JPH0939385A - Heat-sensitive pressure-sensitive recording material and image recording method - Google Patents

Abstract

(57) [PROBLEMS] To provide a heat-sensitive pressure-sensitive recording material capable of arbitrarily performing recording by heating and recording by pressing on the same recording surface. Another object of the present invention is to provide a heat-sensitive pressure-sensitive recording material capable of easily distinguishing a recorded image obtained by heating from a recorded image obtained by pressing and fixing each recording independently. A heat-sensitive pressure-sensitive recording material comprising a support and a pressure-sensitive microcapsule containing a reactant and a co-reactant that reacts with the reactant to form a colored body, and a thermosensitive microcapsule. Further, on the support, a pressure-sensitive microcapsule containing a reactant, a co-reactant that reacts with the reactant to form a colored body, and a co-reaction that forms a colored body having a hue different from that of the colored body. A heat-sensitive pressure-sensitive recording material that holds heat-sensitive microcapsules enclosing the body.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive pressure-sensitive recording material capable of simultaneously performing heat-sensitive recording and pressure-sensitive recording on an arbitrary portion on one sheet, and an image recording method using the same. .

[0002]

2. Description of the Related Art A thermosensitive recording material generally comprises a support provided with a thermosensitive recording layer mainly comprising a colorless or pale-colored electron-donating dye precursor and an electron-accepting compound (a color developer) as main components. Yes, by heating with a thermal head, hot pen, laser light, etc., the electron donor dye precursor and the developer melt,
A color image is obtained by reacting instantaneously.
No. 60, Japanese Patent Publication No. 45-14039 and the like.

[0003] Generally, such a thermosensitive recording material has advantages that an image can be obtained by a relatively simple apparatus, maintenance is easy, and no noise is generated.
It is used in a wide range of fields such as facsimile machines, printers, computer terminal labels, and vending machines such as ticketing.

In a pressure-sensitive recording material, microcapsules containing an electron-donating dye precursor or the like are brought into contact with an electron-accepting compound (developing agent), and pressure is applied thereto to break the microcapsules. A color-forming image is obtained by reacting an electron-donating dye precursor with an electron-accepting compound (a color developer); US Pat. No. 2,712,507;
U.S. Pat. No. 2,730,456; U.S. Pat.
It is disclosed in the specification No. 0 and the like, and is widely used for slips and the like.

As an embodiment of such a pressure-sensitive recording material,
A sheet in which microcapsules containing an electron-donating dye precursor and the like are held on the back surface of the support, a sheet in which a developer is held on the surface of the support, and a developer is electron-donated on the back surface of the support There is a sheet holding microcapsules containing a dye precursor or the like, and these are used in combination as a copy set. In addition, there is a self-coloring type pressure-sensitive recording sheet in which a microcapsule containing an electron-donating dye precursor and the like and a developer are held on the same surface of a support and pressure-sensitive recording can be performed by one sheet. Further, there is a sheet or the like in which microcapsules containing an electron-donating dye precursor or the like are held on the back surface of the self-coloring type pressure-sensitive recording sheet, and a plurality of copy sets can be made by combining these.

In addition to such heat-sensitive recording materials and pressure-sensitive recording materials, there is also a demand for recording materials capable of performing both heat-sensitive recording and pressure-sensitive recording, and several proposals have been made so far. For example, Japanese Patent Application Laid-Open No. 58-132595 discloses that a solid at room temperature
Japanese Patent Application Laid-Open No. 59-171169 discloses a method of applying a pressure above a certain level after printing with a thermal recording head to a pressure-sensitive ink ribbon containing a substance which becomes liquid at 0 ° C. or more and a colorant as a main component. There has been proposed a pressure-sensitive and thermosensitive carbon copying paper in which a hot-melt type carbon layer composed of wax, pigment and dye is provided on the layer. These are those obtained by giving heat sensitivity to a conventional pressure-sensitive backing carbon paper. Further, a heat-sensitive pressure-sensitive transfer recording material combining a transfer layer sheet containing a leuco dye and wax and a developer sheet containing a phenolic color developer is disclosed in JP-A-60-212384, and a heat-sensitive recording layer is provided on the surface of a support. And JP-A-62-1382585, which combines a sheet provided with a dye precursor and a hot-melt substance on the back surface and a sheet provided with a solvent-encapsulated capsule and a developer on the surface of the support. Japanese Patent Application Laid-Open No. 60-1985 discloses a pressure-sensitive thermosensitive copying paper having a heat-sensitive recording layer provided on the surface of a support and a dye precursor-encapsulated capsule and a hot-melt substance provided on the back.
168690, JP-A-62-90282, JP-A-6-90282
No. 247038.

Further, a layer of a mixture of a coloring agent such as carbon and a heat-fusible substance such as wax is provided on the back side of a normal thermosensitive recording paper, and a color recording image is obtained by heating the first sheet. A method in which a heat-fusible substance provided on the back surface of the substrate is melted and transferred to form a recorded image on the second sheet, and a recording image can be formed on the second sheet by pressing with a writing instrument or the like; A method has also been proposed in which a microcapsule containing an electron-accepting dye precursor is held on the back side of paper, whereby the first sheet is colored by heating, and a recorded image is obtained on the second sheet by pressing.

In each of these methods, a recording image is obtained on a second sheet by recording on the front surface of the first sheet and providing a transfer layer by heating or pressing on the back surface of the first sheet. Therefore, only one of thermal recording and pressure-sensitive recording could be performed on the same recording surface. In addition, it is difficult to distinguish the obtained recorded image from that obtained by heat-sensitive recording or that obtained by pressure-sensitive recording, and it is difficult to deal with various uses.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a heat-sensitive and pressure-sensitive recording material in which heat-sensitive recording by heating and pressure-sensitive recording by pressure can be arbitrarily performed on the same recording surface. Another object of the present invention is to provide a heat-sensitive and pressure-sensitive recording material capable of easily distinguishing recorded images by heat-sensitive recording and pressure-sensitive recording, and fixing each record independently.

[0010]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a pressure-sensitive microcapsule containing a reactant and a co-reactant which reacts with the reactant to form a colored body on the same surface of a support, and This has been achieved by a heat-sensitive pressure-sensitive recording material in which heat-sensitive microcapsules are held and an image recording method using the same.
Further, on the same surface of the support, a pressure-sensitive microcapsule containing a reactant, a co-reactant that reacts with the reactant to form a colored body, and a colored body having a hue different from that of the colored body are formed. By holding the heat-sensitive microcapsules containing the co-reactant, it is possible to distinguish the heat-sensitive recorded image obtained by heating from the pressure-sensitive recorded image obtained by pressurization by the difference in color. The recording material could be obtained. Further, at least one of the pressure-sensitive microcapsules and the heat-sensitive microcapsules contains a photocurable resin together with a co-reactant, or a diazo compound is used as a co-reactant, so that pressure-sensitive or heat-sensitive can be obtained by exposure before and after recording. Thus, it was possible to obtain a heat-sensitive pressure-sensitive recording material capable of fixing the recording independently by eliminating one or both of the functions of the sex and the image recording method using the same.

The heat-sensitive pressure-sensitive recording material of the present invention utilizes the function of microcapsules, and two types of microcapsules are used in combination. That is, the heat-sensitive microcapsules have only the function of causing destruction by heat, the development of membrane permeability, etc., and are designed not to be destroyed even when pressure is applied, while the pressure-sensitive microcapsules have only the function of being destroyed by pressure. The microcapsules are designed so that the film material of the microcapsules has heat resistance so that the microcapsules do not break or exhibit membrane permeability even when heat is applied.

As a result, only the co-reactant contained in the heat-sensitive microcapsule reacts with the reactant existing outside the microcapsule in the portion heated by the heating means such as a hot pen or a thermal head to give a colored body. And is recognized as a recorded image. Further, in the portion pressed with a writing instrument, only the co-reactant encapsulated in the pressure-sensitive microcapsule reacts with the reactant present outside the microcapsule to form a colored body, which are recognized as independent recorded images. .
By changing the type of co-reactant contained in each microcapsule and making the hue of the colored body obtained by the reaction different, the hue of the recorded image obtained when heated and the hue of the recorded image obtained when pressed It is also possible to have different hues. For this reason, the image recorded by heat and the image recorded by pressure can be distinguished by color.

Further, by using a photodecomposable diazo compound as a co-reactant in the pressure-sensitive and / or heat-sensitive microcapsules, it is possible to freely control the coloring ability of one or both of the microcapsules. . That is, when a diazo compound having the same absorption wavelength is included in the pressure-sensitive microcapsule and the heat-sensitive microcapsule, by exposing a part of the recording surface, either the color development ability by pressurization or heating can be obtained. One or both can be eliminated simultaneously. Therefore, it is possible to previously form a portion on the recording surface that does not require color development. Further, re-recording can be prevented by exposing the entire surface after recording. Furthermore, when diazo compounds having different absorption wavelengths are included in the pressure-sensitive microcapsules and the heat-sensitive microcapsules, the portions for recording pressure-sensitive and / or heat-sensitive are exposed by exposing at different wavelengths. It can be formed in advance or after recording one of them.

By encapsulating a photocurable resin together with a coreactant in a pressure-sensitive or heat-sensitive microcapsule,
It is possible to arbitrarily eliminate the pressure-sensitive recording property or the heat-sensitive recording property of the recording surface. That is, if a part of the recording surface is exposed in advance before use, the photocurable resin contained in the microcapsules in the exposed part is cured, so that the microcapsules become rigid capsules and do not show pressure sensitivity or heat sensitivity. become. Therefore, it is possible to set a portion that does not require pressure sensitivity or heat sensitivity before recording. Further, if the entire recording surface is exposed after the recording is completed, the pressure sensitivity or heat sensitivity on the entire surface disappears, so that it is possible to prevent additional recording or recoloring due to pressurization or heating. In addition, by setting the absorption wavelength of the photopolymerization initiator added to the pressure-sensitive and heat-sensitive microcapsules to be different, the pressure-sensitive and / or heat-sensitive recordable portion is set in advance or after one of the recording is performed. can do.

As described above, the heat-sensitive and pressure-sensitive recording material of the present invention can be imparted with various functions. Therefore, it is possible to perform heat-sensitive recording and pressure-sensitive recording independently with one sheet.
It is also possible to make two or more copies. In addition to recording by heating with various printers having a thermal head, a heat stamp, and the like, recording by pressing with a writing instrument, a dot printing machine, an embosser, and the like can be performed. It is also useful as a recording material that requires forgery prevention and security.

The reactant and co-reactant used in the heat-sensitive pressure-sensitive recording material of the present invention may be any compound which forms a colored product by the reaction of each other, and is conventionally an inorganic or organometallic compound and a polyvalent hydroxyaromatic compound. It is known that a combination of a group compound, a combination of an electron-donating dye precursor and an electron-accepting compound, a combination of a diazo compound and a coupler such as a hydroxy aromatic compound, etc., and these combinations may be used alone or in combination. It can be used in combination.

The inorganic and organometallic compounds used in the heat-sensitive pressure-sensitive recording material of the present invention include copper nitrate, ferric chloride, iron stearate, copper stearate, silver behenate, iron oleate, iron benzoate and the like. Is mentioned. These can be used alone or in combination of two or more.

Examples of the polyvalent hydroxy aromatic compound used in the heat-sensitive pressure-sensitive recording material of the present invention include tannic acid, catechol, stearyl gallate, propyl gallate, pyrogallol and the like. These can be used alone or in combination of two or more.

The usually colorless or light-colored electron-donating dye precursor used in the heat-sensitive pressure-sensitive recording material of the present invention is typified by those generally used in pressure-sensitive recording paper and heat-sensitive recording paper, but is not particularly limited. Not something. Specific examples include the following, for example.

Examples of the triarylmethane compound and the indolylphthalide compound include 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone) and 3,3-bis (p -Dimethylaminophenyl) phthalide, 3- (p-
Dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (p- Dimethylaminophenyl)-
3- (2-phenylindol-3-yl) phthalide,
3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide,
3,3-bis (2-phenylindol-3-yl)-
5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6
-Dimethylaminophthalide and the like,

As the diphenylmethane-based compound, 4,
4'-bis (dimethylaminophenyl) benzhydryl benzyl ether, N-chlorophenylleuco auramine, N-2,4,5-trichlorophenyl leuco auramine, etc.

As the anilinofluoran compound, 3
-Diethylamino-6-methyl-7-anilinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3-diethylamino-6- Methyl-7- (4-
Methylanilino) fluoran, 3-diethylamino-6
-Methyl-7- (4-n-butylanilino) fluoran, 3-diethylamino-6-methyl-7- (4-ethoxyanilino) fluoran, 3-pyrrolidino-6-methyl-7- (4-methylanilino) fluoran, 3-pyrrolidino-6-methyl-7- (4-n-butylanilino)
Fluoran, 3-pyrrolidino-6-methyl-7- (4-
Ethoxyanilino) fluoran, 3-di-n-propylamino-6-methyl-7-anilinofluoran, 3-di-n-butylamino-6-methyl-7-anilinofluoran, 3-di- n-pentylamino-6-methyl-7-
Anilinofluoran, 3- (N-methyl-NNn-propyl) amino-6-methyl-7-anilinofluoran,
3- (N-ethyl-Nn-propyl) amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N)
-Isoamyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isobutyl) amino-
6-methyl-7-anilinofluoran, 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-tetrahydrofuran-2-ylmethyl) Amino-6-methyl-7-
Anilinofluoran, 3- (N-ethyl-N-tetrahydrofurylmethyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-tetrahydrofuran-2-yl) amino-6 Methyl-7-anilinofluoran, 3- (N-ethyl-N-tetrahydrofuryl)
Amino-6-methyl-7-anilinofluoran, 3-dimethylamino-6-methyl-7-anilinofluoran,
3- (N-methyl-N-ethyl) amino-6-methyl-
7-anilinofluoran, 3-isopentylamino-6
-Methyl-7-anilinofluoran, 3-di-n-butylamino-6-methyl-7- (2-fluoroanilino)
Fluoran, 3-dibutylamino-6-methoxy-7-
Anilinofluoran, 3-di-n-butylamino-6-
Methyl-7- (2,6-dimethylanilino) fluoran, 3- (N-ethyl-N-3-ethoxypropyl) amino-6-methyl-7-anilinofluoran, 3- (N
-Methyl-N-3-ethoxypropyl) amino-6-methyl-7-anilinofluoran, 3-diethylamino-
6-methyl-7- (3-trifluoromethylanilino)
Fluorane, 3-diethylamino-7- (3-trifluoromethylanilino) fluorane, 3-diethylamino-7- (2-chloroanilino) fluorane, 3-diethylamino-7- (3-chloroanilino) fluorane, 3
-Di-n-butylamino-7- (3-chloroanilino)
Fluoran, 3-diethylamino-7- (2-fluoroanilino) fluoran, 3-diethylamino-7- (2
-Methoxyanilino) fluoran, 3-pyrrolidino-7
-(2-chloroanilino) fluoran, 3-pyrrolidino-7- (3-chloroanilino) fluoran, 3-pyrrolidino-7- (2-methoxyanilino) fluoran, 3-
Diethylamino-7- (2-isopentyloxycarbonylanilino) fluorane, 3- (N-ethyl-N-p
-Tolyl) amino-6-methyl-7-anilinofluoran and the like;

Other fluoran compounds and xanthene compounds include 3-pyrrolidino-7-cyclohexylaminofluoran, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-n-octylaminofluoran, 3-diethylamino-7-phenylfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-6-chloro-7-methylfluoran, 3-diethylamino-6-methyl-7-
Chlorofluorane, 3-di-n-butylamino-6-methyl-7-chlorofluorane, 3-diethylamino-7
-(3,4-dichloroanilino) fluoran, 3-ethylamino-6-chlorofluoran, 3-cyclohexylamino-6-chlorofluoran, 3-diethylamino-
7-dibenzylaminofluoran, 3-di-n-butylamino-7- (2-chlorobenzylamino) fluoran, rhodamine B anilinolactam, rhodamine Bp
-Chloroanilinolactam and the like,

Examples of spiro compounds include 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran,
Spiropyran compounds such as 3,3'-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-methylnaphtho- (3-methoxybenzo) spiropyran, and 3-propylspirobenzopyran; 3 ', 6'-bis Diethylamino-5-diethylaminospiro (isobenzofuran-1,9'-fluoren) -3-one, 3 ',
Compounds having a fluorene skeleton such as 6'-bisdimethylamino-5-dimethylaminospiro (isobenzofuran-1,9'-fluoren) -3-one. 3,3-bis-
[2- (4-methoxyphenyl) -2- (4-dimethylaminophenyl) ethenyl] vinylogas triarylmethane compounds such as 4,5,6,7-tetrachlorophthalide. These can be used alone or in combination of two or more.

The total amount of the electron-donating dye precursor used in the heat-sensitive pressure-sensitive recording material of the present invention is 0.01-.
3.0 g / m ² , more preferably 0.03 to 2.0 g /
It is preferably used in the range of about m ² .

The electron-accepting compound (developing agent) used in the heat-sensitive pressure-sensitive recording material of the present invention is generally pressure-sensitive recording paper,
Although it is represented by an acidic substance used for thermal recording paper, it is not particularly limited. For example, polyvalent metal salts such as clay substances, phenol derivatives, aromatic carboxylic acid derivatives, N, N'-diarylthiourea derivatives, and zinc salts of organic compounds can be used.

More specifically, clay materials such as acid clay, activated clay, zeolite, bentonite and kaolin, p-phenylphenol, p-hydroxyacetophenone, 4-
Hydroxy-4′-methyldiphenyl sulfone, 4-hydroxy-4′-isopropoxydiphenyl sulfone,
4-hydroxy-4'-benzenesulfonyloxydiphenyl sulfone, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) Hexane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4- (Hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 2,2-bis (3-chloro-4-hydroxyphenyl) Propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,3-di- [2- (4-hydroxyphenyl) -2-
Propyl] benzene, 1,3-di- [2- (3,4-dihydroxyphenyl) -2-propyl] benzene,
4-di- [2- (4-hydroxyphenyl) -2-propyl] benzene, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone,
2,4'-dihydroxydiphenyl sulfone, 3,3 '
-Dichloro-4,4'-dihydroxydiphenylsulfone, 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone, 3,3'-dichloro-4,4'-dihydroxydiphenylsulfide, 2,2-bis ( Methyl 4-hydroxyphenyl) acetate, butyl 2,2-bis (4-hydroxyphenyl) acetate, 4,4'-thiobis (2-t-butyl-5-methylphenol), benzyl p-hydroxybenzoate, p- Chlorobenzyl hydroxybenzoate, dimethyl 4-hydroxyphthalate, benzyl gallate, stearyl gallate, salicylanilide,
5-chlorosalicylanilide, novolak phenolic resin, modified terpene phenolic resin, 3,5-di-t-butylsalicylic acid, 3,5-di-t-nonylsalicylic acid,
3,5-didodecylsalicylic acid, 3-methyl-5-t-
Dodecyl salicylic acid, 5-cyclohexyl salicylic acid,
3,5-bis (α, α-dimethylbenzyl) salicylic acid, 3-methyl-5- (α-methylbenzyl) salicylic acid, and the like, and metal salts thereof such as zinc, nickel, aluminum, and calcium. These can be used alone or in combination of two or more.

The total amount of the color developer used in the heat-sensitive pressure-sensitive recording material of the present invention is selected according to the kind of the color developer used, but it is 5 with respect to the electron-donating dye precursor.
It is preferably used in the range of 0 to 2000% by weight, more preferably 80 to 1500% by weight.

As the diazo compound used in the heat-sensitive pressure-sensitive recording material of the present invention, a photo-decomposable aromatic diazonium compound is particularly preferable, and specific examples thereof include an aromatic diazonium salt and a diazosulfonate compound. 4-diethylaminobenzenediazonium, 2,5-dibutoxy-4
Morpholinobenzenediazonium, 2,5-diethoxy-4-tolylthiobenzenediazonium, 4-N-ethyl-N-hydroxyethylbenzenediazonium,
-Methyl-4-pyrrolidinobenzenediazonium and the like. These tetrafluoroborate salts, hexafluorophosphate salts and the like are preferred because of their high hydrophobicity. These can be used alone or in combination of two or more.

As the coupler which forms a colored product by reacting with the diazo compound used in the heat-sensitive pressure-sensitive recording material of the present invention, a hydroxy aromatic compound and an active methylene compound are preferable. Specifically, resorcin, phloroglysine, 1- Hydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-dihydroxy-6-sulfanylnaphthalene, 1,5-dihydroxynaphthalene, dihydroxybiphenyl, 2-hydroxy-3-naphthoic anilide,
2-hydroxy-3-naphthoic acid tetradecylamide,
Benzoylacetanilide, 1-phenyl-3-phenylacetamido-5-pyrazolone and the like. These can be used alone or in combination of two or more.

When a diazo compound is used, it is preferable to add a basic compound to improve the reactivity. Specifically, organic amines such as tricyclohexylamine, guanidines such as 1,2-dicyclohexyl-3-phenylguanidine, ureas such as allyl urea and ethylene thiourea, imidazoles such as 4-phenylimidazole, and dibenzylpiperazine And the like, piperidines, amidines, pyrroles, morpholines and the like. These can be used alone or in combination of two or more.

The pressure-sensitive microcapsules and heat-sensitive microcapsules used in the heat-sensitive pressure-sensitive recording material of the present invention are prepared by the conventionally known microencapsulation method, that is, the coacervation method, the interfacial polymerization method, the in-situ method or the like. It can be produced arbitrarily. The difference between the pressure-sensitive microcapsule and the heat-sensitive microcapsule mainly utilizes the difference in the function of the resin as the film material forming the film of the microcapsule.

In the pressure-sensitive microcapsules used in the heat-sensitive pressure-sensitive recording material of the present invention, the co-reactant encapsulated in the microcapsules is brought into contact with the reactants present outside the capsule when the capsule membrane is broken by pressure. It is required that it has a function of reacting to form a colored body, is resistant to heat, and does not break or change the material permeability of the membrane even when heated.

As the film material of the pressure-sensitive microcapsule,
Amino aldehyde resin is mentioned. Aminoaldehyde resin film microcapsules include, for example, urea, thiourea,
By using an amine compound such as alkylurea, acetoguanamine, and melamine with an aldehyde compound such as formaldehyde, acetaldehyde, paraformaldehyde, hexamethylenetetramine, glyoxal, and furfural, or an initial condensation product thereof, in situ
It can be formed by a method. The pressure-sensitive microcapsules preferably have no heat sensitivity, and thermosetting resins such as melamine-formaldehyde resin are particularly preferable. The pressure-sensitive microcapsules have an average particle size of 2 to 15
μm, preferably 3 to 10 μm. The average film thickness is 0.
It is from 01 to 0.3 μm, preferably from 0.05 to 0.2 μm.

The heat-sensitive microcapsules used in the heat-sensitive pressure-sensitive recording material of the present invention are composed of the co-reactant and the capsules encapsulated in the microcapsules when the capsule membrane is destroyed by heating or the membrane permeability is changed. It is required that it has a function of contacting and reacting with a reactant existing outside to form a colored body, and that it is stable and does not cause capsule breakage even when pressure is applied.

The thermosensitive microcapsules need to have thermosensitivity, and a thermoplastic resin is preferable as the film material. Examples of the film material of the microcapsule include polyurethane resin, polyurea resin, polyester resin, polyamide resin, polystyrene resin, and polycarbonate resin. These wall films can be formed by a coacervation method, an interfacial polymerization method, an in situ method, or the like. At this time, it is necessary that the microcapsules do not exhibit pressure sensitivity. Therefore, it is preferable to reduce the particle size of the microcapsules. In order to make the microcapsule wall film have heat sensitivity, the glass transition temperature of the film material as microcapsules is 50 ° C to 170 ° C.
Position is the preferred range. The average particle size of the heat-sensitive microcapsules is 0.1 to 5 μm, preferably 0.2 to 3 μm.
It is. The average film thickness is 0.001 to 0.3 μm, preferably 0.005 to 0.2 μm.

The microcapsule wall film obtained by the interfacial polymerization method can be prepared by reacting a polyvalent isocyanate, a polyvalent isocyanate prepolymer, isothiocyanate with polyvalent amines, polyhydric alcohols, water, etc.
A polyurea film or a polyurethane film can be obtained, and a polyamide resin can be obtained by reacting an acid chloride with an amine or the like.
The interfacial polymerization method capable of obtaining such a resin wall facilitates the production of microcapsules having different thermal characteristics such as the glass transition temperature of the microcapsule wall film.

Examples of the polyvalent isocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate and diphenylmethane-4,4-diisocyanate. , Xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-isocyanate, butylene-1,2-diisocyanate, ethylidyne diisocyanate, cyclohexylene-1, Examples thereof include 2-diisocyanate and cyclohexylene-1,4-diisocyanate. Examples of the polyvalent isocyanate prepolymer include an addition product of hexamethylene diisocyanate and hexanetriol, an addition product of tolylene diisocyanate and trimethylol propane, and an addition product of xylylene diisocyanate and trimethylol propane. These can be used alone or in combination of two or more.

As the polyamine, ethylenediamine,
Hexamethylenediamine, octamethylenediamine, triethylenetetramine, paraphenylenediamine, piperazine, diethylenetriamine and the like,
These can be used alone or in combination of two or more.

As the polyhydric alcohols, catechol,
Resorcin, 3,4-hydroxytoluene, 2,4-dihydroxytoluene, 2,4-dihydroxyethylbenzene, 1,3-naphthalenediol, 1,5-naphthalenediol, O, O'-biphenol, p, p'-biphenol 2,2-bis (p-hydroxyphenyl) propane, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,1,1-trimethylolpropane, hexanetriol , Glycerin, sorbitol and the like. These can be used alone or in combination of two or more. Usually, it is used in a concentration range of 50% or less with respect to the polyisocyanate. Water can also be used as the compound having active hydrogen.

As the photocurable resin used in the heat and pressure sensitive recording material of the present invention, a compound having an ethylenically unsaturated bond is mainly used. Specific examples include the following resins.

Aliphatic, alicyclic, aromatic, araliphatic polyhydric alcohols and poly (meth) acrylates of polyalkylene glycols, aliphatic, alicyclic, aromatic, araliphatic polyhydric alcohols and alkylenes. Poly (meth) acrylate of polyhydric alcohol added with oxide, polyester poly (meth) acrylate, polyurethane poly (meth) acrylate, epoxy poly (meth) acrylate, polyamide poly (meth) acrylate, poly (meth) acryloyloxyalkyl Phosphate ester, vinyl-based or diene-based compound having a (meth) acryloyloxy group in the side chain or terminal, monofunctional (meth) acrylate, vinylpyrrolidone, (meth) acryloyl compound, cyano compound having an ethylenically unsaturated bond , Ethylenically unsaturated bond Mono- or polycarboxylic acids, and alkali metal salts thereof, ammonium salts,
Ethylenically unsaturated (meth) acrylamide or alkyl-substituted (meth) acrylamide and its multimers, such as amine salts, vinyl lactams and polyvinyl lactam compounds, polyethers having ethylenically unsaturated bonds and esters thereof, and ethylenically unsaturated bonds Esters of alcohols, polyalcohols having ethylenically unsaturated bonds and their esters, aromatic compounds having one or more ethylenically unsaturated bonds such as styrene and divinylbenzene, and (meth) acryloyloxy groups having side chains or terminals. And a silicone compound having an ethylenically unsaturated bond, and a polymer or a modified oligoester (meth) acrylate of the above-mentioned compound. These photocurable resins can be used alone or in combination of two or more. It may be used without solvent or diluted with a solvent, and may be used in an emulsion state.

A polymerization inhibitor may be added together with the photocurable resin in order to improve storage stability. Examples of the polymerization inhibitor include quinones such as hydroquinone, phenols such as butyl catechol, ureas, thioamides, and amines.

When the photocurable resin is cured by ultraviolet rays, a photopolymerization initiator can be added to the microcapsules mainly containing the co-reactant and the photocurable resin, if necessary. Benzophenones as photopolymerization initiators,
Xanthones, thioxanthones, benzoins, polycyclic quinones, carbonyl compounds such as alkoxyphenyl ketones, chlorosulfonyl and chloromethyl polynuclear aromatic compounds, chlorosulfonyl and chloromethyl heterocyclic compounds, fluorenones and the like Halogen compounds, optical semiconductors such as titanium dioxide and zinc oxide, metal compounds such as metal carbonyls, metal complexes and uranyl salts, photoreducing dyes such as methylene blue, acriflavine and safranin, organic sulfur compounds, peroxides and silver halides And various azo and diazo compounds.

Specific examples of these include dichloroacetophenone, trichloroacetophenone, 2-dimethoxy-2-phenylacetophenone, benzoin isopropyl ether, benzoin butyl ether, benzophenone, Michler's ketone, 4,4'-diethylaminobenzophenone, chloromethylbenzophenone, chlorosulfonyl. Benzophenone, benzyl dimethyl ketal,
Tetramethylthiuram monosulfide, 9,10-anthraquinone, 2-methyl-9,10-anthraquinone, chlorosulfonylanthraquinone, chloromethylanthraquinone, 9,10-phenanthrenequinone, xanthone, chloroxanthone, thioxanthone, 2,4
-Diethylthioxanthone, chlorosulfonylthioxanthone, chloromethylquinoline, chloromethylbenzothiazole, fluorene, carbon tetrabromide and the like.

The photopolymerization initiator is a photocurable resin,
It is preferably used in the range of 0.1 to 50%,
The range of -20% is more preferably used. When a photopolymerization initiator is used, a hydrogen-donating compound may be used in combination, if necessary. Specific examples of these include diketones such as dimedone and acetylacetone, amines such as triethanolamine, diethanolamine and triethylamine, sulfinic acids and salts thereof such as p-toluenesulfinic acid and benzenesulfinic acid, and thioureas. Can be

The light source for photopolymerizing the photocurable resin or photodecomposing the diazo compound is not particularly limited as long as it is a light source that emits light of a specific wavelength required, but for example, a fluorescent lamp. , A xenon lamp, a halogen lamp, a high pressure mercury lamp, a low pressure mercury lamp, a strobe, and the like. When curing a photo-curable resin with an electron beam,
An electron beam irradiation device is used. It is also possible to irradiate only necessary parts with light from a light source using an optical fiber or the like. An optical filter that transmits light of a specific wavelength can also be used.

In order to stably enclose the various co-reactants in the heat-sensitive and pressure-sensitive microcapsules, it is common to use a hydrophobic substance that is a high boiling point oil that dissolves the various co-reactants. Specific examples of these include paraffin oil, cottonseed oil, soybean oil, corn oil, olive oil, castor oil, fish oil, lard oil, chlorinated paraffin, chlorinated diphenyl, dibutyl phthalate, dioctyl phthalate, tributyl phosphate, tricresyl phosphate. ,
Alkylated naphthalene such as dibutyl maleate, O-dichlorobenzene, diisopropyl naphthalene, 1-
Examples thereof include benzyl alcohol such as phenyltrixylylethane, 1- (3,4-dimethylphenyl) -1-phenylethane, and poly (1-4) isopropylnaphthalene.

Further, in order to improve the solubility of various co-reactants in high boiling point oil, a low boiling point auxiliary solvent may be added. Specific examples of the co-solvent include ethyl acetate,
Butyl acetate, cyclohexanone and the like.

Generally, a high boiling point oil, which is a hydrophobic substance in which a co-reactant is dissolved, is emulsified in water for microencapsulation. Preferred protective colloid agents and emulsifiers used for this are gelatin, gum arabic, casein, and carboxy. Methyl cellulose, polyvinyl alcohol, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, alkylbenzene sulfonic acid, alkylnaphthalene sulfonate, polyoxyethylene sulfate, polyoxyethylene alkyl ether, alkylphenyl ether, sorbitan A fatty acid ester etc. can be mentioned. These can be used alone or in combination of two or more.

If necessary, a capsule protector may be added to the heat and pressure sensitive recording material of the present invention. Specific examples include cellulose powder, starch particles, and talc.

The binder used in the heat-sensitive pressure-sensitive recording material of the present invention includes starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatins, casein, polyvinyl alcohol, silanol-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, polystyrene sulfonic acid. , Sodium polyacrylate, ethylene / acrylic acid copolymer, acrylic acid amide / acrylic acid ester copolymer, acrylic acid amide / acrylic acid ester / methacrylic acid terpolymer, styrene / maleic anhydride copolymer, ethylene/
Water-soluble polymers such as maleic anhydride copolymer, isobutylene / maleic anhydride copolymer, alkali or ammonium salts of alginic acid, polyvinyl acetate, polyurethane, polyacrylate, styrene / butadiene copolymer, carboxy Latexes such as modified styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer, ethylene / vinyl acetate copolymer and the like can be mentioned. These can be used alone or in combination of two or more. The amount of the binder used is preferably in the range of 5 to 40% by weight of the total solids forming the heat-sensitive pressure-sensitive recording material.

The heat-sensitive pressure-sensitive recording material of the present invention may contain a heat-fusible substance, if necessary, in order to improve the thermal response. In this case, those having a melting point of 60 ° C to 180 ° C are preferred, and those having a melting point of 80 ° C to 140 ° C are more preferred.

Examples of the heat-fusible substance (sensitizer) for improving the thermal response include N-hydroxymethylstearic acid amide, stearic acid amide, palmitic acid amide, oleic acid amide, and ethylenebisstearin. Acid amide, ricinoleic acid amide, paraffin wax,
Waxes such as microcrystalline wax, polyethylene wax, rice wax and carnauba wax; naphthol derivatives such as 2-benzyloxynaphthalene; biphenyl derivatives such as p-benzylbiphenyl, 4-allyloxybiphenyl and m-terphenyl;
Polyether compounds such as -bis (3-methylphenoxy) ethane, 2,2'-bis (4-methoxyphenoxy) diethyl ether, bis (4-methoxyphenyl) ether, diphenyl carbonate, dibenzyl oxalate, and di (oxalate) Carbonic acid or oxalic acid diester derivatives such as (p-chlorobenzyl) ester and the like can be mentioned.

These sensitizers can be used alone or in admixture of two or more. Further, it is preferably used in an amount of 20 to 400% by weight based on the developer, from the viewpoint of heat responsiveness, and more preferably 30 to 350% by weight.

The heat and pressure sensitive recording material according to the present invention may contain various materials. For example, as a pigment,
Diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, calcium silicate, magnesium carbonate, basic magnesium carbonate, barium sulfate, titanium oxide, zinc oxide, silicon dioxide, silicic acid, aluminum hydroxide, inorganic pigments such as alumina, urea- An organic pigment such as a formalin resin or a polystyrene resin may be contained as necessary. Also, higher fatty acid metal salts such as zinc stearate and calcium stearate, waxes such as paraffin, oxidized paraffin, polyethylene, oxidized polyethylene, stearic acid amide, and castor wax, dispersants such as sodium dioctylsulfosuccinate, benzophenone-based, benzo. An ultraviolet absorber such as a triazole type, further various surfactants, fluorescent dyes and the like are used as necessary.

As the support used in the present invention, paper,
Various nonwoven fabrics, woven fabrics, plastic films such as polyethylene terephthalate and polypropylene, polyethylene,
Laminated paper laminated with synthetic resin such as polypropylene, synthetic paper, metal foil such as aluminum, glass or the like, or a composite sheet combining these can be used arbitrarily according to the purpose, but is not limited thereto. Absent. These may be opaque, transparent or translucent. In order to make the background appear white or another specific color, a white pigment, a colored dye or a bubble may be contained in the support or on the surface. In particular, when performing aqueous coating on films, etc., when the hydrophilicity of the support is small and it is difficult to apply, easy adhesion treatment such as hydrophilizing the surface by corona discharge or applying various polymers to the surface of the support You may do. In addition, a back coat layer may be provided for curl correction and antistatic.

The heat-sensitive pressure-sensitive recording material of the present invention comprises heat-sensitive microcapsules, pressure-sensitive microcapsules, a method of further providing a recording layer mainly containing a color developer on a support, and heat-sensitive microcapsules. A method of laminating a layer mainly composed of a color developer and a layer mainly composed of a pressure-sensitive microcapsule and a color developer on a support, a thermosensitive microcapsule, a layer mainly composed of a layer mainly composed of a pressure-sensitive microcapsule and a color developer. Examples of the method include a method of laminating a layer on a support, a method of laminating a layer mainly composed of pressure-sensitive microcapsules and a color developer and a layer mainly composed of heat-sensitive microcapsules on a support. There is no particular limitation as long as it is a mode in which heat-sensitive recording and pressure-sensitive recording can be performed. Moreover, when laminating | stacking a layer, you may provide an intermediate | middle layer between layers as needed.

A protective layer may be provided on the heat and pressure sensitive recording material of the present invention. The protective layer is formed mainly of a film-forming material such as a water-soluble polymer and latex. In this case, a hardener such as a compound having an epoxy group or a zirconium salt or a crosslinking agent may be added. other than this,
A light and electron beam curable resin or a thermosetting resin may be smeared and cured to form a protective layer. Further, a protective layer may be formed by bonding a plastic film. Various ultraviolet absorbers may be present in the protective layer in a dispersed state, a dissolved state, or a solution state. In this case, microcapsules containing various ultraviolet absorbers may be used. Even if particulate matter such as pigment is added to the protective layer in order to further improve the writability and the runnability during heating printing, the layer containing the particulate matter such as pigment may be further formed on the protective layer. good. It is preferable that the average particle size of the particles such as pigments is 3.0 μm or less because the image density is not reduced.

In order to improve the printability and heat sensitivity of the heat and pressure sensitive recording material of the present invention, a heat insulating layer may be provided between the support and the recording layer. It is desired that the heat insulating layer efficiently contains air having a large heat insulating effect and has smoothness. This heat-insulating layer can be obtained by, for example, providing a hollow particle, an air capsule containing air therein, an inorganic or organic pigment having many pores, a binder and the like as a main component on a support. In order to obtain the effect of the heat insulating layer, the smear amount is preferably 0.5 to 30 g / m ² . Below this range, the effect of improving the sensitivity is not sufficient, and above this range, it may be difficult to obtain a uniform smooth surface.

The method of forming each layer constituting the heat-sensitive pressure-sensitive recording material of the present invention on the support is not particularly limited, and it can be formed by a conventional method. For example,
A smearing device such as an air knife coater, a blade coater, a bar coater, a curtain coater and the like, various printing machines by a system such as lithographic, letterpress, intaglio, flexo, gravure, screen, hot melt and the like can be used. Further, in addition to the usual drying step, each layer can be held by ultraviolet irradiation or electron beam irradiation.

Further, in the heat-sensitive pressure-sensitive recording layer and / or another layer and / or a layer provided on the surface opposite to the surface provided with the heat-sensitive pressure-sensitive recording layer, electrical, optical, magnetic May contain a material capable of recording information. Further, a back coat layer may be provided on the surface opposite to the surface on which the heat and pressure sensitive recording layer is provided for the purpose of blocking prevention, curl prevention, antistatic prevention and the like. Alternatively, a heat-sensitive pressure-sensitive recording layer or the like may be provided on both surfaces of the support.

[0063]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited to these examples. The parts and percentages shown below are parts by weight and weight%.

Example 1 (A) Preparation of Thermosensitive Microcapsule Solution Encapsulating Electron-Donating Dye Precursor As an electron-donating dye precursor, 3-diethylamino-6 was used.
-Methyl-7-anilinofluorane 16 parts, 1-
After dissolving in 64 parts of (3,4-dimethylphenyl) -1-phenylethane (manufactured by Nippon Petrochemical, trade name; SASN-296), diphenylmethane-4,4'-diisocyanate and 1,2-bis {p- 20 parts of a 1: 1 mixture of (p-isocyanatebenzyl) phenylaminocarbonyloxy} ethane (Sumitomo Bayer Urethane, trade name; Sumidule PF) and 20 parts of ethyl acetate as an auxiliary solvent.
Parts were added and dissolved uniformly. This internal phase oil was mixed with a 5% aqueous solution of polyvinyl alcohol, and the mixture was mixed with a homomixer to obtain 2
It was emulsified and dispersed at 5 ° C. to obtain an emulsion having an average particle size of 1 μm. An aqueous solution obtained by dissolving 8 parts of diethylenetriamine in 42 parts of distilled water was added to the obtained emulsion and heated at 80 ° C. for 3 hours while stirring to obtain a heat-sensitive microcapsule liquid.

(B) Preparation of Pressure-Sensitive Microcapsule Liquid Encapsulating Electron-Donating Dye Precursor 3-Diethylamino-6-as an electron-donating dye precursor
16 parts of methyl-7-anilinofluoran was added to 1- (3,
4-Dimethylphenyl) -1-phenylethane (manufactured by Nippon Petrochemical, trade name; SASN-296) was dissolved in 64 parts. This internal phase oil was adjusted to pH 4.5 with a 5% aqueous solution of a sodium salt of a styrene-maleic anhydride copolymer 100
g) and emulsified and dispersed at 25 ° C. using a homomixer to obtain an emulsion having an average particle size of 5 μm. Melamine powder 5g
Then, 6.5 g of a 37% formaldehyde aqueous solution and 10 g of water were added to adjust the pH to 8, and a melamine-formaldehyde precondensate aqueous solution obtained by heating to about 70 ° C. was added to the obtained emulsion, After heating at 80 ° C. for 2 hours with stirring, the pH was adjusted to 9 to obtain a pressure-sensitive microcapsule solution.

(C) Preparation of color developer dispersion 2,2-bis (4-hydroxyphenyl) propane 30
0 parts together with 700 parts of a 2% aqueous solution of polyvinyl alcohol was pulverized with a paint conditioner;
A dispersion prepared by pulverizing with a paint conditioner 300 parts of di-t-butylsalicylic acid zinc salt and 700 parts of a 2% aqueous polyvinyl alcohol solution was mixed to obtain a developer dispersion. (D) Preparation of Sensitizer Dispersion 300 parts of m-terphenyl, which is a sensitizer, was pulverized together with 700 parts of a 2% aqueous solution of polyvinyl alcohol by a paint conditioner to obtain a sensitizer dispersion.

(E) Preparation of coating solution for heat-sensitive pressure-sensitive recording layer 49 parts of the above-mentioned pressure-sensitive microcapsule solution, 49 parts of heat-sensitive microcapsule solution, 50 parts of developer dispersion, 50 parts of sensitizer dispersion, 10 % Polyvinyl alcohol aqueous solution 50 parts,
40 parts of 40% calcium carbonate dispersion and 62 parts of distilled water were thoroughly mixed to prepare a heat and pressure sensitive recording layer coating liquid.

(F) Preparation of heat-sensitive pressure-sensitive recording material The coating liquid for heat-sensitive pressure-sensitive recording layer prepared in (E) was used as a foamed polyethylene terephthalate film (trade name: Lumirror E manufactured by Toray).
62 # 188), and the mixture was smeared so as to have a coating amount of 8.0 g / m ² and dried to obtain a heat-sensitive pressure-sensitive recording material.

Example 2 In the preparation of the pressure-sensitive microcapsule liquid containing the electron-donating dye precursor in (B) of Example 1, 3-diethylamino-6-methyl-7-anilinofluorane was used as the electron-donating dye precursor. Instead, 3-diethylamino-6-chloro-7-methylfluorane (manufactured by Nippon Soda, trade name; PSD
A heat and pressure sensitive recording material was obtained in the same manner as in Example 1 except that -V)) was used.

Example 3 (B) In the preparation of the pressure-sensitive microcapsule liquid containing an electron-donating dye precursor in (B), 3-diethylamino-6-methyl-7-anilinofluorane was used as the electron-donating dye precursor. In place of 3,3'-bis (1-n-octyl-2-methylindol-3-yl) phthalide
Instead of-(3,4-dimethylphenyl) -1-phenylethane, a diacrylic photocurable resin (KAYARAD R604, Nippon Kayaku Co., Ltd.) was used, and 2-methyl-1- [as a polymerization initiator. Thermal pressure-sensitive recording was performed in the same manner as in Example 1 except that 3.2 parts of 4- (methylthio) phenyl] -2-morpholinopropane-1 (Irgacure 907, Ciba-Geigy Co., Ltd.) was used. Got the material.

Example 4 (G) Preparation of Pressure Sensitive Microcapsule Solution Encapsulating Diazo Compound In the preparation of the pressure-sensitive microcapsule solution encapsulated in the electron-donating dye precursor in Example 1 (B), the electron-donating dye precursor 3 was used. In the same manner as in Example 1 except that 2,5-diethoxy-4-tolylthiobenzenediazonium hexafluorophosphate was used as the diazo compound instead of -diethylamino-6-methyl-7-anilinofluorane, the pressure-sensitive micro A capsule liquid was obtained.

(H) Preparation of Thermosensitive Microcapsule Solution Encapsulated in Electron-Donating Dye Precursor In the preparation of (A) electron-donating dye precursor-encapsulated thermosensitive microcapsule solution of Example 1, as an electron-donating dye precursor Example 3 except that 3,3'-bis (1-n-octyl-2-methylindol-3-yl) phthalide was used in place of 3-diethylamino-6-methyl-7-anilinofluorane. Similarly, a heat-sensitive microcapsule liquid was obtained.

(I) Preparation of coupler dispersion 300 parts of 2-hydroxy-3-ethanolaminocarbonylnaphthalene was added to a 2% aqueous solution of polyvinyl alcohol 70
The mixture was pulverized with a paint conditioner together with 0 parts to obtain a coupler dispersion. (J) Preparation of color developer dispersion 2,2-bis (4-hydroxyphenyl) propane 30
0 part was pulverized with 700 parts of a 2% polyvinyl alcohol aqueous solution by a paint conditioner to obtain a developer dispersion. (K) Preparation of coating liquid for heat-sensitive pressure-sensitive recording layer 49 parts of the pressure-sensitive microcapsule liquid, 49 parts of heat-sensitive microcapsule liquid, 50 parts of coupler dispersion liquid, 50 parts of developer dispersion liquid, and 10% polyvinyl alcohol aqueous solution
Well, 40 parts of 30% starch particle dispersion liquid and 62 parts of distilled water were thoroughly mixed to prepare a heat-sensitive pressure-sensitive recording layer coating liquid.

(L) Preparation of heat-sensitive pressure-sensitive recording material The coating liquid for heat-sensitive pressure-sensitive recording layer prepared in (K) was used as a foamed polyethylene terephthalate film (trade name: Lumirror E manufactured by Toray).
62 # 188), and the mixture was smeared so as to have a coating amount of 8.0 g / m ² and dried to obtain a heat-sensitive pressure-sensitive recording material.

Evaluation The heat-sensitive pressure-sensitive recording material obtained in Example 1 was subjected to heat-sensitive recording using a thermal head. Using a thermal paper print tester (TH-PMD manufactured by Okura Electric Co., Ltd., KJT-256-8MGF1 manufactured by Kyocera) and printing with an applied energy of 60 mj / mm ² , a clear black color image was obtained. Further, when a part of the recording surface was pressurized with an embosser, a clear black color image was obtained as in the case of the thermal recording.

When the heat-sensitive pressure-sensitive recording material obtained in Example 2 was subjected to heat-sensitive recording under the same conditions, a clear black colored image was obtained. Further, when pressure recording was performed under the same conditions, a clear red color image was obtained, and the recorded images by heat-sensitive recording and pressure-sensitive recording could be clearly distinguished.

The heat-sensitive pressure-sensitive recording material obtained in Example 3 was subjected to heat-sensitive recording using a thermal head. Using a thermal paper print tester (TH-PMD manufactured by Okura Electric Co., Ltd., KJT-256-8MGF1 manufactured by Kyocera) and printing with an applied energy of 50 mj / mm ² , a clear black color image was obtained. Further, when a part of the recording surface was pressurized with an embosser, a clear red-colored image was obtained as in the case of the thermal recording. Next, after exposing the entire recording surface,
When a part of the recording surface was pressed again under the same conditions, no color-developed image was obtained, and the function of pressure-sensitive recording was completely lost.

The heat-sensitive pressure-sensitive recording material obtained in Example 4 was subjected to heat-sensitive recording using a thermal head. When a thermal paper printing tester (TH-PMD manufactured by Okura Electric Co., Ltd., KJT-256-8MGF1 manufactured by Kyocera Thermal Head) was used to print with an applied energy of 60 mj / mm ² , a clear red colored image was obtained. Further, when a part of the recording surface was pressurized with an embosser, a clear blue-colored image was obtained as in the case of the thermal recording. Next, after exposing the entire recording surface,
When a part of the recording surface was pressed again under the same conditions, no color-developed image was obtained, and the function of pressure-sensitive recording was completely lost.

[0079]

EFFECT OF THE INVENTION By holding a reactant and a pressure-sensitive microcapsule and a heat-sensitive microcapsule containing a co-reactant which reacts with the reactant to form a colored body on a support, heat-sensitive recording can be performed. A heat-sensitive pressure-sensitive recording material capable of arbitrarily performing pressure-sensitive recording on the same recording surface is obtained, and further, a reaction product and a co-reactant that reacts with the reaction product to form a colored product are provided on a support. By holding the thermosensitive microcapsules containing the pressure-sensitive microcapsules to be encapsulated and the co-reactant to form a colorant having a hue different from that of the colorant, the thermosensitive recording image obtained by heating and pressurization can be obtained. It was possible to distinguish the obtained pressure-sensitive recorded images by the difference in color. Further, by mainly encapsulating the photocurable resin together with the co-reactant in either or both of the pressure-sensitive microcapsules and the heat-sensitive microcapsules, one of the pressure-sensitive and heat-sensitive functions can be obtained by exposing after recording. Alternatively, both functions can be eliminated at the same time, and a heat-sensitive pressure-sensitive recording material capable of fixing can be obtained.

Claims (8)

[Claims] 1. A pressure-sensitive microcapsule and a heat-sensitive microcapsule containing a reactant, and a co-reactant that reacts with the reactant to form a colored body, on the same surface of a support. A heat-sensitive pressure-sensitive recording material, which is capable of performing pressure-sensitive recording and heat-sensitive recording on the same surface. 2. A pressure-sensitive microcapsule containing a reactant, a co-reactant that reacts with the reactant to form a colored body, and a different hue from the colored body on the same surface of the support. A heat-sensitive pressure-sensitive recording material, characterized in that it is possible to carry out pressure-sensitive recording and heat-sensitive recording on the same surface by holding heat-sensitive microcapsules encapsulating a co-reactant forming a colored body. 3. The heat-sensitive pressure-sensitive recording material according to claim 1, wherein the film material of the pressure-sensitive microcapsule is made of melamine-formaldehyde resin. 4. The heat-sensitive pressure-sensitive recording material according to claim 1 or 2, wherein the film material of the heat-sensitive microcapsule is made of a thermoplastic resin. 5. A normally colorless or light-colored electron donor in which at least one of a pressure-sensitive recording material and a heat-sensitive recording material and a co-reactant react with an electron-accepting compound to form a colored body by reacting with the electron-accepting compound. The heat-sensitive pressure-sensitive recording material according to claim 1 or 2, wherein the heat-sensitive pressure-sensitive recording material is a combination of functional dye precursors. 6. A combination of at least one of the reactant and co-reactant for pressure-sensitive recording and heat-sensitive recording is a combination of a coupler and a diazo compound which reacts with the coupler to form a colored product. The heat-sensitive pressure-sensitive recording material according to claim 1 or 2. 7. The heat-sensitive sensation according to claim 1 or 2, wherein at least one of the pressure-sensitive microcapsule and the heat-sensitive microcapsule mainly contains a photocurable resin together with a co-reactant. Pressure recording material. 8. The heat-sensitive pressure-sensitive recording material according to claim 6 or 7, before or / and after performing heat-sensitive recording and / or pressure-sensitive recording, a part or whole surface of the heat-sensitive pressure-sensitive recording material. An image recording method characterized in that the color-developing function of at least one of the pressure-sensitive microcapsules and the heat-sensitive microcapsules in the exposed portion is lost by exposing.