JP2012197387A - Heat-resistant temperature-sensitive pressure-sensitive adhesive - Google Patents
Heat-resistant temperature-sensitive pressure-sensitive adhesive Download PDFInfo
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- JP2012197387A JP2012197387A JP2011063670A JP2011063670A JP2012197387A JP 2012197387 A JP2012197387 A JP 2012197387A JP 2011063670 A JP2011063670 A JP 2011063670A JP 2011063670 A JP2011063670 A JP 2011063670A JP 2012197387 A JP2012197387 A JP 2012197387A
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 65
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 238000002844 melting Methods 0.000 claims abstract description 30
- 230000008018 melting Effects 0.000 claims abstract description 30
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- 125000000524 functional group Chemical group 0.000 claims abstract description 18
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 239000000853 adhesive Substances 0.000 claims description 97
- 230000001070 adhesive effect Effects 0.000 claims description 97
- 239000010408 film Substances 0.000 claims description 27
- 239000010410 layer Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 19
- 239000002390 adhesive tape Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000012790 adhesive layer Substances 0.000 claims description 11
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- 230000000694 effects Effects 0.000 description 4
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、耐熱性を有する感温性粘着剤に関する。 The present invention relates to a temperature-sensitive adhesive having heat resistance.
従来から、粘着力を熱によって可逆的に制御できる粘着剤として、感温性粘着剤がある（例えば、特許文献１参照）。感温性粘着剤は、側鎖結晶性ポリマーを含有しており、この側鎖結晶性ポリマーの融点以上の温度にまで加熱すると、側鎖結晶性ポリマーが流動性を示すことによって粘着力が発現し、融点未満の温度にまで冷却すると、側鎖結晶性ポリマーが結晶化することによって粘着力が低下する。 Conventionally, there is a thermosensitive adhesive as an adhesive whose adhesive force can be reversibly controlled by heat (see, for example, Patent Document 1). The temperature-sensitive adhesive contains a side-chain crystalline polymer, and when heated to a temperature equal to or higher than the melting point of the side-chain crystalline polymer, the side-chain crystalline polymer exhibits fluidity and develops adhesive strength. However, when it is cooled to a temperature lower than the melting point, the side chain crystalline polymer is crystallized, whereby the adhesive strength is lowered.
感温性粘着剤の一使用形態である粘着テープは、特許文献２に記載されている液晶表示装置、有機発光表示装置等の平板表示装置の製造等に使用することができる。具体的には、まず、基材フィルムの両面に感温性粘着剤からなる粘着剤層を設けた粘着テープを介して、可撓性基板を支持体上に固定する。この固定は、粘着剤層を側鎖結晶性ポリマーの融点以上の温度にまで加熱して、粘着力を発現させることによって行う。 The pressure-sensitive adhesive tape which is one usage form of the temperature-sensitive pressure-sensitive adhesive can be used for the production of flat panel display devices such as liquid crystal display devices and organic light-emitting display devices described in Patent Document 2. Specifically, first, a flexible substrate is fixed on a support via an adhesive tape in which an adhesive layer made of a temperature-sensitive adhesive is provided on both surfaces of a base film. This fixing is performed by heating the pressure-sensitive adhesive layer to a temperature equal to or higher than the melting point of the side chain crystalline polymer to develop an adhesive force.
ついで、固定した可撓性基板の表面に、所定の薄膜パターンを形成する。最後に、粘着剤層を側鎖結晶性ポリマーの融点未満の温度に冷却して粘着力を低下させ、可撓性基板を支持体から剥離する。 Next, a predetermined thin film pattern is formed on the surface of the fixed flexible substrate. Finally, the pressure-sensitive adhesive layer is cooled to a temperature lower than the melting point of the side chain crystalline polymer to reduce the adhesive force, and the flexible substrate is peeled off from the support.
一方、特許文献１に記載されているような従来の感温性粘着剤は、易剥離性を有するものの、耐熱性が十分でないという問題がある。そのため、従来の感温性粘着剤を用いた粘着テープでは、高温雰囲気下の工程において、可撓性基板と支持体との熱膨張差に起因する反りや、粘着剤層中の水分・残留溶剤等の揮発による反り・浮き応力等に対応することができず、粘着剤層と可撓性基板との間で剥離が生じてしまう。 On the other hand, the conventional temperature-sensitive adhesive as described in Patent Document 1 has a problem that heat resistance is not sufficient although it has easy peelability. Therefore, in the pressure-sensitive adhesive tape using the conventional temperature-sensitive pressure-sensitive adhesive, warpage caused by a difference in thermal expansion between the flexible substrate and the support in the process under a high-temperature atmosphere, and moisture / residual solvent in the pressure-sensitive adhesive layer Therefore, it is impossible to cope with warpage, floating stress, and the like due to volatilization of the material, and peeling occurs between the adhesive layer and the flexible substrate.
本出願人は、耐熱性を有する感温性粘着剤として、先に特許文献３〜５に記載のような感温性粘着剤を開発した。これら特許文献３〜５に記載されている感温性粘着剤の耐熱性は１５０℃近傍の雰囲気温度に対するものであるが、工程によっては雰囲気温度が２３０℃近傍になることもある。したがって、より高い耐熱性を有する感温性粘着剤の開発が要望されていた。 The present applicant has previously developed a thermosensitive adhesive as described in Patent Documents 3 to 5 as a thermosensitive adhesive having heat resistance. The heat resistance of the temperature-sensitive adhesives described in Patent Documents 3 to 5 is relative to the ambient temperature near 150 ° C, but the ambient temperature may be near 230 ° C depending on the process. Accordingly, there has been a demand for the development of a temperature-sensitive adhesive having higher heat resistance.
本発明の課題は、高い耐熱性を有するとともに、易剥離可能な耐熱性感温性粘着剤を提供することである。 The subject of this invention is providing the heat-resistant thermosensitive adhesive which has high heat resistance and can be peeled easily.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、以下の構成からなる解決手段を見出し、本発明を完成するに至った。
（１）側鎖結晶性ポリマーを含有し、該側鎖結晶性ポリマーの融点未満の温度で粘着力が低下する感温性粘着剤であって、前記側鎖結晶性ポリマーが、１３０℃以上の雰囲気温度で各々の有する官能基が互いに反応するモノマー２種と、側鎖結晶性ポリマーを構成する他のモノマーと、を少なくとも重合させて得られる、重量平均分子量２０万〜１００万の共重合体からなることを特徴とする耐熱性感温性粘着剤。
（２）前記１３０℃以上の雰囲気温度で各々の有する官能基が互いに反応するモノマー２種が、カルボキシル基を有するエチレン性不飽和モノマーおよびヒドロキシル基を有するエチレン性不飽和モノマーであり、前記反応が、エステル化反応である前記（１）記載の耐熱性感温性粘着剤。
（３）前記側鎖結晶性ポリマーを構成する他のモノマーが、炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートと、炭素数１〜６のアルキル基を有する（メタ）アクリレートと、を含む前記（１）または（２）記載の耐熱性感温性粘着剤。
（４）金属キレート化合物をさらに含有する前記（１）〜（３）のいずれかに記載の耐熱性感温性粘着剤。
（５）貼着した被着体を、２２０〜２４０℃の雰囲気温度に曝した後、前記融点未満の温度で取り外す前記（１）〜（４）のいずれかに記載の耐熱性感温性粘着剤。
（６）２３０℃の雰囲気温度を経た後の５℃の雰囲気温度における１８０°剥離強度が、０．６Ｎ／２５ｍｍ以下である前記（１）〜（５）のいずれかに記載の耐熱性感温性粘着剤。
（７）前記（１）〜（６）のいずれかに記載の耐熱性感温性粘着剤からなることを特徴とする耐熱性感温性粘着シート。
（８）前記（１）〜（６）のいずれかに記載の耐熱性感温性粘着剤からなる粘着剤層を、基材フィルムの片面または両面に設けたことを特徴とする耐熱性感温性粘着テープ。
（９）前記（１）〜（６）のいずれかに記載の耐熱性感温性粘着剤からなる粘着剤層を、基材フィルムの両面に設けた耐熱性感温性粘着テープを用いて、平板表示装置を製造する方法であって、粘着力を発現させた前記耐熱性感温性粘着テープを介して、可撓性基板を支持体上に固定する工程と、固定した前記可撓性基板の表面に、薄膜パターンを形成する工程と、ついで前記耐熱性感温性粘着テープを側鎖結晶性ポリマーの融点未満の温度に冷却して粘着力を低下させ、前記可撓性基板を前記支持体から剥離する工程と、を含むことを特徴とする平板表示装置の製造方法。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a solution means having the following constitution and have completed the present invention.
(1) A temperature-sensitive pressure-sensitive adhesive containing a side-chain crystalline polymer and having reduced adhesive strength at a temperature lower than the melting point of the side-chain crystalline polymer, wherein the side-chain crystalline polymer has a temperature of 130 ° C. or higher. A copolymer having a weight average molecular weight of 200,000 to 1,000,000, which is obtained by polymerizing at least two types of monomers each having a functional group that reacts with each other at ambient temperature and another monomer constituting the side chain crystalline polymer A heat-resistant and temperature-sensitive adhesive comprising:
(2) The two types of monomers with which each functional group reacts at an ambient temperature of 130 ° C. or higher are an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group, and the reaction The heat-resistant temperature-sensitive adhesive according to (1), which is an esterification reaction.
(3) Other monomers constituting the side chain crystalline polymer are (meth) acrylates having a linear alkyl group having 16 or more carbon atoms, and (meth) acrylates having an alkyl group having 1 to 6 carbon atoms. The heat-resistant temperature-sensitive adhesive according to (1) or (2), comprising:
(4) The heat-resistant temperature-sensitive adhesive according to any one of (1) to (3), further containing a metal chelate compound.
(5) The heat-resistant thermosensitive adhesive according to any one of (1) to (4), wherein the adhered adherend is exposed to an atmospheric temperature of 220 to 240 ° C. and then removed at a temperature lower than the melting point. .
(6) The heat-resistant temperature sensitivity according to any one of (1) to (5), wherein the 180 ° peel strength at 5 ° C atmospheric temperature after passing through 230 ° C atmospheric temperature is 0.6 N / 25 mm or less. Adhesive.
(7) A heat-resistant temperature-sensitive adhesive sheet, comprising the heat-resistant temperature-sensitive adhesive according to any one of (1) to (6).
(8) A heat-resistant temperature-sensitive adhesive, characterized in that a pressure-sensitive adhesive layer comprising the heat-resistant temperature-sensitive adhesive according to any one of (1) to (6) is provided on one side or both sides of a base film. tape.
(9) Flat display using a heat-resistant temperature-sensitive adhesive tape provided on both surfaces of the base film with the pressure-sensitive adhesive layer comprising the heat-resistant temperature-sensitive adhesive according to any one of (1) to (6) above A method of manufacturing an apparatus, comprising: a step of fixing a flexible substrate on a support via the heat-resistant and temperature-sensitive adhesive tape that exhibits adhesive force; and a surface of the fixed flexible substrate. , Forming a thin film pattern, and then cooling the heat-resistant temperature-sensitive adhesive tape to a temperature below the melting point of the side chain crystalline polymer to reduce the adhesive force, and peeling the flexible substrate from the support. A process for producing a flat panel display device.
なお、本発明における前記「１３０℃以上の雰囲気温度で各々の有する官能基が互いに反応するモノマー２種」とは、官能基（ａ）を有するモノマー（Ａ）と、１３０℃以上の雰囲気温度で官能基（ａ）と反応する官能基（ｂ）を有するモノマー（Ｂ）であることを意味する。
また、本発明における前記「シート」は、シート状のみに限定されるものではなく、本発明の効果を損なわない限りにおいて、シート状ないしフィルム状をも含む概念である。
In the present invention, the “two types of monomers each having a functional group that reacts with each other at an ambient temperature of 130 ° C. or higher” refers to the monomer (A) having a functional group (a) and an ambient temperature of 130 ° C. or higher. It means that the monomer (B) has a functional group (b) that reacts with the functional group (a).
Further, the “sheet” in the present invention is not limited to a sheet shape, and is a concept including a sheet shape or a film shape as long as the effects of the present invention are not impaired.
本発明によれば、１３０℃以上の雰囲気温度で各々の有する官能基が互いに反応するモノマー２種をモノマー単位として含有するので、高温雰囲気下では前記官能基が互いに反応することによって熱硬化を起こし、その結果、弾性率が飛躍的に高まるようになる。そして、この弾性率の高まりと、側鎖結晶性ポリマーを構成する共重合体の重量平均分子量を２０万〜１００万とすることによる凝集力の向上とが相まって、耐熱性を大きく向上させることができる。それゆえ、例えば２３０℃近傍の高温雰囲気下で被着体を加工中に、外的応力や被着体の熱的変形による応力等を受けたとしても、被着体が外れるのを抑制することができる。 According to the present invention, since the monomer units contain two types of monomers that each react with each other at a temperature of 130 ° C. or higher, the functional groups react with each other in a high temperature atmosphere to cause thermosetting. As a result, the elastic modulus increases dramatically. And this increase in elastic modulus combined with the improvement of cohesive force by setting the weight average molecular weight of the copolymer constituting the side chain crystalline polymer to 200,000 to 1,000,000 can greatly improve the heat resistance. it can. Therefore, for example, during processing of the adherend in a high temperature atmosphere near 230 ° C., even if external stress or stress due to thermal deformation of the adherend is applied, it is possible to prevent the adherend from coming off. Can do.
また、被着体から剥離する際には、感温性粘着剤を側鎖結晶性ポリマーの融点未満の温度にまで冷却すれば、側鎖結晶性ポリマーが結晶化することによって粘着力が低下するので、被着体からの剥離を容易に行うことができる。 Further, when peeling from the adherend, if the temperature-sensitive adhesive is cooled to a temperature below the melting point of the side chain crystalline polymer, the side chain crystalline polymer is crystallized and the adhesive strength is reduced. Therefore, peeling from the adherend can be easily performed.
本発明にかかる粘着剤は、耐熱性感温性粘着剤（以下、「感温性粘着剤」と言うことがある。）である。感温性粘着剤とは、温度変化に対応して粘着力が変化する粘着剤を意味する。本発明の感温性粘着剤は、側鎖結晶性ポリマーを含有する。側鎖結晶性ポリマーは、融点未満の温度で結晶化し、かつ融点以上の温度で相転移して流動性を示すポリマーである。すなわち、側鎖結晶性ポリマーは、温度変化に対応して結晶状態と流動状態とを可逆的に起こすポリマーである。 The pressure-sensitive adhesive according to the present invention is a heat-resistant temperature-sensitive pressure-sensitive adhesive (hereinafter sometimes referred to as “temperature-sensitive pressure-sensitive adhesive”). A temperature-sensitive adhesive means an adhesive whose adhesive force changes in response to a temperature change. The temperature-sensitive adhesive of the present invention contains a side chain crystalline polymer. The side chain crystalline polymer is a polymer that is crystallized at a temperature lower than the melting point and exhibits phase flow at a temperature higher than the melting point. That is, the side chain crystalline polymer is a polymer that reversibly causes a crystalline state and a fluid state in response to a temperature change.
前記感温性粘着剤は、融点未満の温度で側鎖結晶性ポリマーが結晶化した際に粘着力が低下する割合で側鎖結晶性ポリマーを含有する。つまり、前記感温性粘着剤は、側鎖結晶性ポリマーを主成分として含有する。これにより、被着体から感温性粘着剤を剥離する際には、感温性粘着剤を側鎖結晶性ポリマーの融点未満の温度に冷却すれば、側鎖結晶性ポリマーが結晶化することによって粘着力が低下する。 The temperature-sensitive adhesive contains the side chain crystalline polymer in such a ratio that the adhesive strength is reduced when the side chain crystalline polymer is crystallized at a temperature lower than the melting point. That is, the thermosensitive adhesive contains a side chain crystalline polymer as a main component. As a result, when the temperature-sensitive adhesive is peeled from the adherend, the side-chain crystalline polymer is crystallized if the temperature-sensitive adhesive is cooled to a temperature below the melting point of the side-chain crystalline polymer. The adhesive strength decreases.
融点とは、ある平衡プロセスにより、最初は秩序ある配列に整合されていた重合体の特定部分が無秩序状態となる温度を意味し、示差熱走査熱量計（ＤＳＣ）により１０℃／分の測定条件で測定して得られる値である。融点としては２０℃以上であるのが好ましく、２０〜６０℃であるのがより好ましい。これにより感温性粘着剤が、通常、室温下で粘着力を発現するようになるので、被着体の固定を室温で行うことができる。融点を所定の値とするには、側鎖結晶性ポリマーの組成等を変えることによって任意に行うことができる。 The melting point means a temperature at which a specific portion of the polymer that is initially aligned in an ordered arrangement becomes disordered by an equilibrium process, and is measured using a differential thermal scanning calorimeter (DSC) at 10 ° C./min. It is a value obtained by measuring with. As melting | fusing point, it is preferable that it is 20 degreeC or more, and it is more preferable that it is 20-60 degreeC. As a result, the temperature-sensitive adhesive usually develops adhesive strength at room temperature, so that the adherend can be fixed at room temperature. The melting point can be arbitrarily set to a predetermined value by changing the composition of the side chain crystalline polymer.
側鎖結晶性ポリマーは、１３０℃以上の雰囲気温度で各々の有する官能基が互いに反応するモノマー２種と、側鎖結晶性ポリマーを構成する他のモノマーと、を少なくとも重合させて得られる共重合体からなる。 The side-chain crystalline polymer is a copolymer obtained by polymerizing at least two monomers each having a functional group that reacts with each other at an ambient temperature of 130 ° C. or higher and another monomer constituting the side-chain crystalline polymer. Composed of coalescence.
１３０℃以上の雰囲気温度で各々の有する官能基が互いに反応するモノマー２種としては、例えばカルボキシル基を有するエチレン性不飽和モノマーと、ヒドロキシル基を有するエチレン性不飽和モノマーとが好適である。これらのモノマーは、通常、１３０〜１４０℃の雰囲気温度でカルボキシル基とヒドロキシル基とが互いに反応してエステル化反応（熱硬化）するので、これらのモノマーをモノマー単位として含有すると、感温性粘着剤の高温雰囲気下における弾性率を飛躍的に高めることができる。 As the two types of monomers in which each functional group reacts with each other at an atmospheric temperature of 130 ° C. or higher, for example, an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group are suitable. These monomers usually undergo esterification reaction (thermosetting) by reacting carboxyl groups and hydroxyl groups with each other at an atmospheric temperature of 130 to 140 ° C. Therefore, when these monomers are contained as monomer units, a temperature-sensitive adhesive The elastic modulus of the agent in a high temperature atmosphere can be dramatically increased.
カルボキシル基を有するエチレン性不飽和モノマーとしては、例えばアクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸等が挙げられ、これらは１種または２種以上を混合して用いてもよい。ヒドロキシル基を有するエチレン性不飽和モノマーとしては、例えば２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシヘキシル（メタ）アクリレート等が挙げられ、これらは１種または２種以上を混合して用いてもよい。なお、１３０℃以上の雰囲気温度で各々の有する官能基が互いに反応するモノマー２種としては、カルボキシル基を有するエチレン性不飽和モノマーおよびヒドロキシル基を有するエチレン性不飽和モノマーに限定されるものではなく、上述した効果が得られる限り所望のモノマーを採用することができる。また、１３０℃以上の雰囲気温度で各々の有する官能基が互いに反応するモノマーは、少なくとも２種であればよく、必要に応じて３種以上を用いてもよい。 Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and the like, and these may be used alone or in combination of two or more. Good. Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate, and the like. You may mix and use a seed | species or more. The two types of monomers with which each functional group reacts at an ambient temperature of 130 ° C. or higher are not limited to ethylenically unsaturated monomers having a carboxyl group and ethylenically unsaturated monomers having a hydroxyl group. As long as the effects described above are obtained, a desired monomer can be employed. Moreover, the monomer which each functional group which each has reacts with each other at the atmospheric temperature of 130 degreeC or more should just be at least 2 types, and may use 3 or more types as needed.
側鎖結晶性ポリマーを構成する他のモノマーとしては、例えば炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレート、炭素数１〜６のアルキル基を有する（メタ）アクリレート等が挙げられる。 Examples of other monomers constituting the side chain crystalline polymer include (meth) acrylates having a linear alkyl group having 16 or more carbon atoms, (meth) acrylates having an alkyl group having 1 to 6 carbon atoms, and the like. .
炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートとしては、例えばセチル（メタ）アクリレート、ステアリル（メタ）アクリレート、エイコシル（メタ）アクリレート、ベヘニル（メタ）アクリレート等の炭素数１６〜２２の線状アルキル基を有する（メタ）アクリレートが挙げられ、これらは１種または２種以上を混合して用いてもよい。炭素数１〜６のアルキル基を有する（メタ）アクリレートとしては、例えばメチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート等が挙げられ、これらは１種または２種以上を混合して用いてもよい。 Examples of the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms include 16 to 22 carbon atoms such as cetyl (meth) acrylate, stearyl (meth) acrylate, eicosyl (meth) acrylate, and behenyl (meth) acrylate. (Meth) acrylates having a linear alkyl group can be used, and these may be used alone or in combination of two or more. Examples of the (meth) acrylate having an alkyl group having 1 to 6 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and the like. Alternatively, two or more kinds may be mixed and used.
側鎖結晶性ポリマーの組成としては、１３０℃以上の雰囲気温度で各々の有する官能基が互いに反応するモノマー２種を合計で１〜２０重量部、好ましくは５〜１５重量部、側鎖結晶性ポリマーを構成する他のモノマーを合計で８０〜９９重量部、好ましくは８５〜９５重量部とするのがよい。 The composition of the side chain crystalline polymer is 1 to 20 parts by weight in total, preferably 5 to 15 parts by weight, and the side chain crystallinity of two types of monomers with which each functional group reacts at an ambient temperature of 130 ° C. or higher. The total amount of other monomers constituting the polymer is 80 to 99 parts by weight, preferably 85 to 95 parts by weight.
重合方法としては、特に限定されるものではなく、例えば溶液重合法、塊状重合法、懸濁重合法、乳化重合法等が挙げられる。例えば溶液重合法を採用する場合には、上述したモノマーを溶剤に混合し、４０〜９０℃程度で２〜１０時間程度攪拌すればよい。 The polymerization method is not particularly limited, and examples thereof include a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method. For example, when the solution polymerization method is employed, the above-described monomer may be mixed in a solvent and stirred at about 40 to 90 ° C. for about 2 to 10 hours.
側鎖結晶性ポリマーを構成する共重合体の重量平均分子量としては、２０万〜１００万であり、好ましくは５０万〜９０万である。共重合体の重量平均分子量があまり小さいと、側鎖結晶性ポリマーの凝集力が不足して耐熱性が低下する傾向があるとともに、被着体から感温性粘着剤を剥離する際に感温性粘着剤が被着体上に残る、いわゆる糊残りが多くなるおそれがある。また、共重合体の重量平均分子量があまり大きいと、感温性粘着剤を側鎖結晶性ポリマーの融点未満の温度に冷却しても側鎖結晶性ポリマーが結晶化し難くなるので、粘着力が低下し難くなる。重量平均分子量は、共重合体をゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定し、得られた測定値をポリスチレン換算した値である。 The weight average molecular weight of the copolymer constituting the side chain crystalline polymer is 200,000 to 1,000,000, preferably 500,000 to 900,000. If the weight average molecular weight of the copolymer is too small, the side chain crystalline polymer will have insufficient cohesive force and heat resistance will tend to decrease, and the temperature sensitivity will be reduced when the temperature-sensitive adhesive is peeled off from the adherend. There is a possibility that so-called adhesive residue may remain on the adherend. In addition, if the weight average molecular weight of the copolymer is too large, the side chain crystalline polymer is difficult to crystallize even if the temperature-sensitive adhesive is cooled to a temperature below the melting point of the side chain crystalline polymer. It becomes difficult to decrease. The weight average molecular weight is a value obtained by measuring the copolymer by gel permeation chromatography (GPC) and converting the obtained measurement value to polystyrene.
一方、感温性粘着剤は、架橋剤をさらに含有するのが好ましい。架橋剤としては、例えばイソシアネート化合物、アジリジン化合物、エポキシ化合物、金属キレート化合物等が挙げられ、特に金属キレート化合物が好ましい。金属キレート化合物をさらに含有すると、感温性粘着剤の耐熱性がより向上する傾向にある。 On the other hand, it is preferable that the temperature-sensitive adhesive further contains a crosslinking agent. Examples of the crosslinking agent include isocyanate compounds, aziridine compounds, epoxy compounds, metal chelate compounds, and the like, and metal chelate compounds are particularly preferable. When the metal chelate compound is further contained, the heat resistance of the temperature-sensitive adhesive tends to be further improved.
金属キレート化合物としては、例えば多価金属のアセチルアセトン配位化合物、アセト酢酸エステル配位化合物等が挙げられ、多価金属としては、例えばアルミニウム、ニッケル、クロム、鉄、チタン、亜鉛、コバルト、マンガン、ジルコニウム等が挙げられ、これらは１種または２種以上を混合して用いてもよい。例示したこれらの金属キレート化合物のうち、アルミニウムのアセチルアセトン配位化合物またはアセト酢酸エステル配位化合物が好ましく、アルミニウムトリスアセチルアセトナートが好適である。 Examples of the metal chelate compound include acetylacetone coordination compounds of polyvalent metals, acetoacetate coordination compounds, etc., and examples of the polyvalent metals include aluminum, nickel, chromium, iron, titanium, zinc, cobalt, manganese, Zirconium etc. are mentioned, and these may be used alone or in combination of two or more. Of these exemplified metal chelate compounds, aluminum acetylacetone coordination compounds or acetoacetate coordination compounds are preferred, and aluminum trisacetylacetonate is preferred.
架橋剤の含有量としては、側鎖結晶性ポリマーを構成する共重合体１００重量部に対して０．１〜１０重量部であるのが好ましく、０．５〜１０重量部であるのがより好ましい。 As content of a crosslinking agent, it is preferable that it is 0.1-10 weight part with respect to 100 weight part of copolymers which comprise a side chain crystalline polymer, and it is more preferable that it is 0.5-10 weight part. preferable.
本発明の感温性粘着剤の使用形態としては、特に限定されるものではなく、例えば基材レスのシート状の形態で使用することもでき、あるいは感温性粘着剤に適当な溶剤を加えて、被着体に直接塗布して乾燥するようにしてもよい。 The usage form of the temperature-sensitive adhesive of the present invention is not particularly limited, and for example, it can be used in the form of a substrate-less sheet, or an appropriate solvent is added to the temperature-sensitive adhesive. Then, it may be applied directly to the adherend and dried.
感温性粘着剤をシート状の形態にし、耐熱性感温性粘着シート（以下、「粘着シート」と言うことがある。）として使用する場合には、その厚さを５〜６０μｍとするのが好ましい。粘着シートの厚さがあまり薄いと、粘着力が低下し、加工時に被着体を固定し難くなるので好ましくない。また、粘着シートの厚さがあまり大きいと、粘着シートの厚さにバラツキを生じるおそれがあるので好ましくない。 When the temperature-sensitive adhesive is made into a sheet form and used as a heat-resistant temperature-sensitive adhesive sheet (hereinafter sometimes referred to as “adhesive sheet”), the thickness is set to 5 to 60 μm. preferable. If the thickness of the pressure-sensitive adhesive sheet is too thin, the pressure-sensitive adhesive force is lowered, and it is difficult to fix the adherend during processing, which is not preferable. Moreover, since the thickness of an adhesive sheet may produce variation when the thickness of an adhesive sheet is too large, it is unpreferable.
粘着シートの両面には、離型処理を施したフィルム、すなわち離型フィルムを設けるのが好ましい。離型フィルムとしては、例えばポリエチレンテレフタレート等からなるフィルムの表面に、シリコーン等の離型剤を塗布したものが挙げられる。粘着シートの両面に離型フィルムを設けるには、例えば感温性粘着剤を溶剤に加えた塗布液を、離型フィルム上に塗布して乾燥させて粘着シートを得、この粘着シートの表面に離型フィルムを配置すればよい。 It is preferable to provide a release-treated film, that is, a release film, on both sides of the pressure-sensitive adhesive sheet. Examples of the release film include those obtained by applying a release agent such as silicone to the surface of a film made of, for example, polyethylene terephthalate. In order to provide release films on both sides of the pressure-sensitive adhesive sheet, for example, a coating solution obtained by adding a thermosensitive adhesive to a solvent is applied onto the release film and dried to obtain a pressure-sensitive adhesive sheet. A release film may be disposed.
塗布液には、例えば可塑剤、老化防止剤、紫外線吸収剤等の各種の添加剤を添加することができる。塗布は、一般的にナイフコーター、ロールコーター、カレンダーコーター、コンマコーター等により行うことができる。また、塗工厚みや塗布液の粘度によっては、グラビアコーター、ロッドコーター等により行うこともできる。なお、感温性粘着剤は、塗布の他、例えば押し出し成形やカレンダー加工によってもシート状に成形することができる。 Various additives such as a plasticizer, an anti-aging agent, and an ultraviolet absorber can be added to the coating solution. The coating can be generally performed with a knife coater, a roll coater, a calendar coater, a comma coater or the like. Further, depending on the coating thickness and the viscosity of the coating solution, a gravure coater, a rod coater or the like can be used. The temperature-sensitive adhesive can be formed into a sheet shape by, for example, extrusion molding or calendaring in addition to application.
本発明の感温性粘着剤は、粘着テープの形態で使用することもできる。粘着テープの形態によれば、上述した粘着シートと同様の効果を奏するとともに、基材フィルムを含む分、粘着シートよりも剛性が高く、取り扱い性に優れるという効果を奏する。 The temperature-sensitive adhesive of the present invention can also be used in the form of an adhesive tape. According to the form of the pressure-sensitive adhesive tape, the same effects as those of the pressure-sensitive adhesive sheet described above are exhibited, and the rigidity of the pressure-sensitive adhesive sheet is higher than that of the pressure-sensitive adhesive sheet and the handleability is excellent.
感温性粘着剤を粘着テープの形態にし、耐熱性感温性粘着テープ（以下、「粘着テープ」と言うことがある。）として使用する場合には、本発明の感温性粘着剤からなる粘着剤層を、基材フィルムの片面または両面に設ければよい。 When the thermosensitive adhesive is in the form of an adhesive tape and used as a heat-resistant thermosensitive adhesive tape (hereinafter sometimes referred to as “adhesive tape”), the adhesive comprising the thermosensitive adhesive of the present invention. What is necessary is just to provide an agent layer in the single side | surface or both surfaces of a base film.
基材フィルムとしては、例えばポリエチレン、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリプロピレン、ポリエステル、ポリアミド、ポリイミド、ポリカーボネート、エチレン酢酸ビニル共重合体、エチレンエチルアクリレート共重合体、エチレンポリプロピレン共重合体、ポリ塩化ビニル等の合成樹脂フィルムが挙げられる。これらのうち、２３０℃近傍の雰囲気温度に曝されても熱変形し難い耐熱性を有するものが好ましい。 Examples of the base film include polyethylene, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyester, polyamide, polyimide, polycarbonate, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene polypropylene copolymer, and polyvinyl chloride. The synthetic resin film is mentioned. Among these, those having heat resistance that hardly undergoes thermal deformation even when exposed to an ambient temperature in the vicinity of 230 ° C. are preferable.
基材フィルムは、単層体または複層体からなるものであってもよく、厚さは、通常、５〜５００μｍ程度である。基材フィルムには、粘着剤層に対する密着性を向上させるため、例えばコロナ放電処理、プラズマ処理、ブラスト処理、ケミカルエッチング処理、プライマー処理等の表面処理を施すことができる。 A base film may consist of a single layer body or a multilayer body, and thickness is about 5-500 micrometers normally. In order to improve the adhesiveness with respect to an adhesive layer, surface treatments, such as a corona discharge process, a plasma process, a blast process, a chemical etching process, a primer process, can be given to a base film, for example.
基材フィルムの片面または両面に粘着剤層を設けるには、感温性粘着剤を溶剤に加えた塗布液を、基材フィルムの片面または両面に塗布して乾燥させればよい。塗布は、上述した粘着シートで説明したのと同じ方法で行うことができる。 In order to provide the pressure-sensitive adhesive layer on one or both sides of the base film, a coating solution in which a temperature-sensitive adhesive is added to a solvent may be applied to one or both sides of the base film and dried. Application | coating can be performed by the same method demonstrated with the adhesive sheet mentioned above.
粘着剤層の厚さとしては、５〜６０μｍであるのが好ましく、５〜５０μｍであるのがより好ましく、５〜４０μｍであるのがさらに好ましい。基材フィルムの両面に粘着剤層を設ける場合には、片面の粘着剤層の厚さと、他面の粘着剤層の厚さは、同じであってもよいし、異なっていてもよい。 As thickness of an adhesive layer, it is preferable that it is 5-60 micrometers, it is more preferable that it is 5-50 micrometers, and it is further more preferable that it is 5-40 micrometers. When providing an adhesive layer on both surfaces of a base film, the thickness of the adhesive layer on one side and the thickness of the adhesive layer on the other surface may be the same or different.
粘着テープは、片面の粘着剤層が本発明の感温性粘着剤からなる限り、他面の粘着剤層の組成は、特に限定されない。他面の粘着剤層を、例えば片面の粘着剤層と同様に本発明の感温性粘着剤からなる粘着剤層で構成する場合には、片面の粘着剤層の組成と、他面の粘着剤層の組成とは、同じであってもよいし、異なっていてもよい。 The composition of the pressure-sensitive adhesive layer on the other side is not particularly limited as long as the pressure-sensitive adhesive layer on one side is composed of the temperature-sensitive pressure-sensitive adhesive of the present invention. When the pressure-sensitive adhesive layer on the other side is composed of, for example, a pressure-sensitive adhesive layer made of the temperature-sensitive pressure-sensitive adhesive of the present invention in the same manner as the pressure-sensitive adhesive layer on one side, the composition of the pressure-sensitive adhesive layer on one side and the pressure-sensitive adhesive on the other side The composition of the agent layer may be the same or different.
また、他面の粘着剤層として、例えば感圧性接着剤からなる粘着剤層を用いることもできる。感圧性接着剤は、粘着性を有するポリマーであり、例えば天然ゴム接着剤、合成ゴム接着剤、スチレン／ブタジエンラテックスベース接着剤、アクリル系接着剤、シリコン系接着剤等が挙げられる。 Further, as the pressure-sensitive adhesive layer on the other surface, for example, a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive can be used. The pressure-sensitive adhesive is an adhesive polymer, and examples thereof include natural rubber adhesives, synthetic rubber adhesives, styrene / butadiene latex base adhesives, acrylic adhesives, and silicon adhesives.
ここで、本発明の感温性粘着剤は、２３０℃近傍の雰囲気温度に対する耐熱性を有しているので、貼着した被着体を２２０〜２４０℃の雰囲気温度に曝した後、側鎖結晶性ポリマーの融点未満の温度で取り外す粘着剤として使用するのが好ましい。雰囲気温度がこのような高温雰囲気になり易い用途としては、例えば上述した平板表示装置の製造用等が挙げられる。次に、本発明の感温性粘着剤の一使用形態である粘着テープの一使用例について、上述した平板表示装置の製造を例に挙げて説明する。 Here, since the temperature-sensitive adhesive of the present invention has heat resistance to an ambient temperature of around 230 ° C., the exposed adherend is exposed to an ambient temperature of 220 to 240 ° C., and then the side chain. It is preferably used as an adhesive that is removed at a temperature below the melting point of the crystalline polymer. As an application in which the atmospheric temperature tends to be such a high temperature atmosphere, for example, for manufacturing the above-described flat panel display device can be cited. Next, an example of the use of the pressure-sensitive adhesive tape, which is one form of use of the temperature-sensitive adhesive of the present invention, will be described by taking as an example the production of the flat panel display described above.
まず、基材フィルムの両面に本発明の感温性粘着剤からなる粘着剤層を設けた粘着テープを介して、可撓性基板を支持体上に固定する。この固定は、雰囲気温度をヒータ等の加熱手段を用いて側鎖結晶性ポリマーの融点以上の温度にまで加熱して行う。これにより、側鎖結晶性ポリマーが流動性を示し粘着剤層の粘着力が発現するので、粘着テープを介して可撓性基板が支持体上に固定される。 First, a flexible substrate is fixed on a support through an adhesive tape provided with an adhesive layer made of the temperature-sensitive adhesive of the present invention on both surfaces of a base film. This fixing is performed by heating the ambient temperature to a temperature equal to or higher than the melting point of the side chain crystalline polymer using a heating means such as a heater. Thereby, since the side chain crystalline polymer exhibits fluidity and the adhesive force of the adhesive layer is expressed, the flexible substrate is fixed on the support via the adhesive tape.
可撓性基板は、可撓性を有しており、その構成材料としては、例えばポリカーボネート、ポリエチレンテレフタレート、ポリメチルメタクリレート、ポリイミド、ポリエチレンナフタレート、ポリエーテルサルフォン、薄膜ガラス、金属箔等が挙げられる。支持体を構成する材料としては、例えばガラス等が挙げられる。 The flexible substrate has flexibility, and examples of the constituent material thereof include polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyimide, polyethylene naphthalate, polyethersulfone, thin film glass, and metal foil. It is done. Examples of the material constituting the support include glass.
可撓性基板を固定した後、該可撓性基板の表面に所定の薄膜パターンを形成する。この薄膜パターン形成中には、雰囲気温度が２３０℃近傍の高温になることがある。粘着テープには、本発明の感温性粘着剤からなる粘着剤層が設けられているので、１３０℃以上の雰囲気温度で各々の有する官能基が互いに反応するモノマー２種をモノマー単位として含有している。したがって、高温雰囲気下では前記官能基が互いに反応して熱硬化を起こし、その結果、弾性率が飛躍的に高まるようになる。そして、この弾性率の高まりと、側鎖結晶性ポリマーを構成する共重合体の重量平均分子量を２０万〜１００万とすることによる凝集力の向上とが相まって、高い耐熱性を示すようになる。それゆえ、この粘着テープによれば、雰囲気温度が２３０℃近傍の高温になったとしても、可撓性基板と支持体との熱膨張差に起因する反りや、粘着剤層中の水分・残留溶剤等の揮発による反り・浮き応力等に対して十分に対応することができ、可撓性基板を支持体上に固定し続けることができる。 After fixing the flexible substrate, a predetermined thin film pattern is formed on the surface of the flexible substrate. During the formation of this thin film pattern, the ambient temperature may reach a high temperature around 230 ° C. Since the pressure-sensitive adhesive tape is provided with a pressure-sensitive adhesive layer made of the temperature-sensitive pressure-sensitive adhesive of the present invention, it contains two monomers as monomer units, each of which has functional groups that react with each other at an ambient temperature of 130 ° C. or higher. ing. Therefore, in a high temperature atmosphere, the functional groups react with each other to cause thermosetting, and as a result, the elastic modulus increases dramatically. And the increase in the elastic modulus and the improvement of the cohesive force due to the weight average molecular weight of the copolymer constituting the side chain crystalline polymer being 200,000 to 1,000,000 are combined to show high heat resistance. . Therefore, according to this pressure-sensitive adhesive tape, even when the ambient temperature becomes a high temperature of about 230 ° C., warpage caused by a difference in thermal expansion between the flexible substrate and the support, moisture / residue in the pressure-sensitive adhesive layer, and the like. It is possible to sufficiently cope with warpage, floating stress, and the like due to volatilization of a solvent and the like, and it is possible to continue fixing the flexible substrate on the support.
一方、本発明の感温性粘着剤に代えて、一般的なアクリル系粘着剤を用いた場合には、以下の問題がある。すなわち、一般的なアクリル系粘着剤を備えたアクリル系粘着テープを被着体に貼着した状態で高温雰囲気下に曝すと、粘着剤層が柔軟になる。その結果、耐熱性が低下する。また、被着体表面に対する粘着剤層の濡れ性が向上し、粘着剤層が被着体表面に存在する凹凸形状によく追従するようになり、いわゆるアンカー効果が発現する。それゆえ、アクリル系粘着テープは、雰囲気温度が下がった際に、初期粘着力に比べて粘着力が高くなり、剥離不良を生じることが多い。 On the other hand, when a general acrylic pressure-sensitive adhesive is used instead of the temperature-sensitive pressure-sensitive adhesive of the present invention, there are the following problems. That is, when an acrylic pressure-sensitive adhesive tape provided with a general acrylic pressure-sensitive adhesive is exposed to a high-temperature atmosphere in a state of being attached to an adherend, the pressure-sensitive adhesive layer becomes flexible. As a result, the heat resistance decreases. Further, the wettability of the pressure-sensitive adhesive layer with respect to the adherend surface is improved, and the pressure-sensitive adhesive layer follows the uneven shape present on the surface of the adherend well, so that a so-called anchor effect is exhibited. Therefore, the acrylic adhesive tape has a higher adhesive force than the initial adhesive force when the ambient temperature is lowered, and often causes poor peeling.
本発明の粘着テープは、側鎖結晶性ポリマーを含有しているため、高温雰囲気下に曝されることで粘着力が初期粘着力より高くなったとしても、雰囲気温度を側鎖結晶性ポリマーの融点未満の温度にまで冷却すれば、側鎖結晶性ポリマーが結晶化することによって粘着力が低下する。具体的には、２３０℃の雰囲気温度を経た後の５℃の雰囲気温度における１８０°剥離強度（以下、「５℃剥離強度」と言うことがある。）が、通常、０．６Ｎ／２５ｍｍ以下になる。したがって、薄膜パターンを形成した後、雰囲気温度をファン等の冷却手段を用いて側鎖結晶性ポリマーの融点未満の温度にまで冷却すれば、粘着剤層の粘着力が十分に低下するので、可撓性基板を支持体から簡単に剥離することができる。 Since the pressure-sensitive adhesive tape of the present invention contains a side-chain crystalline polymer, even if the pressure-sensitive adhesive strength becomes higher than the initial pressure-sensitive adhesive strength when exposed to a high temperature atmosphere, the ambient temperature of the side-chain crystalline polymer is reduced. If it is cooled to a temperature lower than the melting point, the side chain crystalline polymer is crystallized, thereby reducing the adhesive force. Specifically, the 180 ° peel strength (hereinafter sometimes referred to as “5 ° C. peel strength”) at an ambient temperature of 5 ° C. after passing through an ambient temperature of 230 ° C. is usually 0.6 N / 25 mm or less. become. Therefore, after the thin film pattern is formed, if the ambient temperature is cooled to a temperature lower than the melting point of the side chain crystalline polymer using a cooling means such as a fan, the adhesive strength of the adhesive layer is sufficiently reduced. The flexible substrate can be easily peeled from the support.
なお、平板表示装置の製造は、上述した粘着テープに代えて、本発明の感温性粘着剤やその粘着シートを用いても行うことができる。また、本発明の感温性粘着剤、粘着シートおよび粘着テープの用途は、平板表示装置の製造用に限定されるものではなく、例えば半導体、積層セラミックインダクター、抵抗器、フェライト、センサー素子、サーミスタ、バリスタ、セラミック電子部品等のように、耐熱性と易剥離性とが要求される分野において、好適に用いることができる。 In addition, it can replace with the adhesive tape mentioned above, and manufacture of a flat panel display apparatus can also be performed using the temperature sensitive adhesive of this invention, or its adhesive sheet. The uses of the thermosensitive adhesive, the adhesive sheet and the adhesive tape of the present invention are not limited to the production of flat panel display devices. For example, semiconductors, multilayer ceramic inductors, resistors, ferrites, sensor elements, It can be suitably used in fields where heat resistance and easy peelability are required, such as thermistors, varistors, and ceramic electronic components.
以下、合成例および実施例を挙げて本発明を詳細に説明するが、本発明は以下の合成例および実施例のみに限定されるものではない。なお、以下の説明で「部」は重量部を意味する。 EXAMPLES Hereinafter, although a synthesis example and an Example are given and this invention is demonstrated in detail, this invention is not limited only to the following synthesis examples and Examples. In the following description, “part” means part by weight.
（合成例１）
ステアリルアクリレート（日油社製）を４５部、メチルアクリレート（日本触媒社製）を４５部、アクリル酸を５部、２−ヒドロキシエチルアクリレートを５部、およびパーブチルＮＤ（日油社製）を０．２部の割合で、それぞれ酢酸エチル２３０部に添加して混合し、５５℃で４時間撹拌して、これらのモノマーを重合させた。得られた共重合体の重量平均分子量は７０万、融点は３４℃であった。
(Synthesis Example 1)
45 parts of stearyl acrylate (manufactured by NOF Corporation), 45 parts of methyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 5 parts of acrylic acid, 5 parts of 2-hydroxyethyl acrylate, and 0 part of perbutyl ND (manufactured by NOF Corporation) Each of these monomers was polymerized at a ratio of 2 parts by adding to 230 parts of ethyl acetate and mixing and stirring at 55 ° C. for 4 hours. The obtained copolymer had a weight average molecular weight of 700,000 and a melting point of 34 ° C.
（合成例２）
ステアリルアクリレートを４５部に代えて３０部にし、メチルアクリレートを４５部に代えて６０部にした以外は、合成例１と同様にしてモノマーを重合させた。得られた共重合体の重量平均分子量は７０万、融点は２７℃であった。
(Synthesis Example 2)
The monomer was polymerized in the same manner as in Synthesis Example 1 except that stearyl acrylate was changed to 30 parts instead of 45 parts and methyl acrylate was changed to 60 parts instead of 45 parts. The obtained copolymer had a weight average molecular weight of 700,000 and a melting point of 27 ° C.
（比較合成例１）
ステアリルアクリレートを４５部に代えて３５部にし、メチルアクリレートを４５部に代えて６０部にし、２−ヒドロキシエチルアクリレートを添加しなかった以外は、合成例１と同様にしてモノマーを重合させた。得られた共重合体の重量平均分子量は７０万、融点は２９℃であった。
(Comparative Synthesis Example 1)
The monomer was polymerized in the same manner as in Synthesis Example 1 except that stearyl acrylate was changed to 35 parts instead of 45 parts, methyl acrylate was changed to 45 parts and 60 parts were added, and 2-hydroxyethyl acrylate was not added. The obtained copolymer had a weight average molecular weight of 700,000 and a melting point of 29 ° C.
（比較合成例２）
ステアリルアクリレートを４５部に代えて３５部にし、メチルアクリレートを４５部に代えて６０部にし、アクリル酸を添加しなかった以外は、合成例１と同様にしてモノマーを重合させた。得られた共重合体の重量平均分子量は７０万、融点は２９℃であった。
(Comparative Synthesis Example 2)
The monomer was polymerized in the same manner as in Synthesis Example 1 except that stearyl acrylate was replaced with 45 parts, 35 parts, methyl acrylate was replaced with 45 parts, and 60 parts were added, and no acrylic acid was added. The obtained copolymer had a weight average molecular weight of 700,000 and a melting point of 29 ° C.
（比較合成例３）
ステアリルアクリレートを４５部に代えて３０部にし、メチルアクリレートを４５部に代えて６０部にし、攪拌する際の温度を５５℃に代えて８０℃にした以外は、合成例１と同様にしてモノマーを重合させた。得られた共重合体の重量平均分子量は１５万、融点は２７℃であった。
(Comparative Synthesis Example 3)
Monomer in the same manner as in Synthesis Example 1 except that stearyl acrylate was changed to 30 parts instead of 45 parts, methyl acrylate was changed to 45 parts instead of 45 parts, and the stirring temperature was changed to 80 ° C. instead of 55 ° C. Was polymerized. The obtained copolymer had a weight average molecular weight of 150,000 and a melting point of 27 ° C.
（比較合成例４）
ブチルアクリレートを９８部、アクリル酸を２部、およびパーブチルＮＤ（日油社製）を０．２部の割合で、それぞれ酢酸エチル２３０部に添加して混合し、５５℃で４時間撹拌して、これらのモノマーを重合させた。得られた共重合体の重量平均分子量は１００万であった。
(Comparative Synthesis Example 4)
98 parts of butyl acrylate, 2 parts of acrylic acid, and 0.2 part of perbutyl ND (manufactured by NOF Corporation) were added to 230 parts of ethyl acetate, mixed, and stirred at 55 ° C. for 4 hours. These monomers were polymerized. The weight average molecular weight of the obtained copolymer was 1,000,000.
合成例１，２および比較合成例１〜４の各共重合体を表１に示す。なお、重量平均分子量は、共重合体をＧＰＣで測定し、得られた測定値をポリスチレン換算した値である。融点は、ＤＳＣを用いて１０℃／分の測定条件で測定した値である。 Table 1 shows the copolymers of Synthesis Examples 1 and 2 and Comparative Synthesis Examples 1 to 4. The weight average molecular weight is a value obtained by measuring the copolymer by GPC and converting the obtained measurement value to polystyrene. The melting point is a value measured using DSC under measurement conditions of 10 ° C./min.
［実施例１，２および比較例１〜４］
＜粘着シートの作製＞
まず、合成例１，２および比較合成例１〜４で得た各共重合体を、酢酸エチルを用いて固形分が３０重量％になるよう調整して共重合体溶液を得た。ついで、この共重合体溶液１００部に対して固形分換算で架橋剤を１部の割合で添加して塗布液を得た。添加した架橋剤は、以下の通りである。
・実施例１，２および比較例１，３，４：アルミニウムトリスアセチルアセトナート（川研ファインケミカル社製）
・比較例２：コロネートＬ（日本ポリウレタン社製）
[Examples 1 and 2 and Comparative Examples 1 to 4]
<Production of adhesive sheet>
First, the copolymers obtained in Synthesis Examples 1 and 2 and Comparative Synthesis Examples 1 to 4 were adjusted so as to have a solid content of 30% by weight using ethyl acetate to obtain copolymer solutions. Subsequently, a crosslinking agent was added at a ratio of 1 part in terms of solid content to 100 parts of this copolymer solution to obtain a coating solution. The added crosslinking agent is as follows.
Examples 1 and 2 and Comparative Examples 1, 3, and 4: Aluminum trisacetylacetonate (manufactured by Kawaken Fine Chemical Co., Ltd.)
Comparative Example 2: Coronate L (Nippon Polyurethane Co., Ltd.)
この塗布液を離型フィルム上に塗布し、１００℃で１０分間加熱して架橋反応させ、厚さ２０μｍの粘着シートを得、この粘着シートの表面に離型フィルムを配置し、これにより両面に離型フィルムが配置された粘着シートを得た。なお、離型フィルムには、ポリエチレンテレフタレートフィルムの表面にシリコーンを塗布した厚さ５０μｍのものを用いた。 This coating solution is applied onto a release film, and heated at 100 ° C. for 10 minutes to cause a crosslinking reaction to obtain a pressure-sensitive adhesive sheet having a thickness of 20 μm. A pressure-sensitive adhesive sheet with a release film was obtained. As the release film, a polyethylene terephthalate film having a thickness of 50 μm coated with silicone was used.
＜評価＞
得られた粘着シートについて、２３０℃耐熱性および５℃剥離強度を評価した。各評価方法を以下に示すとともに、その結果を表２に示す。
<Evaluation>
About the obtained adhesive sheet, 230 degreeC heat resistance and 5 degreeC peeling strength were evaluated. Each evaluation method is shown below, and the results are shown in Table 2.
（２３０℃耐熱性）
まず、両面の離型フィルムを取り外した粘着シートを介して、厚さ３８μｍのポリイミドフィルム（東レデュポン社製の「カプトン１００Ｈ」）と、厚さ０．７ｍｍの無アルカリガラス（コーニングジャパン社製の「Ｃｏｒｎｉｎｇ１７３７」）とを貼着し、試験片を得た。
(230 ° C heat resistance)
First, a 38 μm-thick polyimide film (“Kapton 100H” manufactured by Toray DuPont) and a 0.7 mm-thick alkali-free glass (manufactured by Corning Japan) through an adhesive sheet from which the release films on both sides were removed. “Corning 1737”) was attached to obtain a test piece.
得られた試験片を、２３０℃の雰囲気温度に設定した真空乾燥機内にポリイミドフィルムが上方を向くようにして１時間静置した。その後、真空乾燥機内から試験片を取出し、ポリイミドフィルムが剥離しているか否かを、目視観察して評価した。判定基準は以下のものを用いた。
○：ポリイミドフィルムが剥離しなかった。
×：ポリイミドフィルムが剥離した。
The obtained test piece was allowed to stand for 1 hour in a vacuum dryer set at an ambient temperature of 230 ° C. with the polyimide film facing upward. Then, the test piece was taken out from the inside of the vacuum dryer, and it was visually observed and evaluated whether or not the polyimide film was peeled off. The following criteria were used.
○: The polyimide film did not peel off.
X: The polyimide film peeled off.
（５℃剥離強度）
２３０℃の雰囲気温度を経た後の５℃の雰囲気温度における１８０°剥離強度を、ＪＩＳ Ｚ０２３７に準拠して測定した。具体的には、まず、上述した２３０℃耐熱性を評価した後の試験片を５℃の雰囲気温度に２０分間静置した。ついで、この５℃の雰囲気温度において、ポリイミドフィルムを、ロードセルを用いて３００ｍｍ／分の速度で１８０°剥離した。
(5 ° C peel strength)
A 180 ° peel strength at an ambient temperature of 5 ° C. after passing through an ambient temperature of 230 ° C. was measured according to JIS Z0237. Specifically, first, the test piece after evaluating the 230 ° C. heat resistance described above was allowed to stand at an ambient temperature of 5 ° C. for 20 minutes. Next, at this ambient temperature of 5 ° C., the polyimide film was peeled 180 ° at a rate of 300 mm / min using a load cell.
表２から明らかなように、実施例１，２は、２３０℃耐熱性に優れ、かつ５℃剥離強度も低い値を示しており、易剥離性に優れるのがわかる。これに対し、１３０℃以上の雰囲気温度で各々の有する官能基が互いに反応するモノマー２種を添加していない比較例１，２、重量平均分子量が２０万未満である比較例３、および一般的なアクリル系粘着剤である比較例４はいずれも、２３０℃耐熱性に劣る結果を示した。なお、一般的なアクリル系粘着剤である比較例４は、２３０℃耐熱性の評価において、ポリイミドフィルムが全て剥離してしまい、それゆえ５℃剥離強度を評価することができなかった。 As is apparent from Table 2, Examples 1 and 2 have excellent heat resistance at 230 ° C. and a low 5 ° C. peel strength, indicating that they are excellent in easy peelability. On the other hand, Comparative Examples 1 and 2 in which two types of monomers each having functional groups that react with each other at an ambient temperature of 130 ° C. or higher are not added, Comparative Example 3 in which the weight average molecular weight is less than 200,000, and general Comparative Example 4 which is a clear acrylic pressure-sensitive adhesive showed a result inferior in heat resistance at 230 ° C. In Comparative Example 4, which is a general acrylic pressure-sensitive adhesive, in the evaluation of 230 ° C. heat resistance, all the polyimide films were peeled off, and therefore the 5 ° C. peel strength could not be evaluated.
Claims (9)
前記側鎖結晶性ポリマーが、
１３０℃以上の雰囲気温度で各々の有する官能基が互いに反応するモノマー２種と、
側鎖結晶性ポリマーを構成する他のモノマーと、を少なくとも重合させて得られる、
重量平均分子量２０万〜１００万の共重合体からなることを特徴とする耐熱性感温性粘着剤。 A temperature-sensitive pressure-sensitive adhesive containing a side-chain crystalline polymer, the adhesive strength of which decreases at a temperature below the melting point of the side-chain crystalline polymer,
The side chain crystalline polymer is
Two monomers each having a functional group that reacts with each other at an ambient temperature of 130 ° C. or higher;
Obtained by polymerizing at least another monomer constituting the side chain crystalline polymer,
A heat-resistant temperature-sensitive pressure-sensitive adhesive comprising a copolymer having a weight average molecular weight of 200,000 to 1,000,000.
前記反応が、エステル化反応である請求項１記載の耐熱性感温性粘着剤。 Two types of monomers each having a functional group that reacts with each other at an ambient temperature of 130 ° C. or higher are an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group,
The heat-resistant temperature-sensitive adhesive according to claim 1, wherein the reaction is an esterification reaction.
炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートと、
炭素数１〜６のアルキル基を有する（メタ）アクリレートと、を含む請求項１または２記載の耐熱性感温性粘着剤。 Other monomers constituting the side chain crystalline polymer,
(Meth) acrylate having a linear alkyl group having 16 or more carbon atoms;
The heat-resistant thermosensitive adhesive according to claim 1 or 2, comprising (meth) acrylate having an alkyl group having 1 to 6 carbon atoms.
粘着力を発現させた前記耐熱性感温性粘着テープを介して、可撓性基板を支持体上に固定する工程と、
固定した前記可撓性基板の表面に、薄膜パターンを形成する工程と、
ついで前記耐熱性感温性粘着テープを側鎖結晶性ポリマーの融点未満の温度に冷却して粘着力を低下させ、前記可撓性基板を前記支持体から剥離する工程と、
を含むことを特徴とする平板表示装置の製造方法。 A method for producing a flat panel display device using a heat-resistant temperature-sensitive adhesive tape provided with the heat-sensitive temperature-sensitive pressure-sensitive adhesive layer according to claim 1 on both surfaces of a base film. There,
A step of fixing a flexible substrate on a support through the heat-resistant and temperature-sensitive adhesive tape that expresses adhesive force;
Forming a thin film pattern on the surface of the fixed flexible substrate;
Next, cooling the heat-resistant temperature-sensitive adhesive tape to a temperature below the melting point of the side chain crystalline polymer to reduce the adhesive force, and peeling the flexible substrate from the support;
A method for manufacturing a flat panel display device.
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| JP2021155645A (en) * | 2020-03-30 | 2021-10-07 | 大成ファインケミカル株式会社 | Biomass (meth)acryl copolymer, coating agent and ink composition comprising the same, and method for producing the same |
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| JP2021155645A (en) * | 2020-03-30 | 2021-10-07 | 大成ファインケミカル株式会社 | Biomass (meth)acryl copolymer, coating agent and ink composition comprising the same, and method for producing the same |
| JP7204216B2 (en) | 2020-03-30 | 2023-01-16 | 大成ファインケミカル株式会社 | Biomass (meth)acrylic copolymer, coating agent and ink composition containing the same, and method for producing the same |
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