JP2001310555A - Microencapsulated transfer imaging system and developing sheet for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a system and a sheet capable of forming a higher gross image and improved in handling after the image is formed. SOLUTION: A microencapsulated transfer imaging system comprises an image forming sheet 20 in which a photosensitive layer 22 is formed on a support member 21, the photosensitive layer 22 at least containing a photosensitive microcapsule 24 which encapsulates a photosensitive composition which increases in viscosity, is hardened or softened by a light having a predetermined wavelength and a chromogenic material corresponding to the predetermined wavelength with which the photosensitive composition reacts, and a developer sheet 10 in which a developing layer 14 is formed on a support member 12, the developing layer 14 containing a developer material which reacts with the chromogenic material to form a color image, wherein after the image forming sheet 20 is image-wise exposed to light and press-contacted with the developer sheet 10 to form an image on the developer sheet 10, the surface of the developer sheet 10 is treated with a surface treating liquid which at least contains a photo-initiator and a photo-curable unsaturated compound, and then radiated with a predetermined light capable of curing the photo-curable unsaturated compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive image forming system of the type using a microcapsule containing a photosensitive composition in an internal phase, and more particularly to a system capable of forming a high gloss image and developing an image after development. The present invention relates to a microencapsulated transfer image system having no stickiness on the surface and excellent in handleability, and an improvement of a color developing sheet for the system.

[0002]

BACKGROUND OF THE INVENTION Photosensitive imaging systems of the type using microcapsules containing a photosensitive composition in the internal phase include U.S. Pat. Nos. 4,399,209 and 4,416,966 and
Some are proposed in U.S. Patent Application No. 320,643, filed January 18,1982.

In these conventional image forming systems using microcapsules, an image forming sheet having a photosensitive layer containing a microcapsule containing a photosensitive composition in an internal phase forms an image on an actinic ray of visible light of a predetermined wavelength. Target (image-
wise). In the most typical embodiment, the photosensitive composition is a photopolymerizable composition containing a polyethylene unsaturated compound and a photoinitiator, and a color former is encapsulated in the microcapsules together with the photopolymerizable composition. Is encapsulated.

The exposure (exposure) of these image forming sheets is
The photopolymerizable composition encapsulated inside the microcapsules is imagewise cured by light irradiated by exposure (exposure). After the exposure (exposure), the image forming sheet includes a color developing sheet having a color developing layer containing a color developing substance that develops a predetermined color by reacting with the color forming agent encapsulated in the microcapsules. A transfer-type photosensitive image forming system in which the photosensitive layer and the developing layer are superposed so as to be in face-to-face contact with each other and passed through a nip between a pair of pressure rollers to apply a uniform destructive force is disclosed in U.S. Pat. No.

In these transfer-type photosensitive image forming systems, when the image forming sheet passes through a pressure roller and comes into contact with a color developing sheet, the microcapsules which have been thickened or cured imagewise by exposure (exposure) are cured. By being imagewise destroyed in response to the situation, the inner phase containing the color former is released, and the released color former migrates to the color developer sheet and reacts with the color developer, thereby causing color development. Form an image.
These imaging systems can be designed to reproduce single or multi-color full color images.

[0006]

However, in these transfer-type photosensitive image forming systems, as described above, the internal phase containing the color former is transferred from the image forming sheet to the color developing sheet, and is transferred to form an image. Therefore, an image to be formed is exposed on the surface, and it is not only difficult to obtain an image having high gloss, but also the internal phase containing the transferred color former,
If it remains on the image surface, it will cause stickiness on the image surface, etc.
There was a problem that there was a difficulty in handling.

Therefore, the present invention has been made in view of the above-mentioned problems, and can form a high gloss image,
It is an object of the present invention to provide a microencapsulated transfer image system which has no stickiness or the like on an image surface after development and is excellent in handleability, and a color developing sheet for the system.

[0008]

In order to solve the above-mentioned problems, a microencapsulated transfer imaging system according to the present invention comprises a photosensitive composition which is thickened or hardened or softened by light of a predetermined wavelength inside a capsule. An image forming sheet having a photosensitive layer containing at least a photosensitive microcapsule containing therein a product and a chromogen substance corresponding to the predetermined wavelength to which the photosensitive composition reacts; and
A color developing sheet containing a color developing substance that forms an image by reacting with the chromogenic substance, and a color developing sheet formed on a support member, comprising: A surface treating solution containing at least a photoinitiator and a photocurable unsaturated compound after imagewise exposing the sheet and forming an image on the sheet for color development by pressure contact with the sheet for color development. Wherein the surface of the color developing sheet is treated, and thereafter, irradiation of predetermined light capable of curing the photocurable unsaturated compound is performed. According to this feature, after the image formation by the pressure contact, a surface protective layer is formed by curing the surface treatment liquid on the surface of the color developing sheet, so that not only a high gloss image can be obtained, but also the image can be obtained. There is no stickiness or the like on the image surface after formation, and the handleability can be improved.

[0009] In the microencapsulated transfer image system of the present invention, it is preferable that the microcapsules include individual capsule walls. If you do this,
By making the size of the microcapsules appropriate, the pixel size of the formed image can be maintained at an appropriate extremely small size, and as a result, an image with excellent resolution can be obtained.

In the microencapsulated transfer image system of the present invention, it is preferable that the chromogenic substance is a substantially colorless electron donating compound, and the developing substance is an electron accepting compound. In this way, by making the chromogenic substance a substantially colorless electron-donating compound, the irradiated light can reach the photosensitive material effectively.

[0011] In the microencapsulated transfer image system of the present invention, the electron accepting compound is preferably selected from the group consisting of acidic clays, aromatic carboxylic acids and their polyvalent metal salts, phenolic resins and their polyvalent metal salts, and aromatic compounds. It is preferably at least one of polymers of aromatic carboxylic acids and aldehydes or acetylene, and polyvalent metal salts thereof. In this case, these electron-accepting compounds have excellent versatility, and can be easily and inexpensively obtained.

The color-developing sheet for a microencapsulated transfer image system of the present invention has a color-developing layer containing at least a reactive color-developing substance which reacts with a predetermined chromogen substance to form an image. A color developing sheet used in the microencapsulated transfer image system formed in the above, wherein the reactive color developing material reacts with the almost colorless chromogen material by pressure contact to form an image. After treating the surface of the color developing sheet with a surface treatment liquid containing at least a photoinitiator and a photocurable unsaturated compound, irradiating a predetermined light capable of curing the photocurable unsaturated compound. Characterized by having a protective layer formed by: According to this feature, after the image formation by the pressure contact, a surface protective layer is formed by curing the surface treatment liquid on the surface of the color developing sheet, so that not only a high gloss image can be obtained, but also the image can be obtained. There is no stickiness or the like on the image surface after formation, and the handleability can be improved.

In the color developing sheet for a microencapsulated transfer image system of the present invention, the photocurable unsaturated compound is preferably a polyfunctional ethylenic photocurable unsaturated compound. In this way, these polyfunctional ethylenic photocurable unsaturated compounds effectively receive active groups (radicals) generated by an appropriate photoinitiator, and efficiently polymerize (cur) by radical polymerization. Will be done.

In the color developing sheet for a microencapsulated transfer image system of the present invention, the photoinitiator is preferably a photoradical initiator. With this configuration, the photo-initiator is a photo-radical initiator, and by irradiating light of a predetermined wavelength corresponding to the photo-radical initiator, the surface treatment liquid is cured quickly and at a relatively low temperature. Can be done.

In the color developing sheet for a microencapsulated transfer image system of the present invention, it is preferable that the reactive color developing material is an electron-accepting compound. If you do this,
The electron accepting compound can obtain good color development,
It is suitable as a reactive developer.

In the color developing sheet for a microencapsulated transfer image system according to the present invention, the electron-accepting compound may be an acid clay, an aromatic carboxylic acid, a polyvalent metal salt thereof, a phenol resin or a polyphenol resin thereof. It is preferably at least one of a valent metal salt, a polymer of an aromatic carboxylic acid and an aldehyde or acetylene, and a polyvalent metal salt thereof. In this way, each of these substances has excellent versatility as a reactive color developing substance, and can be easily and inexpensively obtained.

As used herein, the term "microcapsules" refers not only to microcapsules having individually and individually separated capsule layers, but also to microcapsules formed by dispersing a photosensitive composition in an appropriate binder. It includes both microcapsules in the phase state.

[0018]

Embodiments of the present invention will be described below with reference to the drawings. The image forming system of the present invention is composed of an image forming sheet on which a photosensitive layer containing photosensitive microcapsules is formed, and a color developing sheet used in pairs with the image forming sheet to form an image by transfer. I have. Examples of the image forming sheet and the color developing sheet used in the present invention include an image forming sheet disclosed in U.S. Pat. No. 4,399,298, and a photosensitive composition, a photoinitiator, a color former, a wall forming agent, and a capsule. The development and development techniques can also be used in the present invention.

FIG. 1 shows a typical example of the color developing sheet of the present invention.
Shown in The developing sheet 10 shown in FIG. 1 has a structure in which a developing layer 14 containing a reactive developing substance is provided on one surface of a support member 12 having appropriate mechanical strength.
As the reactive developer used in the above, a developer which is generally used, in particular, a developer used in pressure-sensitive recording can be used.

FIG. 2 shows an example of the image forming sheet used in the present invention. Image forming sheet 2 shown in FIG.
Reference numeral 0 denotes a structure in which a photosensitive layer including the photosensitive microcapsules 24 is formed on one surface of the support member 21 having appropriate mechanical strength. The photosensitive microcapsules 24 shown in FIG. 2 have discrete capsule walls 25, and contain a photosensitive composition curable by visible light of a predetermined wavelength and an internal phase containing a chromogen substance in some cases. It can be obtained by encapsulation.

These image forming sheets 20 are exposed (exposed) by irradiating image light from the photosensitive layer 22 side, and after the exposure (exposure), as described in US Pat. No. 4,399,209. The exposed (exposed) image forming sheet 20 is, as shown in FIG.
In a superimposed state facing the 0 color developing layer 14, it is sandwiched between a pair of rollers and pressed to apply a uniform breaking force.

Further, the photosensitive microcapsule 2 of the present invention
4 is shown in FIG. The photosensitive microcapsule 2
Reference numeral 4 denotes a photo-curable composition which is hardened by actinic radiation, which is light of a predetermined wavelength, as an internal phase inside capsule walls 25 which are individually independent. In the exposed area at the time of the exposure (exposure), the internal phase 26 is solidified or gelled by the photoreaction, whereas in the exposed area of the unexposed (exposure) area, the liquid is not solidified or gelled by the photoreaction. Will remain. In the region of intermediate exposure (exposure), the internal phase is solidified or gelled at an intermediate degree, or part of the internal phase is solidified due to a change in the size of the microcapsules, and the other part is liquid. Is obtained.

Specifically, as shown in FIG. 4, the color development (developing) is achieved by passing a pair of the image forming sheet 20 and the color developing sheet 10 between two pressure rollers. Other means, such as heating, ultrasonic vibrations and exfoliation, may also be used to break the microcapsules.

At the time of color development (development), the photosensitive microcapsules 24 in the unexposed area or the intermediately exposed area where the internal phase is not sufficiently cured by the pressure of the pressure roller are broken, and the internal phase Is released and transferred to the color developing sheet 10, and the image 3 is placed in the color developing layer 14.
0 is formed. At this time, it is not clear whether or not the photosensitive microcapsules 24 in which the internal phase 26 has been hardened in the exposure (exposure) actually break, but since the internal phase 26 is hardened even if it is broken, The transition due to the release of the internal phase contributes little or little to image formation.

Next, in the microencapsulated transfer image system of the present invention, as shown in FIG. 5, a high gloss protective layer 32 made of a photocurable resin is formed on the image formed by developing (developing). Is done.

The color developing sheet 10 used in the present invention
The reactive developer contained in the developer layer 14 of the image forming sheet 20 may react with a chromogen substance associated with the microcapsules 24 contained in the photosensitive layer 22 of the image forming sheet 20 and form a color image. Is selected. In the most typical embodiment, the chromogenic material is a substantially colorless electron-donating compound of the type commonly used in pressure-sensitive recording technology,
The developer substance is preferably an electron-accepting compound.

The reactive developers used in the present invention include those commonly used in carbonless paper, for example, visible clay, activated clay, atabalgit, etc .: sexual acids such as tannic acid, gallic Acid, propyl gallate,
Aromatic carboxylic acids such as benzoic acid, p-t-butyl-
Benzoic acid, 4-methyl-3-nitrobenzoic acid, salicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3-t-butyl-5-methylsalicylic acid, 3,5-di-t-butylsalicylic acid, 3-methyl -5-Penzyl salicylic acid, 3-phenyl-5- (α, α-dimethyl pendyl) salicylic acid, 3-cyclohexyl-5- (α, α-dimethyl pendyl) salicylic acid, 3- (α, α-dimethyl pen (Zyl) -5-methylsalicylic acid, 3,5-di-cyclohexylsalicylic acid, 3,5-di- (α-methylpentyl) salicylic acid, 3,5-di- (α, α-dimethylpenzyl) salicylic acid, 3- ( α-methylpentyl) -5-
(Α, α-dimethylpentyl) salicylic acid, 4-methyl-5-cyclohexylsalicylic acid, 2-hydroxy-1-
Penzyl-3-naphthoic acid, 1-benzoyl-2-hydroxy-3-naphthoic acid, 3-hydroxy-5-cyclohexyl-2-naphthoic acid and the like, and polyvalent metal salts thereof, for example, zinc salts, aluminum salts, magnesium Salts, calcium salts and cobalt salts (U.S. Pat.
3,854146, 3,924,027 and 3,983,292), phenolic compounds such as 6,6-methylenebis- (4-chloro-m-cresol (Japanese Patent Publication No. 40-9809, Japanese Patent Publication No. 4220144) (Publications and JP-B-48-14409): Phenolic resins, such as phenol-aldehyde resins, such as p-phenyl-phenol-formaldehyde resin and phenol-acetylene resins, such as p-tert-butylphenol-acetylene resin ,
And their polyvalent metal salts such as zinc-modified phenyl-formaldehyde resins (disclosed in U.S. Pat. No. 3,732,120), acid polymers such as maleic-rosin resins and maleic anhydride with styrene, ethylene or vinyl methyl ether. It can be selected from among copolymers, aromatic carboxylic acid-acetylene polymers and polyvalent metal salts thereof (disclosed in U.S. Pat. Nos. 3,767,449 and 3,772,052).

The developer is formed on the support member 12 by a method of blending the developer with a commonly known binder. As a binder which contains these developers,
Binder latex, polyvinyl alcohol, maleic anhydride-styrene copolymer starch, gum arabic, and the like can be used. After mixing the developer with a binder, the support member 12 has appropriate mechanical strength. For example, it can be formed by coating one surface of the support member 12 by coating and drying on paper, or may be formed by directly applying the color developer itself without using the binder.

The photocurable composition used for the inner phase 26 of the photosensitive microcapsules 24 includes, in the case of a positive working material, a photoinitiator and a monomer or polymer which can be polymerized to a higher molecular weight. Contains monomers or oligomers or polymers that are cross-linked upon exposure. In the case of a negative working material, a compound which can be depolymerized or decomposed upon exposure is used.

As the material of the photocurable composition in the case of the positive working material, an ethylenically unsaturated organic compound is a useful photosensitive material. These compounds contain at least one ethylene end group per molecule. Typically, liquid ethylenically unsaturated compounds having two or more ethylene end groups per molecule are preferred, and those having a plurality of ethylene end groups include ethylenically unsaturated acid esters of polyhydric alcohols For example, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, (TMPTA) and trimethylolpropane trimethacrylate are exemplified.

Further, the radiation-sensitive composition useful as a material for the photocurable composition includes an acrylate which is derived from a partial reaction of pentaerythritol with acrylic acid, methacrylic acid, an acrylate or a methacrylate. Prepolymers are exemplified. Further, examples of other substances useful as a material for the photocurable composition include, for example, isocyanate-modified acrylates of polyhydric alcohols, esthyl methacrylate, and itaconic esters.

[0032] Photopolymerizable prepolymers are also useful in the present invention. Suitable prepolymers can be selected from commercially available acrylate-terminated polyesters and polyethers, and generally these compounds are end-capped with isocyanate-terminated prepolymers with acrylic acid or methacrylic acid. Generated by

These prepolymers have a molecular weight of about 16,0
It can range up to 00, but in most cases the molecular weight does not exceed about 1000-3000. If the molecular weight of the prepolymer is too high, the viscosity may be so high that the prepolymer may not be properly emulsified in a continuous phase, for example, water which is a solvent for encapsulation. However, even these high-viscosity prepolymers having a high viscosity can be used in the present invention by dissolving and diluting them in a prepolymer or a monomer having a lower molecular weight, such as TMPTA.

The acrylate-terminated urethane prepolymers having an acrylate terminal functional group and useful in the present invention include Chemball 19-4832 and Chempol 19-4833, available from Freeman Chemical Corporation. Upitane 893, 788, 782 and 783 available from Corporation; Ebecryl 220, 204, 210 available from Virginia Chemicals, Inc.
And 240 are exemplified.

Epoxy acrylate prepolymers also useful in the present invention include Chempol 19-4824 and Chempol 19-4825 from Freeman Chemical Corporation, and Celrad 3200, 3700 from Celanese Corporation. And 3701,
Examples include epecryl 600 series prepolymers from Virginia Chemicals, Inc.

Further, the image forming system that operates negatively is as follows.
The inner phase 26 can be obtained by encapsulating a photosoftening composition in microcapsules. Photosoftening materials that may be useful in the present invention include 3-oximino-2-butanone methacrylate, poly-4'alkylacylophenones, and certain resins having quinonediazide residues that undergo major disruption upon exposure to ultraviolet light. Kind.
(E. litchi manis. Am. Chem. Soc. Div. Org. Coat. P.
last. Chem. Prepr. 1980.43, 243-251 and I, Lukak, B, Thimera, Int. on.Modif. Polym. 5 ^th B
latislave. Czech, 3-6 July 1979, IUPAC Oxford, UK 1979, 1, 176-182)

In most cases, the photosensitive composition contains a photoinitiator. A hemolytic photoinitiator that is converted to active by radiation and generates a radical by extracting hydrogen from a hydrogen donor, or a photoinitiator that forms a free radical by complexing with a sensitizer, or a sensitizer. Any of the photoinitiators that otherwise generate radicals in the presence can be used. As long as the photosensitive material used in the photosensitive composition is cured by ionic polymerization, the photoinitiator may be one that generates anions or cations depending on the characteristics of the polymerization.

Photoinitiators useful in the present invention include diaryl ketone derivatives and benzoin alkyl ethers. These photoinitiators are appropriately selected based on the desired system sensitivity. If UV sensitivity is desired, suitable photoinitiators include, for example, alkoxyphenyl ketones, O-acylated oximinoketones, polycyclic quinones, benzophenones and substituted benzophenones, xanthones, thioxanthones And halogenated compounds such as chlorosulfonyl and chloromethyl polynuclear aromatic compounds, chlorosulfonyl and chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethylbenzophenones, fluorenones and haloalkanes. It is often advantageous to use a combination of imaging photoinitiators.
One desirable combination in the case of these ultraviolet sensitivities is a combination of Michler's ketone and benzoin methyl ether (preferable ratio 2: 5). Other useful combinations include 2.2-dimethoxy-2-phenylacetophenone, isopropylxanthone and ethyl p-dimethylaminobenzoate. The latter is preferably for providing a radiation-sensitive composition
Used with TMPTA.

Next, an organic borate salt of a cationic dye which is another organic borate salt suitably used as a photopolymerization initiator in the present invention will be described. The organic borate salt of a cationic dye suitable for the present invention is preferably a compound represented by the following general formula (I).

Embedded image Here, D ⁺ represents a cationic dye, and R ¹ , R ² , R ³
And R ⁴ may be the same or different and include a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group, Selected from an unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted allyl group, and a substituted or unsubstituted silyl group R ¹ , R ² , R ³
And R ⁴ may form a cyclic structure by combining two or more groups thereof.

As the cationic dye represented by D ⁺ ,
It is preferably a dye selected from cationic methine dyes, polymethine dyes, triarylmethane, indoline, azine, xanthene, oxazine and acridine dyes. Further, the cationic dye is preferably a dye selected from cationic cyanine, hemicyanine, rhodamine and azamethine dyes.

The organic borate salt of the organic cationic dye represented by the general formula (1) uses an organic cationic dye and an organic boron compound anion.
It can be obtained by referring to the method described in No. 7A1.

The general formula (I) which can be used in the present invention
As the cationic dye (spectral sensitizing dye) represented by D ⁺ , a wavelength region of 500 nm or more, preferably 550 to 550 nm
Any organic cationic dye having an absorption peak in a wavelength region of 1100 nm can be used.

Examples of the organic cationic dyes usable in the present invention include cationic methine dyes, cationic carbonium dyes, cationic quinone imine dyes, cationic indoline dyes, and cationic styryl dyes. As the methine dye, preferably polymethine dye, cyanine dye, azomethine dye, more preferably cyanine, carbocyanine, dicarbocyanine, tricarbocyanine, hemicyanine, etc.
As the cationic carbonium dye, preferably a triarylmethane dye, a xanthene dye, an acridine dye, more preferably rhodamine and the like, and as the cationic quinone imine dye, preferably an azine dye, an oxazine dye, a thiazine dye, a quinoline dye, Dyes selected from thiazole dyes and the like can be mentioned, and these can be used alone or in combination of two or more.

Many of these organic cationic dye compounds having an absorption peak in the wavelength region of 500 nm or more are known. For example, "Functional dye chemistry"
1981, CMC Publishing Co., pp. 393-416 and "Coloring Materials", 60 [4] 212-224 (1987).

The amount of photoinitiator used in the photosensitive composition is
It depends on the particular photosensitive material chosen. The photoinitiator must be present in an amount sufficient to initiate the photochemical reaction within a short exposure time. Photoinitiators can be used to sequester oxygen present within the microcapsules, and inhibit photopolymerization by performing a non-image forming oxygen sequestration pre-exposure or co-exposure. If the photoinitiators are also consumed in sequestering oxygen, the amount of these photoinitiators is
It must be sufficient to satisfy both the oxygen-sequestering function and the image-forming function.

Various compounds can be used as the chromogenic substance of the present invention. These chromogenic substances can be encapsulated as the above-mentioned internal phase 26 together with the photosensitive composition. It is preferable that the sensitivity of color development by the chromogenic substance does not decrease. Chromogenic substances useful in the present invention are colorless electron-donating compounds. Representative examples of such color formers are substantially colorless compounds having a lactone, lactam, sultone, spiropyran, ester or amide structure in their partial skeleton, such as triarylmethane compounds, bisphenylmethane compounds, xanthene compounds, Fluorans, thiazine compounds, spiropyran compounds and the like. Crystal violet lactone
t Lactone) and Copichem
m) X, IV and XI (a product of the Hilton Davis Company) are often used alone or in combination as color precursors in the present invention.

Further, a chelating agent as a chromogen substance which forms a color image by reacting with a metal salt as a developer when released from the microcapsules is added to the inner phase 26. It can also be formed by internal encapsulation. Some typical examples of this type of useful imaging couple are nickel nitrate / N, N'-bis (2-octanoyloxetyl) dithiooxamide, and Fe
(III) Alum / yellow salt.

Further, a diluent oil can be appropriately added to the internal phase 26 in order to improve the viscosity and the migration property. The addition of these diluent oils is expected to improve the halftone tone development. These diluent oils include alkylated biphenyls (eg, monoisopropyl biphenyl), polychlorinated biphenyls, castor oil, mineral oil, deodorized kerosene, naphthenic mineral oils, dibutyl phthalate, dibutyl fumarate, dibutyl fumarate, and mixtures thereof. Is exemplified. Alkylated biphenyls are generally less toxic and are preferred.

The photosensitive microcapsules used in the present invention can be easily formed by using ordinary techniques such as coacervation, liquid-liquid phase separation, interfacial polymerization and the like. Various melting, dispersion and cooling methods can also be used.

The photosensitive composition is usually lipophilic,
And hydrophilic wall forming substances such as gelatin type substances (U.S. Pat. Nos. 2,730,456 and 2,60).
0,457), for example, gum arabic, polyvinyl alcohol, carboxymethylcellulose; resorcinol-formaldehyde wall forming agent (see US Pat. No. 3,755,190); isocyanate wall forming agent (see US Pat. No. 3,914,914). No. 511); isocyanate-polyol wall forming agents (U.S. Pat. No. 3,796,6).
No. 69); urea-formaldehyde wall formers, especially urea-resorcinol-formaldehyde, whose lipophilicity is enhanced by the addition of resorcinol (U.S. Pat.
001,140, 4,067,376 and 4,089,802), and can be encapsulated in melamine-formaldehyde resin and hydroxypropylcellulose (see U.S. Pat. No. 4,025,455). .

Specific examples of the photocurable polyfunctional ethylenically unsaturated compound forming the protective layer of the present invention are shown below. Compounds containing at least one ethylene end group per molecule, typically liquid ethylenically unsaturated compounds having two or more ethylene end groups per molecule are preferred.
Further, as the liquid ethylenically unsaturated compound having a plurality of ethylene terminal groups, ethylenically unsaturated acid esters of polyhydric alcohols, for example, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate ( TMP
TA) and trimethylolpropane trimethacrylate, and acrylate prepolymers derived from a partial reaction of pentaerythritol with acrylic acid, methacrylic acid, acrylate or methacrylate, and the like.

Next, photopolymerization initiation used to form a protective layer 32 formed of a photocurable resin which is a surface treatment liquid containing at least the photoinitiator of the present invention and a photocurable unsaturated compound. Examples of agents are diaryl ketone derivatives and benzoin alkyl ethers. If UV sensitivity is desired, suitable UV initiators include, for example, alkoxyphenyl ketones, O-acylated oxyimino ketones, polycyclic quinones, benzophenones and substituted benzophenones, xanthones, thioxanthones, Halogenated compounds such as chlorosulfonyl and chloromethyl polynuclear aromatic compounds, chlorosulfonyl and chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethylbenzophenones, fluorenones, and haloalkanes. When visible light sensitivity is desired, a suitable photoinitiator may be an organic borate salt of a cationic dye used as a photoinitiator of a recording material relating to a plasticizer.

Next, the method of forming the protective layer 32 will be described. The polyfunctional ethylenically unsaturated compound obtained by mixing and dissolving the photopolymerization initiator is coated on the image-developing sheet 10. Alternatively, a surface treatment may be performed by applying a solution obtained by dissolving the photopolymerization initiator and the polyfunctional ethylenically unsaturated compound in a non-polar organic solvent such as benzene, chloroform, and ethyl acetate. After the coating treatment, the solvent or the like is quickly dried and cured by irradiating ultraviolet rays to form a glossy protective layer.

The color developer sheet 10 of the present invention is particularly useful in full color image forming systems, such as those described in US Patent Application No. 339,917, filed January 18, 1982. The microcapsules used for full color image formation individually contain cyan, magenta and yellow color formers, and photosensitive compositions having distinctly different sensitivities. The homogeneous mixture of microcapsules is distributed over the surface of the support. An image is formed by decomposing a red component, a green component, and a blue component of an image to be reproduced, and curing the photosensitive composition according to the wavelength of the light of each color by using the light of each color component. Thus, the photosensitive material is imagewise exposed (exposure) for each color component.
Thereafter, the photosensitive microcapsules 24 in the underexposed region and the unexposed region are destroyed and subjected to a pressure that is a uniform destructive force for releasing the color forming agent contained in the internal phase 26. The color former then reacts with the developer material contained on the different support to form a full color image.

The spectral sensitivity of the photosensitive microcapsules 24 is mainly a function of the photoinitiator used in the encapsulated photosensitive composition. In order to design photosensitive microcapsules useful for full color imaging with distinct spectral sensitivities, photoinitiators with mutually exclusive sensitivities in at least three different wavelength regions must be designed or selected. No. That is, the photoinitiator used in the microcapsules containing the cyan color former is substantially less photosensitive than the photoinitiator used in the microcapsules associated with the magenta and yellow color formers, Ideally it should be substantially more photosensitive in the non-photosensitive wavelength region. Similarly, the photoinitiator used in the microcapsules containing the cyan color former is a wavelength at which the photoinitiator used in the microcapsules containing the magenta and yellow color formers is preferentially photosensitive. Have to be substantially less photosensitive in the area,
Ideally not photosensitive. Similar considerations dictate the choice of initiator associated with the microcapsules containing the yellow and magenta color formers.

The color developing sheet of the present invention is useful not only in the above-described type of photosensitive system but also in a normal pressure-sensitive carbonless system.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to Examples. (Example 1) An image forming sheet 20 was manufactured as follows. 11. 110 g of water and Isobam
8 g (16.5%) was placed in a 600 ml stainless steel beaker. The beaker was clamped on a hot plate. An overhead mixer with a 45 ° pitch turbine impeller with six blades is used. After the isobam / water solution is thoroughly mixed (5-10 minutes)
3.1 g of pectin is sprinkled slowly. The mixture is stirred for 15-20 minutes until homogenous, then 0.2 Quadrol (2-hydroxypropylethylenediamine in propylene glycol; a product of BASF) is added, approximately 2-3 drops.

After stirring for 5 to 10 minutes, the mixture is 20% H ₂ S
The pH is adjusted to 4.0 using an O ₄ solution. The overhead mixer speed was increased to 3000 rpm and the internal phase [TMPTA (trimethylolpropane triacrylate) 50.0 g, Irgacure (Irgaccu)
re) 651 (2,2'-dimethoxy-2-phenylacetophenone) 12.0 g, Quanticure (Qua)
nticure) ITX (product of Ward Perkinsop Limited) 1.0 g, Quanticure RPD (product of Ward Perkinsop Limited) 1.0 g, C
1.5 g of VL and 3.0 g of Copichem X (a product of the Hilton Davis Company)] are poured in and emulsified at 3000 rpm for 10 minutes.

After 10 minutes, the mixer speed was 2000 rpm
A solution of 16.6 g of 50% urea, a solution of 0.8 g of resorcinol in 5 g of water, a solution of 21.4 g of 37% formaldehyde, and a solution of 0.5 g of ammonium sulphate in 10 ml of water at 2 min. Is added.

The beaker is covered with foil and an additional 5
Stir for minutes. The hot plate is then activated, and the hot air gun raises the temperature of the capsule formulation to 65
Used to up to ° C. 65 ° C (2000 rpm
m) for 2 hours, the pH is adjusted to 9 with a 20% NaOH solution.
It is adjusted to. 2.8 g of sodium bisulfite are added slowly and the capsule formulation is stirred slowly while cooling to room temperature.

The capsule formulation is mixed with Klucel to give a proportion of 97.5% capsules and 2.5% Klucel (Klucel: product of Hercules Chemical Company) on a dry weight basis. This mixture is 81/2 inches (about 21.6 inches) using a laboratory coater.
cm) on a roll. The mixture is weighed at 80 pounds (approximately
g) Black and white matte basestock (a product of The Mead Corporation) is coated by coating. The drying temperature used in the laboratory coater is set at 190 ° F (about 88 ° C).

The color developing sheet 10 was manufactured as follows. 852 g of water, 25% Tamol (Tamol) 731
(ROHM End Haas Chemical Company) 2
50 g, HT clay 75 g, KC-11 (synthetic developer manufactured by Fuji Photo Film Co., Ltd.) 1000 g, calgon (C
algon) T (Calgon, Inc.) 1
A mixture of 5 g, 30 g of Dequest 2006 (Monsanto Company) was ground to a particle size of less than 5 μm. This mixture contains 2 parts per 65 parts of the mixture.
5 parts RH clay and 10 parts Dow 501 latex were added. The resulting material gave a Mayer bar (a bar coater) at 80 pounds (36.3 kg) black and white enamel pace stock coating amount is coated with a solid content of 30% to 35% on 8~100g / m ² of.

Thereafter, the sheet is made up of Geon.
352 (product of BF Goodrich Company) 2
Prepared by mixing 56 g, 250 g of water containing 1% Triton X-100, and 15 g of polyvinyl alcohol latex (Vinol; a product of Air Products & Chemicals, Inc.) as binder. The composition was overcoated with a # 16 Meyer bar (Bar coater) and dried.

The image forming sheet 2 manufactured as described above
A color image sample (I) developed with respect to the color-developing sheet was created by passing the sheet 0 and the color-developing sheet 10 through the stack of two sheets (opposite sides facing each other) at 500 pli. .

Then, for the color image sample (I), the following composition, ie, 50 g of trimethylolpropane triacrylate (TMPTA), 20 g of dipentaerythritol hydroxypentaacrylate (DPHPA), 1.4 g of isopropylthioxanthone, and ethyl-p-dimethyl After drying a composition comprising 2.5 g of aminobenzoate and 1 g of 2-mercaptobenzoxazole, the composition weighs 4
g / m ² .

Subsequently, the coated surface was irradiated with light using a high-pressure mercury lamp, and light-cured. Thus, a color image sample (II) having the photocured protective layer 32 was obtained. Subsequently, the image densities of the color image sample (I) and the color image sample (II) were measured with a Macbeth TR-927 densitometer.

Table 1 shows the results of measuring the surface glossiness of each sample at an incident angle of 75 degrees. (JIS
(Based on P8142)

【table 1】 As shown in Table 1 above, the color image sample (I
I) showed high maximum density and high gloss.

(Example 2) Next, a full-color sample was prepared as follows. 1. Preparation of photosensitive microcapsules 1-1) Preparation of magenta microcapsules Photosensitive microcapsules were prepared with reference to the examples described in JP-A-2-298340. A) Preparation of internal phase Trimethylolpropane triacrylate (TMPTA)
Add 105 g and 45 g of dipentaerythritol-hydroxypentaacrylate (DPHPA) to a beaker and add about 90
Heated at ° C for 30 minutes. While stirring, the magenta dye precursor (M
-1) 20 g was added and dissolved. The mixture was further heated and stirred at 90 ° C. for 30 minutes, and then cooled to 70 ° C.

Embedded image While stirring, the photoinitiator (1,1′-di-n-heptyl-
0.5 g of 3,3,3 ′, 3 ′,-tetramethylindocarbocyanine triphenyl-n-butyl borate) was added, and further 70 ° C.
For 30 minutes. While stirring, DIDMA (2,6-di-isopropyl-N, N-
1.0 g of dimethylaniline) and stirred for 5 minutes. 0.5 g of 2-mercaptobenzothiazole disulfide was added and stirred for 20 minutes. 10 g of duranate 24A-90PX (Asahi Kasei's polyisocyanate) was added, and the mixture was kept at 70 ° C.

B) Preparation of External Phase 430 g of water was added to a beaker and stirred at 500 rpm with an overhead mixer. Slowly add 8.0 g of VarsaTL502 (sulfonated polyethylene manufactured by National Starch) and further 500 r.
Stirred at pm for 15 minutes. 12.65 g pectin and 0.2 sodium bicarbonate
4 g were mixed, added at 1500 rpm, and stirred for another 2 hours. The pH was adjusted to 6.0 using NaOH, and the mixture was further stirred at 3000 rpm for 10 minutes.

C) Emulsification of the internal phase within the external phase The internal phase was added to the external phase in about 30 seconds. The emulsion was stirred at 300 rpm for 15 minutes to form an emulsion.

D. Formation of melamine formaldehyde outer wall 250 g of water was placed in a beaker, and 22.2 g of melamine was added with stirring. While stirring, 36.5 g of 37% formaldehyde was added. The mixture was heated to 60 ° C and reacted at 60 ° C for 1 hour. (Formation of Melamine Formaldehyde Precondensate) The stirring speed of emulsification was adjusted to 1500 rpm, and the melamine formaldehyde precondensate was injected into the emulsion of C. The pH was adjusted to 6.0 using phosphoric acid. Subsequently, the mixture was cured at 70 ° C. for 60 minutes to form microcapsules having the above-mentioned inner phase as a core. 46.2 g of a 25% aqueous urea solution was added, and stirring was continued for another 60 minutes. The stirring speed was set to 500 rpm and 10 g of 20% NaOH
Was added and cooled to room temperature. The mixture was further stirred at room temperature overnight to obtain a microcapsule dispersion liquid (A). The particle diameter of the obtained microcapsules was 2 to 12 μm, and most was 6 to 7 μm. Further, the solid concentration was measured by an electronic moisture meter manufactured by Shimadzu Corporation to be 25.2% by weight.

1-2 Preparation of Cyan Microcapsules 1-1 Preparation of magenta microcapsules In the description of the preparation of magenta microcapsules, 20 g of a dye precursor C-1 represented by the chemical formula 4 was added in place of the dye precursor M-1, and a photoinitiator was further added. Was changed to 0.85 g of 1,1'-di-n-heptyl-3,3,3 ', 3'-tetramethylindodicarbocyanine-triphenyl-n-butyl borate, and the microcapsule dispersion liquid (B)
I got The particle size of the obtained microcapsules (B) is 2
１２12 μm, mostly 6-7 μm. The solid concentration was measured and found to be 26.3% by weight.

Embedded image

1-3 Preparation of Yellow Microcapsules 1-1 In the description of preparation of magenta microcapsules, 20 g of a dye precursor Y-1 represented by the chemical formula 2 was added in place of the dye precursor M-1, and a photoinitiator was further added. Was changed to 0.8 g of 3,3-dimethyl-1-heptylindo-3'-heptylthiocyanine-triphenyl-n-butyl borate to obtain a microcapsule dispersion liquid (C). The particle diameter of the obtained microcapsules (C) is 5 to 10 μm,
Most were 6-8 μm. Further, the solid concentration was measured and found to be 27.5% by weight.

Embedded image

2. Preparation and Application of Photosensitive Solution Photosensitive solution (III) comprising a microcapsule dispersion was prepared as follows. Microcapsule dispersion liquid (A) 5.6 g Microcapsule dispersion liquid (B) 4.9 g Microcapsule dispersion liquid (C) 4.7 g Polyvinyl alcohol 10% solution 2.5 g PVA117 (manufactured by Kuraray) Ion-exchanged water 16.3 g was prepared. Photosensitive liquid (III) is opaque PET with titanium oxide
The resultant was coated on the top so that the weight after drying was 10 g to prepare a photosensitive donor sheet (III). 3. Preparation of Developing Sheet The following composition was applied on titanium oxide coloring opaque PET so that the weight after drying was 12 g to prepare a developing sheet (III). HRJ4250 (solid content 40% by weight) 15.8 g (Shchenectady Chemical) polyvinyl alcohol 10% solution 2.5 g (PVA117 Kuraray) ion-exchanged water 11.7 g

The photosensitive donor sheet (III) thus formed is passed through a color positive original to form a Red, Gre
Exposure was performed through an en, Blue filter.

After the exposure, a full-color image was formed on the color developing sheet (III) by passing through a pressure roller in close contact with the color developing sheet (III). The obtained full-color image was further subjected to a heating treatment at 60 ° C. for 1 minute to accelerate the color-forming reaction, thereby producing a developed color image sample (III). Next, the following composition, that is, trimethylolpropane triacrylate (TMPTA) 5
0 g, dipentaerythritol hydroxypentaacrylate (DPHPA) 20 g, 1,1'-di-n-heptyl-3,3,3 ', 3'-tetramethylindodicarbocyanine-triphenyl-n-butyl borate. 3g,
A composition comprising 0.2 g of 2-mercaptobenzothiazole was applied such that the weight after application was 4 g / m ² .

Subsequently, the coated surface was irradiated with light by tungsten light and light-cured. Thus, a color image sample (IV) having a photocured protective layer was obtained. Subsequently, the measurement of the image density and the measurement of the surface glossiness of the color image sample (III) and the color image sample (IV) in accordance with Example 1 are shown in Table 2.

[0078]

[Table 2] From Table 2, the color image sample (IV) according to the present invention obtained a full-color image having high image density and gloss.

[0079]

The present invention has the following effects.

(A) According to the first aspect of the present invention, after the image formation by the pressure contact, a surface protective layer is formed by curing a surface treatment liquid on the surface of the color developing sheet, and a high gloss image is formed. Not only can be obtained, but also there is no stickiness of the image surface after image formation, and the handleability can be improved.

(B) According to the second aspect of the invention, by appropriately setting the size of the microcapsules, the pixel size of the image to be formed can be maintained at an appropriate extremely small size. Thus, an image having excellent resolution can be obtained.

(C) According to the third aspect of the present invention, since the chromogenic substance is a substantially colorless electron-donating compound, the irradiated light can reach the photosensitive material effectively.

(D) According to the invention of claim 4, these electron-accepting compounds have excellent versatility and can be obtained easily and at low cost.

(E) According to the fifth aspect of the present invention, after the image formation by the pressure contact, a surface protective layer is formed by curing a surface treatment liquid on the surface of the color developing sheet, and a high gloss image is formed. Not only can be obtained, but also there is no stickiness of the image surface after image formation, and the handleability can be improved.

(F) According to the invention of claim 6, these polyfunctional ethylenic photocurable unsaturated compounds can effectively receive an active group (radical) generated by an appropriate photoinitiator and efficiently Polymerization (hardening) by radical polymerization is performed.

(G) According to the seventh aspect of the present invention, the photo-initiator is a photo-radical initiator, so that the photo-radical initiator is irradiated with light of a predetermined wavelength corresponding to the photo-radical initiator, so that the photo-radical initiator is quickly and relatively irradiated. The surface treatment liquid can be cured at a low temperature.

(H) According to the eighth aspect of the present invention, the electron accepting compound can obtain good color development and is suitable as a reactive color developing material.

(I) According to the ninth aspect of the present invention, each of these substances has excellent versatility as a reactive color developing substance, and can be obtained easily and at low cost.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a structure of a developing sheet (before image formation) used in a microencapsulated transfer image system of the present invention.

FIG. 2 is a cross-sectional view showing a structure of an image forming sheet used in the microencapsulated transfer image system of the present invention.

FIG. 3 is a cross-sectional view showing a configuration of a photosensitive microcapsule used in the microencapsulated transfer image system of the present invention.

FIG. 4 is a view showing a developing (developing) step in the microencapsulated transfer image system of the present invention.

FIG. 5 is a cross-sectional view showing the structure of a color developing sheet (after image formation) used in the microencapsulated transfer image system of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 10 color developing sheet 12 support member 14 color developing layer 20 image forming sheet 21 formaldehyde 21 support member 22 photosensitive layer 24 photosensitive microcapsule 25 capsule wall 26 internal phase 30 image 32 protective layer

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AC01 AD01 AD03 BC31 BC51 BF00 CA44 CC14 CC20 DA10 DA39 FA03 FA26 2H085 AA07 AA16 BB01 BB22 BB35 BB37 CD00 CD15 DD48 2H096 AA00 BA20 EA02 GA54 GA55 HA30 JA04

Claims (9)

[Claims] 1. A capsule comprising a photosensitive composition which is thickened or cured or softened by light of a predetermined wavelength and a chromogen substance corresponding to the predetermined wavelength to which the photosensitive composition reacts, inside a capsule. An image forming sheet in which a photosensitive layer containing at least photosensitive microcapsules is formed on a supporting member, and a developing layer containing a developing substance that forms an image by reacting with the chromogen substance is formed on the supporting member. A formed color developing sheet, and a microencapsulated image forming system using the image forming sheet, imagewise exposing the image forming sheet and contacting the color developing sheet under pressure to form an image on the color developing sheet. After the formation, the surface of the color developing sheet is treated with a surface treatment liquid containing at least a photoinitiator and a photocurable unsaturated compound, and thereafter, the photocurable unsaturated compound is cured by a predetermined amount. A micro-encapsulated transfer image system characterized by irradiating light. 2. The microencapsulated transfer imaging system according to claim 1, wherein the microcapsules include individually independent capsule walls. 3. The microencapsulated transfer image system according to claim 1, wherein the chromogenic substance is a substantially colorless electron donating compound, and the developing substance is an electron accepting compound. 4. The method according to claim 1, wherein the electron accepting compound is an acid clay,
At least one of aromatic carboxylic acids and their polyvalent metal salts, phenolic resins and their polyvalent metal salts, and polymers of aromatic carboxylic acids and aldehydes or acetylene and their polyvalent metal salts; The microencapsulated transfer imaging system of claim 3. 5. A developing device used in a microencapsulated transfer image system in which a developing layer containing at least a reactive developing material which forms an image by reacting with a predetermined chromogen material is formed on a support member. A color sheet, wherein after the reactive color developing substance reacts with the almost colorless chromogenic substance by pressure contact to form an image, it contains at least a photoinitiator and a photocurable unsaturated compound. A microcapsule comprising a protective layer formed by treating the surface of the color developing sheet with a surface treatment liquid to be applied, and then irradiating a predetermined light capable of curing the photocurable unsaturated compound. Color developing sheet for chemical transfer imaging system. 6. The developing sheet for a microencapsulated transfer image system according to claim 5, wherein the photocurable unsaturated compound is a polyfunctional ethylenic photocurable unsaturated compound. 7. The developing sheet for a microencapsulated transfer image system according to claim 5, wherein the photoinitiator is a photoradical initiator. 8. The developing sheet for a microencapsulated transfer image system according to claim 5, wherein the reactive developing substance is an electron-accepting compound. 9. The method according to claim 1, wherein the electron accepting compound is an acid clay,
At least one of aromatic carboxylic acids and their polyvalent metal salts, phenolic resins and their polyvalent metal salts, and polymers of aromatic carboxylic acids and aldehydes or acetylene and their polyvalent metal salts; A color developing sheet for a microencapsulated transfer imaging system according to claim 8.