JPH0355552A - Colored image forming material - Google Patents

Abstract

PURPOSE:To allow low-temp. heating transfer and to prevent the generation in deviation between multicolor transferred images as well as to prevent the color reproduction defect by the discoloration arising from heating by incorporating the condensation product of 1, 2-naphthoquinone diazide-4-sulfonyl chloride and a novolak resin into a colored photosensitive layer. CONSTITUTION:The condensation product of the 1, 2-naphthoquinone diazide-4- sulfonyl chloride and the novolak resin is used as the photosensitive compsn. to be incorporated into the colored photosensitive layer. The condensation product is relatively low in softening point and can attain the heating transfer at a low temp. The condensation product causes a chemical change in its molecular structure in a short period of time upon receipt of the irradiation of active rays. A change in the solubility thereof in a solvent is then resulted. This product is of the type that the exposed parts are dissolved away when a certain kind of solvent is applied thereto. The good transfer is attained and the dimensional deviation is small even if the transfer temp. is relatively lowered.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a colored image-forming material used for color proofing for color proofing in color printing, and more particularly to a colored image-forming material that enables low-temperature heating transfer. .

[Prior Art] It is natural that color sheets for color proofing (also called color paper sheets) are used to save the time and effort of proof printing, which is performed as a pre-process for hon-inkori, which is used for multi-color printing. well known in the field.

As a method for creating a multicolor transfer image using a colored image forming material for color proofing, for example, Japanese Patent Application Laid-Open No. 47-4183
The so-called direct transfer method described in Publication No. 0, in which a colored image is directly transferred and laminated onto the final receiver paper, for example, JP-A-56-50
Examples include the method described in Japanese Patent No. 1217, in which the process of transferring a colored photosensitive layer to image-receiving paper and then repeating the process of forming an image is repeated.

In each of the above methods, the surface of the colored image on the transfer material is not covered with a transparent thermoplastic organic polymer layer, so the gloss of the resulting image surface is too high and the image quality differs from that of the printed material. It has the disadvantage of making an impression.

Color proofs for color proofing are originally used to predict the image reproduction of the final printed matter, so there is a strong desire for colored image-forming materials that can produce transferred images that closely resemble the image quality of the printed matter. was.

For example, in the special W@Sho 59-97140 publication, 1.2
A colored image-forming material having a photosensitive layer containing a condensate of naphthoquinonediazide sulfonyl chloride and birogallol acetone resin is disclosed.

[Problems to be Solved by the Invention] However, the colored image forming material described in JP-A No. 59-97140 has a high softening point of the shrinkage material contained in the photosensitive layer, so that transfer to the transfer material is difficult. Requires high temperature heating. Therefore, when forming a multicolor IIIi image, misalignment occurs between the multicolor transferred images, making it impossible to obtain a good transferred image. In addition, the color of the colored image changes due to high temperature heating, resulting in poor color reproduction and being unsuitable as a color proof.

The present invention has been developed in view of the above-mentioned conventional problems, and enables low-temperature heating transfer, prevents misalignment between multicolor transferred images during multicolor image formation, and prevents poor color reproduction due to rough discoloration due to heating. The purpose of the present invention is to provide colored image-shaped precept materials.

[Means for Solving the Problems] In order to achieve the above object, the colored image forming material according to the present invention is a colored image forming material having a colored photosensitive layer containing at least a photosensitive composition and a colorant on a support. The image forming material is characterized in that the colored photosensitive layer contains a composite of 1,2-naphthoquinonediazide-4-sulfonyl chloride and a novolak resin.

The present invention will be explained in detail below.

In the present invention, a metal shrinkage product such as 1,2-naphthoquinonediazide-4-sulfonyl chloride and a novolac resin is used as the photosensitive composition contained in the colored photosensitive layer. The condensate has a relatively low softening point and can achieve thermal transfer at low temperatures. In addition, when the condensate is irradiated with actinic rays, its molecular structure undergoes a chemical change within a short time,
It is a type of material whose solubility changes with respect to solvents, and when a certain type of solvent is applied, the exposed portion is dissolved and removed.

The novolak resin in the present invention is a resin obtained by condensing phenol, cresols, and formaldehyde in the presence of an acid catalyst. Examples of the phenol cresols include phenol, 0-cresol, , 3,5-xylenol, 2,4-
Examples thereof include xylenol, 2.5-xylenol, p-alkyl group (1 to 8 carbon atoms)@substituted phenol, and the like. The phenol can be used alone or in combination with formaldehyde to obtain a resin.

Among these, preferred novolak resins are phenol,
It is a resin obtained by copolycondensing formaldehyde with at least one selected from National Cresol (or 0-cresol) and p-cresol.For example, phenol formaldehyde resin, m-cresol formaldehyde resin, O- Cresol/formalde and de resin, phenol/p-cresol/formaldehyde copolymer resin, monocresol/p-cresol/formaldehyde copolycondensate resin, 0-cresol/p-cresol/formaldehyde copolycondensate resin, phenol・
Examples include low cresol/p-cresol/formaldehyde copolycondensate resin and phenol/O-cresol/low cresol/formaldehyde copolycondensate resin.

Molecular weight of the novolac resin of the present invention (boristyrene standard)
has a weight average molecular weight MW of 5. OX102~2. OX1
0”, preferably 5.0×1 02 to 3.5
x 1 03 and number average molecular weight Mn is 2.0 x 102 ~ 1
．． Ox104. Preferably 2,0×102 to 1. OX
It is 103.

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

Calculation of number average molecular IMn and tint average molecular depth MW is based on Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka, “Journal of the Chemical Society of Japan”
The method described on pages 800 to 805 (1972) is used to level out the peaks of the oligomer region (connect the centers of the peaks and valleys).

The content of the novolak resin in the photosensitive composition is preferably 30 to 95%, more preferably 50 to 8%.
It is 5% by weight.

The appropriate content of the photosensitive composition in the colored photosensitive layer used in the present invention is, for example, 5 to 80% by weight.

In addition, in the present invention, the colored photosensitive layer may contain a binder in addition to the photosensitive composition, but in this case, the binder must not impair the effects of the present invention, and the preferred binder is A polymer compound is used that is film-forming and solvent-soluble, and preferably dissolves or swells in an alkaline developer.

Specific examples of such polymeric compounds include, for example, polymeric compounds containing a structural unit having an aromatic hydroxyl group represented by the following general formula CI in its molecular structure.

Here, R1 and R2 are a hydrogen atom, an alkyl group, or a carboxylic acid group, R3 is a hydrogen atom, a halogen atom, or an alkyl group, R4 is a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group, and X is a nitrogen atom and an aromatic carbon Connect with atoms 2
In the i group of 1i1i, n is O or 1, and Y is a phenylene group which may have a substituent or a naphthylene group which may have a substituent.

Specific examples of monomers forming such structural units include N-(4-hydroxyphenyl)-(meth)acrylamide, N-(2-hydroxyphenyl)-(meth)acrylamide, N-(4- hydro-oxynaphthyl)
- Monomers of (meth)acrylamides such as (meth)acrylamide; 0-, 11 or p-hydroxyphenyl (meth)acrylate monomers; 01, m1 or p-hydroxystyrene monomers, and the like. Preferably o+, lm- or p-hydrooxyphenyl (meth)
The acrylate monomer is N-(4-hydroxyphenyl)-(meth)acrylamide monomer, most preferably N-(4-hydroxyphenyl)-(meth)acrylamide monomer.

In the present invention, it is preferable to use a copolymer of a monomer forming the structure of the above general formula [E] and any of the following monomers.

Here, R5 represents a hydrogen atom, an alkyl group, or a halogen atom, and R6 represents an alkyl group, a phenyl group, or a naphthyl group.

Aromatic water of the general formula [I] in the above copolymer! The ratio of groups having one group is preferably 1 to 30 mol%.

The proportion of units formed from the acrylonitriles in the polymer compound is preferably 0 to 50 mol%, and more preferably 5 to 40 mol% in consideration of developability. The proportion of structural units formed from the alkyl acrylates is preferably 50 to 95 mol% from the viewpoint of developability with a low alkaline aqueous solution, and most preferably 60 to 95 mol%. Provides excellent developability.

In addition to the above-mentioned structural units, the above-mentioned acrylic acids such as acrylic acid or methacrylic acid may be copolymerized with the above-mentioned structural units in order to finely adjust the developability, and the proportion of the above-mentioned acrylic acids in the polymer compound may be is preferably 0 to 20 mol%, most preferably 0 to 10 mol%, considering the development latitude.

The average molecular weight of such a polymer compound is preferably from 1000 to 100,000, more preferably from 1000 to 30,000, from the viewpoint of developability or resolution when a low alkaline aqueous solution is used as a developer. Preferably, the range is . These polymer compounds can be synthesized by a well-known copolymerization method.

Specific examples of such polymeric compounds include the following CH, (2) Furthermore, in the present invention, a nopolac resin obtained by polycondensation of at least one type of phenol and an active carbonyl compound may also be used as a binder.

These phenols include all compounds in which at least one hydrogen atom bonded to an aromatic ring is substituted with a hydroxyl group, and specifically include phenol, O-cresol, ■-cresol, p-cresol, .5-xylenol, 2,4-xylenol, 2,5-xylenol, carvacrol, thymol, catechol, resorcinol, hydroquinone, vilogol, phloroglucin, alkyl group (1 to 8 carbon atoms) substituted phenol, etc. It will be done.

Examples of active carbonyl compounds include aldehydes and ketones, and specific examples include formaldehyde, acetaldehyde, benzaldehyde, acuturein, furfural, and acetone.

Polymerized resins include phenol formaldehyde novolak resin, 11-cresol formaldehyde novolak resin, phenol/cyclic cresol/formaldehyde copolycondensate resin, phenol/p-cresol/formaldehyde copolycondensate resin, and 11-cresol/p- Cresol/formaldehyde copolycondensate resin, 0-cresol/p-cresol/formaldehyde copolycondensate resin, phenol/O-cresol/m-cresol/
Examples include formaldehyde copolycondensate resin, phenol/O-cresol/p-cresol/formaldehyde copolycondensate resin, phenol/m-cresol/p-cresol/formaldehyde copolycondensate resin, and the like.

Further, other polymeric compounds that can be used as a binder in the present invention include sulfoalkyl esters of (meth)acrylic acid (co)polymers, vinyl acetal (co)polymers, vinyl ether (co)polymers, Also included are acrylic acid (co)polymers, styrene (co)polymers, cellulose derivatives, and the like.

A particularly preferred binder is a polymer compound having a carboxylic acid vinyl ester polymerized unit represented by the following general formula in its molecular structure.

RCOOCH-C port 2 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 CH3 COOCH=C port 2 ■Vinyl blobionate CH3CI-13COOCH-CH2 ■Vinyl acetate CHa (CH2 )2 COOCH=CH20 Vinyl bivalate (CHa)3 0COOCR=C port 2 ■Vinyl turnip acid CH3 (CH2 )4 COOCH-CH2■Vinyl cabrylate CH3 (CH2)S COOC port-C port2■Vinyl caprylate CH3 (CH2)8 COOC}-1=c}-1
2 ■ Vinyl laurate CH3 (C port 2) 10 COOC 1 CH 2 ■ Myristic vinyl CH3 (C port 2) 12 COOC port = C 20 Vinyl valmitate CHs (CH2 ) 14 COOC 10 H20 Vinyl stearate CH3 (C port 2) 16 COOC 1 CH2 @ Versatic Pinyl C 3 1 Rl-C-COOCH-C 2 t R2 (Ri .R2 is an alkyl group, and the sum of its carbon numbers is 7. That is, R' + R2-07 The carboxylic acid vinyl ester monomer is more preferably one in which the main chain of the carboxylic acid has 1 to 4 carbon atoms. Particularly preferred is vinyl acetate.

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 ester, or a polymer that can be copolymerized with carboxylic acid vinyl ester. It may be a copolymer in any composition ratio with the monomer.

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 isobrene, 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 itacone, maleic acid and maleic anhydride, such as diethyl maleate and maleic acid. Diesters of unsaturated dicarboxylic acids such as dibutyl, di-2-ethylhexyl maleate, diptyl fumarate, di-2-ethylhexyl fumarate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid Dodecyl, acrylic! ! 2-chloroethyl, phenyl acrylate, methyl α-chloroacrylate,
α-methylene aliphatic monocarboxylic acid esters such as methyl methacrylate and ethyl ethacrylate; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide; e.g. acrylanilide, p-chloroacrylanilide, m- Anilides such as nitroacrylanilide and di-methoxyacrylanilide, such as methyl 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, 1.1-dimethoxyethylene, 1.2-dimethoxyethylene, 1.
Ethylene derivatives such as 1-dimethoxyrubonylethylene, 1-methyl-1-ditroethylene, such as N-vinylvirol, N-vinylrubazole,
There are vinyl monomers such as N-vinyl compounds such as N-vinylindole, N-vinylpyrrolidene, 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.
Wt%, number average molecular weight (MN) is 1,00
0 to 10,000, weight average molecular weight (MW) is 5
00 to 50,00.0 is preferred.

More preferably, vinegar vinyl polymerized units (especially 40
~95W [%] and a polymer compound having a carboxylic acid vinyl ester polymer unit with a longer chain than vinyl acetate is preferable, and in particular, a polymer compound having a number average molecular ffi (MN) of 2.000 to eo
,ooo, weight average molecular weight (MW) is 10,000~
150,000 is preferred.

In this case, the monomer copolymerized with vinyl acetate to form a polymer compound having vinyl acetate polymerized units may be any monomer as long as it can form a copolymer. You can choose any one from among them.

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■Vinyl acetate-vinyl propionate■Vinyl acetate-vinyl bivalate■Pinyl acetate-vinylacetate■Vinyl acetate-vinyl laurate■Pinylacetate-vinyl stearate■Vinyl acetate-ruversatate Ethylene 0 Vinyl acetate Rubersatic Acid Vinyl-2-ethylhexyl acrylate ■ Vinyl Acetate Vinyl Rubersatic Acid Vinyl Laurate [Co., Ltd.] Vinyl Acetate Rubersatic Acid Nyl Crotonic Acid Propion Dispersed Vinyl Rubersatic Acid O Probionic acid Vinyl Rubersatic acid Vinyl Crotonic acid Bivalic acid Monostearic acid Vinyl maleic acid In the present invention, the colored photosensitive layer contains a dye as a coloring agent,
Pigments are added. In particular, when used for color proofing, the required constant colors, i.e. yellow, magenta, cyan,
Pigments and dyes with a tone that matches black are required, but
Other metal powders, white pigments, and fluorescent pigments are also used. The following examples are some of the many pigments and dyes known in the art.

(C.I means color index).

Victoria Viewer Blue (C.I 42595) Auramine (C.I 41000) Cathylone Brilliant Flavin (Cr Basic 13> Rhodamine 6GCP (C.1 45160) Mouth-Damine B (C.I 45170) Safranin OK70
: 100 (C.I 50240) Erioglaucine I 21090) Shimla Fast Yellow 8GF (C.I 21105) Benzidine Yellow 4 T-5640 (C.I 2
1095 Shimla Fast Red 4015 (C.I.
12355) Lionor Red 7 B4401 (C
．． 1 15830) First Gen Blue TGR -
L (C. + 74160 Lionor Blue SM (
C, 1 26150) Mitsubishi Carbon Black M A
- 100 Mitsubishi Carbon Black #30, #40,
#50}) Cyanine Blue 4920 (manufactured by Dainichiseika Chemicals) Seiryoku First Carmine 1483 (manufactured by Dainichiseika Chemicals) Seiryoku Fast Yellow 1-1-7055 (manufactured by Dainichiseika Chemicals) Colorant in the colored photosensitive layer used in the present invention The content of dye can be 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.For example, in the case of a dye, the content is 5. %
~75%, in the case of pigments, the content is from 5% to 90% by weight
% is appropriate.

The thickness of the colored photosensitive layer can be determined by a method 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. , within the allowable range, the thinner the colored photosensitive layer is, the higher the resolution will be.
Image quality is good. Therefore, the film thickness is from 0.1 μm to
It is usually used in a range of 5 μm.

In addition to the above-mentioned materials, a plasticizer, a coating property improver, etc. may be added to the colored photosensitive layer, if necessary.

Examples of plasticizers include various low-molecular compounds such as phthalates, triphenyl phosphates, and maleates, and examples of coating properties improvers include nonionic surfactants such as ethyl cellulose and polyalkylene ethers. Surfactants such as fluorosurfactants can be mentioned.

Further, the colored photosensitive layer can be divided into two layers: a coloring agent layer made of a colorant and a binder, and a photosensitive layer made of a photosensitive composition and a binder. In this case, it does not matter which layer is present on the support side.

The colored image-forming material of the present invention is imagewise exposed through a color separation mesh film and then developed to form a visible image, and then substantially only the image area is transferred and laminated directly onto the transfer material. At this time, in order to efficiently transfer the colored image onto the transfer surface and to facilitate peeling off the support after image transfer, the surface of the support should be subjected to a release treatment using an appropriate threshold oil-based substance. Alternatively, it is preferable to provide a release layer on the support.

As the magic oil substance, for example, silicone resin, fluororesin, fluorosurfactant, polyolefin, polyamide, etc. can be used.

Since polypropylene films, polyethylene films, etc. exhibit good mold release properties without special mold release treatment, a particularly preferred embodiment is to provide a polypropylene layer or a polyethylene layer that is thinner than the thickness of the support. .

The method for forming a polypropylene layer or a polyethylene layer on a support is as follows: 1) A solution of polyvinyl vinegar powder, polyvinyl chloride, epoxy resin, polyurethane resin, natural rubber, synthetic rubber, etc. dissolved in an organic solvent is used as an adhesive. This is the so-called dry lamination method, in which these adhesives are applied onto a support, dried by hot air or heating, and then a polyethylene film or a polyethylene film is laminated and pressed under heat for lamination.

2) Copolymers of ethylene and vinyl acetate, copolymers of ethylene and acrylic esters, polyamide resins, petroleum resins, O-gins, and waxes are used as adhesives, and these adhesives are heated and melted as they are. While maintaining the condition
Immediately after coating on the support using a doctor blade method, roll coating method, gravure method, reverse roll method, etc.
The so-called hot melt lamination method, in which polypropylene films or polyethylene films are laminated together and laminated by heating at high temperature as necessary and then cooling; 3) Polypropylene or polyethylene film is made into a molten state. The so-called extrusion lamination method involves holding the film, extruding it into a film using an extruder, and pressing and laminating the support while it is still in a molten state. This is a so-called co-extrusion method in which a polypropylene layer or a polyethylene layer is formed on a support film in a single molding process using a standard extruder together with polypropylene or polyethylene in a molten state. etc.

Examples of the release layer include alcohol-soluble polyamide, alcohol-soluble nylon, a blend of a partially esterified resin of a copolymer of styrene and maleic anhydride and methoxymethylated nylon, polyvinyl acetate, polyacrylate, polymethyl Copolymer of methacrylate and acrylate, polyvinyl chloride, copolymer of vinyl chloride and vinyl acetate, polyvinyl butyrate, cellulose acetate phthalate, methyl cellulose, ethyl cellulose, cellulose diacetate, cellulose triacetate 11, polyvinyl alcohol, butyl cellulose , hydroxyethynoresenolose, canoleboxymethinoresenolose,
cyanethylcellulose, cellulose acetate, cellulose triacetate, cellulose acetate butyrate, hydroxybutyrmethylcellulose phthalate,
Hydroxybinyl methylcellulose, hexahydrophthalate, a mixture thereof, and the like can be used.

The thickness of the release layer is suitably in the range of 0.01 μm to 30 μm, particularly preferably in the range of 0.1 μm to 5 μm.

As the support for the colored image-forming material used in the present invention, a polyester film, especially a two-wheel stretched polyethylene terephthalate film, is preferable from the viewpoint of dimensional stability against water and heat, but acetate film, polyvinyl chloride film, polyethylene terephthalate film, etc. Styrene films, polypropylene films, polyethylene films may also be used.

Also, Mae i! Coating methods for coating the colored photosensitive layer on the support include, for example, roll coating, reverse mouth coating, dip coating, air knife coating, gravure coating, gravure offset coating, hopper coating, blade coating, and rondo coating. , wire doctor coating, spray coating, curtain coating, extrusion coating, and other methods are used.

Drying is accomplished by blowing heated air over the coated surface. The heating temperature is preferably 30°C to 200°C, particularly preferably 40°C to 140'C. During drying, the colored photosensitive layer is generally dried while keeping the temperature of the heated air constant, but it is also possible to dry the colored photosensitive layer by increasing the temperature of the heated air in stages. can. Further, the heated air is preferably supplied to the coated surface at a rate of 0.117 seconds to 30 m/sec, and particularly preferably at a rate of 0.5 ml seconds to 20+a/sec. .

An overcoat layer that can dissolve or swell in a developer can also be provided on the colored photosensitive layer. Examples of resins used in the overcoat layer include polyvinyl alcohol, polyethylene oxide, polyacrylic liquid, polyacrylamide, polyvinyl methyl ether, polyvinyl pyrrolidone, polyamide, gum arabic, glue, gelatin, casein, cellulose (e.g. , viscose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxybutyrumethylcellulose, carboxymethylcellulose, etc.), starches (for example, soluble starch, modified starch, etc.), and the like.

The image-wise exposure of the colored image-forming material is carried out by bringing the color separation mesh film into close contact with the colored image-forming material corresponding to each color and exposing the film to ultraviolet light.

As a light source, a mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a tungsten lamp, a xenon lamp, a fluorescent lamp, etc. are used.

Next, development is performed. As a developer for forming a colored image, an alkaline developer containing water as a main solvent is preferably used, and examples of the alkaline agent used in the developer include sodium carbonate, sodium hydrogen carbonate, sodium silicate, and silicate. acid potassium, sodium hydroxide,
Potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic potassium phosphate, dibasic potassium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, bicarbonate Inorganic alkaline agents such as sodium, cum potassium carbonate, ammonium carbonate, ammonium silicate, and organic alkaline agents such as mono-, di- or triethanolamine and tetraalkylammonia hydroxide are used. The content of the alkaline agent in the developer composition is preferably in the range of 0.05 to 30% by weight. It may also contain an organic solvent, a surfactant, a sulfite M salt, a chelating agent such as EDTA, an antifoaming agent such as an organic silane compound, and the like.

In addition, general printing paper such as art paper, coated paper, high-quality paper, synthetic paper, etc. can be used as the transfer material to which the colored image forming material is developed after imagewise exposure and the formed colored image is transferred. can.

Transfer is carried out by bringing the colored image, which has been shaped through imagewise exposure and development, into close contact with the material to be transferred, and applying pressure or applying pressure and heat.

Specifically, this is carried out, for example, by bringing the colored image and the transfer material into close contact with each other and passing them between a pair of nip rolls that are pressurized or pressurized and heated. In the present invention, thermal transfer at low temperatures is possible, and the pressure condition is 1.0 to 10K.
+1/Cm', heating conditions are 60℃~150℃
, the appropriate one-pass speed is in the range of 20 to 160 cn/min.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

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 dispersion of a colored photosensitive composition having the following composition was applied with a wire bar onto the polypropylene surface of a support obtained by dry laminating a polyethylene terephthalate film with a thickness of 50 μm and a polyethylene terephthalate film with a thickness of 25 μm using a dry lamination method. After applying the film to a dry film thickness of 1 μm, it was dried to prepare four colored image forming materials.

Vinyl acetate rubersatate (80:20 parts by weight) copolymer MN 22,000 M W =. 60,000 Pigment black: Carbon black MA-100 (manufactured by Mitsubishi Kasei) Q. 99Q Cyan: Cyanine Blue-4920 (manufactured by Dainichiseika) 0.55 (] Magenta:
Seiryoku First Carmine 1483 (manufactured by Dainichiseika) 0. 680 yellow:
Seika First Yellow Day-7055 (manufactured by Dainichiseika) 0. 68 (7) A color separation net positive film of each color was superimposed on the polyethylene terephthalate film surface of the four-color colored image-forming material obtained by 7 or above, and 5Qc+a was heated using a 4KW metal halide lamp.
Image exposure was carried out for 20 seconds from a distance of
Development was performed by dipping for 0 seconds to form a four-color colored image.

Developer solution> Na2CO3 15Q surfactant (Verex NBL manufactured by Kao Atlas Co., Ltd.) 50! ) Distilled water 1000 (Firstly, the image surface of the black color image and the art paper were brought into close contact with each other, and then passed between a pair of heated Nitro rolls at a speed of 5"O cm/min under a pressure of 5Kg/Cf. After passing, the support was peeled off.The peeling was easily carried out, 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 proof ink image consisting of four colors on the art paper.

The transfer temperature, the dimensional deviation between the four colors, and the degree of color change over time of the image 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 75 μm thick two-wheeled stretched polyethylene terephthalate film using a wire bar so that the dry film thickness was 0.5 μD and dried.

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.

Next, a colored photosensitive layer dispersion having the following composition was applied onto the heat-fusible layer using a wire bar so that the dry film thickness was 1 μm.
Dry.

Vinyl acetate-ethylene (90:10 parts by weight) copolymer MN rich 40,000 MW - 120,000 A color separation net positive film was superimposed on the polyethylene terephthalate film surface of the colored image forming material obtained above, and a 4KW film was applied. Image exposure was carried out for 20 seconds using a metal halide lamp from a distance of 5 Qci, and development was carried out by immersion in the following developing solution for 30 seconds to form a colored image on the support.

Developing solution> 10 ills of NaO surfactant (Verex NBL manufactured by Kao Atlas Co., Ltd.) 50 fJ distilled water 1000 g Next, the image surface of the obtained colored image and high-quality paper were brought together, and a pair of heated 5K between Nitzbrolls! ;By passing at a speed of 5Qcm/min under pressurized conditions of l/Cf,
The colored image was transferred onto high quality paper, and the support of the colored image forming material was peeled off. The colored image, thermofusible viewing layer, and release layer were transferred onto wood-free 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, Toray I01 (1 methanol, 90 a) Next, a colored photosensitive composition dispersion of four colors having the following composition was made by UA, and the dry film thickness was 1 μm. The composition was coated on a release layer to produce four-color image forming materials.

m-Taresol novolac resin (MW-1,000, MN=60◇) 1-naphthoquinone-1,2-diazide-4-sulfonic acid ester 0.616 Q The following binder polymer 4.384 (1 The following pigment The following thoughts Ethyl cellosolve 39.6 g Fluorine surfactant (3M FC-430) 0
．． 25Q Pinder Polymer C H 2 MW=15,000 Pigment Black Carbon Black MA-100 (manufactured by Mitsubishi Ka I5!2) 0.99 (
1 Cyanine: Cyanine Blue 4920 (manufactured by Dainichiseika) 0. 55g magenta:
Seiryoku First Carmine 1483 (manufactured by Dainichiseika) o. eag yellow:
Seika First Yellow} {-7055 (manufactured by Dainichiseika) 0. 680 obtained 4
A color separation mesh positive film of each color is superimposed on the colored photosensitive layer surface of the colored image forming material, imagewise exposed for 60 seconds from a distance of 50 cm using a 4KW metal halide lamp, and developed by immersion in the following developer for 30 seconds. A colored image in four colors was formed.

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

Current solution> Na2CO3 15G surfactant Verex NBL manufactured by Kao Atlas Co., Ltd.) 50 (1) Distilled water 1000 (1 (image receiving layer solution)) Vinyl chloride/vinyl acetate copolymer (composition ratio 75:25, Nissin Chemical) Manufactured by MPR-T-5
> 18o Pentaerythritol Tetraacrylate 11 Q Michler's Ketone 0.1g Penzophenone 0. 640 Baramethoxyphenol 0.018 (] Methyl ethyl ketone 44g The previously obtained yellow image was brought into close contact with the image-receiving layer surface of the image-receiving sheet, and heated between a pair of Nipprols under a pressure of 5K (1/Cf). The yellow color image was transferred onto the image-receiving layer by passing at a speed of 50 cm/min, and the polyethylene terephthalate film on the color image side was peeled off.

Subsequently, the colored image was transferred in the order of magenta, cyan, and black, and the image side of the image-receiving sheet was attached to art paper, and after passing between a pair of Nitro rolls under the same conditions as above, the image-receiving sheet was transferred. 50c with a 4KW metal halide lamp on the polyethylene terephthalate film surface of
The entire surface was exposed for 30 seconds from a distance of m, and then the polyethylene terephthalate film of the image receiving sheet was peeled off.

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

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

(Colored photosensitive layer dispersion liquid composition) ゜m-cresol/p-cresol novolac resin (m/p-6/4.MW-1
,000, MN-6,000) naphthoquinone-1.
2-diazide-4-sulfonic acid ester 0. f316 Q The following binder polymer 4.384 0 The following pigment The following amount Ethyl cellosolve 39.6 9 Fluorine surfactant (FC-430 manufactured by 3M) 0
．． 25o binder polymer phenol-m-cresol-p-cresol (70:
20: 10 parts by weight) Copolymer MN-1,000 MW=2,000 Pigment black: Carbon black MA-100 (manufactured by Mitsubishi Kasei) 0.990 Cyanide: Cyanine Blue-4920 (manufactured by Dainichiseika) 0. 55g magenta:
Seiriki First Carmine 1483 (manufactured by Dainichiseika) 0.68g Yellow: Seika First Yellow H-7055 (manufactured by Dainichiseika) 0. 681; 1. Next, apply an adhesive layer coating solution having the following composition onto the colored photosensitive layer using a wire bar so that the dry film thickness is 5 μm, and dry.
A colored imaging material was prepared.

(Contact @ W1 coating liquid composition) Alicyclic saturated hydrocarbon resin Alcon P-90 (manufactured by Arakawa Chemical, softening point 90°C) 12g Alicyclic saturated hydrocarbon resin Alcon p-100 (manufactured by Arakawa Chemical, softening point 100°C) ) 3g Styrene-butadiene block copolymer Toughblen A (Asahi Kasei Kogyo 1i!) 5 (1 toluene 1001IJ2) Among the colored image-forming materials of each color prepared above, a colored image-forming material using a pigment with a tone matching cyan The adhesive layer surface of the paper and water-resistant white synthetic paper (Beach Coat WEK-110 manufactured by Nisshinbo Co., Ltd.) were brought into close contact, and a distance of 50 cm was applied between a pair of heated nip holes under a pressure of 5 kg/Ct.
The cyan colored imaging material was adhered onto the white synthetic paper via the adhesive layer.

Next, a color separation net positive film corresponding to cyan was superimposed on the support surface of a colored image forming material using a pigment with a tone matching that of cyan, which was adhered onto white synthetic paper, and the film was adhered by a vacuum adhesion method. Image exposure was performed for 20 seconds from a distance of 5Qcm using a 4KW metal halide lamp. Subsequently, after peeling off the support from the cyan colored image forming material after image exposure, development was performed by immersing it in the following developer for 30 seconds, and a white color was obtained. A cyan colored image was formed on synthetic paper.

Developer solution> Sodium carbonate 15 g Surfactant (Perex NBL manufactured by Kao Atlas Co., Ltd.) 50 g Distilled water
1000 (;1) Subsequently, a colored image forming material using a pigment of a tone matching magenta was adhered to the white laminated paper on which a cyan colored image was formed via an adhesive layer, and then the same operation as above was carried out. By applying this, a magenta colored image was formed, and the same operation was repeated for yellow and black to form a color bluefining image consisting of four colors on white synthetic paper. Regarding the same data as in each of the above examples, It is shown in Table 1.

Comparative Example 1 In Example 1, birogallol acetone resin (
The same procedure as in Example 1 was carried out except that 1-naphthoquinone-1,2-diazide-4-sulfonic acid ester (MW=1,000, MN-500) was used.

The same data as for the above-mentioned examples are shown in Table 1.

Comparative Examples 2 to 4 In Examples 2 to 4, the same birogallol acetone resin-naphthoquinone-1,2-diazide-4-sulfonic acid ester as in Comparative Example 1 was used,
Other conditions were the same as in Examples 2 to 4, respectively, and Comparative Example 2
~4. The data are shown in Table-1.

Transfer temperature and X for each of the above examples and comparative examples
The measurement results of the dimensional deviation in the direction, the Y direction, and the degree of coloration of the colored photosensitive layer binder over time 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 during transfer (referred to as the x direction) and in the width direction during transfer (referred to as the y direction). (μm). The dragonfly is 400w+m in the X direction and [
They are arranged at a distance of i00im.

In addition, the degree of coloration over time is the value measured by the degree of binder coloration (yellow coloration a.> of the image transferred to paper as yellow anti-sword vigor. Macbeth anti-IJJ Takido meter R
D-918 was used. If the degree of coloration increases over time, the color change is large and the color fastness is poor. When the degree of coloration increases, the colors of the transferred image, especially cyan, magenta, and yellow, become muddy and the image reproducibility deteriorates.

Table 1 As understood from Table 1, in Examples 1 to 4 of the present invention, good transfer was achieved even at a relatively low transfer temperature, and the dimensional deviation was small. On the other hand, Comparative Examples 1 to 4
Both require considerably high transfer temperatures, and the dimensional deviations are much larger than those of the corresponding examples.

Claims (1)

[Claims] A colored image forming material having a colored photosensitive layer containing at least a photosensitive composition and a colorant on a support, wherein the colored photosensitive layer contains 1,2-naphthoquinonediazide-4-
A colored image-forming material characterized by containing a condensate of sulfonyl chloride and a novolac resin.