WO2023181635A1 - Composition for temporary fixing - Google Patents
Composition for temporary fixing Download PDFInfo
- Publication number
- WO2023181635A1 WO2023181635A1 PCT/JP2023/002751 JP2023002751W WO2023181635A1 WO 2023181635 A1 WO2023181635 A1 WO 2023181635A1 JP 2023002751 W JP2023002751 W JP 2023002751W WO 2023181635 A1 WO2023181635 A1 WO 2023181635A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- skeleton
- resin composition
- acrylate
- photocurable resin
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title description 38
- 239000011342 resin composition Substances 0.000 claims abstract description 31
- 239000011521 glass Substances 0.000 claims abstract description 23
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical group OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 claims abstract description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 125000001425 triazolyl group Chemical group 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 230000001678 irradiating effect Effects 0.000 claims abstract description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 83
- 238000000034 method Methods 0.000 claims description 33
- 239000000853 adhesive Substances 0.000 claims description 23
- 230000001070 adhesive effect Effects 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000001186 cumulative effect Effects 0.000 claims description 3
- 238000010408 sweeping Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 29
- 239000003795 chemical substances by application Substances 0.000 description 23
- -1 methacryloyl group Chemical group 0.000 description 19
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 15
- 238000001723 curing Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000003505 polymerization initiator Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 235000012431 wafers Nutrition 0.000 description 9
- 238000002835 absorbance Methods 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 7
- 238000010943 off-gassing Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- 229920002367 Polyisobutene Polymers 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- PRBBFHSSJFGXJS-UHFFFAOYSA-N (2,2-dimethyl-3-prop-2-enoyloxypropyl) prop-2-enoate;3-hydroxy-2,2-dimethylpropanoic acid Chemical class OCC(C)(C)C(O)=O.C=CC(=O)OCC(C)(C)COC(=O)C=C PRBBFHSSJFGXJS-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=C(C)C=C1 PUBNJSZGANKUGX-UHFFFAOYSA-N 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- SEEVRZDUPHZSOX-WPWMEQJKSA-N [(e)-1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(\C)=N\OC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-WPWMEQJKSA-N 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 2
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical class [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000834 fixative Substances 0.000 description 2
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- DSTUKHPLWATFCG-UHFFFAOYSA-N (2-benzoylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C(=O)C1=CC=CC=C1 DSTUKHPLWATFCG-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- VQYUAFDBUVMFKD-UHFFFAOYSA-N 1-(4-phenylsulfanylphenyl)octane-1,2-dione Chemical compound C1=CC(C(=O)C(=O)CCCCCC)=CC=C1SC1=CC=CC=C1 VQYUAFDBUVMFKD-UHFFFAOYSA-N 0.000 description 1
- RHNJVKIVSXGYBD-UHFFFAOYSA-N 10-prop-2-enoyloxydecyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCCOC(=O)C=C RHNJVKIVSXGYBD-UHFFFAOYSA-N 0.000 description 1
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 1
- XNDAGYLOQWQWIM-UHFFFAOYSA-N 2,2-dimethylpropyl 3-hydroxy-2,2-dimethylpropanoate Chemical class CC(C)(C)COC(=O)C(C)(C)CO XNDAGYLOQWQWIM-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-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
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-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
- BJXNOEBKXNJEMC-UHFFFAOYSA-N 2-decyltetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCC(COC(=O)C=C)CCCCCCCCCC BJXNOEBKXNJEMC-UHFFFAOYSA-N 0.000 description 1
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-UHFFFAOYSA-N 0.000 description 1
- DRXGKQPTFWTTJW-UHFFFAOYSA-N 5-butoxy-2-[4-(4-butoxy-2-hydroxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazin-2-yl]phenol Chemical compound OC1=CC(OCCCC)=CC=C1C1=NC(C=2C(=CC(OCCCC)=CC=2)O)=NC(C=2C(=CC(OCCCC)=CC=2)OCCCC)=N1 DRXGKQPTFWTTJW-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- LLPSGQNMVAHPHF-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.C1=CC=CC=2C3=CC=CC=C3C(C12)(C1=CC=C(C=C1)OCCO)C1=CC=C(C=C1)OCCO Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.C1=CC=CC=2C3=CC=CC=C3C(C12)(C1=CC=C(C=C1)OCCO)C1=CC=C(C=C1)OCCO LLPSGQNMVAHPHF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZGFPUTOTEJOSAY-UHFFFAOYSA-N FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 Chemical compound FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 ZGFPUTOTEJOSAY-UHFFFAOYSA-N 0.000 description 1
- 229920005988 Oppanol® N Polymers 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- SEEVRZDUPHZSOX-UHFFFAOYSA-N [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(C)=NOC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-UHFFFAOYSA-N 0.000 description 1
- HTMMMSIQFWMMIJ-UHFFFAOYSA-N [3-[2,2-dimethyl-3-(6-prop-2-enoyloxyhexanoyloxy)propanoyl]oxy-2,2-dimethylpropyl] 6-prop-2-enoyloxyhexanoate Chemical compound C=CC(=O)OCCCCCC(=O)OCC(C)(C)COC(=O)C(C)(C)COC(=O)CCCCCOC(=O)C=C HTMMMSIQFWMMIJ-UHFFFAOYSA-N 0.000 description 1
- RKNUMSYAXJHDDL-UHFFFAOYSA-N [3-hydroxy-4-(2-hydroxy-4-prop-2-enoyloxybenzoyl)phenyl] prop-2-enoate Chemical compound OC1=CC(OC(=O)C=C)=CC=C1C(=O)C1=CC=C(OC(=O)C=C)C=C1O RKNUMSYAXJHDDL-UHFFFAOYSA-N 0.000 description 1
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- VRNCRGHDRGGBLW-UHFFFAOYSA-N cyclopenta-1,2-diene Chemical compound C1CC=C=C1 VRNCRGHDRGGBLW-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- CVDUUPMTIHXQKC-UHFFFAOYSA-N ethene 1,3,5-triazinane-2,4,6-trione Chemical group C=C.O=C1NC(=O)NC(=O)N1 CVDUUPMTIHXQKC-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- TWCBCCIODCKPGX-UHFFFAOYSA-N octyl 2-[4-[4,6-bis(4-phenylphenyl)-1,3,5-triazin-2-yl]-3-hydroxyphenoxy]propanoate Chemical compound OC1=CC(OC(C)C(=O)OCCCCCCCC)=CC=C1C1=NC(C=2C=CC(=CC=2)C=2C=CC=CC=2)=NC(C=2C=CC(=CC=2)C=2C=CC=CC=2)=N1 TWCBCCIODCKPGX-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
- C08F290/126—Polymers of unsaturated carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5397—Phosphine oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
Definitions
- the present invention relates to a composition used for temporary fixation.
- inorganic materials such as silicon are used as substrates, and the thickness is obtained by forming an insulating film on the surface, forming a circuit, thinning it by grinding, etc.
- a wafer-type substrate of about 100 ⁇ m is often used.
- this measure has been taken by applying a temporary fixing protective tape to the surface opposite to the surface to be ground (also called the back surface), which can be peeled off after the processing process is completed.
- This tape uses an organic resin film as a base material, and although it is flexible, it has insufficient strength and heat resistance, making it unsuitable for use in processes that involve high temperatures.
- a system has been proposed in which a substrate for an electronic device is bonded to a support such as silicon or glass via an adhesive to provide sufficient durability against the conditions of back grinding and back electrode formation processes.
- a support such as silicon or glass
- an adhesive to provide sufficient durability against the conditions of back grinding and back electrode formation processes.
- the adhesive layer used to bond the substrate to the support This requires that the substrate can be bonded to the support without any gaps, has sufficient durability to withstand subsequent processes, and finally that the thinned wafer can be easily peeled off from the support, in other words, it must be temporarily fixed. It is.
- Processing of such wafers mainly includes a spin coating process, a vacuum bonding and photocuring process, a thinning process by grinding and polishing, a high temperature treatment process, a laser peeling process, and a temporary fixing agent removal process.
- the temporary fixing agent In the spin coating process, in order to uniformly form a film of the temporary fixing agent on the wafer, the temporary fixing agent must have an appropriate viscosity and be a Newtonian fluid (or shear rate independent of shear viscosity). ) is required.
- the temporary fixing agent is required to be able to be cured by irradiation with light such as ultraviolet (UV) light on a support such as glass in a short time, and to generate little outgas (low outgas property).
- light such as ultraviolet (UV) light
- UV ultraviolet
- the load is distributed in the in-plane direction and the planarity is maintained by preventing local subsidence of the substrate.
- Temporary fixatives are required to have appropriate hardness.
- adhesive strength with the support, a moderately high elastic modulus to protect edges, and chemical resistance are also required.
- the temporary fixing agent is required to have heat resistance that can withstand long-term high-temperature treatment in vacuum (for example, at 300° C. or more for one hour or more).
- the temporary fixing agent is required to be capable of high-speed peeling using a laser such as a UV laser.
- Patent Document 1 a monofunctional (meth)acrylate whose side chain is an alkyl group having 18 or more carbon atoms and whose homopolymer Tg is -100°C to 60°C; -2) Discloses a temporary fixing composition containing a polyfunctional (meth)acrylate, (B) a polyisobutene homopolymer and/or a polyisobutene copolymer, and (C) a photoradical polymerization initiator, which has high heat resistance and low heat resistance. It is said to have excellent outgassing properties and peelability.
- the laser beam is swept through the glass support to decompose the temporary fixing agent at the irradiated area. form.
- the gas vaporized inside the hole expands at high temperatures, pushing the glass support upward and making it easier to peel off.
- the present invention can provide the following aspects.
- A a polymerizable component that does not have a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, or a phenol skeleton and has a (meth)acryloyl group;
- B a photopolymerization initiator;
- C A non-polymerizable material having one or more selected from the group consisting of a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, and a phenol skeleton, and containing an ultraviolet absorber having a polymerizable functional group.
- the cured product was A light characterized in that the long axis of a recess having a substantially circular footprint formed so as to pierce the surface is 20% or more of the spot diameter, and the depth is 2.3 ⁇ m or more. Curable resin composition.
- Aspect 2 The photocurable resin composition according to aspect 1, wherein the polymerizable component includes a compound having two or more (meth)acryloyl groups.
- Aspect 3 The photocurable resin composition according to aspect 2, wherein the polymerizable component includes a combination of a polyfunctional (meth)acrylate and a monofunctional (meth)acrylate.
- Aspect 4 The photocurable resin composition according to aspect 2 or 3, wherein the polymerizable component includes a combination of a polyfunctional (meth)acrylate and a polymerizable polymer.
- Aspect 5 The photocurable resin composition according to any one of aspects 1 to 4, wherein the amount of the compound having a (meth)acryloyl group is in the range of 20 to 100% by mass with respect to the mass of the entire polymerizable component. .
- Aspect 6 The photocurable resin composition according to any one of aspects 1 to 5, wherein the polymerizable functional group of the ultraviolet absorber is a (meth)acryloyl group.
- a temporary fixing adhesive comprising the photocurable resin composition according to any one of aspects 1 to 6.
- Aspect 8 An adhesive body comprising the temporary fixing adhesive according to aspect 7 and a base material to be bonded with the temporary fixing adhesive.
- Aspect 10 A cured product obtained by curing the photocurable resin composition according to any one of Aspects 1 to 6.
- monofunctional (meth)acrylate refers to a compound having one (meth)acryloyl group in one molecule.
- Polyfunctional (meth)acrylate refers to a compound having two or more (meth)acryloyl groups in one molecule.
- the n-functional (meth)acrylate refers to a compound having n (meth)acryloyl groups in one molecule.
- the polymerizable functional group in the polyfunctional (meth)acrylate may have only an acryloyl group, only a methacryloyl group, or both an acryloyl group and a methacryloyl group.
- composition (hereinafter also simply referred to as "composition” or "temporary fixing agent”) is provided.
- the composition may contain a non-polymerizable component, but the amount of the non-polymerizable component is less than 15% by mass based on the total of 100 parts by mass of the non-polymerizable component and component (A).
- the term "non-polymerizable component” is defined as a component other than component (B), that is, a component that is not used as a photopolymerization initiator in the technical field. More preferably, the composition does not contain non-polymerizable components. If the amount of the non-polymerizable component is 15% by mass or more, a problem will occur in heat resistance.
- the composition becomes a cured product by irradiating it with light having a wavelength of 405 nm and an illuminance of 100 mW/cm 2 for 50 seconds.
- Directional energy with a wavelength of 355 nm, a spot diameter of 40 to 300 ⁇ m, a pulse energy of 50 to 250 ⁇ J, and an energy density of 248 to 11,500 mJ/cm 2 , preferably 360 to 11,500 mJ/cm 2 is applied to the cured body as the cumulative energy per unit area.
- a concave portion having a substantially circular footprint is formed so as to pierce the surface of the cured product when sweeping irradiation is applied through a glass having a thickness of 0.7 mm so that the irradiation amount is 150 to 1000 mJ/cm 2 .
- the long axis is 20% or more of the spot diameter, and the depth is 2.3 ⁇ m or more.
- the (A) component contained in the present composition a polymerizable component having a (meth)acryloyl group, plays a role in forming a (meth)acrylic polymer skeleton.
- a polymerizable organic compound component is preferred.
- Component (A) may preferably include a compound having two or more (meth)acryloyl groups.
- Component (A) may be a monofunctional (meth)acrylate, a bifunctional (meth)acrylate, a trifunctional or more polyfunctional (meth)acrylate, or a mixture thereof.
- component (A) is a combination of a polyfunctional (meth)acrylate and a monofunctional (meth)acrylate (more preferably a combination of a bifunctional (meth)acrylate and a monofunctional (meth)acrylate), a polyfunctional (meth)acrylate, and a polyfunctional (meth)acrylate.
- a combination of an acrylate and a polymerizable polymer (more preferably a combination of a bifunctional (meth)acrylate and a polymerizable polymer), or a combination of a polyfunctional (meth)acrylate, a monofunctional (meth)acrylate, and a polymerizable polymer (more preferably a combination of a difunctional (meth)acrylate and a polymerizable polymer) combinations of functional (meth)acrylates, monofunctional (meth)acrylates, and polymerizable polymers).
- Component (A) does not have a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, or a phenol skeleton (that is, it does not contain the component (C) described below).
- Component (A) preferably does not have a nitrogen atom in its molecule.
- the phenol skeleton refers to a structure in which a hydroxyl group is directly bonded to an aromatic ring. In other words, a structure in which an oxygen atom other than a hydroxyl group is bonded to an aromatic ring is not included in the phenol skeleton according to the definition herein, even if it is a structure derived from phenols. shall be taken as a thing.
- component (A) may contain, aromatic bifunctional (meth)acrylates, alicyclic bifunctional (meth)acrylates, or mixtures thereof are preferred from the viewpoint of providing a rigid structure. Can be mentioned.
- Component (A) may contain an acyclic polyfunctional (meth)acrylate.
- the polyfunctional (meth)acrylate may be a monomer, a polymer, or a mixture thereof. That is, the above-mentioned polymerizable polymer may be a polyfunctional (meth)acrylate polymer.
- the molecular weight of the polyfunctional (meth)acrylate monomer is preferably 900 or less, more preferably 700 or less, most preferably 500 or less, and even more preferably 400 or less.
- aromatic difunctional (meth)acrylates include 9,9-bis[4-(2-hydroxyC 1 -C 20 alkoxy)phenyl]fluorene di(meth)acrylate, C 1 -C 20 alkoxylated bisphenol A Di(meth)acrylate, benzyl di(meth)acrylate, 1,3-bis(2-(meth)acryloyloxyC 1 -C 20 alkyl)benzene, 2,2-bis(4-(meth)acryloxydiethoxyphenyl) ) propane, or structural isomers thereof.
- di(meth)acrylates having a fused ring skeleton such as a fluorene, indene, indecene, anthracene, azulene, or triphenylene skeleton, may be included.
- Examples of alicyclic difunctional (meth)acrylates include C 1 -C 20 alkoxylated hydrogenated bisphenol A di(meth)acrylate, 1,3-di(meth)acryloyloxyadamantane, tricycloC 10 -C 20 alkoxy
- Examples include candimethanol di(meth)acrylate, dicycloC 5 -C 20 di(meth)acrylate, and structural isomers thereof.
- Examples of acyclic difunctional (meth)acrylates include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, stearic acid modified pentaacrylate Examples include erythrol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and caprolactone-modified neopentyl hydroxypivalate glycol di(meth)acrylate.
- component (A) may contain a trifunctional or more polyfunctional (meth)acrylate.
- trifunctional (meth)acrylates include isocyanuric acid ethylene oxide-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris[(meth)acryloyloxyethyl]isocyanurate, etc. Can be mentioned.
- Examples of (meth)acrylates having four or more functional groups include ditrimethylolpropane tetra(meth)acrylate, dimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, and dipentaerythritol pentaacrylate.
- Examples include (meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.
- component (A) a monofunctional (meth)acrylate having a molecular weight of 550 or less is preferable, and a monofunctional alkyl (meth)acrylate having an alkyl group is more preferable.
- the alkyl group is preferably one or more selected from a linear alkyl group, a branched alkyl group, and an alicyclic alkyl group, and one selected from a linear alkyl group and a branched alkyl group.
- component (A) preferably has a long chain and branched or cyclic alkyl group, for example, a carbon number of 18 to 40, more preferably 18 to 32.
- a branched alkyl group such as an isostearyl group, an isotetracosanyl group (2-decyl-1-tetradecanyl group, etc.), an isotriacontanyl group (2-tetradecyl-1-octadecanyl group, etc.), or a cycloalkyl group. It is preferable to have a group.
- a branched alkyl group such as an isostearyl group, an isotetracosanyl group (2-decyl-1-tetradecanyl group, etc.), an isotriacontanyl group (2-tetradecyl-1-octadecanyl group, etc.), or a cycloalkyl group. It is preferable to have a group.
- the low volatility required for temporary fixing compositions can be achieved. properties, chemical resistance, and heat resistance.
- Component (A) includes stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, 2-decyl-1-tetradecanyl (meth)acrylate, 2-dodecyl-1-hexadecanyl (meth)acrylate, One or more selected from the group consisting of 2-tetradecyl-1-octadecanyl (meth)acrylate is preferred.
- component (A)acrylate of the following formula 1 is preferable.
- R 1 is a hydrogen atom or a methyl group, and a hydrogen atom is more preferable.
- R 2 is an alkyl group, and preferably has 18 to 32 carbon atoms. One or more of these (meth)acrylates can be used.
- Examples of monofunctional alkyl (meth)acrylates in which R 2 is an alkyl group having 18 to 32 carbon atoms include stearyl (meth)acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicodecyl (meth)acrylate, and behenyl ( Preferred are (meth)acrylates having a linear or branched alkyl group, such as meth)acrylate, 2-decyl-1-tetradecanyl(meth)acrylate, 2-tetradecyl-1-octadecanyl(meth)acrylate, and the like.
- the polymerizable polymer refers to a polymerizable component having a (meth)acryloyl group other than a monofunctional (meth)acrylate monomer or a polyfunctional (meth)acrylate monomer.
- a polyfunctional (meth)acrylate polymer is preferred.
- Examples of polyfunctional (meth)acrylate polymers include "ART CURE RA-341" and "APB-001” manufactured by Negami Kogyo Co., Ltd.
- the amount of the compound having a (meth)acryloyl group contained in component (A) may be in the range of 20 to 100% by mass, more preferably 40% by mass based on the total mass of component (A). ⁇ 100% by mass, and may range from 60 to 100% by mass.
- the amount of polyfunctional (meth)acrylate may range from 20 to 100% by weight, more preferably from 50 to 100% by weight, based on the total weight of component (A).
- the mass ratio of the polyfunctional (meth)acrylate monomer (more preferably bifunctional (meth)acrylate monomer), monofunctional (meth)acrylate monomer, and polymerizable polymer contained in component (A) is as follows: It may range from 40 to 80:10 to 50:10 to 25.
- component (A) does not contain a polyfunctional (meth)acrylate monomer, but contains a monofunctional (meth)acrylate monomer and a polymerizable polymer in a mass ratio of 50 to 80:20 to 50. It's okay to stay.
- the amount of the non-polymerizable component contained in the present composition may be 0% by mass or more and less than 10% by mass, or 0% by mass or more and less than 5% by mass. More preferably, the composition does not contain any non-polymerizable components except for component (B).
- the photopolymerization initiator which is component (B) contained in the present composition, is a substance that can initiate polymerization of component (A) when irradiated with light.
- component (B) may be a radical photopolymerization initiator.
- a photoradical polymerization initiator is, for example, a compound whose molecules are cleaved and split into two or more radicals by irradiation with ultraviolet rays or visible light (for example, wavelength 350 to 700 nm, preferably 365 to 500 nm, more preferably 385 to 450 nm). say.
- photoradical polymerization initiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis( ⁇ 5 -2,4-cyclopentadiene).
- Component (B) may include one or more types or a combination of two or more types of these.
- component (B) may include an acylphosphine oxide compound.
- Preferred acylphosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
- As a photo-radical polymerization initiator it is highly sensitive, has photofading properties, and has excellent deep curing properties, and the absorption wavelength range for generating radicals extends to a relatively long wavelength range. It is preferable. In the preferred compound described above, the absorption wavelength range is up to about 440 nm, which is significantly different from the absorption wavelength range of the UV absorber used in the UV laser peeling process described below.
- the degree of inhibition of UV curing by the UV absorber is small, and radical polymerization can be initiated with light of a longer wavelength. Therefore, even in the coexistence of a UV absorber, radical polymerization can be initiated and cured efficiently at a relatively high rate.
- the photoradical polymerization initiator can be selected based on absorbance. Specifically, when dissolved at a concentration of 0.1% by mass in a solvent that does not have maximum absorption in the wavelength region of 300 to 500 nm (for example, acetonitrile or toluene), the absorbance at a wavelength of 365 nm is 0. 5 or more, the absorbance is 0.5 or more at a wavelength of 385 nm, and the absorbance is 0.5 or more at a wavelength of 405 nm. , a photoradical polymerization initiator can be selected.
- An example of a compound that satisfies such conditions is 1-[9-ethyl, which has an absorbance of 0.5 or more at a wavelength of 365 nm when dissolved at a concentration of 0.1% by mass in acetonitrile as a solvent.
- bis( ⁇ 5 -2,4-cyclopentadien-1-yl)-bis having an absorption wavelength range of 400 to 500 nm is recommended.
- (2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium can also be used as a photoradical polymerization initiator.
- temporary fixing is not a layer compatible with the UV laser peeling process, and is used for temporary fixation to prevent damage from bonding the substrate to the support substrate to the heating process.
- oxime ester compounds can also be selected as photoradical polymerization initiators for resin compositions.
- acylphosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like. Among these, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is particularly preferred.
- titanocene compounds include bis( ⁇ 5 -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium.
- ⁇ -aminoalkylphenone compounds examples include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1 -(4-morpholin-4-ylphenyl)-butan-1-one and the like.
- oxime ester compounds examples include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]ethanone 1-(O-acetyloxime) and the like. Among these, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) is preferred.
- the amount of the radical photopolymerization initiator (B) used is preferably 0.01 to 5 parts by mass based on 100 parts by mass of component (A) in terms of reaction rate, heat resistance after curing, and low outgas properties. More preferably 0.1 to 1 part by mass.
- component (B) is 0.01 parts by mass or more, sufficient curability can be obtained, and when it is 5 parts by mass or less, low outgas properties and heat resistance are less likely to be impaired.
- the ultraviolet absorber (UV absorber) having a polymerizable functional group which is the component (C) contained in this composition, has molecules that are cut and decomposed and vaporized by irradiation with ultraviolet or visible light laser. is generated at the interface between the support substrate (or substrate) and the temporary fixing agent, thereby causing a loss of the adhesive force between the temporary fixation agent and the support substrate (or substrate) that was maintained until just before the peeling process.
- Component (C) is a compound having one or more types selected from the group consisting of a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, and a phenol skeleton (preferably a hindered phenol skeleton).
- the purpose of having these skeletons is to obtain a degree of overlap between the UV absorption wavelength region and the UV laser wavelength, UV absorption characteristics at the same wavelength, low outgassing properties, and heat resistance.
- the polymerizable functional group contained in component (C) is preferably a (meth)acryloyl group.
- component (C) examples include 2-[2-hydroxy-5-[2-((meth)acryloyloxy)ethyl]phenyl]-2H-benzotriazole, 2-[1-(2-hydroxy-3, 5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl (meth)acrylate, 2-(2-(meth)acryloyloxy,5-methyl)phenyl-2H-benzotriazole, 1 ,1-bis-[2-(meth)acryloyloxy,3-(2H-benzotriazol-2-yl),5-tert-octyl]methane, 2,2'-dihydroxy-4,4'-di(meth) )
- One or more members of the group consisting of acryloyloxybenzophenone are particularly preferred from the viewpoint of compatibility with the resin component, UV absorption properties, low outgassing properties, and heat resistance.
- the UV transmittance of the cured product in this specification is a value obtained by reflectance measurement spectroscopy. Specifically, the transmittance was measured using a reflectance spectrometer (V-650 manufactured by JASCO Corporation) using a cured film with a thickness of approximately 50 ⁇ m sandwiched between PET resin sheets under the following conditions. ) is obtained using
- the amount of component (C) is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, per 100 parts by weight of component (A).
- the amount is 0.01 parts by mass or more, a sufficient UV laser peeling rate can be obtained, and when it is 10 parts by mass or less, the effect of low outgassing property and heat resistance being less likely to be impaired can be obtained.
- the weight average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) in terms of standard polystyrene. Specifically, the weight average molecular weight is determined by creating a calibration curve with commercially available standard polystyrene using a GPC system (SC-8010 manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent under the following conditions. .
- GPC gel permeation chromatography
- a cured product of the composition described above can also be provided.
- Such curing may be performed using a light source described below.
- the cured product is in the form of a cured film with a thickness of 50 ⁇ m, it is preferable that one or more of the following conditions be satisfied, and more preferably that all of the following conditions are satisfied.
- the following conditions can be met, for example, by using a UV absorber.
- the light transmittance in a wavelength region of 395 nm or more among the wavelengths of the light source used for curing is 70% or more.
- the light transmittance in the wavelength range of 385 nm or more and less than 395 nm among the wavelengths of the light source used for curing is 20% or more.
- the light transmittance at the wavelength (355 nm) of the UV laser used for UV laser peeling is 1% or less.
- a temporary fixing agent having such characteristics can be suitably used in a process including a high-temperature vacuum process such as ion implantation, annealing, and electrode formation by sputtering, especially in the back surface process after thinning.
- the cured product to be subjected to laser irradiation which is a feature of the present invention, is produced by irradiating it with light having a wavelength of 405 nm and an illuminance of 100 mW/cm 2 for 50 seconds.
- the viscosity of the composition of the present invention is preferably 100 mPa ⁇ s or more, more preferably 500 mPa ⁇ s or more, and most preferably 1000 mPa ⁇ s or more at 23° C. (under atmospheric pressure) in terms of coatability and workability.
- the viscosity of the composition of the present invention is preferably 10,000 mPa ⁇ s or less, more preferably 5,000 mPa ⁇ s or less, and most preferably 4,000 mPa ⁇ s or less in terms of applicability and workability.
- the pressure is 100 mPa ⁇ s or more, the coating properties, particularly the coating properties by spin coating, are excellent. Workability is excellent when the pressure is 10,000 mPa ⁇ s or less.
- the viscosity can be measured using a known viscometer.
- Spin coating is a method of applying the composition to the surface of the substrate by, for example, dropping a liquid composition onto the substrate and rotating the substrate at a predetermined number of rotations. Spin coating enables efficient production of high-quality coatings.
- the present composition can be used as a temporary fixing resin composition, a temporary fixing adhesive, a pressure-sensitive adhesive sheet, or a temporary fixing adhesive for manufacturing electronic devices.
- the temporary fixing composition, the temporary fixing resin composition, and the temporary fixing adhesive may be collectively referred to as a temporary fixing agent.
- the amount of energy in visible light or ultraviolet rays is 1 to 20,000 mJ. It is preferable to irradiate so that the amount of radiation becomes /cm 2 .
- the energy amount is 1 mJ/cm 2 or more, sufficient adhesion is obtained, and when it is 20,000 mJ/cm 2 or less, productivity is excellent, and decomposition products from the photoradical polymerization initiator are difficult to generate, suppressing outgas generation. be done.
- productivity adhesion, low outgas properties, and easy peelability, it is preferably 1000 to 10000 mJ/cm 2 .
- the substrates to be bonded with the present composition it is preferable that at least one of the substrates be a transparent substrate that transmits light.
- the transparent substrate include inorganic substrates such as crystal, glass, quartz, calcium fluoride, and magnesium fluoride, and organic substrates such as plastic.
- inorganic base materials are preferred because they are versatile and can provide great effects.
- one or more selected from glass and quartz is preferred.
- the laser irradiation conditions that characterize the present invention are those when glass with a thickness of 0.7 mm is selected as the base material.
- the present composition may be photocurable, and the cured product provided thereby has excellent heat resistance and peelability.
- the cured product of the composition of the present invention has a small amount of outgassing even when exposed to high temperatures, and is suitable for joining, sealing, and coating various optical components, optical devices, and electronic components.
- the composition of the present invention is suitable for applications that require a wide variety of durability such as solvent resistance, heat resistance, adhesiveness, etc., particularly for semiconductor manufacturing process applications.
- the cured product of this composition can be used in processes in a wide temperature range from room temperature to high temperatures.
- the heating temperature during the process is preferably 350°C or lower, more preferably 300°C or lower. In a preferred embodiment, the temperature at which the heating mass reduction rate of the cured product is 2% may be 250° C. or higher.
- the bonded body bonded with the present composition has high shear adhesive strength and can withstand thinning processes, etc., and can be easily peeled off after passing through a heating process such as forming an insulating film.
- the cured product of the present composition can be used in a high temperature process, for example, preferably at 200°C or higher, more preferably at 250°C or higher.
- an adhesive body is also provided in which substrates are adhered by using the present composition as an adhesive.
- the adhesive body can be peeled off by applying external force. For example, it can be peeled off by inserting a knife, sheet, or wire into the joint. Alternatively, it is also possible to peel off the adhesive by irradiating the optically transparent base material side of the adhesive body with a UV laser or an IR laser so as to scan the entire surface.
- Curable resin compositions (hereinafter also referred to as liquid resin compositions) having the compositions shown in the table below (unit: parts by mass) were prepared and evaluated. The following compounds were selected as each component.
- A-BPEF-2 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate (“NK ester A-BPEF-2” manufactured by Shin-Nakamura Chemical Co., Ltd.)
- HBPE-4 EO-modified hydrogenated bisphenol A diacrylate (“HBPE-4” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., m+n ⁇ 4)
- HX-620 Caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate (Nippon Kayaku Co., Ltd. "Kayarad HX-620", m+n ⁇ 4)
- HX-220 Caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate (Nippon Kayaku Co., Ltd.
- DDDA 1,10-decanediol diacrylate
- A-DOD-N 1,10-decanediol diacrylate
- DTDA 2-decyl-1-tetradecanyl acrylate
- Light Acrylate DTD-A manufactured by Kyoeisha Chemical Co., Ltd.
- A-DCP Tricyclodecane dimethanol diacrylate (“NK ester A-DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.)
- ISTA Isostearyl acrylate (“ISTA” manufactured by Osaka Organic Chemical Industry Co., Ltd.)
- DCP Tricyclodecane dimethanol dimethacrylate (“NK Ester DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.)
- M-111 Nonylphenol EO modified acrylate (“Aronix M-111” manufactured by Toagosei Co., Ltd., n ⁇ 1)
- M-113 Nonylphenol EO modified acrylate
- component (C) 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine (“Tinuvin 460” manufactured by BASF) 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (“Tinuvin 479” manufactured by BASF) 2-[2-Hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (Otsuka Chemical Co., Ltd.
- PIB Polyisobutene (“Oppanol N 50 SF” manufactured by BASF, weight average molecular weight 565,000)
- the removability after irradiation is excellent if there is no stickiness and the glass support can be easily peeled off by hand from the temporary fixing agent, or if the glass support remains sticky but the glass support is not on the temporary fixing agent.
- the evaluation was performed by defining fair if the glass support could be peeled off by hand from above, and NG if the glass support could not be peeled off by hand from the temporary fixing agent.
- the profile of the concave shape formed on the surface of the temporary fixing agent was measured using a hybrid laser microscope "OPTELICS HYBRID" manufactured by Lasertec Corporation. The major axis and depth were determined. The hole is in the shape of a recess and has a generally circular footprint. Profile measurements were performed with an objective lens magnification of 50 times and a resolution of 0.01 ⁇ m. When the concave shape formed on the surface of the temporary fixing agent was not a perfect circle, the diameter of the longest side (major axis) was measured. The height difference from the outermost surface of the temporary fixing agent to the point where the deepest concave shape was formed was measured and determined as the depth of the hole.
- the support glass and silicon wafer were broken and the exposed temporary fixative was measured.
- the ratio was calculated by dividing the hole diameter (major axis) measured by the above method by the spot diameter set during UV laser irradiation.
- the bonded sample produced by the above method was heat-treated in a high temperature and reduced pressure environment of 300° C. and 20 Pa for 1 hour. Thereafter, the glass and Si wafers were mechanically peeled off from the temporary fixing agent using a cutter, and the appearance of the surfaces of both substrates was checked to evaluate the presence or absence of bleed-out.
- Comparative Examples b1 to b5 which did not contain component (C) that met the conditions of the present invention, all had unsuitable heat resistance.
- Comparative Example b6 which contained component (C) but contained many non-polymerizable components, the size of the holes formed was not appropriate even if the energy irradiation amount was increased.
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Abstract
Provided is a photocurable resin composition which contains: (A) a polymerizable component which does not have any of a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton or a phenol skeleton and has a (meth)acryloyl group; (B) a photopolymerization initiator; and (C) an ultraviolet radiation absorber which has one or more types selected from the group consisting of a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton and a phenol skeleton and has a polymerizable functional group, and in which the amount of non-polymerizable components is at least 0 mass% and less than 15 mass% relative to a total of 100 mass% of contained polymerizable components and component (A). The photocurable resin composition is characterized in that when a cured product, which has been produced by irradiating the photocurable resin composition with light having a wavelength of 405 nm at an illuminance of 100 mW/cm2 for 50 seconds, is subjected to sweeping irradiation with directed energy having a wavelength of 355 nm, a spot diameter of 40-300 μm, a pulsed energy of 50-250 μJ and an energy density of 248-11,500 mJ/cm2 through glass having a thickness of 0.7 mm so that the accumulated energy irradiation amount per unit area is 150-1000 mJ/cm2, the length of a recessed part having a substantially circular footprint formed so as to pierce the surface of the cured product is 20% or more of the spot diameter, and the depth of the recessed part is 2.3 μm or more.
Description
本発明は、仮固定に用いる組成物に関する。
The present invention relates to a composition used for temporary fixation.
電子デバイスの製造にあたっては、シリコンに代表される無機系の材料を基板として用い、その表面への絶縁膜形成、回路形成、研削による薄化等の加工を施すことで得られた、厚さ数百μｍ程度のウエハ型の基板がよく用いられる。しかし基板には脆くて割れやすい材質のものが多いため、特に研削による薄化に際しては破損防止措置が必要である。この措置には、従来、研削対象面の反対側の面（裏面ともいう）に、加工工程終了後に剥離することが可能な、仮固定用保護テープを貼るという方法が採られている。このテープは、有機樹脂フィルムを基材に用いており、柔軟性がある反面、強度や耐熱性が不充分であり、高温となる工程での使用には適さない。
In manufacturing electronic devices, inorganic materials such as silicon are used as substrates, and the thickness is obtained by forming an insulating film on the surface, forming a circuit, thinning it by grinding, etc. A wafer-type substrate of about 100 μm is often used. However, since many substrates are made of brittle and easily broken materials, it is necessary to take measures to prevent damage, especially when thinning them by grinding. Conventionally, this measure has been taken by applying a temporary fixing protective tape to the surface opposite to the surface to be ground (also called the back surface), which can be peeled off after the processing process is completed. This tape uses an organic resin film as a base material, and although it is flexible, it has insufficient strength and heat resistance, making it unsuitable for use in processes that involve high temperatures.
そこで、電子デバイス用基板をシリコンやガラス等の支持体に接着剤を介して接合することによって、裏面研削や裏面電極形成の工程の条件に対する充分な耐久性を付与するシステムが提案されている。この際に重要なのが、基板を支持体に接合する際の接着剤層である。これは基板を支持体に隙間なく接合でき、後の工程に耐えるだけの充分な耐久性が必要であり、最後に薄化したウエハを支持体から簡便に剥離できる、即ち仮固定ができることが必要である。
Therefore, a system has been proposed in which a substrate for an electronic device is bonded to a support such as silicon or glass via an adhesive to provide sufficient durability against the conditions of back grinding and back electrode formation processes. What is important in this case is the adhesive layer used to bond the substrate to the support. This requires that the substrate can be bonded to the support without any gaps, has sufficient durability to withstand subsequent processes, and finally that the thinned wafer can be easily peeled off from the support, in other words, it must be temporarily fixed. It is.
このようなウエハの加工では主に、スピンコート工程、真空接合と光硬化工程、研削・研磨による薄化加工、高温処理工程、レーザー剥離工程、仮固定剤の除去工程が行われる。
Processing of such wafers mainly includes a spin coating process, a vacuum bonding and photocuring process, a thinning process by grinding and polishing, a high temperature treatment process, a laser peeling process, and a temporary fixing agent removal process.
スピンコート工程では、仮固定剤の膜をウエハ上に均一に形成できるようにするために、仮固定剤が適した粘度を有すること及びニュートン流体であること（又はせん断粘度のせん断速度非依存性を持つこと）が求められる。
In the spin coating process, in order to uniformly form a film of the temporary fixing agent on the wafer, the temporary fixing agent must have an appropriate viscosity and be a Newtonian fluid (or shear rate independent of shear viscosity). ) is required.
真空接合／ＵＶ硬化工程では、ガラス等の支持体上で短時間に紫外線（ＵＶ）等光照射による硬化ができること、及びアウトガス発生が少ないこと（低アウトガス性）が仮固定剤に求められる。
In the vacuum bonding/UV curing process, the temporary fixing agent is required to be able to be cured by irradiation with light such as ultraviolet (UV) light on a support such as glass in a short time, and to generate little outgas (low outgas property).
研削・研磨による薄化加工工程では、研削機の荷重が基板に局所的に掛かることによる破損を避けるため、荷重を面内方向に分散させつつ基板の局所的な沈下を防いで平面性を保てる適度な硬度が仮固定剤に求められる。さらに加えて、支持体との接着力、エッジを保護するための弾性率の適度な高さ、及び耐薬品性も求められることになる。
In the thinning process by grinding and polishing, in order to avoid damage due to the load of the grinder being applied locally to the substrate, the load is distributed in the in-plane direction and the planarity is maintained by preventing local subsidence of the substrate. Temporary fixatives are required to have appropriate hardness. In addition, adhesive strength with the support, a moderately high elastic modulus to protect edges, and chemical resistance are also required.
高温処理工程では、真空中での長時間に亘る高温処理（例えば300℃以上で一時間以上）に耐えうる耐熱性が仮固定剤に求められる。
In the high-temperature treatment process, the temporary fixing agent is required to have heat resistance that can withstand long-term high-temperature treatment in vacuum (for example, at 300° C. or more for one hour or more).
レーザー剥離工程では、ＵＶレーザー等のレーザーにより、高速に剥離できることが仮固定剤に求められる。
In the laser peeling process, the temporary fixing agent is required to be capable of high-speed peeling using a laser such as a UV laser.
除去工程では、基板を支持体から簡便に剥離できる易剥離性のほか、剥離後に基板上に接着剤の残渣が残らないための凝集特性、易洗浄性が求められる。
In the removal step, in addition to easy peelability that allows the substrate to be easily peeled off from the support, cohesive properties and easy cleanability are required so that no adhesive residue remains on the substrate after peeling.
こうした背景に鑑み、例えば特許文献１では、（Ａ－１）側鎖が炭素数１８以上のアルキル基で、ホモポリマーのＴｇが－１００℃～６０℃である単官能(メタ)アクリレート、（Ａ－２）多官能(メタ)アクリレート、（Ｂ）ポリイソブテン単独重合体及び／又はポリイソブテン共重合体、及び（Ｃ）光ラジカル重合開始剤を含む仮固定組成物を開示しており、耐熱性、低アウトガス性、剥離性に優れることが謳われている。
In view of this background, for example, in Patent Document 1, (A-1) a monofunctional (meth)acrylate whose side chain is an alkyl group having 18 or more carbon atoms and whose homopolymer Tg is -100°C to 60°C; -2) Discloses a temporary fixing composition containing a polyfunctional (meth)acrylate, (B) a polyisobutene homopolymer and/or a polyisobutene copolymer, and (C) a photoradical polymerization initiator, which has high heat resistance and low heat resistance. It is said to have excellent outgassing properties and peelability.
ウエハ上で硬化した仮固定剤を剥離するにあたっては、ガラス支持体を介してレーザーを掃引照射し、照射箇所の仮固定剤を分解させることで、穴（ガラスで蓋されている状態の凹部）を形成する。穴内で気化したガスが高温で膨らむことで、ガラス支持体が押し上げられ、剥離しやすくなる。
To peel off the temporary fixing agent that has hardened on the wafer, the laser beam is swept through the glass support to decompose the temporary fixing agent at the irradiated area. form. The gas vaporized inside the hole expands at high temperatures, pushing the glass support upward and making it easier to peel off.
しかしながら、仮固定剤の硬化体へとガラス支持体を介して照射したレーザー光のスポット径に対し、十分な大きさの穴が形成されない問題がある。これは、仮固定剤として求められる強度を確保しようとすると、その反面レーザー光に対する反応性が低くなり、十分な大きさの穴が穿たれないことに因る。そしてレーザー光に対する反応性を上げようとしても、必要な耐熱性までもが損われてしまい、最適解が得られていなかった。このため、従来技術からの発展が望まれている。
However, there is a problem in that a hole of sufficient size is not formed with respect to the spot diameter of the laser beam irradiated onto the cured body of the temporary fixing agent through the glass support. This is because, when trying to secure the strength required as a temporary fixing agent, on the other hand, the reactivity to laser light becomes low and holes of sufficient size cannot be drilled. Even when attempts were made to increase the reactivity to laser light, the necessary heat resistance was also compromised, making it impossible to obtain an optimal solution. Therefore, development from the conventional technology is desired.
即ち、本発明では以下の態様を提供できる。
That is, the present invention can provide the following aspects.
態様1.
（Ａ）ベンゾフェノン骨格、トリアゾール骨格、ヒドロキシフェニルトリアジン骨格、及びフェノール骨格のいずれも有さず、かつ(メタ)アクリロイル基を有する重合性成分と、
（Ｂ）光重合開始剤と、
（Ｃ）ベンゾフェノン骨格、トリアゾール骨格、ヒドロキシフェニルトリアジン骨格、及びフェノール骨格からなる群から選択される一種以上を有し、かつ重合性官能基を有する紫外線吸収剤と
を含み、かつ含まれる非重合性成分と（Ａ）成分との合計100質量部に対して、非重合性成分の量が0質量％以上15質量％未満である、光硬化性樹脂組成物であって、
前記光硬化性樹脂組成物を、波長405nmかつ照度100mW/cm2である光を50秒間照射して作製した硬化体に対し、波長355nm、スポット径40～300μm、パルスエネルギー50～250μJ、エネルギー密度248～11500mJ/cm2の指向性エネルギーを、単位面積あたりの積算エネルギー照射量が150～1000mJ/cm2となるように、厚さ0.7mmのガラスを介して掃引照射した際に前記硬化体の表面を穿つように形成される略円形状のフットプリントを有する凹部の長径が、スポット径に対して20%以上の大きさであり、かつ深さが2.3μm以上であることを特徴とする光硬化性樹脂組成物。 Aspect 1.
(A) a polymerizable component that does not have a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, or a phenol skeleton and has a (meth)acryloyl group;
(B) a photopolymerization initiator;
(C) A non-polymerizable material having one or more selected from the group consisting of a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, and a phenol skeleton, and containing an ultraviolet absorber having a polymerizable functional group. A photocurable resin composition in which the amount of the non-polymerizable component is 0% by mass or more and less than 15% by mass with respect to the total of 100 parts by mass of the components and component (A),
A cured product prepared by irradiating the photocurable resin composition with light having a wavelength of 405 nm and an illuminance of 100 mW/cm 2 for 50 seconds, a wavelength of 355 nm, a spot diameter of 40 to 300 μm, a pulse energy of 50 to 250 μJ, and an energy density. When the directional energy of 248 to 11,500 mJ/cm 2 was swept through the glass with a thickness of 0.7 mm so that the cumulative energy irradiation amount per unit area was 150 to 1,000 mJ/cm 2 , the cured product was A light characterized in that the long axis of a recess having a substantially circular footprint formed so as to pierce the surface is 20% or more of the spot diameter, and the depth is 2.3 μm or more. Curable resin composition.
（Ａ）ベンゾフェノン骨格、トリアゾール骨格、ヒドロキシフェニルトリアジン骨格、及びフェノール骨格のいずれも有さず、かつ(メタ)アクリロイル基を有する重合性成分と、
（Ｂ）光重合開始剤と、
（Ｃ）ベンゾフェノン骨格、トリアゾール骨格、ヒドロキシフェニルトリアジン骨格、及びフェノール骨格からなる群から選択される一種以上を有し、かつ重合性官能基を有する紫外線吸収剤と
を含み、かつ含まれる非重合性成分と（Ａ）成分との合計100質量部に対して、非重合性成分の量が0質量％以上15質量％未満である、光硬化性樹脂組成物であって、
前記光硬化性樹脂組成物を、波長405nmかつ照度100mW/cm2である光を50秒間照射して作製した硬化体に対し、波長355nm、スポット径40～300μm、パルスエネルギー50～250μJ、エネルギー密度248～11500mJ/cm2の指向性エネルギーを、単位面積あたりの積算エネルギー照射量が150～1000mJ/cm2となるように、厚さ0.7mmのガラスを介して掃引照射した際に前記硬化体の表面を穿つように形成される略円形状のフットプリントを有する凹部の長径が、スポット径に対して20%以上の大きさであり、かつ深さが2.3μm以上であることを特徴とする光硬化性樹脂組成物。 Aspect 1.
(A) a polymerizable component that does not have a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, or a phenol skeleton and has a (meth)acryloyl group;
(B) a photopolymerization initiator;
(C) A non-polymerizable material having one or more selected from the group consisting of a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, and a phenol skeleton, and containing an ultraviolet absorber having a polymerizable functional group. A photocurable resin composition in which the amount of the non-polymerizable component is 0% by mass or more and less than 15% by mass with respect to the total of 100 parts by mass of the components and component (A),
A cured product prepared by irradiating the photocurable resin composition with light having a wavelength of 405 nm and an illuminance of 100 mW/cm 2 for 50 seconds, a wavelength of 355 nm, a spot diameter of 40 to 300 μm, a pulse energy of 50 to 250 μJ, and an energy density. When the directional energy of 248 to 11,500 mJ/cm 2 was swept through the glass with a thickness of 0.7 mm so that the cumulative energy irradiation amount per unit area was 150 to 1,000 mJ/cm 2 , the cured product was A light characterized in that the long axis of a recess having a substantially circular footprint formed so as to pierce the surface is 20% or more of the spot diameter, and the depth is 2.3 μm or more. Curable resin composition.
態様2.
前記重合性成分が、(メタ)アクリロイル基を2つ以上有する化合物を含む、態様１に記載の光硬化性樹脂組成物。 Aspect 2.
The photocurable resin composition according to aspect 1, wherein the polymerizable component includes a compound having two or more (meth)acryloyl groups.
前記重合性成分が、(メタ)アクリロイル基を2つ以上有する化合物を含む、態様１に記載の光硬化性樹脂組成物。 Aspect 2.
The photocurable resin composition according to aspect 1, wherein the polymerizable component includes a compound having two or more (meth)acryloyl groups.
態様3.
前記重合性成分が、多官能(メタ)アクリレートと単官能(メタ)アクリレートの組み合わせを含む、態様２に記載の光硬化性樹脂組成物。 Aspect 3.
The photocurable resin composition according to aspect 2, wherein the polymerizable component includes a combination of a polyfunctional (meth)acrylate and a monofunctional (meth)acrylate.
前記重合性成分が、多官能(メタ)アクリレートと単官能(メタ)アクリレートの組み合わせを含む、態様２に記載の光硬化性樹脂組成物。 Aspect 3.
The photocurable resin composition according to aspect 2, wherein the polymerizable component includes a combination of a polyfunctional (meth)acrylate and a monofunctional (meth)acrylate.
態様4.
前記重合性成分が、多官能(メタ)アクリレートと重合性ポリマーの組み合わせを含む、態様２又は３に記載の光硬化性樹脂組成物。 Aspect 4.
The photocurable resin composition according to aspect 2 or 3, wherein the polymerizable component includes a combination of a polyfunctional (meth)acrylate and a polymerizable polymer.
前記重合性成分が、多官能(メタ)アクリレートと重合性ポリマーの組み合わせを含む、態様２又は３に記載の光硬化性樹脂組成物。 Aspect 4.
The photocurable resin composition according to aspect 2 or 3, wherein the polymerizable component includes a combination of a polyfunctional (meth)acrylate and a polymerizable polymer.
態様5.
前記重合性成分全体の質量に対して、(メタ)アクリロイル基を有する化合物の量が20～100質量％の範囲である、態様１～４のいずれか一項に記載の光硬化性樹脂組成物。 Aspect 5.
The photocurable resin composition according to any one of aspects 1 to 4, wherein the amount of the compound having a (meth)acryloyl group is in the range of 20 to 100% by mass with respect to the mass of the entire polymerizable component. .
前記重合性成分全体の質量に対して、(メタ)アクリロイル基を有する化合物の量が20～100質量％の範囲である、態様１～４のいずれか一項に記載の光硬化性樹脂組成物。 Aspect 5.
The photocurable resin composition according to any one of aspects 1 to 4, wherein the amount of the compound having a (meth)acryloyl group is in the range of 20 to 100% by mass with respect to the mass of the entire polymerizable component. .
態様6.
前記紫外線吸収剤が有する重合性官能基が（メタ）アクリロイル基であることを特徴とする態様１～５のいずれか一項に記載の光硬化性樹脂組成物。 Aspect 6.
The photocurable resin composition according to any one of aspects 1 to 5, wherein the polymerizable functional group of the ultraviolet absorber is a (meth)acryloyl group.
前記紫外線吸収剤が有する重合性官能基が（メタ）アクリロイル基であることを特徴とする態様１～５のいずれか一項に記載の光硬化性樹脂組成物。 Aspect 6.
The photocurable resin composition according to any one of aspects 1 to 5, wherein the polymerizable functional group of the ultraviolet absorber is a (meth)acryloyl group.
態様7.
態様１～６のいずれか一項に記載の光硬化性樹脂組成物を含む、仮固定用接着剤。 Aspect 7.
A temporary fixing adhesive comprising the photocurable resin composition according to any one of aspects 1 to 6.
態様１～６のいずれか一項に記載の光硬化性樹脂組成物を含む、仮固定用接着剤。 Aspect 7.
A temporary fixing adhesive comprising the photocurable resin composition according to any one of aspects 1 to 6.
態様8.
態様７に記載の仮固定用接着剤と、前記仮固定用接着剤により接着される基材とを含む接着体。 Aspect 8.
An adhesive body comprising the temporary fixing adhesive according to aspect 7 and a base material to be bonded with the temporary fixing adhesive.
態様７に記載の仮固定用接着剤と、前記仮固定用接着剤により接着される基材とを含む接着体。 Aspect 8.
An adhesive body comprising the temporary fixing adhesive according to aspect 7 and a base material to be bonded with the temporary fixing adhesive.
態様9.
態様７に記載の仮固定用接着剤を用いた薄型ウエハの製造方法。 Aspect 9.
A method for manufacturing a thin wafer using the temporary fixing adhesive according to aspect 7.
態様７に記載の仮固定用接着剤を用いた薄型ウエハの製造方法。 Aspect 9.
A method for manufacturing a thin wafer using the temporary fixing adhesive according to aspect 7.
態様10.
態様１～６のいずれか一項に記載の光硬化性樹脂組成物を硬化した硬化体。 Aspect 10.
A cured product obtained by curing the photocurable resin composition according to any one of Aspects 1 to 6.
態様１～６のいずれか一項に記載の光硬化性樹脂組成物を硬化した硬化体。 Aspect 10.
A cured product obtained by curing the photocurable resin composition according to any one of Aspects 1 to 6.
本発明によれば、仮固定用途において、レーザー照射に対する適度な反応性により、レーザー照射時の穴のサイズを適切に制御することが可能であり、しかも優れた耐熱性をも呈する新規な仮固定用組成物が得られる。
According to the present invention, in temporary fixing applications, it is possible to appropriately control the hole size during laser irradiation due to moderate reactivity to laser irradiation, and a novel temporary fixing that also exhibits excellent heat resistance. A composition for use is obtained.
本明細書においては別段の断わりがない限りは、数値範囲はその上限値及び下限値を含むものとする。本明細書において単官能(メタ)アクリレートとは、１分子中に１個の(メタ)アクリロイル基を有する化合物をいう。多官能(メタ)アクリレートとは、１分子中に２個以上の(メタ)アクリロイル基を有する化合物をいう。ｎ官能(メタ)アクリレートとは、１分子中にｎ個の(メタ)アクリロイル基を有する化合物をいう。多官能(メタ)アクリレートにおける重合性官能基としては、アクリロイル基のみを有してもよく、メタクリロイル基のみを有してもよく、アクリロイル基とメタクリロイル基の両方を有してもよい。
In this specification, unless otherwise specified, numerical ranges include their upper and lower limits. In this specification, monofunctional (meth)acrylate refers to a compound having one (meth)acryloyl group in one molecule. Polyfunctional (meth)acrylate refers to a compound having two or more (meth)acryloyl groups in one molecule. The n-functional (meth)acrylate refers to a compound having n (meth)acryloyl groups in one molecule. The polymerizable functional group in the polyfunctional (meth)acrylate may have only an acryloyl group, only a methacryloyl group, or both an acryloyl group and a methacryloyl group.
本発明の実施形態では、（Ａ）ベンゾフェノン骨格、トリアゾール骨格、ヒドロキシフェニルトリアジン骨格、及びフェノール骨格のいずれも有さず、かつ(メタ)アクリロイル基を有する重合性成分と、（Ｂ）光重合開始剤と、（Ｃ）ベンゾフェノン骨格、トリアゾール骨格、ヒドロキシフェニルトリアジン骨格、及びフェノール骨格からなる群から選択される一種以上を有し、かつ重合性官能基を有する紫外線吸収剤とを含む、光硬化性樹脂組成物（以下、単に「組成物」又は「仮固定剤」とも称する）が提供される。当該組成物は、非重合性成分を含んでいてもよいが、その非重合性成分と（Ａ）成分との合計100質量部に対して、非重合性成分の量は15質量%未満である必要がある。なお本明細書において「非重合性成分」とは、（Ｂ）成分以外のもの、すなわち光重合開始剤として当該技術分野で用いられないものであると定義する。当該組成物は非重合性成分を含有しないことがより好ましい。非重合性成分の量が15質量%以上であると、耐熱性に問題が発生する。
In an embodiment of the present invention, (A) a polymerizable component that does not have a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, or a phenol skeleton and has a (meth)acryloyl group; and (B) photopolymerization initiation. and (C) a UV absorber having one or more selected from the group consisting of a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, and a phenol skeleton and having a polymerizable functional group. A resin composition (hereinafter also simply referred to as "composition" or "temporary fixing agent") is provided. The composition may contain a non-polymerizable component, but the amount of the non-polymerizable component is less than 15% by mass based on the total of 100 parts by mass of the non-polymerizable component and component (A). There is a need. In this specification, the term "non-polymerizable component" is defined as a component other than component (B), that is, a component that is not used as a photopolymerization initiator in the technical field. More preferably, the composition does not contain non-polymerizable components. If the amount of the non-polymerizable component is 15% by mass or more, a problem will occur in heat resistance.
当該組成物は、波長405nmかつ照度100mW/cm2である光を50秒間照射することで硬化体となる。当該硬化体に対し、波長355nm、スポット径40～300μm、パルスエネルギー50～250μJ、エネルギー密度248～11500mJ/cm2、好ましくは360～11500mJ/cm2の指向性エネルギーを、単位面積あたりの積算エネルギー照射量が150～1000mJ/cm2となるように、厚さ0.7mmのガラスを介して掃引照射した際に前記硬化体の表面を穿つように形成される略円形状のフットプリントを有する凹部の長径が、スポット径に対して20%以上の大きさであり、かつ深さが2.3μm以上であることを特徴とする。
The composition becomes a cured product by irradiating it with light having a wavelength of 405 nm and an illuminance of 100 mW/cm 2 for 50 seconds. Directional energy with a wavelength of 355 nm, a spot diameter of 40 to 300 μm, a pulse energy of 50 to 250 μJ, and an energy density of 248 to 11,500 mJ/cm 2 , preferably 360 to 11,500 mJ/cm 2 is applied to the cured body as the cumulative energy per unit area. A concave portion having a substantially circular footprint is formed so as to pierce the surface of the cured product when sweeping irradiation is applied through a glass having a thickness of 0.7 mm so that the irradiation amount is 150 to 1000 mJ/cm 2 . The long axis is 20% or more of the spot diameter, and the depth is 2.3 μm or more.
本組成物が含む（Ａ）成分である(メタ)アクリロイル基を有する重合性成分は、(メタ)アクリル重合骨格を形成する役割を担う。重合性成分としては、重合性有機化合物成分が好ましい。（Ａ）成分は好ましくは(メタ)アクリロイル基を2つ以上有する化合物を含んでよい。（Ａ）成分は、単官能(メタ)アクリレート、2官能(メタ)アクリレート、若しくは3官能以上の多官能(メタ)アクリレート、又はそれらの混合物であってよい。また好ましくは（Ａ）成分は、多官能(メタ)アクリレートと単官能(メタ)アクリレートの組み合わせ（より好ましくは2官能(メタ)アクリレートと単官能(メタ)アクリレートの組み合わせ）、多官能(メタ)アクリレートと重合性ポリマーの組み合わせ（より好ましくは2官能(メタ)アクリレートと重合性ポリマーの組み合わせ）、又は多官能(メタ)アクリレートと単官能(メタ)アクリレートと重合性ポリマーの組み合わせ（より好ましくは2官能(メタ)アクリレートと単官能(メタ)アクリレートと重合性ポリマーの組み合わせ）を含んでよい。（Ａ）成分は、ベンゾフェノン骨格、トリアゾール骨格、ヒドロキシフェニルトリアジン骨格、及びフェノール骨格のいずれも有さない（即ち、後述する（Ｃ）成分を含まない）。（Ａ）成分は、分子内に窒素原子を有しないことが好ましい。なお本明細書においてフェノール骨格とは、芳香環にヒドロキシル基が直接結合している構造のことを指す。すなわち、芳香環にヒドロキシル基では無い酸素原子が結合している構造については、たとえそれがフェノール類から誘導された構造であったとしても、本明細書における定義ではそれはフェノール骨格には含まれないものとする。
The (A) component contained in the present composition, a polymerizable component having a (meth)acryloyl group, plays a role in forming a (meth)acrylic polymer skeleton. As the polymerizable component, a polymerizable organic compound component is preferred. Component (A) may preferably include a compound having two or more (meth)acryloyl groups. Component (A) may be a monofunctional (meth)acrylate, a bifunctional (meth)acrylate, a trifunctional or more polyfunctional (meth)acrylate, or a mixture thereof. Preferably, component (A) is a combination of a polyfunctional (meth)acrylate and a monofunctional (meth)acrylate (more preferably a combination of a bifunctional (meth)acrylate and a monofunctional (meth)acrylate), a polyfunctional (meth)acrylate, and a polyfunctional (meth)acrylate. A combination of an acrylate and a polymerizable polymer (more preferably a combination of a bifunctional (meth)acrylate and a polymerizable polymer), or a combination of a polyfunctional (meth)acrylate, a monofunctional (meth)acrylate, and a polymerizable polymer (more preferably a combination of a difunctional (meth)acrylate and a polymerizable polymer) combinations of functional (meth)acrylates, monofunctional (meth)acrylates, and polymerizable polymers). Component (A) does not have a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, or a phenol skeleton (that is, it does not contain the component (C) described below). Component (A) preferably does not have a nitrogen atom in its molecule. Note that in this specification, the phenol skeleton refers to a structure in which a hydroxyl group is directly bonded to an aromatic ring. In other words, a structure in which an oxygen atom other than a hydroxyl group is bonded to an aromatic ring is not included in the phenol skeleton according to the definition herein, even if it is a structure derived from phenols. shall be taken as a thing.
（Ａ）成分が含みうる多官能(メタ)アクリレートとしては、剛直な構造を提供できる観点から、芳香族２官能(メタ)アクリレート、若しくは脂環式２官能(メタ)アクリレート、又はそれらの混合物が挙げられる。（Ａ）成分は、非環式多官能(メタ)アクリレートを含んでいてもよい。多官能(メタ)アクリレートは、モノマーであってもポリマーであってもよく、その混合物であってもよい。即ち、上述した重合性ポリマーは、多官能(メタ)アクリレートのポリマーであってよい。多官能(メタ)アクリレートモノマーの分子量は９００以下が好ましく、７００以下がより好ましく、５００以下が最も好ましく、４００以下が尚更好ましい。
As the polyfunctional (meth)acrylate that component (A) may contain, aromatic bifunctional (meth)acrylates, alicyclic bifunctional (meth)acrylates, or mixtures thereof are preferred from the viewpoint of providing a rigid structure. Can be mentioned. Component (A) may contain an acyclic polyfunctional (meth)acrylate. The polyfunctional (meth)acrylate may be a monomer, a polymer, or a mixture thereof. That is, the above-mentioned polymerizable polymer may be a polyfunctional (meth)acrylate polymer. The molecular weight of the polyfunctional (meth)acrylate monomer is preferably 900 or less, more preferably 700 or less, most preferably 500 or less, and even more preferably 400 or less.
芳香族２官能(メタ)アクリレートの例としては、９，９－ビス[４－(２－ヒドロキシＣ1～Ｃ20アルコキシ)フェニル]フルオレンジ(メタ)アクリレート、Ｃ1～Ｃ20アルコキシ化ビスフェノールＡジ(メタ)アクリレート、ベンジルジ(メタ)アクリレート、１，３－ビス(２－(メタ)アクリロイルオキシＣ1～Ｃ20アルキル)ベンゼン、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、又はそれらの構造異性体といったものが挙げられる。好ましくは、縮合環骨格、例えばフルオレン、インデン、インデセン、アントラセン、アズレン、トリフェニレンの骨格を有するジ(メタ)アクリレートが含まれていてよい。
Examples of aromatic difunctional (meth)acrylates include 9,9-bis[4-(2-hydroxyC 1 -C 20 alkoxy)phenyl]fluorene di(meth)acrylate, C 1 -C 20 alkoxylated bisphenol A Di(meth)acrylate, benzyl di(meth)acrylate, 1,3-bis(2-(meth)acryloyloxyC 1 -C 20 alkyl)benzene, 2,2-bis(4-(meth)acryloxydiethoxyphenyl) ) propane, or structural isomers thereof. Preferably, di(meth)acrylates having a fused ring skeleton, such as a fluorene, indene, indecene, anthracene, azulene, or triphenylene skeleton, may be included.
脂環式２官能(メタ)アクリレートの例としては、Ｃ1～Ｃ20アルコキシ化水添ビスフェノールＡジ(メタ)アクリレート、１，３－ジ(メタ)アクリロイルオキシアダマンタン、トリシクロＣ10～Ｃ20アルカンジメタノールジ(メタ)アクリレート、ジシクロＣ5～Ｃ20ジ(メタ)アクリレート、又はそれらの構造異性体等が挙げられる。
Examples of alicyclic difunctional (meth)acrylates include C 1 -C 20 alkoxylated hydrogenated bisphenol A di(meth)acrylate, 1,3-di(meth)acryloyloxyadamantane, tricycloC 10 -C 20 alkoxy Examples include candimethanol di(meth)acrylate, dicycloC 5 -C 20 di(meth)acrylate, and structural isomers thereof.
非環式２官能(メタ)アクリレートの例としては、１，３－ブタンジオールジ(メタ)アクリレート、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、１，１０－デカンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ネオペンチルグリコール変性トリメチロールプロパンジ(メタ)アクリレート、ステアリン酸変性ペンタエリストールジ(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、カプロラクトン変性ヒドロキシピバリン酸ネオペンチルグリコールジ(メタ)アクリレートといったものが挙げられる。
Examples of acyclic difunctional (meth)acrylates include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, stearic acid modified pentaacrylate Examples include erythrol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and caprolactone-modified neopentyl hydroxypivalate glycol di(meth)acrylate.
また（Ａ）成分は３官能以上の多官能(メタ)アクリレートを含んでいてもよい。３官能(メタ)アクリレートとしては、イソシアヌル酸エチレンオキサイド変性トリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリス［(メタ)アクリロイルオキシエチル］イソシアヌレート等が挙げられる。
In addition, component (A) may contain a trifunctional or more polyfunctional (meth)acrylate. Examples of trifunctional (meth)acrylates include isocyanuric acid ethylene oxide-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris[(meth)acryloyloxyethyl]isocyanurate, etc. Can be mentioned.
４官能以上の(メタ)アクリレートとしては、ジトリメチロールプロパンテトラ(メタ)アクリレート、ジメチロールプロパンテトラ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ペンタエリスリトールエトキシテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等が挙げられる。
Examples of (meth)acrylates having four or more functional groups include ditrimethylolpropane tetra(meth)acrylate, dimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, and dipentaerythritol pentaacrylate. Examples include (meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.
また（Ａ）成分が含んでもよい単官能(メタ)アクリレートとしては、分子量が５５０以下の単官能(メタ)アクリレートが好ましく、アルキル基を有する単官能アルキル(メタ)アクリレートがより好ましい。
Further, as the monofunctional (meth)acrylate that may be included in component (A), a monofunctional (meth)acrylate having a molecular weight of 550 or less is preferable, and a monofunctional alkyl (meth)acrylate having an alkyl group is more preferable.
当該アルキル基としては、直鎖状アルキル基、分岐鎖状アルキル基、及び脂環式アルキル基から選択される一種以上が好ましく、直鎖状アルキル基、及び分岐鎖状アルキル基から選択される一種以上がより好ましい。他成分との相溶性向上の観点からは、（Ａ）成分は長鎖かつ分岐鎖状又は環状のアルキル基を有することが好ましく、例えば炭素数１８～４０、より好ましくは炭素数１８～３２の、例えばイソステアリル基、イソテトラコサニル基（２－デシル－１－テトラデカニル基等）、イソトリアコンタニル基（２－テトラデシル－１－オクタデカニル基等）等の分岐鎖状アルキル基、又はシクロアルキル基を有することが好ましい。このような長鎖・高分子量かつ脂肪族炭化水素の性格の強い成分を用いること（更に好ましくは系全体の脂肪族炭化水素的性質を高めること）で、仮固定用組成物に求められる低揮発性、耐薬品性及び耐熱性を向上できる。
The alkyl group is preferably one or more selected from a linear alkyl group, a branched alkyl group, and an alicyclic alkyl group, and one selected from a linear alkyl group and a branched alkyl group. The above is more preferable. From the viewpoint of improving compatibility with other components, component (A) preferably has a long chain and branched or cyclic alkyl group, for example, a carbon number of 18 to 40, more preferably 18 to 32. , for example, a branched alkyl group such as an isostearyl group, an isotetracosanyl group (2-decyl-1-tetradecanyl group, etc.), an isotriacontanyl group (2-tetradecyl-1-octadecanyl group, etc.), or a cycloalkyl group. It is preferable to have a group. By using such components with long chains, high molecular weight, and strong aliphatic hydrocarbon characteristics (and preferably by increasing the aliphatic hydrocarbon characteristics of the entire system), the low volatility required for temporary fixing compositions can be achieved. properties, chemical resistance, and heat resistance.
（Ａ）成分としては、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート、ベヘニル(メタ)アクリレート、２－デシル－１－テトラデカニル(メタ)アクリレート、２－ドデシル－１－ヘキサデカニル(メタ)アクリレート、２－テトラデシル－１－オクタデカニル(メタ)アクリレートからなる群から選択される一種以上が好ましい。（Ａ）成分としては、下記式１の(メタ)アクリレートが好ましい。
Component (A) includes stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, 2-decyl-1-tetradecanyl (meth)acrylate, 2-dodecyl-1-hexadecanyl (meth)acrylate, One or more selected from the group consisting of 2-tetradecyl-1-octadecanyl (meth)acrylate is preferred. As component (A), (meth)acrylate of the following formula 1 is preferable.
Ｒ2が炭素数１８～３２のアルキル基である単官能アルキル(メタ)アクリレートとしては、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート、ノナデシル(メタ)アクリレート、エイコデシル(メタ)アクリレート、ベヘニル(メタ)アクリレート、２－デシル－１－テトラデカニル(メタ)アクリレート、２－テトラデシル－１－オクタデカニル(メタ)アクリレート等といった、直鎖状又は分岐鎖状のアルキル基を有する(メタ)アクリレートが好ましい。
Examples of monofunctional alkyl (meth)acrylates in which R 2 is an alkyl group having 18 to 32 carbon atoms include stearyl (meth)acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicodecyl (meth)acrylate, and behenyl ( Preferred are (meth)acrylates having a linear or branched alkyl group, such as meth)acrylate, 2-decyl-1-tetradecanyl(meth)acrylate, 2-tetradecyl-1-octadecanyl(meth)acrylate, and the like.
本明細書において重合性ポリマーとは、単官能(メタ)アクリレートモノマー以外、多官能(メタ)アクリレートモノマー以外の、(メタ)アクリロイル基を有する重合性成分をいう。重合性ポリマーとしては、多官能(メタ)アクリレートのポリマーが好ましい。多官能(メタ)アクリレートのポリマーとしては、根上工業社製「ＡＲＴ ＣＵＲＥ ＲＡ－３４１」、「ＡＰＢ－００１」等が挙げられる。
In this specification, the polymerizable polymer refers to a polymerizable component having a (meth)acryloyl group other than a monofunctional (meth)acrylate monomer or a polyfunctional (meth)acrylate monomer. As the polymerizable polymer, a polyfunctional (meth)acrylate polymer is preferred. Examples of polyfunctional (meth)acrylate polymers include "ART CURE RA-341" and "APB-001" manufactured by Negami Kogyo Co., Ltd.
好ましい実施形態においては、（Ａ）成分が含む(メタ)アクリロイル基を有する化合物の量が、（Ａ）成分全体の質量に対して20～100質量%の範囲であってよく、より好ましくは40～100質量%、60～100質量%の範囲であってよい。さらに好ましい実施形態では、多官能(メタ)アクリレートの量が、（Ａ）成分全体の質量に対して20～100質量%、より好ましくは50～100質量%の範囲であってよい。
In a preferred embodiment, the amount of the compound having a (meth)acryloyl group contained in component (A) may be in the range of 20 to 100% by mass, more preferably 40% by mass based on the total mass of component (A). ~100% by mass, and may range from 60 to 100% by mass. In a further preferred embodiment, the amount of polyfunctional (meth)acrylate may range from 20 to 100% by weight, more preferably from 50 to 100% by weight, based on the total weight of component (A).
好ましい実施形態では、（Ａ）成分が含む多官能(メタ)アクリレートモノマー（より好ましくは2官能(メタ)アクリレートモノマー）と、単官能(メタ)アクリレートモノマーと、重合性ポリマーとの質量比が、40～80:10～50:10～25の範囲であってよい。別の実施形態では、（Ａ）成分が多官能(メタ)アクリレートモノマーを含まず、単官能(メタ)アクリレートモノマーと、重合性ポリマーとを質量比で50～80:20～50の配合で含んでいてもよい。
In a preferred embodiment, the mass ratio of the polyfunctional (meth)acrylate monomer (more preferably bifunctional (meth)acrylate monomer), monofunctional (meth)acrylate monomer, and polymerizable polymer contained in component (A) is as follows: It may range from 40 to 80:10 to 50:10 to 25. In another embodiment, component (A) does not contain a polyfunctional (meth)acrylate monomer, but contains a monofunctional (meth)acrylate monomer and a polymerizable polymer in a mass ratio of 50 to 80:20 to 50. It's okay to stay.
好ましい実施形態においては、本組成物が含む非重合性成分の量が０質量%以上10質量%未満、若しくは０質量%以上5質量%未満であってよい。より好ましくは、本組成物は（Ｂ）成分を除き非重合性成分を含まなくてもよい。
In a preferred embodiment, the amount of the non-polymerizable component contained in the present composition may be 0% by mass or more and less than 10% by mass, or 0% by mass or more and less than 5% by mass. More preferably, the composition does not contain any non-polymerizable components except for component (B).
本組成物が含む（Ｂ）成分である光重合開始剤は、光照射を受けて（Ａ）成分の重合を開始できる物質である。好ましくは（Ｂ）成分は、光ラジカル重合開始剤であってよい。光ラジカル重合開始剤は例えば、紫外線或いは可視光線（例えば波長３５０～７００ｎｍ、好ましくは３６５～５００ｎｍ、より好ましくは３８５～４５０ｎｍ）の照射により分子が切断され、２つ以上のラジカルに分裂する化合物をいう。光ラジカル重合開始剤の例としては、ビス（２，４，６－トリメチルベンゾイル）フェニルフォスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス（η5－２，４－シクロペンタジエン－１－イル）－ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）－フェニル）チタニウム、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタン－１－オン、２－ジメチルアミノ－２－（４－メチルベンジル）－１－（４－モルフォリン－４－イルフェニル）－ブタン－１－オン、１－［４－（フェニルチオ）フェニル］－１，２－オクタンジオン ２－Ｏ－ベンゾイルオキシム、及び１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン １－（Ｏ－アセチルオキシム）が挙げられる。（Ｂ）成分は、これらのうち一種以上又は二種以上の組み合わせを含んでよい。
The photopolymerization initiator, which is component (B) contained in the present composition, is a substance that can initiate polymerization of component (A) when irradiated with light. Preferably, component (B) may be a radical photopolymerization initiator. A photoradical polymerization initiator is, for example, a compound whose molecules are cleaved and split into two or more radicals by irradiation with ultraviolet rays or visible light (for example, wavelength 350 to 700 nm, preferably 365 to 500 nm, more preferably 385 to 450 nm). say. Examples of photoradical polymerization initiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis(η 5 -2,4-cyclopentadiene). -1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane -1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one, 1-[4-(phenylthio)phenyl]- Examples include 1,2-octanedione 2-O-benzoyloxime, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime). . Component (B) may include one or more types or a combination of two or more types of these.
好ましくは（Ｂ）成分は、アシルフォスフィンオキサイド系化合物を含んでよい。好ましいアシルフォスフィンオキサイド系化合物としては、ビス（２，４，６－トリメチルベンゾイル）フェニルフォスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイドが挙げられる。光ラジカル重合開始剤としては、高感度であること、光褪色性を有することから深部硬化性に優れることに加え、ラジカルを発生させるための吸収波長領域が比較的長波長領域にまで拡がっていることが好ましい。上述した好ましい化合物では、吸収波長領域は波長約４４０ｎｍまでの範囲であり、後述するＵＶレーザー剥離工程で用いるＵＶ吸収剤の吸収波長領域との差が大きい。つまり、ＵＶ吸収剤によるＵＶ硬化阻害の度合いが小さく、より長波長の光でラジカル重合を開始できる。そのため、ＵＶ吸収剤の共存下であっても比較的高速度で効率良くラジカル重合を開始し、硬化できるという効果が得られる。
Preferably, component (B) may include an acylphosphine oxide compound. Preferred acylphosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. As a photo-radical polymerization initiator, it is highly sensitive, has photofading properties, and has excellent deep curing properties, and the absorption wavelength range for generating radicals extends to a relatively long wavelength range. It is preferable. In the preferred compound described above, the absorption wavelength range is up to about 440 nm, which is significantly different from the absorption wavelength range of the UV absorber used in the UV laser peeling process described below. In other words, the degree of inhibition of UV curing by the UV absorber is small, and radical polymerization can be initiated with light of a longer wavelength. Therefore, even in the coexistence of a UV absorber, radical polymerization can be initiated and cured efficiently at a relatively high rate.
好ましい実施形態においては、光ラジカル重合開始剤を吸光度から選定できる。具体的には、３００～５００ｎｍの波長領域に極大吸収をもたない溶媒（例えば、アセトニトリルやトルエンなど）に０．１質量％の濃度で溶解させた際に、３６５ｎｍの波長において吸光度が０．５以上であること、３８５ｎｍの波長において吸光度が０．５以上であること、及び４０５ｎｍの波長において吸光度が０．５以上であることのいずれかひとつ以上の条件を満たすような化合物の一種以上から、光ラジカル重合開始剤を選択できる。そのような条件を満たす化合物としては例えば、溶媒としてのアセトニトリルに対して０．１質量％の濃度で溶解させた際において、３６５ｎｍの波長において吸光度が０．５以上である１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン １－（Ｏ－アセチルオキシム）、３６５ｎｍと３８５ｎｍの波長において吸光度が０．５以上である１－[４－（フェニルチオ）フェニル]－１，２－オクタンジオン ２－Ｏ－ベンゾイルオキシム、３６５ｎｍと３８５ｎｍと４０５ｎｍの波長において吸光度が０．５以上であるビス（２，４，６－トリメチルベンゾイル）フェニルフォスフィンオキサイド及び２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイドが挙げられる。
In a preferred embodiment, the photoradical polymerization initiator can be selected based on absorbance. Specifically, when dissolved at a concentration of 0.1% by mass in a solvent that does not have maximum absorption in the wavelength region of 300 to 500 nm (for example, acetonitrile or toluene), the absorbance at a wavelength of 365 nm is 0. 5 or more, the absorbance is 0.5 or more at a wavelength of 385 nm, and the absorbance is 0.5 or more at a wavelength of 405 nm. , a photoradical polymerization initiator can be selected. An example of a compound that satisfies such conditions is 1-[9-ethyl, which has an absorbance of 0.5 or more at a wavelength of 365 nm when dissolved at a concentration of 0.1% by mass in acetonitrile as a solvent. -6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), 1-[4-(phenylthio) with absorbance of 0.5 or more at wavelengths of 365 nm and 385 nm phenyl]-1,2-octanedione 2-O-benzoyloxime, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide having an absorbance of 0.5 or more at wavelengths of 365 nm, 385 nm and 405 nm, and 2, 4,6-trimethylbenzoyldiphenylphosphine oxide is mentioned.
また、光ラジカル重合開始剤による硬化性とＵＶレーザー剥離を両立する観点からは、４００～５００ｎｍの範囲に吸収波長領域を有するビス（η5－２，４－シクロペンタジエン－１－イル）－ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）－フェニル）チタニウムも、光ラジカル重合開始剤として使用できる。
In addition, from the viewpoint of achieving both curability with a photoradical polymerization initiator and UV laser peeling, bis(η 5 -2,4-cyclopentadien-1-yl)-bis having an absorption wavelength range of 400 to 500 nm is recommended. (2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium can also be used as a photoradical polymerization initiator.
（Ｂ）光ラジカル重合開始剤としては、反応速度、硬化後の耐熱性、低アウトガス性、後述するＵＶレーザー剥離に用いるＵＶレーザーの波長とも該ＵＶレーザー剥離に用いるＵＶ吸収剤の吸収波長領域とも異なる領域での吸収特性を有する点で、アシルフォスフィンオキサイド系化合物、チタノセン系化合物、又はα－アミノアルキルフェノン系化合物から選択される一種以上が好ましい。また、後述する構造を有する仮固定用組成物の内の、ＵＶレーザー剥離プロセスに対応するための層ではない、加工対象基材のサポート基材との接合から加熱工程までの破損防止の仮固定用途のための樹脂組成物用光ラジカル重合開始剤としては、上記以外に、オキシムエステル系化合物を選択することもできる。
(B) As a photoradical polymerization initiator, the reaction rate, heat resistance after curing, low outgassing property, the wavelength of the UV laser used for UV laser peeling described below, and the absorption wavelength range of the UV absorber used for the UV laser peeling are also important. At least one selected from acylphosphine oxide compounds, titanocene compounds, and α-aminoalkylphenone compounds is preferred in that they have absorption characteristics in different regions. In addition, among the temporary fixing compositions having the structure described below, temporary fixing is not a layer compatible with the UV laser peeling process, and is used for temporary fixation to prevent damage from bonding the substrate to the support substrate to the heating process. In addition to the above, oxime ester compounds can also be selected as photoradical polymerization initiators for resin compositions.
アシルフォスフィンオキサイド系化合物としては、ビス（２，４，６－トリメチルベンゾイル）フェニルフォスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド等が挙げられる。これらの中では、ビス（２，４，６－トリメチルベンゾイル）フェニルフォスフィンオキサイドが特に好ましい。
Examples of the acylphosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like. Among these, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is particularly preferred.
チタノセン系化合物としては、ビス（η5－２，４－シクロペンタジエン－１－イル）－ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）－フェニル）チタニウムが挙げられる。
Examples of titanocene compounds include bis(η 5 -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium.
α－アミノアルキルフェノン系化合物としては、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタン－１－オン、２－ジメチルアミノ－２－（４－メチルベンジル）－１－（４－モルフォリン－４－イルフェニル）－ブタン－１－オン等が挙げられる。
Examples of α-aminoalkylphenone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1 -(4-morpholin-4-ylphenyl)-butan-1-one and the like.
オキシムエステル系化合物としては、１－［４－（フェニルチオ）フェニル］－１，２－オクタンジオン ２－Ｏ－ベンゾイルオキシム、１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン １－（Ｏ－アセチルオキシム）等が挙げられる。これらの中では、１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン １－（Ｏ－アセチルオキシム）が好ましい。
Examples of oxime ester compounds include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]ethanone 1-(O-acetyloxime) and the like. Among these, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) is preferred.
（Ｂ）光ラジカル重合開始剤の使用量は、反応速度及び硬化後の耐熱性、低アウトガス性の点で、（Ａ）成分１００質量部に対して、０．０１～５質量部が好ましく、０．１～１質量部がより好ましい。（Ｂ）成分が０．０１質量部以上であると十分な硬化性が得られ、５質量部以下だと低アウトガス性及び耐熱性が損なわれにくい効果が得られる。
The amount of the radical photopolymerization initiator (B) used is preferably 0.01 to 5 parts by mass based on 100 parts by mass of component (A) in terms of reaction rate, heat resistance after curing, and low outgas properties. More preferably 0.1 to 1 part by mass. When the component (B) is 0.01 parts by mass or more, sufficient curability can be obtained, and when it is 5 parts by mass or less, low outgas properties and heat resistance are less likely to be impaired.
本組成物が含む（Ｃ）成分である重合性官能基を有する紫外線吸収剤（ＵＶ吸収剤）は、紫外線或いは可視光線のレーザーの照射により分子が切断されて分解・気化し、該分解・気化がサポート基材（又は支持体）と仮固定剤の界面で発生することにより、剥離工程直前まで維持されていた仮固定剤・サポート基材（又は支持体）間の接着力を喪失させる化合物を指す。（Ｃ）成分は、ベンゾフェノン骨格、トリアゾール骨格、ヒドロキシフェニルトリアジン骨格、及びフェノール骨格（好ましくはヒンダードフェノール骨格）からなる群から選択される一種以上を有する化合物である。これらの骨格を有するのは、ＵＶ吸収波長領域のＵＶレーザー波長との重なりの度合い、同波長でのＵＶ吸収特性、低アウトガス性、耐熱性を得るためである。（Ｃ）成分が有する重合性官能基は、(メタ)アクリロイル基であることが好ましい。
The ultraviolet absorber (UV absorber) having a polymerizable functional group, which is the component (C) contained in this composition, has molecules that are cut and decomposed and vaporized by irradiation with ultraviolet or visible light laser. is generated at the interface between the support substrate (or substrate) and the temporary fixing agent, thereby causing a loss of the adhesive force between the temporary fixation agent and the support substrate (or substrate) that was maintained until just before the peeling process. Point. Component (C) is a compound having one or more types selected from the group consisting of a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, and a phenol skeleton (preferably a hindered phenol skeleton). The purpose of having these skeletons is to obtain a degree of overlap between the UV absorption wavelength region and the UV laser wavelength, UV absorption characteristics at the same wavelength, low outgassing properties, and heat resistance. The polymerizable functional group contained in component (C) is preferably a (meth)acryloyl group.
（Ｃ）成分の例としては、2-[2-ヒドロキシ-5-[2-(（メタ）アクリロイルオキシ)エチル]フェニル]-2H-ベンゾトリアゾール、2-［1-（2-ヒドロキシ-3，5-ジ-tert-ペンチルフェニル）エチル］-4，6-ジ-tert-ペンチルフェニル（メタ）アクリレート、2-(2-（メタ）アクリロイルオキシ,5-メチル)フェニル-2H-ベンゾトリアゾール、1,1-ビス-[2-（メタ）アクリロイルオキシ,3-(2H-ベンゾトリアゾール-2-イル),5-ターシャリーオクチル]メタン、2,2’-ジヒドロキシ-4,4’-ジ（メタ）アクリロイルオキシベンゾフェノンからなる群の一種以上が、樹脂成分との相溶性、ＵＶ吸収特性、低アウトガス性、耐熱性の点から特に好ましい。
Examples of component (C) include 2-[2-hydroxy-5-[2-((meth)acryloyloxy)ethyl]phenyl]-2H-benzotriazole, 2-[1-(2-hydroxy-3, 5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl (meth)acrylate, 2-(2-(meth)acryloyloxy,5-methyl)phenyl-2H-benzotriazole, 1 ,1-bis-[2-(meth)acryloyloxy,3-(2H-benzotriazol-2-yl),5-tert-octyl]methane, 2,2'-dihydroxy-4,4'-di(meth) ) One or more members of the group consisting of acryloyloxybenzophenone are particularly preferred from the viewpoint of compatibility with the resin component, UV absorption properties, low outgassing properties, and heat resistance.
本明細書における硬化体のＵＶ透過率は、反射率測定分光法により得られる値である。具体的には、透過率は、下記の条件にて、ＰＥＴ樹脂のシートに挟んで作製した厚さ約５０μｍの硬化体のフィルムを用い、反射率分光測定装置（日本分光株式会社製Ｖ－６５０）を使用して得られる。
The UV transmittance of the cured product in this specification is a value obtained by reflectance measurement spectroscopy. Specifically, the transmittance was measured using a reflectance spectrometer (V-650 manufactured by JASCO Corporation) using a cured film with a thickness of approximately 50 μm sandwiched between PET resin sheets under the following conditions. ) is obtained using
セル長：１０mm
測光モード：T (Transmittance)
測定範囲：４５０-２００nm
データ取込間隔：１nm
UV/visバンド幅：２.０nm
レスポンス：medium
走査速度：４０nm/min
光源切換：３４０nm
光源：D２/WI
フィルタ切換：ステップ
補正：ベースライン Cell length: 10mm
Metering mode: T (Transmittance)
Measurement range: 450-200nm
Data acquisition interval: 1nm
UV/vis bandwidth: 2.0nm
Response: medium
Scanning speed: 40nm/min
Light source switching: 340nm
Light source: D2/WI
Filter switching: Step correction: Baseline
測光モード：T (Transmittance)
測定範囲：４５０-２００nm
データ取込間隔：１nm
UV/visバンド幅：２.０nm
レスポンス：medium
走査速度：４０nm/min
光源切換：３４０nm
光源：D２/WI
フィルタ切換：ステップ
補正：ベースライン Cell length: 10mm
Metering mode: T (Transmittance)
Measurement range: 450-200nm
Data acquisition interval: 1nm
UV/vis bandwidth: 2.0nm
Response: medium
Scanning speed: 40nm/min
Light source switching: 340nm
Light source: D2/WI
Filter switching: Step correction: Baseline
（Ｃ）成分の量は、（Ａ）成分１００質量部に対して０．０１～１０質量部が好ましく、０．５～７質量部がより好ましい。０．０１質量部以上だと十分なＵＶレーザー剥離速度が得られ、１０質量部以下だと低アウトガス性及び耐熱性が損なわれにくい効果が得られる。
The amount of component (C) is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, per 100 parts by weight of component (A). When the amount is 0.01 parts by mass or more, a sufficient UV laser peeling rate can be obtained, and when it is 10 parts by mass or less, the effect of low outgassing property and heat resistance being less likely to be impaired can be obtained.
本明細書における重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法によって測定される標準ポリスチレン換算の値である。具体的には、重量平均分子量は、下記の条件にて、溶剤としてテトラヒドロフランを用い、ＧＰＣシステム（東ソー株式会社製ＳＣ－８０１０）を使用し、市販の標準ポリスチレンで検量線を作成して求められる。
The weight average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) in terms of standard polystyrene. Specifically, the weight average molecular weight is determined by creating a calibration curve with commercially available standard polystyrene using a GPC system (SC-8010 manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent under the following conditions. .
流速：１．０ｍｌ／ｍｉｎ
設定温度：４０℃
カラム構成：東ソー株式会社製「ＴＳＫ ｇｕａｒｄｃｏｌｕｍｎ ＭＰ（×Ｌ）」６．０ｍｍＩＤ×４．０ｃｍ１本、及び東ソー株式会社製「ＴＳＫ－ＧＥＬＭＵＬＴＩＰＯＲＥＨＸＬ－Ｍ」７．８ｍｍＩＤ×３０．０ｃｍ（理論段数１６，０００段）２本、計３本（全体として理論段数３２，０００段）
サンプル注入量：１００μｌ（試料液濃度１ｍｇ／ｍｌ）
送液圧力：３９ｋｇ／ｃｍ2
検出器：ＲＩ検出器（示差屈折率検出器） Flow rate: 1.0ml/min
Set temperature: 40℃
Column configuration: one “TSK guardcolumn MP (xL)” 6.0 mm ID x 4.0 cm manufactured by Tosoh Corporation, and “TSK-GELMULTIPOREHXL-M” 7.8 mm ID x 30.0 cm manufactured by Tosoh Corporation (number of theoretical plates 16,000) (32,000 theoretical plates in total)
Sample injection volume: 100μl (sample solution concentration 1mg/ml)
Liquid feeding pressure: 39kg/cm 2
Detector: RI detector (differential refractive index detector)
設定温度：４０℃
カラム構成：東ソー株式会社製「ＴＳＫ ｇｕａｒｄｃｏｌｕｍｎ ＭＰ（×Ｌ）」６．０ｍｍＩＤ×４．０ｃｍ１本、及び東ソー株式会社製「ＴＳＫ－ＧＥＬＭＵＬＴＩＰＯＲＥＨＸＬ－Ｍ」７．８ｍｍＩＤ×３０．０ｃｍ（理論段数１６，０００段）２本、計３本（全体として理論段数３２，０００段）
サンプル注入量：１００μｌ（試料液濃度１ｍｇ／ｍｌ）
送液圧力：３９ｋｇ／ｃｍ2
検出器：ＲＩ検出器（示差屈折率検出器） Flow rate: 1.0ml/min
Set temperature: 40℃
Column configuration: one “TSK guardcolumn MP (xL)” 6.0 mm ID x 4.0 cm manufactured by Tosoh Corporation, and “TSK-GELMULTIPOREHXL-M” 7.8 mm ID x 30.0 cm manufactured by Tosoh Corporation (number of theoretical plates 16,000) (32,000 theoretical plates in total)
Sample injection volume: 100μl (sample solution concentration 1mg/ml)
Liquid feeding pressure: 39kg/cm 2
Detector: RI detector (differential refractive index detector)
本発明の或る実施形態では、上述した組成物の硬化体も提供できる。そのような硬化は、後述する光源を用いて行ってよい。当該硬化体を、厚さ５０μｍの硬化フィルムの形態としたときには、以下の条件をひとつ以上満たすことが好ましく、全て満たすことがより好ましい。以下の条件は、例えばＵＶ吸収剤を用いることにより満たすことができる。
・該硬化フィルムの光透過率の内、硬化に用いる光源の波長の内の３９５ｎｍ以上の波長領域の光透過率が７０％以上であること。
・該硬化フィルムの光透過率の内、硬化に用いる光源の波長の内の３８５ｎｍ以上３９５ｎｍ未満の波長領域の光透過率が２０％以上であること。
・該硬化フィルムの光透過率の内、ＵＶレーザー剥離に用いるＵＶレーザーの波長（３５５ｎｍ）での光透過率が１％以下であること。
これらの条件を満たすことで、実用上十分に高い硬化速度とＵＶレーザー剥離速度を両立させることが可能である。更には、十分に高い硬化速度とＵＶレーザー剥離速度の両立に加え、硬化後の加熱条件下における質量減少の割合を低下（又は高温真空下におけるアウトガス量を低減）させることができる。このような特性を持つ仮固定剤は、特に薄化後の裏面工程においてイオン注入、アニーリングやスパッタによる電極形成といった高温真空プロセスを含むプロセスに、好適に使用することができる。なお、本発明の特徴であるレーザー照射を受ける対象となる硬化体は、波長405nmかつ照度100mW/cm2である光を50秒間照射して作製するものである。 In some embodiments of the present invention, a cured product of the composition described above can also be provided. Such curing may be performed using a light source described below. When the cured product is in the form of a cured film with a thickness of 50 μm, it is preferable that one or more of the following conditions be satisfied, and more preferably that all of the following conditions are satisfied. The following conditions can be met, for example, by using a UV absorber.
- Of the light transmittance of the cured film, the light transmittance in a wavelength region of 395 nm or more among the wavelengths of the light source used for curing is 70% or more.
- Of the light transmittance of the cured film, the light transmittance in the wavelength range of 385 nm or more and less than 395 nm among the wavelengths of the light source used for curing is 20% or more.
- Of the light transmittance of the cured film, the light transmittance at the wavelength (355 nm) of the UV laser used for UV laser peeling is 1% or less.
By satisfying these conditions, it is possible to achieve both a practically high curing rate and a UV laser peeling rate. Furthermore, in addition to achieving both a sufficiently high curing rate and a UV laser peeling rate, it is possible to reduce the rate of mass loss under heating conditions after curing (or reduce the amount of outgassing under high-temperature vacuum conditions). A temporary fixing agent having such characteristics can be suitably used in a process including a high-temperature vacuum process such as ion implantation, annealing, and electrode formation by sputtering, especially in the back surface process after thinning. The cured product to be subjected to laser irradiation, which is a feature of the present invention, is produced by irradiating it with light having a wavelength of 405 nm and an illuminance of 100 mW/cm 2 for 50 seconds.
・該硬化フィルムの光透過率の内、硬化に用いる光源の波長の内の３９５ｎｍ以上の波長領域の光透過率が７０％以上であること。
・該硬化フィルムの光透過率の内、硬化に用いる光源の波長の内の３８５ｎｍ以上３９５ｎｍ未満の波長領域の光透過率が２０％以上であること。
・該硬化フィルムの光透過率の内、ＵＶレーザー剥離に用いるＵＶレーザーの波長（３５５ｎｍ）での光透過率が１％以下であること。
これらの条件を満たすことで、実用上十分に高い硬化速度とＵＶレーザー剥離速度を両立させることが可能である。更には、十分に高い硬化速度とＵＶレーザー剥離速度の両立に加え、硬化後の加熱条件下における質量減少の割合を低下（又は高温真空下におけるアウトガス量を低減）させることができる。このような特性を持つ仮固定剤は、特に薄化後の裏面工程においてイオン注入、アニーリングやスパッタによる電極形成といった高温真空プロセスを含むプロセスに、好適に使用することができる。なお、本発明の特徴であるレーザー照射を受ける対象となる硬化体は、波長405nmかつ照度100mW/cm2である光を50秒間照射して作製するものである。 In some embodiments of the present invention, a cured product of the composition described above can also be provided. Such curing may be performed using a light source described below. When the cured product is in the form of a cured film with a thickness of 50 μm, it is preferable that one or more of the following conditions be satisfied, and more preferably that all of the following conditions are satisfied. The following conditions can be met, for example, by using a UV absorber.
- Of the light transmittance of the cured film, the light transmittance in a wavelength region of 395 nm or more among the wavelengths of the light source used for curing is 70% or more.
- Of the light transmittance of the cured film, the light transmittance in the wavelength range of 385 nm or more and less than 395 nm among the wavelengths of the light source used for curing is 20% or more.
- Of the light transmittance of the cured film, the light transmittance at the wavelength (355 nm) of the UV laser used for UV laser peeling is 1% or less.
By satisfying these conditions, it is possible to achieve both a practically high curing rate and a UV laser peeling rate. Furthermore, in addition to achieving both a sufficiently high curing rate and a UV laser peeling rate, it is possible to reduce the rate of mass loss under heating conditions after curing (or reduce the amount of outgassing under high-temperature vacuum conditions). A temporary fixing agent having such characteristics can be suitably used in a process including a high-temperature vacuum process such as ion implantation, annealing, and electrode formation by sputtering, especially in the back surface process after thinning. The cured product to be subjected to laser irradiation, which is a feature of the present invention, is produced by irradiating it with light having a wavelength of 405 nm and an illuminance of 100 mW/cm 2 for 50 seconds.
組成物の塗布方法としては、スピンコート、スクリーン印刷、各種コーター等の公知の塗布方法を用いることができる。本発明の組成物の粘度は、２３℃（大気圧下）において、塗布性や作業性の点で、１００ｍＰａ・ｓ以上が好ましく、５００ｍＰａ・ｓ以上がより好ましく、１０００ｍＰａ・ｓ以上が最も好ましい。本発明の組成物の粘度は、塗布性や作業性の点で、１００００ｍＰａ・ｓ以下が好ましく、５０００ｍＰａ・ｓ以下がより好ましく、４０００ｍＰａ・ｓ以下が最も好ましい。１００ｍＰａ・ｓ以上だと塗布性、特にスピンコートによる塗布性に優れる。１００００ｍＰａ・ｓ以下だと作業性に優れる。粘度の測定は、公知の粘度計により行うことができる。
As a method for applying the composition, known methods such as spin coating, screen printing, and various coaters can be used. The viscosity of the composition of the present invention is preferably 100 mPa·s or more, more preferably 500 mPa·s or more, and most preferably 1000 mPa·s or more at 23° C. (under atmospheric pressure) in terms of coatability and workability. The viscosity of the composition of the present invention is preferably 10,000 mPa·s or less, more preferably 5,000 mPa·s or less, and most preferably 4,000 mPa·s or less in terms of applicability and workability. When the pressure is 100 mPa·s or more, the coating properties, particularly the coating properties by spin coating, are excellent. Workability is excellent when the pressure is 10,000 mPa·s or less. The viscosity can be measured using a known viscometer.
スピンコートとは、例えば、基板に液状組成物を滴下し、基板を所定の回転数で回転させることにより、組成物を基板表面に塗布する方法である。スピンコートにより、高品質な塗膜を効率良く生産できる。
Spin coating is a method of applying the composition to the surface of the substrate by, for example, dropping a liquid composition onto the substrate and rotating the substrate at a predetermined number of rotations. Spin coating enables efficient production of high-quality coatings.
本組成物は、仮固定用樹脂組成物、仮固定用接着剤、粘着シート、又は電子デバイス製造用仮固定用接着剤として使用できる。本明細書においては、仮固定用組成物、仮固定用樹脂組成物、仮固定用接着剤を、仮固定剤と総称することもある。
The present composition can be used as a temporary fixing resin composition, a temporary fixing adhesive, a pressure-sensitive adhesive sheet, or a temporary fixing adhesive for manufacturing electronic devices. In this specification, the temporary fixing composition, the temporary fixing resin composition, and the temporary fixing adhesive may be collectively referred to as a temporary fixing agent.
本組成物を用いて加工対象基材と光学的に透明なサポート基材（又は支持体）を接着する際は、可視光線若しくは紫外線（波長又は中心波長３６５～４０５ｎｍ）においてエネルギー量が１～２００００ｍＪ／ｃｍ2になるように照射することが好ましい。エネルギー量が１ｍＪ／ｃｍ2以上だと十分な接着性が得られ、２００００ｍＪ／ｃｍ2以下だと生産性が優れ、光ラジカル重合開始剤からの分解生成物が発生しにくく、アウトガスの発生が抑制される。生産性、接着性、低アウトガス性、易剥離性の点で、１０００～１００００ｍＪ／ｃｍ2であることが好ましい。
When bonding a substrate to be processed and an optically transparent support substrate (or support) using this composition, the amount of energy in visible light or ultraviolet rays (wavelength or center wavelength 365 to 405 nm) is 1 to 20,000 mJ. It is preferable to irradiate so that the amount of radiation becomes /cm 2 . When the energy amount is 1 mJ/cm 2 or more, sufficient adhesion is obtained, and when it is 20,000 mJ/cm 2 or less, productivity is excellent, and decomposition products from the photoradical polymerization initiator are difficult to generate, suppressing outgas generation. be done. In terms of productivity, adhesion, low outgas properties, and easy peelability, it is preferably 1000 to 10000 mJ/cm 2 .
本組成物によって接着される基材は、特に制限はないものの、少なくとも一方の基材は光を透過する透明基材が好ましい。透明基材としては、水晶、ガラス、石英、フッ化カルシウム、フッ化マグネシウム等の無機基材、プラスチック等の有機基材等が挙げられる。これらの中では、汎用性があり、大きい効果が得られる点で、無機基材が好ましい。無機基材の中では、ガラス、及び石英から選択される一種以上が好ましい。なお、本発明の特徴であるレーザー照射条件は、基材として厚さ0.7mmのガラスを選択した場合のものである。
Although there are no particular limitations on the substrates to be bonded with the present composition, it is preferable that at least one of the substrates be a transparent substrate that transmits light. Examples of the transparent substrate include inorganic substrates such as crystal, glass, quartz, calcium fluoride, and magnesium fluoride, and organic substrates such as plastic. Among these, inorganic base materials are preferred because they are versatile and can provide great effects. Among the inorganic base materials, one or more selected from glass and quartz is preferred. Note that the laser irradiation conditions that characterize the present invention are those when glass with a thickness of 0.7 mm is selected as the base material.
本組成物は光硬化型であってよく、それにより提供される硬化体は優れた耐熱性及び剥離性を有する。本発明の組成物の硬化体は一実施形態において、高温で曝露されてもアウトガス量が少なく、種々の光学部品や光学デバイス、電子部品の接合、封止、コーティングに好適である。本発明の組成物は、耐溶剤性、耐熱性、接着性等といった、多岐にわたる耐久性が必要とされる用途、特に半導体製造プロセス用途に適している。
The present composition may be photocurable, and the cured product provided thereby has excellent heat resistance and peelability. In one embodiment, the cured product of the composition of the present invention has a small amount of outgassing even when exposed to high temperatures, and is suitable for joining, sealing, and coating various optical components, optical devices, and electronic components. The composition of the present invention is suitable for applications that require a wide variety of durability such as solvent resistance, heat resistance, adhesiveness, etc., particularly for semiconductor manufacturing process applications.
本組成物の硬化体は、室温から高温までの幅広い温度範囲におけるプロセスに使用できる。プロセス中の加熱温度は、３５０℃以下が好ましく、３００℃以下がより好ましい。好ましい実施形態においては、当該硬化体の加熱質量減少率が２％となる温度が、２５０℃以上であってよい。本組成物により接着した接着体は、高いせん断接着力を有するため薄化工程等には耐えることができ、絶縁膜形成等の加熱工程を経た後には容易に剥離できる。高温で使用する場合、本組成物の硬化体は、例えば、好ましくは２００℃以上、より好ましくは２５０℃以上の高温のプロセスで使用できる。
The cured product of this composition can be used in processes in a wide temperature range from room temperature to high temperatures. The heating temperature during the process is preferably 350°C or lower, more preferably 300°C or lower. In a preferred embodiment, the temperature at which the heating mass reduction rate of the cured product is 2% may be 250° C. or higher. The bonded body bonded with the present composition has high shear adhesive strength and can withstand thinning processes, etc., and can be easily peeled off after passing through a heating process such as forming an insulating film. When used at high temperatures, the cured product of the present composition can be used in a high temperature process, for example, preferably at 200°C or higher, more preferably at 250°C or higher.
或る実施形態では、本組成物を接着剤として用いることにより基材を接着した接着体も提供される。当該接着体は、外力を加えることにより剥離できる。例えば、刃物、シート又はワイヤーを、接合部分に差し込むことにより剥離できる。あるいは、当該接着体の光学的に透明な基材側からＵＶレーザー又はＩＲレーザーを全面に走査するように照射することにより剥離することも可能である。
In some embodiments, an adhesive body is also provided in which substrates are adhered by using the present composition as an adhesive. The adhesive body can be peeled off by applying external force. For example, it can be peeled off by inserting a knife, sheet, or wire into the joint. Alternatively, it is also possible to peel off the adhesive by irradiating the optically transparent base material side of the adhesive body with a UV laser or an IR laser so as to scan the entire surface.
以下、実施例及び比較例に基づき本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。
EXAMPLES Hereinafter, the present invention will be explained in more detail based on Examples and Comparative Examples, but the present invention is not limited thereto.
特記しない限り、２３℃、湿度５０％で実験した。下記表に示す組成（単位は質量部）の硬化性樹脂組成物（以下、液状樹脂組成物ということもある）を調製し、評価した。各成分としては、以下の化合物を選択した。
Unless otherwise specified, experiments were conducted at 23° C. and 50% humidity. Curable resin compositions (hereinafter also referred to as liquid resin compositions) having the compositions shown in the table below (unit: parts by mass) were prepared and evaluated. The following compounds were selected as each component.
（組成）
（Ａ）成分として以下を用いた。
A-BPEF-2: 9,9-ビス[4-(2-ヒドロキシエトキシ)フェニル]フルオレンジアクリレート（新中村化学工業社製「NKエステルA-BPEF-2」）
A-BPE-2: エトキシ化ビスフェノールAジアクリレート（新中村化学工業社製「NKエステルA-BPE-2」、下記構造式においてR=-CH2CH2O-、m=n=1）
ABE-300: エトキシ化ビスフェノールAジアクリレート（新中村化学工業社製「NKエステルABE-300」、下記構造式においてR=-CH2CH2O-、m+n≒3） (composition)
The following was used as component (A).
A-BPEF-2: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate (“NK ester A-BPEF-2” manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-BPE-2: Ethoxylated bisphenol A diacrylate (“NK ester A-BPE-2” manufactured by Shin-Nakamura Chemical Co., Ltd., R=-CH 2 CH 2 O-, m=n=1 in the following structural formula)
ABE-300: Ethoxylated bisphenol A diacrylate (“NK Ester ABE-300” manufactured by Shin-Nakamura Chemical Co., Ltd., R=-CH 2 CH 2 O-, m+n≒3 in the following structural formula)
（Ａ）成分として以下を用いた。
A-BPEF-2: 9,9-ビス[4-(2-ヒドロキシエトキシ)フェニル]フルオレンジアクリレート（新中村化学工業社製「NKエステルA-BPEF-2」）
A-BPE-2: エトキシ化ビスフェノールAジアクリレート（新中村化学工業社製「NKエステルA-BPE-2」、下記構造式においてR=-CH2CH2O-、m=n=1）
ABE-300: エトキシ化ビスフェノールAジアクリレート（新中村化学工業社製「NKエステルABE-300」、下記構造式においてR=-CH2CH2O-、m+n≒3） (composition)
The following was used as component (A).
A-BPEF-2: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate (“NK ester A-BPEF-2” manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-BPE-2: Ethoxylated bisphenol A diacrylate (“NK ester A-BPE-2” manufactured by Shin-Nakamura Chemical Co., Ltd., R=-CH 2 CH 2 O-, m=n=1 in the following structural formula)
ABE-300: Ethoxylated bisphenol A diacrylate (“NK Ester ABE-300” manufactured by Shin-Nakamura Chemical Co., Ltd., R=-CH 2 CH 2 O-, m+n≒3 in the following structural formula)
HBPE-4: EO変性水添ビスフェノールAジアクリレート（第一工業製薬社製「HBPE-4」、m+n≒4）
HX-620: カプロラクトン変性ヒドロキシピバリン酸ネオペンチルグリコールジアクリレート（日本化薬社製「カヤラッドHX-620」、m+n≒4）
HX-220: カプロラクトン変性ヒドロキシピバリン酸ネオペンチルグリコールジアクリレート（日本化薬社製「カヤラッドHX-220」、m+n≒2）
DDDA: 1,10-デカンジオールジアクリレート（新中村化学工業社製「A-DOD-N」）
DTDA: 2-デシル-1-テトラデカニルアクリレート（共栄社化学社製「ライトアクリレートDTD-A」）
A-DCP: トリシクロデカンジメタノールジアクリレート（新中村化学工業社製「NKエステルA-DCP」）
ISTA: イソステアリルアクリレート（大阪有機化学工業社製「ISTA」）
DCP: トリシクロデカンジメタノールジメタクリレート（新中村化学工業社製「NKエステルDCP」）
M-111: ノニルフェノールEO変性アクリレート（東亞合成社製「アロニックスM-111」、n≒1）
M-113:ノニルフェノールEO変性アクリレート（東亞合成社製「アロニックスM-113」、n≒4）
RA-341: 多官能メタクリレートポリマー（根上工業社製「ART CURE RA-341」、重量平均分子量80,000、３官能以上のメタクリレートポリマー）
APB-001: 多官能アクリレートポリマー（根上工業社製「APB-001」、重量平均分子量72,000） HBPE-4: EO-modified hydrogenated bisphenol A diacrylate (“HBPE-4” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., m+n≒4)
HX-620: Caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate (Nippon Kayaku Co., Ltd. "Kayarad HX-620", m+n≒4)
HX-220: Caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate (Nippon Kayaku Co., Ltd. "Kayarad HX-220", m+n≒2)
DDDA: 1,10-decanediol diacrylate (“A-DOD-N” manufactured by Shin-Nakamura Chemical Co., Ltd.)
DTDA: 2-decyl-1-tetradecanyl acrylate (“Light Acrylate DTD-A” manufactured by Kyoeisha Chemical Co., Ltd.)
A-DCP: Tricyclodecane dimethanol diacrylate (“NK ester A-DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.)
ISTA: Isostearyl acrylate (“ISTA” manufactured by Osaka Organic Chemical Industry Co., Ltd.)
DCP: Tricyclodecane dimethanol dimethacrylate (“NK Ester DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.)
M-111: Nonylphenol EO modified acrylate (“Aronix M-111” manufactured by Toagosei Co., Ltd., n≒1)
M-113: Nonylphenol EO modified acrylate (“Aronix M-113” manufactured by Toagosei Co., Ltd., n≒4)
RA-341: Multifunctional methacrylate polymer (“ART CURE RA-341” manufactured by Negami Kogyo Co., Ltd., weight average molecular weight 80,000, trifunctional or higher functional methacrylate polymer)
APB-001: Multifunctional acrylate polymer (“APB-001” manufactured by Negami Kogyo Co., Ltd., weight average molecular weight 72,000)
HX-620: カプロラクトン変性ヒドロキシピバリン酸ネオペンチルグリコールジアクリレート（日本化薬社製「カヤラッドHX-620」、m+n≒4）
HX-220: カプロラクトン変性ヒドロキシピバリン酸ネオペンチルグリコールジアクリレート（日本化薬社製「カヤラッドHX-220」、m+n≒2）
DDDA: 1,10-デカンジオールジアクリレート（新中村化学工業社製「A-DOD-N」）
DTDA: 2-デシル-1-テトラデカニルアクリレート（共栄社化学社製「ライトアクリレートDTD-A」）
A-DCP: トリシクロデカンジメタノールジアクリレート（新中村化学工業社製「NKエステルA-DCP」）
ISTA: イソステアリルアクリレート（大阪有機化学工業社製「ISTA」）
DCP: トリシクロデカンジメタノールジメタクリレート（新中村化学工業社製「NKエステルDCP」）
M-111: ノニルフェノールEO変性アクリレート（東亞合成社製「アロニックスM-111」、n≒1）
M-113:ノニルフェノールEO変性アクリレート（東亞合成社製「アロニックスM-113」、n≒4）
RA-341: 多官能メタクリレートポリマー（根上工業社製「ART CURE RA-341」、重量平均分子量80,000、３官能以上のメタクリレートポリマー）
APB-001: 多官能アクリレートポリマー（根上工業社製「APB-001」、重量平均分子量72,000） HBPE-4: EO-modified hydrogenated bisphenol A diacrylate (“HBPE-4” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., m+n≒4)
HX-620: Caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate (Nippon Kayaku Co., Ltd. "Kayarad HX-620", m+n≒4)
HX-220: Caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate (Nippon Kayaku Co., Ltd. "Kayarad HX-220", m+n≒2)
DDDA: 1,10-decanediol diacrylate (“A-DOD-N” manufactured by Shin-Nakamura Chemical Co., Ltd.)
DTDA: 2-decyl-1-tetradecanyl acrylate (“Light Acrylate DTD-A” manufactured by Kyoeisha Chemical Co., Ltd.)
A-DCP: Tricyclodecane dimethanol diacrylate (“NK ester A-DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.)
ISTA: Isostearyl acrylate (“ISTA” manufactured by Osaka Organic Chemical Industry Co., Ltd.)
DCP: Tricyclodecane dimethanol dimethacrylate (“NK Ester DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.)
M-111: Nonylphenol EO modified acrylate (“Aronix M-111” manufactured by Toagosei Co., Ltd., n≒1)
M-113: Nonylphenol EO modified acrylate (“Aronix M-113” manufactured by Toagosei Co., Ltd., n≒4)
RA-341: Multifunctional methacrylate polymer (“ART CURE RA-341” manufactured by Negami Kogyo Co., Ltd., weight average molecular weight 80,000, trifunctional or higher functional methacrylate polymer)
APB-001: Multifunctional acrylate polymer (“APB-001” manufactured by Negami Kogyo Co., Ltd., weight average molecular weight 72,000)
（Ｂ）成分として以下を用いた。
ビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイド（BASF社製「Irgacure 819」） The following was used as component (B).
Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (“Irgacure 819” manufactured by BASF)
ビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイド（BASF社製「Irgacure 819」） The following was used as component (B).
Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (“Irgacure 819” manufactured by BASF)
（Ｃ）成分として以下を用いた。
2,4-ビス(2-ヒドロキシ-4-ブチルオキシフェニル)-6-(2,4-ビス-ブチルオキシフェニル)-1,3,5-トリアジン（BASF社製「Tinuvin 460」）
2-(2-ヒドロキシ-４-[１-オクチルオキシカルボニルエトキシ]フェニル)-4,6-ビス(4-フェニルフェニル)-1,3,5-トリアジン（BASF社製「Tinuvin 479」）
2-[2-ヒドロキシ-5-[2-(メタクリロイルオキシ)エチル]フェニル]-2H-ベンゾトリアゾール（大塚化学社「RUVA-93」）
2-[4-[(2-ヒドロキシ-3-(2’-エチル)ヘキシル)オキシ]-2-ヒドロキシフェニル]-4,6-ビス(2,4-ジメチルフェニル)-1,3,5-トリアジン（BASF社製「Tinuvin 405」）
2,2’-ジヒドロキシ-4,4’-ジアクリロイルオキシベンゾフェノン（大和化成社製「DAINSORB P-66」） The following was used as component (C).
2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine (“Tinuvin 460” manufactured by BASF)
2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (“Tinuvin 479” manufactured by BASF)
2-[2-Hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (Otsuka Chemical Co., Ltd. "RUVA-93")
2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5- Triazine (“Tinuvin 405” manufactured by BASF)
2,2'-dihydroxy-4,4'-diacryloyloxybenzophenone (“DAINSORB P-66” manufactured by Daiwa Kasei Co., Ltd.)
2,4-ビス(2-ヒドロキシ-4-ブチルオキシフェニル)-6-(2,4-ビス-ブチルオキシフェニル)-1,3,5-トリアジン（BASF社製「Tinuvin 460」）
2-(2-ヒドロキシ-４-[１-オクチルオキシカルボニルエトキシ]フェニル)-4,6-ビス(4-フェニルフェニル)-1,3,5-トリアジン（BASF社製「Tinuvin 479」）
2-[2-ヒドロキシ-5-[2-(メタクリロイルオキシ)エチル]フェニル]-2H-ベンゾトリアゾール（大塚化学社「RUVA-93」）
2-[4-[(2-ヒドロキシ-3-(2’-エチル)ヘキシル)オキシ]-2-ヒドロキシフェニル]-4,6-ビス(2,4-ジメチルフェニル)-1,3,5-トリアジン（BASF社製「Tinuvin 405」）
2,2’-ジヒドロキシ-4,4’-ジアクリロイルオキシベンゾフェノン（大和化成社製「DAINSORB P-66」） The following was used as component (C).
2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine (“Tinuvin 460” manufactured by BASF)
2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (“Tinuvin 479” manufactured by BASF)
2-[2-Hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (Otsuka Chemical Co., Ltd. "RUVA-93")
2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5- Triazine (“Tinuvin 405” manufactured by BASF)
2,2'-dihydroxy-4,4'-diacryloyloxybenzophenone (“DAINSORB P-66” manufactured by Daiwa Kasei Co., Ltd.)
非重合性成分として以下を用いた。
PIB: ポリイソブテン（BASF社製「Oppanol N 50 SF」、重量平均分子量565,000） The following was used as the non-polymerizable component.
PIB: Polyisobutene (“Oppanol N 50 SF” manufactured by BASF, weight average molecular weight 565,000)
PIB: ポリイソブテン（BASF社製「Oppanol N 50 SF」、重量平均分子量565,000） The following was used as the non-polymerizable component.
PIB: Polyisobutene (“Oppanol N 50 SF” manufactured by BASF, weight average molecular weight 565,000)
（液状サンプル作製）
材料を60℃で加温混合することで均一な混合物とした。 (Liquid sample preparation)
A homogeneous mixture was obtained by heating and mixing the materials at 60°C.
材料を60℃で加温混合することで均一な混合物とした。 (Liquid sample preparation)
A homogeneous mixture was obtained by heating and mixing the materials at 60°C.
（接合サンプル作製）
作製した液状樹脂組成物を用いて、４インチシリコンウエハ（直径１０ｃｍ×厚さ０．４７ｍｍ）と４インチガラスウエハ（直径１０ｃｍ×厚さ０．７ｍｍ）を貼り合わせた。貼り合わせに際し、樹脂組成物の厚みは仮固定剤に宇部エクシモ社製のシリカ粒子（商品名ハイプレシカ ＴＳ Ｎ３Ｎ 平均粒径５０μｍ）を０．１質量％添加し、混合したものを用いることで調整した。貼り合わせ後、ＬＥＤ積算光量５０００ｍＪ／ｃｍ2（中心波長４０５ｎｍ、照度１００ｍＷ／ｃｍ2、照射時間５０秒）の条件にて硬化させ、接合サンプルを作製した。硬化にはＵＶ－ＬＥＤ（中心波長４０５ｎｍ、照度１００ｍＷ／ｃｍ2、ＣＣＳ社製ＨＬＤＬ－１２０Ｖ０－ＮＷＰＳＣ）を用いた。 (Preparation of bonded sample)
Using the produced liquid resin composition, a 4-inch silicon wafer (diameter 10 cm x thickness 0.47 mm) and a 4-inch glass wafer (diameter 10 cm x thickness 0.7 mm) were bonded together. During lamination, the thickness of the resin composition was adjusted by adding and mixing 0.1% by mass of silica particles manufactured by Ube Eximo Co., Ltd. (trade name Hypresica TS N3N, average particle size 50 μm) to the temporary fixing agent. . After bonding, it was cured under conditions of an integrated LED light amount of 5000 mJ/cm 2 (center wavelength 405 nm, illuminance 100 mW/cm 2 , irradiation time 50 seconds) to produce a bonded sample. For curing, a UV-LED (center wavelength 405 nm, illumination intensity 100 mW/cm 2 , HLDL-120V0-NWPSC manufactured by CCS) was used.
作製した液状樹脂組成物を用いて、４インチシリコンウエハ（直径１０ｃｍ×厚さ０．４７ｍｍ）と４インチガラスウエハ（直径１０ｃｍ×厚さ０．７ｍｍ）を貼り合わせた。貼り合わせに際し、樹脂組成物の厚みは仮固定剤に宇部エクシモ社製のシリカ粒子（商品名ハイプレシカ ＴＳ Ｎ３Ｎ 平均粒径５０μｍ）を０．１質量％添加し、混合したものを用いることで調整した。貼り合わせ後、ＬＥＤ積算光量５０００ｍＪ／ｃｍ2（中心波長４０５ｎｍ、照度１００ｍＷ／ｃｍ2、照射時間５０秒）の条件にて硬化させ、接合サンプルを作製した。硬化にはＵＶ－ＬＥＤ（中心波長４０５ｎｍ、照度１００ｍＷ／ｃｍ2、ＣＣＳ社製ＨＬＤＬ－１２０Ｖ０－ＮＷＰＳＣ）を用いた。 (Preparation of bonded sample)
Using the produced liquid resin composition, a 4-inch silicon wafer (diameter 10 cm x thickness 0.47 mm) and a 4-inch glass wafer (diameter 10 cm x thickness 0.7 mm) were bonded together. During lamination, the thickness of the resin composition was adjusted by adding and mixing 0.1% by mass of silica particles manufactured by Ube Eximo Co., Ltd. (trade name Hypresica TS N3N, average particle size 50 μm) to the temporary fixing agent. . After bonding, it was cured under conditions of an integrated LED light amount of 5000 mJ/cm 2 (center wavelength 405 nm, illuminance 100 mW/cm 2 , irradiation time 50 seconds) to produce a bonded sample. For curing, a UV-LED (center wavelength 405 nm, illumination intensity 100 mW/cm 2 , HLDL-120V0-NWPSC manufactured by CCS) was used.
（レーザー剥離性と穴サイズの評価）
得られた4インチ試験体のガラス支持体側から該試験体全面を走査するように、同試験体を中心に固定した直径１１０ｍｍの真円の面積に、波長３５５ｎｍのＵＶレーザーを照射した。ＵＶレーザー照射条件としては、上記表に示す各条件を、それぞれに対して順次適用し評価を行った。ＵＶレーザーは実施例ｂ１、ｂ２、ｂ３、比較例ｂ３、ｂ６についてはクォークテクノロジー社製「ＱＬＡ－３５５」、その他の試験にはキーエンス社製「MD-U1020C」を使用した。照射後の剥離性は、粘着性がなく、ガラス支持体が仮固定剤上から容易に手で剥離できる状態になっているものをexcellent、粘着性が残っているがガラス支持体が仮固定剤上から手で剥離できる状態になっているものをfair、ガラス支持体が仮固定剤上から手で剥離できない状態のものをNGと定義し評価した。 (Evaluation of laser removability and hole size)
A UV laser with a wavelength of 355 nm was irradiated onto the area of a perfect circle with a diameter of 110 mm fixed with the test piece in the center so as to scan the entire surface of the resulting 4-inch test piece from the glass support side. As for the UV laser irradiation conditions, each condition shown in the table above was sequentially applied and evaluated. As the UV laser, "QLA-355" manufactured by Quark Technology Co., Ltd. was used for Examples b1, b2, and b3 and Comparative Examples b3 and b6, and "MD-U1020C" manufactured by Keyence Corporation was used for other tests. The removability after irradiation is excellent if there is no stickiness and the glass support can be easily peeled off by hand from the temporary fixing agent, or if the glass support remains sticky but the glass support is not on the temporary fixing agent. The evaluation was performed by defining fair if the glass support could be peeled off by hand from above, and NG if the glass support could not be peeled off by hand from the temporary fixing agent.
得られた4インチ試験体のガラス支持体側から該試験体全面を走査するように、同試験体を中心に固定した直径１１０ｍｍの真円の面積に、波長３５５ｎｍのＵＶレーザーを照射した。ＵＶレーザー照射条件としては、上記表に示す各条件を、それぞれに対して順次適用し評価を行った。ＵＶレーザーは実施例ｂ１、ｂ２、ｂ３、比較例ｂ３、ｂ６についてはクォークテクノロジー社製「ＱＬＡ－３５５」、その他の試験にはキーエンス社製「MD-U1020C」を使用した。照射後の剥離性は、粘着性がなく、ガラス支持体が仮固定剤上から容易に手で剥離できる状態になっているものをexcellent、粘着性が残っているがガラス支持体が仮固定剤上から手で剥離できる状態になっているものをfair、ガラス支持体が仮固定剤上から手で剥離できない状態のものをNGと定義し評価した。 (Evaluation of laser removability and hole size)
A UV laser with a wavelength of 355 nm was irradiated onto the area of a perfect circle with a diameter of 110 mm fixed with the test piece in the center so as to scan the entire surface of the resulting 4-inch test piece from the glass support side. As for the UV laser irradiation conditions, each condition shown in the table above was sequentially applied and evaluated. As the UV laser, "QLA-355" manufactured by Quark Technology Co., Ltd. was used for Examples b1, b2, and b3 and Comparative Examples b3 and b6, and "MD-U1020C" manufactured by Keyence Corporation was used for other tests. The removability after irradiation is excellent if there is no stickiness and the glass support can be easily peeled off by hand from the temporary fixing agent, or if the glass support remains sticky but the glass support is not on the temporary fixing agent. The evaluation was performed by defining fair if the glass support could be peeled off by hand from above, and NG if the glass support could not be peeled off by hand from the temporary fixing agent.
上記の方法で作製した接合サンプルから支持体ガラスを剥離した後に、仮固定剤表面に形成された凹形状についてレーザーテック株式会社製ハイブリッドレーザーマイクロスコープ「OPTELICS HYBRID」を用いてプロファイル計測を行い、穴の長径及び深さを求めた。穴は凹部の形状であり、略円形状のフットプリントを有する。プロファイル測定は対物レンズ倍率50倍、解像度0.01μmで実施した。仮固定剤表面に形成された凹形状が真円でない場合、最も長い辺の直径（長径）を測定した。仮固定剤最表面から最も深く凹形状が形成されている箇所までの高度差を測定し穴の深さとした。またUVレーザー照射後に支持体のガラスを手で剥離できなかったサンプルについては、支持体ガラス及びシリコンウエハを割り、露出した仮固定剤の測定を実施した。上記の方法で測定した穴直径（長径）をUVレーザー照射時に設定したスポット径で割ることで比率を計算した。
After peeling the support glass from the bonded sample prepared by the above method, the profile of the concave shape formed on the surface of the temporary fixing agent was measured using a hybrid laser microscope "OPTELICS HYBRID" manufactured by Lasertec Corporation. The major axis and depth were determined. The hole is in the shape of a recess and has a generally circular footprint. Profile measurements were performed with an objective lens magnification of 50 times and a resolution of 0.01 μm. When the concave shape formed on the surface of the temporary fixing agent was not a perfect circle, the diameter of the longest side (major axis) was measured. The height difference from the outermost surface of the temporary fixing agent to the point where the deepest concave shape was formed was measured and determined as the depth of the hole. For samples whose support glass could not be peeled off by hand after UV laser irradiation, the support glass and silicon wafer were broken and the exposed temporary fixative was measured. The ratio was calculated by dividing the hole diameter (major axis) measured by the above method by the spot diameter set during UV laser irradiation.
（耐熱性／ブリードアウト評価）
上記の方法で作製した接合サンプルに対し、３００℃、２０Ｐａの高温減圧環境下で１時間加熱処理を行った。その後カッターを用いてガラス及びSiウエハを仮固定剤から機械的に剥離し、両基材表面の外観確認を行ないブリードアウトの有無を評価した。 (Heat resistance/bleedout evaluation)
The bonded sample produced by the above method was heat-treated in a high temperature and reduced pressure environment of 300° C. and 20 Pa for 1 hour. Thereafter, the glass and Si wafers were mechanically peeled off from the temporary fixing agent using a cutter, and the appearance of the surfaces of both substrates was checked to evaluate the presence or absence of bleed-out.
上記の方法で作製した接合サンプルに対し、３００℃、２０Ｐａの高温減圧環境下で１時間加熱処理を行った。その後カッターを用いてガラス及びSiウエハを仮固定剤から機械的に剥離し、両基材表面の外観確認を行ないブリードアウトの有無を評価した。 (Heat resistance/bleedout evaluation)
The bonded sample produced by the above method was heat-treated in a high temperature and reduced pressure environment of 300° C. and 20 Pa for 1 hour. Thereafter, the glass and Si wafers were mechanically peeled off from the temporary fixing agent using a cutter, and the appearance of the surfaces of both substrates was checked to evaluate the presence or absence of bleed-out.
上記の結果から、本発明の実施例に係る組成物では、レーザー照射により適切なサイズの穴が形成され、かつ耐熱性が良好であった。
From the above results, in the compositions according to the examples of the present invention, holes of an appropriate size were formed by laser irradiation, and the heat resistance was good.
一方、レーザー照射の条件を満たさない比較例ａ１～ａ３については、形成された穴のサイズが適切でなかった。
On the other hand, in Comparative Examples a1 to a3 that did not satisfy the laser irradiation conditions, the sizes of the holes formed were not appropriate.
本発明の条件を満たす（Ｃ）成分を含まない比較例ｂ１～ｂ５はいずれも、耐熱性が不適であった。（Ｃ）成分を含むが、非重合性成分が多い比較例ｂ６は、エネルギー照射量を高くしても形成された穴のサイズが適切ではなかった。
Comparative Examples b1 to b5, which did not contain component (C) that met the conditions of the present invention, all had unsuitable heat resistance. In Comparative Example b6, which contained component (C) but contained many non-polymerizable components, the size of the holes formed was not appropriate even if the energy irradiation amount was increased.
Claims (10)
- （Ａ）ベンゾフェノン骨格、トリアゾール骨格、ヒドロキシフェニルトリアジン骨格、及びフェノール骨格のいずれも有さず、かつ(メタ)アクリロイル基を有する重合性成分と、
（Ｂ）光重合開始剤と、
（Ｃ）ベンゾフェノン骨格、トリアゾール骨格、ヒドロキシフェニルトリアジン骨格、及びフェノール骨格からなる群から選択される一種以上を有し、かつ重合性官能基を有する紫外線吸収剤と
を含み、かつ含まれる非重合性成分と（Ａ）成分との合計100質量部に対して、非重合性成分の量が0質量％以上15質量％未満である、光硬化性樹脂組成物であって、
前記光硬化性樹脂組成物を、波長405nmかつ照度100mW/cm2である光を50秒間照射して作製した硬化体に対し、波長355nm、スポット径40～300μm、パルスエネルギー50～250μJ、エネルギー密度248～11500mJ/cm2の指向性エネルギーを、単位面積あたりの積算エネルギー照射量が150～1000mJ/cm2となるように、厚さ0.7mmのガラスを介して掃引照射した際に前記硬化体の表面を穿つように形成される略円形状のフットプリントを有する凹部の長径が、スポット径に対して20%以上の大きさであり、かつ深さが2.3μm以上であることを特徴とする光硬化性樹脂組成物。 (A) a polymerizable component that does not have a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, or a phenol skeleton and has a (meth)acryloyl group;
(B) a photopolymerization initiator;
(C) A non-polymerizable material having one or more selected from the group consisting of a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, and a phenol skeleton, and containing an ultraviolet absorber having a polymerizable functional group. A photocurable resin composition in which the amount of the non-polymerizable component is 0% by mass or more and less than 15% by mass with respect to the total of 100 parts by mass of the components and component (A),
A cured product prepared by irradiating the photocurable resin composition with light having a wavelength of 405 nm and an illuminance of 100 mW/cm 2 for 50 seconds, a wavelength of 355 nm, a spot diameter of 40 to 300 μm, a pulse energy of 50 to 250 μJ, and an energy density. When the directional energy of 248 to 11,500 mJ/cm 2 was swept through the glass with a thickness of 0.7 mm so that the cumulative energy irradiation amount per unit area was 150 to 1,000 mJ/cm 2 , the cured product was A light characterized in that the long axis of a recess having a substantially circular footprint formed so as to pierce the surface is 20% or more of the spot diameter, and the depth is 2.3 μm or more. Curable resin composition. - 前記重合性成分が、(メタ)アクリロイル基を2つ以上有する化合物を含む、請求項１に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, wherein the polymerizable component includes a compound having two or more (meth)acryloyl groups.
- 前記重合性成分が、多官能(メタ)アクリレートと単官能(メタ)アクリレートの組み合わせを含む、請求項２に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 2, wherein the polymerizable component includes a combination of a polyfunctional (meth)acrylate and a monofunctional (meth)acrylate.
- 前記重合性成分が、多官能(メタ)アクリレートと重合性ポリマーの組み合わせを含む、請求項２又は３に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 2 or 3, wherein the polymerizable component includes a combination of a polyfunctional (meth)acrylate and a polymerizable polymer.
- 前記重合性成分全体の質量に対して、(メタ)アクリロイル基を有する化合物の量が20～100質量％の範囲である、請求項１～４のいずれか一項に記載の光硬化性樹脂組成物。 The photocurable resin composition according to any one of claims 1 to 4, wherein the amount of the compound having a (meth)acryloyl group is in the range of 20 to 100% by mass with respect to the mass of the entire polymerizable component. thing.
- 前記紫外線吸収剤が有する重合性官能基が（メタ）アクリロイル基であることを特徴とする請求項１～５のいずれか一項に記載の光硬化性樹脂組成物。 The photocurable resin composition according to any one of claims 1 to 5, wherein the polymerizable functional group of the ultraviolet absorber is a (meth)acryloyl group.
- 請求項１～６のいずれか一項に記載の光硬化性樹脂組成物を含む、仮固定用接着剤。 A temporary fixing adhesive comprising the photocurable resin composition according to any one of claims 1 to 6.
- 請求項７に記載の仮固定用接着剤と、前記仮固定用接着剤により接着される基材とを含む接着体。 An adhesive body comprising the temporary fixing adhesive according to claim 7 and a base material to be bonded with the temporary fixing adhesive.
- 請求項７に記載の仮固定用接着剤を用いた薄型ウエハの製造方法。 A method for manufacturing a thin wafer using the temporary fixing adhesive according to claim 7.
- 請求項１～６のいずれか一項に記載の光硬化性樹脂組成物を硬化した硬化体。 A cured product obtained by curing the photocurable resin composition according to any one of claims 1 to 6.
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|---|---|---|---|
| PCT/JP2023/002751 WO2023181635A1 (en) | 2022-03-24 | 2023-01-27 | Composition for temporary fixing |
| PCT/JP2023/003109 WO2023181648A1 (en) | 2022-03-24 | 2023-01-31 | Composition for temporary fixation, adhesive for temporary fixation, and method for producing thin wafer |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2023/003109 WO2023181648A1 (en) | 2022-03-24 | 2023-01-31 | Composition for temporary fixation, adhesive for temporary fixation, and method for producing thin wafer |
Country Status (5)
| Country | Link |
|---|---|
| JP (3) | JPWO2023181635A1 (en) |
| KR (1) | KR20240129029A (en) |
| CN (1) | CN118804961A (en) |
| TW (2) | TW202338042A (en) |
| WO (2) | WO2023181635A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024162057A1 (en) * | 2023-01-31 | 2024-08-08 | デンカ株式会社 | Composition |
| WO2024162058A1 (en) * | 2023-01-31 | 2024-08-08 | デンカ株式会社 | Composition for temporary fixing, adhesive for temporary fixing, and thin wafer production method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024162049A1 (en) * | 2023-01-31 | 2024-08-08 | デンカ株式会社 | Composition for temporary fixation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000119262A (en) * | 1998-10-14 | 2000-04-25 | Otsuka Chem Co Ltd | Bisbenzotriazolylphenol compound, ultraviolet absorber, ultraviolet-absorbing polymer, resin composition containing them, and coating material |
| KR20150024708A (en) * | 2013-08-27 | 2015-03-09 | 서울대학교산학협력단 | Benzotriazole based (meth)acrylate copolymer and adhesive composition comprising same |
| WO2022230874A1 (en) * | 2021-04-26 | 2022-11-03 | デンカ株式会社 | Composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06177094A (en) * | 1992-12-10 | 1994-06-24 | Mitsui Toatsu Chem Inc | Tape for grinding rear of wafer and usage thereof |
| US6235387B1 (en) * | 1998-03-30 | 2001-05-22 | 3M Innovative Properties Company | Semiconductor wafer processing tapes |
| WO2004074328A1 (en) * | 2003-02-20 | 2004-09-02 | Ciba Specialty Chemicals Holding Inc. | Photocurable compositions |
| JP6213126B2 (en) * | 2012-10-25 | 2017-10-18 | セントラル硝子株式会社 | Adhesive composition, adhesion method thereof, and peeling method after adhesion |
| JP6844962B2 (en) * | 2016-07-01 | 2021-03-17 | 東京応化工業株式会社 | Laminates, methods for manufacturing them, methods for manufacturing electronic components, and methods for improving the adhesiveness between the separation layer and the substrate in the laminate. |
| EP4148096A4 (en) | 2020-05-21 | 2023-11-01 | Denka Company Limited | Composition |
| JP2023008789A (en) * | 2021-07-02 | 2023-01-19 | 日鉄ケミカル＆マテリアル株式会社 | Composition for adhesive layer, layered product, and producing and processing method for the layered product |
-
2023
- 2023-01-27 WO PCT/JP2023/002751 patent/WO2023181635A1/en unknown
- 2023-01-27 JP JP2024509802A patent/JPWO2023181635A1/ja active Pending
- 2023-01-31 KR KR1020247025747A patent/KR20240129029A/en unknown
- 2023-01-31 TW TW112103342A patent/TW202338042A/en unknown
- 2023-01-31 CN CN202380024627.8A patent/CN118804961A/en active Pending
- 2023-01-31 WO PCT/JP2023/003109 patent/WO2023181648A1/en unknown
- 2023-01-31 JP JP2024509810A patent/JPWO2023181648A1/ja active Pending
- 2023-02-03 TW TW112103785A patent/TW202337884A/en unknown
-
2024
- 2024-07-26 JP JP2024121253A patent/JP2024144632A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000119262A (en) * | 1998-10-14 | 2000-04-25 | Otsuka Chem Co Ltd | Bisbenzotriazolylphenol compound, ultraviolet absorber, ultraviolet-absorbing polymer, resin composition containing them, and coating material |
| KR20150024708A (en) * | 2013-08-27 | 2015-03-09 | 서울대학교산학협력단 | Benzotriazole based (meth)acrylate copolymer and adhesive composition comprising same |
| WO2022230874A1 (en) * | 2021-04-26 | 2022-11-03 | デンカ株式会社 | Composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024162057A1 (en) * | 2023-01-31 | 2024-08-08 | デンカ株式会社 | Composition |
| WO2024162058A1 (en) * | 2023-01-31 | 2024-08-08 | デンカ株式会社 | Composition for temporary fixing, adhesive for temporary fixing, and thin wafer production method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2024144632A (en) | 2024-10-11 |
| WO2023181648A1 (en) | 2023-09-28 |
| JPWO2023181635A1 (en) | 2023-09-28 |
| KR20240129029A (en) | 2024-08-27 |
| JPWO2023181648A1 (en) | 2023-09-28 |
| CN118804961A (en) | 2024-10-18 |
| TW202337884A (en) | 2023-10-01 |
| TW202338042A (en) | 2023-10-01 |
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