CN1769360A - Heat Sensitive Adhesive Materials - Google Patents

Abstract

The invention provides a heat-sensitive adhesive label sheet which has strong adhesion to a rough adherend such as a corrugated cardboard or the like and a polyolefin wrapping paper, has little decrease in adhesion with time, can be activated with low energy, and has good blocking resistance, and provides a heat-sensitive adhesive material comprising a support and, on one surface of the support, at least an adhesive base layer and a heat-sensitive adhesive layer in this order, wherein the base layer comprises a thermoplastic resin having a glass transition temperature (Tg) of-70 ℃ or higher and a hollow filler of less than 0 ℃.

Description

Heat Sensitive Adhesive Materials

Background of the invention

technical field

The present invention relates to a heat-sensitive adhesive material having a heat-sensitive adhesive layer which is non-adhesive at normal temperature, but exhibits adhesiveness by heating, and the adhesiveness continues after exhibiting adhesiveness, It has excellent adhesion to adherends and can be thermally activated by low energy.

Description of related technologies

Adhesive label sheets are increasingly used for price display labels, product description (barcode) labels, quality display labels, measurement display labels, and advertising labels (post-up materials). In addition, various methods such as an inkjet recording method, a heat-sensitive recording method, and a pressure-sensitive recording method have been developed as recording methods for labels.

As such an adhesive label sheet, for example, it is usually a structure in which an adhesive layer and a release paper are laminated on the reverse side of the information recording surface of the label. Since the sheet can be easily bonded by pressing it on the adherend, it has been widely used. In a normal adhesive label sheet, the release paper is removed and used. However, the removed release paper is difficult to recycle and is basically discarded. Then, in recent years, a heat-sensitive adhesive label sheet as a heat-sensitive adhesive material having a heat-sensitive adhesive layer that does not show adhesiveness at normal temperature and does not require a release paper is attracting attention (see Japanese Patent Laid-Open No. 6-25869 Bulletin).

The heat-sensitive adhesive layer in such a heat-sensitive adhesive label sheet contains, for example, a thermoplastic resin, a heat-fusible substance, and, if necessary, an adhesion-imparting agent. (See the 12th edition of "Continuing Notes", pages 131-135, published by the Polymer Press in Showa 55).

However, after the heat-sensitive adhesive layer in the above-mentioned heat-sensitive adhesive label sheet exhibits adhesiveness, the adhesive force decreases with time, and furthermore, high heat energy is required for heat activation.

Then, in order to improve this point, for example, it is proposed to arrange a heat insulating layer containing plastic hollow particles and a water-soluble adhesive between the support body and the heat-sensitive adhesive layer, thereby reducing the thermal energy during thermal activation (high sensitivity). ) (see Patent No. 2683733 and JP-10-152660). According to the above proposal, relatively good results have been obtained regarding the reduction of thermal energy when thermally activating the heat-sensitive adhesive layer. However, in this proposal, since a water-soluble adhesive having no adhesiveness at room temperature is used, the adhesive force to rough adherends such as corrugated cardboard or polyolefin wrapping paper has not yet reached a practical level. In addition, the problem that the adhesive force decreases with time after exhibiting adhesiveness has not yet been solved, and the current situation is that further improvement and development are desired.

In addition, from the standpoint of water resistance, label strength, and smoothness, the demand for films and synthetic papers is rapidly increasing as well as supports. In response to the increase in demand for films and synthetic papers as such supports, there are situations where heat-sensitive adhesive coating liquids are not included. The reasons for such exclusion include the following points.

(1) Since the support body is a film or synthetic paper, it is difficult for the heat-sensitive adhesive layer to penetrate, and troubles such as shrinkage cracks, pinholes, and retention spots are prone to occur during preparation.

(2) Since the support body is a film or synthetic paper, the fixation with the active layer is low, and the active layer is prone to fall off during thermal activation.

(3) Since the support body is a film or synthetic paper, the support body itself is easy to shrink into wrinkles during heating.

(4) Since the support is a film or synthetic paper, it has high strength and is difficult to break. Therefore, when the label attached to the product is peeled off, only the heat-sensitive adhesive layer remains on the product (paste residue), and the appearance deteriorates.

The above (1) can be improved by optimizing the amount of surfactant and dispersant added to the heat-sensitive adhesive layer, etc., but the above (2), (3) and (4) ), there are problems unique to heat-sensitive adhesive materials using films and synthetic papers, and the current situation is that they cannot be completely improved.

Furthermore, as one of the problems of current heat-sensitive adhesive materials, a sticking phenomenon can be cited. The so-called sticking phenomenon refers to a phenomenon in which stickiness is exhibited even though sticking is not expected, and is caused by exposure to a temperature atmosphere higher than normal temperature for a long time, for example. Even in either the state of a roll or the state of cutting it into sheets and stacking it, once adhesion is initiated, the heat-sensitive adhesive layer and the outer surface (the opposite side of the heat-sensitive adhesive layer sandwiching the support) It will stick together, not only causing hindrance on paper feeding, but also having a bad influence on the printing outside.

Then, as a method for preventing sticking, a method of mixing lubricating paraffin wax in a heat-sensitive adhesive coating solution (see Japanese Patent Publication No. 62-21835), and a method of protecting a hot-melt substance with an inorganic compound or colloid particles are disclosed. Surface, suppressing the softening of the hot-melt substance, thereby preventing the method of sticking (see Japanese Patent Application Laid-Open No. 6-57223, Japanese Patent Laid-Open No. 6-100847 and Japanese Patent Laid-Open No. 6-100848), etc. However, if paraffin wax is mixed, not only the sticking preventing effect is insufficient, but also the sticking property is lowered. If the surface of the hot-melt material is protected by inorganic compounds and colloidal particles, it takes time to melt and diffuse the hot-melt material, making it difficult to develop the adhesiveness of the heat-sensitive adhesive coating liquid, and the adhesion ability decreases. The problem is that it is not ideal in terms of practicality. In addition, the sticking phenomenon can be improved by using a plasticizer with a high melting point. However, the current situation is that side effects such as a significant decrease in the adhesive force will occur. In practice, it is necessary to transport and store under low temperature conditions that do not cause sticking.

In addition, for printers, it is desired to be safe, power-saving, and compactly installed. For example, in Japanese Patent Application Laid-Open No. , JP-A-11-311945, JP-A-2001-303036, JP-A-2001-48139, etc., disclose an activation method using a thermal head as a thermal activation method.

As such an activation method, by using a thermal head, the energy consumption during thermal activation is reduced, and the safety and compactness of the device are improved compared with the conventional ones. However, in the case where a thermal head is used as the activation method, since the thermal head performs activation while heating and contacting the heat-sensitive adhesive layer, a large amount of paste-like deposits adhere to the resistor body of the thermal head. The fatal flaws are that the thermal energy cannot be efficiently transferred to the heat-sensitive adhesive layer, which reduces the adhesive force and shortens the life of the thermal head.

As an improvement on such a subject, a method of adding a release layer to the thermal head represented by the above-mentioned Japanese Patent Application Laid-Open No. 11-79152, and a method of bonding a thermal head to a heat-sensitive type in the above-mentioned Japanese Patent Laid-Open No. 11-65451 have been proposed. A method of inserting sheets of film between layers. However, according to the above-mentioned proposal, the thermal conductivity decreases instead, and sufficient heat cannot be supplied to the thermally active layer, and there is a problem that sufficient adhesive force cannot be exhibited. In addition, the manufacturing cost of the thermal head is high, and the current situation that it cannot be widely used in the market .

Summary of the invention

The first object of the present invention is to provide a heat-sensitive adhesive material, which has strong adhesive force to rough surface adherends such as corrugated cardboard and polyolefin packaging paper, and has little decrease in adhesive force over time, and can be used at a low cost. It is thermally activated by energy and has good adhesion resistance. Especially, even if synthetic paper or plastic film is used as a support, the heat-sensitive adhesive layer will not fall off during heat activation, and the shrinkage of the support can be prevented. Wrinkles, no mushy residue when changing labels.

The second object of the present invention is to provide a heat-sensitive adhesive material which can improve the sticking resistance or the decrease of the sticking due to sticking of the pasty residue generated in the activation of the thermal head, showing stable sticking. performance.

In the first aspect of the heat-sensitive adhesive material of the present invention, a thermoplastic resin having a glass transition temperature (Tg) of -70°C or higher than -70°C and less than 0°C is provided between the heat-sensitive adhesive layer and the support. And the bottom layer of hollow filler, when heating, mix the heat-sensitive adhesive layer and the bottom layer to increase the amount of adhesive, so as to improve the adhesion to the adherend and polyolefin packaging paper on rough surfaces such as corrugated cardboard. In addition, by using plastic spherical hollow particles with a high hollow ratio in the bottom layer, a thermal insulation effect is produced, not only the heat-sensitive adhesive layer provided in the upper layer can be activated with low-energy heat, but also the adhesion resistance can be improved. In addition, even in the case of using synthetic paper or plastic film as a support, the heat-sensitive adhesive layer does not come off during heat activation, shrinkage and wrinkling of the support can be prevented, and the occurrence of paste residue at the time of label replacement can be monitored. improve.

The heat-sensitive adhesive material of the present invention, in the second aspect, comprises a heat-sensitive recording layer and a protective layer in this order on a support and one side of the support, and has a thermoplastic resin and a heat-fusible substance on the opposite surface of the support. heat sensitive adhesive layer.

The above protective layer contains polyvinyl alcohol having a reactive carbonyl group and a hydrazide compound. In the heat-sensitive adhesive material of the present invention, the blocking resistance can be improved, the decrease in adhesiveness due to the adhesion of scum generated in the activation of the thermal head can be improved, and stable adhesive performance can be exhibited.

Brief description of the drawings

FIG. 1 is a energized pattern showing a one-dot checkered pattern in a printing matching test method.

Description of the preferred embodiment

(Heat-sensitive adhesive material of the first form)

In the first aspect, the heat-sensitive adhesive material of the present invention includes at least an underlayer and a heat-sensitive adhesive layer in this order on the support and one side of the support, and may further contain other layers as necessary. In addition, various recording layers and protective layers are provided on the other side of the above-mentioned support without the underlayer and the heat-sensitive adhesive layer.

<support>

As the above-mentioned support body, its shape, structure, and size are not particularly limited, and can be appropriately selected according to the purpose. As the above-mentioned shape, for example, a flat plate can be cited. As for the structure, the above-mentioned size can be appropriately selected according to the size of the above-mentioned heat-sensitive adhesive material and the like.

The material of the above-mentioned support is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include inorganic materials and organic materials. Examples of the above-mentioned inorganic material include glass, quartz, silicon, silicon oxide, aluminum oxide, SiO ₂ , metal, and the like. Examples of the above-mentioned organic materials include high-quality paper, art paper, art paper, synthetic paper and other papers, cellulose derivatives such as cellulose triacetate, polyethylene terephthalate (PET), polybutylene terephthalate, etc. Polyester resins such as diester, polycarbonate paper, polystyrene, polymethyl methacrylate, polyamide, polyethylene, polypropylene and other polyolefins, etc. Among them, high-quality paper, coated paper, plastic film, and synthetic paper are preferred, and plastic film and synthetic paper are particularly preferred.

Examples of the above-mentioned synthetic paper include those made of synthetic fibers such as polyethylene, polypropylene, polyethylene terephthalate, and polyamide, and those formed by affixing the above-mentioned materials to a part, one side, or both sides of the paper. synthetic paper. Examples of such synthetic paper include FPG, FGS, GFG, and KPK manufactured by Oji Oil & Chemical Co., Ltd. as commercially available products.

When the support is a film or synthetic paper, the penetration of the heat-sensitive adhesive layer and the like is poorer than that of high-quality paper obtained from pulp or the like, used paper, etc., and the fixing property is also extremely low. In addition, considering the trend of safety, high speed, and economy (ondemand) of thermal activation methods in recent years, the contact activation method using a thermal head has gradually attracted attention. The contact thermal activation by the thermal head has the side effect of cutting off the active layer on the reverse side, especially in thermal activation, in order to activate the label comprehensively, the thermal head itself becomes high temperature, and the heat-sensitive adhesive layer comes off significantly. However, in the present invention, Even when a film or synthetic paper is used as a support, it can prevent the film and synthetic paper from falling off and shrinking during heat activation, and there is no paste residue when the label is replaced.

In order to improve the adhesion of the coating layer, the above-mentioned support is preferably subjected to surface modification treatment by corona discharge treatment, oxidation reaction treatment (chromic acid, etc.), etching treatment, easy adhesion treatment, antistatic treatment and the like. In addition, it is preferable to add a white pigment such as titanium oxide to the above-mentioned support to make it white.

The thickness of the support is not particularly limited and can be appropriately selected according to the purpose, but is preferably 50 to 2000 μm, more preferably 100 to 1000 μm.

<bottom>

The above-mentioned base layer contains a thermoplastic resin having a glass transition temperature (Tg) of -70°C or higher than -70°C and less than 0°C, a hollow filler, and may contain other components depending on the purpose. The glass transition temperature is preferably -70 to -2°C, more preferably -70 to -5°C.

-thermoplastic resin-

The thermoplastic resin having a glass transition temperature (Tg) of -70°C or higher and less than 0°C is not particularly limited and can be appropriately selected according to the purpose. For example, graft-copolymerized vinyl monomers can be used. Natural rubber latex, acrylate copolymer, methacrylate copolymer, acrylate-methacrylate copolymer, acrylate-styrene copolymer, acrylate-methacrylate-styrene copolymer, ethylene-acetic acid Vinyl ester copolymers and the like may be used alone or in combination of two or more.

If a thermoplastic resin with a high glass transition temperature (Tg) exceeding the glass transition temperature (Tg) of the thermoplastic resin in the above-mentioned base layer is used, the characteristics of the base layer cannot be obtained at all, and the adhesion to rough surface adherends such as corrugated cardboard and polyolefin packaging paper The resultant force is weakened, and only the adhesive force of the heat-sensitive adhesive layer arranged on the upper layer is reached.

-Hollow packing-

Although it does not specifically limit as said hollow filler, the inorganic filler or organic filler which is used normally and has a volume average particle diameter of 0.5-10 micrometers is used. Examples of the inorganic filler include calcium carbonate, silicon dioxide, titanium oxide, aluminum hydroxide, clay, calcined clay, magnesium silicate, magnesium carbonate, white carbon, zinc oxide, barium sulfate, surface-treated calcium carbonate, Silica, etc.

Examples of the organic filler include fine powders of urea-formaldehyde resins, styrene-methacrylic acid copolymers, and polystyrene resins.

Among them, considering the problem of low-energy thermal activation (high-sensitivity thermal activation), plastic spherical hollow particles with a volume average particle size of 2.0 to 5.0 μm and a hollow rate of 70% or more are preferred. More preferably, the hollow particles have a maximum particle size of 10.0 μm or less, a volume average particle size of 2.0 to 5.0 μm, and a hollow rate of 70% or more.

Since the heat insulating effect of the above-mentioned particles with a low hollow ratio is insufficient, heat energy from the thermal head is discharged to the outside through the support body, and the high-sensitivity thermal activation effect is deteriorated. If the above-mentioned volume average particle size is larger than 5.0 μm, when a heat-sensitive adhesive layer is provided on the base layer using these particles, the part of the large particles will form a part where the heat-sensitive adhesive layer is not formed, and the adhesive force will easily decrease during heat activation. If it is less than 2.0 μm, it will be difficult to secure a hollow rate of 70% or more, resulting in deterioration of the high-sensitivity thermal activation effect.

The above-mentioned so-called plastic spherical hollow particles refer to hollow particles in a foamed state with thermoplastic resin as the outer shell and air and other gases inside.

Here, the above-mentioned hollow ratio refers to the ratio of the outer diameter to the inner diameter of the hollow fine particles, and is represented by the following mathematical expression 1.

<mathematical expression 1>

Hollow ratio (%) = (inner diameter of hollow particles) / (outer diameter of hollow particles) × 100

Furthermore, from the viewpoint of ensuring adhesive force in a heat activation method using a thermal head, it is preferable that the hollow particles used in the above-mentioned underlayer have a hollow ratio of 70% or more.

As a material constituting the plastic spherical hollow particles satisfying the above conditions, for example, acrylonitrile-vinylidene chloride-methyl methacrylate copolymer and acrylonitrile-methacrylonitrile-isobornyl methacrylate copolymerization are preferred. any of the things.

In addition, as the mass ratio of the thermoplastic resin having a glass transition temperature (Tg) of -70°C or higher than -70°C to less than 0°C in the above-mentioned underlayer and the above-mentioned hollow filler, the above-mentioned hollow filler is preferably 0.1 to 2 parts by mass. If the above-mentioned hollow filler is less than 0.1 parts by mass, the high-sensitivity thermal activation will be deteriorated and the adhesion will be reduced. If it exceeds 2 parts by mass, the adhesion to rough surface adherends such as corrugated cardboard and polyolefin wrapping paper will be reduced. Adhesion of the heat-sensitive adhesive layer in the upper layer.

The mixing mass ratio of the hollow filler to the thermoplastic resin (hollow filler:thermoplastic resin) in the bottom layer is preferably 1:0.5 to 1:3.0, more preferably 1:1.5 to 1:2.5. Within this range, a heat-sensitive adhesive material particularly excellent in adhesion to mirror surfaces such as SUS can be obtained.

In addition, the mixing mass ratio of the hollow filler and the thermoplastic resin in the bottom layer (hollow filler: thermoplastic resin) is preferably 1:6.0 to 1:20.0, more preferably 1:8.0 to 1:16.0. Within such a range, it is possible to obtain a heat-sensitive adhesive material excellent in adhesion to the surface of the environment and the surface of the corrugated cardboard.

The primer layer is not particularly limited, and it can be formed by a known method, for example, it can be suitably formed by a coating method using a primer coating liquid mixed with the above-mentioned components.

Examples of the coating method include paddle coating, gravure coating, gravure offset coating, bar coating, roll coating, knife coating, air knife coating, Dot coating method, U dot coating method, AKKU coating method, smooth coating method, micro gravure coating method, reverse roll method, 4-roll or 5-roll coating method, dip coating method, vertical curtain coating Cloth method, slide coating method, die coating method, etc.

The coating amount of the above primer coating liquid is preferably 1 to 35 g/m ² , more preferably 2 to 25 g/m ² in terms of dry coating amount. If the coating amount of the above primer coating liquid is less than 1 g/m ² , sufficient adhesive force effect cannot be obtained and the heat insulating effect is deteriorated when bonding by heating ^. The effect is saturated, which is not economically preferable.

<Heat-sensitive adhesive layer>

The above-mentioned heat-sensitive adhesive layer contains a thermoplastic resin, an adhesion-imparting agent, a heat-fusible substance, a co-melting agent, and other components as necessary.

-thermoplastic resin-

As the above-mentioned thermoplastic resin, there is no particular limitation, and it can be appropriately selected according to the purpose. If a resin similar to the thermoplastic resin used in the above-mentioned bottom layer is used, since the compatibility between the two resins is good, it is suitable for rough surface adherends such as corrugated cardboard and Polyolefin wrappers have improved adhesion and are therefore preferred.

Examples of the above-mentioned thermoplastic resins include natural rubber latex, acrylate copolymers, methacrylate copolymers, acrylate-methacrylate copolymers, and acrylate-styrene copolymers graft-copolymerized with vinyl monomers. , Acrylate-methacrylate-styrene copolymer, ethylene-vinyl acetate copolymer, etc. These substances may be used alone or in combination of two or more.

The content of the thermoplastic resin in the heat-sensitive adhesive layer is preferably 10 to 60% by mass, more preferably 15 to 50% by mass. When the content of the above-mentioned thermoplastic resin is less than 10% by mass and exceeds 60% by mass, since the adhesive force decreases, it is not preferable. Moreover, when the content rate of a low Tg resin exceeds 60 mass %, trouble (sticking) on storage, such as developing adhesive force, will arise at the temperature of a normal storage environment.

-Hot Fusible Substance-

The above-mentioned hot-melt substance is solid at normal temperature, so it does not impart plasticity to the resin. However, by heating and melting, the resin is swelled or softened to show adhesiveness. After heating and melting, crystallization occurs slowly. Adhesion persists long after the heat source is removed.

As the hot-melt substance, for example, a benzotriazole compound represented by the following structural formula (1) is preferable.

结构式(1)

Structural formula (1)

Wherein, in the above structural formula 1, R ¹ and R ² may be the same or different, and represent any one of a hydrogen atom, an alkyl group and an α,α-dimethylbenzyl group. X represents a hydrogen atom or a halogen atom.

The above-mentioned alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, etc., these groups It can also be further substituted by substituents.

Examples of the substituent include a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, a cyano group, or an alkyl group having a specific substituent (eg, a halogen atom or a nitro group may be substituted), an aryl group, a heterocyclic group, and the like.

Examples of the benzotriazole compound represented by the above structural formula (1) include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert Octylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy- 3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-tert-butylphenyl)-5-chlorobenzotriazole, 2-( 2'-Hydroxy-3',5'-bis(1,1-dimethylbenzyl)phenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylbenzene base) benzotriazole, 2-(2'-hydroxy-3'-sec-butyl-5'-tert-butylphenyl)benzotriazole, etc. These substances may be used alone or in combination of two or more.

Moreover, as said hot-melt substance, the hydroxybenzoate compound represented by following structural formula (2) is preferable.

Structural formula (2)

Wherein, in the above structural formula (2), R ³ represents any one of alkyl, alkenyl, aralkyl and aryl, and these groups can be further substituted by substituents.

Examples of the above-mentioned alkyl group include alkyl groups having 1 to 18 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. , n-nonyl, n-decyl and other linear alkyl groups, isobutyl, isopentyl, 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl , 2-ethylbutyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2-ethylpentyl, 3-ethylpentyl, 2-methyl Heptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, isopropyl, sec-butyl, 1-ethylpropyl , 1-methylbutyl, 1,2-dimethylpropyl, 1-methylheptyl, 1-ethylbutyl, 1,3-dimethylbutyl, 1,2-dimethylbutyl Base, 1-ethyl-2-methylpropyl, 1-methylhexyl, 1-ethylheptyl, 1-propylbutyl, 1-isopropyl-2-methylpropyl, 1-ethyl Base-2-methylbutyl, 1-propyl-2-methylpropyl, 1-ethylhexyl, 1-propylpentyl, 1-isopropylpentyl, 1-isopropyl-2- Methylbutyl, 1-isopropyl-3-methylbutyl, 1-methyloctyl, 1-propylhexyl, 1-isobutyl-3-methylbutyl, neopentyl, tert-butyl Base, tert-hexyl, tert-pentyl, tert-octyl and other branched alkyl groups; cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-tert-butylcyclohexyl, 4-(2-ethylhexyl ) cyclohexyl, bornyl, isobornyl, adamantyl and other cycloalkyl groups, etc., these groups may be further substituted by substituents.

As the above-mentioned alkenyl group, an alkenyl group having 2 to 8 carbon atoms is suitable, for example, vinyl group, allyl group, 1-propenyl group, methacryl group, crotyl group, 1-butenyl group, etc. , 3-butenyl, 2-pentenyl, 4-pentenyl, 2-hexenyl, 5-hexenyl, 2-heptenyl, 2-octenyl, etc., these groups can also be further replaced by a substituent.

The above-mentioned aralkyl group is not particularly limited, and can be appropriately selected according to the purpose. Examples thereof include benzyl, phenylethyl, phenylpropyl, etc., and these groups may be further substituted with substituents.

Examples of the aryl group include phenyl, naphthyl, anthracenyl, fluorenyl, phenanthrenyl, triphenanthrenyl, pyrenyl and the like, and these groups may be further substituted with substituents.

As the substituents of the above-mentioned alkyl, alkenyl, aralkyl and aryl groups, hydroxyl, halogen atom, nitro, carboxyl, cyano or specific substituent (for example, can also be substituted by halogen atom or nitro ) of alkyl, aryl, heterocyclyl, etc.

Examples of the hydroxybenzoate compound represented by the above structural formula (2) include methyl m-hydroxybenzoate, ethyl m-hydroxybenzoate, phenyl m-hydroxybenzoate, methyl p-hydroxybenzoate, p-hydroxybenzene Ethyl formate, Propylene p-hydroxybenzoate, n-Butyl p-hydroxybenzoate, Stearate p-hydroxybenzoate, Cyclohexyl p-hydroxybenzoate, Benzyl p-hydroxybenzoate, 4-paraben Benzyl chloride, 4-methylbenzyl p-hydroxybenzoate, phenyl p-hydroxybenzoate, and the like. These substances may be used alone or in combination of two or more.

In addition, as the above-mentioned hot-melt substance, for example, a compound represented by any one of the following structural formulas (3), (4) and (5) is preferable.

Structural formula (3)

Wherein, in the structural formula (3), R ⁴ and R ⁵ are the same or different from each other, and represent an alkyl or alkoxy group. Y represents a hydrogen atom or a hydroxyl group.

结构式(4)

Structural formula (4)

Wherein, in the structural formula (4), R ⁶ represents any one of a hydrogen atom, a halogen atom, an alkyl group and an alkoxy group. Y represents a hydrogen atom or a hydroxyl group.

结构式(5)

Structural formula (5)

Wherein, in the structural formula (5), R ⁷ represents any one of a hydrogen atom, a halogen atom, an alkyl group and an alkoxy group.

In the above-mentioned structural formulas (3) to (5), examples of the above-mentioned alkyl group include the same groups as those of the above-mentioned structural formula (1).

Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, cyclo Hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like.

As the compound represented by the above structural formula (3), for example, toluoin, anisoin, m-anizoin, deoxytoluoin, deoxyanizoin, 4,4'-diethylbenzoin, 4,4'-diethylbenzoin, , 4'-diethoxybenzoin and so on. These substances may be used alone or in combination of two or more.

As the compound represented by the above structural formula (4), for example, 1-hydroxy-2-naphthoic acid phenyl ester, 1-hydroxy-2-naphthoic acid-p-chlorophenyl ester, 1-hydroxy-2-naphthoic acid-o-chlorophenyl Phenyl ester, 1-hydroxy-2-naphthoic acid-p-methylphenyl ester, 1-hydroxy-2-naphthoic acid-o-methylphenyl ester, 1,4-dihydroxy-2-naphthoic acid phenyl ester, 1,4 -dihydroxy-2-naphthoic acid-p-chlorophenyl ester, 1,4-dihydroxy-2-naphthoic acid o-chlorophenyl ester, etc. These substances may be used alone or in combination of two or more.

As the compound represented by the above structural formula (5), for example, benzoic acid-3-hydroxyphenyl ester, benzoic acid-4-hydroxyphenyl ester, benzoic acid-2-hydroxyphenyl ester, o-methylbenzoic acid-3- Hydroxyphenyl ester, 3-hydroxyphenyl p-chlorobenzoate, etc. These substances may be used alone or in combination of two or more.

The compounds represented by the above structural formulas (1) to (5) are preferably solid at room temperature and melt when heated. The melting point of these compounds is preferably 70°C or higher, more preferably 80°C or higher, and the upper limit is about 200°C.

If the above-mentioned melting point is lower than 70° C., when used as a heat-sensitive adhesive coating liquid, troubles in storage (sticking) such as exhibiting adhesive force at a temperature of a normal storage environment may occur. In addition, troubles in production such as exhibiting adhesive force when coating and drying the heat-sensitive adhesive coating liquid on a support are caused. On the other hand, if the melting point exceeds 200° C., since adhesive force is exhibited, a large amount of energy must be spent, causing trouble in use. In addition, when thermal recording paper is used as a support and adhesive force is exhibited by a large amount of energy, there is a problem that the printed image cannot be read due to color development of the thermal recording layer.

In addition, by setting the volume average particle diameter of the hot-melt material represented by the above structural formulas (1) to (5) to be 0.5 μm or less, the dynamic thermal sensitivity is improved, so that the material becomes compatible with Heat-activated adhesive compatible with thermoplastic resin and adhesion-imparting agent. In addition, by setting the above-mentioned volume average particle diameter, the storage stability at temperature in a normal storage environment is improved (improvement of blocking resistance).

The total content of the compounds represented by the above-mentioned structural formulas (1) to (5) as the above-mentioned hot-melt substance is preferably 25 to 80% by mass, more preferably 35 to 70% by mass, and if the content of the above-mentioned hot-melt substance is less than 25% by mass %, when mixed with a thermoplastic resin with a glass transition temperature (Tg), there will be troubles (sticking) in storage such as showing adhesive force at the temperature of the usual storage environment, and the adhesive force will decrease. If it exceeds 80 % by mass, the adhesion will decrease.

-Adhesive Imparting Agent-

The above-mentioned adhesion-imparting agent is added in order to improve the adhesive force of the heat-sensitive adhesive layer, and it is not particularly limited, and can be appropriately selected from known substances according to the purpose. For example, rosin derivatives (for example, rosin, polyrosin, hydrogenated rosin), terpene-based resins (for example, terpene resins, aromatic denatured terpene resins, terpene-phenol resins, hydrogenated terpene resins), petroleum-based resins, phenolic resins, xylene-based resins, and the like. These tackifiers can remarkably improve the adhesive force of the heat-sensitive adhesive layer by being compatible with thermoplastic resins and hot-melt substances.

The melting point (or softening point) of the above-mentioned tackifier is preferably 80°C or higher, more preferably 80 to 200°C. If the above-mentioned melting point (or softening point) is lower than 80° C., storage troubles (lower sticking resistance) will occur at the temperature in a normal storage environment.

The content of the tackifier in the heat-sensitive adhesive layer is preferably 1 to 30% by mass, more preferably 1 to 20% by mass. If the above-mentioned content is less than 1% by mass, the adhesive force will be significantly reduced, and if it exceeds 30% by mass, troubles in storage at normal storage environment temperatures (decreased sticking resistance) and initial adhesion in low temperature environments will occur. force reduction.

-Co-flux-

The eutectic agent is preferably a compound that is solid at room temperature and melts when heated. The melting point of the compound is preferably 70°C or higher, more preferably 80°C or higher, and its upper limit is about 150°C. If the above-mentioned melting point is lower than 70°C, when used as a heat-sensitive adhesive coating liquid, there will be troubles in storage (sticking) such as showing adhesive force at the temperature of the normal storage environment. , When the heat-sensitive adhesive coating liquid is dried, troubles in production will be caused to show adhesive force. On the other hand, if the melting point exceeds 150° C., the effect of co-melting the hot-melt substance cannot be obtained.

The above-mentioned eutectic agent is not particularly limited, and may be appropriately selected from known materials according to the purpose. From the viewpoint of the effect of co-melting the above-mentioned hot-melt material and the excellent compatibility with thermoplastic resins, it is preferable to use the following structural formula (6 ) represents the dibenzyl oxalate compound.

结构式(6)

Structural formula (6)

Wherein, in the above structural formula (6), Z represents any one of a hydrogen atom, a halogen atom and an alkyl group.

Moreover, as said alkyl group and a halogen atom, the thing similar to the said structural formula (1) is mentioned.

Examples of the dibenzyl oxalate compound represented by the above structural formula (6) include di-p-methylbenzyl oxalate, di-p-ethylbenzyl oxalate, di-p-chlorobenzyl oxalate, and dibenzyl oxalate. These substances may be used alone or in combination of two or more.

In the heat-sensitive adhesive layer, in addition to the above-mentioned components, inorganic substances such as titanium oxide, aluminum oxide, colloidal silica, kaolin, talc, metal stearate, paraffin wax, natural wax, synthetic Organic matter such as wax, natural oil, polystyrene powder, and other components such as dispersants, defoamers, and thickeners may be added as needed.

The heat-sensitive adhesive layer is not particularly limited, and can be formed by a known method, for example, suitably formed by a coating method using a primer coating liquid mixed with the above-mentioned components.

Examples of the coating method include paddle coating, gravure coating, gravure offset coating, bar coating, roll coating, knife coating, air knife coating, Dot coating method, U dot coating method, AKKU coating method, smooth coating method, micro gravure coating method, reverse roll method, 4-roll or 5-roll coating method, dip coating method, vertical curtain coating Cloth method, slide coating method, die coating method, etc.

In addition, the drying conditions at the time of the above coating or printing must be within a temperature range in which the hot-melt substance and the eutectic agent used do not melt. As a drying method, besides hot air drying, a drying method using a heat source such as infrared rays, microwaves, or high-frequency waves can also be used.

The coating amount of the heat-sensitive adhesive layer coating liquid is usually preferably 5 to 30 g/m ² , more preferably 5 to 20 g/m ² in terms of dry coating amount. If the coating amount of the above-mentioned heat-sensitive adhesive layer coating liquid is less than 5 g/m ² , sufficient adhesive force cannot be obtained when bonding by heating. A thermoplastic resin deteriorates the sticking resistance; if it exceeds 30 g/m ² , it is not preferable because the thermal insulation effect of the base layer deteriorates and economical efficiency deteriorates.

The total thickness of the primer layer and the heat-sensitive adhesive layer is preferably 13 to 30 μm. In addition, the thickness of the heat-sensitive adhesive layer relative to the thickness of the base layer is preferably 30% or more and 70% or less.

If the above-mentioned total thickness is less than 13 μm, it will be difficult to adhere to a non-mirror surface such as corrugated cardboard, and if it exceeds 30 μm, peeling will occur between the base layer and the heat-sensitive adhesive layer, and intralayer failure will occur. Furthermore, activation energy can be further reduced by setting the thickness of the heat-sensitive adhesive layer to 30% or more and 70% or less. Usually, the thicker the thickness of the heat-sensitive adhesive layer, the more activation energy is required. If the active layer exceeds 70%, the film and synthetic paper used as the support tend to shrink due to the activation amount above the necessary amount. On the other hand, if it is less than 30%, there will be no fixation effect on the uneven adherend, and the adhesion will be significantly reduced.

The heat-sensitive adhesive material of the present invention has the above-mentioned structure, and the adhesion force to various adherends, especially rough surface adherends such as corrugated cardboard, and polyolefin packaging paper is enhanced, and it is a material that is activated by low energy heat and has good adhesion resistance. .

Next, the heat-sensitive adhesive material of the present invention preferably contains a recording layer and a protective layer in this order on the surface of the heat-sensitive adhesive layer without a support, and further contains other layers as necessary.

The above-mentioned recording layer is not particularly limited and can be appropriately selected according to the purpose. For example, the recording layer is preferably a thermosensitive recording layer, an ink receiving layer for thermal fusion transfer recording, a toner image receiving layer for electrophotography, a silver halide Any of a recording layer for photography and an ink-receiving layer for inkjet. Wherein, a thermosensitive adhesive material for thermosensitive recording provided with a thermosensitive recording layer containing a white dye and a developer is used as the above-mentioned recording layer, or a thermosensitive adhesive material for thermosensitive recording provided with an ink receiving layer for thermal fusion transfer recording is used as the above-mentioned recording layer. The above-mentioned recording layer is extremely useful because it has enhanced adhesive force to adherends, especially adherends with rough surfaces such as corrugated cardboard, and polyolefin wrapping paper, is activated by low-energy heat, and has good blocking resistance.

<Heat-sensitive adhesive materials for heat-sensitive recording>

The thermosensitive recording layer in the above thermosensitive adhesive material for thermosensitive recording contains a color developing agent, a color developing agent, a binder resin, and other components as necessary.

The above-mentioned white dye is not particularly limited, and may be appropriately selected from known substances according to the purpose, for example, disclosed triphenylmethane dyes, fluoran dyes, phenothiazine dyes, auramine dyes, Spiropyran-based dyes, indolinophthalide-based dyes, and the like.

As the above-mentioned white dye, for example, 3,3-bis(p-dimethylaminophenyl)phthalone, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalone ( Alias crystal violet lactone), 3,3-bis(p-dimethylaminophenyl)-6-diethylaminophthalein, 3,3-bis(p-dimethylaminophenyl)-6-chlorophthalein Ketone, 3,3-bis(p-dibutylaminophenyl)phthalone, 3-cyclohexylamino-6-chlorofluoran, 3-dimethylamino-5,7-dimethylfluoran, 3- Diethylamino-7-chlorofluoran, 3-diethylamino-7-methylfluoran, 3-diethylamino-7,8-benzofluoran, 3-diethylamino-6- Methyl-7-chlorofluoran, 3-(N-p-tolyl-N-ethylamino)-6-methyl-7-anilinofluoran, 3-pyrrolidinyl-6-methyl-7- Anilinofluoran, 2-(N-(3'-trifluoromethylphenyl)amino)-6-diethylaminofluoran, 2-(3,6-bis(diethylamino)-9- (o-chloroaniline) xanthrylbenzoic acid lactam), 3-diethylamino-6-methyl-7-(m-trichloromethylanilino)fluorane, 3-diethylamino-7-( p-chloroanilino)fluoran, 3-dibutylamino-7-(p-chloroanilino)fluoran, 3-N-methyl-N-pentylamino-6-methyl-7-anilinofluoran , 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-(N, N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, benzoyl white methylene blue, 6'-chloro-8'-methoxy-benzoindole Bensondolino-pirirospirane, 6'-Bromo-3'-methoxy-benzoindolol-pirinospirane, 3-(2'-Hydroxy-4'-dimethylaminophenyl )-3-(2'-methoxy-5'-chlorophenyl)phthalone, 3-(2'-hydroxy-4'-diethylaminophenyl)-3-(2'-methoxy -5'-nitrophenyl)phthalein, 3-(2'-hydroxy-4'-diethylaminophenyl)-3-(2'-methoxy-5'-methylphenyl)phthalein Ketone, 3-diethylamino-6-methyl-7-(2',4'-dimethylanilino)fluoran, 3-(2'-methoxy-4'-dimethylaminobenzene Base)-3-(2'-hydroxy-4'-chloro-5'-methylphenyl)phthalone, 3-morpholino-7-(N-propyl-trifluoromethylanilino)fluoran , 3-pyrrolidinyl-7-trifluoromethylanilinofluorane, 3-diethylamino-5-chloro-7-(N-benzyl-trifluoromethylanilino)fluoran, 3-pyrrole Alkyl-7-(di-p-chlorophenyl)methylaminofluoran, 3-diethylamino-5-chloro-7-(α-phenylethylamino)fluoran, 3-(N-ethyl -p-tolylamino)-7-(α-phenylethylamino)fluorane, 3-diethylamino-7-(o-methoxycarbonylphenylamino)fluorane, 3-diethylamino- 5-Methyl-7-(α-phenylethylamino)fluoran, 3-diethylamino-7-pyrrolidinylfluoran, 2-chloro-3-(N-methylmethylphenylamino)-7 -(p-Butylanilino)fluoran, 3-(N-benzyl-N-cyclohexylamino)-5,6-benzo-7-α-naphthylamino-4'0-bromofluoran, 3-diethylamino-6-methyl-7-m-tricresyl (Meshi jinno)-4', 5'-benzofluoran, 3-diethylamino-6-methyl-7-(2 ',4'-Dimethylanilino)fluorane, 3-(p-dimethylaminophenyl)-3-(1,1-bis(p-dimethylaminophenyl)ethen-2-yl)phthalein Ketone, 3-(p-dimethylaminophenyl)-3-{1,1-bis(p-dimethylaminophenyl)ethen-2-yl}-6-dimethylaminophthalone, 3-( p-Dimethylaminophenyl)-3-(1-p-dimethylaminophenyl-1-phenylethen-2-yl)phthalone, 3-(p-dimethylaminophenyl-3-(1 - p-Dimethylaminophenyl-1-p-chlorophenylethen-2-yl)-6-dimethylaminophthalone, 3-(4'-dimethylamino-2'-methoxy)- 3-(1”-p-dimethylaminophenyl-1”-p-chlorophenyl-1”, 3”-butadiene-4”-yl)benzophthalene, 3-(4’-dimethyl Amino-2'-benzyloxy)-3-(1"-p-dimethylaminophenyl-1"-phenyl-1",3"-butadiene-4"-yl)benzophthalein , 3-dimethylamino-6-dimethylamino-fluorene-9-spiro-3'-(6'-dimethylamino)phthalone, 3,3-bis{2-(p-dimethylamino Phenyl)-2-(p-methoxyphenyl)vinyl}-4,5,6,7-tetrachlorophthalketone, 3-bis{1,1-bis(4-pyrrolidinylphenyl)ethene -2-yl}-5,6-dichloro-4,7-dibromophthalone, bis(p-dimethylaminostyryl)-1-naphthalenesulfonylmethane, 3-(N-methyl-N -Propylamino)-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3,6-di(dimethylamino)fluoran Spiro(9,3')-6'-dimethylaminophthalone, 3-diethylamino-6-chloro-7-anilinofluoran, 3-N-ethyl-N-(2-ethoxy propyl)amino-6-methyl-7-anilinofluoran, 3-N-ethyl-N-tetrahydrofurfurylamino-6-methyl-7-anilinofluoran, 3-diethyl Amino-6-methyl-7-m-trimethylanilino-4',5'-benzofluoran, 3-N-methyl-N-isobutyl-6-methyl-7-anilinofluoran, 3-N-ethyl-N-isoamyl-6-methyl-7-anilinofluoran, etc. These substances may be used alone or in combination of two or more.

The color former is not particularly limited, and may be appropriately selected from known electron-withdrawing compounds according to the purpose, for example, phenolic compounds, thiophenolic compounds, thiourea derivatives, organic acids or metal salts thereof, and the like. Examples of the developer include 4,4'-isopropylidene diphenol, 3,4'-isopropylidene diphenol, 4,4'-isopropylidene bis(o-methylphenol) , 4,4'-sec-butylene diphenol, 4,4'-isopropylidene bis(o-tert-butylphenol), 4,4'-cyclohexylenephenol, 4,4'-isopropylene Base bis(2-chlorophenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert butylphenol), 4,4'-butylene bis(6-tert-butyl-2-methyl)phenol, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenol ) butane, 1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane, 4,4'-thiobis(6-tert-butyl-2-methyl ) phenol, 4,4'-diphenol sulfone, 4,2'-diphenol sulfone, 4-isopropoxy-4'-hydroxydiphenyl sulfone, 4-benzyloxy-4'-hydroxydiphenyl Sulfone, 4,4'-diphenol sulfoxide, isopropyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, benzyl protocatechuate, stearate gallate, lauryl gallate, octyl gallate, 1,7-bis(4-hydroxyphenylthio)-3,5-oxetane, 1,5-bis(4-hydroxyphenylthio)-3-oxoheptane, 1,3-bis(4 -Hydroxyphenylthio)-propane, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 1,3-bis(4-hydroxyphenylthio)-2-hydroxypropane , N, N'-diphenylthiourea, N, N'-di(m-chlorophenyl)thiourea, salicylaniline, 5-chloro-salicylaniline, salicyl-o-chloroaniline, 2-Hydroxy-3-naphthoic acid, antipyrine complex of zinc thiocyanate, zinc salt of 2-acetoxy-3-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-hydroxy-2 -Naphthoic acid, metal salts of zinc, aluminum, calcium, etc. of hydroxynaphthoic acid, methyl bis(4-hydroxyphenyl)acetate, benzyl bis(4-hydroxyphenyl)acetate, 4-{β-(p- Methoxyphenoxy)ethoxy}salicylic acid, 1,3-bis(4-hydroxycumyl)benzene, 1,4-bis(4-hydroxycumyl)benzene, 2,4'-diphenol Antipyrine complexes of sulfone, 3,3'-diallyl-4,4'-diphenol sulfone, α,α-bis(4-hydroxyphenyl)-α-methyltoluene thiocyanate zinc substance, tetrabromobisphenol A, tetrabromobisphenol S, 4,4'-thiobis(2-methylphenol), 3,4-hydroxy-4'-methyl-diphenol sulfone, 4,4' - Thiobis(2-chlorophenol) and the like. These substances may be used alone or in combination of two or more.

The amount of the color developer to be added to the thermosensitive recording layer is not particularly limited, and can be appropriately selected according to the purpose. It is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass relative to 1 part by mass of the color former.

The above-mentioned binder resin is not particularly limited, and may be appropriately selected from known materials according to the purpose, for example, polyvinyl alcohol, starch or its derivatives, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, etc. Base cellulose, methyl cellulose, ethyl cellulose and other cellulose derivatives, sodium polyacrylate, polyvinylpyrrolidone, acrylamide-acrylate copolymer, acrylamide-acrylate-methacrylic acid terpolymer, benzene Ethylene-maleic anhydride copolymer alkali salt, isobutylene-maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, casein and other water-soluble polymers, in addition to polyvinyl acetate , polyurethane, polyacrylic acid, polyacrylate, polymethacrylate, polybutylmethacrylate, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer and other latex and styrene-butadiene copolymer , latex such as styrene-butadiene-acrylic copolymer, etc. These substances may be used alone or in combination of two or more.

In the above-mentioned thermosensitive recording layer, various thermo-fusible substances can be used as fillers. Examples of the hot-melt material include fatty acids such as stearic acid and n-behenic acid, fatty acid amides such as stearamide and palmitamide, zinc stearate, aluminum stearate, stearic acid Calcium, zinc palmitate, zinc n-docosanoate and other fatty acid metal salts, p-benzylbiphenyl, terphenyl, triphenylmethane, benzyl p-benzyloxybenzoate, β-benzyloxynaphthalene , β-Phenyl Naphthoate, 1-Hydroxy-2-Phenyl Naphthoate, 1-Hydroxy-2-Methyl Naphthoate, Diphenyl Carbonate, Dibenzyl Terephthalate, Dimethyl Terephthalate , 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dibenzyloxynaphthalene, 1,2-bis(phenoxy)ethane, 1,2-bis( 3-Methylphenoxy)ethane, 1,2-bis(4-methylphenoxy)ethane, 1,4-bis(phenoxy)butane, 1,4-bis(phenoxy )2-butane, 1,2-bis(4-methoxyphenylthio)ethane, dibenzoylmethane, 1,4-bis(phenylthio)butane, 1,4-bis(benzene Thio) 2-butane, 1,2-bis(4-methoxyphenylthio)ethane, 1,3-bis(2-vinyloxyethoxy)benzene, 1,4-bis(2 -vinyloxyethoxy)benzene, p-(2-vinyloxyethoxy)biphenyl, p-aryloxybiphenyl, p-alkynephenoxybiphenyl, dibenzoylmethane, 1,3- Dibenzoyl propane, dibenzyl disulfide, 1,1-diphenylethanol, 1,1-diphenylpropanol, p-(benzyloxy)benzylethanol, 1,3-diphenoxy -2-propanol, N-octadecylcarbamoyl-p-methoxycarbonylbenzene, N-octadecylcarbamoylbenzene, dibenzyl oxalate, 1,5-bis(p-methyl oxyphenyloxy)-3-oxapentane, etc. These substances may be used alone or in combination of two or more.

In the above-mentioned thermosensitive recording layer, various auxiliary additive components such as surfactants, lubricants and the like may also be used in combination as necessary. As the lubricant, for example, higher fatty acid or metal salt thereof, higher fatty acid amide, higher fatty acid ester, animal wax, vegetable wax, mineral wax, petroleum wax, etc.,

There is no particular limitation on the above-mentioned heat-sensitive recording layer, and it can be formed by a generally known method. For example, it can be formed as follows. , sand mixer and other dispersing machines, pulverize and disperse until the dispersed particle size is 1-3 μm, and mix it with fillers, hot-melt material (sensitizer) dispersion liquid, etc. according to a certain formula as needed to prepare heat-sensitive records The layer coating solution is coated on a support to form a thermosensitive recording layer.

The thickness of the thermosensitive recording layer varies depending on the composition of the thermosensitive recording layer and the application of the thermosensitive adhesive material, and cannot be generalized, but is preferably 1 to 50 μm. More preferably, it is 3 to 20 μm.

<Heat-sensitive adhesive materials for thermal transfer recording>

The ink-receiving layer for thermal transfer recording in the heat-sensitive adhesive material for thermal transfer recording described above contains a filler, a binder resin, a water-resistant agent, and may contain other components as necessary.

The above-mentioned filler is not particularly limited and can be appropriately selected according to the purpose. For example, calcium carbonate, silicon dioxide, titanium oxide, aluminum hydroxide, clay, calcined clay, magnesium silicate, magnesium carbonate, white carbon, zinc oxide, Barium sulfate, surface-treated calcium carbonate and silicon dioxide, urea-formaldehyde resin, styrene-methacrylic acid copolymer, polystyrene resin and other fine powders.

The above-mentioned binder resin is not particularly limited, and may be appropriately selected from known water-soluble resins according to the purpose, for example, polyvinyl alcohol, starch or derivatives thereof, methoxycellulose, hydroxyethylcellulose, Carboxymethylcellulose, methylcellulose, ethylcellulose and other cellulose derivatives; sodium polyacrylate, polyvinylpyrrolidone, acrylamide-acrylate copolymer, acrylamide-acrylate-methacrylic acid terpolymer substances, styrene-maleic anhydride copolymer alkali salt, isobutylene-maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, casein and other water-soluble polymers, etc. These substances may be used alone or in combination of two or more.

The ratio of the filler to the water-soluble resin in the ink-receiving layer is related to the binding property, and the content mass ratio (solid content) of the filler to the water-soluble resin is preferably 1:0.1 to 0.2.

The above-mentioned water resistance agent is not particularly limited and can be appropriately selected according to the purpose. For example, formaldehyde, glyoxal, chromium alum, melamine, melamine-formaldehyde resin, polyamide resin, polyamide-epichlorohydrin resin can be mentioned. wait.

The proportion of the water-soluble resin in the water-resistant agent is also related to the binding property, and its content mass ratio (solid content) is preferably 0.3 to 0.5 parts of the water-resistant agent relative to 1 part of the water-soluble resin. Such an ink receiving layer is formed by containing a filler and a water-soluble resin, and containing a water-soluble resin and a water-resistant agent at a prescribed ratio. In addition, the surface of the ink receiving layer is calendered by a calender to make it smooth for 500 seconds or More than 500 seconds, in addition to the effect of the above-mentioned fillers, the printing quality is further improved.

-The protective layer-

The above-mentioned protective layer contains polyalcohol having a reactive carbonyl group, a hydrazide compound, and other components as necessary.

Since the protective layer containing such polyvinyl alcohol with a reactive carbonyl group and a hydrazide compound as a crosslinking agent has extremely high heat resistance and water resistance, it is difficult to be affected by pressure, temperature, and humidity. Therefore, the resistance can be greatly improved. Cohesiveness.

The above-mentioned polyvinyl alcohol having a reactive carbonyl group can be produced by a known method such as copolymerizing a vinyl monomer having a reactive carbonyl group with vinyl ester of fatty acid and saponifying the obtained polymer. As the vinyl monomer having a reactive carbonyl group, a group having an ester residue and a group having an acetonyl group can be cited, but vinyl monomers having a diacetonyl group are preferred, and specifically, diacetone acrylamide and Methyldiacetone acrylamide. Vinyl formate, vinyl acetate, vinyl propionate, etc. are mentioned as said fatty acid vinyl ester, Among these, vinyl acetate is especially preferable.

The above-mentioned polyvinyl alcohol (PVA) having a reactive carbonyl group can also be obtained by copolymerizing other vinyl monomers that can be copolymerized. Examples of these copolymerizable vinyl monomers include acrylate, butadiene, ethylene, propylene, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, and itaconic acid.

The content of reactive carbonyl groups in PVA having reactive carbonyl groups is preferably 0.5 to 20 mol% of the total polymer, more preferably 2 to 10 mol% in consideration of water resistance. If the above-mentioned content is less than 2 mol%, the actual water resistance is insufficient, and even if it exceeds 10 mol%, the water resistance cannot be improved more than that, and since it is only expensive, it is not economical. In addition, the degree of polymerization of the PVA having a reactive carbonyl group is preferably 300-3000, more preferably 500-2200. In addition, the degree of saponification of the above-mentioned PVA having a reactive carbonyl group is preferably 80% or more.

The above-mentioned hydrazide compound is not particularly limited as long as it is a compound having a hydrazide group, and can be appropriately selected according to the purpose. Diacid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, lauric acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide Hydrazine, itaconic acid dihydrazide, benzoic acid dihydrazide, glutaric acid dihydrazide, diglycolic acid hydrazide, tartrate dihydrazide, malic acid dihydrazide, isophthalic acid hydrazide, terephthalic acid dihydrazide Formic acid dihydrazide, 2,7-naphthoic acid dihydrazide, polyacrylic acid hydrazide, etc. These substances may be used alone or in combination of two or more. Among these hydrazide compounds, adipic acid dihydrazide is preferable from the viewpoint of water resistance and safety.

The content of the hydrazide compound is preferably 5 to 40 parts by mass, more preferably 15 to 25 parts by mass, based on 100 parts by mass of the polyvinyl alcohol having a reactive carbonyl group.

In the above-mentioned protective layer, it is preferable to contain a filler. The filler may be an alkaline substance, and examples thereof include aluminum hydroxide, calcium carbonate, talc, alkaline silicic acids, etc., and aluminum hydroxide and calcium carbonate are preferred in terms of thermal head compatibility (residue adhesion). , aluminum hydroxide is particularly preferred if pH control through appropriate water solubility is considered. As the filler contained in the above-mentioned thermosensitive recording layer, known materials can be used, and examples thereof include calcium carbonate, zinc oxide, aluminum oxide, titanium dioxide, silicon dioxide, aluminum hydroxide, barium sulfate, talc, kaolin, alumina Inorganic pigments such as earth and clay, or known organic pigments, etc., but are not limited to these. In addition, in consideration of water resistance (water peeling resistance), silica, kaolin, and alumina, which are acidic pigments (pigments showing acidity in aqueous solution), are preferred, and silica is particularly preferred from the viewpoint of color density.

The above-mentioned protective layer is not particularly limited, and can be formed by a generally known method. For example, the protective layer can be formed by preparing a protective layer coating liquid according to a conventional method and coating the coating liquid on the above-mentioned recording layer.

The thickness of the protective layer is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 1.0 to 7.0 μm.

Between the above-mentioned support and the above-mentioned thermosensitive recording layer, an intermediate layer or the like may be provided as necessary. As components constituting these layers, the aforementioned fillers, binders, hot-melt substances, surfactants, and the like can be used.

In addition, the heat-sensitive adhesive material of the present invention can also be provided with a pre-printed layer on the opposite side (recording layer surface) of the heat-sensitive adhesive layer according to the purpose, and can also be provided with a mark as a direction-finding measure on the surface or the heat-sensitive adhesive layer. print. The two types of printing include common printing methods such as UV printing, EB printing, and multifunctional printing. As the printing ink, for example, UV curable ink can be used as the most preferable ink on heat-sensitive recording paper from the viewpoint of quick-drying property. Examples of the aforementioned UV curable inks (UV inks) include UV RNC, UV NVR, UVSOYA, and UV SOYA-RNC UV inks produced by T&K TOKA; FD FL UV inks produced by Toyo Ink Manufacturing Co., Ltd.; and the like.

The heat-sensitive adhesive material of the present invention can be suitably used after cutting before or after thermal activation (heating) of its heat-sensitive adhesive layer, wherein, in the heat-sensitive adhesive material, a cut can also be formed in advance. The aforementioned heat-sensitive adhesive material is advantageous in that it is suitable for use in various applications such as labels and labels.

The shape of the heat-sensitive adhesive material of the present invention is not particularly limited, but preferably, a label shape, a sheet shape, a label sheet shape, a roll shape, and the like are exemplified.

Among them, from the viewpoints of convenience, storage place, and workability, it is preferable to wind up a cylindrical core material and store it in a roll shape in a long shape.

(Heat-sensitive adhesive material of the second form)

In the second aspect, the heat-sensitive adhesive material of the present invention comprises a heat-sensitive recording layer and a protective layer in this order on one side of the support and a thermoplastic resin and a heat-fusible material on the opposite surface of the support. The heat-sensitive adhesive layer may contain another layer as needed.

The above-mentioned thermosensitive recording layer is usually composed of a thermosensitive recording layer and a protective layer. When winding in a roll shape, the protective layer of the thermosensitive recording layer is bonded to the thermosensitive adhesive layer. Due to the factors of pressure, temperature, humidity and time, The heat-sensitive adhesive layer melts, creating a bond. In order to improve chemical resistance and head compatibility, the protective layer is usually composed of inorganic fillers.

The blocking resistance can be improved by using polyvinyl alcohol having a reactive carbonyl group and a hydrazide compound as a crosslinking agent as the resin used for the protective layer. Resins used so far include starches, hydroxycellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, gum arabic, completely (partially) saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, Vinyl alcohol, etc. These resins have insufficient heat resistance and moisture resistance, and if pressure, temperature, and humidity loads are applied to the heat-sensitive adhesive layer in the state of overlapping, the protective layer will become a relatively softened state. Bonding occurs when the heat-sensitive adhesive layer is applied in a molten state. On the contrary, due to the action of polyvinyl alcohol having a reactive carbonyl group and a hydrazide compound as a crosslinking agent, the resin of the protective layer has extremely high heat resistance and moisture resistance, and is hardly affected by applied pressure, temperature, and humidity. In addition, if the resin of the present invention is used, it is difficult for the heat-sensitive adhesive layer to form a molten state, and the blocking resistance can be greatly improved due to the synergistic effect of these substances.

In addition, printed matter of a heat-sensitive adhesive material composed of two layers of the heat-sensitive recording layer and the heat-sensitive adhesive layer of the present invention has been produced and distributed in recent years. When printing the thermosensitive recording layer by a thermal head, if the resin of the protective layer on the thermosensitive recording side uses a resin material with poor heat resistance and moisture resistance other than the present invention, it will fall into a softer state than the protective layer, and it will be in a softer state than the protective layer. The frictional force of the head is increased, and it is easy to cause transmission obstacles. The heat-sensitive adhesive layer on the opposite side is in contact with the flat roller driven by rotation, and the friction with the flat roller generates heat, and adhesion occurs. This phenomenon is remarkable in a high-temperature and high-humidity environment. Therefore, bad effects such as jamming of the label and interruption of transmission may occur. By using the resin of the present invention in the protective layer, since the protective layer does not soften, the frictional force with the thermal head during printing is also controlled, enabling smooth transfer.

-The protective layer-

The protective layer contains polyvinyl alcohol having a reactive carbonyl group and a hydrazide compound, and further contains fillers and other components as necessary.

As the above-mentioned polyvinyl alcohol having a reactive carbonyl group and the above-mentioned hydrazide compound, the same ones as those used for the heat-sensitive adhesive material protective layer of the above-mentioned first embodiment can be used. By containing such reactive carbonyl group-containing polyvinyl alcohol having high heat resistance and moisture resistance in the heat-sensitive adhesive layer, the heat resistance and moisture resistance of the heat-sensitive adhesive layer can be improved, and higher blocking resistance can be realized. In addition, due to the improved heat resistance and moisture resistance of the heat-sensitive adhesive layer itself, it is of course difficult to show the adhesion caused by the frictional heat generated by the rotation of the flat roller during printing of the heat-sensitive recording layer. Even when the heat-sensitive adhesive layer is activated by heat, the mobility with respect to the head can be improved, the adhesion of slag to the head can be prevented, and the decrease in adhesion can be suppressed.

The filler used in the above-mentioned protective layer may be an alkaline substance, and examples thereof include aluminum hydroxide, calcium carbonate, talc, alkaline silicic acids, etc., due to etching of the thermal head (residue adhesion), etc., preferably Aluminum hydroxide and calcium carbonate, aluminum hydroxide is more preferred in consideration of pH control by appropriate water solubility.

-Heat-sensitive adhesive layer-

The above-mentioned heat-sensitive adhesive layer contains a thermoplastic resin and a heat-melt substance, and contains polyvinyl alcohol having a reactive carbonyl group, a hydrazide compound, and other components as necessary.

Examples of the above thermoplastic resins include (meth)acrylate copolymers, styrene-isobutylene copolymers, styrene-acrylate copolymers, styrene-butadiene copolymers, and acrylonitrile-butadiene copolymers. , styrene-vinyl acetate copolymer, vinyl acetate-acrylate copolymer, styrene-vinyl chloride copolymer, ethylene-acrylate copolymer, vinyl acetate-ethylene-vinyl chloride copolymer, vinyl acetate-ethylene - Acrylate copolymer, vinyl acetate-ethylene-styrene copolymer, polybutadiene, polyurethane and other resins. Among these, various copolymers containing acrylate as a monomer component are preferably used from the viewpoint of adhesiveness and weather resistance. These substances may be used alone or in combination.

As the polyvinyl alcohol having a reactive carbonyl group and the hydrazide compound in the heat-sensitive adhesive layer, the same ones as those used for the protective layer of the heat-sensitive adhesive material of the first embodiment can be used.

The above-mentioned polyvinyl alcohol having a reactive carbonyl group is preferably used as a dispersant for a heat-melt substance in a heat-sensitive adhesive layer. Therefore, the adhesive properties can be further improved, and higher blocking resistance and print compatibility can be realized.

By using a hydrazide compound as a crosslinking agent in the heat-sensitive adhesive layer, it has been found that the heat resistance and moisture resistance of the heat-sensitive adhesive layer can be further improved, and higher adhesion resistance and print compatibility can be realized.

The content ratio of the polyvinyl alcohol having a reactive carbonyl group in the heat-sensitive adhesive layer is preferably 3 to 10% by mass of the thermoplastic resin, more preferably 5 to 8% by mass. When it exceeds 10% by mass, the blocking resistance and print matching property are improved, however, conversely, the adhesive property shows a tendency to decrease. When the added amount is less than 3% by mass, there is no adverse effect on the adhesive properties, however, especially the anti-adhesive properties at high temperature and high humidity and the print compatibility are insufficient.

Examples of the hot-melt substances include dicyclohexyl phthalate (melting point 65°C), diphenyl phthalate (melting point 73°C), and N-cyclohexyl-p-toluenesulfonamide (melting point 86°C). , sucrose benzoate (melting point 98°C), ethylene glycol dibenzoate (melting point 70°C), trimethylolethane tribenzoate (melting point 73°C), pentaerythritol tetrabenzoate (melting point 95°C), eight Acetate sucrose (melting point 89°C), catechol dibenzoate (melting point 86°C), etc., and triethylene glycol bis(3-(3-tert-butyl-4-hydroxy-5- Methylphenyl) propionate) (melting point 77°C), 1,6-hexanediol bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (melting point 103°C ) and other hindered phenolic compounds, 2-(5'-(1", 1", 3", 3"-tetramethylbutyl)-2'-hydroxyphenyl)benzotriazole (melting point 103°C), 2-(3',5'-bis-(2",2"-dimethylpropyl)-2'-hydroxyphenyl)benzotriazole (melting point 80°C), 2-(3'-tert-butyl Base-5'-methyl-2'-hydroxyphenyl)-5-chlorobenzotriazole (melting point 138°C), 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5- Chlorobenzotriazole (melting point 155°C), 2-(5-methyl-2-hydroxyphenyl)benzotriazole (melting point 130°C), 2-(3,5-di-tert-amyl-2-hydroxy Triazole compounds such as phenyl)benzotriazole (melting point 80°C), etc. Among these compounds, hindered phenolic compounds and triazole compounds are preferably used from the viewpoint of long-lasting adhesion after heating and adhesion stability over time. In order to further maintain the amorphization of the active layer after melting The duration of the adhesiveness can also be used in combination with these compounds. These heat-fusible substances and compounds are micronized by wet or dry pulverizers such as ball mills, sand mills, paint shakers, Dynomil, attritors, and frequency conversion mixers, and used as aqueous dispersions, and can also be micronized by known methods. Use in capsules. The particle size of the hot-melt material is preferably 10 μm or less, more preferably 5 μm or less, and practically 0.7 to 2 μm.

Specific examples of the adhesion-imparting agent used in the heat-sensitive adhesive layer include terpene resins, aliphatic petroleum resins, aromatic petroleum resins, coumarone indene resins, styrene resins, phenolic resins, Terpene phenolic resin, rosin resin, etc.

In the above heat-sensitive bonding, fillers, etc. can also be added within the range that does not hinder the purpose of the present invention. For example, carbonates, oxides, and hydroxides of aluminum, zinc, calcium, magnesium, barium, and titanium can be used. , sulfate, etc., and inorganic pigments containing viscosity such as natural silica, zeolite, kaolin, calcined kaolin, starch, styrene resin, polyolefin resin, melamine resin, acrylic resin, paraffin wax, natural wax, synthetic wax wait.

In the heat-sensitive adhesive layer, in addition to the thermoplastic resin and the hot-melt substance, a supercooling accelerator that promotes the supercooling of the hot-melt substance and exhibits high adhesive force under a low-temperature environment may be used. Naphthalene derivatives such as 2-benzyloxynaphthalene, biphenyl derivatives such as methyl terphenyl, acetylbiphenyl, p-benzylbiphenyl, and 4-allyloxybiphenyl can be used as the supercooling accelerator. , 1,2-bis(3-methylphenoxy)ethane, 2,2'-bis(4-methoxyphenoxy)diethyl ether, bis(4-methoxyphenyl)ether, etc. Ether compounds, diphenyl carbonate, dibenzyl oxalate, bis(p-chlorobenzyl) oxalate, bis(p-methylbenzyl) oxalate and other carbonic acid or oxalate diester derivatives, among which dibenzyl oxalate derivatives Compounds and biphenyl derivatives have the effect of promoting supercooling of hot-melt substances.

In the heat-sensitive adhesive layer, polymer compounds such as hollow particle acrylic polymers and vinylidene chloride polymers having heat insulating properties can be used as needed. In addition, polymethyl methacrylate or the like mainly using spherical particles can also be used.

In addition to the above-mentioned components, various additives such as curing agents, preservatives, dyes, ultraviolet absorbers, antioxidants, pH adjusters, and defoamers may be added to the heat-sensitive adhesive layer as needed.

-Thermosensitive recording layer, support body-

As the thermosensitive recording layer and the support, the same ones as the thermosensitive recording layer and the support in the first embodiment can be used.

-middle layer-

Between the aforementioned heat-sensitive adhesive layer and the support, an intermediate layer containing an acrylic adhesive is preferably used.

Examples of thermoplastic resins used in the intermediate layer include (meth)acrylate copolymers, styrene-isobutylene copolymers, styrene-acrylate copolymers, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, and styrene-butadiene copolymers. Copolymer, vinyl acetate-acrylate copolymer, styrene-acrylate copolymer, vinyl acetate-ethylene-acrylate copolymer and other resins.

In addition, inorganic or organic fillers, hollow fillers in the state of air cells, waxes, and the like can be suitably used in the intermediate layer as needed.

The adherend to which the heat-sensitive adhesive material of the present invention is attached is not particularly limited, and its size, shape, structure, material, etc. can be appropriately selected according to the purpose. As the above-mentioned material, for example, polyethylene, polypropylene, etc. are suitable. Polyolefin; Acrylic, polyethylene terephthalate (PET), polystyrene, nylon and other resin sheets; SUS, aluminum and other metal sheets; envelopes, corrugated cardboard and other paper products; polyolefin and other packaging, PVC Class wrapping paper, polyethylene non-woven fabrics (envelopes, etc.), etc.

Among them, it is advantageous from the viewpoint of strong adhesive force to adherends on rough surfaces such as corrugated cardboard and polyolefin wrapping paper, and can be adhered firmly.

As the heat activation method of the above-mentioned heat-sensitive adhesive layer in the heat-sensitive adhesive material of the present invention, it is not particularly limited, and can be appropriately selected according to the purpose. method etc.

Among them, the thermal head activation method is preferable, and the following method for activating the heat-sensitive adhesive material of the present invention is particularly preferable. At this time, the recording of the above-mentioned thermosensitive recording layer and the thermal activation of the above-mentioned thermosensitive adhesive layer can be performed by heating both sides of the above-mentioned thermosensitive adhesive material by using an existing thermosensitive recording printing device. method is advantageous.

【Example】

Hereinafter, the present invention will be described in detail by way of examples, however, the present invention is not limited to the following examples.

(Preparation Example 1-1)

-Preparation of primer coating liquid (A-1 liquid)-

Amorphous silica (Nippon Silica Industry Co., Ltd., Nippongel AZ-200, solid content concentration 97% by mass, volume average particle diameter 2.5 μm, oil absorption 320ml/100g) 4.6 parts by mass, acrylic acid 2- Ethylhexyl-methyl methacrylate-styrene copolymer (glass transition temperature (Tg) = -65°C, solid content concentration 55.4% by mass, produced by Showa High Molecule Co., Ltd.) 24.4 parts by mass, surfactant (Dapro W-77, Erementis Japan Corporation) A mixture of 0.1 parts by mass and 70.9 parts by mass of water was used to prepare a primer coating liquid [A-1 liquid].

(Preparation Example 1-2)

-Preparation of primer coating liquid (A-2 liquid)-

Stir and disperse 14.6 parts by mass of plastic spherical hollow particles (1) (acrylonitrile-vinylidene chloride-methyl methacrylate copolymer, solid content concentration 41% by mass, volume average particle diameter 3.6 μm, hollow rate 90%), 21.7 parts by mass of 2-ethylhexyl acrylate-methyl methacrylate-styrene copolymer (glass transition temperature (Tg) = -65°C, solid content concentration 55.4% by mass, produced by Showa High Molecule Co., Ltd.), A mixture of 0.1 parts by mass of a surfactant (Dapro W-77, Erementis Japan Co., Ltd.) and 63.6 parts by mass of water was used to prepare a primer coating liquid [A-2 liquid].

(Preparation example 1-3)

-Preparation of primer coating liquid (A-3 liquid)-

Stir and disperse 18.2 parts by mass of plastic spherical hollow particles (2) (acrylonitrile-methacrylonitrile-isobornyl methacrylate copolymer, solid content concentration 33% by mass, volume average particle diameter 3.0 μm, hollow rate 91%) 24.0 parts by mass of n-butyl acrylate-methyl methacrylate copolymer (glass transition temperature (Tg)=-62°C, solid content concentration 50% by mass, produced by JSR Corporation), surfactant (Dapro W-77 , ェレメンティイス Japan Corporation) and a mixture of 0.1 parts by mass and 57.7 parts by mass of water were used to prepare a primer coating liquid [A-3 liquid].

(preparation example 1-4)

-Preparation of primer coating liquid (A-4 liquid)-

Stir and disperse 22.0 parts by mass of plastic-like spherical hollow particles (3) (acrylonitrile-vinylidene chloride-methyl methacrylate copolymer, solid content concentration 41% by mass, volume average particle diameter 3.2 μm, hollow rate 70%) 16.2 parts by mass of 2-ethylhexyl acrylate-methyl methacrylate-styrene copolymer (glass transition temperature (Tg)=-5°C, solid content concentration 55.4% by mass, produced by Showa High Molecule Co., Ltd.) A mixture of 0.1 parts by mass of a surfactant (Dapro W-77, Erementis Japan Co., Ltd.) and 61.7 parts by mass of water was used to prepare a primer coating liquid [A-4 liquid].

(Preparation example 1-5)

-Preparation of primer coating liquid (A-5 liquid)-

Stir and disperse 30.0 parts by mass of plastic-like spherical hollow particles (4) (acrylonitrile-vinylidene chloride-methyl methacrylate copolymer, solid content concentration 40% by mass, volume average particle diameter 1.5 μm, hollow rate 50%) 12.0 parts by mass of 2-ethylhexyl acrylate-methyl methacrylate-styrene copolymer (glass transition temperature (Tg)=-30°C, solid content concentration 50.0% by mass, produced by Showa High Molecule Co., Ltd.) A mixture of 0.1 parts by mass of a surfactant (Dapro W-77, Erementis Japan Co., Ltd.) and 57.9 parts by mass of water was used to prepare a primer coating liquid [A-5 liquid].

(preparation example 1-6)

-Preparation of primer coating liquid (A-6 liquid)-

Stir and disperse plastic-like spherical hollow particles (2) (acrylonitrile-methacrylonitrile-isobornyl methacrylate copolymer, solid content concentration 33% by mass, volume average particle diameter 3.0 μm, hollow ratio 91%) 6.1 mass Parts, 30.2 parts by mass of ethylene-vinyl acetate-acrylic acid copolymer (glass transition temperature (Tg)=-20°C, solid content concentration 53% by mass, produced by Sumika Chemtex Co., Ltd.), surfactant (Dapro W-77 , ェレメンティイス Japan Corporation) and a mixture of 0.1 parts by mass and 63.6 parts by mass of water were used to prepare a primer coating liquid [A-6 liquid].

(preparation example 1-7)

-Preparation of primer coating liquid (A-7 liquid)-

Stir and disperse plastic-like spherical hollow particles (5) (acrylonitrile-methacrylonitrile-isobornyl methacrylate copolymer, solid content concentration 33 mass%, volume average particle diameter 6.0 μm, hollow rate 91%) 27.3 mass Parts, 2-ethylhexyl acrylate-methyl methacrylate-styrene copolymer (glass transition temperature (Tg)=-65°C, solid content concentration 55.4% by mass, produced by Showa High Molecule Co., Ltd.) 16.3 mass parts, a mixture of 0.1 parts by mass of a surfactant (Dapro W-77, Erementis Japan Co., Ltd.), and 56.3 parts by mass of water, to prepare a primer coating liquid [A-7 liquid].

(preparation example 1-8)

-Preparation of primer coating liquid (A-8 liquid)-

Stir and disperse plastic-like spherical hollow particles (2) (acrylonitrile-methacrylonitrile-isobornyl methacrylate copolymer, solid content concentration 33 mass%, volume average particle diameter 3.0 μm, hollow rate 91%) 18.2 mass 21.8 parts by mass of n-butyl acrylate-methyl acrylate-methyl methacrylate copolymer (glass transition temperature (Tg)=0°C, solid content concentration 55% by mass, produced by JSR Corporation), surfactant ( A primer coating liquid [A-8 liquid] was prepared from a mixture of 0.1 parts by mass of Dapro W-77, 0.1 parts by mass of Erementis Japan, and 59.9 parts by mass of water.

(preparation example 1-9)

-Preparation of primer coating liquid (A-9 liquid)-

Stir and disperse plastic-like spherical hollow particles (2) (acrylonitrile-methacrylonitrile-isobornyl methacrylate copolymer, solid content concentration 33 mass%, volume average particle diameter 3.0 μm, hollow rate 91%) 44.6 mass 6.5 parts by mass of a copolymer of n-butyl acrylate-methyl methacrylate (glass transition temperature (Tg)=-62°C, solid content concentration 50% by mass, produced by JSR Corporation), 6.5 parts by mass of surfactant (Dapro W- 77. A mixture of 0.1 parts by mass of Erementis Japan and 48.8 parts by mass of water was used to prepare a primer coating liquid [A-9 liquid].

(Preparation Example 1-10)

-Preparation of primer coating solution (A-10 solution)-

Stirring and dispersing plastic-like spherical hollow particles (2) (acrylonitrile-methacrylonitrile-isobornyl methacrylate copolymer, solid content concentration 33% by mass, volume average particle diameter 3.0 μm, hollow ratio 91%) 3 mass Parts, n-butyl acrylate-methyl methacrylate copolymer (glass transition temperature (Tg)=-62°C, solid content concentration 50% by mass, produced by JSR Corporation) 34.0 parts by mass, surfactant (Dapro W- 77. A mixture of 0.1 parts by mass of Erementis Japan and 62.9 parts by mass of water was used to prepare a primer coating solution [A-10 solution].

(Preparation Example 1-11)

-Preparation of primer coating liquid (A-11 liquid)-

A 2-ethylhexyl acrylate-methyl methacrylate-styrene copolymer (glass transition temperature (Tg)=-65° C., solid content concentration 55.4% by mass, produced by Showa High Molecular Co., Ltd.) was stirred and dispersed at 90.3 Parts by mass, a mixture of 0.1 parts by mass of a surfactant (Dapro W-77, Erementis Japan Co., Ltd.) and 9.6 parts by mass of water was used to prepare a primer coating liquid [A-11 liquid].

(Preparation Example 1-12)

-Preparation of primer coating liquid (A-12 liquid)-

Stir and disperse 23.4 parts by mass of plastic-like spherical hollow particles (1) (acrylonitrile-vinylidene chloride-methyl methacrylate copolymer, solid content concentration 41% by mass, volume average particle diameter 3.6 μm, hollow rate 90%) , 10 parts by mass of styrene-butadiene copolymer latex (glass transition temperature (Tg)=+4° C.), 0.1 parts by mass of surfactant (Dapro W-77, ェレメンティイス Japan Corporation) and 66.5 parts by mass of water The mixture composed of 2 parts was used to prepare a primer coating liquid [A-12 liquid].

(Preparation Example 2-1)

-Preparation of hot-melt substance dispersion liquid [B-1 liquid]-

Using a sand mill, disperse 40.0 parts by mass of 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (melting point (mp)=138°C) , 6.7 parts by mass of polyvinyl alcohol (30% by mass aqueous solution), 0.2 parts by mass of surfactant (Olfine PD-001, produced by Nissin Chemical Industry Co., Ltd.) and 53.1 parts by mass of water, so that the average particle diameter is 1.0 μm , thereby preparing a hot-melt substance dispersion liquid [B-1 liquid].

(Preparation Example 2-2)

-Preparation of hot-melt substance dispersion liquid [B-2 liquid]-

Using a sand mill, disperse 40.0 parts by mass of 2-(2'-hydroxyl-3', 5'-di-tert-butyl)-5-chlorobenzotriazole (melting point (mp)=152°C), 6.7 parts by mass A mixture of polyvinyl alcohol (30% by mass aqueous solution), 0.2 parts by mass of a surfactant (Olfine PD-001, produced by Nissin Chemical Industry Co., Ltd.) and 53.1 parts by mass of water so that the average particle diameter was 1.0 μm was prepared to prepare thermal Melting substance dispersion liquid [B-2 liquid].

(Preparation example 2-3)

-Preparation of hot-melt substance dispersion liquid [B-3 liquid]-

Using a sand mill, disperse 40.0 parts by mass of 2-(2'-hydroxyl-3', 5'-di-tert-amylphenyl)benzotriazole (melting point (mp)=80°C), 6.7 parts by mass of polyethylene A mixture of alcohol (30% by mass aqueous solution), 0.2 parts by mass of surfactant (Olfine PD-001, produced by Nissin Chemical Industry Co., Ltd.) and 53.1 parts by mass of water, so that the average particle size is 1.0 μm, to prepare hot melt Substance dispersion liquid [B-3 liquid].

(preparation example 2-4)

-Preparation of hot-melt substance dispersion liquid [B-4 liquid]-

Using a sand mill, disperse 40.0 parts by mass of benzyl p-hydroxybenzoate (melting point (mp) = 113 to 115° C.), 6.7 parts by mass of polyvinyl alcohol (30 mass % aqueous solution), 0.2 parts by mass of surfactant (Orfin PD -001, manufactured by Nissin Chemical Industry Co., Ltd.) and 53.1 parts by mass of water so that the average particle diameter is 1.0 μm, to prepare a hot-melt material dispersion [B-4 liquid].

(preparation example 2-5)

-Preparation of hot-melt substance dispersion liquid [B-5 liquid]-

Using a sand mill, disperse 40.0 parts by mass of n-propyl p-hydroxybenzoate (melting point (mp) = 99 to 100° C.), 6.7 parts by mass of polyvinyl alcohol (30 mass % aqueous solution), 0.2 parts by mass of surfactant (Olfine PD-001 (manufactured by Nissin Chemical Industry Co., Ltd.) and 53.1 parts by mass of water were mixed so that the average particle diameter was 1.0 μm to prepare a hot-melt material dispersion [B-5 liquid].

(preparation example 2-6)

-Preparation of hot-melt substance dispersion liquid [B-6 liquid]-

Using a sand mill, disperse 40.0 parts by mass of anisoin (melting point (mp) = 99 to 100°C), 6.7 parts by mass of polyvinyl alcohol (30% by mass aqueous solution), and 0.2 parts by mass of a surfactant (Orfin PD-001, Nissin Chemical Industry Co., Ltd.) and 53.1 parts by mass of water so that the average particle diameter is 1.0 μm, thereby preparing a hot-melt material dispersion liquid [B-6 liquid].

(preparation example 2-7)

-Preparation of hot-melt material dispersion liquid [B-7 liquid]-

Using a sand mill, disperse 40.0 parts by mass of 1-dihydroxy-2-phenylnaphthoate (melting point (mp) = 94 to 96°C), 6.7 parts by mass of polyvinyl alcohol (30% by mass aqueous solution), 0.2 parts by mass of surface A mixture of an active agent (Orfin PD-001, manufactured by Nissin Chemical Industry Co., Ltd.) and 53.1 parts by mass of water so that the average particle diameter is 1.0 μm was prepared to prepare a hot-melt material dispersion [B-7 liquid].

(preparation example 2-8)

-Preparation of hot-melt material dispersion [B-8 liquid]-

Using a sand mill, disperse 40.0 parts by mass of 3-hydroxyphenyl benzoate (melting point (mp) = 135 ° C), 6.7 parts by mass of polyvinyl alcohol (30 mass % aqueous solution), 0.2 parts by mass of surfactant (Olfine PD -001, manufactured by Nissin Chemical Industry Co., Ltd.) and 53.1 parts by mass of water so that the average particle diameter is 1.0 μm, to prepare a hot-melt material dispersion [B-8 liquid].

(Preparation Example 3-1)

-Preparation of co-flux dispersion liquid [C-1 liquid]-

Using a sand mill, disperse 40.0 parts by mass of di-p-methylbenzyl oxalate (melting point (mp) = 101° C.), 6.7 parts by mass of polyvinyl alcohol (30 mass % aqueous solution), 0.2 parts by mass of surfactant (Orfin PD- 001, manufactured by Nissin Chemical Industry Co., Ltd.) and 53.1 parts by mass of water so that the average particle diameter is 1.2 μm, thereby preparing a co-flux dispersion liquid [C-1 liquid].

(Preparation Example 3-2)

-Preparation of co-flux dispersion liquid [C-2 liquid]-

Using a sand mill, disperse 40.0 parts by mass of di-p-methylbenzyl oxalate (melting point (mp) = 80 ° C), 6.7 parts by mass of polyvinyl alcohol (30 mass % aqueous solution), 0.2 parts by mass of surfactant (Olfin PD- 001, manufactured by Nissin Chemical Industry Co., Ltd.) and 53.1 parts by mass of water so that the average particle diameter is 1.2 μm, thereby preparing a co-flux dispersion liquid [C-2 liquid].

(Preparation Example 4-1)

-Preparation of Heat Sensitive Adhesive Coating Liquid [D-1 Liquid]-

10 parts by mass of n-butyl acrylate-methyl acrylate copolymer (glass transition temperature (Tg)=-62°C, solid content concentration 50% by mass, produced by JSR Corporation), 6 parts by mass of polymerized rosin latex (softened temperature 145°C, non-volatile content 50%), 37.5 parts by mass of hot-melt material dispersion [B-1 liquid], and 7 mass parts of co-flux dispersion [C-1 liquid] to prepare a heat-sensitive adhesive Coating liquid [D-1 liquid].

(Preparation Example 4-2)

-Preparation of Heat Sensitive Adhesive Coating Liquid [D-2 Liquid]-

Uniformly mixed with 9 parts by mass of 2-ethylhexyl acrylate-methyl methacrylate-styrene copolymer (glass transition temperature (Tg)=-65°C, solid content concentration 55.4 mass%, Showa High Molecule Co., Ltd. product), 6 parts by mass of terpene phenol latex (softening point 150°C, non-volatile content 50%), 37.5 parts by mass of hot-melt material dispersion [B-2 liquid], 7 mass parts of co-flux dispersion [C-2 liquid] to prepare a heat-sensitive adhesive coating liquid [D-2 liquid].

(Preparation Example 4-3)

-Preparation of Heat Sensitive Adhesive Coating Liquid [D-3 Liquid]-

10 parts by mass of n-butyl acrylate-methyl acrylate copolymer (glass transition temperature (Tg)=-62°C, solid content concentration 50% by mass, produced by JSR Corporation), 6 parts by mass of polymerized rosin latex (softened point 145°C, non-volatile content 50%), 19 parts by mass of hot-melt material dispersion [B-1 liquid], 19 mass parts of hot-melt material dispersion [B-2 liquid], 7 mass parts of co-flux dispersion [Liquid C-1] was used to prepare a heat-sensitive adhesive coating liquid [Liquid D-3].

(Preparation Example 4-4)

-Preparation of Heat Sensitive Adhesive Coating Liquid [D-4 Liquid]-

10 parts by mass of 2-ethylhexyl acrylate-n-butyl acrylate-styrene copolymer (glass transition temperature (Tg) = -30°C, solid content concentration 50.0% by mass, produced by Showa High Molecule Co., Ltd. ), 6 parts by mass of terpene phenol latex (softening point 150°C, non-volatile content 50%), 19 parts by mass of hot-melt dispersion [B-2 liquid], 19 parts by mass of hot-melt dispersion [B- 3 liquids] and 7 parts by mass of the eutectic dispersion liquid [C-1 liquid] to prepare a heat-sensitive adhesive coating liquid [D-4 liquid].

(preparation example 4-5)

-Preparation of Heat Sensitive Adhesive Coating Liquid [D-5 Liquid]-

Uniformly mixed with 9 parts by mass of 2-ethylhexyl acrylate-methyl methacrylate-styrene copolymer (glass transition temperature (Tg)=-5°C, solid content concentration 55.4 mass%, Showa High Molecule Co., Ltd. product), 6 parts by mass of polymerized rosin latex (softening point 145°C, non-volatile content 50%), and 37.5 parts by mass of hot-melt material dispersion liquid [B-4 liquid] to prepare a heat-sensitive adhesive coating liquid [D-5 liquid].

(preparation example 4-6)

-Preparation of Heat Sensitive Adhesive Coating Liquid [D-6 Liquid]-

9.4 parts by mass of ethylene-vinyl acetate-acrylic acid copolymer (glass transition temperature (Tg)=-20°C, solid content concentration 53% by mass, manufactured by Sumika Chemtec Co., Ltd.), 6 parts by mass of terpene phenol A heat-sensitive adhesive coating liquid [D-6 liquid] was prepared from a mixture of latex (softening point 150° C., non-volatile content 50%), and 37.5 parts by mass of a hot-melt dispersion liquid [B-5 liquid].

(preparation example 4-7)

-Preparation of Heat Sensitive Adhesive Coating Liquid [D-7 Liquid]-

10 parts by mass of 2-ethylhexyl acrylate-n-butyl acrylate-styrene copolymer (glass transition temperature (Tg) = -30°C, solid content concentration 50.0% by mass, produced by Showa High Molecule Co., Ltd. ), 6 parts by mass of polymerized rosin latex (softening point 145°C, non-volatile content 50%), 19 parts by mass of hot-melt dispersion [B-4 liquid], 19 parts by mass of hot-melt dispersion [B-5 liquid] to prepare a heat-sensitive adhesive coating liquid [D-7 liquid].

(preparation example 4-8)

-Preparation of Heat Sensitive Adhesive Coating Liquid [D-8 Liquid]-

10 parts by mass of n-butyl acrylate-methyl acrylate copolymer (glass transition temperature (Tg)=-62°C, solid content concentration 50% by mass, produced by JSR Corporation), 6 parts by mass of terpene phenol latex ( Softening point 150°C, non-volatile content 50%), 37.5 parts by mass of hot-melt material dispersion liquid [B-6 liquid] to prepare a heat-sensitive adhesive coating liquid [D-8 liquid].

(preparation example 4-9)

-Preparation of Heat Sensitive Adhesive Coating Liquid [D-9 Liquid]-

Uniformly mixed with 9 parts by mass of 2-ethylhexyl acrylate-methyl methacrylate-styrene copolymer (glass transition temperature (Tg)=-65°C, solid content concentration 55.4 mass%, Showa High Molecule Co., Ltd. product), 6 parts by mass of terpene phenol latex (softening point 150°C, non-volatile content 50%), and 37.5 parts by mass of hot-melt material dispersion liquid [B-7 liquid] to prepare a heat-sensitive adhesive coating Liquid [D-9 liquid].

(Preparation Example 4-10)

-Preparation of Heat Sensitive Adhesive Coating Liquid [D-10 Liquid]-

Uniformly mixed with 9 parts by mass of 2-ethylhexyl acrylate-methyl methacrylate-styrene copolymer (glass transition temperature (Tg)=-65°C, solid content concentration 55.4 mass%, Showa High Molecule Co., Ltd. product), 6 parts by mass of terpene phenol latex (softening point 150°C, non-volatile content 50%), and 37.5 parts by mass of hot-melt material dispersion [B-8 liquid] to prepare a heat-sensitive adhesive coating Liquid [D-10 Liquid].

(Preparation Example 4-11)

-Preparation of Heat Sensitive Adhesive Coating Liquid [D-11 Liquid]-

10 parts by mass of 2-ethylhexyl acrylate-n-butyl acrylate-styrene copolymer (glass transition temperature (Tg) = -30°C, solid content concentration 50.0% by mass, produced by Showa High Molecule Co., Ltd. ), 6 parts by mass of terpene phenol latex (softening point 150°C, non-volatile content 50%), 19 parts by mass of hot-melt dispersion [B-7 liquid], 19 parts by mass of hot-melt dispersion [B- 8 liquids] and 7 parts by mass of the eutectic dispersion liquid [C-1 liquid] to prepare a heat-sensitive adhesive coating liquid [D-11 liquid].

(Example 1)

-Preparation of Heat Sensitive Adhesive Material-

On the side that does not have a coating layer in the coated paper (OK Adonis Laf, produced by Oji Paper Co., Ltd.) with a paper weight of 80 g/ ^m as a support, the primer coating liquid [A-1] is applied to dry and adhere The amount is 15g/m ² , dried to form a bottom layer. The heat-sensitive adhesive layer coating liquid [D-1] was coated on the base layer so that the dry adhesion amount was 10 g/m ² and dried to form a heat-sensitive adhesive layer. A heat-sensitive adhesive material was prepared by the above method.

(Example 2)

-Preparation of Heat Sensitive Adhesive Material-

<Formation of Ink Receiving Layer of Thermal Fusion Transfer Recording Paper>

On high-quality paper with a paper weight of 80 g/ ^m2 as a support, aluminum hydroxide particles with a volume average particle size of 0.4 to 0.5 μm as a pigment component and styrene-maleic anhydride copolymer as a binder resin are used Basic salt resin, prepare a coating solution with a filler/binding resin composition ratio of 1/0.2. The coating liquid was uniformly coated using a wire bar to provide an ink image-receiving layer, thereby preparing an ink-receiving sheet for thermal fusion transfer.

Then, on the support surface of the obtained heat-melt transfer recording paper having no ink receiving layer, the primer coating liquid [A-2] was coated so that the dry adhesion amount was 5 g/m ² and dried to form a primer. The heat-sensitive adhesive layer coating liquid [D-2] was coated on the base layer so that the dry adhesion amount was 10 g/m ² and dried to form a heat-sensitive adhesive layer. A heat-sensitive adhesive material was prepared by the above method.

(Example 3)

-Preparation of Heat Sensitive Adhesive Material-

<Formation of thermosensitive recording layer>

-Preparation of non-foaming heat insulating layer forming coating liquid [E liquid]-

Stirring and dispersing consists of 30 parts by mass of fine hollow particle dispersion (copolymer resin mainly composed of vinylidene chloride-acrylonitrile, solid content concentration of 32 mass%, average particle diameter of 3.6 μm, hollowness of 92%), 10 parts by mass of A mixture of styrene-butadiene copolymer latex (glass transition temperature (Tg)=+4° C.), 0.1 parts by mass of a surfactant (Dapro W-77, ェレメンティス Japan Corporation) and 60 parts by mass of water, Thus, a non-foaming heat insulating layer forming coating liquid [E liquid] was prepared.

-Preparation of Chromogenic Agent Dispersion Liquid [F Liquid]-

Stir and disperse a mixture consisting of 20 parts by mass of 3-di-n-butylamino-6-methyl-7-anilinofluorane, 10 parts by mass of polyvinyl alcohol (10 mass % aqueous solution) and 70 parts by mass of water to prepare a Toner dispersion liquid [F liquid].

-Preparation of developer dispersion liquid [G liquid]-

Dispersion using a sand mill consists of 10 parts by mass of 4-isopropoxy-4'-hydroxydiphenyl sulfone, 25 parts by mass of polyvinyl alcohol (10% by mass aqueous solution), 15 parts by mass of calcium carbonate and 50 parts by mass of water The mixtures were made to have an average particle diameter of about 1.5 μm to prepare a developer dispersion liquid [G liquid].

Next, it was mixed and stirred according to the above-mentioned chromogenic agent dispersion liquid [F liquid]: the above-mentioned chromogenic agent dispersion liquid [G liquid]=1:8 (mass ratio), thereby preparing a thermosensitive recording layer coating liquid [H liquid] . On the surface of single-sided coated paper with an average paper weight of 80 g/m ² , apply the above-mentioned non-foaming heat insulating layer forming coating liquid [E liquid] so that the dry thickness is 4 g/m ² , and dry to set a non-foaming heat insulating layer. Foam insulation. On the non-foaming heat insulating layer, the above-mentioned color developing agent dispersion liquid [F liquid] was coated in a mass of 5 g/m ² after drying, and dried to form a thermosensitive recording layer. Thereafter, a super calendering treatment was performed so that the Wang Yan type smoothness was 2000 seconds, thereby preparing a thermosensitive recording paper having a thermosensitive recording layer.

Then, on the support surface of the obtained heat-melt transfer recording paper having no ink-receiving layer, the primer coating liquid [A-3] was coated so that the dry adhesion amount was 4 g/m ² and dried to form a primer. The heat-sensitive adhesive layer coating liquid [D-3] was coated on the base layer so that the dry adhesion amount was 10 g/m ² , and dried to form a heat-sensitive adhesive layer. A heat-sensitive adhesive material was prepared by the above method.

(Example 4)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 3, the primer coating liquid [A-4] was applied so that the dry adhesion amount was 10 g/m ² , dried to form a primer, and the heat-sensitive adhesive layer coating liquid [D-4] was coated on the primer. 3], except that the dry adhesion amount was 15 g/m ² and dried to form a heat-sensitive adhesive layer, a heat-sensitive adhesive material was prepared in the same manner as in Example 3.

(Example 5)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 3, the primer coating liquid [A-5] was applied so that the dry adhesion amount was 5 g/m ² and dried to form a primer. The heat-sensitive adhesive layer coating liquid [D-4] was coated on the base layer so that the dry adhesion amount was 10 g/m ² , and dried to form a heat-sensitive adhesive layer. In the same manner as in Example 3, a heat-sensitive adhesive layer was prepared. material.

(Example 6)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 1, the primer coating liquid [A-6] was applied so that the dry adhesion amount was 5 g/m ² , dried to form a primer, and the heat-sensitive adhesive layer coating liquid [D-6] was coated on the primer. 5], making the dry adhesion amount to 10 g/m ² , and drying to form a heat-sensitive adhesive layer, a heat-sensitive adhesive material was prepared in the same manner as in Example 1.

(Example 7)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 1, the primer coating liquid [A-6] was applied so that the dry adhesion amount was 5 g/m ² , dried to form a primer, and the heat-sensitive adhesive layer coating liquid [D-6] was coated on the primer. 6], making the dry adhesion amount to 10 g/m ² , and drying to form a heat-sensitive adhesive layer, follow the same method as Example 1 to prepare a heat-sensitive adhesive material.

(Embodiment 8)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 1, the primer coating liquid [A-6] was applied so that the dry adhesion amount was 10 g/m ² , dried to form a primer, and the heat-sensitive adhesive layer coating liquid [D-6] was coated on the primer. 3], except that the dry adhesion amount was 10 g/m ² and dried to form a heat-sensitive adhesive layer, a heat-sensitive adhesive material was prepared in the same manner as in Example 1.

(Example 9)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 1, the primer coating liquid [A-7] was applied so that the dry adhesion amount was 5 g/m ² , dried to form a primer, and the heat-sensitive adhesive layer coating liquid [D-7] was coated on the primer. 3], except that the dry adhesion amount was 10 g/m ² and dried to form a heat-sensitive adhesive layer, a heat-sensitive adhesive material was prepared in the same manner as in Example 1.

(Example 10)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 1, the primer coating liquid [A-9] was applied so that the dry adhesion amount was 10 g/m ² , dried to form a primer, and the heat-sensitive adhesive layer coating liquid [D-9] was coated on the primer. 7], so that the dry adhesion amount is 10 g/m ² , and dry to form a heat-sensitive adhesive layer, follow the same method as Example 1 to prepare a heat-sensitive adhesive material.

(Example 11)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 1, the primer coating liquid [A-9] was applied so that the dry adhesion amount was 10 g/m ² , dried to form a primer, and the heat-sensitive adhesive layer coating liquid [D-9] was coated on the primer. 8], so that the dry adhesion amount is 10 g/m ² , and dry to form a heat-sensitive adhesive layer, follow the same method as Example 1 to prepare a heat-sensitive adhesive material.

(Example 12)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 1, the primer coating liquid [A-10] was applied so that the dry adhesion amount was 10 g/m ² , dried to form a primer, and the heat-sensitive adhesive layer coating liquid [D-10] was coated on the primer. 3], except that the dry adhesion amount was 10 g/m ² and dried to form a heat-sensitive adhesive layer, a heat-sensitive adhesive material was prepared in the same manner as in Example 1.

(Example 13)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 1, the primer coating liquid [A-3] was applied so that the dry adhesion amount was 10 g/m ² , dried to form a primer, and the heat-sensitive adhesive layer coating liquid [D-3] was coated on the primer. 9], so that the dry adhesion amount is 10 g/m ² , and dry to form a heat-sensitive adhesive layer, follow the same method as Example 1 to prepare a heat-sensitive adhesive material.

(Example 14)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 1, the primer coating liquid [A-10] was applied so that the dry adhesion amount was 10 g/m ² , dried to form a primer, and the heat-sensitive adhesive layer coating liquid [D-10] was coated on the primer. 10], making the dry adhesion amount to 10 g/m ² , drying to form a heat-sensitive adhesive layer, the same method as in Example 1 was used to prepare a heat-sensitive adhesive material.

(Example 15)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 1, the primer coating liquid [A-3] was applied so that the dry adhesion amount was 10 g/m ² , dried to form a primer, and the heat-sensitive adhesive layer coating liquid [D-3] was coated on the primer. 11], so that the dry adhesion amount is 10 g/m ² , and dry to form a heat-sensitive adhesive layer, follow the same method as Example 1 to prepare a heat-sensitive adhesive material.

(Example 16)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 3, a protective layer coating liquid of the following composition was applied on the thermosensitive recording layer so that the dry adhesion mass was 3 g/m ² , and calendering treatment was performed so that the dry smoothness of the protective layer was 5000 Seconds, according to the same method as in Example 3, a heat-sensitive adhesive material was prepared.

<Preparation of protective layer coating solution>

40 parts by mass of aluminum hydroxide dispersion (50% by mass of solid content), 6 parts by mass of zinc stearate dispersion (30% by mass of solid content), and 1 part of dioctyl succinate aqueous solution (5% by mass of solid content) were mixed. , 200 parts by mass of PVA having a diacetone group (the diacetone monomer unit content is 4 mass %, the degree of polymerization is 1600, the degree of saponification is 98%, produced by Shin-Etsu Chemical Co., Ltd.) 10 mass % aqueous solution, 40 mass parts of adipyl A hydrazine (crosslinking agent) aqueous solution (solid content: 10% by mass) and a mixture consisting of 43 parts by mass were used to prepare a protective layer coating liquid.

(comparative example 1)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 1, on the surface of the support without the coating layer, apply the heat-sensitive adhesive layer coating liquid [D-1] so that the dry adhesion amount is 10 g/m ² , dry, and form a heat-sensitive adhesive A heat-sensitive adhesive material was prepared in the same manner as in Example 1 except for the layer.

(comparative example 2)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 1, the primer coating liquid [A-8] was applied so that the dry adhesion amount was 10 g/m ² , dried to form a primer, and the heat-sensitive adhesive layer coating liquid [D-8] was coated on the primer. 1], so that the dry adhesion amount was 10 g/m ² , and dried to form a heat-sensitive adhesive layer, a heat-sensitive adhesive material was prepared in the same manner as in Example 1.

(comparative example 3)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 1, the primer coating liquid [A-11] was applied so that the dry adhesion amount was 15 g/m ² , dried to form a primer, and the heat-sensitive adhesive layer coating liquid [D-11] was coated on the primer. 1], so that the dry adhesion amount was 10 g/m ² , and dried to form a heat-sensitive adhesive layer, a heat-sensitive adhesive material was prepared in the same manner as in Example 1.

(comparative example 4)

-Preparation of Heat Sensitive Adhesive Material-

Except in Example 1, the primer coating liquid [A-12] was applied so that the dry adhesion amount was 4 g/m ² , dried to form a primer, and the heat-sensitive adhesive layer coating liquid [D-12] was coated on the primer. 3], except that the dry adhesion amount was 15 g/m ² and dried to form a heat-sensitive adhesive layer, a heat-sensitive adhesive material was prepared in the same manner as in Example 1.

Table 1 Support (paper weight) Recording layer (paper weight) Adhesive bottom layer heat sensitive adhesive layer Coating solution Adhesion amount Coating solution Adhesion amount Example 1 Single-sided coated paper (80g/m ² ) none A-1 15g/ ^m2 D-1 10g/ ^m2 Example 2 Single-sided coated paper (80g/m ² ) Fusion transfer layer (45g/m ² ) A-2 5g/ ^m2 D-2 10g/ ^m2 Example 3 Single-sided coated paper (80g/m ² ) Thermosensitive recording layer (9g/m ² ) A-3 4g/ ^m2 D-3 10g/ ^m2 Example 4 Single-sided coated paper (80g/m ² ) Thermosensitive recording layer (9g/m ² ) A-4 10g/ ^m2 D-3 15g/ ^m2 Example 5 Single-sided coated paper (80g/m ² ) Thermosensitive recording layer (9g/m ² ) A-5 5g/ ^m2 D-4 10g/ ^m2 Example 6 Single-sided coated paper (80g/m ² ) none A-6 5g/ ^m2 D-5 10g/ ^m2 Example 7 Single-sided coated paper (80g/m ² ) none A-6 5g/ ^m2 D-6 10g/ ^m2 Example 8 Single-sided coated paper (80g/m ² ) none A-6 10g/ ^m2 D-3 10g/ ^m2 Example 9 Single-sided coated paper (80g/m ² ) none A-7 5g/ ^m2 D-3 10g/ ^m2 Example 10 Single-sided coated paper (80g/m ² ) none A-9 10g/ ^m2 D-7 10g/ ^m2 Example 11 Single-sided coated paper (80g/m ² ) none A-9 10g/ ^m2 D-8 10g/ ^m2 Example 12 Single-sided coated paper (80g/m ² ) none A-10 10g/ ^m2 D-3 10g/ ^m2 Example 13 Single-sided coated paper (80g/m ² ) none A-3 10g/ ^m2 D-9 10g/ ^m2 Example 14 Single-sided coated paper (80g/m ² ) none A-10 10g/ ^m2 D-10 10g/ ^m2 Example 15 Single-sided coated paper (80g/m ² ) none A-3 10g/ ^m2 D-11 10g/ ^m2 Example 16 Single-sided coated paper (80g/m ² ) thermosensitive recording layer A-3 4g/ ^m2 D-3 10g/ ^m2 Comparative example 1 Single-sided coated paper (80g/m ² ) none none none D-1 10g/ ^m2 Comparative example 2 Single-sided coated paper (80g/m ² ) none A-8 10g/ ^m2 D-1 10g/ ^m2 Comparative example 3 Single-sided coated paper (80g/m ² ) none A-11 15g/ ^m2 D-1 10g/ ^m2 Comparative example 4 Single-sided coated paper (80g/m ² ) none A-12 4g/ ^m2 D-3 15g/ ^m2

Then, with respect to the obtained Examples 1 to 16 and Comparative Examples 1 to 4, the immediate adhesive force, the temporal adhesive force and cohesiveness were evaluated as follows. The results are shown in Table 3, Table 4 and Table 5.

<Measurement of Immediate Adhesion>

Each heat-sensitive adhesive material was cut into a rectangle of 25mm×150mm, and a heat-sensitive printing device (Okura Electric Co., Ltd., TH-PMD) was used. The head conditions: each energy was 0.35mJ/dot, 0.45mJ/dot, Under the conditions of 0.5mJ/dot, printing speed: 4ms/line, and plate pressure: 6kgf/line, heat-activate heat-sensitive adhesive materials. Then, on the adherend (polyolefin wrapping paper and corrugated cardboard), stick it in the longitudinal direction by a rubber roller pressurized to 2kg. stripped under conditions.

The adhesive force at this time was measured by a force gauge (MODEL DPS-5, manufactured by IMADA), and the data were read at intervals of 0.1 second, and expressed as an average value. In addition, the unit is gf/25mm. This test was implemented in the environment of normal temperature environment (23 degreeC, 65%).

<Measurement of adhesive force over time>

Cut each heat-sensitive adhesive material into a rectangle of 25mm×150mm, use a heat-sensitive printing device (Okura Electric Co., Ltd., TH-PMD), and probe conditions: each energy is 0.5mJ/dot, printing speed: 4ms/ Row, plate pressure: Under the condition of 6kgf/row, heat-activate the heat-sensitive adhesive material. Then, on the adherend (polyolefin wrapping paper and corrugated cardboard), stick it in the longitudinal direction by a rubber roller pressurized to 2 kg. stripped under conditions.

The adhesive force at this time was measured with a force gauge (MODEL DPS-5, manufactured by IMADA), and the data were read at intervals of 0.1 seconds, and expressed as an average value. In addition, the unit is gf/25mm. This test was implemented in the environment of normal temperature environment (23 degreeC, 65%).

[Evaluation criteria for PO wrapping paper adhesion]

◎: 1500gf/25mm or more than 1500gf/25mm

○: 1000gf/25mm or more than 1000gf/25mm, less than 1500gf/25mm

△: 700gf/25mm or more than 700gf/25mm, less than 1000gf/25mm

X: Less than 700gf/25mm

[Evaluation criteria for corrugated cardboard adhesion]

◎: 700gf/25mm or above 700gf/25mm

○: 500gf/25mm or more than 500gf/25mm, less than 700gf/25mm

△: 300gf/25mm or more than 300gf/25mm, less than 500gf/25mm

X: Less than 300gf/25mm

<Adhesion evaluation>

In each heat-sensitive adhesive material, one side of the heat-sensitive adhesive layer was brought into contact with the opposite side, and left to stand for 24 hours under a pressure of 200 gf/cm ² and drying at 50°C. Then, the samples left to stand at room temperature were peeled off, and the adhesiveness at that time was evaluated based on the ranks and evaluation criteria shown in Table 2 below.

Table 2 grade Adhesion stripped sound dot transfer peel off 10 Self-respect 9 There are several no sound 8 have There are several 7 have 6 a part of it 5 30～50% 4 50%～all 3 a part of it 2 30～50% 1 50%～all

◎: Level 10

○: Level 8~9

△: Level 6~7

×: Level 5 or below

table 3 Adhesive properties (gf/25mm) PO wrapping paper ①0.30mJ/point (immediately) evaluate ②0.40mJ/point (immediately) evaluate ③0.50mJ/point (immediately) evaluate ④ After a period of time (after 1 week) evaluate Example 1 960 △ 1280 ○ 1440 ○ 1535 ◎ Example 2 1420 ○ 1580 ◎ 1570 ◎ 1490 ○ Example 3 1650 ◎ 1630 ◎ 1640 ◎ 1670 ◎ Example 4 1220 ○ 1580 ◎ 1570 ◎ 1465 ○ Example 5 1030 ○ 1350 ◎ 1600 ◎ 1390 ○ Example 6 1290 ○ 1650 ◎ 1680 ◎ 1760 ◎ Example 7 1370 ○ 1650 ◎ 1680 ◎ 1725 ◎ Example 8 1400 ○ 1750 ◎ 1760 ◎ 1830 ◎ Example 9 930 △ 960 △ 945 △ 1070 △ Example 10 760 △ 770 △ 745 △ 845 △ Example 11 800 △ 825 △ 810 △ 890 △ Example 12 1050 ○ 1560 ◎ 1610 ◎ 1885 ◎ Example 13 1610 ◎ 1575 ◎ 1590 ◎ 1680 ◎ Example 14 890 △ 1380 ○ 1615 ◎ 1925 ◎ Example 15 1585 ◎ 1605 ◎ 1590 ◎ 1655 ◎ Example 16 1590 ◎ 1700 ◎ 1680 ◎ 1680 ◎ Comparative example 1 500 x 640 x 720 △ 715 △ Comparative example 2 600 x 710 △ 725 △ 700 △ Comparative example 3 850 △ 1210 ○ 1450 ○ 1620 ◎ Comparative example 4 650 x 720 △ 715 △ 745 △

Table 4 Adhesive properties (gf/25mm) corrugated cardboard ①0.30mJ/point (immediately) evaluate ②0.40mJ/point (immediately) evaluate ③0.50mJ/point (immediately) evaluate ④ After a period of time (after 1 week) evaluate Example 1 400 △ 520 ○ 610 ○ 680 ○ Example 2 620 ○ 630 ○ 610 ○ 450 △ Example 3 710 ◎ 690 ○ 700 ◎ 640 ○ Example 4 570 ○ 710 ◎ 690 ○ 415 △ Example 5 500 ○ 615 ○ 720 ◎ 400 △ Example 6 650 ○ 730 ◎ 735 ◎ 810 ◎ Example 7 615 ○ 660 ○ 650 ○ 690 ○ Example 8 630 ○ 680 ○ 685 ○ 745 ◎ Example 9 430 △ 415 △ 420 △ 395 △ Example 10 380 △ 395 △ 370 △ 350 △ Example 11 415 △ 405 △ 420 △ 395 △ Example 12 525 ○ 730 ◎ 715 ◎ 855 ◎ Example 13 680 ○ 665 ○ 670 ○ 705 ◎ Example 14 435 △ 650 ○ 730 ◎ 790 ◎ Example 15 640 ○ 655 ○ 645 ○ 640 ○ Example 16 750 ◎ 740 ◎ 740 ◎ 670 ○ Comparative example 1 200 x 250 x 280 x 90 x Comparative example 2 230 x 285 x 290 x 95 x Comparative example 3 350 △ 480 △ 580 ○ 610 ○ Comparative example 4 200 x 290 x 295 x 150 x

table 5 Adhesion (grade) evaluate Example 1 9 ○ Example 2 10 ◎ Example 3 10 ◎ Example 4 10 ◎ Example 5 10 ◎ Example 6 9 ○ Example 7 10 ◎ Example 8 9 ○ Example 9 10 ◎ Example 10 10 ◎ Example 11 10 ◎ Example 12 8 ○ Example 13 10 ◎ Example 14 9 ○ Example 15 10 ◎ Example 16 10 ◎ Comparative example 1 10 ◎ Comparative example 2 10 ◎ Comparative example 3 2 x Comparative example 4 10 ◎

From the results in Tables 3 to 5, it can be confirmed that Comparative Example 1 without a primer layer, Comparative Example 2 in which the glass transition temperature of the thermoplastic resin in the primer layer is 0°C, and the comparison in which the glass transition temperature of the thermoplastic resin in the primer layer is +4°C In Example 4, the adhesive properties of either one deteriorated, especially the adhesive properties over time. In addition, it was confirmed that Comparative Example 3, in which the primer layer did not contain a filler, deteriorated in blocking resistance.

In contrast, Examples 1 to 16 were excellent in adhesive properties, did not decrease in adhesive strength over time, and had good blocking resistance. It can be judged that in Example 16, since the protective layer contained polyvinyl alcohol having a reactive carbonyl group and a hydrazide compound, the blocking resistance was improved.

(Example 17)

-Preparation of Dispersion A-

Uniformly mix 100 parts by mass of 2-(3'-tert-butyl-5'-methyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 50 parts by mass of 10% polyvinyl alcohol solution, 200 parts by mass water, which was pulverized using a ball mill so that the average particle diameter was 1.0 μm, thereby preparing a dispersion liquid A.

-Preparation of Dispersion B-

Uniformly mix 100 parts by mass of bis(p-methylbenzyl) oxalate, 50 parts by mass of 10% polyvinyl alcohol solution, and 200 parts by mass of water, and pulverize them with a ball mill so that the average particle size is 1.0 μm, thereby preparing a dispersion b.

-Preparation of Coating Liquid C for Heat-Sensitive Adhesive Layer-

100 parts by mass of thermoplastic resin emulsion AP5570 (manufactured by Showa High Polymer Co., Ltd., solid content 55% by mass, glass transition temperature -65° C.), 70 parts by mass of adhesive agent latex E100 (manufactured by Arakawa Chemical Co., Ltd., solid content 50%, softening point 145° C.), 540 parts by mass of dispersion A, 150 parts by mass of dispersion B, and 130 parts by mass of water were thoroughly stirred and mixed to prepare heat-sensitive adhesive layer coating liquid C.

-Preparation of primer coating solution D-

According to 100 parts by mass of hollow particle latex ロ-ペイク HP-91 (produced by ロ-ム & ハ-ス company, hollow rate 50%, solid content 27.5 mass %), 220 parts by mass of polymer resin latex AD83 (produced by Showa Polymer Co., Ltd. , main component ethylene vinyl acetate, solid content 56% by mass, glass transition temperature -2° C.), 440 mass parts of water, fully stirred and mixed to prepare the bottom layer coating liquid D. At this time, the ratio of the polymer resin to the underlying hollow particles was 22.2% by mass.

-Preparation of Heat Sensitive Adhesive Material E-

On the surface opposite to the thermosensitive recording layer of thermal head type 120LCS-0 (Support: Yupo Synthetic Paper Film from Oji Oil Chemicals Co., Ltd.) produced by Riko Co., Ltd., use a wire bar to coat the undercoating liquid D so that after drying After drying, the heat-sensitive adhesive layer coating solution C was applied so that the thickness after drying was 15.0 μm, and dried to prepare a heat-sensitive adhesive material E with a total thickness of 35.0 μm.

(Example 18)

Except in Example 17, the polymer resin AD83 (manufactured by Showa High Molecular Co., Ltd., main component ethylene vinyl acetate, solid content 56% by mass, glass transition temperature -2°C) used in the base layer was changed to FREX751 (manufactured by Sumitomo Chemical Co., Ltd., solid content 50% by mass, glass transition temperature -15° C.), the heat-sensitive adhesive material of Example 18 was prepared in the same manner as in Example 17. At this time, the ratio of the polymer resin to the underlying hollow particles was 22.2% by mass.

(Example 19)

The heat-sensitive adhesive material of Example 19 was prepared in the same manner as in Example 18, except that in Example 18, the thickness of the underlayer was 9.0 μm, the thickness of the heat-sensitive adhesive layer was 6.0 μm, and the total thickness was 15.0 μm. At this time, the ratio of the polymer resin to the underlying hollow particles was 22.2% by mass.

(Example 20)

The heat-sensitive adhesive material of Example 20 was prepared in the same manner as in Example 18, except that in Example 18, the thickness of the underlayer was 13.0 μm, the thickness of the heat-sensitive adhesive layer was 7.0 μm, and the total thickness was 20.0 μm. At this time, the ratio of the polymer resin to the underlying hollow particles was 22.2% by mass.

(Example 21)

The heat-sensitive adhesive material of Example 21 was prepared in the same manner as in Example 18, except that in Example 18, the thickness of the underlayer was 21.0 μm, the thickness of the heat-sensitive adhesive layer was 7.0 μm, and the total thickness was 28.0 μm. At this time, the ratio of the polymer resin to the underlying hollow particles was 22.2% by mass.

(Example 22)

Except in Example 21, the hollow particle latex ロ-ペィク HP-91 (produced by ロ-ム & ハ-ス company, hollow rate 50%, solid content 27.5% by mass) of the bottom layer was changed to R300 (produced by Matsumoto Yushi Co., Ltd., The heat-sensitive adhesive material of Preparation Example 22 was prepared in the same manner as in Example 21 except that the hollow rate was 90% and the solid content was 33% by mass. At this time, the ratio of the polymer resin to the underlying hollow particles was 22.2% by mass.

(Example 23)

-Preparation of Primer Coating Solution F-

According to 100 parts by mass of R300 (produced by Matsumoto Yushi Co., Ltd., hollow rate 90%, solid content 33 mass %), 230 parts by mass of polymer resin latex FREX751 (produced by Sumitomo Chemical Co., Ltd., main component ethylene vinyl acetate, solid content 50 mass parts) %, glass transition temperature -15°C), the ratio of 410 parts by mass of water, fully stirred and mixed to prepare the bottom layer coating liquid F. At this time, the ratio of the polymer resin to the underlying hollow particles was 28.6% by mass.

The heat-sensitive adhesive material of Example 23 was prepared in the same manner as in Example 22, except that in Example 22, the primer coating liquid was replaced with the primer coating liquid F.

(Example 24)

-Preparation of Primer Coating Solution G-

According to 100 parts by mass of R300 (produced by Matsumoto Yushi Co., Ltd., hollow rate 90%, solid content 33 mass %), 130 parts by mass of polymer resin latex FREX751 (produced by Sumitomo Chemical Co., Ltd., main component ethylene vinyl acetate, solid content 50 mass parts) %, glass transition temperature -15°C), the ratio of 260 parts by mass of water, fully stirred and mixed to prepare the bottom layer coating liquid G. At this time, the ratio of the polymer resin to the underlying hollow particles was 50.0% by mass.

The heat-sensitive adhesive material of Example 24 was prepared in the same manner as in Example 22, except that in Example 22, the primer coating liquid was replaced with the primer coating liquid G.

(Example 25)

-Preparation of Primer Coating Solution H-

According to 100 parts by mass of R300 (produced by Matsumoto Yushi Co., Ltd., hollow rate 90%, solid content 33 mass %), 60 parts by mass of polymer resin latex FREX751 (produced by Sumitomo Chemical Co., Ltd., main component ethylene vinyl acetate, solid content 50 mass parts) %, glass transition temperature-15°C), the ratio of 155 parts by mass of water, fully stirred and mixed to prepare the bottom layer coating liquid H. At this time, the ratio of the polymer resin to the bottom layer hollow particles was 110.0% by mass.

The heat-sensitive adhesive material of Example 25 was prepared in the same manner as in Example 22, except that in Example 22, the primer coating liquid was replaced with the primer coating liquid H.

(Example 26)

-Preparation of Primer Coating Solution F-

According to 100 parts by mass of hollow particles R300 (produced by Matsumoto Yushi Co., Ltd., hollow rate 90%, solid content 33 mass %), 120 parts by mass of polymer resin latex AP5570 (produced by Showa Polymer Co., Ltd., solid content 55 mass %), glass transition temperature -65° C.), 270 parts by mass of water, and fully stirred and mixed to prepare the bottom layer coating solution I. At this time, the ratio of the polymer resin to the underlying hollow particles was 50.0% by mass.

The heat-sensitive adhesive material of Example 26 was prepared in the same manner as in Example 24, except that in Example 24, the primer coating liquid was replaced with the primer coating liquid I.

(Example 27)

-Preparation of Primer Coating Liquid J-

According to 100 parts by mass of hollow particles R300 (produced by Matsumoto Yushi Co., Ltd., hollow rate 90%, solid content 33 mass %), 120 parts by mass of polymer resin latex AP5570 (produced by Showa Polymer Co., Ltd., solid content 55 mass %), glass transition temperature -65°C), 160 parts by mass of acrylic-siloxane resin latex US224 (manufactured by Toagosei Co., Ltd., solid content 40% by mass, glass transition temperature 10°C), 440 parts by mass of water, fully stirred and mixed to prepare a primer Cloth J. At this time, the ratio of the polymer resin to the underlying hollow particles was 50.0% by mass.

The heat-sensitive adhesive material of Example 27 was prepared in the same manner as in Example 26, except that in Example 26, the primer coating liquid was replaced with the primer coating liquid J.

(comparative example 5)

-Preparation of Primer Coating Liquid K-

According to 100 parts by mass of hollow particle latex ロ-ペイクHP-91 (produced by ロ-ム&ハ-ス company, hollow rate 50%, solid content 27.5 mass %), 410 parts by mass of polyvinyl alcohol aqueous solution (produced by Kuraray Co., Ltd., solid Components 30% by mass, glass transition temperature 100°C or higher), and 240 parts by mass of water were thoroughly stirred and mixed to prepare primer coating solution K.

The heat-sensitive adhesive material of Comparative Example 5 was prepared in the same manner as in Example 17 except that in Example 17, the primer coating liquid was replaced with primer coating liquid K.

(comparative example 6)

Except in Example 17, the hollow particle latex ロ-ペイク HP-91 (produced by ロ-ム & ハ-ス Co., Ltd., hollow rate 50%, solid content 27.5% by mass) of the primer coating liquid was changed to Almatex SPMM-47BF (Mitsui Chemicals Co., Ltd. product, hollow rate 0%, solid content 47.5 mass %), in the same manner as in Example 17, the heat-sensitive adhesive material of Comparative Example 6 was prepared.

(comparative example 7)

In Example 17, the heat-sensitive adhesive material of Comparative Example 7 was obtained in the same manner as in Example 17, except that no primer layer was provided.

With respect to each obtained heat-sensitive adhesive material, each characteristic was evaluated by the following method. The results are shown in Table 6, Table 7 and Table 8.

<Heat Activation Conditions>

Prepare the heat-sensitive adhesive material with a width of 4 cm and a length of 10 cm. The thermal head (manufactured by TEC Corporation, TH-0976SP) is 8 points/mm, the resistance is 500 Ω, and the activation energy is 0.30 mJ under full-point energization. /dot, 0.45mJ/dot, 0.60mJ/dot, printing speed 100mm/second, and plate pressure 6kgf/line. All the tests here were carried out under the environmental conditions of temperature of 22° C. and 65% RH.

<Observation of thermal shrinkage of heat-sensitive adhesive labels>

The heat-induced shrinkage of the thermosensitive adhesive labels activated by the above-mentioned heat was observed visually, and evaluated by the following rating index.

[Grade Index]

○: Heat shrinkage of the label was not observed at all

△: Heat shrinkage of the label is only occasionally found

×: Heat shrinkage of the label is remarkable

<Adhesion measurement>

Attach the activated surface of the activated heat-sensitive adhesive material label to the adherend along the length direction through a rubber roller pressurized to 2kg. After 2 minutes, under the conditions of a peeling angle of 180° and a peeling speed of 300mm/min Perform stripping. The average resistance value of the adhesive force at this time is displayed by numerical value. In addition, the unit is gf/40mm. Here, all the tests were carried out under the environmental conditions of temperature of 22° C. and 65% RH.

[Evaluation criteria for PO wrapping paper adhesion]

◎: 1500gf/40mm or more than 1500gf/40mm

○: 1000gf/40mm or more than 1000gf/40mm, less than 1500gf/40mm

△: 700gf/40mm or more than 700gf/40mm, less than 1000gf/40mm

X: Less than 700gf/40mm

[Evaluation criteria for corrugated cardboard adhesion]

◎: 700gf/40mm or above 700gf/40mm

○: 500gf/40mm or more than 500gf/40mm, less than 700gf/40mm

△: 300gf/40mm or more than 300gf/40mm, less than 500gf/40mm

X: Less than 300gf/40mm

<paste residue>

By the above adhesive force measurement, when the peeled sticker was observed visually, the paste remaining on the corrugated cardboard was evaluated by the following grade index.

○: No trace of paste residue was found at all

△: Occasionally found traces of paste residue

×: Significant traces of paste residue

Table 6 Adhesive properties (gf/40mm) PO wrapping paper 0.30mJ/point evaluate 0.45mJ/point evaluate 0.60mJ/point evaluate Example 17 660 x 980 △ 1160 ○ Example 18 920 △ 1050 ○ 1100 ○ Example 19 1050 ○ 1100 ○ 1390 ○ Example 20 1100 ○ 1220 ○ 1380 ○ Example 21 1490 ○ 1880 ◎ 2330 ◎ Example 22 1980 ◎ 2360 ◎ 2450 ◎ Example 23 2030 ◎ 2440 ◎ 2270 ◎ Example 24 1770 ◎ 2010 ◎ 2400 ◎ Example 25 1680 ◎ 1940 ◎ 2220 ◎ Example 26 2380 ◎ 2650 ◎ 2600 ◎ Example 27 2240 ◎ 2410 ◎ 2440 ◎ Comparative Example 5 110 x 260 x 290 x Comparative Example 6 320 x 510 x 880 △ Comparative Example 7 50 x 220 x 340 x

Table 7 Adhesive properties (gf/40mm) corrugated cardboard 0.30mJ/point evaluate 0.45mJ/point evaluate 0.60mJ/point evaluate Example 17 160 x 400 △ 520 ○ Example 18 250 x 520 ○ 600 ○ Example 19 430 △ 600 ○ 730 ◎ Example 20 580 ○ 770 ◎ 990 ◎ Example 21 740 ◎ 1240 ◎ 1640 ◎ Example 22 1320 ◎ 1790 ◎ 1820 ◎ Example 23 1350 ◎ 1840 ◎ 1690 ◎ Example 24 1100 ◎ 1330 ◎ 1730 ◎ Example 25 940 ◎ 1240 ◎ 1700 ◎ Example 26 1720 ◎ 1810 ◎ 1750 ◎ Example 27 1690 ◎ 1730 ◎ 1700 ◎ Comparative Example 5 10 x 45 x 140 x Comparative example 6 120 x 155 x 460 △ Comparative Example 7 6 x twenty two x 75 x

Table 8 Activation energy 0.30mJ/point Activation energy 0.45mJ/point Activation energy 0.60mJ/point film shrink paste residue film shrink paste residue film shrink paste residue Example 17 ○ △ △ ○ x ○ Example 18 ○ △ △ ○ x ○ Example 19 ○ ○ △ ○ x ○ Example 20 ○ ○ △ ○ x ○ Example 21 ○ ○ △ ○ x ○ Example 22 ○ ○ ○ ○ x ○ Example 23 ○ ○ ○ ○ △ ○ Example 24 ○ ○ ○ ○ ○ ○ Example 25 ○ ○ ○ ○ ○ ○ Example 26 ○ ○ ○ ○ ○ ○ Example 27 ○ ○ ○ ○ ○ ○ Comparative Example 5 ○ x △ x x △ Comparative example 6 x △ x △ x ○ Comparative Example 7 x x x x x x

The result of table 6, table 7 and table 8 is arranged to find that the glass transition temperature of the thermoplastic resin in the bottom layer in comparative example 5 is 100 ℃, which is too high, and the hollow filler in the bottom layer in comparative example 6 has a hollow rate of 0% (without Hollow), Comparative Example 7, since no bottom layer was provided, compared with Examples, any kind of adhesiveness deteriorated.

The evaluation of 0.30mJ/point of embodiment 17 in table 6, the evaluation of 0.30mJ/point of embodiment 17 in table 7, the evaluation of 0.30mJ/point of embodiment 18 in table 7 are all bad, this is Since the heating energy of the thermal head is not optimized, it is clearly known from the results that the heating energy of the thermal head is 0.45 mJ/point and 0.60 mJ/point.

In addition, the film shrinkage evaluation of 0.60mJ/point of Examples 17-22 in Table 8 deteriorated because the heating energy of the thermal head was not optimized, and the heating energy of the thermal head was 0.45mJ/point and 0.60 The results in mJ/point are clearly known.

Therefore, the heat-sensitive adhesive materials of Examples 17 to 27 varied somewhat depending on the conditions of the heating method (activation method). However, it can be confirmed that the heat-sensitive adhesive materials of Examples 17 to 27, when evaluated using approximately optimal heating conditions, that is, the heating energy of the thermal head at 0.45 mJ/point, compared with Comparative Examples 5 to 7, even when synthesized When paper is used as a support, film shrinkage and paste residue do not occur, and it has excellent adhesion to rough adherends such as corrugated cardboard and polyolefin packaging paper.

(Example 2-1)

(1) Preparation of dye dispersion

Dispersion of a composition consisting of 20 parts by mass of 3-dibutylamino-6-methyl-N-7-anilinofluorane, 20 parts by mass of a 10% by mass aqueous solution of polyvinyl alcohol (PVA), and 60 parts by mass of water , so that the average particle size is 0.5 μm.

(2) Preparation of developer

Use a ball mill to disperse 20 parts by mass of 4-isopropoxy-4'-hydroxyl diphenylsulfone, bis(p-methylbenzyl) oxalate, 10 parts by mass of calcium carbonate, and 30 parts by mass of polyvinyl alcohol (PVA) 10% by mass of aqueous solution and 30 parts by mass of water, so that the average particle diameter is 0.5 μm.

(3) Preparation of thermosensitive recording layer coating solution

Mix by 20 mass parts of A liquid, 60 mass parts of B liquid, 30 mass parts of carboxy-denatured PVA (solid content 10 mass %, KL-318, Co., Ltd. kuraray product), 1 mass part of dioctyl thiosuccinate (solid 5% by mass of the above components) to prepare a thermosensitive recording layer coating liquid.

(4) Preparation of protective layer coating solution

Mix by 40 mass parts aluminum hydroxide dispersion liquid (solid content 50 mass %), 6 mass parts zinc stearate dispersion liquid (solid content 30 mass %), 1 mass part dioctyl succinate (solid content 5 mass %) %), 200 parts by mass of PVA having a diacetone group (the diacetone monomer unit content is 4 mass%, the degree of polymerization is 1600, and the degree of saponification is 98%, produced by Shin-Etsu Chemical Co., Ltd.) 10 mass% aqueous solution, 10 mass% A protective layer coating solution was prepared from a composition composed of an aqueous solution of adipic acid hydrazide (crosslinking agent) (solid content: 10% by mass) and 43 parts by mass of water.

(5) Coating of thermosensitive recording layer and protective layer

The thermosensitive recording layer coating solution was coated on a support (high-quality paper with a paper weight of 60 g/m ² ) so that the dry adhesion weight of the dye was 0.6 g/m ² , and dried to form a thermosensitive recording layer. Then, a protective layer coating liquid was coated thereon so that the dry adhesion weight was 3 g/m ² , and calendering was performed after drying so that the smoothness of the protective layer was 5000 seconds.

(6) Preparation of hot-melt material dispersion

Use a ball mill to uniformly mix 100 parts by mass of 2-(3'-tert-butyl-5'-methyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 50 parts by mass of methylcellulose 10% dissolved liquid, 200 parts by mass of water, and dispersed so that the average particle diameter is 1.0 μm.

(7) Preparation of heat-sensitive adhesive liquid

100 parts by mass of thermoplastic resin latex AP5570 (manufactured by Showa High Polymer Co., Ltd., solid content 55 mass%, glass transition temperature -65° C.), 70 parts by mass of adhesion imparting agent latex E100 (main component of terpene alcohol, produced by Arakawa Chemical Co., Ltd. , solid content 50%, softening point 145° C.), 540 parts by mass of hot-melt material dispersion, and 130 parts by mass of water were fully stirred and mixed to prepare a heat-sensitive adhesive solution.

(8) Coating of heat-sensitive adhesive liquid

The heat-sensitive adhesive material of the present invention was prepared by coating on the opposite side of the heat-sensitive recording layer of the above (5) so that the dry adhesion amount was 15 g/m ² and drying.

(Example 2-2)

Except in the (7) heat-sensitive adhesive liquid of embodiment 2-1, according to the drying ratio relative to thermoplastic resin latex AP5570 is 12%, add the PVA (diacetone monomer unit content is 4 mass) that has diacetone group %, the degree of polymerization is 1600, the degree of saponification is 98%, and Shin-Etsu Chemical Co., Ltd.) 10% by mass aqueous solution, the heat-sensitive adhesive material of the present invention was prepared in the same manner as in Example 2-1.

(Example 2-3)

In addition to (7) heat-sensitive adhesive solution in Example 2-1, according to the drying ratio relative to the thermoplastic resin latex AP5570 is 1% by mass, PVA with diacetone group (diacetone monomer unit content is 4 % by mass, the degree of polymerization is 1600, the degree of saponification is 98%, Shin-Etsu Chemical Co., Ltd.) 1 mass% aqueous solution, the heat-sensitive adhesive material of the present invention was prepared in the same manner as in Example 2-1.

(Example 2-4)

In addition to the 10% by mass solution of methylcellulose used in (6) hot-melt dispersion in Example 2-1, PVA having a diacetone group was used at a dry ratio of 2% to the thermoplastic resin latex AP5570 (Diacetone monomer unit content is 4% by mass, degree of polymerization is 1600, degree of saponification is 98%, manufactured by Shin-Etsu Chemical Co., Ltd.) 10% by mass of aqueous solution is replaced, and the heat-sensitive compound of the present invention is prepared in the same manner as in Example 2-1. Adhesive material.

(Example 2-5)

In addition to the heat-sensitive adhesive solution of Examples 2-4, according to the drying ratio relative to the thermoplastic resin latex AP5570 is 10%, adding PVA with diacetone groups (diacetone monomer unit content is 4% by mass, polymerized The heat-sensitive adhesive material of the present invention was prepared in the same manner as in Example 2-4 except that the degree of saponification was 1600, the degree of saponification was 98%, and a 10% aqueous solution produced by Shin-Etsu Chemical Co., Ltd. was produced.

(Example 2-6)

In addition to the heat-sensitive adhesive liquids of Examples 2-4, for PVA having diacetone groups (the diacetone monomer unit content is 4% by mass, the degree of polymerization is 1600, and the degree of saponification is 98%, Shin-Etsu Chemical Co., Ltd. Co., Ltd.) except that a 10% aqueous solution of adipic acid hydrazide (crosslinking agent) was used at a dry ratio of 10%, the heat-sensitive adhesive material of the present invention was prepared in the same manner as in Example 2-4.

(Example 2-7)

In addition to the heat-sensitive adhesive solution of Examples 2-6, according to the drying ratio of 6.5% relative to the thermoplastic resin latex AP5570, add PVA with a diacetone group (diacetone monomer unit content is 4% by mass, polymerized The heat-sensitive adhesive material of the present invention was prepared in the same manner as in Example 2-6 except that the degree of saponification was 1600, the degree of saponification was 98%, and a 10% aqueous solution produced by Shin-Etsu Chemical Co., Ltd. was produced.

(Example 2-8)

Except that the thermoplastic resin latex AP5570 as an intermediate layer is coated between the heat-sensitive adhesive layer and the support in Example 2-7, so that the dry adhesion amount is 15g/m ² , coating and drying are performed, the same as in Example 2 -7 The heat-sensitive adhesive material of the present invention was also prepared.

(Comparative example 2-1)

A heat-sensitive adhesive material of a comparative example was prepared in the same manner as in Example 2-1 except that the following (9) protective layer coating liquid was used instead of (4) protective layer coating liquid of Example 2-1.

(9) Preparation of protective layer coating solution

40 parts by mass of aluminum hydroxide dispersion (50% by mass of solid content), 6 parts by mass of zinc stearate dispersion (30% by mass of solid content), 1 part by mass of dioctyl sulfosuccinate aqueous solution (5% by mass of solid content) ), 200 parts by mass of carboxyl-modified PVA (solid content 10 mass%, KL-318, produced by Co., Ltd.), 12.5% solution of 50 parts by mass of polyamide epichlorohydrin, a composition composed of 43 parts by mass of water, Thus, a protective layer coating liquid was prepared.

(Comparative example 2-2)

A heat-sensitive adhesive material of Comparative Example 2-2 was prepared in the same manner as in Comparative Example 2-1 except that the heat-sensitive adhesive layer used in Example 2-2 was used instead of the heat-sensitive adhesive layer of Comparative Example 2-1.

(Comparative example 2-3)

A heat-sensitive adhesive material of Comparative Example 2-3 was prepared in the same manner as in Comparative Example 2-1 except that the heat-sensitive adhesive layer used in Example 2-3 was used instead of the heat-sensitive adhesive layer of Comparative Example 2-1.

(comparative example 2-4)

A heat-sensitive adhesive material of Comparative Example 2-4 was prepared in the same manner as in Comparative Example 2-1 except that the heat-sensitive adhesive layer used in Example 2-8 was used instead of the heat-sensitive adhesive layer of Comparative Example 2-1.

Then, each heat-sensitive adhesive material obtained in Examples and Comparative Examples was evaluated based on the following method. The results are shown in Table 9.

Table 9:

"Note: In the table, change Examples to -8 to Examples 2-1 to 2-8, and change Comparative Examples 1 to 4 to Comparative Examples 2-1 to 2-4" Adhesion Adhesiveness header compatibility SUS board corrugated cardboard 60℃ 40°C, 90% Scratches on flat panels and thermally sensitive adhesive surfaces Measured after 2 minutes Measured after 7 days Measured after 2 minutes Measured after 7 days 22°C, 65% 40°C, 90% Example 1 2650 2500 1530 1630 8 6 △ △ Example 2 1560 1440 1090 1110 9 6 ◎ △ Example 3 2180 2320 1300 1260 7 6 ○ △ Example 4 2580 2720 1570 1490 7 6 ○ △ Example 5 1950 1880 1210 1180 9 6 ◎ ○ Example 6 2640 2600 1450 1320 10 8 ◎ ○ Example 7 2540 2800 1300 1250 10 10 ◎ ◎ Example 8 2600 3210 2410 2640 9 9 ◎ ◎ Comparative example 1 2670 2520 1510 1580 3 3 △ x Comparative example 2 1570 1430 1110 1140 4 3 ○ x Comparative example 3 2020 2140 1270 1250 3 3 △ x Comparative example 4 2570 2990 2370 2720 2 1 x x

<Activation method>

The heat-sensitive adhesive materials prepared in Examples and Comparative Examples were cut into a size of 4 cm in width and 10 cm in length, and the thermal head (manufactured by TEC Corporation, TH-0976SP) was 8 dots/mm, and the resistance was 500Ω. Under the conditions of activation energy of 26.0mJ/mm ² , printing speed of 100mm/sec, and pressure of 6kgf/line on a silicon flat plate with a diameter of 1cm, the heat-sensitive adhesive layer is in contact with the thermal head, at 22°C, 65%RH Activate the environment.

<Adhesion measurement>

The activated surface of the heat-sensitive adhesive material label activated in the above method is attached to the adherend along the longitudinal direction by a rubber roller with a pressure of 2 kg. After 2 minutes and 7 days, the peeling angle is 180° and the peeling speed is 300mm. /min conditions for stripping. The resistance value of the adhesive force at this time is displayed by numerical value. In addition, the unit is gf/40mm.

<Adhesion test method>

The protective layer of the thermosensitive recording layer of the thermosensitive adhesive material prepared in Examples and Comparative Examples was brought into contact with the thermosensitive adhesive layer, under a pressure of 2 kg/cm ² , at 60°C, 30% RH and 40°C, 90% After storage under the conditions for 24 hours, the sample was peeled off at room temperature, and the adhesiveness at that time was evaluated according to the following ranks.

Level 10: Stripped without sound

Level 9: There is a certain sound when peeling, but peeling without resistance

Level 8: There is a certain sound when peeling off, and there is a certain resistance

Rank 7: Peeling sound and peeling resistance are generated during peeling, and there is peeling resistance but no transfer of the layer is found

Rank 6: Minute dot-like transfer was found when peeled off

Level 5: 30 to 50% transfer on the heat-sensitive adhesive layer or heat-sensitive recording layer when peeled off

Rank 4: Transfer of 50% or more on the heat-sensitive adhesive layer or heat-sensitive recording layer upon peeling

Level 3: The label is partially damaged when peeled off

Level 2: 30-50% damage to the label when peeled off

Level 1: 50% or more damage to the label when peeled off

<Print compatibility test method>

Cut the heat-sensitive adhesive materials prepared in Examples and Comparative Examples into a size of 4 cm in width and 10 cm in length, and conduct electricity on a thermal head (manufactured by TEC Corporation, TH-0976SP) at 8 dots/mm, resistance 500Ω, and 1 dot grid Under the condition that the activation energy is 15.0mJ/mm ² , the printing speed is 100mm/sec, and the pressure of silicon plate with a diameter of 1cm is 6kgf/row, the heat-sensitive adhesive layer is in contact with the thermal head, at 22°C, 65%RH Printing was carried out under an environment of 40° C. and 90% RH. The condition of scratches on the heat-sensitive adhesive surface in contact with the plate roll at this time and the stickiness of the heat-sensitive adhesive surface caused by scratches were observed visually and by hand, and judged according to the following grades. Figure 1 shows the 1-dot checker pattern. Evaluation based on this model is as follows.

[evaluation criteria]

◎: No scratches or sticky feeling

○: Some scratch marks are found, but there is no sticky feeling

△: It can be confirmed that scratch marks are clear, and a certain amount of stickiness can be felt

×: Scratches can be clearly confirmed, and it feels completely sticky

The heat-sensitive adhesive material of the present invention has strong adhesive force to adherends on rough surfaces such as corrugated cardboard and polyolefin wrapping paper, has little decrease in adhesive force over time, can be activated with low energy, and has good adhesion resistance. In particular, even in the case of using synthetic paper or plastic film as a support, there is no detachment of the heat-sensitive adhesive layer during heat activation, shrinkage and wrinkling of the support can be prevented, and paste residue at the time of label replacement can be improved, e.g. For industrial use, commercial use and home use.

Claims (28)

1. A heat-sensitive adhesive material, characterized in that, the material has at least a bottom layer and a heat-sensitive adhesive layer on one side of the support body and the support body successively, The above-mentioned bottom layer contains a thermoplastic resin with a glass transition temperature (Tg) of -70°C or higher than -70°C and less than 0°C and a hollow filler. 2. The heat-sensitive adhesive material according to claim 1, wherein the heat-sensitive adhesive layer contains a thermoplastic resin, an adhesion-imparting agent, and a heat-melt substance. 3. The heat-sensitive adhesive material as claimed in claim 1, wherein the thermoplastic resin in the bottom layer is selected from acrylate copolymer, methacrylate copolymer, acrylate-methacrylate copolymer, acrylate- At least one of a styrene copolymer, an acrylate-methacrylate-styrene copolymer, and an ethylene-vinyl acetate copolymer. 4. The heat-sensitive adhesive material as claimed in claim 1, wherein the hollow filler in the bottom layer is a spherical hollow particle with a volume average particle diameter of 2.0 to 5.0 μm, and the hollow rate of the spherical hollow particle is 70% or 70%. %above. 5. The heat-sensitive adhesive material as claimed in claim 4, wherein the material of the spherical hollow particles is plastic, and the plastic is selected from acrylonitrile-vinylidene chloride-methyl methacrylate copolymer and acrylonitrile-methyl methacrylate. At least one of acrylonitrile-isobornyl methacrylate copolymers. 6. The heat-sensitive adhesive material according to claim 1, wherein the mass ratio of the thermoplastic resin in the base layer to the hollow filler is 0.1 to 2 parts by mass of the hollow filler to 1 part by mass of the thermoplastic resin. 7. The heat-sensitive adhesive material according to claim 1, wherein a mixing mass ratio (hollow filler:thermoplastic resin) of the hollow filler in the base layer to the thermoplastic resin is 1:0.5 to 1:3.0. 8. The heat-sensitive adhesive material according to claim 1, wherein a mixing mass ratio (hollow filler:thermoplastic resin) of the hollow filler in the base layer to the thermoplastic resin is 1:6.0 to 1:20.0. 9. The heat-sensitive adhesive material according to claim 2, wherein the thermoplastic resin in the heat-sensitive adhesive layer is selected from acrylate copolymer, methacrylate copolymer, acrylate-methacrylate copolymer, acrylic acid At least one of ester-styrene copolymer, acrylate-methacrylate-styrene copolymer, and ethylene-vinyl acetate copolymer. 10. The heat-sensitive adhesive material according to claim 2, wherein the heat-melting substance in the heat-sensitive adhesive layer is a benzotriazole compound represented by the following structural formula (1),

Structural formula (1) Wherein, in the above structural formula (1), R ¹ and R ² are the same or different from each other, represent any one of a hydrogen atom, an alkyl group and α, α-dimethylbenzyl, and X represents a hydrogen atom or a halogen atom. 11. The heat-sensitive adhesive material according to claim 2, wherein the heat-melting substance in the heat-sensitive adhesive layer is a paraben compound represented by the following structural formula (2),

Structural formula (2) Wherein, in the above structural formula (2), R ³ represents any one of alkyl, alkenyl, aralkyl and aryl, and these groups can be further substituted by substituents. 12. The heat-sensitive adhesive material as claimed in claim 2, wherein the heat-melting substance in the heat-sensitive adhesive layer is a compound represented by any one of the following structural formulas (3), (4) and (5),

Structural formula (3) Wherein, in the above structural formula (3), R ⁴ and R ⁵ are the same or different from each other, represent an alkyl or alkoxy group, Y represents a hydrogen atom or a hydroxyl group, Structural formula (4) Wherein, in the above structural formula (4), R represents ^any one of a hydrogen atom, a halogen atom, an alkyl group and an alkoxy group, and Y represents a hydrogen atom or a hydroxyl group.

Structural formula (5) Wherein, in the structural formula (5), R ⁷ represents any one of a hydrogen atom, a halogen atom, an alkyl group and an alkoxy group. 13. The heat-sensitive adhesive material as claimed in claim 2, wherein the heat-sensitive adhesive layer further contains a co-melting agent, which is a dibenzyl oxalate compound represented by the following structural formula (6), Structural formula (6) Wherein, in the above structural formula (6), Z represents any one of a hydrogen atom, a halogen atom and an alkyl group. 14. The heat-sensitive adhesive material according to claim 1, wherein the total thickness of the base layer and the heat-sensitive adhesive layer is 13-30 [mu]m. 15. The heat-sensitive adhesive material according to claim 1, wherein a recording layer and a protective layer are contained in this order on the surface of the support having no heat-sensitive adhesive layer. 16. The heat-sensitive adhesive material according to claim 15, wherein the recording layer is a heat-sensitive recording layer, an ink receiving layer for thermal fusion transfer recording, a toner image receiving layer for electrophotography, or a recording layer for silver halide photography. and any one of the ink-receiving layer for inkjet. 17. The heat-sensitive adhesive material according to claim 16, wherein the heat-sensitive recording layer contains a white dye and a color developer. 18. The heat-sensitive adhesive material according to claim 15, wherein the protective layer contains polyvinyl alcohol having a reactive carbonyl group and a hydrazide compound. 19. The heat-sensitive adhesive material according to claim 15, which has an ink image formed by UV curable ink. 20. The heat-sensitive adhesive material according to claim 15, wherein pre-printing with visual information is performed on the recording layer, and matching printing with a direction finding (sensing) function is applied on the heat-sensitive adhesive layer. 21. The heat-sensitive adhesive material according to claim 1, wherein the support is any one of synthetic paper and plastic film. 22. The heat-sensitive adhesive material according to claim 1, wherein the material is in any one of a label shape, a sheet shape, a label sheet shape, and a roll shape. 23. A heat-sensitive adhesive material, characterized in that, the material has a heat-sensitive recording layer and a protective layer with a heat-sensitive adhesive layer on a support body and one surface of the support body, and has a heat-sensitive adhesive layer on the opposite side of the support body. The laminated layer contains a thermoplastic resin and a hot-melt substance; the above-mentioned protective layer contains polyvinyl alcohol and a hydrazide compound having a reactive carbonyl group. 24. The heat-sensitive adhesive material according to claim 23, wherein the heat-sensitive adhesive layer contains polyvinyl alcohol having a reactive carbonyl group. 25. The heat-sensitive adhesive material according to claim 23, wherein polyvinyl alcohol having a reactive carbonyl group is used as a dispersant of the heat-melt substance in the heat-sensitive adhesive layer. 26. The heat-sensitive adhesive material according to claim 24, wherein the heat-sensitive adhesive layer contains a hydrazide compound. 27. The heat-sensitive adhesive material according to claim 24, wherein the content ratio of the polyvinyl alcohol having a reactive carbonyl group in the heat-sensitive adhesive layer is 3 to 10% by mass of the thermoplastic resin. 28. The heat-sensitive adhesive material according to claim 23, wherein an intermediate layer containing an acrylic adhesive is provided between the heat-sensitive adhesive layer and the support.

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