JPH0475061A - Photosensitive and theromosensitive recording material - Google Patents

Abstract

PURPOSE:To contrive the improvement in photopolymerization sensitivity by providing a layer incorporating a microcapsule including an electron donor type noncolor dye, an electron acceptable compound having a polymerizable ethylene group, a photopolymerization initiator and a specified bisphenol derivative on a supporting body. CONSTITUTION:On the supporting body, the layer incorporating the microcapsule including the electron donor type noncolor dye, the electron acceptor compound having a polymerizable ethylene group, the photopolymerization initiator and a phenol derivative represented with formula 1, is provided. In formula 1, X represents alkylene group or cycloalkylene group, Y represents hydrogen atom, alkyl group, alkoxy group or halogen atom and R represents a mono valent group having a polymerizable group. Thus the recording material improved in the photopolymerization sensitivity is obtained.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention relates to a light and heat sensitive recording material that can be used in fields such as facsimiles, recording paper for printers, presentation films, medical recording films, proofs for printing proofs, etc. In particular, it relates to a light and heat sensitive recording material with improved photopolymerization sensitivity.

``Prior art'' Recording materials using electron-donating colorless dyes and electron-accepting compounds include pressure-sensitive paper, thermal paper, and light-sensitive pressure-sensitive paper.

It is already well known as electrically conductive thermal recording paper, thermal transfer paper, etc. For example, UK patent 2140449, US patent 44
80052, 4436920, Special Publication Showa 60-2399
2. JP-A-57-179836, JP-A No. 60-123556
, 60-123557 etc. for details.

However, recording materials that use electron-donating colorless dyes and electron-accepting compounds can be damaged by reheating even after image recording.
It has the disadvantage that non-image areas recolor, and research into improving this problem is being carried out intensively.

As one form of recording material, an attempt has been made to improve stability by microencapsulating an electron-donating colorless dye and separating it from an electron-accepting compound. However, even with this method, the preservation of one image was not satisfactory. Further, as a method for obtaining an image by exposing the image to light and subsequently heating it, a method is known in which a visible image is formed by heat development using a photopolymerizable composition and a heat-sensitive coloring material. This prevents the heat-sensitive component from coming into contact with the area cured by one-image exposure using microcapsules containing a photopolymerizable composition, thereby preventing color development.

However, this method is unsatisfactory since it is not possible to sufficiently suppress color development in photocured areas during thermal development, and fogging occurs in non-image areas.

Also, is there any known method of using an electron-donating colorless dye-containing microcapsule containing a photopolymerizable composition and an electron-accepting compound composition or a photopolymerizable electron-accepting compound composition containing the photopolymerizable composition? The method is not satisfactory in terms of color density.

In order to solve these problems, the present inventors have already devised a recording material in which a layer containing microcapsules containing a two-electron donating colorless dye and an electron-accepting compound having a polymerizable group is provided on a support. did. However, even with this recording material, the photopolymerization sensitivity is not satisfactory, and an improvement in the photopolymerization sensitivity has been desired.

``Problems to be Solved by the Invention'' Accordingly, the purpose of the present invention is to improve the photopolymerization sensitivity in a light- and heat-sensitive recording material using a method of converting a polymer image obtained by photocuring into a visible image by heat development. The aim is to provide what we have achieved.

"Means for Solving the Problems" The object of the present invention is to provide microcapsules encapsulating an electron-donating colorless dye, an electron-accepting compound having a polymerizable ethylene group, a photopolymerization initiator, and the following general formula ( This was achieved using a light and heat sensitive recording material provided with a layer containing a phenol derivative represented by I) and/or (I1).

[In the above general formula (I),
](OR) representing a valence group.

[In the above general formula (I1), 1 Y represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, R represents a monovalent group having a polymerizable group, and n represents 2 or 3] The above general formula Among the groups represented by X in (I), alkyl groups having 3 to 12 carbon atoms and cycloalkyl groups having 5 to 7 carbon atoms are preferable; Alkyl groups of numbers 1 to 4 and halogen atoms are preferable, and among the groups represented by R, acryloyl groups, methacryloyl groups, acryloyloxyalkyl groups, methacryloyloxyfurkyl and vinylbenzyl groups are preferable 1, especially acryloyl groups and methacryloyl groups is preferred.

Among the groups represented by Y in the above general formula (I1), hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, and halogen atoms are preferred, and among the groups represented by R.

Acryloyl, methacryloyl, acryloyloxyalkyl, and methacryloyloxyalkyl are preferred; acryloyl and methacryloyl groups are particularly preferred.

Specific examples of the compound represented by the above general formula (I) include:
2,2-bis(4-acryloyloxyphenyl)propane 2.2-bis(4-methacryloyloxyphenyl)propane, 2,2-bis(3-methyl-4-acryloyloxyphenyl)propane, 2,2-bis (3-
Methyl-4-methacryloyloxyphenyl)propane, 2゜2-bis(3-chloro-4-acryloyloxyphenyl)propane, 2.2-bis(3-chloro-4-
methacryloyloxyphenyl)propane.

2.2-bis(3-sec-butyl-4-acryloyloxyphenyl)propane, 1.1-bis(4-acryloyloxyphenyl)-2-ethylhexane, 1,1
-bis(4-methacryloyloxyphenyl)-2-ethylhexane, 2,2-bis(4-acryloyloxyphenyl)butane, 2,2-bis(4-methacryloyloxyphenyl)butane, 2,2-bis(4- β-acryloyloxyethoxyphenyl)propane, 2゜2-bis(4-β-methacryloyloxyethoxyphenyl)
Examples include propane.

Specific examples of the compound represented by the above general formula (I1) include 1,2-bis(acryloyloxy)benzene, 1,
2-bis(methacryloyloxy)benzene, 1,3-
Bis(acryloyloxy)benzene, 1,3-bis(
methacryloyloxy)benzene, 1,4-bis(acryloyloxy)benzene, 1,4-bis(methacryloyloxy)benzene, +, 2.3-upper 2°(acryloyloxy)benzene, 1,2.3-tris( methacryloyloxy)benzene, +, 3. 5-tris(acryloyloxy)benzene, 1゜3.5-1lis(methacryloyloxy)benzene, 1.3-bis(
acryloyloxy)-4-t-butylbenzene, 1,
4-bis(acryloyloxy)-2,5-dimethylbenzene 13bis(acryloyloxy)-4-chlorobenzene, 1,3-bis(β-acryloyloxyethoxy)benzene, 1,3-bis(β-methacryloyloxyethoxy) Examples include benzene.

The electron-accepting compound having a polymerizable ethylene group according to the present invention is a phenol derivative having one or more monopolymerizable ethylene groups and a phenolic hydroxyl group. Methacryloxyethyl ester of benzoic acid having a hydroxyl group described in 2006, acryloxyethyl ester synthesized by a similar synthesis method, 59-83693, 60-14
esters of benzoic acid and hydroxymethylstyrene having a hydroxyl group as described in No. 1587 and No. 62-99190, hydroxystyrene as described in European Patent No. 29323, Japanese Patent Application Laid-Open No. 167077-1987,
N-vinylimidazole complexes of zinc halide described in No. 62-16708 and No. 63-317558
The color developer monomer etc. described in the issue and the following general formula (
Examples include compounds represented by I11).

In the above formula (Ill), X is a hydrogen atom or a halogen atom, and Y is a monovalent group having a polymerizable ethylene group.

Z represents a hydrogen atom, an alkyl group, a hydroxy group, or an alkoxy group; in the above formula (Ill), among monovalent groups having a polymerizable ethylene group represented by Y, an aralkyl group having a vinyl group, acryloyloxyfurkyl; and methacryloyloxyalkyl groups are preferred.

Next, examples of electron-accepting compounds represented by the above formula (Ill) will be shown.

3-Chloro-4-hydroxybenzoic acid vinyl phenethyl ester, 3-chloro-4-human O-oxybenzoic acid vinyl phenylpropyl ester, 3-chloro-4-hydroxybenzoic acid-(2-7-chloro-Oyloxyethyl) ester , 3-chloro-4-hydroxybenzoic acid-(2-methacryloyloxyethyl) ester, 3-chloro-4-
Hydroxybenzoic acid (2-acryloyloxypropyl) ester, 3-chloro-4-hydroxybenzoic acid
(2-methacryloyloxypropyl) ester, 3-
Chloro-4-hydroxybenzoic acid-(3-acryloyloxypropyl) ester.

3-chloro-4-hydroxybenzoic acid-(3-methacryloyloxypropyl) ester, 3-chloro-4-hydroxybenzoic acid-(4-acryloyloxybutyl) ester
ester, 3-chloro-4hydroxybenzoic acid-(4-
methacryloyloxybutyl) ester, 3-fluoro-
4-Hydroxybenzoic acid-(2-acryloyloxyethyl) ester, 2,4-dihydroxy-6-methylbenzoic acid vinylbenzyl ester, 2,4-dihydroxy-5-methylbenzoic acid vinylbenzyl ester, 2,4
-Dihydroxy-3-methylbenzoic acid vinylbenzyl ester, 2,4-dihydroxy-3-chlorobenzoic acid vinylbenzyl ester 2,4-dihydroxy-6-phenylbenzoic acid vinylbenzyl ester, 2,4-dihydroxybenzoic acid vinylbenzyl ester Ester, 2,4-dihydroxybenzoic acid vinyl phenylpropyl ester2.
Examples include 4-dihydroxybenzoic acid vinylbenzyl ester.

The ratio of the electron-accepting compound having a polymerizable ethylene group and the phenol derivative represented by general formula (I) or (I1) according to the present invention is such that the amount of the phenol derivative used is 50% by weight relative to the electron-accepting compound. It is preferably less than or equal to 40% by weight, particularly preferably less than 40% by weight.

These electron-accepting compounds may be used in combination with other non-polymerizable electron-accepting compounds. Examples of non-polymerizable electron-accepting compounds include phenol derivatives, salicylic acid derivatives, and aromatic carboxylic acids. Metal salts, acid clay,
Examples include bentonite, novolac resin, metal-treated novolac resin, and metal complexes. These examples are from the Tokuko Sho 4
No. 0-9309, Japanese Patent Publication No. 45-14039, Japanese Patent Publication No. 1973
No. 2-140483, JP-A-48-5+510,
JP-A-57-210886, JP-A-58-87089
No., JP-A-59-11286, JP-A-60-1767
No. 95, JP-A No. 61-95988, etc. When these non-polymerizable electron-accepting compounds are used in combination, it is preferable to use the monopolymerizable electron-accepting compound in an amount of 50% by weight or more, preferably 70% by weight or more.

In the present invention, a polymerizable compound having at least one polymerizable ethylene group in one molecule can be used in combination with the electron-accepting compound. Among these, polymerizable compounds having a plurality of ethylenically unsaturated double bonds in the molecule are particularly preferred, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol. These include hydroxypentaacrylate, hexanediol-1°6-dimethacrylate, and diethylene glycol dimethacrylate. When other polymerizable compounds are used in combination, 1% by weight or less of the electron-accepting compound of the present invention, preferably 2% by weight or less of the electron-accepting compound of the present invention.
It is preferable to use 0% by weight or less.

In addition to these compounds, photocrosslinkable compositions such as polyvinyl cinnamate, polycinnamylidene vinyl acetate, α
- A photosensitive resin etc. having a phenylmaleimide group can be added.

Furthermore, in addition to these compounds, a thermal polymerization inhibitor can be added as necessary. Thermal polymerization inhibitors are added to prevent thermal polymerization and polymerization over time of photopolymerizable compositions, thereby improving the chemical stability of photopolymerizable compositions during preparation and storage. can be increased.

As the photopolymerization initiator used in the present invention, one or more compounds can be selected in combination from among the compounds capable of initiating photopolymerization of the above-described ethylenically unsaturated bond-containing compound.

Preferred specific examples of the photopolymerization initiator include the following compounds. Aromatic ketones: For example, benzophenone, 4,4′-bis(dimethylamino)benzophenone, 4-methoxy-4°dimethylaminobenzophenone, 4,4″-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone , benzyl, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, xanthone, thioxanthone, 2-di-O-ruthioxanthone,
2.4-diethylthioxanthone, fluorenone, acridone; and benzoin and benzoin ethers: e.g. benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether; and 2,4,5-triarylimidazole dimer: e.g. 2-(0-chlorophenyl)-4,5-diphenylimidazole dimer,
2-(0-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer,
2-(0-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)=4
．． 5=diphenyl imidazole dimer; and polyhalogen compounds such as carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone and JP-A-53-133428, JP-B-Sho 57-181
No. 9, Special Publication No. 57-6096, U.S. Patent No. 36154
Compounds described in each specification of No. 55, JP-A-58-29
5- having a trihalogen-substituted methyl group described in No. 803
)-Ryazine derivatives: e.g. 2,4.6-tris(trichloromethyl)-S-1 riazine, 2-methoxy-4
, 6-bis(trichloromethyl)-8-triazine, 2
Compounds such as -amino-4,6-bis(trichloromethyl)-S-triazine and 2-(P-methoxystyryl)-4,6-bis(trichloromethyl)-S-triazine.

and organic peroxides such as those described in JP-A-59189340, such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3.5-trimethylcyclohexanone peroxide, benzoyl peroxide, ditertiary-butylshiba-oxyisophthalate, 2.5- Dimethyl-2,5-di(benzoylperoxy)hexane, tert-butylperoxybenzoate, α,α-bis(tert-butylperoxyisopropyl)benzene, dicumyl peroxide,
Compounds such as 3°3', 4,4'-tetra-(tert-butylbaroxycarbonyl)benzophenone. and the 7-dinium salt compounds described for example in US Pat. No. 4,743,530, and for example in European Patent No. 0223.
Organoboron compounds described in No. 587, such as the tetramethylammonium salt of triphenylbutylporate,
Photopolymerization initiators well known in the art, such as tetrabutylammonium salt of triphenylbutylporate, tetramethylammonium salt of tri(P-methoxyphenyl)butylborate, etc.; other diaryliodonium salts, iron allene complexes, etc., can be usefully used.

Furthermore, combinations of two or more types of compounds are known as photopolymerization initiator systems, and such combinations can also be used in the present invention. Examples of combinations of two or more compounds include the combination of 2,4°5-triarylimidazole dimer and mercaptobenzoxazole, and the 4,4'' described in U.S. Pat. No. 3,427,161.
-bis(dimethyl7mino)benzophenone in combination with benzophenone or benzoin methyl ether, benzoyl-N as described in U.S. Pat. No. 4,239,850
- A combination of methylnaphthothiazoline and 2,4-bis(trichloromethyl)-6-(4'-methoxyphenyl)-triazole, and a dialkylaminobenzoic acid ester and dimethylthioxanthone described in JP-A-57-23602. combination, and also JP-A-59-78339
The combination of 4,4'-bis(dimethylamino)benzophenone, benzophenone, and polyhalogenated methyl compound described in the above specification can be mentioned. More preferred examples include a combination of 4,4°-bis(diethylamino)benzophenone and benzophenone, a combination of 2,4-diethylthioxanthone and ethyl 4-dimethylaminobenzoate, and a combination of 4,4′-bis(diethylamino)benzophenone and 2.4 .5-triarylimidazole dimer combinations.

The content of the photopolymerization initiator is preferably 0.01 to 20% by weight, and more preferably 0.2 to 15% by weight, and the most preferable content is 5% by weight, based on the total weight of the photopolymerizable composition. ~10% by weight. If it is less than 0.01% by weight, the sensitivity will be insufficient, and if it exceeds 10% by weight, no increase in sensitivity can be expected.

In addition to the polymerizable electron-accepting compound and the photopolymerization initiator, the recording material of the present invention may contain a spectral sensitizing dye for adjusting the wavelength to which it is sensitive. Various compounds known in the art can be used as the spectral sensitizing dye. Examples of spectral sensitizing dyes include the above-mentioned patents related to photopolymerization initiators,
Re5earch Disclosure, Vol. 2
00. December 1980, Item 20036
and “sensitizers” (Katsumi Tokumaru and Makoto Okawara/eds. Kodansha 19)
You can refer to pages 160-163 of 1987).

As a specific example of a spectral sensitizing dye, for example,
No. 8-15503 discloses a 3-ketocoumarin compound,
JP-A-58-40302 discloses thiopyrylium salts, JP-A-59-28328 and JP-A-60-53300 disclose naphthothiazole merocyanine compounds, JP-A-61
No.-9621, No. 62-3842, JP-A-59-89
No. 303 and No. 60-500 each disclose merocyanine compounds. These spectral sensitizers can extend the spectral sensitivity of the photopolymerization initiator to the visible range. In the above example, a triheromethyl-5-)-lyazine compound is used as a photopolymerization initiator, but it may be combined with other photopolymerization initiators. Spectral sensitizing dyes include keto dyes such as coumarin (including ketocoumarin or sulfonocoumarin) dyes, merostyryl dyes, oxonol dyes, and hemioxonol dyes, non-keto dyes such as non-keto polymethine dyes, anthracene dyes, rhodamine dyes, Acridine dyes, aniline dyes and azo dyes,
Non-keto polymethine dyes such as cyanine, hemicyanine and styryl dyes are included.

In addition, the photopolymerizable composition used in the present invention further includes reducing agents such as oxygen scavengers (
Oxygen scavengers) and active hydrogen donor chain transfer agents, as well as other compounds that promote polymerization in a chain transfer manner, can also be used in combination.

Oxygen scavengers include phosphines, phosphonates, phosphites, stannous salts and other compounds that are easily oxidized by oxygen. Examples include N-phenylglycine, trimethylbarbital acid, NN-dimethyl-2,6-diitupropylaniline, N,N,N-2,4,6-pentamethylaniline. Furthermore, thiols, thioketones, triheromethyl compounds, lophine dimer compounds, iodonium salts, sulfonium salts, azinium salts, organic peroxides, and the like shown below are also useful as polymerization accelerators.

Electron-donating colorless dyes according to the present invention include triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leuco auramine compounds, 0-damine lactam compounds,
There are various compounds such as triphenylmethane compounds, triazene compounds, spiropyran compounds, and fluorene compounds.

Specific examples of phthalides are listed in U.S. Reissued Patent Specification Column 23.0
No. 24, U.S. Pat. No. 3,491,111, U.S. Pat. No. 3,491,112, U.S. Pat. Book No. 3,624.107, Book No. 3,627
, No. 787, No. 3,641,011, No. 3,46
No. 2,828, No. 3,681,390, No. 3,9
20.510, U.S. Patent No. 3,959,571, and specific examples of spiropyrans are U.S. Patent Specification No. 3,971.808.
No. 3,775,424 for pyridine-based and pyrazine-based compounds.

No. 3,853,869 1 No. 4,246,318, specific examples of fluorene compounds are given in Japanese Patent Application No. 6+-2409
It is described in No. 89 etc.

In particular, when used in full-color recording materials, magenta coloring type electron-donating colorless dyes are disclosed in US Patent No. 4,800.
No. 0,149, West German Patent Publication No. 2265.233,
West German Published Patent Publication No. 2409゜112, patent application No. 63-3
No. 33,886, No. 63-256,808, etc., and US Pat. No. 4,800,148 as a yellow coloring type.
No. 4775.656, No. 95074, No. 402
No. 5.090, No. 4446.321, No. 4365.5
No. 03, No. 4820.841, No. 4598.150, and JP-A-62-288827.

No. 62-288828, No. 63-251280, No. 63-251279, No. 63-251278, No. 6
4-25148, British Patent No. 1431.493, etc., and as cyan coloring type, JP-A-63-53542, JP-A-62-270662, JP-A-63-113446, etc.
No. 63-112188, JP-A-213636,
Compounds described in European Patent Publication No. 82822 and the like are useful.

What is the ratio of the electron-donating colorless dye and the electron-accepting compound used in the recording material according to the present invention?

Electron-accepting compound/electron-donating colorless dye from 1 to 100
(molar ratio) is preferred.

Also, the amounts used are per one coloring layer.

The electron-donating colorless dye is preferably 0.1 to 2 g/m2, preferably 0.2 to Ig/m2. The electron-accepting compound is 0.2-
20 g/m2, preferably 0°4 to 10 g/m'.

When the electron-donating colorless dye of the present invention is microencapsulated, it can be produced by a method known in the art. For example, methods utilizing coacervation of hydrophilic wall-forming materials as seen in U.S. Pat. Nos. 2,800,457 and 2,800,458, U.S. Pat.
-446, interfacial polymerization method as seen in US Pat. No. 42-771, US Pat. No. 3,418,250, US Pat.
No. 3, U.S. Pat.
No. 796,669; a method using isocyanate wall materials as found in U.S. Pat. No. 3,914,511;
No. 001140, No. 4087376, No. 408980
A method using a urea-formaldehyde-based or urea-formaldehyde-resorcinol-based wall-forming material as shown in No. 2, a method using a wall-forming material such as melamine-formaldehyde resin or human oxypropyl cellulose as shown in U.S. Pat. No. 4,025,455, Kosho 36-1168,
In-situ method by polymerization of monomers as seen in JP-A No. 51-9079, British Patent No. 95280
7, No. 965,074, the spray drying method as shown in US Pat. No. 3,111,407, and British Patent No. 930,422. Although not limited thereto, it is preferable to emulsify the core material and then form a polymer membrane as the microcapsule wall.

The microcapsule wall of the present invention is particularly effective when a microencapsulation method is used in which polymerization of glue from inside the oil droplet is used. That is, it is possible to obtain capsules, which are desirable as a recording material and have a uniform particle size and excellent storage stability, within a short time.

For example, when polyurethane is used as the capsule wall material, a polyvalent isocyanate and, if necessary, a second substance that reacts with it to form the capsule wall (e.g., polyol, polyamine) are mixed into the oily liquid to be encapsulated and emulsified in water. By dispersing and then increasing the temperature, a polymer formation reaction occurs at the oil droplet interface, forming a microcapsule wall. At this time, a co-solvent with a low boiling point and strong dissolving power can be used in the oily liquid.

In this case, regarding the polyvalent isocyanate to be used and the polyol and polyamine to be reacted with it, US Pat.
No. 268, Special Publication No. 48-40347, No. 49-241
No. 59, JP-A-4880191, JP-A No. 48-84086
No. 1, and you can also use them.

When making microcapsules, water-soluble polymers can be used, and the water-soluble polymers may be any of water-soluble 7-ionic polymers, nonionic polymers, and amphoteric polymers.

As the anionic polymer, both natural and synthetic polymers can be used, and examples thereof include those having a -〇〇〇--5O2- group. Specific anionic natural polymers include gum arabic, alginic acid, pectin, etc., and semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated cellulose, lignin sulfonic acid, etc.

In addition, synthetic products include maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, and vinylbenzenesulfonic acid-based polymers and copolymers. , carboxy-modified polyvinyl alcohol, etc.

Examples of nonionic polymers include polyvinyl alcohol, hydroxyethyl cellulose, and methyl cellulose.

Examples of amphoteric compounds include gelatin.

These water-soluble polymers are used as a 0.01 to 10% by weight aqueous solution.

The size of the capsules used in the present invention is 80 μm or less, and preferably 20 μm or less from the viewpoint of storage stability and handling properties. Also, if the capsule is too small, the surface area for a given solids content will be large and a large amount of wall material will be required. For this reason, the thickness is preferably 0.1 μm or more.

The electron-donating colorless dye according to the present invention may be present in the microcapsules in a solution state or in a solid state. When a solvent is used in combination, the amount of the solvent used in the capsule is preferably 1 to 500 parts by weight per 100 parts by weight of the electron-donating colorless dye.

Natural oil or synthetic oil can be used in combination as the solvent used in the present invention. Examples of these solvents include, for example, cottonseed oil, kerosene 1, paraffin, naphthenic oil, alkylated biphenyls, alkylated terphenyls, chlorine 7-hibarafine, alkylated naphthalenes and 1-phenyl-1
Diarylethanes such as -xylylethane, 1-phenyl-1-p-ethylphenylethane, 1,1'-ditolylethane, and the like. Phthalate ester, phosphate ester, citric acid ester, benzoate ester, alkyl amide,
Fatty acid esters, trimesic acid esters, secondary butyl alcohol, methyl imbutyl ketone, β-ethoxyethyl acetate, methyl seron rub acetate, cyclohexanone, and the like.

Further, during microencapsulation, a volatile solvent may be used in combination as an auxiliary solvent for dissolving the electron-donating colorless dye. Examples of this type of solvent include ethyl acetate, butyl acetate, methylene chloride, and the like.

When the recording material of the present invention is used as a multicolor coloring material, for example, it is made of a multilayer material containing microcapsules containing electron-donating colorless dyes that develop colors in different hues and photocurable compositions that are sensitive to light of different wavelengths in each layer. In addition, it is preferable to provide an intermediate layer containing an ultraviolet absorber between the photosensitive and thermosensitive layers.

The intermediate layer mainly consists of a binder and an ultraviolet absorber, and can contain additives such as a curing agent and polymer latex, if necessary.

As the ultraviolet absorber, compounds known in the industry such as benzotriazole compounds, cinnamic acid ester compounds, aminoarylidenemalonitrile compounds, and benzophenone compounds can be used. The most preferred ultraviolet absorber is a UV absorber with a structure that does not easily diffuse into adjacent layers, such as a polymer or latex copolymerized with an ultraviolet absorber. As such a UV absorber, for example, European patent tube 1
No. 27.819, JP-A No. 59-68731, JP-A No. 59-
No. 26733, No. 59-23344, British Patent 2. M
No. 8,315, JP-A No. 58-M1942, U.S. Patent No. 4
, 307, No. 184 1. 4.202,836, 4.
, No. 202,834, No. 4.207253, No. 4.
No. 178,303, JP-A-47-560, etc. can be referred to.

These ultraviolet absorbers are added to the intermediate layer, but may also be added to the protective layer, photosensitive/thermal layer, antihalation layer, etc., if necessary.

In the present invention, the dispersion of the photocurable crude material and the dispersion and encapsulation of the electron-donating colorless dye are preferably carried out in a water-soluble polymer. Compounds that dissolve 5% by weight or more in water at a temperature of
(including modified starch), gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer hydrolyzate, carboxy-modified polyvinyl alcohol,
Examples include synthetic polymers such as polyacrylamide, saponified vinyl acetate-polyacrylic acid copolymers, and polystyrene sulfonate. Among these, gelatin and polyvinyl alcohol are preferred.

Binders used as necessary in the recording material of the present invention include the above-mentioned water-soluble polymers, polystyrene, polyvinyl formal, polyvinyl butyral, acrylic resins such as polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate, and the like. Solvent-soluble polymers such as copolymers of , phenol resins, styrene-butadiene resins, ethyl cellulose, epoxy resins, urethane resins, or latexes of these polymers can be used.

Among these, gelatin and polyvinyl alcohol are preferred. The recording material of the present invention has a number of purposes such as a coating aid, antistatic properties, improved slipperiness, emulsification and dispersion, and prevention of adhesion.
Various surfactants may be used.

Examples of surfactants include nonionic surfactants such as saponin, polyethylene oxide, polyethylene oxide derivatives such as alkyl ethers of polyethylene oxide, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfate esters, N -7ionic surfactants such as acyl-N-furkyltaurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, amphoteric surfactants such as furkylbetaines and alkylsulfobetaines, and fats. A cationic surfactant such as thick or aromatic quaternary ammonium salts can be used if necessary.

Various additives, including the additives described above, can be added to the recording material of the present invention as necessary. For example, dyes that prevent irradiation and halation,
Typical examples of ultraviolet absorbers, plasticizers, optical brighteners, matting agents, coating aids, curing agents, antistatic agents and slipperiness improvers are R.
e5earch Discosure, Vol. 1
76, December 1978, Item 17643, and the same Vat, 187. November 1979, Ite.
m 18716.

The electron-accepting compound dispersion in the recording material of the present invention is prepared by dissolving the electron-accepting compound alone or in an organic solvent that is insoluble or sparingly soluble in water, and then optionally adding a water-soluble polymer containing a surfactant to the dispersion. It is mixed with an aqueous solution of molecules and used in the form of an emulsified dispersion. As the organic solvent for dissolving the electron-accepting compound, those having a boiling point of 150° C. or lower, such as ethyl acetate, butyl acetate, isopropyl acetate, methylene chloride, chloroform, and toluene, are preferable.

The water-soluble polymer, surfactant, etc. used in dispersing the electron-accepting compound are as described above. A photopolymerization initiator may be used in combination with this electron-accepting compound dispersion, and additives such as a melting point depressant may be added to improve the heat-sensitive coloring sensitivity.

The melting point depressing agent has the function of adjusting the glass transition point of the capsule wall, and includes, for example, phenolic compounds, alcoholic compounds, carbamate esters, sulfonamide compounds, aromatic ethers, and the like. Details of these are described in, for example, Japanese Patent Application Laid-open No. 121990/1983.

The coating liquid for the recording material of the present invention is constituted by adding a photopolymerization initiator and various additives to the above-described microcapsule dispersion and electron-accepting compound dispersion, if necessary. This coating liquid is applied onto a desired support and dried. In the case of producing a multicolor recording material, an intermediate layer and a light and heat sensitive layer are further provided repeatedly or simultaneously on this light and heat sensitive layer.

Also.

Preferably, a protective layer is provided as the top layer.

To apply the coating solution onto the support, use a blade coater.
A rod coater, a knife coater, a roll doctor coater, a comma coater, a reverse roll coater, a transfer roll coater, a gravure coater, a kiss roll coater, a curtain coater, an extrusion coater, etc. can be used. The application method is Re5
EARCH DISCLOSURE, Vol. 20
0. December 1980, Item 20036 can be referred to. The thickness of the recording layer is from 0.1μ to 50μ
μ is appropriate.

Supports include paper, coachite paper, laminated paper, synthetic paper, transparent films such as polyethylene terephthalate film, cellulose triacetate film, polyethylene film, polystyrene film, polycarbonate film, aluminum, zinc, copper, etc. Examples include metal plates and those obtained by subjecting the surface of the above-mentioned support to various treatments such as surface treatment, undercoating, and metal vapor deposition treatment. As a support, Re5earch Discl.
osure, V.

200, December 1980, Item 20036 may also be referred to. Further, these supports can be provided with layers depending on the purpose, such as an antihalation layer on the surface and a slip layer, an anti-stack layer, an anti-curl layer, an adhesive layer, etc. on the back side, if necessary.

After recording an image using a thermal head or the like, the recording material according to the present invention can be cured by exposing the entire surface to light to harden the image area and non-image area, or by exposing the image to harden the exposed area and then uniformly heating it. Nine images are obtained by coloring only the uncured exposed areas.

The recording material according to the present invention can have various configurations depending on the purpose.

One preferred configuration is a configuration in which a layer consisting of minute droplets of a photocurable composition containing an electron-accepting compound and microcapsules containing an electron-donating colorless dye is provided on a support.

Another preferred configuration is a configuration in which a layer in which microcapsules containing an electron-donating colorless dye are present in a continuous phase of a photocurable composition containing an electron-accepting compound is provided on a support. This continuous phase may be a mixture of photocurable composition and binder.

Another preferred configuration is to form a layer on a support in which a photocurable composition containing an electron-accepting compound and microcapsules containing an electron-donating colorless dye are present in a continuous phase mainly consisting of a binder. This is the configuration provided for.

Furthermore, in each of these configurations, a photopolymerization initiator may be used in combination with the electron-accepting compound.

The recording material of the present invention may be a monochromatic so-called B/W recording material or a multicolor recording material.

In the case of a multicolor recording material, for example, a multilayer recording material including microcapsules containing an electron-donating colorless dye that develops colors in different hues and a photocurable composition that is sensitive to light of different wavelengths in each layer may be used. Can be used. For example, a layer containing microcapsules containing an electron-donating colorless dye that develops a cyan color and a photocurable material that is sensitive to wavelength λ1 is provided on a support, and an electron-donating colorless dye that develops a magenta color is placed on the support. Microcapsules containing and wavelength λ
2, a layer containing a light-curable structured material sensitive to light is provided, and a layer containing microcapsules containing an electron-donating colorless dye that develops a yellow color and a photocurable structured material sensitive to wavelength λ3 is provided thereon. A structure in which an intermediate layer is provided between each layer, a structure in which an ultraviolet absorber is contained in this intermediate layer, etc. can be used.

The recording material of the present invention can record with high sensitivity using light in a wide range from ultraviolet light to visible light. Light sources include mercury lamp, xenon lamp, tungsten lamp, metal halide lamp, argon laser, helium neon laser-1
A wide range of light sources can be used, including various lasers such as semiconductor lasers, LEDs, and fluorescent lights.

As an image recording method, various exposure methods can be used, such as close exposure of an original such as a lithographic film, enlarged exposure of a slide or liquid crystal image, and reflection exposure using reflected light from the original.

When performing multicolor recording, image recording may be performed multiple times using light of different wavelengths. Light of different wavelengths can be obtained by changing the light source or changing the optical filter. It can also be obtained by directly printing imagewise with a thermal head.

When the recording material of the present invention is subjected to the imagewise exposure described above, it is subjected to a heat development treatment after the imagewise exposure. As a heating method in this heat development treatment, various conventionally known methods can be used. The heating temperature is generally 80°C to 200°C, preferably 100°C to 160°C. The heating time is 1 second to 5 minutes, preferably 3 seconds to 1 minute. Further, it is preferable that the entire surface is exposed to light after the heat development treatment so that the uncured portions are also photocured.

Examples of the present invention are shown below, but the present invention is not limited thereto.

"Example" Examples-1 to 12 1) Preparation of electron-donating colorless dye capsule liquid 3.
3-bis(I-octyl-2-methylindole-3-
12.49 of phthalide was dissolved in 10.4 g of ethyl acetate, and 12.4 g of dicyclohexyl phthalate, Takenate D-NO~ (manufactured by Takeda Pharmaceutical Co., Ltd.) 279 and Millionate MR200 (manufactured by Japan Polyurethane Industries, Ltd.) 39 was added. This solution was added to a mixed solution of polyvinyl alcohol 4,69 and water 749, and emulsified and dispersed at 20°C to obtain an emulsion with an average particle size of 2.5 μm. Water 1009 was added to the obtained emulsion and heated to 60° C. while stirring, and after 2 hours, an electron-donating colorless dye capsule liquid was obtained.

2), [Preparation of emulsion of photocurable composition] 2-0-chlorophenyl-4,5-diphenylimidazole dimer 0
．． 12G+ and 7-diethylamino-4-methylcoumarin 0.129 and ethyl acetate 8 of N-phenylglycine ethyl ester 0.069 as an auxiliary agent to promote polymerization.
9 solution contains electron-accepting compound 89 (Examples 1 to 8 are β
-Resorcinic acid vinylbenzyl ester, Examples 9-1
1 uses 3-chloro-4-hydroxybenzoic acid β-methacryloyloxyethyl ester, Example 12 uses 3-chloro-4-hydroxybenzoic acid (2゜3-bismethacryloyloxypropyl) ester) and Table 1 The indicated phenol derivative 29 was added. Add this solution to 7.
It was added to a mixed solution of 5% PVA aqueous solution 9,69, 2% nonylphenoxybutanesulfonic acid aqueous solution 0.89, and 2% dodecane sodium sulfonate aqueous solution 0.8g, and 10,000 g was added using a homogenizer (manufactured by Nippon Seiki Co., Ltd.). The mixture was emulsified by rotation for 5 minutes to obtain an emulsion of a photocurable composition.

3), [Preparation of Coating Solution for Photosensitive/Thermosensitive Layer Emulsion of 4 g of child-donating colorless dye capsules and photocurable composition 129 and 1
A coating solution for photosensitive/thermosensitive layers was prepared by mixing with 5% PVA aqueous solution 129.

4), [Preparation of coating solution for protective layer] 10% gelatin aqueous solution 4.59 and distilled water 1.59 and 2%
Nonylphenoxybutanesulfonic acid sodium aqueous solution 0.5
9 and 1% of 2.4~dikuOro 6-hydroxy-s-triazine sodium salt aqueous solution 1.59 and t(O(do) 72 (FUJI-DEVISON CHEMI
CHAL LTD.

A coating solution for a protective layer was prepared by mixing Snowtex Nf in an amount sufficient to give a coating amount of 50 mg/m2.

5), [Preparation and evaluation of recording material] Coating solution for photosensitive/thermosensitive layer was applied onto a 100μ polyethylene terephthalate film using a coating bar so that the dry weight of the coating layer was 89/m2, and heated at 30°C.
and dried for 10 minutes. Apply the coating solution for the protective layer on this layer using a coating bar until the dry weight of the coating layer is 5a/m2.
It was applied and dried at 30°C for 10 minutes.

A step wedge for a mask (Fuji Control Wedge,
i o o ow through Fuji Photo Film Co., Ltd.)
Exposure was performed with ultraviolet light from a high-pressure mercury lamp (Jet Light manufactured by Oak). When the film was then heated for 5 seconds on a hot plate at 110C, a step wedge image (reflection image density: 1°5, non-image area density: 010) with a clear magenta evening color was obtained. Sensitivity comparisons were made by visual evaluation using clear steps (the number of steps in areas where no color is completely developed) of one image. The results are shown in Table 2.

Comparative Example-1 Example 1 without using the phenol derivative in Example 1
A sample was created in the same manner. The samples were evaluated in the same manner as in the examples. The results are shown in Table 2.

Comparative Example-2 Example 9 without using the phenol derivative in Example 9
A sample was created in the same manner. The samples were evaluated in the same manner as in the examples. The results are shown in Table 2.

Comparative example-3 No phenol derivative was used in Example 12.

A sample was prepared in the same manner as in Example 12. The samples were evaluated in the same manner as in the examples. The results are shown in Table 2.

Table 1 (Continued) Table 2 From Table 2, photosensitive recording materials using the phenol derivative having a polymerizable group of the present invention are listed.

obviously high It can be seen that it is the sensitivity.

Claims (1)

[Scope of Claims] 1) Microcapsules containing an electron-donating colorless dye, an electron-accepting compound having a polymerizable ethylene group, a photopolymerization initiator, and a support represented by the following general formula (I) A light and heat sensitive recording material provided with a layer containing a bisphenol derivative. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the above general formula (I), X is an alkylene group or cycloalkylene group, Y is a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and R is a Represents a monovalent group having a polymerizable group. 2) Microcapsules containing an electron-donating colorless dye, an electron-accepting compound having a polymerizable ethylene group, a photopolymerization initiator, and a polyhydric phenol derivative represented by the following general formula (II) are placed on a support. A light- and heat-sensitive recording material provided with a layer containing ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the above general formula (II), Y is a hydrogen atom, an alkyl group,
R represents an alkoxy group or a halogen atom, R represents a monovalent group having a polymerizable group, and n represents 2 or 3. ]