JPWO2017149981A1 - Adhesive composition and adhesive sheet - Google Patents
Adhesive composition and adhesive sheet Download PDFInfo
- Publication number
- JPWO2017149981A1 JPWO2017149981A1 JP2018502572A JP2018502572A JPWO2017149981A1 JP WO2017149981 A1 JPWO2017149981 A1 JP WO2017149981A1 JP 2018502572 A JP2018502572 A JP 2018502572A JP 2018502572 A JP2018502572 A JP 2018502572A JP WO2017149981 A1 JPWO2017149981 A1 JP WO2017149981A1
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- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- mass
- polymer
- group
- 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
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- 239000000853 adhesive Substances 0.000 title claims abstract description 100
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 100
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 103
- 229920000642 polymer Polymers 0.000 claims abstract description 80
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 21
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 15
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 12
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000012790 adhesive layer Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 abstract description 11
- -1 alkyl isocyanate Chemical class 0.000 description 36
- 150000001875 compounds Chemical class 0.000 description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000002243 precursor Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 125000003700 epoxy group Chemical group 0.000 description 9
- 239000002518 antifoaming agent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 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 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 230000003712 anti-aging effect Effects 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 5
- 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 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000005259 measurement Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000000466 oxiranyl group Chemical group 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 239000012156 elution solvent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000001955 polymer synthesis method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-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
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- OQURWGJAWSLGQG-UHFFFAOYSA-N 1-isocyanatopropane Chemical compound CCCN=C=O OQURWGJAWSLGQG-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- DBRHKXSUGNZOLP-UHFFFAOYSA-N 2-(2-isocyanatoethoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCN=C=O DBRHKXSUGNZOLP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- UMLWXYJZDNNBTD-UHFFFAOYSA-N 2-(dimethylamino)-1-phenylethanone Chemical compound CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 1
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- PRJQBLZFLQSJOM-UHFFFAOYSA-N 2-[[1,3-dibromo-2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C(C1CO1)OC(C(C)(C(OCC1CO1)Br)C)Br PRJQBLZFLQSJOM-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- YJQMXVDKXSQCDI-UHFFFAOYSA-N 2-ethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3SC2=C1 YJQMXVDKXSQCDI-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
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- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
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- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
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- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
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- 239000001361 adipic acid Substances 0.000 description 1
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- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229920003180 amino resin Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
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- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- PODOEQVNFJSWIK-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethoxyphenyl)methanone Chemical compound COC1=CC(OC)=CC(OC)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 PODOEQVNFJSWIK-UHFFFAOYSA-N 0.000 description 1
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- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
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- 150000007974 melamines Chemical class 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WYOXPIKARMAQFM-UHFFFAOYSA-N n,n,n',n'-tetrakis(oxiran-2-ylmethyl)ethane-1,2-diamine Chemical compound C1OC1CN(CC1OC1)CCN(CC1OC1)CC1CO1 WYOXPIKARMAQFM-UHFFFAOYSA-N 0.000 description 1
- SJPFBRJHYRBAGV-UHFFFAOYSA-N n-[[3-[[bis(oxiran-2-ylmethyl)amino]methyl]phenyl]methyl]-1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC=1C=C(CN(CC2OC2)CC2OC2)C=CC=1)CC1CO1 SJPFBRJHYRBAGV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
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- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
本発明は、加熱の有無に関わらず、紫外線照射前の粘着力が高く、紫外線照射による粘着力の低下幅も十分に大きく、糊残りが十分少なく、かつ埋め込み性にも優れる粘着剤組成物及びこの粘着剤組成物を用いる粘着シートの提供を目的とする。本発明は、アクリル酸メチルに由来する構造単位及び重合性炭素−炭素二重結合含有基を有するポリマーと、光重合開始剤と、熱硬化剤とを含有し、上記ポリマーを構成する全構造単位に対する上記構造単位の含有割合が１質量％以上６０質量％以下であり、多官能モノマー又は多官能オリゴマーを実質的に含有しない粘着剤組成物である。上記ポリマーは上記重合性炭素−炭素二重結合含有基を側鎖に有することが好ましい。上記重合性炭素−炭素二重結合含有基としては（メタ）アクリロイル基が好ましい。 The present invention is a pressure-sensitive adhesive composition that has high adhesive strength before ultraviolet irradiation regardless of the presence or absence of heating, a sufficiently large decrease in adhesive strength due to ultraviolet irradiation, sufficiently small adhesive residue, and excellent embedding properties, and It aims at providing the adhesive sheet using this adhesive composition. The present invention comprises a structural unit derived from methyl acrylate and a polymer having a polymerizable carbon-carbon double bond-containing group, a photopolymerization initiator, and a thermosetting agent, and all structural units constituting the polymer. The content ratio of the structural unit with respect to is 1% by mass or more and 60% by mass or less, and is a pressure-sensitive adhesive composition containing substantially no polyfunctional monomer or polyfunctional oligomer. The polymer preferably has the polymerizable carbon-carbon double bond-containing group in the side chain. The polymerizable carbon-carbon double bond-containing group is preferably a (meth) acryloyl group.
Description
本発明は、粘着剤組成物及び粘着シートに関する。 The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet.
粘着剤は、部品同士を接着する際に広く用いられている。粘着剤の用途の１つに、一時的に部材同士を接着させておくという仮止めがある。例えば半導体ウエハのダイシング工程では、粘着剤によって半導体ウエハをフレームに仮止めした状態で半導体ウエハの切断を行う。そして、半導体ウエハの切断を終えたら、フレームから半導体ウエハを取り外す。このような仮止めに用いる粘着剤は、十分な粘着力を有しつつも、仮止めが不要となった時には、容易かつ糊残りなく剥離することができるという性能が要求される。また、かかる粘着剤には、部品同士を貼り合わせた後、接着した部品ごと加熱工程に供された場合でも、仮止めが不要となった時に容易かつ糊残りなく剥離することが求められる。 Adhesives are widely used when bonding parts together. One of the uses of the pressure-sensitive adhesive is to temporarily fix the members to each other. For example, in the semiconductor wafer dicing process, the semiconductor wafer is cut in a state where the semiconductor wafer is temporarily fixed to the frame with an adhesive. Then, after the semiconductor wafer has been cut, the semiconductor wafer is removed from the frame. The pressure-sensitive adhesive used for such temporary fixing is required to have a sufficient adhesive force and can be peeled easily and without adhesive residue when temporary fixing is no longer necessary. Such an adhesive is required to be peeled off easily and without adhesive residue even when the components are bonded together and then subjected to the heating process together with the bonded components.
そこで、仮止め等において、粘着剤組成物から形成された粘着剤層を有する粘着シートを用い、仮止めが不要となった時に紫外線照射によって粘着剤層を硬化させ、粘着力を低下させるという技術が提案されている（特開２００１−２４０８４２号公報参照）。 Therefore, a technology that uses a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition in temporary fixing, etc., and cures the pressure-sensitive adhesive layer by ultraviolet irradiation when temporary fixing becomes unnecessary, thereby reducing the adhesive strength. Has been proposed (see JP 2001-240842 A).
しかし、上記従来の粘着剤組成物では、紫外線照射前の粘着力が不十分である上、紫外線照射による粘着力の低下幅も不十分なものに留まり、また、糊残りの低減についても十分なものとは言えない。さらに、上記従来の粘着剤組成物は、被着体へ貼り合わせた状態で加熱すると粘着力が上昇するが、これにより、紫外線照射による粘着力の低下幅がより不十分となり、糊残りが発生してしまうという不都合がある。また、粘着剤組成物には、形成される粘着剤層の埋め込み性に優れ、段差等を有する被着体に対しても良好に用いることができることも要求される。 However, in the above conventional pressure-sensitive adhesive composition, the adhesive strength before ultraviolet irradiation is insufficient, and the decrease in the adhesive strength due to ultraviolet irradiation is also insufficient, and also sufficient for reducing the adhesive residue. Not a thing. In addition, the above conventional pressure-sensitive adhesive composition increases the adhesive strength when heated in a state of being bonded to an adherend, but this results in an insufficient decrease in the adhesive strength due to ultraviolet irradiation, resulting in adhesive residue. There is an inconvenience. Further, the pressure-sensitive adhesive composition is required to be excellent in embedding property of the pressure-sensitive adhesive layer to be formed and to be used satisfactorily for an adherend having a step or the like.
本発明は、以上のような事情に基づいてなされたものであり、その目的は、加熱の有無に関わらず、紫外線照射前の粘着力が十分に高く、紫外線照射による粘着力の低下幅が十分に大きく、糊残りが十分少なく、かつ埋め込み性にも優れる粘着剤組成物及びこの粘着剤組成物を用いる粘着シートを提供することにある。 The present invention has been made on the basis of the circumstances as described above, and its purpose is to provide a sufficiently high adhesive strength before ultraviolet irradiation regardless of the presence or absence of heating, and a sufficient decrease in adhesive strength due to ultraviolet irradiation. It is an object of the present invention to provide a pressure-sensitive adhesive composition that is large, has a small amount of adhesive residue, and has excellent embedding properties, and a pressure-sensitive adhesive sheet using this pressure-sensitive adhesive composition.
上記課題を解決するためになされた発明は、アクリル酸メチルに由来する構造単位（以下、「構造単位（Ｉ）」ともいう）及び重合性炭素−炭素二重結合含有基（以下、「二重結合含有基（Ａ）」ともいう）を有するポリマー（以下、「［Ａ］ポリマー」ともいう）と、光重合開始剤（以下、「［Ｂ］光重合開始剤」ともいう）と、熱硬化剤（以下、「［Ｃ］熱硬化剤」ともいう）とを含有し、上記［Ａ］ポリマーを構成する全構造単位に対する上記構造単位（Ｉ）の含有割合が１質量％以上６０質量％以下であり、多官能モノマー又は多官能オリゴマーを実質的に含有しない粘着剤組成物である。 The invention made in order to solve the above-mentioned problems includes a structural unit derived from methyl acrylate (hereinafter also referred to as “structural unit (I)”) and a polymerizable carbon-carbon double bond-containing group (hereinafter referred to as “double”). A polymer having a bond-containing group (A) ”(hereinafter also referred to as“ [A] polymer ”), a photopolymerization initiator (hereinafter also referred to as“ [B] photopolymerization initiator ”), and thermosetting. And the content ratio of the structural unit (I) with respect to all structural units constituting the polymer [A] is 1% by mass or more and 60% by mass or less. And is a pressure-sensitive adhesive composition substantially free of a polyfunctional monomer or polyfunctional oligomer.
上記課題を解決するためになされた別の発明は、シート状の基材と、上記基材の一方の面に積層される粘着剤層とを備え、上記粘着剤層が、当該粘着剤組成物から形成される粘着シートである。 Another invention made in order to solve the above-mentioned problems comprises a sheet-like base material and a pressure-sensitive adhesive layer laminated on one surface of the base material, and the pressure-sensitive adhesive layer comprises the pressure-sensitive adhesive composition. It is the adhesive sheet formed from.
本発明の粘着剤組成物及び粘着シートによれば、加熱の有無に関わらず、紫外線照射前の粘着力が十分に高く、紫外線照射による粘着力の低下幅も十分に大きく、かつ糊残りを十分低減することができ、また、形成される粘着剤層が埋め込み性に優れ、段差等を有する被着体に対しても好適に用いることができる。また、貼り合わせ状態で加熱される場合でも、紫外線照射により糊残りなく剥離することができる。従って、当該粘着剤組成物及び粘着シートは、加熱工程を有する半導体ウエハのダイシング工程等種々の製造工程において好適に用いることができる。 According to the pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet of the present invention, regardless of the presence or absence of heating, the pressure-sensitive adhesive force before UV irradiation is sufficiently high, the amount of decrease in the pressure-sensitive adhesive strength by UV irradiation is sufficiently large, and the adhesive residue is sufficient Moreover, the pressure-sensitive adhesive layer to be formed is excellent in embeddability and can be suitably used for an adherend having a step or the like. Moreover, even when heated in a bonded state, it can be peeled off without any adhesive residue by ultraviolet irradiation. Therefore, the said adhesive composition and adhesive sheet can be used suitably in various manufacturing processes, such as the dicing process of the semiconductor wafer which has a heating process.
＜粘着剤組成物＞
当該粘着剤組成物は、［Ａ］ポリマーと、［Ｂ］光重合開始剤と、［Ｃ］熱硬化剤とを含有する。また、当該粘着剤組成物は、多官能モノマー又は多官能オリゴマーを実質的に含有しない。当該粘着剤組成物は、［Ａ］〜［Ｃ］成分以外の任意成分を含有していてもよい。<Adhesive composition>
The pressure-sensitive adhesive composition contains [A] a polymer, [B] a photopolymerization initiator, and [C] a thermosetting agent. Moreover, the said adhesive composition does not contain a polyfunctional monomer or a polyfunctional oligomer substantially. The pressure-sensitive adhesive composition may contain an optional component other than the components [A] to [C].
当該粘着剤組成物は、加熱の有無に関わらず、紫外線照射前の粘着力が十分に高く、紫外線照射による粘着力の低下幅が十分に大きく、糊残りが十分少なく、かつ埋め込み性にも優れる。当該粘着剤組成物が上記構成を有することで上記効果を奏する理由については必ずしも明確ではないが、例えば以下のように推察することができる。すなわち、当該粘着剤組成物は［Ａ］〜［Ｃ］成分を含有し、［Ａ］ポリマーは二重結合含有基（Ａ）と共に、上記特定範囲の含有割合のアクリル酸メチルに由来する構造単位（Ｉ）を有している。このアクリル酸メチルに由来する構造単位（Ｉ）は立体的に小さいため、［Ａ］ポリマーと［Ｃ］熱硬化剤とから形成される粘着性を発揮する構造と、被着体との相互作用をより大きいものとすることができ、その結果、硬化前の粘着力を十分に高くすることができる。また、上述のように、アクリル酸メチルに由来する構造単位（Ｉ）が立体的に小さいことで、［Ｂ］光重合開始剤による［Ａ］ポリマーの二重結合含有基（Ａ）間の結合形成がより効果的に起こり、その結果、紫外線照射による硬化後の粘着力の低下幅も十分に大きいものとなり、かつ糊残りが十分に少なくなると考えられる。加えて、当該粘着剤組成物は、多官能モノマー又は多官能オリゴマーを実質的に含有しない。当該粘着剤組成物は、多官能モノマーや多官能オリゴマーを実質的に含有しないことで、粘着剤層の硬化の際に、多官能モノマー等に起因すると考えられるオリゴマー等の低分子量成分の発生を抑制することができると考えられ、その結果、糊残りをさらに十分に少なくすることができる。さらに、［Ａ］ポリマーは上述のように立体的に小さいアクリル酸メチルに由来する構造単位（Ｉ）を上記特定範囲の含有割合で有するものであるため、比較的自由に分子運動することができると考えられ、その結果、当該粘着剤組成物から形成される粘着剤層は、埋め込み性にも優れる。以下、各成分について説明する。 The pressure-sensitive adhesive composition has a sufficiently high adhesive strength before ultraviolet irradiation regardless of the presence or absence of heating, a sufficiently large decrease in adhesive strength due to ultraviolet irradiation, a small amount of adhesive residue, and excellent embedding properties. . The reason why the pressure-sensitive adhesive composition exhibits the above-described effect by having the above-described configuration is not necessarily clear, but can be inferred as follows, for example. That is, the pressure-sensitive adhesive composition contains [A] to [C] components, and the [A] polymer is a structural unit derived from methyl acrylate having a content ratio in the specific range together with the double bond-containing group (A). (I). Since the structural unit (I) derived from methyl acrylate is three-dimensionally small, an adhesive structure formed from [A] polymer and [C] thermosetting agent and the interaction with the adherend Can be made larger, and as a result, the adhesive strength before curing can be made sufficiently high. In addition, as described above, since the structural unit (I) derived from methyl acrylate is sterically small, the bond between the double bond-containing groups (A) of the [A] polymer by the [B] photopolymerization initiator It is considered that the formation occurs more effectively, and as a result, the decrease in the adhesive strength after curing by ultraviolet irradiation is sufficiently large, and the adhesive residue is sufficiently reduced. In addition, the pressure-sensitive adhesive composition is substantially free of a polyfunctional monomer or polyfunctional oligomer. The pressure-sensitive adhesive composition does not substantially contain a polyfunctional monomer or a polyfunctional oligomer, so that when the pressure-sensitive adhesive layer is cured, low molecular weight components such as oligomers that are considered to be caused by the polyfunctional monomer are generated. It is thought that it can suppress, As a result, adhesive residue can further be reduced further enough. Furthermore, since the [A] polymer has the structural unit (I) derived from sterically small methyl acrylate as described above in a content ratio within the specific range, it can relatively freely move in the molecule. As a result, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is also excellent in embeddability. Hereinafter, each component will be described.
＜［Ａ］ポリマー＞
［Ａ］ポリマーは、構造単位（Ｉ）及び二重結合含有基（Ａ）を有するポリマーである。［Ａ］ポリマーは、構造単位（Ｉ）以外に、炭素数４以上１０以下のアルキル基を含む（メタ）アクリル酸アルキルエステルに由来する構造単位（以下、「構造単位（ＩＩ）」ともいう）、ヒドロキシ基を含む構造単位（以下、「構造単位（ＩＩＩ）」ともいう）及び／又はエポキシ基を含む構造単位（以下、「構造単位（ＩＶ）」ともいう）をさらに有することが好ましく、構造単位（Ｉ）〜（ＩＶ）以外のその他の構造単位をさらに有していてもよい。二重結合含有基（Ａ）は、構造単位（ＩＩ）〜（ＩＶ）やその他の構造単位に含まれていてもよい。以下、二重結合含有基（Ａ）及び各構造単位について説明する。<[A] polymer>
[A] The polymer is a polymer having the structural unit (I) and the double bond-containing group (A). [A] The polymer is a structural unit derived from a (meth) acrylic acid alkyl ester containing an alkyl group having 4 to 10 carbon atoms in addition to the structural unit (I) (hereinafter also referred to as “structural unit (II)”). , Preferably having a structural unit containing a hydroxy group (hereinafter also referred to as “structural unit (III)”) and / or a structural unit containing an epoxy group (hereinafter also referred to as “structural unit (IV)”). You may further have other structural units other than unit (I)-(IV). The double bond-containing group (A) may be contained in the structural units (II) to (IV) and other structural units. Hereinafter, the double bond-containing group (A) and each structural unit will be described.
［二重結合含有基（Ａ）］
二重結合含有基（Ａ）は、重合性炭素−炭素二重結合を含む基である。重合性炭素−炭素二重結合は、エチレン性炭素−炭素二重結合を意味する。[Double bond-containing group (A)]
The double bond-containing group (A) is a group containing a polymerizable carbon-carbon double bond. A polymerizable carbon-carbon double bond means an ethylenic carbon-carbon double bond.
二重結合含有基（Ａ）としては、重合性炭素−炭素二重結合を含む基であれば特に限定されないが、例えば（メタ）アクリロイル基、ビニル基、アリル基、スチリル基等が挙げられる。これらの中で、重合性により優れ、紫外線照射後の粘着力の低下幅がより十分に大きくなる観点から、（メタ）アクリロイル基が好ましい。 Although it will not specifically limit as a double bond containing group (A) if it is a group containing a polymerizable carbon-carbon double bond, For example, a (meth) acryloyl group, a vinyl group, an allyl group, a styryl group etc. are mentioned. Among these, a (meth) acryloyl group is preferable from the viewpoints of excellent polymerizability and a sufficiently large decrease in the adhesive strength after ultraviolet irradiation.
［Ａ］ポリマーは、二重結合含有基（Ａ）を、主鎖、側鎖及び末端のいずれに有していてもよいが、重合性炭素−炭素二重結合の重合性を向上し、紫外線照射後の粘着力の低下幅をより十分に大きくする観点から、側鎖に有することが好ましい。 [A] The polymer may have a double bond-containing group (A) in any of the main chain, the side chain, and the terminal, but improves the polymerizability of the polymerizable carbon-carbon double bond, and UV From the viewpoint of sufficiently increasing the decrease in the adhesive strength after irradiation, it is preferable to have the side chain.
側鎖に二重結合含有基（Ａ）が導入された［Ａ］ポリマーを得る方法としては、例えばヒドロキシ基及びエポキシ基のうち少なくとも一方を有する前駆体ポリマーを用意し、（１）前駆体ポリマーのヒドロキシ基に、イソシアネート基及び二重結合含有基（Ａ）を有する化合物のイソシアネート基を反応させる方法、（２）前駆体ポリマーのエポキシ基に、カルボキシ基及び二重結合含有基（Ａ）を有する化合物のカルボキシ基を反応させる方法、（３）前駆体ポリマーのヒドロキシ基に、カルボキシ基及び二重結合含有基（Ａ）を有する化合物のカルボキシ基を脱水縮合反応させる方法、これら（１）〜（３）のうちの複数を併用する方法等が挙げられる。（１）の場合、前駆体ポリマーの側鎖に二重結合含有基（Ａ）が導入されると共にウレタン基が形成される。 As a method for obtaining the polymer [A] in which the double bond-containing group (A) is introduced into the side chain, for example, a precursor polymer having at least one of a hydroxy group and an epoxy group is prepared, and (1) a precursor polymer A method of reacting an isocyanate group of a compound having an isocyanate group and a double bond-containing group (A) with the hydroxy group of (2), (2) a carboxy group and a double bond-containing group (A) to the epoxy group of the precursor polymer A method of reacting a carboxy group of a compound having (3) a method of subjecting a hydroxy group of a precursor polymer to a dehydration condensation reaction of a carboxy group of a compound having a carboxy group and a double bond-containing group (A); The method etc. which use two or more of (3) together are mentioned. In the case of (1), the double bond-containing group (A) is introduced into the side chain of the precursor polymer and a urethane group is formed.
イソシアネート基及び二重結合含有基（Ａ）を有する化合物としては、例えば２−（メタ）アクリロイルオキシエチルイソシアネート、２−（メタ）アクリロイルオキシプロピルイソシアネート等の（メタ）アクリロイルアルキルイソシアネート；２−（２−（メタ）アクリロイルオキシエチルオキシ）エチルイソシアネート、２−（２−（メタ）アクリロイルオキシプロピルオキシ）プロピルイソシアネート等の２−（２−（メタ）アクリロイルオキシアルキルオキシ）アルキルイソシアネートなどが挙げられる。２−（メタ）アクリロイルオキシエチルイソシアネートの市販品としては、例えば昭和電工社の「カレンズＡＯＩ」、「カレンズＭＯＩ」等が挙げられる。２−（２−メタクリロイルオキシエチルオキシ）エチルイソシアネートの市販品としては、例えば昭和電工社の「カレンズＭＯＩＥＧ」等が挙げられる。 Examples of the compound having an isocyanate group and a double bond-containing group (A) include (meth) acryloylalkyl isocyanates such as 2- (meth) acryloyloxyethyl isocyanate and 2- (meth) acryloyloxypropyl isocyanate; 2- (2 Examples include 2- (2- (meth) acryloyloxyalkyloxy) alkyl isocyanate such as-(meth) acryloyloxyethyloxy) ethyl isocyanate and 2- (2- (meth) acryloyloxypropyloxy) propyl isocyanate. Examples of commercially available 2- (meth) acryloyloxyethyl isocyanate include “Karenz AOI” and “Karenz MOI” manufactured by Showa Denko KK. Examples of commercially available 2- (2-methacryloyloxyethyloxy) ethyl isocyanate include “Karenz MOIEG” manufactured by Showa Denko KK.
カルボキシ基及び二重結合含有基（Ａ）を有する化合物としては、例えば（メタ）アクリル酸；カルボキシメチル（メタ）アクリレート、カルボキシエチル（メタ）アクリレート等のカルボキシアルキル（メタ）アクリレートなどが挙げられる。 Examples of the compound having a carboxy group and a double bond-containing group (A) include (meth) acrylic acid; carboxyalkyl (meth) acrylates such as carboxymethyl (meth) acrylate and carboxyethyl (meth) acrylate.
また、側鎖に二重結合含有基（Ａ）が導入された［Ａ］ポリマーを得る別の方法としては、例えばヒドロキシ基及びエポキシ基のうち少なくとも一方を有する前駆体ポリマーを用意し、（４）前駆体ポリマーが有するヒドロキシ基に、ポリイソシアネート化合物のイソシアネート基の１つを反応させ、このポリイソシアネート化合物の他のイソシアネート基に、ヒドロキシ基及び二重結合含有基（Ａ）を有する化合物のヒドロキシ基を反応させる方法、（５）前駆体ポリマーが有するエポキシ基に、ポリカルボン酸化合物のカルボキシ基の１つを反応させ、このポリカルボン酸化合物の他のカルボキシ基に、エポキシ基及び二重結合含有基（Ａ）を有する化合物のエポキシ基を反応させる方法、（６）前駆体ポリマーが有するヒドロキシ基に、ポリカルボン酸化合物のカルボキシ基の１つを脱水縮合により結合させ、このポリカルボン酸化合物の他のカルボキシ基に、ヒドロキシ基及び二重結合含有基（Ａ）を有する化合物のヒドロキシ基を脱水縮合反応させる方法、これら（４）〜（６）のうちの複数を併用する方法等が挙げられる。（４）の場合、前駆体ポリマーの側鎖に二重結合含有基（Ａ）が導入させると共に、複数のウレタン基が形成される。 As another method for obtaining a polymer [A] having a double bond-containing group (A) introduced in the side chain, for example, a precursor polymer having at least one of a hydroxy group and an epoxy group is prepared, and (4 ) One of the isocyanate groups of the polyisocyanate compound is reacted with the hydroxy group of the precursor polymer, and the other isocyanate group of the polyisocyanate compound has a hydroxyl group and a double bond-containing group (A). (5) reacting one of the carboxy groups of the polycarboxylic acid compound with the epoxy group of the precursor polymer, and reacting the other carboxy group of the polycarboxylic acid compound with an epoxy group and a double bond A method of reacting an epoxy group of a compound having a containing group (A), (6) a hydroxy group of a precursor polymer One carboxy group of the polycarboxylic acid compound is bonded by dehydration condensation, and the hydroxy group of the compound having the hydroxy group and the double bond-containing group (A) is dehydrated and condensed to the other carboxy group of the polycarboxylic acid compound. And a method in which a plurality of these (4) to (6) are used in combination. In the case of (4), the double bond-containing group (A) is introduced into the side chain of the precursor polymer, and a plurality of urethane groups are formed.
ポリイソシアネート化合物としては、例えばメチレンジフェニルジイソシアネート（ＭＤＩ）、トリレンジイソシアネート（ＴＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）等が挙げられる。 Examples of the polyisocyanate compound include methylene diphenyl diisocyanate (MDI), tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), and the like.
ポリカルボン酸化合物としては、例えばシュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸等の脂肪族ジカルボン酸、フタル酸、テレフタル酸等の芳香族ジカルボン酸などが挙げられる。 Examples of the polycarboxylic acid compound include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid, and aromatic dicarboxylic acids such as phthalic acid and terephthalic acid.
［Ａ］ポリマー中の二重結合含有基（Ａ）の含有率の下限としては、０．６質量％が好ましく、０．８質量％がより好ましく、０．９質量％がさらに好ましく、１．０質量％が特に好ましい。上記含有率の上限としては、１０質量％が好ましく、５質量％がより好ましく、４質量％がさらに好ましく、３質量％が特に好ましい。二重結合含有基（Ａ）の含有率を上記範囲とすることで、紫外線照射による粘着力の低下幅をより十分に大きくすることができ、かつ糊残りをより十分に低減することができる。［Ａ］ポリマー中の二重結合含有基（Ａ）の含有率（質量％）は、二重結合含有基（Ａ）を構成する各原子の質量の総和をポリマーの総質量で除することによって求めることができる。 [A] The lower limit of the content of the double bond-containing group (A) in the polymer is preferably 0.6% by mass, more preferably 0.8% by mass, still more preferably 0.9% by mass. 0% by mass is particularly preferred. As an upper limit of the said content rate, 10 mass% is preferable, 5 mass% is more preferable, 4 mass% is further more preferable, and 3 mass% is especially preferable. By making the content rate of a double bond containing group (A) into the said range, the fall width of the adhesive force by ultraviolet irradiation can be enlarged more fully, and adhesive residue can be reduced more fully. [A] The content (% by mass) of the double bond-containing group (A) in the polymer is obtained by dividing the total mass of each atom constituting the double bond-containing group (A) by the total mass of the polymer. Can be sought.
［構造単位（Ｉ）］
構造単位（Ｉ）は、アクリル酸メチルに由来する構造単位である。構造単位（Ｉ）は、−ＣＨ２−ＣＨ（ＣＯＯＣＨ３）−で表される構造を有している。[Structural unit (I)]
The structural unit (I) is a structural unit derived from methyl acrylate. The structural unit (I) has a structure represented by —CH 2 —CH (COOCH 3 ) —.
構造単位（Ｉ）の含有割合の下限としては、［Ａ］ポリマーを構成する全構造単位に対して、１質量％であり、５質量％が好ましく、１０質量％がより好ましく、２０質量％がさらに好ましく、３０質量％が特に好ましい。上記含有割合の上限としては、６０質量％であり、５５質量％が好ましく、５０質量％がより好ましく、４５質量％がさらに好ましく、４０質量％が特に好ましい。構造単位（Ｉ）の含有割合を上記範囲とすることで、紫外線照射前の粘着力をより十分に高くすることができ、紫外線照射による粘着力の低下幅をより十分に大きくすることができ、かつ糊残りを十分に低減することができる。また、被着体の表面に段差がある場合においても十分な粘着力を発揮できる性能、すなわち埋め込み性にも優れるものとなる。構造単位（Ｉ）の含有割合が上記下限未満であると、粘着剤層の強度が低下すると考えられ、その結果、紫外線照射前の粘着力の低下、糊残りの発生及び埋め込み性の低下が生じる傾向がある。構造単位（Ｉ）の含有割合が上記上限を超えると、粘着剤層に紫外線を照射した際に［Ａ］ポリマーが架橋によって凝集する効果が低減すると考えられ、その結果、糊残りと埋め込み性の低下が生じる傾向がある。加えて、粘着剤層の柔軟性が低下することにより、紫外線照射前の埋め込み性が低下する傾向がある。 As a minimum of the content rate of structural unit (I), it is 1 mass% with respect to all the structural units which comprise a [A] polymer, 5 mass% is preferable, 10 mass% is more preferable, and 20 mass% is More preferred is 30% by mass. As an upper limit of the said content rate, it is 60 mass%, 55 mass% is preferable, 50 mass% is more preferable, 45 mass% is further more preferable, 40 mass% is especially preferable. By making the content ratio of the structural unit (I) in the above range, the adhesive strength before ultraviolet irradiation can be made sufficiently higher, and the decrease in adhesive strength due to ultraviolet irradiation can be made sufficiently larger, In addition, the adhesive residue can be sufficiently reduced. In addition, even when there is a step on the surface of the adherend, it is possible to exhibit a sufficient adhesive force, that is, excellent embedding property. When the content ratio of the structural unit (I) is less than the above lower limit, it is considered that the strength of the pressure-sensitive adhesive layer is reduced, and as a result, the adhesive strength before ultraviolet irradiation is reduced, the adhesive residue is generated, and the embedding property is reduced. Tend. When the content ratio of the structural unit (I) exceeds the above upper limit, it is considered that the effect that the [A] polymer aggregates by crosslinking when the pressure-sensitive adhesive layer is irradiated with ultraviolet rays is reduced. There is a tendency to decrease. In addition, since the flexibility of the pressure-sensitive adhesive layer is lowered, the embedding property before ultraviolet irradiation tends to be lowered.
［構造単位（ＩＩ）］
構造単位（ＩＩ）は、炭素数４以上１０以下のアルキル基を含む（メタ）アクリル酸アルキルエステルに由来する構造単位である。当該粘着剤組成物は、［Ａ］ポリマーが構造単位（ＩＩ）を有することで、粘着剤層の強度をより高めることができ、その結果、紫外線照射前の粘着力をより高めることができる。[Structural unit (II)]
The structural unit (II) is a structural unit derived from a (meth) acrylic acid alkyl ester containing an alkyl group having 4 to 10 carbon atoms. The said adhesive composition can raise the intensity | strength of an adhesive layer more because [A] polymer has structural unit (II), As a result, the adhesive force before ultraviolet irradiation can be raised more.
炭素数４以上１０以下のアルキル基としては、例えばｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−オクチル基、２−エチルヘキシル基、ｎ−デシル基等が挙げられる。これらの中で、ｎ−ブチル基及び２−エチルヘキシル基が好ましい。 Examples of the alkyl group having 4 to 10 carbon atoms include an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, a 2-ethylhexyl group, and an n-decyl group. Among these, n-butyl group and 2-ethylhexyl group are preferable.
構造単位（ＩＩ）を与えるモノマーとしては、ｎ−ブチル（メタ）アクリレート、ｎ−ペンチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−デシル（メタ）アクリレート等のアルキル（メタ）アクリレートなどが挙げられる。これらの中で、アルキルアクリレートが好ましく、ｎ−ブチルアクリレート及び２−エチルヘキシルアクリレートがより好ましい。 Monomers that give structural unit (II) include n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. And alkyl (meth) acrylates such as n-decyl (meth) acrylate. Among these, alkyl acrylate is preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are more preferable.
［Ａ］ポリマーが構造単位（ＩＩ）を有する場合、構造単位（ＩＩ）の含有割合の下限としては、５質量％が好ましく、１０質量％がより好ましく、３０質量％がさらに好ましく、４０質量％が特に好ましい。上記含有割合の上限としては、９５質量％が好ましく、８０質量％がより好ましく、７０質量％がさらに好ましく、６０質量％が特に好ましい。構造単位（ＩＩ）の含有割合を上記範囲とすることで、粘着剤層の強度をさらに高めることができ、その結果、紫外線照射前の粘着力をさらに高めることができる。 [A] When the polymer has the structural unit (II), the lower limit of the content ratio of the structural unit (II) is preferably 5% by mass, more preferably 10% by mass, further preferably 30% by mass, and 40% by mass. Is particularly preferred. As an upper limit of the said content rate, 95 mass% is preferable, 80 mass% is more preferable, 70 mass% is further more preferable, 60 mass% is especially preferable. By making the content rate of structural unit (II) into the said range, the intensity | strength of an adhesive layer can further be raised and as a result, the adhesive force before ultraviolet irradiation can further be raised.
［構造単位（ＩＩＩ）］
構造単位（ＩＩＩ）は、ヒドロキシ基を含む構造単位である。［Ａ］ポリマーが構造単位（ＩＩＩ）を有することで、紫外線照射前における粘着剤層の粘着力がより向上すると共に、耐水性が向上する。[Structural unit (III)]
The structural unit (III) is a structural unit containing a hydroxy group. [A] When the polymer has the structural unit (III), the adhesive force of the pressure-sensitive adhesive layer before ultraviolet irradiation is further improved and the water resistance is improved.
ヒドロキシ基としては、例えばアルコール性ヒドロキシ基、フェノール性ヒドロキシ基等が挙げられる。これらの中で、紫外線照射前の粘着力がより向上する観点から、アルコール性ヒドロキシ基が好ましい。 Examples of the hydroxy group include alcoholic hydroxy groups and phenolic hydroxy groups. Among these, an alcoholic hydroxy group is preferable from the viewpoint of further improving the adhesive strength before ultraviolet irradiation.
構造単位（ＩＩＩ）を与えるモノマーとしては、例えばヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート；ヒドロキシフェニル（メタ）アクリレート、ヒドロキシナフチル（メタ）アクリレート等のヒドロキシアリール（メタ）アクリレートなどが挙げられる。これらの中で、ヒドロキシアルキル（メタ）アクリレートが好ましく、ヒドロキシアルキルアクリレートがより好ましく、ヒドロキシエチルアクリレートがさらに好ましい。 Examples of monomers that give structural unit (III) include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; hydroxyphenyl (meth) acrylate and hydroxynaphthyl And hydroxyaryl (meth) acrylates such as (meth) acrylates. Among these, hydroxyalkyl (meth) acrylate is preferable, hydroxyalkyl acrylate is more preferable, and hydroxyethyl acrylate is more preferable.
［Ａ］ポリマーが構造単位（ＩＩＩ）を有する場合、構造単位（ＩＩＩ）の含有割合の下限としては、１質量％が好ましく、３質量％がより好ましく、４質量％がさらに好ましく、５質量％が特に好ましい。上記含有割合の上限としては、３０質量％が好ましく、２５質量％がより好ましく、１５質量％がさらに好ましく、１０質量％が特に好ましい。 [A] When the polymer has the structural unit (III), the lower limit of the content of the structural unit (III) is preferably 1% by mass, more preferably 3% by mass, further preferably 4% by mass, and 5% by mass. Is particularly preferred. As an upper limit of the said content rate, 30 mass% is preferable, 25 mass% is more preferable, 15 mass% is further more preferable, and 10 mass% is especially preferable.
［構造単位（ＩＶ）］
構造単位（ＩＶ）は、エポキシ基を含む構造単位である。［Ａ］ポリマーが構造単位（ＩＶ）を有することで、紫外線照射前の粘着剤層の粘着力がより向上すると共に、基材等に対する密着性が向上する。 [Structural unit (IV)]
The structural unit (IV) is a structural unit containing an epoxy group. [A] When the polymer has the structural unit (IV), the adhesive force of the pressure-sensitive adhesive layer before ultraviolet irradiation is further improved, and the adhesion to the substrate and the like is improved.
構造単位（ＩＶ）を与えるモノマーとしては、例えばグリシジル（メタ）アクリレート、オキシラニルエチル（メタ）アクリレート、オキシラニルプロピル（メタ）アクリレート等のオキシラニル基を含む（メタ）アクリレート；オキセタニルメチル（メタ）アクリレート、オキセタニルエチル（メタ）アクリレート、オキセタニルプロピル（メタ）アクリレート等のオキセタニル基を含む（メタ）アクリレートなどが挙げられる。これらの中で、オキシラニル基を含む（メタ）アクリレートが好ましく、オキシラニル基を含むメタクリレートがより好ましく、グリシジルメタクリレートがさらに好ましい。 Examples of the monomer that gives the structural unit (IV) include (meth) acrylates containing oxiranyl groups such as glycidyl (meth) acrylate, oxiranylethyl (meth) acrylate, and oxiranylpropyl (meth) acrylate; oxetanylmethyl (meth) ) Acrylate, oxetanylethyl (meth) acrylate, oxetanylpropyl (meth) acrylate and other (meth) acrylates containing an oxetanyl group. Among these, a (meth) acrylate containing an oxiranyl group is preferred, a methacrylate containing an oxiranyl group is more preferred, and glycidyl methacrylate is more preferred.
［Ａ］ポリマーが構造単位（ＩＶ）を有する場合、構造単位（ＩＶ）の含有割合の下限としては、０．１質量％が好ましく、１質量％がより好ましく、２質量％がさらに好ましく、３質量％が特に好ましい。上記含有割合の上限としては、３０質量％が好ましく、２０質量％がより好ましく、１０質量％がさらに好ましく、５質量％が特に好ましい。 [A] When the polymer has the structural unit (IV), the lower limit of the content ratio of the structural unit (IV) is preferably 0.1% by mass, more preferably 1% by mass, further preferably 2% by mass. Mass% is particularly preferred. As an upper limit of the said content rate, 30 mass% is preferable, 20 mass% is more preferable, 10 mass% is further more preferable, and 5 mass% is especially preferable.
［その他の構造単位］
［Ａ］ポリマーは、構造単位（Ｉ）〜（ＩＶ）以外のその他の構造単位を有していてもよい。その他の構造単位としては、例えばスチレン化合物に由来する構造単位等が挙げられる。スチレン化合物としては、例えば、スチレン、α−メチルスチレン、ｏ−、ｍ−又はｐ−メチルスチレン、ｏ−、ｍ−又はｐ−ヒドロキシスチレン等が挙げられる。その他の構造単位の含有割合の上限としては、［Ａ］ポリマーを構成する全構造単位に対して、３０質量％が好ましく、２０質量％がより好ましく、１０質量％がさらに好ましい。[Other structural units]
[A] The polymer may have other structural units other than the structural units (I) to (IV). Examples of other structural units include structural units derived from styrene compounds. Examples of the styrene compound include styrene, α-methylstyrene, o-, m- or p-methylstyrene, o-, m- or p-hydroxystyrene. As an upper limit of the content rate of another structural unit, 30 mass% is preferable with respect to all the structural units which comprise a [A] polymer, 20 mass% is more preferable, and 10 mass% is further more preferable.
＜［Ａ］ポリマーの合成方法＞
［Ａ］ポリマーの合成方法では、例えば構造単位（Ｉ）〜（ＩＶ）及びその他の構造単位を与える単量体を、アゾビスイソブチロニトリル（ＡＩＢＮ）等のラジカル重合開始剤などを用い、酢酸エチル等の溶媒中で重合することにより前駆体ポリマーを得る。次に、この前駆体ポリマーのヒドロキシ基、エポキシ基等に、二重結合含有基（Ａ）とイソシアネート基、カルボキシ基等とを有する化合物を、ジブチルスズジラウレート等の反応触媒の存在下、酢酸エチル等の溶媒中で反応させる。これにより、前駆体ポリマーに二重結合含有基（Ａ）を導入されるため、［Ａ］ポリマーを合成することができる。<[A] Polymer Synthesis Method>
[A] In the polymer synthesis method, for example, a monomer that gives structural units (I) to (IV) and other structural units is used using a radical polymerization initiator such as azobisisobutyronitrile (AIBN). A precursor polymer is obtained by polymerization in a solvent such as ethyl acetate. Next, a compound having a double bond-containing group (A), an isocyanate group, a carboxy group, etc., in the hydroxy group, epoxy group, etc. of this precursor polymer, ethyl acetate, etc. in the presence of a reaction catalyst such as dibutyltin dilaurate In the solvent. Thereby, since the double bond-containing group (A) is introduced into the precursor polymer, the [A] polymer can be synthesized.
重合における反応温度の下限としては、４０℃が好ましく、６０℃がより好ましい。上記反応温度の上限としては、１５０℃が好ましく、１００℃がより好ましい。重合における反応時間の下限としては、１時間が好ましく、４時間がより好ましい。上記反応時間の上限としては、４８時間が好ましく、２４時間がより好ましい。 As a minimum of reaction temperature in superposition | polymerization, 40 degreeC is preferable and 60 degreeC is more preferable. As an upper limit of the said reaction temperature, 150 degreeC is preferable and 100 degreeC is more preferable. As a minimum of reaction time in superposition | polymerization, 1 hour is preferable and 4 hours is more preferable. The upper limit of the reaction time is preferably 48 hours, more preferably 24 hours.
二重結合含有基（Ａ）の導入反応の反応温度の下限としては、２０℃が好ましく、３０℃がより好ましい。上記反応温度の上限としては、１００℃が好ましく、６０℃がより好ましい。二重結合含有基（Ａ）の導入反応における反応時間の下限としては、１時間が好ましく、３時間がより好ましい。上記反応時間の上限としては、２０時間が好ましく、８時間がより好ましい。 As a minimum of reaction temperature of introduction reaction of a double bond content group (A), 20 ° C is preferred and 30 ° C is more preferred. As an upper limit of the said reaction temperature, 100 degreeC is preferable and 60 degreeC is more preferable. As a minimum of reaction time in introduction reaction of a double bond content group (A), 1 hour is preferred and 3 hours is more preferred. The upper limit of the reaction time is preferably 20 hours, and more preferably 8 hours.
［Ａ］ポリマーのゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算重量平均分子量（Ｍｗ）の下限としては、５万が好ましく、１０万がより好ましく、１５万がさらに好ましく、２０万が特に好ましい。上記Ｍｗの上限としては、５０万が好ましく、４０万がより好ましく、３０万がさらに好ましく、２５万が特に好ましい。当該粘着剤組成物は、［Ａ］ポリマーのＭｗを上記範囲とすることで、紫外線照射前の粘着力をより十分に高くすることができる。 [A] The lower limit of the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is preferably 50,000, more preferably 100,000, even more preferably 150,000, and particularly preferably 200,000. As an upper limit of the Mw, 500,000 is preferable, 400,000 is more preferable, 300,000 is more preferable, and 250,000 is particularly preferable. The said adhesive composition can make adhesive force before ultraviolet irradiation more fully high by making Mw of [A] polymer into the said range.
［Ａ］ポリマーのＧＰＣによるポリスチレン換算数平均分子量（Ｍｎ）に対するＭｗの比（Ｍｗ／Ｍｎ）の下限としては、通常１であり、１．１が好ましい。上記比の上限としては、５が好ましく、３がより好ましく、２がさらに好ましく、１．７が特に好ましい。 [A] The lower limit of the ratio (Mw / Mn) of Mw to the number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer is usually 1 and preferably 1.1. As an upper limit of the ratio, 5 is preferable, 3 is more preferable, 2 is more preferable, and 1.7 is particularly preferable.
本明細書において［Ａ］ポリマーのＭｗ及びＭｎを測定するために用いたＧＰＣの各条件は、以下の通りである。
ＧＰＣカラム：例えば東ソー社の「ＴＳＫｇｅｌ Ｍｕｌｔｉｐｏｒｅ ＨＸＬ−Ｍ」２本、
カラム温度：４０℃
溶出溶媒：テトラヒドロフラン（和光純薬工業社）
流量： １．０ｍＬ／分
試料濃度： ０．０５質量％
試料注入量：１００μＬ
検出器：示差屈折計
標準物質：単分散ポリスチレンIn this specification, each condition of GPC used for measuring Mw and Mn of [A] polymer is as follows.
GPC column: For example, “TSKgel Multipore H XL- M” manufactured by Tosoh Corporation
Column temperature: 40 ° C
Elution solvent: Tetrahydrofuran (Wako Pure Chemical Industries)
Flow rate: 1.0 mL / min Sample concentration: 0.05% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene
［Ａ］ポリマーのガラス転移温度（Ｔｇ）の下限としては、−１００℃が好ましく、−８０℃がより好ましく、−６０℃がさらに好ましく、−４０℃が特に好ましい。上記Ｔｇの上限としては、２０℃が好ましく、０℃がより好ましく、−１０℃がさらに好ましく、−２０℃が特に好ましい。当該粘着剤組成物は、［Ａ］ポリマーのＴｇを上記範囲とすることで、紫外線照射前の粘着力をより向上させることができる。 [A] As a minimum of glass transition temperature (Tg) of a polymer, -100 ° C is preferred, -80 ° C is more preferred, -60 ° C is still more preferred, and -40 ° C is especially preferred. As an upper limit of said Tg, 20 degreeC is preferable, 0 degreeC is more preferable, -10 degreeC is further more preferable, and -20 degreeC is especially preferable. The said adhesive composition can improve the adhesive force before ultraviolet irradiation more by making Tg of [A] polymer into the said range.
本明細書における［Ａ］ポリマーのＴｇは、［Ａ］ポリマーの乾燥フィルムを、示差走査熱量分析計（例えばティー・エイ・インスツルメント社の「ＭＤＳＣＱ２００型」）を用い、窒素雰囲気下、昇温速度２０℃／分、サンプル量２０ｍｇの条件で測定した値である。 The Tg of the [A] polymer in this specification is determined by increasing the dry film of the [A] polymer in a nitrogen atmosphere using a differential scanning calorimeter (for example, “MDSCQ200 type” manufactured by TA Instruments). It is a value measured under conditions of a temperature rate of 20 ° C./min and a sample amount of 20 mg.
＜［Ｂ］光重合開始剤＞
［Ｂ］光重合開始剤は、紫外線の照射によって重合反応を開始することができる成分である。当該粘着剤組成物から形成される粘着剤層は、［Ｂ］光重合開始剤を含まれることで、紫外線照射を照射された際に［Ａ］ポリマーが有する二重結合含有基（Ａ）同士の重合反応で硬化する。その結果、粘着剤層と被着体との相互作用が低減し、粘着力が低下する。<[B] Photopolymerization initiator>
[B] The photopolymerization initiator is a component capable of initiating a polymerization reaction by irradiation with ultraviolet rays. The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition contains [B] a photopolymerization initiator, so that the double bond-containing groups (A) possessed by the polymer [A] when irradiated with ultraviolet irradiation. It is cured by the polymerization reaction. As a result, the interaction between the pressure-sensitive adhesive layer and the adherend is reduced, and the adhesive strength is reduced.
［Ｂ］光重合開始剤としては、例えばベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン−ｎ−ブチルエーテル、ベンゾインイソブチルエーテル、アセトフェノン、ジメチルアミノアセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノ−プロパン−１−オン、４−（２−ヒドロキシエトキシ）フェニル−２−（ヒドロキシ−２−プロピル）ケトン、ベンゾフェノン、ｐ−フェニルベンゾフェノン、４，４’−ジエチルアミノベンゾフェノン、ジクロロベンゾフェノン、２−メチルアントラキノン、２−エチルアントラキノン、２−ｔｅｒｔ−ブチルアントラキノン、２−アミノアントラキノン、２−メチルチオキサントン、２−エチルチオキサントン、２−クロロチオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、ベンジルジメチルケタール、アセトフェノンジメチルケタール、ｐ−ジメチルアミノ安息香酸エステル、オリゴ［２−ヒドロキシ−２−メチル−１［４−（１−メチルビニル）フェニル］プロパノン］、２，４，６−トリメチルベンゾイル−ジフェニル−ホスフィンオキサイド等が挙げられる。これらの中で、１−ヒドロキシシクロヘキシルフェニルケトンが好ましい。 [B] Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, and 2,2-dimethoxy-2-phenyl. Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethyl Minobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, oligo [2-hydroxy-2-methyl-1 [4- (1-methylvinyl) phenyl] propanone], 2, Examples include 4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Of these, 1-hydroxycyclohexyl phenyl ketone is preferred.
［Ｂ］光重合開始剤の市販品としては、例えばＢＡＳＦ社の「Ｉｒｇａｃｕｒｅ１８４」、「同６５１」、「同２９５９」、「同１２７」、「同８１９」、「同７８４」、「同７５４」、「同５００」、「同２５０」、「同２７０」、「同９０７」、「同３６９」、「同３７９ＥＧ」、「同ＯＸＥ ０１」、「同ＯＸＥ ０２」、「Ｌｕｃｉｒｉｎ ＴＰＯ」、「Ｄａｒｏｃｕｒｅ １１７３」、「同ＭＢＦ」等が挙げられる。 [B] Commercially available photopolymerization initiators include, for example, “Irgacure 184”, “651”, “2959”, “127”, “819”, “784” and “754” of BASF. , “Same 500”, “Same 250”, “Same 270”, “Same 907”, “Same 369”, “Same 379 EG”, “Same OXE 01”, “Same OXE 02”, “Lucirin TPO”, “Darocure” 1173 "," same MBF ", and the like.
［Ｂ］光重合開始剤の含有量の下限としては、［Ａ］ポリマー１００質量部に対して、０．１質量部が好ましく、０．５質量部がより好ましく、１質量部がさらに好ましく、２質量部が特に好ましい。上記含有量の上限としては、２０質量部が好ましく、１０質量部がより好ましく、８質量部がさらに好ましく、６質量部が特に好ましい。［Ｂ］光重合開始剤の含有量を上記範囲とすることで、紫外線照射による二重結合含有基（Ａ）同士の重合反応がより効果的に進行し、その結果、紫外線照射後の粘着力の低下幅がさらに十分に大きいものとなり、かつ糊残りがより十分に低減される。 [B] The lower limit of the content of the photopolymerization initiator is preferably 0.1 parts by weight, more preferably 0.5 parts by weight, and even more preferably 1 part by weight with respect to 100 parts by weight of the polymer [A]. 2 parts by mass is particularly preferred. As an upper limit of the said content, 20 mass parts is preferable, 10 mass parts is more preferable, 8 mass parts is further more preferable, 6 mass parts is especially preferable. [B] By setting the content of the photopolymerization initiator in the above range, the polymerization reaction between the double bond-containing groups (A) by ultraviolet irradiation proceeds more effectively, and as a result, the adhesive strength after ultraviolet irradiation. Is further sufficiently large, and the adhesive residue is more sufficiently reduced.
＜［Ｃ］熱硬化剤＞
［Ｃ］熱硬化剤は、加熱によって［Ａ］ポリマーに架橋構造を形成することができる成分である。当該粘着剤組成物は、［Ａ］ポリマー及び［Ｂ］光重合開始剤に加えてさらに［Ｃ］熱硬化剤を含有することで、架橋構造を有する粘着剤層を形成できる。その結果、当該粘着剤組成物は、粘着シートを形成してロール化することで圧力がかかった際の粘着剤層のはみ出しを抑制できる。<[C] thermosetting agent>
[C] The thermosetting agent is a component capable of forming a crosslinked structure in the [A] polymer by heating. The pressure-sensitive adhesive composition can form a pressure-sensitive adhesive layer having a crosslinked structure by further containing a [C] thermosetting agent in addition to the [A] polymer and the [B] photopolymerization initiator. As a result, the pressure-sensitive adhesive composition can suppress the protrusion of the pressure-sensitive adhesive layer when pressure is applied by forming a pressure-sensitive adhesive sheet and rolling it.
［Ｃ］熱硬化剤としては、例えば多官能イソシアネート化合物、多官能エポキシ化合物等が挙げられる。また、［Ｃ］熱硬化剤としては、メラミン化合物、尿素化合物、金属塩化合物、金属キレート化合物、金属アルコキシド化合物、アジリジン化合物、アミン化合物、アミノ樹脂化合物、過酸化物等を用いることもできる。 [C] Examples of the thermosetting agent include polyfunctional isocyanate compounds and polyfunctional epoxy compounds. [C] As the thermosetting agent, melamine compounds, urea compounds, metal salt compounds, metal chelate compounds, metal alkoxide compounds, aziridine compounds, amine compounds, amino resin compounds, peroxides, and the like can also be used.
多官能イソシアネート化合物としては、例えば１，２−エチレンジイソシアネート、１，４−ブチレンジイソシアネート、１，６−ヘキサメチレンジイソシアネート（ＨＤＩ）等の脂肪族ジイソシアネート；シクロペンチレンジイソシアネート、シクロへキシレンジイソシアネート、イソホロンジイソシアネート（ＩＰＤＩ）、水素化トリレンジイソシアネート、水素化キシリレンジイソシアネート等の脂環式ジイソシアネート；トリレンジイソシアネート（ＴＤＩ）、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート（ＭＤＩ）等の芳香族ジイソシアネートなどのジイソシアネート化合物、上記ジイソシアネート化合物の２量体以上の多量体であるポリイソシアネート化合物、上記ポリイソシアネート化合物を変性した化合物などが挙げられる。多官能イソシアネート化合物の市販品としては、例えば東ソー社の「コロネートＬ」、「同ＨＬ」等が挙げられる。 Examples of the polyfunctional isocyanate compound include aliphatic diisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI); cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate. (IPDI), cycloaliphatic diisocyanates such as hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate; diisocyanate compounds such as aromatic diisocyanates such as tolylene diisocyanate (TDI), xylylene diisocyanate, diphenylmethane diisocyanate (MDI), and the above diisocyanates A polyisocyanate compound that is a multimer of a dimer or more of a compound, and a modification of the polyisocyanate compound Things and the like. As a commercial item of a polyfunctional isocyanate compound, Tosoh Corporation's "Coronate L", "Same HL", etc. are mentioned, for example.
多官能エポキシ化合物としては、例えばエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、ジブロモネオペンチルグリコールジグリシジルエーテル、ｏ−フタル酸ジグリシジルエステル、グリセリンポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシリレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’’，Ｎ’’−ペンタグリシジルジエチレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジルエチレンジアミン等が挙げられる。多官能性エポキシ化合物の市販品としては、例えばナガセケムテック社の「ナデコールＥＸ−３１３」、「同ＥＸ−４１２」、「同ＥＸ−５２１」、「同ＥＸ−６１４Ｂ」等が挙げられる。 Examples of the polyfunctional epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, dibromo Neopentyl glycol diglycidyl ether, o-phthalic acid diglycidyl ester, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, N, N, N ′ , N′-tetraglycidyl-m-xylylenediamine, N, N, N ′, N ″, N ′ - penta glycidyl diethylenetriamine, N, N, N ', N'- tetraglycidyl ethylenediamine, and the like. Examples of commercially available products of the polyfunctional epoxy compound include “Nadecoll EX-313”, “Ex-EX-412”, “Ex-521”, and “Ex-614B” manufactured by Nagase Chemtech.
［Ｃ］熱硬化剤の含有量の下限としては、［Ａ］ポリマー１００質量部に対して、０．０５質量部が好ましく、０．０７質量部がより好ましく、０．１質量部がさらに好ましく、０．１２質量部が特に好ましい。上記含有量の上限としては、２質量部が好ましく、１質量部がより好ましく、０．５質量部がさらに好ましく、０．３質量部が特に好ましい。［Ｃ］熱硬化剤の含有量を上記範囲とすることで、粘着シートを形成してロール化することで圧力がかかった際の粘着剤層のはみ出しをさらに抑制できる。 [C] The lower limit of the content of the thermosetting agent is preferably 0.05 parts by mass, more preferably 0.07 parts by mass, and even more preferably 0.1 parts by mass with respect to 100 parts by mass of the polymer [A]. 0.12 parts by mass is particularly preferable. The upper limit of the content is preferably 2 parts by mass, more preferably 1 part by mass, further preferably 0.5 parts by mass, and particularly preferably 0.3 parts by mass. [C] By setting the content of the thermosetting agent in the above range, it is possible to further suppress the protrusion of the pressure-sensitive adhesive layer when pressure is applied by forming a pressure-sensitive adhesive sheet and rolling it.
当該粘着剤組成物は、多官能モノマー又は多官能オリゴマーを実質的に含有しない。当該粘着剤組成物は、多官能モノマー又は多官能オリゴマーを実質的に含有しないので、粘着剤層の硬化の際に、多官能モノマー又は多官能オリゴマーに起因すると考えられる低分子量の成分の発生を抑制することができると考えられ、その結果、糊残りを十分に少なくすることができる。多官能モノマーとしては、例えばジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールトリアクリレート等が挙げられる。多官能オリゴマーとしては、例えば二官能ウレタンアクリレート、四官能ウレタンアクリレート、六官能ウレタンアクリレート、エポキシアクリレート、これらに相当するメタクリレート等が挙げられる。「多官能モノマー又は多官能オリゴマーを実質的に含有しない」とは、多官能モノマー及び多官能オリゴマーの合計含有量が［Ａ］ポリマー１００質量部に対して、例えば１０質量部以下、好ましくは５質量部以下、より好ましくは２質量部以下、特に好ましくは０質量部であることをいう。 The said adhesive composition does not contain a polyfunctional monomer or a polyfunctional oligomer substantially. Since the pressure-sensitive adhesive composition does not substantially contain a polyfunctional monomer or a polyfunctional oligomer, the curing of the pressure-sensitive adhesive layer generates a low molecular weight component that is considered to be caused by the polyfunctional monomer or the polyfunctional oligomer. It is thought that it can suppress, As a result, adhesive residue can fully be decreased. Examples of the polyfunctional monomer include dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and the like. Examples of the polyfunctional oligomer include bifunctional urethane acrylate, tetrafunctional urethane acrylate, hexafunctional urethane acrylate, epoxy acrylate, and methacrylates corresponding to these. “Substantially free of polyfunctional monomer or polyfunctional oligomer” means that the total content of the polyfunctional monomer and polyfunctional oligomer is, for example, 10 parts by mass or less, preferably 5 with respect to 100 parts by mass of the polymer [A]. It means that it is not more than part by mass, more preferably not more than 2 parts by mass, particularly preferably 0 part by mass.
＜任意成分＞
当該粘着剤組成物は、任意成分として、例えば酸化防止剤、老化防止剤、紫外線吸収剤、光安定剤、消泡剤、レベリング剤、帯電防止剤、界面活性剤、保存安定剤、熱重合禁止剤、可塑剤、濡れ性改良剤、密着性付与剤、粘着付与剤（タッキーファイヤー）、溶媒等が挙げられる。<Optional component>
The pressure-sensitive adhesive composition includes, as an optional component, for example, an antioxidant, an anti-aging agent, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a leveling agent, an antistatic agent, a surfactant, a storage stabilizer, and a thermal polymerization prohibition. Agents, plasticizers, wettability improvers, adhesion promoters, tackifiers (tacky fires), solvents and the like.
酸化防止剤としては、例えばブチルヒドロキシトルエン（ＢＨＴ）、ブチルヒドロキシアニソール（ＢＨＡ）、ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、チオジエチレンビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート等が挙げられる。酸化防止剤の市販品としては、例えばＢＡＳＦ社の「Ｉｒｇａｎｏｘ１０３５」、「同１０１０」、「同１０７６」、「同１１３５」、「同１５２０Ｌ」等が挙げられる。 Examples of the antioxidant include butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and the like. Examples of commercially available antioxidants include “Irganox 1035”, “1010”, “1076”, “1135”, and “1520L” of BASF.
老化防止剤としては、例えばフェノール系老化防止剤、アリルアミン系老化防止剤、ケトンアミン系老化防止剤等が挙げられる。老化防止剤の市販品としては、例えば住友化学社の「アンチゲンＷ」、「同Ｓ」、「同Ｐ」、「同３Ｃ」、「同６Ｃ」、「同ＲＤ−Ｇ」、「同ＦＲ」、「同ＡＷ」等が挙げられる。 Examples of the anti-aging agent include phenol-based anti-aging agents, allylamine-based anti-aging agents, and ketone amine-based anti-aging agents. Commercially available anti-aging agents include, for example, “Antigen W”, “S”, “P”, “3C”, “6C”, “RD-G”, and “FR” from Sumitomo Chemical Co., Ltd. , “Same AW” and the like.
紫外線吸収剤としては、例えばベンゾトリアゾール系紫外線吸収剤、トリアジン系紫外線吸収剤等が挙げられる。紫外線吸収剤の市販品としては、例えばＢＡＳＦ社の「ＴＩＮＵＶＩＮ Ｐ」、「同２３４」、「同３２０」、「同３２６」、「同３２７」、「同３２８」、「同２１３」、「同４００」、住友化学社の「スミソーブ１１０」、「同１３０」、「同１４０」、「同２２０」、「同２５０」、「同３００」、「同３２０」、「同３４０」、「同３５０」、「同４００」等が挙げられる。 Examples of ultraviolet absorbers include benzotriazole ultraviolet absorbers and triazine ultraviolet absorbers. Examples of commercially available UV absorbers include “TINUVIN P”, “234”, “320”, “326”, “327”, “328”, “213”, “ 400, Sumitomo Chemical's “Sumisorb 110”, “130”, “140”, “220”, “250”, “300”, “320”, “340”, “350” ", 400", and the like.
消泡剤としては、例えばシリコーン系消泡剤、フッ素原子含有消泡剤、ケイ素原子及びフッ素原子を含まない有機共重合体を含有する消泡剤等が挙げられる。消泡剤の市販品としては、シリコーン系消泡剤として、例えば共栄社化学社の「同ＡＣ−９０１」、「同ＡＣ−９５０」、「同ＡＣ−１１４０」、「同ＡＯ−３」、「同ＡＯ−４ＯＨ」、東レ・ダウコーニング・シリコーン社の「ＦＳ１２６５」、「ＳＨ２００」、「ＳＨ５５００」、「ＳＣ５５４０」、「ＳＣ５５７０」、「Ｆ−１」、「ＳＤ５５９０」等が、フッ素原子含有消泡剤として、ＤＩＣ社の「メガファックＦ−１４２Ｄ」、「同Ｆ−１４４Ｄ」、「同Ｆ−１７８Ｋ」、「同Ｆ−１７９」、「同Ｆ−８１５」等が、ケイ素原子及びフッ素原子を含まない有機共重合体を含有する消泡剤として、共栄社化学社の「フローレンＡＣ−２０２」、「同ＡＣ−３００」、「同ＡＣ−３０３」、「同ＡＣ−３２６Ｆ」、「同ＡＣ−９００」、「同ＡＣ−１１９０」、「同ＡＣ−２０００」などが挙げられる。 Examples of the antifoaming agent include silicone-based antifoaming agents, fluorine atom-containing antifoaming agents, and antifoaming agents containing an organic copolymer that does not contain silicon atoms and fluorine atoms. Examples of commercially available antifoaming agents include silicone-based antifoaming agents such as Kyoeisha Chemical Co., Ltd. “Same AC-901”, “Same AC-950”, “Same AC-1140”, “Same AO-3”, “ "AO-4OH", Toray Dow Corning Silicone's "FS1265", "SH200", "SH5500", "SC5540", "SC5570", "F-1", "SD5590", etc. As foaming agents, DIC's “Mega-Fuck F-142D”, “F-144D”, “F-178K”, “F-179”, “F-815”, etc. are silicon atoms and fluorine atoms. As an antifoaming agent containing an organic copolymer containing no Kyoeisha Chemical Co., Ltd. “Floren AC-202”, “Same AC-300”, “Same AC-303”, “Same AC-326F”, “Same AC -900 " "The AC-1190", and the like, "the AC-2000".
レベリング剤としては、例えば共栄社化学社の「ポリフローＮｏ．７」、「同Ｎｏ．３８」、「同Ｎｏ．５０」、「同Ｎｏ．７５」、「同Ｎｏ．７７」、「同Ｎｏ．９０」、「同Ｎｏ．９５」、「同Ｎｏ．３００」、「同Ｎｏ．４６０」、「同ＡＴＦ」、「同ＫＬ−２４５」等が挙げられる。 Examples of the leveling agent include “Polyflow No. 7”, “No. 38”, “No. 50”, “No. 75”, “No. 77”, and “No. 90” of Kyoeisha Chemical Co., Ltd. "No. 95", "No. 300", "No. 460", "ATF", "KL-245", and the like.
密着性付与剤としては、アルコキシシリル基を有するチオール化合物、リン酸エステル化合物等が挙げられる。これらの化合物は、特に、金属表面に対する密着性を向上する効果を有する。 Examples of the adhesion-imparting agent include thiol compounds having an alkoxysilyl group and phosphate ester compounds. These compounds have the effect of improving the adhesion to the metal surface.
アルコキシシリル基を有するチオール化合物としては、例えばγ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルメチルモノメトキシシラン、γ−メルカプトプロピルメチルジメトキシシランなどのメルカプトアルキル−モノ、ジ又はトリ−メトキシシラン等が挙げられる。市販品としては、東レ・ダウコーニング・シリコーン社の「ＳＨ６０６２」、「同ＡＹ４３−０６２」、チッソ社の「サイラエースＳ８１０」、信越化学工業社の「ＫＢＭ８０３」、「ＫＢＭ４０３」、「ＫＢＥ５１０３」等が挙げられる。 Examples of the thiol compound having an alkoxysilyl group include mercaptoalkyl-mono, di- or tri-methoxysilane such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethylmonomethoxysilane, and γ-mercaptopropylmethyldimethoxysilane. Can be mentioned. Commercially available products include “SH6062” and “AY43-062” from Toray Dow Corning Silicone, “Syra Ace S810” from Chisso, “KBM803”, “KBM403” and “KBE5103” from Shin-Etsu Chemical Co., Ltd. Can be mentioned.
リン酸エステル化合物としては、例えばモノ〔２−（メタ）アクリロイルオキシエチル〕ホスフェート、モノ〔２−（メタ）アクリロイルオキシエチル〕ジフェニルホスフェート、モノ〔２−（メタ）アクリロイルオキシプロピル〕ホスフェート、ビス〔２−（メタ）アクリロイルオキシエチル〕ホスフェート、ビス〔２−（メタ）アクリロイルオキシプロピル〕ホスフェート、トリス〔２−（メタ）アクリロイルオキシエチル〕ホスフェート等が挙げられる。市販品としては、例えば共栄社化学社の「ライトエステルＰ−１Ｍ」、「同Ｐ−２Ｍ」、「ライトアクリレートＰ−１Ａ」、「同Ｐ−２Ａ」、日本化薬社の「ＫＡＹＡＭＥＲ ＰＭ−２」、「同ＰＭ−２１」等が挙げられる。 Examples of the phosphoric acid ester compound include mono [2- (meth) acryloyloxyethyl] phosphate, mono [2- (meth) acryloyloxyethyl] diphenyl phosphate, mono [2- (meth) acryloyloxypropyl] phosphate, bis [ 2- (meth) acryloyloxyethyl] phosphate, bis [2- (meth) acryloyloxypropyl] phosphate, tris [2- (meth) acryloyloxyethyl] phosphate, and the like. Examples of commercially available products include “Light Ester P-1M”, “P-2M”, “Light Acrylate P-1A” and “P-2A” manufactured by Kyoeisha Chemical Co., Ltd., “KAYAMER PM-2” manufactured by Nippon Kayaku Co., Ltd. And "PM-21".
粘着付与剤としては、例えば脂環族飽和炭化水素樹脂、ロジンエステル系、テルペンフェノール系、Ｃ５又はＣ９石油樹脂等が挙げられる。市販品としては、例えば荒川化学工業社の「アルコンＰ−７０」、「同Ｐ−９０」、「同Ｐ−１００」、「同Ｍ−９０」、「同Ｍ−１００」、「同Ｍ−１３５」、「アラスター７００」、「同ＫＥ−３５９」、「タマノル５２１」、「スーパーエステルＡ−７５」、「同Ａ−１１５」等が挙げられる。 Examples of the tackifier include alicyclic saturated hydrocarbon resins, rosin ester series, terpene phenol series, C5 or C9 petroleum resins, and the like. Commercially available products include, for example, “Arcon P-70”, “P-90”, “P-100”, “M-90”, “M-100”, “M-M” of Arakawa Chemical Industries, Ltd. 135 "," Alastor 700 "," Same KE-359 "," Tamanol 521 "," Superester A-75 "," Same A-115 "and the like.
溶媒としては、例えば
トルエン、キシレン等の芳香族系溶媒；
アセトン、メチルエチルケトン、メチルイソブチルケトン、２−メチル−５−ヘキサノン等のケトン系溶媒；
酢酸エチル、酢酸ブチル等のエステル系溶媒；
塩化メチル、ジクロロメタン、ジクロロエタン等のハロゲン系溶媒；
エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノｎ−プロピルエーテル、プロピレングリコール等のグリコールエーテル系溶媒；
プロピレングリコールモノメチルエーテルアセテート等のグリコールエーテルカルボキシレート系溶媒などが挙げられる。Examples of the solvent include aromatic solvents such as toluene and xylene;
Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-methyl-5-hexanone;
Ester solvents such as ethyl acetate and butyl acetate;
Halogen solvents such as methyl chloride, dichloromethane, dichloroethane;
Glycol ether solvents such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol mono n-propyl ether, propylene glycol;
Examples include glycol ether carboxylate solvents such as propylene glycol monomethyl ether acetate.
上記任意成分の使用量としては、本発明の粘着剤組成物の効果を損なわない範囲において、適宜選択することができる。 The amount of the optional component used can be appropriately selected as long as the effect of the pressure-sensitive adhesive composition of the present invention is not impaired.
当該粘着剤組成物の２５℃における粘度の下限としては、１００ｍＰａ・ｓが好ましく、２００ｍＰａ・ｓがより好ましく、３００ｍＰａ・ｓがさらに好ましく、４００ｍＰａ・ｓが特に好ましい。上記粘度の上限としては、５，０００ｍＰａ・ｓが好ましく、３，０００ｍＰａ・ｓがより好ましく、１，５００ｍＰａ・ｓがさらに好ましく、１，０００ｍＰａ・ｓが特に好ましい。当該粘着剤組成物の粘度を上記範囲とすることで、容易に塗工を行うことができ、その結果、粘着剤層を良好に形成することができる。上記粘度は、ＢＭ粘度計を用い、回転数３０ｒｐｍの条件で測定される値である。 As a minimum of the viscosity at 25 degrees C of the said adhesive composition, 100 mPa * s is preferable, 200 mPa * s is more preferable, 300 mPa * s is further more preferable, 400 mPa * s is especially preferable. The upper limit of the viscosity is preferably 5,000 mPa · s, more preferably 3,000 mPa · s, further preferably 1,500 mPa · s, and particularly preferably 1,000 mPa · s. By making the viscosity of the said adhesive composition into the said range, it can coat easily and as a result, an adhesive layer can be formed favorable. The viscosity is a value measured using a BM viscometer at a rotation speed of 30 rpm.
＜粘着剤組成物の調製方法＞
当該粘着剤組成物は、例えば［Ａ］ポリマー、［Ｂ］光重合開始剤、［Ｃ］熱硬化剤及び必要に応じて含有される任意成分を所定の割合で混合することにより調製することができる。<Method for preparing pressure-sensitive adhesive composition>
The pressure-sensitive adhesive composition can be prepared, for example, by mixing [A] polymer, [B] photopolymerization initiator, [C] thermosetting agent and optional components contained as necessary at a predetermined ratio. it can.
＜粘着シート＞
本発明の粘着シートは、シート状の基材と、上記基材の一方の面に積層される粘着剤層とを備え、上記粘着剤層が、当該粘着剤組成物から形成されている。当該粘着シートは、上述した当該粘着剤組成物から形成された粘着剤層を備えるので、紫外線照射前の粘着力が十分に高く、紫外線照射による粘着力の低下幅が十分に大きく、糊残りを十分に低減することができ、かつ埋め込み性にも優れる。従って、当該粘着シートは、種々の被着体に対して高い粘着力で接着させることができ、かつ被着体から容易に剥離することができる。「シート」とは、シート状のものを意味し、例えば、テープやフィルムも含む概念である。<Adhesive sheet>
The pressure-sensitive adhesive sheet of the present invention includes a sheet-like base material and a pressure-sensitive adhesive layer laminated on one surface of the base material, and the pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition. Since the pressure-sensitive adhesive sheet is provided with a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition described above, the pressure-sensitive adhesive force before ultraviolet irradiation is sufficiently high, the decrease in the pressure-sensitive adhesive force due to ultraviolet irradiation is sufficiently large, and the adhesive residue is removed. It can be sufficiently reduced and has excellent embeddability. Therefore, the said adhesive sheet can be adhere | attached with high adhesive force with respect to various adherends, and can peel easily from an adherend. "Sheet" means a sheet-like thing, and is a concept including a tape and a film, for example.
当該粘着シートは、例えば半導体ウエハのダイシング工程を行う際において、半導体ウエハをフレーム等に固定するためのダイシングテープや、電子部品等の製造プロセスにおいて回路素子等を仮固定するための仮固定用テープや、半導体ウエハの製造プロセスにおいて回路素子等を搬送する際に用いる搬送用テープなどとして好適に用いることができる。当該粘着シートは、このようにテープとして使用する以外に、多層配線基板の製造時に用いられる金属箔付きフィルムや、回路形成用転写シートとして用いることもできる。 The pressure-sensitive adhesive sheet is, for example, a dicing tape for fixing a semiconductor wafer to a frame or the like when performing a dicing process of a semiconductor wafer, or a temporary fixing tape for temporarily fixing circuit elements or the like in a manufacturing process of an electronic component or the like. In addition, it can be suitably used as a transport tape used when transporting circuit elements or the like in a semiconductor wafer manufacturing process. In addition to using the pressure-sensitive adhesive sheet as a tape as described above, the pressure-sensitive adhesive sheet can also be used as a film with a metal foil used in the production of a multilayer wiring board or a transfer sheet for circuit formation.
シート状の基材の材質としては特に限定されず、例えば合成樹脂、ガラス、金属、セラミックス等が挙げられる。シート状の基材の平均厚みの下限としては、１０μｍが好ましく、２０μｍがより好ましく、２５μｍがさらに好ましい。上記平均厚みの上限としては、３００μｍが好ましく、２５０μｍがより好ましく、２００μｍがさらに好ましい。 The material of the sheet-like substrate is not particularly limited, and examples thereof include synthetic resin, glass, metal, ceramics, and the like. As a minimum of the average thickness of a sheet-like base material, 10 micrometers is preferred, 20 micrometers is more preferred, and 25 micrometers is still more preferred. The upper limit of the average thickness is preferably 300 μm, more preferably 250 μm, and even more preferably 200 μm.
粘着剤層は、上述の当該粘着剤組成物から形成されているので、紫外線の照射によって効果的に硬化し、その粘着力が大幅に低下する。粘着剤層の平均厚みの下限としては、５μｍが好ましく、１０μｍがより好ましく、２０μｍがさらに好ましく、３０μｍが特に好ましい。上記平均厚みの上限としては、１，０００μｍが好ましく、５００μｍがより好ましく、１００μｍがさらに好ましく、５０μｍが特に好ましい。 Since the pressure-sensitive adhesive layer is formed from the above-mentioned pressure-sensitive adhesive composition, the pressure-sensitive adhesive layer is effectively cured by irradiation with ultraviolet rays, and the pressure-sensitive adhesive force is greatly reduced. As a minimum of average thickness of an adhesive layer, 5 micrometers is preferred, 10 micrometers is more preferred, 20 micrometers is still more preferred, and 30 micrometers is especially preferred. The upper limit of the average thickness is preferably 1,000 μm, more preferably 500 μm, still more preferably 100 μm, and particularly preferably 50 μm.
＜粘着シートの製造方法＞
当該粘着シートは、例えば以下のようにして製造することができる。まず、シート状の基材の少なくとも一方の面上に、アプリケーター等の塗工装置により、当該粘着剤組成物を塗工する。次に、上記塗膜を乾燥させることにより、当該粘着シートを得ることができる。<Method for producing adhesive sheet>
The said adhesive sheet can be manufactured as follows, for example. First, the pressure-sensitive adhesive composition is applied onto at least one surface of a sheet-like base material by a coating apparatus such as an applicator. Next, the said adhesive sheet can be obtained by drying the said coating film.
＜粘着シートの剥離方法＞
当該粘着シートを被着体から剥離する場合、当該粘着シートに紫外線を照射して粘着剤層を硬化させることで容易かつ糊残りなく剥離できる。当該粘着シートの粘着剤層を硬化させる際の紫外線の積算光量は、基材表面の粘着剤層の平均厚み等により適宜選択することができるが、この積算光量の下限としては、１０ｍＪ／ｃｍ２が好ましく、２０ｍＪ／ｃｍ２が好ましい。上記積算光量の上限としては、４，０００ｍＪ／ｃｍ２が好ましく、２，０００ｍＪ／ｃｍ２がより好ましく、１，０００ｍＪ／ｃｍ２がさらに好ましい。紫外線の積算光量を上記範囲とすることで、粘着剤層がより効果的に硬化するため、粘着力をより十分に低下させることができる。光源としては、例えば高圧水銀ランプ、低圧水銀ランプ、超高圧水銀ランプ、メタルハライドランプ、アーク灯、ガリウムランプ等が挙げられる。<Peeling method of adhesive sheet>
When the pressure-sensitive adhesive sheet is peeled from the adherend, the pressure-sensitive adhesive sheet can be peeled easily and without adhesive residue by irradiating the pressure-sensitive adhesive sheet with ultraviolet rays to cure the pressure-sensitive adhesive layer. The cumulative amount of ultraviolet light for curing the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet can be appropriately selected depending on the average thickness of the pressure-sensitive adhesive layer on the surface of the substrate, and the lower limit of this cumulative light amount is 10 mJ / cm 2. Is preferable, and 20 mJ / cm 2 is preferable. The upper limit of the integrated light quantity is preferably 4,000 mJ / cm 2, more preferably 2,000 mJ / cm 2, more preferably 1,000 mJ / cm 2. By setting the cumulative amount of ultraviolet light within the above range, the pressure-sensitive adhesive layer is more effectively cured, and thus the adhesive force can be more sufficiently reduced. Examples of the light source include a high-pressure mercury lamp, a low-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an arc lamp, and a gallium lamp.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。各種物性値の測定方法を以下に示す。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. The measuring method of various physical property values is shown below.
［Ｍｗ］
［Ａ］ポリマーのＭｗは、東ソー社のＧＰＣカラム（「ＴＳＫｇｅｌ Ｍｕｌｔｉｐｏｒｅ ＨＸＬ−Ｍ」）２本を用い、流量：１．０ｍＬ／分、溶出溶媒：テトラヒドロフラン、試料濃度：０．０５質量％、試料注入量：１００μＬ、カラム温度：４０℃、検出器：示差屈折計の分析条件で、単分散ポリスチレンを標準とするＧＰＣにより測定した。[Mw]
[A] Mw of the polymer is 2 TPC GPC columns (“TSKgel Multipore H XL- M”), flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, sample concentration: 0.05 mass%, Sample injection volume: 100 μL, column temperature: 40 ° C., detector: measured by GPC using monodisperse polystyrene as a standard under the analysis conditions of a differential refractometer.
［Ｔｇ］
［Ａ］ポリマーを含む溶液をガラス板の上に薄く引き伸ばし、２５℃で７日間乾燥させて乾燥フィルムを得た。得られた乾燥フィルムを示差走査熱量分析計（ティー・エイ・インスツルメント社の「ＭＤＳＣＱ２００型」）を用い、窒素雰囲気下、昇温速度２０℃／分、サンプル量２０ｍｇの条件で、［Ａ］ポリマーのＴｇ（℃）を測定した。[Tg]
[A] A solution containing the polymer was thinly stretched on a glass plate and dried at 25 ° C. for 7 days to obtain a dry film. Using a differential scanning calorimeter (“TSC Instruments” “MDSCQ200 type”), the resulting dried film was subjected to a temperature increase rate of 20 ° C./min and a sample amount of 20 mg under the conditions of [A The Tg (° C.) of the polymer was measured.
［二重結合含有基（Ａ）の含有率の測定］
［Ａ］ポリマー中の二重結合含有基（Ａ）の含有率（質量％）は、核磁気共鳴装置（Ｂｒｕｋｅｒ社の「ＡＳＣＥＮＤ４００」）を使用し、測定溶媒として重クロロホルムを用いて１３Ｃ−ＮＭＲを測定することにより、［Ａ］ポリマーにおける二重結合含有基（Ａ）を含む構造単位及びそれ以外の構造単位の各構造単位についてその構造と各含有割合とを求め、これらの測定結果から算出した。[Measurement of content of double bond-containing group (A)]
[A] The content (% by mass) of the double bond-containing group (A) in the polymer is 13 C- using a nuclear magnetic resonance apparatus (“ASCEND 400” from Bruker) and deuterated chloroform as a measurement solvent. By measuring NMR, the structure and each content ratio are determined for each structural unit of the structural unit containing the double bond-containing group (A) in the [A] polymer and other structural units, and from these measurement results, Calculated.
［［Ａ］ポリマーの合成］
［Ａ］ポリマーの合成に用いた各単量体について以下に示す。
ＭＡ：メチルアクリレート（東亞合成社）
ＢＡ：ブチルアクリレート（和光純薬工業社）
２ＥＨＡ：２−エチルヘキシルアクリレート（東亞合成社）
ＨＥＡ：２−ヒドロキシエチルアクリレート（大阪有機化学工業社）
ＧＭＡ：グリシジルメタクリレート（三菱レイヨン社）
ＭＭＡ：メチルメタクリレート（三菱レイヨン社）[[A] Synthesis of polymer]
[A] Each monomer used for polymer synthesis is shown below.
MA: Methyl acrylate (Toagosei Co., Ltd.)
BA: Butyl acrylate (Wako Pure Chemical Industries, Ltd.)
2EHA: 2-ethylhexyl acrylate (Toagosei Co., Ltd.)
HEA: 2-hydroxyethyl acrylate (Osaka Organic Chemical Industry Co., Ltd.)
GMA: Glycidyl methacrylate (Mitsubishi Rayon)
MMA: Methyl methacrylate (Mitsubishi Rayon)
［合成例１］
４口フラスコに、単量体としてのＭＡ４０．０質量部、２ＥＨＡ５３．０質量部及びＨＥＡ７．０質量部、ラジカル重合開始剤としてのＡＩＢＮ２質量部並びに溶媒としての酢酸エチル１５０質量部を仕込み、窒素雰囲気下、７０℃で８時間反応させ、さらに８０℃で１時間反応させることにより、前駆体ポリマー（ａ−１）を含む溶液を得た。次に、冷却器及び温度計を備えた４口丸底フラスコに、この前駆体ポリマー（ａ−１）１００質量部（樹脂固形分換算）を含む溶液及び反応触媒としてのジブチルスズジラウレート０．０１質量部を仕込み、撹拌しながら４０℃に加熱した。次いで、２−メタクリロイルオキシエチルイソシアネート（昭和電工社の「カレンズＭＯＩ」、以下、「ＭＯＩ」ともいう）２．４質量部を加え、４０℃で５時間反応を行った。これにより、前駆体ポリマー（ａ−１）中の水酸基とＭＯＩ中のイソシアネート基とが反応し、側鎖に二重結合含有基（Ａ）としてのメタクリロイル基を有するポリマー（Ａ−１）を得た。このポリマー（Ａ−１）のＭｗは２０．６万、Ｔｇは−２５．１℃、二重結合含有基（Ａ）の含有率は１．０質量％であった。[Synthesis Example 1]
In a four-necked flask, charged were 40.0 parts by mass of MA as a monomer, 53.0 parts by mass of EHA and 7.0 parts by mass of HEA, 2 parts by mass of AIBN as a radical polymerization initiator, and 150 parts by mass of ethyl acetate as a solvent. By reacting at 70 ° C. for 8 hours under an atmosphere and further reacting at 80 ° C. for 1 hour, a solution containing the precursor polymer (a-1) was obtained. Next, in a 4-neck round bottom flask equipped with a cooler and a thermometer, a solution containing 100 parts by mass of this precursor polymer (a-1) (resin solid content conversion) and dibutyltin dilaurate 0.01 mass as a reaction catalyst The parts were charged and heated to 40 ° C. with stirring. Subsequently, 2.4 parts by mass of 2-methacryloyloxyethyl isocyanate (“Karenz MOI”, hereinafter referred to as “MOI” by Showa Denko KK) was added, and the reaction was performed at 40 ° C. for 5 hours. Thereby, the hydroxyl group in precursor polymer (a-1) and the isocyanate group in MOI react, and the polymer (A-1) which has a methacryloyl group as a double bond containing group (A) in a side chain is obtained. It was. Mw of this polymer (A-1) was 206,000, Tg was −25.1 ° C., and the content of the double bond-containing group (A) was 1.0% by mass.
［合成例２〜１１］
表１に示す種類及び使用量の単量体及び二重結合含有基導入化合物を用いた以外は、合成例１と同様にして、ポリマー（Ａ−２）〜（Ａ−９）並びに（ＣＡ−１）及び（ＣＡ−２）を合成した。二重結合含有基導入化合物である「ＡＡ」は、アクリル酸（大阪有機化学工業社）を示す。合成したポリマーの二重結合含有基（Ａ）の含有率（質量％）、Ｍｗ及びＴｇについて表１に合わせて示す。[Synthesis Examples 2 to 11]
Polymers (A-2) to (A-9) and (CA-) were prepared in the same manner as in Synthesis Example 1 except that the types and amounts used of the monomers and double bond-containing group-introducing compounds shown in Table 1 were used. 1) and (CA-2) were synthesized. “AA”, which is a double bond-containing group-introducing compound, indicates acrylic acid (Osaka Organic Chemical Industry Co., Ltd.). It shows according to Table 1 about the content rate (mass%) of the double bond containing group (A) of the synthesize | combined polymer, Mw, and Tg.
＜粘着剤組成物の調製＞
粘着剤組成物の調製に用いた［Ａ］ポリマー以外の成分について以下に示す。<Preparation of pressure-sensitive adhesive composition>
Components other than the [A] polymer used for the preparation of the pressure-sensitive adhesive composition are shown below.
［［Ｂ］光重合開始剤］
Ｂ−１：１−ヒドロキシ−シクロヘキシルフェニルケトン（ＢＡＳＦ社の「Ｉｒｇａｃｕｒｅ１８４」）[[B] Photopolymerization initiator]
B-1: 1-hydroxy-cyclohexyl phenyl ketone ("Irgacure 184" from BASF)
［［Ｃ］熱硬化剤］
Ｃ−１：コロネートＬ（東ソー社）[[C] thermosetting agent]
C-1: Coronate L (Tosoh Corporation)
［多官能モノマー］
Ｄ−１：ジペンタエリスリトールヘキサアクリレート（日本化薬社の「ＫＡＹＡＲＡＤ ＤＰＨＡ」）[Polyfunctional monomer]
D-1: Dipentaerythritol hexaacrylate (Nippon Kayaku "KAYARAD DPHA")
［酸化防止剤］
Ｅ−１：Ｉｒｇａｎｏｘ１０３５（ＢＡＳＦ社）[Antioxidant]
E-1: Irganox 1035 (BASF)
［実施例１］
［Ａ］ポリマーとしての（Ａ−１）１００質量部、［Ｂ］光重合開始剤としての（Ｂ−１）４質量部、［Ｃ］熱硬化剤としての（Ｃ−１）０．１５質量部及び酸化防止剤としての（Ｅ−１）０．３質量部を混合することにより、粘着剤組成物（Ｔ−１）を調製した。[Example 1]
[A] 100 parts by mass of (A-1) as a polymer, [B] 4 parts by mass of (B-1) as a photopolymerization initiator, [C] 0.15 parts by mass of (C-1) as a thermosetting agent A pressure-sensitive adhesive composition (T-1) was prepared by mixing 0.3 parts by mass of (E-1) as an antioxidant and an antioxidant.
［実施例２〜９及び比較例１〜３］
下記表２に示す種類及び含有量の各成分を用いた以外は、実施例１と同様にして、粘着剤組成物（Ｔ−２）〜（Ｔ−９）及び（ＣＴ−１）〜（ＣＴ−３）を調製した。表２中の「−」は、該当する成分を用いなかったことを示す。[Examples 2 to 9 and Comparative Examples 1 to 3]
Adhesive compositions (T-2) to (T-9) and (CT-1) to (CT) in the same manner as in Example 1 except that the components of the types and contents shown in Table 2 below were used. -3) was prepared. “-” In Table 2 indicates that the corresponding component was not used.
＜評価＞
上記調製した粘着剤組成物について、下記方法に従って粘着シートを作製し、この粘着シートについて、以下の試験を実施することにより評価した。<Evaluation>
About the prepared adhesive composition, the adhesive sheet was produced according to the following method, and it evaluated by implementing the following tests about this adhesive sheet.
［粘着シートの作製］
上記調製した粘着剤組成物をそのまま塗工液として用い、シート状の基材としてのポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡社の「コスモシャイン４３００」、平均厚み１００μｍ）の表面にアプリケーターを用いて塗布し、次いで、１００℃で３分間乾燥させることにより、基材の表面に平均厚み２５μｍの粘着剤層が積層された粘着シートを得た。[Production of adhesive sheet]
Using the prepared pressure-sensitive adhesive composition as it is as a coating solution, it is applied to the surface of a polyethylene terephthalate (PET) film (Toyobo Cosmo Shine 4300, average thickness 100 μm) as a sheet-like substrate using an applicator. Then, by drying at 100 ° C. for 3 minutes, a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer having an average thickness of 25 μm was laminated on the surface of the base material was obtained.
［ＵＶ前粘着力］
上記作製した粘着シートを、ＳＵＳ３０４製の被着体（エンジニアリングテストサービス社）に貼りあわせて試験片を作成した後、この試験片について、ＪＩＳ−Ｚ０２３７：２００９に準拠する１８０°ピール試験法によって、雰囲気温度２３℃、剥離速度３００ｍｍ／分の条件でピール強度（単位：Ｎ／２５ｍｍ）を測定した。[UV adhesive strength]
The prepared adhesive sheet is bonded to an adherend made of SUS304 (Engineering Test Service) to create a test piece. About this test piece, a 180 ° peel test method based on JIS-Z0237: 2009 is used. The peel strength (unit: N / 25 mm) was measured under the conditions of an atmospheric temperature of 23 ° C. and a peeling rate of 300 mm / min.
ＵＶ前粘着力は、ＳＵＳ３０４製の被着体に対して、１０Ｎ／２５ｍｍ以上の場合は「良好」と、１０Ｎ／２５ｍｍ未満の場合は「不良」と評価できる。 The UV pre-adhesive strength can be evaluated as “good” when it is 10 N / 25 mm or more and “bad” when it is less than 10 N / 25 mm for an adherend made of SUS304.
［ＵＶ後粘着力］
上記「ＵＶ前粘着力」の項で作製した試験片を、（１）２３℃で０．５時間、又は（２）１００℃で１時間加熱処理し、次いで、粘着シートの基材側から高圧水銀ランプ（アイグラフィックス社の「アイグランステージＥＣＳ−４１０ＧＸ」）による積算光量５００ｍＪ／ｃｍ２の紫外線照射を行い、粘着剤層を硬化させた。この場合、基材を透過した紫外線が粘着剤層に照射される。次いで、ＪＩＳ−Ｚ０２３７：２００９に準拠する１８０°ピール試験法によって、雰囲気２３℃、剥離速度３００ｍｍ／分の条件でピール強度を測定した。[After-UV adhesion]
The test piece prepared in the above “UV pre-adhesive strength” section was (1) heat-treated at 23 ° C. for 0.5 hour, or (2) 100 ° C. for 1 hour, and then subjected to high pressure from the substrate side of the pressure-sensitive adhesive sheet. The pressure-sensitive adhesive layer was cured by irradiating with an ultraviolet ray with an accumulated light amount of 500 mJ / cm 2 using a mercury lamp (“Igrand Stage ECS-410GX” manufactured by Eye Graphics). In this case, the pressure-sensitive adhesive layer is irradiated with ultraviolet rays that have passed through the substrate. Next, peel strength was measured under the conditions of an atmosphere of 23 ° C. and a peeling rate of 300 mm / min by a 180 ° peel test method based on JIS-Z0237: 2009.
ＵＶ後粘着力は、ＳＵＳ３０４製の被着体に対して、（１）及び（２）のいずれにおいても１．５Ｎ／２５ｍｍ以下の場合は「良好」と、（１）及び（２）の少なくとも一方で１．５Ｎ／２５ｍｍを超える場合は「不良」と評価できる。 The post-UV adhesive strength is “good” in the case of 1.5 N / 25 mm or less in both (1) and (2) with respect to the adherend made of SUS304, and at least one of (1) and (2) On the other hand, when it exceeds 1.5 N / 25 mm, it can be evaluated as “bad”.
［糊残り］
上記［ＵＶ後粘着力］の（２）１００℃で１時間加熱処理した場合において、紫外線照射後に粘着シートを被着体から剥がした後、被着体の表面における「糊残り」の状態を光学顕微鏡で測定した。具体的には、被着体の表面に最大長さが１μｍ以上の異物（粘着剤層の一部）が認められなかった場合は「Ａ」（良好）と、１μｍ以上の異物が認められた場合は「Ｂ」（不良）と評価した。[Adhesive residue]
In the case of (2) Heat treatment at 100 ° C. for 1 hour in [Post-UV adhesive strength], after the adhesive sheet is peeled off from the adherend after ultraviolet irradiation, the state of “glue residue” on the adherend surface is optically determined. Measured with a microscope. Specifically, when no foreign matter having a maximum length of 1 μm or more (a part of the pressure-sensitive adhesive layer) was found on the surface of the adherend, “A” (good) and foreign matter having a size of 1 μm or more were recognized. The case was evaluated as “B” (defective).
［埋め込み性］
埋め込み性は、以下のようにして評価した。ガラス板の上に、平均厚み２５μｍのＰＥＴフィルムを１０ｍｍ幅にカットしたものを密着させ、段差を形成した。次に、乾燥後の平均厚みが５０μｍになるようにＰＥＴフィルム（東洋紡社の「Ａ４３００」、平均厚み５０μｍ）上に粘着剤組成物を塗布して形成した粘着シートを、上記段差を含む領域に置いた後、その上で２ｋｇローラーを１往復させ圧接することにより貼り合わせた。次いで、１０分間常温で静置し、上記段差周辺の浮きや気泡等の有無を観察し、埋め込み性を評価した。埋め込み性は、浮きや気泡が認められない場合は「Ａ」（良好）と、浮きや気泡が認められた場合は「Ｂ」（不良）と評価した。[Embeddability]
The embedding property was evaluated as follows. On the glass plate, a PET film having an average thickness of 25 μm cut into a width of 10 mm was closely adhered to form a step. Next, a pressure-sensitive adhesive sheet formed by applying a pressure-sensitive adhesive composition on a PET film (“A4300” manufactured by Toyobo Co., Ltd., average thickness 50 μm) so that the average thickness after drying is 50 μm is formed in the region including the steps. After placing, the 2 kg roller was reciprocated once and bonded together by pressing. Subsequently, it was allowed to stand at room temperature for 10 minutes, and the presence or absence of floating or bubbles around the step was observed to evaluate the embedding property. The embedding property was evaluated as “A” (good) when no floating or bubbles were observed, and “B” (bad) when floating or bubbles were observed.
表２の結果から、実施例の粘着剤組成物によれば、紫外線照射前の粘着力が十分高く、加熱の有無に関わらず、紫外線照射による粘着力の低下幅が十分に大きく、糊残りも十分に低減できていることがわかる。また、実施例の粘着剤組成物は、埋め込み性にも優れていることも示されている。 From the results of Table 2, according to the pressure-sensitive adhesive compositions of the examples, the adhesive strength before ultraviolet irradiation is sufficiently high, and regardless of the presence or absence of heating, the decrease in adhesive strength due to ultraviolet irradiation is sufficiently large, and the adhesive residue is also It turns out that it can fully reduce. Moreover, it is also shown that the adhesive composition of an Example is excellent also in the embedding property.
本発明の粘着剤組成物及び粘着シートによれば、加熱の有無に関わらず、紫外線照射前の粘着力が十分に高く、紫外線照射による粘着力の低下幅も十分に大きく、かつ糊残りを十分低減することができ、また、形成される粘着剤層が埋め込み性に優れ、段差等を有する被着体に対しても好適に用いることができる。また、貼り合わせ状態で加熱される場合でも、紫外線照射により糊残りなく剥離することができる。従って、当該粘着剤組成物及び粘着シートは、加熱工程を有する半導体ウエハのダイシング工程等種々の製造工程において好適に用いることができる。
According to the pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet of the present invention, the adhesive strength before ultraviolet irradiation is sufficiently high regardless of the presence or absence of heating, the decrease in adhesive strength due to ultraviolet irradiation is sufficiently large, and the adhesive residue is sufficient Moreover, the pressure-sensitive adhesive layer to be formed is excellent in embeddability and can be suitably used for an adherend having a step or the like. Moreover, even when heated in a bonded state, it can be peeled off without any adhesive residue by ultraviolet irradiation. Therefore, the said adhesive composition and adhesive sheet can be used suitably in various manufacturing processes, such as the dicing process of the semiconductor wafer which has a heating process.
Claims (5)
光重合開始剤と、
熱硬化剤と
を含有し、
上記ポリマーを構成する全構造単位に対する上記構造単位の含有割合が１質量％以上６０質量％以下であり、
多官能モノマー又は多官能オリゴマーを実質的に含有しない粘着剤組成物。A polymer having a structural unit derived from methyl acrylate and a polymerizable carbon-carbon double bond-containing group;
A photopolymerization initiator;
Containing a thermosetting agent,
The content ratio of the structural unit with respect to all structural units constituting the polymer is 1% by mass or more and 60% by mass or less,
A pressure-sensitive adhesive composition containing substantially no polyfunctional monomer or polyfunctional oligomer.
上記基材の一方の面に積層される粘着剤層と
を備え、
上記粘着剤層が、請求項１から請求項４のいずれか１項に記載の粘着剤組成物から形成される粘着シート。A sheet-like substrate;
A pressure-sensitive adhesive layer laminated on one surface of the substrate;
The adhesive sheet in which the said adhesive layer is formed from the adhesive composition of any one of Claims 1-4.
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|---|---|---|---|
| JP2016038365 | 2016-02-29 | ||
| JP2016038365 | 2016-02-29 | ||
| PCT/JP2017/001818 WO2017149981A1 (en) | 2016-02-29 | 2017-01-19 | Adhesive composition and adhesive sheet |
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| JPWO2017149981A1 true JPWO2017149981A1 (en) | 2018-12-20 |
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| KR (1) | KR20180111878A (en) |
| CN (1) | CN108603086A (en) |
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| TWI798394B (en) * | 2018-03-26 | 2023-04-11 | 日商琳得科股份有限公司 | Adhesive composition, adhesive sheet, and method for producing processed product |
| WO2020003919A1 (en) | 2018-06-26 | 2020-01-02 | リンテック株式会社 | Semiconductor processing adhesive tape and method of manufacturing semiconductor device |
| JP7215061B2 (en) * | 2018-10-15 | 2023-01-31 | 大日本印刷株式会社 | Block copolymer, surface conditioner, adhesive composition, adhesive sheet, adhesive protective sheet, laminate, optical member and electronic member |
| KR20210124342A (en) * | 2019-02-06 | 2021-10-14 | 닛토덴코 가부시키가이샤 | adhesive sheet |
| JP7378230B2 (en) * | 2019-06-10 | 2023-11-13 | リンテック株式会社 | Adhesive sheets and laminates |
| CN114901770A (en) * | 2019-12-27 | 2022-08-12 | 日东电工株式会社 | Adhesive sheet |
| KR20220120572A (en) * | 2019-12-27 | 2022-08-30 | 닛토덴코 가부시키가이샤 | adhesive sheet |
| WO2022097471A1 (en) * | 2020-11-09 | 2022-05-12 | デンカ株式会社 | Pressure-sensitive adhesive tape and processing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000068237A (en) * | 1998-08-18 | 2000-03-03 | Lintec Corp | Surface protective sheet at grinding of wafer back face and method for using the same |
| JP2007261035A (en) * | 2006-03-28 | 2007-10-11 | Lintec Corp | Sheet for forming protective film for chip |
| WO2014030699A1 (en) * | 2012-08-23 | 2014-02-27 | リンテック株式会社 | Dicing sheet with protective film formation layer and method for producing chip |
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| JP5781302B2 (en) * | 2010-12-28 | 2015-09-16 | 日東電工株式会社 | Radiation curable pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| JP5687897B2 (en) * | 2010-12-28 | 2015-03-25 | 日東電工株式会社 | Radiation curable pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
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2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000068237A (en) * | 1998-08-18 | 2000-03-03 | Lintec Corp | Surface protective sheet at grinding of wafer back face and method for using the same |
| JP2007261035A (en) * | 2006-03-28 | 2007-10-11 | Lintec Corp | Sheet for forming protective film for chip |
| WO2014030699A1 (en) * | 2012-08-23 | 2014-02-27 | リンテック株式会社 | Dicing sheet with protective film formation layer and method for producing chip |
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| CN108603086A (en) | 2018-09-28 |
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