JP2005343907A - Heat-sensitive adhesive material, adhered article of heat-sensitive adhesive material and method for activating heat-sensitive adhesive material and activating apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-sensitive adhesive material capable of suitably applying to wrap made of polyolefin in a food POS field and a nonwoven fabric (envelope, etc.), not requiring a release paper, not exhibiting adhesiveness before application, exhibiting adhesiveness controlled at someone's request when applied, having low adhesive strength immediately after application, capable of readily being re-applied even if the adhesive material is applied to the adherend by mistake, free from application mistake, increasing adhesive strength with time and not readily causing release from the adherend and enabling desired printing or recording. <P>SOLUTION: The heat-sensitive adhesive material has, on a substrate, a heat-sensitive adhesive layer containing a thermoplastic resin and a solid plasticizer being solid at normal temperature, melted or softened when heated and miscible with the thermoplastic resin and attached to the adherend by heating, and when the adhesive strength to peel off the heat-sensitive adhesive layer from the adherend is determined according to a measuring procedure specified in the adhesive tape/adhesive sheet test method in JIS Z0237, the heat-sensitive adhesive layer exhibits an adhesive strength of ≤300 gf/40-mm to peel off from the adherend two minutes after the application, and an adhesive strength of ≥500 gf/40-mm to peel off from the adherend 24 hours after the application. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  INDUSTRIAL APPLICABILITY The present invention can be applied to adherends (adhesion targets) of various materials including resin, is particularly suitable for the food POS field, does not require a release paper (liner), and is adhesive before application. A heat-sensitive adhesive material suitable for use as a linerless label or the like, a patch of a heat-sensitive adhesive material to which the heat-sensitive adhesive material is applied, and the above-mentioned efficient The present invention relates to an activation method and an activation device for a heat-sensitive adhesive material.

Conventionally, pressure-sensitive adhesive sheets have been used in various fields. In recent years, pressure-sensitive adhesive sheets have been used in price display labels, product display (barcode) labels, quality display labels, weighing display labels, advertisements, etc. It is increasingly used for label applications such as labels (stickers). The conventionally known pressure-sensitive adhesive sheet has a pressure-sensitive adhesive layer on the side opposite to the information recording surface of the label, and the pressure-sensitive adhesive layer is laminated with a release paper (liner). It is designed to be stickable by peeling off the release paper and sticking it to the adherend when sticking to the subject.
However, in the case of such a conventional pressure-sensitive adhesive sheet, there is a problem that the release paper has to be peeled off at the time of sticking, and the sticking work is complicated and disposal of the peeled release paper is required. In addition, since the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet has tackiness, once the release paper is peeled off, the handleability is inferior, and if it is affixed to the adherend etc. carelessly, it is re-applied cleanly. There is a problem that can not be.

  In recent years, heat-sensitive adhesive sheets that do not exhibit adhesiveness at room temperature and do not require release paper have attracted attention. The heat-sensitive pressure-sensitive adhesive layer in the heat-sensitive pressure-sensitive adhesive sheet has, for example, a solid plasticizer and a thermoplastic resin emulsion as essential components, and a mixture obtained by mixing a tackifier and the like on the opposite side of the printing surface on the support. It is formed by coating, and the surface of the heat-sensitive adhesive layer does not exhibit any tackiness at room temperature, but develops tackiness after heating and maintains the tackiness for a while after heating. A heat-sensitive adhesive material using a liquid plasticizer instead of the solid plasticizer is also known. In the heat-sensitive adhesive material, the liquid plasticizer is encapsulated in a microcapsule, and the microplastic is heated. As a result of the capsule shell being broken, or the liquid plasticizer permeates through the shell of the microcapsule, stickiness is developed. In the case of heat-sensitive adhesive materials using these solid plasticizers and liquid plasticizers, the release paper (liner) is unnecessary, which is advantageous in terms of resource saving and environment.

However, despite the above advantages, the conventional heat-sensitive adhesive materials have the following problems.
That is, firstly, in the food POS industry and the like, it has been generally performed to attach a POS label of a heat-sensitive adhesive material to a food wrap. Switching from vinyl wrap to polyolefin wrap. However, the polyolefin wrap has a much lower adhesion and wettability with the heat-sensitive adhesive layer in the heat-sensitive adhesive material as the POS label than the vinyl chloride wrap, and the POS label can be easily used as the polyolefin wrap. It is a problem that it will be peeled off.
Furthermore, polyolefin wraps tend not to contain various additives (such as plasticizers, stabilizers, etc.) contained in vinyl chloride wraps, and are more wettable than vinyl chloride wraps. Since it is inferior, when sticking the said thermosensitive adhesive material on polyolefin wrap, it is a problem that sufficient adhesiveness is not acquired. In recent years, the heat-sensitive adhesive material has been widely used for envelope labels made of polyolefin (polyethylene, etc.) nonwoven fabrics. Even when used for nonwoven fabrics (envelopes and the like), there is a problem that sufficient adhesiveness cannot be obtained.
In order to solve this problem, for example, using a phthalate ester compound as the solid plasticizer (see Patent Document 1), an ester compound composed of a dihydric alcohol or a polyhydric alcohol, and an aromatic monobasic acid, (See Patent Document 2) has been proposed, but it is difficult to say that these are all sufficient solutions.

  The second problem is that the adhesive strength of the heat-sensitive adhesive material attached to the adherend (the adherend) to the adherend decreases with time. In order to solve this problem, for example, an ester compound composed of a polyhydric alcohol and an aromatic monobasic acid is used as a crystallization retarder that suppresses crystallization of the solid plasticizer (see Patent Document 3). Proposals have been made, but it is difficult to say that all of them are sufficient solutions.

  The third problem is that it is difficult to re-apply the heat-sensitive adhesive material after applying it to the adherend. In order to solve this problem, the adhesive force immediately after the thermal activation of the pressure-sensitive adhesive layer in the heat-sensitive adhesive material is somewhat low and can be re-applied after being applied to the adherend. Ideally, the adhesive strength is enhanced and peeling becomes difficult. However, at present, heat-sensitive adhesive materials exhibiting such adhesive properties have not yet been put into practical use.

JP-A-8-20668 JP-A-8-253747 JP-A-9-169870

  INDUSTRIAL APPLICABILITY The present invention solves the conventional problems and can be applied to adherends (adhesion targets) of various materials including resin. In particular, polyolefin wrap and polyolefin nonwoven fabric (envelope) in the field of food POS Etc.), a release paper (liner) is not required, it does not have adhesiveness before application, expresses the adhesiveness (adhesive strength) controlled as desired at the time of application, Adhesive strength to adherend is low, reattachment is easy, and pasting mistakes can be eliminated. Adhesive strength increases with time and does not easily peel off the adherend, and desired printing or recording is performed. It is an object of the present invention to provide a heat-sensitive adhesive material, a sticking body of the heat-sensitive adhesive material, and an efficient activation method and activation device for the heat-sensitive adhesive material.

Means for solving the above problems are as follows.
<1> A thermoplastic resin and a solid plasticizer are included, and a heat-sensitive adhesive layer that is heated and bonded to an adherend is provided on the support,
The heat-sensitive adhesive material is characterized in that the adhesive force of the heat-sensitive adhesive material to the adherend increases with time from immediately after the heat-sensitive adhesive material is bonded to the adherend.
Although the heat-sensitive adhesive material has a heat-sensitive adhesive layer, the heat-sensitive adhesive layer contains the solid plasticizer in a solid state before heating and does not have fluidity. Before the application of the material, that is, before heating, the heat-sensitive adhesive layer does not exhibit adhesiveness. On the other hand, when the thermosensitive adhesive material is applied, by heating, the solid plasticizer melts, and the thermosensitive adhesive material layer has fluidity, is thermally activated, and has adhesive properties. To express. That is, the heat-sensitive adhesive material is not heated until the heat-sensitive adhesive layer is heated at the time of application, so that the heat-sensitive adhesive layer is thermally activated to exhibit adhesiveness and can be applied to an adherend. For this reason, since the adhesive layer which has adhesiveness is unnecessary before sticking, a release paper (liner) becomes unnecessary and it can be set as a linerless structure. In the case of an adhesive material having such an adhesive layer, it is possible to form the linerless structure by forming the surface with a material having a low surface tension and winding the adhesive material. In this case, desired printing or the like cannot be recorded on the surface. Since the heat-sensitive adhesive material is linerless, desired printing or the like can be suitably performed on the surface thereof. In the heat-sensitive adhesive material, the heat-sensitive adhesive layer corresponding to the heated region is thermally activated to exhibit adhesiveness. Therefore, the heat-sensitive adhesive material is adjusted by adjusting the heating region. The adhesive strength of the agent layer can be appropriately controlled to a desired level.
In the heat-sensitive adhesive material, the heat-sensitive adhesive material increases with time from immediately after being bonded to the adherend, and immediately after heating, the solid plasticizer in the heat-sensitive adhesive layer melts, and accordingly, the thermoplastic Since the resin dissolves and has fluidity, peeling is possible. For this reason, even if affixed by mistake, it can be reapplied. On the other hand, after elapse of a certain time after heating, the solid plasticizer is gradually cooled and returned to the solid state. As a result, it does not have fluidity or is in a very low state, and therefore cannot be peeled off and firmly covered. Unlike conventional heat-sensitive adhesive materials, the adhesive strength is not reduced over time.
<2> A thermosensitive material that is solid at room temperature and includes a solid plasticizer that is melted or softened upon heating and is compatible with the thermoplastic resin, and is heated and bonded to the adherend. Having an adhesive layer on the support,
According to the adhesive strength measuring method in the adhesive tape / adhesive sheet test method of JIS Z0237, the adhesive strength when the heat-sensitive adhesive layer is peeled off from the adherend after 2 minutes is 300 gf / 40 mm or less, and 24 hours have elapsed. The heat-sensitive adhesive material is characterized in that the adhesive strength when peeled from the adherend later is 500 gf / 40 mm or more.
Although the heat-sensitive adhesive material has a heat-sensitive adhesive layer, the heat-sensitive adhesive layer contains the solid plasticizer in a solid state before heating and does not have fluidity. Before the application of the material, that is, before heating, the heat-sensitive adhesive layer does not exhibit adhesiveness. On the other hand, when the heat-sensitive adhesive material is applied, by heating, the solid plasticizer melts and the heat-sensitive adhesive layer has fluidity, is thermally activated, and has adhesive properties. To express. That is, the heat-sensitive adhesive material is not heated until the heat-sensitive adhesive layer is heated at the time of application, so that the heat-sensitive adhesive layer is thermally activated to exhibit adhesiveness and can be applied to an adherend. For this reason, since the adhesive layer which has adhesiveness is unnecessary before sticking, a release paper (liner) becomes unnecessary and it can be set as a linerless structure. In the case of an adhesive material having such an adhesive layer, it is possible to form the linerless structure by forming the surface with a material having a low surface tension and winding the adhesive material. In this case, desired printing or the like cannot be recorded on the surface. Since the heat-sensitive adhesive material is linerless, desired printing or the like can be suitably performed on the surface thereof. In the heat-sensitive adhesive material, the heat-sensitive adhesive layer corresponding to the heated region is thermally activated to exhibit adhesiveness. Therefore, the heat-sensitive adhesive material is adjusted by adjusting the heating region. The adhesive strength of the agent layer can be appropriately controlled to a desired level.
In the heat-sensitive adhesive material, the adhesive force when the heat-sensitive adhesive layer is peeled off from the adherend after 2 minutes according to the adhesive force measurement method in the adhesive tape / adhesive sheet test method of JIS Z0237 is 300 gf / The adhesive strength when peeled from the adherend after 24 hours is 500 gf / 40 mm or more, and immediately after heating (after 2 minutes), the solid in the heat-sensitive adhesive layer Since the plasticizer melts and the thermoplastic resin dissolves and has fluidity, it can be peeled off. For this reason, even if affixed by mistake, it can be reapplied. On the other hand, after elapse of a certain time after heating (for example, after elapse of 24 hours), the solid plasticizer is gradually cooled and returned to the solid state. As a result, the solid plasticizer does not have fluidity or is in an extremely low state. Unlike conventional heat-sensitive adhesive materials, which cannot be firmly adhered to the adherend, the adhesive force does not decrease over time.
<3> A heat-sensitive material that includes a thermoplastic resin and a solid plasticizer that is solid at normal temperature and melts or softens when heated and is compatible with the thermoplastic resin, and is bonded to the adherend by heating. Having an adhesive layer on the support,
The heat-sensitive adhesive layer in the rectangular piece of 4.0 cm × 9.0 cm was heated with a thermal head under the conditions of head conditions: 0.45 mJ / dot, printing speed: 4 ms / line, and platen pressure: 6 kgf / line. When activated and affixed to a non-woven fabric made of polyethylene with a rubber roller of 2 kg under pressure, when peeled from the adherend after 2 minutes at a peeling angle of 180 ° and a peeling speed of 300 mm / min. The adhesive strength is 300 gf / 40 mm or less, and the adhesive strength when peeled from the adherend after 24 hours is 500 gf / 40 mm or more.
Although the heat-sensitive adhesive material has a heat-sensitive adhesive layer, the heat-sensitive adhesive layer contains the solid plasticizer in a solid state before heating and does not have fluidity. Before the application of the material, that is, before heating, the heat-sensitive adhesive layer does not exhibit adhesiveness. On the other hand, when the heat-sensitive adhesive material is applied, by heating, the solid plasticizer melts and the heat-sensitive adhesive layer has fluidity, is thermally activated, and has adhesive properties. To express. That is, the heat-sensitive adhesive material is not heated until the heat-sensitive adhesive layer is heated at the time of application, so that the heat-sensitive adhesive layer is thermally activated to exhibit adhesiveness and can be applied to an adherend. For this reason, since the adhesive layer which has adhesiveness is unnecessary before sticking, a release paper (liner) becomes unnecessary and it can be set as a linerless structure. In the case of an adhesive material having such an adhesive layer, it is possible to form the linerless structure by forming the surface with a material having a low surface tension and winding the adhesive material. In this case, desired printing or the like cannot be recorded on the surface. Since the heat-sensitive adhesive material is linerless, desired printing or the like can be suitably performed on the surface thereof. In the heat-sensitive adhesive material, the heat-sensitive adhesive layer corresponding to the heated region is thermally activated to exhibit adhesiveness. Therefore, the heat-sensitive adhesive material is adjusted by adjusting the heating region. The adhesive strength of the agent layer can be appropriately controlled to a desired level.
In the heat-sensitive adhesive material, the heat-sensitive adhesive layer in a 4.0 cm × 9.0 cm rectangular piece is subjected to a head condition of 0.45 mJ / dot, a printing speed of 4 ms / line, and a platen pressure of 6 kgf / line. After being activated with a thermal head under the conditions of the above and affixed to a polyethylene non-woven fabric with a rubber roller with a pressure of 2 kg, the peeling angle: 180 ° and the peeling speed: 300 mm / min. The adhesive strength when peeled from the adherend is 300 gf / 40 mm or less, and the adhesive strength when peeled from the adherend after 24 hours is 500 gf / 40 mm or more. After), the solid plasticizer in the thermosensitive pressure-sensitive adhesive layer melts, and the thermoplastic resin dissolves accordingly and has fluidity. Noh. For this reason, even if affixed by mistake, it can be reapplied. On the other hand, after elapse of a certain time after heating (for example, after elapse of 24 hours), the solid plasticizer is gradually cooled and returned to the solid state. As a result, the solid plasticizer does not have fluidity or is in an extremely low state. It is impossible and is firmly attached to the adherend, and unlike conventional heat-sensitive adhesive materials, the adhesive force does not decrease with time.
<4> The heat-sensitive adhesive material according to any one of <1> to <3>, wherein the solid plasticizer includes at least two types of benzotriazole derivatives.
In the heat-sensitive adhesive material, since the solid plasticizer contains at least two types of benzotriazole derivatives, the adhesive strength is low immediately after heating, so that it is easy to re-apply. It exhibits excellent adhesion to a wide range of adherends including polyolefin wraps and nonwoven fabrics (envelopes, etc.) and does not peel easily.
<5> The heat-sensitive adhesive material according to <4>, wherein the benzotriazole derivative is selected from compounds represented by the following formula (A).
Formula (A)
However, in formula (A), X represents a group represented by the following formula (B). R1 represents a hydrogen atom, a halogen atom, or an alkyl group. m represents an integer of 1 to 4. X represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a group represented by the following (B).
Formula (B)
However, in formula (B), R2 represents a hydrogen atom, a halogen atom, an alkyl group, or a hydroxyl group. n represents an integer of 1 to 5.
In the heat-sensitive adhesive material, since the solid plasticizer contains a specific benzotriazole derivative, the adhesive strength is low immediately after heating and easy to reapply, and the adhesive strength is enhanced after a certain time after heating, Excellent adhesion to a wide range of adherends including polyolefin wraps and non-woven fabrics (envelopes, etc.) and does not peel easily.
<6> The heat-sensitive adhesive material according to <5>, wherein at least two kinds of benzotriazole derivatives are a combination of compounds represented by any of the following formulas (I) to (V).
<7> The heat-sensitive adhesive material according to <6>, wherein one of at least two types of benzotriazole derivatives is a compound represented by the formula (I).
<8> The method according to any one of <6> to <7>, wherein the at least two benzotriazole derivatives are a combination of the compound represented by formula (I) and the compound represented by formula (IV) It is a heat-sensitive adhesive material.
<9> The heat-sensitive adhesive material according to any one of <4> to <8>, wherein the difference in melting point between at least two types of benzotriazole derivatives is 30 ° C. or higher.
<10> The heat-sensitive adhesive material according to any one of <1> to <9>, wherein an average dispersion diameter in the heat-sensitive adhesive layer of the solid plasticizer is 10 μm or less.
<11> The heat-sensitive adhesive material according to any one of <1> to <10>, wherein at least one of the heat-sensitive adhesive layer and the adjacent layer thereof includes a supercooling accelerator.
<12> The heat-sensitive adhesive material according to <11>, wherein an average dispersion diameter in at least one of the heat-sensitive adhesive layer of the supercooling accelerator and the adjacent layer is 10 μm or less.
<13> The heat-sensitive adhesive material according to any one of <1> to <12>, wherein the heat-sensitive adhesive layer includes a tackifier.
<14> The heat-sensitive adhesive material according to any one of <1> to <13>, wherein the support has a recording layer on a surface opposite to the heat-sensitive adhesive layer side.
<15> The heat-sensitive adhesive material according to <14>, wherein the recording layer is any one of a heat-sensitive recording layer, an inkjet recording layer, and an electrophotographic recording layer.
<16> The heat-sensitive material according to any one of <1> to <15>, wherein a heat-insulating layer is provided between at least one of the support and the heat-sensitive recording layer and between the support and the heat-sensitive adhesive layer. Adhesive material.
<17> The heat-sensitive adhesive material according to <16>, wherein the heat insulating layer includes hollow particles having a hollowness of 30% or more with a thermoplastic resin as a shell.
<18> The heat-sensitive adhesive material according to any one of <1> to <17>, which is used by cutting.
<19> The heat-sensitive adhesive material according to any one of <1> to <18>, in which a cut is formed.
<20> The heat-sensitive adhesive material according to any one of <1> to <19>, wherein the adherend is a polyethylene nonwoven fabric.
<21> The heat-sensitive adhesive material according to any one of <1> to <20>, which is wound in a roll shape.
<22> A heat-sensitive adhesive material patch comprising the heat-sensitive adhesive layer in the heat-sensitive adhesive material according to any one of <1> to <21>.
Since the heat-sensitive adhesive material of the present invention is attached to the adhesive body of the heat-sensitive adhesive material, the adherend to which the heat-sensitive adhesive material is attached is made of a polyolefin wrap (film or film). Sheets) and non-woven fabrics (envelopes and the like) exhibit strong adhesive strength, and the heat-sensitive adhesive material portion does not peel or drop off, and is excellent in durability during use.
<23> contacting the heating means with the heat-sensitive adhesive layer in the heat-sensitive adhesive material to thermally activate the heat-sensitive adhesive layer;
The heat-sensitive adhesive material is a heat-sensitive adhesive material according to any one of <1> to <21>, wherein the heat-sensitive adhesive material is thermally activated.
In the heat activation method of the heat-sensitive adhesive material, the heat-sensitive adhesive layer in the heat-sensitive adhesive material exhibits adhesiveness only when it is thermally activated by the heating means.
<24> The heat activation method for a heat sensitive adhesive material according to claim 23, wherein the heat activation of the heat sensitive adhesive layer is performed after cutting the heat sensitive adhesive material.
<25> The thermal activation method for a heat-sensitive adhesive material according to <24>, wherein the cutting of the heat-sensitive adhesive material is performed either before or after recording on the recording layer.
<26> The method for thermally activating a heat-sensitive adhesive material according to any one of <23> to <24>, further including attaching the heat-activated pressure-sensitive adhesive layer to an adherend. .
<27> a heat-sensitive adhesive material, and a heating unit that contacts the heat-sensitive adhesive layer in the heat-sensitive adhesive material and thermally activates the heat-sensitive adhesive layer,
This heat-sensitive adhesive material is the heat-sensitive adhesive material according to any one of <1> to <21>, wherein the heat-sensitive adhesive material has a heat activation device.
In the heat activation device for the heat-sensitive adhesive material, the heat-sensitive adhesive layer in the heat-sensitive adhesive material exhibits adhesiveness only when it is thermally activated by the heating means.
<28> The heat sensitivity according to <27>, wherein the heating unit includes a resistor and a protective film in this order on the ceramic substrate, and the heating temperature can be controlled by changing an energization amount to the resistor. This is a heat activation device for the adhesive material.
<29> The heat activation device for a heat-sensitive adhesive material according to any one of <27> to <28>, wherein the heating unit is at least one of a thermal head and a thin film heater.
<30> The heat-sensitive adhesive material has a recording layer on the surface of the support opposite to the heat-sensitive adhesive layer side,
The heat activation device for heat-sensitive adhesive material according to any one of <27> to <29>, further comprising recording means for performing recording on the recording layer.
<31> The thermal activation device for a heat-sensitive adhesive material according to <30>, wherein the recording unit performs recording by any one of a thermal recording method, an inkjet method, and an electrophotographic method.
<32> The thermal activation device for heat-sensitive adhesive material according to <31>, wherein the recording unit includes a thermal head and a platen roll.
<33> The heat activation device for a heat-sensitive adhesive material according to any one of <27> to <32>, further including holding means for holding the heat-sensitive adhesive material.
<34> The heat activation device for a heat-sensitive adhesive material according to any one of <27> to <33>, further including a cutting unit that cuts the heat-sensitive adhesive material.
<35> The thermal activation device for heat-sensitive adhesive material according to <34>, wherein the cutting means is disposed between the holding means and the heating means and between the holding means and the recording means. It is.
<36> The thermal activation device for a heat-sensitive adhesive material according to <34>, wherein the recording unit is disposed between the holding unit and the cutting unit.

  According to the present invention, it is possible to solve various problems in the past and to be applied to adherends (adhesion targets) of various materials such as resins, and in particular, polyolefin wraps in the field of food POS and polyolefin nonwoven fabrics. (Applicable to envelopes, etc.), release paper (liner) is not required, it does not have adhesiveness before application, expresses desired adhesiveness (adhesive strength) during application, and immediately after application Has low adhesive strength to the adherend, can be easily reapplied, can eliminate pasting mistakes, and the adhesive strength increases with time and does not easily peel off the adherend, so that desired printing or recording can be performed. It is possible to provide a heat-sensitive adhesive material that can also be used, a patch of the heat-sensitive adhesive material, and an efficient activation method and activation device for the heat-sensitive adhesive material.

The heat-sensitive adhesive material of the present invention has a heat-sensitive pressure-sensitive adhesive layer on a support, and further has other layers appropriately selected as necessary, and the application of the heat-sensitive adhesive material. The adhesive strength to the body increases with time from immediately after the heat-sensitive adhesive material is bonded to the adherend.
The fact that the heat-sensitive adhesive material increases with time from immediately after being bonded to the adherend means that the heat-sensitive adhesive layer is formed for 2 minutes according to the adhesive force measurement method in the adhesive tape / adhesive sheet test method of JIS Z0237. It means that the adhesive strength when peeled from the adherend after elapse of time is 300 gf / 40 mm or less, and the adhesive strength when peeled from the adherend after 24 hours is 500 gf / 40 mm or more. Specifically, the heat-sensitive pressure-sensitive adhesive layer in a 4.0 cm × 9.0 cm rectangular piece of the heat-sensitive pressure-sensitive adhesive material has a head condition of 0.45 mJ / dot, a printing speed of 4 ms / line, and a platen pressure: After thermal activation with a thermal head under the conditions of 6 kgf / line and pasting to a polyethylene nonwoven fabric with a 2 kg rubber roller, the peeling angle: 180 °, the peeling speed: 300 mm / min for 2 minutes Adhesive strength when peeled from the adherend after elapse is 300 gf / 40 mm or less, preferably 200 gf / 40 mm or less, and adhesive strength when peeled from the adherend after 24 hours is 500 gf / 40 mm or more And 600 gf / 40 mm or more is preferable.
When the adhesive strength when peeled from the adherend after 2 minutes has passed is 300 gf / 40 mm or less, the heat-sensitive adhesive material can be easily peeled off from the adherend, and after 24 hours have passed. When the adhesive force when peeled from the adherend is 500 gf / 40 mm or more, the heat-sensitive adhesive material has a strong adhesive force after a certain period of time after sticking, and is easily peeled off from the adherend. Can not do it.
In the heat-sensitive adhesive material of the present invention, the adhesive force to the adherend is preferably 300 gf / 40 mm or less, not only after the lapse of 2 minutes but also after the lapse of 1 to 6 hours, and for 1 to 3 hours. It is more preferable that it is 300 gf / 40 mm or less until after the elapse of time, and it is preferably 500 gf / 40 mm or more not only after the elapse of 24 hours but also after 12 hours, and 500 gf / 40 mm or more after 8 hours. It is more preferable that

  Examples of the polyethylene non-woven fabric include those having an air permeability of 10 to 53 according to JIS P8117. Specifically, for example, “Flash Span” manufactured by Asahi DuPont Co., Ltd., Products Co., Ltd. “Tyvek 1073D” (hard type) manufactured by the company is preferred.

-Heat sensitive adhesive layer-
The heat-sensitive adhesive layer contains at least a solid plasticizer and a thermoplastic resin, and further contains other components appropriately selected as necessary.

--Solid plasticizer--
The solid plasticizer is not particularly limited, and may be appropriately selected depending on the purpose as long as it is solid at room temperature and can be melted or softened upon heating and compatible with the thermoplastic resin. When the solid plasticizer is contained in the heat-sensitive adhesive layer, it is advantageous in that the “supercooled state” can be maintained for a relatively long time as compared with the case where it is not contained. In general, the composition containing the thermoplastic resin melts and becomes liquid when heated, and then returns from liquid to solid when cooled. The composition contains the solid plasticizer. Even when cooled below the melting point of the solid plasticizer, the liquid does not return to the solid state immediately, and the liquid (amorphous state) “supercooled state” can be maintained.
In the present invention, the solid plasticizer preferably contains a benzotriazole derivative, and more preferably contains at least two types of benzotriazole derivatives. When the solid plasticizer contains the benzotriazole derivative, the adhesive force immediately after the thermal activation of the heat-sensitive adhesive layer can be kept low enough to be reapplied. This is advantageous in that the adhesive strength after a certain period of time can be increased to such an extent that it cannot be easily peeled off.

  There is no restriction | limiting in particular as said benzotriazole derivative, According to the objective, it can select suitably, For example, what was described in Unexamined-Japanese-Patent No. 11-263949, Unexamined-Japanese-Patent No. 11-269440, etc. are mentioned. . Preferable examples of the benzotriazole derivative include compounds represented by the following formula (A).

Formula (A)

  However, in formula (A), X represents a group represented by the following formula (B). R1 represents a hydrogen atom, a halogen atom, or an alkyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. m represents an integer of 1 to 4. X represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a group represented by the following (B). There is no restriction | limiting in particular as said alkyl group, For example, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned. There is no restriction | limiting in particular as said aryl group, For example, a phenyl group, a toluyl group, etc. are mentioned.

Formula (B)

  However, in formula (B), R2 represents a hydrogen atom, the halogen atom, the alkyl group, or a hydroxyl group. n represents an integer of 1 to 5.

  In the present invention, among the benzotriazole derivatives represented by the formula (A), it is preferable to use a compound represented by any one of the following formulas (I) to (V), which is selected from these: It is more preferable to use a combination of at least two kinds of benzotriazole derivatives, and it is more preferable that one of these is a compound represented by the formula (I). In this case, the adhesive force immediately after the thermal activation of the heat-sensitive adhesive layer can be kept low enough to allow reattachment, while the adhesive force after a certain period of time can be easily peeled off after application. It is advantageous in that it can be increased to the extent that it cannot be performed.

Among the combinations of two benzotriazole derivatives selected from the compounds represented by any one of the formulas (I) to (V), the compound represented by the formula (I) and the formula (IV) A combination with a compound represented by Among the combinations of two benzotriazole derivatives selected from the compounds represented by any one of the formulas (I) to (V), the melting point difference in the combined benzotriazole derivatives is 30 ° C. or more. It is preferable (however, the combination of the compound represented by the formula (I) and the compound represented by the formula (IV) has a melting point difference of less than 30 ° C., and is exemplified as a preferable combination.) .
In the case of these combinations, since the same substituent is present on the benzene ring in the benzotriazole derivative, and because it has an appropriate melting point difference, a strong level of adhesiveness is maintained over time. In addition, it is preferable in that the adhesiveness tends to be stronger than in the case of other combinations due to internal cohesive force.

The content of the benzotriazole derivative in the heat-sensitive adhesive layer is not particularly limited and can be appropriately selected according to the purpose. However, when at least two kinds of the benzotriazole compounds are used, As content in the said thermosensitive adhesive layer, 10-80 mass% is preferable, and 30-60 mass% is more preferable.
Further, the mixing ratio in the at least two kinds of the benzotriazole derivatives is not particularly limited and may be appropriately selected depending on the purpose. For example, the mass ratio is 0.9: 0.1 to 0.1. 1: 0.9 is preferred.

  As the solid plasticizer, in addition to the benzotriazole derivative represented by any of the formulas (I) to (V), a benzotriazole represented by any of the following formulas (VI) to (X) Compound etc. are mentioned.

When a combination of the benzotriazole derivatives represented by any one of the formulas (I) to (V) is used as the solid plasticizer and contained in the heat-sensitive adhesive layer, the formula (I) to As content in the said thermosensitive adhesive layer of the benzotriazole derivative represented by either of Formula (V), 10-80 mass% is preferable, for example, and 30-60 mass% is more preferable.
The compound represented by any one of the formulas (VI) to (X) is preferably used when at least two types of benzotriazole derivatives are used in combination in the heat-sensitive adhesive layer. In this case, the content in the heat-sensitive adhesive layer is not particularly limited and may be appropriately selected according to the purpose. For example, it is preferably 40% by mass or less, and more preferably 10 to 40% by mass. Preferably, 30 mass% or less is further more preferable, and 10-30 mass% is especially preferable.

  The presence of the benzotriazole derivative in the heat-sensitive adhesive layer can be analyzed, for example, as follows. That is, for example, the benzotriazole derivative is extracted from the heat-sensitive adhesive layer with an organic solvent, and is collected by an analytical method such as high performance liquid chromatography or thin layer chromatography, and is structured by infrared spectrophotometry, NMR, or the like. The presence can be confirmed by analysis.

The dispersion average particle size of the solid plasticizer in the heat-sensitive adhesive layer is not particularly limited and can be appropriately selected according to the purpose. However, the smaller the particle size, the easier the melting during heating occurs. These are advantageous in that they are easily compatible with each other. Specifically, the thickness is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 2 μm or less.
The solid plasticizer is preferably contained in the heat-sensitive adhesive layer together with the thermoplastic resin in a total amount of 50% by mass or more, more preferably 60% by mass or more, and more preferably 70% by mass or more. Is particularly preferred.

--- Thermoplastic resin-
The thermoplastic resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include those generally known as thermoplastic resin emulsions. ) Acrylic ester copolymer, styrene-isoprene copolymer, styrene-acrylic ester copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic Acid ester copolymer, ethylene-vinyl chloride copolymer, ethylene-acrylic ester copolymer, vinyl acetate-ethylene-vinyl chloride copolymer, vinyl acetate-ethylene-acrylic ester copolymer, vinyl acetate-ethylene -Styrene copolymer, polybutadiene, polyurethane and the like. These may be used singly or in combination of two or more. Among these, when an acrylic ester copolymer is used, particularly when 2-ethylhexyl acrylate is used, It is preferable at the point which can achieve high adhesion of an adhesive pressure-sensitive adhesive layer.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. For example, a supercooling accelerator, a tackifier, an antiblocking agent, a cohesion improver, a hardening agent, an antiseptic Suitable examples include an agent, a dye, a developer, a pH adjuster, and an antifoaming agent, and among these, a cooling accelerator, a tackifier, an antiblocking agent, a cohesiveness improver, and the like are particularly preferred. It is done.

The supercooling promoter is not particularly limited as long as it has the function of maintaining the above-described “supercooled state” in the heat-sensitive adhesive layer, and can be appropriately selected according to the purpose. Naphthol derivatives such as benzyloxynaphthalene, biphenyl derivatives such as metaterphenyl, 4-acetylbiphenyl, p-benzylbiphenyl, 4-allyloxybiphenyl, 1,2-bis (3-methylphenoxy) ethane, 2,2 ′ -Polyether compounds such as bis (4-methoxyphenoxy) diethyl ether and bis (4-methoxyphenyl) ether, diphenyl carbonate, dibenzyl oxalate, di (p-chlorobenzyl) oxalate, di (p-methyl) oxalate Carbonic acid or oxalic acid diester derivatives such as benzyl) ester. These may be used alone or in combination of two or more. Among these, dibenzyl oxalate derivatives and biphenyl derivatives are preferable.
When the supercooling accelerator is added to the heat-sensitive adhesive layer, the heat-sensitive adhesive layer activated by heating can be improved in fluidity and can be cured over time. This is advantageous. As a result, at the time of heating, the anchoring effect to the adherend can be improved by increasing the fluidity of the heat-sensitive adhesive layer, and further, the adherend is promoted by promoting curing over time. The adhesive force with respect to can be improved.

The supercooling accelerator can be suitably added to the heat-sensitive adhesive layer and its adjacent layer. When added to the heat-sensitive adhesive layer, the addition amount thereof is added to the heat-sensitive adhesive layer. 0.2-2.0 mass parts is preferable with respect to 1.0 mass part of the thermoplastic resin contained, and 0.5-1.5 mass parts is more preferable.
When the supercooling accelerator is added to the heat-sensitive adhesive layer and / or the adjacent layer, the adhesive state of the heat-sensitive adhesive layer activated by heating is favorably maintained, This is advantageous in that a strong adhesive force can be expressed even in an environment.
There is no restriction | limiting in particular as melting | fusing point of the said supercooling property promoter, Although it can select suitably according to the objective, From a viewpoint which makes it possible to fall melting | fusing point of the said solid plasticizer, 60-180 degreeC. Is preferred.
The average dispersion diameter of the supercooling accelerator in the heat-sensitive adhesive layer is not particularly limited and can be appropriately selected according to the purpose. However, the smaller the temperature, the easier the melting during heating occurs, and the thermoplasticity It is advantageous in that compatibility with the resin is facilitated. Specifically, it is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 2 μm or less.

The tackifier is not particularly limited and may be appropriately selected depending on the intended purpose. For example, terpene resin, aliphatic petroleum resin, aromatic petroleum resin, coumarone indene resin, styrene resin, phenol Resin, terpene phenol resin, rosin derivative resin, and the like. These may be used individually by 1 type and may use 2 or more types together.
The addition amount of the tackifier is preferably 2.0 parts by mass or less and more preferably 0.2 to 1.5 parts by mass with respect to 1.0 part by mass of the thermoplastic resin.
In addition, when the addition amount of the said tackifier exceeds 2.0 mass parts, there exists a tendency for it to become easy to produce blocking.

From the viewpoint of preventing this blocking, the antiblocking agent can be preferably used. When the antiblocking agent is added, blocking resistance in a high temperature environment can be improved.
There is no restriction | limiting in particular as said antiblocking agent, Although it can select suitably according to the objective, For example, a wax, another heat melting material, an inorganic filler, etc. are mentioned.

Examples of the wax include waxes such as animal and vegetable waxes and synthetic waxes, higher fatty acids, N-hydroxymethyl stearamide, higher fatty acid amides other than stearic acid amide, higher fatty acid anilides, acetylated aromatic amines, Examples thereof include paraffin wax, wax, carnauba wax, shellac, montan wax, oxidized paraffin, polyethylene wax, and oxidized polyethylene. Examples of the higher fatty acid include stearic acid and behenic acid. Examples of the higher fatty acid amide include stearic acid amide, oleic acid amide, N-methyl stearic acid amide, erucic acid amide, methylol behenic acid amide, methylol stearic acid amide, methylene bis stearic acid amide, and ethylene bis stearic acid amide. Is mentioned. Examples of the higher fatty acid anilide include stearic acid anilide and linoleic acid anilide. Examples of the acetylated products of aromatic amines include acetoluizide.
There is no restriction | limiting in particular as said other heat-meltable raw material, Although it can select suitably according to the objective, For example, a leuco dye, a color developer, etc. are mentioned.
The wax and other heat-meltable materials are preferably those having a high melting point from the viewpoint of not affecting the adhesive force of the heat-sensitive adhesive material layer as much as possible.
The inorganic filler is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include carbonates such as aluminum, zinc, calcium, magnesium, barium, and titanium, oxides, hydroxides, sulfates, and the like. And inorganic pigments containing clays such as natural silica, zeolite, carillon, calcined carion, and the like. The inorganic filler preferably has a low oil absorption from the viewpoint of not affecting the adhesive strength of the heat-sensitive adhesive layer as much as possible.

  As content in the said thermosensitive adhesive layer of these antiblocking agents, 1.5 mass parts or less are preferable with respect to 1.0 mass part of said thermoplastic resins, and 0.6-1.0 mass part is more preferable. . When the content of the antiblocking agent exceeds 1.5 parts by mass, the adhesive strength of the heat-sensitive adhesive material layer tends to be reduced.

The cohesive strength improver is used for the purpose of increasing the adhesive force between the heat-sensitive pressure-sensitive adhesive layer and the support or the cohesive strength in the heat-sensitive pressure-sensitive adhesive layer. There is no restriction | limiting, According to the objective, it can select suitably, For example, an aqueous polymer binder etc. are mentioned suitably.
Examples of the aqueous polymer binder include polyvinyl alcohol, polyvinyl acetate, oxidized starch, etherified starch, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, casein, gelatin, and sodium alginate.
The content of the cohesive strength improver in the heat-sensitive adhesive layer is not particularly limited and can be appropriately selected according to the purpose within a range not impairing the original adhesive force of the heat-sensitive adhesive sheet. 30 mass% or less is preferable with respect to the total solid of the said thermosensitive adhesive layer, and 10 mass% or less is more preferable.

The heat-sensitive adhesive layer can be suitably formed by applying a coating solution containing the various components described above onto the support and drying.
In this case, the coating method is not particularly limited and may be appropriately selected depending on the purpose. For example, a wire bar coating method, a blade coating method, a curtain coating method, a die coating method, a spin coating method, a kneader Examples thereof include a coating method and a dip coating method.
There is no restriction | limiting in particular as thickness of the said thermosensitive adhesive layer, According to the objective, it can select suitably, For example, 2-30 micrometers is preferable and 5-20 micrometers is more preferable.

-Support-
There is no restriction | limiting in particular as said support body, According to the objective, it can select suitably, For example, various base paper etc. are mentioned suitably.
Suitable examples of the base paper include those containing wood pulp and filler as main components.

  Examples of the wood pulp include chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP, and CGP, and pulp such as waste paper pulp such as DIP.

Examples of the filler include known ones such as pigments, binders, sizing agents, fixing agents, yield improvers, cationizing agents, paper strength enhancing agents, and the like.
Examples of the pigment include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, Synthetic silica, aluminum hydroxide, alumina, lithopone, zeolite, magnesium carbonate, white inorganic pigment such as magnesium hydroxide, styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin, melamine resin organic A pigment etc. are mentioned suitably.

The said base paper can be obtained by mixing what contains the said wood pulp and the said filler, and making paper using a well-known paper machine.
Examples of the paper machine include a long net paper machine, a circular net paper machine, and a twin wire paper machine. The papermaking conditions for the base paper are not particularly limited and may be acidic, neutral, or alkaline.
The base paper made using the paper machine can be calendered using a known calendar device. There is no restriction | limiting in particular as said calendar | calender apparatus, For example, the calendar | calender apparatus which consists of a metal roll and a synthetic resin roll etc. are mentioned. The calendar process may be an on-machine process or an off-machine process. After the process, a machine calendar process, a super calendar process, or the like may be further performed to control the flatness of the base paper. Good.

  There is no restriction | limiting in particular as thickness of the said support body, Although it can select suitably according to the objective, Usually, it is about 60-300 micrometers.

-Other layers-
There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, a heat insulation layer (under layer), a recording layer, a protective layer, etc. are mentioned especially suitably.

--- Heat insulation layer (under layer)-
The heat insulating layer (under layer) is a layer containing air, and is not particularly limited as long as it has a heat insulating effect, and can be appropriately selected according to the purpose.
The heat insulating layer (underlayer) is preferably provided between the heat-sensitive adhesive layer and the support and between the recording layer (particularly the heat-sensitive recording layer) and the support. Can do. In this case, when the heat-sensitive pressure-sensitive adhesive layer is thermally activated, the heat energy from the thermal head can be efficiently used, and the heat-sensitive pressure-sensitive adhesive layer can exhibit sufficient adhesive force with a small amount of energy. This is advantageous in that it can. Further, when the recording layer, particularly the heat-sensitive recording layer, is provided on the side of the support opposite to the heat-sensitive adhesive layer, when the heat-sensitive adhesive layer is heated with high energy, the energy is converted to the heat-sensitive adhesive layer. However, the presence of the heat-insulating layer (under layer) provides a sufficient heat-insulating effect to the heat-sensitive recording layer, and the surface fogging in the heat-sensitive recording layer is likely to occur. This is advantageous in that the occurrence of such problems can be effectively prevented.

The air ratio in the heat insulating layer (under layer), that is, the ratio (%) of air in the under layer is not particularly limited and can be appropriately selected according to the purpose. This is advantageous in that the adhesive properties of the heat-sensitive adhesive layer can be effectively improved.
The heat insulating layer (underlayer) can be formed in various forms, and particularly preferably includes a non-foaming form containing hollow particles.
There is no restriction | limiting in particular as said hollow particle, Although it can select suitably according to the objective, For example, what was formed with the acrylic polymer, the vinylidene chloride polymer, etc. is mentioned suitably.
There is no restriction | limiting in particular as the degree of hollowness (hollow rate) in the said hollow particle, Although it can select according to the objective, A thing 30% or more is preferable.

  The heat insulation layer (under layer) can be formed by a known coating method, and examples of the coating method include blade coating, gravure coating, gravure offset coating, bar coating, roll coating, and knife. Coating method, air knife coating method, comma coating method, U comma coating method, AKKU coating method, smoothing coating method, micro gravure coating method, reverse roll coating method, 4 to 5 roll coating method, dip coating method, curtain coating method , Slide coating method, die coating method, and the like.

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

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

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

There is no restriction | limiting in particular as said leuco dye, According to the objective, it can select suitably, For example, a basic leuco dye etc. are mentioned suitably.
Examples of the basic leuco dye include fluoran compounds, triarylmethane compounds, spiro compounds, diphenylmethane compounds, thiazine compounds, lactam compounds, fluorene compounds, and the like.

  Examples of the fluorane compound include 3-diethylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, and 3- (N-methyl-N-cyclohexyl). Amino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isopentylamino) -6-methyl-7-anilinofluorane, 3- (N-isobutyl-N-ethylamino) ) -6-Methyl-7-anilinofluorane, 3- [N-ethyl-N- (3-ethoxypropyl) amino] -6-methyl-7-anilinofluorane, 3- (N-ethyl-N) -Hexylamino) -6-methyl-7-anilinofluorane, 3-dipentylamino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-propylamino) -6-methyl -7-anilinofluorane, 3- (N-ethyl-N-tetrahydrofurylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- (p-chloroanilino) fluorane, 3-diethylamino-6-methyl-7- (p-fluoroanilino) fluorane, 3- (p-toluidinoethylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl- 7- (p-Toluidino) fluorane, 3-diethylamino-7- (3,4-dichloroanilino) fluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-diethylamino-6-chloro-7 -Ethoxyethylaminofluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-diethylamino-7-phenyl Ruoran, 3- (p-preparative Luigi Bruno ethylamino) -6-methyl-7-phenethyl fluoran, and the like.

  Examples of the tolylmethane compound include 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone or CVL), 3,3-bis (p-dimethylaminophenyl). ) Phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylaminoindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindole-3- Yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylamino Phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis (9- Tilcarbazol-3-yl) -5-dimethylaminophthalide, 3,3- (2-phenylindol-3-yl) -5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3- (1- Methylpyrrol-2-yl) -6-dimethylaminophthalide, and the like.

  Examples of the spiro compounds include 3-methylspirodinaphthopyrans, 3-ethylspirodinaphthopyrans, 3,3′-dichlorospirodinaphthopyrans, 3-benzylspirodinaphthopyrans, 3-propylspirodinaphthopyrans. , 3-methylnaphtho- (3-methoxybenzo) spiropyran, 1,3,3-trimethyl-6-nitro-8′-methoxyspiro (indoline-2,2′-benzopyran), and the like.

Examples of the diphenylmethane compound include N-halophenyl-leucooramine, 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether, N-2,4,5-trichlorophenylleucooramine, and the like. .
Examples of the thiazine compounds include benzoyl leucomethylene blue and p-nitrobenzoyl leucomethylene blue.
Examples of the lactam compound include rhodamine B anilinolactam, rhodamine Bp-chloroanilinolactam, and the like.
Examples of the fluorene-based compound include 3,6-bis (dimethylamino) fluorene spiro (9,3 ′)-6′-dimethylaminophthalide, 3,6-bis (dimethylamino) fluorene spiro (9,3). ') -6'-pyrrolidinophthalide, 3-dimethylamino-6-diethylaminofluorene spiro (9,3')-6'-pyrrolidinophthalide, and the like.

  Examples of the color basic leuco dye include 3-diethylamino-6-methyl-7-chlorofluorane, 3-cyclohexylamino-6-chlorofluorane, 3-diethylamino-benzo [α] fluorane, and 3-dibutyl. Amino-benzo [α] fluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-methylfluorane, 3-N-ethyl-N-isoamylamino-benzo [α] fluorane, 3-N-ethyl -Np-methylphenylamino-7-methylfluorane, 3-diethylamino-6,8-dimethylfluorane, 3-dibutylamino-6-methyl-7-bromofluorane, 3,6-bis (diethylaminofluorine) Oran) -γ- (4′-nitro) anilinolactam, bis (1-n-butyl-2-methylin) Allyl-3-yl) phthalide, bis (1-ethyl-2-methylindol-3-yl) phthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindolyl-3- Yl) phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindolyl-3-yl) -4-azaphthalide, 3- (4-diethylaminophenyl) -3- (1-methyl-2-methylindolyl-3-yl) phthalide, 3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-methylindolyl-3-yl) phthalide, 3 , 3-bis (4-dimethylaminophenyl) -6-diethylaminophthalide, 3,7-bis (4-dimethylamino) -10-benzoylphenothiazine, 3,3-bis (4-di Ethylamino-6-ethoxyphenyl) -4-azaphthalide, 3-diethylamino-7-dianilinofluorane, 3-N-ethyl-N-4-methylphenylamino-7-N-methylanilinofluorane, 3- Diethylamino-7-N-dibenzylaminofluorane, 3,6-dimethoxyfluorane, 3,6-dibutoxyfluorane, 3-methoxy-4-lanoxyphenyl-2-cytylquinoline, 2,4-dioctoxi And phenyl-2-cytyrylquinoline.

  The developer is not particularly limited and can be appropriately selected depending on the purpose, and examples generally include those used for pressure-sensitive recording paper and heat-sensitive recording paper, specifically, For example, bis (3-allyl-4-hydroxyphenyl) sulfone, α-naphthol, β-naphthol, p-octylphenol, 4-t-octylphenol, pt-butylphenol, p-phenylphenol, 1,1-bis ( p-hydroxyphenyl) propane, 2,2-bis (p-hydroxyphenyl) propane (also known as bisphenol A or BPA), 2,2-bis (p-hydroxyphenyl) butane, 1,1-bis (p-hydroxy) Phenyl) cyclohexane, 4,4′-thiobisphenol, 4,4′-cyclohexylidene diphenol, 2,2 ′-(2, 5-dibromo-4-hydroxyphenyl) propane, 4,4-isopropylidenebis (2-tert-butylphenol), 2,2′-methylenebis (4-chlorophenol), 4,4′-dihydroxydiphenylsulfone, 4- Hydroxy-4'-methoxydiphenylsulfone, 4-hydroxy-4'-ethoxydiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-butoxydiphenylsulfone, bis- (4-hydroxyphenyl) ) Phenolic compounds such as methyl acetate, bis- (4-hydroxyphenyl) butyl acetate, bis- (4-hydroxyphenyl) acetate benzyl, 2,4-dihydroxy-2′-methoxybenzanilide, benzyl p-hydroxybenzoate P-hydroxybenzoate Aromatic dicarboxylic acids such as dibenzyl 4-hydroxyphthalate, dimethyl 4-hydroxyphthalate, ethyl 5-hydroxyisophthalate, 3,5-di-t-butylsalicylic acid, 3,5-di-α-methylbenzylsalicylic acid, etc. Examples thereof include acid derivatives, aromatic carboxylic acids or metal salts thereof.

  The binder is not particularly limited and may be appropriately selected depending on the intended purpose.For example, starches, cellulose derivatives such as hydroxyethylcellulose, methylcellulose, ethylcellulose, carboxymethylcellulose, proteins such as casein and gelatin, oxidized starch, Aqueous natural polymer compounds such as sucrose such as ester compound starch, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polyacrylic acid soda, acrylic acid amide-acrylic acid ester copolymer, acrylic acid amide-acrylic acid Water-soluble synthetic polymers such as ester-methacrylic acid terpolymer, alkali salt of styrene-maleic anhydride copolymer, latex, polyacrylamide, styrene-maleic anhydride copolymer, etc. Compounds, latexes, water-soluble adhesive resins such as alkali salts of ethylene-maleic anhydride copolymer, polyvinyl acetate, polyurethane, polyacrylic ester, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylic Examples thereof include latex such as acid methyl-butadiene copolymer, acrylonitrile-butadiene-acrylic acid copolymer, and ethylene-vinyl acetate copolymer.

  The sensitizer is used for the purpose of improving the sensitivity of the thermosensitive recording layer. The sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, N-hydroxymethyl Waxes such as stearic acid amide, stearic acid amide, palmitic acid amide, naphthol derivatives such as 2-benzyloxynaphthalene, biphenyl derivatives such as acetylbiphenyl, p-benzylbiphenyl, 4-allyloxybiphenyl, 1,2-bis ( Polyether compounds such as 3-methylphenoxy) ethane, 2,2′-bis (4-methoxyphenoxy) diethyl ether, bis (4-methoxyphenyl) ether, diphenyl carbonate, dibenzyl oxalate, di (p-chloro) oxalate Benzyl) ester and other carbonic acid or oxalic acid diester derivatives, etc. It is below.

Examples of the pigment include diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formalin resin, and the like.
The recording layer can be formed by the coating method described above.

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

-Usage etc.-
The heat-sensitive adhesive material of the present invention can be suitably used by being cut before or after thermal activation (heating) of the heat-sensitive adhesive layer. In this case, A cut may be formed in advance. In these cases, the heat-sensitive adhesive material is advantageous in that it can be suitably used for various uses such as labels and tags.
There is no restriction | limiting in particular as a shape of the heat-sensitive adhesive material of this invention, A sheet form, roll shape, etc. are mentioned suitably.

The adherend to which the heat-sensitive adhesive material of the present invention is affixed is not particularly limited, and its size, shape, structure, material, and the like can be appropriately selected according to the purpose. For example, polyolefins such as polyethylene and polypropylene, resin plates such as acrylic, polyethylene terephthalate (PET), polystyrene and nylon, metal plates such as SUS and aluminum, paper products such as envelopes and cardboard, polyolefin wraps, polyvinyl chloride Preferable examples include wraps made of polyethylene and non-woven fabric made of polyethylene (such as envelopes).
Among these, the polyethylene non-woven fabric (envelope etc.) is generally difficult to apply a heat-sensitive adhesive material, but in the case of the heat-sensitive adhesive material of the present invention, it is possible to express a stronger adhesive force over time, Even the nonwoven fabric made of polyethylene is advantageous in that it can be firmly attached.

  The sticking body of the heat-sensitive adhesive material of the present invention is obtained by sticking the heat-sensitive adhesive material of the present invention to the adherend. Since the heat-sensitive adhesive material of the present invention is attached to the adhesive body of the heat-sensitive adhesive material, the adherend to which the heat-sensitive adhesive material is attached is made of polyolefin wraps (films). Or sheet) or non-woven fabric (envelope or the like), exhibiting a strong adhesive force, the heat-sensitive adhesive material portion does not peel or fall off, and is excellent in durability during use.

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

The heat activation method for the heat-sensitive adhesive material of the present invention includes bringing a heating means into contact with the heat-sensitive pressure-sensitive adhesive layer in the heat-sensitive pressure-sensitive adhesive material of the present invention described above to thermally activate the heat-sensitive pressure-sensitive adhesive layer. Further, other treatments appropriately selected as necessary, for example, affixing the heat-activated pressure-sensitive adhesive layer to an adherend, cutting the heat-sensitive pressure-sensitive adhesive material, recording on the recording layer Further comprising:
The heat activation method of the heat-sensitive adhesive material of the present invention can be preferably carried out using the heat-activating device for the heat-sensitive adhesive material of the present invention. The heat-sensitive adhesive material thermal activation device comprises the heat-sensitive adhesive material of the present invention, and a heating means for thermally activating the heat-sensitive adhesive layer in contact with the heat-sensitive adhesive layer in the heat-sensitive adhesive material. And other means appropriately selected as necessary, for example, a sticking means for sticking the heat-activated pressure-sensitive adhesive layer to an adherend, and a cutting means for cutting the heat-sensitive adhesive material And a recording means for recording on the recording layer.

The heating means is not particularly limited as long as the heat-sensitive adhesive material can be heated, and can be appropriately selected according to the purpose. For example, a resistor and a protective film are provided on a ceramic substrate. Suitable examples include those that are provided in order, and the heating temperature can be controlled by changing the energization amount to the resistor.
Specific examples of the heating means include a thermal head and a thin film heater. As a specific example of the thermal head or thin film heater, a strip-shaped thick film heating resistor is provided on a ceramic substrate, and a protective film made of crystallized glass is provided on the surface of the heating resistor to prevent wear and oxidation. In addition, in order to improve thermal responsiveness, there may be mentioned those in which a glaze layer made of crystallized glass is provided under the heating resistor. In the case of these heating means, it is easy to control the thermal activation conditions to be constant, and it is advantageous in that partial thermal activation is also easy if necessary.
The heat activation of the heat-sensitive adhesive layer by the heating means is preferably performed after the heat-sensitive adhesive material is cut by a cutting means described later.

The recording means is not particularly limited as long as recording can be performed on the recording layer, and can be appropriately selected according to the purpose. For example, any of thermal recording methods, ink jet methods, and electrophotographic methods can be used. Preferred examples include those that can be recorded by him.
A specific example of the recording means preferably includes a thermal head and a platen roll. In this case, since the thermal head can be sufficiently brought into contact with the heat-sensitive adhesive layer, thermal activation of the heat-sensitive adhesive layer can be performed efficiently and reliably. In addition, heating can be controlled on demand, and thermal activation can be performed simultaneously with energization, which is advantageous in that energy consumption for thermal activation can be reduced.

In the present invention, it is preferable that a pressure body capable of holding the heat-sensitive adhesive material together with the heat generating portion is provided at a position facing the heat generating portion provided with the thermal head. In this case, it is preferable in that heat from the heat generating portion can be more efficiently transmitted to the heat-sensitive adhesive layer in the heat-sensitive adhesive material, and thermal activation of the heat-sensitive adhesive layer can be promoted. .
The position of the heat generating part is preferably the near edge, the corner edge or the end face of the thermal head, and a release layer is preferably provided on the surface of the heat generating part. In these cases, it is advantageous in that the heat-sensitive pressure-sensitive adhesive layer that has been thermally activated becomes difficult to contact the thermal head, and transfer to the thermal head is effectively prevented.

  There is no restriction | limiting in particular as an installation place of the said recording means, Although it can select suitably according to the objective, For example, it is preferable to arrange | position between the below-mentioned holding means and a cutting means.

The cutting means is not particularly limited as long as the heat-sensitive adhesive material can be cut, and can be appropriately selected according to the purpose. Examples thereof include a known cutter device.
The installation location of the cutting means is not particularly limited and can be appropriately selected according to the purpose. For example, any of the holding means and the heating means and between the holding means and the recording means can be selected. It is preferable that they are arranged in a crab.
The heat-sensitive adhesive material is preferably cut by the cutting means either before or after recording on the recording layer.

Here, an example of carrying out the heat activation method of the heat-sensitive adhesive material of the present invention using the heat activation device of the heat-sensitive adhesive material of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic explanatory view showing an embodiment of a thermal activation device 1 for a heat-sensitive adhesive material of the present invention having a printer function. FIG. 2 is a schematic cross-sectional explanatory view showing an example of the heat-sensitive adhesive material 2 of the present invention.

  The heat-sensitive adhesive material thermal activation device 1 includes a holding unit 3 that holds a heat-sensitive adhesive material 2 wound in a roll shape, a recording unit 8 that records in a heat-sensitive recording layer 7 of the heat-sensitive adhesive material 2, and A cutter 9 as a cutting means for cutting the heat-sensitive adhesive material 2 into a predetermined length, a heat activation device 10 for thermally activating the heat-sensitive adhesive layer 5 in the heat-sensitive adhesive material 2, and the heat-sensitive adhesive material 2 And a recording means 8 for recording on the thermosensitive recording layer 7.

  The recording means 8 is formed by a thermal head 11 and a platen roll 12. The thermal activation device 10 is formed by a platen roll 13 that is a transport means for transporting the heat-sensitive adhesive material 2 and a thermal head 15 that is a heating means having a heat generating portion 14. The heat generating part 14 is formed by providing a heat generating resistor on a ceramic substrate by thin film technology and providing a protective film made of crystallized glass on the surface of the heat generating resistor. The platen roll 13 also functions as a pressurizing body that sandwiches the heat-sensitive adhesive material 2 with the heat generating portion 14.

  The platen roll 13 may be replaced with the pressure-bonding belt 17 shown in FIG. The thermal head 15 may be replaced with a near edge type thermal head 15a shown in FIG. 5, an end face type thermal head 15b shown in FIG. 6, or a corner edge type thermal head 15c shown in FIG. When these are used, it becomes difficult for the heat-activated heat-sensitive adhesive layer 5 to come into contact with the thermal head 15a, 15b or 15c, and the heat-activated heat-sensitive adhesive layer 5 is transferred to the thermal head. Wrapping of the adhesive material 2 around the thermal head is prevented.

  In addition, as shown in FIG. 8, a release layer 18 may be formed on the surface of the heat generating portion 14 of the thermal head 15 and the periphery thereof by Teflon coating having a thickness of 2 μm. Also in this case, the heat-activated heat-sensitive adhesive layer 5 is difficult to transfer to the heat generating portion 14 of the thermal head 15, and the heat-sensitive adhesive material 2 is prevented from being wound around the thermal head 15 due to the transfer. The

  The thermal head 15 as the heating means may be replaced with a thin film heater 19 as shown in FIG. The thin film heater 19 is provided with a heat generating portion 20, and the heat generating portion 20 is provided with a 1 mm wide strip-shaped thick film heating resistor on a ceramic substrate, and the surface of the thick film heating resistor is made of crystallized glass. It is formed by providing a protective film. In this case, since the contact width with the heat-sensitive adhesive layer 5 is as wide as 1 mm, more efficient thermal activation can be performed.

  As shown in FIG. 2, the heat-sensitive adhesive material 2 has a heat-sensitive adhesive layer 5 on one surface of a high-quality paper 4 as a support, and a heat-insulating layer 6 and a heat-sensitive recording on the other surface of the high-quality paper 4. Layer 7. The thermal recording layer 7 may be replaced with a color-printed printing layer, a thermal transfer (melt transfer) recording layer, an ink jet recording layer, a sublimation transfer recording layer, an electrophotographic recording layer (electrostatic recording layer), or the like. Good.

  The heat-sensitive adhesive material 2 wound in a roll shape is attached to the holding part 3, and heat is applied from the heat generating part 11 a of the thermal head 11 to the heat-sensitive recording layer 7 in the heat-sensitive adhesive material 2 drawn out from the holding part 3. As a result, the thermal recording layer 7 is colored to perform predetermined recording on the thermal recording layer 7. Recording on the heat-sensitive color developing layer 7 is completed, and the heat-sensitive adhesive layer 5 in the heat-sensitive adhesive material 2 being conveyed is in contact with the heat-generating part 14 of the thermal head 15. The heat sensitive adhesive layer 5 is thermally activated.

  Here, since the heat generating part 14 is in contact with the heat-sensitive adhesive layer 5, the heat-sensitive adhesive layer 5 can be reliably thermally activated by causing the heat generating part 14 to generate heat. In addition, the heat from the heat generating part 14 is efficiently transferred to the heat-sensitive adhesive layer 5, and the heat activation is performed simultaneously with energization even if the heat generating part 14 is not put on standby in a state where heat necessary for heat activation is applied. Can be made. For this reason, the energy consumption for heat activation can be reduced, and the heat-sensitive adhesive material 2 is not overheated at the time of heat activation, and the safety of the heat activation device 1 for the heat-sensitive adhesive material Becomes higher. Furthermore, since the heat from the heat generating part 14 is efficiently transmitted to the heat sensitive adhesive layer 5, the heat sensitive adhesive material 2 with the heat sensitive adhesive layer 5 in contact with the heat generating part 14 is thermally activated even if it is moved at high speed. As a result, it is possible to prevent the heat-activated heat-sensitive adhesive layer 5 from being transferred to the heat generating portion 14, and the heat-activated work and the heat-activated heat-sensitive pressure-sensitive adhesive material 2 It excels in the efficiency of the sticking work to a to-be-adhered body.

  Further, when the heat insulating layer 6 exists between the high-quality paper 4 and the heat-sensitive recording layer 7, the heat applied to the heat-sensitive adhesive layer 5 for the thermal activation of the heat-sensitive adhesive layer 5 is the heat-sensitive color development. The heat insulation layer 6 can prevent the heat from being transferred to the layer 7, and the applied heat can be efficiently used for the thermal activation. On the other hand, the heat at the time of the thermal activation is transferred to the heat sensitive recording layer 7, and the heat sensitive recording layer 7 Can be prevented from being unnecessarily colored. In addition, the heat-sensitive adhesive material 2a shown in FIG. 3 has the structure which removed the heat insulation layer 6 from the heat-sensitive adhesive material 2 shown in FIG.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. “Part” and “%” shown below are mass reference values. The coating amount means the coating amount after drying unless otherwise specified.

-Preparation of solid plasticizer dispersion [liquid A]-
As the solid plasticizer, 10 parts of a tribenzotriazole derivative (compound) described in Table 1 (in Table 1, when two kinds of the solid plasticizer are used, each equivalent (5 parts each) was used), As a dispersant, 10 parts of a 10% aqueous solution of polyvinyl alcohol and 20 parts of water are uniformly mixed, and are pulverized using a ball mill until the dispersion average particle size of the solid plasticizer becomes 1.0 μm, thereby dispersing the solid plasticizer. Liquid [A liquid] was prepared.

-Preparation of Supercooling Accelerator Dispersion [Liquid B]-
As the supercooling accelerator, 10 parts of the compounds shown in Table 1 (in the case of “None” in Table 1, the B liquid is not used for the preparation of the C liquid described later), and polyvinyl alcohol as the dispersant. 10 parts of 10% aqueous solution and 20 parts of water are uniformly mixed and pulverized using a ball mill until the dispersion average particle size of the supercooling accelerator becomes 1.0 μm. [Liquid B] was prepared.

-Preparation of heat-sensitive adhesive layer coating solution [C solution]-
400 parts of the solid plasticizer dispersion [Liquid A], 100 parts of 2-ethylhexyl acrylate emulsion (solid content 50%) as the thermoplastic resin emulsion 50%, and terpene phenol 50% as the tackifier 50 parts of the dispersion and 20 parts of the supercooling accelerator dispersion [Liquid B] were mixed to prepare a thermosensitive adhesive layer coating liquid [Liquid C].

(Examples 1-8 and Comparative Examples 1-5)
On one side of the support, the heat-sensitive adhesive layer coating solution [C solution] was applied using a wire bar so that the thermoplastic resin adhesion amount was 3.0 g / m ² and dried. It was cured and stored for 24 hours in a room maintained at a temperature of 29 ° C./humidity of 35% Rh to obtain a heat-sensitive adhesive material.

(Adhesion test)
The obtained heat-sensitive adhesive material was cut into a 4.0 cm × 9.0 cm rectangular piece within a temperature environment condition of 20 ° C./30%, a head condition: 0.54 mJ / dot, a printing speed: 4 ms / line, The thermal recording layer is printed under the condition of platen pressure: 6 kgf / line, the thermal sensitive adhesive layer is printed under the conditions of head condition: 0.45 mJ / dot, printing speed: 4 ms / line, platen pressure: 6 kgf / line. Was heat activated.
Next, a sample for measurement was prepared by adhering two types of adherends of corrugated cardboard and polyethylene non-woven fabric (Tyvek manufactured by DuPont) in the longitudinal direction with a rubber roller of 2 kg under pressure. The sample is allowed to stand in the same environment, and immediately after application (after 2 minutes), after 1 hour, after 1 day (after 24 hours), it is peeled off at a peeling angle of 180 ° C. and a peeling speed of 300 mm / min. I let you. Table 2 shows the adhesive strength for corrugated cardboard, and Table 3 shows the adhesive strength for polyethylene nonwoven fabric. The unit is gf / 40 mm.

  From the above results, the heat-sensitive adhesive material of the present invention can be reapplied immediately after being applied to the adherend, and has the property that the adhesive force increases with time and cannot be easily peeled off. Is clear. In addition, it has similar characteristics to adherends that are difficult to develop adhesive strength such as polyethylene non-woven fabric, and maintains high adhesive strength over time for each adherend. It is clear that has excellent performance that does not exist.

Example 9
In Example 1, as the solid plasticizer, three types (I, II, IV) of benzotriazole derivatives were used, and 400 parts of [Part A] were used equally (equal amount) in three types. Same as 1.
As a result, the adhesive strength to cardboard was 250 gf / 40 mm immediately after pasting (after 2 minutes), 450 gf / 40 mm after 1 hour, and 900 gf / 40 mm after 1 day (after 24 hours). On the other hand, the adhesive strength to the polyethylene nonwoven fabric was 150 gf / 40 mm immediately after application (after 2 minutes), 380 gf / 40 mm after 1 hour, and 800 gf / 40 mm after 1 day (after 24 hours).

(Examples 10 to 13)
In Example 1, two kinds of benzotriazole derivatives as the solid plasticizer, a combination of I and VII in Example 10, a combination of I and VIII in Example 11, and a combination of I and IX in Example 12 Example 13 was the same as Example 1 except that a combination of I and X was used.
As a result, in Example 10, the adhesive strength to the cardboard was 280 gf / 40 mm immediately after application (after 2 minutes), 400 gf / 40 mm after 1 hour, 680 gf / 40 mm after 1 day (after 24 hours). Met. On the other hand, the adhesive strength to the polyethylene nonwoven fabric was 100 gf / 40 mm immediately after application (after 2 minutes), 270 gf / 40 mm after 1 hour, and 720 gf / 40 mm after 1 day (after 24 hours).
In the case of Example 11, the adhesive strength to corrugated cardboard was 420 gf / 40 mm immediately after application (after 2 minutes), 480 gf / 40 mm after 1 hour, and 720 gf / 40 mm after 1 day (after 24 hours). . On the other hand, the adhesive strength to the polyethylene nonwoven fabric was 120 gf / 40 mm immediately after application (after 2 minutes), 350 gf / 40 mm after 1 hour, and 540 gf / 40 mm after 1 day (after 24 hours).
In the case of Example 12, the adhesive strength to cardboard was 380 gf / 40 mm immediately after application (after 2 minutes), 450 gf / 40 mm after 1 hour, and 700 gf / 40 mm after 1 day (after 24 hours). . On the other hand, the adhesive strength to the polyethylene nonwoven fabric was 80 gf / 40 mm immediately after application (after 2 minutes), 400 gf / 40 mm after 1 hour, and 550 gf / 40 mm after 1 day (after 24 hours).
In the case of Example 13, the adhesive strength to cardboard was 360 gf / 40 mm immediately after pasting (after 2 minutes), 390 gf / 40 mm after 1 hour, and 740 gf / 40 mm after 1 day (after 24 hours). . On the other hand, the adhesive strength to the polyethylene nonwoven fabric was 100 gf / 40 mm immediately after application (after 2 minutes), 380 gf / 40 mm after 1 hour, and 530 gf / 40 mm after 1 day (after 24 hours).

The heat-sensitive adhesive material of the present invention can be suitably used as a label that can be suitably affixed to polyolefin wraps, polyolefin nonwoven fabrics (envelopes, etc.) in the field of food POS and the like.
The patch of the heat-sensitive adhesive material of the present invention can be suitably used as a package or the like in the food POS field or the like.
The activation method of the heat-sensitive adhesive material of the present invention can be suitably used as an activation method for labels and the like in the field of food POS and the like.
The activation device for the heat-sensitive adhesive material of the present invention can be suitably used for activating labels and the like in the food POS field and the like.

FIG. 1 is a schematic explanatory view showing a first embodiment of the heat activation device for heat-sensitive adhesive material of the present invention. FIG. 2 is a schematic cross-sectional explanatory view showing a first structural example of the heat-sensitive adhesive material of the present invention. FIG. 3 is a schematic cross-sectional explanatory view showing a second structural example of the heat-sensitive adhesive material of the present invention. FIG. 4 is a schematic explanatory view showing a second embodiment of the heat activation device for heat-sensitive adhesive material of the present invention. FIG. 5 is a schematic explanatory view showing a third embodiment of the heat activation device for heat-sensitive adhesive material of the present invention. FIG. 6 is a schematic explanatory view showing a fourth embodiment of the heat activation device for heat-sensitive adhesive material of the present invention. FIG. 7 is a schematic explanatory view showing a fifth embodiment of the heat activation device for heat-sensitive adhesive material of the present invention. FIG. 8 is a schematic explanatory view showing a sixth embodiment of the heat activation device for heat-sensitive adhesive material of the present invention. FIG. 9 is a schematic explanatory view showing a seventh embodiment of the heat activation device for heat-sensitive adhesive material of the present invention.

Explanation of symbols

2, 2a, 2b Heat-sensitive adhesive material 3 Holding part 4 Support body 5 Heat-sensitive adhesive layer 6 Heat-insulating layer 7 Heat-sensitive recording layer 8 Recording means 9 Cutter 10 Thermal activation device 13 Conveying means, pressurizing body 14, 20 Heating part 15, 15a, 15b, 15c Heating means, thermal head 18 Release layer 19 Heating means, thin film heater

Claims (25)

A thermosensitive adhesive layer that includes a thermoplastic resin and a solid plasticizer and is heated and bonded to an adherend, has a support on the support,
The heat-sensitive adhesive material, wherein the adhesive force of the heat-sensitive adhesive material to the adherend increases with time from immediately after the heat-sensitive adhesive material is bonded to the adherend. A heat-sensitive adhesive layer that includes a thermoplastic resin and a solid plasticizer that is solid at normal temperature and melts or softens when heated and is compatible with the thermoplastic resin, and is bonded to the adherend by heating. On the support,
According to the adhesive strength measuring method in the adhesive tape / adhesive sheet test method of JIS Z0237, the adhesive strength when the heat-sensitive adhesive layer is peeled off from the adherend after 2 minutes is 300 gf / 40 mm or less, and 24 hours have elapsed. A heat-sensitive adhesive material having an adhesive strength of 500 gf / 40 mm or more when peeled from the adherend later.   The heat-sensitive adhesive material according to claim 1, wherein the solid plasticizer contains at least two kinds of benzotriazole derivatives. The heat-sensitive adhesive material according to claim 3, wherein the benzotriazole derivative is selected from compounds represented by the following formula (A).
Formula (A)
However, in formula (A), X represents a group represented by the following formula (B). R1 represents a hydrogen atom, a halogen atom, or an alkyl group. m represents an integer of 1 to 4. X represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a group represented by the following (B).
Formula (B)
However, in formula (B), R2 represents a hydrogen atom, a halogen atom, an alkyl group, or a hydroxyl group. n represents an integer of 1 to 5. The heat-sensitive adhesive material according to claim 4, wherein the at least two kinds of benzotriazole derivatives are a combination of compounds represented by any of the following formulas (I) to (V).
  The heat-sensitive adhesive material according to claim 5, wherein one of at least two kinds of benzotriazole derivatives is a compound represented by the formula (I).   The heat-sensitive adhesive material according to any one of claims 5 to 6, wherein the at least two benzotriazole derivatives are a combination of a compound represented by the formula (I) and a compound represented by the formula (IV).   The heat-sensitive adhesive material according to any one of claims 3 to 7, wherein a difference in melting point between at least two kinds of benzotriazole derivatives is 30 ° C or more.   The heat-sensitive adhesive material according to any one of claims 1 to 8, wherein an average dispersion diameter in the heat-sensitive adhesive layer of the solid plasticizer is 10 µm or less.   The heat-sensitive adhesive material according to any one of claims 1 to 9, wherein at least one of the heat-sensitive adhesive layer and the adjacent layer thereof contains a supercooling accelerator.   The heat-sensitive adhesive material according to claim 10, wherein an average dispersion diameter in at least one of the heat-sensitive adhesive layer of the supercooling accelerator and the adjacent layer is 10 µm or less.   The heat-sensitive adhesive material according to claim 1, wherein the heat-sensitive adhesive layer contains a tackifier.   The heat-sensitive adhesive material according to any one of claims 1 to 12, comprising a recording layer on a surface of the support opposite to the heat-sensitive adhesive layer side.   The heat-sensitive adhesive material according to claim 13, wherein the recording layer is any one of a heat-sensitive recording layer, an ink jet recording layer, and an electrophotographic recording layer.   The heat-sensitive adhesive material according to any one of claims 1 to 14, which is used by cutting.   The heat-sensitive adhesive material according to any one of claims 1 to 15, wherein a cut is formed.   The heat-sensitive adhesive material according to any one of claims 1 to 16, wherein the adherend is a polyethylene non-woven fabric.   The heat-sensitive adhesive material according to any one of claims 1 to 17, which is wound into a roll.   A heat-sensitive adhesive material patch comprising the heat-sensitive adhesive layer of the heat-sensitive adhesive material according to any one of claims 1 to 18 attached thereto. Bringing the heating means into contact with the heat-sensitive adhesive layer in the heat-sensitive adhesive material to thermally activate the heat-sensitive adhesive layer;
The heat-sensitive adhesive material according to claim 1, wherein the heat-sensitive adhesive material is the heat-sensitive adhesive material according to claim 1.   The heat activation method for a heat-sensitive adhesive material according to claim 20, further comprising affixing the heat-activated pressure-sensitive adhesive layer to an adherend. A heat-sensitive adhesive material, and a heating means for thermally activating the heat-sensitive adhesive layer by contacting the heat-sensitive adhesive layer in the heat-sensitive adhesive material,
The heat-sensitive adhesive material according to claim 1, wherein the heat-sensitive adhesive material is the heat-sensitive adhesive material.   The heat activation apparatus for heat-sensitive adhesive material according to claim 22, wherein the heating means is at least one of a thermal head and a thin film heater. The heat-sensitive adhesive material has a recording layer on the surface of the support opposite to the heat-sensitive adhesive layer side,
24. The thermal activation device for a heat-sensitive adhesive material according to claim 22, further comprising recording means for recording on the recording layer. The thermal activation device for a heat-sensitive adhesive material according to any one of claims 22 to 24, further comprising a cutting means for cutting the heat-sensitive adhesive material.