JP2006083222A - Heat-sensitive and pressure-sensitive adhesive label - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-sensitive and pressure-sensitive adhesive label having excellent adhesive strength and thermally activable with low energy. <P>SOLUTION: The heat-sensitive and pressure-sensitive adhesive label is provided with a heat-sensitive and pressure-sensitive adhesive layer consisting essentially of a thermoplastic resin, a pressure-sensitive adhesion imparting agent and a hot-meltable substance on one surface of a support. The heat-sensitive and pressure-sensitive adhesive label is further provided with an elastic under layer consisting essentially of a resin having ≤35 kgf/cm<SP>2</SP>100% modulus specified in JIS K6251 between the support and the heat-sensitive and pressure-sensitive adhesive layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a heat-sensitive pressure-sensitive adhesive and a heat-sensitive pressure-sensitive adhesive label that are non-sticky at room temperature but develop pressure-sensitive adhesive properties. More specifically, the present invention has excellent adhesion to an adherend and can be thermally activated with low energy. The present invention relates to a heat sensitive pressure sensitive adhesive and a heat sensitive pressure sensitive adhesive label using this pressure sensitive adhesive.

  In recent years, the use of adhesive labels for label applications such as price display labels, product display (barcode) labels, quality display labels, weighing display labels, and advertising labels (stickers) has been increasing. There are various recording methods such as an inkjet recording method, a thermal recording method, and a pressure sensitive recording method. Conventionally, a general adhesive label with a configuration in which an adhesive layer and release paper are laminated on the surface opposite to the information recording surface of the label can be simply attached by simply peeling off the release paper at the time of bonding. Widely used. However, the pressure-sensitive adhesive label having a general configuration is used by peeling the release paper, but the peeled release paper is hardly collected and reused, and is almost always disposed of. Therefore, in recent years, heat-sensitive adhesive labels that do not exhibit adhesiveness at room temperature and do not require release paper have attracted attention. In addition, the thermosensitive pressure-sensitive adhesive has a basic structure as described in ("Adhesion Handbook" 12th edition, pages (131-135), published in 1980, published by Kobunshi Shuppankai (non-patent document 1)). Specifically, it contains a heat-meltable substance such as a thermoplastic resin and a solid plasticizer and, if necessary, a tackifier. Thermoplastic resins impart adhesive strength and adhesive strength, and hot melt materials are solid at room temperature, so they do not give plasticity to resins, but they melt by heating to swell or soften the resin. Adhesiveness is developed. The tackifier also works to improve the tackiness. Since the hot-melt material in the heat-sensitive adhesive is slowly crystallized after being melted by heating, the adhesiveness is 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. It is also true that high thermal energy is required when the heat-sensitive adhesive is thermally activated. In order to solve such a problem, for example, in Japanese Patent No. 2683733 (Patent Document 1) and Japanese Patent Laid-Open No. 10-152660 (Patent Document 2), a plastic is provided between the support and the thermosensitive adhesive. A heat insulation layer using hollow particles / water-soluble binder is provided to reduce thermal energy (higher sensitivity) that is thermally activated. However, although relatively good results can be obtained with regard to the reduction of the heat-activated thermal energy of the heat-sensitive adhesive, the adhesive strength against rough surface adherends such as cardboard and polyolefin wrap has not yet reached the practical level. Yes, the problem of low initial adhesive strength after the development of adhesiveness has not been solved.

Japanese Patent No. 2683733 Japanese Patent Laid-Open No. 10-152660 "Adhesion Handbook" 12th edition, pages (131-135), published in 1970

  An object of the present invention is to provide a heat-sensitive pressure-sensitive adhesive label that solves the problems found in conventional heat-active pressure-sensitive adhesives, has excellent adhesive strength, and can be thermally activated with low energy.

That is, the said subject is solved by (1)-(19) of this invention.
(1) In the thermosensitive pressure-sensitive adhesive label having a thermosensitive adhesive layer mainly composed of a thermoplastic resin, a tackifier, and a heat-meltable substance on one side of the support, the support and the thermosensitive adhesive layer A heat-sensitive adhesive label comprising an elastic underlayer mainly composed of a resin having a 100% modulus of 35 kgf / cm ² or less as defined in JIS K6251;
(2) “The resin used for the elastic underlayer is polyether urethane resin, polyester urethane resin, urethane-acrylic composite resin, natural rubber, natural rubber-methyl methacrylate graft polymer, styrene-butadiene polymer, polybutadiene. At least one selected from the group consisting of methyl methacrylate-butadiene polymer, 2-vinylpyridine-styrene-butadiene polymer, and acrylonitrile-butadiene polymer. Heat-sensitive adhesive label ";
(3) “The heat-sensitive adhesive label according to item (1) or (2), wherein the elastic under layer is provided at 5 g / m ² or more”;
(4) “The intermediate layer mainly comprising a thermoplastic resin having a Tg of −70 ° C. to −5 ° C. and plastic spherical hollow particles is provided between the elastic under layer and the heat-sensitive adhesive layer. The heat-sensitive adhesive label according to any one of (1) to (3)
(5) “Tg—70 ° C. to −5 ° C. thermoplastic resin used for the intermediate layer is an acrylic ester copolymer, a methacrylic ester copolymer, an acrylic ester-methacrylic ester copolymer, acrylic acid. Item (4), wherein at least one selected from an ester-styrene copolymer, an acrylic acid ester-methacrylic acid ester-styrene copolymer, and an ethylene-vinyl acetate copolymer is used. Heat-sensitive adhesive label;
(6) “The hollow ratio of the plastic spherical hollow particles used in the intermediate layer is 70% or more and the maximum particle size of the hollow particles is 10.0 μm or less, and at the same time the average particle size is 2.0 to 5. The heat-sensitive adhesive label according to item (4) or (5), which is a 0 μm plastic spherical hollow particle ”;
(7) The item (4) to (4), wherein the material forming the plastic spherical hollow particles is an acrylonitrile-vinylidene chloride-methyl methacrylate or acrylonitrile-methacrylonitrile-isobornyl methacrylate copolymer. The heat-sensitive adhesive label according to any one of Items (6);
(8) “The ratio of Tg-70 ° C. to −5 ° C. thermoplastic resin used in the intermediate layer and plastic spherical hollow particles is 0.1 to 1.0 weight of plastic spherical hollow particles relative to 1 part by weight of the resin. The heat-sensitive adhesive label according to any one of the items (4) to (7),
(9) “In the heat-sensitive adhesive layer mainly composed of a thermoplastic resin, a tackifier, and a heat-meltable substance, the thermoplastic resin is an acrylate copolymer, a methacrylate ester copolymer, an acrylate ester. -Using at least one or more selected from a methacrylate ester copolymer, an acrylate ester-styrene copolymer, an acrylate ester-methacrylate ester-styrene copolymer, and an ethylene-vinyl acetate copolymer. The heat-sensitive adhesive label according to any one of (1) to (8) above;
(10) “A thermosensitive adhesive label provided with a thermosensitive adhesive layer mainly composed of a thermoplastic resin, a tackifier and a thermomeltable substance, wherein the thermomeltable substance is represented by the following general formula (I): The heat-sensitive adhesive label according to any one of (1) to (9), wherein one or more of the indicated benzotriazole compounds are used.

〔一般式（Ｉ）に於いてＲ₁、Ｒ₂は、個別に水素原子、炭素数が１〜８のアルキル基、α,α−ジメチルベンジル基の何れかを表わし、Ｘは、水素原子又は塩素原子を表わす。〕」；
（１１）「熱可塑性樹脂と粘着付与剤及び熱溶融性物質を主成分とする感熱性粘着剤層を設けた感熱性粘着ラベルであって、該熱溶融性物質が下記一般式（II）で示されるヒドロキシ安息香酸エステル化合物を１つ以上用いたものであることを特徴とする前記第（１）項乃至第（９）項のいずれかに記載の感熱性粘着ラベル。

[In General Formula (I), R ₁ and R _{2 each} independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an α, α-dimethylbenzyl group, and X represents a hydrogen atom or Represents a chlorine atom. ]];
(11) “A thermosensitive adhesive label provided with a thermosensitive adhesive layer mainly composed of a thermoplastic resin, a tackifier and a thermomeltable substance, wherein the thermomeltable substance is represented by the following general formula (II): The heat-sensitive adhesive label according to any one of items (1) to (9), wherein one or more of the hydroxybenzoic acid ester compounds shown are used.

〔一般式（II）に於いてＲ_１は、炭素数が１〜１８のアルキル基、シクロヘキシル基、アルケニル基、アラルキル基（芳香環に置換基を有してもよい。）およびフェニル基の何れかを表わす。〕」；
（１２）「熱可塑性樹脂と粘着付与剤及び熱溶融性物質を主成分とする感熱性粘着剤層を設けた感熱性粘着ラベルであって、該熱溶融性物質が下記一般式（III）、（IV）、（Ｖ）で示される化合物を１つ以上用いたものであることを特徴とする前記第（１）項乃至第（９）項のいずれかに記載の感熱性粘着ラベル。

[In General Formula (II), R ₁ represents any of an alkyl group having 1 to 18 carbon atoms, a cyclohexyl group, an alkenyl group, an aralkyl group (which may have a substituent on the aromatic ring), and a phenyl group. Represents. ]];
(12) “A thermosensitive adhesive label provided with a thermosensitive adhesive layer mainly composed of a thermoplastic resin, a tackifier and a thermomeltable substance, wherein the thermomeltable substance is represented by the following general formula (III), The heat-sensitive adhesive label according to any one of items (1) to (9), wherein one or more compounds represented by (IV) and (V) are used.

〔一般式（III）に於いてＲは、互いに異なっていてもよいメチル基、エチル基、メトキシ基又はエトキシ基を表わす。Ｘは、水素原子又は水酸基を表わす。〕

[In the general formula (III), R represents a methyl group, an ethyl group, a methoxy group or an ethoxy group, which may be different from each other. X represents a hydrogen atom or a hydroxyl group. ]

〔一般式（IV）に於いてＲ₁は、水素原子、メチル基、エチル基、メトキシ基、エトキシ基又はハロゲン原子を表わす。Ｙは、水素原子又は水酸基を表わす。〕

[In the general formula (IV), R ₁ represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group or a halogen atom. Y represents a hydrogen atom or a hydroxyl group. ]

〔一般式（Ｖ）に於いてＲ_２は、水素原子、メチル基、エチル基、メトキシ基、エトキシ基又はハロゲン原子を示す。〕」；
（１３）「熱可塑性樹脂と粘着付与剤及び熱溶融性物質を主成分とする感熱性粘着剤層において、該熱溶融性物質がヒンダードフェノール化合物であり、且つ分子構造内に下記一般式（VI）、（VII）、（VIII）何れかの構造を持つヒンダードフェノール化合物を１つ以上用いたものであることを特徴とする前記第（１）項乃至第（９）項のいずれかに記載の感熱性粘着ラベル。

[In the general formula (V), R ₂ represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group or a halogen atom. ]];
(13) In the heat-sensitive adhesive layer mainly composed of a thermoplastic resin, a tackifier, and a heat-meltable substance, the heat-meltable substance is a hindered phenol compound, and the following general formula ( Any one of (1) to (9) above, wherein one or more hindered phenol compounds having a structure of VI), (VII), or (VIII) are used. The heat-sensitive adhesive label described.

〔一般式（VI）、（VII）、（VIII）に於いてＲ_１は、炭素数６以下の分岐状アルキル基を示す。Ｒ_２は、炭素数６以下の直鎖状アルキル基または分岐状アルキル基を示す。〕」；
（１４）「該感熱性粘着剤層中に下記一般式（IX）で示される共融化剤を含有することを特徴とする前記第（１）項乃至第（１３）項のいずれかに記載の感熱性粘着ラベル。

[In the general formulas (VI), (VII) and (VIII), R ₁ represents a branched alkyl group having 6 or less carbon atoms. R ₂ represents a linear or branched alkyl group having 6 or less carbon atoms. ]];
(14) In any one of (1) to (13) above, the eutectic agent represented by the following general formula (IX) is contained in the heat-sensitive adhesive layer. Heat sensitive adhesive label.

〔一般式（IX）に於いてＸは、互いに異なっていてもよい水素原子、炭素数が１〜４のアルキル基、ハロゲン原子の何れかを表わす。〕」；
（１５）「支持体片面に該弾性アンダー層及び感熱性粘着剤層を順次設け、この粘着剤層と反対面にロイコ染料と顕色剤を主成分とする感熱記録層が設けられたことを特徴とする前記第（１）項乃至第（１４）項のいずれかに記載の感熱性粘着ラベル」；
（１６）「支持体が熱溶融転写記録用の受容紙であって、その受容紙の片面に前記弾性アンダー層及び感熱性粘着剤層が順次設けられたことを特徴とする前記第（１）項乃至前記第（１４）項のいずれかに記載の感熱性粘着ラベル」；
（１７）「熱溶融転写記録によって形成されたインク画像を有するものであることを特徴とする前記第（１６）項に記載の感熱性粘着ラベル」；
（１８）「ＵＶインキによって形成されたインク画像を有するものであることを特徴とする前記第（１５）項乃至第（１７）項のいずれかに記載の感熱性粘着ラベル」；
（１９）「ロール状に芯材に巻き付けられたことを特徴とする前記第（１５）項乃至第（１８）項のいずれかに記載の感熱性粘着ラベル」。

[In General Formula (IX), X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, which may be different from each other. ]];
(15) “The elastic under layer and the heat-sensitive adhesive layer are sequentially provided on one surface of the support, and the heat-sensitive recording layer mainly comprising a leuco dye and a developer is provided on the surface opposite to the pressure-sensitive adhesive layer. The heat-sensitive adhesive label according to any one of (1) to (14), which is characterized;
(16) The above (1), wherein the support is a receiving sheet for hot melt transfer recording, and the elastic under layer and the heat-sensitive adhesive layer are sequentially provided on one side of the receiving sheet. The heat-sensitive adhesive label according to any one of Items 1 to 14;
(17) “Thermosensitive adhesive label according to item (16), which has an ink image formed by hot melt transfer recording”;
(18) "The heat-sensitive adhesive label according to any one of (15) to (17) above, having an ink image formed by UV ink";
(19) “The heat-sensitive adhesive label according to any one of (15) to (18)”, wherein the heat-sensitive adhesive label is wound around a core in a roll shape.

  According to the present invention, overcoming the disadvantages found in conventional heat-activatable pressure-sensitive adhesives, strong adhesion to rough surface adherends such as cardboard and adherends such as polyolefin wrap, low energy thermal activation, and The blocking resistance was also good. Such a heat-sensitive adhesive label greatly contributes to the label field and environmental conservation.

Below, the characteristic regarding the heat-sensitive adhesive label of this invention is demonstrated in detail.
The heat-sensitive adhesive label of the present invention is a heat-sensitive pressure-sensitive adhesive label in which a heat-sensitive pressure-sensitive adhesive layer mainly comprising a thermoplastic resin, a tackifier, and a heat-meltable substance is provided on one side of a support. 100% modulus as defined in JIS K6251 (2 mm thick sheet is punched into a dumbbell shape with a 20 mm wide mark at the center, and this dumbbell shaped test piece is subjected to a tensile test. And a tensile layer at a speed of 500 mm / min, and an elastic under layer mainly composed of a resin whose stress is at the time when the marked line has a width of 40 mm is 35 kgf / cm ² or less. The initial adhesive strength is increased by improving the adhesion at the time of attachment to an adherend such as a rough adherend or a polyolefin wrap. In addition, when the heat-sensitive adhesive label of the present invention is thermally activated with a thermal head, the adhesiveness with the thermal head is improved, so that low-energy thermal activity is possible and high sensitivity can be achieved.

  Further, by providing a specific intermediate layer on the elastic under layer and further providing a heat-sensitive adhesive layer, the heat-sensitive adhesive layer can be activated with low energy (high sensitivity). In addition, by partially mixing the heat-sensitive adhesive layer and the intermediate layer, the amount of the adhesive can be increased by using the thermoplastic resin of the intermediate layer effectively. Adhesive strength to the body is increased. In addition, by using plastic spherical hollow particles having a high hollow ratio in the intermediate layer, the heat insulation effect is enhanced, and further low energy thermal activity is possible and high sensitivity can be achieved.

Resins having a 100% modulus of 35 kgf / cm ² or less as defined in JIS K6251 used for the elastic under layer are polyether urethane resin, polyester urethane resin, urethane-acrylic composite resin, natural rubber, natural rubber Examples include methyl methacrylate graft polymer, styrene-butadiene polymer, polybutadiene, methyl methacrylate-butadiene polymer, 2-vinylpyridine-styrene-butadiene polymer, and acrylonitrile-butadiene polymer. Particularly preferably, natural rubber, natural rubber-methyl methacrylate graft polymer, carboxy-modified styrene-butadiene polymer, polybutadiene, carboxy-modified methyl methacrylate-butadiene polymer, 2-vinylpyridine-styrene-butadiene polymer And carboxy-modified acrylonitrile-butadiene-based polymers. In general, these resins are often used as one type, but in some cases, two or more types may be mixed and used.

The resin having a 100% modulus of 35 kgf / cm ² or less used for the elastic underlayer of the present invention is unlike a material used for a conventional heat-activatable pressure-sensitive adhesive, and has a sheet shape that has almost no tack and can measure 100% modulus. Must be resin. Therefore, even if the resin used for the elastic under layer is easily mixed with the heat-sensitive adhesive or the like, the effect of increasing the initial adhesive force is small. In addition, a resin having a 100% modulus of 35 kgf / cm ² or less has a very high cushioning property (high elasticity) and is in close contact with the rough adherend due to being in a layer below the heat-sensitive adhesive layer. The effect of increasing the property is very large, and the effect of amplifying the initial adhesive force is great even if the pressure-sensitive adhesive layer is not as thick as pressure-sensitive adhesive.
As a conventional technique, a styrene-butadiene-based polymer is used as a resin for fixing minute hollow particles in order to increase the sensitivity of the thermosensitive coloring layer, but the 100% modulus as described in the comparative example is 35 kgf / cm ^2. A relatively hard resin exceeding the above is used, and in the case of this under layer, elasticity is hardly considered, and a resin having high heat resistance is selectively used.

Furthermore, you may add an inorganic filler and an organic filler to this elastic under layer to such an extent that elasticity is not dropped extremely. However, when a resin having a 100% modulus exceeding 35 kgf / cm ² as defined in JIS K6251 is used for the elastic underlayer, the rough surface adherend such as cardboard or the adherend such as polyolefin wrap is used. Since the adhesion effect at the time of pasting is not improved at all, the effect of improving the adhesive strength cannot be obtained. Furthermore, since the adhesion with the thermal head does not increase, there is no effect on low energy thermal activation.

  The thermoplastic resin having a Tg of −70 ° C. to −5 ° C. used in the intermediate layer is preferably a thermoplastic resin used in the heat-sensitive adhesive layer in the present invention, and a natural rubber latex or acrylic resin obtained by graft copolymerization with a vinyl monomer. Acid ester copolymer, methacrylate ester copolymer, acrylic acid ester-methacrylic acid ester copolymer, acrylic acid ester-styrene copolymer, acrylic acid ester-methacrylic acid ester-styrene copolymer, ethylene-vinyl acetate It is preferable to use at least one selected from copolymers. In the case of a high Tg resin exceeding the Tg range of the thermoplastic resin used for the intermediate layer, the characteristics of the intermediate layer cannot be obtained at all, and a rough surface adherend such as cardboard or an adherend such as a polyolefin wrap. Adhesive strength with respect to is not improved, and only the heat-sensitive adhesive layer provided in the upper layer becomes adhesive strength.

  In addition, the plastic spherical hollow particles used for the intermediate layer have an average particle diameter of 2.0 to 5.0 μm having a heat insulating effect and a hollow ratio of 70 in consideration of the problem of low energy thermal activation (high sensitivity thermal activation). % Or more of plastic spherical hollow particles are preferred. More preferably, the hollow particles have a maximum particle diameter of 10.0 μm or less and an average particle diameter of 2.0 to 5.0 μm and a hollow ratio of 70% or more. Those having a low hollowness have insufficient heat insulation effect, so that heat energy from the thermal head is released to the outside through the elastic underlayer and the support, and the low energy thermal activation effect is poor.

The plastic spherical hollow particles referred to in the present invention are hollow particles that are made of a thermoplastic resin and contain air or other gas inside and are already in a foamed state. Here, the “hollow ratio” is a ratio of the outer diameter to the inner diameter of the hollow fine particles, and is represented by the following formula.
Hollow ratio (%) = (inner diameter of hollow fine particles) / (outer diameter of hollow fine particles) × 100

  In addition, when the average particle diameter is larger than 5.0 μm, when a heat-sensitive adhesive layer is provided on the adhesive underlayer using these, a large particle part can be a part where the heat-sensitive adhesive layer is not formed, When heat-activated, the adhesive strength tends to decrease. On the other hand, when it is smaller than 2.0 μm, it becomes difficult to ensure a hollow ratio of 70% or more, and as a result, the low energy thermal activation effect is inferior. Moreover, in order to obtain the low energy thermal activation effect using the thermal head, the hollow ratio of the hollow particles used in the intermediate layer is required to be 70% or more. Moreover, as a material which forms the plastic spherical hollow particle which satisfy | fills said conditions, an acrylonitrile-vinylidene chloride-methyl methacrylate copolymer or an acrylonitrile-methacrylonitrile-isobornyl methacrylate copolymer is preferable.

  Moreover, about the ratio of the thermoplastic resin of Tg-70 degreeC--5 degreeC used for this intermediate | middle layer, and a plastic spherical hollow particle, 0.1-1.0 weight part of plastic spherical hollow particles with respect to 1 weight part of resin. When the amount of the plastic spherical hollow particles is less than 0.1 part, the high-sensitivity thermal activation is inferior and the blocking property is further lowered. Conversely, if the amount of plastic spherical hollow particles is more than 1 part, the adhesion to rough surface adherends such as corrugated cardboard and adherends such as polyolefin wrap does not improve, and only the heat-sensitive adhesive layer provided on the upper layer is adhered. It becomes power.

The coating amount of the elastic underlayer of the present invention is usually 5 to 35 g / m ² , preferably 8 to 25 g / m ² as a dry coating amount. If the coating amount of the elastic under layer is less than 5 g / m ² , the adhesion effect at the time of attaching the adherend cannot be obtained. On the other hand, if it exceeds 35 g / m ² , the adhesion effect when adhering the adherend is almost saturated, which is not economical.
Then, usually 0.2 to 10 g / ^{m 2} on a dry coating amount as the coating amount of the intermediate layer is preferably applied in the range of 1 to 5 g / ^{m 2.} If the coating amount of the intermediate layer is less than 0.2 g / m ² , the heat insulating effect during thermal activation cannot be obtained. On the other hand, if it exceeds 10 g / m ² , the adhesive strength and the heat insulating effect are saturated, which is not economical.

  In the heat-sensitive pressure-sensitive adhesive layer mainly composed of the thermoplastic resin of the present invention, a tackifier, and a heat-meltable substance, a natural rubber latex obtained by graft copolymerization of a vinyl monomer and an 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-styrene copolymer, ethylene-vinyl acetate copolymer It is preferable to use at least one selected from the above. By using a resin similar to the resin used for the intermediate layer for the heat-sensitive adhesive layer, the mixing of the resins is improved, so that the adherend such as a corrugated cardboard or a polyolefin wrap is used. Adhesive strength against is improved.

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

  In the heat-meltable substance of the present invention, the compounds represented by the above general formulas (I) to (VIII) are solid at room temperature and melt upon heating. The melting point of these compounds is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and the upper limit is about 200 ° C. When the melting point is less than 70 ° C., storage defects such as an adhesive force appearing at a normal storage environment temperature when used as a heat-sensitive adhesive will occur. In addition, there may be a problem in manufacturing such that adhesive force is exhibited when the heat-sensitive adhesive coating solution is applied to a substrate and dried. On the other hand, if 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 the heat-sensitive recording paper is used as a base material and the adhesive force is developed with a large amount of energy, there is a problem that the printed image cannot be read because the heat-sensitive recording layer is colored.

  Further, by setting the volume average particle diameter of the heat-meltable substance to 0.5 μm or less, the dynamic heat sensitivity is increased, and the heat-sensitive adhesive becomes compatible with the thermoplastic resin and the tackifier at a low energy. Furthermore, by using the above particle diameter, the storage stability at a normal storage environment temperature is improved (in short, the blocking resistance is improved).

In the heat-sensitive adhesive of the present invention, the content of the general formula compound that is a heat-meltable substance in the heat-sensitive adhesive is preferably 25 to 80% by weight, and more preferably 35 to 70% by weight. It is. When the content of the general formula compound, which is a heat-meltable substance, is less than 25% by weight or more than 80% by weight, the adhesive strength may decrease. Further, when combined with a low Tg resin, if the content of the general formula compound is less than 25% by weight, storage problems such as adhesive strength appear at normal storage environment temperatures (blocking) occur.
Next, specific examples of the compounds represented by the general formulas (I) to (VIII) in the hot-melt material of the present invention will be shown.

The benzotriazole compound represented by the general formula (I) is
2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl) -5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) 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, and benzotriazo Two or more kinds of tools may be mixed and used.

The hydroxybenzoic acid ester compound represented by the general formula (II) is:
methyl m-hydroxybenzoate, ethyl m-hydroxybenzoate, phenyl m-hydroxybenzoate, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, n-propyl p-hydroxybenzoate, n-p-hydroxybenzoate n -Butyl, stearyl p-hydroxybenzoate, cyclohexyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, 4-chlorobenzyl p-hydroxybenzoate, 4-methylbenzyl p-hydroxybenzoate, phenyl p-hydroxybenzoate Etc. Two or more kinds of hydroxybenzoic acid ester compounds may be mixed and used.

In the case of the compound represented by the general formula (III),
Toluoin, Anisoin, m-Anisoin, Deoxytoluin, DeoxyAnisoin, 4,4′-DiethylBenzoin, 4,4′-DiethoxyBenzoin, and the like.

In the case of the compound represented by the general formula (IV),
1-hydroxy-2-naphthoic acid phenyl, 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-naphthoic acid-p-chlorophenyl, 1,4-dihydroxy-2-naphtho Acid-o-chlorophenyl and the like can be mentioned.

In the case of the compound represented by the general formula (V),
Examples include benzoic acid-3-hydroxyphenyl, benzoic acid-4-hydroxyphenyl, benzoic acid-2-hydroxyphenyl, o-methylbenzoic acid-3-hydroxyphenyl, and p-chlorobenzoic acid-3-hydroxyphenyl.
Two or more kinds of these compounds represented by the general formulas (III), (IV), and (V) may be mixed and used.

  Examples of the hindered phenol compounds represented by the general formulas (VI), (VII), and (VIII) include compounds represented by the following Tables 1-1 to 1-4.

Two or more hindered phenol compounds represented by the general formulas (VI), (VII), and (VIII) may be mixed and used.
Further, as the eutectic agent used in the heat-sensitive adhesive layer of the present invention, a solidifying agent that is solid at room temperature and melts when heated is used. The melting point of these compounds is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and the upper limit is about 150 ° C. When the melting point is less than 70 ° C., storage defects such as an adhesive force appearing at a normal storage environment temperature when used as a heat-sensitive adhesive will occur. In addition, there may be a problem in manufacturing such that adhesive force is exhibited when the heat-sensitive adhesive coating solution is applied to a substrate and dried. On the other hand, if the melting point exceeds 150 ° C., the effect of eutectic heat-melting substance is lost.

  As the eutectic agent used in the present invention, eutectic agents generally used in heat-sensitive recording materials can be used, but the effect of eutecticizing the hot-melt material and compatibility with thermoplastic resins are excellent. Further, the coagulant is an oxalic acid dibenzyl ester compound represented by the general formula (IX).

The oxalic acid dibenzyl ester compound represented by the general formula (IX) is:
Examples include oxalic acid di-P-methylbenzyl ester, oxalic acid di-P-ethylbenzyl ester, oxalic acid di-P-chlorobenzyl ester, and oxalic acid dibenzyl ester. Also good.

  Furthermore, in order to improve the adhesive strength of the heat-sensitive adhesive, rosin derivatives, terpene resins, petroleum resins, phenol resins and xylene resins, which are tackifiers used in general adhesives for the above components, are used. used.

  As tackifiers that are particularly preferably used for the heat-sensitive adhesive of the present invention, rosin derivatives (rosin, polymerized rosin, hydrogenated rosin), terpene resins (terpene resins, aromatic modified terpene resins, terpene phenol resins, hydrogenated) Terpene resin). These tackifiers are compatible with the thermoplastic resin and the hot-melt material of the present invention, and the adhesive strength of the heat-sensitive adhesive is significantly improved. Moreover, the melting point or softening point of the tackifier in the heat-sensitive adhesive is preferably 80 ° C. or higher, more preferably 80 to 200 ° C. When the temperature is less than 80 ° C., storage defects (decrease in blocking resistance) occur at normal storage environment temperatures. Moreover, the content of the tackifier in the heat-sensitive adhesive is preferably 1 to 30% by weight, and more preferably 1 to 20% by weight. If it is less than 1% by weight, the adhesive strength is remarkably reduced, and if it exceeds 30% by weight, storage problems at normal temperatures (decrease in blocking resistance) and initial adhesive strength at low temperatures are reduced. Occurs.

  In the heat-sensitive adhesive of the present invention, in addition to the above components, in order to prevent blocking, inorganic substances such as titanium oxide, alumina, colloidal silica, kaolin, talc, stearic acid metal salts, paraffin, natural wax, synthetic wax, A natural oil and fat, an organic substance such as polystyrene powder, and a dispersant, an antifoaming agent, a thickener and the like can be used as necessary.

  Drying conditions for coating or printing on the support must be such that 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 application amount of the heat-sensitive adhesive layer is usually 3 to 20 g / m ² , preferably 5 to 15 g / m ² as a dry application amount. If the coating amount of the heat-sensitive adhesive layer is less than 3 g / m ² , a sufficient adhesive force cannot be obtained when performing adhesion by heating, and a thermoplastic resin having a low Tg is used for the intermediate layer. Inferior in blocking resistance. Moreover, when it exceeds 20 g / m < ² >, the heat insulation effect of this intermediate | middle layer will fade, and it is not preferable economically.

  In the present invention, the adhesive under layer and the intermediate layer are sequentially provided on one side of the support, and a thermosensitive recording layer mainly composed of a leuco dye and a developer is provided on the opposite side provided with the thermosensitive adhesive layer. The heat-sensitive adhesive label has a strong adhesive force to each adherend, particularly a rough adherend such as corrugated cardboard, and an adherend such as a polyolefin wrap, and can provide a heat-sensitive adhesive label that is good for low energy thermal activation. It is a very effective adhesive label.

  In the heat-sensitive recording layer of the present invention, a heat-sensitive recording layer mainly composed of a leuco dye and a developer can be formed on the substrate. As the leuco dye used in the heat-sensitive recording layer of the present invention, a leuco dye known in this type of leuco recording material is generally applied. For example, triphenylmethane, fluorane, phenothiazine, auramine, spiropyran And leuco compounds of dyes such as indolinophthalide are preferably used. Specific examples of such leuco dyes include 3,3-bis (p-dimethylaminophenyl) phthalide and 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- (Np-tolyl-N-ethylamino) -6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 2- {N- (3'- Trifluoromethylphenyl) amino} -6-diethylaminofluorane, 2- {3,6-bis (diethylamino) -9- (o-chloroanilino) xanthylbenzoate lactam}, 3-diethylamino-6-methyl-7- ( m-trichloromethylanilino) fluorane, 3-diethylamino-7- (o-chloroanilino) fluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane, 3-N-methyl-N-amylamino-6-methyl- 7-anilinofluorane, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluorane, 3-diethy Amino-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 ' -Diethylaminophenyl) -3- (2'-methoxy-5'-methylphenyl) phthalide, 3-diethylamino-6-methyl-7- (2 ', 4'-dimethylanilino) fluorane, 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-methoxycarbonylphenyl) Amino) fluorane, 3-diethylamino-5-methyl-7- (α-phenylethylamino) fluorane, 3-diethylamino-7-piperidinofluorane, 2-chloro-3- (N-methyltoluidino) -7- ( p-n-butylanilino) fluorane, 3- (N-benzyl-N-cyclohexylamino) -5,6-benzo-7-α-naphthylamino-4'-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-di Tylamino-6-dimethylamino-fluorene-9-spiro-3 '-(6'-dimethylamino) phthalide, 3,3-bis {2- (p-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl } -4,5,6,7-tetrachlorophthalide, 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- Nilinofluorane, 3-N-ethyl-N- (2-ethoxypropyl) amino-6-methyl-7-anilinofluorane, 3-N-ethyl-N-tetrahydrofurfurylamino-6-methyl-7-anilino Fluorane, 3-diethylamino-6-methyl-7-mesitidino-4 ', 5'-benzofluorane, 3-N-methyl-N-isobutyl-6-methyl-7-anilinofluorane, 3-N- And ethyl-N-isoamyl-6-methyl-7-anilinofluorane.

  In the heat-sensitive recording layer of the present invention, various electron-accepting compounds such as phenolic compounds, thiophenolic compounds, thiourea derivatives, organic acids and metal salts thereof can be applied as color developers. it can. Specific examples thereof include 4,4'-isopropylidene bisphenol, 3,4'-isopropylidene bisphenol, 4,4'-isopropylidene bis (o-methylphenol), 4,4'-secondary butylidene bisphenol, 4 , 4'-isopropylidenebis (o-tertiarybutylphenol), 4,4'-cyclohexylidenediphenol, 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 butylphenol L) 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, 1,3 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, zinc thiocyanate Antipyrine complex, zinc salt of 2-acetyloxy-3-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, zinc of hydroxynaphthoic acid, metal salts such as aluminum and calcium, 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, tetrabromobisphenol A, tetra Examples include bromobisphenol S, 4,4'-thiobis (2-methylphenol), 3,4-hydroxy-4'-methyl-diphenylsulfone, 4,4'-thiobis (2-chlorophenol), and the like.

  In order to form the heat-sensitive recording layer of the present invention, a leuco dye and a developer may be bonded and supported on a substrate. In this case, various conventional binders can be used as appropriate. Such binders include, for example, polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylamide / acrylate ester copolymer Water-soluble compounds such as acrylamide / acrylic acid ester / methacrylic acid terpolymers, styrene / maleic anhydride copolymer alkali salts, isobutylene / maleic anhydride copolymer alkali salts, polyacrylamide, sodium alginate, gelatin, casein, etc. In addition to functional polymers, polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, polybutyl methacrylate, vinyl chloride / acetic acid Cycloalkenyl copolymer, ethylene / emulsion and styrene / butadiene copolymer vinyl acetate copolymer, it can be mentioned latices such as styrene / butadiene / acrylic copolymer.

  Further, when the heat-sensitive recording layer is formed according to the present invention, various heat-fusible substances can be used as fillers. Specific examples thereof include fatty acids such as stearic acid and behenic acid, fatty acid amides such as stearic acid amide and palmitic acid amide, fatty acids such as zinc stearate, aluminum stearate, calcium stearate, zinc palmitate and zinc behenate. Metal salts, p-benzylbiphenyl, terphenyl, triphenylmethane, benzyl p-benzyloxybenzoate, β-benzyloxynaphthalene, β-naphthoic acid phenyl ester, 1-hydroxy-2-naphthoic acid phenyl ester, 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-dibenzyloxynaphthalene, 1, 2-bis (phenoxy) ethane, 1,2-bis (3-methylphenoxy) ethane, 1,2-bis (4-methylphenoxy) ethane, 1,4-bis (phenoxy) butane, 1,4-bis ( Phenoxy) -2-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-vinyloxyethoxy) biphenyl , P-aryloxybiphenyl, p-propargyloxybiphenyl, dibenzoyloxymethane, 1,3-dibenzoyloxypropane, dibenzyldi Rufide, 1,1-diphenylethanol, 1,1-diphenylpropanol, p- (benzyloxy) benzyl alcohol, 1,3-diphenoxy-2-propanol, N-octadecylcarbamoyl-p-methoxycarbonylbenzene, N-octadecylcarbamoyl Benzene, oxalic acid dibenzyl ester, 1,5-bis (p-methoxyphenyloxy) -3-oxapentane and the like can be mentioned.

  In the present invention, auxiliary additives commonly used in this type of heat-sensitive recording layer, such as surfactants and lubricants, can be used in combination as required. In this case, examples of the lubricant include higher fatty acids and metal salts thereof, higher fatty acid amides, higher fatty acid esters, animal, vegetable, mineral, and petroleum-based waxes.

  The heat-sensitive recording layer of the present invention can be formed by a generally known method. For example, first, the leuco dye and the developer are separately pulverized and dispersed together with an aqueous binder solution by a dispersing machine such as a ball mill, an attritor, or a sand mill until the dispersed particle size becomes 1 to 3 μm, and a filler as required. A heat-sensitive recording layer can be formed by preparing a heat-sensitive recording layer coating solution by mixing with a thermofusible substance (sensitizer) dispersion and the like and applying the mixture to a substrate.

  In the present invention, if necessary, for example, an undercoat layer is provided between the substrate and the heat-sensitive recording layer, or a water-soluble resin is used on the heat-sensitive recording layer for the purpose of improving image reliability. A protective layer as a main component can be provided, and a back coat layer can also be provided on the back surface of the substrate. In this case, as the components constituting these layers, the above-mentioned fillers, binders, thermofusible substances, surfactants and the like can be used. Further, when the protective layer and the protective layer are not provided, a printed image can be formed directly on the thermal recording layer. As the printing ink, for example, the UV curable ink is quick-drying, so that the thermal recording is performed. It is used as an optimal ink for paper.

In addition, by using a heat-sensitive recording paper as the base material, the adhesive under layer and the intermediate layer are sequentially provided on the back surface (the opposite surface provided with the heat-sensitive recording layer), and a heat-sensitive adhesive layer is further provided. It is possible to obtain a heat-sensitive pressure-sensitive adhesive label capable of heat-sensitive recording which has a strong adhesive force to a body, particularly a rough-surface adherend such as corrugated cardboard, and an adherend such as polyolefin wrap, which is good for low energy thermal activation.
A print image can be formed on a heat-sensitive adhesive label using such a heat-sensitive recording paper as a support and a heat-sensitive adhesive label using a receiving paper for thermal transfer recording as a support. Since the heat-sensitive ink and the electron beam curable ink are quick-drying, they are used as optimum inks for thermal recording paper. (Ink containing a lot of solvent is very difficult to use because it causes color development in the thermal recording layer.)
Moreover, unlike the normal label, the heat-sensitive adhesive label of the present invention has a great merit that it is used in the form of a roll because there is no release paper. For example, since there is no release paper even with the same roll diameter, it is wound about twice as long, so the number of times to set in the label printer can be reduced, and when using the same length roll as before, the roll diameter is small Therefore, there is an advantage that the label printer can be made compact.

  Further, by using a receiving paper for thermal transfer recording as a base material, the adhesive under layer and the intermediate layer of the present invention are sequentially provided on one side, and further a heat-sensitive adhesive layer is provided, so that each adherend, particularly cardboard, etc. Is a very effective label sheet that can provide a heat-sensitive adhesive label sheet for thermal transfer recording with strong adhesion to rough surface adherends and polyolefin wraps, low energy thermal activation and good blocking resistance. It is.

  Such receiving paper for thermal transfer recording of the present invention includes those having an ink image formed by thermal transfer. Such an ink image may be one that has been thermally transferred from the heat-sensitive adhesive label having the heat-sensitive adhesive layer of the present invention, or one that has been formed by another thermal transfer.

  In the ink receiving layer of the receiving paper for thermal transfer recording of the present invention, examples of the filler contained in the ink receiving layer include calcium carbonate, silica, titanium oxide, aluminum hydroxide, clay, fired clay, magnesium silicate, magnesium carbonate, White carbon, zinc oxide, barium sulfate, surface-treated calcium carbonate and silica, urea-formalin resin, styrene / methacrylic acid copolymer, fine powders such as polystyrene, etc. can be used, but are not limited thereto. is not.

  As the water-soluble resin used in the ink receiving layer, various conventional water-soluble resins can be used as appropriate, such as polyvinyl alcohol, starch and derivatives thereof, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose and the like. Cellulose derivatives, polyacrylic acid soda, polyvinylpyrrolidone, acrylamide / acrylic acid ester copolymer, acrylamide / acrylic acid ester / methacrylic acid terpolymer, styrene / maleic anhydride copolymer alkali salt, isobutylene / maleic anhydride co Examples include water-soluble polymers such as polymer alkali salts, polyacrylamide, sodium alginate, gelatin, and casein.

  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 0.2. Specific examples of the water-proofing agent used in the ink receiving layer include formaldehyde, glyoxal, chrome alum, melamine, melamine-formaldehyde resin, polyamide resin, polyamide-epichlorohydrin resin, and the like. The ratio of the water-proofing agent and the water-soluble resin is also related to the blocking property, and the content weight ratio (solid content) is preferably 0.3 to 0.5 with respect to the water-soluble resin 1. 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. Further, the surface of the ink receiving layer is 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.

  Furthermore, by providing the adhesive under layer and the intermediate layer of the present invention sequentially on both surfaces of the substrate, and further providing a heat-sensitive adhesive layer, each adherend, particularly rough surface adherends such as cardboard and polyolefin wraps. It is also possible to obtain a heat-sensitive double-sided pressure-sensitive adhesive paper that has a strong adhesive force to the surface and good blocking resistance.

  In addition, the base material used in the present invention is not particularly limited, such as high-quality paper, art paper, coated paper, other than paper, polyester films such as polyethylene terephthalate and polybutylene terephthalate, cellulose derivative films such as cellulose triacetate, Polyolefin films such as polypropylene and polyethylene, polystyrene films, films obtained by bonding these, and the like can be used.

  Coating methods for providing the coating layer 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, and AKKU. Known coating methods such as coating method, smoothing coating method, microgravure coating method, reverse roll coating method, four or five roll coating method, dip coating method, falling curtain coating method, slide coating method, die coating method, etc. Is available.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, all the parts and% shown below are based on weight.

[Adjustment of elastic underlayer coating solution]
[A'-1 solution]
・ Natural rubber latex <100% modulus: 6 kgf / cm ² >
(Solid content 61%, manufactured by NR-LATEX RETITECHS) 82.0 parts ・ Surfactant Dapro W-77 (manufactured by Elementis Japan) 0.1 part ・ Water 18.0 parts A mixture of the above composition was stirred, An elastic undercoating solution [A′-1 solution] was prepared.

[A'-2 liquid]
・ Natural rubber-methyl methacrylate graft polymer <100% modulus: 6 kgf / cm ² >
(Solid content concentration: 50%, manufactured by MG-10S Restex) 100 parts ・ Surfactant Dapro W-77 (manufactured by Elementis Japan) 0.1 part A mixture of the above composition is stirred to form an elastic undercoating liquid [A′- Two solutions] were prepared.

[A'-3 liquid]
-Polyether urethane resin <100% modulus: 25 kgf / cm < ² >
(VONDIC1310NE manufactured by Dainippon Ink and Chemicals, solid content concentration 50%) 100 parts ・ Surfactant Dapro W-77 (made by Elementis Japan) 0.1 part A mixture of the above composition was stirred to form an elastic undercoating solution [A '-3 solution] was prepared.

[A'-4 liquid]
-Polyether urethane resin <100% modulus: 12 kgf / cm < ² >
(VONDIC1610NE, Dainippon Ink & Chemicals, Inc., solid content concentration 25.6%) 195.3 parts ・ Surfactant Dapro W-77 (made by Elementiment Japan) 0.1 parts ・ Water 4.7 parts Stirring to prepare an elastic under coating solution [A′-4 solution].

[A'-5 liquid]
Polyester urethane resin <100% modulus: 10 kgf / cm ² >
(HYDRAN HW-920, Dainippon Ink & Chemicals, Inc., solid content concentration 50%) 100 parts ・ Surfactant Dapro W-77 (made by Elementis Japan) 0.1 part Stir the mixture of the above composition and apply elastic undercoat Solution [A'-5 solution] was prepared.

[A'-6 liquid]
Polyester urethane resin <100% modulus: 20 kgf / cm < ² >
(HYDRAN HW-930, manufactured by Dainippon Ink & Chemicals, Inc., solid content concentration 50%) 100 parts ・ Surfactant Dapro W-77 (produced by Elementis Japan) 0.1 part A liquid [A'-6 liquid] was prepared.

[A'-7 liquid]
-Urethane-acrylic composite resin <100% modulus: 35 kgf / cm < ² >
(VONCOAT CG-5030, manufactured by Dainippon Ink & Chemicals, Inc., 50% solid content) 100 parts Surfactant Dapro W-77 (made by Elementiment Japan) 0.1 parts Stir the mixture of the above composition and apply elastic undercoat A liquid [A'-7 liquid] was prepared.

[A'-8 liquid]
・ Polybutadiene rubber <100% modulus: 4 kgf / cm ² >
(Nipol LX111K Nippon Zeon solid concentration 55%) 90.9 parts Surfactant Dapro W-77 (Elemente Japan) 0.1 parts Water 9.1 parts Stir the mixture of the above composition, An elastic undercoating solution [A'-8 solution] was prepared.

[A'-9 liquid]
Carboxy-modified acrylonitrile-butadiene-based polymer <100% modulus: 3 kgf / cm ² >
(LACSTAR 4940B, Dainippon Ink & Chemicals, Inc., solid concentration 40%) 125 parts Surfactant DAPRO W-77 (made by Elementis Japan) 0.1 part A mixture of the above composition is stirred to form an elastic undercoating solution [ A′-9 solution] was prepared.

[A'-10 liquid]
Carboxy-modified acrylonitrile-butadiene-based polymer <100% modulus: 7 kgf / cm ² >
(LACSTAR 6541G, manufactured by Dainippon Ink & Chemicals, Inc., solid concentration 41%) 122 parts Surfactant Dapro W-77 (made by Elementis Japan) 0.1 part The mixture comprising the above composition was stirred to form an elastic undercoating solution [ A′-10 solution] was prepared.

[A'-11 solution]
Carboxyl-modified methyl methacrylate-butadiene polymer <100% modulus: 4 kgf / cm ² >
(LACSTAR DM-812, manufactured by Dainippon Ink & Chemicals, Inc., solid concentration: 47%) 106 parts Surfactant Dapro W-77 (produced by Elementis Japan) 0.1 part Stir the mixture of the above composition and apply elastic undercoat A liquid [A'-11 liquid] was prepared.

[A'-12 liquid]
Carboxy-modified styrene-butadiene polymer <100% modulus: 7 kgf / cm < ² >
(LACSTAR 5215A, manufactured by Dainippon Ink & Chemicals, Inc., solid content concentration: 47.5%) 105 parts Surfactant Dapro W-77 (made by Elementis Japan) 0.1 part Stir the mixture of the above composition and apply elastic undercoat A solution [A'-12 solution] was prepared.

[A'-13 solution]
・ Carboxy-modified styrene-butadiene polymer
<100% modulus: 4 kgf / cm ² >
(LACSTAR DS-813, manufactured by Dainippon Ink & Chemicals, Inc., solid content concentration 50%) 100 parts Surfactant Dapro W-77 (made by Elementis Japan) 0.1 part Stir the mixture of the above composition and apply elastic undercoat Liquid [A'-13] was prepared.

[A'-14 liquid]
-2-vinylpyridine-styrene-butadiene polymer <100% modulus: 8 kgf / cm < ² >
(PYRATEX Nippon A & L, solid content: 41%) 122 parts Surfactant Dapro W-77 (Elemente Japan) 0.1 parts A mixture of the above composition is stirred to form an elastic undercoating solution [A'-14 Liquid] was prepared.

[A'-15 solution]
Carboxy-modified methyl methacrylate-butadiene polymer <100% modulus: 39 kgf / cm ² >
(LACSTAR DM-401 manufactured by Dainippon Ink and Chemicals, solid content concentration 41%) 122 parts Surfactant Dapro W-77 (made by Elementis Japan) 0.1 parts Stir the mixture of the above composition and apply elastic undercoat Liquid [A′-15] was prepared.

[A'-16 solution]
Carboxyl-modified styrene-butadiene polymer <100% modulus: 52 kgf / cm ² >
(SMARTEX PA-9159 manufactured by Nippon A & L, solids concentration 48%) 104 parts Surfactant Dapro W-77 (made by Elementis Japan) 0.1 part The mixture of the above composition is stirred to form an elastic undercoating liquid [A '-16 solution] was prepared.

[A'-17 solution]
・ Polyvinyl alcohol K polymer KL-318 10% aqueous solution (manufactured by Kuraray) 100 parts ・ Surfactant Olfine PD-001 (manufactured by Nissin Chemical Industry Co., Ltd.) 1 part -17 solution] was prepared.

[Adjustment of intermediate layer coating solution]
[A-solution]
・ Plastic spherical hollow particles [1]
(Acrylonitrile / vinylidene chloride / methyl methacrylate copolymer)
(Solid content concentration 41%, average particle diameter 3.6 μm, hollow rate 90%) 14.6 parts ・ 2-ethylhexyl acrylate / methyl methacrylate /
Copolymer of styrene (Tg -65 ° C)
(Solid content concentration 55.4%, manufactured by Showa Polymer Co., Ltd.) 21.7 parts Surfactant Dapro W-77 (made by Elementis Japan) 0.1 part Water 63.6 parts A mixture of the above composition is stirred and dispersed. Then, an intermediate layer coating solution [A-1 solution] was prepared.

[Liquid A-2]
・ Plastic spherical hollow particles [2] (acrylonitrile /
Methacrylonitrile / isobonyl methacrylate copolymer)
(Solid content concentration 33%, average particle size 3.0 μm, hollow rate 91%) 18.2 parts n-butyl acrylate / methyl acrylate copolymer (Tg -62 ° C.) (solid content concentration 50%, manufactured by JSR) 24.0 parts ・ Surfactant Dapro W-77 (manufactured by Elementis Japan) 0.1 part ・ Water 57.7 parts A mixture of the above composition was stirred and dispersed, and an adhesive under coating solution [A-2 solution] Was prepared.

[A-3 solution]
・ Plastic spherical hollow particles [3] (acrylonitrile /
Vinylidene chloride / methyl methacrylate copolymer)
(Solid content concentration 41%, average particle size 3.2 μm, hollow ratio 70%) 14.6 parts ・ 2-ethylhexyl acrylate / methyl methacrylate /
Copolymer of styrene (TG-65 ° C)
(Solid content concentration 55.4%, manufactured by Showa Polymer Co., Ltd.) 21.7 parts Surfactant Dapro W-77 (made by Elementis Japan) 0.1 part Water 63.6 parts A mixture of the above composition is stirred and dispersed. Then, an intermediate layer coating solution [A-3 solution] was prepared.

[A-4 solution]
・ Plastic spherical hollow particles [4] (acrylonitrile /
Vinylidene chloride / methyl methacrylate copolymer)
(Solid content concentration 40%, average particle size 1.5 μm, hollow rate 50%) 22.5 parts ・ 2-ethylhexyl acrylate / methyl methacrylate /
Copolymer of styrene (TG-65 ° C)
(Solid content concentration 55.4%, manufactured by Showa Polymer Co., Ltd.) 16.2 parts-Surfactant Dapro W-77 (manufactured by Elementis Japan) 0.1 part-Water 61.2 parts A mixture of the above composition is stirred and dispersed. Then, an intermediate layer coating solution [A-4 solution] was prepared.

[A-5 solution]
・ Plastic spherical hollow particles [2] (acrylonitrile /
Methacrylonitrile / isobonyl methacrylate copolymer)
(Solid content 33%, average particle size 3.0 μm, hollowness 91%) 6.1 parts ・ Ethylene / vinyl acetate / acrylic copolymer (TG-20 ° C.) (Solid content 53%, Sumika Chemtex) 30.2 parts ・ Surfactant Dapro W-77
(Made by Elementis Japan) 0.1 part-Water 63.6 parts The mixture which consists of said composition was stirred and disperse | distributed, and the intermediate | middle layer coating liquid [A-5 liquid] was prepared.

[A-6 solution]
・ Plastic spherical hollow particles [5] (acrylonitrile /
Methacrylonitrile / isobonyl methacrylate copolymer)
(Solid content concentration 33%, average particle size 6.0 μm,
27.3 parts ・ 2-ethylhexyl acrylate / methyl methacrylate
/ Styrene copolymer (TG-65 ° C)
(Solid content 55.4%, Showa High Polymer) 16.3 parts-Surfactant Dapro W-77
(Made by Elementis Japan) 0.1 part Water 56.3 parts A mixture of the above composition was stirred and dispersed to prepare an intermediate layer coating solution [A-6 solution].

[A-7 solution]
・ Plastic spherical hollow particles [2] (acrylonitrile /
Methacrylonitrile / isobonyl methacrylate copolymer)
(Solid content 33%, average particle size 3.0 μm, hollow rate 91%) 18.2 parts N-butyl acrylate / methyl acrylate /
Copolymer of methyl methacrylate (TG-5 ° C)
(Solid content concentration 56.4%, manufactured by Showa High Polymer Co., Ltd.) 21.3 parts ・ Surfactant Dapro W-77 (manufactured by Elementis Japan) 0.1 part ・ Water 60.4 parts A mixture of the above composition was stirred and dispersed. Then, an intermediate layer coating solution [A-7 solution] was prepared.

[A-8 solution]
・ Plastic spherical hollow particles [2] (acrylonitrile /
Methacrylonitrile / isobonyl methacrylate copolymer)
(Solid content concentration 33%, average particle size 3.0 μm, hollow rate 91%) 18.2 parts n-Butyl acrylate / Methyl acrylate /
Copolymer of methyl methacrylate (TG 0 ° C)
(Solid content 55%, manufactured by JSR) 21.8 parts-Surfactant Dapro W-77 (produced by Elementis Japan) 0.1 part-Water 59.9 parts A layer coating solution [A-8 solution] was prepared.

[A-9 solution]
・ Plastic spherical hollow particles [2] (acrylonitrile /
Methacrylonitrile / isobonyl methacrylate copolymer)
(Solid content concentration 33%, average particle size 3.0 μm, hollow rate 91%) 3 parts n-Butyl acrylate / methyl acrylate copolymer (TG-62 ° C.) (Solid content concentration 50%, manufactured by JSR) 34 0.0 part Surfactant Dapro W-77 (made by Elementis Japan) 0.1 part Water 62.9 parts A mixture of the above composition was stirred and dispersed to prepare an intermediate layer coating solution [A-9 solution]. did.

[A-10 solution]
・ Plastic spherical hollow particles [2] (acrylonitrile /
Methacrylonitrile / isobonyl methacrylate copolymer)
(Solid content 33%, average particle size 3.0 μm, hollow rate 91%) 36.4 parts 2-ethylhexyl acrylate / methyl methacrylate /
Copolymer of styrene (TG-65 ° C)
(Concentration of solid content 55.4%, manufactured by Showa Polymer) 10.8 parts-Surfactant Dapro W-77 (produced by Elementis Japan) 0.1 part-Water 52.7 parts A mixture comprising the above composition is stirred. Thus, an intermediate layer coating solution [A-10 solution] was prepared.

[A-11 solution]
・ Plastic spherical hollow particles [1] (acrylonitrile /
Vinylidene chloride / methyl methacrylate copolymer)
(Solid content 41%, average particle size 3.6 μm, hollow rate 90%) 23.4 parts ・ Carboxy-modified styrene-butadiene polymer (TG + 4 ° C.)
(SMARTEX PA-9159 Nippon A & L, solid concentration 48%) 10 parts ・ Surfactant Dapro W-77 (Elemente Japan) 0.1 parts ・ Water 66.5 parts A mixture of the above composition was stirred, An intermediate layer coating solution [A-11 solution] was prepared.

[Preparation of hot melt material dispersion]
[B-1 solution]
2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl)
-5-chlorobenzotriazole (mp 138 ° C) 40.0 parts Polyvinyl alcohol (30% aqueous solution) 6.7 parts Surfactant Orphine PD-001 (manufactured by Nissin Chemical Industry Co., Ltd.) 0.2 parts Water 53.1 parts A mixture [B-1] was obtained by dispersing the mixture consisting of the above using a sand mill so that the average particle size was 1.0 μm.

[Liquid B-2]
2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl)
-5-chlorobenzotriazole (mp 152 ° C) 40.0 parts Polyvinyl alcohol (30% aqueous solution) 6.7 parts Surfactant Olfine PD-001 (manufactured by Nissin Chemical Industry) 0.2 part Water 53.1 parts The mixture consisting of was dispersed using a sand mill so that the average particle size was 1.0 μm to obtain a dispersion [Liquid B-2].

[B-3 solution]
2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl)
Benzotriazole (mp 80 ° C.) 40.0 parts Polyvinyl alcohol (30% aqueous solution) 6.7 parts Surfactant Olfine PD-001 (manufactured by Nissin Chemical Industry Co., Ltd.) 0.2 parts Water 53.1 parts Then, dispersion was carried out using a sand mill so that the average particle diameter was 1.0 μm to obtain a dispersion [B-3].

[B-4 solution]
Benzyl P-hydroxybenzoate (mp113-115 ° C.) 40.0 parts Polyvinyl alcohol (30% aqueous solution) 6.7 parts Surfactant Olfine PD-001 (manufactured by Nissin Chemical Industry) 0.2 part Water 53.1 parts 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 [B-4].

[B-5 solution]
Anisoin (mp 99-100 ° C.) 40.0 parts Polyvinyl alcohol (30% aqueous solution) 6.7 parts Surfactant Olfine PD-001 (manufactured by Nissin Chemical Industry) 0.2 parts Water 53.1 parts Mixture comprising the above composition Was dispersed using a sand mill so that the average particle size was 1.0 μm to obtain a dispersion [B-5].

[B-6 solution]
Phenyl 1-dihydroxy-2-naphthoate (mp 94-96 ° C.) 40.0 parts Polyvinyl alcohol (30% aqueous solution) 6.7 parts Surfactant Olfine PD-001 (manufactured by Nissin Chemical Industry) 0.2 part Water 53 .1 part of 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 [liquid B-6].

[B-7 solution]
Benzoic acid-3-hydroxyphenyl (mp 135 ° C.) 40.0 parts Polyvinyl alcohol (30% aqueous solution) 6.7 parts Surfactant Olfine PD-001 (manufactured by Nissin Chemical Industry) 0.2 part Water 53.1 parts The mixture composed of the composition was dispersed using a sand mill so that the average particle diameter was 1.0 μm to obtain a dispersion [B-7].

[B-8 solution]
General formula (VI) -2 hindered phenol compound (mp 123 ° C.) 40.0 parts Polyvinyl alcohol (30% aqueous solution) 6.7 parts Surfactant Olfine PD-001 (manufactured by Nissin Chemical Industry) 0.2 part Water 53 .1 part of 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 [liquid B-8].

[B-9 solution]
General formula (VII) -1 hindered phenol compound (mp163 ° C.) 40.0 parts Polyvinyl alcohol (30% aqueous solution) 6.7 parts Surfactant Olfine PD-001 (manufactured by Nissin Chemical Industry) 0.2 part Water 53 .1 part of 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 [B-9].

[B-10 solution]
General formula (VIII) -6 hindered phenol compound (mp 106 ° C.) 40.0 parts Polyvinyl alcohol (30% aqueous solution) 6.7 parts Surfactant Olfine PD-001 (manufactured by Nissin Chemical Industry) 0.2 part Water 53 .1 part of 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 [B-10 solution].

[Preparation of eutectic agent dispersion]
[C-1 solution]
Succinic acid di-P-methylbenzyl ester (mp 101 ° C.) 40.0 parts Polyvinyl alcohol (30% aqueous solution) 6.7 parts Surfactant Olfine PD-001 (manufactured by Nissin Chemical Industry) 0.2 part Water 53.1 parts The mixture having the above composition was dispersed using a sand mill so that the average particle size was 1.2 μm to obtain a dispersion [C-1 solution].

[C-2 liquid]
Succinic acid di-P-methylbenzyl ester (mp 80 ° C.) 40.0 parts Polyvinyl alcohol (30% aqueous solution) 6.7 parts Surfactant Olfine PD-001 (manufactured by Nissin Chemical Industry) 0.2 part Water 53.1 parts The mixture having the above composition was dispersed using a sand mill so that the average particle size was 1.2 μm to obtain a dispersion [liquid C-2].

[Adjustment of heat-sensitive adhesive coating solution]
[D-1 solution]
Copolymer of n-butyl acrylate / methyl acrylate (TG -62 ° C) (solid content concentration 50%, manufactured by JSR) 10 parts Polymerized rosin emulsion (softening point 145 ° C, non-volatile content 50%) 6 parts Hot melt material dispersion Liquid [B-1 liquid] 37.5 parts Eutectic agent dispersion liquid [C-1 liquid] 7 parts A mixture comprising the above composition was uniformly mixed to prepare a coating liquid [D-1 liquid].

[D-2 solution]
2-ethylhexyl acrylate / methyl methacrylate /
Copolymer of styrene (TG-65 ° C)
(Solid content 55.4%, Showa High Polymer) 9 parts Terpene phenol emulsion (softening point 150 ° C., non-volatile content 50%) 6 parts Hot melt material dispersion [Liquid B-2] 37.5 parts Eutectic Agent dispersion liquid [C-2 liquid] 7 parts A mixture comprising the above composition was uniformly mixed to prepare a coating liquid [D-2 liquid].

[D-3 solution]
Copolymer of n-butyl acrylate / methyl acrylate (TG -62 ° C) (solid content concentration 50%, manufactured by JSR) 10 parts Polymerized rosin emulsion (softening point 145 ° C, non-volatile content 50%) 6 parts Hot melt material dispersion Liquid [Liquid B-1] 19 parts Heat-meltable substance dispersion [Liquid B-2] 19 parts Eutectic agent dispersion [Liquid C-1] 7 parts D-3 solution] was adjusted.

[D-4 solution]
2-ethylhexyl acrylate / methyl methacrylate /
Copolymer of styrene (TG-5 ° C)
(Solid content concentration 55.4%, Showa High Polymer Co., Ltd.) 9 parts Polymerized rosin emulsion (softening point 145 ° C., nonvolatile content 50%) 6 parts Heat-meltable substance dispersion [liquid B-4] 37.5 parts The mixture consisting of was uniformly mixed to prepare a coating solution [D-4 solution].

[D-5 liquid]
Copolymer of ethylene / vinyl acetate / acrylic (TG-20 ° C)
(Solid content 53%, manufactured by Sumika Chemtex) 9.4 parts Terpene phenol emulsion (softening point 150 ° C., non-volatile content 50%) 6 parts Hot-melting substance dispersion (B-5 liquid) 37.5 parts Eutectic Agent dispersion liquid [C-1 liquid] 7 parts A mixture comprising the above composition was uniformly mixed to prepare a coating liquid [D-5 liquid].

[D-6 solution]
2-ethylhexyl acrylate / n-butyl acrylate /
Copolymer of styrene (TG-30 ° C)
(Solid content concentration 50.0%, manufactured by Showa Polymer Co., Ltd.) 10 parts Polymerized rosin emulsion (softening point 145 ° C., non-volatile content 50%) 6 parts Hot melt material dispersion [liquid B-6] 37.5 parts The mixture consisting of was uniformly mixed to prepare a coating solution [D-6 solution].

[D-7 solution]
n-Butyl acrylate / methyl acrylate copolymer (TG-62 ° C.) (solid content 50%, manufactured by JSR) 10 parts Terpene phenol emulsion (softening point 150 ° C., non-volatile content 50%) 6 parts Fusible substance dispersion [B-7 solution] 37.5 parts A mixture having the above composition was uniformly mixed to prepare a coating solution [D-7 solution].

[D-8 solution]
2-ethylhexyl acrylate / n-butyl acrylate /
Copolymer of styrene (TG-30 ° C)
(Solid content 50.0%, Showa High Polymer) 10 parts Polymerized rosin emulsion (softening point 145 ° C., non-volatile content 50%) 6 parts Hot-melting substance dispersion (B-6 liquid) 19 parts Hot-melting substance Dispersion [B-7] 19 parts A mixture of the above composition was uniformly mixed to prepare a coating solution [D-8].

[D-9 solution]
n-Butyl acrylate / methyl acrylate copolymer (TG-62 ° C.) (solid content 50%, manufactured by JSR) 10 parts Terpene phenol emulsion (softening point 150 ° C., non-volatile content 50%) 6 parts Hot melt dispersion Liquid [B-8 liquid] 37.5 parts A mixture having the above composition was uniformly mixed to prepare a coating liquid [D-9 liquid].

[D-10 solution]
2-ethylhexyl acrylate / methyl methacrylate /
Copolymer of styrene (TG-65 ° C)
(Solid content concentration 55.4%, manufactured by Showa Polymer Co., Ltd.) 9 parts Terpene phenol emulsion (softening point 150 ° C., non-volatile content 50%) 6 parts Heat-meltable substance dispersion [B-9 liquid] 37.5 parts The mixture consisting of was uniformly mixed to prepare a coating solution [D-10 solution].

[D-11 solution]
2-ethylhexyl acrylate / methyl methacrylate /
Copolymer of styrene (TG-65 ° C)
(Solid content concentration 55.4%, manufactured by Showa Polymer Co., Ltd.) 9 parts Terpene phenol emulsion (softening point 150 ° C., non-volatile content 50%) 6 parts Heat-meltable substance dispersion [B-10 liquid] 37.5 parts The mixture consisting of was uniformly mixed to prepare a coating solution [D-11 solution].

[Creation of thermal recording paper]
[Liquid E] Coating liquid for forming non-foaming heat insulation layer Fine hollow particle dispersion (vinylidene chloride /
Copolymer resin mainly composed of acrylonitrile)
(Solid content 32%, average particle size 3.6 μm, hollowness 92%) 30 parts Styrene / butadiene copolymer latex (Tg + 4 ° C.) 10 parts Surfactant Dapro W-77 (made by Elementis Japan) 0. 1 part Water 60 parts A mixture comprising the above composition was stirred and dispersed to prepare a non-foaming heat insulating layer forming coating solution [E solution].

[F liquid] Color former dispersion liquid 3-Di-n-butylamino-6-methyl-7-anilinofluorane 20 parts Polyvinyl alcohol (10% aqueous solution) 10 parts Water 70 parts

[Liquid G] Developer dispersion 4-isopropoxy-4′-hydroxydiphenylsulfone 10 parts Polyvinyl alcohol (10% aqueous solution) 25 parts Calcium carbonate 15 parts Water 50 parts Disperse using a sand mill so that the diameter is about 1.5 μm to prepare [F liquid] and [G liquid], and then mix [F liquid]: [G liquid] = 1: 8 The mixture was stirred to obtain a thermosensitive coloring layer [Liquid H]. The [E-solution] was coated and dried on the surface of an average basis weight of 80 g / m ² substrate so that the weight after drying was 4 g / m ² to provide a non-foaming heat insulating layer. On top of this, after applying the above [F liquid] and drying to give a weight of 5 g / m ² and providing a heat-sensitive color developing layer, a super calender so that the Oken smoothness becomes 2000 seconds. It was processed to obtain a paper coated with a thermosensitive coloring layer.

[Adjustment of protective layer solution]
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 average particle diameter was 1 μm or less.
[Primary dispersion for protective layer]
Aluminum hydroxide 20 parts 10% PVA aqueous solution 20 parts Water 40 parts [Preparation of protective liquid]
Protective layer primary dispersion 10 parts 10% PVA aqueous solution 20 parts 12.5% epichlorohydrin aqueous solution 5 parts 30% zinc stearate dispersion 2 parts Furthermore, the protective layer coating liquid prepared above is dried on the paper coated with the thermosensitive coloring layer. Coating and drying were performed so that the coating amount was 3.0 g / m ² . Thereafter, the paper was processed with a super calender so that the Oken type smoothness was 2000 seconds to obtain the thermal recording paper of the example.

[Example sample preparation and evaluation]
On one side of the base material, an elastic undercoating liquid and a thermosensitive adhesive coating liquid described in Table 2 below were sequentially applied and dried to obtain a thermosensitive adhesive label.

[Adhesion & Thermal Activation Sensitivity (Low Energy)]
Immediately after the measurement, the heat-sensitive adhesive material of the present invention was cut into a 40 mm × 150 mm rectangle, and using a thermal printing device TH-PMD manufactured by Okura Electric Co., Ltd., head conditions: each energy 0.3, 0.4, 0.5 mJ The heat-sensitive adhesive label sheet is thermally activated under the conditions of / dot, printing speed of 4 ms / line, and platen pressure of 6 kgf / line. Subsequently, it was affixed to the adherend (polyolefin wrap and cardboard) in the longitudinal direction with a 2 kg pressure rubber roller and peeled after 1 hour under the conditions of a peeling angle of 180 degrees and a peeling speed of 300 mm / min.

  The adhesive strength at that time was measured with a force gauge, and the values obtained by reading and averaging the data at 0.1 second intervals are shown in the table. The unit is gf / 40 mm. This test was performed under a normal temperature environment (23 ° C., 65%).

[Blocking properties]
The protective layer surface and the heat-sensitive adhesive layer surface of the heat-sensitive recording layer of the same sample were brought into contact and tested at 200 g / cm ² at 50 ° C. under dry conditions for 24 hours. After leaving at room temperature, the sample was peeled off. The blocking property was evaluated in the rank as shown in Table 3 below. Table 4 shows the evaluation results.

Claims (19)

A heat-sensitive adhesive label having a thermoplastic resin, a tackifier, and a heat-sensitive adhesive layer mainly composed of a heat-meltable substance provided on one side of the support, the JIS between the support and the heat-sensitive adhesive layer A heat-sensitive adhesive label comprising an elastic underlayer mainly composed of a resin having a 100% modulus defined by K6251 of 35 kgf / cm ² or less.   The resin used for the elastic under layer is polyether urethane resin, polyester urethane resin, urethane-acrylic composite resin, natural rubber, natural rubber-methyl methacrylate graft polymer, styrene-butadiene polymer, polybutadiene, methyl methacrylate. The heat-sensitive adhesive label according to claim 1, wherein at least one selected from a butadiene-based polymer, a 2-vinylpyridine-styrene-butadiene-based polymer, and an acrylonitrile-butadiene-based polymer is used. The heat-sensitive adhesive label according to claim 1, wherein the elastic under layer is provided at 5 g / m ² or more.   2. An intermediate layer mainly comprising a thermoplastic resin having a Tg of −70 ° C. to −5 ° C. and plastic spherical hollow particles is provided between the elastic under layer and the heat-sensitive adhesive layer. The heat sensitive adhesive label in any one of thru | or 3.   The thermoplastic resin having a Tg of −70 ° C. to −5 ° C. used for the intermediate layer is an acrylic ester copolymer, a methacrylic ester copolymer, an acrylic ester-methacrylic ester copolymer, an acrylic ester-styrene copolymer. The heat-sensitive adhesive label according to claim 4, wherein at least one selected from a polymer, an acrylic ester-methacrylic ester-styrene copolymer, and an ethylene-vinyl acetate copolymer is used.   The plastic spherical hollow particles used for the intermediate layer have a hollow ratio of 70% or more, the maximum particle diameter of the hollow particles is 10.0 μm or less, and at the same time an average particle diameter of 2.0 to 5.0 μm The heat-sensitive adhesive label according to claim 4 or 5, wherein the heat-sensitive adhesive label is a hollow particle.   The material for forming the plastic spherical hollow particles is acrylonitrile-vinylidene chloride-methyl methacrylate or acrylonitrile-methacrylonitrile-isobornyl methacrylate copolymer. Heat sensitive adhesive label.   The ratio of Tg-70 ° C. to −5 ° C. thermoplastic resin and plastic spherical hollow particles used in the intermediate layer is 0.1 to 1.0 part by weight of plastic spherical hollow particles with respect to 1 part by weight of the resin. The heat-sensitive adhesive label according to any one of claims 4 to 7.   In the heat-sensitive adhesive layer mainly composed of a thermoplastic resin, a tackifier, and a heat-meltable substance, the thermoplastic resin is an acrylate copolymer, a methacrylate ester copolymer, an acrylate ester-methacrylate ester. 2. At least one selected from a copolymer, an acrylic ester-styrene copolymer, an acrylic ester-methacrylic ester-styrene copolymer, and an ethylene-vinyl acetate copolymer is used. The thermosensitive adhesive label in any one of thru | or 8. A thermosensitive pressure-sensitive adhesive label provided with a heat-sensitive adhesive layer mainly composed of a thermoplastic resin, a tackifier, and a heat-meltable substance, wherein the heat-meltable substance is represented by the following general formula (I) The heat-sensitive adhesive label according to any one of claims 1 to 9, wherein one or more compounds are used.

[In General Formula (I), R ₁ and R _{2 each} independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an α, α-dimethylbenzyl group, and X represents a hydrogen atom or Represents a chlorine atom. ] A heat-sensitive adhesive label provided with a heat-sensitive adhesive layer mainly composed of a thermoplastic resin, a tackifier, and a heat-meltable substance, wherein the heat-meltable substance is represented by the following general formula (II) The heat-sensitive adhesive label according to any one of claims 1 to 9, wherein one or more acid ester compounds are used.

[In General Formula (II), R ₁ represents any of an alkyl group having 1 to 18 carbon atoms, a cyclohexyl group, an alkenyl group, an aralkyl group (which may have a substituent on the aromatic ring), and a phenyl group. Represents. ] A thermosensitive adhesive label provided with a thermosensitive adhesive layer mainly composed of a thermoplastic resin, a tackifier and a thermomeltable substance, wherein the thermomeltable substance is represented by the following general formulas (III), (IV), The heat-sensitive adhesive label according to any one of claims 1 to 9, wherein one or more compounds represented by (V) are used.

[In the general formula (III), R represents a methyl group, an ethyl group, a methoxy group or an ethoxy group, which may be different from each other. X represents a hydrogen atom or a hydroxyl group. ]

[In the general formula (IV), R ₁ represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group or a halogen atom. Y represents a hydrogen atom or a hydroxyl group. ]

[In the general formula (V), R ₂ represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group or a halogen atom. ] In the heat-sensitive adhesive layer mainly composed of a thermoplastic resin, a tackifier, and a heat-meltable substance, the heat-meltable substance is a hindered phenol compound, and the following general formula (VI), ( The heat-sensitive adhesive label according to any one of claims 1 to 9, wherein one or more hindered phenol compounds having a structure of VII) or (VIII) are used.

[In the general formulas (VI), (VII) and (VIII), R ₁ represents a branched alkyl group having 6 or less carbon atoms. R ₂ represents a linear or branched alkyl group having 6 or less carbon atoms. ] The heat-sensitive adhesive label according to any one of claims 1 to 13, wherein the heat-sensitive adhesive layer contains a eutectic agent represented by the following general formula (IX).

[In General Formula (IX), X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, which may be different from each other. ]   The elastic under layer and the heat-sensitive adhesive layer are sequentially provided on one surface of the support, and a heat-sensitive recording layer mainly comprising a leuco dye and a developer is provided on the surface opposite to the pressure-sensitive adhesive layer. Item 15. The heat-sensitive adhesive label according to any one of Items 1 to 14.   15. The support according to claim 1, wherein the support is a receiving paper for hot melt transfer recording, and the elastic under layer and the heat-sensitive adhesive layer are sequentially provided on one side of the receiving paper. The heat-sensitive adhesive label described.   The heat-sensitive adhesive label according to claim 16, which has an ink image formed by hot melt transfer recording.   The heat-sensitive adhesive label according to claim 15, which has an ink image formed by UV ink. The heat-sensitive adhesive label according to any one of claims 15 to 18, wherein the heat-sensitive adhesive label is wound around a core material in a roll shape.