JPH06115246A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a recording material excellent in photopolymerization sensitivity, developed color density and the shelf stability of non-image portions, respectively, by using a phenolic derivative represented by a specified general formular as an electron-accepting compound provided on a support of the recording material. CONSTITUTION:A recording material which is used for recording paper and the like for a printer has a microcapsule containing an electrondonating colorless dye and a layer containing an electron-accepting compound, which are provided on a support, respectively. In this case, the electron-accepting compound is a phenolic derivative as represented by the general formula shown separately, provided that, in the formula, R1 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a phenyl group which optionally has substituents, while R2 represents an alkyl group having an acryloyloxy group or a methacryloyloxy group and, further, R3 represents a hydrogen atom or an alkyl group. The layer containing the electron-accepting compound optionally contains a photopolymerization initiator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material that can be used in the fields of recording papers for facsimiles, printers, etc., presentation films, medical recording films, print proofs, etc. The present invention relates to a light and heat sensitive recording material having good sensitivity, excellent color development, and excellent stability in non-image area and image area.

[0002]

2. Description of the Related Art Recording materials using an electron-donating colorless dye and an electron-accepting compound are pressure-sensitive paper, thermal paper, photosensitive pressure-sensitive paper,
It is already well known as an electrically conductive recording paper and thermal transfer. For example, British Patent 2140449 and US Patent 448.
0052, same 4436920, Japanese Patent Publication No. 60-2399.
2, JP-A-57-179836, 60-12355.
6, the same 60-123557 and so on. However, the recording material using the electron-donating colorless dye and the electron-accepting compound has a drawback that the non-image area is recolored due to reheating after image recording. Has been done.

As a form of a recording material which solves these problems, (1) an attempt to microencapsulate a polymerizable composition and an electron-donating colorless dye, (2) an electron-donating colorless dye containing a photopolymerizable composition An attempt to use an electron-accepting compound or a photopolymerizable electron-accepting compound containing microcapsules and a photopolymerizable composition, (3) a capsule containing an electron-donating colorless dye, and a photopolymerizable composition Attempts and the like using an electron-accepting compound or a photopolymerizable electron-accepting compound have been devised. However, these recording materials were not satisfactory in photopolymerization sensitivity, could not sufficiently suppress the color development of the photocured part during heat development, had fog color development, and were also unsatisfactory in terms of color density. .

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide 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, which has good photopolymerization sensitivity and color development. It is an object of the present invention to provide a recording material having high density and good storage stability in the non-image area.

[0005]

The object of the present invention is to provide a recording material comprising a support, on which microcapsules containing an electron-donating colorless dye and a layer containing an electron-accepting compound are provided.
A recording material, characterized in that the electron-accepting compound is a phenol derivative represented by the following general formula (I):

[0006]

[Chemical 2]

(Wherein R ₁ is a hydrogen atom, a halogen atom,
It represents an alkyl group, an alkoxy group or a phenyl group which may have a substituent, R ₂ represents an alkyl group having an acryloyloxy group or a methacryloyloxy group, and R ₃ represents a hydrogen atom or an alkyl group. ) And a recording material characterized by containing a photopolymerization initiator in the electron-accepting compound. The recording material according to the present invention has a non-image area formed by curing the image area and the non-image area by exposing the entire surface after image recording with a thermal head or the like, or by uniformly heating the exposed area. An image is obtained by coloring only the uncured portion of the exposed portion.

In the above general formula (I), the group represented by R ₁ is a hydrogen atom, a halogen atom (particularly preferably a chlorine atom or a fluorine atom), an alkyl group having 1 to 5 carbon atoms, an alkoxy group (particularly Methyl group, ethyl group, isopropyl group,
A methoxy group is preferable), and a phenyl group which may have a substituent (for example, a phenyl group, a halogen-substituted phenyl group, an alkyl-substituted phenyl group is preferable) is preferable.
Further, when R ₁ is a group other than a hydrogen atom, an O-substituted product with respect to the hydroxy group is preferable. The group represented by R ₂ is preferably an alkyl group having an acryloyloxy group or a methacryloyloxy group having 5 to 20 carbon atoms, and the alkyl group is an alkoxy group, an aryloxy group, a halogen atom, an aryl group or the like. It may contain a substituent, an oxygen atom, a sulfur atom, or a phenylene residue. The alkyl group may have two or more polymerizable groups. R ₃ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Specific examples of the group represented by R ₂ include:
2-acryloyloxyethyl group, 2-methacryloyloxyethyl group, 3-acryloyloxypropyl group,
3-methacryloyloxypropyl group, 2-acryloyloxypropyl group, 2-methacryloyloxypropyl group, 4-acryloyloxybutyl group, 4-methacryloyloxybutyl group, 5-methacryloyloxypentyl, 5-acryloyloxypentyl, 6-acryloyl Oxyhexyl group, 6-methacryloyloxyhexyl group, 8-acryloyloxyoctyl group, 8-methacryloyloxyoctyl group, 10-acryloyloxydecyl group, 10-methacryloyloxydecyl group, 4
-(Acryloyloxymethyl) benzyl group, 4- (methacryloyloxymethyl) benzyl group, 3- (acryloyloxymethyl) benzyl group, 3- (methacryloyloxymethyl) benzyl group, 2- (acryloyloxymethyl) benzyl group, 2 -(Methacryloyloxymethyl) benzyl group, 12-methacryloyloxide decyl group, 2- (β-acryloyloxyethoxy) ethyl group, 2- (β-methacryloyloxyethoxy) ethyl group, 2,3-bis (methacryloyloxy) propyl Groups and the like.

Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto. 4- (N-β-methacryloyloxyethylsulfamoyl) phenol, 4- (N-β-acryloyloxyethylsulfamoyl) phenol, 4- (N-γ-methacryloyloxypropylsulfamoyl) phenol 4- (N-γ-acryloyloxypropylsulfamoyl) phenol, 4- [N- (6-methacryloyloxyhexyl) sulfamoyl] phenol, 4- [N- (6-acryloyloxyhexyl) sulfamoyl] Phenol, 4- (N-methyl-N-β-methacryloyloxyethylsulfamoyl) phenol, 4- (N-methyl-N-β-acryloyloxyethylsulfamoyl) phenol, 4- (N- Methyl-N-γ-methacryloyloxypropylsulfamoyl) fur Enol, 4- (N-methyl-N-γ-acryloyloxypropylsulfamoyl) phenol, 4- [N-methyl-N- (6-methacryloyloxyhexyl) sulfamoyl] phenol, 4- [N- Methyl-N- (6-acryloyloxyhexyl) sulfamoyl] phenol, 4- (N-ethyl-N-γ-methacryloyloxypropylsulfamoyl) phenol, 4- (N-ethyl-N-γ-acryloyloxy) Propylsulfamoyl) phenol, 4- [N- (5-methacryloyloxypentyl) sulfamoyl] phenol,

2-chloro-4- (N-β-methacryloyloxyethylsulfamoyl) phenol, 2-chloro-4- (N-β-acryloyloxyethylsulfamoyl) phenol, 2-chloro- 4- (N-γ-methacryloyloxypropylsulfamoyl) phenol, 2-chloro-4- (N-γ-acryloyloxypropylsulfamoyl) phenol, 2-chloro-4- [N- (6- Methacryloyloxyhexyl) sulfamoyl] phenol, 2-chloro-4- [N- (6-acryloyloxyhexyl) sulfamoyl] phenol, 2-chloro-4- (N-methyl-N-β-methacryloyloxyethylsulfa Moyl) phenol, 2-chloro-4- (N-methyl-N-β-acryloyloxy Ethylsulfamoyl) phenol, 2-chloro-4- (N-methyl-N-γ-methacryloyloxypropylsulfamoyl) phenol, 2-chloro-4- (N-methyl-N-γ-acryloyloxy) Propylsulfamoyl) phenol, 2-chloro-4- [N-methyl-N- (6-methacryloyloxyhexyl) sulfamoyl] phenol, 2-chloro-4- [N-methyl-N- (6-acryloyl) Oxyhexyl) sulfamoyl] phenol, 2-chloro-4- (N-ethyl-N-γ-methacryloyloxypropylsulfamoyl) phenol, 2-chloro-4- (N-ethyl-N-γ-acryloyloxy) Propylsulfamoyl) phenol, 2-chloro-4- [N- (5-methacryloyloxype Chill) sulfamoyl] phenol,

The phenol derivative represented by the general formula (I) according to the present invention can be obtained by reacting the corresponding phenolsulfonyl chloride with an amine derivative.

As these electron-accepting compounds, a plurality of other electron-accepting compounds having a polymerizable ethylene group may be used in combination. Specifically, methacryloyloxyethyl ester of benzoic acid having a hydroxy group described in JP-A No. 63-173682 and acryloyloxyethyl ester which can be synthesized by a similar synthetic method and 59-
No. 83693, No. 60-141587, No. 62-99.
No. 190, an ester of benzoic acid having a hydroxy group and hydroxymethylstyrene, hydroxystyrene described in European Patent No. 29323, and JP-A Nos. 62-167077 and 62-16708. N-vinyl imidazole complex of zinc halide, the monomer described in JP-A-63-317558, and 3-halo-4-described in Japanese Patent Application No. 2-156381.
Hydroxybenzoate, Japanese Patent Application No. 2-150319
Examples thereof include the resorcinic acid ester derivatives described. An example of some of these is 4-hydroxybenzoic acid-
(2-methacryloyloxyethyl) ester, 2,4
-Dihydroxybenzoic acid- (2-methacryloyloxyethyl) ester, 2,4-dihydroxybenzoic acid vinylbenzyl ester, 2,4-dihydroxybenzoic acid-
(3-methacryloyloxypropyl) ester, 2,
4-dihydroxybenzoic acid- (4-methacryloyloxybutyl) ester, 2,4-dihydroxybenzoic acid-
(6-methacryloyloxyhexyl) ester, 2,
4-Dihydroxy-6-methylbenzoic acid vinylbenzyl ester, β-methacryloyloxyethoxysalicylic acid and its zinc salt, 3-chloro-4-hydroxybenzoic acid- (2-methacryloyloxyethyl) ester, 3
-Chloro-4-hydroxybenzoic acid vinylphenethyl ester, 3-chloro-4-hydroxybenzoic acid- (2-
Acryloyloxyethyl) ester, 3-chloro-4
-Hydroxybenzoic acid- (3-methacryloyloxypropyl) ester, 3-chloro-4-hydroxybenzoic acid- (3-acryloyloxypropyl) ester, 3
-Chloro-4-hydroxybenzoic acid- (4-methacryloyloxybutyl) ester, 3-chloro-4-hydroxybenzoic acid- (6-methacryloyloxyhexyl)
Ester, 3-chloro-4-hydroxybenzoic acid- (6
-Acryloyloxyhexyl) ester, 3-fluoro-4-hydroxybenzoic acid- (6-methacryloyloxyhexyl) ester and the like. The content of these other electron-accepting compounds having a polymerizable ethylene group is preferably 70% by weight or less, and particularly preferably 60% or less with respect to the phenol derivative of the present invention.

Further, it may be used in combination with other non-polymerizable electron-accepting compound. The non-polymerizable electron-accepting compounds include phenol derivatives, salicylic acid derivatives,
Metal salt of aromatic carboxylic acid, acid clay, bentonite,
Novolac resin, metal-treated novolac resin, metal complex,
And a polymer of the phenol derivative according to the present invention. Examples of these are JP-B-40-9309, JP-B-45-14039, JP-A-52-140483,
JP-A-48-51510, JP-A-57-210886
JP-A-58-87089, JP-A-59-1128
6, JP-A-60-176795, JP-A-61-95.
No. 988 and the like. As an example of some of these, the phenolic compound is 2,2′-bis (4
-Hydroxyphenyl) propane, 1,1'-bis (3
-Chloro-4-hydroxyphenyl) cyclohexane,
1,1′-bis (4-hydroxyphenyl) cyclohexane, 1,1′-bis (3-chloro-4-hydroxyphenyl) 2-ethylbutane, 4,4′-sec-isooctylidene diphenol, 4 , 4'-sec-butylidene diphenol, 4,4'-isopentylidenephenol
And p-hydroxybenzoic acid benzyl. Examples of salicylic acid derivatives include 3-dodecylsalicylic acid, 3,5
-Di (α-methylbenzyl) salicylic acid, 3,5-di (ter-octyl) salicylic acid, 3-dodecyl-5-
Methylsalicylic acid, 5-α- (p-α-methylbenzylphenyl) ethylsalicylic acid, 3-α-methylbenzyl-5-ter-octylsalicylic acid, 3,5-dinonylsalicylic acid, 3-nonyl-5-ter-butyl Salicylic acid, 4-dodecyloxysalicylic acid, 3-α, α-dimethylbenzyl-6-methylsalicylic acid, 3,5-bis-
α, α-dimethylbenzyl-6-methylsalicylic acid, etc.,
And these zinc, aluminum and nickel salts.
When these non-polymerizable electron-accepting compounds are used in combination, the electron-accepting compound having a polymerizable ethylene group is added to
It is preferable to use 0% by weight or more, preferably 70% by weight or more.

The photocurable composition according to the present invention may be used in combination with a polymerizable compound having at least one polymerizable ethylene group in the molecule. For example, acrylic acid and its salts, acrylic acid esters, acrylamides, methacrylic acid and its salts, methacrylic acid esters, methacrylamides, maleic anhydride, maleic acid esters,
Examples thereof include itaconic acid, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, aryl ethers and allyl esters. Of these, a polymerizable compound having a plurality of ethylenically unsaturated double bonds in the molecule is particularly preferable. For example, acrylic acid ester of polyvalent alcohol such as trimethylolpropane and pentaerythritol. And methacrylic acid ester, and acrylate or methacrylate
Epoxy resin, acrylate or methacrylate
There are polyesters with terminal ends. Specific examples of particularly preferable compounds include ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, Hexanediol-1,6-dimethacrylate
And diethylene glycol dimethacrylate. The molecular weight of the polyfunctional monomer is preferably about 100 to about 5000, more preferably about 300 to about 2.
It is 000.

In addition to these compounds, for example, polyvinyl cinnamate, polycinnamylidene vinyl acetate, and a photosensitive resin having an α-phenylmaleimide group can be added as a photocrosslinking composition. Further, in addition to these compounds, a thermal polymerization inhibitor can be added if necessary. The thermal polymerization inhibitor is added to prevent thermal polymerization of the photopolymerizable composition or polymerization over time, which makes the chemical stability of the photopolymerizable composition during preparation or storage. Can be increased.

The photopolymerization initiator preferably used in the present invention is selected from the compounds capable of initiating photopolymerization of the electron-accepting compound having a polymerizable ethylene group and the compound having an ethylenically unsaturated double bond. It is possible to select one kind or a combination of two or more kinds of compounds. The following compounds can be mentioned as preferable specific examples of the photopolymerization initiator. Aromatic ketones: for example, benzophenone, 4,
4'-bis (dimethylamino) benzophenone, 4-methoxy-4'-dimeraminobenzophenone, 4,4 '
-Dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, anthraquinone, 2-ter-butylanthraquinone, 2-
Methyl anthraquinone, xanthone, thioxanthone,
2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone, acridone; and benzoin and benzoin ethers: eg benzoin methyl ether.
Ter, benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether; and 2,
4,5-triallyl imidazole dimer: eg 2-
(O-Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2-
(O-Fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5
-Diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer;
And polyhalogen compounds such as carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone and JP-A-53-133428, JP-B-57-1819, JP-B-57-6096, U.S. Pat. The compounds described in the respective specifications of 3615455,
S-triazine derivatives having a trihalogen-substituted methyl group described in JP-A-58-29803: for example, 2,
4,6-Tris (trichloromethyl) -S-triazine, 2-methoxy-4,6-bis (trichloromethyl)
Compounds such as -S-triazine, 2-amino-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine; and For example, JP-A-59-18
9340 Organic peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, benzoimper oxide, benzoylperoxide, di-ter-butyldiper-oxyisophthalate, 2,5-dimethyl-2,5-di (benzoylper)
(Oxy) hexane, ter-butylperoxybenzoate, α, α′-bis (ter-butylperoxyisopropyl) benzene, dicumylperoxide, 3,
Compounds such as 3 ', 4,4'-tetra- (ter-butylperoxycarbonyl) benzophenone, and azinium salt compounds described in, for example, U.S. Pat. No. 4,743,530; and organic compounds described in, for example, European Patent No. 223587. Boron compound: For example, tetramethylammonium salt of triphenylbutylborate, tetrabutylammonium salt of triphenylbutylborate, tri (p-
Photopolymerization initiators known in the art such as tetramethylammonium salts of methoxyphenyl) butyl borate and iron allene complexes can be usefully used. As a photopolymerization initiator system, a combination of two or more compounds is known, and those combinations can be used in the present invention. Examples of the combination of two or more kinds of compounds include a combination of 2,4,5-triallyl-imidazole dimer and mercaptobenzoxazole and the like described in US Pat. No. 3,427,161. , 4'-Bis (dimethylamino) benzophenone and benzophenone or benzoin methyl ether, benzoyl-N- as described in U.S. Pat. No. 4,239,850.
Methylnaphthothiazoline and 2,4-bis (trichloromethyl) -6- (4'-methoxyphenyl) -triazo-
Combination, a combination of dialkylaminobenzoic acid ester and quinmethylthioxanthone described in JP-A-57-23602, and JP-A-59-783.
The combination of three kinds of 4,4′-bis (dimethylamino) benzophenone, benzophenone and polyhalogenated methyl compound described in No. 39 can be mentioned. More preferred examples include a combination of 4,4′-bis (diethylamino) benzophenone and benzophenone, 2,4-
Examples include a combination of diethylthioxanthone and ethyl 4-dimethylaminobenzoate, and a combination of 4,4′-bis (diethylamino) benzophenone and 2,4,5-triallyl-imidazole dimer.

Among these photopolymerization initiators, particularly preferred compounds include benzoin ethers, S-triazine derivatives having a trihalogen-substituted methyl group, organic peroxides, azinium salt compounds and organic boron compounds. it can. The content of the photopolymerization initiator is preferably 0.01 to 20% by weight based on the total weight of the photopolymerization composition,
And more preferably, it is 0.2 to 15% by weight, and the most preferable content is 5 to 10% by weight. If it is less than 0.01% by weight, the sensitivity is insufficient, and if it exceeds 10% by weight, an increase in sensitivity cannot be expected.

The recording material of the present invention may contain, in addition to the polymerizable electron-accepting compound and the photopolymerization initiator, a spectral sensitizing dye for adjusting the photosensitive wavelength thereof. As the spectral sensitizing dye, various compounds known in the art can be used. Examples of the spectral sensitizing dye are the above-mentioned patents relating to the photopolymerization initiator and Research Disclosure.
e, Vol. 200, December 1980, Item 2
Reference can be made to pages 160 to 163 and the like of 0036 and “sensitizer” (Katsumi Tokumaru, Shin Okawara / edited by Kodansha 1987). Specific examples of the spectral sensitizing dye include, for example, JP-A-58-15503, 3-ketocoumarin compound, JP-A-58-40302, thiopyrylium salt, and JP-B-59-28328. No. 60-53300 discloses a naphthothiazo-merocyanine compound in Japanese Patent Publication No.
1-9621, 62-3842, JP-A-59-8.
Nos. 9303 and 60-60104 disclose merocyanine compounds, respectively. With these spectral sensitizers, the spectral sensitivity of the photopolymerization initiator can be extended to the visible range. In the above example, the trihalomethyl-S-triazine compound is taken as the photopolymerization initiator,
You may combine with another photoinitiator. Spectral sensitizing dyes include keto dyes such as coumarin (including ketocoumarin or sulfonocoumarin) dyes, merostyryl dyes, oxonol dyes and myoxonol dyes, non-keto polymethine dyes, anthracene dyes,
Rhodamine dyes, acridine dyes, aniline dyes, azo dyes, non-ketopolymethine dyes such as cyanine, hemicyanine and styryl dyes are included.

In the photopolymerizable composition used in the present invention, a reducing agent such as an oxygen scavenger and a chain transfer agent of an active hydrogen donor, and a chain are further added as an auxiliary agent for accelerating the polymerization. It is also possible to use in combination with other compounds that accelerating the polymerization. Oxygen scavengers are phosphines, phosphonates, phosphites, stannous salts and other compounds that are easily oxidized by oxygen. For example, N-phenylglycine, trimethylbarbituric acid, N, N-dimethyl-2,6-diisopropylaniline, N, N, N-2,4,6-pentamethylaniline and the like. Further, the following thiols, thioketones, trihalomethyl compounds, lophine dimer compounds, iodonium salts, sulfonium salts, azinium salts, organic peroxides and the like are also useful as the polymerization accelerator.

The electron-donating colorless dyes according to the present invention include triphenylmethanephthalide compounds, fluorane compounds, phenothiazine compounds, indolylphthalide compounds, leuco-olamine compounds, rhodamine-lactam compounds, and tri compounds. There are various compounds such as phenylmethane compounds, triazene compounds, spiropyran compounds, and fluorene compounds. Specific examples of the phthalides include US Reissue Patent Specification No. 23024 and US Patent Specification No. 34.
No. 9111, No. 3491112, No. 349111
No. 6 and No. 3509174, and specific examples of fluoranes are described in US Pat. No. 3,624,107 and No. 36277.
No. 87, No. 3641011, No. 3462828,
No. 3681390, No. 3920510, No. 3
No. 959571, specific examples of spiropyrans are US Pat. No. 3,971,808, and pyridine compounds and pyrazine compounds are US Pat. No. 3,775,424, No. 38.
No. 53869, No. 4246318, fluorene compounds and the like.

Particularly when used in a full color recording material,
Examples of magenta-coloring type electron-donating colorless dyes include US Pat. No. 4,705,776 and West German Patent Publication 2265.
No. 233, West German Patent Publication No. 2409112, JP-A No. 2-178087, and JP-A No. 62-71692.
US Pat. No. 4,775,656 as a yellow-color type
No. 4540790, No. 4025090, No. 44
No. 46321, No. 4820841, No. 4598150
No. 6, JP-A-62-288827 and JP-A-62-28882.
No. 8, No. 63-251280, No. 63-251279.
No. 63-251278, British Patent No. 143149.
U.S. Pat. No. 40, No. 3, etc., as cyan color developing type
62866, 4123439 and 4153609.
No. 4,295,663, No. 4,814,320, JP-A Nos. 61-87758, 62-270662, 63.
-53542, 63-1128188, 63-1
13446, JP-A 1-213636, JP-B-61
Compounds described in, for example, No. 4856 and European Patent Publication No. 82822 are useful.

The ratio of the electron-donating colorless dye and the electron-accepting compound used in the recording material according to the present invention is
1 to 100 for electron-accepting compound / electron-donating colorless dye
(Molar ratio) is preferable. In addition, the amount of these used is 0.1 to 2 g / m 2 for the electron-donating colorless dye per color forming layer.
² preferably 0.2 to 1 g / m ² , the electron accepting compound is 0.2 to 20 g / m ^2, preferably 0.4 to 10 g
/ M ² used.

When the electron-donating colorless dye of the present invention is microencapsulated, it can be prepared by a method known in the art. For example, US Pat. Nos. 2,800,457 and 2,804.
Coacervation of hydrophilic wall forming material as seen in No. 58
, A method utilizing an application, US Pat. No. 3,287,154,
British Patent No. 990443, Japanese Patent Publication No. 38-19574
No. 42-446, No. 42-771, U.S. Pat. No. 3,418,250, No. 36.
No. 60304, by polymer deposition, US Pat. No. 3,796,669, using the isocyanate polyol wall material, US Pat. No. 3,914,511.
US Pat. Nos. 4,001,140, 4,087,376, and 40, using the isocyanate wall material found in U.S. Pat.
No. 89802, a method of using a wall-forming material such as melamine-formaldehyde resin and hydroxypropyl cellulose, which uses a urea-formaldehyde type, urea formaldehyde-resorcinol type wall material, JP-B-36-
9168, in-situ method by polymerization of monomers found in JP-A-51-9079, British Patent No. 9528.
No. 07, 965074, electrolytic dispersion cooling method,
U.S. Pat. No. 3,111,407, British Patent No. 930422.
There is a spray-drying method etc. Although not limited thereto, it is preferable to form a polymer film as a microcapsule wall after emulsifying the core substance. As a method of producing the microcapsule wall of the present invention, the effect is particularly large when the microencapsulation method by polymerizing the reactant from the inside of the oil droplet is used. That is,
Within a short period of time, it is possible to obtain capsules having a uniform particle size and excellent as a raw material, which is preferable as a recording material.

For example, when polyurethane is used as the capsule wall material, the polyvalent isosoaneate and, if necessary, the second substance (eg, polyol, polyamine) which reacts with it to form a capsule wall should be encapsulated. By mixing in an oily liquid, emulsifying and dispersing in water, and then raising the temperature, a polymer forming reaction occurs at the oil droplet interface to form a microcapsule wall. At this time, an auxiliary solvent having a low boiling point and a strong dissolving power can be used in the oily liquid. In this case, the polyvalent isocyanate used and the partner polyol and polyamine which react with it are described in US Pat.
281383, 3737695, 379326
No. 8, Japanese Patent Publication No. 40-40347, No. 49-24159.
JP-A-48-80191 and JP-A-48-84086, and they can be used. A water-soluble polymer can be used when making microcapsules. The water-soluble polymer is a water-soluble anionic polymer,
Either a nonionic polymer or an amphoteric polymer may be used. As the anionic polymer, a natural one or a synthetic one can be used, and examples thereof include those having a —COO—, —SO ₂ — group and the like. Specifically, anionic natural polymers include arabic gum, alginic acid, pectin, etc., and semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated starch, sulfated cellulose. , Lignin sulfonic acid, etc. As synthetic products, maleic anhydride (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, vinylbenzenesulfonic acid-based polymers and copolymers, Examples of nonionic polymers having carboxy-modified polyvinyl alcohol and the like include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose and the like. Examples of amphoteric compounds include gelatin. 0.01 to 10% by weight of these water-soluble polymers
Used as an aqueous solution of.

The size of the capsule used in the present invention is 80 μm.
m or less, and particularly preferably 20 μm or less from the viewpoint of storability and handleability. If the capsule is too small, the surface area for a certain solid content becomes large and a large amount of wall material is required. Therefore, 0.1 μm or more is preferable. The electron-donating colorless dye according to the present invention may be present in the microcapsule 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 with respect to 100 parts by weight of the electron-donating colorless dye.

A natural oil or a synthetic oil can be used in combination as the solvent used in the present invention. Examples of these solvents include cottonseed oil, kerosene, paraffin, naphthene oil, alkylated biphenyl, alkylated ta-phenyl,
Chlorinated paraffins, alkylated naphthalenes and diallylethanes such as 1-phenyl-1-xylylethane, 1-phenyl-1-p-ethylphenylethane, 1,1'-ditolylethane, phthalates, phosphates, quenches. Acid ester, benzoic acid ester, alkylamide, fatty acid ester, trimesic acid ester, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate,
Examples include cyclohexanone. A volatile solvent may be used as an auxiliary solvent for dissolving the electron-donating colorless dye during microencapsulation. 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, a microcapsule containing an electron-donating colorless dye that develops different hues and a photocurable composition that is sensitive to light of different wavelengths are formed in each layer. An intermediate layer containing a UV absorber and / or a polymer thereof is provided between the light and heat sensitive layers. The intermediate layer is mainly composed of a binder and an ultraviolet absorber, and may contain additives such as a curing agent and a polymer latex, if necessary. As the ultraviolet absorber, an ultraviolet absorber matched to the fractionation wavelength can be used. For example, a benzotriazole compound, an aminoallylidenemalonnitrile compound, a benzophenone compound, a cinnamic acid ester compound, an aminibutadiene compound. Compounds known in the art such as can be used. These UV absorbers are added to the intermediate layer, but may be added to the protective layer, the light and heat sensitive layer, the antihalation layer and the like, if necessary.

In the present invention, the dispersion of the photocurable composition and the dispersion and encapsulation of the electron-donating colorless dye are preferably carried out in a water-soluble polymer, but a water-soluble composition which can be preferably used in the present invention is used. 25 ° as a polymer
Compounds of C which are soluble in water in an amount of 5% by weight or more are preferred. Specifically, proteins such as gelatin, gelatin derivatives, albumin and casein, cellulose derivatives such as methylcellulose and carboxymethylcellulose, and alginic acid. Soda, sugar derivatives such as starches (including modified starch), gum arabic, polyvinyl alcohol, styrene-
Examples thereof include maleic anhydride copolymer hydrolyzate, carboxy-modified polyvinyl alcohol, polyacrylamide, saponified vinyl acetate-polyacrylic acid copolymer, and synthetic polymers such as polystyrene sulfonate. Of these, gelatin and polyvinyl alcohol are preferred.

As the binder used as required in the recording material according to the present invention, the above water-soluble polymer, polystyrene, polyvinyl formal, polyvinyl butyral,
Acrylic resin: for example, polymethylmethacrylate, polybutylacrylate, polymethylmethacrylate, polybutylmethacrylate or their copolymers, phenol resin, styrene-butadiene resin, ethylcellulose -
Solvent-soluble polymers such as epoxy resins and urethane resins, or polymer latexes thereof can be used.
Of these, gelatin and polyvinyl alcohol are preferred. In the recording material of the present invention, various surfactants may be used for various purposes such as coating aid, antistatic property, slip property improvement, emulsion dispersion, and adhesion prevention. Examples of the surfactant include saponin which is a nonionic surfactant, polyethylene oxide, a polyethylene oxide derivative such as alkyl ether of polyethylene oxide, an alkyl sulfonate, an alkylbenzene sulfonate, an alkylnaphthalene sulfonate, an alkyl sulfate. ester,
Anionic surfactants such as N-acyl-N-alkylitaurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, amphoteric surfactants such as alkyl betaines and alkyl sulfobetaines, If necessary, a cationic surfactant such as an aliphatic or aromatic quaternary ammonium salt can be used. Various additives can be added to the recording material of the present invention, if necessary, including the additives described above. For example, dyes, ultraviolet absorbers, plasticizers, optical brighteners, which prevent irradiation and halation,
Typical examples of matting agents, coating aids, curing agents, antistatic agents and slipperiness improving agents are Research Disclosure.
e, Vol. 176, December 1978, Item 1
7643, and Vol. 187, November 1979,
Item 18716.

The coating liquid of the recording material of the present invention contains the above-mentioned microcapsule dispersion liquid, a mixed dispersion of the electron-accepting compound and the polymer compound of the present invention, a photopolymerization initiator and various additives. Composed. This coating liquid is applied on a desired support and dried. In the case of a multicolor recording material, an intermediate layer containing an ultraviolet absorber and / or a polymer thereof, and a light and heat sensitive layer are repeatedly provided on this light and heat sensitive layer. Further, it is preferable to provide a protective layer on the uppermost layer.

To apply the coating solution onto the support,
Doctor, Rod coater, Knife coater, Roller coder coater, Comma coater, Liver roll coater, Transfer roll coater, Gravure coater
It is possible to use a water, kiss roll coater, a car coater, an extrusion coater or the like. As a coating method, Research Disclosure,
Vol. 200, December 1980, Item 200
You can refer to item 36. The thickness of the recording paper is 0.1μ
m to 50 μm is suitable. The support may be paper, paper
Supports such as tied paper, laminated paper, synthetic paper, transparent films such as polyethylene terephthalate film, polystyrene film, polycarbonate film, metal plates such as aluminum, zinc and copper, Examples of the support include those obtained by subjecting the surface of the support to various treatments such as surface treatment, undercoating and metal vapor deposition treatment. As the support, Research Disclosure, Vo
l. 200, December 1980, Item 20036
The support of item can also be referred to. If necessary, these supports may be provided with an antihalation layer on the front surface, and a slip layer, an antistatic layer, a curl prevention layer, a pressure-sensitive adhesive layer or the like on the back surface.

The recording material of the present invention can record with high sensitivity by light in a wide range from ultraviolet light to visible light. As the light source, mercury lamp, xenon lamp, tungsten lamp,
Various lasers such as metal halide lamps, argon lasers, helium neon lasers, semiconductor lasers, LEs.
A wide range of light sources such as D and fluorescent lamps can be used. As an image recording method, various exposure methods such as contact exposure of a document such as a lith film, enlargement exposure of a slide or a liquid crystal image, and reflection exposure using reflected light of the document can be used. When performing multicolor recording, image recording may be performed multiple times using lights having different wavelengths. Light having different wavelengths can be obtained by changing the light source or the optical filter. It can also be obtained by directly printing an image with a thermal head. When the recording material of the present invention is imagewise exposed, 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 10 ° C.
0 ° C to 160 ° C. The heating time is 1 second to 5 minutes, preferably 3 seconds to 1 minute. Alternatively, the entire surface may be exposed after the heat development treatment to photo-cur the uncured portion.

[0034]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. Example 1 1). [Preparation of Electron Donor Colorless Dye Capsule Liquid] 3,3-bis (1-octyl-2-methylindole)
8.9 g of 3-yl) phthalide was dissolved in 16.9 g of ethyl acetate, and 20 g of Takenate D-110N (manufactured by Takeda Pharmaceutical Co., Ltd.) and 2 g of Millionate MR200 (manufactured by Nippon Polyurethane Industry Co., Ltd.) were added. . Add this solution to 8
% Phthalated gelatin 41 g and a 10% sodium dodecylbenzenesulfonate solution 1.4 g were added and emulsified and dispersed at 20 ° C. to obtain an emulsion. 14 g of water and 71 g of a 2.9% triethylenepentamine aqueous solution were added to the obtained emulsion, and the mixture was heated to 60 ° C. with stirring, and after 2 hours, a capsule liquid having an average particle size of 0.5 μm was obtained.

2). [Preparation of Emulsion of Photocurable Composition] 2-O-chlorophenyl-4,5-as a photopolymerization initiator
0.12 g of diphenyl imidazole dimer and 7-diethylamino-4-methylcoumarin as a spectral sensitizing dye.
12 g and a solution of N-phenylglycine ethyl ester 0.06 g of isopropyl acetate 3 g as an auxiliary agent for accelerating the polymerization, and 2-chloro-4 as an electron accepting compound.
8 g of-(N-methyl-N-β-methacryloyloxyethylsulfamoyl) phenol were added. This solution was added to a mixed solution of 13 g of a 13% gelatin aqueous solution and 0.8 g of a 2% nonylphenoxybutanesulfonic acid bis-2-ethylhexyl ester sodium salt aqueous solution, and was rotated 10,000 times with a homogenizer (manufactured by Nippon Seiki Co., Ltd.). For 5 minutes to obtain an emulsion of the photocurable composition.

3). [Preparation of coating liquid for light and heat sensitive layer] 4 g of the electron-donating colorless dye capsules, 12 g of emulsion of the photosensitive composition and 12 g of 15% gelatin aqueous solution were mixed to prepare a coating liquid for light and heat sensitive layer.

4). [Preparation of coating liquid for protective layer] 4.5 g of 10% gelatin aqueous solution, 4.5 g of distilled water and 2%
0.5 g of an aqueous solution of N-octylsulfonyl-N-propylglycine potassium salt and 0.3 g of a 2% aqueous solution of triethylene glycol mono-p-nonylphenyl ether monosodium sulfobutyl ether and 2% N, N-bis (Vinylsulfonylacetyl) ethylenediamine aqueous solution 0.5 g and Syloid 72 (FUJI-DEVISON CHEM
ICHAL LTD. The coating liquid for the protective layer was prepared by mixing the coating liquid) in an amount such that the coating amount was 50 mg / m ² .

5). [Preparation of test sample] A 100 μm thick polyethylene terephthalate film support was coated with a coating solution for the light and heat sensitive layer using a coating bar so that the dry weight of the coating layer was 8 g / m ^2. , Dried at 30 ° C for 10 minutes. A coating solution for protective layer was applied onto this layer using a coating bar so that the dry weight of the coating layer was 2 g / m ² , and the sample was similarly dried to obtain a sample.

An image was developed on the obtained light and heat sensitive recording material and exposed to ultraviolet light for 60 seconds from a 1000 W high pressure mercury lamp (Jetlight manufactured by Oak Corporation) through a lith film. Then, when heated with a hot plate at 110 ° C. for 5 seconds, a clear magenta colored image was obtained. The image density is 2.
At 20, the density of the non-image area was 0.08. Further, in order to examine the storability of the obtained image, it was left for 24 hours under the conditions of 40 ° C. and 90 RH%, and the color density of the image part did not change and the fog density of the non-image part was 0.10. .

Example 2 1). [Preparation of Capsule Solution] 2-anilino-3-methyl-6-diethylaminofluorane 14.0 g, Takenate D110N (capsule wall agent manufactured by Takeda Pharmaceutical Co., Ltd.) 60 g, and Smith 200.
(Sumitomo Chemical Co., Ltd. UV absorber) 2 g, 1-phenyl-2-xylylethane 55 g, and methylene chloride 55
It was dissolved in g mixed solvent. This electron-donating colorless dye solution was added with 100 g of an 8% polyvinyl alcohol aqueous solution and 40 g of water.
Then, the mixture was mixed with an aqueous solution of 1.4 g of 2% sodium salt of dioctyl sulfosuccinate and emulsified with a homogenizer. Further, 150 g of water was added and reacted at 40 ° C. for 3 hours to obtain capsules having a capsule size of 0.7 μm.

2). [Preparation of Electron Accepting Compound Dispersion] 2-O-chlorophenyl-4,5-as a photopolymerization initiator
0.12 g of diphenyl imidazole dimer and 7-diethylamino-4-methylcoumarin as a spectral sensitizing dye.
12 g and a solution of 0.06 g of N-phenylglycine ethyl ester as an auxiliary agent for accelerating the polymerization and 8 g of ethyl acetate, and 2-chloro-4- (N
8 g of -methyl-N-β-methacryloyloxyethylsulfamoyl) phenol were added. Add to this solution 7.
5% polyvinyl alcohol aqueous solution 9.6 g and 2% nonylphenoxybutanesulfonic acid soda aqueous solution 0.8 g and 2
% Aqueous solution of sodium dodecane sulfonate (0.8 g) was added and the mixture was emulsified with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to obtain an emulsified dispersion of an electron accepting compound.

3). [Preparation of Recording Material] 4.0 g of the electron-donating colorless dye capsule liquid, 12 g of the electron-accepting compound dispersion liquid, and 5.0 g of a 15% polyvinyl alcohol aqueous solution were stirred and mixed to prepare a coating liquid. A 70 μm thick transparent polyethylene terephthalate (PE
T) A film was coated on the film so that the solid content was 15 g / m ² and dried. On the heat-sensitive layer, a protective layer containing the following solid components was further formed at 2.5 g / m ² . Silicon-modified polyvinyl alcohol (PVAR-2105, manufactured by Kuraray Co., Ltd.) 2 parts by weight Colloidal silica (SNO-TEX 30, manufactured by Nissan Chemical Co., Ltd.) 3 parts by weight Emulsion of paraffin wax (Hydrin Z-, manufactured by Chukyo Yushi Co., Ltd.) 7) 0.9 parts by weight Zinc stearate emulsion (Hydrin Z-7 manufactured by Chukyo Yushi Co., Ltd.) 0.2 parts by weight

4). [Image Recording and Evaluation] When the obtained recording material was printed at 30 mJ / mm ² using a thermal printing tester manufactured by Kyocera Corp., a clear black image was obtained. The obtained image was exposed with a 1000 W high-pressure mercury lamp (Jetlight manufactured by Oak Co.), and the sample was printed again by a thermal printing tester, but no color was printed on the unprinted part.

Example 3 2-O-chlorophenyl-4,5-diphenylimidazole dimer, 7-diethylamino-4-methylcoumarin, used in the preparation of the electron-accepting compound dispersion of Example 2, The electron-accepting compound dispersion was purified in the same manner as in Example 2 without using N-phenylglycine ethyl ester. A coating liquid was prepared by stirring and mixing 4.0 g of the electron-donating colorless dye capsule aqueous solution of Example 2, 12 g of the electron-accepting compound dispersion liquid, and 5.0 g of a 15% polyvinyl alcohol aqueous solution. This coating solution was applied to 50 g / m ² of neutral paper so that the solid content was 15 g / m ² , and dried. On the heat-sensitive layer, 2.5 g of the protective layer used in Example 2 was further added.
/ M ^{2 was} formed. The obtained recording material was used by Kyocera Corporation.
When printing was performed at 30 mJ / mm ² using a thermal printing tester, a clear black image was obtained.

Example 4 Instead of 2-chloro-4- (N-methyl-N-β-methacryloyloxyethylsulfamoyl) phenol of Example 1, 2-chloro-4- [N- (6-methacryloyl) was used. A recording material was prepared in the same manner as in Example 1 except that [oxyhexyl) sulfamoyl] was used. When the obtained recording material was exposed and heated in the same manner as in Example 1, a clear magenta image was obtained. Image density is 1.
In 73, the density of the non-image area was 0.06. The storability of the obtained image was evaluated in the same manner as in Example 1. As a result, the color density of the image area did not change, and the fog density of the non-image area was 0.09.

Example 5 Instead of 2-chloro-4- (N-methyl-N-β-methacryloyloxyethylsulfamoyl) phenol of Example 1, 2-chloro-4- [N-methyl-N- (6
A recording material was prepared in the same manner as in Example 1 except that methacryloyloxyhexyl) sulfamoyl] phenol was used. When the obtained recording material was exposed and heated in the same manner as in Example 1, a clear magenta image was obtained. Image density is 2.28 and non-image density is 0.07
Met. The storability of the obtained image was evaluated in the same manner as in Example 1. As a result, the color density of the image area did not change, and the fog density of the non-image area was 0.09.

Comparative Example 1 1). [Preparation of Electron Donor Colorless Dye Capsule Liquid] 3,3-bis (1-octyl-2-methylindole)
8.9 g of 3-yl) phthalide was dissolved in 16.9 g of ethyl acetate, and 20 g of Takenate D-110N (manufactured by Takeda Pharmaceutical Co., Ltd.) and 2 g of Millionate MR200 (manufactured by Nippon Polyurethane Industry Co., Ltd.) were added. . Add this solution to 8
% Phthalated gelatin 41 g and a 10% sodium dodecylbenzenesulfonate solution 1.4 g were added and emulsified and dispersed at 20 ° C. to obtain an emulsion. 14 g of water and 71 g of a 2.9% triethylenepentamine aqueous solution were added to the obtained emulsion, and the mixture was heated to 60 ° C. with stirring, and after 2 hours, a capsule liquid having an average particle size of 0.5 μm was obtained.

2). [Preparation of Emulsion of Photocurable Composition] 2-O-chlorophenyl-4,5-as a photopolymerization initiator
0.12 g of diphenyl imidazole dimer and 7-diethylamino-4-methylcoumarin as a spectral sensitizing dye.
8 g of 2,4-dihydroxybenzoic acid vinylbenzyl ester as an electron-accepting compound was added to a solution of 12 g and 0.06 g of N-phenylglycine ethyl ester as an auxiliary agent for accelerating polymerization in 3 g of isopropyl acetate. This solution was added to a mixed solution of 13 g of a 13% gelatin aqueous solution and 0.8 g of a 2% nonylphenoxybutanesulfonic acid bis-2-ethylhexyl ester sodium salt aqueous solution, and a homogenizer (manufactured by Nippon Seiki Co., Ltd.) 1
It was emulsified at 0000 rpm for 5 minutes to obtain an emulsion of the photocurable composition.

3). [Preparation of coating liquid for light and heat sensitive layer] 4 g of the electron-donating colorless dye capsules, 12 g of emulsion of the photosensitive composition and 12 g of 15% gelatin aqueous solution were mixed to prepare a coating liquid for light and heat sensitive layer.

4). [Preparation of Coating Solution for Protective Layer] The same coating solution for protective layer as in Example 1 was prepared.

5). [Preparation and Evaluation of Test Sample] A light and heat sensitive recording material was obtained in the same manner as in Example 1. When the obtained light and heat sensitive recording material was exposed and heat-developed in the same manner as in Example 1, a clear magenta colored image was obtained. The image density was 1.50, but the non-image part density was 0.55. In addition, in order to examine the storability of the obtained image, it was left for 24 hours under the conditions of 40 ° C. and 90 RH%, but the color density of the image part did not change, but the fog density of the non-image part was 0.75. Increased.

Comparative Example 2 4-Hydroxybenzoic acid- (2-methacryloyloxyethyl) was used in place of 2,4-dihydroxybenzoic acid vinylbenzyl ester used in the electron accepting compound of Comparative Example 1.
An electron-accepting compound emulsion was obtained in the same manner as in Comparative Example 1 except that the ester was used. When a light and heat sensitive recording material was obtained in the same manner as in Comparative Example 1 and subjected to exposure and heat development in the same manner as in Example 1, an image of magenta color development was obtained, but the image density was 0.75.

[0053]

The recording material of the present invention has a high image density,
In addition, the fog density in the non-image area is low, and the stability of the non-image area is extremely good.

Claims (2)

[Claims] 1. A recording material comprising a support, on which microcapsules containing an electron-donating colorless dye and a layer containing an electron-accepting compound are provided, wherein the electron-accepting compound is represented by the following general formula (I): A recording material characterized by being a phenol derivative. General formula (I) (In the formula, R ₁ is a hydrogen atom, a halogen atom, an alkyl group,
An alkoxy group or a phenyl group which may have a substituent is represented, R ₂ is an alkyl group having an acryloyloxy group or a methacryloyloxy group, and R ₃ is a hydrogen atom or an alkyl group. ) 2. The recording material according to claim 1, wherein the layer containing the electron-accepting compound contains a photopolymerization initiator.