JPH08183248A - Self-coloring pressure-sensitive recording sheet, manufacturing method thereof, and recording method of self-coloring pressure-sensitive recording sheet - Google Patents

Abstract

PURPOSE: To provide a color self-forming pressure-sensitive recording sheet preventing the alteration of a recording image and prevented from contamination due to handling. CONSTITUTION: A color self-forming pressure-sensitive recording layer 2 having microcapsules including a colorless or light-colored basic dye and a couple in a single-layered or laminated state, an active energy beam curable resin layer 3 and a shaping sheet 4 having an uneven shape peelable from the interface with the resin layer 3 are successively provided on a support 1. When the shaping sheet 4 is peeled after recording, the uneven surface of the active energy beam curable resin layer 3 appears and alteration can be prevented.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a self-coloring pressure-sensitive recording sheet provided with an active energy ray-curable resin layer and a mold sheet having an uneven shape that can be peeled from the interface with the active energy ray-curable resin layer. It prevents tampering after recording, does not stain when handling, is water resistant,
Provided is a self-coloring pressure-sensitive recording sheet having oil resistance, chemical resistance and little dust.

[0002]

2. Description of the Related Art Conventionally, a pressure-sensitive recording sheet has a color-forming agent layer mainly containing microcapsules containing oil droplets in which an electron-donating organic color-developing agent (hereinafter simply referred to as "color-forming agent") is dissolved on one side of a support. And a developer layer containing, as a main component, an electron-accepting developer (hereinafter simply referred to as a developer) that develops color when contacted with the above-mentioned color former on one surface of the support, There is a middle paper having a color developer layer on its surface and a lower paper having a developer layer on one side of the support. These three types of sheets are upper paper, lower paper or upper paper, middle paper, lower paper in this order. Is used in combination as a copy set. The self-coloring pressure-sensitive recording sheet is a developed form of the pressure-sensitive recording sheet, and has microcapsules containing a color-forming agent and a color developer on the same surface, and pressure-sensitive recording is possible with one sheet.

The self-coloring pressure-sensitive recording sheet is convenient because pressure-sensitive recording can be carried out by one sheet, but careless pressure or friction during storage causes the capsule to break and develop color, and the self-coloring pressure-sensitive recording layer becomes dirty. It has the drawback that it will end up. In order to prevent this stain and from a printing problem, it is considered that the surface of the self-coloring pressure-sensitive recording sheet is smoothed by a super calendar or the like. However, in the case of a super calender or the like, it is difficult to obtain a smooth surface like a lower sheet because the pressure destroys the capsules to cause a coloring reaction and stain the self-coloring pressure-sensitive recording layer. Heretofore, as a method for obtaining a smooth surface, a method of pressing an undried coating surface to a cast mirror surface (Japanese Patent Laid-Open No. 61-143181) or coating an electron beam curing resin on a self-coloring pressure-sensitive recording layer has been used. A method has been proposed in which a synthetic resin film, a metal foil or the like is brought into close contact with the surface of the resin to cure the electron beam curable resin layer while transferring the surface shape (Japanese Patent Laid-Open No. 5-8533). Further, as a problem of the conventional self-coloring pressure-sensitive recording sheet, there is a possibility that the characters and numbers are tampered with after pressure recording.

When a self-coloring pressure-sensitive recording sheet having such an electron beam curable resin layer on the surface is used for recording, if the surface is smooth, the recording can be tampered with after recording. If the surface has irregularities,
When pressure printing is performed, there are problems such as shading and character breaks in printing. Further, when the surface is a self-coloring pressure-sensitive recording layer, it becomes a problem because it becomes dirty during handling.

It is an object of the present invention to prevent tampering with a self-coloring pressure-sensitive recording sheet, and at the same time to prevent the fate of the self-coloring pressure-sensitive recording sheet from becoming dirty during handling during storage.

[0005]

[Means for Solving the Problems] In order to solve such a problem, the present inventors have found the following method as a result of intensive research. That is, a self-coloring pressure-sensitive recording layer having a microcapsule containing a colorless or light-colored basic dye and a developer in a single layer or laminated state on a support, an active energy ray curable resin layer and the active energy ray curable A mold-equipped sheet having an uneven shape that can be peeled from the interface with the mold resin layer is provided in order. A barrier layer may be provided between the self-coloring pressure-sensitive recording layer and the active energy ray-curable resin layer. It is preferable that a self-coloring pressure-sensitive recording layer is further provided on the patterned sheet. Production of the self-coloring pressure-sensitive recording sheet of the present invention,
A self-coloring pressure-sensitive recording layer having a microcapsule containing a colorless or light-colored basic dye and a developer in a single layer or a laminated state is provided on a support, and a barrier layer is further provided if necessary, and a self-coloring pressure-sensitive recording is provided. The recording layer or the barrier layer and the typed sheet are bonded together via the active energy ray-curable resin layer, and then the active energy ray is irradiated to manufacture. The recording method of the self-coloring pressure-sensitive recording sheet of the present invention is characterized in that the pressure-sensitive recording of information is carried out, and then the sheet with a pattern is peeled off.

The information can be prevented from being tampered with by recording the information on the self-coloring pressure-sensitive recording sheet of the present invention under pressure and then peeling off the pattern sheet. That is, if the characters or numbers written on the self-coloring pressure-sensitive recording layer are corrected after removing the typed sheet, since the surface has unevenness, the shade of the characters, the size of the line, etc. will change, You can see at a glance that it has been tampered with. Further, if the self-coloring pressure-sensitive recording layer is provided on the side of the patterning sheet to be peeled off, by separately storing this patterning sheet, it is possible to check whether alteration has been performed or not. In addition, since the self-coloring pressure-sensitive recording layer is overcoated with the active energy ray-curable resin layer and the sheet with a mold, it is possible to prevent stains during storage or during handling before recording.

The coating liquid for forming the self-coloring recording layer of the present invention is a microcapsule, a color developer, an inorganic pigment, an adhesive,
It is composed of a tilting agent, and various other auxiliaries known in the field of pressure-sensitive recording sheet manufacturing can be appropriately added. As the microcapsules of the pressure-sensitive recording sheet, gelatin-based capsules by the coacervation method have been the mainstream, but nowadays, synthetic microcapsules by the in-situ polymerization method and the interfacial polymerization method are the mainstream. Examples of the resin for a microcapsule wall film formed by the in-situ polymerization method include melamine-formaldehyde resin and urea-formaldehyde resin. Examples of the resin for the microcapsule wall film obtained by the interfacial polymerization method include polyurethane resin and polyurea resin.

As the color developing agent for the pressure-sensitive recording sheet, generally, acid clay, activated clay, attapulgite, zeolite,
Inorganic developers such as bentonite, silica and aluminum silicate, phenolic polymers such as phenol-aldehyde polymers and phenol-acetylene polymers, and organic developers such as salicylic acid derivatives are known. Among them, the organic color developer has a higher printing density than the inorganic color developer and is excellent in fastness to light such as sunlight. Examples of the basic dye that is used by being encapsulated in microcapsules in the present invention include 3,3-bis (p-dimethylaminophenyl)-
6-dimethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindole)
3-yl) phthalide and other triarylmethane compounds, 4,4-bis-dimethylaminobenzhydrylbenzyl ether, N-2,4,5-trichlorophenylleuco auramine and other diphenylmethane compounds, 7-
Diethylamino-3-chlorofluorane, 7-diethylamino-3-chloro-2-methylfluorane, 2-phenylamino-3-methyl-6- (N-ethyl-Np-
Fluorane-based compounds such as trilylamino) fluorane,
Thiazine compounds such as benzoyl leuco methylene blue and p-nitrobenzoyl leuco methylene blue, 3-
Examples thereof include spiro compounds such as methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-propyl-spiro-dinaphthopyran, and 3-propyl-spiro-dibenzopiperane.

Examples of the organic developer used in the present invention include salicylic acid, 3-phenylsalicylic acid,
3-cyclohexylsalicylic acid, 3-tert-butyl-5
-Methylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3-phenyl-5- (α, α-dimethylbenzyl) salicylic acid,
3-Cyclohexyl-5- (α, α-dimethylbenzyl) salicylic acid, 3- (α, α-dimethylbenzyl)-
5-methylsalicylic acid, 3,5-dicyclohexylsalicylic acid, 3,5-di- (α-methylbenzyl) salicylic acid, 3,5-di- (α, α-dimethylbenzyl) salicylic acid, 3- (α-methylbenzyl) -5- (α, α-dimethylbenzyl) salicylic acid, 4-methyl-5-cyclohexylsalicylic acid, 2-hydroxy-1-benzyl-
3-naphthoic acid, 1-benzoyl-2-hydroxy-3
-Naphthoic acid, 3-hydroxy-5-cyclohexyl-
2-naphthoic acid, 2-hydroxy-4-[(4-carboxy-5-hydroxy) phenyl] -1-naphthoic acid,
3-Methyl-5- (iso) nonylsalicylic acid, 3-methyl-5- (iso) dodecylsalicylic acid, 3-methyl-5
-(Iso) pentadecyl salicylic acid, 3-methyl-5-
(Α-Methylbenzyl) salicylic acid, 3-methyl-5-
(Α, α-Dimethylbenzyl) salicylic acid, 3,5-di-sec-butylsalicylic acid, 3,5-di-tert-butyl-6-methylsalicylic acid, 3-tert-butyl-5-phenylsalicylic acid, 3,5 -Di-tert-amylsalicylic acid, 3-cyclohexyl-5- (iso) nonylsalicylic acid, 3-phenyl-5- (iso) nonylsalicylic acid, 3
-(Α-methylbenzyl) -5- (iso) nonylsalicylic acid, 3-isopropyl-5- (iso) nonylsalicylic acid, 3- (iso) nonylsalicylic acid, 3- (iso) nonyl-5-methylsalicylic acid, 3- (Iso) nonyl-5-
Cyclohexyl salicylic acid, 3- (iso) nonyl-5-
Phenylsalicylic acid, 3- (iso) nonyl-5- (α-
Methylbenzyl) salicylic acid, 3- (iso) nonyl-5
-(4, α-Dimethylbenzyl) salicylic acid, 3- (iso) nonyl-5- (α, α-dimethylbenzyl) salicylic acid, 3- (α, α-dimethylbenzyl) -5- (iso) nonylsalicylic acid, 5 -(Iso) nonylsalicylic acid, 3- (iso) nonyl-6-methylsalicylic acid, 3-
tert-Butyl-5- (iso) nonylsalicylic acid, 3,5
-Di (iso) nonylsalicylic acid, 3- (iso) dodecylsalicylic acid, 3- (iso) dodecyl-5-methylsalicylic acid, 3- (iso) dodecyl-6-methylsalicylic acid,
3-isopropyl-5- (iso) dodecylsalicylic acid,
3- (iso) dodecyl-5-ethylsalicylic acid, 5-
(Iso) dodecylsalicylic acid, 3- (iso) pentadecylsalicylic acid, 3- (iso) pentadecyl-5-methylsalicylic acid, 3- (iso) pentadecyl-6-methylsalicylic acid, 5- (iso) pentadecylsalicylic acid, 3-
Cyclohexyl-5- (α-methylbenzyl) salicylic acid, 3-phenyl-5- (α-methylbenzyl) salicylic acid, 3- (α-methylbenzyl) salicylic acid, 3-
(Α-Methylbenzyl) -6-methylsalicylic acid, 3-
(Α-Methylbenzyl) -6-methylsalicylic acid, 3-
(Α-Methylbenzyl) -5-phenylsalicylic acid, 3
-(Α-methylbenzyl) -5-bromosalicylic acid, 3
-(Α, 4-Dimethylbenzyl) -5-methylsalicylic acid, 3,5-di (α, 4-dimethylbenzyl) salicylic acid, 3- (α, α-dimethylbenzyl) -6-methylsalicylic acid, 5- (4 -Mesitylmethylbenzyl) salicylic acid, benzylated styrenated salicylic acid, 2-hydroxy-3- (α, α-dimethylbenzyl) -1-naphthoic acid or 3-hydroxy-7- (α, α-dimethylbenzyl) -2 -Aromatic carboxylic acids such as naphthoic acid, pinenic salicylic acid, benzylated styrenated salicylic acid and polyvalent metal salts. Specific examples of polyvalent metals include magnesium, calcium, zinc, aluminum,
Examples include iron, cobalt, nickel and the like. These may be used alone or as a mixture. In addition, (iso) alkyl shows isoalkyl or normal alkyl. Further, the isononyl group, the isododecyl group and the isopentadecyl group are defined as substituents formed by addition of propylene trimer, propylene tetramer or 1-butene trimer and propylene pentamer, respectively.

As the inorganic pigment, zinc oxide, magnesium oxide, titanium oxide, aluminum hydroxide, calcium carbonate, magnesium sulfate, calcium sulfate, etc. are appropriately used. As the adhesive, for example, starch, casein, gum arabic, carboxymethyl cellulose, polyvinyl alcohol, styrene / butadiene copolymer latex, vinyl acetate latex and the like are blended. As the tilting agent, starch granules having a particle size larger than that of capsules, cellulose powder, inorganic powder and the like are used. The self-coloring pressure-sensitive recording sheet is prepared by mixing and stirring each of the above-mentioned coating liquid components and then coating the coating liquid on a support, or separately preparing a coating liquid containing a capsule and a coating liquid containing a color developer, and laminating the coating liquid on a support. It is obtained by coating. The coating amount is not particularly limited, but is about 5 to 12 g / m ^{2 in} dry weight. The coating liquid thus prepared is used to support high-quality paper, coated paper, synthetic paper, film, etc. by a normal coating device such as an air knife coater, a blade coater, a roll coater, a size press coater, a curtain coater, and a short dwell coater. When applied on the body, a self-coloring pressure-sensitive recording layer is formed.

The active energy ray curable resin used in the present invention can be selected, for example, from the following compounds. (A) Radical-polymerizable monofunctional monomer Acrylic acid, ethyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, triloxyethyl acrylate, Nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, 1,3-dioxolane acrylate, phenoxydiethylene glyco-
Acrylate, benzyl acrylate, butoxyethyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, glycidyl acrylate, carbitol acrylate, isobornyl acrylate and the like. (B) Radical-polymerizable polyfunctional monomer 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, dicyclopentanyl diacrylate, butylene glycol diacrylate, pentaerythritol diacrylate , Trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate and the like. (C) Radical polymerizable oligomer (prepolymer) Polyester (poly) acrylate and urethane (poly)
Acrylate, epoxy (poly) acrylate, polyol (poly) acrylate and the like.

Further, 2-chloroethyl vinyl ether,
Cationic polymerizable monomers and / or oligomers such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, triethylene glycol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether can also be used. Incidentally, in the case of incorporating the cationically polymerizable monomer and / or oligomer, a cationic polymerization initiator is required. The cationic polymerization initiator is not particularly limited as long as it is a substance that initiates cationic polymerization by irradiation with active energy rays, and examples thereof include a diazonium salt, an iodonium salt, a sulfonium salt, and a metallocene compound. The amount of the cationic polymerization initiator added is 0.1 to 1 with respect to 100 parts by weight of the cationically polymerizable monomer and / or oligomer.
About 0 parts by weight is preferable, and if it is less than 0.1 parts by weight, the polymerization initiation ability tends to be insufficient, and if it is more than 10 parts by weight, the effect is saturated and the solubility of the cationic polymerization initiator becomes poor. There may be adverse effects such as poor transparency of the coating film.

The coating amount of the resin which is cured by active energy rays is not necessarily limited, but if it is less than 0.1 g / m ² , the desired effect of the present invention cannot be expected and exceeds 20 g / m ² . With such a coating amount, the recording density of the obtained self-coloring pressure-sensitive recording sheet may be significantly lowered, so that the coating density is 0.1 to 20 g / m ² , more preferably 0.5 to 10 g / m ² . It is desirable to adjust the range. In the active energy ray-curable resin component, in addition to the prepolymer and the monomer as described above, if necessary, for example, a non-active energy ray-curable resin, a pigment,
Additives such as a defoaming agent, a leveling agent, a lubricant, a surfactant, a plasticizer, and an ultraviolet absorber can be appropriately added.
Examples of the non-active energy ray curable resin include acrylic resin, silicon resin, alkyd resin, fluororesin, butyral resin and the like.

The method of applying these active energy ray-curable resins is not particularly limited, and for example, a usual coating means such as a bar coater, a roll coater, an air knife coater, a gravure coater, an offset gravure coater or the like can be appropriately used. It is also possible to pretreat the coating surface and the bonding surface by corona discharge treatment, radiation treatment, plasma treatment or the like in advance to control the wettability and adhesion of the active energy ray-curable resin. In the active energy ray-curable resin described above, if necessary, various auxiliary agents such as dyes, pigments, wetting agents, defoaming agents, dispersants, antistatic agents, leveling agents, lubricants, etc. may inhibit desired effects. It can be added as appropriate within the range not specified. Examples of the active energy ray include ultraviolet rays, electron rays, X-rays, γ-rays and the like, but ultraviolet rays and electron rays are preferable from the viewpoint of easy handling and safety. Especially in the case of electron beam, it has excellent transparency and can be irradiated from the opaque substrate side. It does not generate heat and does not cause bluing of the pressure-sensitive color development layer. It is particularly preferable because it has various advantages such as low viscosity, light resistance, excellent storage stability of the coating composition, and high productivity.

The resin component can be heated to adjust the viscosity, if necessary. Resin viscosity is 10 to 1000
0 cps, more preferably 100-5000 cp
s is suitable. If it is lower than 10 cps, the resin may exude during bonding, or the self-coloring pressure-sensitive recording layer or the barrier layer may be impregnated, resulting in insufficient bonding, or coloring or desensitization of the pressure-sensitive recording layer. There is 10
If it is higher than 000 cps, the coated surface becomes non-uniform and it may be difficult to obtain a uniform bonded surface. The amount of electron beam to be irradiated is preferably 0.1 to 15 Mrad, more preferably 0.5 to 10 Mrad. By the way,
If it is less than 0.1 Mrad, the resin component cannot be sufficiently cured, and excessive electron beam irradiation exceeding 15 Mrad may cause color development or discoloration of the pressure-sensitive recording sheet.
As the electron beam irradiation method, for example, a scanning method, a curtain beam method, a broad beam method, or the like can be adopted, and an accelerating voltage for irradiation is preferably about 100 to 300 KV.

In the self-coloring pressure-sensitive recording sheet of the present invention, when the active energy ray-curable resin layer is directly provided on the pressure-sensitive recording layer, some resins have a desensitizing effect on the pressure-sensitive recording layer. In such a case, it is preferable to provide a barrier layer containing a water-soluble resin and / or a water-dispersible resin in order to impart a barrier property to the active energy ray-curable resin. Examples of the water-soluble resin and / or the water-dispersible resin include the following substances. As the water-soluble resin, fully saponified or partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol having an acetoacetyl group introduced by reacting polyvinyl alcohol with diketene, polyvinyl alcohol and fumaric acid, phthalic anhydride, trimellitic anhydride , A reaction product of a polycarboxylic acid such as itaconic anhydride, or an esterification product of these reaction products, and further, an ethylenic vinyl ester such as vinyl acetate and maleic acid, fumaric acid, itaconic acid, crotonic acid, acrylic acid or methacrylic acid. Sulfonic acid-modified polyvinyl alcohol obtained as a saponified product of a copolymer with a saturated carboxylic acid, a copolymer of vinyl acetate and an olefin such as ethylene, propylene, isobutylene, α-octene, α-dodecene, and α-octadodecene. Me obtained by saponification Nitrile-modified polyvinyl alcohol, a nitrile-modified polyvinyl alcohol obtained as a saponification product of a copolymer of vinyl acetate with nitriles such as acrylonitrile and methacrylonitrile, a copolymer of vinyl acetate with amides such as acrylamide and methacrylamide. Amide-modified polyvinyl alcohol, vinyl acetate and N
-Pyrrolidone-modified polyvinyl alcohol obtained by saponifying a copolymer with vinylpyrrolidone, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethyl cellulose, caseins, acacia, oxidized starch, etherified starch, dialdehyde starch, esterified starch and other starches. Examples of the water-dispersible resin include styrene-butadiene copolymer emulsion, vinyl acetate-vinyl chloride-ethylene copolymer emulsion, methacrylate-butadiene copolymer emulsion and the like. Specific examples of the pigment include calcium carbonate, zinc oxide, aluminum oxide, titanium dioxide, silicon dioxide, aluminum hydroxide, barium sulfate,
Inorganic pigments such as zinc sulfate, talc, kaolin, clay, calcined clay, colloidal silica, styrene microballs, nylon powder, polyethylene powder, urea
Examples thereof include formalin resin fillers and organic pigments such as raw starch granules. Among these, kaolin is particularly preferable because it has excellent water resistance and barrier properties.

Further, in the coating liquid for forming the barrier layer, if necessary, a curing agent such as glyoxal, methylolmelamine, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, magnesium chloride, boric acid or ammonium chloride. May be added, if necessary, zinc stearate, calcium stearate, stearic acid amide,
Lubricants such as polyethylene wax, carnauba wax, paraffin wax and ester wax, surfactants such as sodium dioctyl sulfosuccinate, sodium dodecylbenzene sulfonate, sodium lauryl alcohol sulfate / sodium salt, alginate and fatty acid metal salt, benzophenone type, triazole type It is also possible to appropriately add various auxiliaries such as an ultraviolet absorber, a defoaming agent, a fluorescent dye, a coloring dye and the like.

The coating liquid for forming the barrier layer is generally prepared as an aqueous coating liquid, and if necessary, a mixer,
The mixture is sufficiently mixed and dispersed by a mixing / stirring machine such as an attritor, a ball mill, a roll mill, and then coated on the self-coloring pressure-sensitive recording layer by various known coating devices. After application
It can also be cured and dried by irradiating it with ultraviolet rays or electron beams.
When a curing agent is used in combination, the curing agent can be applied not only in the coating liquid for forming the barrier layer but also separately from the coating liquid for forming the barrier layer. There is an advantage that a strong curing agent can be selected without having to worry about the pot life of.

The coating amount of the coating liquid for forming the barrier layer is not particularly limited, but if it is less than 0.1 g / m ² , the desired effect cannot be sufficiently obtained, and 10 g / m ²
If it exceeds m ² , the recording density of the self-coloring pressure-sensitive recording sheet may be remarkably reduced. Therefore, the dry weight is generally 0.1 to 10 g / m ² , preferably 0.5 to 5 g / m ^2.
It is adjusted within a range. The smoothness of the barrier layer formed as described above is not particularly limited.

The self-coloring pressure-sensitive recording layer surface or barrier layer surface thus obtained and the patterning sheet are bonded together via an active energy ray-curable resin layer. After pasting,
This active energy ray-curable resin layer is irradiated with active energy rays to be cured. At this time, the concavo-convex shape of the surface of the mold sheet that comes into contact with the active energy ray curable resin layer is transferred to the active energy ray curable resin layer surface.
The uneven shape includes embosses, patterns, marks, logos or patterns.

At present, the method for imprinting patterns, marks, logos or patterns having uneven shapes on a sheet of paper, polymer film or the like is such that the uneven shape is directly stamped on a metal roll or a flat plate in advance. It is common to press the sheet continuously or periodically and copy it as an uneven shape on the sheet surface. Further, it is necessary that the releasability from the interface between the typed sheet and the active energy ray-curable resin layer is good, and at least when the typed sheet is peeled off, the active energy ray-curable resin layer is a self-coloring pressure-sensitive recording layer or a barrier. In order to remain in the layer, the adhesive force A between the typed sheet and the active energy ray-curable resin layer needs to be smaller than the adhesive force B between the active energy ray-curable resin layer and the pressure-sensitive recording layer or the barrier layer. There is. In order to do this, 1) select a typed sheet that has a weak adhesion to the active energy ray-curable resin, or 2) select an active energy ray-curable resin that has a weak adhesion to the typed sheet. However, in the case of 2) the active energy ray curable resin, which has a weak adhesive force to the typed sheet, the adhesive force is generally weak also to the self-coloring pressure-sensitive recording layer or the barrier layer. The method 1) is more preferable. Here, a film such as a polyethylene terephthalate film, a polypropylene film, or a polyethylene film as the mold sheet shows a weak adhesive force to general active energy ray-curable resins. It is preferable that the mold sheet is transparent when the recording surface is checked immediately after recording. However, even if it is opaque, there is no problem because the patterned sheet may be peeled off after recording. When a completely opaque typed sheet or a transparent typed sheet colored in the same color as the color of the recording surface is used, it is possible to conceal the recording until the typed sheet is peeled off. Further, the self-coloring pressure-sensitive recording layer or the barrier layer is subjected to a treatment for enhancing the adhesiveness such as corona discharge treatment so that the adhesive force B between the active energy ray-curable resin layer and the self-coloring pressure-sensitive recording layer or the barrier layer is It is also effective to increase. Furthermore, a release agent such as a silicone compound or a fluorine compound is applied to the surface of the patterned sheet that is to be bonded to the active energy ray-curable resin layer, and the adhesive force between the patterned sheet and the active energy ray-curable resin layer is applied. It is also possible to weaken A. Comprehensively considering the above, the polyethylene terephthalate film (PET film) is the most preferable in view of the releasability, strength and cost. Here, the thickness of the mold sheet is 3 to 50 μm, preferably 6 to 25 μm. If the thickness is less than 3 μm, wrinkles are likely to occur during bonding, which may cause a manufacturing problem, and tearing may be more likely to occur during peeling.

As a method of bonding, 1) an active energy ray-curable resin is applied on the surface of the self-coloring pressure-sensitive recording layer or the barrier layer, and is bonded to a mold sheet having an uneven shape, 2) active energy ray curing. The mold resin is coated on a mold sheet having an uneven shape and is bonded to the surface of the self-coloring pressure-sensitive recording layer or the barrier layer. 3) The active energy ray curable resin is uneven to the surface of the self-coloring pressure-sensitive recording layer or the barrier layer. There is a method in which both are applied on a shaped sheet having a shape and then attached. The device for laminating is not particularly limited, but it is usually carried out by passing it between two rolls (nip rolls) under a pressure not breaking the capsule.

In order to further clarify the effects of the present invention, examples and comparative examples will be described below, but the present invention is not limited to these. Further, "parts" and "%" in the examples represent "parts by weight" and "% by weight", respectively, unless otherwise specified.

Example 1 [Preparation of coating liquid for microcapsules] Crystal violet lactone 10 was added to 100 parts of diisopropylnaphthalene.
Part is heated and dissolved, and an aromatic polyvalent isocyanate (manufactured by Nippon Polyurethane Co., Millionate MR) is added to the dye solution.
500) 4 parts and 8 parts of a trimer of hexamethylene diisocyanate having a biuret bond, which is an aliphatic polyvalent isocyanate, were dissolved. A 2% aqueous solution of polyvinyl alcohol (PVA-117 manufactured by Kuraray Co., Ltd.) 300 was added to this solution.
Added to the part and emulsified with a homomixer to give an average particle size of 8
A μm dispersion was obtained. To this dispersion was added 2 parts of polyvalent amine consisting of bisphenol A, epichlorohydrin and alkylamine, and the mixture was stirred at room temperature for 15 minutes, then heated to 90 ° C. and reacted for 4 hours. Then, it cooled to room temperature and obtained the microcapsule dispersion liquid. 60 parts of wheat starch and 2 parts of oxidatively modified starch were added to the above microcapsule dispersion.
90 parts of a 5% aqueous solution was mixed and stirred to prepare a microcapsule coating liquid. [Preparation of color developer coating liquid] 100 parts of zinc 3,5-di (α-methylbenzyl) salicylate was dissolved in 100 parts of toluene and emulsified in 150 parts of 3% polyvinyl alcohol aqueous solution using a homomixer. Then, toluene was subjected to steam distillation to obtain an aqueous dispersion of the developer fine particles. 700 parts of calcium carbonate, 100 parts of zinc oxide, 200 parts of 25% aqueous solution of oxidatively modified starch, and 160 parts of styrene-butadiene copolymer latex were mixed with this aqueous dispersion and stirred to prepare a developer coating liquid. [Formation of Pressure Sensitive Recording Layer] First, a microcapsule coating liquid was applied to the surface of a base paper having a basis weight of 40 g / m ² by an air knife coater so that the dry coating amount was 4 g / m ² .
Next, the developer coating liquid was applied thereon by an air knife coater so that the dry coating amount was 6 g / m ² . [Formation of overcoat layer] Each prepolymer mixture of polyester polyacrylate and polyurethane polyacrylate (Plastic polyacrylate and polyurethane polyacrylate) was preliminarily pressed on a PET film having a striped pattern as an uneven shape by pressing a heated stencil. Ltd., the 78E204) dry coating amount was coated to a 4g / m ^2, electro curtain type electron beam irradiation apparatus immediately after bonding and self-coloring property pressure sensitive recording sheets (ES
I, CB: 150 type) to treat the resin component by treatment with an irradiation amount of 3 Mrad to obtain a pressure sensitive recording sheet having an electron beam curable resin and an overcoat layer of a PET film having unevenness. .

Example 2 The procedure of Example 1 was repeated, except that the pressure-sensitive recording layer was prepared by the following method. [Preparation of Microcapsule Dispersion Liquid] 6 parts of crystal violet lactone were dissolved by heating in 100 parts of diisopropylnaphthalene (KMC-113 manufactured by Kureha Chemical Co., Ltd.) to obtain an internal phase liquid. Then, 20% caustic soda aqueous solution was added dropwise to 200 parts of a 3% aqueous solution of ethylene-maleic anhydride copolymer (manufactured by Monsanto Co., Ltd., EMA31) to adjust the pH to 6.0, and this internal phase solution was emulsified and dispersed. Then let the system go to 55
The temperature was raised to ° C. Separately, 37% formaldehyde aqueous solution 4
15 parts of melamine was added to 5 parts and reacted at 60 ° C. for 15 minutes to prepare a prepolymer aqueous solution. This prepolymer aqueous solution was added dropwise to the emulsion, and the mixture was further stirred with stirring.
After 1N-hydrochloric acid was added dropwise to adjust the pH to 5.3, the temperature was raised to 80 ° C. and kept for 1 hour, the pH was lowered to 3.5 with 0.2N hydrochloric acid, and the mixture was kept warm for 3 hours and then released. After cooling, a microcapsule dispersion having an average particle size of 5μ was obtained. [Preparation of One-Part Coating Liquid for Self-Coloring Pressure-Sensitive Recording Sheet] 100 parts of the microcapsule dispersion described above, 50 parts of an aqueous dispersion (40%) of the developer fine particles obtained in Example 1, and styrene-butadiene 50 parts of polymer latex, 45 parts of wheat starch,
100 parts of calcium carbonate was mixed and stirred to obtain a coating liquid. [Formation of Pressure Sensitive Recording Layer] The above coating liquid was applied to the surface of a base paper having a basis weight of 40 g / m ² by an air knife coater so that the dry coating amount was 8 g / m ² .

Example 3 Example 3 was repeated except that a polyethylene film having an uneven shape was used instead of the PET film.

Example 4 In Example 1, a protective layer coating liquid prepared by the following method was prepared between the self-coloring pressure-sensitive recording layer and the overcoat layer.
The procedure of Example 1 was repeated, except that the coating amount after drying was 4 g / m ² and the protective layer was provided. [Preparation of coating liquid for barrier layer] To 1000 parts of an 8% aqueous solution of polyvinyl alcohol (PVA-117 manufactured by Kuraray Co., Ltd.), 50% of kaolin (UW-90 manufactured by Engelhard) is added.
200 parts of the aqueous dispersion was mixed with stirring to obtain a barrier layer coating liquid.

Example 5 40 g instead of the 40 g / m ² base paper in Example 1
/ M ² of synthetic paper (manufactured by Oji Yuka, YUPO) was used in the same manner as in Example 1.

Comparative Example 1 In Example 1, a pressure-sensitive recording sheet having only a self-coloring pressure-sensitive recording layer without an overcoat layer was used. [Evaluation] (1) Coloring property The self-coloring pressure-sensitive recording sheet prepared by the above method was passed through a super calender with a linear pressure set to 50 kg / cm to develop a color, and after 1 hour, a Macbeth color densitometer RD-9.
It was measured at 41. (2) Tampering property The self-coloring pressure-sensitive recording sheet prepared by the above method was printed using a typewriter (Olympia: Competence MD). After printing, in Examples 1 to 5, the typed sheet was peeled off, and in Comparative Example 1, the same typewriter was used again to print different characters on the previously printed recording image. <Evaluation Criteria> ○ It was clearly understood that the print had unevenness and was tampered with. × There was no shading in the print, and it was not possible to know that the print was tampered with. (2) Abrasion resistance A self-coloring pressure-sensitive recording sheet is cut into a piece of 3 cm × 15 cm, and fixed on a sample stand of a Southerland type lab tester (manufactured by Toyo Seiki Co., Ltd.) with its coated surface facing upward. Also, a high-quality paper cut into the same size was fixed to the friction body, and the sheet of the sample base and the paper of the friction body were rubbed in an arc shape 10 times so that they were exactly overlapped, and fixed on the sample base. The colored stains of No. 1 were sensory evaluated according to the following evaluation criteria. <Evaluation Criteria> ◎ No stain is observed.

[0029]

[Table 1]

[0030]

EFFECT OF THE INVENTION Stable recording is obtained during recording before peeling of the patterning sheet, and after the patterning sheet is peeled, a printing defect occurs even if a further recording is attempted, so that falsification can be prevented. Further, from the time of storage before recording to the time of peeling the patterned sheet after recording, even if a mechanical force such as friction or a chemical action is applied, it does not become dirty. Moreover, almost no dust is generated.

[Brief description of drawings]

FIG. 1 is a sectional view showing the constitution of an embodiment of a self-coloring pressure-sensitive recording sheet of the present invention.

FIG. 2 is a cross-sectional view showing a state in which the pattern sheet of the self-coloring pressure-sensitive recording sheet of the present invention is peeled off.

[Explanation of symbols]

 1 Support 2 Self-coloring pressure-sensitive recording layer 3 Active energy ray curable resin layer 4 Typed sheet

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location B41M 5/165 C08F 2/46 MDT

Claims (5)

[Claims] 1. A self-coloring pressure-sensitive recording layer having a microcapsule containing a colorless or light-colored basic dye and a developer in a single layer or laminated state on a support, an active energy ray-curable resin layer, and the activity. A self-coloring pressure-sensitive recording sheet comprising, in order, a sheet with a mold having an uneven shape that can be peeled from the interface with an energy ray-curable resin layer. 2. The self-coloring pressure-sensitive recording sheet according to claim 1, wherein a barrier layer is provided between the self-coloring pressure-sensitive recording layer and the active energy ray-curable resin layer. 3. The self-coloring pressure-sensitive recording sheet according to claim 1, further comprising a self-coloring pressure-sensitive recording layer on the mold sheet. 4. A self-coloring pressure-sensitive recording layer having a microcapsule containing a colorless or light-colored basic dye and a color developer in a single layer or a laminated state is provided on a support, and a barrier layer is further provided if necessary. The self-coloring pressure-sensitive recording layer or the barrier layer and the typed sheet are bonded together via an active energy ray-curable resin layer, and then the active energy ray is irradiated, according to any one of claims 1 to 3. Method for producing color forming pressure-sensitive recording sheet. 5. The method for recording a self-coloring pressure-sensitive recording sheet according to claim 1, wherein the pressure-sensitive recording of the information is followed by peeling off the mold sheet.