor,
For example, when exposed to actinic rays, it causes a chemical change in its molecular structure within a short period of time, its solubility in a solvent changes, and when some kind of solvent is applied, the exposed or unexposed part becomes It includes all compounds such as monomers, prepolymers, or polymers that are dissolved away.

Examples of usable photoconductors are so-called negative / positive type photoconductors in which the solubility in exposed areas is lowered, and photocrosslinking type photosensitizers represented by those obtained by esterifying polyvinyl alcohol with cinnamic acid. System, a system in which a diazonium salt or a condensate thereof is mixed with polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, etc., and a system in which an aromatic azide compound is used as a photocrosslinking agent and a binder such as a cyclized rubber, etc., Further, a photosensitive resin utilizing photoradical polymerization or photoionic polymerization can also be used.

The photopolymerization system contains a vinyl compound and / or a vinylidene compound, and a photopolymerization initiator. As the vinyl compound or vinylidene compound,
Various things can be used arbitrarily. Suitable vinyl or vinylidene compounds that can be used in the photosensitive layer include
For example unsaturated esters of polyols, especially esters of acrylic acid or methacrylic acid, such as ethylene glycol diacrylate, glycerine triacrylate, polyacrylates, ethylene glycol dimethacrylate,
1,3-propanediol dimethacrylate, polyethylene glycol dimethacrylate, 1,2,4-butanetriol-trimethacrylate, trimethylolethane triacrylate, pentaerythritol di-, tri-, and tetramethacrylate, pentaerythritol di-, tri -, And-tetraacrylate, dipentaerythritol-polyacrylate, 1,3-propanediol-diacrylate, 1,5-pentanediol-
Dimethacrylates, bis-acrylates and bis-methacrylates of polyethylene glycol with molecules of 200 to 400 and similar compounds; unsaturated amides, in particular their alkylene chains having α, ω-diamines optionally opened by carbon atoms. Mention may be made of unsaturated amides of acrylic acid and methacrylic acid and ethylenebis-methacrylamide. However, it is not limited to these.

Further, as the photopolymerization initiator, those having a small absorption in the visible region are more preferable, and examples thereof include the following compounds. However, it is not limited to these. That is, benzophenone, Michler's ketone [4,4 '
-Bis- (dimethylamino) benzophenone], 4,4
Aromatic ketones such as'-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthraquinone, and other aromatic ketones, benzoin, benzoin methyl ether, benzoin Benzoin ethers such as ethyl ether and benzoin phenyl ether, methyl benzoin, ethyl benzoin and other benzoins, as well as 2- (o-chlorophenyl) -4,5-diphenyl imidazole duplexes, 2-
(O-Chlorophenyl) -4,5- (m-methoxyphenyl) imidazole duplex, 2- (o-fluorophenyl) -4,5-diphenylimidazole duplex, 2-
(O-Methoxyphenyl) -4,5-diphenylimidazole duplex, 2- (p-methoxyphenyl) -4,5
-Diphenylimidazole double body, 2,4-di (p-methoxyphenyl) -5-phenylimidazole double body,
2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole double body, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole double body,
And U.S. Pat. No. 3,479,185, British Patent No. 1,
2,4,5-such as similar duplexes described in US Pat. No. 047,569 and US Pat. No. 3,784,557.
Mention may be made of the triacryl imidazole duplex.

Further, as a so-called positive / positive type in which the solubility of the exposed area is increased, there is, for example, a photosensitive composition containing o-quinonediazide as a photosensitizer, and specifically, 1,2-benzoquinonediazide. -4-Sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-
A compound obtained by condensing sulfonyl chloride or 1,2-naphthoquinonediazide-6-sulfonyl chloride with a compound containing a hydroxyl group and / or an amino group is preferably used.

Examples of the hydroxyl group-containing compound include trihydroxybenzophenone, hydroxyanthraquinone, bisphenol A, phenol novolac resin, resorcin benzaldehyde condensation resin and pyrogallol acetone condensation resin. Examples of the amino group-containing compound include aniline, p-aminodiphenylamine,
There are p-aminobenzophenone, 4,4-diaminobenzophenone, 4,4-diaminodiphenylamine and the like.

Regarding the above-mentioned o-quinonediazide compound, further described in J. "Light Sensit" by Kosar
live System ”(Wiley & Sons,
New York, 1965) and Ken Matsunaga, "Photosensitive Polymer" (Kodansha, 1977).

Further, as a positive / positive type, it contains a compound capable of generating an acid upon irradiation with actinic rays, a compound having at least one bond decomposable by an acid, and a novolak resin containing two or three different phenols. It is also possible to use a photosensitive composition.

In the present invention, the content of the photoconductor in the colored photosensitive layer is, for example, preferably 5 to 80% by weight.

The photosensitive colored recording layer may contain a binder whether it is a single layer or divided into two or more layers. Such a binder is film-forming and solvent-soluble. Preferably, a polymer compound that can be dissolved or swollen with an alkaline developer can be used.

Specific examples of such a polymer compound include polymer compounds containing a structural unit having an aromatic hydroxyl group represented by the following general formula (I) in the molecular structure.

[0022]

[Chemical 1] In formula (I), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group or a carboxylic acid group. R
¹³ is a hydrogen atom, a halogen atom or an alkyl group, R
¹⁴ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. X represents a divalent organic group connecting a nitrogen atom and an aromatic carbon atom. n is 0 or 1. Y represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent.

Specific examples of the monomer forming the structural unit represented by the general formula (I) include N- (4
-Hydroxyphenyl)-(meth) acrylamide, N
Monomers of (meth) acrylamides such as-(2-hydroxyphenyl)-(meth) acrylamide, N- (4-hydroxynaphthyl)-(meth) acrylamide; o
-, M- or p-hydroxyphenyl (meth) acrylate monomer; o-, m- or p-hydroxystyrene monomer and the like. Preferably, o-, m-
Or p-hydroxyphenyl (meth) acrylate monomer and N- (4-hydroxyphenyl)-(meth) acrylamide monomer, and more preferably N-.
It is a (4-hydroxyphenyl)-(meth) acrylamide monomer.

In the present invention, it is preferable to use, as a binder, a copolymer of a monomer forming the structure represented by the general formula (I) and the following monomers.

[0025]

[Chemical 2] In the above formulas, R ¹⁵ represents a hydrogen atom, an alkyl group or a halogen atom, and R ¹⁶ represents an alkyl group, a phenyl group or a naphthyl group.

When the above copolymer is used, the ratio of the group having an aromatic hydroxyl group represented by the general formula (I) in the copolymer is preferably 1 to 30 mol%.

The proportion of the unit formed from the acrylonitrile in the copolymer is preferably 0 to 50 mol%, and in view of developability, it is preferably 5 to 40 mol%. The proportion of structural units formed from the above alkyl acrylates is preferably 50 to 95 mol% from the viewpoint of developability with a low alkaline aqueous solution, and 60 to 95 mol% is the most suitable developability. give.

In addition to the above structural units, the above-mentioned polymer compound is a structural unit obtained by copolymerizing the above-mentioned acrylic acids such as acrylic acid or methacrylic acid for the purpose of finely adjusting the developability. Good. In that case, considering the development latitude, the proportion of acrylic acid in the polymer compound is preferably 0 to 20 mol%, and most preferably 0 to 10 mol%.

The weight average molecular weight of the polymer compound is
From the viewpoint of developability or resolution when a low alkaline aqueous solution is used as the developer, it is 1,000 to 100,000.
And more preferably 1,000 to 30,0.
A range of 00 is preferable. These polymer compounds can be synthesized by a well-known copolymerization method.

Specific examples of such polymer compounds include copolymers having the following structures.

[0031]

[Chemical 3] (Weight average molecular weight: 1,000 to 30,000) 1: m: n = (1 to 25) :( 5 to 40) :( 50 to 9)
5)

Further, in the image-forming material of the present invention, a polymer compound having a carboxylic acid vinyl ester polymer unit represented by the following general formula in its molecular structure can also be preferably used as a binder constituting the colored photosensitive layer. RCOOCH = CH ₂ However, R represents an alkyl group having a prime number of 1 to 17.

Any polymer compound having the above-mentioned structure can be arbitrarily used, but as the carboxylic acid vinyl ester monomer for constituting the polymerized unit represented by the above general formula, the following examples are given. preferable. The name and chemical formula are shown together. (1) Vinyl acetate CH ₃ COOCH = C
H ₂ (2) Vinyl propionate CH ₃ CH ₂ COOC
H = CH ₂ (3) vinyl butyrate CH ₃ (CH ₂ ) ₂ C
OOCH = CH ₂ (4) vinyl pivalate (CH ₃ ) ₃ CCOO
CH = CH ₂ (5) Vinyl caproate CH ₃ (CH ₂ ) ₄ C
OOCH = CH ₂ (6) Vinyl caprylate CH ₃ (CH ₂ ) ₆ C
OOCH = CH ₂ (7) Vinyl caprate CH ₃ (CH ₂ ) ₈ C
OOCH = CH ₂ (8) vinyl laurate CH ₃ (CH ₂ ) ₁₀
COOCH = CH ₂ (9) Vinyl myristate CH ₃ (CH ₂ ) ₁₂
COOCH = CH ₂ (10) Vinyl palmitate CH ₃ (CH ₂ ) ₁₄
COOCH = CH ₂ (11) Vinyl stearate CH ₃ (CH ₂ ) ₁₆
COOCH = CH ₂ (12) vinyl versatate

[0034]

[Chemical 4] (R ¹ and R ² are alkyl groups, and the sum of their carbon numbers is 7
Is. That is, R ¹ + R ² = C ₇ H ₁₆ ) The carboxylic acid vinyl ester monomer is more preferably one having 1 to 4 carbon atoms constituting the main chain of the carboxylic acid. Vinyl acetate is particularly preferable. The R also includes an alkyl group having a substituent, that is, a vinyl ester of a substituted carboxylic acid is also included in the polymerized unit.

The polymer compound may be a polymer prepared by polymerizing one kind of carboxylic acid vinyl ester, or a polymer prepared by copolymerizing two or more kinds of carboxylic acid vinyl ester, or a carboxylic acid vinyl ester and a copolymer thereof. It may be a copolymer of any other possible monomer in any component ratio.

Examples of the monomer unit which can be used in combination with the polymer unit represented by the above general formula include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, for example, styrene and α-methyl. Styrene, p-methylstyrene, p-
Styrenes such as chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, for example itaconic acid, maleic acid, unsaturated aliphatic dicarboxylic acids such as maleic anhydride, such as diethyl maleate, dibutyl maleate,
Diesters of unsaturated dicarboxylic acids such as di-2-ethylhexyl maleate, dibutyl fumarate, di-2-ethylhexyl fumarate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid Α-, such as dodecyl, 2-chloroethyl acrylate, phenyl acrylate, α-methyl methyl acrylate, methyl methacrylate, ethyl methacrylate
Methylene aliphatic monocarboxylic acid esters, for example, acrylonitrile, nitriles such as methacrylonitrile,
For example, amides such as acrylamide, anilides such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, etc. Vinyl ethers, vinyl chloride, vinylidene chloride, vinylidene cyanide, eg 1
-Methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene and other ethylene derivatives such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole,
N-, such as N-vinylpyrrolidene and N-vinylpyrrolidone
There are vinyl monomers such as vinyl compounds. These vinyl monomers generally have a structure in which an unsaturated double bond is cleaved and are present in the polymer compound.

When the polymer compound represented by the above general formula is used in the present invention, it is particularly preferable to use a vinyl acetate polymer unit in the molecular structure. Among them, those having 40 to 95 wt% of vinyl acetate polymer units and having a number average molecular weight (MN) of 1,000 to 100,0.
No. 00, weight average molecular weight (MW) is 5,000 to 5
Those of 0,000 are preferable.

More preferably, a polymer compound having a vinyl acetate polymer unit (particularly 40 to 95 wt%) and a carboxylic acid vinyl ester polymer unit having a longer chain than vinyl acetate is preferable, and particularly, a number average molecular weight (MN) is 2,000
0-60,000, weight average molecular weight (MW) is 10.0
It is preferably from 0 to 150,000.

In this case, the monomer constituting the polymer compound having vinyl acetate polymerized units by copolymerization with vinyl acetate may be any monomer as long as it can form a copolymer. You can choose it from your body.

The copolymers that can be used as the polymer compound in the present invention are listed below by showing the monomer components. However, as a matter of course, the present invention is not limited to the following examples. (1) Vinyl acetate-acrylic acid ester (2) Vinyl acetate-maleic acid ester (3) Vinyl acetate-ethylene (4) Vinyl acetate-carboxylic acid vinyl ester (5) Vinyl acetate-styrene (6) Vinyl acetate-crotonic acid (7) Vinyl acetate-maleic acid (8) Vinyl acetate-2-ethylhexyl acrylate (9) Vinyl acetate-di-2-ethylhexyl maleate (10) Vinyl acetate-methyl vinyl ether (11) Vinyl acetate-vinyl chloride (12) Vinyl acetate-N-vinylpyrrolidone (13) Vinyl acetate-vinyl propionate (14) Vinyl acetate-vinyl pivalate (15) Vinyl acetate-vinyl versatate (16) Vinyl acetate-vinyl laurate (17) Vinyl acetate-stearin Vinyl acetate (18) Vinyl acetate-versatic acid vinyl Ru-ethylene (19) Vinyl acetate-vinyl versatate-2-ethylhexyl acrylate (20) Vinyl acetate-vinyl versatate-vinyl laurate (21) Vinyl acetate-vinyl versatate-crotonic acid (22) Vinyl propionate-versatitic Vinylate (23) Vinyl propionate-vinyl versatate-
Crotonic acid (24) pivalic acid-vinyl stearate-maleic acid

In the present invention, a novolac resin may be used as the binder. The novolak resin is generally obtained by polycondensation of at least one phenol and an active carbonyl compound, and any of such novolak resins can be used.

The above-mentioned phenols include all compounds in which at least one hydrogen atom bonded to an aromatic ring is substituted with a hydroxyl group. Specific examples of such phenols include phenol, o-cresol, and m. -Cresol, p-cresol, 3,5-xylenol, 2,4
-Xylenol, 2,5-xylenol, carvacrol, thymol, catechol, resorcin, hydroquinone, pyrogallol, phloroglucin, alkyl group (having 1 to 8 carbon atoms) substituted phenol and the like can be mentioned.

The above-mentioned active carbonyl compounds include, for example, aldehydes and ketones, and specific examples thereof include formaldehyde, acetaldehyde, benzaldehyde, acrolein, furfural and acetone.

As the novolac resin, phenol formaldehyde novolac resin, m-cresol formaldehyde novolac resin, phenol / m-cresol / formaldehyde copolycondensate resin, phenol
p-cresol-formaldehyde copolycondensate resin, m
-Cresol / p-cresol / formaldehyde copolycondensate resin, o-cresol / p-cresol / formaldehyde copolycondensate resin, phenol / o-cresol / m-cresol / formaldehyde copolycondensate resin, phenol / o- Examples thereof include cresol / p-cresol / formaldehyde copolycondensate resin and phenol / m-cresol / p-cresol / formaldehyde copolycondensate resin.

A preferred novolac resin is phenol formaldehyde novolac resin, having a weight average molecular weight (MW) of 3,500 to 500 and a number average molecular weight (MN).
Is preferably in the range of 1,000 to 200.

The molecular weight of the high molecular compound in this specification including the molecular weight of the above novolak resin is measured by GPC.
(Gel permeation chromatography method). The number average molecular weight (MN) and the weight average molecular weight (MW) can be calculated by the method described in Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka, “Chemical Society of Japan”, pages 800 to 805 (1972). Shall be leveled (connecting the peak and valley centers).

In the novolak resin, a method for confirming the amount ratio of different phenols used in the synthesis is pyrolysis gas chromatography (PG
C) is used. Regarding the pyrolysis gas chromatography, its principle, equipment and experimental conditions are, for example, edited by The Chemical Society of Japan, Tsuge “New Experimental Chemistry Course”, Vol. 19, Polymer Chemistry [I] pp. 474-485 (Maruzen, 1978). Published) etc., and the qualitative analysis method of novolak resin by pyrolysis gas chromatography is described by Morio Tsuge and Tanaka.
The method is based on the method described in "Analytical Chemistry" Vol. 18, pages 47-52 (1969) by Takashi and T. Tanaka.

In the present invention, a novolak resin [referred to as component (b)] in the colored recording layer, and a polymer compound [component (c) having a carboxylic acid vinyl ester polymer unit represented by the above general formula in its molecular structure]. When it is included, it is preferable that it is contained in a weight ratio range of (b) / (c) = 5/95 to 80/20. Within this range, it is preferable in terms of color reproducibility, thermal deformation (dimensional deviation), and color fastness. A particularly preferable ratio of the components (b) and (c) is (b) / (c) = 10/90 to 60 / by weight.
The range is 40.

Further, in the present invention, other polymer compounds usable as the binder for the colored recording layer include sulfoalkyl ester of (meth) acrylic acid (co) polymer, vinyl acetal (co) polymer, Vinyl ether (co) polymers, acrylamide (co) polymers, styrene (co) polymers, cellulose derivatives and the like can also be mentioned.

The photosensitive composition of the present invention can be used as an image forming material. For example, it can be used as a colored image forming material when used as a color proof. In this case, the colored photosensitive layer of the colored image forming material is image-wise removed by imagewise exposure and subsequent development to form a colored image.

Dyes and pigments are added as colorants to the colored photosensitive layer. In particular, when used for color proofing, pigments and dyes that have a color tone matching those of the ordinary colors required, that is, yellow, magenta, cyan, and black are required, but other metal powders, white pigments, and fluorescent pigments are also required. Are also used. When applying the present invention to color proofing, many pigments and dyes known in the art can be used, such as:

(C.I means color index). Victoria Pure Blue (CI 42595) Auramine (CI 41000) Catillon Brilliant Flavin (CI Basic 1
3) Rhodamine 6GCP (CI 45160) Rhodamine B (CI 45170) Safranine OK 70: 100 (CI 50240) Erioglaucin X (CI 42080) Fast Black HB (CI 26150) No. 1201 Lionol Yellow (C.I. 2109
0) Lionol Yellow GRO (CI 21090) Shimla First Yellow 8GF (CI 2110)
5) Benzidine Yellow 4T-564D (C.I 2109
5) Shimla Fast Red 4015 (C.I 1235
5) Lionol Red 7B4401 (CI 15830) Fastgen Blue TGR-L (CI 7416)
0) Lionol Blue SM (CI 26150) Mitsubishi Carbon Black MA-100 Mitsubishi Carbon Black # 30, # 40, # 50

When a colorant is used in the present invention, the ratio of the colorant / binder in the colored photosensitive layer is a method known to those skilled in the art in consideration of the target optical density and the removability of the colored photosensitive layer from a developer. Can be determined by For example, in the case of a dye, its content is preferably 5% to 75% by weight,
In the case of pigments, their content is preferably between 5% and 90% by weight.
% Is appropriate.

The thickness of the colored photosensitive layer is determined by a method known to those skilled in the art according to the target optical density, the kind of the coloring agent used in the colored photosensitive layer (dye, pigment, carbon black) and its content. However, if the thickness of the colored photosensitive layer is as thin as possible within the allowable range, the resolution is higher and the image quality is better. Thus, the membrane thickness is preferably usually being used in the range of ^{0.1g / m 2 ~5g / m 2} .

In carrying out the present invention, a plasticizer, a coatability improving agent and the like may be further added to the photosensitive composition, if necessary. As plasticizers, various low molecular weight compounds, for example, phthalic acid esters, triphenyl phosphates, maleic acid esters, and as coatability improvers, surfactants such as fluorine-based surfactants and ethyl cellulose polyalkylene ethers are typical. Examples thereof include nonionic activators.

When the photosensitive composition of the present invention is used to form an image forming material, particularly a colored image forming material, the colored photosensitive layer is a colored layer containing a colorant and a binder, and a photosensitive layer containing a photosensitive composition. It can also be divided into two layers. In this case, either layer may be disposed on the support side.

When the photosensitive composition of the present invention is used to form an image-forming material, the support used is arbitrary, but a transparent support is preferably used. As the transparent support, a polyester film, particularly a biaxially stretched polyethylene terephthalate film is preferable from the viewpoint of dimensional stability against water and heat. Besides, an acetate film, a polyvinyl chloride film, a polyethylene film, a polypropylene film, a polyethylene film and the like can be used. The thickness of the transparent support provided with the protective layer is about 5 to 100 μm,
Particularly, about 10 to 50 μm is preferable, and the transparent support provided with the heat softening layer has a thickness of 20 to 200 μm, particularly 50 to 100 μm.
μm is preferred.

For the protective layer of the present invention, a water-soluble polymer or an alkali-soluble polymer is used. For example, polyvinyl alcohol, modified vinyl acetate resin, methyl vinyl ether, maleic anhydride copolymer, polyvinylpyrrolidone, gelatin, arabic gum, cellulose such as methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, water-soluble nylon, alcohol-soluble nylon, poly It can be formed by applying and drying a solution of a polymer substance such as acrylic acid, a carboxyl group-containing acrylic resin, a water-soluble polyester, a water-dispersible polyester, or polyethylene oxide.

As the protective layer used for the photopolymerizable photosensitive layer,
A protective layer having a low oxygen permeability is provided in order to prevent a decrease in sensitivity due to oxygen. For example, polyvinyl alcohol, modified vinyl acetate resin, and arabic rubber are preferable.

As the protective layer used for the o-quinonediazide-containing photosensitive layer, it is necessary to use a protective layer having excellent nitrogen permeability. As the protective layer having excellent nitrogen permeability, celluloses such as methyl cellulose and hydroxylpropyl cellulose, and polyacrylic acid are preferable.

The protective layer may be any known one other than those mentioned above, and it can be dissolved in a developing solution at the time of development, in particular, a water-soluble polymer such as polyvinyl alcohol or cellulose having a thickness of about 0.01 to 5 μm, particularly 0.03. It is preferably about 1 μm.

The image forming material can be used in the form of transferring an image to a material to be transferred. At this time, in order to efficiently perform transfer onto the material to be transferred and to facilitate peeling of the support after image transfer, that is, in order to enhance releasability between the support and the image forming layer, support The body surface may be subjected to a release treatment or a release layer may be provided on the support surface.
These will be described later.

In the image forming method of the present invention, an image portion is formed by exposing and developing an image forming material having the photosensitive composition of the present invention, and at least the formed image portion is a transfer material (for example, main paper). To obtain a transferred image.
The cover sheet may be peeled off before exposure or after exposure, but before exposure it is preferable from the viewpoint of enhancing sharpness.

When the image forming method of the present invention is embodied as a multicolor image forming method, the basic method is as follows.
It is as follows. The first color colored image is formed on the first color colored image forming material, at least the colored image is transferred to the transfer material, and the support is peeled off. Further, after forming the second-color coloring image on the second-color coloring image forming material, the second-color registration mark image formed in association with the second-color coloring image is registered with the first-color registration mark image on the transfer material. , The second colored image is transferred onto the first colored image, and the support is peeled off to obtain a two-color aligned image. Similarly, the colored images of the third color and the fourth color are also transferred onto the material to be transferred to obtain a multicolor image. In some cases, this multicolor image may be indirectly transferred onto another transfer material to obtain a multicolor image. A method of this kind is disclosed in JP-A-47-41830 and 59-9714.
No. 0, No. 60-28649 and US Pat. No. 37751.
No. 13, etc.

In the image forming method of the present invention, the image forming material is usually imagewise exposed through a color separation mask or the like and then developed to form an image. At this time, only the image portion of the image obtained on the support may be directly transferred and laminated on the transfer material. That is, it is preferable that only the colored image layer that substantially forms an image is transferred and laminated. In this case, in order to efficiently perform the transfer onto the surface to be transferred and to facilitate the peeling of the support after the image transfer, the surface of the support is subjected to a release treatment with an appropriate oil-repellent substance, or the support is It is preferable to provide a release layer on the top. In the present invention, the release treatment or the release layer with these oil repellent substances is referred to as a heat softening layer.

As such an oil-repellent substance, for example, silicone resin, fluororesin, fluorosurfactant, polyolefin, polyamide or the like can be used, and as the release layer, for example, alcohol-soluble polyamide or alcohol-soluble nylon can be used. Blend of partially esterified resin of styrene and maleic anhydride copolymer with methoxymethylated nylon, polyvinyl acetate, polyacrylate, copolymer of polymethylmethacrylate and acrylate, polyvinyl chloride, vinyl chloride And vinyl acetate copolymer, polyvinyl butyrate, cellulose acetate phthalate, methyl cellulose, cellulose triacetate,
Polyvinyl alcohol, butyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, cyanoethyl cellulose, cellulose acetate, cellulose triacetate, cellulose acetate butyrate,
Hydroxypropyl methyl cellulose phthalate, hydroxypropyl methyl cellulose hexahydrophthalate, or a mixture thereof can be used.

The thickness of the release layer is preferably from 0.01 μm to
It is in the range of 50 μm, particularly preferably 5 μm to 50 μm.
The range is m. As a particularly preferred embodiment of the heat-softening layer provided to enhance releasability, a polypropylene layer thinner than the thickness of the support, a polyethylene layer, an ionomer resin layer,
Alternatively, an example in which an ethylene-vinyl acetate resin layer is provided can be given.

As a method for providing a polypropylene layer, a polyethylene layer, an ionomer resin layer, an ethylene-vinyl acetate resin layer or the like on a support, particularly the transparent support,

(1) Polyvinyl acetate, polyvinyl chloride,
Using a solution of epoxy resin, polyurethane resin, natural rubber, synthetic rubber, etc. dissolved in an organic solvent as an adhesive,
After coating these adhesives on a support and drying with hot air or heating, polypropylene film, ethylene-
A so-called dry laminating method in which vinyl acetate films or polyethylene films are superposed and pressure-bonded under heating to laminate;

(2) a copolymer of ethylene and vinyl acetate,
A doctor blade on the support while using ethylene / acrylic acid ester copolymer, polyamide resin, petroleum resin, rosins, waxes or a mixture thereof as an adhesive and heating these adhesives as they are to keep them in a molten state. Method, roll coating method, gravure method, reverse roll method, etc., and then immediately laminate polypropylene film, polyethylene film, ethylene-vinyl acetate film, and if necessary, heat at high temperature and then laminate by cooling. So-called hot melt laminating method;

(3) A so-called extrusion laminating method in which polypropylene, polyethylene and ethylene-vinyl acetate resin are kept in a molten state and extruded into a film by an extruder, and while this is in a molten state, a support is pressure-bonded and laminated. ;

(4) When a film to be a support is formed by the melt extrusion method, a plurality of extruders are used together with polypropylene, polyethylene and ethylene-vinyl acetate resin in a molten state to form a support film once. Forming a polypropylene layer, a polyethylene layer, and an ethylene-vinyl acetate layer on top, so-called co-extrusion method, etc.

(5) The heat softening layer can be provided by any of the methods (1) to (4).

As a method of providing the protective layer on the cover sheet made of a transparent support, the above-mentioned (1) to (4) can be applied, but the coating method may be used.

In the image forming method of the present invention, the developer used for developing the image forming material can be arbitrarily used as long as it has a developing action for developing the material to be processed. It is preferable to use a developer containing an alkali agent and an anionic surfactant.

Alkali agents that can be used include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium or ammonium phosphate dibasic or tertiary acid, sodium metasilicate, Inorganic alkaline agents such as sodium carbonate and ammonia, (2) mono, di, or trimethylamine, mono,
Organic amine compounds such as di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di-, or triethanolamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, and the like can be mentioned.

The anionic surfactants that can be used include (1) higher alcohol sulfates (for example, sodium salt of lauryl alcohol sulfate, ammonium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, secondary sodium alkyl). (Sulfate, etc.), (2) Fatty alcohol phosphate ester salts (eg,
(Sodium salt of cetyl alcohol phosphate, etc.) (3) Alkylaryl sulfonates (for example, sodium dodecylbenzenesulfonate, sodium isopropylnaphthalenesulfonate, sodium dinaphthalenesulfonate, sodium metanitrobenzenesulfonate, etc.) (4) Alkyl amide sulfonates

[0078]

[Chemical 5] (5) Sulfonates of dibasic aliphatic ester (for example, dioctyl sodium sulfosuccinate, dihexyl sodium succinate, etc.) (6) Formaldehyde condensate of alkylnaphthalene sulfonate (for example, formaldehyde of sodium cibutylnaphthalene sulfonate) Condensate and the like). What is an alkaline agent and an anionic surfactant?
Any combination can be used.

[0079]

EXAMPLES Examples and comparative examples of the present invention will be described below. In the following, "parts" means "parts by weight" unless otherwise specified. As a matter of course, the present invention is not limited to the embodiments described below and can take various aspects.

First, examples of the present inventions 1 to 4 and 7 will be given. Example 1-1 Ethylene-vinyl acetate resin (vinyl acetate content 14% by weight) having a thickness of 30 μm was extruded and laminated on a polyethylene terephthalate film having a thickness of 75 μm by a lamination method. Layer) A dispersion of the colored photosensitive composition having the following composition was applied on the surface of the layer using a wire bar so that the dry film thickness was 1 μm, and then dried.

Colored Photosensitive Composition Michler's Ketone 0.219 g Pentaerythritol Tetraacrylate 4.384 g The following Binder Polymer 4.384 g The following pigment The amount below: Ethyl Cellosolve 39.6 g Fluorine-based surfactant (FC-430 manufactured by 3M Co.) 0. 25 g Binder polymer (polymer compound) Vinyl acetate-vinyl versatate (80:20 parts by weight) copolymer MN = 22,000 MW = 60,000

Pigment Black: Carbon Black MA-100 (manufactured by Mitsubishi Kasei Co.) 0.99 g Cyan: Cyanine Blue 4920 (manufactured by Dainichiseika Co., Ltd.) 0.55 g Magenta: Seika Fast Carmine 1483 (manufactured by Dainichiseika Co., Ltd.) 68 g Yellow: Seika Fast Yellow H-7055 (manufactured by Dainichiseika Co., Ltd.) 0.68 g Next, a protective layer coating solution having the following composition was applied on a 25 μm polyethylene terephthalate film to a dry film thickness of 0.5 μm, After drying, a cover sheet having a protective layer was prepared.

Protective Layer Coating Liquid Polyvinyl alcohol (manufactured by Nippon Gosei Co., Ltd.) 1 part Hydroxypropylmethylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Demineralized water 98 parts The protective layer side of this cover sheet is brought into close contact with the colored photosensitive layer previously coated, 3K between a pair of heated nip rollers
It was passed at a speed of 5 m / min under a pressurizing condition of g / cm ² .

As described above, a four-color negative type colored image forming material was obtained. 100 sheets of this negative type colored image-forming material were laminated in a single-wafer sheet and placed in a constant temperature bath at 55 ° C. to check for blocking. No blocking occurred after 3, 7 and 30 days. The color-separated mesh negative film of each color is superposed on the polyethylene terephthalate film surface of the four-color coloring image forming material, and image exposure is performed from a transparent support side having a protective layer for 20 seconds from a distance of 50 cm with a 4 kW metal halide lamp, and the above cover sheet. The polyethylene terephthalate film of was peeled off. Then, it is developed by immersing it in the following developing solution for 30 seconds.
A colored image of color was formed. At this time, the protective layer was dissolved and removed.

<Developer> Na ₂ CO ₃ 15 g Surfactant (Pelex NBL manufactured by Kao Atlas Co., Ltd.) 50 g Distilled water 1000 g Next, a pair of heated nip rolls are brought into close contact with the image surface of the black image and the art paper. After passing the gap at a speed of 50 cm / min under a pressure of 5 kg / cm ² , the support was peeled off. The peeling was easy, and only the black image portion was transferred onto the art paper.

Subsequently, the colored images were transferred in the order of cyan, magenta and yellow, whereby a color proofing image consisting of four colors was obtained on the art paper. In this example, since only the image portion was transferred, the finish was very close to the actual printed matter. On the other hand, in Example 1-1, when the only difference was that the cover sheet was peeled off before imagewise exposure, improvement in resolution and improvement in sharpness were observed (Invention 4).

Example 1-2 A colored image-forming material was prepared in the same manner as in Example 1 except that the coating solution for protective layer was coated on a 20 μm polypropylene film so that the dry film thickness was 0.5 μm. 100 sheets were laminated with single-wafer sheets in the same manner as in Example 1-1, and 5
It was placed in a constant temperature bath at 5 ° C. and examined for blocking. Three
No blocking occurred on day, 7 days, and 30 days later.

Comparative Example 1-1 A polyethylene terephthalate film having a thickness of 75 μm and ethylene having a thickness of 30 μm were formed in the same manner as in Example 1-1.
On a support laminated with a vinyl acetate resin (vinyl acetate content 14% by weight), the same colored photosensitive composition dispersion as in Example 1-1 was applied using a wire bar so that the dry film thickness was 1 μm. .

Next, the coating solution for protective layer of Example 1-1 was applied onto the colored photosensitive layer using a wire bar so that the dry film thickness was 0.5 μm, and dried. 100 sheets of this negative type colored image-forming material were laminated in a single-wafer sheet and placed in a constant temperature bath at 55 ° C. to check for blocking. Already after 3 days, the light-sensitive layer had caused blocking and had partial omissions.

Example 1-3 The coating solution for the protective layer of Example 1-1 was prepared to have a width of 640 mm and a length of 10
It was coated on a polyethylene terephthalate film having a thickness of 00 m and a thickness of 25 μm so that the dry film thickness was 0.5 μm, dried, and wound. This was set in a laminating delivery device.

Next, a polyethylene terephthalate film having a width of 640 mm, a length of 1000 m and a thickness of 75 μm was laminated with an ethylene-vinyl acetate resin (vinyl acetate content 14% by weight) having a thickness of 30 μm in the same manner as in Example 1-1. The body was set on the delivery device. And Example 1-1
With a wire bar coater, the colored photosensitive composition dispersion of
It was applied and dried so that the dry film thickness was 1 μm. At that time, the protective layer on the polyethylene terephthalate and the colored photosensitive layer were laminated so as to be in close contact with each other and wound into a coil. Since there is a cover sheet, the coated surface may peel off,
It wasn't uneven.

Comparative Example 1-2 Next, a polyethylene terephthalate film having a width of 640 mm, a length of 1000 m and a thickness of 75 μm was laminated with a 30 μm thick ethylene-vinyl acetate resin (vinyl acetate content 14% by weight). It was set in the delivery device.
Then, the colored photosensitive composition dispersion of Example 1-1 was applied and dried with a wire bar coater to a dry film thickness of 1 μm, and this was wound into a coil. It adhered to the back surface and the coated surface came off or became uneven. Therefore, the protective layer could not be applied on the colored photosensitive layer.

Next, examples of the present inventions 5 to 10 will be given. Example 2-1 A 100 μm thick polyethylene terephthalate film was coated with a coating solution for a photosensitive layer having the following composition using a wire bar,
The coating was applied so that the dry film thickness was 1 μm.

[0094]

[Chemical 6]

Ethyl cellosolve 42.8 parts

Pigment Carbon black MA-100 (manufactured by Mitsubishi Kasei Co., Ltd.) 0.6 part Next, a protective layer coating solution having the following composition was used with a wire bar so that the dry film thickness was 0.5 μm on the colored photosensitive layer. Application,
Dried.

Protective Layer Coating Liquid Polyvinyl alcohol (manufactured by Nippon Gosei Co., Ltd.) 2 parts Demineralized water 98 parts 100 sheets of this positive type colored image-forming material sheet is laminated and placed in a constant temperature bath at 55 ° C. to check for blocking. It was No blocking occurred after 3, 7 and 30 days.

Example 2-2 A coating solution for a photosensitive layer having the following composition was formed on a polyethylene terephthalate film having a thickness of 100 μm by using a wire bar.
The coating was applied so that the dry film thickness was 1 μm. 2,3,5-Trihydroxybenzophenone-naphthoquinone-1,2 diazidosulfonic acid ester 0.616 g Vinyl acetate-vinyl versatic acid (80:20 parts by weight) copolymer 4.384 g MN = 22,000 MW = 60 1,000

Pigment Carbon black MA-100 (manufactured by Mitsubishi Kasei) 0.99 g Ethyl cellosolve 39.6 g Fluorine-based surfactant (FC-430 manufactured by 3M) 0.25 g Next, a protective layer coating solution having the following composition is applied to a wire. Using a bar, apply a dry film thickness of 0.5 μm on the colored photosensitive layer,
Dried.

Protective Layer Coating Solution Hydroxypropylmethylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts Demineralized water 98 parts This positive type colored image-forming material is laminated in 100 sheets with single-wafer sheets and placed in a constant temperature bath at 55 ° C. to determine whether blocking occurs. I checked. Blocking occurred after 3, 7, and 30 days.

Comparative Example 2-1 Example 2-1 except that the protective layer was not coated on the colored photosensitive layer.
Same as. 100 sheets of this positive type colored image forming material were laminated in a single sheet and placed in a thermostatic chamber at 55 ° C., and the presence or absence of blocking was examined. Already after 3 days, the photosensitive layer had blocked and had partial omissions.

Comparative Example 2-2 Example 2-2 except that a protective layer was not coated on the colored photosensitive layer.
Same as. 100 sheets of this positive type colored image forming material were laminated as a single sheet and placed in a constant temperature bath at 55 ° C., and the presence or absence of blocking was examined. Already after 3 days, the photosensitive layer had blocked and had partial omissions.

Example 3-1 A support ethylene-vinyl acetate resin in which an ethylene-vinyl acetate resin having a thickness of 30 μm (vinyl acetate content 14% by weight) was extruded and laminated on a polyethylene terephthalate film having a thickness of 75 μm by a laminating method. The colored photosensitive composition dispersion liquid having the following composition was applied on the surface using a wire bar so that the dry film thickness was 1 μm, and then dried.

2,3,4-Trihydroxybenzophenone-naphthoquinone-1,2-diazidosulfonic acid ester 0.616 g Vinyl acetate-vinyl versatic acid (80:20 parts by weight) copolymer 4.384 g MN = 22 , 000 MW = 60,000 The following pigments The amount below Ethyl cellosolve 39.6 g Fluorocarbon surfactant (FC-430 manufactured by 3M Co.) 0.25 g

Pigment Black: Carbon Black MA-100 (manufactured by Mitsubishi Kasei) 0.99 g Cyan: Cyanine Blue 4920 (manufactured by Dainichiseika Co., Ltd.) 0.55 g Magenta: Seika Fast Carmine 1483 (manufactured by Dainichiseika Co., Ltd.) 68 g Yellow: Seika Fast Yellow H-7055 (manufactured by Dainichiseika Co., Ltd.) 0.68 g Next, a protective layer coating solution having the following composition was used with a wire bar so that the dry film thickness was 0.05 μm on the colored photosensitive layer. It was applied and dried.

Protective Layer Coating Liquid Hydroxypropylmethylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts Demineralized water 98 parts This positive type colored image-forming material is laminated in 100 sheets with single-wafer sheets and placed in a constant temperature bath at 55 ° C. for blocking. I checked. No blocking occurred after 3, 7 and 30 days.

A color separation net positive film of each color is overlaid on the polyethylene terephthalate film surface of the four colored image forming material and 50 cm with a 4 KW metal halide lamp.
Image exposure for 20 seconds from the distance
Development was performed by dipping for 2 seconds to form a 4-color colored image. At that time, the protective layer was dissolved in the developing solution.

<Developer> Na ₂ CO ₃ 15 g Surfactant (Perex NBL manufactured by Kao Atlas Co., Ltd.) 50 g Distilled water 1000 g Next, the image surface of the black image and the art paper were brought into close contact with each other, and 8
5 kg / cm between a pair of nip rolls heated to 0 ° C
After passing under a pressure condition of ² at a speed of 50 cm / min, the support was peeled off. The peeling was easy, and only the black image portion was transferred onto the art paper.

Subsequently, the colored images were transferred in the order of cyan, magenta, and yellow, whereby a color proofing image consisting of four colors was obtained on the art paper. According to the present embodiment, only the image portion was transferred, and the finish was very close to the actual printed matter.

Example 3-2 A colored image-forming material was prepared in the same manner as in Example 3-1, except that the coating solution for protective layer having the following composition was applied to the colored photosensitive layer to a dry film thickness of 0.03 μm. Protective layer coating liquid Polyacrylic acid resin (Jurima-AT-613 (manufactured by Nippon Pure Chemical Co., Ltd.) 2 parts Demineralized water 98 parts Laminate 100 sheets in the same manner as in Example 3-1 and stack them in a constant temperature bath at 55 ° C. Then, the presence or absence of blocking was examined and no blocking occurred after 3, 7, and 30 days.

Example 3-3 A colored image-forming material was prepared in the same manner as in Example 3-1, except that the coating solution for protective layer having the following composition was applied to the colored photosensitive layer to give a dry film thickness of 0.03 μm. . Protective layer coating liquid Hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts Silicon dioxide (trade name; Syloid 404 (manufactured by Fuji Devison Co., Ltd.) 0.2 parts Demineralized water 98 parts As in Example 1-1, a single sheet 100 The sheets were laminated and placed in a constant temperature bath at 55 ° C., and the presence or absence of blocking was examined, and blocking did not occur after 3, 7, and 30 days.

Comparative Example 3-1 Example 3-1 except that the protective layer was not coated on the colored photosensitive layer.
Same as.

100 sheets of this positive type colored image-forming material were laminated as single-wafer sheets and placed in a constant temperature bath at 55 ° C., and the presence or absence of blocking was examined. Already after 1 day, the light-sensitive layer was blocked and partially missing.

[0114]

According to the present inventions 1 to 4, the interface between the protective layer and the cover sheet is good, and the releasability is good. Invention 4
According to the above, the sharpness is further improved. According to the present inventions 5 to 7, the following effects can be obtained. That is, the o-quinonediazide-containing photosensitive layer does not have polymerization inhibition by oxygen unlike the photopolymerizable photosensitive layer, has a high softening point (Tg) of the photosensitive layer, and nitrogen gas is generated during exposure. Was not done. However, a protective layer is required to prevent blocking when the blocking performance is improved during storage in product packaging and the adhesion to the support is weak for colored image transfer materials such as color proof, and for photosensitive materials having a low Tg of the photosensitive layer. Is. However, the gas permeability of the protective layer conventionally used for the photopolymerizable photosensitive layer is poor, and when this protective layer is used for the o-quinonediazide photosensitive layer, bubbles are generated in the photosensitive layer. Therefore, by using a water-soluble polymer with good gas permeability, we achieved both bubble prevention and blocking performance during exposure.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Junko Makino 1 Sakura-cho, Hino-shi, Tokyo Konica stock company (72) Inventor Tetsuya Masuda 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd. In-house (72) Inventor Hideaki Mochizuki 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd.

Claims (7)

[Claims] 1. A colored image-forming material having a heat-softening layer, a colored photosensitive layer containing a photosensitive composition and a colorant, a protective layer and a cover sheet in this order on a support. 2. A colored image-forming material having a heat-softening layer, a colored photosensitive layer composed of a photosensitive composition and a colorant, a protective layer and a cover sheet in this order on a support is imagewise exposed, and the cover sheet is peeled off. A method for forming a transfer image, which comprises performing post-development to form an image, and then transferring the image to a material to be transferred. 3. A heat-softening layer is formed on a support, a colored photosensitive layer is applied on the heat-softening layer, and the coating is dried, and then a cover sheet comprising a transparent support is provided with a sheet having a protective layer. A method for producing a colored image-forming material, which comprises laminating on the colored photosensitive layer. 4. The transfer image forming method according to claim 2, wherein the cover sheet is peeled off before imagewise exposing the colored image forming material. 5. A colored image-forming material comprising a support and an o-quinonediazide-containing colored photosensitive layer provided on the support, the protective layer being provided on the o-quinonediazide-containing colored photosensitive layer. 6. A colored image-forming material having a heat-softening layer, a colored photosensitive layer containing o-quinonediazide and a colorant and a protective layer on a support is imagewise exposed and then developed to form a colored image, A transfer image forming method characterized by forming a transfer image by transferring this to a material to be transferred. 7. A colored image forming material, a method for producing the same and a transfer image forming method according to claim 1, wherein the support is a transparent support.