US20230407142A1 - Adhesive sheet - Google Patents
Adhesive sheet Download PDFInfo
- Publication number
- US20230407142A1 US20230407142A1 US18/456,441 US202318456441A US2023407142A1 US 20230407142 A1 US20230407142 A1 US 20230407142A1 US 202318456441 A US202318456441 A US 202318456441A US 2023407142 A1 US2023407142 A1 US 2023407142A1
- Authority
- US
- United States
- Prior art keywords
- adhesive
- adhesive layer
- adhesive sheet
- epoxy resin
- protective layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 129
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 123
- 239000012790 adhesive layer Substances 0.000 claims abstract description 100
- 239000011241 protective layer Substances 0.000 claims abstract description 74
- 239000003822 epoxy resin Substances 0.000 claims abstract description 59
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 59
- 239000012943 hotmelt Substances 0.000 claims abstract description 13
- 239000002216 antistatic agent Substances 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 239000006078 metal deactivator Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 3
- 229920006332 epoxy adhesive Polymers 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract 2
- 239000010410 layer Substances 0.000 claims description 17
- 229920000728 polyester Polymers 0.000 claims description 7
- 229920005749 polyurethane resin Polymers 0.000 claims description 4
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 2
- 238000005187 foaming Methods 0.000 description 30
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- 238000001723 curing Methods 0.000 description 27
- -1 polyethylene terephthalate Polymers 0.000 description 20
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 18
- 238000013329 compounding Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 239000004088 foaming agent Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 229920005862 polyol Polymers 0.000 description 11
- 150000003077 polyols Chemical class 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 230000006870 function Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000003094 microcapsule Substances 0.000 description 9
- 239000005011 phenolic resin Substances 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000037380 skin damage Effects 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 230000002940 repellent Effects 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- 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
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical class O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
- UFXYYTWJETZVHG-UHFFFAOYSA-N 1,3-diisocyanatobutane Chemical compound O=C=NC(C)CCN=C=O UFXYYTWJETZVHG-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- ZOQVDXYAPXAFRW-UHFFFAOYSA-N 2,5-diethyl-1h-imidazole Chemical compound CCC1=CNC(CC)=N1 ZOQVDXYAPXAFRW-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- HSDVRWZKEDRBAG-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COC(CCCCC)OCC1CO1 HSDVRWZKEDRBAG-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
- ZVHYOUBYDHIYOJ-UHFFFAOYSA-N 4-n,4-n-dinitrosobenzene-1,4-dicarboxamide Chemical compound NC(=O)C1=CC=C(C(=O)N(N=O)N=O)C=C1 ZVHYOUBYDHIYOJ-UHFFFAOYSA-N 0.000 description 1
- ZRSCAJHLPIPKBU-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazol-4-ol Chemical compound N1C(O)=C(C)N=C1C1=CC=CC=C1 ZRSCAJHLPIPKBU-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 150000004008 N-nitroso compounds Chemical class 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920013629 Torelina Polymers 0.000 description 1
- 239000004742 Torelina™ Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-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
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 150000001540 azides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IRLQAJPIHBZROB-UHFFFAOYSA-N buta-2,3-dienenitrile Chemical compound C=C=CC#N IRLQAJPIHBZROB-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentenylidene Natural products C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 239000000539 dimer Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003349 semicarbazides Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 210000003813 thumb Anatomy 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/24—Presence of a foam
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2463/00—Presence of epoxy resin
Definitions
- the present invention relates to an adhesive sheet having a protective layer on the surface of an adhesive layer.
- Adhesive sheets are used for fixing parts and members in fields such as the electric and electronic field, the automobile related field and the civil engineering and construction field.
- the adhesive sheet is provided with a layer of an adhesive agent such as an epoxy-based or acrylic-based one having high adhesiveness in order to realize strong adhesion to an adherend.
- Non-Patent Document 1 Non-Patent Document 1
- an object of the present invention is to provide an adhesive sheet which can protect an adhesion surface and does not cause blocking or skin damage even if a release liner is not used.
- the present inventors have conducted intensive studies to solve the above-mentioned object and resultantly found that it is very effective to provide a protective layer on at least a part of the surface of an adhesive layer, leading to completion of the present invention.
- the present invention relates to an adhesive sheet having an adhesive layer on at least a part of one or both sides of a base, characterized in that the adhesive sheet has a protective layer on at least a part of the surface of the adhesive layer.
- the adhesive sheet of the present invention can protect the adhesion surface and does not cause blocking or skin damage even without using a release liner. Further, by including substances having various functions such as, for example, an antistatic agent, a coloring agent, a hard coat agent, a lubricant, a heat dissipating material, a metal deactivator, an antioxidant and a flame retardant in the protective layer, various functions can be imparted to the adhesive sheet without impairing properties of the adhesive layer.
- FIG. 1 is a schematic sectional view showing an embodiment of the adhesive sheet of the present invention.
- FIG. 3 is a graph showing the results of reflection IR measurement of the surface compositions of the protective layer (before foaming) of the adhesive sheet of Example 6 and the adhesive layer (before foaming) of the adhesive sheet of Comparative Example 1.
- FIG. 1 is a schematic sectional view showing one embodiment of the adhesive sheet of the present invention.
- an adhesive layer 2 is provided on one entire surface of a base 1
- a protective layer 3 is provided on the entire surface of the adhesive layer 2 .
- the present invention is not limited to this embodiment, and for example, the adhesive layers 2 may be provided on both sides of the base 1 .
- the protective layer 3 may contain functional components such as an antistatic agent, a coloring agent, a hard coat agent, a lubricant, a heat dissipating material, a metal deactivator, an antioxidant, a flame retardant, a water/oil repellent and a solvent resistant resin which will be described in detail later. Thereby, a desired function other than protection can be imparted to the protective layer 3 .
- the adhesive layer 2 may also contain functional components which are the same as or different from those in the protective layer 3 .
- Two types of the protective layer 3 can be provided.
- a protective layer having a two-layered structure in which, on the surface of the protective layer 3 a provided on the adhesive layer 2 , another protective layer 3 b is further provided may be permissible.
- the protective layer 3 having such a two-layered structure may be formed by additionally coating the protective layer 3 b on the protective layer 3 a , or may be formed by separating in the coating process.
- the protective layer may have a three or more-layered structure.
- the protective layer 3 a and the protective layer 3 b may be provided at different positions on the surface of the adhesive layer 2 , respectively.
- the base 1 used in the present invention is a member for supporting the adhesive layer 2 as shown in FIG. 1 .
- the base 1 may be a single-layered base composed of one member as shown in FIG. 1 or a base composed of a laminate having a laminated structure in which one member and another member are pasted with a bonding adhesive for lamination.
- the base 1 may have flexibility or may have resilience, and its properties are appropriately selected depending on the application. In applications where the stiffness and shape retention capacity of the adhesive sheet are required, the base 1 is preferably a base composed of a laminate.
- the member constituting the base 1 is preferably a resin film, a nonwoven fabric or paper, and more preferably a resin film.
- the member is preferably at least one member selected from the group consisting of a resin film, a nonwoven fabric and paper, and at least one is preferably a resin film.
- the adhesive layer 2 used in the present invention is provided on at least a part of one or both sides of a base.
- the type of the adhesive layer 2 is not particularly limited, but is preferably a thermosetting adhesive layer containing a thermosetting resin, a curing agent and a curing catalyst, more preferably an expansion adhesive layer containing a temperature-sensitive foaming agent, particularly preferably a foamable epoxy adhesive layer in which the thermosetting resin is an epoxy resin.
- the epoxy resin preferably contains a polyfunctional epoxy resin.
- the type of the polyfunctional epoxy resin is not limited, novolak-type epoxy resins such as a phenol novolak type and a cresol novolak type, and a mixture thereof are preferable.
- novolak-type epoxy resin When a novolak-type epoxy resin is used, the glass transition temperature of the cured product becomes high, so that the adhesive force tends to be stable even at high temperatures.
- epoxy resins other than the polyfunctional epoxy resin may be used in combination.
- the physical properties such as softening temperature, melt viscosity, glass transition temperature and storage elastic modulus of the epoxy resin can be controlled easily and in detail.
- the liquid epoxy resin can also be used for the purpose of pre-dispersing components such as a thermally expandable microcapsule in power or grain state contained in the temperature-sensitive foaming agent, or for the purpose of uniformly mixing components of the epoxy resin.
- the crystalline epoxy resin is non-tacky solid at normal temperature, while acts as a reactive diluent at melting temperature or more since melt viscosity lowers significantly at melting temperature or more.
- the softening temperature of an epoxy resin can be measured using a ring and ball softening temperature test method prescribed in JIS K 2207.
- the foaming temperature of the thermally expandable microcapsule is a temperature at which volume variation of the thermally expandable microcapsule occurs, and it can be selected, for example, from a range of 70° C. or more and 200° C. or less, preferably 100° C. or more and 180° C. or less.
- the content and the volume expansion modulus of the temperature-sensitive foaming agent can be appropriately determined according to, for example, the strength and the adhesive force required for the cured adhesive layer 2 and the expansion modulus required for the adhesive sheet.
- the content of the temperature-sensitive foaming agent is preferably 0.5 to 20 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass of resin components in the adhesive layer 2 .
- the increase factor of the thickness of the adhesive sheet after foaming can be, for example, 1.1 times or more and 10 times or less.
- the other resins include a polyester resin, a butyral resin, a urethane resin, a carboxyl group-terminated butadiene nitrile rubber (CTBN) and epoxy-modified butadiene.
- CTBN carboxyl group-terminated butadiene nitrile rubber
- a urethane resin is most preferable from the standpoint of flexibility and adhesiveness.
- the urethane resin is, in general, a resin containing a soft segment composed of a polyol monomer unit and a hard segment composed of a polyfunctional isocyanate compound or a low molecular glycol monomer unit.
- the polyol used in the urethane resin is a compound having two or more hydroxyl groups.
- the number of a hydroxyl group of the polyol is preferably 2 to 3, more preferably 2 from the standpoint of enhancing properties such as rubber elasticity elongation recovery rate.
- the polyol for example, polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol and castor oil-based polyol can be used. Two or more polyols may be used in combination.
- polyfunctional isocyanate compound used as the cross-linking agent for crosslinking a polyol for example, polyfunctional aliphatic isocyanate compounds, polyfunctional alicyclic isocyanate compounds, and polyfunctional aromatic isocyanate compounds can be used. Further, trimethylolpropane adducts of these compounds, a biuret body reacted with water, and a trimer having an isocyanurate ring can also be used. Two or more polyfunctional isocyanate compounds may be used in combination.
- polyfunctional aliphatic isocyanate compound examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
- polyfunctional alicyclic isocyanate compound examples include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate.
- polyfunctional aromatic diisocyanate compound examples include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate and xylylene diisocyanate.
- the urethane resin is obtained by curing a composition containing the polyol and the polyfunctional isocyanate compound explained above.
- a composition containing the polyol and the polyfunctional isocyanate compound explained above Particularly, low crystallinity linear polyester type polyurethane resins are preferable, and hexanediol copolyester type polyurethane resins and polytetramethylene glycol type polyurethane resins are more preferable, from the standpoint of properties such as rubber elastic elongation recovery rate.
- the content of the urethane resin is preferably 60 parts by mass or less in 100 parts by mass of resin components in the adhesive layer 2 .
- the adhesive layer 2 contains a heat resistant filler from the standpoint of heat resistance and thermal conductivity.
- the kind of the heat resistant filler is not particularly restricted, and the heat resistant filler includes, for example, inorganic fillers such as aluminum oxide, magnesium oxide, calcium oxide, aluminum hydroxide, magnesium hydroxide, boron nitride, silicon nitride, silicon oxide and talc (magnesium silicate). Two or more heat resistant fillers may be used in combination.
- the content of the heat resistant filler is preferably 20 to 300 parts by mass, more preferably 20 to 100 parts by mass with respect to 100 parts by mass of resin components in the adhesive agent.
- the adhesive layer 2 may contain additives such as antioxidants such as phenol type antioxidants and sulfur-based antioxidants, silane coupling agents such as epoxy-modified alkoxysilanes, thixotropic agents such as fumed silica, and pigments and dyes for identification, if necessary.
- antioxidants such as phenol type antioxidants and sulfur-based antioxidants
- silane coupling agents such as epoxy-modified alkoxysilanes
- thixotropic agents such as fumed silica
- pigments and dyes for identification if necessary.
- the adhesive layer 2 may be a continuous layer, or a discontinuous layer constituted of a plurality of patterns such as stripes and dots. Further, irregularities such as emboss may be formed on the surface of the adhesive layer 2 .
- irregularities such as emboss may be formed on the surface of the adhesive layer 2 .
- tackiness of the surface of the adhesive layer 2 can be decreased, or the adhesive force of the adhesive layer can be controlled, or the adhesive layer 2 can be formed only on the necessary portion. Since ununiformity of the surface of the adhesive layer 2 as described above is alleviated or annihilated in foaming, an adverse effect on adhesive force due to its ununiformity does not occur easily.
- the thickness of the adhesive layer 2 may be appropriately determined depending on the intended use. Usually, it is 2 to 300 ⁇ m, preferably 2 to 150 ⁇ m.
- the protective layer 3 used in the present invention is provided on at least a part of the surface of the adhesive layer.
- the protective layer 3 is preferably a layer that flows, decomposes or sublimates by heating when bonding the adhesive sheet, and, as a result, does not prevent the adhesive layer 2 from adhering to an adherend.
- the protective layer 3 is a hot-melt protective layer and the adhesive layer 2 is an expandable adhesive layer (an adhesive layer containing a temperature-sensitive foaming agent)
- the hot-melt protective layer flows, and the components constituting the protective layer diffuse into the adhesive layer under the influence of foaming.
- the hot-melt protective layer almost disappears from the surface of the adhesive layer, and the adhesive sheet adheres to an adherend without impairing the original adhesiveness of the adhesive agent.
- the protective layer 3 is a part of a member constituting the adhesive sheet at the time of use, and for example, a release liner that is peeled at the time of use is not the protective layer 3 .
- the type of the hot-melt substance contained in the protective layer 3 is not limited, and it may be a component which is a solid at normal temperature, and flows to the extent that at least it diffuses into the adhesive layer by heating when bonding the adhesive sheet (for example, a thermoplastic resin component).
- the glass transition temperature (Tg) of the hot-melt substance is preferably 100° C. or lower, the melting temperature thereof is preferably 200° C. or lower, and the softening temperature thereof is preferably 180° C. or lower.
- the hot-melt substance itself may be a functional component, or a functional component may be blended with the hot-melt substance.
- the functional component include an antistatic agent, a coloring agent, a hard coat agent, a lubricant, a heat dissipating material, a metal deactivator, an antioxidant, a flame retardant, a water/oil repellent, and a solvent resistant resin.
- the functional component is a hot-melt substance, it is preferable that the functional component flows by heating when bonding the adhesive sheet and diffuses into the adhesive layer.
- the functional component is not a hot-melt substance, it is preferable to include a hot-melt binder together with the functional component.
- the adhesive sheet can be given distinctiveness by coloring. Specifically, for example, it is possible to prevent an incorrect installation of the adhesive sheet having different configurations or adhesives on both sides.
- the type of the coloring agent is not particularly limited, and a commercially available product may be used.
- the protective layer 3 contains a hard coat agent
- scratch resistance can be imparted to the adhesive sheet.
- the type of the hard coat agent is not particularly limited, and a commercially available product may be used.
- printing may be performed on the protective layer 3 containing a hard coat agent by a method such as gravure printing containing a coloring agent. Such a method can be used, for example, when it is desired to display information (Lot or notice) of the adhesive sheet on the adhesive sheet.
- the adhesive sheet can be provided with slipperiness. Specifically, for example, the frictional resistance when arranging the adhesive sheet inside the portable electronic device can be reduced, and the adhesive sheet can be easily arranged even in a complex and intricate place.
- the type of the lubricant is not particularly limited, and a commercially available product may be used.
- the protective layer 3 contains a metal deactivator, it is possible to prevent the adherend (metal) from deteriorating the adhesive layer of the adhesive sheet.
- the type of the metal deactivator is not particularly limited, and a commercially available product may be used.
- the protective layer 3 contains a flame retardant
- flame retardancy can be imparted to the adhesive sheet.
- the type of the flame retardant is not particularly limited, and a commercially available product may be used.
- the protective layer 3 contains a solvent-resistant resin
- solvent resistance can be imparted to the adhesive sheet.
- the type of the solvent-resistant resin is not particularly limited, and a commercially available product may be used.
- the adhesive sheet of the present invention is an adhesive sheet having the protective layer 3 described above, and more specifically, the adhesive sheet has the adhesive layer 2 on at least a part of one side or both sides of the base 1 , and has the protective layer 3 on at least a part of the surface of the adhesive layer 2 .
- the adhesive sheet of the present invention does not require a release liner.
- the protective layer 3 may be provided on one adhesive layer, and the release liner may be provided on the other adhesive layer 2 .
- the adhesive sheet of the present invention preferably has a thickness before foaming and curing of 10 to 1000 ⁇ m, more preferably 10 to 250 ⁇ m, and particularly preferably 20 to 200 ⁇ m.
- the method for producing the adhesive sheet of the present invention is not particularly limited.
- a single-sided adhesive sheet it can be manufactured by forming the adhesive layer 2 on one surface of the base 1 and then forming the protective layer 3 on the surface of the adhesive layer 2 .
- the adhesive layer 2 can be formed by a conventionally known method such as a solution coating method, a melt coating method, a melt extrusion method, and a rolling method.
- the melt coating method can be performed without a solvent, and does not require a solvent removing step and processing equipment, and is therefore preferable in terms of productivity and economy.
- the epoxy resin preferably contains a crystalline epoxy resin.
- the melt viscosity of the epoxy resin can be reduced, and the speed of melt coating can be increased.
- a known coating method may be appropriately used depending on the type of the material.
- the thumb was pressed against the sheet surface with a small force, and the presence or absence of stickiness when peeled off in a very short time was sensuously tested to determine the presence or absence of stickiness.
- the shear adhesive force of the adhesive sheet after foaming as shown in FIG. 2 was measured.
- An SPCC plate manufactured by Nissin Steel Co., Ltd., trade name: SPCC-SB NCB, 1.0 mm thick, 12 ⁇ 100 mm
- the sample attachment area was 10 ⁇ 10 mm
- the foaming and curing conditions were 10 minutes at 180° C.
- the tensile speed was 200 mm/min.
- the pencil hardness of the adhesive sheet before coaming was measured according to JIS K5600 “Testing methods for paints”.
- the contact angle of the adhesive sheet before foaming was measured according to JIS R3257 “Testing method of wettability of glass substrate”.
- For the contact angle of water industrial purified water A300 manufactured by AS ONE Corporation was used, and for the contact angle of an oil, TOYOTA genuine Auto Fluid WS (ATF) was used.
- the shear adhesive force of an adhesive sheet before foaming contaminated with ATF was measured by the same procedure as the method for evaluating the adhesiveness, and the percentage of the shear adhesive force of the contaminated adhesive sheet was calculated when the shear adhesive force of a non-contaminated sheet was taken as 100%.
- the contaminated adhesive sheet was obtained by immersing an adhesive sheet in ATF for 1 second, sandwiching the sheet with a dry waste paper, and allowing the waste paper to absorb excess ATF on the surface of the sheet.
- the surface of a sheet was rubbed three times in reciprocation with absorbent cotton impregnated with toluene at a pressure of 0.1 MPa, and the solvent resistance was evaluated according to the following criteria.
- the static friction coefficient of an adhesive sheet before foaming was measured according to JIS K7125 “Plastics-Film and sheeting-Determination of the coefficients of friction”.
- Adhesive Protective kind sheet layer Compounding — Thickness ( ⁇ m) 0 Expandable adhesive 50 layer ( ⁇ m) Base ( ⁇ m) 75 Expandable adhesive 50 layer ( ⁇ m) Tackiness positive Foreign matter adherence C Adhesiveness (after foaming) (N/cm 2 ) 579 Function Surface resistance ( ⁇ 10 12 ⁇ ) 37.8 evaluation Visual discrimination C Pencil hardness 3B Contact Water 72° angle Oil 27° Contamination resistant 55% adhesiveness Solvent resistance C Thermal conductivity (W/mK) 0.119 Static friction coefficient Unmeasurable due to tackiness Flame retardancy C
- FIG. 3 is a graph showing the result. As apparent from this result, an epoxy-derived absorption peak exists on the surface of the adhesive layer of the adhesive sheet of Comparative Example 1, but no peak exists on the surface of the protective layer of the adhesive sheet of Example 6. Therefore, the adhesive sheet of Example 6 does not cause skin damage due to the epoxy resin component.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
An adhesive sheet includes an adhesive layer provided on at least a part of one side or both sides of a base, wherein the adhesive layer is a foamable epoxy adhesive layer containing a polyfunctional epoxy resin and an epoxy resin other than the polyfunctional epoxy resin, and a hot-melt protective layer is provided on at least a part of a surface of the adhesive layer away from the base, and the protective layer contains at least one additive selected from the group consisting of an antistatic agent, a lubricant, and a metal deactivator.
Description
- This application is a continuation of U.S. patent application Ser. No. 16/637,711, filed Feb. 7, 2020, which is the U.S. National Phase under 35 U.S.C. § 371 of International Application PCT/JP2017/029187, filed Aug. 10, 2017, each disclosure of which is herein incorporated by reference in its entirety. The International Application was published under PCT Article 21(2) in the language other than English.
- The applicant herein explicitly rescinds and retracts any prior disclaimers or disavowals or any amendment/statement otherwise limiting claim scope made in any parent, child or related prosecution history with regard to any subject matter supported by the present application.
- The present invention relates to an adhesive sheet having a protective layer on the surface of an adhesive layer.
- Adhesive sheets are used for fixing parts and members in fields such as the electric and electronic field, the automobile related field and the civil engineering and construction field. The adhesive sheet is provided with a layer of an adhesive agent such as an epoxy-based or acrylic-based one having high adhesiveness in order to realize strong adhesion to an adherend.
- Adhesive sheets before use are required to protect the surface (adhesion surface) of an adhesive layer from foreign matter, dust, scratches and deterioration, in order to prevent a decrease in the adhesion strength. Also, in order to prevent unintentional adhesion to an unintended location (so-called blocking) and to prevent contamination of the operator's hand, protection of the adhesion surface is said to be indispensable.
-
Patent Document 1 discloses a thermosetting adhesive tape or sheet provided with a release liner in order to make it difficult for foreign substances such as dust and dirt to adhere to the surface of the thermosetting adhesive layer.Patent Document 2 discloses an invention that facilitates handling by providing a liner made of a resin film on the adhesion surface of an adhesive sheet for fixing electric components. - However, for an adhesive tape or sheet having a release liner, it is necessary to introduce equipment having a liner winding mechanism in an automatic process of continuously assembling members. Further, since the unnecessary release liner becomes dust, it is not preferable from the viewpoint of global environmental protection.
- On the other hand,
Patent Document 3 discloses a technique in which an inorganic filler is contained in an adhesive layer in order to improve the blocking resistance of the adhesive layer. Further,Patent Document 4 discloses a technique in which a second pressure-sensitive adhesive layer containing a plurality of fine particles is provided on a first pressure-sensitive adhesive layer to make a release sheet unnecessary. - However, although these inventions can prevent blocking and improve work efficiency without using a release liner, there is a concern that the adhesive may affect the skin. In particular, epoxy-based adhesives and acrylic-based adhesives are known to cause skin damage (Non-Patent Document 1), and even the inclusion of fine particles such as an inorganic filler in the adhesive layer cannot avoid such skin damage.
-
- Patent Document 1: JP 2012-51994
- Patent Document 2: JP 2008-280436
- Patent Document 3: JP H08-60108
- Patent Document 4: JP 2017-19993
-
- Non-Patent Document 1: Edited by Three Bond Co., Ltd. “Three Bond Technical News No. 40” issued on Dec. 25, 1992
- The present invention has been made to solve the above-mentioned problems of the prior art. That is, an object of the present invention is to provide an adhesive sheet which can protect an adhesion surface and does not cause blocking or skin damage even if a release liner is not used.
- The present inventors have conducted intensive studies to solve the above-mentioned object and resultantly found that it is very effective to provide a protective layer on at least a part of the surface of an adhesive layer, leading to completion of the present invention.
- That is, the present invention relates to an adhesive sheet having an adhesive layer on at least a part of one or both sides of a base, characterized in that the adhesive sheet has a protective layer on at least a part of the surface of the adhesive layer.
- The adhesive sheet of the present invention can protect the adhesion surface and does not cause blocking or skin damage even without using a release liner. Further, by including substances having various functions such as, for example, an antistatic agent, a coloring agent, a hard coat agent, a lubricant, a heat dissipating material, a metal deactivator, an antioxidant and a flame retardant in the protective layer, various functions can be imparted to the adhesive sheet without impairing properties of the adhesive layer.
-
FIG. 1 is a schematic sectional view showing an embodiment of the adhesive sheet of the present invention. -
FIG. 2 is a schematic view for explaining a method for testing the shear adhesive force of an example. -
FIG. 3 is a graph showing the results of reflection IR measurement of the surface compositions of the protective layer (before foaming) of the adhesive sheet of Example 6 and the adhesive layer (before foaming) of the adhesive sheet of Comparative Example 1. -
FIG. 1 is a schematic sectional view showing one embodiment of the adhesive sheet of the present invention. In the embodiment shown inFIG. 1 (a) , anadhesive layer 2 is provided on one entire surface of abase 1, and aprotective layer 3 is provided on the entire surface of theadhesive layer 2. However, the present invention is not limited to this embodiment, and for example, theadhesive layers 2 may be provided on both sides of thebase 1. - The
adhesive layer 2 may be provided on a part of one or both sides of thebase 1. In this case, as shown inFIG. 1 (b) , theprotective layer 3 may be provided so as to cover the entire surface of theadhesive layer 2 and the entire surface of the base on which the adhesive layer is not provided, or as shown inFIG. 1 (c) , it may be provided so as to cover only the entire surface of theadhesive layer 2. Further, as shown inFIG. 1 (d) , theprotective layer 3 may be provided on a part of the surface of theadhesive layer 2. - The
protective layer 3 may contain functional components such as an antistatic agent, a coloring agent, a hard coat agent, a lubricant, a heat dissipating material, a metal deactivator, an antioxidant, a flame retardant, a water/oil repellent and a solvent resistant resin which will be described in detail later. Thereby, a desired function other than protection can be imparted to theprotective layer 3. Further, theadhesive layer 2 may also contain functional components which are the same as or different from those in theprotective layer 3. - Two types of the
protective layer 3 can be provided. For example, as shown inFIG. 1(e) , a protective layer having a two-layered structure in which, on the surface of theprotective layer 3 a provided on theadhesive layer 2, anotherprotective layer 3 b is further provided may be permissible. Theprotective layer 3 having such a two-layered structure may be formed by additionally coating theprotective layer 3 b on theprotective layer 3 a, or may be formed by separating in the coating process. Further, the protective layer may have a three or more-layered structure. Further, as shown inFIG. 1 (f) , theprotective layer 3 a and theprotective layer 3 b may be provided at different positions on the surface of theadhesive layer 2, respectively. Theprotective layer 3 a and theprotective layer 3 b are, for example, layers containing functional components different from each other. Thereby, two different functions can be given to the entire surface (FIG. 1 (e) ), or two different functions can be given to different positions (FIG. 1 (f) ). - Hereinafter, each configuration of the adhesive sheet of the present invention will be described.
- The
base 1 used in the present invention is a member for supporting theadhesive layer 2 as shown inFIG. 1 . - The
base 1 is not particularly limited, but is preferably a heat-resistant insulating base. Although the level of heat resistance varies depending on the application to be used, for example, the melting temperature of thebase 1 is preferably 200° C. or higher, more preferably 250° C. or higher. Further, for example, the continuous use temperature of thebase 1 measured in accordance with UL-746B is preferably 100° C. or higher, more preferably 150° C. or higher. - The
base 1 may be a single-layered base composed of one member as shown inFIG. 1 or a base composed of a laminate having a laminated structure in which one member and another member are pasted with a bonding adhesive for lamination. Thebase 1 may have flexibility or may have resilience, and its properties are appropriately selected depending on the application. In applications where the stiffness and shape retention capacity of the adhesive sheet are required, thebase 1 is preferably a base composed of a laminate. - The member constituting the
base 1 is preferably a resin film, a nonwoven fabric or paper, and more preferably a resin film. When the base is a base composed of a laminate, the member is preferably at least one member selected from the group consisting of a resin film, a nonwoven fabric and paper, and at least one is preferably a resin film. - Specific examples of the resin film includes polyester type resins such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN) and aromatic polyester; polycarbonates; polyarylates; polyurethanes; polyamide type resins such as polyamide and polyether amide; polyimide type resins such as polyimide, polyether imide and polyamideimide; polysulfone type resins such as polysulfone and polyether sulfone; polyether ketone type resins such as polyether ketone and polyether ether ketone; polyphenylene sulfide (PPS); and modified polyphenylene oxide. Two or more resin films may be used in combination. Among them, polyphenylene sulfide (PPS), polyethylene naphthalate (PEN), polyimide and polyether ether ketone are preferred.
- The
base 1 may be subjected to a corona treatment or a primer treatment in order to improve the adhesion with theadhesive layer 2. - The thickness of the
base 1 may be appropriately selected depending on the intended use. Generally, it is 2 to 200 μm, preferably 9 to 100 μm, more preferably 12 to 50 μm. - As shown in
FIG. 1 , theadhesive layer 2 used in the present invention is provided on at least a part of one or both sides of a base. - The type of the
adhesive layer 2 is not particularly limited, but is preferably a thermosetting adhesive layer containing a thermosetting resin, a curing agent and a curing catalyst, more preferably an expansion adhesive layer containing a temperature-sensitive foaming agent, particularly preferably a foamable epoxy adhesive layer in which the thermosetting resin is an epoxy resin. - The epoxy resin preferably contains a polyfunctional epoxy resin. Although the type of the polyfunctional epoxy resin is not limited, novolak-type epoxy resins such as a phenol novolak type and a cresol novolak type, and a mixture thereof are preferable. When a novolak-type epoxy resin is used, the glass transition temperature of the cured product becomes high, so that the adhesive force tends to be stable even at high temperatures.
- As the epoxy resin, epoxy resins other than the polyfunctional epoxy resin may be used in combination. By use of the polyfunctional epoxy resin and other epoxy resins in admixture, the physical properties such as softening temperature, melt viscosity, glass transition temperature and storage elastic modulus of the epoxy resin can be controlled easily and in detail. In general, when an epoxy resin of low softening temperature or in liquid state is mixed, flowability in heating and flexibility before and after curing, of the adhesive layer can be enhanced. In contrast, when an epoxy resin of high softening temperature or in semi-solid or solid state is mixed, tackiness of the surface of the adhesive layer can be decreased. Further, the liquid epoxy resin can also be used for the purpose of pre-dispersing components such as a thermally expandable microcapsule in power or grain state contained in the temperature-sensitive foaming agent, or for the purpose of uniformly mixing components of the epoxy resin.
- Specific examples of the epoxy resin which can be mixed as described above include bisphenol type epoxy resins such as a bisphenol A type, a dimer acid-modified bisphenol A type and a bisphenol F type; epoxy resins having an aliphatic skeleton such as hexane diol diglycidyl ether; phenoxy resins (polyhydroxy polyethers synthesized from bisphenols and epichlorohydrin); and crystalline epoxy resins. The crystalline epoxy resin is non-tacky solid at normal temperature, while acts as a reactive diluent at melting temperature or more since melt viscosity lowers significantly at melting temperature or more. For this reason, when the crystalline epoxy resin is contained in the
adhesive layer 2, flowability in heating of theadhesive layer 2 can be more enhanced, acting advantageously on thermal expansion of theadhesive layer 2. Since it is non-tacky solid at room temperature, it is useful for reducing stickiness of the surface of the adhesive layer, or for rendering the surface of the adhesive layer non-sticky. When theadhesive layer 2 is formed by a melt coating method, the melt viscosity of the epoxy resin can be lowered to enhance the speed of melt coating, by heating at temperatures not lower than the melting temperature of the crystalline epoxy resin. - The number-average molecular weight of the epoxy resin is generally 100 to 60000 in terms of standard polystyrene by GPC. The epoxy equivalent of the epoxy resin is generally 50 to 30000 g/eq.
- The curing agent used for the
adhesive layer 2 is not particularly limited, but when an epoxy resin is used, a phenol resin is preferable. When a phenol resin is used as a curing agent and used in combination with an imidazole-based compound as a curing catalyst described later, the curing time can be reduced and the heat resistance can be improved. In addition, the use of a phenol resin as a curing agent facilitates design of heat resistance and electric characteristics. The addition amount of the phenol resin is theoretically determined so that the number of hydroxyl equivalents of the phenol resin relative to the number of epoxy equivalents of the epoxy resin is about 1:1. The ratio of the number of hydroxyl equivalents of the phenolic resin to the number of epoxy equivalents of the epoxy resin is usually 0.5 to 2.0, preferably 0.8 to 1.2. - The curing catalyst used for the
adhesive layer 2 is not particularly limited, but when a phenol resin is used as the curing agent, an imidazole compound is preferable. When an imidazole compound is used as a curing catalyst and used in combination with a phenol resin as a curing agent, the curing time is shortened and the heat resistance is improved. In addition, the imidazole-based compound has the advantage that it can be used as a single catalyst and has a very fine particle size grade as compared with other curing catalysts, so that it is easy to use. - Specific examples of the imidazole-based compound include imidazole derivatives such as 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2,4-diethylimidazole and 2-phenyl-4-methyl-5-hydroxyimidazole. Two or more imidazole-based compounds may be used in combination. Among them, 2-phenyl-4,5-dihydroxymethylimidazole is preferable. The content of the imidazole-based compound is preferably 0.1 to 1.0 part by mass, more preferably 0.3 to 0.8 parts by mass with respect to 100 parts by mass of resin components in the adhesive layer.
- The temperature-sensitive foaming agent used in the
adhesive layer 2 includes, for example, inorganic foaming agents such as ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrite, ammonium borohydride and azides; organic foaming agents such as alkane fluorides such as trichloromonofluoromethane, azo compounds such as azobisisobutyronitrile, hydrazine compounds such as p-toluene sulfonyl hydrazide, semi-carbazide compounds such as p-toluene sulfonyl semi-carbazide, triazole compounds such as and N-nitroso compounds such as N,N-dinitrosoterephthalamide; thermally expandable microcapsules obtained by microcapsulating a thermal expansion agent composed of a hydrocarbon compound. Two or more temperature-sensitive foaming agents may be used in combination. When an epoxy resin is used, thermally expandable microcapsules are preferable from the standpoint of no inhibition of curing of the epoxy resin and reduction of adverse effects exerted on physical properties of the epoxy resin. - The thermally expandable microcapsule is a microcapsule having a thermoplastic resin having a gas barrier property as a shell and enclosing a thermal expansion agent inside the shell. When the thermally expandable microcapsule is heated, the thermoplastic resin as a shell softens and the volume of the thermal expansion agent increases, thereby expanding the capsule. For example, vaporization of a hydrocarbon compound having low boiling point can be utilized for expansion of the capsule.
- The expansion (foaming) temperature of the thermally expandable microcapsule is preferably not less than the softening temperature of the epoxy resin and not more than the activation temperature of the curing reaction of the epoxy resin. When this foaming temperature is not less than the softening temperature of the epoxy resin, the thermal expansion agent can be expanded sufficiently in the softened epoxy resin and the thickness of the expandable
adhesive layer 2 after foaming can be made uniform. When this foaming temperature is not more than the activation temperature of the curing reaction of the epoxy resin, curing of an epoxy resin before foaming can be prevented. Further, when melt or solution coating is contained in the production process of the adhesive sheet, gelling of an epoxy resin during these coating steps and an accompanying drying step can be prevented, by adjusting the softening temperature of an epoxy resin to be not more than the activation temperature of the curing reaction. - The softening temperature of an epoxy resin can be measured using a ring and ball softening temperature test method prescribed in JIS K 2207. The foaming temperature of the thermally expandable microcapsule is a temperature at which volume variation of the thermally expandable microcapsule occurs, and it can be selected, for example, from a range of 70° C. or more and 200° C. or less, preferably 100° C. or more and 180° C. or less.
- The content and the volume expansion modulus of the temperature-sensitive foaming agent can be appropriately determined according to, for example, the strength and the adhesive force required for the cured
adhesive layer 2 and the expansion modulus required for the adhesive sheet. The content of the temperature-sensitive foaming agent is preferably 0.5 to 20 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass of resin components in theadhesive layer 2. The increase factor of the thickness of the adhesive sheet after foaming can be, for example, 1.1 times or more and 10 times or less. - It is preferable that other resins (heat resistant resin) are added to the
adhesive layer 2 from the standpoint of close adhesion to thebase 1, flexibility when bending the adhesive sheet, a leveling property in coating an adhesive and prevention of liquid drip in conducting heating, foaming and curing. Specific examples the other resins include a polyester resin, a butyral resin, a urethane resin, a carboxyl group-terminated butadiene nitrile rubber (CTBN) and epoxy-modified butadiene. Among them, a urethane resin is most preferable from the standpoint of flexibility and adhesiveness. - The urethane resin is, in general, a resin containing a soft segment composed of a polyol monomer unit and a hard segment composed of a polyfunctional isocyanate compound or a low molecular glycol monomer unit. The polyol used in the urethane resin is a compound having two or more hydroxyl groups. The number of a hydroxyl group of the polyol is preferably 2 to 3, more preferably 2 from the standpoint of enhancing properties such as rubber elasticity elongation recovery rate. As the polyol, for example, polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol and castor oil-based polyol can be used. Two or more polyols may be used in combination.
- As the polyfunctional isocyanate compound used as the cross-linking agent for crosslinking a polyol, for example, polyfunctional aliphatic isocyanate compounds, polyfunctional alicyclic isocyanate compounds, and polyfunctional aromatic isocyanate compounds can be used. Further, trimethylolpropane adducts of these compounds, a biuret body reacted with water, and a trimer having an isocyanurate ring can also be used. Two or more polyfunctional isocyanate compounds may be used in combination.
- Specific examples of the polyfunctional aliphatic isocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
- Specific examples of the polyfunctional alicyclic isocyanate compound include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate.
- Specific examples of the polyfunctional aromatic diisocyanate compound include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate and xylylene diisocyanate.
- The urethane resin is obtained by curing a composition containing the polyol and the polyfunctional isocyanate compound explained above. Particularly, low crystallinity linear polyester type polyurethane resins are preferable, and hexanediol copolyester type polyurethane resins and polytetramethylene glycol type polyurethane resins are more preferable, from the standpoint of properties such as rubber elastic elongation recovery rate.
- The content of the urethane resin is preferably 60 parts by mass or less in 100 parts by mass of resin components in the
adhesive layer 2. - It is preferable that the
adhesive layer 2 contains a heat resistant filler from the standpoint of heat resistance and thermal conductivity. The kind of the heat resistant filler is not particularly restricted, and the heat resistant filler includes, for example, inorganic fillers such as aluminum oxide, magnesium oxide, calcium oxide, aluminum hydroxide, magnesium hydroxide, boron nitride, silicon nitride, silicon oxide and talc (magnesium silicate). Two or more heat resistant fillers may be used in combination. The content of the heat resistant filler is preferably 20 to 300 parts by mass, more preferably 20 to 100 parts by mass with respect to 100 parts by mass of resin components in the adhesive agent. - The
adhesive layer 2 may contain additives such as antioxidants such as phenol type antioxidants and sulfur-based antioxidants, silane coupling agents such as epoxy-modified alkoxysilanes, thixotropic agents such as fumed silica, and pigments and dyes for identification, if necessary. - The
adhesive layer 2 may be a continuous layer, or a discontinuous layer constituted of a plurality of patterns such as stripes and dots. Further, irregularities such as emboss may be formed on the surface of theadhesive layer 2. By making theadhesive layer 2 discontinuous or forming irregularities such as emboss on the surface of theadhesive layer 2, tackiness of the surface of theadhesive layer 2 can be decreased, or the adhesive force of the adhesive layer can be controlled, or theadhesive layer 2 can be formed only on the necessary portion. Since ununiformity of the surface of theadhesive layer 2 as described above is alleviated or annihilated in foaming, an adverse effect on adhesive force due to its ununiformity does not occur easily. - The thickness of the
adhesive layer 2 may be appropriately determined depending on the intended use. Usually, it is 2 to 300 μm, preferably 2 to 150 μm. - As shown in
FIG. 1 , theprotective layer 3 used in the present invention is provided on at least a part of the surface of the adhesive layer. Theprotective layer 3 is preferably a layer that flows, decomposes or sublimates by heating when bonding the adhesive sheet, and, as a result, does not prevent theadhesive layer 2 from adhering to an adherend. In particular, it is more preferable that at normal temperature (the temperature at which the adhesive sheet is stored before use), the surface of theadhesive layer 2 is protected to prevent foreign matter, scratches and blocking, and at higher temperature (curing temperature of the adhesive sheet in use), the components constituting theprotective layer 3 are dispersed and absorbed in theadhesive layer 2. For example, when theprotective layer 3 is a hot-melt protective layer and theadhesive layer 2 is an expandable adhesive layer (an adhesive layer containing a temperature-sensitive foaming agent), microbubbles are generated in the expandable adhesive layer due to heating in bonding the adhesive sheet, and at the same time, the hot-melt protective layer flows, and the components constituting the protective layer diffuse into the adhesive layer under the influence of foaming. As a result, the hot-melt protective layer almost disappears from the surface of the adhesive layer, and the adhesive sheet adheres to an adherend without impairing the original adhesiveness of the adhesive agent. - The
protective layer 3 is a part of a member constituting the adhesive sheet at the time of use, and for example, a release liner that is peeled at the time of use is not theprotective layer 3. - When the
protective layer 3 is a hot-melt protective layer, the type of the hot-melt substance contained in theprotective layer 3 is not limited, and it may be a component which is a solid at normal temperature, and flows to the extent that at least it diffuses into the adhesive layer by heating when bonding the adhesive sheet (for example, a thermoplastic resin component). The glass transition temperature (Tg) of the hot-melt substance is preferably 100° C. or lower, the melting temperature thereof is preferably 200° C. or lower, and the softening temperature thereof is preferably 180° C. or lower. - By allowing the
protective layer 3 to contain a functional component, it is also possible to impart a desired function other than protection to theprotective layer 3. The hot-melt substance itself may be a functional component, or a functional component may be blended with the hot-melt substance. Specific examples of the functional component include an antistatic agent, a coloring agent, a hard coat agent, a lubricant, a heat dissipating material, a metal deactivator, an antioxidant, a flame retardant, a water/oil repellent, and a solvent resistant resin. When the functional component is a hot-melt substance, it is preferable that the functional component flows by heating when bonding the adhesive sheet and diffuses into the adhesive layer. On the other hand, when the functional component is not a hot-melt substance, it is preferable to include a hot-melt binder together with the functional component. - When the
protective layer 3 contains an antistatic agent, an antistatic property can be imparted to the adhesive sheet. For example, sparks due to static electricity in the adhesive sheet manufacturing process (during feeding and transporting) can be suppressed, and defective peeling during feeding of the adhesive sheet can be prevented. The type of the antistatic agent is not particularly limited, and a commercially available product may be used. - When the
protective layer 3 contains a coloring agent, the adhesive sheet can be given distinctiveness by coloring. Specifically, for example, it is possible to prevent an incorrect installation of the adhesive sheet having different configurations or adhesives on both sides. The type of the coloring agent is not particularly limited, and a commercially available product may be used. - When the
protective layer 3 contains a hard coat agent, scratch resistance can be imparted to the adhesive sheet. Specifically, for example, when a small component is fixed to a predetermined portion inside a recent portable electronic device, it is possible to prevent the adhesive sheet from hitting another component and lowering the insulation. The type of the hard coat agent is not particularly limited, and a commercially available product may be used. Alternatively, printing may be performed on theprotective layer 3 containing a hard coat agent by a method such as gravure printing containing a coloring agent. Such a method can be used, for example, when it is desired to display information (Lot or notice) of the adhesive sheet on the adhesive sheet. - When the
protective layer 3 contains a lubricant, the adhesive sheet can be provided with slipperiness. Specifically, for example, the frictional resistance when arranging the adhesive sheet inside the portable electronic device can be reduced, and the adhesive sheet can be easily arranged even in a complex and intricate place. The type of the lubricant is not particularly limited, and a commercially available product may be used. - When the
protective layer 3 contains a heat dissipating material, the adhesive sheet can be provided with thermal conductivity. The heat dissipating material is preferably used together with the binder resin. After the binder resin melts and disappears, the heat dissipating material stays in the vicinity of the surface of the adhesive layer, so that the thermal conductivity of the surface layer of the adhesive sheet can be particularly improved. As a result, for example, even if the surface of the adherend has uneven temperature, the adhesive layer can be foamed and cured uniformly. The type of the heat dissipating material is not particularly limited, and a commercially available product may be used. - When the
protective layer 3 contains a metal deactivator, it is possible to prevent the adherend (metal) from deteriorating the adhesive layer of the adhesive sheet. The type of the metal deactivator is not particularly limited, and a commercially available product may be used. - When the
protective layer 3 contains an antioxidant, oxidative deterioration of the adhesive sheet can be prevented. The type of the antioxidant is not particularly limited, and a commercially available product may be used. - When the
protective layer 3 contains a flame retardant, flame retardancy can be imparted to the adhesive sheet. The type of the flame retardant is not particularly limited, and a commercially available product may be used. - When the
protective layer 3 contains a water/oil repellent, the adhesive sheet can be provided with waterproof and oil-proof properties. Specifically, for example, it is possible to prevent adhesion of foreign matters including water and oil during the manufacturing process of the adhesive sheet, and prevent occurrence of defective products. The type of the water/oil repellent is not particularly limited, and a commercially available product may be used. - When the
protective layer 3 contains a solvent-resistant resin, solvent resistance can be imparted to the adhesive sheet. The type of the solvent-resistant resin is not particularly limited, and a commercially available product may be used. - The thickness of the
protective layer 3 is generally 0.01 to 30 μm, preferably 0.03 to 20 μm, and more preferably 0.05 to 15 μm. - The adhesive sheet of the present invention is an adhesive sheet having the
protective layer 3 described above, and more specifically, the adhesive sheet has theadhesive layer 2 on at least a part of one side or both sides of thebase 1, and has theprotective layer 3 on at least a part of the surface of theadhesive layer 2. The adhesive sheet of the present invention does not require a release liner. However, for example, in the case of a double-sided adhesive sheet, theprotective layer 3 may be provided on one adhesive layer, and the release liner may be provided on the otheradhesive layer 2. - When the
adhesive layer 2 contains a temperature-sensitive foaming agent, the adhesive sheet of the present invention preferably has a thickness before foaming and curing of 10 to 1000 μm, more preferably 10 to 250 μm, and particularly preferably 20 to 200 μm. - The method for producing the adhesive sheet of the present invention is not particularly limited. In the case of a single-sided adhesive sheet, it can be manufactured by forming the
adhesive layer 2 on one surface of thebase 1 and then forming theprotective layer 3 on the surface of theadhesive layer 2. Theadhesive layer 2 can be formed by a conventionally known method such as a solution coating method, a melt coating method, a melt extrusion method, and a rolling method. The melt coating method can be performed without a solvent, and does not require a solvent removing step and processing equipment, and is therefore preferable in terms of productivity and economy. When the melt coating method is used, the epoxy resin preferably contains a crystalline epoxy resin. In this case, by heating at temperatures not lower than the melting temperature of the crystalline epoxy resin, the melt viscosity of the epoxy resin can be reduced, and the speed of melt coating can be increased. For theprotective layer 3, a known coating method may be appropriately used depending on the type of the material. - The present invention will be further illustrated by examples below, but the present invention is not limited to them.
- The following components were mixed in amounts shown in Table 1 (parts by mass), to obtain an expandable adhesive agent.
-
-
- “EP1”: epoxy resin (semisolid, melt viscosity of butylcarbitol 60% solution is 220 to 300 mPa·s (25° C.), epoxy equivalent 180 g/eq, novolak, general type)
- “EP2”: epoxy resin (liquid, viscosity 13,000 mPa·s, epoxy equivalent 188 g/eq, general-purpose epoxy resin)
-
-
- “E”: linear polyester polyurethane (softening temperature 87° C., molecular weight 222300, hydroxyl group content 0.1%, adhesive and flexible type)
-
-
- “T1”: phenol resin (softening temperature 110° C., hydroxyl group equivalent 97 g/eq, highly heat resistant type)
- “T2”: 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Chemicals Corporation, trade name 2PHZ-PW, melting temperature 220° C., active region 141 to 153° C., initiation region 153 to 168° C.)
-
-
- “H”: temperature-sensitive foaming agent (average particle size 15 μm, expansion starting temperature 125 to 135° C., maximum expansion temperature 150 to 160° C.)
-
-
- “J1”: magnesium oxide (
average particle size 3 μm, thermally conductive, heat resistant and electrically insulating type) - “J2”: magnesium silicate (
average particle size 5 μm, thermally conductive, heat resistant and electrically insulating type)
- “J1”: magnesium oxide (
-
TABLE 1 Compounding 1Epoxy resin EP1 80 EP2 20 Elastomer E 34 Curing agent, catalyst T1 54 T2 0.4 Temperature- sensitive H 6 foaming agent Heat resistant filler J1 24 J2 24 - The following materials constituting each of protective layers were prepared.
-
-
- antistatic agent (manufactured by Chukyo Yushi Co., Ltd., trade name S-495, Tg 55° C.): 100 parts by mass
-
-
- hard coating agent (manufactured by Goo Chemical Co., Ltd., trade name PLAS COAT Z-565, Tg 64° C., softening temperature 170 to 175° C.): 100 parts by mass
- dye (manufactured by Shachihata Inc., trade name Stampink S-1): 1 part by mass
-
-
- hard coating agent (manufactured by Goo Chemical Co., Ltd., trade name PLAS COAT Z-565, Tg 64° C., softening temperature 170 to 175° C.): 100 parts by mass
- dye (manufactured by Shachihata Inc., trade name Stampink S-1): 1 part by mass
-
-
- hard coating agent (manufactured by Goo Chemical Co., Ltd., trade name PLAS COAT Z-565, Tg 64° C., softening temperature 170 to 175° C.): 100 parts by mass
-
-
- fluorine-based coating agent (manufactured by AGC SEIMI Chemical Co., Ltd., SF-Coat (registered trademark) SWK-601): 100 parts by mass
-
-
- solvent resistant acryl emulsion (manufactured by Mitsui Chemicals, Inc., BONRON (registered trademark) XHS-50,
Tg 60° C.): 100 parts by mass
- solvent resistant acryl emulsion (manufactured by Mitsui Chemicals, Inc., BONRON (registered trademark) XHS-50,
-
-
- heat dissipating material (manufactured by 3M, trade name Platelets006): 100 parts by mass linear polyester polyurethane (softening temperature 87° C., molecular weight 222300, hydroxyl group content 0.1%, adhesive and flexible type): 50 parts by mass
-
-
- lubricant (manufactured by Chukyo Yushi Co., Ltd., trade name Rezem P677, melting
temperature 80° C.): 100 parts by mass
- lubricant (manufactured by Chukyo Yushi Co., Ltd., trade name Rezem P677, melting
-
-
- flame retardant (manufactured by Otsuka Chemical Co., Ltd., trade name SPB-100, melting temperature 110° C.): 100 parts by mass
- linear polyester polyurethane (softening temperature 87° C., molecular weight 222300, hydroxyl group content 0.1%, adhesive and flexible type): 50 parts by mass
- The expandable adhesive agent of compounding 1 was applied to both sides of a base (PPS resin, manufactured by Toray Industries, Inc., TORELINA (registered trademark) #100-3030, 75 μm) so that the each thickness after drying was 50 μm, and thereafter, dried at 90° C. for 5 minutes to remove the solvent, forming an expandable adhesive layer. On the surface of the expandable adhesive layer, protective layers having the compoundings and thicknesses shown in Tables 2 and 3 were formed, to obtain adhesive sheets of Examples 1 to 10.
- An adhesive sheet was obtained in the same manner as in Example 1, except that the protective layer was not formed.
- The adhesive sheets of Examples 1 to 10 and Comparative Example 1 were evaluated according to the following methods. The results are shown in Tables 2 to
- The thickness of the protective layer of the adhesive sheet before foaming was determined by subtracting the thickness of the adhesive sheet without the protective layer from the thickness of the adhesive sheet with the protective layer. Each thickness was measured by a thickness gauge test method according to JIS Z 0237 “Testing methods of pressure-sensitive adhesive tapes and sheets”.
- For the tackiness, the thumb was pressed against the sheet surface with a small force, and the presence or absence of stickiness when peeled off in a very short time was sensuously tested to determine the presence or absence of stickiness.
- In an atmosphere of 40° C., 0.1 g of 20-30 mesh sea sand manufactured by Wako Pure Chemical Industries, Ltd. was sprinkled on the sheet surface, then, the sheet was turned 180° so that the side on which the sea sand was sprinkled faced downward. Thereafter, the surface of the sheet was visually observed and evaluated according to the following criteria.
-
- “A”: No sea sand attached at all.
- “B”: 4 or less sea sands attached.
- “C”: 5 or more sea sands attached.
- According to the tensile shear adhesive force test method described in JIS Z1541 “High potential pressure sensitive adhesive double coated tapes”, the shear adhesive force of the adhesive sheet after foaming as shown in
FIG. 2 was measured. An SPCC plate (manufactured by Nissin Steel Co., Ltd., trade name: SPCC-SB NCB, 1.0 mm thick, 12×100 mm) was used as an adherend. The sample attachment area was 10×10 mm, the foaming and curing conditions were 10 minutes at 180° C., and the tensile speed was 200 mm/min. First, as shown inFIG. 2(A) , theadhesive sheet 4 before foaming was placed on theSPCC plate 5, and further, anotherSPCC plate 5 was placed via two metal interspace gauges (0.300 mm) 6. Next, as shown inFIG. 2(B) , theadhesive sheet 4 was foamed and cured, and a tensile shear adhesive force test (23° C.) was performed on theadhesive sheet 4 after foaming. - The surface resistance (Ω) of the adhesive sheet before foaming was measured according to JIS K6911 “Testing methods for thermosetting plastics”.
- The front and back of the adhesive sheet before foaming were visually observed and evaluated according to the following criteria.
-
- “A”: the front and back could be discriminated
- “B”: the front and back could not be discriminated
- The pencil hardness of the adhesive sheet before coaming was measured according to JIS K5600 “Testing methods for paints”.
- The contact angle of the adhesive sheet before foaming was measured according to JIS R3257 “Testing method of wettability of glass substrate”. For the contact angle of water, industrial purified water A300 manufactured by AS ONE Corporation was used, and for the contact angle of an oil, TOYOTA genuine Auto Fluid WS (ATF) was used.
- The shear adhesive force of an adhesive sheet before foaming contaminated with ATF was measured by the same procedure as the method for evaluating the adhesiveness, and the percentage of the shear adhesive force of the contaminated adhesive sheet was calculated when the shear adhesive force of a non-contaminated sheet was taken as 100%. The contaminated adhesive sheet was obtained by immersing an adhesive sheet in ATF for 1 second, sandwiching the sheet with a dry waste paper, and allowing the waste paper to absorb excess ATF on the surface of the sheet.
- The surface of a sheet was rubbed three times in reciprocation with absorbent cotton impregnated with toluene at a pressure of 0.1 MPa, and the solvent resistance was evaluated according to the following criteria.
-
- “A”: No surface roughness was visually recognized at all.
- “B”: Whitened but not eluted.
- “C”: The adhesive layer was eluted into the absorbent cotton.
- The thermal conductivity of an adhesive sheet after foaming was measured using a quick thermal conductivity meter manufactured by Kyoto Electronics Manufacturing Co., Ltd. at thin film measurement mode. Specifically, three kinds of reference blocks having known thermal conductivity were placed on an aluminum plate (10 mm thick, 250×350 mm), and a test piece for measurement (45×100 mm) was placed thereon, and further, a sensor probe (trade name PD-11, 40×97 mm, 820 g) for measuring thermal conductivity equipped with heater wire and a thermocouple was placed thereon, and measurement was started. As the reference block, foamed polyethylene (thermal conductivity 0.0347 W/mK), silicone rubber (thermal conductivity 0.236 W/mK) and quartz glass (thermal conductivity 1.416) were used.
- The static friction coefficient of an adhesive sheet before foaming was measured according to JIS K7125 “Plastics-Film and sheeting-Determination of the coefficients of friction”.
- A test was performed on a sample obtained by subjecting an adhesive sheet having a sample size used in the UL94V test to foaming and curing in a thermostat, and the flame retardancy of the sample was evaluated according to the following criteria.
-
- “A”: The test passed the UL94V test under VO test conditions.
- “B”: A part of the sample did not burn and remained after two flame contacts, with the flame contact time of the UL94V test being 2 seconds.
- “C”: All of the sample burned.
-
TABLE 2 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Adhesive Protective Kind Anti- Coloring HC, HC Water Solvent sheet layer static Printing oilrepellent resistant Compounding 2 3 4/5 5 6 7 Thickness (μm) 3 10 10 10 <1 10 Expandable adhesive 50 50 50 50 50 50 layer (μm) Base (μm) 75 75 75 75 75 75 Expandable adhesive 50 50 50 50 50 50 layer (μm) Tackiness None None None None None None Foreign matter adherence A A A A A A Adhesiveness (after foaming) (N/cm2) 408 308 299 322 113 195 Function Surface resistance (×1012Ω) 0.1 — — — — — evaluation Visual discrimination — A A — — — Pencil hardness — — — B — — Contact Water — — — — 112° — angle Oil — — — — 77° — Contamination resistant — — — — 82% — adhesiveness Solvent resistance — — — — — A -
TABLE 3 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Adhesive Protective Kind Heat Lubrication Flame Flame sheet layer dissipation retardancy retardancy Compounding 8 9 10 10 Thickness (μm) 15 <1 13 7 Expandable adhesive 50 50 50 50 layer (μm) Base (μm) 75 75 75 75 Expandable adhesive 50 50 50 50 layer (μm) Tackiness None None None None Foreign matter adherence A A A A Adhesiveness (after foaming) (N/cm2) 226 551 326 369 Function Thermal conductivity (W/mK) 0.157 — — — evaluation Static friction coefficient — 0.35 — — Flame retardancy — — A B -
TABLE 4 Comparative. Ex. 1 Adhesive Protective Kind — sheet layer Compounding — Thickness (μm) 0 Expandable adhesive 50 layer (μm) Base (μm) 75 Expandable adhesive 50 layer (μm) Tackiness positive Foreign matter adherence C Adhesiveness (after foaming) (N/cm2) 579 Function Surface resistance (×1012Ω) 37.8 evaluation Visual discrimination C Pencil hardness 3B Contact Water 72° angle Oil 27° Contamination resistant 55% adhesiveness Solvent resistance C Thermal conductivity (W/mK) 0.119 Static friction coefficient Unmeasurable due to tackiness Flame retardancy C - Reflection IR measurement was performed on the surface composition of the protective layer (before foaming) of the adhesive sheet of Example 6 and the adhesive layer (before foaming) of the adhesive sheet of Comparative Example 1.
FIG. 3 is a graph showing the result. As apparent from this result, an epoxy-derived absorption peak exists on the surface of the adhesive layer of the adhesive sheet of Comparative Example 1, but no peak exists on the surface of the protective layer of the adhesive sheet of Example 6. Therefore, the adhesive sheet of Example 6 does not cause skin damage due to the epoxy resin component. - The adhesive sheet of the present invention can protect the adhesive surface and does not cause blocking or skin damage even without using a release liner. Moreover, various functions can be given to the adhesive sheet without impairing the properties of the adhesive layer. Therefore, it is useful for various uses in a wide range of fields such as the electric and electronic fields, the automobile-related fields, and the civil engineering and construction fields.
-
-
- 1: base
- 2: adhesive layer
- 3: protective layer
- 3 a: protective layer
- 3 b: protective layer
- 4: adhesive sheet
- 5: SPCC plate
- 6: metal interspace gauge
Claims (5)
1. An adhesive sheet comprising an adhesive layer provided on at least a part of one side or both sides of a base, wherein
the adhesive layer is a foamable epoxy adhesive layer containing a polyfunctional epoxy resin and an epoxy resin other than the polyfunctional epoxy resin, and
a hot-melt protective layer is provided on at least a part of a surface of the adhesive layer away from the base, and the protective layer contains at least one additive selected from the group consisting of an antistatic agent, a lubricant, and a metal deactivator.
2. The adhesive sheet according to claim 1 , wherein the thickness of the adhesive layer is 2 to 300 μm.
3. The adhesive sheet according to claim 1 , wherein a print layer is formed on the protective layer.
4. The adhesive sheet according to claim 1 , wherein the adhesive layer further contains a linear polyester type polyurethane resin.
5. The adhesive sheet according to claim 1 , wherein the adhesive layer contains 20 parts by mass or more of a liquid epoxy resin which is the epoxy resin other than the polyfunctional epoxy resin, per 100 parts by mass of epoxy resin components in the adhesive layer.
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PCT/JP2017/029187 WO2019030914A1 (en) | 2017-08-10 | 2017-08-10 | Adhesive sheet |
US202016637711A | 2020-02-07 | 2020-02-07 | |
US18/456,441 US20230407142A1 (en) | 2017-08-10 | 2023-08-25 | Adhesive sheet |
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PCT/JP2017/029187 Continuation WO2019030914A1 (en) | 2017-08-10 | 2017-08-10 | Adhesive sheet |
US16/637,711 Continuation US11781042B2 (en) | 2017-08-10 | 2017-08-10 | Adhesive sheet |
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JP2021026102A (en) * | 2019-08-02 | 2021-02-22 | エルジー ディスプレイ カンパニー リミテッド | Flexible display device and method of manufacturing the same |
JP2021155495A (en) * | 2020-03-25 | 2021-10-07 | 大日本印刷株式会社 | Manufacturing method of expandable adhesive sheet and article |
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JPWO2019030914A1 (en) | 2020-09-03 |
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KR20230054477A (en) | 2023-04-24 |
KR20200036872A (en) | 2020-04-07 |
US11781042B2 (en) | 2023-10-10 |
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CN111051453A (en) | 2020-04-21 |
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