JP2006257320A - Heat-sensitive adhesive and heat-sensitive adhesive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-sensitive adhesive having strong adhesive strength to a rough surface adherend such as corrugated cardboard, and a polyolefin wrap film, hardly causing deterioration of the adhesive strength with time, capable of being thermally activated with a low energy, and having good blocking resistance; and to provide a heat-sensitive adhesive material. <P>SOLUTION: The heat-sensitive adhesive contains at least a thermoplastic resin and a hot-melt material which contains at least one kind of a compound represented by structural formula (I) and a compound represented by general formula (II), (In the formulas, R<SP>1</SP>is a hydrogen atom or an alkyl group; and n is an integer of 1-5). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is a heat-sensitive adhesive that is non-adhesive at room temperature but develops adhesiveness upon heating, and maintains adhesiveness even after the occurrence of adhesiveness, and adhesive to rough surface adherends such as cardboard and polyolefin wrap. The present invention relates to a heat-sensitive pressure-sensitive adhesive material that is strong, has little decrease in adhesive strength over time, can be thermally activated with low energy, and has excellent blocking resistance.

In recent years, adhesive labels with information recording layers have been increasingly used for various purposes such as price display labels, product display (barcode) labels, quality display labels, weighing display labels, and advertising labels (stickers). is doing. Various methods such as an ink jet recording method, a thermal recording method, and a pressure sensitive recording method are provided for recording the adhesive label on the information recording layer.
Conventionally known adhesive labels generally have a configuration in which an adhesive layer and release paper are laminated on the side opposite to the information recording surface. This pressure-sensitive adhesive label can be easily bonded by simply peeling off the release paper at the time of bonding and applying pressure.

As described above, the pressure-sensitive adhesive label is usually used after the release paper is peeled off, but the peeled release paper is hardly reused by collection and is almost always discarded. Therefore, in recent years, attention has been paid to a heat-sensitive adhesive label having a heat-sensitive adhesive layer that does not exhibit adhesiveness at room temperature and does not require a release paper.
As the thermosensitive adhesive label, for example, a thermosensitive adhesive layer containing a thermoplastic resin and a thermomeltable substance and, if necessary, a tackifier is proposed (see Non-Patent Document 1). ).
The thermoplastic resin imparts adhesive strength and adhesive strength. The heat-meltable substance is solid at room temperature, so it does not give plasticity to the resin, but melts by heating to swell or soften the resin and develop adhesiveness. The tackifier has a function of improving tackiness. Furthermore, since the heat-meltable substance in the heat-sensitive adhesive layer is slowly crystallized after being melted by heating, the adhesiveness can be maintained for a long time even after the heat source is removed. However, the conventional heat-sensitive adhesive has a problem that the adhesive strength after the development of adhesiveness decreases with time.

  In order to solve such a problem, for example, as a thermoplastic resin, an ethylene-vinyl acetate copolymer having a glass transition temperature (Tg) of 0 ° C. or higher, or a thermoplastic resin having a glass transition temperature of −5 ° C. or higher (ethylene (Excluding vinyl acetate copolymer) and the like have been proposed (see Patent Document 1 and Patent Document 2). According to these proposals, although a relatively good result can be obtained for the adhesive strength to a stainless steel plate or the like, there is a problem that the adhesive strength to a vinyl chloride wrap or a polyolefin wrap has not yet reached a practical level.

Further, the heat-sensitive adhesive is usually a heat-sensitive adhesive label provided with a heat-sensitive adhesive layer on one side of the support, and in addition to the heat-sensitive adhesive layer, the support is not provided with the heat-sensitive adhesive layer. It is used for heat-sensitive adhesive labels having a heat-sensitive recording layer on the surface. Furthermore, the use of various food products in wraps and for so-called food POS which is stuck on the wrap, or for distribution and delivery used by attaching cardboard or the like is increasing.
However, conventional heat-sensitive adhesives have insufficient adhesive strength to vinyl chloride wrap, polyolefin wrap, cardboard and the like, which hinders practical application of heat-sensitive adhesive labels themselves.
For this reason, Patent Document 3 uses a thermosensitive adhesive in which an undercoat layer containing non-foamed hollow particles is provided between a support and a thermosensitive recording layer, and dicyclohexyl phthalate is a solid plasticizer. Heat sensitive adhesive labels have been proposed. Since this thermosensitive adhesive label is provided with an undercoat layer, the thermosensitive recording layer is almost satisfactory in terms of improving the thermal sensitivity of the thermosensitive recording layer and preventing the color development of the thermosensitive recording layer that occurs during thermal activation. However, when the pressure-sensitive adhesive label is overlaid, blocking occurs at about 40 ° C., which does not satisfy about 50 ° C. expected as a practical level.

In recent years, it has become a common recognition of mankind to run economies and production activities in consideration of environmental conservation. The Environment Agency reported about 70 chemical substances suspected of having endocrine disrupting effects in 1997. Of these about 70 chemicals, the phthalate ester description is found. Thus, it is feared that the phthalate ester mainly used as a plasticizer is taken into the human body through the food chain, destroys the hormone balance in the body, and adversely affects the reproductive function.
Therefore, many of the conventionally known heat-sensitive adhesives use the phthalate ester as a solid plasticizer, and the present situation is that it is strongly desired to provide an alternative material.

JP-A-6-57226 JP-A-6-57233 JP-A-9-265260 "Adhesion Handbook" 12th edition, pages (131-135), published in 1970

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention overcomes the disadvantages found in conventional heat-sensitive adhesives, has strong adhesion to rough surface adherends such as corrugated cardboard and polyolefin wrap, has little decrease in adhesive strength over time, and can be heated with low energy. Phthalic acid that can be activated, has good blocking resistance, and is used as a heat-meltable substance (also called a solid plasticizer) in conventional heat-sensitive adhesives from the viewpoint of environmental issues An object is to provide a heat-sensitive adhesive and a heat-sensitive adhesive material using a substance in place of an ester.

ただし、前記構造式（ＩＩ）中、Ｒ^１は、水素原子、又はアルキル基を表す。ｎは１〜５の整数を表す。
＜２＞ 熱溶融性物質が、体積平均粒子径１．２μｍ以下の固体微粒子である前記＜１＞に記載の感熱性粘着剤である。
＜３＞ 熱溶融性物質の感熱性粘着剤における含有量が、２５〜８０質量％である前記＜１＞から＜２＞のいずれかに記載の感熱性粘着剤である。
＜４＞ 熱可塑性樹脂が、アクリル酸エステル共重合体、メタクリル酸エステル共重合体、アクリル酸エステル−メタクリル酸エステル共重合体、アクリル酸エステル−スチレン共重合体、アクリル酸エステル−メタクリル酸エステル−スチレン共重合体及びエチレン−酢酸ビニル共重合体から選択される少なくとも１種である前記＜１＞から＜３＞のいずれかに記載の感熱性粘着剤である。
＜５＞ 更に粘着付与剤を含有し、該粘着付与剤が、ロジン系エステル樹脂、テルペン樹脂、芳香族変性テルペン樹脂、テルペンフェノール樹脂及び水素添加テルペン樹脂から選択される少なくとも１種である前記＜１＞から＜４＞のいずれかに記載の感熱性粘着剤である。
＜６＞ 支持体と、該支持体の一方の面上に、前記＜１＞から＜５＞のいずれかに記載の感熱性粘着剤を含む感熱性粘着剤層とを有することを特徴とする感熱性粘着材料である。
＜７＞ 支持体における感熱性粘着剤層とは反対側の面に、記録層を有する前記＜６＞に記載の感熱性粘着材料である。
＜８＞ 記録層が、感熱記録層、インクジェット記録層、熱転写用インク受容層、及び電子写真記録層のいずれかである前記＜７＞に記載の感熱性粘着材料である。
＜９＞ 感熱記録層が、少なくともロイコ染料及び顕色剤を含む前記＜８＞に記載の感熱性粘着材料である。
＜１０＞ 支持体と感熱性粘着剤層との間に中空粒子とバインダー樹脂とを含む中間層を有する前記＜６＞から＜９＞のいずれかに記載の感熱性粘着材料である。
＜１１＞ ラベル状、シート状、及びロール状のいずれかである前記＜６＞から＜１０＞のいずれかに記載の感熱性粘着材料である。 Means for solving the problems are as follows. That is,
<1> It contains at least a thermoplastic resin and a heat-meltable substance, and the heat-meltable substance is at least a compound represented by the following structural formula (I) and a compound represented by the structural formula (II). It is a heat sensitive adhesive characterized by including either.

However, in the structural formula (II), R ¹ represents a hydrogen atom or an alkyl group. n represents an integer of 1 to 5.
<2> The heat-sensitive adhesive according to <1>, wherein the heat-meltable substance is a solid fine particle having a volume average particle diameter of 1.2 μm or less.
<3> The heat-sensitive adhesive according to any one of <1> to <2>, wherein the content of the heat-meltable substance in the heat-sensitive adhesive is 25 to 80% by mass.
<4> Thermoplastic resin is acrylic acid ester copolymer, methacrylic acid ester copolymer, acrylic acid ester-methacrylic acid ester copolymer, acrylic acid ester-styrene copolymer, acrylic acid ester-methacrylic acid ester- The heat-sensitive adhesive according to any one of <1> to <3>, which is at least one selected from a styrene copolymer and an ethylene-vinyl acetate copolymer.
<5> Further containing a tackifier, wherein the tackifier is at least one selected from rosin ester resins, terpene resins, aromatic modified terpene resins, terpene phenol resins, and hydrogenated terpene resins. The heat-sensitive adhesive according to any one of <1> to <4>.
<6> A support and a heat-sensitive adhesive layer containing the heat-sensitive adhesive according to any one of <1> to <5> on one surface of the support. It is a heat-sensitive adhesive material.
<7> The heat-sensitive adhesive material according to <6>, wherein the support has a recording layer on a surface opposite to the heat-sensitive adhesive layer.
<8> The heat-sensitive adhesive material according to <7>, wherein the recording layer is any one of a heat-sensitive recording layer, an inkjet recording layer, a thermal transfer ink receiving layer, and an electrophotographic recording layer.
<9> The heat-sensitive adhesive material according to <8>, wherein the heat-sensitive recording layer contains at least a leuco dye and a developer.
<10> The heat-sensitive adhesive material according to any one of <6> to <9>, further including an intermediate layer including hollow particles and a binder resin between the support and the heat-sensitive adhesive layer.
<11> The heat-sensitive adhesive material according to any one of <6> to <10>, which is any one of a label shape, a sheet shape, and a roll shape.

ただし、前記構造式（Ｉ）中、Ｒ^１及びＲ^２は、互いに同一であってもよいし、異なっていてもよく、水素原子、又はアルキル基を表す。ｍ及びｎは、１〜５の整数を表す。 The heat-sensitive adhesive of the present invention contains at least a thermoplastic resin and a heat-meltable substance, and the heat-meltable substance is at least one selected from compounds represented by the following structural formula (I) including. In the heat-sensitive adhesive of the present invention, the adhesive strength to a rough surface adherend such as corrugated cardboard or polyolefin wrap is strong, the adhesive strength is less decreased over time, can be thermally activated with low energy, and A heat-sensitive adhesive material having good blocking resistance can be provided.

However, in the structural formula (I), 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.

  The heat-sensitive adhesive material of the present invention has a support and a heat-sensitive adhesive layer containing the heat-sensitive adhesive of the present invention on one surface of the support. In the heat-sensitive adhesive material of the present invention, the heat-sensitive pressure-sensitive adhesive layer contains the heat-sensitive pressure-sensitive adhesive of the present invention, so that the adhesive force to rough surface adherends such as corrugated cardboard and polyolefin wrap is strong. It is possible to provide a heat-sensitive adhesive label, a heat-sensitive adhesive label sheet and the like that have little decrease in adhesive strength, can be thermally activated with low energy, and have good blocking resistance.

  According to the present invention, it is possible to solve various problems in the past, strong adhesion to rough surface adherends such as corrugated cardboard and polyolefin wrap, less decrease in adhesion over time, and heat activation with low energy, In addition, a heat-sensitive adhesive and a heat-sensitive adhesive material having good blocking resistance can be provided.

(Thermosensitive adhesive)
The heat-sensitive adhesive of the present invention contains at least a thermoplastic resin and a heat-meltable substance, and further contains a tackifier and, if necessary, other components.

-Hot-melting material-
The heat-meltable substance is solid at normal temperature, so it does not give plasticity to the resin, but melts by heating to swell or soften the resin, develops adhesiveness, melts by heating, and then slowly crystallizes. Therefore, the adhesiveness can be maintained for a long time even after the heat source is removed.

  As the hot-melt material, at least one of a compound represented by the following structural formula (I) and a compound represented by the structural formula (II) is used.

In the structural formula (II), R ¹ represents a hydrogen atom or an optionally branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, or a t-butyl group. , Etc.
n represents an integer of 1 to 5.

  Examples of the compound represented by the structural formula (I) include tri-2,4-xylene phosphine, tri-2,5-xylene phosphine, tri-2,6-xylene phosphine, and tri-3,4-xylene. Examples include phosphine and tri-3,5-xylenephosphine. These may be used individually by 1 type and may use 2 or more types together.

  As the compound represented by the structural formula (II), specifically, compounds represented by the following structural formula are suitable. These may be used individually by 1 type and may use 2 or more types together.

As the compound represented by any one of the structural formulas (I) and (II), a compound that is solid at room temperature and melts when heated is used. The melting point of these compounds is preferably 70 ° C. or higher, and more preferably 80 ° C. or higher. In this case, the upper limit of the compound is about 200 ° C. When the melting point is less than 70 ° C., when a heat-sensitive adhesive material is used, there may be problems in storage, such as an adhesive force appearing at a normal storage environment temperature, and a heat-sensitive adhesive coating solution. In some cases, production troubles such as the development of adhesive strength may occur when coating and drying the coating on the support. On the other hand, when the melting point exceeds 200 ° C., a large amount of energy is required to develop adhesive force, resulting in practical problems. In addition, when a thermal recording paper is used as a support and an adhesive force is developed with a large amount of energy, the thermal recording layer may be colored, and a printed image may not be read.
In the heat-meltable substance of the present invention, when two or more compounds represented by at least one of the structural formulas (I) and (II) are mixed and used, the heat activation energy can be lowered ( In particular, when two or more kinds of heat-melting substances having similar structures are mixed and used, the effect is improved and the delay property is improved.

The volume average particle diameter of the hot-melt material is preferably 1.2 μm or less, more preferably 1.0 μm or less, and even more preferably 0.5 μm or less. As a result, the dynamic thermal activity sensitivity is increased, and the heat-sensitive adhesive is obtained by being compatible with the thermoplastic resin and the tackifier at low energy. In addition, when the volume average particle diameter of the hot-melt material is 0.5 μm or less, the storage stability at a normal storage environment temperature may be improved (in short, the blocking resistance is improved).
Here, the volume average particle diameter of the heat-meltable substance means a 50% volume average particle diameter, and can be measured by, for example, a laser diffraction / scattering method. Specifically, it is an average particle diameter corresponding to 50% of the cumulative distribution in the dispersion, measured by a laser diffraction / scattering particle size distribution measuring device “LA700” manufactured by Horiba, Ltd.

  The content of the heat-meltable substance in the heat-sensitive adhesive is preferably 25 to 80% by mass, and more preferably 35 to 70% by mass. When the content of the hot-melt material is less than 25% by mass or more than 80% by mass, the adhesive strength may be lowered in any case. In addition, when combined with a resin having a low glass transition temperature (Tg), if the content of the heat-meltable substance is less than 25% by mass, an adhesive force is exhibited at a normal storage environment temperature. May occur.

-Thermoplastic resin-
The thermoplastic resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, if a resin similar to the thermoplastic resin used in the intermediate layer is used, the compatibility of the resins in both layers is improved. Since it improves, the adhesive force with respect to rough surface adherends, such as a corrugated cardboard, improves, and is preferable.
The thermoplastic resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, natural rubber latex obtained by graft copolymerization with a vinyl-based monomer, acrylate copolymer, methacrylic acid Examples include ester copolymers, acrylic ester-methacrylic ester copolymers, acrylic ester-styrene copolymers, acrylic ester-methacrylic ester-styrene copolymers, and ethylene-vinyl acetate copolymers. These may be used individually by 1 type and may use 2 or more types together.

  10-60 mass% is preferable and, as for content in the said thermosensitive adhesive of the said thermoplastic resin, 15-50 mass% is more preferable. When the content of the thermoplastic resin is less than 10% by mass or more than 60% by mass, both are undesirable because the adhesive strength is lowered. Moreover, when the content rate of low Tg resin exceeds 60 mass%, the malfunction on storage (blocking) will arise, such as adhesive force expressing by the temperature in normal storage environment.

-Tackifier-
The tackifier is not particularly limited as long as it can improve the adhesive strength of the heat-sensitive adhesive, and can be appropriately selected from known ones according to the purpose. For example, a rosin derivative (for example, Rosin, polymerized rosin, hydrogenated rosin, etc.), terpene resins (for example, terpene resins, aromatic modified terpene resins, terpene phenol resins, hydrogenated terpene resins, etc.), petroleum resins, phenol resins, xylene resins, etc. Is mentioned. 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.

  5-30 mass% is preferable and, as for content in the said thermosensitive adhesive of the said tackifier, 5-20 mass% is more preferable. When the content is less than 5% by mass, the adhesive strength may be reduced. When the content exceeds 30% by mass, storage defects (decrease in blocking resistance) or low temperature may occur at a normal storage environment temperature. Decrease in initial adhesive strength in the environment may occur.

In the heat-sensitive adhesive of the present invention, in addition to the above-mentioned components, eutectic agents, inorganic substances such as titanium oxide, alumina, colloidal silica, kaolin, talc, stearic acid metal salts, paraffin, natural waxes are used for preventing blocking. In addition, organic substances such as synthetic wax, natural fats and oils, polystyrene powder, and the like can be further added with a dispersant, an antifoaming agent, a thickener, and the like as necessary.
Examples of the eutectic agent include oxalic acid di-p-methylbenzyl ester, oxalic acid di-p-ethylbenzyl ester, oxalic acid di-p-chlorobenzyl ester, and oxalic acid dibenzyl ester.

  By applying the heat-sensitive adhesive of the present invention to one side of the support, the adhesive strength to rough surface adherends such as corrugated cardboard and polyolefin wrap is strong, there is little decrease in the adhesive strength over time, and thermal activation with low energy It is possible to obtain a heat-sensitive adhesive material having good blocking resistance. In addition, by applying the recording layer on one side of the support and applying the heat-sensitive adhesive of the present invention on the other side, the adhesive strength against rough surface adherends such as cardboard and polyolefin wrap is strong and anti-blocking. A heat-sensitive adhesive material for recording with good properties can be obtained.

(Heat-sensitive adhesive material)
The heat-sensitive adhesive material of the present invention comprises a support and at least the heat-sensitive adhesive layer of the present invention on one surface of the support, an intermediate layer (under layer), and further if necessary. It has other layers. On the other hand, the surface of the support opposite to the heat-sensitive adhesive layer has a recording layer.

<Support>
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 can 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, According to the objective, it can select suitably, For example, an inorganic material or an organic material is mentioned. 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, polyethylene, and polypropylene. Among these, high-quality paper, art paper, coated paper and the like are particularly preferable. These may be used individually by 1 type and may use 2 or more types together.

The support is preferably surface-modified by corona discharge treatment, oxidation reaction treatment (chromic acid or the like), etching treatment, easy adhesion treatment, antistatic treatment, etc. for the purpose of improving the adhesion of the coating layer. Moreover, it is preferable to add a white pigment such as titanium oxide to the support to make it white.
There is no restriction | limiting in particular as thickness of the said support body, According to the objective, it can select suitably, 50-2,000 micrometers is preferable and 100-1,000 micrometers is more preferable.

<Thermosensitive adhesive layer>
The heat-sensitive adhesive layer contains the heat-sensitive adhesive of the present invention, and further contains other components as necessary.
Examples of the other components include, for example, titanium oxide, alumina, colloidal silica, kaolin, talc, and other inorganic materials, stearic acid metal salts, paraffin, natural wax, synthetic wax, natural fat, polystyrene powder, etc. Organic substances can be added, and other components such as a dispersant, an antifoaming agent, and a thickener can be added as necessary.

The heat-sensitive pressure-sensitive adhesive layer is not particularly limited and can be formed according to a known method. For example, the heat-sensitive pressure-sensitive adhesive layer is suitably formed by a coating method using a heat-sensitive pressure-sensitive adhesive layer coating solution obtained by blending the above components. be able to.
Examples of the coating method include 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.
It should be noted that the drying conditions during the coating or printing must be dried in a temperature range in which the hot-melt material and the eutectic agent used do not melt. As a means for drying, in addition to hot air drying, a drying method using a heat source using infrared rays, microwaves, and high frequencies can be used.

The coating amount of the heat-sensitive adhesive layer coating liquid is usually preferably ² to 35 g / m ² , more preferably 5 to 25 g / m ^{2 in} terms of dry coating amount. When the coating amount of the coating solution for the heat-sensitive adhesive layer is less than 2 g / m ² , sufficient adhesion may not be obtained when performing adhesion by heating, and the glass transition temperature ( Since a thermoplastic resin having a low Tg) is used, the blocking resistance may be inferior, and if it exceeds 35 g / m ² , the heat insulating effect of the intermediate layer is reduced, and the economical efficiency is deteriorated.

  The heat-sensitive adhesive material of the present invention has the above-described configuration, so that it has strong adhesive force to rough surface adherends such as corrugated cardboard and polyolefin wrap, has little decrease in adhesive force over time, and can be activated with low energy. In addition, the anti-blocking property is good.

<Recording layer>
The recording layer is a layer capable of recording an image or the like, and is not particularly limited and can be appropriately selected according to the purpose. For example, a thermal recording layer, an inkjet recording layer, a thermal transfer ink receiving layer, an electron Preferred examples include a photographic recording layer.
The recording layer is preferably provided on the surface of the support opposite to the surface on which the heat-sensitive adhesive layer is provided.
In these recording layers, information such as images and characters appropriately selected according to the purpose can be recorded (formed) in a single color (for example, black) or in multiple colors (two colors, three colors, full color, etc.). Moreover, you may give a monochromatic or multicolor printing process. There is no restriction | limiting in particular as this printing processing, Although it can select suitably according to the objective, UV processing printing using the ink containing UV curable resin is preferable from a viewpoint of an improvement of an anti-blocking characteristic.

  Among these recording layers, a thermal recording layer and a thermal transfer ink receiving layer are preferable, and a thermal recording layer is particularly preferable. When the recording layer is the heat-sensitive recording layer, for example, separately from heating the heat-sensitive adhesive layer, by applying heat imagewise from the heat-sensitive recording layer side, a desired color image can be obtained. Recording (formation) can be performed on the heat-sensitive recording layer, and added value can be given to the heat-sensitive adhesive material.

-Thermal recording layer-
The heat-sensitive recording layer is not particularly limited and may be appropriately selected depending on the purpose. For example, the heat-sensitive recording layer contains a leuco dye and a developer as main components, and further contains a binder resin, a sensitizer and the like. And the like.

The leuco dye is not particularly limited and may be appropriately selected from known ones according to the purpose. Examples thereof include triphenylmethane dyes, fluoran dyes, phenothiazine dyes, auramine dyes, and spiropyran dyes. Indolinophthalide dyes are publicly listed.
Examples of the leuco dye include 3,3-bis (p-dimethylaminophenyl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also called crystal violet lactone), 3, 3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) -6-chlorophthalide, 3,3-bis (p-dibutylaminophenyl) phthalide, 3- Cyclohexylamino-6-chlorofluorane, 3-dimethylamino-5,7-dimethylfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7,8- Benzfluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3- N-p-tolyl-N-ethylamino) -6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 2- {N- (3'-trifluoromethyl) Phenyl) amino} -6-diethylaminofluorane, 2- {3,6-bis (diethylamino) -9- (o-chloroanilino) xanthylbenzoate lactam}, 3-diethylamino-6-methyl-7- (m-trichloro) Methylanilino) fluorane, 3-diethylamino-7- (o-chloroanilino) fluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane, 3-N-methyl-N-amylamino-6-methyl-7-ani Linofluorane, 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-benzoindolino-pyrospirane, 6'-bromo-3'-methoxy-benzoindolino-pyrospirane, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy-5 ' -Chlorophenyl) phthalide, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy-5'-nitrophenyl) phthalide, 3- (2'-hydroxy-4'-diethylamino) Phenyl) -3- (2′-methoxy-5′-methylphenyl) phthalide, 3-diethylamino-6-methyl-7- (2 ′, 4′-dimethylanilino) fluoro 3- (2′-methoxy-4′-dimethylaminophenyl) -3- (2′-hydroxy-4′-chloro-5′-methylphenyl) phthalide, 3-morpholino-7- (N-propyl- Trifluoromethylanilino) fluorane, 3-pyrrolidino-7-trifluoromethylanilinofluorane, 3-diethylamino-5-chloro-7- (N-benzyl-trifluoromethylanilino) fluorane, 3-pyrrolidino-7 -(Di-p-chlorophenyl) methylaminofluorane, 3-diethylamino-5-chloro-7- (α-phenylethylamino) 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-methyltoluidino) -7- (pn-butylanilino) fluorane 3- (N-benzyl-N-cyclohexylamino) -5,6-benzo-7-α-naphthylamino-4′0-bromofluorane, 3-diethylamino-6-methyl-7-mesitidino-4 ′, 5′-benzofluorane, 3-diethylamino-6-methyl-7- (2 ′, 4′-dimethylanilino) fluorane, 3- (p-dimethylaminophenyl) -3- {1,1-bis (p -Dimethylaminophenyl) ethylene-2-yl} phthalide, 3- (p-dimethylaminophenyl) -3- {1,1-bis (p-dimethylaminophenyl) ethylene-2-yl } -6-dimethylaminophthalide, 3- (p-dimethylaminophenyl) -3- (1-p-dimethylaminophenyl-1-phenylethylene-2-yl) phthalide, 3- (p-dimethylaminophenyl- 3- (1-p-dimethylaminophenyl-1-p-chlorophenylethylene-2-yl) -6-dimethylaminophthalide, 3- (4′-dimethylamino-2′-methoxy) -3- (1 ″ -P-dimethylaminophenyl-1 "-p-chlorophenyl-1", 3 "-butadiene-4" -yl) benzophthalide, 3- (4'-dimethylamino-2'-benzyloxy) -3- (1 " -P-dimethylaminophenyl-1 "-phenyl-1", 3 "-butadiene-4" -yl) benzophthalide, 3-dimethylamino-6-dimethylamino-fluorene-9 Spiro-3 '-(6'-dimethylamino) phthalide, 3,3-bis {2- (p-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl} -4,5,6,7-tetra Chlorophthalide, 3-bis {1,1-bis (4-pyrrolidinophenyl) ethylene-2-yl} -5,6-dichloro-4,7-dibromophthalide, bis (p-dimethylaminostyryl)- 1-naphthalenesulfonylmethane, 3- (N-methyl-N-propylamino) -6-methyl-7-anilidefluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3,6-bis ( Dimethylamino) fluorane spiro (9,3 ′)-6′-dimethylaminophthalide, 3-diethylamino-6-chloro-7-anilinofluorane, 3-N-ethyl-N- (2-ethoxy) (Lopyl) amino-6-methyl-7-anilinofluorane, 3-N-ethyl-N-tetrahydrofurfurylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-mesitidino -4 ', 5'-benzofluorane, 3-N-methyl-N-isobutyl-6-methyl-7-anilinofluorane, 3-N-ethyl-N-isoamyl-6-methyl-7-anilino Examples include fluoran. These may be used individually by 1 type and may use 2 or more types together.

  The developer is not particularly limited and can be appropriately selected from known electron-accepting compounds according to the purpose. For example, phenolic compounds, thiophenolic compounds, thiourea derivatives, organic acids And metal salts thereof. Examples of the developer include 4,4'-isopropylidenebisphenol, 3,4'-isopropylidenebisphenol, 4,4'-isopropylidenebis (o-methylphenol), 4,4'-secondary butylidene. Bisphenol, 4,4'-isopropylidenebis (o-tertiarybutylphenol), 4,4'-cyclohexylidene diphenol, 4,4'-isopropylidenebis (2-chlorophenol), 2,2'-methylenebis ( 4-methyl-6-tertiarybutylphenol), 2,2'-methylenebis (4-ethyl-6-tertiarybutylphenol), 4,4'-butylidenebis (6-tertiarybutyl-2-methyl) phenol, 1, 1,3-tris (2-methyl-4-hydroxy-5-tertiary buty Phenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 4,4'-thiobis (6-tertiarybutyl-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, P-hydroxybenzoic acid Isopropyl acid, benzyl P-hydroxybenzoate, benzyl protocatechuate, stearyl gallate, lauryl gallate, octyl gallate, 1,7-bis (4-hydroxyphenylthio) -3,5-dioxaheptane, 1,5 -Bis (4-hydroxyphenylthio) -3-oxaheptane, , 3-bis (4-hydroxyphenylthio) -propane, 2,2'-methylenebis (4-ethyl-6-tertiarybutylphenol), 1,3-bis (4-hydroxyphenylthio) -2-hydroxypropane, N, N'-diphenylthiourea, N, N'-di (m-chlorophenyl) thiourea, salicylanilide, 5-chloro-salicylanilide, salicyl-o-chloroanilide, 2-hydroxy-3-naphthoic acid, thiocyanate Zinc acid antipyrine complex, 2-acetyloxy-3-naphthoic acid zinc salt, 2-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, hydroxynaphthoic acid zinc, aluminum, calcium and other metal salts Bis- (4-hydroxyphenyl) acetic acid methyl ester, bis- (4-hydroxyphenyl) ) Acetic acid benzyl ester, 4- {β- (p-methoxyphenoxy) ethoxy} salicylic acid, 1,3-bis (4-hydroxycumyl) benzene, 1,4-bis (4-hydroxycumyl) benzene, 2, 4'-diphenolsulfone, 3,3'-diallyl-4,4'-diphenolsulfone, antipyrine complex of α, α-bis (4-hydroxyphenyl) -α-methyltoluenethiocyanate zinc, tetrabromobisphenol A Tetrabromobisphenol S, 4,4′-thiobis (2-methylphenol), 3,4-hydroxy-4′-methyl-diphenylsulfone, 4,4′-thiobis (2-chlorophenol), and the like. These may be used individually by 1 type and may use 2 or more types together.

  The addition amount of the developer in the heat-sensitive recording layer is not particularly limited and may be appropriately selected depending on the purpose. It is preferably 1 to 20 parts by weight with respect to 1 part by weight of the color former, and 2 to 10 parts by weight. Part is more preferred.

  The binder resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, polyvinyl alcohol, starch or derivatives thereof, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose and the like Cellulose derivatives, sodium polyacrylate, polyvinylpyrrolidone, acrylamide / acrylic acid ester copolymer, acrylamide / acrylic acid ester / methacrylic acid terpolymer, styrene / maleic anhydride copolymer alkali salt, isobutylene / maleic anhydride In addition to water-soluble polymers such as acid copolymer alkali salts, polyacrylamide, sodium alginate, gelatin, and casein, polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylic acid ester , Polymethacrylic acid ester, polybutyl methacrylate, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer emulsion, etc., and styrene / butadiene copolymer, latex such as styrene / butadiene / acrylic copolymer Etc. These may be used individually by 1 type and may use 2 or more types together.

  Various heat-fusible substances can be used as fillers in the heat-sensitive recording layer. Examples of the heat-fusible substance include fatty acids such as stearic acid and behenic acid, fatty acid amides such as stearic acid amide and palmitic acid amide, zinc stearate, aluminum stearate, calcium stearate, zinc palmitate, behen Fatty acid metal salts such as zinc acid, p-benzylbiphenyl, terphenyl, triphenylmethane, benzyl p-benzyloxybenzoate, β-benzyloxynaphthalene, β-naphthoic acid phenyl ester, 1-hydroxy-2-naphthoic acid phenyl Esters, 1-hydroxy-2-naphthoic acid methyl ester, diphenyl carbonate, terephthalic acid dibenzyl ester, terephthalic acid dimethyl ester, 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dibenzyloxynaphth Talene, 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-butene, 1,2-bis (4-methoxyphenylthio) ethane, dibenzoylmethane, 1,4-bis (phenylthio) butane, 1,4-bis (phenylthio) -2- Butene, 1,2-bis (4-methoxyphenylthio) ethane, 1,3-bis (2-vinyloxyethoxy) benzene, 1,4-bis (2-vinyloxyethoxy) benzene, p- (2-vinyl Oxyethoxy) biphenyl, p-aryloxybiphenyl, p-propargyloxybiphenyl, dibenzoyloxymethane, 1,3-dibenzoyloxypropane, Benzyl disulfide, 1,1-diphenylethanol, 1,1-diphenylpropanol, p- (benzyloxy) benzyl alcohol, 1,3-diphenoxy-2-propanol, N-octadecylcarbamoyl-p-methoxycarbonylbenzene, N-octadecyl Examples thereof include carbamoylbenzene, succinic acid dibenzyl ester, 1,5-bis (p-methoxyphenyloxy) -3-oxapentane and the like. These may be used individually by 1 type and may use 2 or more types together.

  In the thermosensitive recording layer, various auxiliary additive components such as a surfactant and a lubricant can be used in combination as required. Examples of the lubricant include higher fatty acids or metal salts thereof, higher fatty acid amides, higher fatty acid esters, animal waxes, vegetable waxes, mineral waxes, petroleum waxes and the like.

The thermosensitive recording layer is not particularly limited and can be formed by a generally known method. For example, a leuco dye, a developer separately from a binder, other components, a ball mill, an attritor, a sand mill, etc. After being pulverized and dispersed with a disperser of 1 to 3 μm until the dispersed particle size becomes 1 to 3 μm, the mixture is mixed with a filler, a heat-fusible substance (sensitizer) dispersion liquid, etc., if necessary, and mixed in a predetermined formulation to form a heat-sensitive recording layer. A heat-sensitive recording layer can be formed by preparing a coating solution and coating it on a support.
The thickness of the heat-sensitive recording layer varies depending on the composition of the heat-sensitive recording layer, the application of the heat-sensitive adhesive material, and the like, and cannot be specified unconditionally, but is preferably 1 to 50 μm, more preferably 3 to 20 μm.

-Ink receiving layer for thermal transfer recording-
The ink-receiving layer for thermal transfer recording contains a filler, a binder resin, and a water-proofing agent, and further contains other components as necessary.

  The filler is not particularly limited and can be appropriately selected depending on the purpose. For example, calcium carbonate, silica, titanium oxide, aluminum hydroxide, clay, calcined clay, magnesium silicate, magnesium carbonate, white carbon, Examples thereof include zinc oxide, barium sulfate, surface-treated calcium carbonate and silica, urea-formalin resin, styrene / methacrylic acid copolymer, and fine powders such as polystyrene.

There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably from well-known water-soluble resin, For example, polyvinyl alcohol, starch or its derivative (s), methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose Cellulose derivatives such as ethyl cellulose; sodium polyacrylate, polyvinylpyrrolidone, acrylamide / acrylic acid ester copolymer, acrylamide / acrylic acid ester / methacrylic acid terpolymer, styrene / maleic anhydride copolymer alkali salt, isobutylene / Water-soluble polymer compounds such as maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, casein and the like. These may be used individually by 1 type and may use 2 or more types together.
The ratio of the filler to the water-soluble resin in the ink receiving layer is related to the blocking property, and the content ratio (solid content) of the filler to the water-soluble resin is preferably 1: 0.1 to 1: 0.2.

The water-proofing agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include formaldehyde, glyoxal, chrome alum, melamine, melamine-formaldehyde resin, polyamide resin, and polyamide-epichlorohydrin resin. .
The ratio of the water-resistant agent and the water-soluble resin is also related to the blocking property, and the content ratio (solid content) of the water-resistant resin 1 is preferably 0.3 to 0.5. As described above, the ink receiving layer is formed by containing a filler and a water-soluble resin, and further containing a water-soluble resin and a water-proofing agent in a specific ratio, and the surface of the ink receiving layer is further smoothed by a calendar or the like. By processing at a temperature of 500 seconds or more, the print quality can be further improved in addition to the effect of the filler.

-Intermediate layer-
The intermediate layer (under layer) is preferably provided between the heat-sensitive adhesive layer and the support and between the recording layer (particularly the heat-sensitive recording layer) and the support. Can do. In this case, when the heat-sensitive pressure-sensitive adhesive layer is thermally activated, the heat energy from the thermal head can be efficiently used, and the heat-sensitive pressure-sensitive adhesive layer can exhibit sufficient adhesive force with a small amount of energy. This is advantageous in that it can. Further, when the recording layer, particularly the heat-sensitive recording layer, is provided on the side of the support opposite to the heat-sensitive adhesive layer, when the heat-sensitive adhesive layer is heated with high energy, the energy is converted to the heat-sensitive adhesive layer. However, the presence of the intermediate layer (under layer) provides a sufficient heat insulating effect to the thermal recording layer, and the background fogging in the thermal recording layer is likely to occur. This is advantageous in that the occurrence of such problems can be effectively prevented.

The air ratio in the intermediate layer (underlayer), that is, the ratio (%) of air occupying the underlayer is not particularly limited and can be appropriately selected depending on the purpose. It is advantageous in that the adhesive property of the heat-sensitive adhesive layer can be effectively improved.
The intermediate layer (under layer) can be formed in various forms, and particularly preferably includes a non-foaming form and containing hollow particles.
Examples of the hollow particles include fine hollow particles having a hollow ratio of about 30 to 95% using a thermoplastic resin as a soot, or porous pigments.
The said hollow particle means the hollow particle which made the thermoplastic resin the shell, contains air and other gas inside, and has already become a foamed state. Here, the hollow ratio means the ratio of the volume based on the outer diameter of the hollow microparticle to the volume based on the inner diameter.

The fine hollow particles having a hollow ratio of about 30 to 95% using the thermoplastic resin as a soot are those containing air or other gas inside and are already in a foamed state. The average particle diameter of the fine hollow particles is preferably 0.2 to 20 μm, and more preferably 0.5 to 10 μm. When the average particle diameter (particle outer diameter) is less than 0.2 μm, it is difficult to technically make it hollow, and the role of the intermediate layer may be insufficient. Since the surface smoothness of the heat-sensitive adhesive layer is reduced, the heat-sensitive adhesive layer is not uniformly applied, and more heat-sensitive adhesive may be required in order to make it more uniform. Therefore, it is desirable that such a fine hollow particle distribution has a uniform distribution spectrum with a small variation and a particle diameter in the above range.
Furthermore, in the present invention, plastic spherical hollow particles having a hollow ratio of 30% or more can be used, but 70% or more is more preferable. When the hollow ratio is less than 30%, the heat insulating property is insufficient, and thus heat energy is released to the outside through the support, and the thermal efficiency of the pressure-sensitive adhesive activation may deteriorate.

As described above, the fine hollow particles are made of a thermoplastic resin, and the thermoplastic resin is preferably a copolymer resin mainly composed of vinylidene chloride and acrylonitrile.
The porous pigment used in the intermediate layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include organic pigments such as urea formaldehyde resin and inorganic pigments such as shirasu earth.

In order to form the non-foaming intermediate layer of the present invention, the above-mentioned fine hollow particles and porous pigment are dispersed in water together with a binder resin, and this is applied onto a support and dried. In this case, the coating amount of the fine hollow particles is preferably 1 g or more per 1 m ² of the support, and more preferably ^{2 to} 15 g. The coating amount of the binder resin is not particularly limited and can be appropriately selected from an amount sufficient to strongly bond the intermediate layer to the support. Usually, the total amount of the fine hollow particles and the binder resin The content is preferably 2 to 50% by mass.

The binder resin used when forming the non-foaming intermediate layer is appropriately selected from at least one of conventionally known water-soluble polymers and aqueous polymer emulsions. Examples of the binder resin include water-soluble polymers such as polyvinyl alcohol, starch or derivatives thereof, cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylamide / acrylic. Acid ester copolymer, acrylamide / acrylic ester / methacrylic acid terpolymer, alkali styrene / maleic anhydride copolymer alkali salt, isobutylene / maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, casein Etc.
Examples of the aqueous polymer emulsion include latex such as styrene / butadiene copolymer, styrene / butadiene / acrylic copolymer, vinyl acetate resin, vinyl acetate / acrylic acid copolymer, and styrene / acrylic acid ester copolymer. And emulsions such as acrylic ester resins and polyurethane resins.

  The foamable filler is a hollow plastic filler containing a thermoplastic resin as a reed and containing a foaming agent of a low-boiling solvent inside, and various types are applied. In the case of a state, 2-50 micrometers is preferable, and in a foaming state, 10-100 micrometers is preferable and 10-50 micrometers is more preferable. There are no particular limitations on the thermoplastic resin used as a base for the plastic filler, and it can be appropriately selected according to the purpose. For example, polystyrene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, Examples thereof include acrylic ester resins, polyacrylonitrile, polybutadiene, and copolymers thereof. Further, as the foaming agent contained in the bag, propane, butane or a mixture thereof is generally used.

As a method for forming the foamable intermediate layer, the foamable plastic filler described above can be applied and dried on a support together with a binder resin, and then a hot plate can be adhered to the coated surface to heat and foam the plastic filler. That's fine. The application amount of the plastic filler is preferably 1 g or more, more preferably ² to 5 g as an unfoamed filler with respect to 1 m ² of the support. Moreover, the usage-amount of a binder should just be an quantity which makes a foamable intermediate | middle layer bind | bond strongly with respect to a support body, Usually, it is 5-5 with respect to the total amount of an unfoamed filler and a binder. 50 mass% is preferable. The heating foaming temperature is a temperature at which the thermoplastic resin constituting the filler ridge is softened. The expansion ratio is usually preferably 2 to 4 times, more preferably 2 to 3 times, and is appropriately selected so as to achieve the above foaming.

As described above, since the surface of the foamable intermediate layer formed on the support is considerably uneven, the surface is smoothed by calendering after the foamable intermediate layer is formed (after heating and foaming). It is preferable that one or a plurality of undercoat layers can be provided on the surface or the lower surface of the foamable intermediate layer as necessary.
In the intermediate layer, a filler, a thermofusible substance (sensitizer), a surfactant, and the like can be used in combination with the fine hollow particles, the porous pigment, the foamable filler, and the binder, if necessary. . In this case, examples of the filler include inorganic fine powders such as calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, surface-treated calcium and silica, and the like. And organic fine powders such as urea-formalin resin, styrene / methacrylic acid copolymer and polystyrene resin.
Examples of the heat-fusible substance (sensitizer) include, in addition to higher fatty acids or esters thereof, amides or metal salts, various waxes, condensates of aromatic carboxylic acids and amines, benzoic acid phenyl esters, higher Examples include linear glycols, dialkyl 3,4-epoxy-hexahydrophthalates, higher ketones, p-benzylbiphenyl and other thermofusible organic compounds having a melting point of about 50 to 200 ° C.

  The intermediate layer (underlayer) is not particularly limited and can be formed by a known coating method. Examples of the coating method include a blade coating method, a gravure coating method, a gravure offset coating method, a bar coating method, Roll coating method, knife coating method, air knife coating method, comma coating method, U comma coating method, AKKU coating method, smoothing coating method, micro gravure coating method, reverse roll coating method, 4 to 5 roll coating method, dip coating Method, curtain coating method, slide coating method, die coating method and the like.

-Protective layer-
The protective layer can be provided on the recording layer for the purpose of improving barrier properties, head matching properties, writing properties on the recording material, and the like.
There is no restriction | limiting in particular as said protective layer, According to the objective, it can select suitably, For example, what has a pigment, a binder, a crosslinking agent, a lubricant etc. as a main component is mentioned.
The protective layer can be suitably formed by the above-described coating method.

  In the heat-sensitive adhesive material of the present invention, a printed image can be formed on the recording layer or the protective layer on the recording layer. As the printing ink, for example, a UV-curable ink is heat-sensitive because it is quick-drying. It is used as an optimal ink for recording paper. Examples of the UV curable ink (UV ink) include UV RNC, UV NVR, UV SOYA, and UV SOYA-RNC UV inks manufactured by T & K TOKA; FD FL UV ink manufactured by Toyo Ink Manufacturing Co., Ltd. It is done.

The heat-sensitive adhesive material of the present invention can be suitably used by being cut before or after thermal activation of the heat-sensitive adhesive layer (at the time of heating). A cut may be formed in advance. 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 roll form, etc. are mentioned suitably.

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).
Among these, the polyethylene non-woven fabric (envelope etc.) is generally difficult to apply a heat-sensitive adhesive material, but in the case of the heat-sensitive adhesive material of the present invention, it is possible to express a stronger adhesive force over time, Even the nonwoven fabric made of polyethylene is advantageous in that it can be firmly attached.

The method for thermally activating the heat-sensitive adhesive layer in the heat-sensitive adhesive material of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an activation method and an activation method using a thermal head.
Among these, the activation method using a thermal head is preferable, and the following 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 heat-sensitive recording layer and heat activation of the heat-sensitive adhesive layer by heating both surfaces of the heat-sensitive adhesive material using an existing heat-sensitive recording printer device. Is advantageous.

  The heat-sensitive adhesive material of the present invention has been described in detail above. However, the present invention is not limited to the above-described embodiment, and various modifications may be made without departing from the gist of the present invention. For example, by applying the intermediate layer and the thermally active pressure-sensitive adhesive layer to both sides of the support, the adhesive strength to rough surface adherends such as corrugated cardboard and polyolefin wrap is strong, the adhesive strength is not reduced with time, and the energy is low. A heat-sensitive double-sided pressure-sensitive adhesive paper that can be thermally activated and has good blocking resistance can also be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example at all.

Example 1
-[Liquid A] Preparation of hot melt material dispersion-
A mixture having the following composition was dispersed using a sand mill so that the volume average particle diameter was 1.0 μm to prepare a hot-melt material dispersion [liquid A].
・ Tri-2,5-xylenephosphine (melting point (mp): 153 to 156 ° C.) 30.0 parts by mass ・ 30% by mass aqueous polyvinyl alcohol solution 5.0 parts by mass ・ Surfactant (alkyl- Allyl sulfonate) 0.15 parts by mass Water 64.85 parts by mass

-[Liquid B] Preparation of heat-sensitive adhesive dispersion-
・ Methyl methacrylate-2-ethylhexyl acrylate copolymer emulsion (glass transition temperature (Tg): −65 ° C., non-volatile content 50%) 10 mass parts ・ Polymerized rosin emulsion (softening point 145 ° C., non-volatile content 50%) 6.5 mass parts ・ Hot-melting substance dispersion (liquid A) ... 33.3 mass parts

Next, the heat-sensitive adhesive dispersion [Liquid B] was applied and dried on the back of 80 g / m ² single-sided coated paper to a dry mass of 16 g / m ² to prepare a heat-sensitive adhesive label.

(Example 2)
In Example 1, a heat-sensitive adhesive label was produced in the same manner as in Example 1 except that the following hot-meltable substance dispersion [Liquid C] was used instead of the hot-meltable substance dispersion [Liquid A]. .
-[Liquid C] Preparation of hot-melt material dispersion-
A mixture having the following composition was dispersed using a ball mill so that the volume average particle diameter was 0.45 μm to prepare a hot-melt material dispersion (liquid C).
・ Tri-2,5-xylenephosphine (melting point (mp): 153 to 156 ° C.) 30.0 mass parts ・ 30 mass% polyvinyl alcohol aqueous solution… 5.0 mass parts ・ Surfactant (polyalkylene) (Ethylene) glycolalkylphenyl ether) 0.15 parts by mass Water ... 64.85 parts by mass

(Example 3)
In Example 2, instead of tri-2,5-xylenephosphine (melting point (mp): 153 to 156 ° C.) in the hot-melt material dispersion [liquid C], tri-2,4-xylenephosphine (melting point (mp ): 158 ° C.) A heat-sensitive adhesive label was produced in the same manner as in Example 2 except that it was used.

Example 4
In Example 2, instead of tri-2,5-xylenephosphine (melting point (mp): 153 to 156 ° C.) in the hot-melt material dispersion [liquid C], tri-3,5-xylenephosphine (melting point (mp ): 160 to 162 ° C.) A heat-sensitive adhesive label was produced in the same manner as in Example 2.

(Example 5)
-[Liquid D] Preparation of coating solution for forming non-foaming intermediate layer-
A mixture having the following composition was stirred and dispersed to prepare a non-foaming intermediate layer-forming coating solution [Liquid D]. Fine hollow particle dispersion (copolymer resin mainly composed of vinylidene chloride / acrylonitrile, solid content concentration 32 30% by mass ・ Styrene / butadiene copolymer latex (glass transition temperature (Tg): + 4 ° C.) 10 mass parts ・ Water ・ ・・ 60 parts by mass

-[E solution] Preparation of color former dispersion-
A mixture having the following composition was dispersed using a sand mill so that the volume average particle diameter was 1.5 μm to prepare [E solution] color former dispersion.
3-di-n-butylamino-6-methyl-7-anilinofluorane: 20 parts by mass 10% by weight aqueous polyvinyl alcohol solution: 10 parts by mass Water: 70 parts by mass

-[F solution] Preparation of developer dispersion-
A mixture having the following composition was dispersed using a sand mill so that the volume average particle diameter was 1.5 μm to prepare [F liquid] developer dispersion.
· 4-isopropoxy-4'-hydroxydiphenylsulfone · · · 10 parts · 10% by weight polyvinyl alcohol aqueous solution · · 25 parts · calcium carbonate · · 15 parts · water · · · 50 parts

Next, the [E liquid] color developer dispersion, [E liquid], and [F liquid] developer dispersion were mixed and stirred so that [E liquid]: [F liquid] = 1: 8. A thermosensitive recording layer coating solution [G solution] was prepared.
Next, the [Liquid D] non-foaming intermediate layer forming coating solution was applied and dried on the surface of the support so that the mass after drying was 4 g / m ² to provide a non-foaming intermediate layer. On the non-foamable intermediate layer, the above heat-sensitive recording layer coating solution [G solution] was applied and dried so that the mass after drying was 5 g / m ² to provide a heat-sensitive recording layer.
On the obtained heat-sensitive recording layer, the following protective layer coating solution was applied and dried so that the mass upon drying was 3 g / m ^2, and the super calender so that the Oken smoothness was 2000 seconds. A thermal recording paper was prepared by processing.

-Preparation of coating solution for protective layer-
A protective layer primary dispersion was prepared by pulverizing and dispersing a mixture having the following composition in a vertical sand mill so that the volume average particle diameter was 1 μm or less.
[Primary dispersion for protective layer]
Aluminum hydroxide: 20 parts by mass 10% by weight polyvinyl alcohol (PVA) aqueous solution: 20 parts by mass Water: 40 parts by mass Next, the protective layer primary dispersion is used to protect the following composition. A layer coating solution was prepared.
[Composition of protective coating solution]
-Primary dispersion of protective layer-10 parts by mass-10% by weight polyvinyl alcohol (PVA) aqueous solution-20 parts by weight-12.5% by weight aqueous epichlorohydrin solution-5 parts by weight-30% by weight zinc stearate dispersion Liquid: 2 parts by mass

  Next, in Example 2, a heat-sensitive adhesive label was produced in the same manner as in Example 2 except that the above-mentioned heat-sensitive recording paper was used instead of the single-sided coated paper.

(Example 6)
-[Liquid H] Preparation of Hot Melting Substance Dispersion-
A mixture having the following composition was dispersed using a ball mill so that the volume average particle diameter was 0.45 μm to prepare a dispersion [liquid H].
・ Tri-2,5-xylenephosphine (melting point (mp): 153 to 156 ° C.) 15.0 parts by mass ・ Tri-3,5-xylenephosphine (melting point (mp): 160 to 162 ° C.) -15.0 parts by mass-30% by weight aqueous polyvinyl alcohol solution-5.0 parts by mass-Surfactant (polyalkylene (ethylene) glycol alkyl phenyl ether)-0.15 parts by mass-Water-64 .85 parts by mass

Next, a heat-sensitive adhesive dispersion [Liquid I] having the following composition was applied and dried on the back surface of a single-side coated paper of 80 g / m ^{2 so} that the dry mass was 16 g / m ² to prepare a heat-sensitive adhesive label. .
-[Liquid I] Composition of thermosensitive adhesive dispersion-
・ Methyl methacrylate-n-butyl acrylate copolymer emulsion (glass transition temperature (Tg): −65 ° C., non-volatile content 50%) 10 mass parts ・ Polymerized rosin emulsion (softening point 145 ° C., non-volatile content 50%) ) ... 6.5 parts by mass ・ Hot meltable substance dispersion (liquid H) ... 33.3 parts by mass

(Example 7)
In Example 1, a heat-sensitive adhesive label was produced in the same manner as in Example 1 except that the following hot-melt substance dispersion [Liquid J] was used instead of the hot-melt substance dispersion [Liquid A]. .
-[J liquid] Preparation of hot melt material dispersion-
A mixture having the following composition was dispersed using a sand mill so that the volume average particle diameter was 0.6 μm to prepare a dispersion [liquid J].
・ Tri-2,5-xylenephosphine (melting point (mp): 153 to 156 ° C.) 30.0 parts ・ 30% by mass aqueous polyvinyl alcohol solution 5.0 parts by mass ・ Surfactant (polyalkylene ( (Ethylene) glycol alkyl phenyl ether) ... 0.15 parts by mass Water ... 64.85 parts by mass

(Example 8)
-[Liquid K] Preparation of hot melt substance dispersion-
A mixture having the following composition was dispersed using a sand mill so that the volume average particle diameter was 1.0 μm to prepare a hot-melt material dispersion (liquid K).
Tri-2,4-xylenephosphine (melting point (mp): 158 ° C.) 50.0 parts by mass 30% by weight aqueous polyvinyl alcohol solution 8.3 parts by mass Surfactant (alkyl-allylsulfone) Acid salt) ... 0.1 part by mass-water ... 66.6 parts by mass

Next, the heat-sensitive adhesive dispersion liquid [L] having the following composition was applied and dried on the back surface of the single-side coated paper of 80 g / m ^{2 so} as to have a dry mass of 16 g / m ² to prepare a heat-sensitive adhesive label. .
-[Liquid L] Composition of heat-sensitive adhesive dispersion-
・ Methyl methacrylate-n-butyl acrylate copolymer emulsion (glass transition temperature (Tg): −62 ° C., non-volatile content 50%) 10 mass parts ・ Polymerized rosin emulsion (softening point 145 ° C., non-volatile content 50%) ) ... 3 parts by mass ・ Hot-melting substance dispersion (liquid K) ... 70.0 parts by mass

Example 9
-[M liquid] Preparation of hot melt material dispersion-
A mixture having the following composition was dispersed using a ball mill so that the volume average particle diameter was 0.40 μm to prepare a hot-melt material dispersion (liquid M).
・ Tri-2,5-xylenephosphine (melting point (mp): 153 to 156 ° C.) 50.0 mass parts 30 mass% polyvinyl alcohol aqueous solution 8.3 mass parts Surfactant (polyalkylene (Ethylene) glycol alkyl phenyl ether) ... 0.25 parts by mass Water: 64.45 parts by mass

Next, a heat-sensitive adhesive dispersion liquid [N solution] having the following composition was applied and dried on the back surface of one-side coated paper of 80 g / m ^{2 so} as to have a dry mass of 16 g / m ² , thereby preparing a heat-sensitive adhesive label. .
-Composition of [N liquid] thermosensitive adhesive dispersion-
・ Methyl methacrylate-n-butyl acrylate copolymer emulsion (glass transition temperature (Tg): −62 ° C., non-volatile content 50%) 15.0 mass parts ・ Polymerized rosin emulsion (softening point 145 ° C., non-volatile content) 50%) ··· 3 parts by mass · Hot-melting substance dispersion (liquid M) ··· 6.2 parts by mass

(Example 10)
-[O solution] Preparation of intermediate layer coating solution-
A mixture having the following composition was stirred and dispersed to prepare an intermediate layer coating solution [O solution].
・ Plastic spherical hollow particles (1) (acrylonitrile / vinylidene chloride / methyl methacrylate copolymer, solid content concentration 41 mass%, average particle diameter 3.6 μm, hollow ratio 90%)... 14.6 mass parts -Copolymer of ethylhexyl acrylate / methyl methacrylate / styrene (glass transition temperature (Tg): -65 ° C, solid content concentration 55.4% by mass, manufactured by Showa Polymer Co., Ltd.) ... 21.7 parts by mass Activator (Dapro W-77, manufactured by Elementis Japan Co., Ltd.) ... 0.1 parts by mass-Water ... 63.6 parts by mass

Next, an intermediate layer by coating and drying the intermediate layer coating solution on the back surface of the single-sided coated paper 80 g / m ² and [O solution] As after drying mass is 5 g / m ^2. On this intermediate | middle layer, the heat-sensitive adhesive dispersion liquid [I liquid] of the said Example 6 was apply | coated and dried so that it might become dry mass 11g / m < ² >, and the heat-sensitive adhesive label was produced.

(Comparative Example 1)
In Example 1, the same as Example 1 except that tri-2,5-xylenephosphine (melting point (mp): 153 to 156 ° C.) of the heat-meltable substance dispersion [liquid A] was replaced with dicyclohexyl phthalate. Thus, a heat-sensitive adhesive label was produced.

(Comparative Example 2)
Example 1 is the same as Example 1 except that tri-2,5-xylenephosphine (melting point (mp): 153 to 156 ° C.) of the hot-melt material dispersion [liquid A] is replaced with diphenyl phthalate. Thus, a heat-sensitive adhesive label was produced.

(Comparative Example 3)
In Comparative Example 1, a heat-sensitive adhesive label was produced in the same manner as in Comparative Example 1, except that the heat-sensitive recording paper of Example 5 was used instead of the single-sided coated paper.

  Next, for each of the heat-sensitive adhesive labels of Examples 1 to 10 and Comparative Examples 1 to 3, the adhesive properties (after 1 hour and after 1 day) and blocking resistance were evaluated as follows. The results are shown in Table 2.

<Evaluation of adhesive properties>
Each obtained heat-sensitive adhesive material was cut into a rectangle of 40 mm × 150 mm, and using a heat-sensitive printing apparatus (manufactured by Okura Electric Co., Ltd., TH-PMD), head conditions: each energy: 0.40 mJ / dot, 0.50 mJ The heat-sensitive adhesive material was thermally activated under the conditions of / dot, printing speed: 4 ms / line, and platen pressure: 6 kgf / line. Subsequently, it was stuck to the corrugated cardboard under each environmental condition in the longitudinal direction with a 2 kg pressure rubber roller, and peeled under the conditions of a peeling angle of 180 degrees and a peeling speed of 300 mm / min after 1 hour and 1 day.
The adhesive strength at that time was measured with a force gauge (MODEL DPS-5, manufactured by IMADA), and the data was read and averaged at intervals of 0.1 seconds. The unit is gf / 40 mm. This test was carried out under a normal temperature environment (23 ° C., 65% RH).

<Evaluation of blocking resistance>
The surface opposite to the heat-sensitive adhesive layer surface of each of the obtained heat-sensitive adhesive materials was brought into contact, and a pressure of 200 gf / cm ² was applied and left under a dry condition at 50 ° C. for 24 hours. Then, after leaving at room temperature, the sample was peeled off, and the blocking resistance at that time was evaluated according to the criteria shown in Table 1. Rank 7 or higher is a practical level.

実施例１〜１０は、比較例１〜３に比べて、粘着特性（１時間後、１日後）、及び耐ブロッキング性が良好であることが認められる。

It is recognized that Examples 1 to 10 have better adhesive properties (after 1 hour and after 1 day) and blocking resistance than Comparative Examples 1 to 3.

・３０質量％ポリビニルアルコール水溶液・・・５.０質量部
・界面活性剤（アルキル−アリルスルホン酸塩）・・・０.１５質量部
・水・・・６４.８５質量部 (Example 11)
-[Liquid A] Preparation of hot melt material dispersion-
A mixture having the following composition was dispersed using a sand mill so as to have a volume average particle size of 1.0 μm to prepare a hot melt material dispersion [liquid A].
・ Hot-melting substance represented by the following structural formula (tris (pt-butoxyphenyl) phosphine, melting point (mp) = 150 ° C.) 30.0 parts by mass

-30% by weight aqueous polyvinyl alcohol solution-5.0 parts by weight-Surfactant (alkyl-allyl sulfonate)-0.15 parts by weight-Water-64.85 parts by weight

Next, a heat-sensitive adhesive dispersion liquid [B] having the following composition was applied and dried on one side (back surface) of a single-side coated paper of 80 g / m ^{2 so} as to have a dry mass of 16 g / m ^2, and a heat-sensitive adhesive label. Was made.
-Composition of [B liquid] thermosensitive adhesive dispersion-
・ Methyl methacrylate-butyl acrylate copolymer emulsion (glass transition temperature (Tg): −62 ° C., non-volatile content 50%) ... 10 parts by mass ・ Polymerized rosin emulsion (softening point 145 ° C., non-volatile content 50%)・ ・ 6.5 parts by mass ・ The above-mentioned heat-meltable substance dispersion (liquid A)...

・３０質量％ポリビニルアルコール水溶液・・・５.０質量部
・界面活性剤（ポリアルキレン（エチレン）グリコールアルキルフェニルエーテル）・・・０.１５質量部
・水・・・６４.８５質量部 (Example 12)
In Example 11, a heat-sensitive adhesive label was produced in the same manner as in Example 11 except that the following hot-melt substance dispersion [Liquid C] was used instead of the hot-melt substance dispersion [Liquid A].
-[Liquid C] Preparation of hot-melt material dispersion-
A mixture having the following composition was dispersed using a ball mill so that the volume average particle diameter was 0.45 μm to prepare a hot-melt material dispersion (liquid C).
・ Hot-melting substance represented by the following structural formula (tris (pt-butoxyphenyl) phosphine, melting point (mp) = 150 ° C.) 30.0 parts by mass

-30% by weight aqueous polyvinyl alcohol solution-5.0 parts by mass-Surfactant (polyalkylene (ethylene) glycol alkyl phenyl ether)-0.15 parts by mass-Water-64.85 parts by mass

(Example 13)
In Example 12, the hot-melt material in the hot-melt material dispersion [liquid C] is a hot-melt material represented by the following structural formula (tris (p-methoxyphenyl) phosphine, melting point (mp) = 131 to 132. A heat-sensitive adhesive label was produced in the same manner as in Example 12 except that the temperature was changed to [° C.].

(Example 14)
-[Liquid D] Preparation of coating solution for forming non-foaming intermediate layer-
A mixture having the following composition was stirred and dispersed to prepare a non-foaming intermediate layer-forming coating solution [Liquid D]. Fine hollow particle dispersion (copolymer resin mainly composed of vinylidene chloride / acrylonitrile, solid content concentration 32 30% by mass ・ Styrene / butadiene copolymer latex (glass transition temperature (Tg): + 4 ° C.) 10 mass parts ・ Water ・ ・・ 60 parts by mass

-[E solution] Preparation of color former dispersion-
A mixture having the following composition was dispersed using a sand mill so that the volume average particle diameter was 1.5 μm to prepare [E solution] color former dispersion.
3-di-n-butylamino-6-methyl-7-anilinofluorane: 20 parts by mass 10% by weight aqueous polyvinyl alcohol solution: 10 parts by mass Water: 70 parts by mass

-[F solution] Preparation of developer dispersion-
A mixture having the following composition was dispersed using a sand mill so that the volume average particle diameter was 1.5 μm to prepare [F liquid] developer dispersion.
· 4-isopropoxy-4'-hydroxydiphenylsulfone · · · 10 parts · 10% by weight polyvinyl alcohol aqueous solution · · 25 parts · calcium carbonate · · 15 parts · water · · · 50 parts

Next, the [E liquid] color developer dispersion, [E liquid], and [F liquid] developer dispersion were mixed and stirred so that [E liquid]: [F liquid] = 1: 8. A thermosensitive recording layer coating solution [G solution] was prepared.
Next, the [Liquid D] non-foaming intermediate layer forming coating solution was applied and dried on the surface of the support so that the mass after drying was 4 g / m ² to provide a non-foaming intermediate layer. On the non-foamable intermediate layer, the above heat-sensitive recording layer coating solution [G solution] was applied and dried so that the mass after drying was 5 g / m ² to provide a heat-sensitive recording layer.
On the obtained heat-sensitive recording layer, the following protective layer coating solution was applied and dried so that the mass upon drying was 3 g / m ^2, and the super calender so that the Oken smoothness was 2000 seconds. A thermal recording paper was prepared by processing.

-Preparation of coating solution for protective layer-
A protective layer primary dispersion was prepared by pulverizing and dispersing a mixture having the following composition in a vertical sand mill so that the volume average particle diameter was 1 μm or less.
[Primary dispersion for protective layer]
Aluminum hydroxide: 20 parts by mass 10% by weight polyvinyl alcohol (PVA) aqueous solution: 20 parts by mass Water: 40 parts by mass Next, the protective layer primary dispersion is used to protect the following composition. A layer coating solution was prepared.
[Composition of protective coating solution]
-Primary dispersion of protective layer-10 parts by mass-10% by weight polyvinyl alcohol (PVA) aqueous solution-20 parts by weight-12.5% by weight aqueous epichlorohydrin solution-5 parts by weight-30% by weight zinc stearate dispersion Liquid: 2 parts by mass

  Next, in Example 12, a heat-sensitive adhesive label was produced in the same manner as in Example 12 except that the above-mentioned heat-sensitive recording paper was used instead of the single-sided coated paper.

・下記構造式で表される熱溶融性物質（トリス（ｐ−ｔ−ブトキシフェニル）ホスフィン、融点（ｍｐ）＝１５０℃）・・・１５.０質量部

・３０質量％ポリビニルアルコール水溶液・・・５.０質量部
・界面活性剤（ポリアルキレン（エチレン）グリコールアルキルフェニルエーテル）・・・０.１５質量部
・水・・・６４.８５質量部 (Example 15)
-[Liquid H] Preparation of Hot Melting Substance Dispersion-
A mixture having the following composition was dispersed using a ball mill so as to have an average particle diameter of 0.45 μm to prepare a hot-melt material dispersion (liquid H).
・ Hot-melting substance represented by the following structural formula (tris (p-methoxyphenyl) phosphine, melting point (mp) = 131 to 132 ° C.) 15.0 parts by mass

・ Hot-melting substance represented by the following structural formula (tris (pt-butoxyphenyl) phosphine, melting point (mp) = 150 ° C.) 15.0 parts by mass

-30% by weight aqueous polyvinyl alcohol solution-5.0 parts by mass-Surfactant (polyalkylene (ethylene) glycol alkyl phenyl ether)-0.15 parts by mass-Water-64.85 parts by mass

-[Liquid I] Preparation of thermosensitive adhesive dispersion-
A heat-sensitive adhesive dispersion [Liquid I] having the following composition was applied and dried on one side (back side) of 80 g / m ² single-side coated paper so that the mass after drying was 16 g / m ^2. Produced.
・ Methyl methacrylate-2-ethylhexyl acrylate copolymer emulsion (glass transition temperature (Tg): −65 ° C., non-volatile content 50%) 10 mass parts ・ Polymerized rosin emulsion (softening point 145 ° C., non-volatile content 50%) 6.5 mass parts ・ Hot-melting substance dispersion (liquid H) 33.3 mass parts

・３０質量％ポリビニルアルコール水溶液・・・５.０質量部
・界面活性剤（ポリアルキレン（エチレン）グリコールアルキルフェニルエーテル）・・・０.１５質量部
・水・・・６４.８５質量部 (Example 16)
In Example 11, a heat-sensitive adhesive label was produced in the same manner as in Example 11 except that the following hot-melt substance dispersion [Liquid J] was used instead of the hot-melt substance dispersion [Liquid A]. .
-[J liquid] Preparation of hot melt material dispersion-
A mixture having the following composition was dispersed using a sand mill so that the volume average particle diameter was 0.6 μm to prepare a hot-melt material dispersion (liquid J).
・ Hot-melting substance represented by the following structural formula (tris (pt-butoxyphenyl) phosphine, melting point (mp) = 150 ° C.) 30.0 parts by mass

-30% by weight aqueous polyvinyl alcohol solution-5.0 parts by mass-Surfactant (polyalkylene (ethylene) glycol alkyl phenyl ether)-0.15 parts by mass-Water-64.85 parts by mass

・下記構造式で表される熱溶融性物質（トリス（ｐ−ｔ−ブトキシフェニル）ホスフィン、融点（ｍｐ）＝１５０℃）・・・１５.０質量部

・３０質量％ポリビニルアルコール水溶液・・・５.０質量部
・界面活性剤（ポリアルキレン（エチレン）グリコールアルキルフェニルエーテル）・・・０.１５質量部
・水・・・６４.８５質量部 (Example 17)
In Example 11, a heat-sensitive adhesive label was produced in the same manner as in Example 11 except that the following hot-melt substance dispersion liquid [K liquid] was used instead of the hot-melt substance dispersion liquid [A liquid]. .
-[Liquid K] Preparation of hot melt substance dispersion-
A mixture having the following composition was dispersed using a ball mill so as to have an average particle diameter of 0.45 μm to prepare a hot melt material dispersion [liquid K].
・ Hot-melting substance represented by the following structural formula (tri-2,4-xylylphosphine, melting point (mp) = 158 ° C.) 15.0 parts by mass

・ Hot-melting substance represented by the following structural formula (tris (pt-butoxyphenyl) phosphine, melting point (mp) = 150 ° C.) 15.0 parts by mass

-30% by weight aqueous polyvinyl alcohol solution-5.0 parts by mass-Surfactant (polyalkylene (ethylene) glycol alkyl phenyl ether)-0.15 parts by mass-Water-64.85 parts by mass

(Comparative Example 4)
In Example 11, a heat-sensitive adhesive label was prepared in the same manner as in Example 11 except that the hot-melt substance in the [A liquid] hot-melt substance dispersion was changed to dicyclohexyl phthalate.

(Comparative Example 5)
In Example 11, a heat-sensitive adhesive label was produced in the same manner as in Example 11 except that the hot-melt substance in the hot-melt substance dispersion was changed to diphenyl phthalate.

(Comparative Example 6)
A heat-sensitive adhesive label was prepared in the same manner as in Comparative Example 4 except that the heat-sensitive recording paper prepared in Example 14 was used instead of the single-sided coated paper of Comparative Example 4.

  Next, about each heat-sensitive adhesive label of obtained Examples 11-16 and Comparative Examples 4-6, it is the same as Examples 1-10 and Comparative Examples 1-3, and adhesive property (after 1 hour and 1 day later) ) And blocking resistance were evaluated. The results are shown in Table 3.

実施例１１〜１７は、比較例４〜６に比べて、粘着特性（１時間後、１日後）、及び耐ブロッキング性が良好であることが認められる。

It is recognized that Examples 11 to 17 have better adhesive properties (after 1 hour and after 1 day) and blocking resistance than Comparative Examples 4 to 6.

The heat-sensitive adhesive material using the heat-sensitive adhesive of the present invention has strong adhesion to rough surface adherends such as corrugated cardboard and polyolefin wrap, has little decrease in adhesion over time, and can be activated with low energy. In addition, the anti-blocking property is good, and for example, it is suitably used widely for industrial, commercial and household use.

Claims (11)

It contains at least a thermoplastic resin and a heat-meltable substance, and the heat-meltable substance contains at least one of a compound represented by the following structural formula (I) and a compound represented by the structural formula (II). A heat-sensitive adhesive characterized by containing.

However, in the structural formula (II), R ¹ represents a hydrogen atom or an alkyl group. n represents an integer of 1 to 5.   The heat-sensitive adhesive according to claim 1, wherein the heat-meltable substance is a solid fine particle having a volume average particle diameter of 1.2 µm or less.   The heat-sensitive adhesive according to any one of claims 1 to 2, wherein the content of the heat-meltable substance in the heat-sensitive adhesive is 25 to 80% by mass.   The thermoplastic resin is an acrylic ester copolymer, a methacrylic ester copolymer, an acrylic ester-methacrylic ester copolymer, an acrylic ester-styrene copolymer, an acrylic ester-methacrylic ester-styrene copolymer. The heat-sensitive adhesive according to any one of claims 1 to 3, which is at least one selected from a coalescence and an ethylene-vinyl acetate copolymer.   5. A tackifier is further contained, and the tackifier is at least one selected from rosin ester resins, terpene resins, aromatic modified terpene resins, terpene phenol resins and hydrogenated terpene resins. The heat-sensitive adhesive according to any one of the above.   A heat-sensitive adhesive material comprising a support and a heat-sensitive adhesive layer containing the heat-sensitive adhesive according to any one of claims 1 to 5 on one surface of the support.   The heat-sensitive adhesive material according to claim 6, 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 7, wherein the recording layer is any one of a heat-sensitive recording layer, an inkjet recording layer, a thermal transfer ink receiving layer, and an electrophotographic recording layer.   The heat-sensitive adhesive material according to claim 8, wherein the heat-sensitive recording layer contains at least a leuco dye and a developer.   The heat sensitive adhesive material in any one of Claim 6 to 9 which has an intermediate | middle layer containing a hollow particle and binder resin between a support body and a heat sensitive adhesive layer. The heat-sensitive adhesive material according to any one of claims 6 to 10, which is any one of a label shape, a sheet shape, and a roll shape.