JP2016124936A - Adhesive sheet - Google Patents
Adhesive sheet Download PDFInfo
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- JP2016124936A JP2016124936A JP2014265688A JP2014265688A JP2016124936A JP 2016124936 A JP2016124936 A JP 2016124936A JP 2014265688 A JP2014265688 A JP 2014265688A JP 2014265688 A JP2014265688 A JP 2014265688A JP 2016124936 A JP2016124936 A JP 2016124936A
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- Prior art keywords
- pressure
- sensitive adhesive
- adhesive sheet
- weight
- adhesive layer
- Prior art date
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- Granted
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- 239000000853 adhesive Substances 0.000 title claims abstract description 51
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 51
- 239000012790 adhesive layer Substances 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 117
- 239000006260 foam Substances 0.000 claims description 46
- 239000010410 layer Substances 0.000 claims description 41
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 32
- 229920000098 polyolefin Polymers 0.000 claims description 26
- 229920006243 acrylic copolymer Polymers 0.000 claims description 20
- 238000012360 testing method Methods 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 description 23
- 239000003431 cross linking reagent Substances 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 229920002799 BoPET Polymers 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 9
- -1 polyethylene Polymers 0.000 description 9
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 8
- 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 description 8
- 150000001875 compounds Chemical class 0.000 description 8
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- 239000012948 isocyanate Substances 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 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 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
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- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 5
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
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- 229910052782 aluminium Inorganic materials 0.000 description 3
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- FYRCDEARNUVZRG-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CC(C)CC(C)(C)C1 FYRCDEARNUVZRG-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 1
- UPTHZKIDNHJFKQ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OCC(O)CO UPTHZKIDNHJFKQ-UHFFFAOYSA-N 0.000 description 1
- NFWPZNNZUCPLAX-UHFFFAOYSA-N 4-methoxy-3-methylaniline Chemical compound COC1=CC=C(N)C=C1C NFWPZNNZUCPLAX-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 208000030984 MIRAGE syndrome Diseases 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VRFNYSYURHAPFL-UHFFFAOYSA-N [(4-methylphenyl)sulfonylamino]urea Chemical compound CC1=CC=C(S(=O)(=O)NNC(N)=O)C=C1 VRFNYSYURHAPFL-UHFFFAOYSA-N 0.000 description 1
- JUIBLDFFVYKUAC-UHFFFAOYSA-N [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C(CC)CCCC JUIBLDFFVYKUAC-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 230000005250 beta ray Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 235000010985 glycerol esters of wood rosin Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011980 kaminsky catalyst Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- TVLSRXXIMLFWEO-UHFFFAOYSA-N prochloraz Chemical compound C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl TVLSRXXIMLFWEO-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
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- 238000010008 shearing Methods 0.000 description 1
- 125000004079 stearyl 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])[H] 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、熱収縮率が小さく、携帯電子機器を構成する部品を機器本体に接着固定した場合に表示画面へのはみ出しが少ない粘着シートに関する。 The present invention relates to a pressure-sensitive adhesive sheet that has a low thermal shrinkage rate and has little protrusion to a display screen when components constituting a portable electronic device are bonded and fixed to a device body.
画像表示装置又は入力装置を搭載した携帯電子機器（例えば、携帯電話、携帯情報端末等）においては、組み立てのために粘着シートが用いられている。具体的には、例えば、携帯電子機器の表面を保護するためのカバーパネルをタッチパネルモジュール又はディスプレイパネルモジュールに接着したり、タッチパネルモジュールとディスプレイパネルモジュールとを接着したりするために粘着シートが用いられている。このような粘着シートは、例えば、額縁状等の形状に打ち抜かれ、表示画面の周辺に配置されるようにして用いられる（例えば、特許文献１〜３）。 In a portable electronic device (for example, a mobile phone, a portable information terminal, etc.) equipped with an image display device or an input device, an adhesive sheet is used for assembly. Specifically, for example, an adhesive sheet is used to bond a cover panel for protecting the surface of a portable electronic device to a touch panel module or a display panel module, or to bond a touch panel module and a display panel module. ing. Such an adhesive sheet is used, for example, by being punched into a frame shape or the like and arranged around the display screen (for example, Patent Documents 1 to 3).
近年、携帯電子機器の大画面化に伴って、粘着シートの大型化が進んでいる。また、粘着シートは額縁状等の形状で用いられることから、粘着シートの狭幅化も進んでいる。このため、携帯電子機器を高温環境下に放置したり、携帯電子機器自体の発熱が生じたりした場合に、表示画面の周辺に配置された額縁状等の形状の粘着シートの収縮が生じることで、粘着シートが表示画面にはみ出す（映り込む）という問題が発生している。 In recent years, with the enlargement of screens of portable electronic devices, the size of adhesive sheets has been increasing. In addition, since the pressure-sensitive adhesive sheet is used in a shape such as a frame shape, the width of the pressure-sensitive adhesive sheet is also being reduced. For this reason, when the portable electronic device is left in a high temperature environment or the portable electronic device itself generates heat, the adhesive sheet having a frame shape or the like disposed around the display screen shrinks. There is a problem that the adhesive sheet protrudes (appears) on the display screen.
本発明は、熱収縮率が小さく、携帯電子機器を構成する部品を機器本体に接着固定した場合に表示画面へのはみ出しが少ない粘着シートを提供することを目的とする。 An object of the present invention is to provide a pressure-sensitive adhesive sheet that has a small heat shrinkage rate and has little protrusion to a display screen when components constituting a portable electronic device are bonded and fixed to a device body.
本発明は、基材の少なくとも一方の面に粘着剤層を有する粘着シートであって、前記基材は、ＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率が５％以下であり、粘着シートの８０℃におけるせん断ずれ長さが９０μｍ以下である粘着シートである。
以下に本発明を詳述する。
The present invention is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on at least one surface of a base material, and the base material has a thermal shrinkage rate at 80 ° C. in the TD direction and / or MD direction of 5% or less. The pressure-sensitive adhesive sheet has a shear displacement length at 80 ° C. of 90 μm or less.
The present invention is described in detail below.
本発明者は、基材の少なくとも一方の面に粘着剤層を有する粘着シートにおいて、基材のＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率を特定範囲に調整し、かつ、粘着シートの８０℃におけるせん断ずれ長さを特定範囲に調整して高温下での凝集力を高めることで、粘着シートの熱収縮率を低下させ、携帯電子機器を構成する部品を機器本体に接着固定した場合の粘着シートの表示画面へのはみ出し（映り込み）を抑制できることを見出し、本発明を完成させるに至った。 The present inventor adjusted the heat shrinkage rate at 80 ° C. in the TD direction and / or MD direction of the base material to a specific range in the pressure sensitive adhesive sheet having the pressure sensitive adhesive layer on at least one surface of the base material, and the pressure sensitive adhesive sheet By adjusting the shear deviation length at 80 ° C. to a specific range and increasing the cohesive force at high temperature, the thermal shrinkage rate of the pressure-sensitive adhesive sheet is reduced, and the components constituting the portable electronic device are bonded and fixed to the device body In this case, it was found that the sticking out of the display sheet of the adhesive sheet (reflection) can be suppressed, and the present invention has been completed.
本発明の粘着シートは、基材の少なくとも一方の面に粘着剤層を有する。
上記基材は、ＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率が５％以下であり、本発明の粘着シートは、８０℃におけるせん断ずれ長さが９０μｍ以下である。上記基材のＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率を上記範囲に調整し、かつ、粘着シートの８０℃におけるせん断ずれ長さを上記範囲に調整して高温下での凝集力を高めることで、上記基材自体が熱により収縮しにくくなるとともに、粘着シートが高温下でせん断方向にずれにくくなり、上記基材の収縮が抑制される。これにより、粘着シートの熱収縮率を低下させ、携帯電子機器を構成する部品を機器本体に接着固定した場合の粘着シートの表示画面へのはみ出し（映り込み）を抑制することができる。
The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer on at least one surface of the substrate.
The base material has a thermal shrinkage rate at 80 ° C. in the TD direction and / or MD direction of 5% or less, and the pressure-sensitive adhesive sheet of the present invention has a shear deviation length at 80 ° C. of 90 μm or less. The heat shrinkage rate at 80 ° C. in the TD direction and / or MD direction of the base material is adjusted to the above range, and the shear deviation length of the pressure-sensitive adhesive sheet at 80 ° C. is adjusted to the above range, and the cohesive force at high temperature By increasing the thickness, the base material itself is less likely to shrink due to heat, and the pressure-sensitive adhesive sheet is less likely to shift in the shear direction at high temperatures, thereby suppressing the shrinkage of the base material. Thereby, the thermal contraction rate of an adhesive sheet can be reduced and the protrusion (reflection) of the adhesive sheet to the display screen at the time of fixing the components which comprise a portable electronic device to an apparatus main body can be suppressed.
上記基材のＴＤ方向及びＭＤ方向の両方の８０℃における熱収縮率が５％を超えると、上記基材自体が熱により収縮しやすくなり、粘着シートの熱収縮率が大きくなり、粘着シートの表示画面へのはみ出し（映り込み）を充分に抑制できない。上記基材のＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率は、４％以下が好ましく、２％以下がより好ましい。なお、上記基材は、ＴＤ方向又はＭＤ方向のいずれか一方の８０℃における熱収縮率が５％以下であればよいが、ＴＤ方向及びＭＤ方向の両方の８０℃における熱収縮率が５％以下であることが好ましい。
上記基材のＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率の下限は特に限定されず、小さければ小さいほうがよいが、好ましい下限は０．０１％、より好ましい下限は０．１％である。
When the heat shrinkage rate at 80 ° C. in both the TD direction and the MD direction of the base material exceeds 5%, the base material itself is easily shrunk by heat, and the heat shrinkage rate of the pressure sensitive adhesive sheet is increased. Projection (reflection) on the display screen cannot be sufficiently suppressed. The thermal shrinkage rate at 80 ° C. in the TD direction and / or MD direction of the substrate is preferably 4% or less, and more preferably 2% or less. In addition, the said base material should just have 5% or less of the heat shrinkage rate in 80 degreeC of either TD direction or MD direction, but the heat shrinkage rate in 80 degreeC of both TD direction and MD direction is 5%. The following is preferable.
The lower limit of the heat shrinkage rate at 80 ° C. in the TD direction and / or the MD direction of the substrate is not particularly limited, and it is better if it is small. However, the preferable lower limit is 0.01%, and the more preferable lower limit is 0.1%. is there.
図１に、基材又は粘着シートのＴＤ方向及びＭＤ方向の８０℃における熱収縮率の測定方法を示す模式図を示す。
まず、基材又は粘着シートを一辺１０ｃｍの正方形に裁断して試験片を作製する。図１に示すように、試験片６をアルミ板７に貼り付け、試験片６を切断線Ａにより一辺５ｃｍの正方形に裁断した後、試験片６及びアルミ板７を８０℃で７２時間加熱し、加熱前後のＴＤ方向及びＭＤ方向の収縮率を算出する。
In FIG. 1, the schematic diagram which shows the measuring method of the thermal contraction rate in 80 degreeC of the TD direction and MD direction of a base material or an adhesive sheet is shown.
First, a base material or an adhesive sheet is cut into a square having a side of 10 cm to produce a test piece. As shown in FIG. 1, the
上記基材のＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率を上記範囲に調整する方法として、押出成形にて上記基材を作製する場合は、例えば、上記基材の作製時にＴＤ方向及び／又はＭＤ方向に延伸せず、残留応力を低く抑える方法、高温下で上記基材の延伸を実施し、熱固定させる方法等が挙げられる。なかでも、延伸することで、押出成形時の圧力により上記基材を薄くすることができ、また、延伸方向に分子が配向し機械強度の向上が見込めることから、高温下で上記基材の延伸を実施し、熱固定させる方法が好ましい。
また、押出成形ではなく、上記基材の材料を溶媒に溶かした溶液をフィルム上に塗布し、乾燥させ溶媒を揮発させることにより上記基材を作製すると、残留応力が低く上記ＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率が上記範囲に調整された基材を作製しやすくなる。
As a method of adjusting the thermal shrinkage rate at 80 ° C. in the TD direction and / or MD direction of the base material to the above range, when the base material is manufactured by extrusion molding, for example, in the TD direction at the time of manufacturing the base material And / or a method of keeping the residual stress low without stretching in the MD direction, a method of stretching the substrate at a high temperature, and heat fixing. Among them, by stretching, the substrate can be thinned by the pressure at the time of extrusion, and since the molecules are oriented in the stretching direction and an improvement in mechanical strength can be expected, the stretching of the substrate at a high temperature is possible. A method of performing heat setting and heat fixing is preferable.
Further, when the substrate is produced by applying a solution obtained by dissolving the material of the substrate in a solvent on a film, drying and volatilizing the solvent instead of extrusion, the residual stress is low and the TD direction and / or It becomes easy to produce a base material whose heat shrinkage rate at 80 ° C. in the MD direction is adjusted to the above range.
上記基材は特に限定されず、例えば、樹脂フィルム、発泡体等からなることが好ましい。なかでも、上記基材は、発泡体からなることが好ましい。一般的に発泡体は熱により収縮しやすいが、上記ＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率が上記範囲に調整された発泡体を用いることで、粘着シートの熱収縮率を低下させ、携帯電子機器を構成する部品を機器本体に接着固定した場合の粘着シートの表示画面へのはみ出し（映り込み）を抑制することができる。
上記発泡体は、ポリオレフィン発泡体が特に好ましい。上記ポリオレフィン発泡体は緩衝性を有するため、上記ポリオレフィン発泡体を用いることで、粘着シートの耐衝撃性を高めることができる。
The said base material is not specifically limited, For example, it is preferable to consist of a resin film, a foam, etc. Especially, it is preferable that the said base material consists of a foam. Generally, foams are easily shrunk by heat, but the heat shrinkage rate of the pressure-sensitive adhesive sheet is reduced by using a foam whose heat shrinkage rate at 80 ° C. in the TD direction and / or MD direction is adjusted to the above range. Thus, it is possible to prevent the adhesive sheet from appearing on the display screen (reflection) when the parts constituting the portable electronic device are bonded and fixed to the device body.
The foam is particularly preferably a polyolefin foam. Since the said polyolefin foam has buffering property, the impact resistance of an adhesive sheet can be improved by using the said polyolefin foam.
上記ポリオレフィン発泡体は、ポリオレフィン系樹脂を含む発泡体であれば特に限定されず、例えば、ポリエチレン系発泡体、ポリプロピレン系発泡体、エチレン−プロピレン系発泡体等が挙げられるが、上記ＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率を上記範囲に調整するためには、重合触媒として四価の遷移金属を含むメタロセン化合物を用いて得られたポリオレフィン系樹脂を含む発泡体（本明細書において「メタロセン系ポリオレフィン発泡体」ともいう）が好ましい。なかでも、メタロセン化合物を用いて得られたポリエチレン系樹脂を含む発泡体（本明細書において「メタロセン系ポリエチレン発泡体」ともいう）がより好ましい。
上記メタロセン化合物として、例えば、カミンスキー触媒等が挙げられる。
The polyolefin foam is not particularly limited as long as it is a foam containing a polyolefin resin, and examples thereof include a polyethylene foam, a polypropylene foam, an ethylene-propylene foam, and the like. Alternatively, in order to adjust the thermal shrinkage at 80 ° C. in the MD direction to the above range, a foam containing a polyolefin-based resin obtained by using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst (in the present specification, Also referred to as “metallocene polyolefin foam”. Among these, a foam containing a polyethylene resin obtained by using a metallocene compound (also referred to as “metallocene polyethylene foam” in the present specification) is more preferable.
Examples of the metallocene compounds include Kaminsky catalysts.
上記メタロセン系ポリエチレン発泡体に含まれる上記メタロセン化合物を用いて得られたポリエチレン系樹脂として、例えば、上記メタロセン化合物を用いて、エチレンと、必要に応じて配合される他のα−オレフィンとを共重合することにより得られたポリエチレン系樹脂等が挙げられる。上記他のα−オレフィンとして、例えば、プロペン、１−ブテン、１−ペンテン、１−ヘキセン等が挙げられる。 As a polyethylene resin obtained using the metallocene compound contained in the metallocene polyethylene foam, for example, using the metallocene compound, ethylene and another α-olefin blended as necessary may be used. Examples thereof include polyethylene-based resins obtained by polymerization. Examples of the other α-olefin include propene, 1-butene, 1-pentene, 1-hexene and the like.
上記メタロセン系ポリエチレン発泡体は、上記メタロセン化合物を用いて得られたポリエチレン系樹脂に加えて、更に、他のオレフィン系樹脂を含んでいてもよい。上記他のオレフィン系樹脂として、例えば、ポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体等が挙げられる。
なお、この場合、上記メタロセン系ポリエチレン発泡体における上記メタロセン化合物を用いて得られたポリエチレン系樹脂の含有量は、４０重量％以上が好ましい。上記メタロセン化合物を用いて得られたポリエチレン系樹脂の含有量が４０重量％以上であると、上記メタロセン系ポリエチレン発泡体の厚みが薄くても高い圧縮強度を得ることができる。
The metallocene polyethylene foam may further contain another olefin resin in addition to the polyethylene resin obtained using the metallocene compound. Examples of the other olefin-based resin include polyethylene, polypropylene, ethylene-propylene copolymer, and the like.
In this case, the content of the polyethylene resin obtained by using the metallocene compound in the metallocene polyethylene foam is preferably 40% by weight or more. When the content of the polyethylene resin obtained by using the metallocene compound is 40% by weight or more, high compressive strength can be obtained even if the metallocene polyethylene foam is thin.
上記ポリオレフィン発泡体は、架橋されていることが好ましい。上記ポリオレフィン発泡体を架橋することで、上記ＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率を上記範囲に調整しやすくなる。
上記ポリオレフィン発泡体を架橋する方法は特に限定されず、例えば、上記ポリオレフィン発泡体に電子線、α線、β線、γ線等の電離性放射線を照射する方法、上記ポリオレフィン発泡体に予め配合しておいた有機過酸化物を加熱により分解させる方法等が挙げられる。
The polyolefin foam is preferably cross-linked. By crosslinking the polyolefin foam, it becomes easy to adjust the heat shrinkage rate at 80 ° C. in the TD direction and / or MD direction to the above range.
The method for crosslinking the polyolefin foam is not particularly limited. For example, a method of irradiating the polyolefin foam with ionizing radiation such as electron beam, α ray, β ray, γ ray, Examples include a method of decomposing the organic peroxide by heating.
上記ポリオレフィン発泡体の密度の好ましい下限は０．１ｇ／ｃｍ３、好ましい上限は０．６ｇ／ｃｍ３である。上記密度が０．１ｇ／ｃｍ３未満であると、上記ポリオレフィン発泡体自体が熱により収縮しやすくなり、粘着シートの熱収縮率が大きくなることがある。上記密度が０．６ｇ／ｃｍ３を超えると、粘着シートの耐衝撃性が低下することがある。上記密度のより好ましい下限は０．２ｇ／ｃｍ３である。
なお、ポリオレフィン発泡体の密度は、ＪＩＳＫ−６７６７に準拠してミラージュ社製の電子比重計（商品名「ＥＤ１２０Ｔ」）を使用して測定し算出できる。
A preferred lower limit of the density of the polyolefin foam 0.1 g / cm 3, a preferred upper limit is 0.6 g / cm 3. When the density is less than 0.1 g / cm 3 , the polyolefin foam itself tends to shrink due to heat, and the thermal shrinkage rate of the pressure-sensitive adhesive sheet may increase. When the density exceeds 0.6 g / cm 3 , the impact resistance of the pressure-sensitive adhesive sheet may be lowered. A more preferable lower limit of the density is 0.2 g / cm 3 .
The density of the polyolefin foam can be measured and calculated using an electronic hydrometer (trade name “ED120T”) manufactured by Mirage in accordance with JISK-6767.
上記ポリオレフィン発泡体の発泡倍率の好ましい下限は１．４倍、好ましい上限は１０倍であり、より好ましい下限は１．７倍、より好ましい上限は５倍である。
なお、ポリオレフィン発泡体の発泡倍率は、上述した方法で算出した密度の逆数から算出できる。
The preferable lower limit of the expansion ratio of the polyolefin foam is 1.4 times, the preferable upper limit is 10 times, the more preferable lower limit is 1.7 times, and the more preferable upper limit is 5 times.
The expansion ratio of the polyolefin foam can be calculated from the reciprocal of the density calculated by the method described above.
上記ポリオレフィン発泡体の厚み方向の平均セル径の好ましい下限１０μｍ、好ましい上限は５００μｍである。上記平均セル径が１０μｍ未満であると、粘着シートの柔軟性が損なわれ、被着体に対する貼り付け性が低下することがある。上記平均セル径が５００μｍを超えると、上記ポリオレフィン発泡体自体が熱により収縮しやすくなり、粘着シートの熱収縮率が大きくなることがある。上記平均セル径のより好ましい下限は３０μｍ、より好ましい上限は３００μｍである。
なお、厚み方向のセル径とは、ポリオレフィン発泡体中に存在するセル（気泡）の厚み方向の径（サイズ）を意味し、ポリオレフィン発泡体の厚み方向の平均セル径は、ポリオレフィン発泡体を厚み方向に切断し、断面を光学顕微鏡（例えば、キーエンス社製のＶＨＸ−７００Ｆ）により４５０倍で観察し、ランダムに選択した３０箇所の厚み方向のセル径を測定し、これらを平均して算出できる。
A preferred lower limit of 10 μm and a preferred upper limit of the average cell diameter in the thickness direction of the polyolefin foam are 500 μm. When the average cell diameter is less than 10 μm, the flexibility of the pressure-sensitive adhesive sheet is impaired, and the sticking property to the adherend may be lowered. When the average cell diameter exceeds 500 μm, the polyolefin foam itself tends to shrink due to heat, and the heat shrinkage rate of the pressure-sensitive adhesive sheet may increase. A more preferable lower limit of the average cell diameter is 30 μm, and a more preferable upper limit is 300 μm.
The cell diameter in the thickness direction means the diameter (size) of the cells (bubbles) in the thickness direction in the polyolefin foam, and the average cell diameter in the thickness direction of the polyolefin foam is the thickness of the polyolefin foam. The cross section is observed at 450 times with an optical microscope (for example, VHX-700F manufactured by Keyence Corporation), the cell diameters in 30 thickness directions selected at random are measured, and these can be calculated by averaging them. .
上記ポリオレフィン発泡体の製造方法は特に限定されないが、ポリオレフィン系樹脂と発泡剤とを含有する発泡性樹脂組成物を調製し、この発泡性樹脂組成物を押出機を用いてシート状に押出加工する際に発泡剤を発泡させ、得られたポリオレフィン発泡体を必要に応じて架橋する方法が好ましい。
上記発泡剤は特に限定されず、上記ポリオレフィン発泡体に一般的に用いられる発泡剤を用いることができ、例えば、アゾジカルボンアミド、Ｎ，Ｎ’−ジニトロソペンタメチレンテトラミン、ｐ−トルエンスルホニルセミカルバジド等が挙げられる。上記発泡剤の含有量は、上記ＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率を上記範囲に調整するためには、上記ポリオレフィン系樹脂１００重量部に対する好ましい下限が０．１重量部、好ましい上限が２０重量部であり、より好ましい下限が１重量部、より好ましい上限が１０重量部である。
The method for producing the polyolefin foam is not particularly limited, but a foamable resin composition containing a polyolefin resin and a foaming agent is prepared, and the foamable resin composition is extruded into a sheet using an extruder. In this case, it is preferable to foam the foaming agent and crosslink the obtained polyolefin foam as necessary.
The foaming agent is not particularly limited, and foaming agents generally used for the polyolefin foam can be used. For example, azodicarbonamide, N, N′-dinitrosopentamethylenetetramine, p-toluenesulfonyl semicarbazide, etc. Is mentioned. In order to adjust the heat shrinkage rate at 80 ° C. in the TD direction and / or MD direction to the above range, the content of the foaming agent is preferably 0.1 parts by weight with respect to 100 parts by weight of the polyolefin resin. A preferred upper limit is 20 parts by weight, a more preferred lower limit is 1 part by weight, and a more preferred upper limit is 10 parts by weight.
上記基材の厚みは特に限定されないが、１００〜２２０μｍが好ましい。上記厚みが１００μｍ未満であると、粘着シートの耐衝撃性が低下することがある。上記厚みが２２０μｍを超えると、携帯電子機器を構成する部品を機器本体に接着固定する用途における近年の粘着シートの薄化のニーズに応えることが困難になることがある。 Although the thickness of the said base material is not specifically limited, 100-220 micrometers is preferable. When the thickness is less than 100 μm, the impact resistance of the pressure-sensitive adhesive sheet may be lowered. When the thickness exceeds 220 μm, it may be difficult to meet the recent needs for thinning the pressure-sensitive adhesive sheet in applications in which components constituting the portable electronic device are bonded and fixed to the device body.
本発明の粘着シートは、８０℃におけるせん断ずれ長さが９０μｍ以下である。粘着シートの８０℃におけるせん断ずれ長さが９０μｍを超えると、粘着シートが高温下でせん断方向にずれやすくなり、上記基材の収縮を充分に抑制することができない。粘着シートの８０℃におけるせん断ずれ長さは、８０μｍ以下が好ましく、７０μｍ以下がより好ましい。
本発明の粘着シートの８０℃におけるせん断ずれ長さの下限は特に限定されず、小さければ小さいほうがよいが、好ましい下限は１μｍ、より好ましい下限は５μｍである。
The pressure-sensitive adhesive sheet of the present invention has a shear deviation length of 90 μm or less at 80 ° C. When the shear deviation length at 80 ° C. of the pressure-sensitive adhesive sheet exceeds 90 μm, the pressure-sensitive adhesive sheet tends to be displaced in the shear direction at high temperature, and the shrinkage of the substrate cannot be sufficiently suppressed. The shear deviation length of the pressure-sensitive adhesive sheet at 80 ° C. is preferably 80 μm or less, and more preferably 70 μm or less.
The lower limit of the shear deviation length at 80 ° C. of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, and it is better if it is small. However, the preferable lower limit is 1 μm, and the more preferable lower limit is 5 μm.
図２に、粘着シートの８０℃におけるせん断ずれ長さの測定方法を示す模式図を示す。
まず、両面に粘着剤層を有する粘着シートを縦５ｍｍ×横２０ｍｍの平面長方形状に裁断して試験片を作製し、両面の離型フィルムを剥離除去する（試験片Ｂとする）。図２に示すように、試験片Ｂの上面の粘着剤層に対して厚み２５μｍのＰＥＴフィルムＣを、下面の粘着剤層に対して長さ１００ｍｍ、幅２０ｍｍの金属台座Ｄ（ＳＵＳ製）をそれぞれ貼り付けて試験サンプルを作製する。この試験サンプルの上面のＰＥＴフィルムＣをおもりＥにより水平方向（矢印方向）に５０ｇの荷重を加えて３分間引っ張る。測定は８０℃にて行う。その後、下面の金属台座Ｄに接着している粘着剤層の一端（固定治具側の端）の位置を基準として、上面のＰＥＴフィルムＣに接着している粘着剤層の一端（固定治具側の端）が上面のＰＥＴフィルムＣの引っ張り方向にずれた距離Ｌを測定する。
なお、下面の金属台座Ｄに接着している粘着剤層と上面のＰＥＴフィルムＣとが面一状になるように試験片Ｂの粘着剤層上に上面のＰＥＴフィルムＣを貼り付ける。また、上面のＰＥＴフィルムＣの一端の移動量をμｍ単位で測定できる検出器（図示せず）を設置する。
In FIG. 2, the schematic diagram which shows the measuring method of the shear shift | offset | difference length in 80 degreeC of an adhesive sheet is shown.
First, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on both sides is cut into a plane rectangular shape of 5 mm long × 20 mm wide to produce a test piece, and the release films on both sides are peeled and removed (referred to as test piece B). As shown in FIG. 2, a PET film C having a thickness of 25 μm is formed on the adhesive layer on the upper surface of the test piece B, and a metal base D (manufactured by SUS) having a length of 100 mm and a width of 20 mm is formed on the adhesive layer on the lower surface. A test sample is prepared by pasting each of them. A 50 g load is applied in the horizontal direction (arrow direction) to the PET film C on the upper surface of the test sample by a weight E and pulled for 3 minutes. The measurement is performed at 80 ° C. Thereafter, one end (fixing jig) of the pressure-sensitive adhesive layer bonded to the PET film C on the upper surface with reference to the position of one end (end on the fixing jig side) of the pressure-sensitive adhesive layer bonded to the metal base D on the lower surface. The distance L at which the side edge) is displaced in the pulling direction of the PET film C on the upper surface is measured.
In addition, the upper surface PET film C is affixed on the adhesive layer of the test piece B so that the adhesive layer adhering to the metal pedestal D on the lower surface and the PET film C on the upper surface are flush with each other. In addition, a detector (not shown) that can measure the amount of movement of one end of the PET film C on the upper surface in units of μm is installed.
粘着シートの８０℃におけるせん断ずれ長さを上記範囲に調整する方法として、上記粘着剤層に含まれるアクリル共重合体の組成、重量平均分子量、分子量分布等を調整する方法、異なる組成、重量平均分子量、分子量分布等のアクリル共重合体を混合する方法、上記粘着剤層に含まれる粘着付与樹脂の軟化点、含有量等を調整する方法、上記粘着剤層の架橋度を調整する方法が好ましい。 As a method for adjusting the shear deviation length of the pressure-sensitive adhesive sheet at 80 ° C. to the above range, a method for adjusting the composition, weight average molecular weight, molecular weight distribution, etc. of the acrylic copolymer contained in the pressure-sensitive adhesive layer, different composition, weight average A method of mixing an acrylic copolymer such as molecular weight and molecular weight distribution, a method of adjusting the softening point of the tackifier resin contained in the pressure-sensitive adhesive layer, a content and the like, and a method of adjusting the degree of crosslinking of the pressure-sensitive adhesive layer are preferable. .
上記粘着剤層は、アクリル粘着剤を含有することが好ましい。上記アクリル粘着剤は、アクリル共重合体と粘着付与樹脂とを含有することが好ましい。
上記アクリル共重合体は、ブチルアクリレート（ＢＡ）と２−エチルヘキシルアクリレート（２ＥＨＡ）とを含むモノマー混合物を共重合して得られることが好ましい。全モノマー混合物に占めるブチルアクリレートの含有量、及び、２−エチルヘキシルアクリレートの含有量は特に限定されないが、ブチルアクリレートの好ましい含有量は５０〜９９重量％、２−エチルヘキシルアクリレートの好ましい含有量は１０〜５０重量％である。
The pressure-sensitive adhesive layer preferably contains an acrylic pressure-sensitive adhesive. The acrylic pressure-sensitive adhesive preferably contains an acrylic copolymer and a tackifying resin.
The acrylic copolymer is preferably obtained by copolymerizing a monomer mixture containing butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA). The content of butyl acrylate in the total monomer mixture and the content of 2-ethylhexyl acrylate are not particularly limited, but the preferable content of butyl acrylate is 50 to 99% by weight, and the preferable content of 2-ethylhexyl acrylate is 10 to 10%. 50% by weight.
上記モノマー混合物は、必要に応じてブチルアクリレート及び２−エチルヘキシルアクリレート以外の共重合可能な他の重合性モノマーを含んでいてもよい。
上記共重合可能な他の重合性モノマーとして、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸イソプロピル等のアルキル基の炭素数が１〜３の（メタ）アクリル酸アルキルエステル、メタクリル酸トリデシル、（メタ）アクリル酸ステアリル等のアルキル基の炭素数が１３〜１８の（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸ヒドロキシアルキル、グリセリンジメタクリレート、（メタ）アクリル酸グリシジル、２−メタクリロイルオキシエチルイソシアネート、（メタ）アクリル酸、イタコン酸、無水マレイン酸、クロトン酸、マレイン酸、フマル酸等の官能性モノマーが挙げられる。
The monomer mixture may contain other polymerizable monomers other than butyl acrylate and 2-ethylhexyl acrylate as necessary.
Examples of other polymerizable monomers that can be copolymerized include, for example, carbon number of alkyl groups such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. 1 to 3 (meth) acrylic acid alkyl ester, tridecyl methacrylate, and (meth) acrylic acid alkyl ester having 13 to 18 carbon atoms such as stearyl (meth) acrylate, hydroxyalkyl (meth) acrylate , Glycerin dimethacrylate, glycidyl (meth) acrylate, 2-methacryloyloxyethyl isocyanate, (meth) acrylic acid, itaconic acid, maleic anhydride, crotonic acid, maleic acid, fumaric acid and the like.
上記モノマー混合物を共重合して上記アクリル共重合体を得るには、上記モノマー混合物を、重合開始剤の存在下にてラジカル反応させればよい。上記モノマー混合物をラジカル反応させる方法、即ち、重合方法としては、従来公知の方法が用いられ、例えば、溶液重合（沸点重合又は定温重合）、乳化重合、懸濁重合、塊状重合等が挙げられる。
上記重合開始剤は特に限定されず、例えば、有機過酸化物、アゾ化合物等が挙げられる。上記有機過酸化物として、例えば、１，１−ビス（ｔ−ヘキシルパーオキシ）−３，３，５−トリメチルシクロヘキサン、ｔ−ヘキシルパーオキシピバレート、ｔ−ブチルパーオキシピバレート、２，５−ジメチル−２，５−ビス（２−エチルヘキサノイルパーオキシ）ヘキサン、ｔ−ヘキシルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノエート、ｔ−ブチルパーオキシラウレート等が挙げられる。上記アゾ化合物として、例えば、アゾビスイソブチロニトリル、アゾビスシクロヘキサンカルボニトリル等が挙げられる。これらの重合開始剤は単独で用いてもよいし、２種以上を併用してもよい。
In order to copolymerize the monomer mixture to obtain the acrylic copolymer, the monomer mixture may be radically reacted in the presence of a polymerization initiator. As a method of radical reaction of the monomer mixture, that is, a polymerization method, a conventionally known method is used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like.
The said polymerization initiator is not specifically limited, For example, an organic peroxide, an azo compound, etc. are mentioned. Examples of the organic peroxide include 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5 -Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Examples include isobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-butylperoxylaurate. Examples of the azo compound include azobisisobutyronitrile and azobiscyclohexanecarbonitrile. These polymerization initiators may be used alone or in combination of two or more.
上記アクリル共重合体の重量平均分子量（Ｍｗ）は、４０万〜１５０万が好ましい。重量平均分子量が４０万未満であると、粘着シートが高温下でせん断方向にずれやすくなり、上記基材の収縮を充分に抑制することができないことがある。重量平均分子量が１５０万を超えると、上記粘着剤層の粘着力が低くなりすぎることがある。重量平均分子量のより好ましい下限は６０万、より好ましい上限は１４０万であり、更に好ましい下限は７０万、更に好ましい上限は１３０万である。
重量平均分子量を上記範囲に調整するためには、重合開始剤、重合温度等の重合条件を調整すればよい。
なお、重量平均分子量（Ｍｗ）とは、ＧＰＣ（Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ：ゲルパーミエーションクロマトグラフィ）による標準ポリスチレン換算の重量平均分子量である。
The acrylic copolymer preferably has a weight average molecular weight (Mw) of 400,000 to 1,500,000. If the weight average molecular weight is less than 400,000, the pressure-sensitive adhesive sheet tends to shift in the shear direction at high temperatures, and the shrinkage of the substrate may not be sufficiently suppressed. When the weight average molecular weight exceeds 1,500,000, the adhesive strength of the pressure-sensitive adhesive layer may be too low. The more preferable lower limit of the weight average molecular weight is 600,000, the more preferable upper limit is 1.4 million, the still more preferable lower limit is 700,000, and the further preferable upper limit is 1.3 million.
In order to adjust the weight average molecular weight to the above range, polymerization conditions such as a polymerization initiator and a polymerization temperature may be adjusted.
In addition, a weight average molecular weight (Mw) is a weight average molecular weight of standard polystyrene conversion by GPC (Gel Permeation Chromatography: gel permeation chromatography).
上記粘着付与樹脂として、例えば、ロジンエステル系樹脂、水添ロジン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、クマロンインデン系樹脂、脂環族飽和炭化水素系樹脂、Ｃ５系石油樹脂、Ｃ９系石油樹脂、Ｃ５−Ｃ９共重合系石油樹脂等が挙げられる。これらの粘着付与樹脂は単独で用いてもよいし、２種以上を併用してもよい。
上記粘着付与樹脂の軟化点は特に限定されないが、７０〜１８０℃が好ましい。軟化点が７０℃未満であると、上記粘着付与樹脂が高温で軟化し、粘着シートが高温下でせん断方向にずれやすくなることがある。軟化点が１８０℃を超えると、上記粘着剤層のタックが損なわれ被着体に対する貼り付け性が低下することがある。上記粘着付与樹脂の軟化点のより好ましい下限は８０℃、より好ましい上限は１７０℃であり、更に好ましい下限は９０℃、更に好ましい上限は１６０℃である。
Examples of the tackifier resins include rosin ester resins, hydrogenated rosin resins, terpene resins, terpene phenol resins, coumarone indene resins, alicyclic saturated hydrocarbon resins, C5 petroleum resins, and C9 resins. Examples thereof include petroleum resins and C5-C9 copolymer petroleum resins. These tackifying resins may be used alone or in combination of two or more.
Although the softening point of the said tackifying resin is not specifically limited, 70-180 degreeC is preferable. When the softening point is less than 70 ° C., the tackifying resin is softened at a high temperature, and the pressure-sensitive adhesive sheet may be easily displaced in the shearing direction at a high temperature. When the softening point exceeds 180 ° C., the tackiness of the pressure-sensitive adhesive layer is impaired, and the sticking property to the adherend may be lowered. The more preferable lower limit of the softening point of the tackifier resin is 80 ° C., the more preferable upper limit is 170 ° C., the still more preferable lower limit is 90 ° C., and the still more preferable upper limit is 160 ° C.
上記粘着付与樹脂の含有量は特に限定されないが、上記アクリル共重合体１００重量部に対する好ましい下限は１０重量部、好ましい上限は５０重量部である。上記粘着付与樹脂の含有量が１０重量部未満であると、上記粘着剤層の粘着力が低くなりすぎることがある。上記粘着付与樹脂の含有量が５０重量部を超えると、上記粘着剤層が硬くなって粘着力又はタックが低下することがある。上記粘着付与樹脂の含有量のより好ましい上限は４５重量部、更に好ましい上限は４０重量部である。 Although content of the said tackifying resin is not specifically limited, The preferable minimum with respect to 100 weight part of said acrylic copolymers is 10 weight part, and a preferable upper limit is 50 weight part. When the content of the tackifying resin is less than 10 parts by weight, the adhesive strength of the pressure-sensitive adhesive layer may be too low. When content of the said tackifying resin exceeds 50 weight part, the said adhesive layer may become hard and adhesive force or tack may fall. A more preferred upper limit of the content of the tackifying resin is 45 parts by weight, and a more preferred upper limit is 40 parts by weight.
上記粘着剤層は、架橋剤が添加されることにより上記粘着剤層を構成する樹脂（上記アクリル共重合体及び／又は上記粘着付与樹脂）の主鎖間に架橋構造が形成されていることが好ましい。
上記架橋剤は特に限定されず、例えば、イソシアネート系架橋剤、アジリジン系架橋剤、エポキシ系架橋剤、金属キレート型架橋剤等が挙げられる。なかでも、イソシアネート系架橋剤が好ましい。上記粘着剤層にイソシアネート系架橋剤が添加されることで、イソシアネート系架橋剤のイソシアネート基と上記粘着剤層を構成する樹脂中のアルコール性水酸基とが反応して、上記粘着剤層の架橋が緩くなる。従って、上記粘着剤層は、断続的に加わる剥離応力を分散させることができ、強い衝撃が加わった場合に被着体の変形に伴って生じる剥離応力に対し、被着体からの剥離耐性がより向上する。
上記架橋剤の添加量は、上記アクリル共重合体１００重量部に対して０．０１〜１０重量部が好ましく、０．１〜３重量部がより好ましい。
In the pressure-sensitive adhesive layer, a crosslinking structure may be formed between main chains of the resin (the acrylic copolymer and / or the tackifying resin) constituting the pressure-sensitive adhesive layer by adding a crosslinking agent. preferable.
The said crosslinking agent is not specifically limited, For example, an isocyanate type crosslinking agent, an aziridine type crosslinking agent, an epoxy-type crosslinking agent, a metal chelate type crosslinking agent etc. are mentioned. Of these, isocyanate-based crosslinking agents are preferred. By adding an isocyanate-based crosslinking agent to the pressure-sensitive adhesive layer, the isocyanate group of the isocyanate-based crosslinking agent reacts with the alcoholic hydroxyl group in the resin constituting the pressure-sensitive adhesive layer, thereby cross-linking the pressure-sensitive adhesive layer. It becomes loose. Therefore, the pressure-sensitive adhesive layer can disperse the peeling stress applied intermittently, and has a resistance to peeling from the adherend against the peeling stress caused by the deformation of the adherend when a strong impact is applied. More improved.
The addition amount of the crosslinking agent is preferably 0.01 to 10 parts by weight and more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the acrylic copolymer.
上記粘着剤層の架橋度は、高すぎても低すぎても、上記粘着剤層が被着体の変形に伴って生じる剥離応力によって被着体から剥離しやすくなることがあるので、５〜４０重量％が好ましく、１０〜４０重量％がより好ましく、１５〜３５重量％が特に好ましい。
なお、粘着剤層の架橋度は、粘着剤層をＷ１（ｇ）採取し、この粘着剤層を酢酸エチル中に２３℃にて２４時間浸漬して不溶解分を２００メッシュの金網で濾過し、金網上の残渣を真空乾燥して乾燥残渣の重量Ｗ２（ｇ）を測定し、下記式（１）により算出する。
架橋度（重量％）＝１００×Ｗ２／Ｗ１ （１）
Even if the degree of crosslinking of the pressure-sensitive adhesive layer is too high or too low, the pressure-sensitive adhesive layer may be easily peeled off from the adherend due to the peeling stress caused by the deformation of the adherend. 40 weight% is preferable, 10-40 weight% is more preferable, 15-35 weight% is especially preferable.
The degree of cross-linking of the pressure-sensitive adhesive layer was determined by collecting W1 (g) of the pressure-sensitive adhesive layer, immersing this pressure-sensitive adhesive layer in ethyl acetate at 23 ° C. for 24 hours, and filtering the insoluble matter with a 200-mesh wire mesh. The residue on the wire net is vacuum-dried, and the weight W2 (g) of the dry residue is measured, and calculated by the following formula (1).
Crosslinking degree (% by weight) = 100 × W2 / W1 (1)
上記粘着剤層は、必要に応じて、可塑剤、乳化剤、軟化剤、充填剤、顔料、染料等の添加剤、ロジン系樹脂等のその他の樹脂等を含有していてもよい。 The pressure-sensitive adhesive layer may contain plasticizers, emulsifiers, softeners, fillers, additives such as pigments and dyes, and other resins such as rosin resins, if necessary.
本発明の粘着シートは、上記基材の少なくとも一方の面に上記粘着剤層を有していれば、上記基材の片面に粘着剤層を有していてもよいし、上記基材の両面に粘着剤層を有していてもよい。また、本発明の粘着シートにおいては、両面の粘着剤層が同じ組成であってもよいし、それぞれ異なる組成であってもよい。 As long as the pressure-sensitive adhesive sheet of the present invention has the pressure-sensitive adhesive layer on at least one surface of the base material, it may have a pressure-sensitive adhesive layer on one side of the base material, or both surfaces of the base material. May have an adhesive layer. In the pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive layers on both sides may have the same composition or different compositions.
上記粘着剤層の厚みは特に限定されないが、片面の粘着剤層の厚みの好ましい下限が１０μｍ、好ましい上限が１００μｍである。上記厚みが１０μｍ未満であると、上記粘着剤層の粘着力が低くなりすぎることがある。上記厚みが１００μｍを超えると、被着体に貼り合わせた粘着シートを高温に晒した後で剥がしたい場合に、粘着シートの剥離性が低下することがある。上記粘着剤層の厚みのより好ましい下限は１５μｍ、より好ましい上限は８０μｍである。 Although the thickness of the said adhesive layer is not specifically limited, The preferable minimum of the thickness of the adhesive layer of one side is 10 micrometers, and a preferable upper limit is 100 micrometers. If the thickness is less than 10 μm, the adhesive strength of the pressure-sensitive adhesive layer may be too low. When the thickness exceeds 100 μm, the peelability of the pressure-sensitive adhesive sheet may be lowered when the pressure-sensitive adhesive sheet bonded to the adherend is desired to be peeled off after being exposed to high temperature. The minimum with more preferable thickness of the said adhesive layer is 15 micrometers, and a more preferable upper limit is 80 micrometers.
本発明の粘着シートは、粘着シートをＳＵＳ板に加熱圧着して９０°剥離試験を行ったときの粘着力が５Ｎ／２５ｍｍ以上であることが好ましい。上記９０°剥離試験を行ったときの粘着力が５Ｎ／２５ｍｍ未満であると、上記粘着剤層の粘着力が低くなりすぎることがある。上記９０°剥離試験を行ったときの粘着力は、７Ｎ／２５ｍｍ以上がより好ましい。
上記９０°剥離試験を行ったときの粘着力の上限は特に限定されず、高ければ高いほどよいが、好ましい上限は７０Ｎ／２５ｍｍ、より好ましい上限は６０Ｎ／２５ｍｍである。
なお、粘着シートをＳＵＳ板に加熱圧着して９０°剥離試験を行ったときの粘着力は、ＪＩＳ−Ｚ−０２３７に準拠して測定できる。
The pressure-sensitive adhesive sheet of the present invention preferably has a pressure-sensitive adhesive strength of 5 N / 25 mm or more when the pressure-sensitive adhesive sheet is subjected to thermocompression bonding to a SUS plate and subjected to a 90 ° peel test. If the adhesive strength when the 90 ° peel test is performed is less than 5 N / 25 mm, the adhesive strength of the adhesive layer may be too low. The adhesive strength when the 90 ° peel test is performed is more preferably 7 N / 25 mm or more.
The upper limit of the adhesive strength when the 90 ° peel test is performed is not particularly limited, and the higher the better, but the preferable upper limit is 70 N / 25 mm, and the more preferable upper limit is 60 N / 25 mm.
In addition, the adhesive force when carrying out the 90 degree peeling test by heat-pressing an adhesive sheet to a SUS board can be measured based on JIS-Z-0237.
本発明の粘着シートは、総厚みの好ましい下限が５０μｍ、好ましい上限が４００μｍである。総厚みが５０μｍ未満であると、粘着シートの耐衝撃性が低下することがある。総厚みが４００μｍを超えると、粘着シートは、携帯電子機器を構成する部品を機器本体に接着固定する用途に適さないことがある。総厚みのより好ましい下限は８０μｍ、より好ましい上限は３００μｍである。 The pressure-sensitive adhesive sheet of the present invention has a preferable lower limit of the total thickness of 50 μm and a preferable upper limit of 400 μm. When the total thickness is less than 50 μm, the impact resistance of the pressure-sensitive adhesive sheet may be lowered. When the total thickness exceeds 400 μm, the pressure-sensitive adhesive sheet may not be suitable for use in bonding and fixing components constituting the portable electronic device to the device body. A more preferable lower limit of the total thickness is 80 μm, and a more preferable upper limit is 300 μm.
本発明の粘着シートの製造方法として、例えば、以下のような方法が挙げられる。
まず、アクリル共重合体、粘着付与樹脂、必要に応じて架橋剤等に溶剤を加えて粘着剤ａの溶液を作製して、この粘着剤ａの溶液を基材の表面に塗布し、溶液中の溶剤を完全に乾燥除去して粘着剤層ａを形成する。次に、形成された粘着剤層ａの上に離型フィルムをその離型処理面が粘着剤層ａに対向した状態に重ね合わせる。
次いで、上記離型フィルムとは別の離型フィルムを用意し、この離型フィルムの離型処理面に粘着剤ｂの溶液を塗布し、溶液中の溶剤を完全に乾燥除去することにより、離型フィルムの表面に粘着剤層ｂが形成された積層フィルムを作製する。得られた積層フィルムを粘着剤層ａが形成された基材の裏面に、粘着剤層ｂが基材の裏面に対向した状態に重ね合わせて積層体を作製する。そして、上記積層体をゴムローラ等によって加圧することによって、基材の両面に粘着剤層を有し、かつ、粘着剤層の表面が離型フィルムで覆われた両面粘着シートを得ることができる。
As a manufacturing method of the adhesive sheet of this invention, the following methods are mentioned, for example.
First, a solution of an adhesive a is prepared by adding a solvent to an acrylic copolymer, a tackifier resin, and a cross-linking agent as required, and the solution of the adhesive a is applied to the surface of the substrate. The solvent is completely removed by drying to form the pressure-sensitive adhesive layer a. Next, the release film is superimposed on the formed pressure-sensitive adhesive layer a so that the release treatment surface faces the pressure-sensitive adhesive layer a.
Next, a release film different from the above release film is prepared, a solution of the adhesive b is applied to the release treatment surface of the release film, and the solvent in the solution is completely removed by drying, thereby releasing the release film. A laminated film in which the pressure-sensitive adhesive layer b is formed on the surface of the mold film is produced. The obtained laminated film is laminated on the back surface of the base material on which the pressure-sensitive adhesive layer a is formed, with the pressure-sensitive adhesive layer b facing the back surface of the base material to produce a laminate. And by pressing the said laminated body with a rubber roller etc., the double-sided adhesive sheet which has an adhesive layer on both surfaces of a base material, and the surface of the adhesive layer was covered with the release film can be obtained.
また、同様の要領で積層フィルムを２組作製し、これらの積層フィルムを基材の両面のそれぞれに、積層フィルムの粘着剤層を基材に対向させた状態に重ね合わせて積層体を作製し、この積層体をゴムローラ等によって加圧することによって、基材の両面に粘着剤層を有し、かつ、粘着剤層の表面が離型フィルムで覆われた両面粘着シートを得てもよい。 In addition, two sets of laminated films are produced in the same manner, and a laminated body is produced by superposing these laminated films on both sides of the base material with the adhesive layer of the laminated film facing the base material. The laminate may be pressed by a rubber roller or the like to obtain a double-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on both surfaces of the substrate and having the surface of the pressure-sensitive adhesive layer covered with a release film.
本発明の粘着シートの用途は特に限定されないが、携帯電子機器を構成する部品を機器本体に接着固定する用途が好ましい。具体的には、本発明の粘着シートは、例えば、携帯電子機器の液晶表示パネルを機器本体に接着固定する粘着シートとして用いることができる。
これらの用途における本発明の粘着シートの形状は特に限定されないが、長方形、額縁状、円形、楕円形、ドーナツ型等が挙げられる。これらの用途において本発明の粘着シートが長方形、額縁状等である場合、本発明の粘着シートのサイズは特に限定されず、外径の対角線が４インチ以上の大きなサイズであってもよい。
Although the use of the adhesive sheet of this invention is not specifically limited, The use which adheres and fixes the components which comprise a portable electronic device to an apparatus main body is preferable. Specifically, the pressure-sensitive adhesive sheet of the present invention can be used, for example, as a pressure-sensitive adhesive sheet for bonding and fixing a liquid crystal display panel of a portable electronic device to a device body.
The shape of the pressure-sensitive adhesive sheet of the present invention in these applications is not particularly limited, and examples thereof include a rectangle, a frame shape, a circle, an ellipse, and a donut shape. In these applications, when the pressure-sensitive adhesive sheet of the present invention has a rectangular shape, a frame shape or the like, the size of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, and the diagonal of the outer diameter may be a large size of 4 inches or more.
本発明の粘着シートは、熱収縮率が小さいものであり、ＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率が０．５％以下であることが好ましい。本発明の粘着シートのＴＤ方向及びＭＤ方向の両方の８０℃における熱収縮率が０．５％を超えると、粘着シートの表示画面へのはみ出し（映り込み）を充分に抑制できないことがある。本発明の粘着シートのＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率は、０．３％以下がより好ましい。なお、本発明の粘着シートは、ＴＤ方向又はＭＤ方向のいずれか一方の８０℃における熱収縮率が０．５％以下であることが好ましいが、ＴＤ方向及びＭＤ方向の両方の８０℃における熱収縮率が０．５％以下であることがより好ましい。
本発明の粘着シートを用いて携帯電子機器を構成する部品を機器本体に接着固定する場合には、本発明の粘着シートのＴＤ方向又はＭＤ方向のうち８０℃における熱収縮率がより小さいほうを、携帯電子機器の縦軸又は横軸のうち粘着シートの表示画面へのはみ出し（映り込み）が顕著にあらわれるほうに用いればよい。
本発明の粘着シートのＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率の下限は特に限定されず、小さければ小さいほうがよいが、好ましい下限は０．０１％、より好ましい下限は０．１％である。
The pressure-sensitive adhesive sheet of the present invention has a small heat shrinkage rate, and the heat shrinkage rate at 80 ° C. in the TD direction and / or MD direction is preferably 0.5% or less. When the heat shrinkage rate at 80 ° C. in both the TD direction and the MD direction of the pressure-sensitive adhesive sheet of the present invention exceeds 0.5%, the protrusion (reflection) of the pressure-sensitive adhesive sheet to the display screen may not be sufficiently suppressed. As for the thermal contraction rate in 80 degreeC of the TD direction and / or MD direction of the adhesive sheet of this invention, 0.3% or less is more preferable. In addition, although it is preferable that the thermal contraction rate in 80 degreeC of any one of TD direction or MD direction is 0.5% or less, the adhesive sheet of this invention is heat in 80 degreeC of both TD direction and MD direction. The shrinkage rate is more preferably 0.5% or less.
When the components constituting the portable electronic device are bonded and fixed to the device body using the pressure-sensitive adhesive sheet of the present invention, the one having the smaller heat shrinkage rate at 80 ° C. in the TD direction or MD direction of the pressure-sensitive adhesive sheet of the present invention. Of the vertical axis or the horizontal axis of the portable electronic device, the protrusion (reflection) on the display screen of the pressure-sensitive adhesive sheet may be used significantly.
The lower limit of the heat shrinkage rate at 80 ° C. in the TD direction and / or the MD direction of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, and it is better if it is small. However, the preferred lower limit is 0.01%, and the more preferred lower limit is 0.1. %.
本発明によれば、熱収縮率が小さく、携帯電子機器を構成する部品を機器本体に接着固定した場合に表示画面へのはみ出しが少ない粘着シートを提供することができる。 According to the present invention, it is possible to provide a pressure-sensitive adhesive sheet that has a low thermal shrinkage rate and that has little protrusion to the display screen when components constituting a portable electronic device are bonded and fixed to the device body.
以下に実施例を挙げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
（粘着剤Ａの調製）
ブチルアクリレート６１．９重量部、２−エチルヘキシルアクリレート２０重量部、メチルアクリレート１５重量部、アクリル酸３重量部、２−ヒドロキシエチルアクリレート０．１重量部を共重合してアクリル共重合体（重量平均分子量Ｍｗ＝１２０万、分子量分布Ｍｗ／Ｍｎ＝２１．５）を得た。
得られたアクリル共重合体１００重量部に粘着付与樹脂としてＡ−１００（ロジンエステル樹脂、荒川化学社製、軟化点１００℃）を１０重量部、Ｄ−１６０（ロジンエステル樹脂、荒川化学社製、軟化点１５０℃）を１５重量部、Ｇ１５０（テルペンフェノール樹脂、ヤスハラケミカル社製、軟化点１００℃）を１０重量部混ぜ、固形分３８重量％の酢酸エチル溶液を作製した。そこへ架橋剤としてコロネートＬ−５５（イソシアネート系架橋剤、日本ポリウレタン社製）を１．４重量部混ぜ、充分に攪拌し、粘着剤Ａを作製した。
(Preparation of adhesive A)
Acrylic copolymer (weight average) was prepared by copolymerizing 61.9 parts by weight of butyl acrylate, 20 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of methyl acrylate, 3 parts by weight of acrylic acid, and 0.1 parts by weight of 2-hydroxyethyl acrylate. Molecular weight Mw = 1,200,000, molecular weight distribution Mw / Mn = 21.5).
10 parts by weight of A-100 (rosin ester resin, manufactured by Arakawa Chemical Co., Ltd., softening point 100 ° C.) as a tackifier resin and 100 parts by weight of the obtained acrylic copolymer, D-160 (rosin ester resin, manufactured by Arakawa Chemical Co., Ltd.) 15 parts by weight of softening point 150 ° C.) and 10 parts by weight of G150 (terpene phenol resin, Yashara Chemical Co., Ltd., softening point 100 ° C.) were mixed to prepare an ethyl acetate solution having a solid content of 38% by weight. Thereto, 1.4 parts by weight of Coronate L-55 (isocyanate-based crosslinking agent, manufactured by Nippon Polyurethane Co., Ltd.) was mixed as a crosslinking agent, and the mixture was sufficiently stirred to prepare adhesive A.
（粘着剤Ｂの調製）
ブチルアクリレート９６．９重量部、アクリル酸３重量部、２−ヒドロキシエチルアクリレート０．１重量部を共重合してアクリル共重合体（重量平均分子量Ｍｗ＝９０万、分子量分布Ｍｗ／Ｍｎ＝１１）を得た。
得られたアクリル共重合体に酢酸エチルを混ぜ、固形分５０重量％の酢酸エチル溶液を作製した。そこへ架橋剤としてコロネートＬ−５５（イソシアネート系架橋剤、日本ポリウレタン社製）をアクリル共重合体１００重量部に対して２．０重量部混ぜ、充分に攪拌し、粘着剤Ｂを作製した。
(Preparation of adhesive B)
Acrylic copolymer (weight average molecular weight Mw = 900,000, molecular weight distribution Mw / Mn = 11) by copolymerizing 96.9 parts by weight of butyl acrylate, 3 parts by weight of acrylic acid and 0.1 part by weight of 2-hydroxyethyl acrylate Got.
Ethyl acetate was mixed with the obtained acrylic copolymer to prepare an ethyl acetate solution having a solid content of 50% by weight. Coronate L-55 (isocyanate-based crosslinking agent, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent was mixed with 2.0 parts by weight with respect to 100 parts by weight of the acrylic copolymer, and sufficiently stirred to prepare an adhesive B.
（粘着剤Ｃの調製）
ブチルアクリレート７１．９重量部、２−エチルヘキシルアクリレート２５重量部、アクリル酸３重量部、２−ヒドロキシエチルアクリレート０．１重量部を共重合してアクリル共重合体（重量平均分子量Ｍｗ＝４５万、分子量分布Ｍｗ／Ｍｎ＝１１）を得た。
得られたアクリル共重合体１００重量部に粘着付与樹脂としてＤ−１３５（ロジンエステル樹脂、荒川化学社製、軟化点１３５℃）を２０重量部混ぜ、固形分５０重量％の酢酸エチル溶液を作製した。そこへ架橋剤としてコロネートＬ−５５（イソシアネート系架橋剤、日本ポリウレタン社製）を１．４重量部混ぜ、充分に攪拌し、粘着剤Ｃを作製した。
(Preparation of adhesive C)
Acrylic copolymer (weight average molecular weight Mw = 450,000, copolymerized 71.9 parts by weight of butyl acrylate, 25 parts by weight of 2-ethylhexyl acrylate, 3 parts by weight of acrylic acid, and 0.1 part by weight of 2-hydroxyethyl acrylate) Molecular weight distribution Mw / Mn = 11) was obtained.
20 parts by weight of D-135 (rosin ester resin, manufactured by Arakawa Chemical Co., Ltd., softening point 135 ° C.) as a tackifying resin was mixed with 100 parts by weight of the obtained acrylic copolymer to prepare an ethyl acetate solution having a solid content of 50% by weight. did. Then, 1.4 parts by weight of Coronate L-55 (isocyanate-based crosslinking agent, manufactured by Nippon Polyurethane Co., Ltd.) was mixed as a crosslinking agent, and the mixture was sufficiently stirred to prepare adhesive C.
（粘着剤Ｄの調製）
ブチルアクリレート６６．９重量部、２−エチルヘキシルアクリレート２５重量部、エチルアクリレート５重量部、アクリル酸３重量部、２−ヒドロキシエチルアクリレート０．１重量部を共重合してアクリル共重合体（重量平均分子量Ｍｗ＝６０万、分子量分布Ｍｗ／Ｍｎ＝１５）を得た。
得られたアクリル共重合体１００重量部に粘着付与樹脂としてエステルガムＨ（ロジンエステル樹脂、荒川化学社製、軟化点６８℃）を１０重量部、Ｄ−１３５（ロジンエステル樹脂、荒川化学社製、軟化点１３５℃）を１５重量部、Ｇ１３０（テルペンフェノール樹脂、ヤスハラケミカル社製、軟化点１３０℃）を１０重量部混ぜ、固形分５０重量％の酢酸エチル溶液を作製した。そこへ架橋剤としてコロネートＬ−５５（イソシアネート系架橋剤、日本ポリウレタン社製）を１．８重量部混ぜ、充分に攪拌し、粘着剤Ｄを作製した。
(Preparation of adhesive D)
Acrylic copolymer (weight average) was obtained by copolymerizing 66.9 parts by weight of butyl acrylate, 25 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of ethyl acrylate, 3 parts by weight of acrylic acid, and 0.1 part by weight of 2-hydroxyethyl acrylate. Molecular weight Mw = 600,000, molecular weight distribution Mw / Mn = 15).
10 parts by weight of ester gum H (rosin ester resin, manufactured by Arakawa Chemical Co., Ltd., softening point 68 ° C.) as a tackifier resin, 100 parts by weight of the obtained acrylic copolymer, D-135 (rosin ester resin, manufactured by Arakawa Chemical Co., Ltd.) 15 parts by weight of softening point 135 ° C.) and 10 parts by weight of G130 (terpene phenol resin, Yashara Chemical Co., Ltd., softening point 130 ° C.) were mixed to prepare an ethyl acetate solution having a solid content of 50% by weight. Thereto, 1.8 parts by weight of Coronate L-55 (isocyanate-based cross-linking agent, manufactured by Nippon Polyurethane Co., Ltd.) was mixed as a cross-linking agent, and stirred sufficiently to prepare adhesive D.
（実施例１）
（１）両面粘着シートの製造
厚み２５μｍの離型ＰＥＴフィルムを用意し、この離型ＰＥＴフィルムの離型処理面に粘着剤Ａを塗布し、１００℃で５分間乾燥させることにより、厚み５０μｍの粘着剤層を形成した。
粘着剤層を、厚み１００μｍのポリオレフィン発泡体（ＴＤ方向の８０℃における熱収縮率５．５％、ＭＤ方向の８０℃における熱収縮率３．５％）の表面と貼り合わせた。なお、ポリエチレン発泡体のＴＤ方向及びＭＤ方向の８０℃における熱収縮率は、図１に示す測定方法で測定した。次いで、同様の要領で、ポリオレフィン発泡体の反対の表面にも上記と同じ粘着剤層を貼り合わせた。これにより、ポリオレフィン発泡体の両面に粘着剤層を有し、かつ、粘着剤層の表面が厚み２５μｍの離型ＰＥＴフィルムで覆われた両面粘着シートを得た。
Example 1
(1) Production of double-sided pressure-sensitive adhesive sheet A release PET film having a thickness of 25 μm was prepared, adhesive A was applied to the release-treated surface of this release PET film, and dried at 100 ° C. for 5 minutes, whereby a thickness of 50 μm was obtained. An adhesive layer was formed.
The pressure-sensitive adhesive layer was bonded to the surface of a polyolefin foam having a thickness of 100 μm (thermal shrinkage of 5.5% at 80 ° C. in the TD direction and 3.5% at 80 ° C. in the MD direction). In addition, the thermal contraction rate in 80 degreeC of the TD direction and MD direction of a polyethylene foam was measured with the measuring method shown in FIG. Next, in the same manner, the same pressure-sensitive adhesive layer as above was bonded to the opposite surface of the polyolefin foam. Thereby, the double-sided adhesive sheet which has an adhesive layer on both surfaces of the polyolefin foam, and the surface of the adhesive layer was covered with the mold release PET film with a thickness of 25 micrometers was obtained.
（２）両面粘着シートの８０℃におけるせん断ずれ長さの測定
図２に示す測定方法で両面粘着シートの８０℃におけるせん断ずれ長さを測定した。得られた８０℃におけるせん断ずれ長さは、３５．２μｍであった。
(2) Measurement of shear deviation length at 80 ° C. of double-sided PSA sheet The shear deviation length at 80 ° C. of the double-sided PSA sheet was measured by the measurement method shown in FIG. The obtained shear deviation length at 80 ° C. was 35.2 μm.
（実施例２〜５、比較例１〜７）
表１に記載されたとおり基材の種類、物性及び厚み、並びに、粘着剤の種類及び粘着剤層の厚みを変更したこと以外は実施例１と同様にして、両面粘着シートを得た。その後、実施例１と同様にして、両面粘着シートの８０℃におけるせん断ずれ長さを測定した。
(Examples 2-5, Comparative Examples 1-7)
As described in Table 1, a double-sided PSA sheet was obtained in the same manner as in Example 1 except that the type of substrate, physical properties and thickness, and the type of PSA and the thickness of the PSA layer were changed. Thereafter, in the same manner as in Example 1, the shear deviation length of the double-sided PSA sheet at 80 ° C. was measured.
＜評価＞
実施例、比較例で得られた両面粘着シートについて下記の評価を行った。評価結果を表１に示す。
<Evaluation>
The following evaluation was performed about the double-sided adhesive sheet obtained by the Example and the comparative example. The evaluation results are shown in Table 1.
（１）熱収縮率
図１に示す測定方法で両面粘着シートのＴＤ方向及びＭＤ方向の８０℃における熱収縮率を測定した。熱収縮率が０．５％未満であった場合を○、０．５％以上であった場合を×とした。
(1) Thermal contraction rate The thermal contraction rate in 80 degreeC of the TD direction and MD direction of a double-sided adhesive sheet was measured with the measuring method shown in FIG. The case where the heat shrinkage rate was less than 0.5% was evaluated as ○, and the case where it was 0.5% or more was evaluated as ×.
本発明によれば、熱収縮率が小さく、携帯電子機器を構成する部品を機器本体に接着固定した場合に表示画面へのはみ出しが少ない粘着シートを提供することができる。 According to the present invention, it is possible to provide a pressure-sensitive adhesive sheet that has a low thermal shrinkage rate and that has little protrusion to the display screen when components constituting a portable electronic device are bonded and fixed to the device body.
６ 試験片
７ アルミ板
Ａ 切断線
Ｂ 試験片
Ｃ ＰＥＴフィルム
Ｄ 金属台座
Ｅ おもり
Ｌ せん断ずれ長さ（粘着剤層の一端が上面のＰＥＴフィルムＣの引っ張り方向にずれた距離）
6 Test piece 7 Aluminum plate A Cutting line B Test piece C PET film D Metal base E Weight L Shear shift length (distance where one end of the adhesive layer is shifted in the pulling direction of the upper PET film C)
Claims (10)
前記基材は、ＴＤ方向及び／又はＭＤ方向の８０℃における熱収縮率が５％以下であり、
粘着シートの８０℃におけるせん断ずれ長さが９０μｍ以下である
ことを特徴とする粘着シート。 An adhesive sheet having an adhesive layer on at least one surface of a substrate,
The base material has a thermal shrinkage at 80 ° C. in the TD direction and / or MD direction of 5% or less,
A pressure-sensitive adhesive sheet, wherein the pressure-sensitive adhesive sheet has a shear deviation length at 80 ° C. of 90 μm or less.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7115623B1 (en) | 2021-12-02 | 2022-08-09 | 東洋インキＳｃホールディングス株式会社 | A foamed adhesive tape for fixing electronic device parts, and an electronic device using the foamed adhesive tape for fixing electronic device parts. |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7115623B1 (en) | 2021-12-02 | 2022-08-09 | 東洋インキＳｃホールディングス株式会社 | A foamed adhesive tape for fixing electronic device parts, and an electronic device using the foamed adhesive tape for fixing electronic device parts. |
| JP2023082458A (en) * | 2021-12-02 | 2023-06-14 | 東洋インキＳｃホールディングス株式会社 | Foamed adhesive tape for fixing electronic apparatus parts, and electronic apparatus including foamed adhesive tape for fixing electronic apparatus parts |
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| JP6460788B2 (en) | 2019-01-30 |
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