JP5365796B2 - Heat sensitive adhesive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-sensitive self-adhesive material having sufficient adhesive characteristics after heating, excellent blocking resistance before heating and excellent transportability in a printer. <P>SOLUTION: The heat-sensitive self-adhesive material formed by successively laminating a thermoplastic layer and a heat-sensitive self-adhesive layer containing a thermoplastic resin, a tackifier, a solid plasticizer and a non-heat fusible material is provided. The thermoplastic layer includes complex viscosity of &ge;1&times;10<SP>5</SP>Pa s at 50&deg;C and &le;1&times;10<SP>3</SP>Pa s at 150&deg;C and the non-heat fusible material is a spherical particle having an average particle diameter larger than the thickness of the heat-sensitive self-adhesive layer. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a heat-sensitive adhesive material that does not require a release paper, and more particularly, to a heat-sensitive adhesive material such as a heat-sensitive adhesive label that does not require a release paper that exhibits adhesiveness by heat.

  In recent years, labels for heat-sensitive recording having adhesive properties have been used in a wide range of fields such as the POS field, but usually a release paper is usually stuck on a pressure-sensitive adhesive layer. However, although such a thermal recording label having adhesiveness is useful, it has many disadvantages. That is, the release paper is peeled off when the label is applied to the article, and the peeled release paper is hardly reused by collection and is almost always disposed of as waste. Moreover, it is also a waste of space for the wound body, which leads to high costs. Further, when a label is attached to an article, the work of peeling the release paper is a burden on the operator.

  In order to solve these problems, there has been proposed a thermal recording label having adhesiveness that does not use release paper. For example, a thermosensitive pressure-sensitive adhesive layer has been proposed that contains a thermoplastic resin and a heat-meltable substance and, if necessary, a tackifier (see Non-Patent Document 1). Specifically, Patent Document 1 (Japanese Patent Laid-Open No. 2000-096015) proposes a hot-melt adhesive. The hot-melt pressure-sensitive adhesive exhibits tackiness upon activation (activation), and imparts tackiness (adhesiveness) by being cooled and solidified after being bonded to an adherend. In addition, in the heat-sensitive adhesive layer, a type containing a thermoplastic resin and a heat-meltable substance and, if necessary, a tackifier has been proposed. The adhesiveness by the thermal head can be expressed like the label.

  As a subject of these heat-sensitive adhesives, not only adhesive properties after activation but also non-adhesive properties before activation are required. That is, it has been verified as an important issue that a strong adhesive force is expressed while giving good handling properties such as blocking performance and printer transportability. For the anti-blocking property, for example, it has been proposed to select a high melting point or a high molecular weight as an operation of the characteristics of the solid plasticizer used. It does not have sufficient characteristics for thermal head activation purposes. In Patent Document 2 (Japanese Patent Application Laid-Open No. 10-258477), it is proposed to laminate a layer having a large amount of a solid plasticizer component on a layer having a small amount of a solid plasticizer component. Is preferentially expressed, and since it has many low molecular components, it is structurally brittle and inferior in storage with time. In addition, Patent Document 3 (Japanese Patent Laid-Open No. 08-1000015), Patent Document 4 (Japanese Patent Laid-Open No. 2002-114953), Patent Document 5 (Japanese Patent Laid-Open No. 2008-063435), and Patent Document 6 (Japanese Patent Laid-Open No. 2008-066355). In order to give other materials the function of preventing blocking, a means such as adding a polyolefin wax or an inorganic filler, or adding a silicone resin has been devised. Since it works in the direction of inhibiting adhesiveness, it does not show sufficient characteristics as well. Patent Document 7 (Japanese Patent Laid-Open No. 11-279495) proposes to provide a thermoplastic resin layer on a heat-sensitive adhesive layer. However, the dynamic friction coefficient related to printer transportability is high, and after activation, Seriously affects dimensional stability.

  The object of the present invention is to take into account the present situation of the above-mentioned thermal recording labels or mere heat-adhesive labels, while having sufficient adhesive properties after heating, having good blocking resistance before heating, and being a printer. An object of the present invention is to provide a heat-sensitive adhesive material having good transportability.

That is, according to the present invention,
(1) A heat-sensitive adhesive material obtained by sequentially laminating a thermoplastic layer, and then a thermoplastic resin, a tackifier, a solid plasticizer, and a heat-sensitive adhesive layer containing a non-thermomeltable substance on a support. The thermoplastic layer has a complex viscosity of 1 × 10 ⁵ Pa · s or more at 50 ° C. and 1 × 10 ³ Pa · s or less at 150 ° C., and the non-thermomeltable substance is heat sensitive. A heat-sensitive adhesive material, characterized by being spherical particles having an average particle diameter larger than the film thickness of the adhesive layer,
(2) The thermosensitive adhesive material as described in 1 above, wherein the thermoplastic layer comprises at least a thermoplastic resin and a solid plasticizer,
(3) The heat-sensitive adhesive material as described in 1 or 2 above, wherein the ratio of the weight average particle diameter (Dw) and the number average particle diameter (Dn) of the spherical particles is 1.5 or less.
(4) The heat-sensitive adhesive material as described in 3 above, wherein the spherical particles are silicone or a material coated with silicone,
(5) The heat-sensitive adhesive material according to any one of 1 to 4, wherein a heat insulating layer containing a hollow filler is provided between the support and the thermoplastic layer,
(6) The heat-sensitive adhesive material as described in any one of 1 to 5 above, which has a recording layer on the surface of the support opposite to the heat-sensitive adhesive layer.
(7) The heat-sensitive adhesive material as described in 6 above, further comprising a protective layer on the recording layer,
(8) The recording layer is any one of a thermosensitive recording layer, a thermal melt transfer recording ink receiving layer, an electrophotographic toner image receiving layer, a silver halide photographic recording layer, and an ink jet ink receiving layer. The heat-sensitive adhesive material according to 6 or 7,
(9) The heat-sensitive adhesive material according to any one of 6 to 8, wherein the support is any one of synthetic paper and a plastic film,
(10) The heat-sensitive adhesive material according to any one of 7 to 9, which is any one of a label shape, a sheet shape, and a roll shape,
Is provided.

  According to the present invention, there is provided a heat-sensitive adhesive material that has sufficient adhesive properties after heating, has good blocking resistance before heating, and has good transportability in a printer.

Hereinafter, the present invention will be described in more detail.
The heat-sensitive adhesive material of the present invention is formed by sequentially laminating a thermoplastic layer and a heat-sensitive adhesive layer on a support. By using spherical particles with a particle size larger than the layer thickness for the heat-sensitive adhesive layer, the particles are present on the outermost surface so that contact with other substances is due to the presence of these particles. Since it becomes point contact, it becomes difficult to stick. The term “film thickness” as used herein refers to the coating thickness of the heat-sensitive adhesive layer in a region where spherical particles are not present, and can be confirmed by cross-sectional observation using a scanning electron microscope (SEM). This function does not cause blocking when left standing under pressure, and does not cause jam in the printer conveyance path because the frictional force is reduced. However, since the spherical particles will act in the direction of inhibiting adhesion this time after being activated as they are, if you want to have adhesive force by heating, the particles are buried from the surface and the adhesive surface is sufficiently covered. It is necessary to contact the kimono. Therefore, when inactive, it must be a solid substrate that supports the spherical particles as a scaffold when pressure is applied.On the other hand, when heated, the layer has the characteristic of having fluidity so that the spherical particles are buried. It can be solved by providing it. At this time, the thermoplastic layer needs to have a complex viscosity of 1 × 10 ⁵ Pa · s or more at 50 ° C., and needs to have a complex viscosity of 1 × 10 ³ Pa · s or less at 150 ° C. When the complex viscosity is less than 1 × 10 ⁵ Pa · s at 50 ° C., the spherical particles tend to sink into the lower layer due to pressure. For example, when the environment is under pressure such as storage in a roll state, the surface is smooth inside. In order to become, it sticks on the opposite side. On the other hand, when the complex viscosity is higher than 1 × 10 ³ Pa · s at 150 ° C., the particles are unlikely to sink, so that irregularities remain on the surface and inhibit the function of the heat-sensitive adhesive.

  Here, the complex viscosity referred to in the present invention means that the thermoplastic layer coating liquid is dried and solidified by a blow dryer set at 40 ° C. to produce cylindrical pellets having a diameter of 15 mm and a height of 1 mm, and a rheometer (Jusco Inta). This is a value measured under conditions of an auto tension of 3N, a frequency of 1 Hz, and an applied strain of 1% by raising the temperature to 50 ° C. or 150 ° C. with VAR-100 manufactured by National Corporation.

  There is no restriction | limiting in particular as a thermoplastic resin in a heat-sensitive adhesive layer, Although it can select suitably according to the objective, (meth) acrylic-type polymer emulsion is used suitably. The (meth) acrylic polymer emulsion is not particularly limited, and those generally used for various acrylic pressure-sensitive adhesives can be used. For example, (meth) acrylic acid ester is charged all at once, polymerization method, monomer sequential addition It can be easily produced by a known emulsion polymerization method such as a polymerization method, an emulsion monomer sequential addition polymerization method or a seed polymerization method.

Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, ( (Meth) acrylic acid 2-hydroxyethyl etc. are mentioned. These may be used alone or in combination of two or more.
Further, in order to impart storage stability to the obtained emulsion, a small amount of (meth) acrylic acid may be used instead of the (meth) acrylic acid ester. Furthermore, a copolymerizable monomer such as vinyl acetate or styrene can be used in combination as long as it does not impair the adhesive properties of the (meth) acrylic acid ester polymer.
As for the glass transition temperature of the polymer which has the said (meth) acrylic acid ester as a main component, -70 degreeC--30 degreeC is preferable. When the glass transition temperature is higher than −30 ° C., the tackiness may be lowered, and when it is lower than −70 ° C., the blocking resistance may be lowered.
The emulsifier used in the acrylic polymer emulsion may be an anionic emulsifier, partially saponified polyvinyl alcohol, etc., and the amount used is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polymer. 0.5 parts by mass to 3 parts by mass is more preferable.
The content of the thermoplastic resin in the heat-sensitive adhesive layer is preferably 10% by mass to 60% by mass, and more preferably 15% by mass to 50% by mass. When the content of the thermoplastic resin is less than 10% by mass or more than 60% by mass, both of them are not preferable because the adhesive strength is lowered. On the other hand, when the content of the low glass transition temperature (Tg) resin exceeds 60% by mass, there may be a storage defect (blocking) such as an adhesive force developed at a normal storage environment temperature.

  As the solid plasticizer in the heat-sensitive adhesive layer, one that is solid at room temperature and melts when heated is used. The melting point of the solid plasticizer is preferably 80 ° C. or higher, and the upper limit is about 200 ° C. When the melting point is less than 80 ° C., a storage defect (blocking) occurs, for example, when a heat-sensitive adhesive material is used, an adhesive force develops at a normal storage environment temperature. In addition, there may be a problem in production such that the adhesive force is developed when the heat-sensitive adhesive layer coating solution is applied to the substrate and dried. When the melting point exceeds 200 ° C., a large amount of energy is required to develop the adhesive force, resulting in practical problems. In addition, when a thermal recording paper is used as a base material and an adhesive force is expressed with a large amount of energy, there is a problem that a printed image cannot be read because the thermal recording layer is colored.

  Examples of the solid plasticizer include a benzotriazole compound represented by the following structural formula (1), a triphenylphosphine compound represented by the following structural formula (2), a compound represented by the following structural formula (3), Further, hydroxybenzoic acid ester compounds represented by the following structural formula (4), compounds represented by the following structural formulas (5) to (11), and the like can be given.

・ Structural formula (1)

However, in the structural formula (1), R ¹ and R ² may be the same as or different from each other, and represent any one of a hydrogen atom, an alkyl group, and an α, α-dimethylbenzyl group. . X represents either a hydrogen atom or a halogen atom.
As the alkyl group in the structural formula (1), those having 1 to 8 carbon atoms are preferable, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group. , N-heptyl group and the like, and these may be further substituted with a substituent.
Examples of the substituent include a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, a cyano group, an alkyl group optionally having a specific substituent (for example, a halogen atom, a nitro group), an aryl group, a heterocyclic group, and the like. Is mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the benzotriazole compound represented by the structural formula (1) include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-5′-t-octylphenyl). Benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amyl) Phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-t-butylphenyl) -5-chlorobenzotriazole, 2- [2′-hydroxy-3 ′, 5′-di (1,1) -Dimethylbenzyl) phenyl] benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy) 3'-sec-butyl-5'-t-butylphenyl) benzotriazole, and the like.

・ Structural formula (2)

・ Structural formula (3)

・ Structural formula (4)

However, in said structural formula (4), R < ³ > is a C1-C18 alkyl group, a cyclohexyl group, an alkenyl group, an aralkyl group (the aromatic ring may have a substituent), and a phenyl group Represents one of the following.
Examples of the hydroxybenzoic acid ester compound represented by the structural formula (4) include, for example, methyl m-hydroxybenzoate, ethyl m-hydroxybenzoate, phenyl m-hydroxybenzoate, methyl p-hydroxybenzoate, p- Ethyl hydroxybenzoate, n-propyl p-hydroxybenzoate, n-butyl p-hydroxybenzoate, stearyl p-hydroxybenzoate, cyclohexyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, p-hydroxybenzoic acid 4 -Chlorobenzyl, 4-methylbenzyl p-hydroxybenzoate, phenyl p-hydroxybenzoate, and the like.

・ Structural formula (5)

However, in the structural formula (5), R ⁴ and R ⁵ may be the same as or different from each other, and represent either an alkyl group or an alkoxy group. Y represents either a hydrogen atom or a hydroxyl group.

Structural formula (6)

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

・ Structural formula (7)

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

In the structural formulas (5) to (7), examples of the alkyl group include those similar to the structural formula (1).
Examples of the alkoxy group in the structural formulas (5) to (7) include a methoxy group, an ethoxy group, a propyloxy group, an i-propyloxy group, a butoxy group, an i-butoxy group, a t-butoxy group, and a pentyloxy group. Hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, and the like.
Examples of the compound represented by the structural formula (5) include toluoin, anisoin, m-anisoin, deoxytoluoin, deoxyanisoin, 4,4′-diethylbenzoin, 4,4′-diethoxybenzoin, and the like. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
Examples of the compound represented by the structural formula (6) include phenyl 1-hydroxy-2-naphthoate, 1-hydroxy-2-naphthoic acid-p-chlorophenyl, 1-hydroxy-2-naphthoic acid-o-chlorophenyl. 1-hydroxy-2-naphthoic acid-p-methylphenyl, 1-hydroxy-2-naphthoic acid-o-methylphenyl, 1,4-dihydroxy-2-naphthoic acid phenyl, 1,4-dihydroxy-2-naphtho Acid-p-chlorophenyl, 1,4-dihydroxy-2-naphthoic acid-o-chlorophenyl and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
Examples of the compound represented by the structural formula (7) include benzoic acid-3-hydroxyphenyl, benzoic acid-4-hydroxyphenyl, benzoic acid-2-hydroxyphenyl, o-methylbenzoic acid-3-hydroxyphenyl, p-chlorobenzoic acid-3-hydroxyphenyl, and the like.

Structural formula (8)

However, in the structural formula (8), R ¹ and R ² may be the same as or different from each other, and represent a hydrogen atom or an alkyl group. m and n represent the integer of 1-5.

Structural formula (9)

Structural formula (10)

However, in the structural formula (10), R ¹ represents a hydrogen atom or an alkyl group. n represents an integer of 1 to 5.

The solid plasticizers represented by the structural formulas (1) to (10) can be used by pulverizing them to a volume average particle size of 10 μm or less, preferably 3 μm or less. Further, by making the volume average particle diameter finer, for example, 0.5 μm or less, the dynamic thermal sensitivity is increased and the thermoplastic resin and the tackifier are compatible with low energy to become a thermoactive adhesive.
The solid plasticizer can be used in combination with the compounds represented by the structural formulas (1) to (10) at an arbitrary ratio in addition to using one kind alone, but the mixing ratio in that case is arbitrary. It is possible to adjust.

In the present invention, as a solid plasticizer from the viewpoint of adhesiveness to corrugated cardboard in an environment of 0 ° C., at least one of the structural formula (1), the structural formula (2), and the structural formula (3). It is preferable to use the compound represented, The mixture of the said Structural formula (1) and the said Structural formula (2), and the compound of the said Structural formula (3) are especially preferable.
The content of the solid plasticizer in the heat-sensitive adhesive layer is preferably 25% by mass to 80% by mass, and more preferably 35% by mass to 70% by mass. When the content of the solid plasticizer is less than 25% by mass, when combined with a thermoplastic resin, blocking is likely to occur and the adhesive strength may be reduced. When the content exceeds 80% by mass, the adhesive strength is increased. Reduction may occur.

  The tackifier is added to improve the adhesive strength of the heat-sensitive adhesive layer, and is not particularly limited and can be appropriately selected from known ones according to the purpose. For example, a rosin derivative (for example, rosin , Polymerized rosin, hydrogenated rosin), terpene resins (for example, terpene resins, aromatic modified terpene resins, terpene phenol resins, hydrogenated terpene resins), petroleum resins, phenol resins, xylene resins and the like. These tackifiers are compatible with the thermoplastic resin and the hot-melt material, and can significantly improve the adhesive strength of the heat-sensitive adhesive.

  The melting point (or softening point) of the tackifier is preferably 80 ° C. or higher, and more preferably 80 to 200 ° C. If the melting point (or softening point) is less than 80 ° C., storage defects (decrease in blocking resistance) may occur at normal storage environment temperatures.

1-30 mass% is preferable and, as for content in the said heat-sensitive adhesive layer of the said tackifier, 10-20 mass% is more preferable.
When the content is less than 1% by mass, the adhesive strength may be reduced. When the content is more than 30% by mass, a storage defect at a normal storage environment temperature (blocking resistance decreases) or The initial adhesive strength may be reduced in a low temperature environment.

  In the heat-sensitive adhesive layer of the present invention, spherical particles are used as a non-heat-meltable substance. Non-heat-meltable substances are substances that do not cause melting or decomposition phenomena such as organic low molecular weight compounds when heated. Specifically, inorganic fillers, organic fillers, organic filler-inorganic filler composite fillers, etc. Are preferred.

Examples of the spherical inorganic filler include silica and glass beads, and examples of the spherical organic filler include benzoguanamine-formaldehyde condensate, benzoguanamine-melamine-formaldehyde condensate, melamine-formaldehyde condensate, polymethyl methacrylate cross-linked product, poly Examples include butyl methacrylate cross-linked products, urea-formalin resins, styrene-methacrylic acid copolymers, epoxy resins, polystyrene resins, and polyester resins. Examples of the composite filler of spherical organic filler-inorganic filler include silica-acrylic composite compounds. In addition to these, silicone resin particles having excellent releasability can be used, and examples thereof include silicone rubber, silicone resin particles, and composite particles of silicone rubber and silicone resin.
In addition, those whose surface properties are changed by a silane coupling agent or a titanate coupling agent can also be used.

  Among these non-heat-meltable substances, organic fillers are preferable, among which silicone-based particles, polymethyl methacrylate cross-linked products (cross-linked PMMA particles), and polystyrene resins are more preferable. Particular preference is given to particles (ie silicone or a material coated with silicone). Considering the expression (activation) of adhesiveness by the thermal head, since the silicone is excellent in releasability, the thermal head is less damaged and has excellent head matching properties.

The average particle diameter of the spherical particles is preferably 5 to 30 μm, more preferably 8 to 20 μm, from the viewpoint of expressing the adhesive function of the coated thermosensitive adhesive layer. Further, that the spherical particles are close to monodisperse means that the particle size distribution range is narrow, specifically, the ratio of the weight average particle diameter (Dw) to the number average particle diameter (Dn) is 1.5 or less. It is. By using a material close to monodispersion, the amount of spherical particles necessary to maintain the blocking performance can be reduced, so that the adhesive property which is a contradiction item is positively affected.
The average particle diameter, weight average particle diameter (Dw) and number average particle diameter (Dn) of the spherical particles referred to in the present invention are measured using a Coulter Multisizer (manufactured by Beckman Coulter, Inc.).

The mass ratio of the non-thermomeltable spherical particles to the thermoplastic resin (non-thermomeltable substance / thermoplastic resin) is preferably 0.1 to 2.0, and more preferably 0.2 to 1.2.
If the mass ratio of the non-heat-meltable substance is less than 0.1, the blocking resistance is lowered because it is in the same state as the presence of the heat-sensitive adhesive layer surface, while it exceeds 2.0. In some cases, the adhesiveness may decrease. The mass ratio of the non-heat-meltable material to the heat-melt material (non-heat-meltable material / heat-meltable material) is preferably 0.1 to 1.0, more preferably 0.1 to 0.5. .
When the mass ratio of the non-heat-meltable substance is less than 0.1, the blocking resistance may be lowered, and when it exceeds 0.5, the tackiness may be lowered.

  Any method may be used for introducing the spherical particles of the present invention into the film, but it is preferable to disperse them in the coating solution in advance and then apply and dry them. At this time, if the particles themselves are made of silicone, or if the surface is made of silicone with a chemical such as a silane coupling agent with respect to spherical particles of other materials, other components in the liquid are repelled when dried, It is preferable because it appears cleanly on the spherical particle surface.

  If necessary, other components such as a eutectic agent, a dispersant, an antifoaming agent, a thickener, and an antiblocking agent can be added to the heat-sensitive adhesive layer.

  The thermoplastic layer of the present invention needs to have the complex viscosity characteristics described above, and may be provided with a resin alone or a mixture as long as it has this characteristic. Examples of the resin alone include those having a low polymerization degree among polymers such as urethane resin and acrylic resin having a melting temperature of 50 to 150 ° C. The mixture is preferably a combination of a resin and a low-molecular-weight organic combination because of good heat response. Among them, by using a combination of materials similar to the heat-sensitive adhesive layer, which is a thermoplastic resin as a resin and a solid plasticizer as an organic low molecule, a material having good affinity with the upper layer and interlayer bonding can be produced.

  The heat-sensitive adhesive material of the present invention comprises a support and a thermoplastic layer and a heat-sensitive adhesive layer sequentially provided on one surface of the support, and the support and the heat-sensitive material as necessary. A heat insulating layer can be provided between the pressure-sensitive adhesive layers, and further has other layers as necessary.

  The support is not particularly limited in its shape, structure, size and the like, and can be appropriately selected according to the purpose. Examples of the shape include a flat plate shape, May be a single layer structure or a laminated structure, and the size may be appropriately selected according to the size of the heat-sensitive adhesive material.

There is no restriction | limiting in particular as a material of the said support body, Although it can select suitably according to the objective, It divides roughly into an inorganic material and an organic material. Examples of the inorganic material include glass, quartz, silicon, silicon oxide, aluminum oxide, SiO ₂ and metal. Examples of the organic material include paper such as fine paper, art paper, coated paper, and synthetic paper; cellulose derivatives such as cellulose triacetate; polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate; polycarbonate, polystyrene, poly Examples thereof include polyolefins such as methyl methacrylate, polyamide, polyethylene, and polypropylene. Among these, fine paper, coated paper, plastic film, and synthetic paper are particularly preferable.

The support is preferably subjected to surface modification such as corona discharge treatment, oxidation reaction treatment (chromic acid, etc.), etching treatment, easy adhesion treatment, antistatic treatment, etc. for the purpose of improving the adhesion of the coating layer. In addition, it is preferable to add a white pigment such as titanium oxide to the support.
There is no restriction | limiting in particular as thickness of the said support body, Although it can select suitably according to the objective, 50 micrometers-2,000 micrometers are preferable and 100 micrometers-1,000 micrometers are more preferable.
By applying the heat-sensitive adhesive of the present invention to one surface of a substrate, a heat-sensitive adhesive material having strong adhesive strength against vinyl chloride wrap and polyolefin wrap, particularly cardboard, and good blocking resistance can be obtained.

  The heat-sensitive pressure-sensitive adhesive layer and the thermoplastic layer are prepared, for example, by coating with a conventionally known bar coater, roll coater, applicator, hot melt coater, and the like, followed by drying with hot air, infrared, microwave, high frequency, or the like. .

  The coating thickness of the thermosensitive adhesive layer is adjusted by the average particle diameter of the spherical particles. The average particle size is preferably 30 to 95%, more preferably 50 to 90%. When it is less than 30%, spherical particles may fall off the heat-sensitive adhesive layer due to rubbing or the like. On the other hand, if it is thicker than 95%, the spherical particles are hidden from the surface of the layer, so that the anti-blocking effect is lost.

  The coating thickness of the thermoplastic layer is adjusted from the relationship between the spherical particles and the thickness of the heat-sensitive adhesive layer. When the heat-sensitive adhesive layer has a thickness of 80% of the average particle diameter of the spherical particles, the film thickness of the thermoplastic layer is set to 20% or more. The total ratio of the film thickness of the heat-sensitive adhesive layer and the thermoplastic layer to the average particle diameter of the spherical particles is preferably 100% or more, but it is preferable that the upper limit is 300%. Beyond that, wrinkles and the like are likely to occur due to shrinkage of the layer after film formation, and this is disadvantageous in terms of cost.

Adhesion of the thermoplastic layer and heat-sensitive adhesive layer, dry coating amount in the normal 2~35g / ^{m 2,} and preferably applied in the range of 5 to 25 g / ^{m 2.} When the coating amount is less than 2 g / m ² , sufficient adhesion cannot be obtained when performing adhesion by heating. Moreover, when it exceeds 35 g / m < ² >, an adhesion | attachment function will be saturated and it is not preferable economically.

  In the present invention, a heat insulating layer can be provided between the thermoplastic layer and the support. The heat insulation layer contains at least a thermoplastic resin and a hollow filler such as hollow particles, and further contains other components as necessary. By providing the heat insulating layer, the thermal efficiency can be improved and the adhesive strength can be improved.

  As the thermoplastic resin, a thermoplastic resin having a glass transition temperature (Tg) of −70 ° C. to −30 ° C. can be used. Examples of these resins include natural rubber latex obtained by graft copolymerization with a vinyl monomer, styrene-butadiene copolymer, acrylic ester copolymer, methacrylic ester copolymer, and acrylic ester-methacrylic ester copolymer. Acrylic ester-acrylonitrile copolymer, acrylic ester-acrylonitrile-vinyl acetate copolymer, acrylic ester-styrene copolymer, acrylic ester-methacrylic ester-styrene copolymer, ethylene-vinyl acetate copolymer A polymer etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, acrylic ester copolymer, acrylic ester-acrylonitrile copolymer, acrylic ester-acrylonitrile-vinyl acetate-copolymer, acrylic ester-styrene copolymer, acrylic ester-methacrylic ester- Styrene copolymers are particularly preferred.

The hollow particles are preferably spherical plastic hollow particles having a volume average particle diameter of 2.0 μm to 5.0 μm and a hollow ratio of 70% or more, and the maximum particle diameter of the hollow particles is 10.0 μm or less. In addition, spherical hollow particles having a volume average particle diameter of 2.0 μm to 5.0 μm and a hollow ratio of 70% or more are more preferable. The hollowness is more preferably 85 to 95%.
If the hollow ratio is less than 70%, the heat insulation effect is insufficient, so that the heat energy from the thermal head is released to the outside through the support, and the effect of improving the adhesive strength may be inferior. When the volume average particle diameter exceeds 5.0 μm, when a heat-sensitive adhesive layer is provided on the heat insulating layer using such hollow particles, a portion where the heat-sensitive adhesive layer is not formed is formed in a large particle portion. When the thermal activation is performed, the adhesive strength may be easily reduced. When the thermal conductivity is less than 2.0 μm, it is difficult to secure a hollow ratio of 70% or more, and the adhesive strength improving effect may be inferior. .
Here, the spherical plastic hollow particles mean hollow particles that are made of a thermoplastic resin as a shell and contain air or other gas inside and are already in a foamed state. The hollow ratio means the ratio of the volume based on the outer diameter and the volume based on the inner diameter of the hollow fine particles.

  The material of the spherical hollow particles is not particularly limited and may be appropriately selected depending on the intended purpose.For example, vinylidene chloride-acrylonitrile copolymer, acrylonitrile-vinylidene chloride-methyl methacrylate copolymer, acrylonitrile- Examples thereof include methacrylonitrile-isobonyl methacrylate copolymer.

  The mixing ratio of the thermoplastic resin having the glass transition temperature (Tg) in the heat insulation layer of −70 ° C. to −30 ° C. and the hollow particles is 0.1 part by mass of the hollow particles with respect to 1 part by mass of the thermoplastic resin. ˜2 parts by mass is preferable, and 0.3 part by mass to 1 part by mass is more preferable. When the hollow particle is less than 0.1 part by mass, the effect of improving the adhesive strength may be inferior, and when it exceeds 2 parts by mass, the binding force of the hollow under layer may be inferior and the adhesive force may be weakened.

There is no restriction | limiting in particular in a heat insulation layer, Although it can form according to a well-known method, For example, it can form suitably by the apply | coating method using the heat insulation layer coating liquid formed by mix | blending the said component.
As the coating method, for example, blade coating method, gravure coating method, gravure offset coating method, bar coating method, roll coating method, knife coating method, air knife coating method, comma coating method, U comma coating method, AKKU coating method, Examples thereof include a smoothing coating method, a micro gravure coating method, a reverse roll coating method, a four or five roll coating method, a dip coating method, a falling curtain coating method, a slide coating method, and a die coating method.

The coating amount of the heat insulating layer coating solution is preferably ^1g / ^{m 2 ~35g} / m 2 on a dry coating ^{amount, 1g / m 2 ~5g / m} 2 is more preferable. When the coating amount of the heat insulation layer coating solution is less than 1 g / m ² , sufficient adhesion cannot be obtained when performing adhesion by heating, and the heat insulation effect may be inferior, and when it exceeds 35 g / m ^2. , Adhesive strength and heat insulation effect may be saturated.

  In the heat-sensitive adhesive material of the present invention, a recording layer may be provided on the surface of the support opposite to the heat-sensitive adhesive layer, and a protective layer and other layers may be provided as necessary.

  The recording layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a heat-sensitive recording layer, a heat-melt transfer recording ink-receiving layer, an electrophotographic toner image-receiving layer, and a silver halide photographic recording. A layer, an ink-jet ink image-receiving layer, and the like are preferable. Among these, as the recording layer, a heat-sensitive adhesive material for heat-sensitive recording provided with a heat-sensitive recording layer containing a leuco dye and a developer, or an ink-receiving layer for hot-melt transfer recording was provided as the recording layer. The heat-sensitive adhesive material for thermal transfer recording has strong adhesion to various adherends, especially rough surface adherends such as cardboard and polyolefin wrap, low energy thermal activation, and good blocking resistance. Useful.

  The leuco dyes (color formers) used in the heat-sensitive recording layer are applied singly or as a mixture of two or more. As such leuco dyes, the following are applied to this type of heat-sensitive recording material. Although used arbitrarily, it is not limited to this. For example, leuco compounds such as triphenylmethane, fluorane, phenothiazine, auramine, spiropyran, and indinophthalide are preferably used. Specific examples of such leuco dyes include those shown below.

  3,3-bis (p-dimethylaminophenyl) -phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylamine phthalide (also known as crystal violet lactone), 3,3-bis (p- Dimethylaminophenyl) -6-diethylaminophthalide, 3,3-3-3-bis (p-diethylaminophenyl) -6-chlorophthalide, 3,3-bis (p-dibutylaminophenyl) phthalide, 3-cyclohexylamino-6- Chlorofluorane, 3-dimethylamino-5,7-dimethylfluorane, 3-diethylamino-7-chlorofluorane, 3-dimethylamino-7-methylfluorane, 3-diethylamino-7,8-benzfluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3- (Np-tolyl-N-ethyl) Ruamino) -6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 2- [N- (3′-trifluoromethylphenyl) amino] -6-diethylaminofluor Oran, 2- [3,6-bis (diethylamine) -9- (o-chloroanilino) xanthylbenzoate lactam], 3-diethylamino-6-methyl-7- (m-trichloromethylanilino) fluorane, 3-diethylamino -7- (o-chloroanilino) fluorane, 3-di-n-butylamino-7- (o-chloroanilino) fluorane, 3-N-methyl-Nn-amylamino-6-methyl-7-anilinofluorane 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) fluorane, benzoylleucomethylene blue, 6'-chloro-8'-methoxy-benzoindoli No-spiropyran, 6'-bromo-3'-methoxy-benzoindolino-spiropyran, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy-5'-chlorophenyl) Phthalide, 3- (2′-hydroxy-4′-dimethylaminophenyl) -3- (2′methoxy-5′-nitrophenyl) phthalide, 3- (2′-methoxy-4′-dimethylaminophenyl) -3 -(2'-Hydroxy-4'-chloro-5'-methylphenyl) phthalide, 3- (N-ethyl-N-tetrahydrofurfuryl) amino-6 -Methyl-7-anilinofluorane, 3-N-ethyl-N- (2-ethoxypropyl) amino-6-methyl-7-anilinofluorane, 3-N-methyl-N-isobutyl-6-methyl -7-anilinofluorane, 3-morpholino-7- (N-propyl-trifluoromethylanilino) fluorane, 3-pyrrolidino-7-m-trifluoromethylanilinofluorane, 3-diethylamino-5-chloro -7- (N-benzyl-trifluoromethylanilino) fluorane, 3-pyrrolidino-7- (di-p-chlorophenyl) methylaminofluorane, 3-diethylamino-5-chloro-7- (α-phenylethyl) Amino) fluorane, 3- (N-ethyl-p-toluidino) -7- (α-phenylethylamino) fluorane, 3-diethylamino-7 -(O-methoxycarbonylphenylamino) fluorane, 3-diethylamino-5-methyl-7- (α-phenylethylamino) fluorane, 3-diethylamino-7-piperidinofluorane, 2-chloro-3- (N -Methyl toluidino) -7- (pn-butylanilino) fluorane, 3- (N-methyl-N-isopropylamino) -6-methyl-7-anilinofluorane, 3-di-n-butylamino-6- Methyl-7-anilinofluorane, 3,6-bis (dimethylamino) fluorane spiro (9,3 ')-6'-dimethylaminophthalide, 3- (N-benzyl-N-cyclohexylamino) -5 , 6-Benzo-7-α-naphthylamino-4′-bromofluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-die Tylamino-6-methyl-7-mesitidino-4 ′, 5′-benzofluorane, 3-N-methyl-N-isopropyl-6-methyl-7-anilinofluorane, 3-N-ethyl-N-isoamyl Examples include -6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- (2 ', 4'-dimethylanilino) fluorane.

  In the present invention, as the developer used in the heat-sensitive recording layer, various electron-accepting compounds that cause the coloration by contacting the leuco dye under heat, a solvent, or the like, or an oxidizing agent is applied. Such a thing is conventionally well-known and the following are mentioned as the specific example, However It is not limited only to this.

  4,4′-isopropylidenediphenol, 4,4′-isopropylidenebis (o-methylphenol), 4,4′-secondary butylidenebisphenol 4,4′-isopropylidenebis (2-tertiary-butylphenol), zinc p-nitrobenzoate, 1,3,5-tris (4-tertiarybutyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 2,2- (3,4'-dihydroxydiphenyl) propane, Bis (4-hydroxy-3-methylphenyl) sulfide, 4- [β- (p-methoxyphenoxy) ethoxy] salicylic acid, 1,7-bis (4-hydroxyphenylthio) -3,5-dioxaheptane, 1 , 5-bis (4-hydroxyphenylthio) -5-oxapentane, phthalic acid monobenzyl ester Calcium acid, 4,4′-cyclohexylidenediphenol, 4,4′-isopropylidenebis (2, -chlorophenol), 2,2′-methylenebis (4-methyl-6-tertiarybutylphenol), 4,4 '-Butylidenebis (6-tertiarybutyl-2-methyl) phenol, 1,1,3-tris (2-methyl-4-hydroxy-5-tertiarybutylphenyl) butane, 1,1,3-tris (2 -Methyl-4-hydroxy-5-cyclohexylphenyl) butane, 4,4'-thiobis (6-tertiarybutyl-2-methyl) phenol, 4,4'-diphenolsulfone, 4-isopropoxy-4'-hydroxy Diphenylsulfone, 4-benzyloxy-4'-hydroxydiphenylsulfone, 4,4'-diphenolsulfur Foxide, isopropyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, benzyl protocatechuate, stearyl gallate, lauryl gallate, octyl gallate, 1,3-bis (4-hydroxyphenylthio) -propane, N, N '-Diphenylthiourea, N, N'-di (m-chlorophenyl) thiourea, salicylanilide, methyl bis- (4-hydroxyphenyl) acetate, benzyl bis- (4-hydroxyphenyl) acetate, 1,3-bis (4-hydroxyphenyl) benzyl acetate, 1,3-bis (4-hydroxycumyl) benzene, 1,4-bis (4-hydroxycumyl) benzene, 2,4′-diphenolsulfone, 2,2 ′ -Diallyl-4,4'-diphenolsulfone, 3,4-dihydroxyphenyl-4'-methyl Phenylsulfone, zinc 1-acetyloxy-2-naphthoate, zinc 2-acetyloxy-1-naphthoate, zinc 2-acetyloxy-3-naphthoate, α, α-bis (4-hydroxyphenyl) -α- Examples include methyltoluene, an antipyrine complex of zinc thiocyanate, tetrabromobisphenol A, tetrabromobisphenol S, 4,4′-thiobis (2-methylphenol), 4,4′-thiobis (2-chlorophenol), and the like.

  In the present invention, the developer used in the heat-sensitive recording layer is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass with respect to 1 part by mass of the color former. These color formers and color developers can be used alone or in admixture of two or more.

  A preferred binder resin for use in the thermosensitive recording layer is a resin having a hydroxyl group or a carboxyl group in the molecule. Examples of such resins include polyvinyl acetals such as polyvinyl butyral and polyvinyl acetoacetal, cellulose derivatives such as ethyl cellulose, cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate, and epoxy resins. It is not limited. Moreover, these binder resins are applied individually or in mixture of 2 or more types.

  In the heat-sensitive recording layer of the present invention, a heat-fusible substance can be used alone or in combination of two or more as an auxiliary additive component if necessary. Examples of heat-fusible substances include higher fatty acids or their esters, amides or metal salts, various waxes, condensation products of aromatic carboxylic acids and amines, benzoic acid phenyl esters, higher linear glycols, 3, 4 Examples include, but are not limited to, those having a melting point of about 50 to 200 ° C., such as epoxy-hexahydrophthalate dialkyl, higher ketones, and other heat-fusible organic compounds.

  In the case of obtaining the heat-sensitive recording layer in the present invention, an additive component commonly used for this type of heat-sensitive recording medium, if necessary, together with a leuco dye, a developer, a binder resin, for example, a filler, a surfactant, a lubricant, a pressure An anti-coloring agent or the like can be used in combination as long as the transparency of the heat-sensitive recording layer is not impaired.

  In this case, as a filler, for example, calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, kaolin, talc, surface-treated inorganic fine powder such as calcium and silica, Examples thereof include organic fine powders such as urea-formalin resin, styrene / methacrylic acid copolymer, polystyrene resin, and vinylidene chloride resin. Examples of the lubricant include higher fatty acids and metal salts thereof, higher fatty acid amides, higher fatty acid esters, various animal, vegetable, mineral, and petroleum waxes.

  The heat-sensitive recording layer is prepared by uniformly dispersing or dissolving the color former, developer, and binder resin in a solvent, and coating and drying this on a support made of fine paper or film. Is not particularly limited. The dispersed particle size of the thermal recording layer coating solution is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less. The film thickness of the heat-sensitive recording layer is about 1 to 50 μm, preferably about 3 to 20 μm, although it depends on the composition of the heat-sensitive recording layer and the application of the thermoadhesive label.

  The recording method of the heat-sensitive recording layer of the present invention is not particularly limited depending on the purpose of use, such as a thermal pen, a thermal head, or laser heating.

  In the present invention, a protective layer can be provided on the thermosensitive recording layer. The protective layer used in the present invention improves the so-called head matching properties such as transparency, chemical resistance, water resistance, friction resistance, light resistance and thermal head durability, corrosion resistance, and lubricity of the thermal recording layer. Therefore, it is important as a component of the present invention. The protective layer includes a film formed mainly with a water-soluble resin or a hydrophobic resin, a film formed mainly with an ultraviolet curable resin or an electron beam curable resin, and the like. Examples of such resins include water-soluble resins, aqueous emulsions, hydrophobic resins and ultraviolet curable resins, and electron beam curable resins.

  Specific examples of the water-soluble resin include, for example, polyvinyl alcohol, modified polyvinyl alcohol, cellulose derivatives (methylcellulose, methoxycellulose, hydroxycellulose, etc.), casein, gelatin, polyvinylpyrrolidone, styrene-maleic anhydride copolymer, diisobutylene- Maleic anhydride copolymer, polyacrylamide, modified polyacrylamide, methyl vinyl ether-maleic anhydride copolymer, carboxy-modified polyethylene, polyvinyl alcohol / acrylamide block copolymer, melamine-formaldehyde resin, urea-formaldehyde resin, etc. .

  Examples of the resin or hydrophobic resin for aqueous emulsion include polyvinyl acetate, polyurethane, styrene / butadiene copolymer, styrene / butadiene / acrylic copolymer, polyacrylic acid, polyacrylic ester, vinyl chloride / acetic acid. Examples thereof include vinyl copolymers, polybutyl methacrylate, polyvinyl butyral, polyvinyl acetal, methyl cellulose, ethyl cellulose, and ethylene / vinyl acetate copolymers.

  Further, copolymers of these resins and silicon segments are also preferably used. These may be used alone or in combination, and if necessary, a curing agent may be added to cure the resin.

The type of the ultraviolet curable resin is not particularly limited as long as it is a monomer, oligomer or prepolymer that undergoes a polymerization reaction upon irradiation with ultraviolet rays and is cured to become a resin, and various known ones can be used.
The type of the electron beam curable resin is not particularly limited, but particularly preferable electron beam curable resins include an electron beam curable resin having a branched molecular structure of five or more functional groups having a polyester skeleton and a silicon-modified electron beam curable resin. The main component.

  In order to improve head matching, inorganic and / or organic fillers and lubricants can be added to the protective layer as long as the surface smoothness is not deteriorated. The particle size of the filler is preferably 0.3 μm or less. In this case, the filler is preferably selected so that the amount of oil supply is 30 ml / 100 or more, more preferably 80 ml / 100 g or more.

  As these inorganic and / or organic fillers, one or two or more of pigments commonly used in this type of thermal recording medium can be selected. Specific examples thereof include calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, surface-treated inorganic pigments such as calcium and silica, urea-formalin resin, Examples thereof include organic pigments such as styrene / methacrylic acid copolymers and polystyrene resins. As the lubricant, those mentioned in the description of the heat-sensitive recording layer can be used.

  There is no restriction | limiting in particular in the coating system of a protective layer, It can apply by a conventionally well-known method. A preferable thickness of the protective layer is 0.1 to 20 μm, more preferably 0.5 to 10 μm. If the thickness of the protective layer is too thin, the function as a protective layer such as storage stability and head matching of the thermoadhesive label is insufficient, and if it is too thick, the thermal sensitivity of the thermosensitive recording layer is lowered, resulting in cost reduction. Is also disadvantageous.

The heat insulating layer or the like can be further provided between the support and the thermosensitive recording layer as necessary.
As the components constituting these layers, pigments containing the hollow particles, binders, thermofusible substances, surfactants, and the like can be used.

  The heat-sensitive adhesive material of the present invention can be suitably used by being cut before or after thermal activation (heating) of the heat-sensitive adhesive layer. In this case, the heat-sensitive adhesive material is preliminarily used in the heat-sensitive adhesive material. A cut may be formed. The heat-sensitive adhesive material is advantageous in that it can be suitably used for various uses such as labels and tags. There is no restriction | limiting in particular as a shape of the heat sensitive adhesive material of this invention, A label form, a sheet form, a label sheet form, a roll form etc. are mentioned suitably. Among these, from the viewpoint of convenience, storage location, and handleability, it is preferable to wind it around a cylindrical core material and to store it by winding it into a long roll.

The method for thermally activating the thermosensitive adhesive layer in the thermosensitive adhesive material of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an activation method using hot air, Examples thereof include an activation method using a roll and an activation method using a thermal head. Among these, the activation method using a thermal head is preferable, and the thermal activation method for the heat-sensitive adhesive material of the present invention is particularly preferable.
In this case, it is possible to perform recording on the thermosensitive recording layer and thermal activation of the thermosensitive adhesive layer by heating both surfaces of the thermosensitive adhesive material using an existing thermal recording printer device. It is advantageous.

  The adherend to which the heat-sensitive adhesive material of the present invention is affixed is not particularly limited, and its size, shape, structure, material, and the like can be appropriately selected according to the purpose. For example, polyolefins such as polyethylene and polypropylene, resin plates such as acrylic, polyethylene terephthalate (PET), polystyrene and nylon, metal plates such as SUS and aluminum, paper products such as envelopes and cardboard, polyolefin wraps, polyvinyl chloride Preferable examples include wraps made of polyethylene and non-woven fabric made of polyethylene (such as envelopes).

  Next, the present invention will be described in more detail with reference to examples. The parts and% shown below are based on mass.

(Liquid A) Dye dispersion 3-dibutylamino-6-methyl-7-anilinofluorane 20 parts Polyvinyl alcohol 10% aqueous solution 20 parts Water 60 parts (Liquid B) Developer dispersion 4-hydroxy-4'- Isopropoxydiphenylsulfone 10 parts Polyvinyl alcohol 10% aqueous solution 25 parts Calcium carbonate 15 parts Water 50 parts

The mixture having the above composition was dispersed using a sand mill so that the average particle diameter was 2.0 μm or less, and (A liquid) and (B liquid) were adjusted. Next, the mixture was stirred so that the mass ratio of (A liquid) and (B liquid) was (A liquid) :( B liquid) = 1: 8 to obtain a thermosensitive recording layer forming liquid (C liquid). This heat-sensitive recording layer forming liquid (C liquid) is applied and dried on the surface of single-sided coated paper (OK Adonis Rough, Oji Paper Co., Ltd.) having a basis weight of 80 g / m ² so that the dry adhesion amount is 5 g / m ^2. After providing the heat-sensitive recording layer, the paper was formed with a heat-sensitive recording layer by super calendering so that the Beck smoothness was 600 to 700 seconds.

[Liquid D] Solid plasticizer dispersion, 30 parts of triphenylphosphine, 30% polyvinyl alcohol aqueous solution (L-3266, manufactured by Nippon Gosei Kagaku), 5 parts, surfactant (Newcol-290M, manufactured by Nippon Emulsifier Co., Ltd.), 0.2 parts 65 parts of water

  The mixture having the above composition was dispersed using a sand mill so that the average particle size was 1.0 μm to obtain a dispersion [solution D].

[Liquid E] Non-heat-meltable substance dispersion / non-heat-melting spherical particles 30 parts / 30% polyvinyl alcohol aqueous solution (N-3 Synthetic Chemical Co., Ltd. L-3266) 5 parts / surfactant (Nippon Emulsifier Newcol-290M) 0.2 part water 65 parts

  A mixture having the above composition was dispersed using a sand mill to obtain a dispersion [solution E].

[F liquid] Heat-sensitive adhesive layer liquid / 2-ethylhexyl acrylate copolymer emulsion 10 parts (glass transition temperature (Tg): −80 ° C., non-volatile content 50%)
・ Terpene-based tackifier emulsion (Arakawa Chemical Industries, Tamanol E-100, nonvolatile content 50%) 7 parts ・ Solid plasticizer dispersion [Liquid D] 30 parts ・ Non-heat-meltable substance dispersion [Liquid E] 3 Part

  The mixture which consists of the said composition was mixed and the heat-sensitive adhesive layer liquid [F liquid] was obtained.

[Example 1]
On the back side of the heat-sensitive color-developing layer-coated paper, an acrylic emulsion X1482 manufactured by Chubu Seiden Co., Ltd. is applied and dried as a thermoplastic layer so as to have a film thickness of 5 μm. A heat-sensitive adhesive layer solution [F solution] using (PMMA, average particle size of 10 μm, Dw / Dn = 2.3) was laminated, coated and dried to a film thickness of 8 μm. As for the film thickness, a cross-section was taken out perpendicular to the coated sample using a microtome (RM2265 manufactured by Leica). Subsequently, the thickness was measured with a scanning electron microscope (SEM S3100, manufactured by Hitachi High-Tech) in a field perpendicular to the cross section.

[Example 2]
As the thermoplastic layer, the thermoplastic layer and the heat-sensitive adhesive layer were the same as in Example 1 except that the [F liquid] containing 0 part of the non-thermomeltable substance dispersion was applied and dried to a film thickness of 5 μm. Were laminated.

Example 3
As in Example 2, except that Chemisnow MX1000 (PMMA, average particle diameter 10 μm, Dw / Dn = 1.4) manufactured by Soken Chemical Co., Ltd. was used as non-heat-melting spherical particles, and the mixing amount was reduced to 2 parts. A plastic layer and a heat-sensitive adhesive layer were laminated.

Example 4
The thermoplastic layer and the heat-sensitive layer were the same as in Example 3 except that Tospearl 1110 (silicone, average particle diameter 11 μm, Dw / Dn = 1.4) manufactured by Momentive Performance Materials was used as the non-heat-meltable spherical particles. A pressure-sensitive adhesive layer was laminated.

Example 5
[Liquid G] Coating solution for heat insulation layer, plastic spherical hollow particles (acrylonitrile / vinylidene chloride / methyl methacrylate copolymer)
(Solid content concentration 41%, average particle size 3.6 μm, hollow rate 90%) 15 parts thermoplastic resin B-1 (2-ethylhexyl acrylate copolymer emulsion (glass transition temperature (Tg): −80 ° C., non-volatile) Min. 50%)) 24 parts surfactant (Dapro W-77 manufactured by Elementis Japan) 0.1 parts water 60 parts

A mixture having the above composition was stirred and dispersed to prepare a heat insulating layer coating solution [G solution]. A heat-insulating layer coating solution [G solution] is applied to the back surface of the heat-sensitive color-developing layer-coated paper so as to have an adhesion amount of 5 g / m ² , dried, and the thermoplastic layer and heat-sensitive adhesive layer of Example 3 are further formed thereon. Were sequentially applied and dried.

[Comparative Example 1]
On the back side of the heat-sensitive color-developing layer-coated paper, a heat-sensitive adhesive layer liquid [F liquid] excluding non-heat-melting spherical particles was applied and dried to a film thickness of 13 μm.

[Comparative Example 2]
A film having a film thickness of 13 μm using silica (Mizusawa Chemical Co., Ltd. Mizukasil P-527) instead of non-heat-melting spherical particles as the heat-sensitive adhesive layer liquid [F liquid] on the back surface of the heat-sensitive coloring layer-coated paper. The coating was dried so that

[Comparative Example 3]
On the back side of the heat-sensitive color-developing layer-coated paper, a heat-sensitive adhesive layer liquid [F liquid] containing 0 part of a non-heat-meltable substance dispersion is applied and dried to a film thickness of 13 μm, and further styrene- Acrylic ester copolymer emulsion (BASF Corporation, JONCRYL775; glass transition temperature 37 ° C.) was laminated, coated and dried so as to be ² g / m ² as a thermoplastic resin.

[Comparative Example 4]
What used silicone KMP-590 (average particle diameter of 2.0 micrometers) made from Shin-Etsu Chemical Co., Ltd. as a non-heat-melting spherical particle as a heat-sensitive adhesive layer liquid [F liquid] on the back surface of the paper coated with the heat-sensitive coloring layer. The film was applied and dried to a film thickness of 13 μm.

[Comparative Example 5]
On the back side of the paper coated with the heat-sensitive color-developing layer, a film using a swellable mica (NTS-10 manufactured by Topy Industries Co., Ltd.) instead of non-heat-melting spherical particles as the heat-sensitive adhesive layer liquid [F liquid]. The coating was dried to a thickness of 13 μm.

[Comparative Example 6]
As a heat-sensitive adhesive layer, a non-heat-meltable substance dispersion liquid is not included, a solid plasticizer dispersion liquid [D liquid] is 50 parts, and the solid plasticizer component is larger than the thermoplastic layer [liquid F] with a film thickness of 8 μm. A thermoplastic layer and a heat-sensitive adhesive layer were laminated in the same manner as in Example 2 except that the coating and drying were performed.

[Comparative Example 7]
A thermoplastic layer and a thermosensitive adhesive layer were laminated in the same manner as in Example 1 except that Superflex E-4800 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was applied and dried as a thermoplastic layer so as to have a film thickness of 5 μm.

[Comparative Example 8]
A thermoplastic layer and a thermosensitive adhesive layer were laminated in the same manner as in Example 1 except that Superflex 500 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was applied and dried as a thermoplastic layer so as to have a film thickness of 5 μm.

  Subsequently, the thermal adhesive labels obtained in these examples and comparative examples were evaluated. The results are shown in Table 1, Table 2 and Table 3.

[Complex viscosity]:
The coating liquid of the thermoplastic layer was dried by a blow dryer set to 40 ° C. to prepare a cylindrical pellet having a diameter of 15 mm × height of 1 mm, and a rheometer (VAR-100 manufactured by Jusco International Co., Ltd.) was used. The temperature was raised to temperature. The complex viscosity was measured under the conditions of auto tension 3N, frequency 1 Hz, applied strain 1%.
[Blocking property]:
The heat-sensitive recording layer and the pressure-sensitive adhesive layer of the same label sample were brought into contact with each other, tested at 60 ° C. for 24 hours under a pressure of ² kg / cm ² , left at room temperature, and then the sample was peeled off. The blocking property was evaluated according to the following rank.
A: No blocking (no peeling noise)
○: No blocking occurred (with peeling sound)
Δ: Slightly blocking ×: Complete sticking [Coefficient of dynamic friction]:
A coated sample was placed on a friction tester (3K-34B manufactured by Shinto Kagaku Co., Ltd.), a stainless steel ball indenter was placed on the thermally active surface, and measurement was performed under conditions of a load of 50 g and a sweep speed of 75 mm / min.
[Adhesiveness]:
The coated sample is cut into a 40 mm × 150 mm rectangle, and using a thermal printing device (manufactured by Okura Electric Co., Ltd., TH-PMD), head conditions: energy 0.50 mJ / dot, printing speed: 2 inch / sec, Platen pressure: Thermally activated under the condition of 6 kgf / line. Next, this activated sample was applied to the adherend (C liner cardboard) in the longitudinal direction with a 2 kg pressure rubber roller, and after 1-day storage, it was peeled off under conditions of a peeling angle of 180 degrees and a peeling speed of 300 mm / min. It was. The adhesive force was measured with a force gauge (DPS-5 manufactured by Imada Co., Ltd.), and the read numerical values were averaged.
A: 15 N or more (sticking firmly)
○: 10N or more (sufficiently attached)
Δ: 5 to 10 N (somewhat weak against external force)
×: Less than 5N (desorbed when pasted for a long time)
[Printer transportability when inactive]:
Except that the printing energy was set to zero, a paper jam (discharge failure) was confirmed when 100 sample paper pieces were continuously discharged under the same conditions as in the above-described adhesive evaluation.
A: Paper was discharged continuously for 100 sheets.
○: Although discharged normally, a little.
Δ: The paper meandered during discharge.
X: Paper jam occurred.
[Activation sensitivity]:
Except for changing the printing speed, the adhesive strength was measured in the same manner as the above-mentioned adhesive evaluation, and the speed at which the adhesive strength began to decrease was compared. The larger the speed value, the faster the sensitivity and the lower the energy consumption.

As described above, the heat-sensitive adhesive materials of Examples 1 to 5 are a heat-sensitive adhesive containing a thermoplastic layer on a support, and then a thermoplastic resin, a tackifier, a solid plasticizer, and a non-thermomeltable substance. The thermoplastic layer has a complex viscosity of 1 × 10 ⁵ Pa · s or more at 50 ° C., 1 × 10 ³ Pa · s or less at 150 ° C., and the non-heated layer. Since the fusible substance is a spherical particle having an average particle diameter larger than the film thickness of the heat-sensitive adhesive layer, it has sufficient adhesive properties after heating as compared with Comparative Examples 1 to 8, but is resistant to blocking before heating. It can be seen that the transportability of the printer is good.

JP 2000-096015 A Japanese Patent Laid-Open No. 10-258477 Japanese Patent Laid-Open No. 08-1000015 JP 2002-114953 A JP 2008-063435 A JP 2008-063535 A JP-A-11-279495

"Handbook of Adhesion", 12th edition, pages 131-135, published in 1970

Claims (10)

A heat-sensitive adhesive material comprising a thermoplastic layer, a thermoplastic resin, a tackifier, a solid plasticizer, and a heat-sensitive adhesive layer containing a non-thermomeltable material sequentially laminated on a support, The thermoplastic layer has a complex viscosity of 1 × 10 ⁵ Pa · s or more at 50 ° C. and 1 × 10 ³ Pa · s or less at 150 ° C., and the non-thermomeltable material is a heat-sensitive adhesive. A heat-sensitive adhesive material, which is a spherical particle having an average particle diameter larger than the film thickness of the layer.   The heat-sensitive adhesive material according to claim 1, wherein the thermoplastic layer comprises at least a thermoplastic resin and a solid plasticizer.   The heat-sensitive adhesive material according to claim 1 or 2, wherein the ratio of the weight average particle diameter (Dw) to the number average particle diameter (Dn) of the spherical particles is 1.5 or less.   The heat-sensitive adhesive material according to claim 3, wherein the spherical particles are silicone or a material coated with silicone.   The heat-sensitive adhesive material according to any one of claims 1 to 4, wherein a heat insulating layer containing a hollow filler is provided between the support and the thermoplastic layer.   6. The heat-sensitive adhesive material according to claim 1, further comprising a recording layer on a surface of the support opposite to the heat-sensitive adhesive layer.   The heat-sensitive adhesive material according to claim 6, further comprising a protective layer on the recording layer.   The recording layer is any one of a heat-sensitive recording layer, a thermal-melt transfer recording ink-receiving layer, an electrophotographic toner image-receiving layer, a silver halide photographic recording layer, and an ink-jet ink image-receiving layer. Item 8. The heat-sensitive adhesive material according to Item 6 or 7.   The heat-sensitive adhesive material according to any one of claims 6 to 8, wherein the support is any one of synthetic paper and a plastic film.   The heat-sensitive adhesive material according to any one of claims 7 to 9, wherein the heat-sensitive adhesive material is in a label shape, a sheet shape, or a roll shape.