JP4554308B2 - Heat-sensitive adhesive label sheet - Google Patents

Description

  The present invention relates to a heat-sensitive pressure-sensitive adhesive label sheet having a heat-sensitive pressure-sensitive adhesive layer that is non-sticky at normal temperature but exhibits adhesiveness upon heating. More specifically, the present invention has excellent adhesive strength to an adherend and low energy. The present invention relates to a heat-sensitive adhesive label sheet having a heat-sensitive adhesive layer using a heat-sensitive heat-sensitive adhesive.

  In recent years, the use of pressure-sensitive adhesive sheets for labels such as labels for price display, labels for product display (barcode), labels for quality display, labels for weighing display, labels for advertising (stickers) has increased. ing. There are various recording methods such as an inkjet recording method, a thermal recording method, and a pressure sensitive recording method. Conventionally, a general pressure-sensitive adhesive sheet with a configuration in which a pressure-sensitive adhesive layer and release paper are laminated on the side 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 sheet 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, attention has been paid to a heat-sensitive adhesive sheet that does not exhibit adhesiveness at room temperature and does not require a release paper. For example, Japanese Patent Application Laid-Open No. 9-20079 (Patent Document 1) is provided with a barrier layer that is activated by light or heat to develop tackiness on the pressure-sensitive adhesive layer. JP-A-2001-64603 (Patent Document 2) contains a plasticizer that is solid at normal temperature in the thermal adhesive layer coating solution, and is usually non-adhesive and can be made adhesive by heating. JP-A-2002-114955 (Patent Document 3) discloses a heat-sensitive adhesive layer comprising a heat-sensitive adhesive mainly composed of fine particles of a thermoplastic resin and a plasticizer. A heat-sensitive adhesive sheet having the following has been proposed.

  In addition, the thermosensitive adhesive is basically a thermoplastic resin as described in "Adhesion Handbook" 12th edition, pages (131-135), published in 1980, published by Kobunshi Shuppankai. And a hot-melt material such as a solid plasticizer and, if necessary, a tackifier. What was described in the said patent documents 2 and 3 is what improved such a heat-sensitive adhesive layer. 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 Patent Document 2, Japanese Patent No. 2683733 (Patent Document 4), and Japanese Patent Laid-Open No. 10-152660 (Patent Document 5), a support and a heat-sensitive adhesive are used. A heat insulating layer using a plastic hollow particle / water-soluble binder is provided between the two and a reduction in thermal energy (higher sensitivity) is proposed. However, although relatively good results can be obtained with respect to the reduction of the heat-activated thermal energy of the heat-sensitive adhesive, a water-soluble binder that does not exhibit adhesiveness at room temperature is used. The adhesive strength to the kimono and polyolefin wrap has not yet reached the practical level. Moreover, the problem that the adhesive force after adhesive expression falls with time is not solved.

JP-A-9-20079 JP 2001-64603 A JP 2002-114955 A Japanese Patent No. 2683733 Japanese Patent Laid-Open No. 10-152660

  The present invention eliminates the problems seen in conventional heat-activatable pressure-sensitive adhesives, has excellent adhesion to rough surface adherends such as corrugated cardboard, polyolefin wrap, etc., has no decrease in adhesive strength over time, and is resistant to blocking. In addition, an object of the present invention is to provide a heat-sensitive pressure-sensitive adhesive label sheet which is excellent in thermal activity with low energy.

  As a result of intensive studies in order to solve the above problems, the present inventors have a thermoplastic resin having a Tg of −70 ° C. to −10 ° C. as a main component between the support and the heat-sensitive adhesive layer. By providing an adhesive under layer and further providing an intermediate layer mainly composed of a thermoplastic resin having a Tg of −70 ° C. to −5 ° C. and plastic spherical hollow particles on the adhesive under layer, the above problem can be solved. Based on this finding, the present invention has been completed.

〔一般式（Ｉ）に於いて、Ｒ_１、Ｒ_２は、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。〕」；
（５）「該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の１種以上であることを特徴とする前記（１）〜（３）の何れかに記載の感熱性粘着ラベルシート。

〔一般式（II）に於いて、Ｒ_３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。〕」；
（６）「該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、該熱溶融性物質が下記一般式（III）、（IV）、（Ｖ）の何れかで示される化合物の１種以上であることを特徴とする前記（１）〜（３）の何れかに記載の感熱性粘着ラベルシート。

〔一般式（III）に於いて、Ｒ_４はメチル基、エチル基、メトキシ基又はエトキシ基を表わし、Ｘ’は水素原子又は水酸基を表わす。〕

〔一般式（IV）に於いて、Ｒ_５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し、Ｙは水素原子又は水酸基を表わす。〕

〔一般式（Ｖ）に於いて、Ｒ_６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。〕」；
（７）「該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）の何れかで示される構造を有するヒンダードフェノール化合物の１種以上であることを特徴とする前記（１）〜（３）の何れかに記載の感熱性粘着ラベルシート。

〔一般式（VI）、（VII）、（VIII）に於いて、Ｒ_７は炭素数６以下の分岐状アルキル基を表わし、Ｒ_８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表わす。〕」；
（８）「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（１）〜（７）の何れかに記載の感熱性粘着ラベルシート。

〔一般式（IX）に於いて、Ｘ”は、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。〕」；
（９）「支持体片面に少なくとも該粘着アンダー層、中間層、感熱性粘着剤層を順次設け、さらに支持体の該感熱性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（１）〜（８）の何れかに記載の感熱性粘着ラベルシート」；
（１０）「該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該粘着アンダー層、中間層、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（１）〜（８）の何れかに記載の感熱性粘着ラベルシート」；
（１１）「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（１０）に記載の感熱性粘着ラベルシート」；
（１２）「ＵＶ硬化性インク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（１）〜（１４）の何れかに記載の感熱性粘着ラベルシート」；
（１３）「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（１）〜（１２）の何れかに記載の感熱性粘着ラベルシート」。
That is, the said subject is solved by (1)-( 13 ) of this invention.
(1) "on one side of a support, at least the adhesive under layer, an intermediate layer, a sequentially provided a heat-sensitive adhesive label sheet及beauty sensitive heat adhesive layer,
The adhesive under layer is an adhesive under layer mainly composed of a thermoplastic resin having a Tg of −70 ° C. to −10 ° C.,
The intermediate layer is mainly composed of a thermoplastic resin having a Tg of −70 ° C. to −5 ° C. and plastic spherical hollow particles, and the ratio of the thermoplastic resin to the plastic spherical hollow particles is plastic relative to 1 part by weight of the thermoplastic resin. It is an intermediate layer that is 0.1 to 1.0 part by weight of spherical hollow particles ,
The heat-sensitive adhesive layer is mainly composed of a thermoplastic resin, a tackifier, and a hot-melt material .
The thermoplastic resin of the adhesive under layer, intermediate layer and heat-sensitive adhesive layer is an acrylic ester copolymer, a methacrylic ester copolymer, an acrylic ester-methacrylic ester copolymer, an acrylic ester-styrene copolymer. A thermosensitive pressure-sensitive adhesive label sheet, which is at least one thermoplastic resin selected from a polymer, an acrylic ester-methacrylic ester-styrene copolymer, and an ethylene-vinyl acetate copolymer ;
( 2 ) “The plastic spherical hollow particles used in the intermediate layer have a hollowness of 70% or more and a maximum particle size of the hollow particles of 10.0 μm or less and an average particle size of 2.0 to The heat-sensitive adhesive label sheet according to (1) above, which is a 5.0 μm plastic spherical hollow particle ”;
( 3 ) "The material for forming the plastic spherical hollow particles is an acrylonitrile-vinylidene chloride-methyl methacrylate copolymer or an acrylonitrile-methacrylonitrile-isobornyl methacrylate copolymer (1 ) Or (2) heat-sensitive adhesive label sheet ”;
( 4 ) "In the heat-sensitive adhesive layer mainly composed of the thermoplastic resin, the tackifier and the heat-meltable substance, the heat-meltable substance is a kind of benzotriazole compound represented by the following general formula (I) It is the above, The heat-sensitive adhesive label sheet in any one of said (1)-( 3 ) characterized by the above-mentioned;

[In general formula (I), R < ₁ >, R < ₂ > represents either a hydrogen atom, a C1-C8 alkyl group, and (alpha), (alpha)-dimethylbenzyl group, X is a hydrogen atom or chlorine Represents an atom. ]];
( 5 ) "In the heat-sensitive adhesive layer mainly composed of the thermoplastic resin, the tackifier and the heat-meltable substance, the heat-meltable substance is a hydroxybenzoic acid ester compound represented by the following general formula (II): 1 or more types, The heat-sensitive adhesive label sheet in any one of said (1)-( 3 ) characterized by the above-mentioned.

[In the general formula (II), R ₃ represents 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 either. ]];
( 6 ) “In the heat-sensitive adhesive layer mainly composed of the thermoplastic resin, the tackifier and the heat-meltable substance, the heat-meltable substance is represented by the following general formulas (III), (IV) and (V): The heat-sensitive adhesive label sheet according to any one of the above (1) to (3) , wherein the heat-sensitive adhesive label sheet is one or more kinds of compounds represented by any of the above.

[In the general formula (III), R ₄ represents a methyl group, an ethyl group, a methoxy group or an ethoxy group, and X ′ represents a hydrogen atom or a hydroxyl group. ]

[In the general formula (IV), R ₅ represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group or a halogen atom, and Y represents a hydrogen atom or a hydroxyl group. ]

[In the general formula (V), R ₆ represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group or a halogen atom. ]];
( 7 ) “In the heat-sensitive adhesive layer mainly composed of the thermoplastic resin, the tackifier and the heat-meltable substance, the heat-meltable substance is a hindered phenol compound, and the molecular structure has the following general formula: (VI), (VII), or (VIII) is one or more hindered phenol compounds having a structure represented by any one of (1) to (3) above. Adhesive label sheet.

[In the general formulas (VI), (VII) and (VIII), R ₇ represents a branched alkyl group having 6 or less carbon atoms, and R ₈ is a linear alkyl group or branched alkyl group having 6 or less carbon atoms. Represents a group. ]];
( 8 ) “The heat-sensitive adhesive label according to any one of (1) to (7) , wherein the heat-sensitive adhesive layer contains a eutectic agent represented by the following general formula (IX): Sheet.

[In general formula (IX), X ″ represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom.] ”
( 9 ) “At least the adhesive under layer, the intermediate layer, and the heat-sensitive adhesive layer are sequentially provided on one side of the support, and the leuco dye and the developer are the main components on the surface opposite to the heat-sensitive adhesive layer of the support. A heat-sensitive adhesive label sheet according to any one of (1) to (8) , wherein a heat-sensitive recording layer is provided;
( 10 ) “The support is a receiving paper for hot melt transfer recording, and the adhesive under layer, the intermediate layer, and the heat-sensitive adhesive layer are sequentially provided on one side of the receiving paper. (1) to (8) heat-sensitive adhesive label sheet according to any one of the above items;
( 11 ) "The heat-sensitive adhesive label sheet according to (10) above, having an ink image formed by hot melt transfer recording";
( 12 ) "The heat-sensitive adhesive label sheet according to any one of (1) to (14) above, which has an ink image formed with a UV curable ink";
( 13 ) “The heat-sensitive adhesive label sheet according to any one of (1) to (12) above, which is wound around a core in a roll shape”.

  According to the present invention, the disadvantages of conventional heat-activatable pressure-sensitive adhesives are overcome, the adhesive strength against rough surface adherends such as corrugated cardboard and polyolefin wrap is strong, and there is little decrease in the adhesive strength over time, even with low energy. It is possible to provide a heat-sensitive pressure-sensitive adhesive label sheet that is excellent in thermal activation and also has good blocking resistance. Such a heat-sensitive adhesive label sheet does not require a release paper and contributes greatly to the label field and environmental conservation.

Below, the characteristic regarding the heat-sensitive adhesive label sheet of this invention is demonstrated in detail.
The heat-sensitive pressure-sensitive adhesive label sheet of the present invention is a heat-sensitive pressure-sensitive adhesive label sheet 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 the support. An adhesive underlayer mainly composed of a thermoplastic resin having a Tg of −70 ° C. to −10 ° C. is provided on the support side between the adhesive and the heat-sensitive adhesive layer, and Tg-70 ° C. By providing an intermediate layer mainly composed of a thermoplastic resin at −5 ° C. and plastic spherical hollow particles, the adhesive strength to rough surface adherends such as corrugated cardboard and polyolefin wrap is strong, and low energy thermal activation, Also, the blocking resistance is improved.

  By providing the heat-sensitive adhesive layer on the adhesive under layer, the heat-sensitive adhesive layer, the intermediate layer, and the adhesive under layer are mixed with each other at the time of heating. By using the plastic resin well and increasing the amount of the adhesive, the adhesive strength to rough surface adherends such as cardboard and polyolefin wrap becomes stronger. In addition, by using plastic spherical hollow particles with a high hollow ratio for the intermediate layer, a heat-insulating effect is born, and the heat-sensitive adhesive layer provided on the upper layer can be thermally activated with low energy or can improve blocking resistance. It has become possible.

  The Tg-70 ° C to -10 ° C thermoplastic resin used for the adhesive underlayer and the Tg-70 ° C to -5 ° C thermoplastic resin used for the intermediate layer are heat used for the heat-sensitive adhesive layer in the present invention. Plastic rubber is preferred, natural rubber latex graft copolymerized with vinyl monomers, acrylate ester copolymer, methacrylate ester copolymer, acrylate ester-methacrylate ester copolymer, acrylate ester-styrene copolymer It is preferable to use at least one selected from acrylic ester-methacrylic ester-styrene copolymer and ethylene-vinyl acetate copolymer. In the case of a high Tg resin exceeding the Tg range of the thermoplastic resin used for the adhesive under layer and the intermediate layer, the characteristics of the adhesive under layer and the intermediate layer cannot be obtained at all, and rough surface adherends such as cardboard and polyolefin Adhesive strength with respect to wrapping or the like is weak, and the adhesive strength of only the heat-sensitive adhesive layer provided in the upper layer is obtained. On the other hand, most resins have a Tg of −70 ° C. or higher, and there is no particular problem even in the case of a low Tg resin that is less than the Tg range of the thermoplastic resin of the present invention.

  Moreover, 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). The above 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 hollow ratio have insufficient heat insulation effect, so that heat energy from the thermal head is released to the outside through the support, and the high sensitivity 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 as a shell and already in a foamed state containing air or other gas inside. 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.

  In addition, when the average particle size is larger than 5.0 μm, when a heat-sensitive adhesive layer is provided on the intermediate layer using these, a large particle part is a part where the heat-sensitive adhesive layer is not formed, When 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 highly sensitive thermal activation effect is inferior. Moreover, in order to ensure the adhesive force by the thermal activation system using a thermal head, the hollow ratio of the hollow particles used for the intermediate layer is preferably 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. On the contrary, when the amount of plastic spherical hollow particles is more than 1.0 part by weight, the adhesive strength to rough surface adherends such as corrugated cardboard and polyolefin wrap is reduced, and only the thermosensitive adhesive layer provided in the upper layer becomes the adhesive strength. End up.

As an application quantity of the adhesion underlayer of this invention, it is 2-35 g / m < ² > by dry application quantity, Preferably it applies in the range of 4-25 g / m < ² >. When the coating amount of the adhesive under layer is less than 2 g / m ² , sufficient adhesion cannot be obtained when performing adhesion after thermal activation. On the other hand, if it exceeds 35 g / m ² , the adhesive strength and the heat insulation effect are saturated, which is not economically preferable.

Then, the coating amount of the intermediate layer usually 0.2 to 10 g / ^{m 2} on a dry coating amount, is applied preferably 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 insulation 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 adhesive underlayer and intermediate layer for the heat-sensitive adhesive layer, the resin can be mixed well, so the adhesiveness to rough surface adherends such as cardboard and polyolefin wrap Will improve.

  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. In addition, when the content of the low Tg resin exceeds 60% by weight, it is not preferable because a storage defect (blocking) occurs, such as an adhesive force developing at a temperature in a normal storage environment.

  In the heat-meltable substance of the present invention, the compounds represented by the general formulas (I) to (V) and the hindered phenol compounds having the structures represented by the general formulas (VI) to (VIII) are solid at room temperature. Those that melt on heating are 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 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. When the melting point exceeds 200 ° C., a large amount of energy is required to develop the adhesive force, resulting in practical problems. In addition, when 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 size of the hot-melt material to 0.5 μm or less, the dynamic thermal sensitivity is increased, and it becomes compatible with the thermoplastic resin and the tackifier at low energy to become a thermally active adhesive. 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, a heat-meltable substance (for example, a compound represented by the general formulas (I) to (V) or a general formula (VI) to (VIII)) The content of the hindered phenol compound having a structure is preferably 25 to 80% by weight, more preferably 35 to 70% by weight. If the content of the hot-melt material is less than 25% by weight or more than 80% by weight, the adhesive strength may be lowered. Further, when combined with a low Tg resin, if the content of the heat-meltable substance 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 (V) and the hindered phenol compounds having the structures represented by the general formulas (VI) to (VIII) in the hot-melt material of the present invention. Indicates.
As the benzotriazole compound represented by the general formula (I),
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) benzotriazol Etc., and it may be mixed benzotriazole two or more.

As the hydroxybenzoic acid ester compound represented by the general formula (II),
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.

As the compound represented by the general formula (III),
Examples include toluoin, anisoin, m-anisoin, deoxytoluoin, deoxyanisoin, 4,4'-diethylbenzoin, 4,4'-diethoxybenzoin.

As 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.

As 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 having the structures represented by the general formulas (VI), (VII), and (VIII) include compounds shown in the following table.

  Two or more types of hindered phenol compounds having a structure represented by the general formulas (VI), (VII), and (VIII) may be used.

  Furthermore, it is preferable to use a eutectic agent in the heat-sensitive adhesive layer of the present invention, and as the eutectic agent, a material 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 troubles (blocking) occur, for example, when it is contained in the heat-sensitive adhesive layer, adhesive strength is exhibited at a normal storage environment temperature. 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, as the coagulant, oxalic acid dibenzyl ester compound represented by the general formula (IX) is used.

As the succinic acid dibenzyl ester compound represented by the general formula (IX),
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. A mixture of two or more oxalic acid dibenzyl ester compounds is used. Also good.

  Furthermore, in order to improve the adhesive strength of the heat-sensitive adhesive, a tackifier used in a general adhesive is used in combination with the above components. Examples of the tackifier include rosin derivatives, terpene resins, and petroleum-based adhesives. Resins, phenolic resins and xylene resins are used.

  As tackifiers that are particularly preferably used for the heat-sensitive adhesive in the present invention, rosin derivatives (rosin, polymerized rosin, hydrogenated rosin), terpene resins (terpene resin, aromatic modified terpene resin, terpene phenol resin, hydrogenated) Terpene resin). These tackifiers are compatible with the thermoplastic resin and the hot-melt material, and the adhesive force of the heat-sensitive adhesive is remarkably 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. The content of the tackifier in the heat-sensitive adhesive is preferably 1 to 30% by weight, 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 in 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.

  In the present invention, by applying the above heat-sensitive adhesive to one side of a substrate (support), the adhesive strength to each adherend, particularly corrugated cardboard, vinyl chloride wrap, polyolefin wrap, etc. is strong, and blocking resistance. In addition, a good heat-sensitive adhesive sheet can be obtained. This heat-sensitive adhesive sheet is suitable for use as a label.

  And the heat-sensitive adhesive label sheet of the present invention provided with an adhesive under layer and a heat-sensitive adhesive layer on one side of the support has an adhesive force to each adherend, particularly a rough adherend such as cardboard, polyolefin wrap, etc. It is a heat-sensitive adhesive label sheet that is strong, has low energy thermal activation, and has good blocking resistance.

  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. When 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 and the adhesive under layer. Therefore, it is inferior to blocking resistance. Moreover, when it exceeds 20 g / m < ² >, the heat insulation effect of an intermediate | middle layer will fade, and it is economically unpreferable.

  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 sheet is a very effective label with strong adhesion to each adherend, particularly rough surface adherends such as cardboard, polyolefin wrap, etc., low energy thermal activation, and good blocking resistance. It is a sheet.

  In the present invention, a heat-sensitive recording layer mainly comprising a leuco dye and a developer can be formed on a substrate (support). As the leuco dye used in the heat-sensitive recording layer in the present invention, leuco dyes generally known in this type of leuco recording material are 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 addition, as the color developer used in the heat-sensitive recording layer in the present invention, various electron-accepting compounds such as phenolic compounds, thiophenolic compounds, thiourea derivatives, organic acids and metal salts thereof are applied. be able to. 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 a heat-sensitive recording layer in 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. Examples of such binders include polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose, polyacrylic acid soda, polyvinylpyrrolidone, acrylamide / acrylic acid 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.

  In the present invention, when a heat-sensitive recording layer is formed, 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.

In the present invention, if necessary, an undercoat layer is provided between the base material (support) and the heat-sensitive recording layer, or for the purpose of improving image reliability on the heat-sensitive recording layer, for example, A protective layer mainly composed of a water-soluble resin can also be provided. 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 heat-sensitive recording paper as the base material, the adhesive under layer and the intermediate layer were sequentially provided on the back surface (opposite surface provided with the heat-sensitive recording layer), and a heat-sensitive adhesive layer was further provided. It is possible to obtain a heat-sensitive adhesive label which has a strong adhesive force to a body, particularly a rough-surface adherend such as cardboard, or an adherend such as polyolefin wrap, and is capable of thermal recording 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. Inks and electron beam curable inks are quick-drying, so they are used as optimal inks on thermal recording paper. (Solvent-rich inks cause color development in the thermal recording layer and are very difficult to use. .)
Further, unlike the normal label, the heat-sensitive adhesive label sheet of the present invention has no merit when it is used in a roll shape because there is no release paper. For example, even when the roll diameter is the same, the length is about twice as long as there is no release paper, so the number of times the paper is set in the label printer can be reduced. This is advantageous because the label printer can be made compact.

  The heat-sensitive recording layer in the present invention can be formed by a generally known method. For example, first, the leuco dye and 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 is preferably 1 to 3 μm, and then as necessary. A heat-sensitive recording layer can be formed by preparing a heat-sensitive recording layer coating solution by mixing with a filler, a heat-fusible substance (sensitizer) dispersion, and the like, and applying the mixture to a substrate.

  By using a receiving paper for thermal transfer recording on a substrate (support), 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. In particular, it is possible to obtain a very effective heat-sensitive adhesive label sheet for thermal transfer recording having strong adhesion to rough surface adherends such as cardboard and polyolefin wrap, low energy thermal activation, and good blocking resistance. it can.

  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, sodium polyacrylate, 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-resistant 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 (support) used in the present invention is not particularly limited, such as high-quality paper, art paper, coated paper, etc., other than paper, polyester films such as polyethylene terephthalate and polybutylene terephthalate, and cellulose triacetate. A cellulose derivative film, a polyolefin film such as polypropylene or polyethylene, a polystyrene film, or a film obtained by bonding them together 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, micro gravure 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 adhesive underlayer coating solution]
[A'-1 liquid]
・ 2-ethylhexyl acrylate / methyl methacrylate /
Copolymer of styrene (Tg-65 ° C)
(Solid content concentration 55.4%, manufactured by Showa Polymer Co., Ltd.) 90.3 parts Surfactant Dapro W-77 (made by Elementis Japan) 0.1 part Water 9.6 parts A mixture of the above composition is stirred. Then, an adhesive under coating solution [A′-1 solution] was prepared.

[A'-2 liquid]
-Copolymer of n-butyl acrylate / methyl acrylate (Tg-62 ° C) (solid content 50%, manufactured by JSR) 100 parts-Surfactant Dapro W-77 (made by Elementis Japan) 0.1 part The mixture consisting of was stirred to prepare an adhesive undercoating liquid [A′-2].

[A'-3 liquid]
-Copolymer of styrene / acrylic acid ester (Tg-10 ° C) (solid content concentration 55%, Showa High Polymer Co., Ltd.) 90.9 parts-Surfactant Dapro W-77 (made by Elementis Japan) 0.1 part -9.1 parts of water The mixture which consists of the said composition was stirred, and the adhesion under coating liquid [A'-3 liquid] was prepared.

[A'-4 liquid]
・ Acrylic acid ester copolymer (Tg−5 ° C.) (solid content concentration: 52%, manufactured by Showa Polymer Co., Ltd.) 96.2 parts ・ Surfactant Dapro W-77 (made by Elementis Japan) 0.1 part ・ Water 3 .8 parts A mixture comprising the above composition was stirred to prepare an adhesive undercoating solution [A'-4 solution].

[Adjustment of intermediate layer coating solution]
[A-1 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 / isobornyl 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%) 22.5 parts ・ 2-ethylhexyl acrylate /
Copolymer of methyl methacrylate / styrene (Tg-5 ° C.) (solid content concentration 55.4%, manufactured by Showa Polymer Co., Ltd.) 16.7 parts Surfactant Dapro W-77 (produced by Elementis Japan) 0.1 Parts-Water 61.7 parts The mixture which consists of the said composition was stirred and disperse | distributed, and the intermediate | middle layer coating liquid [A-3 liquid] 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%) 22.0 parts ・ 2-ethylhexyl acrylate /
Copolymer of n-butyl acrylate / styrene (Tg-30 ° C.) (solid content concentration 50.0%, manufactured by Showa Polymer Co., Ltd.) 20.0 parts Surfactant Dapro W-77 (produced by Elementis Japan) 0. 1 part-Water 57.9 parts The mixture which consists of the said composition was stir-dispersed, and the intermediate | middle layer coating liquid [A-4 liquid] was prepared.

[A-5 solution]
・ Plastic spherical hollow particles [2] (acrylonitrile /
Methacrylonitrile / isobornyl methacrylate copolymer)
(Solid content concentration 33%, average particle size 3.0 μm, hollow rate 91%) 6.1 parts ・ Ethylene / vinyl acetate / acrylic copolymer (Tg-20 ° C.) (solid content concentration 53%, Sumika Chemtex) 30.2 parts ・ Surfactant Dapro W-77 (manufactured by Elementis Japan) 0.1 part ・ Water 63.6 parts A mixture of the above composition was stirred and dispersed to prepare an intermediate layer coating solution [A-5 solution Was prepared.

[A-6 solution]
・ Plastic spherical hollow particles [5] (acrylonitrile /
Methacrylonitrile / isobornyl methacrylate copolymer)
(Solid concentration 33%, average particle size 6.0 μm,
27.3 parts ・ 2-ethylhexyl acrylate /
Copolymer of methyl methacrylate / styrene (Tg-65 ° C.) (solid content concentration 55.4%, manufactured by Showa Polymer Co., Ltd.) 16.3 parts Surfactant Dapro W-77 (produced 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 / isobornyl 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-7 solution] was prepared.

[A-8 solution]
・ Plastic spherical hollow particles [2] (acrylonitrile /
Methacrylonitrile / isobornyl methacrylate copolymer)
(Solid content concentration 33%, average particle size 3.0 μm, hollow rate 91%) 30.3 parts n-butyl acrylate / methyl acrylate copolymer (Tg-62 ° C.) (solid content concentration 50%, manufactured by JSR) ) 10.0 parts-Surfactant Dapro W-77 (made by Elementis Japan) 0.1 part-Water 59.6 parts A mixture of the above composition was stirred and dispersed to prepare an intermediate layer coating solution [A-8 solution] Was prepared.

[A-9 solution]
・ Plastic spherical hollow particles [2] (acrylonitrile /
Methacrylonitrile / isobornyl 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 [1] (acrylonitrile /
Vinylidene chloride / methyl methacrylate copolymer)
(Solid content concentration 41%, average particle size 3.6 μm, hollow rate 90%) 23.4 parts ・ Styrene / butadiene copolymer latex (Tg + 4 ° C.) (solid content concentration 48%, manufactured by Nippon A & L) 10 parts ・ Interface Activator DAPRO W-77 (manufactured by Elementis Japan) 0.1 part ・ Water 66.5 parts A mixture comprising the above composition was stirred to prepare an intermediate layer coating solution [A-10 solution].

[Preparation of hot melt material dispersion]
[B-1 solution]
2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl)
-5-chlorobenzotriazole (mp 138 ° 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-1 solution].

[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 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-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) 0.2 part ・ Water 53.1 parts From the above composition The resulting mixture was dispersed using a sand mill so that the average particle size 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 diameter was 1.0 μm, to obtain a dispersion [liquid B-4].

[B-5 solution]
・ Anisoin (mp99-100 ° 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-5].

[B-6 solution]
・ Phenyl 1-hydroxy-2-naphthoate (mp94-96 ° 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 parts A 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 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-7].

[B-8 solution]
・ Hindered phenol compound of general formula (VI) -2 (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 parts Water 53.1 parts A 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]
・ Hindered phenol compound of general formula (VII) -1 (mp163 ° C.) 40.0 parts ・ Polyvinyl alcohol (30% aqueous solution) 6.7 parts ・ Surfactant Olfine PD-001 (manufactured by Nissin Chemical Industry) 2 parts Water 53.1 parts A mixture [B-9] was obtained by dispersing the mixture having the above composition using a sand mill so that the average particle size was 1.0 µm.

[B-10 solution]
・ Hindered phenol compound of general formula (VIII) -6 (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 parts Water 53.1 parts A mixture of 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].

[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 [solution C-1].

[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 50%, manufactured by JSR) 10 parts ・ Polymerized rosin emulsion (softening point 145 ° C., non-volatile content 50%) 6 parts 37.5 parts of active substance dispersion liquid [B-1 liquid]-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 / styrene copolymer
(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 Hot melt material dispersion [B-2 Liquid] 37.5 parts-Eutectic agent dispersion liquid [C-2 liquid] 7 parts A mixture of 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 50%, manufactured by JSR) 10 parts ・ Polymerized rosin emulsion (softening point 145 ° C., non-volatile content 50%) 6 parts 19 parts of heat-soluble substance dispersion liquid (B-1 liquid) 19 parts of heat-meltable substance dispersion liquid (B-2 liquid) 7 parts of eutectic agent dispersion liquid (C-1 liquid) 7 parts Thus, a coating solution [D-3 solution] was prepared.

[D-4 solution]
・ 2-ethylhexyl acrylate /
Copolymer of methyl methacrylate / styrene (Tg-5 ° C.) (solid content concentration 55.4%, Showa High Polymer) 9 parts ・ Polymerized rosin emulsion (softening point 145 ° C., non-volatile content 50%) 6 parts ・ Heat 37.5 parts of meltable substance dispersion [B-4 solution] A mixture of the above composition 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 concentration 53%, manufactured by Sumika Chemtex) 9.4 parts-Terpene phenol emulsion (softening point 150 ° C, nonvolatile content 50%) 6 parts・ Hot-melting substance dispersion (liquid B-5) 37.5 parts ・ Eutectic agent dispersion (liquid C-1) 7 parts A mixture of the above composition is uniformly mixed to form a coating liquid [liquid D-5] It was adjusted.

[D-6 solution]
・ 2-ethylhexyl acrylate /
n-Butyl acrylate / styrene copolymer
(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-melting substance dispersion [B-6 Liquid] 37.5 parts A mixture having the above composition was uniformly mixed to prepare a coating liquid [D-6 liquid].

[D-7 solution]
・ Copolymer of n-butyl acrylate / methyl acrylate (Tg−62 ° C.) (solid content concentration 50%, manufactured by JSR) 10 parts ・ Terpene phenol emulsion (softening point 150 ° C., nonvolatile content 50%) 6 parts 37.5 parts of active substance dispersion liquid [B-7 liquid] A mixture of the above composition was uniformly mixed to prepare a coating liquid [D-7 liquid].

[D-8 solution]
・ 2-ethylhexyl acrylate /
n-Butyl acrylate / styrene copolymer
(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-melting substance dispersion [B-6 Liquid] 19 parts ・ Hot-melting substance dispersion liquid [B-7 liquid] 19 parts A mixture of the above composition was uniformly mixed to prepare a coating liquid [D-8 liquid].

[D-9 solution]
・ Copolymer of n-butyl acrylate / methyl acrylate (Tg−62 ° C.) (solid content concentration 50%, manufactured by JSR) 10 parts ・ Terpene phenol emulsion (softening point 150 ° C., nonvolatile content 50%) 6 parts 37.5 parts of active substance dispersion (B-8 solution) A mixture of the above composition was uniformly mixed to prepare a coating solution (D-9 solution).

[D-10 solution]
・ 2-ethylhexyl acrylate /
Methyl methacrylate / styrene copolymer
(Tg-65 ° C.) (solid content concentration 55.4%, manufactured by Showa Polymer Co., Ltd.) 9 parts ・ Terpene phenol emulsion (softening point 150 ° C., nonvolatile content 50%) 6 parts ・ Hot-melting substance dispersion [B-9 Liquid] 37.5 parts A mixture comprising the above composition was uniformly mixed to prepare a coating liquid [D-10 liquid].

[D-11 solution]
・ 2-ethylhexyl acrylate /
Methyl methacrylate / styrene copolymer
(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 Hot melt material dispersion [B-10 Liquid] 37.5 parts A mixture having the above composition was uniformly mixed to prepare a coating liquid [D-11 liquid].

[Creation of thermal recording paper]
[Liquid E] Coating liquid for forming non-foaming heat insulation layer ・ Dispersion of fine hollow particles (vinylidene chloride /
Copolymer resin mainly composed of acrylonitrile)
(Solid content concentration 32%, average particle size 3.6 μm, hollowness 92%) 30 parts ・ Styrene / butadiene copolymer latex (Tg + 4 ° C.) 10 parts ・ Surfactant Dapro W-77 (manufactured by Elementis Japan) 0 .1 part Water 60 parts A mixture of 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

[G liquid] Developer dispersion liquid 4-isopropoxy-4'-hydroxydiphenyl sulfone 10 parts Polyvinyl alcohol (10% aqueous solution) 25 parts Calcium carbonate 15 parts Water 50 parts

[F liquid] and [G liquid] are prepared by dispersing the mixture having the above composition using a sand mill so that the average particle diameter is about 1.5 μm, and then [F liquid]: [G liquid ] Was mixed and stirred so that the ratio was 1: 8 to obtain a heat-sensitive recording 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 coating the above [F liquid] and drying so that the weight becomes 5 g / m ² and providing a heat-sensitive recording layer, the super calender so that the Oken type smoothness becomes 2000 seconds. The heat-sensitive recording layer-coated paper was obtained by processing.

[Adjustment of protective layer coating 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 [protective layer coating solution]
・ 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 coated with a thermosensitive coloring layer. It was coated and dried on paper so that the dry 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 adhesive undercoat solution, an intermediate layer coating solution and a heat-sensitive adhesive coating solution listed in Table 2 below were sequentially applied and dried to obtain a heat-sensitive adhesive label sheet.

<Adhesive strength and thermal activation sensitivity (low energy)>
1) Immediately after measurement of adhesive strength A heat-sensitive adhesive material was cut into a 25 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.

2) Measurement of adhesive strength over time A heat-sensitive adhesive material was cut into a 25 mm × 150 mm rectangle, and using a thermal printing device TH-PMD manufactured by Okura Electric, head conditions: each energy 0.5 mJ / dot, printing speed 4 ms / line, The heat-sensitive adhesive label sheet is thermally activated under the condition of a 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 was peeled after one week 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 / 25 mm. This test was performed in a room temperature environment (23 ° C., 65%).

<Blocking property>
The protective layer surface or base material surface of the heat-sensitive recording layer of the same sample was brought into contact with the heat-sensitive adhesive layer surface, tested at 200 g / cm ² at 50 ° C. under dry conditions for 24 hours, and then allowed to stand at room temperature. And the blocking property at that time was evaluated according to the rank as shown in Table 3 below.

Claims (13)

On one side of a support, at least the adhesive under layer, an intermediate layer, a sequentially provided a heat-sensitive adhesive label sheet及beauty sensitive heat adhesive layer,
The adhesive under layer is an adhesive under layer mainly composed of a thermoplastic resin having a Tg of −70 ° C. to −10 ° C.,
The intermediate layer is mainly composed of a thermoplastic resin having a Tg of −70 ° C. to −5 ° C. and plastic spherical hollow particles, and the ratio of the thermoplastic resin to the plastic spherical hollow particles is plastic relative to 1 part by weight of the thermoplastic resin. It is an intermediate layer that is 0.1 to 1.0 part by weight of spherical hollow particles ,
The heat-sensitive adhesive layer is mainly composed of a thermoplastic resin, a tackifier, and a hot-melt material .
The thermoplastic resin of the adhesive under layer, intermediate layer and heat-sensitive adhesive layer is an acrylic ester copolymer, a methacrylic ester copolymer, an acrylic ester-methacrylic ester copolymer, an acrylic ester-styrene copolymer. A thermosensitive pressure-sensitive adhesive label sheet, which is at least one thermoplastic resin selected from a polymer, an acrylic ester-methacrylic ester-styrene copolymer, and an ethylene-vinyl acetate copolymer . The plastic spherical hollow particles used for the intermediate layer have a hollow ratio of 70% or more and a maximum particle size of the hollow particles of 10.0 μm or less and an average particle size of 2.0 to 5.0 μm. The heat-sensitive adhesive label sheet according to claim 1, which is a plastic spherical hollow particle. Material forming the plastic spherical hollow particles, acrylonitrile - claim 1 or 2, characterized in that the isobornyl methacrylate copolymer - vinylidene chloride - methyl methacrylate copolymer or acrylonitrile - methacrylonitrile Heat-sensitive adhesive label sheet. In the thermosensitive pressure-sensitive adhesive layer mainly composed of the thermoplastic resin, the tackifier, and the heat-meltable substance, the heat-meltable substance is at least one benzotriazole compound represented by the following general formula (I). The heat-sensitive adhesive label sheet according to any one of claims 1 to 3 .

[In general formula (I), R < ₁ >, R < ₂ > represents either a hydrogen atom, a C1-C8 alkyl group, and (alpha), (alpha)-dimethylbenzyl group, X is a hydrogen atom or chlorine Represents an atom. ] In the heat-sensitive adhesive layer mainly composed of the thermoplastic resin, the tackifier, and the heat-meltable substance, the heat-meltable substance is one or more of hydroxybenzoic acid ester compounds represented by the following general formula (II). The heat-sensitive adhesive label sheet according to any one of claims 1 to 3 , wherein the heat-sensitive adhesive label sheet is provided.

[In the general formula (II), R ₃ represents 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 either. ] In the heat-sensitive adhesive layer mainly composed of the thermoplastic resin, the tackifier, and the heat-meltable substance, the heat-meltable substance is represented by any one of the following general formulas (III), (IV), and (V). The heat-sensitive adhesive label sheet according to any one of claims 1 to 3 , wherein the heat-sensitive adhesive label sheet is one or more kinds of compounds.

[In the general formula (III), R ₄ represents a methyl group, an ethyl group, a methoxy group or an ethoxy group, and X ′ represents a hydrogen atom or a hydroxyl group. ]

[In the general formula (IV), R ₅ represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group or a halogen atom, and Y represents a hydrogen atom or a hydroxyl group. ]

[In the general formula (V), R ₆ 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 the thermoplastic resin, the tackifier and the heat-meltable substance, the heat-meltable substance is a hindered phenol compound, and the following general formula (VI) in the molecular structure: The heat-sensitive adhesive label sheet according to any one of claims 1 to 3 , wherein the heat-sensitive adhesive label sheet is one or more of a hindered phenol compound having a structure represented by any one of (VII) and (VIII).

[In the general formulas (VI), (VII) and (VIII), R ₇ represents a branched alkyl group having 6 or less carbon atoms, and R ₈ is a linear alkyl group or branched alkyl group having 6 or less carbon atoms. Represents a group. ] The heat-sensitive adhesive label sheet according to any one of claims 1 to 7 , wherein the heat-sensitive adhesive layer contains a eutectic agent represented by the following general formula (IX).

[In general formula (IX), X ″ represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom.] At least the adhesive under layer, the intermediate layer, and the heat-sensitive adhesive layer are sequentially provided on one side of the support, and the heat-sensitive recording layer mainly comprises a leuco dye and a developer on the surface opposite to the heat-sensitive adhesive layer of the support. the heat-sensitive adhesive label sheet according to any one of claims 1 to 8, characterized in that is provided. The support is a receiving paper for thermal melting transfer recording, according to claim 1 to 8, characterized in that the PSA under layer on one side of the receiving paper, an intermediate layer, the heat-sensitive adhesive layer is sequentially provided The heat-sensitive adhesive label sheet according to any one of the above. The heat-sensitive adhesive label sheet according to claim 10 , which has an ink image formed by hot-melt transfer recording. The heat-sensitive adhesive label sheet according to any one of claims 1 to 11, characterized in that having an ink image formed by the UV-curable ink. The heat-sensitive adhesive label sheet according to any one of claims 1 to 12 , wherein the heat-sensitive adhesive label sheet is wound around a core material in a roll shape.