JP2012036278A - Laminate - Google Patents
Laminate Download PDFInfo
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- JP2012036278A JP2012036278A JP2010176616A JP2010176616A JP2012036278A JP 2012036278 A JP2012036278 A JP 2012036278A JP 2010176616 A JP2010176616 A JP 2010176616A JP 2010176616 A JP2010176616 A JP 2010176616A JP 2012036278 A JP2012036278 A JP 2012036278A
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- Prior art keywords
- pressure
- sensitive adhesive
- composition layer
- polyester resin
- adhesive composition
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- 239000000203 mixture Substances 0.000 claims abstract description 76
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 73
- 229920001225 polyester resin Polymers 0.000 claims abstract description 68
- 239000004645 polyester resin Substances 0.000 claims abstract description 68
- 239000000853 adhesive Substances 0.000 claims abstract description 47
- 230000001070 adhesive effect Effects 0.000 claims abstract description 47
- 238000003860 storage Methods 0.000 claims abstract description 22
- 239000003431 cross linking reagent Substances 0.000 claims description 23
- 150000002009 diols Chemical class 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002390 adhesive tape Substances 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 50
- 238000001035 drying Methods 0.000 description 28
- -1 alicyclic dicarboxylic acids Chemical class 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 18
- 229920000139 polyethylene terephthalate Polymers 0.000 description 17
- 239000005020 polyethylene terephthalate Substances 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 16
- 239000005056 polyisocyanate Substances 0.000 description 16
- 229920001228 polyisocyanate Polymers 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 15
- 239000010936 titanium Substances 0.000 description 15
- 229910052719 titanium Inorganic materials 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 12
- 239000000539 dimer Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000012847 fine chemical Substances 0.000 description 9
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 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
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- LHOBKFFUEUQRQX-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,5-diol Chemical compound OCC(C)CC(C)(C)CO LHOBKFFUEUQRQX-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
- WVQHODUGKTXKQF-UHFFFAOYSA-N 2-ethyl-2-methylhexane-1,1-diol Chemical compound CCCCC(C)(CC)C(O)O WVQHODUGKTXKQF-UHFFFAOYSA-N 0.000 description 1
- BRSICLJIUFXBCB-UHFFFAOYSA-N 2-methyloctane-1,1-diol Chemical compound CCCCCCC(C)C(O)O BRSICLJIUFXBCB-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- YWVFNWVZBAWOOY-UHFFFAOYSA-N 4-methylcyclohexane-1,2-dicarboxylic acid Chemical compound CC1CCC(C(O)=O)C(C(O)=O)C1 YWVFNWVZBAWOOY-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XNFGZQXMDBREDW-FLFKKZLDSA-N [(e)-dodec-2-enoyl] (e)-dodec-2-enoate Chemical compound CCCCCCCCC\C=C\C(=O)OC(=O)\C=C\CCCCCCCCC XNFGZQXMDBREDW-FLFKKZLDSA-N 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas 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
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 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
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、ポリエステル系感圧性粘着剤組成物層を含み、粘着テープや粘着シート等に好適な積層体に関する。 The present invention relates to a laminate including a polyester-based pressure-sensitive adhesive composition layer and suitable for an adhesive tape, an adhesive sheet, and the like.
ポリエステル系感圧性粘着剤は、アクリル系感圧性粘着剤と比較して低臭気である、生分解性を付与できるなどの利点がある。しかし、ポリエステル系感圧性粘着剤組成物に用いるポリエステルは、分子の両末端に架橋剤と反応可能な官能基がある為、高分子量のものを用いると、架橋点間の距離が長くなることによって耐熱保持性が低下するおそれがあった。また、耐熱保持性の低下を避けるために低分子量のものを用いると、架橋点間の距離が短くなることによって、粘着力が低下するおそれがあった。 The polyester-based pressure-sensitive adhesive has advantages such as low odor and biodegradability compared to the acrylic-based pressure-sensitive adhesive. However, since the polyester used in the polyester-based pressure-sensitive adhesive composition has functional groups capable of reacting with the crosslinking agent at both ends of the molecule, if a high molecular weight one is used, the distance between the crosslinking points becomes long. There was a possibility that heat-resistant retention might fall. In addition, when a low molecular weight material is used in order to avoid a decrease in heat resistance, the adhesive strength may be reduced due to a decrease in the distance between the crosslinking points.
耐熱性等を向上させるために、特許文献１には、ガラス転移温度（Ｔｇ）が異なる２種類のポリエステルをブレンドしたポリエステル系感圧性接着剤組成物が提案されている。 In order to improve heat resistance and the like, Patent Document 1 proposes a polyester-based pressure-sensitive adhesive composition in which two kinds of polyesters having different glass transition temperatures (Tg) are blended.
しかしながら、特許文献１のポリエステル系感圧性接着剤組成物では、粘着力及び耐熱保持性を向上させるには未だ不充分であった。 However, the polyester-based pressure-sensitive adhesive composition of Patent Document 1 is still insufficient to improve the adhesive strength and heat resistance retention.
そこで、本発明は、ポリエステル系感圧性粘着剤組成物層を含む積層体として、粘着力及び耐熱保持性を向上させることができる積層体を提供する。 Then, this invention provides the laminated body which can improve adhesive force and heat resistance retention property as a laminated body containing a polyester-type pressure-sensitive adhesive composition layer.
前記目的を達成するため、本発明の積層体は、感圧性粘着剤組成物層Ａと、前記感圧性粘着剤組成物層Ａの両面に設けられた感圧性粘着剤組成物層Ｂとを含む積層体であって、前記感圧性粘着剤組成物層Ａは、２００℃における貯蔵弾性率が２５〜４０ｋＰａであるポリエステル樹脂により形成されており、前記感圧性粘着剤組成物層Ｂは、２００℃における貯蔵弾性率が１０〜２０ｋＰａであるポリエステル樹脂により形成されている、積層体である。 In order to achieve the object, the laminate of the present invention includes a pressure-sensitive adhesive composition layer A and a pressure-sensitive adhesive composition layer B provided on both surfaces of the pressure-sensitive adhesive composition layer A. In the laminate, the pressure-sensitive adhesive composition layer A is formed of a polyester resin having a storage elastic modulus of 25 to 40 kPa at 200 ° C., and the pressure-sensitive adhesive composition layer B is 200 ° C. It is a laminate formed of a polyester resin having a storage elastic modulus of 10 to 20 kPa.
本発明の積層体によれば、上記構成を有することにより、粘着力及び耐熱保持性を向上させることができる。 According to the laminate of the present invention, it is possible to improve adhesive strength and heat resistance retention by having the above-described configuration.
本発明において、粘着力及び耐熱保持性をより向上させるには、前記感圧性粘着剤組成物層Ａの厚さが１０〜２００μｍであり、かつ前記感圧性粘着剤組成物層Ｂの厚さが５〜３０μｍであることが好ましい。 In the present invention, the pressure-sensitive adhesive composition layer A has a thickness of 10 to 200 μm and the pressure-sensitive adhesive composition layer B has a thickness of 10 to 200 μm in order to further improve the adhesive strength and heat resistance retention. It is preferable that it is 5-30 micrometers.
本発明では、前記感圧性粘着剤組成物層Ａ及びＢを形成するポリエステル樹脂が、いずれも架橋されていることが好ましい。ポリエステル樹脂を架橋させることによって凝集力が高まるため、粘着力をより向上させることができるからである。 In the present invention, it is preferable that the polyester resins forming the pressure-sensitive adhesive composition layers A and B are all crosslinked. This is because the cohesive force is increased by crosslinking the polyester resin, so that the adhesive force can be further improved.
本発明では、前記感圧性粘着剤組成物層Ａを形成するポリエステル樹脂のゲル分率が７０〜９５重量％であり、かつ前記感圧性粘着剤組成物層Ｂを形成するポリエステル樹脂のゲル分率が３０〜６５重量％であることが好ましい。ゲル分率が前記範囲内であれば、粘着剤として適した凝集力が得られ、粘着力及び耐熱保持性をより向上させることができるからである。この場合、前記ポリエステル樹脂を架橋するための架橋剤が、３官能以上の多価イソシアネートであることが好ましい。ポリエステル樹脂のゲル分率を前記の好適な範囲内に容易に制御できるからである。 In this invention, the gel fraction of the polyester resin which forms the said pressure-sensitive adhesive composition layer A is 70 to 95 weight%, and the gel fraction of the polyester resin which forms the said pressure-sensitive adhesive composition layer B Is preferably 30 to 65% by weight. If the gel fraction is within the above range, a cohesive force suitable as a pressure-sensitive adhesive can be obtained, and the pressure-sensitive adhesive force and heat resistance retention can be further improved. In this case, the cross-linking agent for cross-linking the polyester resin is preferably a trifunctional or higher polyvalent isocyanate. This is because the gel fraction of the polyester resin can be easily controlled within the preferred range.
本発明では、前記感圧性粘着剤組成物層Ａ及びＢを形成するポリエステル樹脂が、植物由来のジカルボン酸と、植物由来のジオールとから製造されていることが好ましい。植物由来の原料を使用することによって、地球環境への負荷を低減することができるからである。 In this invention, it is preferable that the polyester resin which forms the said pressure sensitive adhesive composition layers A and B is manufactured from the plant-derived dicarboxylic acid and the plant-derived diol. This is because the burden on the global environment can be reduced by using plant-derived raw materials.
上述した本発明の効果を有効に発揮させるには、本発明の積層体を粘着テープ又は粘着シートに適用することが好ましい。 In order to effectively exhibit the effects of the present invention described above, it is preferable to apply the laminate of the present invention to an adhesive tape or an adhesive sheet.
本発明の積層体は、ＪＩＳ Ｃ ２１０７に基づいて測定された粘着力が１０Ｎ／２０ｍｍ以上であり、かつ０．５ｋｇの荷重に対する耐熱保持温度が１００℃以上であることが好ましい。なお、上記粘着力及び耐熱保持温度は、いずれも後述する実施例に記載の方法で測定される。 The laminate of the present invention preferably has an adhesive strength measured according to JIS C 2107 of 10 N / 20 mm or more and a heat-resistant holding temperature for a load of 0.5 kg of 100 ° C. or more. In addition, both the said adhesive force and heat-resistant holding temperature are measured by the method as described in the Example mentioned later.
以下、本発明の実施形態について、図面を参照しながら説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
図１は、本発明の積層体の一例を示す断面図である。図１に示す積層体は、感圧性粘着剤組成物層Ａ（以下、単に「組成物層Ａ」ともいう）と、組成物層Ａの両面に設けられた感圧性粘着剤組成物層Ｂ（以下、単に「組成物層Ｂ」ともいう）とを含む積層体である。 FIG. 1 is a cross-sectional view showing an example of the laminate of the present invention. 1 includes a pressure-sensitive adhesive composition layer A (hereinafter also simply referred to as “composition layer A”) and a pressure-sensitive adhesive composition layer B (which is provided on both surfaces of the composition layer A). Hereinafter, it is simply referred to as “composition layer B”).
組成物層Ａは、２００℃における貯蔵弾性率が２５〜４０ｋＰａであるポリエステル樹脂により形成されている。また、組成物層Ｂは、２００℃における貯蔵弾性率が１０〜２０ｋＰａであるポリエステル樹脂により形成されている。本発明では、組成物層Ａ及びＢが上記特定の範囲内の貯蔵弾性率を有するため、粘着力及び耐熱保持性を向上させることができる。なお、上記の貯蔵弾性率の値は、具体的には後述する実施例に記載された測定方法で測定される値である。 The composition layer A is formed of a polyester resin having a storage elastic modulus at 200 ° C. of 25 to 40 kPa. The composition layer B is formed of a polyester resin having a storage elastic modulus at 200 ° C. of 10 to 20 kPa. In the present invention, since the composition layers A and B have a storage elastic modulus within the specific range, the adhesive force and the heat resistance retention can be improved. In addition, the value of said storage elastic modulus is a value specifically measured by the measuring method described in the Example mentioned later.
また、本発明の積層体は、金属腐食性のある酸官能基の含有量を低減できるため、電子用途の接合にも適しており、また低臭気なので、家庭での接着用テープとしても使用することが可能である。 Moreover, since the laminate of the present invention can reduce the content of acid functional groups having metal corrosive properties, it is also suitable for bonding for electronic applications, and also has low odor, so it can be used as an adhesive tape at home. It is possible.
さらに、本発明の積層体は紫外線照射による架橋工程が不要なので、任意の着色が可能である。なお、従来のアクリル系感圧性粘着剤で厚手の粘着テープや粘着シートを得る際には、紫外線重合などが用いられているが、この場合、紫外線が粘着剤を透過する必要がある為、薄い着色しかできないという課題があった。 Furthermore, since the laminated body of this invention does not require the crosslinking process by ultraviolet irradiation, arbitrary coloring is possible. In addition, when obtaining a thick pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet with a conventional acrylic pressure-sensitive pressure-sensitive adhesive, ultraviolet polymerization or the like is used, but in this case, it is thin because ultraviolet rays need to permeate the pressure-sensitive adhesive. There was a problem that only coloring was possible.
上記貯蔵弾性率を調整する方法としては、種々の方法があるが、例えば、貯蔵弾性率を上げる場合は、ポリエステル樹脂の原料モノマーとして、高Ｔｇのモノマーを使用すればよい。高Ｔｇのモノマーとしては、セバシン酸、プロパンジオール、ブタンジオールなどの脂肪族モノマーを挙げることができる。また、貯蔵弾性率を下げる場合は、例えば、後述する架橋剤の配合量を低減すればよい。 There are various methods for adjusting the storage elastic modulus. For example, when increasing the storage elastic modulus, a high Tg monomer may be used as a raw material monomer for the polyester resin. Examples of the high Tg monomer include aliphatic monomers such as sebacic acid, propanediol, and butanediol. Moreover, what is necessary is just to reduce the compounding quantity of the crosslinking agent mentioned later, for example when reducing a storage elastic modulus.
組成物層Ａを形成するポリエステル樹脂の２００℃における貯蔵弾性率は、耐熱保持性をより向上させるには、２７ｋＰａ以上であることが好ましく、３０ｋＰａ以上であることがより好ましい。また、粘着力をより向上させるには、３８ｋＰａ以下であることが好ましく、３５ｋＰａ以下であることがより好ましい。上記観点を総合すると、組成物層Ａを形成するポリエステル樹脂の２００℃における貯蔵弾性率は、２５〜４０ｋＰａであり、２７〜３８ｋＰａであることが好ましく、３０〜３５ｋＰａであることがより好ましい。 The storage elastic modulus at 200 ° C. of the polyester resin forming the composition layer A is preferably 27 kPa or more, and more preferably 30 kPa or more in order to further improve the heat resistance retention. Moreover, in order to improve adhesive force more, it is preferable that it is 38 kPa or less, and it is more preferable that it is 35 kPa or less. When the said viewpoint is put together, the storage elastic modulus in 200 degreeC of the polyester resin which forms the composition layer A is 25-40 kPa, It is preferable that it is 27-38 kPa, and it is more preferable that it is 30-35 kPa.
組成物層Ｂを形成するポリエステル樹脂の２００℃における貯蔵弾性率は、耐熱保持性をより向上させるには、１２ｋＰａ以上であることが好ましく、１３ｋＰａ以上であることがより好ましい。また、粘着力をより向上させるには、１８ｋＰａ以下であることが好ましく、１７ｋＰａ以下であることがより好ましい。上記観点を総合すると、組成物層Ｂを形成するポリエステル樹脂の２００℃における貯蔵弾性率は、１０〜２０ｋＰａであり、１２〜１８ｋＰａであることが好ましく、１３〜１７ｋＰａであることがより好ましい。なお、図１に示す積層体において、上側の組成物層Ｂを形成するポリエステル樹脂と、下側の組成物層Ｂを形成するポリエステル樹脂とは、２００℃における貯蔵弾性率が１０〜２０ｋＰａである限り、同一のポリエステル樹脂であっても、異なるポリエステル樹脂であってもよい。 The storage elastic modulus at 200 ° C. of the polyester resin forming the composition layer B is preferably 12 kPa or more, and more preferably 13 kPa or more in order to further improve the heat resistance retention. Moreover, in order to improve adhesive force more, it is preferable that it is 18 kPa or less, and it is more preferable that it is 17 kPa or less. When the said viewpoint is put together, the storage elastic modulus in 200 degreeC of the polyester resin which forms the composition layer B is 10-20 kPa, it is preferable that it is 12-18 kPa, and it is more preferable that it is 13-17 kPa. In the laminate shown in FIG. 1, the polyester resin forming the upper composition layer B and the polyester resin forming the lower composition layer B have a storage elastic modulus at 200 ° C. of 10 to 20 kPa. As long as they are the same polyester resin or different polyester resins.
組成物層Ａの厚さは１０〜２００μｍであることが好ましく、３０〜２００μｍであることがより好ましい。組成物層Ａの厚さが１０μｍ以上であれば、粘着力をより向上させることができる。また、組成物層Ａの厚さが２００μｍ以下であれば、耐熱保持性をより向上させることができる。 The thickness of the composition layer A is preferably 10 to 200 μm, and more preferably 30 to 200 μm. If the thickness of the composition layer A is 10 μm or more, the adhesive strength can be further improved. Moreover, if the thickness of the composition layer A is 200 μm or less, the heat resistance retention can be further improved.
組成物層Ｂの厚さは５〜３０μｍであることが好ましい。組成物層Ｂの厚さが５μｍ以上であれば、粘着力をより向上させることができる。また、組成物層Ｂの厚さが３０μｍ以下であれば、耐熱保持性をより向上させることができる。 The thickness of the composition layer B is preferably 5 to 30 μm. If the thickness of the composition layer B is 5 μm or more, the adhesive force can be further improved. Moreover, if the thickness of the composition layer B is 30 μm or less, the heat resistance retention can be further improved.
また、粘着力及び耐熱保持性を向上させる観点から、組成物層Ｂの厚さより組成物層Ａの厚さが厚いことが好ましく、厚さの比が、Ａ：Ｂ=４：１〜４０：１の範囲内であることがより好ましい。 Further, from the viewpoint of improving the adhesive strength and heat resistance retention, the thickness of the composition layer A is preferably larger than the thickness of the composition layer B, and the thickness ratio is A: B = 4: 1 to 40: More preferably, it is within the range of 1.
組成物層Ａ及びＢを形成するポリエステル樹脂を調製するためのジカルボン酸成分は、脂肪族系二塩基酸成分として以下に示す多価カルボン酸、又はそのアルキルエステル若しくは酸無水物、あるいは植物由来のダイマー酸を使用できる。例えば、アジピン酸、アゼライン酸、セバシン酸、１，４−シクロヘキサンジカルボン酸、１，３−シクロヘキサンジカルボン酸、１，２−シクロヘキサンジカルボン酸、４−メチル−１，２−シクロヘキサンジカルボン酸、ドデセニル無水琥珀酸、フマル酸、琥珀酸、ドデカン二酸、ヘキサヒドロ無水フタル酸、テトラヒドロ無水フタル酸等、マレイン酸、無水マレイン酸、イタコン酸、シトラコン酸等の脂肪族や脂環族ジカルボン酸類が挙げられる。なかでも、環境負荷の低減の観点から、植物由来のジカルボン酸が好ましく、特に植物由来のダイマー酸やセバシン酸が好ましい。 The dicarboxylic acid component for preparing the polyester resin forming the composition layers A and B is a polyvalent carboxylic acid shown below as an aliphatic dibasic acid component, or an alkyl ester or acid anhydride thereof, or a plant-derived Dimer acid can be used. For example, adipic acid, azelaic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dodecenyl anhydride Examples thereof include aliphatic and alicyclic dicarboxylic acids such as acid, fumaric acid, succinic acid, dodecanedioic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, maleic acid, maleic anhydride, itaconic acid, citraconic acid and the like. Of these, plant-derived dicarboxylic acids are preferable from the viewpoint of reducing environmental burden, and plant-derived dimer acid and sebacic acid are particularly preferable.
また、本発明では、上記ジカルボン酸成分として、本発明の効果を損なわない程度に芳香族系二塩基酸も使用できる。芳香族系二塩基酸としては、テレフタル酸、イソフタル酸、オルソフタル酸、１，５−ナフタレンジカルボン酸、２，６−ナフタレンジカルボンル酸、４，４’−ジフェニルジカルボン酸、２，２’−ジフェニルジカルボン酸、４，４’−ジフェニルエーテルジカルボン酸等が挙げられる。 In the present invention, an aromatic dibasic acid can also be used as the dicarboxylic acid component to the extent that the effects of the present invention are not impaired. Aromatic dibasic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 2,2'-diphenyl Examples thereof include dicarboxylic acid and 4,4′-diphenyl ether dicarboxylic acid.
組成物層Ａ及びＢを形成するポリエステル樹脂を調製するためのジオール成分としては、エチレングリコ−ル、１，２−プロピレングリコール、１，３−プロパンジオ−ル、２−メチル−１，３プロパンジオール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、１，５−ペンタンジオ−ル、１，６−ヘキサンジオ−ル、３−メチル−１，５−ペンタンジオール、ネオペンチルグリコール、ジエチレングリコール、ジプロピレングリコール、２，２，４−トリメチル−１，５−ペンタンジオール、２−エチル−２−ブチルプロパンジオール、１，９−ノナンジオール、２−メチルオクタンジオール、１，１０−デカンジオール、植物由来のダイマージオール等が挙げられる。なかでも、環境負荷の低減の観点から、植物由来のジオールが好ましく、特に植物由来のダイマージオールや１，４−ブタンジオールが好ましい。 Examples of the diol component for preparing the polyester resins forming the composition layers A and B include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, and 2-methyl-1,3-propane. Diol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, Neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,5-pentanediol, 2-ethyl-2-butylpropanediol, 1,9-nonanediol, 2-methyloctanediol, 1, Examples include 10-decanediol and plant-derived dimer diol. Of these, plant-derived diols are preferable from the viewpoint of reducing environmental burden, and plant-derived dimer diol and 1,4-butanediol are particularly preferable.
ダイマー酸やダイマージオールが粘着剤を形成するポリマーに好ましく用いられる理由は、沸点が高いため縮合重合の際に蒸発しにくい点と、アルキルの側鎖を有しているので、低Ｔｇのポリマーを得ることができる点にある。 The reason why dimer acid or dimer diol is preferably used for the polymer forming the pressure-sensitive adhesive is that it has a high boiling point and is difficult to evaporate during condensation polymerization, and since it has an alkyl side chain, a low Tg polymer is used. It is in the point that can be obtained.
組成物層Ａ及びＢを形成するポリエステル樹脂の調製方法（縮合方法）は、縮合反応で生成する縮合水やモノアルコールを、反応系内に不活性ガスを吹き込み不活性ガスと共に反応系外に吹き出す方法や、減圧下で溜去する方法等で進められ、生産性を考慮すると、重合時間を短縮できる減圧法が好ましい。反応温度や減圧度は限定されないが、反応温度は、通常、１８０〜２６０℃であり、好ましくは１９０〜２２０℃である。反応温度を１８０℃以上とすることにより、重合速度の低下を防止できる。また、反応温度を２６０℃以下とすることにより、得られる樹脂の劣化を防止できる。一方、減圧度は、通常、０．１〜１０ｋＰａであり、好ましくは０．５〜４ｋＰａである。減圧度を０．１ｋＰａ以上とすることにより、製造コストを低減できる。また、減圧度を１０ｋＰａ以下とすることにより、重合速度の低下を防止できる。 The polyester resin preparation method (condensation method) for forming the composition layers A and B is a method in which condensed water or monoalcohol generated by the condensation reaction is blown out of the reaction system together with an inert gas. In consideration of productivity, the reduced pressure method that can shorten the polymerization time is preferable. Although reaction temperature and a pressure reduction degree are not limited, Reaction temperature is 180-260 degreeC normally, Preferably it is 190-220 degreeC. By setting the reaction temperature to 180 ° C. or higher, a decrease in polymerization rate can be prevented. Moreover, deterioration of resin obtained can be prevented by making reaction temperature 260 degrees C or less. On the other hand, the degree of vacuum is usually 0.1 to 10 kPa, preferably 0.5 to 4 kPa. By setting the degree of vacuum to 0.1 kPa or more, the manufacturing cost can be reduced. Moreover, the fall of a polymerization rate can be prevented by making decompression degree into 10 kPa or less.
縮合反応に用いられる触媒としては、公知のポリエステルの重合触媒が使用でき、例えば、チタン系、錫系、アンチモン系、亜鉛系、ゲルマニウム系等の種々の金属化合物や、ｐ−トルエンスルホン酸や硫酸等の強酸化合物を使用することができる。 As the catalyst used in the condensation reaction, known polyester polymerization catalysts can be used, for example, various metal compounds such as titanium, tin, antimony, zinc, and germanium, p-toluenesulfonic acid, sulfuric acid, and the like. Strong acid compounds such as can be used.
本発明では、架橋剤により上記ポリエステル樹脂を架橋してもよい。架橋剤は、特に限定されないが、ゲル分率を粘着剤として好適な範囲に容易に制御するには、３官能以上の多価イソシアネートを使用することが好ましい。この様な架橋剤としてはポリイソシアネートが使用でき、好ましくはヘキサメチレンジイソシアネートを原料としたポリイソシアネートを使用することができる。これらの架橋剤は２種以上を併用しても良い。なお、前記多価イソシアネートの配合量は、用いるイソシアネートの種類によって異なるが、架橋後のポリエステル樹脂のゲル分率が、後述する好適な範囲内となるように適宜調整すればよい。 In the present invention, the polyester resin may be crosslinked with a crosslinking agent. Although a crosslinking agent is not specifically limited, In order to easily control a gel fraction to a suitable range as an adhesive, it is preferable to use polyfunctional isocyanate more than trifunctional. As such a cross-linking agent, polyisocyanate can be used, and preferably, polyisocyanate using hexamethylene diisocyanate as a raw material can be used. Two or more of these crosslinking agents may be used in combination. In addition, although the compounding quantity of the said polyhydric isocyanate changes with kinds of isocyanate to be used, what is necessary is just to adjust suitably so that the gel fraction of the polyester resin after bridge | crosslinking may become in the suitable range mentioned later.
組成物層Ａを形成するポリエステル樹脂のゲル分率は、粘着剤として適した凝集力が得られ、粘着力及び耐熱保持性をより向上させる観点から、７０〜９５重量％であることが好ましく、７５〜９５重量％であることがより好ましく、７５〜９０重量％であることが更に好ましく、８０〜９０重量％であることが更により好ましい。同様の観点から、組成物層Ｂを形成するポリエステル樹脂のゲル分率は、３０〜６５重量％であることが好ましく、３５〜６０重量％であることがより好ましく、４０〜６０重量％であることが更に好ましく、４０〜５５重量％であることが更により好ましい。 The gel fraction of the polyester resin forming the composition layer A is preferably 70 to 95% by weight from the viewpoint of obtaining cohesive force suitable as a pressure-sensitive adhesive and further improving the pressure-sensitive adhesive force and heat resistance retention. It is more preferably 75 to 95% by weight, still more preferably 75 to 90% by weight, and even more preferably 80 to 90% by weight. From the same viewpoint, the gel fraction of the polyester resin forming the composition layer B is preferably 30 to 65% by weight, more preferably 35 to 60% by weight, and 40 to 60% by weight. Is more preferable, and it is still more preferable that it is 40 to 55 weight%.
上記ポリエステル樹脂のゲル分率は、架橋剤の配合量、加熱温度、加熱時間等で調整できる。なお、上記のゲル分率の値は、具体的には後述する実施例に記載された測定方法で測定される値である。 The gel fraction of the said polyester resin can be adjusted with the compounding quantity of a crosslinking agent, heating temperature, heating time, etc. In addition, the value of said gel fraction is a value specifically measured by the measuring method described in the Example mentioned later.
本発明では、高ゲル分率化を目的に、ゲル化剤を用いてもよい。ゲル化剤としては、テトラ−ｎ−ブチルチタネート、チタンテトライソプロポキシド、ブチル錫オキシド、ジオクチル錫ジラウレートなどが挙げられる。これらの触媒は２種以上を併用しても良い。 In the present invention, a gelling agent may be used for the purpose of increasing the gel fraction. Examples of the gelling agent include tetra-n-butyl titanate, titanium tetraisopropoxide, butyltin oxide, dioctyltin dilaurate, and the like. Two or more of these catalysts may be used in combination.
本発明の積層体の形成方法は、特に限定されないが、例えば、以下の方法が例示できる。まず、組成物層Ａを形成するためのポリエステル樹脂含有粘着剤溶液Ａ（図示せず）と、組成物層Ｂを形成するためのポリエステル樹脂含有粘着剤溶液Ｂ（図示せず）とをそれぞれ調製し、剥離処理した支持体（図示せず）にそれぞれ塗布し、乾燥させることによって、組成物層Ａを形成するためのシートＡ（図示せず）と、組成物層Ｂを形成するためのシートＢ（図示せず）とを形成する。次いで、シートＡの両面にシートＢを貼り合わせ、適宜、熟成させることによって本発明の積層体を得ることができる。なお、積層体の態様としては、粘着シート、粘着テープ等が挙げられる。 Although the formation method of the laminated body of this invention is not specifically limited, For example, the following method can be illustrated. First, a polyester resin-containing pressure-sensitive adhesive solution A (not shown) for forming the composition layer A and a polyester resin-containing pressure-sensitive adhesive solution B (not shown) for forming the composition layer B are prepared. Then, the sheet A (not shown) for forming the composition layer A and the sheet for forming the composition layer B are respectively applied to a support (not shown) subjected to a release treatment and dried. B (not shown). Subsequently, the laminated body of this invention can be obtained by bonding the sheet | seat B on both surfaces of the sheet | seat A, and making it age suitably. In addition, as an aspect of a laminated body, an adhesive sheet, an adhesive tape, etc. are mentioned.
本発明によれば、例えば、ＪＩＳ Ｃ ２１０７に基づいて測定された粘着力が１０Ｎ／２０ｍｍ以上であり、かつ０．５ｋｇの荷重に対する耐熱保持温度が１００℃以上である積層体を提供できる。なお、上記粘着力の上限は特に限定されないが、例えば２０Ｎ／２０ｍｍ以下である。上記耐熱保持温度の上限についても特に限定されないが、例えば２００℃以下である。 According to the present invention, for example, it is possible to provide a laminate having an adhesive strength measured based on JIS C 2107 of 10 N / 20 mm or more and a heat-resistant holding temperature for a load of 0.5 kg of 100 ° C. or more. In addition, although the upper limit of the said adhesive force is not specifically limited, For example, it is 20 N / 20mm or less. The upper limit of the heat resistant holding temperature is not particularly limited, but is, for example, 200 ° C. or lower.
以下、本発明の実施例について比較例と併せて説明するが、本発明は下記の実施例に限定して解釈されるものではない。なお、以下の記載において、「部」は「重量部」を示す。 Examples of the present invention will be described below together with comparative examples, but the present invention is not construed as being limited to the following examples. In the following description, “part” means “part by weight”.
＜ポリエステル樹脂溶液ａ−１の作製方法＞
撹拌器、温度計、流出用冷却機を装備した反応缶内に、ダイマージオール(クローダジャパン社製、プリポール２０３３、重量平均分子量：５３４)３５部、セバシン酸(豊国製油社製)１００部、１，４−ブタンジオール（和光純薬工業社製）４０部、及びチタンテトライソプロポキシド（和光純薬工業社製)０．５部を仕込み、０．８ｋＰａに減圧し、２００℃で６時間重合を行った後、固形分濃度が５０重量％になるようにトルエンで希釈して、ポリエステル樹脂溶液ａ−１を得た。
<Method for producing polyester resin solution a-1>
In a reaction vessel equipped with a stirrer, a thermometer, and an outflow cooler, 35 parts of dimerdiol (manufactured by Croda Japan, Prepol 2033, weight average molecular weight: 534), 100 parts of sebacic acid (manufactured by Toyokuni Oil Co., Ltd.), 1 , 4-butanediol (Wako Pure Chemical Industries, Ltd.) 40 parts and titanium tetraisopropoxide (Wako Pure Chemical Industries, Ltd.) 0.5 parts were charged, the pressure was reduced to 0.8 kPa, and polymerization was conducted at 200 ° C. for 6 hours. Then, it was diluted with toluene so that the solid content concentration was 50% by weight to obtain a polyester resin solution a-1.
＜ポリエステル樹脂溶液ａ−２の作製方法＞
ダイマージオールの配合量を１７部、１，４−ブタンジオールの配合量を４２部としたこと以外は、ポリエステル樹脂溶液ａ−１と同様にして、ポリエステル樹脂溶液ａ−２を得た。
<Method for producing polyester resin solution a-2>
A polyester resin solution a-2 was obtained in the same manner as the polyester resin solution a-1, except that the amount of dimer diol was 17 parts and the amount of 1,4-butanediol was 42 parts.
＜ポリエステル樹脂溶液ａ−３の作製方法＞
ダイマージオールの配合量を５２部、１，４−ブタンジオールの配合量を３８部としたこと以外は、ポリエステル樹脂溶液ａ−１と同様にして、ポリエステル樹脂溶液a−３を得た。
<Method for producing polyester resin solution a-3>
A polyester resin solution a-3 was obtained in the same manner as the polyester resin solution a-1, except that the amount of dimer diol was 52 parts and the amount of 1,4-butanediol was 38 parts.
＜ポリエステル樹脂溶液ａ−４の作製方法＞
ダイマージオールの配合量を８部、１，４−ブタンジオールの配合量を４５部としたこと以外は、ポリエステル樹脂溶液ａ−１と同様にして、ポリエステル樹脂溶液a−４を得た。
<Method for producing polyester resin solution a-4>
A polyester resin solution a-4 was obtained in the same manner as the polyester resin solution a-1, except that the amount of dimer diol was 8 parts and the amount of 1,4-butanediol was 45 parts.
＜ポリエステル樹脂溶液ｂの作製方法＞
撹拌器、温度計、流出用冷却機を装備した反応缶内に、ダイマージオール(クローダジャパン社製、プリポール２０３３、重量平均分子量：５３４)１００部、ダイマー酸(クローダジャパン社製、プリポール１００９、重量平均分子量：５６６)９９部、及びチタンテトライソプロポキシド（和光純薬工業社製)０．５部を仕込み、０．８ｋＰａに減圧し、２００℃で６時間重合を行った後、固形分濃度が５０重量％になるようにトルエンで希釈して、ポリエステル樹脂溶液ｂを得た。
<Method for producing polyester resin solution b>
In a reaction vessel equipped with a stirrer, a thermometer, and an outflow cooler, 100 parts of dimer diol (manufactured by Croda Japan, Prepol 2033, weight average molecular weight: 534), dimer acid (manufactured by Croda Japan, Pripol 1009, weight) Average molecular weight: 566) 99 parts and 0.5 parts of titanium tetraisopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.) were charged, the pressure was reduced to 0.8 kPa, polymerization was carried out at 200 ° C. for 6 hours, and then the solid content concentration Was diluted with toluene so as to be 50% by weight to obtain a polyester resin solution b.
＜実施例１＞
ポリエステル樹脂溶液ａ−１（固形分重量で１００部）と、ポリイソシアネート系架橋剤であるデュラネートＴＰＡ−１００(旭化成ケミカルズ社製)１５部と、チタン系触媒であるＴＣ７５０（マツモトファインケミカル社製）０．１部とを配合し、粘着剤溶液を得た。この粘着剤溶液を乾燥後の厚さが１００μｍになるように、剥離処理したポリエチレンテレフタレートフィルムの剥離処理面に塗布し、１００℃で３分間乾燥することによって架橋させ、シートＡ−１を得た。別途、ポリエステル樹脂溶液ｂ（固形分重量で１００部）と、ポリイソシアネート系架橋剤であるデュラネートＴＰＡ−１００(旭化成ケミカルズ社製)１．５部と、チタン系触媒であるＴＣ７５０（マツモトファインケミカル社製）０．１部とを配合し、粘着剤溶液を得た。この粘着剤溶液を乾燥後の厚さが１０μｍになるように、剥離処理したポリエチレンテレフタレートフィルムの剥離処理面に塗布し、１００℃で３分間乾燥することによって架橋させ、シートＢ−１を得た。次いで、シートＡ−１（中心層）の両面にシートＢ−１（外側層）をハンドローラーで貼り合せて積層し、更に５０℃の雰囲気で３日間熟成させ、実施例１の粘着シートを得た。
<Example 1>
Polyester resin solution a-1 (100 parts by weight in solids), 15 parts of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals) which is a polyisocyanate-based crosslinking agent, and TC750 (manufactured by Matsumoto Fine Chemicals) which is a titanium catalyst 0 1 part was mix | blended and the adhesive solution was obtained. The pressure-sensitive adhesive solution was applied to a release-treated surface of a polyethylene terephthalate film that had been subjected to a release treatment so that the thickness after drying was 100 μm, and was crosslinked by drying at 100 ° C. for 3 minutes to obtain a sheet A-1. . Separately, polyester resin solution b (100 parts by weight in solid content), 1.5 parts of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals) which is a polyisocyanate-based crosslinking agent, and TC750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) which is a titanium catalyst. ) 0.1 part, and an adhesive solution was obtained. The pressure-sensitive adhesive solution was applied to a release-treated surface of a polyethylene terephthalate film that had been subjected to a release treatment so that the thickness after drying was 10 μm, and was crosslinked by drying at 100 ° C. for 3 minutes to obtain a sheet B-1. . Next, the sheet B-1 (outer layer) is laminated on both sides of the sheet A-1 (center layer) with a hand roller and laminated, and further aged in an atmosphere at 50 ° C. for 3 days to obtain the pressure-sensitive adhesive sheet of Example 1. It was.
＜実施例２＞
ポリエステル樹脂溶液ａ−１（固形分重量で１００部）と、ポリイソシアネート系架橋剤であるデュラネートＴＰＡ−１００(旭化成ケミカルズ社製) １５部と、チタン系触媒であるＴＣ７５０（マツモトファインケミカル社製）０．１部とを配合し、粘着剤溶液を得た。この粘着剤溶液を乾燥後の厚さが３０μｍになるように、剥離処理したポリエチレンテレフタレートフィルムの剥離処理面に塗布し、１００℃で３分間乾燥することによって架橋させ、シートＡ−２を得た。別途、ポリエステル樹脂溶液ｂ（固形分重量で１００部）と、ポリイソシアネート系架橋剤であるデュラネートＴＰＡ−１００(旭化成ケミカルズ社製)１．５部と、チタン系触媒であるＴＣ７５０（マツモトファインケミカル社製）０．１部とを配合し、粘着剤溶液を得た。この粘着剤溶液を乾燥後の厚さが５μｍになるように、剥離処理したポリエチレンテレフタレートフィルムの剥離処理面に塗布し、１００℃で３分間乾燥することによって架橋させ、シートＢ−２を得た。次いで、シートＡ−２の両面にシートＢ−２をハンドローラーで貼り合せて積層し、更に５０℃の雰囲気で３日間熟成させ、実施例２の粘着シートを得た。
<Example 2>
Polyester resin solution a-1 (100 parts by weight of solid content), 15 parts of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals) which is a polyisocyanate-based crosslinking agent, and TC750 (manufactured by Matsumoto Fine Chemicals) which is a titanium-based catalyst 0 1 part was mix | blended and the adhesive solution was obtained. The pressure-sensitive adhesive solution was applied to the release-treated surface of the polyethylene terephthalate film that had been subjected to a release treatment so that the thickness after drying was 30 μm, and was crosslinked by drying at 100 ° C. for 3 minutes to obtain a sheet A-2. . Separately, polyester resin solution b (100 parts by weight in solid content), 1.5 parts of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals) which is a polyisocyanate-based crosslinking agent, and TC750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) which is a titanium catalyst. ) 0.1 part, and an adhesive solution was obtained. This pressure-sensitive adhesive solution was applied to a release-treated surface of a polyethylene terephthalate film that had been subjected to a release treatment so that the thickness after drying was 5 μm, and was crosslinked at 100 ° C. for 3 minutes to obtain a sheet B-2. . Next, the sheet B-2 was laminated on both surfaces of the sheet A-2 with a hand roller and laminated, and further aged for 3 days in an atmosphere at 50 ° C., to obtain an adhesive sheet of Example 2.
＜実施例３＞
ポリエステル樹脂溶液ａ−１（固形分重量で１００部）と、ポリイソシアネート系架橋剤であるデュラネートＴＰＡ−１００(旭化成ケミカルズ社製)１５部と、チタン系触媒であるＴＣ７５０（マツモトファインケミカル社製）０．１部とを配合し、粘着剤溶液を得た。この粘着剤溶液を乾燥後の厚さが２００μｍになるように、剥離処理したポリエチレンテレフタレートフィルムの剥離処理面に塗布し、１００℃で３分間乾燥することによって架橋させ、シートＡ−３を得た。別途、ポリエステル樹脂溶液ｂ（固形分重量で１００部）と、ポリイソシアネート系架橋剤であるデュラネートＴＰＡ−１００(旭化成ケミカルズ社製)１．５部と、チタン系触媒であるＴＣ７５０（マツモトファインケミカル社製）０．１部とを配合し、粘着剤溶液を得た。この粘着剤溶液を乾燥後の厚さが３０μｍになるように、剥離処理したポリエチレンテレフタレートフィルムの剥離処理面に塗布し、１００℃で３分間乾燥することによって架橋させ、シートＢ−３を得た。次いで、シートＡ−３の両面にシートＢ−３をハンドローラーで貼り合せて積層し、更に５０℃の雰囲気で３日間熟成させ、実施例３の粘着シートを得た。
<Example 3>
Polyester resin solution a-1 (100 parts by weight in solids), 15 parts of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals) which is a polyisocyanate-based crosslinking agent, and TC750 (manufactured by Matsumoto Fine Chemicals) which is a titanium catalyst 0 1 part was mix | blended and the adhesive solution was obtained. The pressure-sensitive adhesive solution was applied to a release-treated surface of a polyethylene terephthalate film that had been subjected to a release treatment so that the thickness after drying was 200 μm, and was crosslinked by drying at 100 ° C. for 3 minutes to obtain a sheet A-3. . Separately, polyester resin solution b (100 parts by weight in solid content), 1.5 parts of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals) which is a polyisocyanate-based crosslinking agent, and TC750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) which is a titanium catalyst. ) 0.1 part, and an adhesive solution was obtained. This pressure-sensitive adhesive solution was applied to a release-treated surface of a polyethylene terephthalate film that had been subjected to a release treatment so that the thickness after drying was 30 μm, and was crosslinked by drying at 100 ° C. for 3 minutes to obtain a sheet B-3. . Next, the sheet B-3 was laminated on both sides of the sheet A-3 with a hand roller and laminated, and further aged in an atmosphere at 50 ° C. for 3 days to obtain an adhesive sheet of Example 3.
＜実施例４＞
ポリエステル樹脂溶液ａ−２（固形分重量で１００部）と、ポリイソシアネート系架橋剤であるデュラネートＴＰＡ−１００(旭化成ケミカルズ社製)２０部と、チタン系触媒であるＴＣ７５０（マツモトファインケミカル社製）０．１部とを配合し、粘着剤溶液を得た。この粘着剤溶液を乾燥後の厚さが２００μｍになるように、剥離処理したポリエチレンテレフタレートフィルムの剥離処理面に塗布し、１００℃で３分間乾燥することによって架橋させ、シートＡ−４を得た。別途、ポリエステル樹脂溶液ｂ（固形分重量で１００部）と、ポリイソシアネート系架橋剤であるデュラネートＴＰＡ−１００(旭化成ケミカルズ社製)１．２部と、チタン系触媒であるＴＣ７５０（マツモトファインケミカル社製）０．１部とを配合し、粘着剤溶液を得た。この粘着剤溶液を乾燥後の厚さが５μｍになるように、剥離処理したポリエチレンテレフタレートフィルムの剥離処理面に塗布し、１００℃で３分間乾燥することによって架橋させ、シートＢ−４を得た。次いで、シートＡ−４の両面にシートＢ−４をハンドローラーで貼り合せて積層し、更に５０℃の雰囲気で３日間熟成させ、実施例４の粘着シートを得た。
<Example 4>
Polyester resin solution a-2 (100 parts by weight in solid content), 20 parts of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals) which is a polyisocyanate crosslinking agent, and TC750 (manufactured by Matsumoto Fine Chemicals) which is a titanium catalyst 0 1 part was mix | blended and the adhesive solution was obtained. This pressure-sensitive adhesive solution was applied to the release-treated surface of a polyethylene terephthalate film that had been subjected to a release treatment so that the thickness after drying was 200 μm, and was crosslinked by drying at 100 ° C. for 3 minutes to obtain a sheet A-4. . Separately, polyester resin solution b (100 parts by weight in solid content), 1.2 parts of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals) which is a polyisocyanate-based crosslinking agent, and TC750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) which is a titanium catalyst. ) 0.1 part, and an adhesive solution was obtained. This pressure-sensitive adhesive solution was applied to the release-treated surface of a polyethylene terephthalate film that had been subjected to a release treatment so that the thickness after drying was 5 μm, and was crosslinked by drying at 100 ° C. for 3 minutes to obtain a sheet B-4. . Subsequently, the sheet B-4 was laminated on both surfaces of the sheet A-4 with a hand roller, and further aged in an atmosphere at 50 ° C. for 3 days to obtain an adhesive sheet of Example 4.
＜実施例５＞
ポリエステル樹脂溶液ａ−３（固形分重量で１００部）と、ポリイソシアネート系架橋剤であるデュラネートＴＰＡ−１００(旭化成ケミカルズ社製)１３部と、チタン系触媒であるＴＣ７５０（マツモトファインケミカル社製）０．１部とを配合し、粘着剤溶液を得た。この粘着剤溶液を乾燥後の厚さが１００μｍになるように、剥離処理したポリエチレンテレフタレートフィルムの剥離処理面に塗布し、１００℃で３分間乾燥することによって架橋させ、シートＡ−５を得た。別途、ポリエステル樹脂溶液ｂ（固形分重量で１００部）と、ポリイソシアネート系架橋剤であるデュラネートＴＰＡ−１００(旭化成ケミカルズ社製)２．５部と、チタン系触媒であるＴＣ７５０（マツモトファインケミカル社製）０．１部とを配合し、粘着剤溶液を得た。この粘着剤溶液を乾燥後の厚さが１０μｍになるように、剥離処理したポリエチレンテレフタレートフィルムの剥離処理面に塗布し、１００℃で３分間乾燥することによって架橋させ、シートＢ−５を得た。次いで、シートＡ−５の両面にシートＢ−５をハンドローラーで貼り合せて積層し、更に５０℃の雰囲気で３日間熟成させ、実施例５の粘着シートを得た。
<Example 5>
Polyester resin solution a-3 (100 parts by weight in solids), 13 parts of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals) which is a polyisocyanate-based crosslinking agent, and TC750 (manufactured by Matsumoto Fine Chemicals) which is a titanium catalyst 0 1 part was mix | blended and the adhesive solution was obtained. This pressure-sensitive adhesive solution was applied to a release-treated surface of a polyethylene terephthalate film that had been subjected to a release treatment so that the thickness after drying was 100 μm, and was crosslinked by drying at 100 ° C. for 3 minutes to obtain a sheet A-5. . Separately, polyester resin solution b (100 parts by weight in solid content), 2.5 parts of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals Co., Ltd.), a polyisocyanate crosslinking agent, and TC750 (manufactured by Matsumoto Fine Chemical Co., Ltd.), a titanium catalyst. ) 0.1 part, and an adhesive solution was obtained. This pressure-sensitive adhesive solution was applied to a release-treated surface of a polyethylene terephthalate film that had been subjected to a release treatment so that the thickness after drying was 10 μm, and was crosslinked by drying at 100 ° C. for 3 minutes to obtain a sheet B-5. . Next, the sheet B-5 was laminated on both surfaces of the sheet A-5 with a hand roller and laminated, and further aged for 3 days in an atmosphere at 50 ° C. to obtain an adhesive sheet of Example 5.
＜比較例１＞
ポリエステル樹脂溶液ｂ（固形分重量で１００部）と、ポリイソシアネート系架橋剤であるデュラネートＴＰＡ−１００(旭化成ケミカルズ社製)２．５部と、チタン系触媒であるＴＣ７５０（マツモトファインケミカル社製）０．１部とを配合し、粘着剤溶液を得た。この粘着剤溶液を乾燥後の厚さが１００μｍになるように、剥離処理したポリエチレンテレフタレートフィルムの剥離処理面に塗布し、１００℃で３分間乾燥することによって架橋させ、シートＢ−６を得た。次いで、得られたシートＢ−６を中心層とし、この両面に、実施例１で得られたシートＢ−１をハンドローラーで貼り合せて積層し、更に５０℃の雰囲気で３日間熟成させ、比較例１の粘着シートを得た。
<Comparative Example 1>
Polyester resin solution b (100 parts by weight in solid content), 2.5 parts of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals) which is a polyisocyanate crosslinking agent, and TC750 (manufactured by Matsumoto Fine Chemicals) which is a titanium catalyst 0 1 part was mix | blended and the adhesive solution was obtained. This pressure-sensitive adhesive solution was applied to the release-treated surface of a polyethylene terephthalate film that had been subjected to a release treatment so that the thickness after drying was 100 μm, and was crosslinked by drying at 100 ° C. for 3 minutes to obtain a sheet B-6. . Then, using the obtained sheet B-6 as a central layer, the sheet B-1 obtained in Example 1 was laminated on both sides with a hand roller, and further aged for 3 days in an atmosphere at 50 ° C. A pressure-sensitive adhesive sheet of Comparative Example 1 was obtained.
＜比較例２＞
ポリエステル樹脂溶液ｂ（固形分重量で１００部）と、ポリイソシアネート系架橋剤であるデュラネートＴＰＡ−１００(旭化成ケミカルズ社製)１．０部と、チタン系触媒であるＴＣ７５０（マツモトファインケミカル社製）０．１部とを配合し、粘着剤溶液を得た。この粘着剤溶液を乾燥後の厚さが１０μｍになるように、剥離処理したポリエチレンテレフタレートフィルムの剥離処理面に塗布し、１００℃で３分間乾燥することによって架橋させ、シートＢ−７を得た。次いで、実施例１で得られたシートＡ−１の両面に、シートＢ−７をハンドローラーで貼り合せて積層し、更に５０℃の雰囲気で３日間熟成させ、比較例２の粘着シートを得た。
<Comparative example 2>
Polyester resin solution b (100 parts by weight in solids), 1.0 part of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals) which is a polyisocyanate crosslinking agent, and TC750 (manufactured by Matsumoto Fine Chemicals) which is a titanium catalyst 0 1 part was mix | blended and the adhesive solution was obtained. This pressure-sensitive adhesive solution was applied to the release-treated surface of a polyethylene terephthalate film that had been subjected to a release treatment so that the thickness after drying was 10 μm, and was crosslinked at 100 ° C. for 3 minutes to obtain a sheet B-7. . Next, the sheet B-7 was laminated on both surfaces of the sheet A-1 obtained in Example 1 with a hand roller, and further aged in an atmosphere at 50 ° C. for 3 days to obtain a pressure-sensitive adhesive sheet of Comparative Example 2. It was.
＜比較例３＞
ポリエステル樹脂溶液ａ−３（固形分重量で１００部）と、ポリイソシアネート系架橋剤であるデュラネートＴＰＡ−１００(旭化成ケミカルズ社製)１３部と、チタン系触媒であるＴＣ７５０（マツモトファインケミカル社製）０．１部とを配合し、粘着剤溶液を得た。この粘着剤溶液を乾燥後の厚さが１０μｍになるように、剥離処理したポリエチレンテレフタレートフィルムの剥離処理面に塗布し、１００℃で３分間乾燥することによって架橋させ、シートＡ−６を得た。次いで、実施例１で得られたシートＡ−１の両面にシートＡ−６をハンドローラーで貼り合せて積層し、更に５０℃の雰囲気で３日間熟成させ、比較例３の粘着シートを得た。
<Comparative Example 3>
Polyester resin solution a-3 (100 parts by weight in solids), 13 parts of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals) which is a polyisocyanate-based crosslinking agent, and TC750 (manufactured by Matsumoto Fine Chemicals) which is a titanium catalyst 0 1 part was mix | blended and the adhesive solution was obtained. This pressure-sensitive adhesive solution was applied to a release-treated surface of a polyethylene terephthalate film that had been subjected to a release treatment so that the thickness after drying was 10 μm, and was crosslinked by drying at 100 ° C. for 3 minutes to obtain a sheet A-6. . Next, the sheet A-6 was laminated on both surfaces of the sheet A-1 obtained in Example 1 with a hand roller, and further aged in an atmosphere at 50 ° C. for 3 days to obtain an adhesive sheet of Comparative Example 3. .
＜比較例４＞
実施例１で得られたシートＢ−１を、単層シートのまま５０℃の雰囲気で３日間熟成させ、比較例４の粘着シートを得た。
<Comparative example 4>
The sheet B-1 obtained in Example 1 was aged in an atmosphere of 50 ° C. for 3 days as a single-layer sheet to obtain a pressure-sensitive adhesive sheet of Comparative Example 4.
＜比較例５＞
実施例１で得られたシートＡ−１を、単層シートのまま５０℃の雰囲気で３日間熟成させ、比較例５の粘着シートを得た。
<Comparative Example 5>
The sheet A-1 obtained in Example 1 was aged for 3 days in an atmosphere of 50 ° C. as a single-layer sheet to obtain a pressure-sensitive adhesive sheet of Comparative Example 5.
＜比較例６＞
ポリエステル樹脂溶液ａ−４（固形分重量で１００部）と、ポリイソシアネート系架橋剤であるデュラネートＴＰＡ−１００(旭化成ケミカルズ社製)１５部と、チタン系触媒であるＴＣ７５０（マツモトファインケミカル社製）０．１部とを配合し、粘着剤溶液を得た。この粘着剤溶液を乾燥後の厚さが１００μｍになるように、剥離処理したポリエチレンテレフタレートフィルムの剥離処理面に塗布し、１００℃で３分間乾燥することによって架橋させ、シートＡ−７を得た。次いで、シートＡ−７の両面に実施例１で得られたシートＢ−１をハンドローラーで貼り合せて積層し、更に５０℃の雰囲気で３日間熟成させ、比較例６の粘着シートを得た。
<Comparative Example 6>
Polyester resin solution a-4 (100 parts by weight in solid content), 15 parts of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals) which is a polyisocyanate crosslinking agent, and TC750 (manufactured by Matsumoto Fine Chemicals) which is a titanium catalyst 0 1 part was mix | blended and the adhesive solution was obtained. This pressure-sensitive adhesive solution was applied to a release-treated surface of a polyethylene terephthalate film that had been subjected to a release treatment so that the thickness after drying was 100 μm, and was crosslinked by drying at 100 ° C. for 3 minutes to obtain a sheet A-7. . Next, the sheet B-1 obtained in Example 1 was laminated on both surfaces of the sheet A-7 with a hand roller and laminated, and further aged for 3 days in an atmosphere of 50 ° C., to obtain a pressure-sensitive adhesive sheet of Comparative Example 6. .
上記シートＡ−１〜Ａ−７及びシートＢ−１〜Ｂ−７、並びに実施例及び比較例の粘着シートについて、下記評価を行った。結果を表１に示す。 The following evaluation was performed about the adhesive sheet of the said sheet | seat A-1 to A-7, sheet | seat B-1 to B-7, and an Example and a comparative example. The results are shown in Table 1.
＜貯蔵弾性率Ｇ’＞
乾燥後（架橋後）で積層前のシートＡ−１〜Ａ−７及びシートＢ−１〜Ｂ−７について、それぞれ直径８ｍｍφの円形状に切り抜いた後、ポリエチレンテレフタレートフィルムから剥がし、更に厚さが３ｍｍになるように複数枚貼り合せて、測定サンプルを作製した。この測定サンプルを、パラレルプレート(せん断試験用)を用いて、Ｒｈｅｏｍｅｔｒｉｃ Ｓｃｉｅｎｔｉｆｉｃ社製「Ａｄｖａｎｃｅｄ Ｒｈｅｏｍｅｔｒｉｃ Ｅｘｐａｎｓｉｏｎ Ｓｙｓｔｅｍ（ＡＲＥＳ）」により、周波数１Ｈｚ、測定範囲−７０〜２００℃、昇温速度５℃／分の条件で測定し、温度２００℃における測定値を貯蔵弾性率Ｇ’とした。
<Storage elastic modulus G '>
After drying (after crosslinking) and before lamination, the sheets A-1 to A-7 and the sheets B-1 to B-7 are cut into circular shapes with a diameter of 8 mmφ, and then peeled off from the polyethylene terephthalate film. A plurality of sheets were laminated so as to be 3 mm to prepare a measurement sample. Using a parallel plate (for shear test), this measurement sample was subjected to a frequency of 1 Hz, a measurement range of −70 to 200 ° C., and a temperature increase rate of 5 ° C./min by “Advanced Rheometric Expansion System (ARES)” manufactured by Rheometric Scientific. Measurement was performed under conditions, and the measured value at a temperature of 200 ° C. was defined as storage elastic modulus G ′.
＜ゲル分率＞
乾燥後（架橋後）で積層前のシートＡ−１〜Ａ−７及びシートＢ−１〜Ｂ−７について、それぞれ５ｃｍ×５ｃｍのサイズで切り出した後、ポリエチレンテレフタレートフィルムから剥がし、更に０．２μｍ径の孔を有するポリテトラフルオロエチレンシート（日東電工社製、商品名「ＮＴＦ１１２２」）に包んだ後、該ポリテトラフルオロエチレンシートの縁部を凧糸で縛り、その際の重量を測定し、該重量を浸漬前重量とした。つまり、該浸漬前重量は、粘着剤組成物層と、ポリテトラフルオロエチレンシートと、凧糸との総重量である。また、ポリテトラフルオロエチレンシートと凧糸との総重量も測定しておき、該重量を包袋重量とした。次に、上記ポリテトラフルオロエチレンシートで包んだ状態のサンプルを、トルエン（５０ｍＬ）中に浸漬し、２３℃にて７日間静置した。その後、上記サンプルを取り出して、アルミニウム製カップに移し、１３０℃で２時間乾燥してトルエンを除去した後、サンプルの重量を測定し、該重量を浸漬後重量とした。そして、下記の式からゲル分率を算出した。
ゲル分率（重量％）＝（浸漬後重量−包袋重量）／（浸漬前重量−包袋重量）×１００
<Gel fraction>
After drying (after crosslinking) and before lamination, the sheets A-1 to A-7 and the sheets B-1 to B-7 were cut out in a size of 5 cm × 5 cm, then peeled off from the polyethylene terephthalate film, and further 0.2 μm. After wrapping in a polytetrafluoroethylene sheet having a diameter hole (manufactured by Nitto Denko Corporation, trade name “NTF1122”), the edge of the polytetrafluoroethylene sheet is tied with a string, and the weight at that time is measured. This weight was defined as the weight before immersion. That is, the weight before immersion is the total weight of the pressure-sensitive adhesive composition layer, the polytetrafluoroethylene sheet, and the kite string. Further, the total weight of the polytetrafluoroethylene sheet and the kite string was also measured, and the weight was used as the wrapping weight. Next, the sample wrapped with the polytetrafluoroethylene sheet was immersed in toluene (50 mL) and allowed to stand at 23 ° C. for 7 days. Thereafter, the sample was taken out, transferred to an aluminum cup, dried at 130 ° C. for 2 hours to remove toluene, the weight of the sample was measured, and the weight was taken as the weight after immersion. And the gel fraction was computed from the following formula.
Gel fraction (% by weight) = (weight after immersion−wrapping bag weight) / (weight before immersion−wrapping bag weight) × 100
＜粘着力＞
各実施例及び比較例で得られた粘着シートの一方の面に、コロナ処理を施した厚さ２５μｍのポリエチレンテレフタレートフィルムを貼り付けて、長さ１１０ｍｍ×幅２０ｍｍに切り出して、これを測定片とした。この測定片をステンレス鋼板に貼付し、測定片上で２ｋｇのローラーを一往復させて圧着した後、ＪＩＳ Ｃ ２１０７(１８０度引き剥がし法)に基づいて粘着力の測定を行なった。ただし、引張り速度は３００ｍｍ／分とした。
<Adhesive strength>
A polyethylene terephthalate film with a thickness of 25 μm subjected to corona treatment is attached to one surface of the pressure-sensitive adhesive sheet obtained in each example and comparative example, cut into a length of 110 mm and a width of 20 mm, and this is used as a measurement piece. did. This measurement piece was affixed to a stainless steel plate, and a 2 kg roller was reciprocated once on the measurement piece for pressure bonding, and then the adhesive strength was measured based on JIS C 2107 (180 degree peeling method). However, the pulling speed was 300 mm / min.
＜耐熱保持性＞
各実施例及び比較例で得られた粘着シートの一方の面に、厚さ９０μｍのアルミテープを貼付し、１０ｍｍ×１００ｍｍに切り出して、これを測定片とした。この測定片の一方の先端から２０ｍｍをベークライト板（１２５ｍｍ×２５ｍｍ、厚み２ｍｍ）に貼付し、貼付箇所上で５ｋｇのローラーを一往復させて圧着し、８０℃の雰囲気下で圧着直後から３０分放置した後に、他方の先端に０．５ｋｇの分銅をかけ、最低測定温度を６０℃とし、昇温速度１℃／分の条件で昇温していき、貼付状態の保持が可能な最高温度（耐熱保持温度）を調べた。耐熱保持温度が高いほど耐熱保持性が良好であることを示す。なお、比較例２，３，５は、測定温度が６０℃の段階で貼付状態の保持ができなかった。
<Heat resistance retention>
An aluminum tape having a thickness of 90 μm was applied to one surface of the pressure-sensitive adhesive sheet obtained in each of the examples and comparative examples, and was cut into 10 mm × 100 mm, which was used as a measurement piece. Attach 20 mm from one end of this measurement piece to a bakelite plate (125 mm x 25 mm, thickness 2 mm), and reciprocate a 5 kg roller on the application location, and press for 30 minutes immediately after pressure bonding in an 80 ° C atmosphere. After standing, place a weight of 0.5 kg on the other tip, set the minimum measurement temperature to 60 ° C, raise the temperature at a rate of temperature increase of 1 ° C / min, and maintain the maximum temperature ( (Heat-resistant holding temperature) was investigated. The higher the heat resistant holding temperature, the better the heat resistant retaining property. In Comparative Examples 2, 3, and 5, the pasting state could not be maintained when the measurement temperature was 60 ° C.
表１に示すように、本発明の実施例は、粘着力及び耐熱保持性のいずれもが良好な値を示した。一方、比較例は、粘着力及び耐熱保持性の少なくとも一方について、実施例に比べ顕著に劣る結果が得られた。 As shown in Table 1, the examples of the present invention showed good values for both adhesive strength and heat resistance retention. On the other hand, the comparative example was significantly inferior to the examples with respect to at least one of adhesive strength and heat resistance retention.
Ａ 感圧性粘着剤組成物層（２００℃における貯蔵弾性率が２５〜４０ｋＰａであるポリエステル樹脂により形成）
Ｂ 感圧性粘着剤組成物層（２００℃における貯蔵弾性率が１０〜２０ｋＰａであるポリエステル樹脂により形成）
A pressure-sensitive adhesive composition layer (formed with a polyester resin having a storage modulus of 25 to 40 kPa at 200 ° C.)
B Pressure-sensitive adhesive composition layer (formed with a polyester resin having a storage elastic modulus at 200 ° C. of 10 to 20 kPa)
Claims (8)
前記感圧性粘着剤組成物層Ａは、２００℃における貯蔵弾性率が２５〜４０ｋＰａであるポリエステル樹脂により形成されており、
前記感圧性粘着剤組成物層Ｂは、２００℃における貯蔵弾性率が１０〜２０ｋＰａであるポリエステル樹脂により形成されている、積層体。 A pressure-sensitive adhesive composition layer A and a laminate comprising pressure-sensitive adhesive composition layer B provided on both sides of the pressure-sensitive adhesive composition layer A,
The pressure-sensitive adhesive composition layer A is formed of a polyester resin having a storage elastic modulus at 200 ° C. of 25 to 40 kPa,
The said pressure sensitive adhesive composition layer B is a laminated body currently formed with the polyester resin whose storage elastic modulus in 200 degreeC is 10-20 kPa.
前記感圧性粘着剤組成物層Ｂの厚さが、５〜３０μｍである請求項１記載の積層体。 The thickness of the pressure-sensitive adhesive composition layer A is 10 to 200 μm,
The laminate according to claim 1, wherein the pressure-sensitive adhesive composition layer B has a thickness of 5 to 30 µm.
前記感圧性粘着剤組成物層Ｂを形成するポリエステル樹脂のゲル分率が、３０〜６５重量％である請求項３記載の積層体。 The gel fraction of the polyester resin forming the pressure-sensitive adhesive composition layer A is 70 to 95% by weight,
The laminate according to claim 3, wherein a gel fraction of the polyester resin forming the pressure-sensitive adhesive composition layer B is 30 to 65% by weight.
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| WO2013146079A1 (en) * | 2012-03-29 | 2013-10-03 | 日東電工株式会社 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet for surface protection |
| JP2013216874A (en) * | 2012-03-16 | 2013-10-24 | Nitto Denko Corp | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| JP2014208741A (en) * | 2013-03-26 | 2014-11-06 | 東洋紡株式会社 | Polyester resin aqueous dispersion and adhesive composition using the same |
| WO2020218174A1 (en) * | 2019-04-23 | 2020-10-29 | 三菱ケミカル株式会社 | Adhesive and adhesive sheet |
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| JP2013216874A (en) * | 2012-03-16 | 2013-10-24 | Nitto Denko Corp | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| US9902886B2 (en) | 2012-03-16 | 2018-02-27 | Nitto Denko Corporation | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| WO2013146079A1 (en) * | 2012-03-29 | 2013-10-03 | 日東電工株式会社 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet for surface protection |
| JP2013203979A (en) * | 2012-03-29 | 2013-10-07 | Nitto Denko Corp | Adhesive composition and adhesive sheet for surface protection |
| JP2014208741A (en) * | 2013-03-26 | 2014-11-06 | 東洋紡株式会社 | Polyester resin aqueous dispersion and adhesive composition using the same |
| WO2020218174A1 (en) * | 2019-04-23 | 2020-10-29 | 三菱ケミカル株式会社 | Adhesive and adhesive sheet |
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