JPH04195046A - Recording material - Google Patents

Abstract

PURPOSE:To increase color density and to improve the shelf stability of a non- image area by enveloping a color developing component in microcapsules and using an org. compd. having specified max. absorption wavelength in a specified spectral absorption wavelength range as a photopolymn. initiator. CONSTITUTION:At least one kind of component taking part in color development or vanishment is enveloped in microcapsules and a prescribed photopolymn. initiator is used in a photosetting compsn. for forming a latent image by exposure. This initiator is a 2-substd. phenyl-4,6-bistrihalomethyl-s-triazine deriv. having 330-345nm max. absorption wavelength in the spectral absorption wavelength range of 270-400nm in acetonitrile.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a recording material that can be used in fields such as recording paper for facsimile machines, printers, etc., presentation films, medical recording films, proofreading proofs, etc.
In particular, it relates to light and heat sensitive recording materials with improved polymerizability at specific wavelengths.

``Prior Art J 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 is being carried out to improve this problem.

Forms of recording materials that solve these problems include (1) attempts to microcapsule a polymerizable composition and an electron-donating colorless dye; (2) microcapsules containing an electron-donating colorless dye containing a photopolymerizable composition and light Attempt to use an electron-accepting compound composition or a photopolymerizable electron-accepting compound composition containing a polymeric composition, (3) containing a capsule containing a child-donating colorless dye and a photopolymerizable composition. Attempts have been made to use electron-accepting compound compositions or photopolymerizable electron-accepting compound compositions. In the case of multicolored recording materials, for example, microcapsules containing electron-donating colorless dyes that produce different hues and microcapsules that are sensitive to light of different wavelengths are being used. It is also possible to use a multilayer recording material configuration, with each layer containing a curable composition. For example, a microcapsule containing an electron-donating colorless dye that develops a cyan color and a wavelength λ
1, a layer containing a photocurable composition sensitive to light is provided on a support, and on the layer, microcapsules containing an electron-donating colorless dye that develops a magenta color and a photocurable composition sensitive to wavelength λ2 are provided. A layer containing the above is provided, and a layer containing microcapsules containing an electron-donating colorless dye that develops a yellow color and a photocurable composition sensitive to wavelength λ3 is provided thereon. In this case, if the division of the sensitive layer that develops each color is not sharp, color mixing will occur, which will reduce the commercial value of the recording material. ``Problems to be Solved by the Invention'' It is an object of the present invention to provide a photo- and heat-sensitive recording material which has high two-color density and improved storage stability in non-image areas, and which has improved photopolymerizability in a specific wavelength range.

[Means for Solving the Problems] The object of the present invention is to form a latent image on a photocurable composition by exposure to light, and by heating, components involved in color development or decolorization move within the photosensitive material in accordance with the latent image. In the light- and heat-sensitive recording material that forms a color image, at least one component involved in color development or decolorization is encapsulated in microcapsules, and in the photocurable composition, 270% in acetonitrile is added as a photopolymerization initiator. Achieved by a light and heat sensitive recording material characterized by using a 2-substituted phenyl-4,6-bistrihalomethyl-S-triazine derivative with spectral absorption at ~400 nm and maximum absorption wavelength within the range of 330-345 nm. It was done.

The recording material according to the present invention is exposed to light of 390 to 400 nm or less, the exposed area is cured, and then.

The recording material according to the present invention, in which two images can be obtained by uniformly heating only the uncured portions of the non-exposed portions, can have various configurations depending on the purpose.

One preferred configuration is a configuration in which a layer consisting of microcapsules containing an electron-donating colorless dye, an electron-accepting compound having a polymerizable ethylene group, and a photocurable composition containing a photopolymerization initiator is provided on a support. It is.

Another preferred configuration is to provide a layer on a support, comprising a microcapsule containing an electron-donating colorless dye, an electron-accepting compound, a compound having a bipolymerizable ethylene group, and a photocurable composition containing a photopolymerization initiator. This is the configuration provided.

Another preferred configuration is a configuration in which a layer consisting of microcapsules containing an electron-donating colorless dye, a compound having a dipolymerizable ethylene group, and a photopolymerization initiator, and an electron-accepting compound is provided on a support.

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

The 2-fliI-substituted phenyl-4,6-bistrihalomethyl-s-triazine derivatives according to the present invention are as follows-
Those represented by Funagura (I) to (II[) are preferred.

In the above formula (1), the group represented by R1 is an alkoxy group, an alkyl group, an acyloxy group, a sulfonyloxy group, or a halogen atom, and in the above formula (I [), R2 represents The group represented by the above formula (III) is an alkyl group or an aryl group, and X represents a halogen atom.
), among the groups represented by R3, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms; Oxy group, alkoxycarbonyl group having 2 to 20 carbon atoms, 2 acyloxy group having 2 to 20 carbon atoms, 10
6 representing a gen atom In the above formula (I), the number of carbon atoms in the group represented by R1 is 1 to 2
0 alkyl group, alkoxy group having 1 to 20 carbon atoms,
An acyloxy group having 2 to 20 carbon atoms and a halogen atom are preferred, and these substituents may be further substituted.

In the above formula (I[), the number of carbon atoms in the group represented by R2 is 1 to
An alkyl group having 20 carbon atoms and an aryl group having 6 to 20 carbon atoms are preferable, and these substituents may have further substitutions.

In the above formula (I), the number of carbon atoms in the group represented by R3 is 1 to 2
0 alkyl group, alkoxo group having 1 to 20 carbon atoms,
An acyloxy group having 2 to 20 carbon atoms and a halogen atom are preferable, and these substituents may have further substitution.In the above formulas (I) to (III), the halogen atom represented by X is chlorine, Atoms are preferred.

Specific examples of the 2-substituted phenyl-4,6-bistrihalomethyl-S-triazine derivatives according to the present invention include 2-substituted phenyl-4,6-bistrihalomethyl-S-triazine derivatives.
- (4-(4-acetoxyphenylcarbonylamino)phenyl)-4,6-pisdrichloromethyl-S-triazine, 2-(4-(4-propionyloxyphenylcarbonylamino)phenyl)-4,6-pis Dolichloromethyl-S-triazine, 2-(4-(4-myristoyloxyphenylcarbonylamino)phenyl)
-4,6-pisdochloromethyl-S-) riazine, 2
- C4-(4-stearoyloxyphenylcarbonylamino)phenyl)-4,6-pisdolichloromethyl-s-triazine, 2-(4-(4-phenoxyacetyloxyphenylcarbonylamino)phenyl)-4,
6-pisdochloromethyl-S-triazine, 2-(4
-(4-phenylacetyloxyphenylcarbonylamino)phenyl)-4,6-pisdolichloromethyl-S
-triazine, 2- (4-(4-benzoyloxyphenylcarbonylamino)phenyl)-4,6-pisdrichloromethyl-S-triazine, 2- (4-(4-
benzyloxyphenylcarbonylamino)phenyl)
-4,6-pisdochloromethyl-s-triazine, 2
-C4-(4-Toluenesulfonyloxyphenylcarbonylamino)phenyl)-4,6-pisdolichloromethyl-sh riazine, 2- (4-(4-methylphenylcarbonylamino)phenyl]-4゜6- Pisdolichloromethyl-S-triazine, 2-(4-(4-chlorophenylcarbonylamino)phenyl)-4,6-
Pisdolichloromethyl-S-triazine, 2-(4-acetylaminophenyl)-,4,6-pisdolychloromethyl-S-triazine, 2-(4-octanoylaminophenyl)-4,6-pisdolichloromethyl-S-triazine Chloromethyl-S-)riazine, 2-(4-myristoylaminophenyl)-4
, 6-pisdochloromethyl-S-triazine, 2-(
4-stearoylaminophenyl)-4,6-pisdolichloromethyl-s-h riazine, ■,6-bis(4-(
4-(4,6-pisdrichloromethyl-S-triazin-2-yl)phenyl]aminocarbonylphenoxycarbonyl]hexane, 1,8-bis(4-(4,6-pisdrichloromethyl-S-triazine) -2-yl)phenyl-minocarbonyl]octane, 2- (4-(2-
phenylethynyl)phenyl]-4,6-pisdochloromethyl-S-triazine.

2-(4-(2-p-ethylphenylethynyl)phenyl)-4,6-pisdolichloromethyl-S-triazine, 2-(4-(2-p-octylphenylethynyl)
phenyl)-4,6-pisdolichloromethyl-S-triazine, 2-C4-(2-p-octyloxyphenylethynyl)phenyl)-4,6-pisdolichloromethyl-S-triazine, 2-(4 -(2-p-Phenylphenylethynyl)phenyl2-4,6-pisdolichloromethyl-S-triazine, 2-C4-(2-p-acetyloxyphenylethynyl)phenyl]-4,6-pisdolichloro Methyl-s-triazine.

Examples of the electron-accepting compound having a polymerizable ethylene group according to the present invention include phenol derivatives having one or more 9-polymerizable ethylene groups and a phenolic hydroxyl group. Methacryloxyethyl ester of benzoic acid having a hydroxy group described in No. 63-173682, acryloxyethyl ester synthesized by a similar synthesis method, No. 59-83693, No. 60-14
Ester of benzoic acid having a hydroxyl group and hydroxymethylstyrene as described in No. 1587 and No. 62-99190, hydroxystyrene described in European Patent No. 29323, Japanese Patent Application Laid-open No. 62-1.67077 and European Patent No. 62-99190, N-vinylimidazole complexes of zinc halide described in No. 62-16708 and No. 63-31755
In the above formula (V), X represents a hydrogen atom or a halogen atom, and Y represents a hydrogen atom or a halogen atom.
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 (V), among the monovalent groups having a polymerizable ethylene group represented by Y, an aralkyl group having a vinyl group, an acryloyloxyalkyl group; and methacryloyloxyalkyl groups are preferred.

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

3-chloro-4-hydroxybenzoic acid vinyl phenethyl ester, 3-chloro-4-hydroxybenzoic acid vinyl phenylpropyl ester, 3-chloro-4-hydroxybenzoic acid-(2-acryloyloxyethyl) ester, 3-chloro-4 -Hydroxybenzoic acid-(2-methacryloyloxyethyl) ester, 3-chloro-4-
Hydroxybenzoic acid-(6-methacryloyloxyhexyl) ester, 3-chloro-4-hydroxybenzoic acid-(6-acryloyloxyhexyl) 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-4-hydroxybenzoic acid-(4
-methacryloyloxybutyl) ester, 3-fluoro-4-hydroxybenzoic acid-(2-acryloyloxyethyl) ester, 2,4-dihydroxy-6-methylbenzoic acid vinylbenzyl ester, 2,4-dihydroquinol-5-methylbenzoic acid acid vinyl benzyl ester, 2,
4-Dihydroquine-3-methylbenzoic acid vinylbenzyl ester, 2,4-dihydroxo-3-chlorobenzoic acid vinylbenzyl ester.

2,4-dihydroxy-6-phenylbenzoic acid vinylbenzyl ester, 2,4-dihydroxybenzoic acid vinylphenethyl ester, 2,4-dihydroxybenzoic acid vinylphenylpropyl ester.

2.4-dihydroxobenzoic acid vinylbenzyl ester 1,2-acryloyloxy-4-hydroxybenzoic acid-(2-acryloyl quinethyl) ester, 2-methacryloyloxy-4-hydroxybenzoic acid-(2-methacryloyloxyethyl) ) ester, 2,4-dihydroxybenzoic acid (2,3-bismethacryloyloxypropyl) ester, 2,4-dihydroxybenzoic acid (2
, 3-bisacryloyloxypropyl) ester, etc. These electron-accepting compounds may be used in combination with other non-polymerizable electron-accepting compounds. , phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, 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
2-140483, JP 48-51510, JP 57-210886, JP 58-87089,
JP-A-59-11286, JP-A-60-176795
No. 61-95988, etc. To illustrate some of these, phenolic compounds include 2,2'-bis(4-hydroxyphenyl)propane, 1,1'-bis(3-chloro-4-hydroxyphenyl)cyclohexane, 1.1 -bis(4-hydroxyphenyl)cyclohexane, 1, l-bis(3-chloro-4-hydroxyphenyl)-2-ethylbutane, 4.
4'-5ec-isooctylidene diphenol, 4.4
-sec-butylidene diphenol, 4,4-isopentylidenephenol, benzyl p-hydroxybenzoate, and the like. Salicylic acid derivatives include 3-dodecylsalicylic acid, 3,5-di(α-methylbenzyl)salicylic acid, 3,5-ter-octylsalicylic acid, 3-dodecyl-5-methylsalicylic acid, 5-α-(p- α-Methylbenzylphenyl)ethylsalicylic acid, total α-methylhensyl-5-ter-octylsalicylic acid, 3-nonyl-5-methylsalicylic acid, 3,5-dinonylsalicylic acid, 3-nonyl-5-ter-butylsalicylic acid, 4
-dodecyloxysalicylic acid, 3-α,α-dimethylbenzyl-6-methylsalicylic acid, 3゜5-bis-α,α
-dimethylbenzyl-6-methylsalicylic acid, etc., and their zinc, aluminum, and nickel salts.

When these electron-accepting compounds other than the present invention are used in combination, it is preferable to use the electron-accepting compound of the present invention in an amount of 50% by weight or more, preferably 70% by weight or more.

Related to the present invention. Examples of polymerizable compounds having at least one polymerizable ethylene group in one molecule used in the photocurable composition include acrylic acid and its salts, acrylic esters, acrylamides, methacrylic acid and its salts,
Methacrylic esters, methacrylamides: Maleic anhydride, maleic esters, itaconic acid, itaconic esters, styrenes: Vinyl ethers, vinyl esters: N-vinyl heterocyclics, nearyl ethers, allyl esters, etc. can be mentioned.

Among these, polymerizable compounds having a plurality of ethylenically unsaturated double bonds in the molecule are particularly preferred; for example, acrylic esters and methacrylic esters of polyhydric alcohols such as trimethylolpropane and pentaerythritol; and Examples include acrylate- or methacrylate-terminated epoxy resins, acrylate- or methacrylate-terminated polyesters, and the like. Specific examples of particularly preferred compounds include, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, hexanediol-1,6-dimethacrylate, and diethylene glycol dimethacrylate. methacrylate, etc.

The molecular weight of the polyfunctional monomer is about 100 to about 50
00 is preferred, more preferably about 300 to about 200
It is 0.

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.

The photopolymerization initiator according to the present invention may be used in combination with a compound capable of initiating photocombination of other ethylenically unsaturated bond-containing compounds.

The content of the photopolymerization initiator is preferably from 0.01 to 20% by weight, and more preferably from 02 to 15% by weight, and most preferably from 5 to 10% by weight, based on the total weight of the photopolymerizable composition. Weight%. If it is less than 10% by weight, the sensitivity will be insufficient, and if it exceeds 10% by weight, no increase in sensitivity can 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 wavelength of light 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,
Research Disclosure, Vol.
200. December 1980, Item 20036
and “sensitizers” (Katsumi Tokumaru/edited by Okawamotosuke, Kodansha 1)
987), pages 160-163, etc., can be referred to.

In addition, the photopolymerizable composition used in the present invention further includes reducing agents such as oxygen scavengers (
A chain transfer agent such as oxygen (oxygen 5cave mer) and an active hydrogen donor, and 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. For example, N-phenylglycine, trimethylbarbital acid, N.

N-dimethyl-2,6-dimaprobylaniline, N,
N, N-2,4,6-pentamethylaniline and the like.

Furthermore, thiols, thioketones, trihalomethyl 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, leucoauramine compounds, rhodamine lactam compounds, and triphenylmethane compounds. , triazene compounds, spiropyran compounds, and fluorene compounds.

Specific examples of phthalides are given in U.S. Reissue Patent Specification No. 23.0.
No. 24, U.S. Pat. No. 3,491.111, U.S. Pat. No. 3,491.112, U.S. Pat.

Specific examples of fluorans are given in U.S. Pat. No. 3,624.
No. 107, No. 3,627.787, No. 3,641
, No. 011, No. 3,462,828, No. 3,68
No. 1,390, No. 3,920.510, No. 3,9
No. 59,571, specific examples of spiropyrans are given in US Pat. No. 3,971.808, and pyridine and pyrazine compounds are given in US Patent No. 3,775,424.

No. 3,853,869, No. 4,246,318, and specific examples of fluorene compounds are given in Japanese Patent Application No. 61-2409.
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. 4540790, No. 4
No. 025.090, No. 4446.321, No. 4365
．． No. 503, No. 4820.841, No. 4598.15
No. 0, 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 color developing type, Japanese Patent Application Laid-Open No. 63-53542, Japanese Patent Application Publication No. 62-270662, Japanese Patent Application Publication No. 63-11.3446, British Patent No. 63-112188, Compounds described in European Patent Publication No. 1-213636, European Patent Publication No. 82822, etc. 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 Ol~2g/m'',
0.2-Ig/m'', electron-accepting compound: 0.2-2
0 g/m2, preferably 0.4 to 10 g/m' When the electron-donating colorless dye of the present invention to be used is microencapsulated, it can be prepared 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 wall-forming materials such as urea-formaldehyde-based and urea-formaldehyde-resorcinol-based materials as seen in No. 2, a method using wall-forming materials such as melamine-formaldehyde resin and hydroxypropyl cellulose as seen in U.S. Pat. -9168,
Japanese Unexamined Patent Publication No. 51-. In situ process by polymerization of monomers, as found in British Patent No. 9079, British Patent No. 9528.
No. 07, electrolytic dispersion cooling method found in No. 965074,
US Patent No. 3111407, UK Patent No. 930422
There is a spray drying method as seen in the issue. 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 using a microencapsulation method by polymerizing a glue actant from inside an oil droplet. That is, it is possible to obtain capsules which are desirable as a recording material with 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 No. 48-80191, JP-A No. 48-8408
No. 6, and they can also be used.

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

As the anionic polymer, both natural and synthetic polymers can be used, such as -〇〇〇-1-SO2-
Examples include those having a group or the like. Specific anionic natural polymers include gum arabic, alginic acid, pectin, etc., and semi-synthetic products include carboxymethyl cellulose, phthalated seratin, 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.

Gelatin is an amphoteric compound.

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

The size of the capsule 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. Furthermore, if the capsule is too small, the surface area for a given solid 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 oils or synthetic oils can be used in conjunction with the solvent used in the present invention. Examples of these solvents include, for example, cottonseed oil, kerosene 1, paraffins, naphthenic oils, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins, alkylated naphthalenes and 1-phenyl-1-
Diarylethanes such as xylylethane, -phenyl-1-p-ethylphenylethane, 1.1'-ditolylethane and the like. Phthalic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc. .

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. 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 optionally contains additives such as a curing agent and polymer latex. can contain.

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 UV absorber is a UV absorber with a structure that makes it difficult to diffuse into adjacent layers, such as a polymer or latex copolymerized with a UV absorber. As such a UV absorber, for example, European Patent No. 1
No. 27.819, JP-A No. 59-68731, JP-A No. 59-
No. 26733, No. 59-23344, British Patent No. 2,1
18,315, JP-A-58-111942, U.S. Pat. No. 4,307,184, U.S. Pat.
No. 178,303, JP-A-47-560, etc. can be referred to.

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

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. 5 for C water
Compounds that dissolve at least % by weight are preferred, and specifically include gelatin, gelatin derivatives, proteins such as albumin and casein, cellulose derivatives such as methylcellulose and carboxymethylcellulose, sodium alginate, and sugar derivatives such as starches (including modified starches). Synthetic polymers such as gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer hydrolyzate, carboxine-modified polyvinyl alcohol, polyacrylamide, saponified vinyl acetate-polyacrylic acid copolymer, polystyrene sulfonate, etc. can give. 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 , phenolic resins, styrene-butadiene resins, ethyl cellulose, epoxy resins, and 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 may be used for various 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 -Anionic surfactants such as acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, amphoteric surfactants such as alkyl betaines and alkyl sulfobetaines, fatty acids or aromatic A cationic surfactant such as acid quaternary ammonium salts may be used if necessary.

Various additives, including the additives mentioned 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 Disclosure, Vol.
176, December 1978, Item 17643, and Vo1.187. November 1979, Item
18716.

The coating liquid for the recording material of the present invention is composed of the above-mentioned microcapsule dispersion, electron-accepting compound dispersion, photopolymerization initiator, and various additives.
It is coated 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 on the top layer.

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 Re5earch Disclosure, Vol.
200. December 1980, [tem 20036 for reference. The thickness of the recording layer is from 01μ to 5μ.
0μ or 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.

1, 200. December 1980, Item 20036
You can also refer to the supporting material in section 2. 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.

The recording material of the present invention can record with high sensitivity using light in a wide range from ultraviolet light to visible light. As a light source, a wide range of light sources can be used, including mercury lamps, xenon lamps, tungsten lamps, metal halide lamps, various types of racers such as argon racers, helium neon racers, and semiconductor racers, LEDs, and fluorescent lights.

As an image recording method, various exposure methods can be used, such as close exposure of an original such as 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. Further, when the recording material of the present invention obtained by direct imagewise printing with a thermal head is subjected to the above-mentioned imagewise exposure, a heat development treatment is performed 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. Heating time is 1
The time period is from seconds to 5 minutes, preferably from 3 seconds to 1 minute. Further, after the heat development treatment, the entire surface may be exposed to light to photocure the uncured portions.

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

"Example" Example-1 1) [Preparation of electron-donating colorless dye capsule liquid 3.3
-bis(1-cutyl-2-methylindol-3-yl) phthalide 89g to 16 ethyl acetate! 20 g of Takenate D-11ON (manufactured by Takeda Pharmaceutical Co., Ltd.) and 2 g of Millionate MR200 (manufactured by Japan Polyurethane Industries, Ltd.) were added. This solution was dissolved in 42 g of 8% phthalated gelatin and 10% Add to a mixture of 1.4 g of sodium dodecylbenzenesulfonate solution,
An emulsion was obtained by emulsification and dispersion at 0"C. 14 g of water and 72 g of a 2.9% triethylenepentamine aqueous solution were added to the obtained emulsion.
After 2 hours, a capsule liquid with an average particle size of 05 μm was obtained.

2), Preparation of Emulsion of Photocurable Composition 3 0.13 g of the photopolymerization initiator shown in Table 1, 0.2 g of 2-mercaptophenothiazine and 3 g of isopropyl acetate as auxiliary agents for promoting polymerization. 5 g of 3-chloro-4-hydroxybenzoic acid-(6-methacryloyloxyhexyl) ester was added to the solution. This solution was added to a mixed solution of 13 g of a 13% aqueous seratin solution, 0.8 g of a 2% aqueous solution of sodium nonylphenoxybutanesulfonate, and 0.8 g of a 2% aqueous solution of sodium sulfosuccinic acid bis-2-ethylhexyl ester. (manufactured by Seiki Co., Ltd.)
The mixture was emulsified at 10,000 rotations for 5 minutes to obtain an emulsion of a photocurable composition.

3), [Preparation of coating solution for photosensitive/thermosensitive layer] 4 g of electron-donating colorless dye capsules, 12 g of emulsion of photocurable composition, and 1
A coating solution for photosensitive/thermosensitive layers was prepared by mixing with 12 g of a 5% aqueous gelatin solution.

4) Preparation of coating solution for protective layer C: 4.5 g of 10% aqueous gelatin solution, 1.5 g of distilled water, and 2%
0.5 g of N-octylsulfonyl-N-propylglycine potassium salt aqueous solution and 0.3 g of 2% triethylene glycol monop-nonylphenyl ether monoradium sulfobutyl ether aqueous solution and 2% N,N'-bis(vinylsulfonylacetyl) Ethylenecyamine aqueous solution 0.5
g and Thyroid 72 (FIJJ[-DEV[SON C
(manufactured by HEMICHAL LTD) with an application amount of 50mg/
A coating solution for a protective layer was prepared by mixing an amount equal to m'.

5), [Preparation and evaluation of recording material] The coating solution for the photosensitive/thermosensitive layer was coated on a 100 μm polyethylene terephthalate film using a coating bar so that the dry weight of the coated layer was 8 g/m2, and the coating solution was coated at 30°. C
and dried for 10 minutes. The coating liquid for the protective layer was applied on this layer using a coating bar until the dry weight of the standing cloth layer was 2 g/m'.
It was wrapped in a tube so that it would look like this, and dried at 30°C for 10 minutes.

The resulting light- and heat-sensitive recording material was coated with an F evaluation-I step wedge [density difference 0. +5
, 15 density steps, Fuji Step Guide P (manufactured by Fuji Photo Film Co., Ltd.) and optical interference filter "Evaluation-2"
Step wedge and optical interference filter (2)] The light from a 6kw HI-IQ light source (manufactured by Dainippon Screen Co., Ltd., P-824-GX, using D bulb) was
It was exposed to light for seconds, and then heated for 5 seconds on a hot plate at 120°C. Sensitivity was defined as the number of step wedges in which the color density of the light- and heat-sensitive recording material corresponded to 10% of the unexposed area. This table shows the sensitivity when exposed to two different wavelengths.
Shown in 2.

Table 1 Table 2 --- is less than 1 stage According to Table 2, the light and heat sensitive recording materials (Samples Nos. 1 to 4) using the photopolymerization initiator according to the present invention have high sensitivity on the short wavelength side. And the sensitivity is low on the long wavelength side, 400 nm.
It can be seen that fractionation is possible.

[Brief explanation of the drawing]

FIG. 1 shows the spectral characteristics of the optical interference filter used during exposure.

Claims (1)

[Scope of Claims] 1) A latent image is formed on the photocurable composition by exposure, and components involved in color development or decolorization are moved within the photosensitive material according to the latent image by heating to form a color image. In the light and heat sensitive recording material, at least one component involved in color development or color erasure is encapsulated in microcapsules, and the photocurable composition contains 2 in acetonitrile as a photopolymerization initiator.
2-substituted phenyl- with spectral absorption in the range of 70 to 400 nm and maximum absorption wavelength in the range of 330 to 345 nm.
A photosensitive and thermosensitive recording material characterized by using a 4,6-bistrihalomethyl-S-triazine derivative. 2) In claim 1), at least one microencapsulated component involved in color development or decolorization is an electron-donating colorless dye, and the photocurable composition is an electron-accepting compound having a polymerizable ethylene group. and a photopolymerization initiator. 3) In claim 1), at least one component involved in color development or decolorization that is microencapsulated is an electron-donating colorless dye, and the photocurable composition is a compound having a polymerizable ethylene group and a photopolymerizable component. A light and heat sensitive recording material comprising an initiator. 4) The photosensitive and thermosensitive method according to claim 1, wherein the photocurable composition comprises a compound having a polymerizable ethylene group and a photopolymerization initiator, and the photocurable composition is microencapsulated together with an electron-donating colorless dye. Recording materials.