JPH0872397A - Thermal recording material, manufacturing method thereof, and recording method of the thermal recording material - Google Patents

Abstract

(57) [Summary] [Purpose] Stable recording is obtained at the time of recording before peeling of the die-molded sheet, and after the peeling of the die-molded sheet, even if an attempt is made to perform further recording, a printing defect occurs, and therefore falsification can be prevented. A thermosensitive color-developing recording layer 2, an active energy ray-curable resin layer 4, and the active material containing a colorless or light basic dye and a coloring agent capable of coloring on contact with the dye on a support 1. A mold-equipped sheet 5 having an irregular shape that can be peeled from the interface with the energy ray-curable resin layer 4 is provided in order. After recording, the mold sheet 5 is peeled off, and the active energy ray curable resin layer 4 is removed.
Uneven surface appears, and no further recording is possible.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosensitive recording medium capable of preventing falsification after recording, a method for producing the same, and a recording method for the thermal recording medium.

[0002]

2. Description of the Related Art A thermal recording material utilizing various thermal recording methods in which a plurality of color-forming substances are brought into contact with each other by heat to obtain a recorded image is well known. Since such a thermal recording material is relatively inexpensive, and the recording device is compact and its maintenance is easy, it is used not only as a recording medium for facsimiles and various computers but also in a wide range of fields.

One of the fields of use thereof is, for example, POS.
(point of sales) Thermal recording label, tag for system,
Cards, etc. can be mentioned, but with the expansion of the system,
The number of cases where the thermosensitive recording medium itself has the same function as currency has also been increasing. In such applications, it is particularly required to take measures to prevent forgery of the recording material. As one example, there is a demand for heat-sensitive recording paper that has been embossed. At present, a method of imprinting a pattern, a mark, a logo or a pattern having an uneven shape on a sheet of paper, a polymer film or the like is usually performed as follows. This is a method in which an uneven shape is directly stamped on a metal roll or a flat plate in advance, and this is continuously or periodically pressed against the sheet to be copied on the sheet surface as the uneven shape. Note that, hereinafter, the patterns, marks, logos, patterns, and the like having an uneven shape will be simply referred to as an uneven shape.

[0004]

When the thermal recording paper is imprinted by these methods, the adhesiveness between the edge portion of the uneven shape and the thermal head deteriorates, and a defective coloring portion (line break) occurs. There was a problem with recordability. In addition, there is a case where a method of pre-molding on the base paper of the thermal recording paper is taken, but when the water-based paint is smeared, the base paper expands and contracts, and the mold attached becomes thin, or in the worst case, disappears. In some cases, there was a problem with mold stability.

The present invention does not have the problem of recording suitability due to the above-described defective coloring portion (line break) and has excellent mold stability, a method for producing the same, and recording of the same. The purpose is to provide a method.

[0006]

The thermal recording material of the present invention comprises:
Thermosensitive color-developing recording layer, active energy ray-curable resin layer, and active energy ray-curable resin layer containing a colorless or light-colored basic dye and a coloring agent capable of coloring on the support. A patterned sheet having an uneven shape that can be peeled from the interface with is sequentially provided.

At least one intermediate layer made of an aqueous composition may be provided between the heat-sensitive color forming recording layer and the active energy ray-curable resin layer. A layer containing a pigment may be provided on the patterned sheet. This layer may be the uppermost layer or a layer immediately above the typed sheet, and its position varies depending on the constitutional conditions of other layers formed on the typed sheet. It is preferable that a thermosensitive color recording layer is further provided on the mold sheet side. This layer may be the uppermost layer or may be a layer immediately above the typed sheet, and its position varies depending on the constitutional conditions of the other layers formed on the typed sheet. The layer containing a pigment may have the function of a thermosensitive color recording layer.

In the method for producing a thermosensitive recording medium of the present invention, a thermosensitive color recording layer containing a colorless or light-colored basic dye and a coloring agent capable of coloring when contacted with the dye is provided on a support, If necessary, an intermediate layer made of an aqueous composition is further provided, and the thermosensitive color-developing recording layer or the intermediate layer and the typed sheet are bonded together via the active energy ray-curable resin layer, and then irradiated with active energy rays. Can be manufactured.

The recording method of the heat-sensitive recording material of the present invention is characterized in that after the information is thermally recorded from the side of the patterning sheet, the patterning sheet is peeled off.

[0010]

When the mold is directly attached to the recording surface of the thermosensitive recording medium, since the recording surface has irregularities, the concave surface or the edge portion makes poor contact with the recording head. Etc. occur. On the other hand, in the present invention, when the uneven shape of the typed sheet is only on the side of the active energy ray-curable resin layer and there is no unevenness on the side that contacts the recording head, when recording from the typed sheet side Since the recording surface is a smooth flat surface, the contact with the recording head is uniform, so that a defective coloring portion (line break) does not occur.
Also, for example, when the die-molded sheet is very thin, it is difficult to avoid unevenness on the side in contact with the recording head.
In such a case, the unevenness is filled when the pigment-containing layer is applied on the pattern-formed sheet, and the surface of the pigment-containing layer that comes into contact with the recording head is smoothed by calendering at that time. As a result, the recording surface can be made a smooth flat surface when recording is performed from the die-attached sheet side, and a defective coloring portion (line break portion) or the like does not occur.

In any case, since the active energy ray-curable resin layer has irregularities on the mold sheet, the active energy ray-curable resin layer is formed so as to fill the irregularities. Therefore, after the recording with the recording head, when the mold sheet is peeled from the interface with the active energy ray-curable resin layer, the uneven surface of the mold sheet is transferred and formed on the surface of the active energy ray-curable resin layer. become. After the release of the typed sheet as described above, further recording is performed by the recording head for the purpose of tampering with the recording on the thermosensitive recording medium whose surface is covered with the uneven active energy ray-curable resin layer. However, since the surface is uneven, line breaks and the like occur and recording cannot be performed satisfactorily.

Furthermore, if a heat-sensitive recording layer is further provided on the side of the patterning sheet to be peeled off, it is possible to check whether or not tampering has been carried out by storing this patterning sheet separately. . Further, when the active energy ray-curable resin layer is made of a resin having relatively low heat resistance, the resin layer having low heat resistance directly contacts the thermal head during recording such as falsification after peeling the typed sheet. Therefore, sticking is likely to occur, and the unevenness of the surface acts on this situation to further promote sticking,
It becomes more and more difficult to record after peeling the typed sheet. still,
Even if the active energy ray-curable resin layer, which has relatively low heat resistance, is used in this way, it is completely problematic if a heat-resistant film is used for the typed sheet when recording from the typed sheet. There is no.

The support of the thermosensitive recording medium in the present invention is not particularly limited as long as it is a flexible sheet-like material. For example, generally known various kinds of coated paper, fine paper, synthetic paper, metallized paper. Paper sheets such as colored paper; plastic films such as polyethylene terephthalate, polypropylene and polyethylene; metal foils such as copper, iron and aluminum; cloth and the like, or a laminated body or a laminated body thereof are appropriately used. From the viewpoint of image quality, it is preferable to select one having excellent surface smoothness and heat insulating property or cushioning property among the above, and providing an appropriate undercoat layer between the support and the thermosensitive coloring layer, or surface smoothness, It is also effective to use a synthetic resin film having excellent heat insulating properties and cushioning properties. In particular, a polyolefin-based or polyester-based synthetic resin film having microporosity inside is useful. Examples of products of such synthetic resin film include, for example, YUPO manufactured by Oji Yuka Synthetic Paper Co., Ltd., Peach coat manufactured by Nisshinbo Co., Ltd., Toyopearl manufactured by Toyobo Co., Ltd.,
Crisper etc. are mentioned.

In the present invention, first, on the support as described above,
A thermosensitive color recording layer is provided. The combination of the colorless or light-colored basic dye contained in the thermosensitive color-developing recording layer and the organic or inorganic colorant is not particularly limited, and may be a color reaction caused by contact between the two due to heat. Any combination can be used. For example, various types are known as colorless to light basic dyes,
For example:

3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3,3-bis (p
-Dimethylaminophenyl) phthalide, 3-p-dimethylaminophenyl-3- (1-methylpyrrol-3-yl) -6-dimethylaminophthalide and other triallylmethane dyes, 4,4'-bis-dimethyl Aminobenzhydryl benzyl ether, N-halophenyl-leuco auramine, N-2,4,5-trichlorophenyl leuco auramine and other diphenylmethane dyes, benzoyl leuco methylene blue, p-nitrobenzoyl leuco methylene blue and other thiazine dyes, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran,
3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho (6 '
-Methoxybenzo) spiropyran, 3-propyl-spiro-dibenzopyran and other spiro dyes, rhodamine-B
-Lactam dyes such as anilinolactam, rhodamine (p-nitroanilino) lactam, rhodamine (o-chloroanilino) lactam, 3- (N-ethyl-Ni)
Pentyl) amino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-cyclohexyl) amino-
6-Methyl-7-anilinofluorane, 3-dibutylamino- (N-methyl-N-cyclohexyl) amino-6
-Methyl-7-anilinofluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-7
-Methoxyfluorane, 3-diethylamino-7-chlorofluorane, 3- (N-ethyl-N-isoamylamino) -7- (o-chlorophenylamino) fluorane,
Fluorane dyes such as 3-pyrrolidino-6-methyl-7-p-butylphenylaminofluorane. Other examples include the colorless or light-colored basic dyes described in JP-A-3-79387.

Various kinds of inorganic or organic acidic substances which are colored by contact with a basic colorless dye are also known. Examples thereof include activated clay, acid clay, attapulgite, bentonite, colloidal silica, and aluminum silicate. Acidic substance, 4-hydroxy-4'-isopropyloxydiphenyl sulfone, 4,4'-isopropylidenediphenyl (bisphenol A), 4-tert-butylphenol, 4-hydroxydiphenoxide, 4-hydroxyacetophenol, 4- ( In addition to zinc salt of 3-p-tolylsulfonylpropyloxy) salicylic acid, etc., JP-A-3-
Coloring agents described in No. 79387 can be mentioned.

In the present invention, the use ratio of the basic dye and the acidic substance in the recording layer is appropriately selected according to the kind. Generally, 1 to 50 parts by weight, preferably 1 to 10 parts by weight of an acidic substance is used with respect to 1 part by weight of a basic dye. To prepare a coating solution containing these substances, water is generally used as a dispersion medium, and stirring with a ball mill, attritor, sand mill, etc.
A basic dye and an acidic substance are dispersed together or separately by a pulverizer to prepare a coating liquid.

Examples of the water-soluble resin and / or the water-dispersible resin of the adhesive (binder) used in the coating liquid include the following substances. As water-soluble resin; starches, hydroxyethyl cellulose, methyl cellulose,
Carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohol, diisobutylene
Examples thereof include maleic anhydride copolymer salt, styrene / maleic anhydride copolymer salt, ethylene / acrylic acid copolymer salt, styrene / acrylic acid copolymer salt and the like.

As the water-dispersible resin: styrene / butadiene copolymer emulsion, vinyl acetate-vinyl chloride-
Examples thereof include ethylene copolymer emulsions. The binder is used in an amount of 10 to 40% by weight, preferably 15 to 35% by weight, based on the total solids. In addition, in order to provide sufficient water resistance, it is preferable that the binder contains a water-dispersible resin in an amount of 50% by weight or more.

Further, various auxiliaries can be added to the coating solution, for example, sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl alcohol sulfate / sodium salt, alginate, fatty acid metal salt and the like. Examples thereof include dispersants, benzophenone-based and triazole-based ultraviolet absorbers, other defoamers, fluorescent dyes, coloring dyes and the like.

If necessary, lubricants such as zinc stearate, calcium stearate, polyethylene wax, carnauba wax, paraffin wax and ester wax, kaolin, clay, talc, calcium carbonate, calcined clay, titanium oxide, diatomaceous earth and fine anhydrous silica. , Inorganic pigments such as activated clay, and stearic acid amides, stearic acid methylenebisamides, oleic acid amides, palmitic acid amides, perfumed oleic acid amides, aliphatic acid amides such as coconut fatty acid amides, 1,2-diphenoxyethane,
1,2-bis (3-methylphenoxine) ethane, 1,
Ethers such as 2-bis (4-methylphenoxine) ethane, 1-hydroxy-2-naphthoic acid phenyl ester, dibenzyl lalephthalate, dibenzyl oxalate,
Esters such as bis (p-chlorobenzyl oxalate) and benzyl p-benzyloxybenzoate, aromatic compounds such as p-benzylbiphenyl and m-terphenyl, and various known heat-fusible substances are used as sensitizers. It can also be added.

The coating method of the heat-sensitive color forming recording layer is not particularly limited and can be formed according to a conventionally well-known and commonly used technique, for example, bar coating, air knife coating, rod blade coating, pure blade coating, short dwell. It is formed by a method of applying and drying a coating liquid by coating or the like. When a plastic film is used as a support, the coating efficiency can be increased by subjecting the surface to treatments such as corona discharge and electron beam irradiation. The coating amount of the coating liquid is also not particularly limited, but it is usually in the range of about ² to ²⁰ g / m ² , preferably about 3 to 15 g / m ² in terms of dry weight.

In the heat-sensitive recording material of the present invention, the heat-sensitive color-developing recording layer surface thus obtained and the typed sheet are bonded together by using an active energy ray-curable resin, and a barrier property to the active energy ray-curable resin is imparted. Therefore, it is preferable to provide an intermediate layer on the thermosensitive color recording layer. The middle layer is
In order to prevent fog of the thermosensitive color recording layer and deterioration of color developability, it must be formed from an aqueous coating composition. This water-based coating composition contains a water-soluble resin and / or a water-dispersible resin, and if necessary, a pigment. Where water-soluble resin and /
Alternatively, the following substances are exemplified as the water-dispersible resin.

As a water-soluble resin; completely 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, anhydrous Reaction products with polyvalent carboxylic acids such as trimellitic acid and itaconic anhydride, or esterification products of these reaction products, and further vinyl acetate and maleic acid, fumaric acid, itaconic acid, crotonic acid, acrylic acid, methacrylic acid, etc. As a saponification product of a carboxy-modified polyvinyl alcohol, which is obtained as a saponification product of a copolymer of ethylenically unsaturated carboxylic acid, and a copolymer of vinyl acetate and an olefin sulfonic acid such as ethylene sulfonic acid and allyl sulfonic acid, or a salt thereof. Sulfonic acid obtained Sex polyvinyl alcohol, vinyl acetate and ethylene, propylene, isobutylene, alpha-octene, alpha-Dotesen, alpha-Okutadodesen like copolymers of olefins modified polyvinyl alcohol obtained by saponifying with olefins, vinyl acetate and acrylonitrile,
Nitrile-modified polyvinyl alcohol obtained as a saponification product of a copolymer with nitriles such as methacrylonitrile, an amide-modified polyvinyl alcohol obtained by saponifying a copolymer of vinyl acetate and acrylamide such as methacrylamide, Pyrrolidone-modified polyvinyl alcohol obtained by saponifying a copolymer of vinyl acetate and N-vinylpyrrolidone, a cellulose derivative such as methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, casein, gum arabic, oxidized starch, etherified starch, diester. There are starches such as aldehyde starch and esterified starch.

The water-dispersible resin includes styrene-butadiene copolymer emulsion, vinyl acetate-vinyl chloride-ethylene copolymer emulsion, methacrylate-butadiene copolymer emulsion and the like. Specific examples of pigments include inorganic carbonates such as calcium carbonate, zinc oxide, aluminum oxide, titanium dioxide, silicon dioxide, aluminum hydroxide, barium sulfate, zinc sulfate, talc, kaolin, clay, calcined clay, colloidal silica, and styrene microballs. , Nylon powder, polyethylene powder,
Examples include urea / formalin resin fillers and organic pigments such as raw starch granules. Of these, kaolin is particularly preferable because it has excellent water resistance and barrier properties.

Further, in the coating solution for forming the intermediate 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. Lubricants such as zinc stearate, calcium stearate, stearic acid amide, polyethylene wax, carnauba wax, paraffin wax, ester wax, etc., sodium dioctyl sulfosuccinate, sodium dodecylbenzene sulfonate, lauryl alcohol sulfate may be added as required. Various kinds of auxiliary agents such as surfactants such as ester / sodium salt, alginate, and fatty acid metal salt, ultraviolet absorbers such as benzophenone-based and triazole-based, antifoaming agents, fluorescent dyes, coloring dyes, etc. can be added as appropriate. .

The coating liquid for forming the intermediate layer is generally prepared as an aqueous coating liquid, and if necessary, sufficiently mixed and dispersed by a mixing / stirring machine such as a mixer, attritor, ball mill or roll mill, It is coated on the thermosensitive recording layer by various known coating devices. After coating, it can 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 intermediate layer, but also separately from the coating liquid for forming the intermediate 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 intermediate 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 is not obtained.
If it exceeds the range, the recording sensitivity of the thermosensitive recording medium may be lowered, so that the dry weight is generally adjusted in the range of 0.1 to 10 g / m ² , preferably 0.5 to 5 g / m ² . The intermediate layer formed as described above preferably has a Beck's smoothness of about 200 to 20,000 seconds. 200
If it is less than 2 seconds, the recording density, image quality or barrier property tends to be insufficient, and if it is more than 20000 seconds, the adhesion to the active energy ray-curable resin layer to be stuck may be deteriorated. In order to adjust to such a range of smoothness, surface smoothing treatment may be performed with a super calendar or the like, if necessary.

The heat-sensitive color-developing recording layer surface or the intermediate layer surface thus obtained and the patterning sheet are bonded together using an active energy ray-curable resin. After bonding, the active energy ray-curable resin layer is irradiated with active energy ray to be cured. At this time, the uneven surface of the sheet with a mold that comes into contact with the active energy ray-curable resin layer is transferred to the surface of the active energy ray-curable resin layer. The uneven shape includes embosses, patterns, marks, logos or patterns.

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 thermosensitive color recording layer or The adhesive force A between the patterned sheet and the active energy ray-curable resin layer is set so that it remains in the intermediate layer, and the adhesive force A between the active energy ray-curable resin layer and the thermosensitive color recording layer or the intermediate layer. It must be smaller than B.

In order to do so, 1) select a typed sheet having a weak adhesion to the active energy ray-curable resin, or 2) an active energy ray-curable type having a weak adhesion to the typed sheet. It is possible to select a resin, but 2)
In the case of the active energy ray-curable resin, which has a weak adhesive strength to the typed sheet, the adhesive strength is generally weak also to the thermosensitive color recording layer or the intermediate layer, and the method of 1) is more preferable. Considering polyethylene terephthalate film, polypropylene film, polyethylene film, etc. as the typed sheet, the surface of these films is specially roughened or easily treated (corona discharge treatment, plasma discharge treatment, anchor coat treatment). Unless otherwise applied, it exhibits weak adhesion to general active energy ray-curable resins. Needless to say, in controlling the adhesive force A, the design elements of the mold, such as the depth, shape, area, and distribution of the unevenness of the uneven shape of the die-attached sheet, have a great influence.

Further, the thermosensitive color recording layer or the intermediate 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 thermosensitive color recording layer or the intermediate layer is increased. It is also effective to raise it. Furthermore, a release agent such as a silicone compound or a fluorine compound is applied to the surface of the typed sheet that is to be bonded to the active energy ray curable resin layer, and the adhesive strength between the typed sheet and the active energy ray curable resin layer is applied. It is also possible to weaken A.

Further, it is preferable that the patterning sheet has heat resistance in terms of preventing sticking by the thermal head. Examples of such a typed sheet include a polyethylene terephthalate film and a polyimide film. In order to apply a mold to these films, generally, an uneven shape is directly stamped on a metal roll or a flat plate in advance, and if necessary, these are pressed continuously or periodically to the film in a heated state. There is a method of copying the film surface as an uneven shape.

Comprehensively looking at the above, the workability of the uneven shape,
The polyethylene terephthalate film is the most preferable in terms of the releasability, heat resistance, strength and cost. Here, the thickness of the mold sheet is 3 to 50 μm, preferably 6 to 30 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 occur during peeling. Also, 5
If it is thicker than 0 μm, it becomes difficult for the energy from the thermal head to be transmitted, and the color development sensitivity tends to be remarkably lowered.

It is preferable that the patterning sheet has an uneven shape only on one side, that is, the surface bonded to the active energy ray-curable resin layer, that is, the contacting side, in order to flatten the contact surface of the head during recording. . However, for clear recording, it is preferable to make the pattern sheet as thin as possible in order to reduce heat loss. However, when the die-molded sheet becomes thin, it is unavoidable that the side in contact with the recording head has an uneven shape. In such a case, the pigment-containing layer provided on the patterning sheet to be described later may be used so as to play a role as such a concavo-convex shape sealing layer. That is, such a filling effect can be expected even in the coating step in forming the layer containing the pigment, and further, when the surface of the layer containing the pigment is smoothed by subjecting the layer to calendering or the like. It can be expected to have a blocking effect. In this way, the layer containing the pigment fulfills two functions as an uneven sealing layer and an original function of preventing sticking.

It is preferable that the mold sheet is transparent when checking the recording surface 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, it is preferable to provide a layer containing a pigment on the patterned sheet in order to further improve the effect of preventing sticking. The layer containing the pigment may be provided in advance before the die-attached sheet is attached, or may be provided after the die-attached sheet is attached. The pigment-containing layer is not particularly limited as long as it can effectively prevent sticking, but it is preferable to apply a composition containing fine particles such as an inorganic or organic pigment or a lubricant. Specifically, a water-based coating composition containing a water-soluble resin and / or a water-dispersible resin and a pigment as the main components used in the above-mentioned intermediate layer, and an active energy ray-curable resin and a pigment described below are mainly used. Examples thereof include active energy ray-curable resin composition as a component.

A thermosensitive color-developing recording layer may be further provided on the mold-bearing sheet side, and if necessary, an intermediate layer may be provided between the mold-provided sheet and the thermosensitive color-developing recording layer, or on the thermosensitive color-developing recording layer. A layer containing a pigment may be provided. The layer containing the pigment may also serve as the thermosensitive color recording layer. When the thermosensitive color recording layer is further provided in this manner, it is possible to store it as a record for recording after peeling the typed sheet, and by any chance tampering with further recording on the thermosensitive recording surface on the support. Even if the above is attempted, it is possible to perform a collation check with this copy, and a double tampering prevention effect can be obtained. The heat-sensitive color recording layer and the intermediate layer may be provided in the same manner as the heat-sensitive color recording layer and the intermediate layer described above.

The active energy ray-curable resin used for bonding is not particularly limited as long as it can be cured by irradiation with active energy rays, but coloration of the thermosensitive coloring layer due to heating, unevenness of the substrate, From the viewpoint of no curling, it is preferable that the drying step is not involved, and for this reason, a solvent-free one is preferable. The viscosity of the resin is 10
About 10,000 cps, more preferably 100 to 50
About 100 cps is suitable. Below 10 cps,
At the time of bonding, the resin may exude, or the thermosensitive coloring layer or the intermediate layer may be impregnated, resulting in insufficient bonding, or coloring or desensitization of the thermosensitive coloring layer may occur.
If it is higher than cps, the coated surface becomes non-uniform and it may be difficult to obtain a uniform bonded surface.

Curing with active energy rays used for bonding
The coating amount of the mold resin is not particularly limited,
0.1 g / m²If less than, the desired effect can be sufficiently obtained.
Not possible, 15g / m²Recording on thermal recording media
Dry weight is generally used because it may reduce sensitivity.
0.1-15g / m², Preferably 0.5 to 10 g / m
²Adjusted in a range of degrees. Active energy ray hardening type tree
Fats are, for example, the monomers and oligomers shown below.
Alternatively, a mixture of these is used. (A) Radical-polymerizable monofunctional monomer Acrylic acid, ethyl acrylate, hexyl acrylate
2-ethylhexyl acrylate, 2-hydroxy
Ethyl acrylate, 2-hydroxypropyl acryl
, Tetrahydrofurfuryl acrylate, phenoki
Ciethyl acrylate, triloxyethyl acrylate
Nonylphenoxyethyl acrylate, tetrahydr
Rofurfuryloxyethyl acrylate, 1,3-dio
Xolan acrylate, phenoxydiethylene glyco
Acrylate, benzyl acrylate, butoxyethyl
Acrylate, cyclohexyl acrylate, disic
Lopentanyl acrylate, dicyclopentenyl acryl
Rate, glycidyl acrylate, carbitol acryl
Rate, isobornyl acrylate, etc. (B) Radical-polymerizable polyfunctional monomer 1,6-hexanediol diacrylate, neo-penti
Ruglycol diacrylate, diethylene glycol di
Acrylate, tripropylene glycol diacreyl
G, dicyclopentanyl diacrylate, butylene glycol
Cold diacrylate, pentaerythritol diacry
Rate, trimethylolpropane triacrylate,
Ropylene oxide modified trimethylolpropane triac
Relate, pentaerythritol triacrylate, diester
Trimethylolpropane tetraacrylate, dipenta
Erythritol hexaacrylate, caprolactone
Dipentaerythritol hexaacrylate, tetra
Methylol methane tetraacrylate etc. (C) Radical polymerizable oligomer (prepolymer) Polyester (poly) acrylate and urethane (poly)
Acrylate, Epoxy (poly) acrylate, Polio
(Poly) acrylate etc.

Further, 2-chloroethyl vinyl ether,
It is also possible to use cationically polymerizable monomers and / or oligomers such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether. it can. A cation polymerization initiator is necessary when the cation polymerizable monomer and / or oligomer is added. 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 diazonium salts, iodonium salts, sulfonium salts, metallocene compounds and the like. The amount of these cationic polymerization initiators added is 0.1 to 1 with respect to 100 parts by weight of the cationically polymerizable monomer or / and 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, not only the effect is saturated, but also the solubility of the cationic polymerization initiator deteriorates, There may be adverse effects such as poor transparency of the coating film.

As a method for laminating, 1) an active energy ray-curable resin is applied on the surface of a thermosensitive color recording layer or an intermediate layer and laminated with a mold sheet, and 2) an active energy ray-curable resin is molded sheet. It is applied on the surface and bonded to the surface of the thermosensitive color recording layer or the intermediate layer. 3) A method of applying and bonding the active energy ray-curable resin on both the surface of the thermosensitive color recording layer or the intermediate layer and the pattern sheet. To be

When the heat-sensitive color recording layer is provided on the pattern-formed sheet, (a) it is provided after the heat-sensitive recording material and the pattern-formed sheet are bonded together, and (b) the heat-sensitive color recording layer is previously provided on the pattern-formed sheet. After that, any method of laminating with the thermal recording medium may be adopted. Incidentally, when the typed sheet is made considerably thin, if a thermosensitive color recording layer is provided on the typed sheet in advance, wrinkles and fluffiness are likely to occur, which may make operation difficult.
In such a case, if the method a) is adopted, there is an advantage that stable operation is easy. In addition, if there is no problem in operation, it is recommended to use a film with extremely high heat resistance and strength, or to preliminarily provide a thermosensitive color recording layer on the mold sheet using a substrate with a certain thickness. The method has less loss and is more easily applicable to the production of a large variety of small lots in the case where the same thermosensitive recording medium is used and a support or a product in which the thermosensitive color recording layer on the support side is replaced is manufactured.

The device for laminating is not particularly limited, but it is usually carried out by passing it between two rolls (nip rolls) under appropriate pressure. The method of applying the active energy ray-curable resin 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, etc. is appropriately used. In addition, the coating surface and the bonding surface are previously subjected to corona discharge treatment,
It is also possible to control the wettability and adhesion of the active energy ray-curable resin by pretreatment by radiation treatment, plasma treatment or the like.

If necessary, various auxiliary agents such as dyes, pigments, wetting agents, defoamers, dispersants, antistatic agents, leveling agents and lubricants may be added to the above-mentioned active energy ray-curable resin. It can be appropriately added within a range that does not impair the effect. Active energy rays include ultraviolet rays, electron rays, X
Rays, γ rays and the like can be mentioned, 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 irradiation from the side of the opaque substrate is possible, less heat is generated, and fogging of the thermosensitive coloring layer (decrease in whiteness due to coloring due to heat) is less likely to initiate radical photopolymerization. It is particularly preferable because it has various advantages such as no need for compounding an agent, little odor, light resistance, excellent storage stability of the coating composition, and high productivity.

When an electron beam is used, it is desirable that the amount of the electron beam to be irradiated be adjusted within the range of about 1 to 200 kGy as the absorbed dose. If it is less than 1 kGy, a sufficient irradiation effect cannot be obtained, and irradiation exceeding 200 kGy is not preferable because it may deteriorate the substrate such as papers and certain plastic films. As the electron beam irradiation method, for example, a scanning method, a curtain beam method, a broad beam method or the like is adopted, and the acceleration voltage at the time of irradiating the electron beam needs to be controlled by the thickness of the base material on the irradiation side. However, about 150 to 300 kV is suitable.

When ultraviolet rays are used as the active energy rays, it is necessary to incorporate a photoradical polymerization initiator into the coating composition. , 2-
Diethoxyacetophenone, benzyl dimethyl ketal, diphenyl disulfide, anthraquinone, 1-chloroanthraquinone, 2-ethylanthraquinone, 2-
One or more radical polymerization initiators such as ter-butylanthraquinone, N, N′-tetraethyl-4,4′-diaminobenzophenone and 1,1-dichloroacetophenone are appropriately mixed. The amount of the photo-radical polymerization initiator used is desirably adjusted within the range of 0.2 to 10% by weight, preferably 0.5 to 5% by weight, based on the total composition. As a light source for UV irradiation, 1 to 50 UV lamps (for example, several mmHg
Low, medium and high pressure mercury lamps with operating pressures of up to about 10 atmospheres), xenon lamps, tungsten lamps, etc. are used. When ultraviolet rays are used, the opaque substrate is difficult to pass through, so that it can be applied to the case of using a transparent sheet with a pattern, and it is necessary to irradiate from the side of the sheet with a pattern.

[0048]

EXAMPLES The present invention will be described in more detail below with reference to FIG. 1 by way of examples, but the present invention is not limited to these examples.
FIG. 1 is a sectional view showing the construction of an embodiment of the thermal recording material of the present invention. In addition, the part in an example shows a weight part.

Example A coating solution prepared by mixing and stirring 45 parts of solution A, 80 parts of solution B, 50 parts of 20% aqueous solution of oxidized starch, and 10 parts of water shown below was prepared at 80 g / m ² as a support. Synthetic paper 1 (trade name: YUPO, made by Oji Okaka Synthetic Paper) has a coating amount of 8 g / m ² after drying.
And dried to form a thermosensitive color recording layer 2. [Preparation of solution A] 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-phenylaminofluorane 1
A composition consisting of 0 part, 5 parts of a 5% aqueous solution of methyl cellulose, and 30 parts of water was pulverized by a sand mill until the average particle size became 3 μm. [Preparation of solution B] 20 parts of benzyl 4-hydroxybenzoate,
A composition consisting of 5 parts of a 5% aqueous solution of methyl cellulose and 55 parts of water was pulverized with a sand mill until the average particle size became 3 μm.

Next, on the thermosensitive color recording layer 2 obtained as described above, 1000 parts of an 8% aqueous solution of acetoacetylated polyvinyl alcohol (trade name: Z-200, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), calcium carbonate ( Product Name: Softon 180
0, manufactured by Bihoku Kouka Co., Ltd.), a composition for an intermediate layer consisting of 100 parts of water and 100 parts of water is applied and dried so that the applied amount after drying is 3 g / m ^2, and further smoothed by a super calendar. The intermediate layer 3 having a Bekk smoothness of 5000 seconds was formed.

Next, electron beam curable resin (Ebecryl)
810; Daicel UCB) in a dry weight of 4 g / m
Polyethylene terephthalate film 5 (E5001, 25 μm), which is an active energy ray-curable resin layer 4 applied and formed so as to be ² and a mold sheet in which a striped pattern is formed in an uneven shape by pressing a heated mold plate in advance.
Thickness, manufactured by Toyobo Co., Ltd., and then laminated with a laminator, and immediately thereafter, an electron beam irradiation device (electro curtain CB-150;
Electron beam with an absorbed dose of 30 kGy was irradiated from the polyethylene terephthalate film side at an accelerating voltage of 175 kV by using ESI.

Next, after subjecting the polyethylene terephthalate film 5 to corona treatment, a composition similar to the above-mentioned intermediate layer was applied and dried so that the applied amount after drying was 4 g / m ^2. It was calendered to form Layer 6 containing the pigment.

The recording material thus obtained was subjected to the first recording by using a test printer equipped with a thermal head for sublimation transfer recording. Thereafter, the polyethylene terephthalate film 5 was peeled off as shown in FIG. FIG. 2 is a cross-sectional view showing a state in which the polyethylene terephthalate film 5, which is the die-molded sheet of the thermosensitive recording medium of the present invention, is peeled off. The polyethylene terephthalate film 5 could be peeled smoothly without any problem at the interface with the electron beam curable resin layer 4 (the peeling force was 100 to 150 g / 50 mm).
Next, using a test printer equipped with an ordinary thermal head, a second recording different from the first recording assumed by the inventors for recording for falsification was performed. The first of these
The following items were evaluated for the first and second recorded images, and the results are shown in Table 1.

[Coloring property] The image quality of the recorded image was visually evaluated. ○: No influence of the typed sheet is observed on the color image. That is, even when the print was overlapped on the mold part, no print defect was observed in that part. X: The color image shows the influence of the mold of the mold sheet. That is, defective printing was recognized in the portion where the printing was overlapped on the mold. [Sticking] O: Recording was extremely smooth without sticking to the recording head. X: The recording material adhered to the recording head, causing poor running.

[0055]

[Table 1]

[Evaluation] As is clear from the results shown in Table 1,
In the first recording, the influence of the mold of the mold sheet was not observed at all, and there were no defective coloring points. In the second recording, a lot of color-developing defects were observed at the edge of the die of the die-attached sheet, and print defects such as print distortion and color-developing defects that were considered to be caused by sticking were also observed. Therefore, even if an attempt is made to falsify the record after the pattern sheet is peeled off, it is inevitable that a defective color-developing portion will occur in the record at that time, so that it is easily understood that the falsification has been performed. In addition to the electron beam curable resin, a wide range of resins can be selected. For example, in a conventional thermal recording material, heat resistance must be taken into consideration when an electron beam curable resin is used for the overcoat layer that is in direct contact with the head. However, such a resin having excellent heat resistance often lacks flexibility, and when the coating amount is large, there is a possibility that the resin may be broken or broken. On the other hand, since the active energy ray-curable resin layer used in the present invention does not come into direct contact with the head, it is not necessary to give great consideration to heat resistance, and it suffices to consider only flexibility and thermal conductivity. The resin excellent in such a property easily causes sticking if it comes into direct contact with the head, so that recording after peeling the typed sheet becomes impossible, and a more excellent tamper-proof effect is obtained. Will be obtained. Further, it is possible to control the peeling force when peeling the film by appropriately selecting the active energy ray-curable resin.

The surface of the active energy ray-curable resin layer is protected by being covered with the patterning sheet even if it has a complicated uneven shape from the time of storage before recording to the removal of the patterning sheet after recording. . That is, in the meantime, the typed sheet completely prevents them even if it receives a mechanical force or a chemical action from the outside, or the typed sheet itself receives some scratches or damages, so that the internal activity is reduced. The uneven surface of the energy ray curable resin layer is protected. Specifically, it is possible to prevent scratches and prevent coloring and desensitization caused by chemicals or solvents.

[0058]

EFFECT OF THE INVENTION Stable recording is obtained at the time of recording before the release of the patterning sheet, and a printing failure occurs even if further recording is attempted after the patterning sheet is removed, so that falsification can be prevented. Further, since the surface of the active energy ray-curable resin layer having an uneven shape is protected by being covered with the mold sheet from the time of storage before recording to the peeling of the mold sheet after recording, mechanical force from the outside is protected. The uneven shape can be maintained even when subjected to a chemical action.

[Brief description of drawings]

FIG. 1 is a sectional view showing the structure of an embodiment of a thermosensitive recording medium of the present invention.

FIG. 2 is a cross-sectional view showing a state in which a polyethylene terephthalate film 5, which is a patterned sheet of the thermosensitive recording medium of the present invention, is peeled off.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Support 2 Thermosensitive color recording layer 3 Intermediate layer 4 Active energy ray curable resin layer 5 Sheet with mold 6 Layer containing pigment

Claims (7)

[Claims] 1. A heat-sensitive color recording layer, an active energy ray-curable resin layer, and an active energy containing a colorless or light-colored basic dye and a colorant capable of forming a color on contact with the dye on a support. A heat-sensitive recording medium, which is provided with, in order, a patterned sheet having an uneven shape that can be peeled from the interface with a line-curable resin layer. 2. The heat-sensitive recording material according to claim 1, wherein at least one intermediate layer made of an aqueous composition is provided between the heat-sensitive color forming recording layer and the active energy ray-curable resin layer. 3. The heat-sensitive recording material according to claim 1 or 2, further comprising a layer containing a pigment on the patterned sheet. 4. The heat-sensitive recording material according to claim 1, further comprising a heat-sensitive color recording layer on the mold sheet side. 5. The thermosensitive recording medium according to claim 3, wherein the layer containing a pigment serves as a thermosensitive color recording layer. 6. A thermosensitive color recording layer containing a colorless or pale basic dye and a coloring agent capable of coloring when contacted with the dye is provided on a support, and an intermediate layer comprising an aqueous composition is further provided. The thermosensitive color-developing recording layer or the intermediate layer, which is provided as necessary, and the typed sheet are bonded together via an active energy ray-curable resin layer, and then irradiated with active energy rays. Of the method for producing a thermosensitive recording medium. 7. The recording method for a thermosensitive recording medium according to claim 1, wherein after the information is heat-recorded from the side of the typed sheet, the typed sheet is peeled off.