JPH0373952A - Photosensitive composition and image forming method - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. causing no dimensional change by incorporating an o-quinonediazido compd., novolak resin and a high molecular compd. having a polymerizable unit of specified vinyl ester of carboxylic acid in the molecular structure and specifying the weight ratio of the novolak resin to the high molecular compd. CONSTITUTION:An o-quinonediazido compd., novolak resin and a high molecular compd. having a polymerizable unit of vinyl ester of carboxylic acid represented by formula I (where R is 1-17C alkyl) in the molecular structure are incorporated and the weight ratio of the novolak resin to the high molecular compd. is regulated to 5/95-80/20. A photosensitive compsn. not requiring high temp. for transfer even when applied to a transfer type photosensitive material, capable of preventing a dimensional change and having satisfactory discoloration resistance and superior color reproducibility is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive composition and an image forming method using an image forming material containing the photosensitive composition.

The present invention can be used, for example, as a color proof photosensitive m-acid for color proofing in color printing, and a color proof transfer image forming method.

[Conventional technology]

A photosensitive composition containing an 0-quinonediazide compound is
For example, it is used in the field of photosensitive materials for printing. Before actual printing in multicolor printing, a color sheet called a color proof is sometimes used for proof printing. Sexual compositions may be used.

O-quinonediazide compounds are generally used with polymeric compounds that can function as binders.

This type of prior art includes Japanese Patent Publication No. 56-501217, Japanese Patent Application Laid-open No. 97140-1982, and Japanese Patent Application Laid-Open No. 47-41830.
No. describes a photosensitive composition containing an 0-quinonediazide compound and a novolac type phenolic resin.

[Problem that the invention seeks to solve]

However, the conventional photosensitive U parabolite described above uses this composition to make a photosensitive material, exposes and develops it to obtain an image, and when transferring the image to a transfer material such as paper, the transfer is performed at a high temperature. Requires heating. For this reason, transfer materials such as paper,
Alternatively, the photosensitive material itself may expand or deform due to heat, resulting in a dimensional shift in the transferred image.

Such dimensional deviations are extremely problematic when used, for example, as a color proof for proofreading as described above.

This is because a proper calibration image cannot be obtained due to positional deviation between the multiple colors.

Further, the photosensitive composition using the above-mentioned novolac type phenol resin has a problem of poor discoloration resistance.

On the other hand, photosensitive materials using photosensitive compositions are generally required to have good color reproducibility. It is hoped that proofs will be obtained.

The present invention has been made in view of the above-mentioned circumstances, and provides a photosensitive U acid that does not require high-temperature heating for transfer even when applied to transfer-type photosensitive materials, and therefore does not cause dimensional deviations. Another object of the present invention is to provide an image forming method for obtaining a transferred image using a photosensitive material using such a photosensitive composition.

Another object of the present invention is to provide a photosensitive composition that has good color fastness and excellent color reproducibility, and the above-described image forming method using the same.

[Means for solving problems]

The object of the present invention is as follows: (a) 0-quinonediazide compound (b) Novolac resin (C) A polymer compound having in its molecular structure a carboxylic acid vinyl ester polymerized unit represented by the following general formula RCOOCH= CHz However, R is Represents an alkyl group having 1 to 17 carbon atoms.

Achieved by a photosensitive composition containing the above (b) and (c) in a weight ratio range of (b)/(c) = 5/95 to 80/20. be done.

In addition, an image forming material having the above-mentioned photosensitive composition may be exposed to light.
This is achieved by an image forming method in which an image area is formed by development, and at least the formed image area is transferred to a transfer material to obtain a transferred image.

In one preferred embodiment of this image forming method,
It is possible to adopt a configuration in which only the image portion is transferred to the transfer target material.

The present invention will be explained in more detail below.

The photosensitive composition of the present invention contains an 0-quinonediazide compound. Any 0-quinonediazide compound can be used as long as it can function as a photosensitizer.

Specifically, for example, 1,2-benzoquinonediazide-4
- Condensation of sulfonyl chloride, 1.2-naphthoquinonediazide-4-sulfonyl chloride, 1.2-naphthoquinonediazide-5-sulfonyl chloride, 1.2-naphthoquinonediazide-6-sulfonyl chloride and a compound containing a hydroxyl group and/or an amino group. Compounds are preferably used.

Examples of the hydroxyl group-containing compound include trihydroxybenzophenone, dihydroxyanthraquinone, bisphenol A1 phenol novolak resin, resorcinol benzaldehyde condensation resin, and hyrogallol acetone condensation resin. Examples of amino group-containing compounds include aniline, P-anodiphenylamine, P-aminobenzophenone, 4,4''-diaminophenylamine, and 4゜4゛-cyaminobenzophenone.

Regarding quinonediazide compounds, including those described here, please refer to J. Kosar, "Light Sensitive Systems J".
i-Live System), New York City, John Wysoe & Sons, Inc., 1965), and "Photosensitive Polymer" by Yonematsu and Inui (Kodansha, 1977).

Next, the photosensitive composition of the present invention contains a polymer compound having a carboxylic acid vinyl ester polymerized unit represented by the following general formula in its molecular structure.

RCOOCH=　CHz However, R represents an alkyl group having 1 to 17 carbon atoms.

Any polymer compound having the above structure can be used, but as the carboxylic acid vinyl ester monomer for constituting the polymerized unit represented by the above general formula, the following examples are preferable. The name and chemical formula are also shown.

■Vinyl acetate CH+C00CH= CH2
■Vinyl propionate CH3CH3CO0CH=
CHz■Vinyl butyrate CH3(CL)zcO
Ocl(=CL■vinyl pivalate (CHI)
3CCOOCH= CI'h■Vinyl caproate
CH3 (C8z) 4COOcH= CHt■Vinyl caprylate CHs (CHz) hcOOcH=
CHz■Vinyl caprate CHs (CHz)
*C00C1(-Cut■ Vinyl laurate CH
s (CHt) +. C00CH= Cut■Vinyl myristate CHs (CHz) IzcOOcH=
CIIz [phase] Vinyl pulpate CH3 (CB
, ) , cOOcH-CHz ■ Vinyl stearate
CH3 (CHz) + 1. C00CR= CH□@vinyl versatate CHs R' -C-C00CH= CI! 2 (R1, RZ are alkyl groups, and the sum of their carbon numbers is 7. In other words, it is in the form R' + R''-CrH1bO) As a carboxylic acid vinyl ester monomer, carbon atoms constituting the main chain of carboxylic acid Those having a number of 1 to 4 are more preferred. Vinyl acetate is particularly preferred.

Note that the above R also includes an alkyl group having a substituent, that is, a vinyl ester of a substituted carboxylic acid is also included in the polymerization unit.

The polymer compound may be a polymer obtained by polymerizing one type of carboxylic acid vinyl ester, a polymer obtained by copolymerizing two or more types of carboxylic acid vinyl esters, or a polymer that can be copolymerized with carboxylic acid vinyl ester. It may be a copolymer with monomers in any composition ratio.

Examples of monomer units that can be used in combination with the polymerized unit represented by the above general formula include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, such as styrene, α-methylstyrene, p - Styrenes such as methylstyrene and p-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride, such as diethyl maleate, Diesters of unsaturated dicarboxylic acids such as diptyl maleate, di-2-ethylhexyl maleate, dibutyl fumarate, di-2-ethylhexyl fumarate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, Dodecyl acrylate, 2-chloroethyl acrylate,
α-methylene aliphatic monocarboxylic acid esters such as phenyl acrylate, α-methyl chloroacrylate, methyl methacrylate, and ethyl methacrylate; Nitriles such as acrylonitrile and methacrylonitrile; Amides such as acrylamide; e.g. acrylic anilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, etc., e.g. evamethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether,
Vinyl ethers such as β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-methoxyethylene, l.

Ethylene derivatives such as 1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene, such as N-vinylpyrol, N-vinylcarbazole,
There are vinyl monomers such as N-vinyl compounds such as N-vinylindole, N-vinylvirolone, and N-vinylpyrrolidone. These vinyl monomers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved.

Particularly preferred polymer compounds for use in the present invention are those having vinyl acetate polymerization units in their molecular structure. Among them, vinyl acetate polymerization units are 40 to 95.
−t%, the number average molecular weight (MN) is i,
ooo~100.000, weight average molecular weight (MW
) is preferably 5.000 to soo, ooo.

More preferably, vinyl acetate polymerized units (especially 40
~95 wt%) and polymeric compounds having a carboxylic acid vinyl ester polymer unit with a longer chain than vinyl acetate are preferred, especially those with a number average molecular weight (MN) of 2.000 to 60.0.
00, weight average molecular it (MW) is 10,000-15
A value of 0.000 is preferred.

In this case, the monomer that copolymerizes with vinyl acetate to form a polymer compound having vinyl acetate polymerized units may be any monomer that can form a copolymer, such as among the monomers listed above. You can arbitrarily choose from.

Copolymers that can be used as polymer compounds in the present invention are listed below by indicating their monomer components. However, it goes without saying that the invention is not limited to the following examples.

■Vinyl acetate-ethylene ■Vinyl-styrene acetate ■Vinyl acetate-crotonic acid ■Vinyl acetate-maleic acid ■Vinyl acetate-2-ethylhexyl acrylate ■Vinyl acetate-2-ethylhexyl maleate ■Vinyl acetate-methyl vinyl ether ■Vinyl acetate-chloride Vinyl ■ Vinyl acetate - N- Vinylpyrrolidone [Phase] Vinyl acetate - Vinyl propionate ■ Vinyl acetate -
Vinyl pivalate ■ Vinyl acetate Rubersatate ■ Vinyl acetate - Vinyl laurate [Phase] Vinyl acetate - Vinyl stearate ■ Vinyl acetate -
Vinyl versatate - ethylene [phase] Vinyl acetate - vinyl versatate - 2-ethylhexyl acrylate - Vinyl acetate - vinyl versatate - vinyl laurate [phase] Vinyl acetate - vinyl versatate - crotonic acid [phase] Vinyl propionate-Vinyl satisocyanate [Phase] Vinyl propionate-Vinyl satisocyanate-Crotonic acid [Phase] Pivalic acid-Vinyl stearate-Maleic acid Next, the photosensitive composition of the present invention contains a novolac resin. However, this novolak resin functions as a binder in the photosensitive composition together with the above-mentioned polymer compound.

Novolak resins are generally obtained by polycondensation of at least one type of phenol and an active carbonyl compound, but any such novolak resin 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, and specific examples of such phenols include, for example:
Phenol, 0-cresol, m-cresol, p-cresol, 3,5 xylenol, 2,4-xylenol, 2,5-xylenol, carvacrol, thymol,
Examples include catechol, resorcinol, hydroquinone, pyrogallol, phloroglucin, alkyl group (1 to 8 carbon atoms) W-substituted phenol, and the like.

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

Examples of the novolak resin include phenol formaldehyde novolak resin, m-talesol formaldehyde novolak resin, phenol/m-cresol/formaldehyde copolycondensate resin, phenol/p-cresol/formaldehyde copolycondensate resin, m-cresol/p -cresol/formaldehyde copolycondensate resin,
0-cresol/p-cresol/formaldehyde copolycondensate resin, phenol/0-cresol/m-cresol/formaldehyde copolycondensate resin, phenol/0-cresol/p-cresol/formaldehyde copolycondensate resin, phenol・m-cresol, p-cresol, formaldehyde copolycondensate resin, etc. can be mentioned.

A preferred novolac resin is a phenol formaldehyde novolac resin, which has a weight average molecular weight MW of 3500.
~500. The number average molecular weight MN is preferably in the range of 1000 to 200.

The molecular weight of the novolak resin is measured by GPC (gel permeation chromatography).

Calculation of number average molecular weight MN and weight average molecular weight 11 MW is based on Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Shanaka, “Journal of the Chemical Society of Japan” 8.
By the method described on pages 00 to 805 (1972),
The test shall be performed by leveling the peaks of the oligomer region (connecting the centers of the peaks and valleys).

In addition, in the novolac resin, pyrolysis gas chromatography (PGC) is used as a method for confirming the quantitative ratio of different phenols used in the synthesis thereof.

The principle of pyrolysis gas chromatography is
If the equipment and experimental conditions are
"New Experimental Chemistry Course" Volume 19, Polymer Chemistry CI) 47
The method for qualitative analysis of novolac resins using pyrolysis gas chromatography is described in pages 4 to 485 (Maruzen, 1978), etc., and the method for qualitative analysis of novolac resins using pyrolysis gas chromatography is described in “Analytical Chemistry” No. 18 by Morio Tsuge, Takashi Shanaka, and Masayuki Shanaka. vol., pages 47-52 (1969).

In the photosensitive composition of the present invention, a novolac resin (referred to as component (b)) and a polymer compound (referred to as component (e)) having a carboxylic acid vinyl ester polymerized unit represented by the above general formula in its molecular structure. ) means (b) / (
c) Contained in a weight ratio range of = 5/95 to 80/20.

If the amount of component (b) is less than this range, problems will arise in color reproducibility. On the other hand, if component (b) exceeds this range, deformation (dimensional deviation) due to heat will occur and the color fastness will be poor.

Particularly preferred proportions of components (b) and (c) are (by weight) (
b)/(c) It is in the range of -10/90 to 60/40.

The photosensitive composition of the present invention can be used to constitute an image-forming material, and can be used as a colored image-forming material, for example, when used as a color proof.

In this case, the colored photosensitive layer of the colored image-forming material is removed in an imagewise manner by development following imagewise exposure 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 with the usual colors required, i.e., yellow, magenta, cyan, and colors matching the blank, are required, as well as metal powders,
White pigments and fluorescent pigments are also used. When applying the present invention to color proofing, many pigments and dyes known in the art can be used, such as those described below.

(C, I mean color index).

Victoria Pure Blue (C, I-42595) Auramine (C, I 41000) Cathylone Brilliant Flavin (C, I Basic 13) Rhodamine 6 G CP (C, I 45160) Rhodamine B (C, I 45170) Safranin OK
2O: 100 (C,I 50240)Erioglaucine Fast Yellow 80F (C, I 21105) Benzidine Yellow 4T-564D (C, I 21095) Sim Woofer Thread 4015 (C, I 12355') Lionor Red 7 B12O3 (C, I 15830
') First Gen Blue TGR-L (C, I 74160) Geonor Blue 3M (C, I 26150 ') Mitsubishi Carbon Black MA-100 Mitsubishi Carbon Black #30. #40. #50
When using a colorant in the present invention, the ratio of colorant/binder in the colored photosensitive layer is determined by a method known to those skilled in the art, taking into consideration the target optical density and the removability of the colored photosensitive layer to a developer. I can do it.

For example, in the case of dyes, preferably the content is 5% by weight.
% to 75%, and in the case of pigments, the content is preferably 5% to 90% by weight.

The thickness of the colored photosensitive layer can be determined by methods known to those skilled in the art, depending on the target optical density, the type of colorant (dye, pigment, carbon black) used in the colored photosensitive layer, and its content. , II of the colored photosensitive layer if it is within the allowable range! The thinner the J thickness is, the higher the resolution and the better the image quality. Therefore, the film thickness is usually preferably used in a range of 0.1 g/m to 5 g/m.

When carrying out the present invention, plasticity and coating properties improvers and the like may be further added to the photosensitive composition as required.

Plasticizers include various low-molecular compounds such as phthalate esters, triphenyl phosphates, maleate esters, and coating properties improvers include surfactants such as fluorine surfactants and ethyl cellulose polyalkylene ether. Examples include nonionic surfactants.

When forming an image forming material, especially a colored image forming material, using the photosensitive composition of the present invention, the colored photosensitive layer consists of two layers: a colored layer made of a colorant and a binder, and a photosensitive layer made of a photosensitive composition. It can also be divided into layers. In this case, it does not matter which layer is placed on the support side.

When forming an image forming material using the photosensitive composition of the present invention, any support can be used, but a transparent support is preferably used. As the transparent support, a polyester film, particularly a biaxially oriented polyethylene terephthalate film, is preferred in terms of dimensional stability against water and heat. In addition, acetate film, polyvinyl chloride film,
Polyethylene film, polypropylene film, polyethylene film, etc. can be used.

The image forming material can be used to transfer an image to a transfer material. The material to be transferred at this time.

In order to efficiently transfer the image to cultivated soil and to facilitate peeling off the support after image transfer, that is, to improve the releasability between the support and the image forming layer, a release treatment is applied to the surface of the support. or a release layer can be provided on the surface of the support. These will be described later.

In the image forming method of the present invention, an image forming material having the photosensitive composition of the present invention is exposed and developed to form an image area, and at least the formed image area is transferred to a transfer material to form a transferred image. It's something you get.

When the image forming method of the present invention is embodied as, for example, a multicolor image forming method, the basic method is as follows (I):
It can be broadly classified into method (II).

(1) A first colored image forming material having a colored image form for the first color and a bottom layer on a support is superimposed on a transfer material, at least the colored image form bottom layer is transferred to the transferred material, and the support is Peel off. Next, image exposure is performed through a first color film original corresponding to the first color, and then development processing is performed to form a colored image of the first color on the transfer material.

Next, at least a colored image forming layer of a second colored image forming material having a colored image forming layer of a second color different in tone from the first color is transferred onto the first colored colored image layer on the transfer material. Then, an alignment image of the second color film original corresponding to the second color (generally called a registration mark image is used)
is registered with the first color registration mark image, image exposure is performed through the second color film original, followed by development processing to obtain a two color matched image on the transferred material. Thereafter, similar processing is performed for the third and fourth colors to obtain a multicolor image.

This method is known from Japanese Patent Publication No. 47-27441 and Japanese Patent Publication No. 56-501217.

(n) Forming a first color colored image on a first color colored image forming material, transferring at least the colored image to a transfer material, and peeling off the support. Further, after forming a second color colored image on the second color colored image forming material, while registering the second color register mark image formed accordingly with the first color register mark image on the transfer target material. , transferring a second color colored image onto the first color colored image and peeling off the support to obtain a two color matched image. Similarly, colored images of the third color and the fourth color are also transferred onto the transfer material to obtain a multicolor image.

In some cases, this multicolor image may be indirectly transferred onto another transfer material to obtain a multicolor image.

This type of method is disclosed in Japanese Patent Application Laid-open Nos. 47-41830, 59-97140, 60-28649 and US Pat. No. 3,775.113.

In the image forming method of the present invention, the image forming material is usually imagewise exposed through a color separation mask and then developed.
An image is formed. At this time, an embodiment may be adopted in which only the image portion from the image obtained on the support is directly transferred and laminated onto the transfer material. That is, in one preferred embodiment, only the colored image layer that substantially forms the image is transferred and laminated. In this case, in order to efficiently transfer the image onto the surface to be transferred and to make it easier to peel off the support after image transfer, the surface of the support should be subjected to a release treatment with an appropriate oil-repellent substance, or the support should be It is preferable to provide a release layer thereon.

Examples of such oil-repellent substances include silicone resins, fluororesins, fluorosurfactants, polyolefins,
Polyamide, etc. can be used, and as the release layer, for example, alcohol-soluble polyamide, alcohol-soluble nylon, a blend of partially esterified resin of a copolymer of styrene and maleic anhydride and methoxymethylated nylon, polyamide, etc. can be used. Vinyl acetate, polyacrylate, copolymer of polymethyl methacrylate and acrylate, polyvinyl chloride, copolymer of vinyl chloride and vinyl acetate, polyvinyl butylade, cellulose acetate phthalate, methylcellulose, ethylcellulose, cellulose diacetate, triacetic acid Cellulose, 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 mixtures thereof can be used. .

The thickness of the release layer is preferably in the range of o.oi.mu.m to 10 .mu.m, particularly preferably in the range of 0.1 .mu.m to 5 .mu.m.

In order to improve mold releasability, a particularly preferred embodiment includes providing a polypropylene layer or a polyethylene layer that is thinner than the thickness of the support.

The method for forming a polypropylene layer or polyethylene layer on a support is as follows: (1) A solution of polyvinyl acetate, polyvinyl chloride, epoxy resin, polyurethane resin, natural rubber, synthetic rubber, etc. dissolved in an organic solvent is used as an adhesive. After applying these adhesives on a support and drying with hot air or heating, a polypropylene film or a polyethylene film is overlaid and laminated by pressing under heat.
So-called dry tunate method: (2) A copolymer of ethylene and vinyl acetate, a copolymer of ethylene and acrylic ester, a polyamide resin, a petroleum resin, a rosin, a wax, or a mixture thereof is used as an adhesive. After applying the adhesive onto the support using a doctor blade method, roll coating method, gravure method, reverse roll method, etc. while heating the adhesive and keeping it in a molten state,
The so-called hot-melt lamination method, in which polypropylene or polyethylene films are immediately laminated together and laminated by heating at a high temperature if necessary and then cooling; (3) The polypropylene or polyethylene is kept in a molten state and then extruded. This is the so-called extrusion lamination method, in which the film is extruded into a film using a machine, and while it is still in a molten state, a support is bonded and laminated; Examples include a so-called coextrusion method in which a polypropylene layer or a polyethylene layer is formed on a support film by molding two times with polypropylene or polyethylene in a molten state using a machine.

In the image forming method of the present invention, any developer used for developing the image forming material can be used as long as it has a developing action to develop the material to be processed. Preferably, a developer containing an alkaline agent and an anionic surfactant is used.

Usable alkaline agents include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, and lithium hydroxide.

Sodium or ammonium salts of secondary or tertiary phosphates, sodium metasilicate, sodium carbonate.

Inorganic alkaline agents such as ammonia, (2) Mono-, di-, or trimethylamine, mono-, di-,
or triethylamine, mono- or di-isopropylamine, n-butylamine, mono-, di- or triethanolamine, mono-, di- or tri-isopropanolamine, ethylene ion.

Examples include organic amine compounds such as ethylenediimine.

In addition, as anionic surfactants that can be used, (1)
Higher alcohol sulfate esters (e.g., sodium salt of lauryl alcohol sulfate, ammonium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, sulfuric acid alkyl sulfate, etc.), (2) Salts of aliphatic alcohol phosphate esters (e.g.,
Sodium salt of cetyl alcohol phosphate ester, etc.> (3) Alkylaryl sulfonate salts (eg, dodecylbenzenesulfonic acid sodium salt, isopropylnaphthalenesulfonic acid sodium salt).

dinaphthalenesulfonic acid sodium salt, metanitrobenzenesulfonic acid sodium salt, etc.) (4) Alkylamide sulfonates (5) Sulfonic acid salts of dibasic aliphatic esters (e.g. sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, etc.) ) (6) Formaldehyde condensates of alkylnaphthalene sulfonates (for example, formaldehyde condensates of sodium dibutylnaphthalene sulfonate, etc.).

The alkaline agent and anionic surfactant can be used in any combination.

〔Example〕

Examples of the present invention and comparative examples will be described below.

It should be noted that, as a matter of course, the present invention is not limited only to the embodiments described below, but can take various forms.

Example 1 A colored photosensitive composition dispersion having the following composition was dried using a wire bar on the polypropylene surface of a support obtained by dry laminating a 25 μm thick polypropylene film on a 50 μm thick polyethylene terephthalate film. After coating to a film thickness of 1 μm, it was dried to produce four colored image forming materials.

■Vinyl acetate rubersatate (80: 20 parts by weight) copolymer M N = 22.000 MW = 60. OOO ■ PR-50716 manufactured by Sumitomo Duress ■ (novolac type phenol-formaldehyde resin) A mixture of the above ■ and ■ at a weight ratio of ■;■ = 90:10 Ri-tan black: Carbon black MA-100 (Mitsubishi ) 0.99g cyanide
Nidianin Blue 4920 (manufactured by Dainichiseika) 0.55 g Magenta:
Seika First Carmiso 1483 (manufactured by Dainichiseika Chemicals) 0.68 g Yellow: Seika First Yellow H-7055 (manufactured by Dainichiseika Chemicals) 0.68 g or more on the polyethylene terephthalate film surface of the four-color colored image forming material obtained The color-separated positive films of each color were superimposed, image-wise exposed for 20 seconds from a distance of 50 cm using a metal halide lamp, and developed by immersion in the following developer for 30 seconds to form a colored image of four colors. .

(Developer) N a zC0315g Surfactant (Perex NBL manufactured by Kao Atlas Co., Ltd.) 50g Distilled water 1000g Next, the image surface of the black image was brought into close contact with the art paper, and 5kg/kg was passed between a pair of heated nib rolls. The support was peeled off after passing under pressure conditions of - at a speed of 50 cm/min.The peeling was easily performed and only the black image area was transferred onto the art paper.

Subsequently, colored images were transferred in the order of cyan, magenta, and yellow, thereby obtaining a color proofing image consisting of four colors on the art paper.

Data regarding transfer temperature, dimensional deviation between four colors, degree of color change over time, and color reproducibility are shown in Table 1. In this example, only the image area was transferred, so the finished product was very similar to the actual printed matter.

Example 2 A release layer solution having the following composition was applied onto a two-wheeled stretched polyethylene terephthalate film with a thickness of 75 μm using a wire bar so as to have a dry film thickness of 0.5 μm, and dried.

Next, the colored photosensitive layer dispersion according to the following &Il precepts was placed on the heat-adhesive layer.
Using a wire bar, it was coated and dried to a dry film thickness of 1 μm.

Next, a heat-adhesive layer solution having the following composition was applied onto the release layer to a dry film thickness of 7 μm and dried.

■Vinyl acetate-ethylene (90: 10 parts by weight) copolymer MN = 40,000 MW = 120,000 ■PR-50716 (novolak type phenol-formaldehyde resin) manufactured by Sumitomo Duress ■Replace the above ■ and ■ with ■: ■ A color separation mesh positive film was superimposed on the polyethylene terephthalate film surface of the colored image forming material obtained by mixing at a weight ratio of =40:60, and image exposure was performed for 20 seconds from a distance of 50aIl using a 4KW metal halide lamp. , development was carried out by immersing it in the following developing solution for 30 seconds to form a colored image on the support.

Developer solution> NaOH Log surfactant (Perex NBL manufactured by Kao Atlas Co., Ltd.) 50 g Distilled water 1000 g Next,
The image surface of the obtained colored image and the high-quality paper are superimposed, and the image is passed between a pair of heated nip rolls at a speed of 50 values/min under a pressure of 5-/d. The colored image was transferred onto a high-quality paper, and the colored image, the heat-adhesive layer, and the release layer obtained by peeling off the support of the colored image-forming material were transferred onto high-quality paper. Table 1 shows the same data as in Example 1.

Example 3 A release layer solution having the following composition was applied onto a polyethylene terephthalate film having a thickness of 75 μm so that the dry film thickness was 0.5 μm to prepare a support having a releasable surface.

(Release layer solution) Torezin F-30 (alcohol-soluble nylon, manufactured by Toshi) 10 g methanol 90 g Next, four colored photosensitive composition dispersions having the following composition were prepared, and the dry film thickness was 1.
It was coated on the release layer so as to have a thickness of .mu.m, thereby producing four-color image forming materials.

t-Butylphenol-naphthoquinone-1,2-diazide sulfonic acid ester 0.616 g The following binder polymer 4.3848 The following pigment The following amount Ethyl cellosolve 39.6 g Fluorine surfactant (manufactured by 3M, FC-430) 0 .25g Bin-Polymer ■ Vinyl acetate Rubersatic Acid Vinyl Laurate-Crotonic Acid (55: 20: 20: 5 parts by weight) Copolymer M
N=32.000 MW-72,000 ■Sumitomo Duress special PR-50716 (novolac type phenol-formaldehyde resin) A mixture of the above ■ and ■ at a weight ratio of ■:■=50:50. : Carbon blank MA-100 (manufactured by Mitsubishi Kasei) 0.99g cyan Nidianin Blue 4920 (manufactured by Dainichiseika) 0.55g Magenta: Seiriki First Car ξn 1483 (manufactured by Dainichiseika) 0.68g Yellow: Seika First Yellow H-7055 (manufactured by Dainichiseika) 0.68 g 4
A color separation mesh positive film of each color was superimposed on the colored photosensitive layer surface of the colored image forming material, image exposure was performed for 60 seconds from a distance of 50C1l using a 4KW metal halide lamp, and development was performed by immersing it in the following developer for 30 seconds. , 4
A colored image was formed.

Next, an image-receiving layer solution having the following composition was applied onto another polyethylene terephthalate film to a dry film thickness of 20 μm and dried to prepare an image-receiving sheet.

<Developer> Nazc Os 15
g Surfactant (Perefux NBL manufactured by Kao Atlas Co., Ltd.) 50 g Distilled water
1000 g (image receiving layer solution) Vinyl chloride/vinyl acetate copolymer (composition ratio 75:25, MPR-T-5 manufactured by Nissin Chemical Co., Ltd.
) 18g pentaerythritol tetraacrylate
l1g michler's ketone
0.1g benzophenone
0.64 g paramethoxyphenol
0.018 g methyl ethyl ketone
44g of the previously obtained yellow image was brought into close contact with the image-receiving layer surface of the image-receiving sheet, and heated at 50C between a pair of heated nip rolls under a pressure of 5 kg/cd.
The yellow color image was transferred onto the image-receiving layer by passing at a speed of 11/min, and the polyethylene terephthalate film on the color image side was peeled off.

Subsequently, the colored image is transferred in the order of magenta, cyan, and black, and the image side of the image-receiving sheet is brought into close contact with art paper, and the image-receiving sheet is passed between a pair of nip rolls under the same conditions as described above. 50 with a 4KH metal halide lamp on the polyethylene terephthalate film surface.
Full exposure was given for 30 seconds from a distance of 1.5 cm, after which the polyethylene terephthalate film of the image receiving sheet was peeled off.

A multicolor proofing image was formed on the art paper. Table 1 shows the same data as in each of the above examples.

Example 4 A colored photosensitive layer dispersion having the following composition was applied onto the polypropylene surface of a support obtained by dry laminating a 25 μm thick polypropylene film on a 50 μm thick polyethylene terephthalate film using a wire bar. It was coated and dried to a dry film thickness of 1 μm.

(Colored photosensitive layer dispersion composition) 2.3.4-) Lihydroxybenzophenone naphthoquinone-1,2-diazide sulfonic acid ester 0.616 g The following binder polymer 4.384 g The following pigment The following amount Ethyl cellosolve 39. 6 g Fluorine surfactant (FC-430 manufactured by 3M) 0.25 g Bin-polymer ■ Vinyl acetate-vinyl stearate-2-ethylhexyl acrylate (70: 20: 10 parts by weight) copolymer MN =51
,000 MW=95. OOO ■PR-50716 (novolac type phenol-formaldehyde resin) manufactured by Sumitomo Duress■ A mixture of the above and ■ at a weight ratio of ■:■=80:20.Nira-fuki black: Carbon black MA-100 (Mitsubishi Chemical (Manufactured by Dainichiseika) 0.99g Cyanide Nidianin Blue 4920 (Dainichiseika) 0.55g Magenta:
Seika First Carmiso 1483 (manufactured by Dainichiseika) 0.68 g Yellow:
Seika First Yellow H-7055 (manufactured by Dainichiseika) 0.68g Next, an adhesive layer coating solution with the following composition was applied onto the colored photosensitive layer using a wire bar to a dry film thickness of 5 μm, and dried. A colored imaging material was prepared.

(Adhesive layer coating liquid composition) Alicyclic saturated hydrocarbon resin Alcon P-90 (Akayo Kagaku, softening point 90°C) 12g Alicyclic saturated hydrocarbon resin Alcon P-100 (Akayo Kagaku, softening point 100 ℃) 3g Styrene-butadiene block copolymer Toughblen A (manufactured by Asahi Kaoru Kogyo) 5g toluene 100 - Coloring using a pigment with a tone matching cyan among the colored image forming materials of each color prepared above The adhesive layer surface of the image forming material and the water-resistant white synthetic paper (Nisshinbo type peach coat WE)
K-110) and passed between a pair of heated nip rolls at a speed of 50 cm/min under a pressure of 5 kg/cd to form a white composite cyan colored image forming material via an adhesive layer. Glued onto paper.

Next, a color separation mesh positive film corresponding to cyan is superimposed on the support surface of a colored image forming material using a pigment of a tone matching that of cyan, which is adhered onto white synthetic paper, and the film is adhered by a vacuum adhesion method. Image exposure was performed for 20 seconds from a distance of 50 value using a 4KW/tal halide lamp, and then the support was peeled off from the cyan colored image forming material after image exposure, and developed by immersing it in the following developer for 30 seconds. A cyan colored image was formed on white synthetic paper.

Developer solution> Sodium carbonate 15g Surfactant (Perex NBL manufactured by Kao Atlas Co., Ltd.) 50g Distilled water 1000g Subsequently, on the white synthetic paper on which the cyan colored image was formed,
After adhering a colored image-forming material using a pigment with a tone matching magenta via an adhesive layer, the same operation as above is performed to form a colored image in magenta color, and the same operation is also performed for yellow and black. This was repeated to form a color proofing image consisting of four colors on white synthetic paper. Table 1 shows the same data as in each of the above examples.

Comparative Example 1 In Example 1, the following was used as the binder polymer.

Binder polymer Vinyl acetate-vinyl versatate (80:20 parts by weight) copolymer MN depth 22.000 MW = 60.000 All other conditions were the same as in Example 1 to form a colored image and transfer the image. went. Table 1 shows the transfer temperature, dimensional deviation between the four colors, degree of color change over time, and color reproducibility of the obtained color proofing image.

Comparative Example 2 In Example 2, the following was used as the binder polymer.

Binder polymer Vinyl acetate-ethylene (90:10 parts by weight) copolymer MN = 40.000 MW = 120.000 All other conditions were the same.A colored image was formed and image transfer was performed in the same manner as in Example 2. . Table 1 shows the same data as each example for the obtained color proofing images.

Comparative Example 3 In Example 3, the following was used as the binder polymer.

Vine - Volmer Vinyl acetate - Vinyl versatate - Vinyl laurate - Crotonic acid (55:20:20:5 parts by weight) copolymer M N =
32.000 M W = 72.000 A colored image was formed and image transfer was performed in the same manner as in Example 3 except for the following conditions. Regarding the obtained color proofing images, the same data as in each of the above examples are shown in the table below.
Shown in ■.

Comparative Example 4 In Example 4, the following was used as the binder polymer.

Polymer vinyl acetate-hinyl stearate-2-ethylhexyl acrylate (70:20:10 parts by weight) copolymer MN-51,000 MW = 95.000 All other conditions were the same as in Example 4. A colored image was formed and image transfer was performed. Regarding the obtained color proofing images, the same data as in each of the above examples are shown in the table below.
Shown in 1.

Comparative Example 5 In Example 1, only the following novolak resin was used as the binder polymer, and 5DR was used as the developer.
Example 1 was carried out in the same manner as in Example 1, except that -1 (Konica PS plate developer; manufactured by Konica ■) was used.

Similar data for the examples described above are shown in Table 1.

Binder polymer (Novolak) Sumitomo Dures ■
PR-50716 (novolac type phenol-formaldehyde resin) Comparative Examples 6 to 8 In Examples 2 to 4, the same binder polymer and developer as in Comparative Example 5 were used, and the other conditions were as in Examples 2 to 4, respectively. Comparative Examples 6 to 8 in the same manner as 4.
And so. The data are shown in Table-1.

Evaluation results of Examples 1 to 4 and Comparative Examples 1 to 8 Transfer temperature, dimensional deviation in the X direction and Y direction, degree of coloration over time of the colored photosensitive layer binder, and color for each of the above Examples and Comparative Examples The measurement results of reproducibility are shown in Table 1 below.

In Table 1, dimensional deviation refers to the deviation between the register marks at the four corners of the image, and the deviation in each direction in the transfer direction (X direction) and the width width direction (Y direction). (μm). The dragonfly is 400m in the X direction and 600m in the Y direction.
are located at a distance of

The degree of coloration over time is a value obtained by measuring the degree of coloration of the binder (brown coloration) of an image transferred to paper as yellow reflection density. For measurement, Macbeth reflection densitometer RD-9
18 was used. Items whose degree of coloration increases over time are
Large discoloration and poor color fastness. When the degree of coloration increases, the colors of the transferred image, especially cyan, magenta, and yellow, become muddy and the image reproducibility deteriorates.

Color reproducibility was evaluated as follows by visually comparing the obtained colored image with the printed matter to determine whether a difference in color could be perceived.

○: 90% or more of the judges did not perceive a difference in color.

Δ: 30 to 40% of judges sensed a difference in color.

As can be understood from Table 1, in Examples 1 to 4 of the present invention, good transfer was achieved even at a relatively low transfer temperature, dimensional deviation was small, and the degree of coloration over time was small.
Color reproducibility is also good and excellent. On the other hand, comparative example 1
In Examples 4 to 4, it is possible to obtain an image with low dimensional deviation and degree of coloration over time by lowering the transfer temperature, but there remains a problem in color reproducibility.

In addition, Comparative Examples 5 to 8 all require a considerably high transfer temperature, and the dimensional deviation and degree of coloration over time are significantly reduced [Effects of the Invention] As described above, according to the present invention, when a transfer type is used, It is possible to provide a photosensitive composition that does not require high temperatures, can prevent dimensional deviations, has good color fastness, and has excellent color reproducibility, and an image forming method.

Claims (1)

[Scope of Claims] 1. (a) o-quinonediazide compound (b) novolac resin (c) polymer compound having carboxylic acid vinyl ester polymerized units represented by the following general formula in its molecular structure RCOOCH=CH_2 provided that R represents an alkyl group having 1 to 17 carbon atoms. A photosensitive composition comprising: (b) and (c) in a weight ratio range of (b)/(c) = 5/95 to 80/20. 2. Image formation in which an image forming material having the photosensitive composition according to claim 1 is exposed and developed to form an image area, and at least the formed image area is transferred to a transfer material to obtain a transferred image. Method.