JP6639842B2 - Composition - Google Patents
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- Publication number
- JP6639842B2 JP6639842B2 JP2015182615A JP2015182615A JP6639842B2 JP 6639842 B2 JP6639842 B2 JP 6639842B2 JP 2015182615 A JP2015182615 A JP 2015182615A JP 2015182615 A JP2015182615 A JP 2015182615A JP 6639842 B2 JP6639842 B2 JP 6639842B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- mass
- composition
- parts
- acrylate
- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 123
- 239000000853 adhesive Substances 0.000 claims description 86
- 230000001070 adhesive effect Effects 0.000 claims description 86
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 59
- 239000010703 silicon Substances 0.000 claims description 54
- 229910052710 silicon Inorganic materials 0.000 claims description 54
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- -1 acryl Chemical group 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 13
- 229920000459 Nitrile rubber Polymers 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 150000007524 organic acids Chemical class 0.000 claims description 11
- 239000011256 inorganic filler Substances 0.000 claims description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 239000000806 elastomer Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000004310 lactic acid Substances 0.000 claims description 6
- 235000014655 lactic acid Nutrition 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000005350 fused silica glass Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000007870 radical polymerization initiator Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000008199 coating composition Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000000178 monomer Substances 0.000 description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 21
- 235000012431 wafers Nutrition 0.000 description 21
- 238000012360 testing method Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 10
- 229920002799 BoPET Polymers 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 238000007654 immersion Methods 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 7
- 229920002725 thermoplastic elastomer Polymers 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000013065 commercial product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000004831 Hot glue Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 229920006332 epoxy adhesive Polymers 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000005338 frosted glass Substances 0.000 description 3
- 239000005337 ground glass Substances 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 1
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 1
- SBUBPFHJZHQNNT-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene hydrogen peroxide Chemical compound OO.OO.CC(C)C1=CC=CC=C1C(C)C SBUBPFHJZHQNNT-UHFFFAOYSA-N 0.000 description 1
- NLOCXQZOOGBEEN-UHFFFAOYSA-N 1-(1-hydroxypropan-2-yloxy)-3-phenoxypropan-2-ol Chemical compound OCC(C)OCC(O)COC1=CC=CC=C1 NLOCXQZOOGBEEN-UHFFFAOYSA-N 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 241000283153 Cetacea Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical group CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 239000004204 candelilla wax Substances 0.000 description 1
- 235000013868 candelilla wax Nutrition 0.000 description 1
- 229940073532 candelilla wax Drugs 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000012185 ceresin wax Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Description
本発明は、例えば、色々な部材を加工するに際しての部材の仮固定方法であり、それに好適な組成物と接着剤組成物と被覆剤組成物に関するものである。本発明は、例えば、シリコンインゴットからシリコンウエハを加工するに際して、当該部材を仮固定する方法と、当該用途に好適な（メタ）アクリル系仮固定用接着剤組成物に関する。 The present invention relates to, for example, a method for temporarily fixing members when processing various members, and relates to a composition, an adhesive composition, and a coating composition suitable for the method. The present invention relates to, for example, a method of temporarily fixing the member when processing a silicon wafer from a silicon ingot, and a (meth) acrylic temporary fixing adhesive composition suitable for the use.
シリコンウエハ等の半導体実装部品等の仮固定用接着剤としては、両面テープやホットメルト系接着剤、エポキシ系接着剤が使用されている。これらの接着剤にて接合又は積層した部材を、所定の形状に切削加工後、接着剤を除去し、加工部材を製造することが行われている。例えば、半導体実装部品に関しては、これらの部品を両面テープにて基材に固定した後、所望の部品に切削加工を行い、更に両面テープに紫外線を照射することにより部品からの剥離を行っている。ホットメルト系接着剤の場合には、部材を接合し、加熱により間隙に接着剤を浸透させた後、所望の部品に切削加工を行い、有機溶剤中で接着剤の剥離を行っている。エポキシ系接着剤の場合には、主剤と硬化剤を計量、混合して部材と接合後、所望の部品に切削加工を行い、有機溶剤中で接着剤の剥離を行っている。 As an adhesive for temporarily fixing a semiconductor mounting component such as a silicon wafer, a double-sided tape, a hot-melt adhesive, or an epoxy adhesive is used. A member joined or laminated with these adhesives is cut into a predetermined shape, and then the adhesive is removed to produce a processed member. For example, with respect to semiconductor mounted components, after fixing these components to the base material with a double-sided tape, a desired component is cut, and further, the double-sided tape is irradiated with ultraviolet rays to be separated from the component. . In the case of a hot-melt adhesive, the members are joined, the adhesive is penetrated into the gap by heating, then the desired part is cut, and the adhesive is peeled off in an organic solvent. In the case of an epoxy-based adhesive, a main component and a curing agent are measured and mixed, joined to a member, then cut into a desired part, and the adhesive is peeled off in an organic solvent.
しかしながら、両面テープは、厚み精度を出すのが困難であったり、接着強度が弱いために部品加工時に剥離できなかったりする、といった問題があった。両面テープは、１００℃以上の熱をかけないと剥離できないといった問題があった。両面テープは、紫外線照射により剥離させる場合には、被着体の透過性が乏しいと剥離できないといった問題があった。 However, the double-sided tape has problems in that it is difficult to obtain thickness accuracy and that the adhesive cannot be peeled off at the time of component processing due to low adhesive strength. The double-sided tape has a problem that it cannot be peeled off unless heat of 100 ° C. or more is applied. When the double-sided tape is peeled off by ultraviolet irradiation, there is a problem that it cannot be peeled off if the adherence of the adherend is poor.
ホットメルト系接着剤は、接着時に１００℃以上の熱をかけなければ貼ることができず、使用できる部材に制約があった。ホットメルト系接着剤は、剥離時に有機溶剤を使用する必要があり、アルカリ溶剤やハロゲン系有機溶剤の洗浄工程が煩雑であり、作業環境的にも問題となっていた。 Hot-melt adhesives cannot be applied unless heat of 100 ° C. or higher is applied at the time of bonding, and there are restrictions on the members that can be used. The hot-melt adhesive requires the use of an organic solvent at the time of peeling, and the washing process of an alkaline solvent or a halogen-based organic solvent is complicated, which has been a problem in the working environment.
エポキシ系接着剤は、主剤と硬化剤の計量と混合が不十分な場合、著しい接着性の低下を起こすことがあった。エポキシ系接着剤は、ホットメルト系接着剤と同様、剥離時に有機溶剤を使用する必要があった。エポキシ系接着剤は、アルカリ溶剤やハロゲン系有機溶剤の洗浄工程が煩雑であり、作業環境的にも問題となっていた。エポキシ系接着剤は、硬化速度が遅く、硬化までの間、十分な硬化時間を保持しておく必要があった。 Epoxy adhesives may cause a significant decrease in adhesion if the metering and mixing of the base agent and the curing agent are insufficient. The epoxy adhesive has to use an organic solvent at the time of peeling, like the hot melt adhesive. The epoxy-based adhesive requires a complicated washing process for an alkaline solvent or a halogen-based organic solvent, and has been problematic in terms of working environment. The epoxy-based adhesive has a low curing speed, and it is necessary to maintain a sufficient curing time until curing.
これらの問題を解決するために、特許文献１〜３では（メタ）アクリレートを含有する仮固定用接着剤が提案されていた。 In order to solve these problems, Patent Literatures 1 to 3 have proposed temporary fixing adhesives containing (meth) acrylate.
特許文献１では、接着剤成分に光開始剤及び炭酸水素ナトリウムを加えることによって、紫外線で硬化し、初期せん断力が高く、温水中での剥離性に優れる光硬化型接着剤が提案された。しかしながら、熱ラジカル重合開始剤を使用することにより、被着体の透過性が乏しくても硬化できることについて、記載がない。 Patent Literature 1 proposes a photocurable adhesive which is cured by ultraviolet rays by adding a photoinitiator and sodium bicarbonate to an adhesive component, has a high initial shear force, and has excellent releasability in warm water. However, there is no description that curing can be performed by using a thermal radical polymerization initiator even when the adherend has poor permeability.
特許文献２では、酸性リン酸基と不飽和結合とをそれぞれ１個以上有する単量体、無機充填剤及び／又はチキソトロピー剤を配合したチップ部品仮固定用接着剤が提案された。しかしながら、炭酸水素塩に関する記載はない。 Patent Literature 2 proposes an adhesive for temporary fixing of a chip component in which a monomer having at least one acidic phosphate group and at least one unsaturated bond, an inorganic filler and / or a thixotropic agent are blended. However, there is no description about bicarbonate.
特許文献３では、（メタ）アクリロイル基を有するモノマー及び／又はオリゴマー、重合開始剤、β−ジケトンキレート及び／又はβ−ケトエステル、２５〜３００質量部の無機フィラーを含有する仮固定用接着剤が提案された。しかしながら、炭酸水素塩に関する記載はない。 In Patent Document 3, a temporary fixing adhesive containing a monomer and / or oligomer having a (meth) acryloyl group, a polymerization initiator, a β-diketone chelate and / or a β-ketoester, and 25 to 300 parts by mass of an inorganic filler is disclosed. was suggested. However, there is no description about bicarbonate.
切削加工後の部材の寸法精度及び接着仮固定までの硬化速度を向上させるために、接着性に優れ、剥離液中での剥離性に優れるといった、組成物が望まれていた。本発明は、前記従来技術に鑑みてなされたものである。 In order to improve the dimensional accuracy of the member after cutting and the curing speed until temporary fixing of the adhesive, a composition having excellent adhesiveness and excellent exfoliation in a stripping solution has been desired. The present invention has been made in view of the related art.
即ち、本発明は、（１）（メタ）アクリレート、（２）熱ラジカル重合開始剤、（３）還元剤、（４）炭酸水素塩、（５）無機充填剤を含有してなる組成物であり、更に、（６）エラストマー成分を含有する該組成物であり、（１）の（メタ）アクリレートが、ヒドロキシアルキル（メタ）アクリレートを含有してなる該組成物であり、（１）１００質量部に対して、（２）の使用量が０．１〜１０質量部であり、（３）の使用量が０．０１〜５質量部であり、（４）の使用量が０．１〜２０質量部である該組成物であり、該組成物を第一剤及び第二剤の二剤に分け、第一剤が少なくとも（２）を含有してなり、第二剤が少なくとも（３）を含有してなる二剤型組成物であり、該組成物からなる仮固定用組成物であり、該組成物からなる接着剤組成物であり、該組成物からなる被覆剤組成物であり、用途がシリコン接着用、樹脂接着用及びガラス接着用からなる群のうちの１種以上である該組成物であり、用途がシリコン被覆用、樹脂被覆用及びガラス被覆用からなる群のうちの１種以上である該組成物であり、該組成物を用いて、部材を接着仮固定し、前記組成物を硬化し、仮固定された部材を加工し、加工された部材を剥離液に浸漬することにより、前記組成物の硬化体を取り外す部材の仮固定方法であり、剥離液の温度が４０℃以上である該部材の仮固定方法であり、該組成物を用いて、部材を接着仮固定し、前記組成物を硬化し、仮固定された部材を加工し、加工された部材を加熱処理することにより、前記組成物の硬化体を取り外す部材の仮固定方法であり、該組成物を用いて、シリコンインゴットを基材に接着仮固定した後、シリコンインゴットを切断してシリコンウエハを作製し、シリコンウエハを剥離液に浸漬することにより、シリコンウエハを基材から取り外すシリコンウエハの製造方法であり、剥離液の温度が４０℃以上である該シリコンウエハの製造方法であり、該組成物を用いて、シリコンインゴットを基材に接着仮固定した後、シリコンインゴットを切断してシリコンウエハを作製し、基材を加熱処理することにより、シリコンウエハを基材から取り外すシリコンウエハの製造方法であり、該組成物を使用して被着体を接着又は被覆してなる接合体であり、被着体がシリコン、樹脂及びガラスからなる群のうちの１種以上である該接合体である。 That is, the present invention provides a composition comprising (1) (meth) acrylate, (2) a thermal radical polymerization initiator, (3) a reducing agent, (4) a hydrogen carbonate, and (5) an inorganic filler. And (6) the composition containing an elastomer component, wherein the (meth) acrylate of (1) is a composition containing a hydroxyalkyl (meth) acrylate, and (1) 100 mass The amount of (2) is 0.1 to 10 parts by mass, the amount of (3) is 0.01 to 5 parts by mass, and the amount of (4) is 0.1 to 10 parts by mass. 20 parts by mass of the composition, wherein the composition is divided into two parts, a first part and a second part, wherein the first part contains at least (2) and the second part is at least (3) And a temporary fixing composition comprising the composition, and an adhesive comprising the composition. A composition, which is a coating composition comprising the composition, wherein the application is at least one member from the group consisting of silicon bonding, resin bonding, and glass bonding, and the application is silicon. The composition, which is one or more members of the group consisting of coating, resin coating, and glass coating. The composition is temporarily fixed by using the composition, and the composition is cured and temporarily fixed. A method for temporarily fixing a member from which a cured body of the composition is removed by processing the processed member and immersing the processed member in a stripping solution, wherein the temperature of the member is 40 ° C. or higher. A fixing method, using the composition, adhesively temporarily fixed the member, cured the composition, processed the temporarily fixed member, and heat-processed the processed member, by heating the processed member A method for temporarily fixing a member from which a cured body is removed, wherein the composition is Then, after the silicon ingot is temporarily fixed to the base material by bonding, the silicon ingot is cut to prepare a silicon wafer, and the silicon wafer is immersed in a stripping solution, thereby removing the silicon wafer from the base material. A method for producing a silicon wafer in which the temperature of a stripping liquid is 40 ° C. or higher, and the silicon ingot is temporarily fixed to a substrate using the composition, and then the silicon ingot is cut to produce a silicon wafer. A method for producing a silicon wafer, wherein the silicon wafer is removed from the substrate by heat-treating the substrate, and a bonded body obtained by bonding or covering the adherend using the composition. The joined body, wherein the body is at least one member from the group consisting of silicon, resin, and glass.
本発明は、接着性に優れ、剥離液中での剥離性に優れる。 INDUSTRIAL APPLICABILITY The present invention is excellent in adhesiveness and excellent in peelability in a peeling solution.
以下に、本実施形態を詳細に説明する。 Hereinafter, the present embodiment will be described in detail.
本実施形態で使用する（１） （メタ）アクリレートとしては、（メタ）アクリル基を有する化合物が好ましく、（メタ）アクリロイル基を有する化合物がより好ましい。（メタ）アクリレートとしては、モノマー及び／又はオリゴマーが好ましい。（メタ）アクリロイル基を有するモノマー及び／又はオリゴマーとしては、以下のものが挙げられる。 As (1) (meth) acrylate used in the present embodiment, a compound having a (meth) acryl group is preferable, and a compound having a (meth) acryloyl group is more preferable. As the (meth) acrylate, a monomer and / or an oligomer is preferable. Examples of the monomer and / or oligomer having a (meth) acryloyl group include the following.
（１−１）アルキル（メタ）アクリレート
アルキル（メタ）アクリレートとしては、一般式（Ａ）で示される(メタ)アクリル系モノマー等が挙げられる。
(1-1) Alkyl (meth) acrylate Examples of the alkyl (meth) acrylate include a (meth) acrylic monomer represented by the general formula (A).
一般式（Ａ） Ｚ−Ｏ−Ｒ１
（式中、Ｚは（メタ）アクリロイル基を示し、Ｒ１は炭素数１〜１０のアルキル基を表す。）
General formula (A) ZOR 1
(In the formula, Z represents a (meth) acryloyl group, and R 1 represents an alkyl group having 1 to 10 carbon atoms.)
Ｒ１は、炭素数１〜１０のアルキル基が好ましく、１〜３のアルキル基がより好ましい。炭素数１０を超えると表面硬化性が低下してベタツキが見られ、硬化速度が低下する場合がある。 R 1 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. When the number of carbon atoms exceeds 10, the surface curability is reduced, stickiness is observed, and the curing speed may be reduced.
このような（メタ）アクリル系モノマーとしては、メチル（メタ）アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート及びイソプロピル(メタ)アクリレート等が挙げられ、これらの１種以上が使用できる。これらの中では、安価で接着性が良好な点で、メチル（メタ）アクリレートが好ましい。 Examples of such (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate, and one or more of these can be used. Among these, methyl (meth) acrylate is preferable in that it is inexpensive and has good adhesiveness.
（１−２）ビスフェノール骨格を有する（メタ）アクリル系モノマー
ビスフェノール骨格を有する（メタ）アクリル系モノマーとしては、一般式（Ｂ）で示される(メタ)アクリル系モノマー等が挙げられる。
(1-2) (Meth) acrylic monomer having a bisphenol skeleton Examples of the (meth) acrylic monomer having a bisphenol skeleton include a (meth) acrylic monomer represented by the general formula (B).
一般式（Ｂ）
Ｚ−Ｏ−（Ｒ２Ｏ）ｐ−Ｃ６Ｈ４−Ｃ（Ｒ３）（Ｒ’３）−Ｃ６Ｈ４−Ｏ−（Ｒ２’Ｏ）ｐ’−Ｚ
（式中、Ｚは（メタ）アクリロイル基を示し、Ｒ２、Ｒ２’は−Ｃ２Ｈ４−、−Ｃ３Ｈ６−、−ＣＨ２ＣＨ（ＣＨ３） −、−Ｃ４Ｈ８−又は−Ｃ６Ｈ１２−を示し、Ｒ３、Ｒ’３は水素又は炭素数１〜４のアルキル基を示し、ｐ、ｐ’は０〜８の整数を示す。）
General formula (B)
Z-O- (R 2 O) p -C 6 H 4 -C (R 3) (R '3) -C 6 H 4 -O- (R 2' O) p '-Z
(In the formula, Z represents a (meth) acryloyl group, and R 2 and R 2 ′ represent —C 2 H 4 —, —C 3 H 6 —, —CH 2 CH (CH 3 ) —, and —C 4 H 8. - or -C 6 H 12 - indicates, R 3, R '3 represents an alkyl group having 1 to 4 carbon hydrogen or carbon, p, p' is an integer of 0-8).
このような（メタ）アクリル系モノマーとしては、２，２−ビス（４−（メタ）アクリロキシフェニル）プロパン、２，２−ビス（４−（メタ）アクリロキシエトキシフェニル）プロパン、２，２−ビス（４−（メタ）アクリロキシジエトキシフェニル）プロパン、２，２−ビス（４−（メタ）アクリロキシテトラエトキシフェニル）プロパン、２，２−ビス（４−（メタ）アクリロキシポリエトキシフェニル）プロパン、２，２−ビス（４−（メタ）アクリロキシプロポキシフェニル）プロパン等が挙げられ、これらの１種以上が使用できる。これらの中では、効果が大きい点で、２，２−ビス（４−（メタ）アクリロキシポリエトキシフェニル）プロパンが好ましい。 Such (meth) acrylic monomers include 2,2-bis (4- (meth) acryloxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2 -Bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxy) Phenyl) propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane and the like, and one or more of these can be used. Among them, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane is preferable because of its large effect.
（１−３）ジシクロペンテニルオキシアルキル（メタ）アクリレート
ジシクロペンテニルオキシアルキレン（メタ）アクリレートとしては、一般式（Ｃ）で示される(メタ)アクリル系モノマー等が挙げられる。
(1-3) Dicyclopentenyloxyalkyl (meth) acrylate Examples of the dicyclopentenyloxyalkylene (meth) acrylate include a (meth) acrylic monomer represented by the general formula (C).
このような（メタ）アクリル系モノマーとしては、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンテニルオキシジエチレングリコール（メタ）アクリレート、ジシクロペンテニルオキシトリエチレングリコール（メタ）アクリレート及びジシクロペンテニルオキシプロピレングリコール（メタ）アクリレート等が挙げられ、これらの１種以上が使用できる。これらの中では、表面硬化性が良く、容易に入手できる点で、ジシクロペンテニルオキシエチル（メタ）アクリレートが好ましい。Ｒ４は、樹脂強度が大きい点で、１〜４個の炭素原子を有するアルキレン基が好ましく、エチレン基がより好ましい。ｑは、硬化体の樹脂強度が大きい点で、１〜３が好ましく、１がより好ましい。 Such (meth) acrylic monomers include dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxydiethylene glycol (meth) acrylate, dicyclopentenyloxytriethylene glycol (meth) acrylate, and dicyclopentenyloxypropylene glycol (Meth) acrylate and the like, and one or more of these can be used. Among them, dicyclopentenyloxyethyl (meth) acrylate is preferred because it has good surface curability and is easily available. R 4 is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an ethylene group, from the viewpoint of high resin strength. q is preferably 1 to 3, and more preferably 1 in that the resin strength of the cured body is large.
（１−４）芳香族基を有する（メタ）アクリレート
芳香族基を有する（メタ）アクリレートとしては、一般式（Ｄ）で示される(メタ)アクリル系モノマー等が挙げられる。
(1-4) (Meth) acrylate having an aromatic group Examples of the (meth) acrylate having an aromatic group include a (meth) acrylic monomer represented by the general formula (D).
一般式（Ｄ） Ｚ−Ｏ−（Ｒ５Ｏ）ｒ−Ｒ６
（式中、Ｚは（メタ）アクリロイル基を示し、Ｒ５は−Ｃ２Ｈ４−、−Ｃ３Ｈ６−、−ＣＨ２ＣＨ（ＣＨ３） −、−Ｃ４Ｈ８−又は−Ｃ６Ｈ１２−を示し、Ｒ６はフェニル基又は炭素数１〜３のアルキル基を有するフェニル基を示し、ｑは１〜１０の整数を示す。）
General formula (D) Z—O— (R 5 O) r —R 6
(Wherein, Z represents a (meth) acryloyl group, R 5 represents —C 2 H 4 —, —C 3 H 6 —, —CH 2 CH (CH 3 ) —, —C 4 H 8 —, or —C 6 H 12 - indicates, R 6 represents a phenyl group having a phenyl group or an alkyl group having 1 to 3 carbon atoms, q is an integer of 1 to 10).
このような（メタ）アクリル系モノマーとしては、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、フェノキシプロピル（メタ）アクリレート、フェノキシジプロピレングリコール（メタ）アクリレート及びフェノキシポリプロピレングリコール（メタ）アクリレート等が挙げられ、これらの１種以上が使用できる。これらの中では、効果が大きい点で、フェノキシエチル（メタ）アクリレートが好ましい。 Such (meth) acrylic monomers include phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxypropyl (meth) acrylate, phenoxydipropylene glycol (meth) acrylate and Phenoxy polypropylene glycol (meth) acrylate and the like can be mentioned, and one or more of these can be used. Of these, phenoxyethyl (meth) acrylate is preferred because of its great effect.
（１−５）ヒドロキシル基を有する（メタ）アクリル系モノマー
ヒドロキシル基を有する（メタ）アクリル系モノマーとしては、一般式（Ｅ）で示される(メタ)アクリル系モノマー等が挙げられる。
(1-5) (Meth) acrylic monomer having a hydroxyl group Examples of the (meth) acrylic monomer having a hydroxyl group include a (meth) acrylic monomer represented by the general formula (E).
一般式（Ｅ） Ｚ−Ｏ−（Ｒ７Ｏ）ｓ−Ｈ
（式中、Ｚは（メタ）アクリロイル基を示し、Ｒ７は−Ｃ２Ｈ４−、−Ｃ３Ｈ６−、−ＣＨ２ＣＨ（ＣＨ３） −、−Ｃ４Ｈ８−又は−Ｃ６Ｈ１２−を示し、ｓは１〜１０の整数を示す。）
General formula (E) Z—O— (R 7 O) s —H
(Wherein, Z represents a (meth) acryloyl group, R 7 represents —C 2 H 4 —, —C 3 H 6 —, —CH 2 CH (CH 3 ) —, —C 4 H 8 —, or —C 6 H 12 - indicates, s is an integer of 1 to 10).
このような（メタ）アクリル系モノマーとしては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート及びヒドロキシブチル（メタ）アクリレート等といったヒドロキシアルキル（メタ）アクリレートが挙げられ、これらの１種以上が使用できる。これらの中では、安価で接着性が良好な点で、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレートからなる群のうちの１種以上が好ましい。 Examples of such a (meth) acrylic monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. One or more can be used. Among these, at least one of the group consisting of 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate is preferable from the viewpoint of low cost and good adhesion.
（１−６）多価アルコールの（メタ）アクリル酸エステル。
多価アルコールの（メタ）アクリル酸エステルとしては、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート等が挙げられる。これらの中では、皮膚刺激性が低い点で、１，９−ノナンジオールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレートからなる群のうちの１種以上が好ましい。
(1-6) (meth) acrylic acid esters of polyhydric alcohols.
Examples of the polyhydric alcohol (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and tri (meth) acrylate. Propylene glycol di (meth) acrylate and the like. Among them, at least one of a group consisting of 1,9-nonanediol di (meth) acrylate and tripropylene glycol di (meth) acrylate is preferable from the viewpoint of low skin irritation.
（１−７）（メタ）アクリロイル基を有するオリゴマー
（メタ）アクリロイル基を有するオリゴマーとしては、１，２−ポリブタジエン末端ウレタン（メタ）アクリレート（例えば、日本曹達社製、「ＴＥ−２０００」、「ＴＥＡ−１０００」）、その水素添加物（例えば、日本曹達社製、「ＴＥＡＩ−１０００」）、１，４−ポリブタジエン末端ウレタン（メタ）アクリレート（例えば、大阪有機化学社製、「ＢＡＣ−４５」）、ポリイソプレン末端（メタ）アクリレート、ポリエステル系ウレタン（メタ）アクリレート（例えば、日本合成社製、「ＵＶ−３０００Ｂ」）、ポリエーテル系ウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート、ビスフェノールＡ型エポキシ（メタ）アクリレート（例えば、大阪有機化学社製、「ビスコート＃５４０」、昭和高分子社製、「ビスコートＶＲ−７７」）等が挙げられる。（メタ）アクリロイル基を有するオリゴマーは、（メタ）アクリロイルオキシ基を有するウレタンプレポリマーを含む。
(1-7) Oligomers having (meth) acryloyl groups Examples of oligomers having (meth) acryloyl groups include 1,2-polybutadiene-terminated urethane (meth) acrylates (for example, Nippon Soda Co., Ltd., "TE-2000", TEA-1000 "), its hydrogenated product (for example," TEAI-1000 ", manufactured by Nippon Soda Co., Ltd.), 1,4-polybutadiene-terminated urethane (meth) acrylate (for example," BAC-45 ", manufactured by Osaka Organic Chemical Co., Ltd.) ), Polyisoprene terminal (meth) acrylate, polyester urethane (meth) acrylate (for example, “UV-3000B” manufactured by Nippon Gohsei), polyether urethane (meth) acrylate, polyester (meth) acrylate, bisphenol A type Epoxy (meth) acrylate (for example, Osaka Organic Chemical Company , "BISCOAT # 540", Showa High Polymer Co., Ltd., "BISCOAT VR-77"), and the like. The oligomer having a (meth) acryloyl group includes a urethane prepolymer having a (meth) acryloyloxy group.
（メタ）アクリル系モノマーの中では、効果が大きい点で、（１−５）ヒドロキシル基を有する（メタ）アクリル系モノマーを含有することが好ましい。（メタ）アクリル系モノマー中の、（１−５）ヒドロキシル基を有する（メタ）アクリル系モノマーの含有割合は、（メタ）アクリル系モノマー１００質量部中、５〜９９質量部が好ましく、１０〜９５質量部がより好ましい。 Among the (meth) acrylic monomers, it is preferable to include a (meth) acrylic monomer having a (1-5) hydroxyl group, from the viewpoint of great effect. The content ratio of the (meth) acrylic monomer having a (1-5) hydroxyl group in the (meth) acrylic monomer is preferably from 5 to 99 parts by mass, and more preferably from 10 to 10 parts by mass, per 100 parts by mass of the (meth) acrylic monomer. 95 parts by mass is more preferred.
（メタ）アクリル系モノマーの中では、効果が大きい点で、（１−４）芳香族基を有する（メタ）アクリレート、（１−５）ヒドロキシアルキル（メタ）アクリレート及び（１−６）多価アルコールの（メタ）アクリル酸エステルを併用することが好ましい。 Among (meth) acrylic monomers, (1-4) (meth) acrylate having an aromatic group, (1-5) hydroxyalkyl (meth) acrylate and (1-6) polyvalent It is preferable to use a (meth) acrylate of alcohol in combination.
（１−４）、（１−５）及び（１−６）の含有割合は、（１−４）、（１−５）及び（１−６）の合計１００質量部中、質量比で、（１−４）：（１−５）：（１−６）＝１〜３０：６０〜９５：１〜３０が好ましく、５〜１５：７０〜９０：５〜１５がより好ましい。 The content ratio of (1-4), (1-5) and (1-6) is represented by a mass ratio in a total of 100 parts by mass of (1-4), (1-5) and (1-6). (1-4) :( 1-5) :( 1-6) = 1 to 30:60 to 95: 1 to 30, preferably 5 to 15:70 to 90: 5 to 15.
本実施形態で使用する（２）熱ラジカル重合開始剤としては、有機過酸化物が好ましい。有機過酸化物としては、クメンハイドロパーオキサイド、パラメンタンハイドロパーオキサイド、ターシャリーブチルハイドロパーオキサイド、ジイソプロピルベンゼンジハイドロパーオキサイド、メチルエチルケトンパーオキサイド、ベンゾイルパーオキサイド及びターシャリーブチルパーオキシベンゾエート等が挙げられる。これらの１種以上が使用できる。これらの中では、（３）との反応性の点で、クメンハイドロパーオキサイドが好ましい。 As the (2) thermal radical polymerization initiator used in the present embodiment, an organic peroxide is preferable. Examples of the organic peroxide include cumene hydroperoxide, paramenthane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, and tertiary butyl peroxybenzoate. . One or more of these can be used. Among them, cumene hydroperoxide is preferred in view of reactivity with (3).
（２）の使用量は、（１）１００質量部に対して、０．１〜１０質量部が好ましく、０．５〜７質量部がより好ましく、１〜５質量部が最も好ましい。０．５質量部未満では硬化速度が遅い場合があり、１０質量部を越えると貯蔵安定性が遅い場合がある。 The amount of (2) used is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 7 parts by mass, most preferably from 1 to 5 parts by mass, per 100 parts by mass of (1). If the amount is less than 0.5 part by mass, the curing speed may be slow, and if it exceeds 10 parts by mass, the storage stability may be slow.
本実施形態で使用する（３）還元剤は、例えば、（２）熱ラジカル重合開始剤と反応し、ラジカルを発生する公知の還元剤であれば使用できる。（３）還元剤としては、（２）との反応性の点で、還元性を有する金属塩が好ましい。還元性を有する金属塩としては、バナジルアセチルアセトネート、バナジウムアセチルアセトネート、コバルトアセチルアセトネート、銅アセチルアセトネート、ナフテン酸バナジル、ステアリン酸バナジル、ナフテン酸銅、酢酸銅、オクチル酸コバルト等が挙げられる。これらの１種以上が使用できる。これらの中では、バナジルアセチルアセトネートが好ましい。 As the reducing agent (3) used in the present embodiment, for example, any known reducing agent that reacts with (2) a thermal radical polymerization initiator to generate a radical can be used. (3) As the reducing agent, a metal salt having a reducing property is preferable in view of reactivity with (2). Examples of the metal salt having a reducing property include vanadyl acetylacetonate, vanadium acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, vanadyl naphthenate, vanadyl stearate, copper naphthenate, copper acetate, and cobalt octylate. Can be One or more of these can be used. Of these, vanadyl acetylacetonate is preferred.
（３）の使用量は、（１）１００質量部に対して、０．０１〜５質量部が好ましく、０．０５〜２質量部がより好ましい。０．０１質量部以上だと硬化速度が速く、接着性が大きく、５質量部以下だと未反応の成分が残らず、接着性が大きい。 (3) is preferably used in an amount of 0.01 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, per 100 parts by mass of (1). When the amount is 0.01 part by mass or more, the curing speed is high and the adhesiveness is large. When the amount is 5 parts by mass or less, unreacted components do not remain and the adhesiveness is large.
本実施形態で使用する（４）炭酸水素塩としては、炭酸水素リチウム、炭酸水素ナトリウム及び炭酸水素カリウム等のアルカリ金属炭酸水素塩、炭酸水素アンモニウム等が挙げられる。これらの中では、効果が大きい点で、アルカリ金属炭酸水素塩が好ましい。アルカリ金属炭酸水素塩の中では、炭酸水素ナトリウムが好ましい。
（４）の使用量は、（１）１００質量部に対して、０．１〜２０質量部が好ましく、０．５〜１５質量部がより好ましい。０．１質量部以上だと剥離液に浸漬した際の剥離性を向上し、２０質量部以下だと接着性を低下することもない。
Examples of (4) bicarbonate used in the present embodiment include alkali metal bicarbonates such as lithium bicarbonate, sodium bicarbonate and potassium bicarbonate, and ammonium bicarbonate. Of these, alkali metal bicarbonates are preferred because of their great effect. Of the alkali metal bicarbonates, sodium bicarbonate is preferred.
The amount of (4) used is preferably from 0.1 to 20 parts by mass, more preferably from 0.5 to 15 parts by mass, per 100 parts by mass of (1). When the amount is 0.1 parts by mass or more, the releasability when immersed in a stripping solution is improved, and when the amount is 20 parts by mass or less, the adhesiveness does not decrease.
本実施形態で使用する（５）無機充填剤としては、石英、石英ガラス、溶融シリカ、複合酸化物等のガラス粉、球状シリカ等のシリカ粉等、球状アルミナ、破砕アルミナ、酸化マグネシウム、酸化ベリリウム、酸化チタン等の酸化物類、窒化ホウ素、窒化ケイ素、窒化アルミニウム等の窒化物類、炭化ケイ素等の炭化物類、水酸化アルミニウム、水酸化マグネシウム等の水酸化物類、銅、銀、鉄、アルミニウム、ニッケル、チタン等の金属類や合金類、ダイヤモンド、カーボン等の炭素系充填材等が挙げられる。これらの１種以上が使用できる。これらの中では、容易に入手可能であり、組成物への充填性に優れる点で、ガラス粉が好ましい。ガラス粉としては、石英、石英ガラス、溶融シリカ、球状シリカ、複合酸化物からなる群のうちの１種以上が好ましく、溶融シリカ、球状シリカ、複合酸化物からなる群のうちの１種以上がより好ましく、溶融シリカが最も好ましい。
（５）無機充填剤は、（４）炭酸水素塩を除くことが好ましい。
(5) Inorganic fillers used in the present embodiment include quartz, quartz glass, fused silica, glass powder such as composite oxide, silica powder such as spherical silica, spherical alumina, crushed alumina, magnesium oxide, beryllium oxide. , Oxides such as titanium oxide, boron nitride, silicon nitride, nitrides such as aluminum nitride, carbides such as silicon carbide, hydroxides such as aluminum hydroxide and magnesium hydroxide, copper, silver, iron, Examples include metals and alloys such as aluminum, nickel and titanium, and carbon-based fillers such as diamond and carbon. One or more of these can be used. Among these, glass powder is preferable because it is easily available and has excellent filling properties into the composition. As the glass powder, at least one selected from the group consisting of quartz, quartz glass, fused silica, spherical silica, and composite oxide is preferable, and at least one selected from the group consisting of fused silica, spherical silica, and composite oxide is preferred. More preferred, fused silica is most preferred.
(5) The inorganic filler preferably excludes (4) bicarbonate.
（５）の使用量は、（１）１００質量部に対して、２０〜３００質量部が好ましく、３０〜２５０質量部がより好ましい。２０質量部以上だと粘度及び接着性が向上し、沈降分離がなく、３００質量部以下だと粘度が低く、作業上、不具合が生じない。 The use amount of (5) is preferably from 20 to 300 parts by mass, more preferably from 30 to 250 parts by mass, per 100 parts by mass of (1). When the amount is 20 parts by mass or more, the viscosity and adhesiveness are improved, and sedimentation does not occur. When the amount is 300 parts by mass or less, the viscosity is low, and no trouble occurs in operation.
本実施形態では、切削加工後の部材の寸法精度を向上し、高い接着性を得るために、（６）エラストマー成分を使用することが好ましい。 In the present embodiment, it is preferable to use an elastomer component (6) in order to improve the dimensional accuracy of the member after cutting and obtain high adhesiveness.
本実施形態で使用する（６）エラストマー成分としては、（メタ）アクリロニトリル−ブタジエン−（メタ）アクリル酸共重合体、（メタ）アクリロニトリル−ブタジエン−（メタ）アクリレート共重合体、メチル（メタ）アクリレート−ブタジエン−スチレン共重合体、（メタ）アクリロニトリル−スチレン−ブタジエン共重合体、並びに、（メタ）アクリロニトリル−ブタジエンゴム、線状ポリウレタン、スチレン−ブタジエンゴム、クロロプレンゴム及びブタジエンゴム等の各種合成ゴム、天然ゴム、スチレン−ポリブタジエン−スチレン系合成ゴムといったスチレン系熱可塑性エラストマー、ポリエチレン−ＥＰＤＭ合成ゴムといったオレフィン系熱可塑性エラストマー、並びに、カプロラクトン型、アジペート型及びＰＴＭＧ型といったウレタン系熱可塑性エラストマー、ポリブチレンテレフタレート−ポリテトラメチレングリコールマルチブロックポリマーといったポリエステル系熱可塑性エラストマー、ナイロン−ポリオールブロック共重合体といったポリアミド系熱可塑性エラストマー、１，２−ポリブタジエン系熱可塑性エラストマー、並びに、塩ビ系熱可塑性エラストマー等が挙げられる。これらのエラストマー成分は相溶性が良ければ、１種以上が使用できる。 As the (6) elastomer component used in the present embodiment, (meth) acrylonitrile-butadiene- (meth) acrylic acid copolymer, (meth) acrylonitrile-butadiene- (meth) acrylate copolymer, methyl (meth) acrylate -Butadiene-styrene copolymer, (meth) acrylonitrile-styrene-butadiene copolymer, and various synthetic rubbers such as (meth) acrylonitrile-butadiene rubber, linear polyurethane, styrene-butadiene rubber, chloroprene rubber, and butadiene rubber; Natural rubber, styrene-based thermoplastic elastomer such as styrene-polybutadiene-styrene-based synthetic rubber, olefin-based thermoplastic elastomer such as polyethylene-EPDM synthetic rubber, and caprolactone-type, adipate-type and PTMG-type Urethane-based thermoplastic elastomer, polyester-based thermoplastic elastomer such as polybutylene terephthalate-polytetramethylene glycol multi-block polymer, polyamide-based thermoplastic elastomer such as nylon-polyol block copolymer, 1,2-polybutadiene-based thermoplastic elastomer, In addition, a PVC-based thermoplastic elastomer can be used. One or more of these elastomer components can be used as long as they have good compatibility.
これらの中では、（メタ）アクリレートに対する溶解性や接着性の点で、メチル（メタ）アクリレート−ブタジエン−スチレン共重合体及び／又は（メタ）アクリロニトリル−ブタジエンゴムが好ましく、その併用がより好ましい。併用する場合、その使用割合は、メチル（メタ）アクリレート−ブタジエン−スチレン共重合体と（メタ）アクリロニトリル−ブタジエンゴムの合計１００質量部中、質量比で、メチル（メタ）アクリレート−ブタジエン−スチレン共重合体：（メタ）アクリロニトリル−ブタジエンゴム＝５０〜９５：５〜５０が好ましく、６０〜８０：２０〜４０がより好ましい。（メタ）アクリロニトリル−ブタジエンゴムを使用する場合、（メタ）アクリロニトリル含量（ニトリル含量）は３６〜４５質量％が好ましい。 Among them, methyl (meth) acrylate-butadiene-styrene copolymer and / or (meth) acrylonitrile-butadiene rubber are preferable from the viewpoint of solubility and adhesion to (meth) acrylate, and the combination thereof is more preferable. When used in combination, the ratio of the methyl (meth) acrylate-butadiene-styrene copolymer and the (meth) acrylonitrile-butadiene rubber in the total mass of 100 parts by mass is methyl (meth) acrylate-butadiene-styrene copolymer. Polymer: (meth) acrylonitrile-butadiene rubber = 50 to 95: 5 to 50 is preferable, and 60 to 80:20 to 40 is more preferable. When (meth) acrylonitrile-butadiene rubber is used, the (meth) acrylonitrile content (nitrile content) is preferably from 36 to 45% by mass.
（６）の使用量は、（１）１００質量部に対して、１〜３０質量部が好ましく、３〜２５質量部がより好ましい。１質量部以上だと粘度及び接着性が向上し、３０質量部以下だと、粘度が低く、作業上、不具合が生じない。 The amount of (6) used is preferably from 1 to 30 parts by mass, more preferably from 3 to 25 parts by mass, per 100 parts by mass of (1). When the amount is 1 part by mass or more, the viscosity and adhesiveness are improved, and when the amount is 30 parts by mass or less, the viscosity is low and no trouble occurs in operation.
本実施形態の組成物は、空気に接している部分の硬化を迅速にするために各種パラフィン類を使用できる。パラフィン類としては、パラフィンワックス、マイクロクリスタリンワックス、カルナバろう、蜜ろう、ラノリン、鯨ろう、セレシン及びカンデリラろう等が挙げられる。これらの１種以上が使用できる。 In the composition of the present embodiment, various paraffins can be used in order to quickly cure a portion in contact with air. Examples of paraffins include paraffin wax, microcrystalline wax, carnauba wax, beeswax, lanolin, whale wax, ceresin and candelilla wax. One or more of these can be used.
パラフィン類の使用量は、（１）１００質量部に対して、０．１〜５質量部が好ましく、０．３〜２．５質量部がより好ましい。０．１質量部未満では空気に接している部分の硬化が悪くなる場合があり、５質量部を超えると接着強度が低下する場合がある。 The amount of the paraffin used is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 2.5 parts by mass, per 100 parts by mass of (1). If the amount is less than 0.1 part by mass, the curing of the portion in contact with the air may be poor, and if it exceeds 5 parts by mass, the adhesive strength may be reduced.
本実施形態の組成物は、貯蔵安定性を改良する目的で、重合禁止剤を含む各種の酸化防止剤等を使用できる。本実施形態の組成物は、接着性を改良する目的で、リン酸塩を使用することができる。他にも所望によりカップリング剤、可塑剤、充填剤、着色剤及び防腐剤等の既に知られている物質を使用することもできる。 In the composition of the present embodiment, various antioxidants including a polymerization inhibitor can be used for the purpose of improving storage stability. In the composition of the present embodiment, a phosphate can be used for the purpose of improving adhesiveness. Other known substances such as coupling agents, plasticizers, fillers, coloring agents and preservatives can be used if desired.
本実施形態としては、二剤型の組成物として使用することが挙げられる。二剤型については、本実施形態の組成物の必須成分全てを貯蔵中は混合せず、組成物を第一剤及び第二剤に分け、第一剤に少なくとも（２）を、第二剤に少なくとも（３）を別々に貯蔵する。リン酸塩は第二剤に貯蔵することが好ましい。この場合、両剤を同時に又は別々に被着体に塗布して接触、硬化することにより、二剤型の組成物として使用できる。 The present embodiment includes use as a two-part composition. For the two-pack type, all the essential components of the composition of the present embodiment are not mixed during storage, the composition is divided into a first part and a second part, and at least (2) is added to the first part and the second part Store at least (3) separately. Preferably, the phosphate is stored in a second agent. In this case, the two agents can be used as a two-part composition by simultaneously or separately applying and contacting and curing the adherend.
別の実施形態としては、第一剤及び第二剤のいずれか一方又は両方に（メタ）アクリレート及びその他の任意の成分を予め含有せしめ、使用時に両者を混合することにより、一剤型の組成物として使用できる。 In another embodiment, one or both of the first agent and the second agent contain (meth) acrylate and other optional components in advance, and the two components are mixed at the time of use to form a one-part composition. Can be used as an object.
これらの実施態様の中では、貯蔵安定性に優れる点で、二剤型の組成物として使用することが好ましい。 Among these embodiments, from the viewpoint of excellent storage stability, it is preferable to use a two-part composition.
本実施形態の組成物は、仮固定用組成物として使用することが挙げられる。本実施形態の組成物は、接着剤組成物や被覆剤組成物として使用することが挙げられる。
以下、本実施形態の組成物を仮固定用接着剤組成物として使用する場合について例示する。
The composition of the present embodiment may be used as a temporary fixing composition. The composition of the present embodiment may be used as an adhesive composition or a coating composition.
Hereinafter, a case where the composition of the present embodiment is used as an adhesive composition for temporary fixing will be exemplified.
本実施形態の仮固定用接着剤組成物の使用方法としては、固定する一方の部材又は支持基板の接着面に接着剤組成物を適量塗布し、続いてもう一方の部材を重ね合わせるという方法や、予め仮固定する部材を多数積層しておき、接着剤組成物を隙間に浸透させて塗布させる方法等により接着剤組成物を塗布し、仮固定用接着剤組成物を硬化させ、部材同士を仮固定する方法等が挙げられる。 As a method of using the temporary fixing adhesive composition of the present embodiment, a method of applying an appropriate amount of the adhesive composition to an adhesive surface of one member to be fixed or a support substrate, and then overlapping the other member, A number of members to be temporarily fixed are laminated in advance, and the adhesive composition is applied by a method of penetrating and applying the adhesive composition to the gaps and the like, and the adhesive composition for temporary fixing is cured, and the members are joined together. A temporary fixing method and the like can be given.
本実施形態の仮固定用接着剤組成物は、二剤の正確な計量を必要とせず、不完全な計量や混合、時には二剤の接触だけでも、常温で硬化する。本発明は、仮固定用接着剤組成物を硬化する際に紫外線を必要としないため、作業性に優れる。 The adhesive composition for temporary fixing of the present embodiment does not require accurate metering of two components, and cures at room temperature only by incomplete metering and mixing, and sometimes even contact of the two components. The present invention does not require ultraviolet light when curing the temporary fixing adhesive composition, and thus has excellent workability.
本実施形態の仮固定用接着剤組成物は各種被着体を仮固定し、部材を所望の形状に切断、研削、研磨等の加工を施した後、該部材を剥離液に浸漬することにより、組成物を部材から剥離することができる。 The temporary fixing adhesive composition of the present embodiment temporarily fixes various adherends, cuts the member into a desired shape, performs grinding, polishing or the like, and then immerses the member in a stripping liquid. The composition can be peeled from the member.
仮固定方法としては、本実施形態の仮固定用接着剤組成物を用いて、部材を接着仮固定し、前記仮固定用接着剤組成物の硬化体を作製し、該仮固定された部材を加工し、加工された部材を剥離液に浸漬し、前記仮固定用接着剤組成物の硬化体を取り外す仮固定方法等が挙げられる。 As the temporary fixing method, using the temporary fixing adhesive composition of the present embodiment, the members are temporarily bonded and fixed, a cured body of the temporary fixing adhesive composition is prepared, and the temporarily fixed member is removed. A temporary fixing method or the like may be used in which the processed member is immersed in a stripping solution and the cured body of the temporary fixing adhesive composition is removed.
剥離液としては、水及び／又は酸性液が好ましく、酸性液がより好ましい。酸性液としては、有機酸を含有する水溶液が好ましい。有機酸としては、乳酸、クエン酸等が挙げられる。これらの１種以上が使用できる。これらの中では、乳酸が好ましい。有機酸を含有する水溶液中の有機酸の濃度は、５〜８０質量％が好ましく、１５〜５０質量％がより好ましい。 As the stripping liquid, water and / or an acidic liquid is preferable, and an acidic liquid is more preferable. As the acidic liquid, an aqueous solution containing an organic acid is preferable. Examples of the organic acid include lactic acid and citric acid. One or more of these can be used. Of these, lactic acid is preferred. The concentration of the organic acid in the aqueous solution containing the organic acid is preferably from 5 to 80% by mass, more preferably from 15 to 50% by mass.
本実施形態の仮固定方法では、剥離液として、乳酸水溶液を用いることが、液中での剥離性が短時間に達成でき、生産性が向上する点で、好ましい。仮固定用接着剤組成物の硬化体と剥離液との接触の方法については、剥離液中に接合体毎浸漬する方法が、簡便である点で、好ましい。剥離液の温度は、液中での剥離性が短時間に達成でき、生産性が向上する点で、４０℃以上が好ましく、４５℃以上がより好ましく、５０℃以上が最も好ましい。剥離液の温度は、液中での剥離性が短時間に達成でき、生産性が向上する点で、１００℃以下が好ましく、９５℃以下がより好ましく、９０℃以下が最も好ましい。 In the temporary fixing method of the present embodiment, it is preferable to use an aqueous solution of lactic acid as the stripping liquid, since the strippability in the liquid can be achieved in a short time, and the productivity is improved. Regarding the method of contacting the cured body of the temporary fixing adhesive composition with the stripping solution, a method of immersing the bonded body together in the stripping solution is preferable because it is simple. The temperature of the stripping solution is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, and most preferably 50 ° C. or higher, from the viewpoint that the releasability in the solution can be achieved in a short time and the productivity is improved. The temperature of the stripping solution is preferably 100 ° C. or lower, more preferably 95 ° C. or lower, and most preferably 90 ° C. or lower, from the viewpoint that the releasability in the solution can be achieved in a short time and the productivity is improved.
仮固定方法としては、本実施形態の仮固定用接着剤組成物を用いて、部材を接着仮固定し、前記組成物を硬化し、該仮固定された部材を加工し、加工された部材を加熱処理することにより、前記組成物の硬化体を取り外す部材の仮固定方法等が挙げられる。加熱処理の温度は、６０〜４００℃が好ましく、１００〜３００℃がより好ましく、１５０〜２５０℃がより好ましい。 As the temporary fixing method, using the temporary fixing adhesive composition of the present embodiment, the members are temporarily bonded and fixed, the composition is cured, the temporarily fixed member is processed, and the processed member is processed. A method for temporarily fixing a member from which a cured body of the composition is removed by performing a heat treatment may be used. The temperature of the heat treatment is preferably from 60 to 400C, more preferably from 100 to 300C, and even more preferably from 150 to 250C.
前記の方法で部材を固定した後、本実施形態においては、仮固定された部材を所望の形状に切断、研削、研磨、孔開け等の加工を施した後、該部材を剥離液に浸漬することにより、接着剤組成物の硬化体を部材から剥離することができる。 After fixing the member by the above method, in the present embodiment, the temporarily fixed member is cut into a desired shape, ground, polished, subjected to a process such as drilling, and then the member is immersed in a stripping liquid. Thereby, the cured body of the adhesive composition can be peeled from the member.
本実施形態の仮固定用接着剤組成物は、シリコン、樹脂、カーボン、金属、サファイア及びガラスからなる群のうちの１種以上の接着に使用することが好ましく、シリコン、樹脂及びガラスからなる群のうちの１種以上の接着に使用することがより好ましく、シリコンの接着に使用することが最も好ましい。 The temporary fixing adhesive composition of the present embodiment is preferably used for bonding at least one of a group consisting of silicon, resin, carbon, metal, sapphire and glass, and a group consisting of silicon, resin and glass. It is more preferably used for bonding one or more of the above, and most preferably used for bonding silicon.
シリコンの接着に使用する場合、特に、シリコンインゴットを切断してシリコンウエハを製造する場合に、本発明の仮固定用接着剤組成物は、大きな効果を有する。 The adhesive composition for temporary fixing of the present invention has a great effect when used for bonding silicon, particularly when a silicon wafer is manufactured by cutting a silicon ingot.
シリコンウエハを製造する方法としては、本発明の仮固定用接着剤組成物を用いて、シリコンインゴットを基材に接着仮固定した後、シリコンインゴットを切断してシリコンウエハを作製し、シリコンウエハを剥離液に浸漬し、シリコンウエハを基材から取り外す方法等が挙げられる。 As a method of manufacturing a silicon wafer, using a temporary fixing adhesive composition of the present invention, after temporarily bonding a silicon ingot to a base material, cutting the silicon ingot to produce a silicon wafer, A method in which the silicon wafer is immersed in a stripping solution and the silicon wafer is removed from the base material may be used.
シリコンインゴットは、固体シリコンを加熱炉内で融解、凝固させる方法等により得られる。シリコンインゴットは、ワイヤーソー等により切断する。ワイヤーソーとしては、ピアノ線等が挙げられる（特許文献４〜５参照）。シリコンウエハは、太陽電池や半導体等に使用する。 The silicon ingot is obtained by a method of melting and solidifying solid silicon in a heating furnace. The silicon ingot is cut by a wire saw or the like. Examples of the wire saw include a piano wire (see Patent Documents 4 and 5). Silicon wafers are used for solar cells, semiconductors, and the like.
以下の実験例により本実施形態を詳細に説明するが、本実施形態はこれら実験例に限定されるものではない。各使用材料の使用量の単位は質量部で示す。特記しない限り、温度２３℃、湿度５０％ＲＨの環境下で、行った。 The present embodiment will be described in detail with reference to the following experimental examples, but the present embodiment is not limited to these experimental examples. The unit of the amount of each used material is shown in parts by mass. Unless otherwise specified, the test was performed in an environment of a temperature of 23 ° C. and a humidity of 50% RH.
調製例１
剥離液の調製
仮固定用接着剤組成物の硬化体を浸漬する剥離液として、表１に示す剥離液を調製した。剥離液１〜３は酸と水を表１に示す質量比で混合し、調製した。
Preparation Example 1
Preparation of Release Liquid As a release liquid for immersing the cured product of the temporary fixing adhesive composition, a release liquid shown in Table 1 was prepared. Strippers 1 to 3 were prepared by mixing acid and water at the mass ratios shown in Table 1.
実験例１
表２の組成で各使用材料を混合して、第一剤と第二剤からなる仮固定用接着剤組成物を調製し、物性を評価した。結果を表２に示した。
Experimental example 1
Each used material was mixed with the composition shown in Table 2 to prepare a temporary fixing adhesive composition comprising a first agent and a second agent, and the physical properties were evaluated. The results are shown in Table 2.
（使用材料）
２−ヒドロキシエチルメタクリレート：市販品
フェノキシエチルメタクリレート：市販品
１．９−ノナンジオールジメタクリレート：市販品
クメンハイドロパーオキサイド：市販品
バナジルアセチルアセトネート：市販品
メチルメタクリレート−ブタジエン−スチレン共重合体（ＭＭＡ−ＢＤ−ＳＴ共重合体）：市販品
アクリロニトリル−ブタジエンゴム（ＡＮ−ＢＤゴム）：高ニトリルＮＢＲ、ニトリル含量４１質量％、市販品
炭酸水素ナトリウム：市販品
炭酸カルシウム：市販品
パラフィン類：パラフィンワックス、市販品
乳酸、市販品
クエン酸、市販品
ＳＰＣＣ：ＳＰＣＣ−Ｄブラスト処理鋼板、市販品
シリコンウエハ（Ｓｉウエハ）：市販品
シリコンインゴット（Ｓｉインゴット）：市販品
(Material used)
2-hydroxyethyl methacrylate: commercially available phenoxyethyl methacrylate: commercially available 1.9-nonanediol dimethacrylate: commercially available cumene hydroperoxide: commercially available vanadyl acetylacetonate: commercially available methyl methacrylate-butadiene-styrene copolymer (MMA) -BD-ST copolymer): Commercial acrylonitrile-butadiene rubber (AN-BD rubber): High nitrile NBR, Nitrile content 41 mass%, Commercial sodium bicarbonate: Commercial calcium carbonate: Commercial paraffins: Paraffin wax , Commercial product lactic acid, commercial product citric acid, commercial product SPCC: SPCC-D blasted steel plate, commercial product silicon wafer (Si wafer): commercial product silicon ingot (Si ingot): commercial product
物性については、次のようにして測定した。 Physical properties were measured as follows.
［固着時間］
ＪＩＳ Ｋ−６８５６に従い、測定した。試験片（１００ｍｍ×２５ｍｍ×１．６ｍｍｔ、ＳＰＣＣ−Ｄブラスト処理）を２枚用意した。１枚の試験片の片側に第一剤と第二剤を等量混合したものを塗布し、その後直ちにもう１枚の試験片を重ね合わせて貼り合せたものを試料とした。試料の固着時間（単位：分）は、温度２３℃、湿度５０％ＲＨの環境下で、プッシュプルゲージで引っ張ってから、０．４ＭＰa以上の強度が測定されるまでの時間を測定した。
[Fixing time]
It was measured according to JIS K-6856. Two test pieces (100 mm × 25 mm × 1.6 mmt, SPCC-D blast treatment) were prepared. One test piece was coated on one side with a mixture of an equal amount of the first agent and the second agent, and immediately thereafter, another test piece was overlaid and bonded to obtain a sample. The fixing time (unit: minute) of the sample was determined by measuring the time from when the sample was pulled with a push-pull gauge in an environment at a temperature of 23 ° C. and a humidity of 50% RH until a strength of 0.4 MPa or more was measured.
［引張り接着強さ］
ＪＩＳ Ｋ６８４９（１９９４）に従い、測定した。試験片（１５ｍｍ×１５ｍｍ×０．７２５ｍｍｔ、Ｓｉウエハ）を２枚用意した。１枚の試験片の片側に第一剤と第二剤を等量混合したものを塗布し、その後、直ちにもう１枚の試験片（擦りガラス（青板ガラス、１５ｍｍ×１５ｍｍ×０．７ｍｍｔ、Ｒａ：５μｍ））を、接着部位を直径８ｍｍの円形として、重ね合わせて貼り合わせた後、２３℃で２４時間養生したものを試料とした。試料の引張接着強さ（単位：ＭＰａ）は、温度２３℃、湿度５０％ＲＨの環境下において、引張速度１０ｍｍ／分で測定した。
[Tensile adhesive strength]
It was measured according to JIS K6849 (1994). Two test pieces (15 mm × 15 mm × 0.725 mmt, Si wafer) were prepared. One side of one test piece was coated with a mixture of the first and second agents in an equal amount, and immediately thereafter, another test piece (frosted glass (blue glass, 15 mm × 15 mm × 0.7 mmt, Ra : 5 μm)), and the laminate was laminated and bonded at an adhesion site of 8 mm in diameter, and then cured at 23 ° C. for 24 hours to obtain a sample. The tensile bond strength (unit: MPa) of the sample was measured at a tensile speed of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% RH.
［２３℃水膨潤率（％）］
ＰＥＴフィルム上に、１ｍｍ厚のシリコンシートからなる型枠を配置した。仮固定用接着剤組成物を型枠に流し込んだ。仮固定用接着剤組成物を流し込んだ型枠の表面に１ｍｍ厚のＰＥＴフィルムを配置した。即ち、２枚のＰＥＴフィルムの間に、仮固定用接着剤組成物が流し込まれた型枠を挟み込んだ構造体を作製した。その後、仮固定用接着剤組成物を、２３℃で２４時間養生し、厚さ１ｍｍの仮固定用接着剤組成物の硬化体を作製した。作製した硬化体を２５ｍｍ×２５ｍｍの正方形状に切断した後、得られた硬化体を、ＡＳＴＭ Ｄ５７０の吸水率測定法に準じて測定した。水膨潤率（％）は下記の式から求めた。水は２３℃の純水を用いた。硬化体を水に６０分間浸漬した後に測定した。
水膨潤率（％）＝１００×（水浸漬後の硬化体質量−水浸漬前の硬化体質量）／（水浸漬前の硬化体質量）
[23 ° C water swelling ratio (%)]
A mold made of a 1 mm thick silicon sheet was placed on the PET film. The adhesive composition for temporary fixing was poured into a mold. A PET film having a thickness of 1 mm was arranged on the surface of the mold into which the adhesive composition for temporary fixing was poured. That is, a structure was prepared in which a mold in which the adhesive composition for temporary fixing was poured was sandwiched between two PET films. Thereafter, the temporary fixing adhesive composition was cured at 23 ° C. for 24 hours to prepare a cured product of the temporary fixing adhesive composition having a thickness of 1 mm. After the prepared cured product was cut into a 25 mm × 25 mm square shape, the obtained cured product was measured according to the water absorption measurement method of ASTM D570. The water swelling ratio (%) was determined from the following equation. Pure water of 23 ° C. was used as water. It was measured after immersing the cured product in water for 60 minutes.
Water swelling ratio (%) = 100 × (mass of cured body after immersion in water−mass of cured body before immersion in water) / (mass of cured body before immersion in water)
［５０℃水膨潤率（％）］
ＰＥＴフィルム上に、１ｍｍ厚のシリコンシートからなる型枠を配置した。仮固定用接着剤組成物を型枠に流し込んだ。仮固定用接着剤組成物を流し込んだ型枠の表面に１ｍｍ厚のＰＥＴフィルムを配置した。即ち、２枚のＰＥＴフィルムの間に、仮固定用接着剤組成物が流し込まれた型枠を挟み込んだ構造体を作製した。その後、仮固定用接着剤組成物を、２３℃で２４時間養生し、厚さ１ｍｍの仮固定用接着剤組成物の硬化体を作製した。作製した硬化体を２５ｍｍ×２５ｍｍの正方形状に切断した後、得られた硬化体を、ＡＳＴＭ Ｄ５７０の吸水率測定法に準じて測定した。水膨潤率（％）は下記の式から求めた。水は５０℃の純水を用いた。硬化体を水に６０分間浸漬した後に測定した。
水膨潤率（％）＝１００×（水浸漬後の硬化体質量−水浸漬前の硬化体質量）／（水浸漬前の硬化体質量）
[50 ° C water swelling ratio (%)]
A mold made of a 1 mm thick silicon sheet was placed on the PET film. The adhesive composition for temporary fixing was poured into a mold. A PET film having a thickness of 1 mm was arranged on the surface of the mold into which the adhesive composition for temporary fixing was poured. That is, a structure was prepared in which a mold in which the adhesive composition for temporary fixing was poured was sandwiched between two PET films. Thereafter, the temporary fixing adhesive composition was cured at 23 ° C. for 24 hours to prepare a cured product of the temporary fixing adhesive composition having a thickness of 1 mm. After the prepared cured product was cut into a 25 mm × 25 mm square shape, the obtained cured product was measured according to the water absorption measurement method of ASTM D570. The water swelling ratio (%) was determined from the following equation. Pure water of 50 ° C. was used as water. It was measured after immersing the cured product in water for 60 minutes.
Water swelling ratio (%) = 100 × (mass of cured body after immersion in water−mass of cured body before immersion in water) / (mass of cured body before immersion in water)
［ガラス転移温度（℃）］
ＰＥＴフィルム上に、１ｍｍ厚のシリコンシートからなる型枠を配置した。仮固定用接着剤組成物を型枠に流し込んだ。仮固定用接着剤組成物を流し込んだ型枠の表面に１ｍｍ厚のＰＥＴフィルムを配置した。即ち、２枚のＰＥＴフィルムの間に、仮固定用接着剤組成物が流し込まれた型枠を挟み込んだ構造体を作製した。その後、仮固定用接着剤組成物を、２３℃で２４時間養生し、厚さ１ｍｍの仮固定用接着剤組成物の硬化体を作製した。硬化体をカッターにて長さ５０ｍｍ×幅５ｍｍに切断し、ガラス転移温度測定用硬化体とした。ガラス転移温度は、セイコー電子産業社製、動的粘弾性測定装置「ＤＭＳ２１０」により測定した。窒素雰囲気下で、前記硬化体に１Ｈｚの引張方向の応力及び歪みを加え、毎分２℃の昇温速度で昇温しながらｔａｎδを測定し、該ｔａｎδのピークトップの温度をガラス転移温度とした。
[Glass transition temperature (° C)]
A mold made of a 1 mm thick silicon sheet was placed on the PET film. The adhesive composition for temporary fixing was poured into a mold. A PET film having a thickness of 1 mm was arranged on the surface of the mold into which the adhesive composition for temporary fixing was poured. That is, a structure was prepared in which a mold in which the adhesive composition for temporary fixing was poured was sandwiched between two PET films. Thereafter, the temporary fixing adhesive composition was cured at 23 ° C. for 24 hours to prepare a cured product of the temporary fixing adhesive composition having a thickness of 1 mm. The cured product was cut into a length of 50 mm and a width of 5 mm with a cutter to obtain a cured product for measuring a glass transition temperature. The glass transition temperature was measured by a dynamic viscoelasticity measuring device “DMS210” manufactured by Seiko Instruments Inc. Under a nitrogen atmosphere, a stress and strain in the tensile direction of 1 Hz were applied to the cured body, and tan δ was measured while increasing the temperature at a rate of 2 ° C. per minute. The temperature of the peak top of tan δ was defined as the glass transition temperature. did.
［沈降安定性評価］
接着剤組成物を１００ｃｃのガラス容器に移し、４０℃の環境下で８週間放置した。その後、沈降層の厚みと液層全体の厚みを測定し、（沈降安定性評価）＝（沈降層の厚み）／（液層全体の厚み）×１００（％）により、沈降安定性を評価した。
[Evaluation of sedimentation stability]
The adhesive composition was transferred to a 100 cc glass container and left in a 40 ° C. environment for 8 weeks. Thereafter, the thickness of the sedimentation layer and the thickness of the entire liquid layer were measured, and the sedimentation stability was evaluated according to (evaluation of sedimentation stability) = (thickness of the sedimentation layer) / (thickness of the entire liquid layer) × 100 (%). .
実験例２
表３に示す仮固定用接着剤組成物と剥離液を使用し、Ｓｉインゴット加工試験を行い、物性を評価した。結果を表３に示した。
Experimental example 2
Using the temporary fixing adhesive composition and the stripping solution shown in Table 3, a Si ingot processing test was performed to evaluate physical properties. The results are shown in Table 3.
［Ｓｉインゴット加工試験］
１２５ｍｍ×１２５ｍｍ×４００ｍｍのＳｉ（シリコン）インゴットと擦りガラス（青板ガラス、１２５ｍｍ×４００ｍｍ×２０ｍｍｔ、Ｒａ：５μｍ）を表３に示す仮固定用接着剤組成物にて接着硬化させた。具体的には、以下のように行った。
擦りガラス表面に仮固定用接着剤組成物を塗布した。仮固定用接着剤組成物の表面にＳｉインゴットを配置し、接着した。更にワイヤーソー装置にＳｉインゴットと擦りガラスの接着試験体を取り付けるために、擦りガラス（Ｓｉインゴットを貼り合せていない面）に表３に示す仮固定用接着剤組成物を塗布し、仮固定用接着剤組成物の表面にアルミ製の治具を貼り合わせた。その後、接着試験体を２３℃で２４時間養生した。養生した接着試験体のＳｉインゴット部分のみをワイヤーソー装置を使用して１８０μｍ厚に切断した。切断中のＳｉインゴットの脱落の有無を観察した（Ｓｉインゴット加工試験（脱落状態））。Ｓｉインゴットのみを切断した接着試験体を２３℃の純水に３０分間浸漬し、切断されたＳｉウエハが脱落しないかを観察した（Ｓｉインゴット加工試験（洗浄試験））。次いで、接着試験体を表３に示す剥離液に浸漬した。剥離液に浸漬してから、Ｓｉウエハと青板ガラスが全て剥離するまでの時間を測定した（Ｓｉインゴット加工試験（剥離時間））。この時、接着試験体の剥離状態についても観察した（Ｓｉインゴット加工試験（剥離状態））。最後に、アルミ製の治具をホットプレートにて２００℃、１時間加熱し、アルミ製の治具と擦りガラスが分離できるかを確認した（治具剥離）。剥離状態では、界面で剥離することが、基材や部材の表面上に、仮固定用接着剤組成物の糊残りがない点で、好ましい。
[Si ingot processing test]
A 125 mm × 125 mm × 400 mm Si (silicon) ingot and a frosted glass (blue plate glass, 125 mm × 400 mm × 20 mmt, Ra: 5 μm) were bonded and cured with the temporary fixing adhesive composition shown in Table 3. Specifically, the procedure was performed as follows.
The temporary fixing adhesive composition was applied to the ground glass surface. A Si ingot was placed on the surface of the temporary fixing adhesive composition and bonded. Further, in order to attach an adhesion test specimen of the Si ingot and the ground glass to the wire saw device, the temporary fixing adhesive composition shown in Table 3 is applied to the ground glass (the surface on which the Si ingot is not bonded), and the temporary fixing adhesive composition is applied. An aluminum jig was bonded to the surface of the adhesive composition. Thereafter, the adhesive test specimen was cured at 23 ° C. for 24 hours. Only the Si ingot portion of the cured adhesion test specimen was cut to a thickness of 180 μm using a wire saw device. The presence or absence of the Si ingot falling during the cutting was observed (Si ingot processing test (dropped state)). The adhesive test body cut only from the Si ingot was immersed in pure water at 23 ° C. for 30 minutes, and it was observed whether the cut Si wafer did not fall off (Si ingot processing test (cleaning test)). Next, the adhesion test piece was immersed in the stripping solution shown in Table 3. The time from immersion in the stripping solution until the Si wafer and the blue plate glass were all stripped was measured (Si ingot processing test (peeling time)). At this time, the peeled state of the adhesive specimen was also observed (Si ingot processing test (peeled state)). Finally, the aluminum jig was heated on a hot plate at 200 ° C. for 1 hour, and it was confirmed whether the aluminum jig and the frosted glass could be separated (jig peeling). In the peeled state, peeling at the interface is preferable in that there is no adhesive residue of the temporary fixing adhesive composition on the surface of the substrate or member.
本実施形態の仮固定用接着剤組成物を使用することにより、短時間で硬化し、高い接着強度を発現できる。本実施形態の仮固定用接着剤組成物は沈降分離がなく、長期保存性に優れる。仮固定用接着剤組成物の硬化体は剥離液に接触することにより接着強度が低下し、部材間の接着力又は部材と治具との接着力が低下するので、容易に部材の回収ができる。本実施形態の仮固定用接着剤組成物は、水に浸漬することにより、早く剥離できる。本実施形態の仮固定用接着剤組成物を使用して、シリコンインゴットを切断した場合、シリコンインゴットが脱落せず、良好な加工性を示した。
（４）炭酸水素塩と（５）無機充填剤を併用しない場合、（４）炭酸水素塩又は（５）無機充填剤が沈降し、本実施形態の効果を示さなかった（実験例１−４、実験例１−５）。（４）炭酸水素塩の代わりに炭酸カルシウムを使用した場合、剥離液に浸漬してもＳｉウエハが剥離しなかった（実験例１−６）。
By using the adhesive composition for temporary fixing of the present embodiment, it can be cured in a short time and can exhibit high adhesive strength. The adhesive composition for temporary fixing of the present embodiment has no sedimentation and separation, and is excellent in long-term storage properties. Since the cured product of the temporary fixing adhesive composition comes into contact with the peeling liquid, the adhesive strength is reduced, and the adhesive force between the members or the adhesive force between the members and the jig is reduced, so that the members can be easily collected. . The temporary fixing adhesive composition of this embodiment can be quickly peeled off by immersion in water. When the silicon ingot was cut using the temporary fixing adhesive composition of the present embodiment, the silicon ingot did not fall off and showed good workability.
When (4) bicarbonate and (5) inorganic filler were not used in combination, (4) bicarbonate or (5) inorganic filler settled and did not show the effect of the present embodiment (Experimental Examples 1-4) Experimental Example 1-5). (4) When calcium carbonate was used instead of the bicarbonate, the Si wafer did not peel even when immersed in a peeling solution (Experimental Example 1-6).
本実施形態は、例えば、以下の特徴を有する。
本実施形態は、接着性が大きいので、切削加工後の部材の寸法精度及び接着仮固定までの硬化速度を向上する。本実施形態により、水中での剥離性に優れ、剥離しても部材に糊残りがないといった、環境的にも作業性にも優れた組成物が得られる。
本実施形態の組成物は、二剤を混合することにより短時間で硬化する。このためにエポキシ系接着剤に比べて、作業性及び作業時間短縮の点で著しく優れている。その硬化体は、加工時に用いる切削水等に影響されずに、高い接着強度を発現できるので、部材の加工時にずれを生じ難く、寸法精度面で優れた部材が容易に得られる。組成物の硬化体は剥離液に接触することにより接着強度が低下し、部材間の接着性、又は、部材と治具との接着性が低下するので、容易に部材の回収ができる。本実施形態の組成物は、従来の組成物に比べて、高価で、発火性の強い、或いは、人体に有毒なガスを発生する有機溶剤を用いる必要がない。本実施形態の組成物は、組成物の硬化体が４０℃以上の剥離液と接触すると膨潤し、フィルム状に部材から回収できるので、作業性に優れる。
This embodiment has, for example, the following features.
In the present embodiment, since the adhesiveness is high, the dimensional accuracy of the member after the cutting and the curing speed up to the temporary fixing of the adhesive are improved. According to the present embodiment, a composition excellent in environment and workability, such as excellent peelability in water and no adhesive residue even after peeling, can be obtained.
The composition of the present embodiment cures in a short time by mixing two agents. For this reason, it is remarkably excellent in workability and work time reduction as compared with the epoxy adhesive. The cured body can exhibit high adhesive strength without being affected by the cutting water or the like used during processing, so that it is unlikely that a deviation occurs during processing of the member, and a member excellent in dimensional accuracy can be easily obtained. When the cured product of the composition comes into contact with the release liquid, the adhesive strength is reduced, and the adhesiveness between the members or the adhesiveness between the member and the jig is reduced, so that the member can be easily collected. The composition of the present embodiment does not require the use of an organic solvent that is expensive, highly ignitable, or generates a gas toxic to the human body, compared to the conventional composition. The composition of the present embodiment is excellent in workability because the cured product of the composition swells when it comes into contact with a stripping liquid at 40 ° C. or higher and can be recovered from the member in the form of a film.
Claims (18)
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