JP2015187238A - Temperature-sensitive adhesive - Google Patents
Temperature-sensitive adhesive Download PDFInfo
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- JP2015187238A JP2015187238A JP2014065474A JP2014065474A JP2015187238A JP 2015187238 A JP2015187238 A JP 2015187238A JP 2014065474 A JP2014065474 A JP 2014065474A JP 2014065474 A JP2014065474 A JP 2014065474A JP 2015187238 A JP2015187238 A JP 2015187238A
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- temperature
- sensitive adhesive
- crystalline polymer
- chain crystalline
- side chain
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- 239000000853 adhesive Substances 0.000 title claims abstract description 81
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 81
- 229920000642 polymer Polymers 0.000 claims abstract description 62
- 238000002844 melting Methods 0.000 claims abstract description 29
- 230000008018 melting Effects 0.000 claims abstract description 29
- 230000007423 decrease Effects 0.000 claims abstract description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 29
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 29
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 29
- 239000002390 adhesive tape Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 150000002222 fluorine compounds Chemical class 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 13
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 9
- 239000013522 chelant Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 19
- -1 acryl group Chemical group 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 238000000034 method Methods 0.000 description 8
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- 239000012790 adhesive layer Substances 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
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- 239000011347 resin Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
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- 229910052782 aluminium Inorganic materials 0.000 description 3
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 229920002223 polystyrene Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 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
- 239000012298 atmosphere Substances 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
- 238000012662 bulk polymerization Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-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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- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 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
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Abstract
Description
本発明は、感温性粘着剤に関する。 The present invention relates to a temperature-sensitive adhesive.
フラットパネルディスプレイ（ＦＰＤ）等の製造工程において、ガラス、プラスチック等からなる基板の仮固定に、粘着シートや粘着テープ等が用いられている。このような用途に使用される粘着テープ等には、一度貼り付けた粘着テープを再剥離するうえで、易剥離性が要求される。 In a manufacturing process of a flat panel display (FPD) or the like, an adhesive sheet, an adhesive tape, or the like is used for temporarily fixing a substrate made of glass, plastic, or the like. The adhesive tape used for such applications is required to be easily peelable when the adhesive tape once applied is re-peeled.
本出願人は、仮固定に好適な粘着テープとして、先に特許文献１に記載の感温性粘着テープを開発した。感温性粘着テープは、粘着剤層が側鎖結晶性ポリマーを含有しており、側鎖結晶性ポリマーの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。 The present applicant has previously developed the temperature-sensitive adhesive tape described in Patent Document 1 as an adhesive tape suitable for temporary fixing. The temperature-sensitive adhesive tape contains a side-chain crystalline polymer in the pressure-sensitive adhesive layer, and when cooled to a temperature below the melting point of the side-chain crystalline polymer, the side-chain crystalline polymer is crystallized to cause adhesive strength. Decreases.
しかし、特許文献１に記載のような従来の感温性粘着テープを使用しても、剥離時に基板を破損することがあった。このような場合において、基板を破損することなく剥離するには、室温（２３℃）よりも低い温度（例えば、５℃）にまで冷却する必要があった。そのため、従来の感温性粘着テープには、室温よりも低い温度に冷却するプロセスが必要となり、その結果、設備や環境が必要となり、それに伴ってコストが高くなる場合があった。この問題は、感温性粘着テープとともに１００℃以上の高温雰囲気下に曝された基板から感温性粘着テープを剥離する場合に顕著であった。 However, even when a conventional temperature-sensitive adhesive tape as described in Patent Document 1 is used, the substrate may be damaged during peeling. In such a case, in order to peel without damaging the substrate, it was necessary to cool to a temperature lower than room temperature (23 ° C.) (for example, 5 ° C.). Therefore, the conventional temperature-sensitive adhesive tape requires a process of cooling to a temperature lower than room temperature. As a result, equipment and environment are required, and the cost may be increased accordingly. This problem was significant when the temperature-sensitive adhesive tape was peeled from the substrate exposed to a high-temperature atmosphere of 100 ° C. or more together with the temperature-sensitive adhesive tape.
本発明の課題は、剥離性に優れる感温性粘着剤を提供することである。 The subject of this invention is providing the temperature sensitive adhesive which is excellent in peelability.
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）粘着付与剤および側鎖結晶性ポリマーを含有し、前記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、前記粘着付与剤は、軟化点が１４０℃以上であり、かつ含有量が側鎖結晶性ポリマー１００重量部に対して４０〜１００重量部である、感温性粘着剤。
（２）前記融点が、２４℃以上である、前記（１）に記載の感温性粘着剤。
（３）前記粘着付与剤が、重合ロジンエステルである、前記（１）または（２）に記載の感温性粘着剤。
（４）前記側鎖結晶性ポリマーが、反応性フッ素化合物と、側鎖結晶性ポリマーを構成する他のモノマーとの共重合体からなる、前記（１）〜（３）のいずれかに記載の感温性粘着剤。
（５）前記反応性フッ素化合物が、下記一般式（Ｉ）で表される化合物である、前記（４）に記載の感温性粘着剤。
（６）金属キレート化合物をさらに含有する、前記（１）〜（５）のいずれかに記載の感温性粘着剤。
（７）貼着した被着体を、１００〜２２０℃の温度に曝した後、前記融点未満の温度で取り外す、前記（１）〜（６）のいずれかに記載の感温性粘着剤。
（８）前記（１）〜（７）のいずれかに記載の感温性粘着剤からなる、感温性粘着シート。
（９）前記（１）〜（７）のいずれかに記載の感温性粘着剤からなる粘着剤層を、フィルム状の基材の片面または両面に積層してなる、感温性粘着テープ。
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 tackifier and a side chain crystalline polymer and having reduced adhesive strength at a temperature lower than the melting point of the side chain crystalline polymer, the tackifier having a softening point Is a temperature-sensitive pressure-sensitive adhesive having a temperature of 140 ° C. or higher and a content of 40 to 100 parts by weight with respect to 100 parts by weight of the side chain crystalline polymer.
(2) The temperature-sensitive adhesive according to (1), wherein the melting point is 24 ° C. or higher.
(3) The temperature-sensitive adhesive according to (1) or (2), wherein the tackifier is a polymerized rosin ester.
(4) The side chain crystalline polymer is a copolymer of a reactive fluorine compound and another monomer constituting the side chain crystalline polymer, according to any one of (1) to (3). Temperature sensitive adhesive.
(5) The temperature-sensitive adhesive according to (4), wherein the reactive fluorine compound is a compound represented by the following general formula (I).
(6) The temperature-sensitive adhesive according to any one of (1) to (5), further including a metal chelate compound.
(7) The temperature-sensitive adhesive according to any one of (1) to (6), wherein the adhered adherend is exposed to a temperature of 100 to 220 ° C. and then removed at a temperature lower than the melting point.
(8) A temperature-sensitive adhesive sheet comprising the temperature-sensitive adhesive according to any one of (1) to (7).
(9) A temperature-sensitive adhesive tape obtained by laminating an adhesive layer comprising the temperature-sensitive adhesive according to any one of (1) to (7) on one side or both sides of a film-like substrate.
本発明によれば、剥離性に優れるという効果がある。 According to the present invention, there is an effect of excellent peelability.
〔感温性粘着剤〕
以下、本発明の一実施形態に係る感温性粘着剤について詳細に説明する。本実施形態の感温性粘着剤は、側鎖結晶性ポリマーを含有し、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。
[Temperature sensitive adhesive]
Hereinafter, the temperature-sensitive adhesive according to an embodiment of the present invention will be described in detail. The temperature-sensitive adhesive of this embodiment contains a side chain crystalline polymer, and the adhesive strength is reduced at a temperature below the melting point of the side chain crystalline polymer.
（側鎖結晶性ポリマー）
側鎖結晶性ポリマーは、融点を有するポリマーであり、この融点未満の温度で結晶化し、かつ融点以上の温度では相転位して流動性を示す。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感温性を有する。これにより、温度変化に対応して粘着−非粘着を可逆的に起こす物性を感温性粘着剤に付与することができる。
(Side-chain crystalline polymer)
The side chain crystalline polymer is a polymer having a melting point, crystallizes at a temperature lower than the melting point, and undergoes phase transition at a temperature higher than the melting point to exhibit fluidity. That is, the side chain crystalline polymer has temperature sensitivity that reversibly causes a crystalline state and a fluid state in response to a temperature change. Thereby, the physical property which raise | generates adhesion-non-adhesion reversibly corresponding to a temperature change can be provided to a thermosensitive adhesive.
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になる温度であり、示差熱走査熱量計（ＤＳＣ）によって１０℃／分の測定条件で測定して得られる値のことを意味するものとする。 The melting point is a temperature at which a specific portion of the polymer that was initially aligned in an ordered arrangement becomes disordered by an equilibrium process, and is measured at 10 ° C./min by a differential thermal scanning calorimeter (DSC). It shall mean the value obtained by measurement.
本実施形態の感温性粘着剤は、融点未満の温度で側鎖結晶性ポリマーが結晶化したとき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、本実施形態の感温性粘着剤は、側鎖結晶性ポリマーを主成分として含有していることから、被着体から感温性粘着剤を剥離するときには、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。また、感温性粘着剤を側鎖結晶性ポリマーの融点以上の温度に加熱すれば、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回復するので、繰り返し使用することができる。 The temperature-sensitive adhesive of this embodiment contains a side-chain crystalline polymer in such a ratio that the adhesive strength decreases when the side-chain crystalline polymer is crystallized at a temperature below the melting point. That is, since the temperature-sensitive adhesive of this embodiment contains a side-chain crystalline polymer as a main component, when peeling the temperature-sensitive adhesive from the adherend, the temperature-sensitive adhesive is on the side. If it is cooled to a temperature lower than the melting point of the chain crystalline polymer, the side chain crystalline polymer is crystallized to reduce the adhesive strength. In addition, if the temperature-sensitive adhesive is heated to a temperature equal to or higher than the melting point of the side chain crystalline polymer, the adhesive strength is restored by the fluidity of the side chain crystalline polymer, so that it can be used repeatedly.
側鎖結晶性ポリマーの融点は、２４℃以上であるのが好ましく、２５℃以上であるのがより好ましく、２６℃以上であるのがさらに好ましい。これにより、室温（２３℃）で、側鎖結晶性ポリマーが結晶化するので、室温剥離が可能になる。融点の上限値としては、６０℃であるのが好ましい。融点は、側鎖結晶性ポリマーの組成等を変えることによって調整することができる。 The melting point of the side chain crystalline polymer is preferably 24 ° C. or higher, more preferably 25 ° C. or higher, and even more preferably 26 ° C. or higher. As a result, the side chain crystalline polymer crystallizes at room temperature (23 ° C.), and thus room temperature peeling becomes possible. The upper limit of the melting point is preferably 60 ° C. The melting point can be adjusted by changing the composition of the side chain crystalline polymer.
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感温性を有する重合体であれば特に限定されるものではないが、反応性フッ素化合物と、側鎖結晶性ポリマーを構成する他のモノマーとの共重合体からなるのが好ましい。これにより、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る粘着力の低下に加えて、フッ素化合物に起因する離型性も加わるので、粘着力を十分に低下させることができ、被着体から容易に剥離することができる。 The side chain crystalline polymer is not particularly limited as long as it is a polymer having a temperature sensitivity that reversibly causes a crystalline state and a fluidized state in response to a temperature change. It preferably consists of a copolymer with other monomers constituting the chain crystalline polymer. As a result, if the temperature-sensitive adhesive is cooled to a temperature lower than the melting point of the side chain crystalline polymer, in addition to the decrease in adhesive force due to crystallization of the side chain crystalline polymer, the mold release caused by the fluorine compound Since adhesiveness is also added, the adhesive force can be sufficiently reduced and can be easily peeled off from the adherend.
反応性フッ素化合物とは、反応性を示す官能基を有するフッ素化合物のことを意味するものとする。反応性を示す官能基としては、例えば、ビニル基、アリル基、（メタ）アクリル基、（メタ）アクリロイル基、（メタ）アクリロキシ基等のエチレン性不飽和二重結合を有する基；エポキシ基（グリシジル基およびエポキシシクロアルキル基を含む）；メルカプト基；カルビノール基；カルボキシル基；シラノール基；フェノール基；アミノ基；水酸基等が挙げられる。 The reactive fluorine compound means a fluorine compound having a reactive functional group. Examples of reactive functional groups include groups having an ethylenically unsaturated double bond such as vinyl group, allyl group, (meth) acryl group, (meth) acryloyl group, (meth) acryloxy group; epoxy group ( A glycidyl group and an epoxycycloalkyl group); a mercapto group; a carbinol group; a carboxyl group; a silanol group; a phenol group; an amino group;
反応性フッ素化合物の具体例としては、上述した一般式（Ｉ）で表される化合物等が挙げられる。一般式（Ｉ）中、Ｒ1は基：ＣＨ2＝ＣＨＣＯＯＲ2−またはＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＲ2−（式中、Ｒ2はアルキレン基を示す。）を示す。アルキレン基としては、例えば、メチレン基、エチレン基、トリメチレン基、メチルエチレン基、プロピレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基等の炭素数１〜６の直鎖または分枝したアルキレン基等が挙げられる。 Specific examples of the reactive fluorine compound include compounds represented by the general formula (I) described above. In the general formula (I), R 1 represents a group: CH 2 ═CHCOOR 2 — or CH 2 ═C (CH 3 ) COOR 2 — (wherein R 2 represents an alkylene group). Examples of the alkylene group include straight-chain or branched alkylene groups having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a propylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Etc.
一般式（Ｉ）で表される化合物の具体例としては、下記式（Ｉａ），（Ｉｂ）で表される化合物等が挙げられる。
反応性フッ素化合物は、市販のものを用いることができる。市販の反応性フッ素化合物としては、例えば、いずれも大阪有機化学工業（株）製の「ビスコート３Ｆ」、「ビスコート３ＦＭ」、「ビスコート４Ｆ」、「ビスコート８Ｆ」、「ビスコート８ＦＭ」、共栄社化学（株）製の「ライトエステルＭ−３Ｆ」等が挙げられる。 Commercially available fluorine compounds can be used. Examples of commercially available reactive fluorine compounds include “Biscoat 3F”, “Biscoat 3FM”, “Biscoat 4F”, “Biscoat 8F”, “Biscoat 8FM” manufactured by Osaka Organic Chemical Industry Co., Ltd., Kyoeisha Chemical ( "Light Ester M-3F" manufactured by Co., Ltd.
一方、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、極性モノマー等が挙げられる。 On the other hand, as other monomers constituting the side chain crystalline polymer, for example, (meth) acrylate having a linear alkyl group having 16 or more carbon atoms, (meth) acrylate having an alkyl group having 1 to 6 carbon atoms, polarity And monomers.
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る。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る。極性モノマーとしては、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、フマル酸等のカルボキシル基含有エチレン不飽和単量体；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）アクリレート等のヒドロキシル基を有するエチレン不飽和単量体等が挙げられる。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 16 carbon atoms such as cetyl (meth) acrylate, stearyl (meth) acrylate, eicosyl (meth) acrylate, and behenyl (meth) acrylate. Examples include (meth) acrylates having 22 linear alkyl groups. 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. Examples of polar monomers include carboxyl group-containing ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta And ethylenically unsaturated monomers having a hydroxyl group such as acrylate and 2-hydroxyhexyl (meth) acrylate. You may use these 1 type or in mixture of 2 or more types.
側鎖結晶性ポリマーの組成は、反応性フッ素化合物と、側鎖結晶性ポリマーを構成する他のモノマーとを、重量比で１：９９〜２０：８０、好ましくは１：９９〜１０：９０の割合で重合させた共重合体がよい。 The composition of the side chain crystalline polymer is such that the reactive fluorine compound and the other monomer constituting the side chain crystalline polymer are in a weight ratio of 1:99 to 20:80, preferably 1:99 to 10:90. A copolymer polymerized in proportion is preferred.
また、側鎖結晶性ポリマーの組成は、反応性フッ素化合物を１〜２０重量部、好ましくは１〜１０重量部、炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートを１０〜９９重量部、好ましくは２０〜９９重量部、炭素数１〜６のアルキル基を有する（メタ）アクリレートを０〜７０重量部、および極性モノマーを０〜１０重量部の割合で重合させた共重合体が好ましく、反応性フッ素化合物を１〜１０重量部、炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートを２５〜３０重量部、炭素数１〜６のアルキル基を有する（メタ）アクリレートを６０〜６５重量部、および極性モノマーを１〜１０重量部の割合で重合させた共重合体がより好ましい。 The composition of the side chain crystalline polymer is 1 to 20 parts by weight, preferably 1 to 10 parts by weight of the reactive fluorine compound, and 10 to 99 (meth) acrylate having a linear alkyl group having 16 or more carbon atoms. A copolymer obtained by polymerizing a part by weight, preferably 20 to 99 parts by weight, 0 to 70 parts by weight of a (meth) acrylate having an alkyl group having 1 to 6 carbon atoms, and 0 to 10 parts by weight of a polar monomer. 1 to 10 parts by weight of a reactive fluorine compound, 25 to 30 parts by weight of a (meth) acrylate having a linear alkyl group having 16 or more carbon atoms, and an alkyl group having 1 to 6 carbon atoms (meth) A copolymer obtained by polymerizing 60 to 65 parts by weight of acrylate and 1 to 10 parts by weight of a polar monomer is more preferable.
側鎖結晶性ポリマーの重量平均分子量は１００，０００以上、好ましくは３００，０００〜９００，０００であるのがよい。重量平均分子量があまり小さいと、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、重量平均分子量があまり大きいと、側鎖結晶性ポリマーを融点未満の温度にしても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、側鎖結晶性ポリマー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 side chain crystalline polymer is 100,000 or more, preferably 300,000 to 900,000. When the weight average molecular weight is too small, there is a possibility that so-called adhesive residue that the temperature-sensitive adhesive remains on the adherend when the temperature-sensitive adhesive is peeled from the adherend increases. On the other hand, if the weight average molecular weight is too large, it is difficult to crystallize even if the side chain crystalline polymer is at a temperature lower than the melting point. The weight average molecular weight is a value obtained by measuring the side chain crystalline polymer by gel permeation chromatography (GPC) and converting the obtained measurement value to polystyrene.
（粘着付与剤）
本実施形態の感温性粘着剤は、上述した側鎖結晶性ポリマーに加えて、粘着付与剤をさらに含有する。本実施形態の粘着付与剤は、軟化点が１４０℃以上、好ましくは１５０℃以上である。軟化点の上限値は、特に限定されないが、あまり高軟化点の粘着付与剤は調製困難であることから、通常、１７０℃以下、好ましくは１６５℃以下である。軟化点は、ＪＩＳ Ｋ ５９０２に規定される環球法に従って測定される値である。
(Tackifier)
The temperature-sensitive adhesive of this embodiment further contains a tackifier in addition to the above-described side chain crystalline polymer. The tackifier of this embodiment has a softening point of 140 ° C or higher, preferably 150 ° C or higher. The upper limit of the softening point is not particularly limited, but it is usually 170 ° C. or lower, preferably 165 ° C. or lower because a tackifier having a high softening point is difficult to prepare. The softening point is a value measured according to the ring and ball method defined in JIS K 5902.
本実施形態では、上述した粘着付与剤を、側鎖結晶性ポリマー１００重量部に対して、４０〜１００重量部、好ましくは５０〜１００重量部の割合で含有する。このような高い割合で軟化点１４０℃以上という高軟化点の粘着付与剤を含有すると、被着体を固定するのに必要な粘着性を維持しつつ感温性粘着剤中の側鎖結晶性ポリマーの割合を適度に少なくでき、それゆえ融点未満の温度において粘着力が十分に低下するようになり、結果として剥離性が向上する。つまり、本実施形態によれば、側鎖結晶性ポリマーの組成を変更することなく、高軟化点の粘着付与剤を特定の割合で含有させることによって簡単に剥離性を向上させることができる。したがって、例えば側鎖結晶性ポリマーの融点を２４℃以上にすれば、室温（２３℃）よりも低い温度（例えば、５℃）にまで冷却することなく、室温で確実に剥離することが可能になる。また、本実施形態の感温性粘着剤は、剥離性に優れることから、貼着した被着体を１００〜２２０℃の温度に曝したとしても、融点未満の温度に冷却すれば、スムーズに被着体を取り外すことができる。 In this embodiment, the tackifier mentioned above is contained in a proportion of 40 to 100 parts by weight, preferably 50 to 100 parts by weight, with respect to 100 parts by weight of the side chain crystalline polymer. When the tackifier having a high softening point of 140 ° C. or higher is contained at such a high ratio, the side chain crystallinity in the temperature-sensitive adhesive is maintained while maintaining the adhesiveness necessary for fixing the adherend. The proportion of the polymer can be appropriately reduced, and therefore the adhesive strength is sufficiently lowered at a temperature below the melting point, and as a result, the peelability is improved. That is, according to the present embodiment, the releasability can be easily improved by containing a high softening point tackifier at a specific ratio without changing the composition of the side chain crystalline polymer. Therefore, for example, if the melting point of the side chain crystalline polymer is 24 ° C. or higher, it is possible to reliably peel at room temperature without cooling to a temperature lower than room temperature (23 ° C.) (for example, 5 ° C.). Become. Moreover, since the temperature sensitive adhesive of this embodiment is excellent in peelability, even if the adhered adherend is exposed to a temperature of 100 to 220 ° C., if it is cooled to a temperature lower than the melting point, it will be smooth. The adherend can be removed.
粘着付与剤の組成は、軟化点が１４０℃以上である限り、特に限定されないが、例えばロジン系樹脂、テルペン系樹脂、炭化水素系樹脂、エポキシ系樹脂、ポリアミド系樹脂、フェノール系樹脂、ケトン系樹脂等が挙げられ、これらは１種または２種以上を混合して用いてもよい。例示したこれらの粘着付与剤のうち、上述した側鎖結晶性ポリマーとの相溶性に優れる上で、ロジン系樹脂が好ましい。 The composition of the tackifier is not particularly limited as long as the softening point is 140 ° C. or higher. For example, rosin resin, terpene resin, hydrocarbon resin, epoxy resin, polyamide resin, phenol resin, and ketone resin Examples thereof include resins, and these may be used alone or in combination of two or more. Among these exemplified tackifiers, a rosin resin is preferable in terms of excellent compatibility with the above-described side chain crystalline polymer.
ロジン系樹脂としては、例えばロジン誘導体等が挙げられる。ロジン誘導体としては、例えばガムロジン、ウッドロジン、トール油ロジン等の未変性ロジン（生ロジン）をアルコール類によりエステル化したロジンのエステル化合物や、水添ロジン、不均化ロジン、重合ロジン等の変性ロジンをアルコール類によりエステル化した変性ロジンのエステル化合物等のロジンエステル類；未変性ロジン、変性ロジンや、各種ロジン誘導体等のロジン類の金属塩；未変性ロジン、変性ロジンや、各種ロジン誘導体等にフェノールを酸触媒で付加させて熱重合することにより得られるロジンフェノール樹脂等が挙げられる。 Examples of the rosin resin include rosin derivatives. Examples of rosin derivatives include rosin ester compounds obtained by esterifying unmodified rosin (raw rosin) such as gum rosin, wood rosin and tall oil rosin with alcohols, and modified rosins such as hydrogenated rosin, disproportionated rosin and polymerized rosin. Rosin esters, such as ester compounds of modified rosin esterified with alcohols; metal salts of rosins such as unmodified rosin, modified rosin, and various rosin derivatives; unmodified rosin, modified rosin, various rosin derivatives, etc. Examples thereof include rosin phenol resins obtained by adding phenol with an acid catalyst and performing thermal polymerization.
例示したこれらのロジン誘導体のうち、重合ロジンエステルが特に好ましい。重合ロジンエステルは、市販のものを用いることができる。具体例としては、例えば荒川化学工業（株）製の「ペンセルＤ−１６０」等が挙げられる。 Among these exemplified rosin derivatives, a polymerized rosin ester is particularly preferable. A commercially available polymerized rosin ester can be used. Specific examples include “Pencel D-160” manufactured by Arakawa Chemical Industries, Ltd.
（架橋剤）
感温性粘着剤は、架橋剤を含有するのが好ましい。架橋剤としては、例えば金属キレート化合物、アジリジン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。架橋剤として金属キレート化合物を採用すると、感温性粘着剤の耐熱性が向上する傾向にある。
(Crosslinking agent)
The temperature-sensitive adhesive preferably contains a crosslinking agent. Examples of the crosslinking agent include metal chelate compounds and aziridine compounds, and metal chelate compounds are particularly preferable. When a metal chelate compound is employed as the cross-linking agent, the heat resistance of the temperature-sensitive adhesive tends to be 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る。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る。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 metal chelate compounds include acetylacetone coordination compounds and acetoacetate coordination compounds of polyvalent metals. Examples of the polyvalent metal include aluminum, nickel, chromium, iron, titanium, zinc, cobalt, manganese, and zirconium. You may use these 1 type or in mixture of 2 or more types. Of these exemplified metal chelate compounds, aluminum acetylacetone coordination compounds or acetoacetate coordination compounds are preferred, and aluminum trisacetylacetonate is preferred.
架橋剤の含有量は、特に限定されず、側鎖結晶性ポリマー１００重量部に対して０．１〜１０重量部程度である。 Content of a crosslinking agent is not specifically limited, About 0.1-10 weight part with respect to 100 weight part of side chain crystalline polymers.
（添加剤）
感温性粘着剤は、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含有していてもよい。
(Additive)
The temperature-sensitive adhesive may contain various additives such as a plasticizer, an anti-aging agent, and an ultraviolet absorber.
〔感温性粘着剤の製造方法〕
感温性粘着剤の製造方法としては、特に限定されず、例えば、側鎖結晶性ポリマーを構成するモノマーを重合して得られた側鎖結晶性ポリマーと、溶剤とを混合した共重合体溶液に、粘着付与剤を添加して塗布液を得、この塗布液を乾燥させる方法などが挙げられる。
[Method for producing temperature-sensitive adhesive]
The method for producing the temperature-sensitive adhesive is not particularly limited. For example, a copolymer solution in which a side chain crystalline polymer obtained by polymerizing a monomer constituting the side chain crystalline polymer and a solvent is mixed. And a method of adding a tackifier to obtain a coating solution and drying the coating solution.
側鎖結晶性ポリマーの重合方法としては、特に限定されず、例えば溶液重合法、塊状重合法、懸濁重合法、乳化重合法等が採用可能である。例えば溶液重合法を採用する場合には、側鎖結晶性ポリマーを構成する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。溶剤としては、公知のものを用いることができる。感温性粘着剤に架橋剤や添加剤を含有させる場合、架橋剤や添加剤を共重合体溶液に添加すればよい。 The polymerization method of the side chain crystalline polymer is not particularly limited, and for example, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method and the like can be employed. For example, when the solution polymerization method is employed, the above-described monomers constituting the side chain crystalline polymer may be mixed in a solvent and stirred at about 40 to 90 ° C. for about 2 to 10 hours. A well-known thing can be used as a solvent. When the crosslinking agent or additive is contained in the temperature-sensitive adhesive, the crosslinking agent or additive may be added to the copolymer solution.
〔感温性粘着シート〕
感温性粘着シートは、上述した感温性粘着剤のみからなり、基材レスのシート状の形態である。感温性粘着シートの厚さは、特に限定されず、好ましくは１５〜４００μｍである。感温性粘着シートの表面には、離型フィルムを積層するのが好ましい。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等が挙げられる。
[Temperature sensitive adhesive sheet]
A temperature-sensitive adhesive sheet consists only of the above-mentioned temperature-sensitive adhesive, and is a base-less sheet-like form. The thickness of the temperature-sensitive adhesive sheet is not particularly limited, and is preferably 15 to 400 μm. A release film is preferably laminated on the surface of the temperature-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 polyethylene terephthalate or the like.
〔感温性粘着テープ〕
感温性粘着テープは、上述した感温性粘着剤からなる粘着剤層を、フィルム状の基材の片面または両面に積層してなる。すなわち、感温性粘着テープの構成は、フィルム状の基材と、この基材の片面に積層された粘着剤層とからなる２層構成；またはフィルム状の基材と、この基材の両面にそれぞれ積層された粘着剤層とからなる３層構成である。フィルム状とは、フィルム状のみに限定されるものではなく、本実施形態の効果を損なわない限りにおいて、フィルム状ないしシート状をも含む概念である。
[Temperature sensitive adhesive tape]
The temperature-sensitive adhesive tape is formed by laminating an adhesive layer composed of the above-described temperature-sensitive adhesive on one or both surfaces of a film-like substrate. That is, the structure of the temperature-sensitive adhesive tape is a two-layer structure comprising a film-like substrate and an adhesive layer laminated on one surface of the substrate; or a film-like substrate and both surfaces of the substrate. It is the 3 layer structure which consists of an adhesive layer each laminated | stacked. The film shape is not limited to a film shape, and is a concept including a film shape or a sheet shape as long as the effects of the present embodiment are not impaired.
基材の構成材料としては、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が挙げられる。 Examples of the constituent material of the base material include polyethylene, polyethylene terephthalate, polypropylene, polyester, polyamide, polyimide, polycarbonate, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene polypropylene copolymer, and polyvinyl chloride. Resin.
基材は、単層体または複層体のいずれであってもよく、その厚さは、通常、５〜５００μｍ程度である。基材には、粘着剤層に対する密着性を高める上で、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されていてもよい。 The substrate may be either a single layer or a multilayer and its thickness is usually about 5 to 500 μm. The base material may be subjected to surface treatment such as corona discharge treatment, plasma treatment, blast treatment, chemical etching treatment, primer treatment, etc. in order to improve the adhesion to the pressure-sensitive adhesive layer.
基材の片面または両面に粘着剤層を設けるには、例えば、上述した塗布液を、コーター等によって基材の片面または両面に塗布して乾燥させればよい。コーターとしては、例えばナイフコーター、ロールコーター、カレンダーコーター、コンマコーター、グラビアコーター、ロッドコーター等が挙げられる。 In order to provide the pressure-sensitive adhesive layer on one side or both sides of the substrate, for example, the above-described coating solution may be applied to one side or both sides of the substrate with a coater or the like and dried. Examples of the coater include a knife coater, a roll coater, a calendar coater, a comma coater, a gravure coater, and a rod coater.
粘着剤層の厚さは、特に限定されず、好ましくは５〜６０μｍ、より好ましくは１０〜６０μｍ、さらに好ましくは１０〜５０μｍである。 The thickness of an adhesive layer is not specifically limited, Preferably it is 5-60 micrometers, More preferably, it is 10-60 micrometers, More preferably, it is 10-50 micrometers.
感温性粘着テープが３層構成である場合、片面の粘着剤層と、他面の粘着剤層とは、厚さ、組成は、同じであってもよいし、異なっていてもよい。 When the temperature-sensitive adhesive tape has a three-layer structure, the thickness and composition of the adhesive layer on one side and the adhesive layer on the other side may be the same or different.
他面の粘着剤層を、例えば感圧性接着剤からなる粘着剤層で構成することもできる。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、アクリル系接着剤等が挙げられる。 The pressure-sensitive adhesive layer on the other side can also be constituted by a pressure-sensitive adhesive layer made of, for example, a pressure-sensitive adhesive. The pressure-sensitive adhesive is a polymer having tackiness, and examples thereof include natural rubber adhesives, synthetic rubber adhesives, styrene / butadiene latex base adhesives, and acrylic adhesives.
感温性粘着テープの表面には、離型フィルムを積層するのが好ましい。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等が挙げられる。 A release film is preferably laminated on the surface of the temperature-sensitive adhesive tape. Examples of the release film include those obtained by applying a release agent such as silicone to the surface of a film made of polyethylene terephthalate or the like.
上述した感温性粘着剤の用途としては、易剥離性が要求される分野の粘着剤として好適に使用することができる。具体的には、感温性粘着剤は、ＦＰＤの製造工程におけるプラスチック基板の仮固定用として好適に使用することができる。被着体としては、特に限定されないが、ＬＥＤやＦＰＤ等における大型化および薄型化されたガラス、プラスチック等からなる基板が好適である。 As a use of the above-mentioned temperature-sensitive adhesive, it can be suitably used as an adhesive in a field where easy peelability is required. Specifically, the temperature-sensitive adhesive can be suitably used for temporarily fixing a plastic substrate in the FPD manufacturing process. Although it does not specifically limit as a to-be-adhered body, The board | substrate which consists of glass, a plastics, etc. which were enlarged and thinned in LED, FPD, etc. is suitable.
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）
ステアリルアクリレートを２８部、メチルアクリレートを６２部、アクリル酸を５部、および反応性フッ素化合物（上述した式（Ｉａ）で表される大阪有機化学工業（株）製の「ビスコート３Ｆ」）を５部の割合で、それぞれ酢酸エチル：トルエン＝８：２（重量比）の混合溶媒２００部に加えて混合し、５５℃で４時間撹拌して、これらのモノマーを重合させた。得られた共重合体である側鎖結晶性ポリマーの重量平均分子量は５２５，０００、融点は２６℃であった。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。
(Synthesis example)
28 parts of stearyl acrylate, 62 parts of methyl acrylate, 5 parts of acrylic acid, and 5 reactive fluorine compounds ("Biscoat 3F" manufactured by Osaka Organic Chemical Industry Co., Ltd. represented by the formula (Ia) described above) In a proportion of 200 parts, each was added to and mixed with 200 parts of a mixed solvent of ethyl acetate: toluene = 8: 2 (weight ratio) and stirred at 55 ° C. for 4 hours to polymerize these monomers. The obtained side chain crystalline polymer, which was a copolymer, had a weight average molecular weight of 525,000 and a melting point of 26 ° C. 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１〜４および比較例１〜３］
＜感温性粘着シートの作製＞
まず、合成例で得た共重合体を、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粘着付与剤（荒川化学工業（株）製の軟化点１５０℃以上の重合ロジンエステル「ペンセルＤ−１６０」）を表１に示す割合で添加し、さらに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）を１０部の割合で添加して塗布液を得た。
[Examples 1-4 and Comparative Examples 1-3]
<Preparation of temperature-sensitive adhesive sheet>
First, the copolymer obtained in the synthesis example was adjusted using ethyl acetate so that the solid content was 30% by weight to obtain a copolymer solution. Subsequently, the ratio shown in Table 1 is a tackifier (polymerized rosin ester “Pencel D-160” having a softening point of 150 ° C. or higher manufactured by Arakawa Chemical Industries, Ltd.) in terms of solid content with respect to 100 parts of this copolymer solution. Further, aluminum trisacetylacetonate (manufactured by Kawaken Fine Chemical Co., Ltd.) was added at a ratio of 10 parts to obtain a coating solution.
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、感温性粘着剤からなる厚さ２５μｍの感温性粘着シートを得た。なお、離型フィルムは、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５０μのものを用いた。 This coating solution was applied onto a release film and heated at 100 ° C. for 10 minutes to cause a crosslinking reaction, thereby obtaining a thermosensitive adhesive sheet having a thickness of 25 μm made of a thermosensitive adhesive. The release film used was a polyethylene terephthalate film having a thickness of 50 μm obtained by applying silicone.
＜評価＞
得られた感温性粘着シートについて、１８０°剥離強度を評価した。評価方法を以下に示すとともに、その結果を表１に示す。
<Evaluation>
About the obtained temperature sensitive adhesive sheet, 180 degree peeling strength was evaluated. The evaluation method is shown below, and the results are shown in Table 1.
（１８０°剥離強度）
得られた感温性粘着シートについて、５０℃および２３℃の各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、離型フィルムを取り外した感温性粘着シートを介して、幅２５ｍｍ、厚さ２５μｍのポリイミドフィルム（東レ・デュポン社製の「１００Ｈ」）を以下の条件でガラス製の台座上に貼着した。ついで、貼着した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。
(180 ° peel strength)
About the obtained temperature sensitive adhesive sheet, 180 degree peel strength in each atmospheric temperature of 50 degreeC and 23 degreeC was measured based on JISZ0237. Specifically, first, a polyimide film having a width of 25 mm and a thickness of 25 μm (“100H” manufactured by Toray DuPont) is made of glass under the following conditions through a temperature-sensitive adhesive sheet from which a release film is removed. Sticked on the pedestal. Next, the adhered polyimide film was peeled 180 ° at a rate of 300 mm / min using a load cell.
（５０℃）
５０℃の雰囲気温度で感温性粘着シートを介してポリイミドフィルムを台座に貼着して２０分間静置した後、１８０°剥離し、剥離強度を測定した。剥離強度の測定値から貼付性を以下の基準で評価した。
○：０．０５Ｎ／２５ｍｍ以上
×：０．０５Ｎ／２５ｍｍ未満
(50 ° C)
A polyimide film was attached to a pedestal via a temperature-sensitive adhesive sheet at an ambient temperature of 50 ° C., and allowed to stand for 20 minutes, then peeled 180 °, and the peel strength was measured. From the measured peel strength, the pastability was evaluated according to the following criteria.
○: 0.05 N / 25 mm or more ×: Less than 0.05 N / 25 mm
（２３℃）
５０℃の雰囲気温度で感温性粘着シートを介してポリイミドフィルムを台座に貼着し、雰囲気温度を２００℃に上げ、この雰囲気温度で２０分間静置した後、雰囲気温度を２３℃に下げ、この雰囲気温度で２０分間静置した後、１８０°剥離し、剥離強度を測定した。剥離強度の測定値から剥離性を以下の基準で評価した。
○：０．４Ｎ／２５ｍｍ以下
×：０．４Ｎ／２５ｍｍよりも高い
(23 ° C)
Attach the polyimide film to the pedestal via a temperature-sensitive adhesive sheet at an ambient temperature of 50 ° C., raise the ambient temperature to 200 ° C., leave it at this ambient temperature for 20 minutes, lower the ambient temperature to 23 ° C., After leaving still at this atmospheric temperature for 20 minutes, it peeled 180 degree | times and measured peeling strength. The peelability was evaluated according to the following criteria from the measured peel strength.
○: 0.4 N / 25 mm or less ×: higher than 0.4 N / 25 mm
表１から明らかなように、比較例１，２は、粘着付与剤の含有量が４０重量部未満であり、側鎖結晶性ポリマーの割合が高すぎたため、５０℃（融点以上の温度）で貼付性を有する一方で、２３℃（室温）で剥離性を有さないことがわかる。
実施例１〜４は、粘着付与剤の含有量が側鎖結晶性ポリマー１００重量部に対して４０〜１００重量部であるので、５０℃（融点以上の温度）で貼付性を有しつつ、２３℃（室温）で剥離性を有することがわかる。
一方、比較例３は、粘着付与剤の含有量が１００重量部を超え、側鎖結晶性ポリマーの割合が低いすぎたため、５０℃（融点以上の温度）でも貼着しなかった。
なお、比較例１では、Ｔｍ（２６℃）より低い２３℃における剥離強度が、Ｔｍより高い５０℃における剥離強度よりも高い値を示した。これは、主に、２３℃における剥離強度の測定に際し、一旦感温性粘着シートを高温（２００℃）に曝すことで粘着力が上り、そこからＴｍより低い２３℃に冷却しても、２００℃でのアンカー効果がまだ残っているためと推察される。
As is apparent from Table 1, in Comparative Examples 1 and 2, the content of the tackifier was less than 40 parts by weight, and the proportion of the side chain crystalline polymer was too high. It can be seen that, while having stickability, it has no peelability at 23 ° C. (room temperature).
In Examples 1 to 4, since the content of the tackifier is 40 to 100 parts by weight with respect to 100 parts by weight of the side chain crystalline polymer, while having stickability at 50 ° C. (temperature above the melting point) It turns out that it has peelability at 23 ° C. (room temperature).
On the other hand, since the content of the tackifier exceeded 100 parts by weight and the ratio of the side chain crystalline polymer was too low, Comparative Example 3 did not stick even at 50 ° C. (temperature above the melting point).
In Comparative Example 1, the peel strength at 23 ° C. lower than Tm (26 ° C.) was higher than the peel strength at 50 ° C. higher than Tm. This is mainly because, when measuring the peel strength at 23 ° C., once the temperature-sensitive adhesive sheet is exposed to a high temperature (200 ° C.), the adhesive strength increases, and even if it is cooled to 23 ° C. lower than Tm, it is 200 This is probably because the anchor effect at ℃ still remains.
Claims (9)
前記粘着付与剤は、軟化点が１４０℃以上であり、かつ含有量が側鎖結晶性ポリマー１００重量部に対して４０〜１００重量部である、感温性粘着剤。 A temperature-sensitive pressure-sensitive adhesive containing a tackifier and a side-chain crystalline polymer, the adhesive strength of which decreases at a temperature lower than the melting point of the side-chain crystalline polymer,
The tackifier is a temperature-sensitive adhesive having a softening point of 140 ° C or higher and a content of 40 to 100 parts by weight with respect to 100 parts by weight of the side chain crystalline polymer.
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| TW104109319A TWI646169B (en) | 2014-03-27 | 2015-03-24 | Thermosensitivity adhesive agent, thermosensitivity adhesive sheet, and thermosensitivity adhesive tape |
| KR1020150042388A KR102344755B1 (en) | 2014-03-27 | 2015-03-26 | Temperature sensitive adhesive |
| CN201510138016.3A CN104946171B (en) | 2014-03-27 | 2015-03-26 | Response to temperature adhesive |
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| CN113993961A (en) * | 2019-06-12 | 2022-01-28 | 霓达株式会社 | Temperature-sensitive adhesive |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012102212A (en) * | 2010-11-09 | 2012-05-31 | Nitta Corp | Easily peelable pressure-sensitive adhesive sheet and easily peelable pressure-sensitive adhesive tape |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3485412B2 (en) | 1996-03-15 | 2004-01-13 | ニッタ株式会社 | Temporary adhesive tape for laminated ceramic capacitor laminating process and method for producing laminated ceramic capacitor |
| KR101639700B1 (en) * | 2009-02-16 | 2016-07-14 | 니타 가부시키가이샤 | Heat-sensitive adhesive and heat-sensitive adhesive tape |
| JP5714349B2 (en) | 2011-01-31 | 2015-05-07 | ニッタ株式会社 | Easy peelable adhesive sheet and easy peelable adhesive tape |
| JP2012197387A (en) * | 2011-03-23 | 2012-10-18 | Nitta Corp | Heat-resistant temperature-sensitive pressure-sensitive adhesive |
| KR20140074958A (en) * | 2011-09-26 | 2014-06-18 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Pressure-sensitive adhesives with a (meth)acrylic-based elastomeric material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012102212A (en) * | 2010-11-09 | 2012-05-31 | Nitta Corp | Easily peelable pressure-sensitive adhesive sheet and easily peelable pressure-sensitive adhesive tape |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017098077A (en) * | 2015-11-24 | 2017-06-01 | デクセリアルズ株式会社 | Anisotropic conductive film and connection method |
| JP2018028055A (en) * | 2016-05-24 | 2018-02-22 | ザ・ボーイング・カンパニーＴｈｅ Ｂｏｅｉｎｇ Ｃｏｍｐａｎｙ | Novel thermoresponsive adhesive material, method of making the material, and methods of use |
| JP2020143282A (en) * | 2016-05-24 | 2020-09-10 | ザ・ボーイング・カンパニーＴｈｅ Ｂｏｅｉｎｇ Ｃｏｍｐａｎｙ | Novel thermoresponsive adhesive material, method for making the material and method for utilizing the same |
| JP7038749B2 (en) | 2016-05-24 | 2022-03-18 | ザ・ボーイング・カンパニー | New heat-responsive adhesive, how to make its material and how to use it |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20150112871A (en) | 2015-10-07 |
| TWI646169B (en) | 2019-01-01 |
| CN104946171B (en) | 2018-12-14 |
| TW201540810A (en) | 2015-11-01 |
| JP6289960B2 (en) | 2018-03-07 |
| CN104946171A (en) | 2015-09-30 |
| KR102344755B1 (en) | 2021-12-29 |
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