JPH01213635A - Material and method for forming transferred image - Google Patents

Abstract

PURPOSE:To obtain a color image for proof which is approximate to an actual printed matter without the presence of a macromolecular film in a non-pattern part by having a photosensitive composition with which an exposed image can be formed possessed not in a microcapsule itself but in a continuous phase and removing the microcapsule in the non-image part with development. CONSTITUTION:The microcapsule basically contains only coloring composition and a photosensitive body participant of the formation of exposed image is incorporated in the continuous phase. By performing a specified developing process to a transfer sheet after exposing the image, the solubility of the photosensitive body in the continuous phase to developer is changed according to the exposed image and the continuous phase is removed from the transfer sheet according to the exposed image. When the photosensitive body which is used in such a case is a positive sensitive material, a positive image is freely formed and when it is a negative sensitive material, a negative image can be freely formed. In case of pressurizing and transferring the transferred image forming material where the image is exposed on a body to be transferred, the microcapsule does not exist in the non-pattern part and a part of the microcapsule is destroyed with a pressure, so that the stain of texture of the non-pattern part can be prevented from occurring.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a transfer image forming material and a transfer image forming method used for forming color proofs and the like.

[Prior Art] In any of the printing methods, lithography, letterpress, or gravure, a picture or photographic image is expressed as a set of halftone dots, and in the case of color printing, the main colors are indigo, red, yellow, and ink. Since the four colors of printing ink are overprinted, a printing plate is created for each color. To make these printing plates,
A halftone dot positive or halftone negative film is required for each color separated printing ink from a color original. The production of these color separation halftone films requires specialized technology, and the quality of the finished product almost never achieves the goals of the planner or customer, and the halftone film must be corrected or replaced during the proofing process. It is normal to do so.

To calibrate the halftone film, create printing plates for each color using the halftone film corresponding to each color, and reproduce a color image by attaching each printing plate to a printing machine and printing in color. However, many proof printing methods are used to examine the corrected parts of the halftone film. This method is
Color images can be easily reproduced from halftone film because the quality is not stable due to many variables such as printing press configuration, ink-water balance, ink amount, etc., and the time required is long. A method is desired.

In contrast, this is a simple color image reproduction method.

US Pat. No. 3,060,024, US Pat. No. 3,671,236
The method described in Japanese Unexamined Patent Publication No. 59-97140 is known.

The first method is described in U.S. Pat. No. 3,060,024, in which an uncolored photopolymerizable photosensitive film that is tacky at room temperature is laminated on an image-receiving sheet by heating, and then the tackiness changes by image exposure. , and then a colored image is formed depending on the degree of adhesion of the applied colored powder.

The second method is described in U.S. Pat. No. 3,671,236, in which a photosensitive film containing a colored photosensitive composition is laminated on an image-receiving sheet, and then a colored image is formed by imagewise exposure and development. It is something.

The third method is described in JP-A No. 59-97140, in which a colored photosensitive film is subjected to imagewise exposure, then developed to form a colored image, and then a photopolymerizable photosensitive composition is formed. A color image is obtained by transferring and laminating the colored image layer onto an image-receiving layer consisting of an image-receiving layer, and then the image-receiving layer on which the color image is formed is re-transferred to the surface of another image-receiving sheet.

However, the above 1. Second. In the third method, there is a polymer film on the image receiving sheet not only in the image area but also in the non-image area, so it looks quite different from the actual printed matter in which the ink is crushed into the paper with a blanket and absorbed to form the image. However, it has been difficult to replace the proof printing method.

As a means to solve the above drawbacks, by using a photosensitive film containing a colorant microencapsulated, the polymer film on the image-receiving sheet, which was essential for image formation in the above method, is no longer necessary, and the pressure roller A transfer image forming method can be considered in which a colored internal phase material is crushed into paper and absorbed to form an image, thereby obtaining a color image that closely resembles an actual printed matter.

As a transfer image forming material using the microcapsules, there has been known a method in which a photosensitive compound is incorporated into the microcapsule particles as a composition. For example, a transferred image in which a photosensitive colored recording layer containing microcapsules containing a photocurable composition as an internal phase (discontinuous phase) and a non-photosensitive microcapsule binder (continuous phase) is provided on a support. By exposing the forming material imagewise and photo-curing the internal phase of the microcapsules in the exposed areas, the uncured microcapsules in the unexposed areas can be cured by overlapping the transfer sheet with the object to be transferred and applying pressure without developing. Method of obtaining an image by transferring only the capsule to the object to be transferred (Japanese Patent Laid-Open No. 62-12
No. 5358), photo-degradable microcapsules containing a compound that generates an acid upon irradiation with light as an internal phase substance and a chemical bond that is decomposed by acid as a microcapsule wall material are used to support the photo-degradable microcapsules. on the body,
If necessary, the image forming material coated with a non-photosensitive binder is image-exposed to reduce the mechanical strength of the microcapsule walls in the exposed area, so that the transfer sheet can be transferred without being developed. A method of obtaining an image by transferring only the photodegradable microcapsules in the exposed area to the transfer target by applying pressure by overlapping the body (Japanese Patent Laid-Open No. 62-576
Publication No. 47), etc.

[Problems to be Solved by the Invention] However, in the above method, when the image-exposed transfer image forming material is pressure-transferred onto the transfer target, microcapsules are present also in the non-image area. There was a disadvantage that part of it was destroyed by pressure, causing background stains in non-image areas.

An object of the present invention is to provide a transfer image forming material and a transfer image forming method that can easily obtain a color image for proofing that does not contain a polymer film in the non-image area and that closely resembles the actual printed matter. It is about providing.

[Means for Solving the Problems] In the present invention, the photosensitive composition for forming an exposed image is not contained in the microcapsules themselves but in the continuous phase,
The above problem was solved by removing the microcapsules in the non-image area by development. That is, the microcapsules basically contain only the coloring composition and do not have a photoreceptor that participates in the formation of exposed images. The photoreceptor involved in forming the exposed image is included in the continuous phase. After the image is exposed to the transfer sheet, a predetermined development process is performed to change the solubility of the photoreceptor in the developer in the continuous phase in accordance with the exposed image, and the continuous phase is removed from the transfer sheet in accordance with the exposed image. Further, when the photoreceptor to be removed is a positive photosensitive material, a positive image can be freely formed, and when it is a negative photosensitive material, a negative image can be freely formed.

That is, the gist of the present invention is to have a colored recording layer on at least one surface of a support, the colored recording layer consisting of a continuous phase and a discontinuous phase uniformly dispersed throughout the colored recording layer, and the continuous phase Contains photosensitive substances and contains alkali.

The solubility in an aqueous developer, which may be present, is changed by light irradiation, and the discontinuous phase is composed of microcapsules containing a colorant that is insoluble in the developer; The present invention relates to a method for forming a transfer image, which is characterized in that image exposure is carried out using the above developer, development is performed using the developer described above to form an image, and the image is transferred under pressure onto a material to be transferred.

The present invention will be explained in detail below.

Supports used in the present invention include polymer films such as polyethylene terephthalate film, polyacetate film, polyvinyl chloride film, polystyrene film, polyethylene film, and polypropylene film, and papers such as high-quality paper, art paper, and release paper. , aluminum, magnesium, copper, zinc, chromium, nickel,
Metal sheets such as iron can be used. In particular, it is preferable to use a biaxially oriented polyethylene terephthalate film having a thickness of about 0.5 to 500 JLm and having good transparency and thermal stability.

These supports may be used as they are, but in order to improve the transferability of the image after image formation, they may be subjected to mold release treatment using an appropriate oil-repellent substance such as silicone resin, fluororesin, or fluorosurfactant. Alternatively, an undercoat layer of alcohol-soluble polyamide, alcohol-soluble nylon, partial esterified product of styrene/maleic anhydride copolymer, polyvinyl alcohol, etc., having a thickness of about luLm may be provided.

The colored recording layer used in the present invention is: (1) a photosensitive colored recording layer containing microcapsules (discontinuous phase component) containing a coloring material as an internal phase and a photosensitive substance, or (2) containing a coloring material as an internal phase. A colored layer containing microcapsules and a non-photosensitive binder that is soluble or swellable in a developer, and a photosensitive colored recording layer that is provided with a photosensitive resist layer containing a photosensitive substance on the colored layer. .

Microcapsules containing the colorant as an internal phase are produced by appropriately using known techniques.

An example of such known technology is "Manufacturing method, properties, and applications of microcapsules" edited by the Department of Pharmaceutical Physical Chemistry, Faculty of Pharmaceutical Sciences, Tokyo University of Science.
(IPC, published in 1978), Microcapsule Research Joint Line “New microcapsule technology, its application development, comprehensive technical data collection of application examples” (Management Development Center,
(Published in 1978), and also published in 1978-12
Interfacial polymerization methods described in JP-A Nos. 6481 and 62-209437: JP-A-55-75736 and JP-A-55-1481
Coacervation method described in Publication No. 91: JP-A-62-
No. 209438, No. 62-125358, No. 55-1
No. 5691, No. 55-51431, Special Publication No. 1982-82
Examples include the in 5 in situ method described in each publication of No. 09. Although the microencapsulation method is not limited to the above, it is preferable to emulsify the internal phase of the microcapsules and then form a polymer film as the microcapsule wall. 5
Preferably it is 0 gm, more preferably 1 to 25 gm.

Dyes and pigments are added as colorants used in the inner phase of microcapsules. Especially when used for color proofing,
Pigments and dyes with tones matching the usual colors required for this purpose, such as yellow, magenta, cyan, and black, are required, but other metal powders, white pigments, fluorescent pigments, etc. are also used. The following examples are some of the many pigments and dyes known in the art.

(C,1, means color index).

Victoria Pure Blue (C, 1,42595) Auramine (C01,41000) Cathylone Brilliant Flavin (C, 1, Basic Rhodamine 6GCP (C, 1,45160) Rhodamine a
(C, 1,45170) Safranin 0K70:100
(C, 1, 50240) Elioglauci: / X (
C, 1, 42080) Fast Black 118 (
C, 1, 26150) No, 1201 Lionor Yellow (C01, 21090) Lionor Yellow GR
Q ((:, 1.21Q90) Shimla Fast Yellow 8GF (C, 1, 21105) Benzidine Yellow 4T-564D (C, 1, 21095) Shimla Fast Red 4015 (C, 1, 1235
5) Lionollet 7B4401 (C, 1, 15
830) First Gen Blue TGR-L (C,1
, 74160) Lionor Blue SM (C, 1, 2
6150) Mitsubishi Carbon Black MA-100 Mitsubishi Carbon Black 130. Cloud 40,150 In addition, the inner phase of the microcapsule contains a solvent, a viscous substance,
Monomers, photoinitiators, etc. can be added as appropriate. Examples include kerosene, naphtha, mineral oils such as paraffin oil, alkylated naphthalenes, alkylated biphenyls, hydrogenated terphenyls, alkylated diphenylmethanes,
Chlorinated paraffins, phthalic acid compounds (e.g. diethyl phthalate, dibutyl phthalate, dioctyl phthalate), salicylic acid compounds! Synthetic oils such as S (e.g. ethyl salicylate), vegetable oils such as peanut oil, linseed oil, soybean oil, corn oil, castor oil, toluene, n-hexane, carbon tetrachloride, butyl acetate, benzene. Volatile solvents, hexanediol, butanediol, diacrylates and dimethacrylates of neopentyl glycol, trimethylolpropane triacrylate and trimethacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxy diacrylates and dimethacrylates of alkylenated bisphenol A, polyhydric alcohols (trimethylolpropane, pentaerythritol, neopentyl glycol,
hydroxypolyether polyacrylates made by adding alkylene oxide to (glycerin, etc.), polyol acrylate compounds such as those mentioned above, polyester acrylate compounds such as polyester acrylates and methacrylates made by adding polybasic acids and polyhydric alcohols,
Urethane acrylate compounds, epoxy compounds (epoxy resins, epoxidized fats and oils, epoxidized polybutadiene, fatty acid modified There are epoxy acrylates made by reacting (meth)acrylic acid, (meth)acrylates having a hydroxyl group, and (meth)acrylates having a carboxyl group with (epoxy resin, etc.). Or a mixture of these may be used.

In addition, when a polyol acrylate compound, a polyester acrylate compound, a urethane acrylate compound, or an epoxy acrylate compound is included as part or all of the internal phase, by adding a photopolymerization initiator, a sensitizer, etc. to the internal phase, The image after development and transfer to transfer paper can be solidified by light irradiation.

Further, as the photopolymerization initiator, any conventionally known one can be used, and for example, benzoin, benzoin alkyl ether, benzophenone, anthraquinone, benzyl, Michler's ketone, a complex system of biimidazole and Michler's ketone, etc. can be suitably used. In addition, in order to effectively sensitize the visible light of an argon ion laser, for example, a composite system of biimidazole and a dialkylaminostyryl derivative, 2,4.6-tris(trichloromethyl)-1,3, A composite system of 5-)-riazine and a cyanine dye derivative, a composite system of 2,4,6-tris(trichloromethyl)-1,3,5-)riazine and a thiapyrylium derivative, etc. are suitable.

When the photosensitive substance used in the continuous phase of the present invention is irradiated with actinic rays, its molecular structure undergoes a chemical change in a short period of time, its solubility changes in the solvent, and certain types of When a solvent is applied, all compounds whose exposed portions are dissolved and removed, and all compounds whose unexposed portions are dissolved and removed are included. Specifically, for example, 0-quinonediazide compounds, 0-nitrobenzyl carbinol ester compounds, etc. are included as photosensitive substances, and these can be used alone or as appropriate, and are soluble in aqueous solutions or solvents that may contain alkali. The photosensitive material includes a photoinsolubilized photosensitive layer that may be used in combination with a polymer, a diazo compound, a compound having an addition-polymerizable vinyl group, etc., and may be used alone or may contain an alkali as appropriate. Examples include photo-insolubilizable photosensitive layers that may be used by mixing with polymers soluble in aqueous solutions or solvents.

The above-mentioned O-quinonediazide compounds are compounds having at least one O-quinonediaside group, preferably an O-penzoquinonediazide group or an O-naphthoquinonediazide group, and include known compounds of various structures, such as J.・"Light Sensitive Systems" by Kosar (published by John Wiley & Sams, 1965), No. 3
Compounds described in detail on pages 39 to 353 are included.

For example, various hydroxyl compounds and benzoquinone-1
, 2-diazide sulfonic acid, naphthoquinone-1,2-diazide sulfonic acid, and the like.

The hydroxyl compounds used include polyhydroxybenzophenones, such as dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, octahydroxybenzophenone, or derivatives thereof, such as halogen atoms, alkyl groups, aryl groups, aralkyl groups, and carboxylic acids. Examples include substituted products of groups, etc., or condensation resins of phenols such as phenol, cresol and pyrogallol, and carbonyl group-containing compounds such as formaldehyde, benzaldehyde and acetone, particularly resins obtained by condensation in the presence of an acidic catalyst.

Preferred hydroxyl compounds include trihydroxybenzophenone, tetrahydroxybenzophenone, phenol-formaldehyde resin, cresol-formaldehyde resin, pyrogallol-acetone resin, resorcinol-benzaldehyde resin, more preferably 2, 3.
4-trihydroxybenzophenone, 2,3,4.4
'-tetrahydroxybenzophenone, pyrogallol
Examples include acetone resin.

The 0-nitrobenzyl carbinol ester compound is obtained by reacting 0-nitrobenzyl (meth)acrylic acid ester with 0-nitrobenzyl alcohol and (meth)acrylic acid chloride in the presence of a polymerization initiator such as benzoyl peroxide. Below, seven polymers containing vinyl groups such as (meth)acrylic acid, (meth)acrylic acid ester, acrylonitrile, N-(4-hydroxyphenyl)(meth)acrylamide, N-(4-cyanophenyl)(meth)acrylamide, etc. - and those obtained by copolymerizing according to a conventional method and having a molecular weight of about 1.000 to soo or soo.

Typical specific examples of O-quinonediazide compounds include:
1.2-naphthoquinone-2-diazido-5-sulfonic acid, 1.2-naphthoquinone-2-diazido-4-sulfonic acid, 1,2-naphthoquinone-2-diazido-6-sulfonic acid, etc. and the above polyhydroxybenzophenone. O-naphthoquinone cyacytosulfonic acid ester; benzoquinone-
1,2-diazide sulfonic acid or naphthoquinone-1,2
- Ester of diazide sulfonic acid and phenol-formaldehyde resin or cresol-formaldehyde resin: Naphthoquinone-1,2-diazide-5-sulfonic acid and resorcinol-benzaldehyde resin described in JP-A-56-1044 ester of naphthoquinone-1,2-diazide sulfonic acid and pyrogallol described in U.S. Pat. No. 3,635,709.
Ester of acetone resin: naphthoquinone-1,2-diazide described in JP-A-55-76346
Examples include esters of 5-sulfonic acid and resorcinol-pyrogallol-acetone copolycondensate.

As a widely used O-quinonediazide compound, a compound obtained by esterifying O-naphthoquinone cyasitosulfonyl chloride with a polyester having a hydroxyl group at the terminal is disclosed in JP-A-50-117503. A homopolymer of p-hydroxystyrene or a copolymer with other copolymerizable monomers as described in JP-A-50-113305 is esterified with O-naphthoquinone cyasitosulfonyl chloride; Ester of bisphenol formaldehyde resin and 0-quinonediazide sulfonic acid described in Japanese Patent Publication No. 54-29922: U.S. Patent No. 3,859,
Condensate of copolymer of alkyl acrylate, acryloyloxyalkyl carbonate, hydroxyalkyl acrylate, etc. and 0-quinonediazide sulfonyl chloride described in the specification of No. 099: Japanese Patent Publication No. 49-17
Reaction products of copolymerization products of styrene and phenol derivatives and O-quinonediazide sulfonic acid described in No. 481: p-aminostyrene as described in U.S. Pat. No. 3,759,711 and others An amide of a copolymer with a copolymerizable monomer and 0-naphthoquinone cyacytosulfonic acid or 0-naphthoquinonecyacytocarboxylic acid is mentioned.

As the diazo compound, a polymeric diazonium salt represented by the following general formula is preferred.

In the formula, R, , R, and R3 are each the same or different,
represents a hydrogen atom, an alkyl group or an alkoxy group, R represents a hydrogen atom, an alkyl group or a phenyl group, X represents a counter anion, n represents a number from 1 to 200, and R
Examples of the alkyl group and alkoxy group of I, R* and R3 include alkyl groups having 1 to 5 carbon atoms and alkoxy groups having 1 to 5 carbon atoms, and examples of the alkyl group of R include those having 1 to 5 carbon atoms. -5 alkyl groups may be mentioned.

Such photosensitive diazo resins can be prepared by known methods such as Photographic Science and Engineering (Photo, Sci, Eng), Vol. 17, p. 33 (1973), U.S. Patent No. 2,063,631, 2
, No. 679,498 according to the methods described in each specification,
It can be obtained by polycondensing a diazonium salt with an aldehyde such as paraformaldehyde, acetaldehyde, or benzaldehyde in sulfuric acid, phosphoric acid, or hydrochloric acid.

Usually, the molar ratio of diazonium salt and aldehyde is 1:0.6 to 1:2, preferably 1:0.
A highly sensitive photosensitive diazo resin can be obtained by charging the components at a ratio of 7 to 1:1.5 and reacting at a low temperature for a short time, for example, at a temperature of 10° C. or lower, for about 3 hours.

The counter anion of the diazo resin includes an anion that forms a stable salt with the diazo resin and solubilizes the resin in an aqueous solution or solvent that may contain an alkali. These include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenyl phosphoric acid, and sulfonic acids, typical examples being methanesulfonic acid, chloroethanesulfonic acid, dodecanesulfonic acid, benzene sulfonic acid, etc. Sulfonic acids, toluenesulfonic acid, mesitylenesulfonic acid and anthraquinonesulfonic acid, 2-hydroxy-
4-methoxybenzophenone-5-sulfonic acid, hydroquinone sulfonic acid, 4-acetylbenzenesulfonic acid,
Aliphatic and aromatic sulfonic acids such as dimethyl-5-sulfoisophthalate, 2,2',4,4'-tetrahydroxybenzophenone, 1,2,3-trihydroxybenzophenone, 2,2',4-) Aromatic compounds containing hydroxyl groups such as hydroxybenzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, perhalogen acids such as C-O1,104, 1/2 S
o, 2-11/2 Z n Cl 2''-, etc., but are not limited to these.

Compounds having an addition-polymerizable vinyl group include compounds having a boiling point of 100°C or higher under normal pressure and having two or more polymerizable terminal ethylene groups, such as unsaturated carboxylic acids, unsaturated carboxylic acids, and aliphatic polyesters. Esters with hydroxy compounds, esters between unsaturated carboxylic acids and aromatic polyhydroxy compounds, unsaturated carboxylic acids and polyhydric carboxylic acids, and polyhydric hydroxy compounds such as the aforementioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds. Examples include esters obtained by the esterification reaction of
For example, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, hydroquinone di(meth)acrylate, etc.
Acrylate, pyrogallol triacrylate, 2.2
'-bis(4-acryloxy-jethoxyphenyl)propane and the like. Other examples include (meth)acrylamides such as ethylenebis(meth)acrylamide and hexamethylenebis(meth)acrylamide, vinyl urethane compounds, and epoxy(meth)acrylate.

A compound having an addition-polymerizable vinyl group is usually used together with a binder and a photoinitiator activated by actinic radiation.

Examples of the binder include copolymers containing at least (meth)acrylic acid and (meth)acrylic acid alkyl ester as constituent components. (Meth)acrylic acid alkyl esters include methyl (meth)acrylate, (
Examples include ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc., and one or more of these are (meth)acrylate. It can be obtained by copolymerizing with acrylic acid and, if necessary, acrylonitrile, N-(4-cyanophenyl)(meth)acrylamide, or styrene, etc., according to a conventional method. Usually, the molecular weight is 1.000 to so, Use something about ooo.

Furthermore, as the photopolymerization initiator, conventionally known ones can be used, and for example, the same kind of compounds as those that can be added to the internal phase of the microcapsules mentioned above can be used.

Examples of polymer compounds include polyamide, polyether, polyester, polycarbonate, polystyrene, polyurethane, polyvinyl chloride and its copolymers, polyvinyl butyral resin, polyvinyl formal resin,
Examples include shellac, epoxy resin, phenol resin, and acrylic resin.

Preferably, the copolymers shown in (1) to (IZ) below, which usually have a weight average molecular weight of 1,000 to 200,000, are used.

(1) Hetamine-1 having an aromatic hydroxyl group, e.g.
-hydroxyphenyl)acrylamide or N-(4-
hydroxyphenyl) methacrylamide, 0-+ m-
+ P-Hydroxystyrene, 〇-1m-1p-hydroxyphenyl-acrylate or methacrylate, (2) Hetamine-1 having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (3) Acrylic acid , methacrylic acid, alpha, beta-unsaturated carboxylic acids such as maleic anhydride, (4) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, acrylic acid-
(Substituted) alkyl acrylates such as 2-chloroethyl, 2-hydroxyethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, etc. (hereinafter referred to as blank space) (5) Methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 2
-Hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-
(Substituted) alkyl methacrylates such as dimethylaminoethyl methacrylate, (6) acrylamide, methacrylamide, N-methylolmethacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N- Acrylamides or methacrylamides such as hydroxyethyl acrylamide, N-phenylacrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenylacrylamide, (7) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, Vinyl ethers such as butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, (8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, etc. (9) Styrene, α-methylstyrene, methylstyrene, chloro Styrenes such as methylstyrene, (10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, (11) Olefins such as ethylene, propylene, imbutylene, butadiene, isoprene, (12) ) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylatetrile, etc. Furthermore, monomers that can be copolymerized with the above-mentioned 100% salts may be copolymerized; It also includes, but is not limited to, copolymers obtained by polymerization modified with glycidyl methacrylate, glycidyl acrylate, and the like.

More specifically, a hydroxyl group-containing copolymer containing the monomers listed in (1) and (2) above is preferred, and an aromatic hydroxyl group-containing copolymer is even more preferred.

Further, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, natural resin, etc. may be added to the above copolymer as necessary.

When the colored recording layer of the present invention is made up of two layers, the colored layer containing the aforementioned microcapsules and the negative photosensitive composition layer, the binder constituting the colored layer is a film-forming product and a solvent-soluble binder. A polymer compound that can be dissolved or swelled is used.

In addition to the above-mentioned polymer compounds, specific examples of polymer compounds suitably used in the colored layer include acrylic acid, methacrylic acid and their alkyl esters or sulfoalkyl esters, phenol resins, polyvinyl butyral, polyacrylamide, ethyl cellulose, acetic acid, etc. Cellulose derivatives such as cellulose acetate, cellulose acetate propionate, cellulose acetate, benzyl cellulose, cellulose propionate, other polystyrene, polyvinyl chloride,
Examples include chlorinated rubber, polyisobutylene, polybutadiene, polyvinyl acetate, and copolymers thereof, cellulose acetate, cellulose propionate, cellulose acetate phthalate, and the like.

In order to produce the image forming material according to the present invention, the photosensitive composition described above may be dissolved in a suitable solvent, the microcapsules described above may be dispersed in this solution, and the solution may be coated on a support.

As a solvent, water, methanol, ethanol, acetone, ethyl acetate, methyl cellosolve, ethyl cellosolve,
dioxane, methyl ethyl ketone, cyclohexanone,
Diethylene glycol monomethyl ether, γ-butyrolactone, tetrahydrofuran, methylene chloride,
Examples include ethylene chloride, dimethyl sulfoxide, dimethyl formamide, etc., and these can be used alone or in combination of two or more.

Next, a method of forming an image using the above image forming material will be explained.

The image forming material according to the present invention produced in this manner is first imagewise exposed to actinic light.

Image exposure can use conventional radiation sources. Exposure techniques that may be used include a variety of light sources, such as ultra-high pressure mercury lamps, tungsten lamps, mercury lamps, xenon lamps, fluorescent lamps, CRT light sources, laser light sources, etc., using ultraviolet or visible light.

If the image-forming material of the present invention is subjected to image exposure using such a light source and then developed using an aqueous alkaline solution or an aqueous solution containing an organic solvent and an alkali, a corresponding image is formed on the support and a colored transfer sheet is formed. get.

The alkaline aqueous solution has a pH of 8 to 13. Preferably pH 9
~12. In addition, this aqueous solution may further contain a buffer, a surfactant, a dye, or a pigment.

Suitable alkaline agents include inorganic alkaline agents such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium bicarbonate, and trimethylamine. , diethylamine, monoisopropylamine, n-butylamine, monoethanolamine, jetanolamine, triethanolamine and the like, and these can be used alone or in combination. Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; alkylbenzene sulfonates; , alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts, etc.; amphoteric surfactants such as alkyl betaines, amino acids, etc. can be used; It is appropriate to contain it within a range of % by weight.

When an organic solvent is mixed into an aqueous solution containing an alkali, it is appropriate to contain the organic solvent in an amount of 1 to 50% by volume, preferably 2 to 25% by volume.

As the organic solvent, for example, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, diacetone alcohol, etc. can be included as necessary, and it is particularly preferable to select one from those that are miscible with water.

The colored transfer sheet is usually applied to the transfer target at a temperature of 25 to 200"C.
A desired image can be formed on the transfer target by pressing with a roller or the like at a speed of 11 to 300 kg/cm'' and 0.05 to 50 m/min.

As the material to be transferred, paper such as high-quality paper, art paper, and coated paper, plastic film such as polyester film, acetate film, and polypropylene film, metal film such as aluminum film and copper film, or composite materials thereof are used.

Also, numerous techniques can be used to rupture microcapsules. The most common technique is the application of pressure rollers. The amount of pressure applied should be adjusted so that microcapsules in unexposed or underexposed areas are forced to rupture and exude their contents.

Besides pressure, microcapsules can be designed to rupture by heat or ultrasonically.

[Effects of the Invention] As explained above, according to the transfer image forming material and the transfer image forming method of the present invention, the photosensitive composition for forming an exposed image is not contained in the microcapsules but in the continuous phase,
Since the microcapsules in the non-image areas are removed during development, it is possible to obtain a color image for proofing that closely resembles the actual printed matter without causing background smudges in the non-image areas.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples.
It will be clear that the invention is not limited to these examples.

Synthesis Example 1 (Production method of microcapsules) Into a 500su stainless steel beaker, 250g of water, 2.5g of Z
onyl-A (manufactured by DuPont, surfactant), 1.0g
Newcol 7073F (surfactant made by Nippon Nyukazai) was weighed, and the pH was adjusted to 4.0 using a 20% aqueous sulfuric acid solution.
After adjusting the aqueous solution to 7% using a homogenizer,
While stirring at 000 r, p, m, 52 g of the composition for internal phase described below was added, and stirring was continued for 1 hour to obtain an emulsion. Next, the temperature was set to 65°C, and the rotation speed of the homogenizer was set to 300°r, p, 1. 8.3 in 10g of water
g of urea, 0.8 g of resorcinol in 10 g of water, 2
1°6g formalin (37%), 0°6 in 10g water
g of ammonium sulfate was added at 2 minute intervals, and heating and stirring was continued for 3 hours.Heating was then stopped, 2.8 g of sodium bisulfite was added, and after cooling the capsule preparation to room temperature, water, methyl cellosolve were added. Wash the microcapsules with
It was filtered and taken out. The average particle diameter of the obtained microcapsules was 4 JLm.

As the internal phase, 6 g of Mitsubishi Carbon Black (registered trademark) Mloo (manufactured by Mitsubishi Chemical Industries, Ltd.) as a black pigment was dispersed in 70 g of trimethylolpropane triacrylate.

In addition, three types of microcapsules using each pigment were obtained in the same manner except that the following yellow, magenta, or cyan pigments were used instead of the black pigment in the inner phase.

Pigment yellow: Lionor Yellow GR (manufactured by Toyo Ink Manufacturing ■) Magenta: Fastgen Super Red (manufactured by Dainippon Ink Chemical Industry ■) Cyan: Lionor Blue NCB (manufactured by Toyo Ink Manufacturing ■) (Example 1) The following photosensitive Apply the coating solution to the polyethylene terephthalate (hereinafter referred to as PET) support using a wire bar #6.
The mixture was coated onto a film to obtain four types of transfer image forming materials each having a colored recording layer corresponding to each of the four colors and having a film thickness of 6 μm.

After vacuum adhering the image film to the PET film side of the transfer image forming material, 1OOIJ/cm" from the film side.
After image exposure, sodium carbonate was dissolved in one volume of water at 25° C. and developed by rubbing for 1 minute with a developer adjusted to pH 9 to obtain colored image transfer sheets corresponding to each of the four colors.

The colored image transfer sheet is pressed onto peach coated paper using a 200 kg/cm'' pressure fixing roller so that the colored image and the peach coated paper are in contact with each other, and the transferred image is obtained on the beach coated paper. A good transferred image was obtained by repeating the transfer on the same beach coated paper using

(Example 2) Photosensitive coating below! 11 solution with wire bar #6.

Coated on the support l)ET film to a film thickness of 6 μm.
Four color transfer image forming materials each having m colored recording layers were obtained.

A colored image transfer sheet was obtained in the same manner as in Example 1 except that the transfer image forming material was used, and image ft transfer was performed. As a result, a good transferred image was obtained on peach coated paper.

(Example 3) Apply the photosensitive coating solution below with a wire bar #6.

A PET film serving as a support was coated with a film thickness of 6 pm, and a polyvinyl alcohol aqueous solution was further coated with a film thickness of 21 Lm to obtain transfer image forming materials for each of the four colors.

A colored image transfer sheet was obtained in the same manner as in Example 1 except for using the transfer image forming material, and the image was transferred. As a result,
Good transferred images were obtained on peach coated paper.

(Example 4) The following colored layer coating solution was coated on a PET film as a support to a thickness of 6 gm using wire bar well 6 to form a colored layer, and the following photosensitive coating solution was further coated on wire bar well 6 to form a colored layer. Step 6: Coat the colored layer to a thickness of 2 μm, and further apply a polyvinyl alcohol aqueous solution to a thickness of 2 μm.
pm to obtain transfer image forming materials for each of the four colors.

A colored image transfer sheet was obtained in the same manner as in Example 1 except for using the transfer image forming material, and the image was transferred. As a result,
Good transferred images were obtained on peach coated paper.

Claims (2)

[Claims] (1) having a colored recording layer on at least one surface of the support;
The colored recording layer consists of a continuous phase and a discontinuous phase that is uniformly dispersed throughout the colored recording layer, and the continuous phase contains a photosensitive substance and is soluble in an aqueous developer that may contain an alkali. 1. A transfer image forming material, wherein the discontinuous phase changes upon irradiation with light, and the discontinuous phase consists of microcapsules containing a coloring material insoluble in the developer. (2) having a colored recording layer on at least one surface of the support;
The colored recording layer consists of a continuous phase and a discontinuous phase that is uniformly dispersed throughout the colored recording layer, and the continuous phase contains a photosensitive substance and is soluble in an aqueous developer that may contain an alkali. is changed by light irradiation, and the discontinuous phase is subjected to image exposure to a transfer image forming material consisting of microcapsules containing a coloring material insoluble in the developer, and is developed with the developer to form an image. . A transfer image forming method, which comprises transferring the image onto a transfer material under pressure.