WO2021044833A1 - Back grinding tape - Google Patents
Back grinding tape Download PDFInfo
- Publication number
- WO2021044833A1 WO2021044833A1 PCT/JP2020/030939 JP2020030939W WO2021044833A1 WO 2021044833 A1 WO2021044833 A1 WO 2021044833A1 JP 2020030939 W JP2020030939 W JP 2020030939W WO 2021044833 A1 WO2021044833 A1 WO 2021044833A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sensitive adhesive
- pressure
- meth
- polyurethane
- mass
- Prior art date
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- 239000004814 polyurethane Substances 0.000 claims abstract description 182
- 229920002635 polyurethane Polymers 0.000 claims abstract description 182
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 114
- 239000000203 mixture Substances 0.000 claims abstract description 107
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 51
- 239000002608 ionic liquid Substances 0.000 claims abstract description 45
- 229920005862 polyol Polymers 0.000 claims abstract description 42
- 150000003077 polyols Chemical class 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 239000003999 initiator Substances 0.000 claims abstract description 25
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 24
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 24
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 191
- 239000010410 layer Substances 0.000 claims description 115
- -1 1-ethyl-3-methylimidazolium cation Chemical class 0.000 claims description 100
- 239000000463 material Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000012790 adhesive layer Substances 0.000 claims description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 17
- 239000000194 fatty acid Substances 0.000 claims description 17
- 229930195729 fatty acid Natural products 0.000 claims description 17
- 150000002892 organic cations Chemical class 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 150000002891 organic anions Chemical class 0.000 claims description 8
- 239000002356 single layer Substances 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 150000001449 anionic compounds Chemical class 0.000 claims description 5
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 4
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- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 45
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 44
- 230000001070 adhesive effect Effects 0.000 description 41
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- 125000000217 alkyl group Chemical group 0.000 description 8
- 125000005233 alkylalcohol group Chemical group 0.000 description 8
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- OPJWPPVYCOPDCM-UHFFFAOYSA-N 2-ethylhexyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)CCCC OPJWPPVYCOPDCM-UHFFFAOYSA-N 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
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- 125000002947 alkylene group Chemical group 0.000 description 4
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- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 4
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
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- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 3
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- GFRHRWJBYWRSJE-UHFFFAOYSA-N bis(16-methylheptadecyl) hexanedioate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCCCCCCCCC(C)C GFRHRWJBYWRSJE-UHFFFAOYSA-N 0.000 description 1
- ANFWGAAJBJPAHX-UHFFFAOYSA-N bis(fluorosulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical compound CC[N+]=1C=CN(C)C=1.FS(=O)(=O)[N-]S(F)(=O)=O ANFWGAAJBJPAHX-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229940075495 isopropyl palmitate Drugs 0.000 description 1
- 229940113915 isostearyl palmitate Drugs 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940105132 myristate Drugs 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229940073665 octyldodecyl myristate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D11/00—Constructional features of flexible abrasive materials; Special features in the manufacture of such materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D11/00—Constructional features of flexible abrasive materials; Special features in the manufacture of such materials
- B24D11/02—Backings, e.g. foils, webs, mesh fabrics
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Definitions
- the present invention relates to a back grind tape preferably used for processing semiconductor wafers.
- the present application claims priority based on Japanese Patent Application No. 2019-162092 filed in Japan on September 5, 2019, the contents of which are incorporated herein by reference.
- a semiconductor wafer backgrinding process is being performed in the semiconductor device manufacturing process.
- the front surface (front surface) of the semiconductor wafer is protected with a back grind tape, and then the back surface of the semiconductor wafer is ground to make the semiconductor wafer thinner.
- Patent Document 1 describes a base material layer, an unevenness absorbing resin layer, an antistatic layer, and an adhesive resin layer. Adhesive films for processing semiconductor wafers provided in order are disclosed.
- the adhesive film for semiconductor wafer processing described in Patent Document 1 needs to be manufactured by laminating each layer after forming a sheet, so that the manufacturing procedure is complicated. Further, the back grind tape is required to have an adhesive force capable of fixing an adherend such as a semiconductor wafer to the back grind tape with sufficient strength. However, when the back grind tape with high adhesive strength is attached to the adherend, the adherend is processed, and then the back grind tape is peeled off, the adhesive layer of the back grind tape is transferred to the adherend. The rest may occur.
- the present invention has been made in view of the above circumstances, has sufficient unevenness absorbing property, antistatic property, and adhesive strength, is less likely to leave adhesive residue after peeling the backgrinding tape, and requires less manufacturing process. It is an object of the present invention to provide a manufacturable back grind tape.
- the first aspect of the present invention is the following back grind tape.
- a back grind tape having a sheet-shaped base material and an adhesive layer formed on one side of the base material.
- the pressure-sensitive adhesive layer is made of a cured product of the pressure-sensitive adhesive composition and has a thickness of 50 to 500 ⁇ m.
- the pressure-sensitive adhesive composition contains a polyurethane (A), a (meth) acrylate monomer (B), a chain transfer agent (C), a photopolymerization initiator (D), and an ionic liquid (E).
- the polyurethane (A) contains a polyurethane (a1) having a skeleton containing a structure derived from a polyoxyalkylene polyol and a structure derived from a polyisocyanate, and having a (meth) acryloyl group at a plurality of ends.
- the backgrinding tape of the first aspect of the present invention can preferably include the following features as described below.
- the following features may preferably be a combination of two or more.
- [2] The back grind tape according to [1], wherein the pressure-sensitive adhesive layer has a single-layer structure.
- [3] The back grind tape according to [1] or [2], wherein the (meth) acrylate monomer (B) contains a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate.
- the ionic liquid (E) is any of [1] to [3], which is a compound containing an organic cation selected from the group consisting of a quaternary ammonium ion, an iminium ion, and a sulfonium ion.
- the back grind tape described.
- the ionic liquid (E) is 1-ethyl-3-methylimidazolium cation and / or 4-methyl-1-octyl pyridinium cation, bis (fluorosulfonyl) imide anion ((FSO 2) 2 N -
- [7] The backgrinding tape according to any one of [1] to [6], wherein the chain transfer agent (C) is a polyfunctional thiol.
- the pressure-sensitive adhesive composition 20 to 50% by mass of the polyurethane (A), 35-79% by mass of the (meth) acrylate monomer (B), 0.5 to 8.0% by mass of the chain transfer agent (C), 0.01 to 5.0% by mass of the photopolymerization initiator (D), The ionic liquid (E) is contained in an amount of 0.4 to 6.0% by mass.
- the back grind tape according to any one of [1] to [10].
- the present invention it is possible to provide a backgrinding tape having sufficient unevenness absorbing property, antistatic property, and adhesive strength, and in which adhesive residue is unlikely to occur after the backgrinding tape is peeled off.
- the pressure-sensitive adhesive layer is a cured product of the pressure-sensitive adhesive composition, and has sufficient unevenness absorption, antistatic property, and adhesive strength. Therefore, it is not necessary to separately provide the layer having the unevenness absorbing property, the layer having the antistatic property, and the layer having the adhesive force, and the tape can be manufactured in a small number of manufacturing steps. Therefore, the backgrinding tape of the present invention is used to protect the surface of an adherend having an uneven portion on the surface, such as a semiconductor wafer having bumps formed on the surface. Suitable as a tape.
- the back grind tape (hereinafter, also referred to as “BG tape”) in the present embodiment has a sheet-like base material and an adhesive layer formed on one side of the base material.
- the pressure-sensitive adhesive layer is composed of a cured product of the pressure-sensitive adhesive composition described later, and preferably has a single-layer structure.
- the shape of the "tape” referred to here is not limited to a strip shape, but may be any shape, and includes a rectangular or disc-shaped sheet.
- the material of the base material can be appropriately selected, and examples thereof include a resin material.
- Resin materials include polyolefins such as polyethylene (PE) and polypropylene (PP); polyester sheets such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate; polyvinyl chloride (PVC); polyimide (PI). ; Polyphenylene terephide (PPS); ethylene vinyl acetate (EVA); polytetrafluoroethylene (PTFE) and the like.
- PE, PP, and PET are preferably used because a sheet having appropriate flexibility can be obtained.
- As the resin material only one kind may be used alone, or two or more kinds may be mixed and used.
- the substrate may be transparent or opaque.
- the resin sheet When a resin sheet made of a resin material is used as the base material, the resin sheet may have a single layer or a multi-layer structure having two or more layers (for example, a three-layer structure).
- the resin material constituting each layer may be a resin material containing only one type alone or a resin material containing two or more types.
- a base material that has been subjected to antistatic treatment may be used as the base material.
- the antistatic treatment applied to the base material is not particularly limited, but a method of providing an antistatic layer on at least one surface of the base material, a method of kneading an antistatic agent into the base material, and the like can be used. Further, the surface on which the pressure-sensitive adhesive layer of the base material is formed is subjected to easy-adhesion treatment such as acid treatment, alkali treatment, primer treatment, corona treatment, plasma treatment, ultraviolet treatment, ozone treatment, etc., if necessary. You may.
- the thickness of the base material can be appropriately selected according to the material of the base material and the like.
- the thickness of the base material is, for example, 10 to 1000 ⁇ m. It is preferably 50 to 300 ⁇ m.
- the thickness of the base material is 10 ⁇ m or more, the rigidity (stiffness) of the BG tape becomes high. Therefore, when the BG tape is attached to or peeled off from the semiconductor wafer as an adherend, the BG tape tends to be less likely to have wrinkles and floats. Further, when the thickness of the base material is 1000 ⁇ m or less, the BG tape attached to the semiconductor wafer can be easily peeled off from the semiconductor wafer, and workability (handleability, handling) is improved.
- the pressure-sensitive adhesive layer is composed of a cured product of the pressure-sensitive adhesive composition described later.
- the pressure-sensitive adhesive layer attaches the BG tape to the surface of the adherend sufficiently.
- the pressure-sensitive adhesive layer absorbs and smoothes the unevenness of the surface of the adherend, that is, the gaps between the unevenness of the adherend are preferably filled by the pressure-sensitive adhesive layer, thereby improving the accuracy of the back grind process. Has a role.
- the pressure-sensitive adhesive layer reduces the peeling charge generated when the BG tape is peeled from the adherend. Further, the pressure-sensitive adhesive layer of the BG tape of the present embodiment does not leave adhesive residue even when the BG tape is peeled off. Further, the pressure-sensitive adhesive layer of the BG tape of the present embodiment is unlikely to cause contamination of the adherend after the BG tape is peeled off by the ionic liquid (E) described later.
- the thickness of the pressure-sensitive adhesive layer of the present embodiment can be arbitrarily selected, but is preferably 50 to 500 ⁇ m, more preferably 60 to 400 ⁇ m, and even more preferably 70 to 300 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer is 50 ⁇ m or more, the unevenness absorption and adhesive strength of the BG tape become good.
- the thickness of the pressure-sensitive adhesive layer is 500 ⁇ m or less, the film thickness of the pressure-sensitive adhesive layer can be easily controlled.
- the thickness of the pressure-sensitive adhesive layer largely depends on the height of the uneven portion on the surface of the adherend.
- the thickness of the pressure-sensitive adhesive layer is preferably equal to or greater than the height of the uneven portion on the surface so that sufficient uneven absorption can be obtained. Therefore, for example, when the unevenness of the surface is a bump formed on the semiconductor wafer, it is preferable that the thickness of the pressure-sensitive adhesive layer is twice or more the height dimension of the bump.
- the bump height is usually 30-200 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer is preferably 200 ⁇ m or more, and when the bump height is 200 ⁇ m, the thickness of the pressure-sensitive adhesive layer is 400 ⁇ m or more.
- the pressure-sensitive adhesive layer may have a single-layer structure, or may have a multi-layer structure in which the pressure-sensitive adhesive layer of the present embodiment and one or more other pressure-sensitive adhesive layers different from the pressure-sensitive adhesive layer of the present embodiment are laminated. You may.
- a conventionally known pressure-sensitive adhesive layer can be used. In the present embodiment, when the pressure-sensitive adhesive layer has a multi-layer structure, the pressure-sensitive adhesive layer of the present embodiment needs to be present on the outermost surface.
- a layer other than the pressure-sensitive adhesive layer may be present between the pressure-sensitive adhesive layer and the base material within a range that does not hinder the curing of the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer preferably has a single-layer structure.
- the gel fraction of the pressure-sensitive adhesive layer can be arbitrarily selected, but is preferably 50 to 65% by mass. When the gel fraction is 50% by mass or more, the generation of adhesive residue due to peeling the BG tape attached to the adherend can be more effectively suppressed. Further, when the gel fraction is 65% by mass or less, the pressure-sensitive adhesive layer has sufficient fluidity, and the unevenness absorption of the BG tape becomes even better.
- the gel fraction of the pressure-sensitive adhesive layer is more preferably 52% by mass or more. Further, the gel fraction of the pressure-sensitive adhesive layer is more preferably 63% by mass or less.
- the surface resistivity of the pressure-sensitive adhesive layer is preferably less than 1 ⁇ 10 11 ⁇ / ⁇ , and more preferably less than 1 ⁇ 10 10 ⁇ / ⁇ .
- the lower limit of the surface resistivity of the pressure-sensitive adhesive layer can be arbitrarily selected, but may be, for example, 1 ⁇ 10 6 ⁇ / ⁇ or more.
- the BG tape may be provided with a transparent or opaque separator on the surface of the pressure-sensitive adhesive layer opposite to the base material for the purpose of protecting the pressure-sensitive adhesive layer.
- the separator is preferably laminated directly on the surface of the pressure-sensitive adhesive layer.
- the material of the separator can be arbitrarily selected, but for example, paper, a plastic film, or the like can be used, and it is preferable to use a plastic film from the viewpoint of excellent surface smoothness.
- the plastic film used as the separator is not particularly limited as long as it can protect the above-mentioned pressure-sensitive adhesive layer, and examples thereof include polyethylene, polypropylene, polyethylene terephthalate (PET), and polybutene.
- the thickness of the separator can be selected arbitrarily. For example, it is preferably 5 to 300 ⁇ m, more preferably 10 to 200 ⁇ m, and even more preferably 25 ⁇ m to 100 ⁇ m.
- the pressure-sensitive adhesive composition of the present embodiment contains polyurethane (A), (meth) acrylate monomer (B), a chain transfer agent (C), a photopolymerization initiator (D), and an ionic liquid (E). Including.
- the (meth) acrylate monomer may mean a methacrylate monomer and / or an acrylate monomer.
- the polyurethane (A) includes the polyurethane (a1) described later. Although it may be composed of only polyurethane (a1), polyurethane (A) includes not only polyurethane (a1) but also polyurethane (a2), which will be described later, for the purpose of adjusting the cohesive force of the cured product of the pressure-sensitive adhesive composition. It may be included. It is preferable that the polyurethane (A) does not contain components other than the polyurethane (a1) and the polyurethane (a2) contained if necessary.
- Polyurethane (a1) has a skeleton containing a structure derived from a polyoxyalkylene polyol and a structure derived from a polyisocyanate.
- polyurethane (a1) has a plurality of (meth) acryloyl groups at the ends. It may have a (meth) acryloyl group at all ends.
- the terminal (meth) acryloyl group of the polyurethane (a1) is preferably a part of the (meth) acryloyloxy group.
- the (meth) acryloyl group may mean a meta-acryloyl group and / or an acryloyl group.
- the (meth) acryloyloxy group may mean a metaacryloyloxy group and / or an acryloyloxy group.
- the "plurality of ends" of polyurethane means two or more ends.
- “Multiple ends” means two ends when the polyurethane is a linear polymer, and two or more ends out of the same number of ends as the number of each branched chain when the polyurethane is a branched polymer. is there.
- Polyurethane (a2) Polyurethane (a2), like polyurethane (a1), has a skeleton containing a structure derived from a polyoxyalkylene polyol and a structure derived from a polyisocyanate. Polyurethane (a2), unlike polyurethane (a1), has a (meth) acryloyl group at only one end. The terminal (meth) acryloyl group of the polyurethane (a2) is preferably a part of the (meth) acryloyloxy group.
- the terminal of the polyurethane (a2) having no (meth) acryloyl group preferably has any one selected from an isocyanato group, a structure derived from an alkyl alcohol, and a structure derived from an alkyl isocyanate, and has a structure derived from an alkyl alcohol. Is more preferable.
- the polyoxyalkylene polyol having a structure derived from the polyoxyalkylene polyol contained in the skeletons of the polyurethane (a1) and the polyurethane (a2) preferably has an alkylene chain having 2 to 4 carbon atoms. Specific examples include polyoxyethylene polyol, polyoxypropylene polyol, polyoxybutylene polyol and the like.
- the polyoxyalkylene polyol having a structure derived from the polyoxyalkylene polyol may contain one type of alkylene chain or may contain two or more types of alkylene chains.
- the polyoxyalkylene polyol having a structure derived from the polyoxyalkylene polyol is preferably one having two or three hydroxyl groups at the terminal (diol type or triol type polyoxyalkylene polyol), and is preferably a polyoxyalkylene glycol (diol). Type) is more preferable, and polypropylene glycol having an alkylene chain having 3 carbon atoms is particularly preferable.
- the hydroxyl value is preferably 20 to 120 mgKOH / g, more preferably 30 to 100 mgKOH / g, and further preferably 40 to 80 mgKOH / g. preferable.
- polypropylene glycol include polypropylene glycol (Actcol D-2000; manufactured by Mitsui Chemicals, number average molecular weight 2000, diol type) having a hydroxyl group (hydroxy group) having a hydroxyl value of 56 mgKOH / g at the end. Be done.
- the hydroxyl value of the polyoxyalkylene polyol is the hydroxyl value of the polyoxyalkylene polyol measured according to JIS K0070. That is, it means the number of mg of potassium hydroxide required to neutralize free acetic acid when 1 g of polyoxyalkylene polyol is acetylated. Specifically, it can be obtained by acetylating the hydroxyl groups in the sample (polyoxyalkylene polyol) with acetic anhydride and titrating the free acetic acid generated at that time with a potassium hydroxide solution.
- the number average molecular weight of the polyoxyalkylene polyol is preferably 500 to 5,000, more preferably 800 to 4,000, and even more preferably 1,000 to 3,000.
- the BG tape having a pressure-sensitive adhesive layer made of a cured product of the pressure-sensitive adhesive composition containing polyurethane (A) synthesized using the polyoxyalkylene polyol has high peel strength. It becomes.
- the polyurethane (A) synthesized using the polyoxyalkylene polyol contains a sufficient amount of urethane bonds. Therefore, the cured product obtained by curing the pressure-sensitive adhesive composition containing polyurethane (A) has a good cohesive force.
- the structure derived from the polyoxyalkylene polyol contained in the skeletons of the polyurethane (a1) and the polyurethane (a2) may be of only one type, or may be a structure containing two or more types.
- Polyurethane (a1) and polyurethane (a2) may have a structure in which two or more different polyoxyalkylene polyol-derived structures are bonded with a polyisocyanate-derived structure in between.
- the structure derived from the polyoxyalkylene polyol contained in the skeleton of the polyurethane (a1) and the structure derived from the polyoxyalkylene polyol contained in the skeleton of the polyurethane (a2) may be the same or different. ..
- Polyisocyanate having a structure derived from the polyisocyanate contained in the skeletons of the polyurethane (a1) and the polyurethane (a2) a compound having a plurality of isocyanato groups can be used, and it is preferable to use a diisocyanate.
- the diisocyanate include tolylene diisocyanate and its hydrogen additive, xylylene diisocyanate and its hydrogen additive, diphenylmethane diisocyanate and its hydrogen additive, 1,5-naphthylene diisocyanate and its hydrogen additive, hexamethylene diisocyanate, and trimethyl.
- Examples thereof include hexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexyldiisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, norbornan diisocyanate and the like.
- polystyrene resin it is preferable to use a hydrogenated isophorone diisocyanate or diphenylmethane diisocyanate from the viewpoint of controlling the light resistance of the polyurethane (A) synthesized using the polyisocyanate and the reactivity with the polyoxyalkylene polyol.
- a hydrogenated diphenylmethane diisocyanate it is more preferable to use a hydrogenated diphenylmethane diisocyanate in terms of reactivity with a polyoxyalkylene polyol.
- polyisocyanate having a structure derived from polyisocyanate examples include hydrogenated diphenylmethane diisocyanate (Desmodule W, manufactured by Sumika Covestro Urethane) and isophorone diisocyanate (Desmodule I, manufactured by Sumika Covestro Urethane). Can be mentioned.
- the polyisocyanate-derived structure contained in the skeletons of the polyurethane (a1) and the polyurethane (a2) may be of only one type, or may be a structure containing two or more types. Further, the structure derived from polyisocyanate contained in the skeleton of polyurethane (a1) and the structure derived from polyisocyanate contained in the skeleton of polyurethane (a2) may be the same or different.
- polyurethane (a1) and polyurethane (a2) can be synthesized at the same time.
- Polyurethane (A) can be efficiently produced, which is preferable.
- the proportion of polyurethane (a1) contained in polyurethane (A) is preferably 80 to 100%, more preferably 90 to 100%, and even more preferably 100% of polyurethane (A) on the basis of the number of molecules.
- the proportion of polyurethane (a2) contained in polyurethane (A) is preferably 0 to 20%, more preferably 0 to 10%, and even more preferably 0% of polyurethane (A) on the basis of the number of molecules.
- polyurethane (A) Of all the number of ends contained in polyurethane (A) (the total number of the number of ends of polyurethane (a1) and the number of ends of polyurethane (a2) contained as needed), 90 to 100 based on the number of molecules. It is preferable that a (meth) acryloyl group is introduced into%, more preferably 95 to 100%, still more preferably 100%. If necessary, it may be 90 to 93%, 93 to 97%, 97 to 100%, or the like. When the amount of the (meth) acryloyl group introduced is 90% or more based on the number of molecules among all the terminals contained in the polyurethane (A), it is obtained by curing the pressure-sensitive adhesive composition containing the polyurethane (A). The cohesive force of the cured product is sufficiently high.
- the ratio of the number of terminals into which the (meth) acryloyl group is introduced based on the number of molecules among all the number of terminals contained in polyurethane (A) is determined by the infrared absorption spectrum (IR) method and the nuclear magnetic resonance spectrum (NMR) method. It can be calculated using the result of analyzing the polyurethane (A) using the above.
- the ratio of the number of introduced terminals can be adjusted by the method for producing polyurethane (A) described later.
- the mass average molecular weight of polyurethane (A) is preferably 30,000 to 200,000, more preferably 50,000 to 150,000, and even more preferably 60,000 to 100,000. ..
- the mass average molecular weight of the polyurethane (A) is 30,000 or more, the cured product obtained by curing the pressure-sensitive adhesive composition containing the polyurethane (A) has good flexibility. Further, when the mass average molecular weight of the polyurethane (A) is 200,000 or less, the pressure-sensitive adhesive composition containing the polyurethane (A) is easy to handle and has good workability.
- the mass average molecular weight of polyurethane (A) is a polystyrene-equivalent value measured by gel permeation chromatography (GPC-101; Showa Denko KK Shodex®) (hereinafter referred to as GPC). ..
- GPC gel permeation chromatography
- the measurement conditions of GPC are as follows. Column: LF-804 (manufactured by Showa Denko KK) Column temperature: 40 ° C Sample: 0.2% by mass tetrahydrofuran solution of polyurethane (A) Flow rate: 1 ml / min Eluent: Tetrahydrofuran Detector: RI detector (differential refractive index detector)
- the content of polyurethane (A) in the pressure-sensitive adhesive composition of the present embodiment can be arbitrarily selected, but is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, and 30 to 40% by mass. It is more preferably by mass%.
- the content of the polyurethane (A) is 20% by mass or more, the cured product obtained by curing the pressure-sensitive adhesive composition has a sufficient cohesive force, and an excellent adhesive force can be obtained.
- the softness of the pressure-sensitive adhesive layer is within an appropriate range, and air bubbles are less likely to be caught between the pressure-sensitive adhesive layer and the adherend.
- the cured product obtained by curing the pressure-sensitive adhesive composition has sufficient flexibility. Therefore, the BG tape using this cured product as the pressure-sensitive adhesive layer has good wettability to the adherend.
- the (meth) acrylate monomer (B) is not particularly limited as long as it is a compound other than polyurethane (A) and has a (meth) acryloyloxy group.
- the (meth) acrylate monomer (B) only one compound having a (meth) acryloyloxy group may be used alone, or two or more thereof may be mixed and used.
- a monofunctional (meth) acrylate may be used, a polyfunctional (meth) acrylate may be used, or a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate. You may use both of.
- the (meth) acrylate may mean a metal acrylate and / or an acrylate.
- monofunctional (meth) acrylate means a (meth) acrylate having only one (meth) acryloyloxy group.
- polyfunctional in the polyfunctional (meth) acrylate means a (meth) acrylate having two or more (meth) acryloyloxy groups.
- the (meth) acrylate monomer (B) includes a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate from the viewpoint of the cohesiveness of the cured product obtained by curing the pressure-sensitive adhesive composition and the curability of the pressure-sensitive adhesive composition. It is preferable to use it in combination with an acrylate, and it is more preferable to contain a monofunctional (meth) acrylate and a trifunctional or higher (meth) acrylate, in particular, a monofunctional (meth) acrylate and three (meth) acrylates. Most preferably, it contains a trifunctional (meth) acrylate having an acryloyloxy group.
- Examples of the monofunctional (meth) acrylate include cyclic alkyl (meth) acrylate such as alkyl (meth) acrylate and isobornyl (meth) acrylate, alkoxyalkyl (meth) acrylate, alkoxy (poly) alkylene glycol (meth) acrylate, and hydroxy.
- the adhesive strength (peeling force) and gel fraction of the cured product obtained by curing the pressure-sensitive adhesive composition are such that when the cured product is used as the pressure-sensitive adhesive layer of the BG tape.
- the alkyl (meth) acrylate it is more preferable to use an alkyl (meth) acrylate having an alkyl group having 4 to 10 carbon atoms.
- alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
- 2-ethylhexyl (meth) acrylate and / or n-butyl (meth) acrylate examples include 2-ethylhexyl (meth) acrylate and / or n-butyl (meth) acrylate.
- the polyfunctional (meth) acrylate is a compound other than polyurethane (A) and having a plurality of (meth) acryloyloxy groups.
- the polyfunctional (meth) acrylate it is preferable to use a poly (meth) acrylate of a polyol compound.
- Specific examples of the polyfunctional (meth) acrylate include polyethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tripropylene glycol.
- trimethylolpropane tri (meth) acrylate is preferably used as the polyfunctional (meth) acrylate from the viewpoint of curability of the pressure-sensitive adhesive
- both monofunctional (meth) acrylate and polyfunctional (meth) acrylate are contained as the (meth) acrylate monomer (B), when the total of the (meth) acrylate monomer (B) is 100 mol%, it is simple. It is preferable to contain 85 to 99 mol% of functional (meth) acrylate and 1 to 15 mol% of polyfunctional (meth) acrylate. In this case, the content of the monofunctional (meth) acrylate is more preferably 90 to 99 mol%, further preferably 95 to 98 mol%. The content of the polyfunctional (meth) acrylate is more preferably 1 to 10 mol%, further preferably 2 to 5 mol%.
- the BG tape using this cured product as the pressure-sensitive adhesive layer can obtain sufficient unevenness absorption, and when it is attached to an adherend having an uneven portion on the surface, it is placed between the BG tape and the uneven portion of the adherend. It is preferable because voids are less likely to occur.
- the BG tape using the cured product of the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer is less likely to remain adhesive when peeled from the adherend. ,preferable.
- the content of the polyfunctional (meth) acrylate is 1 mol% or more, the cured product obtained by curing the pressure-sensitive adhesive composition It is preferable that the fluidity does not become too large. Further, when the content of the polyfunctional (meth) acrylate is 15 mol% or less, the fluidity of the cured product obtained by curing the pressure-sensitive adhesive composition is high when the cured product is used as the pressure-sensitive adhesive layer of the BG tape. This is a preferable range.
- the BG tape using the cured product as the pressure-sensitive adhesive layer has sufficient unevenness absorbing property, and when it is attached to an adherend having an uneven portion on the surface, it is placed between the BG tape and the uneven portion of the adherend. It is preferable because voids are less likely to occur.
- the content of the (meth) acrylate monomer (B) in the pressure-sensitive adhesive composition of the present embodiment can be arbitrarily selected, but is preferably 35 to 79% by mass, more preferably 40 to 73% by mass. , 40 to 66% by mass, more preferably 45 to 65% by mass. If necessary, it may be 45 to 60% by mass, 50 to 58% by mass, or the like.
- the content of the (meth) acrylate monomer (B) is 35% by mass or more, the viscosity of the pressure-sensitive adhesive composition does not become too high and the coatability is excellent, which is preferable.
- the content of the (meth) acrylate monomer (B) is 79% by mass or less, the viscosity of the pressure-sensitive adhesive composition does not become too low, and the thickness of the coating film made of the pressure-sensitive adhesive composition can be easily controlled. ,preferable.
- the chain transfer agent (C) is contained in the pressure-sensitive adhesive composition for the purpose of controlling the unevenness absorption and gel fraction of the cured product obtained by curing the pressure-sensitive adhesive composition.
- the chain transfer agent (C) it is preferable to use a thiol compound.
- polyfunctional thiols can be preferably used.
- a polyfunctional thiol is a compound having two or more mercapto groups in the molecule.
- the polyfunctional thiol is not particularly limited, and is, for example, 1,2-ethanedithiol, 1,4-bis (3-mercaptobutylyloxy) butane, tetraethylene glycol bis (3-mercaptopropionate), and trimethylol.
- the chain transfer agent (C) it is preferable to use pentaerythritol tetrakis (3-mercaptobutyrate)
- the content of the chain transfer agent (C) in the pressure-sensitive adhesive composition of the present embodiment can be arbitrarily selected, but is preferably 0.5 to 8.0% by mass, preferably 0.7 to 6.0% by mass. It is more preferably 1.0 to 5.0% by mass, and particularly preferably 3.0 to 4.5% by mass.
- the content of the chain transfer agent (C) is 0.5% by mass or more, the fluidity of the cured product obtained by curing the pressure-sensitive adhesive composition is high when the cured product is used as the pressure-sensitive adhesive layer of the BG tape. It is in a preferable range.
- the BG tape using the cured product as the pressure-sensitive adhesive layer has sufficient unevenness absorbing property and is less likely to generate voids between the cured product and the uneven portion of the adherend.
- the content is 8.0% by mass or less, it is preferable that the BG tape using the cured product of the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer is less likely to leave adhesive residue when peeled from the adherend.
- the photopolymerization initiator (D) is not particularly limited, but a photoradical polymerization initiator is preferable.
- the photopolymerization initiator (D) include a carbonyl-based photopolymerization initiator, a sulfide-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a quinone-based photopolymerization initiator, and a sulfochloride-based photopolymerization initiator.
- a thioxanthone-based photopolymerization initiator or the like can be used.
- a carbonyl-based photopolymerization initiator and / or an acylphosphine oxide-based photopolymerization initiator is used from the viewpoint of transparency of the cured product obtained by photocuring the pressure-sensitive adhesive composition.
- a 2,4,6-trimethylbenzoyldiphenylphosphine oxide agent and / or a 1-hydroxycyclohexyl-phenylketone is preferable to use.
- the content of the photopolymerization initiator (D) in the pressure-sensitive adhesive composition of the present embodiment is preferably 0.01 to 5.0% by mass, and preferably 0.05 to 3.0% by mass. More preferably, it is 0.1 to 2.0% by mass. If necessary, it may be 0.2 to 1.5% by mass, 0.3 to 1.2% by mass, or the like.
- the content of the photopolymerization initiator (D) is 0.01% by mass or more, the photocuring of the pressure-sensitive adhesive composition proceeds sufficiently. Further, when the content of the photopolymerization initiator (D) is 5% by mass or less, the low molecular weight component does not become too large during photocuring of the pressure-sensitive adhesive composition. Therefore, it is preferable that the BG tape using the cured product of the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer is less likely to leave adhesive residue when peeled from the adherend.
- the ionic liquid (E) in the present embodiment refers to a molten salt compound (ionic compound) having a melting point of 100 ° C. or lower. More preferably, it is a molten salt compound having a melting point of room temperature (25 ° C.) or lower.
- the ionic liquid (E) may be composed of one kind of compound or two or more kinds of compounds.
- the ionic liquid may mean a salt compound that exists in a liquid state in the above temperature range, and may not contain a solvent.
- the ionic liquid (E) it is preferable to use an organic salt compound in which an organic cation and an inorganic anion or an organic anion are combined.
- Q 1 represents an alkyl group, an aryl group, substituent such as a heterocyclic group.
- organic cations quaternary nitrogen atoms such as ammonium, iminium, and sulfonium are preferable.
- these organic cations include pyridinium cation, piperidinium cation, pyrrolidinium cation, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, pyrazolium cation, tetraalkylammonium cation and trialkyl.
- examples include sulfonium cations.
- imidazolium cations and pyridinium cations are preferably used.
- a pressure-sensitive adhesive layer containing an ionic liquid (E) using an imidazolium cation or a pyridinium cation as an organic cation is preferable because it has excellent antistatic properties.
- imidazolium cation used as an organic cation examples include 1-methylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, and 1-butyl. Examples thereof include -3-methylimidazolium cation and 1,2,3-trimethylimidazolium cation. Among these imidazolium cations, 1-ethyl-3-methylimidazolium cation is preferably used.
- pyridinium cation used as the organic cation include, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4- Methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-hexyl-4-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 4-methyl-1-octylpyridinium cation, etc. Be done.
- 1-hexyl-4-methylpyridinium cation, 4-methyl-1-octylpyridinium cation and the like are preferably used.
- the inorganic anion is not particularly limited as long as it can form a molten salt compound having a melting point of 100 ° C. or lower.
- the inorganic anions such as, Cl -, Br -, I -, AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F (HF) m - (. m is an integer of 0 or more) - and the like, 2 N (CN).
- the organic anion is not particularly limited as long as it can form a molten salt compound having a melting point of 100 ° C. or lower.
- the organic anions for example, CH 3 COO -, CF 3 COO -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, (CF 3 SO 2) 3 C -, C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO - and the like -, (CF 3 SO 2) (CF 3 CO) N Be done.
- an anion containing a fluorine atom as the inorganic anion or the organic anion.
- an anion containing a fluorine atom By using an anion containing a fluorine atom, an ionic liquid (E) having excellent ionic conductivity can be obtained. Therefore, the BG tape using the ionic liquid (E) containing a fluorine-containing anion is particularly excellent in antistatic property.
- the fluorine-containing organic anion are preferable among anions containing fluorine atoms, in particular, (FSO 2) 2 N - , (CF 3 SO 2) 2 N - is preferably used, (FSO 2 ) It is more preferable to use 2 N ⁇ .
- the ionic liquid (E) As the ionic liquid (E), a commercially available one may be used. Of these, 1-ethyl-3-methylimidazolium cation and bis (fluorosulfonyl) imide anion ((FSO 2) 2 N -) ionic liquid consisting of (Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Erekuseru AS-110 ), 4-methyl-1-octyl - pyridinium cations and bis (fluorosulfonyl) imide anion ((FSO 2) 2 N -) ionic liquid consisting of (Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Erekuseru aS-804 ) Is preferable.
- the pressure-sensitive adhesive layer containing AS-110 and / or AS-804 as the ionic liquid (E) is preferable because it has excellent antistatic properties.
- the content of the ionic liquid (E) in the pressure-sensitive adhesive composition of the present embodiment can be arbitrarily selected, but is preferably 0.4 to 6.0% by mass, preferably 0.5 to 5.0% by mass. More preferably, it is more preferably 1.0 to 3.0% by mass. If necessary, it may be 0.4 to 2.0% by mass, 2.0 to 4.0% by mass, or the like.
- the content of the ionic liquid (E) is 0.4% by mass or more, the surface resistance value of the pressure-sensitive adhesive layer becomes sufficiently low. As a result, the antistatic performance of the BG tape having the adhesive layer is improved.
- the pressure-sensitive adhesive composition of the present embodiment contains polyurethane (A), (meth) acrylate monomer (B), a chain transfer agent (C), a photopolymerization initiator (D), and an ionic liquid (E). It may be contained, and if necessary, a fatty acid ester (F) may be contained.
- the fatty acid ester (F) controls the adhesive force of the BG tape using the cured product of the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer, and also has the adhesiveness (wetting property) and the foam removal property (on the adherend) of the pressure-sensitive adhesive layer.
- the BG sheet is contained in the pressure-sensitive adhesive composition for the purpose of improving (easiness of removal of air bubbles sandwiched during bonding).
- an ester of a fatty acid and an alkyl alcohol can be used, and from the viewpoint of compatibility with other components, a fatty acid having 8 to 18 carbon atoms and a branched hydrocarbon group having 3 to 18 carbon atoms It is preferable to use an ester with a monofunctional alcohol having, and / or a fatty acid ester selected from an ester of an unsaturated fatty acid having 14 to 18 carbon atoms and an alcohol having 2 to 4 functionalities.
- ester of a fatty acid having 8 to 18 carbon atoms and a monofunctional alcohol having a branched hydrocarbon group having 3 to 18 carbon atoms examples include isostearyl laurate, isopropyl myristate, isosetyl myristate, octyldodecyl myristate, and isopropyl palmitate.
- isostearyl palmitate isosetyl stearate, 2-ethylhexyl stearate, octyldodecyl oleate, diisostearyl adipate, diisocetyl sebacate, trioleyl trimeritate, triisocetyl trimeritate and the like.
- isopropyl myristate, isopropyl palmitate, and 2-ethylhexyl stearate are preferably used, and isopropyl myristate and / or 2-ethylhexyl stearate is particularly preferable.
- esters of unsaturated fatty acids having 14 to 18 carbon atoms and alcohols having 2 to 4 functionalities include unsaturated fatty acids such as myristoleic acid, oleic acid, linoleic acid, linolenic acid, isostriatic acid, and isostearic acid, and ethylene.
- esters with alcohols such as glycols, propylene glycols, glycerins, trimethylolpropanes, pentaerythritols, and sorbitans.
- the content of the fatty acid ester (F) in the pressure-sensitive adhesive composition of the present embodiment can be arbitrarily selected, but is preferably 3 to 18% by mass, more preferably 5 to 15% by mass.
- the adhesive strength of the BG tape using the cured product of the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer is in a preferable range, and the adhesiveness of the pressure-sensitive adhesive layer and the laminating property and Good defoaming property.
- the BG tape using the cured product of the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer contains the fatty acid ester (F) when peeled from the adherend. It is preferable because adhesive residue is unlikely to occur.
- the pressure-sensitive adhesive composition of the present embodiment may contain a solvent, but is more preferably a solvent-free one containing substantially no solvent.
- a solvent for example, a solvent can be used as a leveling agent and / or a softening agent.
- the pressure-sensitive adhesive composition of the present embodiment is solvent-free, excellent productivity can be obtained because the step of heating and drying the solvent can be omitted when forming the pressure-sensitive adhesive layer of the BG tape using the pressure-sensitive adhesive composition.
- the productivity improvement effect by omitting the step of heating and drying the solvent is remarkable. Therefore, it is preferable that there is no solvent.
- the meaning of "substantially free of solvent” in the pressure-sensitive adhesive composition means that the content of the solvent in the pressure-sensitive adhesive composition is 0 to 1.0% by mass, preferably 0. It is about 0.5% by mass, more preferably 0 to 0.1% by mass.
- the pressure-sensitive adhesive composition of the present embodiment may contain other additives, if necessary, as long as the effects of the present invention are not impaired.
- Additives include, for example, plasticizers, surface lubricants, antioxidants, antioxidants, light stabilizers, UV absorbers, polymerization inhibitors, light stabilizers such as benzotriazoles, phosphate esters and others. Examples include flame retardants and dyes.
- the reaction between the hydroxy group and the isocyanato group is carried out in any step in the presence of an organic solvent inert to the isocyanato group, such as dibutyltin dilaurate, dibutyltin diethylhexoate.
- an organic solvent inert such as dibutyltin dilaurate, dibutyltin diethylhexoate.
- a urethanization catalyst such as dioctyltin dilaurate.
- the reaction between the hydroxy group and the isocyanato group is preferably carried out continuously at 30 to 100 ° C. for 1 to 5 hours in any of the steps.
- the amount of the urethanization catalyst used is preferably 50 to 500 mass ppm with respect to the total mass of the reactant (raw material).
- polyoxyalkylene polyol and polyisocyanate are mixed at a ratio in which the isocyanato group weight (molecular number standard, the same applies hereinafter) is larger than the hydroxy group weight (molecular number standard, the same applies hereinafter).
- the polyoxyalkylene polyol is reacted with the polyisocyanate to synthesize a polyurethane having an isocyanato group at the terminal as a precursor of the polyurethane (A).
- Specific examples of the polyoxyalkylene polyol and the polyisocyanate used as raw materials are as illustrated in the section of polyurethane (A).
- the molecular weight (degree of polymerization) of the polyurethane having an isocyanato group at the terminal can be adjusted by adjusting the ratio of the isocyanato group amount to the hydroxy group amount contained in the raw material. Specifically, the smaller the excess amount of the isocyanato group with respect to the hydroxy group amount, the larger the molecular weight of the polyurethane having an isocyanato group at the terminal. Further, the larger the excess amount of the isocyanato group with respect to the hydroxy group amount, the smaller the molecular weight of the polyurethane having an isocyanato group at the terminal.
- the mass average molecular weight of the target polyurethane (A) is adjusted by adjusting the molecular weight of the polyurethane having an isocyanato group at the terminal.
- a polyurethane having an isocyanato group at the terminal is reacted with a compound having a hydroxy group and a (meth) acryloyl group to have a structure containing a polyoxyalkylene polyol-derived structure and a polyisocyanate-derived structure.
- Polyurethane (A) containing polyurethane (a1) having a (meth) acryloyl group at the end of is produced.
- the terminal (meth) acryloyl group of the produced polyurethane (A) is preferably a part of the (meth) acryloyloxy group.
- the compound having a hydroxy group and a (meth) acryloyl group is not particularly limited, but is hydroxyalkyl such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
- Examples thereof include monool having a (meth) acryloyl group derived from various polyols such as.
- These compounds having a hydroxy group and a (meth) acryloyl group may be used alone or in combination of two or more.
- 2-hydroxyethyl (meth) is obtained from the viewpoint of reactivity with the isocyanato group of polyurethane having an isocyanato group at the terminal and photocurability of the pressure-sensitive adhesive composition.
- the polyurethane (A) has an isocyanato group at the terminal in combination with a compound having a hydroxy group and a (meth) acryloyl group and an alkyl alcohol having no (meth) acryloyl group and having one hydroxy group. It may be produced by reacting with polyurethane.
- the alkyl alcohol may be any as long as it does not have a (meth) acryloyl group and has one hydroxy group, and linear, branched, alicyclic alkyl alcohols and the like can be used and is not particularly limited. ..
- the above alkyl alcohol may be used alone or in combination of two or more.
- Polyurethane (A) is obtained by reacting a compound having a hydroxy group and a (meth) acryloyl group, an alkyl alcohol having no (meth) acryloyl group and having one hydroxy group, and a polyurethane having an isocyanato group at the terminal.
- the amount of (meth) acryloyl group introduced into polyurethane having an isocyanato group at the terminal can be adjusted by producing.
- a polyurethane (A) containing a plurality of types of polyurethane having different amounts of introduced (meth) acryloyl groups at the ends is produced.
- the plurality of types of polyurethanes include polyurethanes (a1) having a plurality of (meth) acryloyl groups at the ends.
- the plurality of types of polyurethane include not only polyurethane (a1) but also polyurethane in which at least a part of the plurality of ends has a structure derived from the above alkyl alcohol.
- the produced plurality of types of polyurethanes include polyurethanes in which at least some of the plurality of ends do not have a (meth) acryloyl group. Furthermore, among the plurality of types of polyurethane produced, polyurethane (a2) having a (meth) acryloyl group at only one terminal may be included.
- reaction between the hydroxy group and the isocyanato group is preferably carried out continuously at 30 to 100 ° C. for 1 to 5 hours in any of the steps.
- the amount of the urethanization catalyst used is preferably 50 to 500 mass ppm with respect to the total mass of the reactant (raw material).
- polyurethane having a hydroxy group at the terminal is synthesized as a precursor of polyurethane (A). Specifically, first, the polyoxyalkylene polyol and the polyisocyanate are charged at a ratio in which the hydroxy group amount (based on the number of molecules, the same applies hereinafter) is larger than the amount of the isocyanato group (based on the number of molecules, the same applies hereinafter). Then, the polyoxyalkylene polyol is reacted with the polyisocyanate to synthesize a polyurethane having a hydroxy group at the terminal as a precursor of the polyurethane (A).
- the molecular weight (degree of polymerization) of the polyurethane having a hydroxy group at the terminal can be adjusted by adjusting the ratio of the hydroxy group amount to the isocyanato group amount contained in the raw material. Specifically, the smaller the excess amount of the hydroxy group amount with respect to the isocyanato group amount, the larger the molecular weight of the polyurethane having a hydroxy group at the terminal. Further, the larger the excess amount of the hydroxy group with respect to the isocyanato group amount, the smaller the molecular weight of the polyurethane having a hydroxy group at the terminal.
- the mass average molecular weight of the target polyurethane (A) is adjusted by adjusting the molecular weight of the polyurethane having a hydroxy group at the terminal.
- a polyurethane having a hydroxy group at the terminal is reacted with a compound having an isocyanato group and a (meth) acryloyl group to have a structure containing a polyoxyalkylene polyol-derived structure and a polyisocyanate-derived structure.
- Polyurethane (A) containing polyurethane (a1) having a (meth) acryloyl group at the end of is produced.
- the terminal (meth) acryloyl group of the produced polyurethane (A) is preferably a part of the (meth) acryloyloxy group.
- the compound having an isocyanato group and a (meth) acryloyl group is not particularly limited, but is limited to 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, and 1,1-bis (acryloyloxymethyl) ethyl. Examples thereof include isocyanate. Examples of commercially available compounds having an isocyanato group and a (meth) acryloyl group include Karenz MOI (registered trademark) and Karenz AOI (registered trademark) manufactured by Showa Denko KK. These compounds having an isocyanato group and a (meth) acryloyl group may be used alone or in combination of two or more.
- 2- (meth) acryloyl from the viewpoint of reactivity with the hydroxy group of polyurethane having a hydroxy group at the terminal and photocurability of the pressure-sensitive adhesive composition. It is preferable to use oxyethyl isocyanate.
- the polyurethane (A) has a hydroxy group at the terminal in combination with a compound having an isocyanato group and a (meth) acryloyl group and an alkyl isocyanate having no (meth) acryloyl group and having one isocyanato group. It may be produced by reacting with polyurethane.
- the alkyl isocyanate may be any as long as it does not have a (meth) acryloyl group and has one isocyanato group, and linear type, branched type, alicyclic type alkyl isocyanate and the like can be used and is not particularly limited. ..
- the above alkyl isocyanate may be used alone or in combination of two or more.
- Polyurethane (A) is obtained by reacting a compound having an isocyanato group and a (meth) acryloyl group, an alkyl isocyanate having no (meth) acryloyl group and having one isocyanato group, and a polyurethane having a hydroxy group at the terminal.
- the amount of (meth) acryloyl group introduced into polyurethane having a hydroxy group at the terminal can be adjusted by producing.
- a polyurethane (A) containing a plurality of types of polyurethane having different amounts of introduced (meth) acryloyl groups at the ends is produced.
- the plurality of types of polyurethanes include polyurethanes (a1) having a plurality of (meth) acryloyl groups at the ends.
- the plurality of types of polyurethane include not only polyurethane (a1) but also polyurethane in which at least a part of the plurality of ends has a structure derived from the above-mentioned alkyl isocyanate.
- the produced plurality of types of polyurethanes include polyurethanes in which at least some of the plurality of ends do not have a (meth) acryloyl group. Furthermore, among the plurality of types of polyurethane produced, polyurethane (a2) having a (meth) acryloyl group at only one terminal may be included.
- the pressure-sensitive adhesive composition of the present embodiment contains the polyurethane (A) obtained by the above synthesis method, the (meth) acrylate monomer (B), the chain transfer agent (C), and the photopolymerization initiator (D).
- the ionic liquid (E) can be produced by a method of mixing the fatty acid ester (F) added as needed and other additives.
- the method of mixing each component contained in the pressure-sensitive adhesive composition of the present embodiment is not particularly limited, and can be carried out by using, for example, a stirring device equipped with a stirring blade such as a homodisper or a paddle blade. ..
- the method for producing the BG tape of the present embodiment is not particularly limited, and the BG tape can be produced by using a known method.
- an adhesive composition is applied onto a sheet-shaped base material, and a separator is laminated to form a laminate.
- the pressure-sensitive adhesive composition is irradiated with ultraviolet rays via a separator to photo-cure the pressure-sensitive adhesive composition.
- a BG tape having a pressure-sensitive adhesive layer made of a cured product of the pressure-sensitive adhesive composition formed on the base material can be obtained.
- the method of applying the pressure-sensitive adhesive composition to the base material is not particularly limited and can be appropriately selected.
- various coaters such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater are used. Examples thereof include a method to be used and a screen printing method.
- Examples of the light source for photocuring the pressure-sensitive adhesive composition include a black light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, and a xenon lamp.
- the light irradiation intensity is preferably a condition in which the pressure-sensitive adhesive composition can be sufficiently cured and the gel fraction of the cured product is in the range of 50 to 65% by mass. For example, 50 to It is preferably 3000 mW / cm 2. If the light irradiation intensity is weak, it takes time to cure and the productivity decreases.
- the pressure-sensitive adhesive composition is irradiated with ultraviolet rays via a transparent separator, but when the base material is transparent, ultraviolet rays may be irradiated from the base material side, and an opaque separator is used. May be good.
- the BG tape of the present embodiment can be used, for example, for applications where it is attached to an adherend having an uneven portion on the surface and then peeled off. Specifically, it can be suitably used as a back grind tape for semiconductor wafer processing, which is attached to a surface on which bumps of a semiconductor wafer are formed to protect the surface of the semiconductor wafer and is peeled off after a predetermined wafer processing step. ..
- the peel strength (adhesive strength) of the BG tape is determined, for example, in the back grind step in the processing step of the semiconductor device. , It is necessary to have peeling strength (adhesive strength) for firmly fixing the BG tape to the semiconductor wafer. On the other hand, the peel strength of the BG tape needs to be such that the parts of the semiconductor device are not damaged when the BG tape is peeled from the semiconductor wafer after a predetermined processing step.
- the peeling strength of the BG tape used for the above applications is such that the peeling speed is 0.3 m / min.
- the thickness of the pressure-sensitive adhesive layer is 50 to 200 ⁇ m, it is preferably 10 to 300 gf / 25 mm, more preferably 15 to 200 gf / 25 mm, and further preferably 20 to 150 gf / 25 mm. preferable.
- the thickness of the pressure-sensitive adhesive layer is 200 to 500 ⁇ m, it is preferably 50 to 500 gf / 25 mm, more preferably 60 to 400 gf / 25 mm, and even more preferably 70 to 300 gf / 25 mm.
- a specific method for measuring the peel strength of the BG tape will be described later in Examples.
- the BG tape of the present embodiment has a pressure-sensitive adhesive layer made of a cured product of the pressure-sensitive adhesive composition of the present embodiment on one side of a sheet-like base material. Therefore, the BG tape of the present embodiment has sufficient adhesive strength, and it is difficult for adhesive residue to be transferred to the adherend after the BG tape is peeled off, and moreover, unevenness absorption and antistatic are performed. Excellent in prevention. Therefore, the BG tape of the present embodiment is suitable for applications where it is attached to an adherend having an uneven portion on the surface and then peeled off.
- the BG tape of the present embodiment can be suitably used as, for example, a BG tape that is attached when performing a back grind step of a semiconductor wafer having an uneven portion composed of bumps on the surface and is peeled off after the back grind step.
- the semiconductor wafer is fixed with sufficient adhesive force by the BG tape of the present embodiment.
- the BG tape has sufficient unevenness absorption, gaps are unlikely to occur between the BG tape attached to the semiconductor wafer and the periphery of the bump. Therefore, it is possible to prevent the water used in the back grind process from entering the gap between the BG tape and the periphery of the bump and contaminating the semiconductor wafer.
- the BG tape of the present embodiment has sufficient antistatic properties, it is possible to suppress peeling charge when the BG tape attached to the semiconductor wafer is peeled off after the backgrinding step. Further, after the back grind step, adhesive residue is less likely to occur around the bumps of the semiconductor wafer from which the BG tape has been peeled off, which is preferable.
- the BG tape of the present embodiment can have a single-layer structure in which the pressure-sensitive adhesive layer is a cured product of the pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive layer can be formed only by performing the step of forming one layer. Therefore, the BG tape of the present embodiment has fewer manufacturing steps than, for example, a case where a BG tape having a layer having unevenness absorbing property, a layer having antistatic property, and a layer having adhesive strength is formed. Can be easily manufactured with.
- Neostan U-810 manufactured by Nitto Kasei Co., Ltd. was charged with 0.8 g.
- the obtained polyurethane (A-1) was analyzed using the infrared absorption spectrum (IR) method. As a result, no peak derived from the isocyanato group was observed. Therefore, it was confirmed that the polyurethane (A-1) is a polyurethane (a1) in which an acryloyloxy group is introduced at all terminals.
- IR infrared absorption spectrum
- the obtained polyurethane (A-2) was analyzed using the infrared absorption spectrum (IR) method. As a result, no peak derived from the isocyanato group was observed. Therefore, it was confirmed that the polyurethane (A-2) is a polyurethane (a1) in which an acryloyloxy group is introduced at all terminals.
- PE1 Pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko KK)
- NR1 1,3,5-Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trione (manufactured by Showa Denko KK)
- TPO Omnirad TPO H
- IGM Resins BV 2,4,6-trimethylbenzoyldiphenylphosphine oxide
- IGM Resins BV 184
- Omnirad 184 1-Hydroxycyclohexyl-phenylketone (manufactured by IGM Resins BV)
- Elexel AS-110 1-Ethyl-3-methylimidazolium bis (fluorosulfonyl) imide (manufactured by Dai-ichi Kogyo Seiyaku Co
- ⁇ Making BG tape> As a sheet-like base material, a PET film having a thickness of 50 ⁇ m (manufactured by Toyobo Co., Ltd., trade name: ester (trademark) film E5100) was prepared. Then, the pressure-sensitive adhesive composition of Example 1 was applied onto the corona-treated surface of the base material using an applicator so that the thickness after curing was 150 ⁇ m.
- a silicone-based ultra-light peeling PET film manufactured by Toyobo Co., Ltd., product name: E7006
- a silicone-based ultra-light peeling PET film having a thickness of 75 ⁇ m was attached to the coated surface of the pressure-sensitive adhesive composition using a rubber roller.
- an ultraviolet irradiation device manufactured by Eye Graphics Co., Ltd., UV irradiation device 3 kW, high-pressure mercury lamp
- the pressure-sensitive adhesive composition was photocured by irradiating with ultraviolet rays under the condition of an irradiation amount of 1000 mJ / cm 2.
- BG tape was prepared.
- Comparative Example 4 the thickness of the pressure-sensitive adhesive composition after curing was adjusted to 30 ⁇ m. As a result, BG tapes of Examples 2 to 9 and Comparative Examples 1 to 4 were obtained.
- the BG tape was cut into a size of 120 mm in length and 120 mm in width, and left for 3 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH for humidity control.
- the peeling PET film is peeled off to expose the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is used under the condition of an applied voltage of 100 V ⁇ 60 seconds using a high resistivity meter (High Restor-UX manufactured by Mitsubishi Chemical Analytech Co., Ltd.).
- the surface resistivity on the side was measured. Then, it was evaluated according to the following criteria. It can be said that the smaller the surface resistivity, the less likely it is that peeling charge is generated when the BG tape attached to the semiconductor wafer is peeled off, and the BG tape has excellent antistatic properties.
- the BG tape was cut into a size of 25 mm in length and 50 mm in width, and the separator was peeled off to expose the adhesive layer. Then, the surface of the exposed pressure-sensitive adhesive layer and the bumps of a wafer with bumps (WALTS-TEG FC150SCJY LF (PI) manufactured by Waltz, bump height: 75 ⁇ m, bump size: diameter 90 ⁇ m) were placed facing each other. Then, a rubber roller (diameter: 85 mm, width: 50 mm) having a mass of 2 kg (load 19.6 N) is reciprocated three times at a speed of 10 mm / sec on the base material of the BG tape to transfer the BG tape and the bumped wafer. I pasted them together.
- WALTS-TEG FC150SCJY LF (PI) manufactured by Waltz, bump height: 75 ⁇ m, bump size: diameter 90 ⁇ m
- BG tape was cut into a size of 25 mm in length and 50 mm in width, and the separator was peeled off to expose the adhesive layer. Then, the surface of the exposed pressure-sensitive adhesive layer was placed facing the bumps of a wafer with bumps (WALTS-TEG FC150SCJY LF (PI) manufactured by Waltz, bump height: 75 ⁇ m, bump size: diameter 90 ⁇ m).
- a rubber roller (diameter: 85 mm, width: 50 mm) having a mass of 2 kg (load 19.6 N) is reciprocated three times at a speed of 10 mm / sec on the base material of the BG tape to transfer the BG tape and the bumped wafer. I pasted them together.
- the bumped wafer bonded to the BG tape was left at 23 ° C. for 24 hours, and then the BG tape was applied at approximately 2 m / min. It was peeled off by hand at a moderate speed. Then, the surface of the bumped wafer was observed with a digital optical microscope (RH-2000 manufactured by Hirox Co., Ltd.), and the presence or absence of adhesive residue and contamination by ionic liquid was evaluated according to the following criteria. The results are shown in Table 1.
- the “adhesive residue” means that the adhesive layer itself remains attached to the wafer surface and the wafer surface is sticky.
- the “contamination by the ionic liquid” means that the ionic liquid bleeding out from the pressure-sensitive adhesive layer adheres to the wafer surface and the wafer surface is wet.
- Adhesive composition on a 75 ⁇ m-thick peeling PET film (manufactured by Higashiyama Film Co., Ltd., trade name: Clean Sepa (trademark) HY-S10-2) so that the thickness after curing is 150 ⁇ m using an applicator. I applied the thing.
- the thickness after curing was adjusted to 30 ⁇ m.
- the coated surface of the pressure-sensitive adhesive composition was covered with a silicone-based ultra-light peeling PET film (manufactured by Toyobo Co., Ltd., product name: E7006) having a thickness of 75 ⁇ m.
- the irradiation distance is 25 cm
- the lamp moving speed is 1.0 m / min
- the irradiation amount is 1000 mJ / cm 2 .
- Ultraviolet rays were irradiated through the ultra-light peeling PET film, and the pressure-sensitive adhesive composition was cured to obtain a cured product (adhesive layer).
- the cured product (adhesive layer) was cut out to a size of about 1 g, and the PET films on both sides were peeled off to prepare a sample for measurement, and the mass thereof was measured.
- B Mass of measurement sample before immersion in toluene
- the BG tapes of Examples 1 to 9 using the pressure-sensitive adhesive composition containing 0.4 to 6% by mass of the ionic liquid all have a surface resistivity of the pressure-sensitive adhesive layer of 1 ⁇ . It was less than 10 11 ⁇ / ⁇ and had excellent antistatic properties.
- the BG tapes of Examples 1 to 9 all had sufficient peel strength of 10 gf / 25 mm or more, and the evaluation of unevenness absorption and adhesive residue / contamination was " ⁇ (good)". ..
- the evaluation of the surface resistivity of the pressure-sensitive adhesive layer was “x (impossible)".
- the evaluation of adhesive residue / contamination was “x (impossible)”.
- the BG tape of Comparative Example 3 using the pressure-sensitive adhesive composition containing no chain transfer agent and the BG tape of Comparative Example 4 having a thickness of the pressure-sensitive adhesive layer of 30 ⁇ m have a peeling force of less than 10 gf / 25 mm and absorb unevenness. The evaluation of sex was "x (impossible)”.
- a backgrind tape that has sufficient unevenness absorption, antistatic property, adhesive strength, is less likely to cause adhesive residue, and can be manufactured with a small number of manufacturing steps.
- the back grind tape can be preferably used as an application for protecting the surface of a semiconductor wafer in the semiconductor wafer processing process and peeling it off after the processing process.
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Abstract
A back grinding tape having a sheet-shaped substrate and an adhesive agent layer formed on one surface of the substrate, wherein the adhesive agent layer comprises a cured product of an adhesive agent composition and is 50-500 μm thick, the adhesive agent composition includes a polyurethane (A), a (meth)acrylate monomer (B), a chain transfer agent (C), a photopolymerization initiator (D), and 0.4-6 mass% of an ionic liquid (E), and the polyurethane (A) includes a polyurethane (a1) having a skeleton that includes a structure derived from a polyoxyalkylene polyol and a structure derived from a polyisocyanate, and having (meth)acryloyl groups at a plurality of ends.
Description
本発明は、半導体ウエハ加工用に好適に用いられるバックグラインドテープに関する。
本願は、２０１９年９月５日に、日本に出願された特願２０１９－１６２０９２号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a back grind tape preferably used for processing semiconductor wafers.
The present application claims priority based on Japanese Patent Application No. 2019-162092 filed in Japan on September 5, 2019, the contents of which are incorporated herein by reference.
本願は、２０１９年９月５日に、日本に出願された特願２０１９－１６２０９２号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a back grind tape preferably used for processing semiconductor wafers.
The present application claims priority based on Japanese Patent Application No. 2019-162092 filed in Japan on September 5, 2019, the contents of which are incorporated herein by reference.
半導体デバイスの薄型化の要求に伴って、半導体デバイスの製造工程において半導体ウエハのバックグラインド工程が行われている。半導体ウエハのバックグラインド工程では、半導体ウエハの表面（正面）をバックグラインドテープで保護した上で、半導体ウエハの裏面を研削し、半導体ウエハを薄型化している。
With the demand for thinner semiconductor devices, a semiconductor wafer backgrinding process is being performed in the semiconductor device manufacturing process. In the back grind process of a semiconductor wafer, the front surface (front surface) of the semiconductor wafer is protected with a back grind tape, and then the back surface of the semiconductor wafer is ground to make the semiconductor wafer thinner.
従来、半導体ウエハの表面を保護するために用いられるバックグラインドテープとして、種々のものが提案されている。近年では、はんだ等からなるバンプ（電極）が表面に形成された半導体ウエハなどの、表面に凹凸部分を有する半導体ウエハに対しても、十分な凹凸吸収性を有するバックグラインドテープが求められている。
Conventionally, various back grind tapes used for protecting the surface of a semiconductor wafer have been proposed. In recent years, there has been a demand for a back grind tape having sufficient unevenness absorption even for a semiconductor wafer having uneven portions on the surface, such as a semiconductor wafer having bumps (electrodes) made of solder or the like formed on the surface. ..
また、従来、バックグラインドテープを半導体ウエハから剥離する際に、剥離帯電と呼ばれる静電気が発生して、半導体ウエハの回路が破壊されたり、半導体ウエハに異物が付着したりする場合があった。このため、バックグラインドテープにおいては、十分な帯電防止性を有することが要求されている。
凹凸吸収性と帯電防止性の両性能を兼ね備えるバックグラインドテープとして、例えば、特許文献１には、基材層と、凹凸吸収性樹脂層と、帯電防止層と、粘着性樹脂層と、をこの順番に備える半導体ウエハ加工用粘着性フィルムが開示されている。 Further, conventionally, when the backgrinding tape is peeled from the semiconductor wafer, static electricity called peeling charge is generated, and the circuit of the semiconductor wafer may be destroyed or foreign matter may adhere to the semiconductor wafer. Therefore, the back grind tape is required to have sufficient antistatic properties.
As a backgrinding tape having both unevenness absorbing and antistatic properties, for example, Patent Document 1 describes a base material layer, an unevenness absorbing resin layer, an antistatic layer, and an adhesive resin layer. Adhesive films for processing semiconductor wafers provided in order are disclosed.
凹凸吸収性と帯電防止性の両性能を兼ね備えるバックグラインドテープとして、例えば、特許文献１には、基材層と、凹凸吸収性樹脂層と、帯電防止層と、粘着性樹脂層と、をこの順番に備える半導体ウエハ加工用粘着性フィルムが開示されている。 Further, conventionally, when the backgrinding tape is peeled from the semiconductor wafer, static electricity called peeling charge is generated, and the circuit of the semiconductor wafer may be destroyed or foreign matter may adhere to the semiconductor wafer. Therefore, the back grind tape is required to have sufficient antistatic properties.
As a backgrinding tape having both unevenness absorbing and antistatic properties, for example, Patent Document 1 describes a base material layer, an unevenness absorbing resin layer, an antistatic layer, and an adhesive resin layer. Adhesive films for processing semiconductor wafers provided in order are disclosed.
しかしながら、特許文献１に記載の半導体ウエハ加工用粘着性フィルムは、各層をそれぞれシート化した後に貼り合わせて製造する必要があるため、製造手順が煩雑である。
また、バックグラインドテープにおいては、半導体ウエハなどの被着体をバックグラインドテープに十分な強度で固定できる粘着力を有することが求められる。しかし、粘着力の高いバックグラインドテープを被着体に貼付してから被着体を加工し、その後にバックグラインドテープを剥離すると、バックグラインドテープの粘着剤層が被着体に転写される糊残りが発生する場合がある。 However, the adhesive film for semiconductor wafer processing described in Patent Document 1 needs to be manufactured by laminating each layer after forming a sheet, so that the manufacturing procedure is complicated.
Further, the back grind tape is required to have an adhesive force capable of fixing an adherend such as a semiconductor wafer to the back grind tape with sufficient strength. However, when the back grind tape with high adhesive strength is attached to the adherend, the adherend is processed, and then the back grind tape is peeled off, the adhesive layer of the back grind tape is transferred to the adherend. The rest may occur.
また、バックグラインドテープにおいては、半導体ウエハなどの被着体をバックグラインドテープに十分な強度で固定できる粘着力を有することが求められる。しかし、粘着力の高いバックグラインドテープを被着体に貼付してから被着体を加工し、その後にバックグラインドテープを剥離すると、バックグラインドテープの粘着剤層が被着体に転写される糊残りが発生する場合がある。 However, the adhesive film for semiconductor wafer processing described in Patent Document 1 needs to be manufactured by laminating each layer after forming a sheet, so that the manufacturing procedure is complicated.
Further, the back grind tape is required to have an adhesive force capable of fixing an adherend such as a semiconductor wafer to the back grind tape with sufficient strength. However, when the back grind tape with high adhesive strength is attached to the adherend, the adherend is processed, and then the back grind tape is peeled off, the adhesive layer of the back grind tape is transferred to the adherend. The rest may occur.
本発明は、上記事情に鑑みてなされたものであり、十分な凹凸吸収性、帯電防止性、粘着力を有し、かつバックグラインドテープを剥離した後に糊残りが生じにくく、しかも少ない製造工程で製造可能なバックグラインドテープを提供することを目的とする。
The present invention has been made in view of the above circumstances, has sufficient unevenness absorbing property, antistatic property, and adhesive strength, is less likely to leave adhesive residue after peeling the backgrinding tape, and requires less manufacturing process. It is an object of the present invention to provide a manufacturable back grind tape.
本発明の第一の態様は以下のバックグラインドテープである。
［１］ シート状の基材と、前記基材の片面に形成された粘着剤層とを有するバックグラインドテープであって、
前記粘着剤層が、粘着剤組成物の硬化物からなり、厚みが５０～５００μｍであり、
前記粘着剤組成物が、ポリウレタン（Ａ）と、（メタ）アクリレートモノマー（Ｂ）と、連鎖移動剤（Ｃ）と、光重合開始剤（Ｄ）と、イオン液体（Ｅ）とを含み、
前記ポリウレタン（Ａ）が、ポリオキシアルキレンポリオール由来の構造およびポリイソシアネート由来の構造を含む骨格を有し、複数の末端に（メタ）アクリロイル基を有するポリウレタン（ａ１）を含み、
前記粘着剤組成物がイオン液体（Ｅ）を０．４～６．０質量％含有することを特徴とするバックグラインドテープ。 The first aspect of the present invention is the following back grind tape.
[1] A back grind tape having a sheet-shaped base material and an adhesive layer formed on one side of the base material.
The pressure-sensitive adhesive layer is made of a cured product of the pressure-sensitive adhesive composition and has a thickness of 50 to 500 μm.
The pressure-sensitive adhesive composition contains a polyurethane (A), a (meth) acrylate monomer (B), a chain transfer agent (C), a photopolymerization initiator (D), and an ionic liquid (E).
The polyurethane (A) contains a polyurethane (a1) having a skeleton containing a structure derived from a polyoxyalkylene polyol and a structure derived from a polyisocyanate, and having a (meth) acryloyl group at a plurality of ends.
A back grind tape, wherein the pressure-sensitive adhesive composition contains 0.4 to 6.0% by mass of an ionic liquid (E).
［１］ シート状の基材と、前記基材の片面に形成された粘着剤層とを有するバックグラインドテープであって、
前記粘着剤層が、粘着剤組成物の硬化物からなり、厚みが５０～５００μｍであり、
前記粘着剤組成物が、ポリウレタン（Ａ）と、（メタ）アクリレートモノマー（Ｂ）と、連鎖移動剤（Ｃ）と、光重合開始剤（Ｄ）と、イオン液体（Ｅ）とを含み、
前記ポリウレタン（Ａ）が、ポリオキシアルキレンポリオール由来の構造およびポリイソシアネート由来の構造を含む骨格を有し、複数の末端に（メタ）アクリロイル基を有するポリウレタン（ａ１）を含み、
前記粘着剤組成物がイオン液体（Ｅ）を０．４～６．０質量％含有することを特徴とするバックグラインドテープ。 The first aspect of the present invention is the following back grind tape.
[1] A back grind tape having a sheet-shaped base material and an adhesive layer formed on one side of the base material.
The pressure-sensitive adhesive layer is made of a cured product of the pressure-sensitive adhesive composition and has a thickness of 50 to 500 μm.
The pressure-sensitive adhesive composition contains a polyurethane (A), a (meth) acrylate monomer (B), a chain transfer agent (C), a photopolymerization initiator (D), and an ionic liquid (E).
The polyurethane (A) contains a polyurethane (a1) having a skeleton containing a structure derived from a polyoxyalkylene polyol and a structure derived from a polyisocyanate, and having a (meth) acryloyl group at a plurality of ends.
A back grind tape, wherein the pressure-sensitive adhesive composition contains 0.4 to 6.0% by mass of an ionic liquid (E).
本発明の第一の態様の上記バックグラインドテープは、次に述べるように、以下の特徴を好ましく含むことができる。以下の特徴は２つ以上を好ましく組み合わせてよい。
［２］ 前記粘着剤層が、単層構造である［１］に記載のバックグラインドテープ。
［３］ 前記（メタ）アクリレートモノマー（Ｂ）が、単官能（メタ）アクリレートおよび多官能（メタ）アクリレートを含有する、［１］または［２］に記載のバックグラインドテープ。 The backgrinding tape of the first aspect of the present invention can preferably include the following features as described below. The following features may preferably be a combination of two or more.
[2] The back grind tape according to [1], wherein the pressure-sensitive adhesive layer has a single-layer structure.
[3] The back grind tape according to [1] or [2], wherein the (meth) acrylate monomer (B) contains a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate.
［２］ 前記粘着剤層が、単層構造である［１］に記載のバックグラインドテープ。
［３］ 前記（メタ）アクリレートモノマー（Ｂ）が、単官能（メタ）アクリレートおよび多官能（メタ）アクリレートを含有する、［１］または［２］に記載のバックグラインドテープ。 The backgrinding tape of the first aspect of the present invention can preferably include the following features as described below. The following features may preferably be a combination of two or more.
[2] The back grind tape according to [1], wherein the pressure-sensitive adhesive layer has a single-layer structure.
[3] The back grind tape according to [1] or [2], wherein the (meth) acrylate monomer (B) contains a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate.
［４］ 前記イオン液体（Ｅ）が、第四級アンモニウムイオン、イミニウムイオン、およびスルホニウムイオンからなる群から選択される有機カチオンを含む化合物である、［１］～［３］のいずれかに記載のバックグラインドテープ。
［５］ 前記イオン液体（Ｅ）が、フッ素含有有機アニオンを含む化合物である、［１］～［４］のいずれかに記載のバックグラインドテープ。 [4] The ionic liquid (E) is any of [1] to [3], which is a compound containing an organic cation selected from the group consisting of a quaternary ammonium ion, an iminium ion, and a sulfonium ion. The back grind tape described.
[5] The backgrinding tape according to any one of [1] to [4], wherein the ionic liquid (E) is a compound containing a fluorine-containing organic anion.
［５］ 前記イオン液体（Ｅ）が、フッ素含有有機アニオンを含む化合物である、［１］～［４］のいずれかに記載のバックグラインドテープ。 [4] The ionic liquid (E) is any of [1] to [3], which is a compound containing an organic cation selected from the group consisting of a quaternary ammonium ion, an iminium ion, and a sulfonium ion. The back grind tape described.
[5] The backgrinding tape according to any one of [1] to [4], wherein the ionic liquid (E) is a compound containing a fluorine-containing organic anion.
［６］ 前記イオン液体（Ｅ）が、１－エチル－３－メチルイミダゾリウムカチオンおよび／または４－メチル－１－オクチルピリジニウムカチオンと、ビス（フルオロスルホニル）イミドアニオン（（ＦＳＯ２）２Ｎ－）とを含む化合物である［１］～［５］のいずれかに記載のバックグラインドテープ。
［７］ 前記連鎖移動剤（Ｃ）が、多官能チオールである、［１］～［６］のいずれかに記載のバックグラインドテープ。
［８］ 前記粘着剤層のゲル分率が５０～６５質量％である、［１］～［７］のいずれかに記載のバックグラインドテープ。 [6] The ionic liquid (E) is 1-ethyl-3-methylimidazolium cation and / or 4-methyl-1-octyl pyridinium cation, bis (fluorosulfonyl) imide anion ((FSO 2) 2 N - The back grind tape according to any one of [1] to [5], which is a compound containing () and.
[7] The backgrinding tape according to any one of [1] to [6], wherein the chain transfer agent (C) is a polyfunctional thiol.
[8] The backgrinding tape according to any one of [1] to [7], wherein the gel content of the pressure-sensitive adhesive layer is 50 to 65% by mass.
［７］ 前記連鎖移動剤（Ｃ）が、多官能チオールである、［１］～［６］のいずれかに記載のバックグラインドテープ。
［８］ 前記粘着剤層のゲル分率が５０～６５質量％である、［１］～［７］のいずれかに記載のバックグラインドテープ。 [6] The ionic liquid (E) is 1-ethyl-3-methylimidazolium cation and / or 4-methyl-1-octyl pyridinium cation, bis (fluorosulfonyl) imide anion ((FSO 2) 2 N - The back grind tape according to any one of [1] to [5], which is a compound containing () and.
[7] The backgrinding tape according to any one of [1] to [6], wherein the chain transfer agent (C) is a polyfunctional thiol.
[8] The backgrinding tape according to any one of [1] to [7], wherein the gel content of the pressure-sensitive adhesive layer is 50 to 65% by mass.
［９］ 前記粘着剤層の表面抵抗率が１×１０１１Ω／□未満である、［１］～［８］のいずれかに記載のバックグラインドテープ。
［１０］ 前記（メタ）アクリレートモノマー（Ｂ）の合計を１００モル％としたときに、前記単官能（メタ）アクリレートを８５～９９モル％、前記多官能（メタ）アクリレートを１～１５モル％含有する、［３］～［９］のいずれかに記載のバックグラインドテープ。 [9] The backgrinding tape according to any one of [1] to [8], wherein the surface resistivity of the pressure-sensitive adhesive layer is less than 1 × 10 11 Ω / □.
[10] When the total of the (meth) acrylate monomer (B) is 100 mol%, the monofunctional (meth) acrylate is 85 to 99 mol%, and the polyfunctional (meth) acrylate is 1 to 15 mol%. The back grind tape according to any one of [3] to [9], which is contained.
［１０］ 前記（メタ）アクリレートモノマー（Ｂ）の合計を１００モル％としたときに、前記単官能（メタ）アクリレートを８５～９９モル％、前記多官能（メタ）アクリレートを１～１５モル％含有する、［３］～［９］のいずれかに記載のバックグラインドテープ。 [9] The backgrinding tape according to any one of [1] to [8], wherein the surface resistivity of the pressure-sensitive adhesive layer is less than 1 × 10 11 Ω / □.
[10] When the total of the (meth) acrylate monomer (B) is 100 mol%, the monofunctional (meth) acrylate is 85 to 99 mol%, and the polyfunctional (meth) acrylate is 1 to 15 mol%. The back grind tape according to any one of [3] to [9], which is contained.
［１１］ 前記粘着剤組成物が、
前記ポリウレタン（Ａ）を２０～５０質量％、
前記（メタ）アクリレートモノマー（Ｂ）を３５～７９質量％、
前記連鎖移動剤（Ｃ）を０．５～８．０質量％、
前記光重合開始剤（Ｄ）を０．０１～５．０質量％、
前記イオン液体（Ｅ）を０．４～６．０質量％含む、
［１］～［１０］のいずれかに記載のバックグラインドテープ。
［１２］ 前記粘着剤組成物が、更に脂肪酸エステル（Ｆ）を含有する、［１］～［１１］のいずれかに記載のバックグラインドテープ。 [11] The pressure-sensitive adhesive composition
20 to 50% by mass of the polyurethane (A),
35-79% by mass of the (meth) acrylate monomer (B),
0.5 to 8.0% by mass of the chain transfer agent (C),
0.01 to 5.0% by mass of the photopolymerization initiator (D),
The ionic liquid (E) is contained in an amount of 0.4 to 6.0% by mass.
The back grind tape according to any one of [1] to [10].
[12] The backgrinding tape according to any one of [1] to [11], wherein the pressure-sensitive adhesive composition further contains a fatty acid ester (F).
前記ポリウレタン（Ａ）を２０～５０質量％、
前記（メタ）アクリレートモノマー（Ｂ）を３５～７９質量％、
前記連鎖移動剤（Ｃ）を０．５～８．０質量％、
前記光重合開始剤（Ｄ）を０．０１～５．０質量％、
前記イオン液体（Ｅ）を０．４～６．０質量％含む、
［１］～［１０］のいずれかに記載のバックグラインドテープ。
［１２］ 前記粘着剤組成物が、更に脂肪酸エステル（Ｆ）を含有する、［１］～［１１］のいずれかに記載のバックグラインドテープ。 [11] The pressure-sensitive adhesive composition
20 to 50% by mass of the polyurethane (A),
35-79% by mass of the (meth) acrylate monomer (B),
0.5 to 8.0% by mass of the chain transfer agent (C),
0.01 to 5.0% by mass of the photopolymerization initiator (D),
The ionic liquid (E) is contained in an amount of 0.4 to 6.0% by mass.
The back grind tape according to any one of [1] to [10].
[12] The backgrinding tape according to any one of [1] to [11], wherein the pressure-sensitive adhesive composition further contains a fatty acid ester (F).
本発明によれば、十分な凹凸吸収性、帯電防止性、粘着力を有し、かつバックグラインドテープを剥離した後に糊残りが生じにくいバックグラインドテープを提供できる。
しかも、本発明のバックグラインドテープは、粘着剤層が粘着剤組成物の硬化物であり、十分な凹凸吸収性、帯電防止性、粘着力を有する。このため、凹凸吸収性を有する層と帯電防止性を有する層と粘着力を有する層とを別々に設けなくてもよく、前記テープは少ない製造工程で製造可能である。
したがって、本発明のバックグラインドテープは、表面にバンプが形成された半導体ウエハなど、表面に凹凸部分を有する被着体のバックグラインド工程を行う際に、表面を保護するために使用されるバックグラインドテープとして好適である。 According to the present invention, it is possible to provide a backgrinding tape having sufficient unevenness absorbing property, antistatic property, and adhesive strength, and in which adhesive residue is unlikely to occur after the backgrinding tape is peeled off.
Moreover, in the back grind tape of the present invention, the pressure-sensitive adhesive layer is a cured product of the pressure-sensitive adhesive composition, and has sufficient unevenness absorption, antistatic property, and adhesive strength. Therefore, it is not necessary to separately provide the layer having the unevenness absorbing property, the layer having the antistatic property, and the layer having the adhesive force, and the tape can be manufactured in a small number of manufacturing steps.
Therefore, the backgrinding tape of the present invention is used to protect the surface of an adherend having an uneven portion on the surface, such as a semiconductor wafer having bumps formed on the surface. Suitable as a tape.
しかも、本発明のバックグラインドテープは、粘着剤層が粘着剤組成物の硬化物であり、十分な凹凸吸収性、帯電防止性、粘着力を有する。このため、凹凸吸収性を有する層と帯電防止性を有する層と粘着力を有する層とを別々に設けなくてもよく、前記テープは少ない製造工程で製造可能である。
したがって、本発明のバックグラインドテープは、表面にバンプが形成された半導体ウエハなど、表面に凹凸部分を有する被着体のバックグラインド工程を行う際に、表面を保護するために使用されるバックグラインドテープとして好適である。 According to the present invention, it is possible to provide a backgrinding tape having sufficient unevenness absorbing property, antistatic property, and adhesive strength, and in which adhesive residue is unlikely to occur after the backgrinding tape is peeled off.
Moreover, in the back grind tape of the present invention, the pressure-sensitive adhesive layer is a cured product of the pressure-sensitive adhesive composition, and has sufficient unevenness absorption, antistatic property, and adhesive strength. Therefore, it is not necessary to separately provide the layer having the unevenness absorbing property, the layer having the antistatic property, and the layer having the adhesive force, and the tape can be manufactured in a small number of manufacturing steps.
Therefore, the backgrinding tape of the present invention is used to protect the surface of an adherend having an uneven portion on the surface, such as a semiconductor wafer having bumps formed on the surface. Suitable as a tape.
以下、本発明の好ましい例である、実施形態について詳細に説明する。ただし、本発明は、以下に示す実施形態のみに限定されるものではない。本発明の範囲内において、必要に応じて、種類、量、組成、比率、形、及びサイズなどについて、省略、変更、及び／又は追加することも可能である。
Hereinafter, embodiments, which are preferable examples of the present invention, will be described in detail. However, the present invention is not limited to the embodiments shown below. Within the scope of the present invention, it is possible to omit, change, and / or add the type, amount, composition, ratio, shape, size, and the like, if necessary.
＜バックグラインドテープ＞
本実施形態におけるバックグラインドテープ（以下、「ＢＧテープ」とも言う。）は、シート状の基材と、基材の片面に形成された粘着剤層とを有する。粘着剤層は、後述する粘着剤組成物の硬化物からなり、好ましくは単層構造である。なお、ここでいう「テープ」の形状は、帯状のものに限らず、任意の形状であって良く、矩形や円板状のシートも含まれる。 <Backgrind tape>
The back grind tape (hereinafter, also referred to as “BG tape”) in the present embodiment has a sheet-like base material and an adhesive layer formed on one side of the base material. The pressure-sensitive adhesive layer is composed of a cured product of the pressure-sensitive adhesive composition described later, and preferably has a single-layer structure. The shape of the "tape" referred to here is not limited to a strip shape, but may be any shape, and includes a rectangular or disc-shaped sheet.
本実施形態におけるバックグラインドテープ（以下、「ＢＧテープ」とも言う。）は、シート状の基材と、基材の片面に形成された粘着剤層とを有する。粘着剤層は、後述する粘着剤組成物の硬化物からなり、好ましくは単層構造である。なお、ここでいう「テープ」の形状は、帯状のものに限らず、任意の形状であって良く、矩形や円板状のシートも含まれる。 <Backgrind tape>
The back grind tape (hereinafter, also referred to as “BG tape”) in the present embodiment has a sheet-like base material and an adhesive layer formed on one side of the base material. The pressure-sensitive adhesive layer is composed of a cured product of the pressure-sensitive adhesive composition described later, and preferably has a single-layer structure. The shape of the "tape" referred to here is not limited to a strip shape, but may be any shape, and includes a rectangular or disc-shaped sheet.
（基材）
基材の材質は、適宜選択可能であり、例えば、樹脂材料などが挙げられる。樹脂材料としては、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等のポリオレフィン；ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート等のポリエステルシート；ポリ塩化ビニル（ＰＶＣ）；ポリイミド（ＰＩ）；ポリフェニレンサルファイド（ＰＰＳ）；エチレン酢酸ビニル（ＥＶＡ）；ポリテトラフルオロエチレン（ＰＴＦＥ）などが挙げられる。これらの樹脂材料の中でも、適度な可撓性を有するシートが得られるため、ＰＥ、ＰＰ、ＰＥＴを用いることが好ましい。樹脂材料は、１種のみ単独で用いてもよいし、２種以上を混合して用いてもよい。基材は透明であっても、不透明であってもよい。 (Base material)
The material of the base material can be appropriately selected, and examples thereof include a resin material. Resin materials include polyolefins such as polyethylene (PE) and polypropylene (PP); polyester sheets such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate; polyvinyl chloride (PVC); polyimide (PI). ; Polyphenylene terephide (PPS); ethylene vinyl acetate (EVA); polytetrafluoroethylene (PTFE) and the like. Among these resin materials, PE, PP, and PET are preferably used because a sheet having appropriate flexibility can be obtained. As the resin material, only one kind may be used alone, or two or more kinds may be mixed and used. The substrate may be transparent or opaque.
基材の材質は、適宜選択可能であり、例えば、樹脂材料などが挙げられる。樹脂材料としては、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等のポリオレフィン；ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート等のポリエステルシート；ポリ塩化ビニル（ＰＶＣ）；ポリイミド（ＰＩ）；ポリフェニレンサルファイド（ＰＰＳ）；エチレン酢酸ビニル（ＥＶＡ）；ポリテトラフルオロエチレン（ＰＴＦＥ）などが挙げられる。これらの樹脂材料の中でも、適度な可撓性を有するシートが得られるため、ＰＥ、ＰＰ、ＰＥＴを用いることが好ましい。樹脂材料は、１種のみ単独で用いてもよいし、２種以上を混合して用いてもよい。基材は透明であっても、不透明であってもよい。 (Base material)
The material of the base material can be appropriately selected, and examples thereof include a resin material. Resin materials include polyolefins such as polyethylene (PE) and polypropylene (PP); polyester sheets such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate; polyvinyl chloride (PVC); polyimide (PI). ; Polyphenylene terephide (PPS); ethylene vinyl acetate (EVA); polytetrafluoroethylene (PTFE) and the like. Among these resin materials, PE, PP, and PET are preferably used because a sheet having appropriate flexibility can be obtained. As the resin material, only one kind may be used alone, or two or more kinds may be mixed and used. The substrate may be transparent or opaque.
基材として樹脂材料からなる樹脂シートを用いる場合、樹脂シートは、単層であってもよいし、二層以上の多層構造（例えば三層構造）であってもよい。多層構造を有する樹脂シートにおいて、各層を構成する樹脂材料は、１種のみを単独で含む樹脂材料であってもよいし、２種以上を含む樹脂材料であってもよい。
When a resin sheet made of a resin material is used as the base material, the resin sheet may have a single layer or a multi-layer structure having two or more layers (for example, a three-layer structure). In the resin sheet having a multi-layer structure, the resin material constituting each layer may be a resin material containing only one type alone or a resin material containing two or more types.
基材としては、帯電防止処理が施されているものを用いても良い。基材に施される帯電防止処理としては、特に限定されないが、基材の少なくとも片面に帯電防止層を設ける方法、基材に帯電防止剤を練り込む方法などを用いることができる。
さらに、基材の粘着剤層が形成される面には、必要に応じて、酸処理、アルカリ処理、プライマー処理、コロナ処理、プラズマ処理、紫外線処理、オゾン処理等の易接着処理が施されていてもよい。 As the base material, a base material that has been subjected to antistatic treatment may be used. The antistatic treatment applied to the base material is not particularly limited, but a method of providing an antistatic layer on at least one surface of the base material, a method of kneading an antistatic agent into the base material, and the like can be used.
Further, the surface on which the pressure-sensitive adhesive layer of the base material is formed is subjected to easy-adhesion treatment such as acid treatment, alkali treatment, primer treatment, corona treatment, plasma treatment, ultraviolet treatment, ozone treatment, etc., if necessary. You may.
さらに、基材の粘着剤層が形成される面には、必要に応じて、酸処理、アルカリ処理、プライマー処理、コロナ処理、プラズマ処理、紫外線処理、オゾン処理等の易接着処理が施されていてもよい。 As the base material, a base material that has been subjected to antistatic treatment may be used. The antistatic treatment applied to the base material is not particularly limited, but a method of providing an antistatic layer on at least one surface of the base material, a method of kneading an antistatic agent into the base material, and the like can be used.
Further, the surface on which the pressure-sensitive adhesive layer of the base material is formed is subjected to easy-adhesion treatment such as acid treatment, alkali treatment, primer treatment, corona treatment, plasma treatment, ultraviolet treatment, ozone treatment, etc., if necessary. You may.
基材の厚さは、基材の材質などに応じて適宜選択できる。ＢＧテープが、表面に凹凸部分を有する半導体ウエハに貼付され、その後に剥離される用途に用いられるものであって、基材として樹脂シートを用いる場合、基材の厚さは、例えば１０～１０００μｍであることが好ましく、好ましくは５０～３００μｍである。基材の厚さが１０μｍ以上であると、ＢＧテープの剛性（コシ）が高くなる。そのため、ＢＧテープを、被着体である半導体ウエハに貼り付けたり剥離したりする際に、ＢＧテープにしわおよび浮きが生じ難くなる傾向がある。また、基材の厚さが１０００μｍ以下であると、半導体ウエハに貼り付けたＢＧテープを、半導体ウエハから剥離しやすくなり、作業性（取扱い性、ハンドリング）が良好となる。
The thickness of the base material can be appropriately selected according to the material of the base material and the like. When the BG tape is attached to a semiconductor wafer having an uneven portion on the surface and then peeled off, and a resin sheet is used as the base material, the thickness of the base material is, for example, 10 to 1000 μm. It is preferably 50 to 300 μm. When the thickness of the base material is 10 μm or more, the rigidity (stiffness) of the BG tape becomes high. Therefore, when the BG tape is attached to or peeled off from the semiconductor wafer as an adherend, the BG tape tends to be less likely to have wrinkles and floats. Further, when the thickness of the base material is 1000 μm or less, the BG tape attached to the semiconductor wafer can be easily peeled off from the semiconductor wafer, and workability (handleability, handling) is improved.
（粘着剤層）
基材の片面には、単層の粘着剤層が形成されている。粘着剤層は、後述する粘着剤組成物の硬化物からなる。ＢＧテープが、表面に凹凸部分を有する半導体ウエハなどの被着体に貼付され、その後に剥離される用途に用いられる場合、粘着剤層は、ＢＧテープを被着体の表面に十分な接着力で固定することにより、バックグラインド工程中の被着体の表面を保護する役割を有する。また、粘着剤層は、被着体表面の凹凸を吸収して平滑にすることにより、すなわち、被着体の凹凸の隙間が粘着剤層により好ましく埋められることで、バックグラインド工程の精度を高める役割を有する。さらに、粘着剤層は、ＢＧテープを被着体から剥離する際に発生する剥離帯電を低減させる。また、本実施形態のＢＧテープの有する粘着剤層は、ＢＧテープを剥離しても糊残りが生じない。また、本実施形態のＢＧテープの有する粘着剤層は、ＢＧテープを剥離した後の被着体に、後述するイオン液（Ｅ）による汚染が生じ難い。 (Adhesive layer)
A single adhesive layer is formed on one side of the base material. The pressure-sensitive adhesive layer is composed of a cured product of the pressure-sensitive adhesive composition described later. When the BG tape is applied to an adherend such as a semiconductor wafer having an uneven portion on the surface and then peeled off, the pressure-sensitive adhesive layer attaches the BG tape to the surface of the adherend sufficiently. By fixing with, it has a role of protecting the surface of the adherend during the back grind process. Further, the pressure-sensitive adhesive layer absorbs and smoothes the unevenness of the surface of the adherend, that is, the gaps between the unevenness of the adherend are preferably filled by the pressure-sensitive adhesive layer, thereby improving the accuracy of the back grind process. Has a role. Further, the pressure-sensitive adhesive layer reduces the peeling charge generated when the BG tape is peeled from the adherend. Further, the pressure-sensitive adhesive layer of the BG tape of the present embodiment does not leave adhesive residue even when the BG tape is peeled off. Further, the pressure-sensitive adhesive layer of the BG tape of the present embodiment is unlikely to cause contamination of the adherend after the BG tape is peeled off by the ionic liquid (E) described later.
基材の片面には、単層の粘着剤層が形成されている。粘着剤層は、後述する粘着剤組成物の硬化物からなる。ＢＧテープが、表面に凹凸部分を有する半導体ウエハなどの被着体に貼付され、その後に剥離される用途に用いられる場合、粘着剤層は、ＢＧテープを被着体の表面に十分な接着力で固定することにより、バックグラインド工程中の被着体の表面を保護する役割を有する。また、粘着剤層は、被着体表面の凹凸を吸収して平滑にすることにより、すなわち、被着体の凹凸の隙間が粘着剤層により好ましく埋められることで、バックグラインド工程の精度を高める役割を有する。さらに、粘着剤層は、ＢＧテープを被着体から剥離する際に発生する剥離帯電を低減させる。また、本実施形態のＢＧテープの有する粘着剤層は、ＢＧテープを剥離しても糊残りが生じない。また、本実施形態のＢＧテープの有する粘着剤層は、ＢＧテープを剥離した後の被着体に、後述するイオン液（Ｅ）による汚染が生じ難い。 (Adhesive layer)
A single adhesive layer is formed on one side of the base material. The pressure-sensitive adhesive layer is composed of a cured product of the pressure-sensitive adhesive composition described later. When the BG tape is applied to an adherend such as a semiconductor wafer having an uneven portion on the surface and then peeled off, the pressure-sensitive adhesive layer attaches the BG tape to the surface of the adherend sufficiently. By fixing with, it has a role of protecting the surface of the adherend during the back grind process. Further, the pressure-sensitive adhesive layer absorbs and smoothes the unevenness of the surface of the adherend, that is, the gaps between the unevenness of the adherend are preferably filled by the pressure-sensitive adhesive layer, thereby improving the accuracy of the back grind process. Has a role. Further, the pressure-sensitive adhesive layer reduces the peeling charge generated when the BG tape is peeled from the adherend. Further, the pressure-sensitive adhesive layer of the BG tape of the present embodiment does not leave adhesive residue even when the BG tape is peeled off. Further, the pressure-sensitive adhesive layer of the BG tape of the present embodiment is unlikely to cause contamination of the adherend after the BG tape is peeled off by the ionic liquid (E) described later.
本実施形態の粘着剤層の厚みは任意に選択できるが、好ましくは５０～５００μｍであり、６０～４００μｍであることがより好ましく、７０～３００μｍであることが更に好ましい。粘着剤層の厚みが５０μｍ以上であると、ＢＧテープの凹凸吸収性および粘着力が良好となる。また、粘着剤層の厚みが５００μｍ以下であると、粘着剤層の膜厚制御が容易となる。
The thickness of the pressure-sensitive adhesive layer of the present embodiment can be arbitrarily selected, but is preferably 50 to 500 μm, more preferably 60 to 400 μm, and even more preferably 70 to 300 μm. When the thickness of the pressure-sensitive adhesive layer is 50 μm or more, the unevenness absorption and adhesive strength of the BG tape become good. Further, when the thickness of the pressure-sensitive adhesive layer is 500 μm or less, the film thickness of the pressure-sensitive adhesive layer can be easily controlled.
本実施形態のＢＧテープが、表面に凹凸部分を有する被着体に貼付されるテープである場合、粘着剤層の厚みは、被着体表面の凹凸部分の高さに大きく依存する。粘着剤層の厚みは、十分な凹凸吸収性が得られるように、表面の凹凸部分の高さ以上とすることが好ましい。したがって、例えば、表面の凹凸が半導体ウエハに形成されたバンプである場合、粘着剤層の厚みをバンプの高さ寸法の２倍以上とすることが好ましい。バンプの高さは通常３０～２００μｍである。例えば、バンプの高さが１００μｍである場合には、粘着剤層の厚みを２００μｍ以上とすることが好ましく、バンプの高さが２００μｍである場合には、粘着剤層の厚みを４００μｍ以上とすることが好ましい。
粘着剤層は、単層構造であってもよいし、本実施形態の粘着剤層と、本実施形態の粘着剤層とは異なる１層以上の他の粘着剤層を積層した多層構造であってもよい。他の粘着剤層としては、従来公知の粘着剤層を用いることができる。本実施形態において、粘着剤層が多層構造である場合、本実施形態の粘着剤層が最表面に存在する必要がある。また、本実施形態のＢＧテープにおいては、粘着剤層の硬化を阻害しない範囲内で、粘着剤層と基材との間に粘着剤層以外の層が存在していても良い。工程短縮の面から、粘着剤層は単層構造であることが好ましい。 When the BG tape of the present embodiment is a tape to be attached to an adherend having an uneven portion on the surface, the thickness of the pressure-sensitive adhesive layer largely depends on the height of the uneven portion on the surface of the adherend. The thickness of the pressure-sensitive adhesive layer is preferably equal to or greater than the height of the uneven portion on the surface so that sufficient uneven absorption can be obtained. Therefore, for example, when the unevenness of the surface is a bump formed on the semiconductor wafer, it is preferable that the thickness of the pressure-sensitive adhesive layer is twice or more the height dimension of the bump. The bump height is usually 30-200 μm. For example, when the bump height is 100 μm, the thickness of the pressure-sensitive adhesive layer is preferably 200 μm or more, and when the bump height is 200 μm, the thickness of the pressure-sensitive adhesive layer is 400 μm or more. Is preferable.
The pressure-sensitive adhesive layer may have a single-layer structure, or may have a multi-layer structure in which the pressure-sensitive adhesive layer of the present embodiment and one or more other pressure-sensitive adhesive layers different from the pressure-sensitive adhesive layer of the present embodiment are laminated. You may. As another pressure-sensitive adhesive layer, a conventionally known pressure-sensitive adhesive layer can be used. In the present embodiment, when the pressure-sensitive adhesive layer has a multi-layer structure, the pressure-sensitive adhesive layer of the present embodiment needs to be present on the outermost surface. Further, in the BG tape of the present embodiment, a layer other than the pressure-sensitive adhesive layer may be present between the pressure-sensitive adhesive layer and the base material within a range that does not hinder the curing of the pressure-sensitive adhesive layer. From the viewpoint of shortening the process, the pressure-sensitive adhesive layer preferably has a single-layer structure.
粘着剤層は、単層構造であってもよいし、本実施形態の粘着剤層と、本実施形態の粘着剤層とは異なる１層以上の他の粘着剤層を積層した多層構造であってもよい。他の粘着剤層としては、従来公知の粘着剤層を用いることができる。本実施形態において、粘着剤層が多層構造である場合、本実施形態の粘着剤層が最表面に存在する必要がある。また、本実施形態のＢＧテープにおいては、粘着剤層の硬化を阻害しない範囲内で、粘着剤層と基材との間に粘着剤層以外の層が存在していても良い。工程短縮の面から、粘着剤層は単層構造であることが好ましい。 When the BG tape of the present embodiment is a tape to be attached to an adherend having an uneven portion on the surface, the thickness of the pressure-sensitive adhesive layer largely depends on the height of the uneven portion on the surface of the adherend. The thickness of the pressure-sensitive adhesive layer is preferably equal to or greater than the height of the uneven portion on the surface so that sufficient uneven absorption can be obtained. Therefore, for example, when the unevenness of the surface is a bump formed on the semiconductor wafer, it is preferable that the thickness of the pressure-sensitive adhesive layer is twice or more the height dimension of the bump. The bump height is usually 30-200 μm. For example, when the bump height is 100 μm, the thickness of the pressure-sensitive adhesive layer is preferably 200 μm or more, and when the bump height is 200 μm, the thickness of the pressure-sensitive adhesive layer is 400 μm or more. Is preferable.
The pressure-sensitive adhesive layer may have a single-layer structure, or may have a multi-layer structure in which the pressure-sensitive adhesive layer of the present embodiment and one or more other pressure-sensitive adhesive layers different from the pressure-sensitive adhesive layer of the present embodiment are laminated. You may. As another pressure-sensitive adhesive layer, a conventionally known pressure-sensitive adhesive layer can be used. In the present embodiment, when the pressure-sensitive adhesive layer has a multi-layer structure, the pressure-sensitive adhesive layer of the present embodiment needs to be present on the outermost surface. Further, in the BG tape of the present embodiment, a layer other than the pressure-sensitive adhesive layer may be present between the pressure-sensitive adhesive layer and the base material within a range that does not hinder the curing of the pressure-sensitive adhesive layer. From the viewpoint of shortening the process, the pressure-sensitive adhesive layer preferably has a single-layer structure.
粘着剤層のゲル分率は任意に選択できるが、５０～６５質量％であることが好ましい。ゲル分率が５０質量％以上であると、被着体に貼付したＢＧテープを剥離することによる糊残りの発生をより効果的に抑制できる。また、ゲル分率が６５質量％以下であると、粘着剤層が十分な流動性を有するものとなり、ＢＧテープの凹凸吸収性がより一層良好となる。粘着剤層のゲル分率は、５２質量％以上であることがより好ましい。また、粘着剤層のゲル分率は、６３質量％以下であることがより好ましい。
The gel fraction of the pressure-sensitive adhesive layer can be arbitrarily selected, but is preferably 50 to 65% by mass. When the gel fraction is 50% by mass or more, the generation of adhesive residue due to peeling the BG tape attached to the adherend can be more effectively suppressed. Further, when the gel fraction is 65% by mass or less, the pressure-sensitive adhesive layer has sufficient fluidity, and the unevenness absorption of the BG tape becomes even better. The gel fraction of the pressure-sensitive adhesive layer is more preferably 52% by mass or more. Further, the gel fraction of the pressure-sensitive adhesive layer is more preferably 63% by mass or less.
（粘着剤層のゲル分率の測定）
粘着剤層のゲル分率の測定は、以下の方法で行うことができる。まず、ＢＧテープから約１ｇとなるサイズにシートを切り出し、このシートから基材を剥がして測定用サンプルとし、測定用サンプルの質量を測定する。続いて、測定用サンプルを５０ｍｌのトルエンに浸漬し、室温で７２時間静置する。その後、測定用サンプルをトルエン中から取り出し、８０℃で５時間乾燥し、再び質量を測定する。そして、下記式に基づいて、ゲル分率を測定する。
ゲル分率（％）＝［Ａ／Ｂ］×１００
Ａ：トルエンに浸漬した後の測定用サンプルの質量（トルエンの質量は含まない）
Ｂ：トルエンに浸漬する前の測定用サンプルの質量 (Measurement of gel fraction of adhesive layer)
The gel fraction of the pressure-sensitive adhesive layer can be measured by the following method. First, a sheet is cut out from the BG tape to a size of about 1 g, and the base material is peeled off from this sheet to prepare a measurement sample, and the mass of the measurement sample is measured. Subsequently, the measurement sample is immersed in 50 ml of toluene and allowed to stand at room temperature for 72 hours. Then, the measurement sample is taken out from the toluene, dried at 80 ° C. for 5 hours, and the mass is measured again. Then, the gel fraction is measured based on the following formula.
Gel fraction (%) = [A / B] x 100
A: Mass of measurement sample after immersion in toluene (mass of toluene is not included)
B: Mass of measurement sample before immersion in toluene
粘着剤層のゲル分率の測定は、以下の方法で行うことができる。まず、ＢＧテープから約１ｇとなるサイズにシートを切り出し、このシートから基材を剥がして測定用サンプルとし、測定用サンプルの質量を測定する。続いて、測定用サンプルを５０ｍｌのトルエンに浸漬し、室温で７２時間静置する。その後、測定用サンプルをトルエン中から取り出し、８０℃で５時間乾燥し、再び質量を測定する。そして、下記式に基づいて、ゲル分率を測定する。
ゲル分率（％）＝［Ａ／Ｂ］×１００
Ａ：トルエンに浸漬した後の測定用サンプルの質量（トルエンの質量は含まない）
Ｂ：トルエンに浸漬する前の測定用サンプルの質量 (Measurement of gel fraction of adhesive layer)
The gel fraction of the pressure-sensitive adhesive layer can be measured by the following method. First, a sheet is cut out from the BG tape to a size of about 1 g, and the base material is peeled off from this sheet to prepare a measurement sample, and the mass of the measurement sample is measured. Subsequently, the measurement sample is immersed in 50 ml of toluene and allowed to stand at room temperature for 72 hours. Then, the measurement sample is taken out from the toluene, dried at 80 ° C. for 5 hours, and the mass is measured again. Then, the gel fraction is measured based on the following formula.
Gel fraction (%) = [A / B] x 100
A: Mass of measurement sample after immersion in toluene (mass of toluene is not included)
B: Mass of measurement sample before immersion in toluene
粘着剤層の表面抵抗率は、１×１０１１Ω／□未満であることが好ましく、１×１０１０Ω／□未満であることがより好ましい。表面抵抗率が１×１０１１Ω／□未満であると、被着体に貼付したＢＧテープを剥離した際の剥離帯電が低減され、より一層帯電防止性に優れたＢＧテープとなる。粘着剤層の表面抵抗率の下限は任意に選択できるが、例えば、１×１０６Ω／□以上などであってもよい。
The surface resistivity of the pressure-sensitive adhesive layer is preferably less than 1 × 10 11 Ω / □, and more preferably less than 1 × 10 10 Ω / □. When the surface resistivity is less than 1 × 10 11 Ω / □, the peeling charge when the BG tape attached to the adherend is peeled off is reduced, and the BG tape has further excellent antistatic properties. The lower limit of the surface resistivity of the pressure-sensitive adhesive layer can be arbitrarily selected, but may be, for example, 1 × 10 6 Ω / □ or more.
（セパレーター）
ＢＧテープには、粘着剤層を保護する目的で、粘着剤層の基材と反対側の表面に、透明又は不透明なセパレーターが設けられていてもよい。セパレーターは、粘着剤層の表面に直接ラミネートされていることが好ましい。セパレーターの材料としては任意に選択できるが、例えば、紙、プラスチックフィルムなどを用いることができ、表面平滑性に優れる点からプラスチックフィルムを用いることが好ましい。セパレーターとして用いられるプラスチックフィルムとしては、上記した粘着剤層を保護し得るものであれば、特に限定されず、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート（ＰＥＴ）、ポリブテンなどが挙げられる。セパレーターの厚さは任意に選択できる。例えば、５～３００μｍであることが好ましく、１０～２００μｍであることがより好ましく、２５μｍ～１００μｍであることがさらに好ましい。 (separator)
The BG tape may be provided with a transparent or opaque separator on the surface of the pressure-sensitive adhesive layer opposite to the base material for the purpose of protecting the pressure-sensitive adhesive layer. The separator is preferably laminated directly on the surface of the pressure-sensitive adhesive layer. The material of the separator can be arbitrarily selected, but for example, paper, a plastic film, or the like can be used, and it is preferable to use a plastic film from the viewpoint of excellent surface smoothness. The plastic film used as the separator is not particularly limited as long as it can protect the above-mentioned pressure-sensitive adhesive layer, and examples thereof include polyethylene, polypropylene, polyethylene terephthalate (PET), and polybutene. The thickness of the separator can be selected arbitrarily. For example, it is preferably 5 to 300 μm, more preferably 10 to 200 μm, and even more preferably 25 μm to 100 μm.
ＢＧテープには、粘着剤層を保護する目的で、粘着剤層の基材と反対側の表面に、透明又は不透明なセパレーターが設けられていてもよい。セパレーターは、粘着剤層の表面に直接ラミネートされていることが好ましい。セパレーターの材料としては任意に選択できるが、例えば、紙、プラスチックフィルムなどを用いることができ、表面平滑性に優れる点からプラスチックフィルムを用いることが好ましい。セパレーターとして用いられるプラスチックフィルムとしては、上記した粘着剤層を保護し得るものであれば、特に限定されず、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート（ＰＥＴ）、ポリブテンなどが挙げられる。セパレーターの厚さは任意に選択できる。例えば、５～３００μｍであることが好ましく、１０～２００μｍであることがより好ましく、２５μｍ～１００μｍであることがさらに好ましい。 (separator)
The BG tape may be provided with a transparent or opaque separator on the surface of the pressure-sensitive adhesive layer opposite to the base material for the purpose of protecting the pressure-sensitive adhesive layer. The separator is preferably laminated directly on the surface of the pressure-sensitive adhesive layer. The material of the separator can be arbitrarily selected, but for example, paper, a plastic film, or the like can be used, and it is preferable to use a plastic film from the viewpoint of excellent surface smoothness. The plastic film used as the separator is not particularly limited as long as it can protect the above-mentioned pressure-sensitive adhesive layer, and examples thereof include polyethylene, polypropylene, polyethylene terephthalate (PET), and polybutene. The thickness of the separator can be selected arbitrarily. For example, it is preferably 5 to 300 μm, more preferably 10 to 200 μm, and even more preferably 25 μm to 100 μm.
＜粘着剤組成物＞
次に、本実施形態のＢＧテープにおいて、粘着剤層の材料として使用した粘着剤組成物について詳細に説明する。
本実施形態の粘着剤組成物は、ポリウレタン（Ａ）と、（メタ）アクリレートモノマー（Ｂ）と、連鎖移動剤（Ｃ）と、光重合開始剤（Ｄ）と、イオン液体（Ｅ）とを含む。なお（メタ）アクリレートモノマーとは、メタアクリレートモノマー、及び／又はアクリレートモノマーを意味して良い。 <Adhesive composition>
Next, the pressure-sensitive adhesive composition used as the material of the pressure-sensitive adhesive layer in the BG tape of the present embodiment will be described in detail.
The pressure-sensitive adhesive composition of the present embodiment contains polyurethane (A), (meth) acrylate monomer (B), a chain transfer agent (C), a photopolymerization initiator (D), and an ionic liquid (E). Including. The (meth) acrylate monomer may mean a methacrylate monomer and / or an acrylate monomer.
次に、本実施形態のＢＧテープにおいて、粘着剤層の材料として使用した粘着剤組成物について詳細に説明する。
本実施形態の粘着剤組成物は、ポリウレタン（Ａ）と、（メタ）アクリレートモノマー（Ｂ）と、連鎖移動剤（Ｃ）と、光重合開始剤（Ｄ）と、イオン液体（Ｅ）とを含む。なお（メタ）アクリレートモノマーとは、メタアクリレートモノマー、及び／又はアクリレートモノマーを意味して良い。 <Adhesive composition>
Next, the pressure-sensitive adhesive composition used as the material of the pressure-sensitive adhesive layer in the BG tape of the present embodiment will be described in detail.
The pressure-sensitive adhesive composition of the present embodiment contains polyurethane (A), (meth) acrylate monomer (B), a chain transfer agent (C), a photopolymerization initiator (D), and an ionic liquid (E). Including. The (meth) acrylate monomer may mean a methacrylate monomer and / or an acrylate monomer.
（ポリウレタン（Ａ））
ポリウレタン（Ａ）は、後述のポリウレタン（ａ１）を含む。ポリウレタン（ａ１）のみからなってもよいが、ポリウレタン（Ａ）には、ポリウレタン（ａ１）だけでなく、粘着剤組成物の硬化物における凝集力を調節する目的で、後述するポリウレタン（ａ２）が含まれていてもよい。ポリウレタン（Ａ）には、ポリウレタン（ａ１）と、必要に応じて含有されるポリウレタン（ａ２）以外の成分は含まれないことが好ましい。 (Polyurethane (A))
The polyurethane (A) includes the polyurethane (a1) described later. Although it may be composed of only polyurethane (a1), polyurethane (A) includes not only polyurethane (a1) but also polyurethane (a2), which will be described later, for the purpose of adjusting the cohesive force of the cured product of the pressure-sensitive adhesive composition. It may be included. It is preferable that the polyurethane (A) does not contain components other than the polyurethane (a1) and the polyurethane (a2) contained if necessary.
ポリウレタン（Ａ）は、後述のポリウレタン（ａ１）を含む。ポリウレタン（ａ１）のみからなってもよいが、ポリウレタン（Ａ）には、ポリウレタン（ａ１）だけでなく、粘着剤組成物の硬化物における凝集力を調節する目的で、後述するポリウレタン（ａ２）が含まれていてもよい。ポリウレタン（Ａ）には、ポリウレタン（ａ１）と、必要に応じて含有されるポリウレタン（ａ２）以外の成分は含まれないことが好ましい。 (Polyurethane (A))
The polyurethane (A) includes the polyurethane (a1) described later. Although it may be composed of only polyurethane (a1), polyurethane (A) includes not only polyurethane (a1) but also polyurethane (a2), which will be described later, for the purpose of adjusting the cohesive force of the cured product of the pressure-sensitive adhesive composition. It may be included. It is preferable that the polyurethane (A) does not contain components other than the polyurethane (a1) and the polyurethane (a2) contained if necessary.
［ポリウレタン（ａ１）］
ポリウレタン（ａ１）は、ポリオキシアルキレンポリオール由来の構造およびポリイソシアネート由来の構造を含む骨格を有する。また、ポリウレタン（ａ１）は、複数の末端に（メタ）アクリロイル基を有する。全ての末端に（メタ）アクリロイル基を有してもよい。ポリウレタン（ａ１）の有する末端の（メタ）アクリロイル基は、（メタ）アクリロイルオキシ基の一部であることが好ましい。（メタ）アクリロイル基は、メタアクリロイル基及び／又はアクリロイル基を意味してよい。（メタ）アクリロイルオキシ基は、メタアクリロイルオキシ基、及び／又はアクリロイルオキシ基を意味してよい。 [Polyurethane (a1)]
Polyurethane (a1) has a skeleton containing a structure derived from a polyoxyalkylene polyol and a structure derived from a polyisocyanate. In addition, polyurethane (a1) has a plurality of (meth) acryloyl groups at the ends. It may have a (meth) acryloyl group at all ends. The terminal (meth) acryloyl group of the polyurethane (a1) is preferably a part of the (meth) acryloyloxy group. The (meth) acryloyl group may mean a meta-acryloyl group and / or an acryloyl group. The (meth) acryloyloxy group may mean a metaacryloyloxy group and / or an acryloyloxy group.
ポリウレタン（ａ１）は、ポリオキシアルキレンポリオール由来の構造およびポリイソシアネート由来の構造を含む骨格を有する。また、ポリウレタン（ａ１）は、複数の末端に（メタ）アクリロイル基を有する。全ての末端に（メタ）アクリロイル基を有してもよい。ポリウレタン（ａ１）の有する末端の（メタ）アクリロイル基は、（メタ）アクリロイルオキシ基の一部であることが好ましい。（メタ）アクリロイル基は、メタアクリロイル基及び／又はアクリロイル基を意味してよい。（メタ）アクリロイルオキシ基は、メタアクリロイルオキシ基、及び／又はアクリロイルオキシ基を意味してよい。 [Polyurethane (a1)]
Polyurethane (a1) has a skeleton containing a structure derived from a polyoxyalkylene polyol and a structure derived from a polyisocyanate. In addition, polyurethane (a1) has a plurality of (meth) acryloyl groups at the ends. It may have a (meth) acryloyl group at all ends. The terminal (meth) acryloyl group of the polyurethane (a1) is preferably a part of the (meth) acryloyloxy group. The (meth) acryloyl group may mean a meta-acryloyl group and / or an acryloyl group. The (meth) acryloyloxy group may mean a metaacryloyloxy group and / or an acryloyloxy group.
本発明において、ポリウレタンの「複数の末端」とは２以上の末端を意味する。「複数の末端」とは、ポリウレタンが直鎖ポリマーである場合、２つの末端であり、ポリウレタンが分岐ポリマーである場合、各分岐鎖の本数と同じ数の末端のうちの２つ以上の末端である。
また、本発明において、（メタ）アクリロイル基とは、化学式ＣＨ２＝ＣＨ－ＣＯ－で表される官能基、および化学式ＣＨ２＝Ｃ（ＣＨ３）－ＣＯ－で表される官能基から選択される一種以上を意味する。 In the present invention, the "plurality of ends" of polyurethane means two or more ends. "Multiple ends" means two ends when the polyurethane is a linear polymer, and two or more ends out of the same number of ends as the number of each branched chain when the polyurethane is a branched polymer. is there.
Further, in the present invention, the (meth) acryloyl group is selected from a functional group represented by the chemical formula CH 2 = CH-CO- and a functional group represented by the chemical formula CH 2 = C (CH 3) -CO-. Means more than one kind to be done.
また、本発明において、（メタ）アクリロイル基とは、化学式ＣＨ２＝ＣＨ－ＣＯ－で表される官能基、および化学式ＣＨ２＝Ｃ（ＣＨ３）－ＣＯ－で表される官能基から選択される一種以上を意味する。 In the present invention, the "plurality of ends" of polyurethane means two or more ends. "Multiple ends" means two ends when the polyurethane is a linear polymer, and two or more ends out of the same number of ends as the number of each branched chain when the polyurethane is a branched polymer. is there.
Further, in the present invention, the (meth) acryloyl group is selected from a functional group represented by the chemical formula CH 2 = CH-CO- and a functional group represented by the chemical formula CH 2 = C (CH 3) -CO-. Means more than one kind to be done.
［ポリウレタン（ａ２）］
ポリウレタン（ａ２）は、ポリウレタン（ａ１）と同様に、ポリオキシアルキレンポリオール由来の構造およびポリイソシアネート由来の構造を含む骨格を有する。ポリウレタン（ａ２）は、ポリウレタン（ａ１）と異なり、１つの末端のみに（メタ）アクリロイル基を有する。ポリウレタン（ａ２）の有する末端の（メタ）アクリロイル基は、（メタ）アクリロイルオキシ基の一部であることが好ましい。ポリウレタン（ａ２）の有する（メタ）アクリロイル基を有さない末端は、イソシアナト基、アルキルアルコール由来の構造、アルキルイソシアネート由来の構造から選ばれるいずれかを有することが好ましく、アルキルアルコール由来の構造を有することがより好ましい。 [Polyurethane (a2)]
Polyurethane (a2), like polyurethane (a1), has a skeleton containing a structure derived from a polyoxyalkylene polyol and a structure derived from a polyisocyanate. Polyurethane (a2), unlike polyurethane (a1), has a (meth) acryloyl group at only one end. The terminal (meth) acryloyl group of the polyurethane (a2) is preferably a part of the (meth) acryloyloxy group. The terminal of the polyurethane (a2) having no (meth) acryloyl group preferably has any one selected from an isocyanato group, a structure derived from an alkyl alcohol, and a structure derived from an alkyl isocyanate, and has a structure derived from an alkyl alcohol. Is more preferable.
ポリウレタン（ａ２）は、ポリウレタン（ａ１）と同様に、ポリオキシアルキレンポリオール由来の構造およびポリイソシアネート由来の構造を含む骨格を有する。ポリウレタン（ａ２）は、ポリウレタン（ａ１）と異なり、１つの末端のみに（メタ）アクリロイル基を有する。ポリウレタン（ａ２）の有する末端の（メタ）アクリロイル基は、（メタ）アクリロイルオキシ基の一部であることが好ましい。ポリウレタン（ａ２）の有する（メタ）アクリロイル基を有さない末端は、イソシアナト基、アルキルアルコール由来の構造、アルキルイソシアネート由来の構造から選ばれるいずれかを有することが好ましく、アルキルアルコール由来の構造を有することがより好ましい。 [Polyurethane (a2)]
Polyurethane (a2), like polyurethane (a1), has a skeleton containing a structure derived from a polyoxyalkylene polyol and a structure derived from a polyisocyanate. Polyurethane (a2), unlike polyurethane (a1), has a (meth) acryloyl group at only one end. The terminal (meth) acryloyl group of the polyurethane (a2) is preferably a part of the (meth) acryloyloxy group. The terminal of the polyurethane (a2) having no (meth) acryloyl group preferably has any one selected from an isocyanato group, a structure derived from an alkyl alcohol, and a structure derived from an alkyl isocyanate, and has a structure derived from an alkyl alcohol. Is more preferable.
「ポリオキシアルキレンポリオール由来の構造」
ポリウレタン（ａ１）およびポリウレタン（ａ２）の骨格に含まれるポリオキシアルキレンポリオール由来の構造となるポリオキシアルキレンポリオールとしては、炭素数２～４のアルキレン鎖を有するものであることが好ましい。具体例としては、ポリオキシエチレンポリオール、ポリオキシプロピレンポリオール、ポリオキシブチレンポリオールなどが挙げられる。 "Structure derived from polyoxyalkylene polyol"
The polyoxyalkylene polyol having a structure derived from the polyoxyalkylene polyol contained in the skeletons of the polyurethane (a1) and the polyurethane (a2) preferably has an alkylene chain having 2 to 4 carbon atoms. Specific examples include polyoxyethylene polyol, polyoxypropylene polyol, polyoxybutylene polyol and the like.
ポリウレタン（ａ１）およびポリウレタン（ａ２）の骨格に含まれるポリオキシアルキレンポリオール由来の構造となるポリオキシアルキレンポリオールとしては、炭素数２～４のアルキレン鎖を有するものであることが好ましい。具体例としては、ポリオキシエチレンポリオール、ポリオキシプロピレンポリオール、ポリオキシブチレンポリオールなどが挙げられる。 "Structure derived from polyoxyalkylene polyol"
The polyoxyalkylene polyol having a structure derived from the polyoxyalkylene polyol contained in the skeletons of the polyurethane (a1) and the polyurethane (a2) preferably has an alkylene chain having 2 to 4 carbon atoms. Specific examples include polyoxyethylene polyol, polyoxypropylene polyol, polyoxybutylene polyol and the like.
ポリオキシアルキレンポリオール由来の構造となるポリオキシアルキレンポリオールは、１種類のアルキレン鎖を含むものであってもよいし、２種類以上のアルキレン鎖を含むものであってもよい。
ポリオキシアルキレンポリオール由来の構造となるポリオキシアルキレンポリオールは、末端に２つまたは３つの水酸基を有するもの（ジオール型またはトリオール型のポリオキシアルキレンポリオール）であることが好ましく、ポリオキシアルキレングリコール（ジオール型）であることがより好ましく、炭素数３のアルキレン鎖を有するポリプロピレングリコールであることが特に好ましい。 The polyoxyalkylene polyol having a structure derived from the polyoxyalkylene polyol may contain one type of alkylene chain or may contain two or more types of alkylene chains.
The polyoxyalkylene polyol having a structure derived from the polyoxyalkylene polyol is preferably one having two or three hydroxyl groups at the terminal (diol type or triol type polyoxyalkylene polyol), and is preferably a polyoxyalkylene glycol (diol). Type) is more preferable, and polypropylene glycol having an alkylene chain having 3 carbon atoms is particularly preferable.
ポリオキシアルキレンポリオール由来の構造となるポリオキシアルキレンポリオールは、末端に２つまたは３つの水酸基を有するもの（ジオール型またはトリオール型のポリオキシアルキレンポリオール）であることが好ましく、ポリオキシアルキレングリコール（ジオール型）であることがより好ましく、炭素数３のアルキレン鎖を有するポリプロピレングリコールであることが特に好ましい。 The polyoxyalkylene polyol having a structure derived from the polyoxyalkylene polyol may contain one type of alkylene chain or may contain two or more types of alkylene chains.
The polyoxyalkylene polyol having a structure derived from the polyoxyalkylene polyol is preferably one having two or three hydroxyl groups at the terminal (diol type or triol type polyoxyalkylene polyol), and is preferably a polyoxyalkylene glycol (diol). Type) is more preferable, and polypropylene glycol having an alkylene chain having 3 carbon atoms is particularly preferable.
例えば、ポリオキシアルキレンポリオールが、ポリプロピレングリコールである場合、水酸基価は２０～１２０ｍｇＫＯＨ／ｇであることが好ましく、３０～１００ｍｇＫＯＨ／ｇであることがより好ましく、４０～８０ｍｇＫＯＨ／ｇであることがさらに好ましい。ポリプロピレングリコールの具体例としては、例えば、水酸基価が５６ｍｇＫＯＨ／ｇの水酸基（ヒドロキシ基）を末端に有するポリプロピレングリコール（アクトコールＤ－２０００；三井化学製、数平均分子量２０００、ジオール型）などが挙げられる。
For example, when the polyoxyalkylene polyol is polypropylene glycol, the hydroxyl value is preferably 20 to 120 mgKOH / g, more preferably 30 to 100 mgKOH / g, and further preferably 40 to 80 mgKOH / g. preferable. Specific examples of polypropylene glycol include polypropylene glycol (Actcol D-2000; manufactured by Mitsui Chemicals, number average molecular weight 2000, diol type) having a hydroxyl group (hydroxy group) having a hydroxyl value of 56 mgKOH / g at the end. Be done.
ここで、ポリオキシアルキレンポリオールの水酸基価とは、ＪＩＳＫ００７０にしたがって測定されたポリオキシアルキレンポリオールの水酸基価である。すなわち、ポリオキシアルキレンポリオール１ｇをアセチル化させたときの遊離酢酸を中和するのに必要とする水酸化カリウムのｍｇ数を意味する。具体的には、無水酢酸を用いて試料（ポリオキシアルキレンポリオール）中の水酸基をアセチル化し、その際に生じる遊離酢酸を水酸化カリウム溶液で滴定することにより求めることができる。
Here, the hydroxyl value of the polyoxyalkylene polyol is the hydroxyl value of the polyoxyalkylene polyol measured according to JIS K0070. That is, it means the number of mg of potassium hydroxide required to neutralize free acetic acid when 1 g of polyoxyalkylene polyol is acetylated. Specifically, it can be obtained by acetylating the hydroxyl groups in the sample (polyoxyalkylene polyol) with acetic anhydride and titrating the free acetic acid generated at that time with a potassium hydroxide solution.
ポリオキシアルキレンポリオールの数平均分子量は、５００～５，０００であることが好ましく、８００～４，０００であることがより好ましく、１，０００～３，０００であることがさらに好ましい。ポリオキシアルキレンポリオールの数平均分子量が５００以上であると、これを用いて合成したポリウレタン（Ａ）を含む粘着剤組成物の硬化物からなる粘着剤層を有するＢＧテープが、剥離強度の高いものとなる。また、ポリオキシアルキレンポリオールの数平均分子量が５，０００以下であると、これを用いて合成したポリウレタン（Ａ）が十分な量のウレタン結合を含むものとなる。このため、ポリウレタン（Ａ）を含む粘着剤組成物を硬化させた硬化物は、凝集力が良好なものとなる。
The number average molecular weight of the polyoxyalkylene polyol is preferably 500 to 5,000, more preferably 800 to 4,000, and even more preferably 1,000 to 3,000. When the number average molecular weight of the polyoxyalkylene polyol is 500 or more, the BG tape having a pressure-sensitive adhesive layer made of a cured product of the pressure-sensitive adhesive composition containing polyurethane (A) synthesized using the polyoxyalkylene polyol has high peel strength. It becomes. Further, when the number average molecular weight of the polyoxyalkylene polyol is 5,000 or less, the polyurethane (A) synthesized using the polyoxyalkylene polyol contains a sufficient amount of urethane bonds. Therefore, the cured product obtained by curing the pressure-sensitive adhesive composition containing polyurethane (A) has a good cohesive force.
ポリウレタン（ａ１）およびポリウレタン（ａ２）の骨格に含まれるポリオキシアルキレンポリオール由来の構造は、それぞれ１種類のみであってもよいし、２種類以上を含む構造であってもよい。
ポリウレタン（ａ１）およびポリウレタン（ａ２）は、２種以上の異なるポリオキシアルキレンポリオール由来の構造が、ポリイソシアネート由来の構造を挟んで結合された構造を有していてもよい。
ポリウレタン（ａ１）の骨格に含まれるポリオキシアルキレンポリオール由来の構造と、ポリウレタン（ａ２）の骨格に含まれるポリオキシアルキレンポリオール由来の構造とは、同じであってもよいし、異なっていてもよい。 The structure derived from the polyoxyalkylene polyol contained in the skeletons of the polyurethane (a1) and the polyurethane (a2) may be of only one type, or may be a structure containing two or more types.
Polyurethane (a1) and polyurethane (a2) may have a structure in which two or more different polyoxyalkylene polyol-derived structures are bonded with a polyisocyanate-derived structure in between.
The structure derived from the polyoxyalkylene polyol contained in the skeleton of the polyurethane (a1) and the structure derived from the polyoxyalkylene polyol contained in the skeleton of the polyurethane (a2) may be the same or different. ..
ポリウレタン（ａ１）およびポリウレタン（ａ２）は、２種以上の異なるポリオキシアルキレンポリオール由来の構造が、ポリイソシアネート由来の構造を挟んで結合された構造を有していてもよい。
ポリウレタン（ａ１）の骨格に含まれるポリオキシアルキレンポリオール由来の構造と、ポリウレタン（ａ２）の骨格に含まれるポリオキシアルキレンポリオール由来の構造とは、同じであってもよいし、異なっていてもよい。 The structure derived from the polyoxyalkylene polyol contained in the skeletons of the polyurethane (a1) and the polyurethane (a2) may be of only one type, or may be a structure containing two or more types.
Polyurethane (a1) and polyurethane (a2) may have a structure in which two or more different polyoxyalkylene polyol-derived structures are bonded with a polyisocyanate-derived structure in between.
The structure derived from the polyoxyalkylene polyol contained in the skeleton of the polyurethane (a1) and the structure derived from the polyoxyalkylene polyol contained in the skeleton of the polyurethane (a2) may be the same or different. ..
「ポリイソシアネート由来の構造」
ポリウレタン（ａ１）およびポリウレタン（ａ２）の骨格に含まれるポリイソシアネート由来の構造となるポリイソシアネートとしては、イソシアナト基を複数有する化合物を用いることができ、ジイソシアネートを用いることが好ましい。
ジイソシアネートとしては、例えば、トリレンジイソシアネートおよびその水素添加物、キシリレンジイソシアネートおよびその水素添加物、ジフェニルメタンジイソシアネートおよびその水素添加物、１，５－ナフチレンジイソシアネートおよびその水素添加物、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、テトラメチルキシリレンジイソシアネート、イソホロンジイソシアネート、４，４’－ジシクロヘキシルジイソシアネート、１，３－ビス（イソシアネートメチル）シクロヘキサン、ノルボルナンジイソシアネート等が挙げられる。 "Structure derived from polyisocyanate"
As the polyisocyanate having a structure derived from the polyisocyanate contained in the skeletons of the polyurethane (a1) and the polyurethane (a2), a compound having a plurality of isocyanato groups can be used, and it is preferable to use a diisocyanate.
Examples of the diisocyanate include tolylene diisocyanate and its hydrogen additive, xylylene diisocyanate and its hydrogen additive, diphenylmethane diisocyanate and its hydrogen additive, 1,5-naphthylene diisocyanate and its hydrogen additive, hexamethylene diisocyanate, and trimethyl. Examples thereof include hexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexyldiisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, norbornan diisocyanate and the like.
ポリウレタン（ａ１）およびポリウレタン（ａ２）の骨格に含まれるポリイソシアネート由来の構造となるポリイソシアネートとしては、イソシアナト基を複数有する化合物を用いることができ、ジイソシアネートを用いることが好ましい。
ジイソシアネートとしては、例えば、トリレンジイソシアネートおよびその水素添加物、キシリレンジイソシアネートおよびその水素添加物、ジフェニルメタンジイソシアネートおよびその水素添加物、１，５－ナフチレンジイソシアネートおよびその水素添加物、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、テトラメチルキシリレンジイソシアネート、イソホロンジイソシアネート、４，４’－ジシクロヘキシルジイソシアネート、１，３－ビス（イソシアネートメチル）シクロヘキサン、ノルボルナンジイソシアネート等が挙げられる。 "Structure derived from polyisocyanate"
As the polyisocyanate having a structure derived from the polyisocyanate contained in the skeletons of the polyurethane (a1) and the polyurethane (a2), a compound having a plurality of isocyanato groups can be used, and it is preferable to use a diisocyanate.
Examples of the diisocyanate include tolylene diisocyanate and its hydrogen additive, xylylene diisocyanate and its hydrogen additive, diphenylmethane diisocyanate and its hydrogen additive, 1,5-naphthylene diisocyanate and its hydrogen additive, hexamethylene diisocyanate, and trimethyl. Examples thereof include hexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexyldiisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, norbornan diisocyanate and the like.
これらのポリイソシアネートの中でも、これを用いて合成したポリウレタン（Ａ）の耐光性、およびポリオキシアルキレンポリオールとの反応性の制御の点から、イソホロンジイソシアネートまたはジフェニルメタンジイソシアネートの水素添加物を用いることが好ましく、ポリオキシアルキレンポリオールとの反応性の点で、ジフェニルメタンジイソシアネートの水素添加物を用いることがより好ましい。
Among these polyisocyanates, it is preferable to use a hydrogenated isophorone diisocyanate or diphenylmethane diisocyanate from the viewpoint of controlling the light resistance of the polyurethane (A) synthesized using the polyisocyanate and the reactivity with the polyoxyalkylene polyol. , It is more preferable to use a hydrogenated diphenylmethane diisocyanate in terms of reactivity with a polyoxyalkylene polyol.
ポリイソシアネート由来の構造となるポリイソシアネートの具体例としては、ジフェニルメタンジイソシアネートの水素添加物（デスモジュールＷ、住化コベストロウレタン製）、イソホロンジイソシアネート（デスモジュールＩ、住化コベストロウレタン製）などが挙げられる。
Specific examples of the polyisocyanate having a structure derived from polyisocyanate include hydrogenated diphenylmethane diisocyanate (Desmodule W, manufactured by Sumika Covestro Urethane) and isophorone diisocyanate (Desmodule I, manufactured by Sumika Covestro Urethane). Can be mentioned.
ポリウレタン（ａ１）およびポリウレタン（ａ２）の骨格に含まれるポリイソシアネート由来の構造は、それぞれ１種類のみであってもよいし、２種類以上を含む構造であってもよい。
また、ポリウレタン（ａ１）の骨格に含まれるポリイソシアネート由来の構造と、ポリウレタン（ａ２）の骨格に含まれるポリイソシアネート由来の構造とは、同じであってもよいし、異なっていてもよい。 The polyisocyanate-derived structure contained in the skeletons of the polyurethane (a1) and the polyurethane (a2) may be of only one type, or may be a structure containing two or more types.
Further, the structure derived from polyisocyanate contained in the skeleton of polyurethane (a1) and the structure derived from polyisocyanate contained in the skeleton of polyurethane (a2) may be the same or different.
また、ポリウレタン（ａ１）の骨格に含まれるポリイソシアネート由来の構造と、ポリウレタン（ａ２）の骨格に含まれるポリイソシアネート由来の構造とは、同じであってもよいし、異なっていてもよい。 The polyisocyanate-derived structure contained in the skeletons of the polyurethane (a1) and the polyurethane (a2) may be of only one type, or may be a structure containing two or more types.
Further, the structure derived from polyisocyanate contained in the skeleton of polyurethane (a1) and the structure derived from polyisocyanate contained in the skeleton of polyurethane (a2) may be the same or different.
ポリウレタン（ａ１）およびポリウレタン（ａ２）の骨格に含まれるポリイソシアネート由来の構造およびポリオキシアルキレンポリオール由来の構造が同じである場合、ポリウレタン（ａ１）とポリウレタン（ａ２）とを同時に合成することができ、ポリウレタン（Ａ）を効率よく製造でき、好ましい。
When the structure derived from polyisocyanate and the structure derived from polyoxyalkylene polyol contained in the skeletons of polyurethane (a1) and polyurethane (a2) are the same, polyurethane (a1) and polyurethane (a2) can be synthesized at the same time. , Polyurethane (A) can be efficiently produced, which is preferable.
ポリウレタン（Ａ）に含まれるポリウレタン（ａ１）の割合は、分子数基準でポリウレタン（Ａ）の８０～１００％であることが好ましく、９０～１００％がより好ましく、１００％がさらに好ましい。
ポリウレタン（Ａ）に含まれるポリウレタン（ａ２）の割合は、分子数基準でポリウレタン（Ａ）の０～２０％であることが好ましく、０～１０％がより好ましく、０％がさらに好ましい。
ポリウレタン（Ａ）に含まれるポリウレタン（ａ１）の割合が８０％以上であると、ポリウレタン（Ａ）を含む粘着剤組成物の硬化物が、十分に凝集力の大きいものとなり、好ましい。 The proportion of polyurethane (a1) contained in polyurethane (A) is preferably 80 to 100%, more preferably 90 to 100%, and even more preferably 100% of polyurethane (A) on the basis of the number of molecules.
The proportion of polyurethane (a2) contained in polyurethane (A) is preferably 0 to 20%, more preferably 0 to 10%, and even more preferably 0% of polyurethane (A) on the basis of the number of molecules.
When the ratio of the polyurethane (a1) contained in the polyurethane (A) is 80% or more, the cured product of the pressure-sensitive adhesive composition containing the polyurethane (A) has a sufficiently large cohesive force, which is preferable.
ポリウレタン（Ａ）に含まれるポリウレタン（ａ２）の割合は、分子数基準でポリウレタン（Ａ）の０～２０％であることが好ましく、０～１０％がより好ましく、０％がさらに好ましい。
ポリウレタン（Ａ）に含まれるポリウレタン（ａ１）の割合が８０％以上であると、ポリウレタン（Ａ）を含む粘着剤組成物の硬化物が、十分に凝集力の大きいものとなり、好ましい。 The proportion of polyurethane (a1) contained in polyurethane (A) is preferably 80 to 100%, more preferably 90 to 100%, and even more preferably 100% of polyurethane (A) on the basis of the number of molecules.
The proportion of polyurethane (a2) contained in polyurethane (A) is preferably 0 to 20%, more preferably 0 to 10%, and even more preferably 0% of polyurethane (A) on the basis of the number of molecules.
When the ratio of the polyurethane (a1) contained in the polyurethane (A) is 80% or more, the cured product of the pressure-sensitive adhesive composition containing the polyurethane (A) has a sufficiently large cohesive force, which is preferable.
ポリウレタン（Ａ）に含まれる全ての末端数（ポリウレタン（ａ１）の末端数と、必要に応じて含有されるポリウレタン（ａ２）の末端数との合計数）のうち、分子数基準で９０～１００％に（メタ）アクリロイル基が導入されていることが好ましく、９５～１００％がより好ましく、１００％がさらに好ましい。必要に応じて、９０～９３％や、９３～９７％や、９７～１００％などであってもよい。ポリウレタン（Ａ）に含まれる全ての末端数のうち、（メタ）アクリロイル基の導入量が分子数基準で９０％以上であると、ポリウレタン（Ａ）を含む粘着剤組成物を硬化して得られる硬化物の凝集力が十分に高いものとなる。
Of all the number of ends contained in polyurethane (A) (the total number of the number of ends of polyurethane (a1) and the number of ends of polyurethane (a2) contained as needed), 90 to 100 based on the number of molecules. It is preferable that a (meth) acryloyl group is introduced into%, more preferably 95 to 100%, still more preferably 100%. If necessary, it may be 90 to 93%, 93 to 97%, 97 to 100%, or the like. When the amount of the (meth) acryloyl group introduced is 90% or more based on the number of molecules among all the terminals contained in the polyurethane (A), it is obtained by curing the pressure-sensitive adhesive composition containing the polyurethane (A). The cohesive force of the cured product is sufficiently high.
ポリウレタン（Ａ）に含まれる全ての末端数のうち、分子数基準で（メタ）アクリロイル基が導入されている末端数の割合は、赤外線吸収スペクトル（ＩＲ）法、核磁気共鳴スペクトル（ＮＭＲ）法などを用いてポリウレタン（Ａ）を分析した結果を用いて算出できる。
The ratio of the number of terminals into which the (meth) acryloyl group is introduced based on the number of molecules among all the number of terminals contained in polyurethane (A) is determined by the infrared absorption spectrum (IR) method and the nuclear magnetic resonance spectrum (NMR) method. It can be calculated using the result of analyzing the polyurethane (A) using the above.
ポリウレタン（Ａ）に含まれているポリウレタン（ａ１）とポリウレタン（ａ２）の含有量の割合、すなわち、ポリウレタン（Ａ）に含まれる全ての末端数のうち、分子数基準で（メタ）アクリロイル基が導入されている末端数の割合は、後述するポリウレタン（Ａ）の製造方法により調整できる。
The ratio of the contents of polyurethane (a1) and polyurethane (a2) contained in polyurethane (A), that is, the (meth) acryloyl group based on the number of molecules among all the terminals contained in polyurethane (A). The ratio of the number of introduced terminals can be adjusted by the method for producing polyurethane (A) described later.
ポリウレタン（Ａ）の質量平均分子量は、３０，０００～２００，０００であることが好ましく、５０，０００～１５０，０００であることがより好ましく、６０，０００～１００，０００であることがさらに好ましい。ポリウレタン（Ａ）の質量平均分子量が３０，０００以上であると、ポリウレタン（Ａ）を含む粘着剤組成物を硬化して得られる硬化物が、良好な柔軟性を有するものとなる。また、ポリウレタン（Ａ）の質量平均分子量が２００，０００以下であると、ポリウレタン（Ａ）を含む粘着剤組成物は、取り扱いが容易で、作業性が良好なものとなる。
The mass average molecular weight of polyurethane (A) is preferably 30,000 to 200,000, more preferably 50,000 to 150,000, and even more preferably 60,000 to 100,000. .. When the mass average molecular weight of the polyurethane (A) is 30,000 or more, the cured product obtained by curing the pressure-sensitive adhesive composition containing the polyurethane (A) has good flexibility. Further, when the mass average molecular weight of the polyurethane (A) is 200,000 or less, the pressure-sensitive adhesive composition containing the polyurethane (A) is easy to handle and has good workability.
（ポリウレタン（Ａ）の質量平均分子量の測定方法）
ポリウレタン（Ａ）の質量平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ－１０１；昭和電工株式会社製Ｓｈｏｄｅｘ（登録商標））（以下、ＧＰＣという。）により測定されたポリスチレン換算の値である。ＧＰＣの測定条件は以下のとおりである。
カラム：ＬＦ－８０４（昭和電工株式会社製）
カラム温度：４０℃
試料：ポリウレタン（Ａ）の０．２質量％テトラヒドロフラン溶液
流量：１ｍｌ／分
溶離液：テトラヒドロフラン
検出器：ＲＩ検出器（示差屈折率検出器） (Method for measuring mass average molecular weight of polyurethane (A))
The mass average molecular weight of polyurethane (A) is a polystyrene-equivalent value measured by gel permeation chromatography (GPC-101; Showa Denko KK Shodex®) (hereinafter referred to as GPC). .. The measurement conditions of GPC are as follows.
Column: LF-804 (manufactured by Showa Denko KK)
Column temperature: 40 ° C
Sample: 0.2% by mass tetrahydrofuran solution of polyurethane (A) Flow rate: 1 ml / min Eluent: Tetrahydrofuran Detector: RI detector (differential refractive index detector)
ポリウレタン（Ａ）の質量平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ－１０１；昭和電工株式会社製Ｓｈｏｄｅｘ（登録商標））（以下、ＧＰＣという。）により測定されたポリスチレン換算の値である。ＧＰＣの測定条件は以下のとおりである。
カラム：ＬＦ－８０４（昭和電工株式会社製）
カラム温度：４０℃
試料：ポリウレタン（Ａ）の０．２質量％テトラヒドロフラン溶液
流量：１ｍｌ／分
溶離液：テトラヒドロフラン
検出器：ＲＩ検出器（示差屈折率検出器） (Method for measuring mass average molecular weight of polyurethane (A))
The mass average molecular weight of polyurethane (A) is a polystyrene-equivalent value measured by gel permeation chromatography (GPC-101; Showa Denko KK Shodex®) (hereinafter referred to as GPC). .. The measurement conditions of GPC are as follows.
Column: LF-804 (manufactured by Showa Denko KK)
Column temperature: 40 ° C
Sample: 0.2% by mass tetrahydrofuran solution of polyurethane (A) Flow rate: 1 ml / min Eluent: Tetrahydrofuran Detector: RI detector (differential refractive index detector)
本実施形態の粘着剤組成物中におけるポリウレタン（Ａ）の含有量は任意に選択できるが、２０～５０質量％であることが好ましく、２５～４５質量％であることがより好ましく、３０～４０質量％であることがさらに好ましい。ポリウレタン（Ａ）の含有量が２０質量％以上であると、粘着剤組成物を硬化して得られる硬化物は、十分な凝集力を有するものとなり、優れた粘着力が得られる。また、この硬化物を粘着剤層として用いたＢＧテープは、粘着剤層の柔らかさが適正範囲となり、粘着剤層と被着体との間への気泡の挟み込みが生じにくい。また、ポリウレタン（Ａ）の含有量が５０質量％以下であると、粘着剤組成物を硬化して得られる硬化物は、十分な柔軟性を有するものとなる。したがって、この硬化物を粘着剤層として用いたＢＧテープは、被着体に対する濡れ性が良好である。
The content of polyurethane (A) in the pressure-sensitive adhesive composition of the present embodiment can be arbitrarily selected, but is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, and 30 to 40% by mass. It is more preferably by mass%. When the content of the polyurethane (A) is 20% by mass or more, the cured product obtained by curing the pressure-sensitive adhesive composition has a sufficient cohesive force, and an excellent adhesive force can be obtained. Further, in the BG tape using this cured product as the pressure-sensitive adhesive layer, the softness of the pressure-sensitive adhesive layer is within an appropriate range, and air bubbles are less likely to be caught between the pressure-sensitive adhesive layer and the adherend. Further, when the content of the polyurethane (A) is 50% by mass or less, the cured product obtained by curing the pressure-sensitive adhesive composition has sufficient flexibility. Therefore, the BG tape using this cured product as the pressure-sensitive adhesive layer has good wettability to the adherend.
（（メタ）アクリレートモノマー（Ｂ））
（メタ）アクリレートモノマー（Ｂ）は、ポリウレタン（Ａ）以外であって、（メタ）アクリロイルオキシ基を有する化合物であればよく、特に限定されない。（メタ）アクリレートモノマー（Ｂ）としては、（メタ）アクリロイルオキシ基を有する化合物を、１種のみ単独で用いてもよいし、２種以上を混合して用いてもよい。（メタ）アクリレートモノマー（Ｂ）としては、単官能（メタ）アクリレートを用いてもよいし、多官能（メタ）アクリレートを用いてもよいし、単官能（メタ）アクリレートと多官能（メタ）アクリレートの両方を用いてもよい。なお（メタ）アクリレートは、メタアクリレート、及び／又はアクリレートを意味してよい。 ((Meta) Acrylate Monomer (B))
The (meth) acrylate monomer (B) is not particularly limited as long as it is a compound other than polyurethane (A) and has a (meth) acryloyloxy group. As the (meth) acrylate monomer (B), only one compound having a (meth) acryloyloxy group may be used alone, or two or more thereof may be mixed and used. As the (meth) acrylate monomer (B), a monofunctional (meth) acrylate may be used, a polyfunctional (meth) acrylate may be used, or a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate. You may use both of. The (meth) acrylate may mean a metal acrylate and / or an acrylate.
（メタ）アクリレートモノマー（Ｂ）は、ポリウレタン（Ａ）以外であって、（メタ）アクリロイルオキシ基を有する化合物であればよく、特に限定されない。（メタ）アクリレートモノマー（Ｂ）としては、（メタ）アクリロイルオキシ基を有する化合物を、１種のみ単独で用いてもよいし、２種以上を混合して用いてもよい。（メタ）アクリレートモノマー（Ｂ）としては、単官能（メタ）アクリレートを用いてもよいし、多官能（メタ）アクリレートを用いてもよいし、単官能（メタ）アクリレートと多官能（メタ）アクリレートの両方を用いてもよい。なお（メタ）アクリレートは、メタアクリレート、及び／又はアクリレートを意味してよい。 ((Meta) Acrylate Monomer (B))
The (meth) acrylate monomer (B) is not particularly limited as long as it is a compound other than polyurethane (A) and has a (meth) acryloyloxy group. As the (meth) acrylate monomer (B), only one compound having a (meth) acryloyloxy group may be used alone, or two or more thereof may be mixed and used. As the (meth) acrylate monomer (B), a monofunctional (meth) acrylate may be used, a polyfunctional (meth) acrylate may be used, or a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate. You may use both of. The (meth) acrylate may mean a metal acrylate and / or an acrylate.
本発明において、単官能（メタ）アクリレートにおける「単官能」とは、（メタ）アクリロイルオキシ基の数が、１つのみである（メタ）アクリレートを意味する。
また、本発明において、多官能（メタ）アクリレートにおける「多官能」とは、（メタ）アクリロイルオキシ基の数が、２つ以上である（メタ）アクリレートを意味する。 In the present invention, "monofunctional" in a monofunctional (meth) acrylate means a (meth) acrylate having only one (meth) acryloyloxy group.
Further, in the present invention, the "polyfunctional" in the polyfunctional (meth) acrylate means a (meth) acrylate having two or more (meth) acryloyloxy groups.
また、本発明において、多官能（メタ）アクリレートにおける「多官能」とは、（メタ）アクリロイルオキシ基の数が、２つ以上である（メタ）アクリレートを意味する。 In the present invention, "monofunctional" in a monofunctional (meth) acrylate means a (meth) acrylate having only one (meth) acryloyloxy group.
Further, in the present invention, the "polyfunctional" in the polyfunctional (meth) acrylate means a (meth) acrylate having two or more (meth) acryloyloxy groups.
（メタ）アクリレートモノマー（Ｂ）としては、粘着剤組成物を硬化して得られる硬化物の凝集力および粘着剤組成物の硬化性の観点から、単官能（メタ）アクリレートと多官能（メタ）アクリレートとを組み合わせて用いることが好ましく、単官能（メタ）アクリレートと３官能以上の（メタ）アクリレートとを含有することがより好ましく、特に、単官能（メタ）アクリレートと、３個の（メタ）アクリロイルオキシ基を有する３官能（メタ）アクリレートとを含有することが最も好ましい。
The (meth) acrylate monomer (B) includes a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate from the viewpoint of the cohesiveness of the cured product obtained by curing the pressure-sensitive adhesive composition and the curability of the pressure-sensitive adhesive composition. It is preferable to use it in combination with an acrylate, and it is more preferable to contain a monofunctional (meth) acrylate and a trifunctional or higher (meth) acrylate, in particular, a monofunctional (meth) acrylate and three (meth) acrylates. Most preferably, it contains a trifunctional (meth) acrylate having an acryloyloxy group.
単官能（メタ）アクリレートとしては、例えば、アルキル（メタ）アクリレート、イソボルニル（メタ）アクリレートなどの環状アルキル（メタ）アクリレート、アルコキシアルキル（メタ）アクリレート、アルコキシ（ポリ）アルキレングリコール（メタ）アクリレート、ヒドロキシ基含有（メタ）アクリレート、カルボキシ基含有（メタ）アクリレート、フッ素化アルキル（メタ）アクリレート、ジアルキルアミノアルキル（メタ）アクリレート、（メタ）アクリルアミド、エポキシ基含有（メタ）アクリレート、（メタ）アクリロイルモルホリンなどが挙げられる。
Examples of the monofunctional (meth) acrylate include cyclic alkyl (meth) acrylate such as alkyl (meth) acrylate and isobornyl (meth) acrylate, alkoxyalkyl (meth) acrylate, alkoxy (poly) alkylene glycol (meth) acrylate, and hydroxy. Group-containing (meth) acrylate, carboxy group-containing (meth) acrylate, fluorinated alkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylate, (meth) acrylamide, epoxy group-containing (meth) acrylate, (meth) acryloylmorpholine, etc. Can be mentioned.
これらの単官能（メタ）アクリレートの中でも、粘着剤組成物を硬化させて得られる硬化物の粘着力（剥離力）およびゲル分率が、硬化物をＢＧテープの粘着剤層として用いた場合に、より適正な範囲となりやすいため、アルキル（メタ）アクリレートを含有することが好ましい。
アルキル（メタ）アクリレートとしては、炭素数４～１０のアルキル基を有するアルキル（メタ）アクリレートを用いることがより好ましい。具体的には、アルキル（メタ）アクリレートとして、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート等が挙げられる。これらの中でも特に、２－エチルヘキシル（メタ）アクリレートおよび／またはｎ－ブチル（メタ）アクリレートを用いることが好ましい。 Among these monofunctional (meth) acrylates, the adhesive strength (peeling force) and gel fraction of the cured product obtained by curing the pressure-sensitive adhesive composition are such that when the cured product is used as the pressure-sensitive adhesive layer of the BG tape. , It is preferable to contain an alkyl (meth) acrylate because it tends to be in a more appropriate range.
As the alkyl (meth) acrylate, it is more preferable to use an alkyl (meth) acrylate having an alkyl group having 4 to 10 carbon atoms. Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Among these, it is particularly preferable to use 2-ethylhexyl (meth) acrylate and / or n-butyl (meth) acrylate.
アルキル（メタ）アクリレートとしては、炭素数４～１０のアルキル基を有するアルキル（メタ）アクリレートを用いることがより好ましい。具体的には、アルキル（メタ）アクリレートとして、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート等が挙げられる。これらの中でも特に、２－エチルヘキシル（メタ）アクリレートおよび／またはｎ－ブチル（メタ）アクリレートを用いることが好ましい。 Among these monofunctional (meth) acrylates, the adhesive strength (peeling force) and gel fraction of the cured product obtained by curing the pressure-sensitive adhesive composition are such that when the cured product is used as the pressure-sensitive adhesive layer of the BG tape. , It is preferable to contain an alkyl (meth) acrylate because it tends to be in a more appropriate range.
As the alkyl (meth) acrylate, it is more preferable to use an alkyl (meth) acrylate having an alkyl group having 4 to 10 carbon atoms. Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Among these, it is particularly preferable to use 2-ethylhexyl (meth) acrylate and / or n-butyl (meth) acrylate.
多官能（メタ）アクリレートは、ポリウレタン（Ａ）以外であって、（メタ）アクリロイルオキシ基を複数有している化合物である。多官能（メタ）アクリレートとしては、ポリオール化合物のポリ（メタ）アクリレートを用いることが好ましい。
多官能（メタ）アクリレートとしては、具体的には、ポリエチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリエチレングリコールジ（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、ヒドロキシピバリン酸エステルネオペンチルグリコールジ（メタ）アクリレート、１，３－ビス（ヒドロキシエチル）－５，５－ジメチルヒダントインジ（メタ）アクリレート、α，ω－ジ（メタ）アクリルビスジエチレングリコールフタレート、トリメチロールプロパントリ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（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、ジアクリロキシエチルフォスフェート、ペンタエリスリトールテトラ（メタ）アクリレートなどが挙げられる。これらの中でも、多官能（メタ）アクリレートとして、粘着剤組成物の硬化性の観点から、トリメチロールプロパントリ（メタ）アクリレートを用いることが好ましい。 The polyfunctional (meth) acrylate is a compound other than polyurethane (A) and having a plurality of (meth) acryloyloxy groups. As the polyfunctional (meth) acrylate, it is preferable to use a poly (meth) acrylate of a polyol compound.
Specific examples of the polyfunctional (meth) acrylate include polyethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tripropylene glycol. Di (meth) acrylate, hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, 1,3-bis (hydroxyethyl) -5,5-dimethylhydantoin di (meth) acrylate, α, ω-di (meth) acrylic Bisdiethylene glycol phthalate, trimethylpropantri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( Examples thereof include meta) acrylate, diacryloxyethyl phosphate, pentaerythritol tetra (meth) acrylate and the like. Among these, trimethylolpropane tri (meth) acrylate is preferably used as the polyfunctional (meth) acrylate from the viewpoint of curability of the pressure-sensitive adhesive composition.
多官能（メタ）アクリレートとしては、具体的には、ポリエチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリエチレングリコールジ（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、ヒドロキシピバリン酸エステルネオペンチルグリコールジ（メタ）アクリレート、１，３－ビス（ヒドロキシエチル）－５，５－ジメチルヒダントインジ（メタ）アクリレート、α，ω－ジ（メタ）アクリルビスジエチレングリコールフタレート、トリメチロールプロパントリ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（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、ジアクリロキシエチルフォスフェート、ペンタエリスリトールテトラ（メタ）アクリレートなどが挙げられる。これらの中でも、多官能（メタ）アクリレートとして、粘着剤組成物の硬化性の観点から、トリメチロールプロパントリ（メタ）アクリレートを用いることが好ましい。 The polyfunctional (meth) acrylate is a compound other than polyurethane (A) and having a plurality of (meth) acryloyloxy groups. As the polyfunctional (meth) acrylate, it is preferable to use a poly (meth) acrylate of a polyol compound.
Specific examples of the polyfunctional (meth) acrylate include polyethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tripropylene glycol. Di (meth) acrylate, hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, 1,3-bis (hydroxyethyl) -5,5-dimethylhydantoin di (meth) acrylate, α, ω-di (meth) acrylic Bisdiethylene glycol phthalate, trimethylpropantri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( Examples thereof include meta) acrylate, diacryloxyethyl phosphate, pentaerythritol tetra (meth) acrylate and the like. Among these, trimethylolpropane tri (meth) acrylate is preferably used as the polyfunctional (meth) acrylate from the viewpoint of curability of the pressure-sensitive adhesive composition.
（メタ）アクリレートモノマー（Ｂ）として、単官能（メタ）アクリレートおよび多官能（メタ）アクリレートの両方を含有する場合、（メタ）アクリレートモノマー（Ｂ）の合計を１００モル％としたときに、単官能（メタ）アクリレートを８５～９９モル％、多官能（メタ）アクリレートを１～１５モル％含有することが好ましい。この場合、単官能（メタ）アクリレートの含有量は、９０～９９モル％であることがより好ましく、９５～９８モル％であることがさらに好ましい。また、多官能（メタ）アクリレートの含有量は、１～１０モル％であることがより好ましく、２～５モル％であることがさらに好ましい。
When both monofunctional (meth) acrylate and polyfunctional (meth) acrylate are contained as the (meth) acrylate monomer (B), when the total of the (meth) acrylate monomer (B) is 100 mol%, it is simple. It is preferable to contain 85 to 99 mol% of functional (meth) acrylate and 1 to 15 mol% of polyfunctional (meth) acrylate. In this case, the content of the monofunctional (meth) acrylate is more preferably 90 to 99 mol%, further preferably 95 to 98 mol%. The content of the polyfunctional (meth) acrylate is more preferably 1 to 10 mol%, further preferably 2 to 5 mol%.
単官能（メタ）アクリレートと多官能（メタ）アクリレートとを含有する場合、単官能（メタ）アクリレートの含有量が８５モル％以上であると、粘着剤組成物を硬化して得られる硬化物の流動性が、硬化物をＢＧテープの粘着剤層として用いた場合に好ましい範囲となる。したがって、この硬化物を粘着剤層として用いたＢＧテープは、十分な凹凸吸収性が得られ、表面に凹凸部分を有する被着体に貼付した場合に、被着体の凹凸部分との間に空隙が発生しにくく、好ましい。また、単官能（メタ）アクリレートの含有量が９９モル％以下であると、粘着剤組成物の硬化物を粘着剤層として用いたＢＧテープを、被着体から剥離した際に糊残りしにくく、好ましい。
When a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate are contained, if the content of the monofunctional (meth) acrylate is 85 mol% or more, the cured product obtained by curing the pressure-sensitive adhesive composition The fluidity is in a preferable range when the cured product is used as the pressure-sensitive adhesive layer of the BG tape. Therefore, the BG tape using this cured product as the pressure-sensitive adhesive layer can obtain sufficient unevenness absorption, and when it is attached to an adherend having an uneven portion on the surface, it is placed between the BG tape and the uneven portion of the adherend. It is preferable because voids are less likely to occur. Further, when the content of the monofunctional (meth) acrylate is 99 mol% or less, the BG tape using the cured product of the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer is less likely to remain adhesive when peeled from the adherend. ,preferable.
単官能（メタ）アクリレートと多官能（メタ）アクリレートとを含有する場合、多官能（メタ）アクリレートの含有量が１モル％以上であると、粘着剤組成物を硬化して得られる硬化物の流動性が大きくなりすぎず好ましい。また、多官能（メタ）アクリレートの含有量が１５モル％以下であると、粘着剤組成物を硬化して得られる硬化物の流動性が、硬化物をＢＧテープの粘着剤層として用いた場合に好ましい範囲となる。したがって、硬化物を粘着剤層として用いたＢＧテープが、十分な凹凸吸収性を有するものとなり、表面に凹凸部分を有する被着体に貼付した場合に、被着体の凹凸部分との間に空隙が発生しにくく、好ましい。
When a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate are contained, if the content of the polyfunctional (meth) acrylate is 1 mol% or more, the cured product obtained by curing the pressure-sensitive adhesive composition It is preferable that the fluidity does not become too large. Further, when the content of the polyfunctional (meth) acrylate is 15 mol% or less, the fluidity of the cured product obtained by curing the pressure-sensitive adhesive composition is high when the cured product is used as the pressure-sensitive adhesive layer of the BG tape. This is a preferable range. Therefore, the BG tape using the cured product as the pressure-sensitive adhesive layer has sufficient unevenness absorbing property, and when it is attached to an adherend having an uneven portion on the surface, it is placed between the BG tape and the uneven portion of the adherend. It is preferable because voids are less likely to occur.
本実施形態の粘着剤組成物中における（メタ）アクリレートモノマー（Ｂ）の含有量は任意に選択できるが、３５～７９質量％であることが好ましく、４０～７３質量％であることがより好ましく、４０～６６質量％であることが更に好ましく、４５～６５質量％であることが特に好ましい。必要に応じて、４５～６０質量％や、５０～５８質量％などであってもよい。（メタ）アクリレートモノマー（Ｂ）の含有量が３５質量％以上であると、粘着剤組成物の粘度が高くなりすぎることがなく、塗工性に優れるため好ましい。また、（メタ）アクリレートモノマー（Ｂ）の含有量が７９質量％以下であると、粘着剤組成物の粘度が低くなりすぎることがなく、粘着剤組成物からなる塗膜の厚みを制御し易く、好ましい。
The content of the (meth) acrylate monomer (B) in the pressure-sensitive adhesive composition of the present embodiment can be arbitrarily selected, but is preferably 35 to 79% by mass, more preferably 40 to 73% by mass. , 40 to 66% by mass, more preferably 45 to 65% by mass. If necessary, it may be 45 to 60% by mass, 50 to 58% by mass, or the like. When the content of the (meth) acrylate monomer (B) is 35% by mass or more, the viscosity of the pressure-sensitive adhesive composition does not become too high and the coatability is excellent, which is preferable. Further, when the content of the (meth) acrylate monomer (B) is 79% by mass or less, the viscosity of the pressure-sensitive adhesive composition does not become too low, and the thickness of the coating film made of the pressure-sensitive adhesive composition can be easily controlled. ,preferable.
（連鎖移動剤（Ｃ））
連鎖移動剤（Ｃ）は、粘着剤組成物を硬化させた硬化物の凹凸吸収性およびゲル分率を制御する目的で、粘着剤組成物中に含有させる。
連鎖移動剤（Ｃ）としては、チオール化合物を用いることが好ましい。特に、多官能チオールを好ましく用いることができる。多官能チオールは、分子内に２個以上のメルカプト基を有する化合物である。 (Chain transfer agent (C))
The chain transfer agent (C) is contained in the pressure-sensitive adhesive composition for the purpose of controlling the unevenness absorption and gel fraction of the cured product obtained by curing the pressure-sensitive adhesive composition.
As the chain transfer agent (C), it is preferable to use a thiol compound. In particular, polyfunctional thiols can be preferably used. A polyfunctional thiol is a compound having two or more mercapto groups in the molecule.
連鎖移動剤（Ｃ）は、粘着剤組成物を硬化させた硬化物の凹凸吸収性およびゲル分率を制御する目的で、粘着剤組成物中に含有させる。
連鎖移動剤（Ｃ）としては、チオール化合物を用いることが好ましい。特に、多官能チオールを好ましく用いることができる。多官能チオールは、分子内に２個以上のメルカプト基を有する化合物である。 (Chain transfer agent (C))
The chain transfer agent (C) is contained in the pressure-sensitive adhesive composition for the purpose of controlling the unevenness absorption and gel fraction of the cured product obtained by curing the pressure-sensitive adhesive composition.
As the chain transfer agent (C), it is preferable to use a thiol compound. In particular, polyfunctional thiols can be preferably used. A polyfunctional thiol is a compound having two or more mercapto groups in the molecule.
多官能チオールとしては、特に限定されないが、例えば、１，２－エタンジチオール、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、テトラエチレングリコールビス（３－メルカプトプロピオネート）、トリメチロールエタントリス（３－メルカプトブチレート）、トリメチロールプロパントリス（３－メルカプトブチレート）、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、トリス－[（３－メルカプトプロピオニルオキシ）－エチル]－イソシアヌレート、ジペンタエチスリトールヘキサキス（３－メルカプトプロピオネート）等が挙げられる。連鎖移動剤（Ｃ）としては、上記の中でも、粘着剤組成物の反応性の観点から、ペンタエリスリトールテトラキス（３－メルカプトブチレート）を用いることが好ましい。
The polyfunctional thiol is not particularly limited, and is, for example, 1,2-ethanedithiol, 1,4-bis (3-mercaptobutylyloxy) butane, tetraethylene glycol bis (3-mercaptopropionate), and trimethylol. Ethantris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate) 3-Mercaptopropionate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion, tris- [ (3-Mercaptopropionyloxy) -ethyl] -isocyanurate, dipentaethylolhexakis (3-mercaptopropionate) and the like can be mentioned. Among the above, as the chain transfer agent (C), it is preferable to use pentaerythritol tetrakis (3-mercaptobutyrate) from the viewpoint of the reactivity of the pressure-sensitive adhesive composition.
本実施形態の粘着剤組成物中における連鎖移動剤（Ｃ）の含有量は任意に選択できるが、０．５～８．０質量％であることが好ましく、０．７～６．０質量％であることがより好ましく、１．０～５．０質量％であることがさらに好ましく、３．０～４．５質量％であることが特に好ましい。連鎖移動剤（Ｃ）の含有量が０．５質量％以上であると、粘着剤組成物を硬化して得られる硬化物の流動性が、硬化物をＢＧテープの粘着剤層として用いた場合に好ましい範囲となる。したがって、硬化物を粘着剤層として用いたＢＧテープが、十分な凹凸吸収性を有するものとなり、被着体の凹凸部分との間に空隙が発生しにくく、好ましい。含有量が８．０質量％以下であると、粘着剤組成物の硬化物を粘着剤層として用いたＢＧテープを、被着体から剥離した際に糊残りしにくく、好ましい。
The content of the chain transfer agent (C) in the pressure-sensitive adhesive composition of the present embodiment can be arbitrarily selected, but is preferably 0.5 to 8.0% by mass, preferably 0.7 to 6.0% by mass. It is more preferably 1.0 to 5.0% by mass, and particularly preferably 3.0 to 4.5% by mass. When the content of the chain transfer agent (C) is 0.5% by mass or more, the fluidity of the cured product obtained by curing the pressure-sensitive adhesive composition is high when the cured product is used as the pressure-sensitive adhesive layer of the BG tape. It is in a preferable range. Therefore, it is preferable that the BG tape using the cured product as the pressure-sensitive adhesive layer has sufficient unevenness absorbing property and is less likely to generate voids between the cured product and the uneven portion of the adherend. When the content is 8.0% by mass or less, it is preferable that the BG tape using the cured product of the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer is less likely to leave adhesive residue when peeled from the adherend.
（光重合開始剤（Ｄ））
光重合開始剤（Ｄ）は、特に限定されるものではないが、光ラジカル重合開始剤が好ましい。光重合開始剤（Ｄ）としては、例えば、カルボニル系光重合開始剤、スルフィド系光重合開始剤、アシルホスフィンオキサイド系光重合開始剤、キノン系光重合開始剤、スルホクロリド系光重合開始剤、チオキサントン系光重合開始剤などを用いることができる。これらの光重合開始剤（Ｄ）中でも、粘着剤組成物を光硬化させて得られる硬化物の透明性の観点から、カルボニル系光重合開始剤および／またはアシルホスフィンオキサイド系光重合開始剤を用いることが好ましく、具体的には、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剤および／または１－ヒドロキシシクロヘキシル－フェニルケトンを用いることが好ましい。 (Photopolymerization Initiator (D))
The photopolymerization initiator (D) is not particularly limited, but a photoradical polymerization initiator is preferable. Examples of the photopolymerization initiator (D) include a carbonyl-based photopolymerization initiator, a sulfide-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a quinone-based photopolymerization initiator, and a sulfochloride-based photopolymerization initiator. A thioxanthone-based photopolymerization initiator or the like can be used. Among these photopolymerization initiators (D), a carbonyl-based photopolymerization initiator and / or an acylphosphine oxide-based photopolymerization initiator is used from the viewpoint of transparency of the cured product obtained by photocuring the pressure-sensitive adhesive composition. Specifically, it is preferable to use a 2,4,6-trimethylbenzoyldiphenylphosphine oxide agent and / or a 1-hydroxycyclohexyl-phenylketone.
光重合開始剤（Ｄ）は、特に限定されるものではないが、光ラジカル重合開始剤が好ましい。光重合開始剤（Ｄ）としては、例えば、カルボニル系光重合開始剤、スルフィド系光重合開始剤、アシルホスフィンオキサイド系光重合開始剤、キノン系光重合開始剤、スルホクロリド系光重合開始剤、チオキサントン系光重合開始剤などを用いることができる。これらの光重合開始剤（Ｄ）中でも、粘着剤組成物を光硬化させて得られる硬化物の透明性の観点から、カルボニル系光重合開始剤および／またはアシルホスフィンオキサイド系光重合開始剤を用いることが好ましく、具体的には、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剤および／または１－ヒドロキシシクロヘキシル－フェニルケトンを用いることが好ましい。 (Photopolymerization Initiator (D))
The photopolymerization initiator (D) is not particularly limited, but a photoradical polymerization initiator is preferable. Examples of the photopolymerization initiator (D) include a carbonyl-based photopolymerization initiator, a sulfide-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a quinone-based photopolymerization initiator, and a sulfochloride-based photopolymerization initiator. A thioxanthone-based photopolymerization initiator or the like can be used. Among these photopolymerization initiators (D), a carbonyl-based photopolymerization initiator and / or an acylphosphine oxide-based photopolymerization initiator is used from the viewpoint of transparency of the cured product obtained by photocuring the pressure-sensitive adhesive composition. Specifically, it is preferable to use a 2,4,6-trimethylbenzoyldiphenylphosphine oxide agent and / or a 1-hydroxycyclohexyl-phenylketone.
本実施形態の粘着剤組成物中における光重合開始剤（Ｄ）の含有量は、０．０１～５．０質量％であることが好ましく、０．０５～３．０質量％であることがより好ましく、０．１～２．０質量％であることがさらに好ましい。必要に応じて、０．２～１．５質量％や、０．３～１．２質量％などであってもよい。光重合開始剤（Ｄ）の含有量が０．０１質量％以上であると、粘着剤組成物の光硬化が十分に進行する。また、光重合開始剤（Ｄ）の含有量が５質量％以下であると、粘着剤組成物の光硬化時に低分子量成分が多くなりすぎることがない。このため、粘着剤組成物の硬化物を粘着剤層として用いたＢＧテープを、被着体から剥離した際に糊残りしにくく、好ましい。
The content of the photopolymerization initiator (D) in the pressure-sensitive adhesive composition of the present embodiment is preferably 0.01 to 5.0% by mass, and preferably 0.05 to 3.0% by mass. More preferably, it is 0.1 to 2.0% by mass. If necessary, it may be 0.2 to 1.5% by mass, 0.3 to 1.2% by mass, or the like. When the content of the photopolymerization initiator (D) is 0.01% by mass or more, the photocuring of the pressure-sensitive adhesive composition proceeds sufficiently. Further, when the content of the photopolymerization initiator (D) is 5% by mass or less, the low molecular weight component does not become too large during photocuring of the pressure-sensitive adhesive composition. Therefore, it is preferable that the BG tape using the cured product of the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer is less likely to leave adhesive residue when peeled from the adherend.
（イオン液体（Ｅ））
本実施形態におけるイオン液体（Ｅ）とは、融点が１００℃以下の溶融塩化合物（イオン性化合物）を指す。より好ましくは、融点が室温（２５℃）以下の溶融塩化合物である。イオン液体（Ｅ）は、１種類の化合物からなるものでもよく、２種類以上の化合物からなるものでもよい。前記イオン液体は、上記温度範囲において液体状態で存在する塩化合物を意味して良く、溶媒は含まなくてよい。 (Ionic liquid (E))
The ionic liquid (E) in the present embodiment refers to a molten salt compound (ionic compound) having a melting point of 100 ° C. or lower. More preferably, it is a molten salt compound having a melting point of room temperature (25 ° C.) or lower. The ionic liquid (E) may be composed of one kind of compound or two or more kinds of compounds. The ionic liquid may mean a salt compound that exists in a liquid state in the above temperature range, and may not contain a solvent.
本実施形態におけるイオン液体（Ｅ）とは、融点が１００℃以下の溶融塩化合物（イオン性化合物）を指す。より好ましくは、融点が室温（２５℃）以下の溶融塩化合物である。イオン液体（Ｅ）は、１種類の化合物からなるものでもよく、２種類以上の化合物からなるものでもよい。前記イオン液体は、上記温度範囲において液体状態で存在する塩化合物を意味して良く、溶媒は含まなくてよい。 (Ionic liquid (E))
The ionic liquid (E) in the present embodiment refers to a molten salt compound (ionic compound) having a melting point of 100 ° C. or lower. More preferably, it is a molten salt compound having a melting point of room temperature (25 ° C.) or lower. The ionic liquid (E) may be composed of one kind of compound or two or more kinds of compounds. The ionic liquid may mean a salt compound that exists in a liquid state in the above temperature range, and may not contain a solvent.
イオン液体（Ｅ）としては、有機カチオンと、無機アニオンもしくは有機アニオンとを組み合わせた有機塩化合物を用いることが好ましい。
有機カチオンとしては、オニウムが挙げられる。具体的には、第四級窒素原子のアンモニウム（代表構造：Ｑ１ ４Ｎ＋）、イミニウム（代表構造：Ｑ２ ２Ｃ＝Ｎ＋Ｑ１ ２）、スルホニウム（代表構造：Ｑ１ ３Ｓ＋）、オキソニウム（代表構造：Ｑ１ ２Ｏ＋）、第四級リン原子のホスホニウム（代表構造：Ｑ１ ４Ｐ＋）、ヨードニウム（代表構造：Ｑ１ ２Ｉ＋）等が挙げられる。 As the ionic liquid (E), it is preferable to use an organic salt compound in which an organic cation and an inorganic anion or an organic anion are combined.
Examples of the organic cation include onium. Specifically, ammonium quaternary nitrogen atom (representative structure: Q 1 4 N +), iminium (representative structure: Q 2 2 C = N + Q 1 2), sulfonium (representative structure: Q 1 3 S + ), oxonium (representative structure: Q 1 2 O +), phosphonium quaternary phosphorus atom (representative structure: Q 1 4 P +), iodonium (representative structure: Q 1 2 I +), and the like.
有機カチオンとしては、オニウムが挙げられる。具体的には、第四級窒素原子のアンモニウム（代表構造：Ｑ１ ４Ｎ＋）、イミニウム（代表構造：Ｑ２ ２Ｃ＝Ｎ＋Ｑ１ ２）、スルホニウム（代表構造：Ｑ１ ３Ｓ＋）、オキソニウム（代表構造：Ｑ１ ２Ｏ＋）、第四級リン原子のホスホニウム（代表構造：Ｑ１ ４Ｐ＋）、ヨードニウム（代表構造：Ｑ１ ２Ｉ＋）等が挙げられる。 As the ionic liquid (E), it is preferable to use an organic salt compound in which an organic cation and an inorganic anion or an organic anion are combined.
Examples of the organic cation include onium. Specifically, ammonium quaternary nitrogen atom (representative structure: Q 1 4 N +), iminium (representative structure: Q 2 2 C = N + Q 1 2), sulfonium (representative structure: Q 1 3 S + ), oxonium (representative structure: Q 1 2 O +), phosphonium quaternary phosphorus atom (representative structure: Q 1 4 P +), iodonium (representative structure: Q 1 2 I +), and the like.
上記の有機カチオンの代表構造において、Ｑ１はアルキル基、アリール基、ヘテロ環基等の置換基を表す。Ｑ２は水素原子または置換基を表す。分子中の複数のＱ１、分子中の複数のＱ２、または分子中のＱ１とＱ２は、互いに結合して環を形成してもよい。さらに、分子中の２つのＱ１または２つのＱ２が共同して二重結合の基（例えば、＝Ｏ、＝Ｓ、＝ＮＱ２）を形成してもよい。
In a representative structure of the organic cation, Q 1 represents an alkyl group, an aryl group, substituent such as a heterocyclic group. Q 2 is a hydrogen atom or a substituent. More for Q 1 in a molecule, Q 1, Q 2 of the plurality Q 2 'or in the molecule, in the molecule may be bonded to each other to form a ring. Furthermore, two for Q 1 or 2 Q 2 'is jointly double bond group in the molecule (e.g., = O, = S, = NQ 2) may be formed.
上記の有機カチオンの中でも、第四級窒素原子のアンモニウム、イミニウム、スルホニウムが好ましい。これらの有機カチオンとしては、例えば、ピリジニウムカチオン、ピペリジニウムカチオン、ピロリジニウムカチオン、イミダゾリウムカチオン、テトラヒドロピリミジニウムカチオン、ジヒドロピリミジニウムカチオン、ピラゾリウムカチオン、テトラアルキルアンモニウムカチオン、トリアルキルスルホニウムカチオンなどが挙げられる。これらの有機カチオンの中でも、イミダゾリウムカチオン、ピリジニウムカチオンが好ましく用いられる。
Among the above organic cations, quaternary nitrogen atoms such as ammonium, iminium, and sulfonium are preferable. Examples of these organic cations include pyridinium cation, piperidinium cation, pyrrolidinium cation, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, pyrazolium cation, tetraalkylammonium cation and trialkyl. Examples include sulfonium cations. Among these organic cations, imidazolium cations and pyridinium cations are preferably used.
有機カチオンとして、イミダゾリウムカチオン、ピリジニウムカチオンを用いたイオン液体（Ｅ）を含む粘着剤層は、帯電防止性に優れるため、好ましい。
A pressure-sensitive adhesive layer containing an ionic liquid (E) using an imidazolium cation or a pyridinium cation as an organic cation is preferable because it has excellent antistatic properties.
有機カチオンとして用いられるイミダゾリウムカチオンの具体例としては、例えば、１－メチルイミダゾリウムカチオン、１－エチル－３－メチルイミダゾリウムカチオン、１－エチル－２，３－ジメチルイミダゾリウムカチオン、１－ブチル－３－メチルイミダゾリウムカチオン、１，２，３－トリメチルイミダゾリウムカチオン等が挙げられる。これらのイミダゾリウムカチオンの中でも、１－エチル－３－メチルイミダゾリウムカチオンが好ましく用いられる。
Specific examples of the imidazolium cation used as an organic cation include 1-methylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, and 1-butyl. Examples thereof include -3-methylimidazolium cation and 1,2,3-trimethylimidazolium cation. Among these imidazolium cations, 1-ethyl-3-methylimidazolium cation is preferably used.
有機カチオンとして用いられるピリジニウムカチオンの具体例としては、例えば、１－エチルピリジニウムカチオン、１－ブチルピリジニウムカチオン、１－へキシルピリジニウムカチオン、１－ブチル－３－メチルピリジニウムカチオン、１－ブチル－４－メチルピリジニウムカチオン、１－へキシル－３－メチルピリジニウムカチオン、１－へキシル－４－メチルピリジニウムカチオン、１－ブチル－３，４－ジメチルピリジニウムカチオン、４－メチル－１－オクチルピリジニウムカチオンなどが挙げられる。これらのピリジニウムカチオンの中でも、１－へキシル－４－メチルピリジニウムカチオン、４－メチル－１－オクチルピリジニウムカチオンなどが好ましく用いられる。
Specific examples of the pyridinium cation used as the organic cation include, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4- Methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-hexyl-4-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 4-methyl-1-octylpyridinium cation, etc. Be done. Among these pyridinium cations, 1-hexyl-4-methylpyridinium cation, 4-methyl-1-octylpyridinium cation and the like are preferably used.
無機アニオンとしては、融点が１００℃以下の溶融塩化合物を形成できるものであれば特に限定されない。無機アニオンとしては、例えば、Ｃｌ－、Ｂｒ－、Ｉ－、ＡｌＣｌ４
－、Ａｌ２Ｃｌ７
－、ＢＦ４
－、ＰＦ６
－、ＣｌＯ４
－、ＮＯ３
－、ＡｓＦ６
－、ＳｂＦ６
－、ＮｂＦ６
－、ＴａＦ６
－、Ｆ（ＨＦ）ｍ
－（ｍは０以上の整数である。）、（ＣＮ）２Ｎ－等が挙げられる。
The inorganic anion is not particularly limited as long as it can form a molten salt compound having a melting point of 100 ° C. or lower. The inorganic anions such as, Cl -, Br -, I -, AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F (HF) m - (. m is an integer of 0 or more) - and the like, 2 N (CN).
有機アニオンとしては、融点が１００℃以下の溶融塩化合物を形成できるものであれば特に限定されない。有機アニオンとしては、例えば、ＣＨ３ＣＯＯ－、ＣＦ３ＣＯＯ－、ＣＨ３ＳＯ３
－、ＣＦ３ＳＯ３
－、（ＣＦ３ＳＯ２）２Ｎ－、（ＦＳＯ２）２Ｎ－、（ＣＦ３ＳＯ２）３Ｃ－、Ｃ４Ｆ９ＳＯ３
－、（Ｃ２Ｆ５ＳＯ２）２Ｎ－、Ｃ３Ｆ７ＣＯＯ－、（ＣＦ３ＳＯ２）（ＣＦ３ＣＯ）Ｎ－等が挙げられる。
The organic anion is not particularly limited as long as it can form a molten salt compound having a melting point of 100 ° C. or lower. The organic anions, for example, CH 3 COO -, CF 3 COO -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, (CF 3 SO 2) 3 C -, C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO - and the like -, (CF 3 SO 2) (CF 3 CO) N Be done.
無機アニオンもしくは有機アニオンとしては、上記の中でも特に、フッ素原子を含むアニオンを用いることが好ましい。フッ素原子を含むアニオンを用いることで、イオン伝導性に優れるイオン液体（Ｅ）となる。そのため、フッ素含有アニオンを含むイオン液体（Ｅ）を用いたＢＧテープは特に帯電防止性に優れるものとなる。帯電防止性の観点からは、フッ素原子を含むアニオンの中でもフッ素含有有機アニオンが好ましく、特に、（ＦＳＯ２）２Ｎ－、（ＣＦ３ＳＯ２）２Ｎ－を用いることが好ましく、（ＦＳＯ２）２Ｎ－を用いることがより好ましい。
Among the above, it is preferable to use an anion containing a fluorine atom as the inorganic anion or the organic anion. By using an anion containing a fluorine atom, an ionic liquid (E) having excellent ionic conductivity can be obtained. Therefore, the BG tape using the ionic liquid (E) containing a fluorine-containing anion is particularly excellent in antistatic property. From the viewpoint of antistatic properties, the fluorine-containing organic anion are preferable among anions containing fluorine atoms, in particular, (FSO 2) 2 N - , (CF 3 SO 2) 2 N - is preferably used, (FSO 2 ) It is more preferable to use 2 N −.
イオン液体（Ｅ）としては、市販のものを使用してもよい。中でも、１－エチル－３－メチルイミダゾリウムカチオンとビス（フルオロスルホニル）イミドアニオン（（ＦＳＯ２）２Ｎ－）からなるイオン液体（第一工業製薬（株）製、商品名：エレクセル ＡＳ－１１０）、４－メチル－１－オクチル－ピリジニウムカチオンとビス（フルオロスルホニル）イミドアニオン（（ＦＳＯ２）２Ｎ－）からなるイオン液体（第一工業製薬（株）製、商品名：エレクセル ＡＳ－８０４）が好ましい。イオン液体（Ｅ）として、上記ＡＳ－１１０および／またはＡＳ－８０４を含む粘着剤層は、帯電防止性に優れるため、好ましい。
As the ionic liquid (E), a commercially available one may be used. Of these, 1-ethyl-3-methylimidazolium cation and bis (fluorosulfonyl) imide anion ((FSO 2) 2 N -) ionic liquid consisting of (Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Erekuseru AS-110 ), 4-methyl-1-octyl - pyridinium cations and bis (fluorosulfonyl) imide anion ((FSO 2) 2 N -) ionic liquid consisting of (Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Erekuseru aS-804 ) Is preferable. The pressure-sensitive adhesive layer containing AS-110 and / or AS-804 as the ionic liquid (E) is preferable because it has excellent antistatic properties.
本実施形態の粘着剤組成物中におけるイオン液体（Ｅ）の含有量は任意に選択できるが、０．４～６．０質量％であることが好ましく、０．５～５．０質量％であることがより好ましく、１．０～３．０質量％であることがさらに好ましい。必要に応じて、０．４～２．０質量％や、２．０～４．０質量％などであってもよい。イオン液体（Ｅ）の含有量が０．４質量％以上であると、粘着剤層の表面抵抗値が十分に低くなる。その結果、粘着剤層を有するＢＧテープの帯電防止性能が良好になる。イオン液体（Ｅ）の含有量が６．０質量％以下であると、ＢＧテープを剥離した後の被着体に、ＢＧテープからブリードアウトしたイオン液体（Ｅ）が転写されることによる汚染（被着体表面が濡れた状態）が生じ難い。
The content of the ionic liquid (E) in the pressure-sensitive adhesive composition of the present embodiment can be arbitrarily selected, but is preferably 0.4 to 6.0% by mass, preferably 0.5 to 5.0% by mass. More preferably, it is more preferably 1.0 to 3.0% by mass. If necessary, it may be 0.4 to 2.0% by mass, 2.0 to 4.0% by mass, or the like. When the content of the ionic liquid (E) is 0.4% by mass or more, the surface resistance value of the pressure-sensitive adhesive layer becomes sufficiently low. As a result, the antistatic performance of the BG tape having the adhesive layer is improved. When the content of the ionic liquid (E) is 6.0% by mass or less, contamination due to transfer of the ionic liquid (E) bleeding out from the BG tape to the adherend after the BG tape is peeled off (contamination ( It is unlikely that the surface of the adherend will be wet).
（脂肪酸エステル（Ｆ））
本実施形態の粘着剤組成物は、ポリウレタン（Ａ）と、（メタ）アクリレートモノマー（Ｂ）と、連鎖移動剤（Ｃ）と、光重合開始剤（Ｄ）と、イオン液体（Ｅ）とを含み、さらに必要に応じて、脂肪酸エステル（Ｆ）を含有してもよい。
脂肪酸エステル（Ｆ）は、粘着剤組成物の硬化物を粘着剤層として用いたＢＧテープにおける粘着力を制御するとともに、粘着剤層のラミネート性（濡れ性）および泡抜け性（被着体にＢＧシートを貼り合わせ時に挟み込んだ気泡の抜けやすさ）を向上させる目的で粘着剤組成物中に含有させる。 (Fatty acid ester (F))
The pressure-sensitive adhesive composition of the present embodiment contains polyurethane (A), (meth) acrylate monomer (B), a chain transfer agent (C), a photopolymerization initiator (D), and an ionic liquid (E). It may be contained, and if necessary, a fatty acid ester (F) may be contained.
The fatty acid ester (F) controls the adhesive force of the BG tape using the cured product of the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer, and also has the adhesiveness (wetting property) and the foam removal property (on the adherend) of the pressure-sensitive adhesive layer. The BG sheet is contained in the pressure-sensitive adhesive composition for the purpose of improving (easiness of removal of air bubbles sandwiched during bonding).
本実施形態の粘着剤組成物は、ポリウレタン（Ａ）と、（メタ）アクリレートモノマー（Ｂ）と、連鎖移動剤（Ｃ）と、光重合開始剤（Ｄ）と、イオン液体（Ｅ）とを含み、さらに必要に応じて、脂肪酸エステル（Ｆ）を含有してもよい。
脂肪酸エステル（Ｆ）は、粘着剤組成物の硬化物を粘着剤層として用いたＢＧテープにおける粘着力を制御するとともに、粘着剤層のラミネート性（濡れ性）および泡抜け性（被着体にＢＧシートを貼り合わせ時に挟み込んだ気泡の抜けやすさ）を向上させる目的で粘着剤組成物中に含有させる。 (Fatty acid ester (F))
The pressure-sensitive adhesive composition of the present embodiment contains polyurethane (A), (meth) acrylate monomer (B), a chain transfer agent (C), a photopolymerization initiator (D), and an ionic liquid (E). It may be contained, and if necessary, a fatty acid ester (F) may be contained.
The fatty acid ester (F) controls the adhesive force of the BG tape using the cured product of the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer, and also has the adhesiveness (wetting property) and the foam removal property (on the adherend) of the pressure-sensitive adhesive layer. The BG sheet is contained in the pressure-sensitive adhesive composition for the purpose of improving (easiness of removal of air bubbles sandwiched during bonding).
脂肪酸エステル（Ｆ）としては、脂肪酸とアルキルアルコールとのエステルを用いることができ、他の成分との相溶性の観点から、炭素数８～１８の脂肪酸と炭素数３～１８の分岐炭化水素基を有する単官能アルコールとのエステル、および／又は、炭素数１４～１８の不飽和脂肪酸と２～４官能のアルコールとのエステルから選ばれる脂肪酸エステルを用いることが好ましい。
As the fatty acid ester (F), an ester of a fatty acid and an alkyl alcohol can be used, and from the viewpoint of compatibility with other components, a fatty acid having 8 to 18 carbon atoms and a branched hydrocarbon group having 3 to 18 carbon atoms It is preferable to use an ester with a monofunctional alcohol having, and / or a fatty acid ester selected from an ester of an unsaturated fatty acid having 14 to 18 carbon atoms and an alcohol having 2 to 4 functionalities.
炭素数８～１８の脂肪酸と炭素数３～１８の分岐炭化水素基を有する単官能アルコールとのエステルとしては、ラウリン酸イソステアリル、ミリスチン酸イソプロピル、ミリスチン酸イソセチル、ミリスチン酸オクチルドデシル、パルミチン酸イソプロピル、パルミチン酸イソステアリル、ステアリン酸イソセチル、ステアリン酸２－エチルヘキシル、オレイン酸オクチルドデシル、アジピン酸ジイソステアリル、セバシン酸ジイソセチル、トリメリト酸トリオレイル、およびトリメリト酸トリイソセチル等が挙げられる。これらの中でも、ミリスチン酸イソプロピル、パルミチン酸イソプロピル、ステアリン酸２－エチルヘキシルを用いることが好ましく、ミリスチン酸イソプロピルおよび／またはステアリン酸２－エチルヘキシルを用いることが特に好ましい。
Examples of the ester of a fatty acid having 8 to 18 carbon atoms and a monofunctional alcohol having a branched hydrocarbon group having 3 to 18 carbon atoms include isostearyl laurate, isopropyl myristate, isosetyl myristate, octyldodecyl myristate, and isopropyl palmitate. , Isostearyl palmitate, isosetyl stearate, 2-ethylhexyl stearate, octyldodecyl oleate, diisostearyl adipate, diisocetyl sebacate, trioleyl trimeritate, triisocetyl trimeritate and the like. Among these, isopropyl myristate, isopropyl palmitate, and 2-ethylhexyl stearate are preferably used, and isopropyl myristate and / or 2-ethylhexyl stearate is particularly preferable.
炭素数１４～１８の不飽和脂肪酸と２～４官能のアルコールとのエステルとしては、ミリストレイン酸、オレイン酸、リノール酸、リノレン酸、イソパルミチン酸、およびイソステアリン酸などの不飽和脂肪酸と、エチレングリコール、プロピレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、およびソルビタンなどのアルコールとのエステルが挙げられる。
The esters of unsaturated fatty acids having 14 to 18 carbon atoms and alcohols having 2 to 4 functionalities include unsaturated fatty acids such as myristoleic acid, oleic acid, linoleic acid, linolenic acid, isoparmitic acid, and isostearic acid, and ethylene. Examples include esters with alcohols such as glycols, propylene glycols, glycerins, trimethylolpropanes, pentaerythritols, and sorbitans.
本実施形態の粘着剤組成物中における脂肪酸エステル（Ｆ）の含有量は任意に選択できるが、３～１８質量％であることが好ましく、５～１５質量％であることがより好ましい。
脂肪酸エステル（Ｆ）の含有量が３質量％以上であると、粘着剤組成物の硬化物を粘着剤層として用いたＢＧテープにおける粘着力が好ましい範囲になるとともに、粘着剤層のラミネート性および泡抜け性が良好となる。脂肪酸エステル（Ｆ）の含有量が１８質量％以下であると、粘着剤組成物の硬化物を粘着剤層として用いたＢＧテープを、被着体から剥離した際に脂肪酸エステル（Ｆ）を含む糊残りが生じにくく、好ましい。 The content of the fatty acid ester (F) in the pressure-sensitive adhesive composition of the present embodiment can be arbitrarily selected, but is preferably 3 to 18% by mass, more preferably 5 to 15% by mass.
When the content of the fatty acid ester (F) is 3% by mass or more, the adhesive strength of the BG tape using the cured product of the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer is in a preferable range, and the adhesiveness of the pressure-sensitive adhesive layer and the laminating property and Good defoaming property. When the content of the fatty acid ester (F) is 18% by mass or less, the BG tape using the cured product of the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer contains the fatty acid ester (F) when peeled from the adherend. It is preferable because adhesive residue is unlikely to occur.
脂肪酸エステル（Ｆ）の含有量が３質量％以上であると、粘着剤組成物の硬化物を粘着剤層として用いたＢＧテープにおける粘着力が好ましい範囲になるとともに、粘着剤層のラミネート性および泡抜け性が良好となる。脂肪酸エステル（Ｆ）の含有量が１８質量％以下であると、粘着剤組成物の硬化物を粘着剤層として用いたＢＧテープを、被着体から剥離した際に脂肪酸エステル（Ｆ）を含む糊残りが生じにくく、好ましい。 The content of the fatty acid ester (F) in the pressure-sensitive adhesive composition of the present embodiment can be arbitrarily selected, but is preferably 3 to 18% by mass, more preferably 5 to 15% by mass.
When the content of the fatty acid ester (F) is 3% by mass or more, the adhesive strength of the BG tape using the cured product of the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer is in a preferable range, and the adhesiveness of the pressure-sensitive adhesive layer and the laminating property and Good defoaming property. When the content of the fatty acid ester (F) is 18% by mass or less, the BG tape using the cured product of the pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer contains the fatty acid ester (F) when peeled from the adherend. It is preferable because adhesive residue is unlikely to occur.
（溶剤）
本実施形態の粘着剤組成物は、溶剤を含んでもよいが、溶剤を実質的に含まない無溶剤のものであることがより好ましい。
本実施形態の粘着剤組成物が溶剤を含む場合、例えば、レベリング剤および／または軟化剤として溶剤を用いることができる。 (solvent)
The pressure-sensitive adhesive composition of the present embodiment may contain a solvent, but is more preferably a solvent-free one containing substantially no solvent.
When the pressure-sensitive adhesive composition of the present embodiment contains a solvent, for example, a solvent can be used as a leveling agent and / or a softening agent.
本実施形態の粘着剤組成物は、溶剤を含んでもよいが、溶剤を実質的に含まない無溶剤のものであることがより好ましい。
本実施形態の粘着剤組成物が溶剤を含む場合、例えば、レベリング剤および／または軟化剤として溶剤を用いることができる。 (solvent)
The pressure-sensitive adhesive composition of the present embodiment may contain a solvent, but is more preferably a solvent-free one containing substantially no solvent.
When the pressure-sensitive adhesive composition of the present embodiment contains a solvent, for example, a solvent can be used as a leveling agent and / or a softening agent.
本実施形態の粘着剤組成物が無溶剤である場合、これを用いてＢＧテープの粘着剤層を形成する際に、溶媒を加熱乾燥する工程を省略できるため、優れた生産性が得られる。特に、本実施形態の粘着剤組成物を用いて、厚みが５０μｍを超える粘着剤層を有するＢＧテープを製造する場合には、溶媒を加熱乾燥する工程を省略することによる生産性向上効果が顕著となるため、無溶剤であることが好ましい。
When the pressure-sensitive adhesive composition of the present embodiment is solvent-free, excellent productivity can be obtained because the step of heating and drying the solvent can be omitted when forming the pressure-sensitive adhesive layer of the BG tape using the pressure-sensitive adhesive composition. In particular, when a BG tape having a pressure-sensitive adhesive layer having a thickness of more than 50 μm is produced using the pressure-sensitive adhesive composition of the present embodiment, the productivity improvement effect by omitting the step of heating and drying the solvent is remarkable. Therefore, it is preferable that there is no solvent.
本発明において、粘着剤組成物が「溶剤を実質的に含まない」の意味は、粘着剤組成物中における溶剤の含有量が０～１．０質量％であることを意味し、好ましくは０～０．５質量％であり、より好ましくは０～０．１質量％である。
In the present invention, the meaning of "substantially free of solvent" in the pressure-sensitive adhesive composition means that the content of the solvent in the pressure-sensitive adhesive composition is 0 to 1.0% by mass, preferably 0. It is about 0.5% by mass, more preferably 0 to 0.1% by mass.
（その他）
本実施形態の粘着剤組成物は、本発明の効果を損なわない範囲で、必要に応じて、その他の添加剤を含有していてもよい。添加剤としては、例えば、可塑剤、表面潤滑剤、酸化防止剤、老化防止剤、光安定剤、紫外線吸収剤、重合禁止剤、ベンゾトリアゾール系等の光安定剤、リン酸エステル系およびその他の難燃剤、染料などが挙げられる。 (Other)
The pressure-sensitive adhesive composition of the present embodiment may contain other additives, if necessary, as long as the effects of the present invention are not impaired. Additives include, for example, plasticizers, surface lubricants, antioxidants, antioxidants, light stabilizers, UV absorbers, polymerization inhibitors, light stabilizers such as benzotriazoles, phosphate esters and others. Examples include flame retardants and dyes.
本実施形態の粘着剤組成物は、本発明の効果を損なわない範囲で、必要に応じて、その他の添加剤を含有していてもよい。添加剤としては、例えば、可塑剤、表面潤滑剤、酸化防止剤、老化防止剤、光安定剤、紫外線吸収剤、重合禁止剤、ベンゾトリアゾール系等の光安定剤、リン酸エステル系およびその他の難燃剤、染料などが挙げられる。 (Other)
The pressure-sensitive adhesive composition of the present embodiment may contain other additives, if necessary, as long as the effects of the present invention are not impaired. Additives include, for example, plasticizers, surface lubricants, antioxidants, antioxidants, light stabilizers, UV absorbers, polymerization inhibitors, light stabilizers such as benzotriazoles, phosphate esters and others. Examples include flame retardants and dyes.
＜粘着剤組成物の製造方法＞
次に、本実施形態の粘着剤組成物の製造方法について、例を挙げて詳細に説明する。以下、本実施形態の粘着剤組成物に含まれる成分のうち、ポリウレタン（Ａ）については、好ましい合成方法について例を挙げて説明する。本実施形態の粘着剤組成物に含まれる成分のうち、（メタ）アクリレートモノマー（Ｂ）、連鎖移動剤（Ｃ）、光重合開始剤（Ｄ）、イオン液体（Ｅ）、脂肪酸エステル（Ｆ）など、ポリウレタン（Ａ）を除く各成分については、市販品を容易に購入できるし、各成分として用いる化合物の種類によってそれぞれ合成方法が異なるため、合成方法の説明を省略する。 <Manufacturing method of adhesive composition>
Next, the method for producing the pressure-sensitive adhesive composition of the present embodiment will be described in detail with reference to an example. Hereinafter, among the components contained in the pressure-sensitive adhesive composition of the present embodiment, the polyurethane (A) will be described with reference to a preferable synthetic method. Among the components contained in the pressure-sensitive adhesive composition of the present embodiment, (meth) acrylate monomer (B), chain transfer agent (C), photopolymerization initiator (D), ionic liquid (E), fatty acid ester (F). For each component other than polyurethane (A), a commercially available product can be easily purchased, and the synthesis method differs depending on the type of compound used as each component. Therefore, the description of the synthesis method will be omitted.
次に、本実施形態の粘着剤組成物の製造方法について、例を挙げて詳細に説明する。以下、本実施形態の粘着剤組成物に含まれる成分のうち、ポリウレタン（Ａ）については、好ましい合成方法について例を挙げて説明する。本実施形態の粘着剤組成物に含まれる成分のうち、（メタ）アクリレートモノマー（Ｂ）、連鎖移動剤（Ｃ）、光重合開始剤（Ｄ）、イオン液体（Ｅ）、脂肪酸エステル（Ｆ）など、ポリウレタン（Ａ）を除く各成分については、市販品を容易に購入できるし、各成分として用いる化合物の種類によってそれぞれ合成方法が異なるため、合成方法の説明を省略する。 <Manufacturing method of adhesive composition>
Next, the method for producing the pressure-sensitive adhesive composition of the present embodiment will be described in detail with reference to an example. Hereinafter, among the components contained in the pressure-sensitive adhesive composition of the present embodiment, the polyurethane (A) will be described with reference to a preferable synthetic method. Among the components contained in the pressure-sensitive adhesive composition of the present embodiment, (meth) acrylate monomer (B), chain transfer agent (C), photopolymerization initiator (D), ionic liquid (E), fatty acid ester (F). For each component other than polyurethane (A), a commercially available product can be easily purchased, and the synthesis method differs depending on the type of compound used as each component. Therefore, the description of the synthesis method will be omitted.
＜ポリウレタン（Ａ）の合成方法＞
以下、本実施形態の粘着剤組成物に含まれるポリウレタン（Ａ）の好ましい合成方法の一例について説明する。なお、ポリウレタン（Ａ）の合成方法は、以下に示す合成方法に限定されるものではなく、合成に用いる原料および設備などの条件によって、適宜変更可能である。 <Synthesis method of polyurethane (A)>
Hereinafter, an example of a preferable synthetic method for the polyurethane (A) contained in the pressure-sensitive adhesive composition of the present embodiment will be described. The method for synthesizing the polyurethane (A) is not limited to the synthesis method shown below, and can be appropriately changed depending on the conditions such as the raw materials and equipment used for the synthesis.
以下、本実施形態の粘着剤組成物に含まれるポリウレタン（Ａ）の好ましい合成方法の一例について説明する。なお、ポリウレタン（Ａ）の合成方法は、以下に示す合成方法に限定されるものではなく、合成に用いる原料および設備などの条件によって、適宜変更可能である。 <Synthesis method of polyurethane (A)>
Hereinafter, an example of a preferable synthetic method for the polyurethane (A) contained in the pressure-sensitive adhesive composition of the present embodiment will be described. The method for synthesizing the polyurethane (A) is not limited to the synthesis method shown below, and can be appropriately changed depending on the conditions such as the raw materials and equipment used for the synthesis.
以下に示すポリウレタン（Ａ）の合成方法において、ヒドロキシ基とイソシアナト基との反応は、いずれの工程においても、イソシアナト基に不活性な有機溶媒の存在下で、ジブチルスズジラウレート、ジブチルスズジエチルヘキソエート、ジオクチルスズジラウレートなどのウレタン化触媒を用いて行うことができる。また、ヒドロキシ基とイソシアナト基との反応は、いずれの工程においても、３０～１００℃で１～５時間継続して行うことが好ましい。ウレタン化触媒の使用量は、反応物（原料）の総質量に対して、５０～５００質量ｐｐｍであることが好ましい。
In the method for synthesizing polyurethane (A) shown below, the reaction between the hydroxy group and the isocyanato group is carried out in any step in the presence of an organic solvent inert to the isocyanato group, such as dibutyltin dilaurate, dibutyltin diethylhexoate. This can be done using a urethanization catalyst such as dioctyltin dilaurate. Further, the reaction between the hydroxy group and the isocyanato group is preferably carried out continuously at 30 to 100 ° C. for 1 to 5 hours in any of the steps. The amount of the urethanization catalyst used is preferably 50 to 500 mass ppm with respect to the total mass of the reactant (raw material).
ポリウレタン（Ａ）を合成するには、まず、ポリオキシアルキレンポリオールとポリイソシアネートとを、イソシアナト基量（分子数基準、以下同じ）がヒドロキシ基量（分子数基準、以下同じ）より多くなる割合で仕込む。その後、ポリオキシアルキレンポリオールとポリイソシアネートとを反応させて、ポリウレタン（Ａ）の前駆体として、末端にイソシアナト基を有するポリウレタンを合成する。原料として用いられるポリオキシアルキレンポリオールおよびポリイソシアネートの具体的な例は、ポリウレタン（Ａ）の項で例示したとおりである。
In order to synthesize polyurethane (A), first, polyoxyalkylene polyol and polyisocyanate are mixed at a ratio in which the isocyanato group weight (molecular number standard, the same applies hereinafter) is larger than the hydroxy group weight (molecular number standard, the same applies hereinafter). Prepare. Then, the polyoxyalkylene polyol is reacted with the polyisocyanate to synthesize a polyurethane having an isocyanato group at the terminal as a precursor of the polyurethane (A). Specific examples of the polyoxyalkylene polyol and the polyisocyanate used as raw materials are as illustrated in the section of polyurethane (A).
このとき、原料中に含まれるヒドロキシ基量に対するイソシアナト基量の比を調整することにより、末端にイソシアナト基を有するポリウレタンの分子量（重合度）を調整できる。具体的には、ヒドロキシ基量に対するイソシアナト基量の過剰量が少ないほど、末端にイソシアナト基を有するポリウレタンの分子量は大きくなる。また、ヒドロキシ基量に対するイソシアナト基量の過剰量が多いほど、末端にイソシアナト基を有するポリウレタンの分子量は小さくなる。本実施形態では、末端にイソシアナト基を有するポリウレタンの分子量を調整することにより、目的物であるポリウレタン（Ａ）の質量平均分子量を調整する。
At this time, the molecular weight (degree of polymerization) of the polyurethane having an isocyanato group at the terminal can be adjusted by adjusting the ratio of the isocyanato group amount to the hydroxy group amount contained in the raw material. Specifically, the smaller the excess amount of the isocyanato group with respect to the hydroxy group amount, the larger the molecular weight of the polyurethane having an isocyanato group at the terminal. Further, the larger the excess amount of the isocyanato group with respect to the hydroxy group amount, the smaller the molecular weight of the polyurethane having an isocyanato group at the terminal. In the present embodiment, the mass average molecular weight of the target polyurethane (A) is adjusted by adjusting the molecular weight of the polyurethane having an isocyanato group at the terminal.
次に、末端にイソシアナト基を有するポリウレタンと、ヒドロキシ基および（メタ）アクリロイル基を有する化合物とを反応させて、ポリオキシアルキレンポリオール由来の構造およびポリイソシアネート由来の構造を含む骨格を有し、複数の末端に（メタ）アクリロイル基を有するポリウレタン（ａ１）を含むポリウレタン（Ａ）を生成する。生成されたポリウレタン（Ａ）の有する末端の（メタ）アクリロイル基は、（メタ）アクリロイルオキシ基の一部であることが好ましい。
Next, a polyurethane having an isocyanato group at the terminal is reacted with a compound having a hydroxy group and a (meth) acryloyl group to have a structure containing a polyoxyalkylene polyol-derived structure and a polyisocyanate-derived structure. Polyurethane (A) containing polyurethane (a1) having a (meth) acryloyl group at the end of is produced. The terminal (meth) acryloyl group of the produced polyurethane (A) is preferably a part of the (meth) acryloyloxy group.
ヒドロキシ基および（メタ）アクリロイル基を有する化合物としては、特に限定されないが、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート；１，３－ブタンジオールモノ（メタ）アクリレート、１，４－ブタンジオールモノ（メタ）アクリレート、１，６－ヘキサンジオールモノ（メタ）アクリレート、３－メチルペンタンジオールモノ（メタ）アクリレート等の各種ポリオール由来の（メタ）アクリロイル基を有するモノオール等が挙げられる。これらのヒドロキシ基および（メタ）アクリロイル基を有する化合物は、単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。これらのヒドロキシ基および（メタ）アクリロイル基を有する化合物の中でも、末端にイソシアナト基を有するポリウレタンのイソシアナト基との反応性、および粘着剤組成物の光硬化性の点から、２－ヒドロキシエチル（メタ）アクリレートを用いることが好ましい。
The compound having a hydroxy group and a (meth) acryloyl group is not particularly limited, but is hydroxyalkyl such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Meta) acrylate; 1,3-butanediol mono (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, 3-methylpentanediol mono (meth) acrylate Examples thereof include monool having a (meth) acryloyl group derived from various polyols such as. These compounds having a hydroxy group and a (meth) acryloyl group may be used alone or in combination of two or more. Among these compounds having a hydroxy group and a (meth) acryloyl group, 2-hydroxyethyl (meth) is obtained from the viewpoint of reactivity with the isocyanato group of polyurethane having an isocyanato group at the terminal and photocurability of the pressure-sensitive adhesive composition. ) It is preferable to use acrylate.
また、ポリウレタン（Ａ）は、ヒドロキシ基および（メタ）アクリロイル基を有する化合物とともに、（メタ）アクリロイル基を有さず、ヒドロキシ基を１個有するアルキルアルコールを併用して、末端にイソシアナト基を有するポリウレタンと反応させることにより、生成してもよい。
アルキルアルコールとしては、（メタ）アクリロイル基を有さず、ヒドロキシ基を１個有するものであればよく、直鎖型、分岐型、脂環型のアルキルアルコールなどを用いることができ、特に限定されない。上記アルキルアルコールは、１種のみ単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。 Further, the polyurethane (A) has an isocyanato group at the terminal in combination with a compound having a hydroxy group and a (meth) acryloyl group and an alkyl alcohol having no (meth) acryloyl group and having one hydroxy group. It may be produced by reacting with polyurethane.
The alkyl alcohol may be any as long as it does not have a (meth) acryloyl group and has one hydroxy group, and linear, branched, alicyclic alkyl alcohols and the like can be used and is not particularly limited. .. The above alkyl alcohol may be used alone or in combination of two or more.
アルキルアルコールとしては、（メタ）アクリロイル基を有さず、ヒドロキシ基を１個有するものであればよく、直鎖型、分岐型、脂環型のアルキルアルコールなどを用いることができ、特に限定されない。上記アルキルアルコールは、１種のみ単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。 Further, the polyurethane (A) has an isocyanato group at the terminal in combination with a compound having a hydroxy group and a (meth) acryloyl group and an alkyl alcohol having no (meth) acryloyl group and having one hydroxy group. It may be produced by reacting with polyurethane.
The alkyl alcohol may be any as long as it does not have a (meth) acryloyl group and has one hydroxy group, and linear, branched, alicyclic alkyl alcohols and the like can be used and is not particularly limited. .. The above alkyl alcohol may be used alone or in combination of two or more.
ヒドロキシ基および（メタ）アクリロイル基を有する化合物と、（メタ）アクリロイル基を有さず、ヒドロキシ基を１個有するアルキルアルコールと、末端にイソシアナト基を有するポリウレタンとを反応させて、ポリウレタン（Ａ）を生成させることにより、末端にイソシアナト基を有するポリウレタンに対する（メタ）アクリロイル基の導入量を調整できる。
Polyurethane (A) is obtained by reacting a compound having a hydroxy group and a (meth) acryloyl group, an alkyl alcohol having no (meth) acryloyl group and having one hydroxy group, and a polyurethane having an isocyanato group at the terminal. The amount of (meth) acryloyl group introduced into polyurethane having an isocyanato group at the terminal can be adjusted by producing.
より詳細には、上記反応によれば、ポリウレタン（Ａ）として、末端の（メタ）アクリロイル基の導入量が異なる複数種のポリウレタンを含むものが生成される。複数種のポリウレタンの中には、複数の末端に（メタ）アクリロイル基を有するポリウレタン（ａ１）が含まれる。さらに、複数種のポリウレタンの中には、ポリウレタン（ａ１）だけでなく、複数の末端のうち少なくとも一部の末端が上記アルキルアルコール由来の構造を有しているポリウレタンが含まれる。したがって、生成した複数種のポリウレタンの中には、複数の末端のうち少なくとも一部の末端が（メタ）アクリロイル基を有さないポリウレタンが含まれる。さらに、生成した複数種のポリウレタンの中には、１つの末端にのみ（メタ）アクリロイル基を有するポリウレタン（ａ２）も含まれ得る。
More specifically, according to the above reaction, a polyurethane (A) containing a plurality of types of polyurethane having different amounts of introduced (meth) acryloyl groups at the ends is produced. The plurality of types of polyurethanes include polyurethanes (a1) having a plurality of (meth) acryloyl groups at the ends. Further, the plurality of types of polyurethane include not only polyurethane (a1) but also polyurethane in which at least a part of the plurality of ends has a structure derived from the above alkyl alcohol. Therefore, the produced plurality of types of polyurethanes include polyurethanes in which at least some of the plurality of ends do not have a (meth) acryloyl group. Furthermore, among the plurality of types of polyurethane produced, polyurethane (a2) having a (meth) acryloyl group at only one terminal may be included.
＜ポリウレタン（Ａ）の合成方法の他の例＞
次に、ポリウレタン（Ａ）の好ましい合成方法の他の例について説明する。
以下に示すポリウレタン（Ａ）の合成方法においても上記の合成方法の例と同様に、ヒドロキシ基とイソシアナト基との反応は、いずれの工程においても、イソシアナト基に不活性な有機溶媒の存在下で、ジブチルスズジラウレート、ジブチルスズジエチルヘキソエート、ジオクチルスズジラウレートなどのウレタン化触媒を用いて行うことができる。また、ヒドロキシ基とイソシアナト基との反応は、いずれの工程においても、３０～１００℃で１～５時間継続して行うことが好ましい。ウレタン化触媒の使用量は、反応物（原料）の総質量に対して、５０～５００質量ｐｐｍであることが好ましい。 <Other examples of methods for synthesizing polyurethane (A)>
Next, another example of a preferable synthetic method of polyurethane (A) will be described.
In the method for synthesizing polyurethane (A) shown below, the reaction between the hydroxy group and the isocyanato group is carried out in the presence of an organic solvent inert to the isocyanato group in any of the steps, as in the example of the above synthesis method. , Dibutyltin dilaurate, dibutyltin diethylhexoate, dioctyltin dilaurate and other urethanization catalysts can be used. Further, the reaction between the hydroxy group and the isocyanato group is preferably carried out continuously at 30 to 100 ° C. for 1 to 5 hours in any of the steps. The amount of the urethanization catalyst used is preferably 50 to 500 mass ppm with respect to the total mass of the reactant (raw material).
次に、ポリウレタン（Ａ）の好ましい合成方法の他の例について説明する。
以下に示すポリウレタン（Ａ）の合成方法においても上記の合成方法の例と同様に、ヒドロキシ基とイソシアナト基との反応は、いずれの工程においても、イソシアナト基に不活性な有機溶媒の存在下で、ジブチルスズジラウレート、ジブチルスズジエチルヘキソエート、ジオクチルスズジラウレートなどのウレタン化触媒を用いて行うことができる。また、ヒドロキシ基とイソシアナト基との反応は、いずれの工程においても、３０～１００℃で１～５時間継続して行うことが好ましい。ウレタン化触媒の使用量は、反応物（原料）の総質量に対して、５０～５００質量ｐｐｍであることが好ましい。 <Other examples of methods for synthesizing polyurethane (A)>
Next, another example of a preferable synthetic method of polyurethane (A) will be described.
In the method for synthesizing polyurethane (A) shown below, the reaction between the hydroxy group and the isocyanato group is carried out in the presence of an organic solvent inert to the isocyanato group in any of the steps, as in the example of the above synthesis method. , Dibutyltin dilaurate, dibutyltin diethylhexoate, dioctyltin dilaurate and other urethanization catalysts can be used. Further, the reaction between the hydroxy group and the isocyanato group is preferably carried out continuously at 30 to 100 ° C. for 1 to 5 hours in any of the steps. The amount of the urethanization catalyst used is preferably 50 to 500 mass ppm with respect to the total mass of the reactant (raw material).
この合成方法を用いてポリウレタン（Ａ）を合成する場合、上記の合成方法の例と異なり、ポリウレタン（Ａ）の前駆体として、末端にヒドロキシ基を有するポリウレタンを合成する。
具体的には、まず、ポリオキシアルキレンポリオールとポリイソシアネートとを、ヒドロキシ基量（分子数基準、以下同じ）がイソシアナト基量（分子数基準、以下同じ）より多くなる割合で仕込む。その後、ポリオキシアルキレンポリオールとポリイソシアネートとを反応させて、ポリウレタン（Ａ）の前駆体として、末端にヒドロキシ基を有するポリウレタンを合成する。 When synthesizing polyurethane (A) using this synthesis method, unlike the above example of the synthesis method, polyurethane having a hydroxy group at the terminal is synthesized as a precursor of polyurethane (A).
Specifically, first, the polyoxyalkylene polyol and the polyisocyanate are charged at a ratio in which the hydroxy group amount (based on the number of molecules, the same applies hereinafter) is larger than the amount of the isocyanato group (based on the number of molecules, the same applies hereinafter). Then, the polyoxyalkylene polyol is reacted with the polyisocyanate to synthesize a polyurethane having a hydroxy group at the terminal as a precursor of the polyurethane (A).
具体的には、まず、ポリオキシアルキレンポリオールとポリイソシアネートとを、ヒドロキシ基量（分子数基準、以下同じ）がイソシアナト基量（分子数基準、以下同じ）より多くなる割合で仕込む。その後、ポリオキシアルキレンポリオールとポリイソシアネートとを反応させて、ポリウレタン（Ａ）の前駆体として、末端にヒドロキシ基を有するポリウレタンを合成する。 When synthesizing polyurethane (A) using this synthesis method, unlike the above example of the synthesis method, polyurethane having a hydroxy group at the terminal is synthesized as a precursor of polyurethane (A).
Specifically, first, the polyoxyalkylene polyol and the polyisocyanate are charged at a ratio in which the hydroxy group amount (based on the number of molecules, the same applies hereinafter) is larger than the amount of the isocyanato group (based on the number of molecules, the same applies hereinafter). Then, the polyoxyalkylene polyol is reacted with the polyisocyanate to synthesize a polyurethane having a hydroxy group at the terminal as a precursor of the polyurethane (A).
このとき、原料中に含まれるイソシアナト基量に対するヒドロキシ基量の比を調整することにより、末端にヒドロキシ基を有するポリウレタンの分子量（重合度）を調整できる。具体的には、イソシアナト基量に対するヒドロキシ基量の過剰量が少ないほど、末端にヒドロキシ基を有するポリウレタンの分子量は大きくなる。また、イソシアナト基量に対するヒドロキシ基量の過剰量が多いほど、末端にヒドロキシ基を有するポリウレタンの分子量の分子量は小さくなる。本実施形態では、末端にヒドロキシ基を有するポリウレタンの分子量の分子量を調整することにより、目的物であるポリウレタン（Ａ）の質量平均分子量を調整する。
At this time, the molecular weight (degree of polymerization) of the polyurethane having a hydroxy group at the terminal can be adjusted by adjusting the ratio of the hydroxy group amount to the isocyanato group amount contained in the raw material. Specifically, the smaller the excess amount of the hydroxy group amount with respect to the isocyanato group amount, the larger the molecular weight of the polyurethane having a hydroxy group at the terminal. Further, the larger the excess amount of the hydroxy group with respect to the isocyanato group amount, the smaller the molecular weight of the polyurethane having a hydroxy group at the terminal. In the present embodiment, the mass average molecular weight of the target polyurethane (A) is adjusted by adjusting the molecular weight of the polyurethane having a hydroxy group at the terminal.
次に、末端にヒドロキシ基を有するポリウレタンと、イソシアナト基および（メタ）アクリロイル基を有する化合物とを反応させて、ポリオキシアルキレンポリオール由来の構造およびポリイソシアネート由来の構造を含む骨格を有し、複数の末端に（メタ）アクリロイル基を有するポリウレタン（ａ１）を含むポリウレタン（Ａ）を生成する。生成されたポリウレタン（Ａ）の有する末端の（メタ）アクリロイル基は、（メタ）アクリロイルオキシ基の一部であることが好ましい。
Next, a polyurethane having a hydroxy group at the terminal is reacted with a compound having an isocyanato group and a (meth) acryloyl group to have a structure containing a polyoxyalkylene polyol-derived structure and a polyisocyanate-derived structure. Polyurethane (A) containing polyurethane (a1) having a (meth) acryloyl group at the end of is produced. The terminal (meth) acryloyl group of the produced polyurethane (A) is preferably a part of the (meth) acryloyloxy group.
イソシアナト基および（メタ）アクリロイル基を有する化合物としては、特に限定されないが、２－（メタ）アクリロイルオキシエチルイソシアネート、２－（メタ）アクリロイルオキシプロピルイソシアネート、１，１－ビス（アクリロイルオキシメチル）エチルイソシアネート等が挙げられる。また、イソシアナト基および（メタ）アクリロイル基を有する化合物の市販品としては、例えば、昭和電工株式会社製のカレンズＭＯＩ（登録商標）、カレンズＡＯＩ（登録商標）などが例示できる。これらのイソシアナト基および（メタ）アクリロイル基を有する化合物は、単独で使用してもよいし、２種以上を組み合わせて使用してもよい。これらのイソシアナト基および（メタ）アクリロイル基を有する化合物の中でも、末端にヒドロキシ基を有するポリウレタンのヒドロキシ基との反応性、および粘着剤組成物の光硬化性の点から、２－（メタ）アクリロイルオキシエチルイソシアネートを用いることが好ましい。
The compound having an isocyanato group and a (meth) acryloyl group is not particularly limited, but is limited to 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, and 1,1-bis (acryloyloxymethyl) ethyl. Examples thereof include isocyanate. Examples of commercially available compounds having an isocyanato group and a (meth) acryloyl group include Karenz MOI (registered trademark) and Karenz AOI (registered trademark) manufactured by Showa Denko KK. These compounds having an isocyanato group and a (meth) acryloyl group may be used alone or in combination of two or more. Among these compounds having an isocyanato group and a (meth) acryloyl group, 2- (meth) acryloyl from the viewpoint of reactivity with the hydroxy group of polyurethane having a hydroxy group at the terminal and photocurability of the pressure-sensitive adhesive composition. It is preferable to use oxyethyl isocyanate.
また、ポリウレタン（Ａ）は、イソシアナト基および（メタ）アクリロイル基を有する化合物とともに、（メタ）アクリロイル基を有さず、イソシアナト基を１個有するアルキルイソシアネートを併用して、末端にヒドロキシ基を有するポリウレタンと反応させることにより、生成してもよい。
アルキルイソシアネートとしては、（メタ）アクリロイル基を有さず、イソシアナト基を１個有するものであればよく、直鎖型、分岐型、脂環型のアルキルイソシアネートなどを用いることができ、特に限定されない。上記アルキルイソシアネートは、１種のみ単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。 Further, the polyurethane (A) has a hydroxy group at the terminal in combination with a compound having an isocyanato group and a (meth) acryloyl group and an alkyl isocyanate having no (meth) acryloyl group and having one isocyanato group. It may be produced by reacting with polyurethane.
The alkyl isocyanate may be any as long as it does not have a (meth) acryloyl group and has one isocyanato group, and linear type, branched type, alicyclic type alkyl isocyanate and the like can be used and is not particularly limited. .. The above alkyl isocyanate may be used alone or in combination of two or more.
アルキルイソシアネートとしては、（メタ）アクリロイル基を有さず、イソシアナト基を１個有するものであればよく、直鎖型、分岐型、脂環型のアルキルイソシアネートなどを用いることができ、特に限定されない。上記アルキルイソシアネートは、１種のみ単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。 Further, the polyurethane (A) has a hydroxy group at the terminal in combination with a compound having an isocyanato group and a (meth) acryloyl group and an alkyl isocyanate having no (meth) acryloyl group and having one isocyanato group. It may be produced by reacting with polyurethane.
The alkyl isocyanate may be any as long as it does not have a (meth) acryloyl group and has one isocyanato group, and linear type, branched type, alicyclic type alkyl isocyanate and the like can be used and is not particularly limited. .. The above alkyl isocyanate may be used alone or in combination of two or more.
イソシアナト基および（メタ）アクリロイル基を有する化合物と、（メタ）アクリロイル基を有さず、イソシアナト基を１個有するアルキルイソシアネートと、末端にヒドロキシ基を有するポリウレタンとを反応させて、ポリウレタン（Ａ）を生成させることにより、末端にヒドロキシ基を有するポリウレタンに対する（メタ）アクリロイル基の導入量を調整できる。
Polyurethane (A) is obtained by reacting a compound having an isocyanato group and a (meth) acryloyl group, an alkyl isocyanate having no (meth) acryloyl group and having one isocyanato group, and a polyurethane having a hydroxy group at the terminal. The amount of (meth) acryloyl group introduced into polyurethane having a hydroxy group at the terminal can be adjusted by producing.
より詳細には、上記反応によれば、ポリウレタン（Ａ）として、末端の（メタ）アクリロイル基の導入量が異なる複数種のポリウレタンを含むものが生成される。複数種のポリウレタンの中には、複数の末端に（メタ）アクリロイル基を有するポリウレタン（ａ１）が含まれる。さらに、複数種のポリウレタンの中には、ポリウレタン（ａ１）だけでなく、複数の末端のうち少なくとも一部の末端が上記アルキルイソシアネート由来の構造を有しているポリウレタンが含まれる。したがって、生成した複数種のポリウレタンの中には、複数の末端のうち少なくとも一部の末端が（メタ）アクリロイル基を有さないポリウレタンが含まれる。さらに、生成した複数種のポリウレタンの中には、１つの末端にのみ（メタ）アクリロイル基を有するポリウレタン（ａ２）も含まれ得る。
More specifically, according to the above reaction, a polyurethane (A) containing a plurality of types of polyurethane having different amounts of introduced (meth) acryloyl groups at the ends is produced. The plurality of types of polyurethanes include polyurethanes (a1) having a plurality of (meth) acryloyl groups at the ends. Further, the plurality of types of polyurethane include not only polyurethane (a1) but also polyurethane in which at least a part of the plurality of ends has a structure derived from the above-mentioned alkyl isocyanate. Therefore, the produced plurality of types of polyurethanes include polyurethanes in which at least some of the plurality of ends do not have a (meth) acryloyl group. Furthermore, among the plurality of types of polyurethane produced, polyurethane (a2) having a (meth) acryloyl group at only one terminal may be included.
＜粘着剤組成物に含まれる各成分の混合方法＞
本実施形態の粘着剤組成物は、上記の合成方法により得られたポリウレタン（Ａ）と、（メタ）アクリレートモノマー（Ｂ）と、連鎖移動剤（Ｃ）と、光重合開始剤（Ｄ）と、イオン液体（Ｅ）と、必要に応じて添加される脂肪酸エステル（Ｆ）およびその他の添加剤とを混合する方法により製造できる。
本実施形態の粘着剤組成物に含まれる各成分を混合する方法は、特に限定されるものではなく、例えば、ホモディスパー、パドル翼などの攪拌翼を取り付けた攪拌装置を用いて行うことができる。 <Method of mixing each component contained in the pressure-sensitive adhesive composition>
The pressure-sensitive adhesive composition of the present embodiment contains the polyurethane (A) obtained by the above synthesis method, the (meth) acrylate monomer (B), the chain transfer agent (C), and the photopolymerization initiator (D). , The ionic liquid (E) can be produced by a method of mixing the fatty acid ester (F) added as needed and other additives.
The method of mixing each component contained in the pressure-sensitive adhesive composition of the present embodiment is not particularly limited, and can be carried out by using, for example, a stirring device equipped with a stirring blade such as a homodisper or a paddle blade. ..
本実施形態の粘着剤組成物は、上記の合成方法により得られたポリウレタン（Ａ）と、（メタ）アクリレートモノマー（Ｂ）と、連鎖移動剤（Ｃ）と、光重合開始剤（Ｄ）と、イオン液体（Ｅ）と、必要に応じて添加される脂肪酸エステル（Ｆ）およびその他の添加剤とを混合する方法により製造できる。
本実施形態の粘着剤組成物に含まれる各成分を混合する方法は、特に限定されるものではなく、例えば、ホモディスパー、パドル翼などの攪拌翼を取り付けた攪拌装置を用いて行うことができる。 <Method of mixing each component contained in the pressure-sensitive adhesive composition>
The pressure-sensitive adhesive composition of the present embodiment contains the polyurethane (A) obtained by the above synthesis method, the (meth) acrylate monomer (B), the chain transfer agent (C), and the photopolymerization initiator (D). , The ionic liquid (E) can be produced by a method of mixing the fatty acid ester (F) added as needed and other additives.
The method of mixing each component contained in the pressure-sensitive adhesive composition of the present embodiment is not particularly limited, and can be carried out by using, for example, a stirring device equipped with a stirring blade such as a homodisper or a paddle blade. ..
＜ＢＧテープの製造方法＞
次に、本実施形態のＢＧテープの製造方法の例について説明する。
本実施形態のＢＧテープの製造方法は、特に限定されるものではなく、公知の方法を用いて製造できる。
例えば、シート状の基材上に、粘着剤組成物を塗布し、セパレーターをラミネートして積層体とする。その後、セパレーターを介して粘着剤組成物に紫外線を照射し、粘着剤組成物を光硬化させる。このことにより、基材上に、粘着剤組成物の硬化物からなる粘着剤層が形成されたＢＧテープが得られる。 <Manufacturing method of BG tape>
Next, an example of the method for manufacturing the BG tape of the present embodiment will be described.
The method for producing the BG tape of the present embodiment is not particularly limited, and the BG tape can be produced by using a known method.
For example, an adhesive composition is applied onto a sheet-shaped base material, and a separator is laminated to form a laminate. Then, the pressure-sensitive adhesive composition is irradiated with ultraviolet rays via a separator to photo-cure the pressure-sensitive adhesive composition. As a result, a BG tape having a pressure-sensitive adhesive layer made of a cured product of the pressure-sensitive adhesive composition formed on the base material can be obtained.
次に、本実施形態のＢＧテープの製造方法の例について説明する。
本実施形態のＢＧテープの製造方法は、特に限定されるものではなく、公知の方法を用いて製造できる。
例えば、シート状の基材上に、粘着剤組成物を塗布し、セパレーターをラミネートして積層体とする。その後、セパレーターを介して粘着剤組成物に紫外線を照射し、粘着剤組成物を光硬化させる。このことにより、基材上に、粘着剤組成物の硬化物からなる粘着剤層が形成されたＢＧテープが得られる。 <Manufacturing method of BG tape>
Next, an example of the method for manufacturing the BG tape of the present embodiment will be described.
The method for producing the BG tape of the present embodiment is not particularly limited, and the BG tape can be produced by using a known method.
For example, an adhesive composition is applied onto a sheet-shaped base material, and a separator is laminated to form a laminate. Then, the pressure-sensitive adhesive composition is irradiated with ultraviolet rays via a separator to photo-cure the pressure-sensitive adhesive composition. As a result, a BG tape having a pressure-sensitive adhesive layer made of a cured product of the pressure-sensitive adhesive composition formed on the base material can be obtained.
基材に粘着剤組成物を塗布する方法は、特に限定されず、適宜選択可能である。例えば、基材に粘着剤組成物を塗布する方法として、グラビアロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーコーター、コンマコーター、ダイレクトコーター等の各種コーターを用いる方法、スクリーン印刷法等が挙げられる。
The method of applying the pressure-sensitive adhesive composition to the base material is not particularly limited and can be appropriately selected. For example, as a method of applying the adhesive composition to the base material, various coaters such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater are used. Examples thereof include a method to be used and a screen printing method.
粘着剤組成物を光硬化させる際の光源としては、ブラックライト、低圧水銀灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、キセノンランプ等が挙げられる。
光の照射強度は、粘着剤組成物を充分に硬化させることができ、かつ硬化物のゲル分率が５０～６５質量％の範囲内となるような条件であることが好ましく、例えば、５０～３０００ｍＷ／ｃｍ２であることが好ましい。なお、光の照射強度が弱いと硬化に時間がかかり、生産性が低下する。 Examples of the light source for photocuring the pressure-sensitive adhesive composition include a black light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, and a xenon lamp.
The light irradiation intensity is preferably a condition in which the pressure-sensitive adhesive composition can be sufficiently cured and the gel fraction of the cured product is in the range of 50 to 65% by mass. For example, 50 to It is preferably 3000 mW / cm 2. If the light irradiation intensity is weak, it takes time to cure and the productivity decreases.
光の照射強度は、粘着剤組成物を充分に硬化させることができ、かつ硬化物のゲル分率が５０～６５質量％の範囲内となるような条件であることが好ましく、例えば、５０～３０００ｍＷ／ｃｍ２であることが好ましい。なお、光の照射強度が弱いと硬化に時間がかかり、生産性が低下する。 Examples of the light source for photocuring the pressure-sensitive adhesive composition include a black light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, and a xenon lamp.
The light irradiation intensity is preferably a condition in which the pressure-sensitive adhesive composition can be sufficiently cured and the gel fraction of the cured product is in the range of 50 to 65% by mass. For example, 50 to It is preferably 3000 mW / cm 2. If the light irradiation intensity is weak, it takes time to cure and the productivity decreases.
本実施形態では、透明なセパレーターを介して粘着剤組成物に紫外線を照射したが、基材が透明である場合、基材側から紫外線を照射してもよく、セパレーターとして不透明なものを用いてもよい。
In the present embodiment, the pressure-sensitive adhesive composition is irradiated with ultraviolet rays via a transparent separator, but when the base material is transparent, ultraviolet rays may be irradiated from the base material side, and an opaque separator is used. May be good.
＜ＢＧテープの用途および求められる性能＞
本実施形態のＢＧテープは、例えば、表面に凹凸部分を有する被着体に貼付され、その後に剥離される用途に用いることができる。具体的には、半導体ウエハのバンプが形成された面に貼付して、半導体ウエハの表面を保護し、所定のウエハ加工工程の後に剥離される半導体ウエハ加工用のバックグラインドテープとして好適に使用できる。 <Applications and required performance of BG tape>
The BG tape of the present embodiment can be used, for example, for applications where it is attached to an adherend having an uneven portion on the surface and then peeled off. Specifically, it can be suitably used as a back grind tape for semiconductor wafer processing, which is attached to a surface on which bumps of a semiconductor wafer are formed to protect the surface of the semiconductor wafer and is peeled off after a predetermined wafer processing step. ..
本実施形態のＢＧテープは、例えば、表面に凹凸部分を有する被着体に貼付され、その後に剥離される用途に用いることができる。具体的には、半導体ウエハのバンプが形成された面に貼付して、半導体ウエハの表面を保護し、所定のウエハ加工工程の後に剥離される半導体ウエハ加工用のバックグラインドテープとして好適に使用できる。 <Applications and required performance of BG tape>
The BG tape of the present embodiment can be used, for example, for applications where it is attached to an adherend having an uneven portion on the surface and then peeled off. Specifically, it can be suitably used as a back grind tape for semiconductor wafer processing, which is attached to a surface on which bumps of a semiconductor wafer are formed to protect the surface of the semiconductor wafer and is peeled off after a predetermined wafer processing step. ..
本実施形態のＢＧテープを、表面にバンプが形成された半導体ウエハの表面を保護する用途に用いる場合、ＢＧテープの剥離強度（粘着力）は、例えば、半導体デバイスの加工工程におけるバックグラインド工程において、半導体ウエハにＢＧテープがしっかりと固定される剥離強度（粘着力）を有する必要がある。一方、ＢＧテープの剥離強度は、所定の加工工程の後、ＢＧテープを半導体ウエハから剥離する際に、半導体デバイスの部品を破損させない程度の強度である必要がある。
When the BG tape of the present embodiment is used for protecting the surface of a semiconductor wafer having bumps formed on the surface, the peel strength (adhesive strength) of the BG tape is determined, for example, in the back grind step in the processing step of the semiconductor device. , It is necessary to have peeling strength (adhesive strength) for firmly fixing the BG tape to the semiconductor wafer. On the other hand, the peel strength of the BG tape needs to be such that the parts of the semiconductor device are not damaged when the BG tape is peeled from the semiconductor wafer after a predetermined processing step.
これらの観点から、上記の用途に用いられるＢＧテープの剥離強度は、剥離速度が０．３ｍ／ｍｉｎ．であって、粘着剤層の厚みが５０～２００μｍである場合、１０～３００ｇｆ／２５ｍｍであることが好ましく、１５～２００ｇｆ／２５ｍｍであることがより好ましく、２０～１５０ｇｆ／２５ｍｍであることがさらに好ましい。粘着剤層の厚みが２００～５００μｍである場合、５０～５００ｇｆ／２５ｍｍであることが好ましく、６０～４００ｇｆ／２５ｍｍであることがより好ましく、７０～３００ｇｆ／２５ｍｍであることがさらに好ましい。ＢＧテープの剥離強度の具体的な測定方法は、実施例において後述する。
From these viewpoints, the peeling strength of the BG tape used for the above applications is such that the peeling speed is 0.3 m / min. When the thickness of the pressure-sensitive adhesive layer is 50 to 200 μm, it is preferably 10 to 300 gf / 25 mm, more preferably 15 to 200 gf / 25 mm, and further preferably 20 to 150 gf / 25 mm. preferable. When the thickness of the pressure-sensitive adhesive layer is 200 to 500 μm, it is preferably 50 to 500 gf / 25 mm, more preferably 60 to 400 gf / 25 mm, and even more preferably 70 to 300 gf / 25 mm. A specific method for measuring the peel strength of the BG tape will be described later in Examples.
本実施形態のＢＧテープは、シート状の基材の片面に、本実施形態の粘着剤組成物の硬化物からなる粘着剤層を有する。このため、本実施形態のＢＧテープは、十分な粘着力を有し、かつＢＧテープを剥離した後の被着体に粘着剤層が転写される糊残りが生じにくく、しかも凹凸吸収性および帯電防止性に優れる。したがって、本実施形態のＢＧテープは、表面に凹凸部分を有する被着体に貼付され、その後に剥離される用途に好適である。
The BG tape of the present embodiment has a pressure-sensitive adhesive layer made of a cured product of the pressure-sensitive adhesive composition of the present embodiment on one side of a sheet-like base material. Therefore, the BG tape of the present embodiment has sufficient adhesive strength, and it is difficult for adhesive residue to be transferred to the adherend after the BG tape is peeled off, and moreover, unevenness absorption and antistatic are performed. Excellent in prevention. Therefore, the BG tape of the present embodiment is suitable for applications where it is attached to an adherend having an uneven portion on the surface and then peeled off.
本実施形態のＢＧテープは、例えば、表面にバンプからなる凹凸部分を有する半導体ウエハのバックグラインド工程を行う際に貼付され、バックグラインド工程後に剥離されるＢＧテープとして、好適に用いることができる。この場合、本実施形態のＢＧテープによって半導体ウエハが十分な粘着力で固定される。しかも、ＢＧテープが十分な凹凸吸収性を有しているため、半導体ウエハに貼付されたＢＧテープとバンプ周辺との間に空隙が発生しにくい。よって、バックグラインド工程で使用する水が、ＢＧテープとバンプ周辺との間の空隙に侵入して、半導体ウエハが汚染されることを防止できる。また、本実施形態のＢＧテープは、十分な帯電防止性を有しているため、バックグラインド工程後、半導体ウエハに貼付したＢＧテープを剥離した際における剥離帯電を抑制できる。さらに、バックグラインド工程後、ＢＧテープを剥離した半導体ウエハのバンプ周辺に、糊残りが発生しにくく、好ましい。
The BG tape of the present embodiment can be suitably used as, for example, a BG tape that is attached when performing a back grind step of a semiconductor wafer having an uneven portion composed of bumps on the surface and is peeled off after the back grind step. In this case, the semiconductor wafer is fixed with sufficient adhesive force by the BG tape of the present embodiment. Moreover, since the BG tape has sufficient unevenness absorption, gaps are unlikely to occur between the BG tape attached to the semiconductor wafer and the periphery of the bump. Therefore, it is possible to prevent the water used in the back grind process from entering the gap between the BG tape and the periphery of the bump and contaminating the semiconductor wafer. Further, since the BG tape of the present embodiment has sufficient antistatic properties, it is possible to suppress peeling charge when the BG tape attached to the semiconductor wafer is peeled off after the backgrinding step. Further, after the back grind step, adhesive residue is less likely to occur around the bumps of the semiconductor wafer from which the BG tape has been peeled off, which is preferable.
本実施形態のＢＧテープは、粘着剤層が粘着剤組成物の硬化物からなる単層構造とすることができる。この場合、１つの層を形成する工程を行うだけで粘着剤層を形成できる。よって、本実施形態のＢＧテープは、例えば、凹凸吸収性を有する層と帯電防止性を有する層と粘着力を有する層とが備えられたＢＧテープを形成する場合と比較して、少ない製造工程で容易に製造できる。
The BG tape of the present embodiment can have a single-layer structure in which the pressure-sensitive adhesive layer is a cured product of the pressure-sensitive adhesive composition. In this case, the pressure-sensitive adhesive layer can be formed only by performing the step of forming one layer. Therefore, the BG tape of the present embodiment has fewer manufacturing steps than, for example, a case where a BG tape having a layer having unevenness absorbing property, a layer having antistatic property, and a layer having adhesive strength is formed. Can be easily manufactured with.
以下、実施例および比較例により本発明をさらに具体的に説明する。なお、本発明は、以下の実施例のみに限定されない。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.
＜ポリウレタン（Ａ－１）の合成＞
温度計、撹拌器、滴下ロート、乾燥管付き冷却管を備えた反応器に、ジフェニルメタンジイソシアネートの水素添加物（デスモジュールＷ、住化コベストロウレタン製）を０．５５ｋｇ（２．１ｍｏｌ）と、水酸基価が５６ｍｇＫＯＨ／ｇのヒドロキシ基を末端に有するポリプロピレングリコール（アクトコールＤ－２０００；三井化学製、数平均分子量２０００）を４．０１ｋｇ（２．０ｍｏｌ）と、ウレタン化触媒であるジオクチルスズ（ネオスタンＵ－８１０、日東化成社製）を０．８ｇとを仕込んだ。 <Synthesis of polyurethane (A-1)>
A reactor equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube was charged with 0.55 kg (2.1 mol) of a hydrogenated diphenylmethane diisocyanate (Death Module W, manufactured by Sumika Cobestrolurethane). 4.01 kg (2.0 mol) of polypropylene glycol (Actcol D-2000; manufactured by Mitsui Chemicals, number average molecular weight 2000) having a hydroxy group having a hydroxyl value of 56 mgKOH / g at the end, and dioctyltin (a urethanization catalyst) Neostan U-810 (manufactured by Nitto Kasei Co., Ltd.) was charged with 0.8 g.
温度計、撹拌器、滴下ロート、乾燥管付き冷却管を備えた反応器に、ジフェニルメタンジイソシアネートの水素添加物（デスモジュールＷ、住化コベストロウレタン製）を０．５５ｋｇ（２．１ｍｏｌ）と、水酸基価が５６ｍｇＫＯＨ／ｇのヒドロキシ基を末端に有するポリプロピレングリコール（アクトコールＤ－２０００；三井化学製、数平均分子量２０００）を４．０１ｋｇ（２．０ｍｏｌ）と、ウレタン化触媒であるジオクチルスズ（ネオスタンＵ－８１０、日東化成社製）を０．８ｇとを仕込んだ。 <Synthesis of polyurethane (A-1)>
A reactor equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube was charged with 0.55 kg (2.1 mol) of a hydrogenated diphenylmethane diisocyanate (Death Module W, manufactured by Sumika Cobestrolurethane). 4.01 kg (2.0 mol) of polypropylene glycol (Actcol D-2000; manufactured by Mitsui Chemicals, number average molecular weight 2000) having a hydroxy group having a hydroxyl value of 56 mgKOH / g at the end, and dioctyltin (a urethanization catalyst) Neostan U-810 (manufactured by Nitto Kasei Co., Ltd.) was charged with 0.8 g.
その後、反応器を６０℃まで昇温して４時間反応させ、ポリウレタン（Ａ）の前駆体として、イソシアナト基を両末端に有するポリウレタンを得た。続いて、反応器に２－ヒドロキシエチルアクリレート２３．２２ｇ（０．２ｍｏｌ）を加え、７０℃まで昇温して２時間反応させ、質量平均分子量６７，０００のポリウレタン（Ａ－１）を４．５８ｋｇ得た。
After that, the temperature of the reactor was raised to 60 ° C. and the reaction was carried out for 4 hours to obtain polyurethane having isocyanato groups at both ends as a precursor of polyurethane (A). Subsequently, 23.22 g (0.2 mol) of 2-hydroxyethyl acrylate was added to the reactor, the temperature was raised to 70 ° C., and the reaction was carried out for 2 hours to add polyurethane (A-1) having a mass average molecular weight of 67,000. I got 58 kg.
得られたポリウレタン（Ａ－１）を赤外線吸収スペクトル（ＩＲ）法を用いて分析した。その結果、イソシアナト基由来のピークが観察されなかった。したがって、ポリウレタン（Ａ－１）は、全ての末端にアクリロイルオキシ基が導入されているポリウレタン（ａ１）であることが確認できた。
The obtained polyurethane (A-1) was analyzed using the infrared absorption spectrum (IR) method. As a result, no peak derived from the isocyanato group was observed. Therefore, it was confirmed that the polyurethane (A-1) is a polyurethane (a1) in which an acryloyloxy group is introduced at all terminals.
＜ポリウレタン（Ａ－２）の合成＞
ジフェニルメタンジイソシアネートの水素添加物に代えて、イソホロンジイソシアネート（デスモジュールＩ、住化コベストロウレタン製）２．１ｍｏｌを用いたこと以外は、ポリウレタン（Ａ－１）の合成法と同様にして、質量平均分子量６６，０００のポリウレタン（Ａ－２）を得た。 <Synthesis of polyurethane (A-2)>
Mass average in the same manner as the synthetic method of polyurethane (A-1) except that 2.1 mol of isophorone diisocyanate (Death Module I, manufactured by Sumika Covestro Urethane) was used instead of the hydrogenated diphenylmethane diisocyanate. A polyurethane (A-2) having a molecular weight of 66,000 was obtained.
ジフェニルメタンジイソシアネートの水素添加物に代えて、イソホロンジイソシアネート（デスモジュールＩ、住化コベストロウレタン製）２．１ｍｏｌを用いたこと以外は、ポリウレタン（Ａ－１）の合成法と同様にして、質量平均分子量６６，０００のポリウレタン（Ａ－２）を得た。 <Synthesis of polyurethane (A-2)>
Mass average in the same manner as the synthetic method of polyurethane (A-1) except that 2.1 mol of isophorone diisocyanate (Death Module I, manufactured by Sumika Covestro Urethane) was used instead of the hydrogenated diphenylmethane diisocyanate. A polyurethane (A-2) having a molecular weight of 66,000 was obtained.
得られたポリウレタン（Ａ－２）を赤外線吸収スペクトル（ＩＲ）法を用いて分析した。その結果、イソシアナト基由来のピークが観察されなかった。したがって、ポリウレタン（Ａ－２）は、全ての末端にアクリロイルオキシ基が導入されているポリウレタン（ａ１）であることが確認できた。
The obtained polyurethane (A-2) was analyzed using the infrared absorption spectrum (IR) method. As a result, no peak derived from the isocyanato group was observed. Therefore, it was confirmed that the polyurethane (A-2) is a polyurethane (a1) in which an acryloyloxy group is introduced at all terminals.
＜粘着剤組成物の調製＞
このようにして得られたポリウレタン（Ａ）と、表１に示す（メタ）アクリレートモノマー（Ｂ）と連鎖移動剤（Ｃ）と光重合開始剤（Ｄ）とイオン液体（Ｅ）と脂肪酸エステル（Ｆ）とを、表１に記載の割合で配合し、２５℃でディスパーを用いて混合し、実施例１～実施例９および比較例１～比較例４の粘着剤組成物を得た。 <Preparation of adhesive composition>
The polyurethane (A) thus obtained, the (meth) acrylate monomer (B) shown in Table 1, the chain transfer agent (C), the photopolymerization initiator (D), the ionic liquid (E), and the fatty acid ester ( F) and F) were blended at the ratios shown in Table 1 and mixed at 25 ° C. using a disper to obtain the pressure-sensitive adhesive compositions of Examples 1 to 9 and Comparative Examples 1 to 4.
このようにして得られたポリウレタン（Ａ）と、表１に示す（メタ）アクリレートモノマー（Ｂ）と連鎖移動剤（Ｃ）と光重合開始剤（Ｄ）とイオン液体（Ｅ）と脂肪酸エステル（Ｆ）とを、表１に記載の割合で配合し、２５℃でディスパーを用いて混合し、実施例１～実施例９および比較例１～比較例４の粘着剤組成物を得た。 <Preparation of adhesive composition>
The polyurethane (A) thus obtained, the (meth) acrylate monomer (B) shown in Table 1, the chain transfer agent (C), the photopolymerization initiator (D), the ionic liquid (E), and the fatty acid ester ( F) and F) were blended at the ratios shown in Table 1 and mixed at 25 ° C. using a disper to obtain the pressure-sensitive adhesive compositions of Examples 1 to 9 and Comparative Examples 1 to 4.
表１中に記載の下記記号は、以下に示す化合物である。
２ＥＨＡ：２－エチルヘキシルアクリレート（東亜合成株式会社製）
ＢＵＡ：ｎ－ブチルアクリレート（東亜合成株式会社製）
ＡＣＭＯ：アクリロイルモルホリン（新中村化学工業株式会社製）
ＴＭＰＴＡ：トリメチロールプロパントリアクリレート（東亜合成株式会社製） The following symbols described in Table 1 are the compounds shown below.
2EHA: 2-ethylhexyl acrylate (manufactured by Toagosei Co., Ltd.)
BUA: n-Butyl acrylate (manufactured by Toagosei Co., Ltd.)
ACMO: Acryloyl morpholine (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
TMPTA: Trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd.)
２ＥＨＡ：２－エチルヘキシルアクリレート（東亜合成株式会社製）
ＢＵＡ：ｎ－ブチルアクリレート（東亜合成株式会社製）
ＡＣＭＯ：アクリロイルモルホリン（新中村化学工業株式会社製）
ＴＭＰＴＡ：トリメチロールプロパントリアクリレート（東亜合成株式会社製） The following symbols described in Table 1 are the compounds shown below.
2EHA: 2-ethylhexyl acrylate (manufactured by Toagosei Co., Ltd.)
BUA: n-Butyl acrylate (manufactured by Toagosei Co., Ltd.)
ACMO: Acryloyl morpholine (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
TMPTA: Trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd.)
ＰＥ１：ペンタエリスリトールテトラキス（３－メルカプトブチレート）（昭和電工株式会社製）
ＮＲ１：１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン（昭和電工株式会社製）
ＴＰＯ（Ｏｍｎｉｒａｄ ＴＰＯ Ｈ）：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（ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製）
１８４（Ｏｍｎｉｒａｄ １８４）：１－ヒドロキシシクロヘキシル－フェニルケトン（ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製）
エレクセル ＡＳ－１１０：１－エチル－３－メチルイミダゾリウムビス（フルオロスルホニル）イミド（第一工業製薬株式会社製）
エレクセル ＡＳ－８０４：４－メチル－１－オクチル－ピリジニウム・ビス（フルオロスルホニル）イミド（第一工業製薬株式会社製）
エキセパールＩＰＭ：ミリスチン酸イソプロピル（花王株式会社製）
エキセパールＥＨ－Ｓ：ステアリン酸２－エチルヘキシル（花王株式会社製） PE1: Pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko KK)
NR1: 1,3,5-Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trione (manufactured by Showa Denko KK)
TPO (Omnirad TPO H): 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by IGM Resins BV)
184 (Omnirad 184): 1-Hydroxycyclohexyl-phenylketone (manufactured by IGM Resins BV)
Elexel AS-110: 1-Ethyl-3-methylimidazolium bis (fluorosulfonyl) imide (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
Elexel AS-804: 4-Methyl-1-octyl-pyridinium bis (fluorosulfonyl) imide (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
Exepearl IPM: Isopropyl myristate (manufactured by Kao Corporation)
Exepearl EHS: 2-ethylhexyl stearate (manufactured by Kao Corporation)
ＮＲ１：１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン（昭和電工株式会社製）
ＴＰＯ（Ｏｍｎｉｒａｄ ＴＰＯ Ｈ）：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（ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製）
１８４（Ｏｍｎｉｒａｄ １８４）：１－ヒドロキシシクロヘキシル－フェニルケトン（ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製）
エレクセル ＡＳ－１１０：１－エチル－３－メチルイミダゾリウムビス（フルオロスルホニル）イミド（第一工業製薬株式会社製）
エレクセル ＡＳ－８０４：４－メチル－１－オクチル－ピリジニウム・ビス（フルオロスルホニル）イミド（第一工業製薬株式会社製）
エキセパールＩＰＭ：ミリスチン酸イソプロピル（花王株式会社製）
エキセパールＥＨ－Ｓ：ステアリン酸２－エチルヘキシル（花王株式会社製） PE1: Pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko KK)
NR1: 1,3,5-Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trione (manufactured by Showa Denko KK)
TPO (Omnirad TPO H): 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by IGM Resins BV)
184 (Omnirad 184): 1-Hydroxycyclohexyl-phenylketone (manufactured by IGM Resins BV)
Elexel AS-110: 1-Ethyl-3-methylimidazolium bis (fluorosulfonyl) imide (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
Elexel AS-804: 4-Methyl-1-octyl-pyridinium bis (fluorosulfonyl) imide (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
Exepearl IPM: Isopropyl myristate (manufactured by Kao Corporation)
Exepearl EHS: 2-ethylhexyl stearate (manufactured by Kao Corporation)
＜ＢＧテープの作製＞
シート状の基材として、厚さ５０μｍＰＥＴフィルム（東洋紡株式会社製、商品名：エステル（商標）フィルムＥ５１００）を用意した。そして、基材のコロナ処理面上に、アプリケーターを用いて実施例１の粘着剤組成物を、硬化後の厚さが１５０μｍとなるように塗布した。 <Making BG tape>
As a sheet-like base material, a PET film having a thickness of 50 μm (manufactured by Toyobo Co., Ltd., trade name: ester (trademark) film E5100) was prepared. Then, the pressure-sensitive adhesive composition of Example 1 was applied onto the corona-treated surface of the base material using an applicator so that the thickness after curing was 150 μm.
シート状の基材として、厚さ５０μｍＰＥＴフィルム（東洋紡株式会社製、商品名：エステル（商標）フィルムＥ５１００）を用意した。そして、基材のコロナ処理面上に、アプリケーターを用いて実施例１の粘着剤組成物を、硬化後の厚さが１５０μｍとなるように塗布した。 <Making BG tape>
As a sheet-like base material, a PET film having a thickness of 50 μm (manufactured by Toyobo Co., Ltd., trade name: ester (trademark) film E5100) was prepared. Then, the pressure-sensitive adhesive composition of Example 1 was applied onto the corona-treated surface of the base material using an applicator so that the thickness after curing was 150 μm.
次いで、粘着剤組成物の塗布面に、セパレーターとして、厚さ７５μｍのシリコーン系の超軽剥離ＰＥＴフィルム（東洋紡株式会社製、品名：Ｅ７００６）を、ゴムローラーを使用して貼り合わせた。
その後、セパレーターを介して粘着剤組成物に、紫外線照射装置（アイグラフィックス株式会社製、ＵＶ照射装置３ｋＷ、高圧水銀ランプ）を使用して、照射距離２５ｃｍ、ランプ移動速度１．０ｍ／分、照射量１０００ｍＪ／ｃｍ２の条件で紫外線を照射し、粘着剤組成物を光硬化させた。このことにより、基材上に、粘着剤組成物の硬化物である粘着剤層と、セパレーターとが積層された実施例１のＢＧテープを得た。 Next, a silicone-based ultra-light peeling PET film (manufactured by Toyobo Co., Ltd., product name: E7006) having a thickness of 75 μm was attached to the coated surface of the pressure-sensitive adhesive composition using a rubber roller.
Then, using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., UV irradiation device 3 kW, high-pressure mercury lamp) on the pressure-sensitive adhesive composition via a separator, an irradiation distance of 25 cm, a lamp moving speed of 1.0 m / min, and so on. The pressure-sensitive adhesive composition was photocured by irradiating with ultraviolet rays under the condition of an irradiation amount of 1000 mJ / cm 2. As a result, the BG tape of Example 1 in which the pressure-sensitive adhesive layer, which is a cured product of the pressure-sensitive adhesive composition, and the separator were laminated on the base material was obtained.
その後、セパレーターを介して粘着剤組成物に、紫外線照射装置（アイグラフィックス株式会社製、ＵＶ照射装置３ｋＷ、高圧水銀ランプ）を使用して、照射距離２５ｃｍ、ランプ移動速度１．０ｍ／分、照射量１０００ｍＪ／ｃｍ２の条件で紫外線を照射し、粘着剤組成物を光硬化させた。このことにより、基材上に、粘着剤組成物の硬化物である粘着剤層と、セパレーターとが積層された実施例１のＢＧテープを得た。 Next, a silicone-based ultra-light peeling PET film (manufactured by Toyobo Co., Ltd., product name: E7006) having a thickness of 75 μm was attached to the coated surface of the pressure-sensitive adhesive composition using a rubber roller.
Then, using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., UV irradiation device 3 kW, high-pressure mercury lamp) on the pressure-sensitive adhesive composition via a separator, an irradiation distance of 25 cm, a lamp moving speed of 1.0 m / min, and so on. The pressure-sensitive adhesive composition was photocured by irradiating with ultraviolet rays under the condition of an irradiation amount of 1000 mJ / cm 2. As a result, the BG tape of Example 1 in which the pressure-sensitive adhesive layer, which is a cured product of the pressure-sensitive adhesive composition, and the separator were laminated on the base material was obtained.
次に、実施例１の粘着剤組成物に代えて、実施例２～実施例９および比較例１～比較例４の粘着剤組成物をそれぞれ用いて、実施例１のＢＧテープと同様にして、ＢＧテープを作製した。なお、比較例４については粘着剤組成物の硬化後の厚さが３０μｍとなるように調整した。その結果、実施例２～実施例９および比較例１～比較例４のＢＧテープが得られた。
Next, instead of the pressure-sensitive adhesive composition of Example 1, the pressure-sensitive adhesive compositions of Examples 2 to 9 and Comparative Examples 1 to 4 are used, respectively, in the same manner as the BG tape of Example 1. , BG tape was prepared. In Comparative Example 4, the thickness of the pressure-sensitive adhesive composition after curing was adjusted to 30 μm. As a result, BG tapes of Examples 2 to 9 and Comparative Examples 1 to 4 were obtained.
次に、実施例１～実施例９および比較例１～比較例４のＢＧテープについて、以下に示す項目の評価を行った。
＜表面抵抗率の測定＞
ＢＧテープを縦１２０ｍｍ、横１２０ｍｍの大きさに切り取り、温度２３℃、相対湿度５０％ＲＨの環境下に３時間放置して調湿した。その後、剥離ＰＥＴフィルムを剥がして粘着剤層を露出させ、印加電圧１００Ｖ×６０秒の条件で、高抵抗率計（株式会社三菱化学アナリテック製、ハイレスタ－ＵＸ）を使用して、粘着剤層側の表面抵抗率を測定した。そして、以下の基準で評価した。表面抵抗率が小さいほど、半導体ウエハに貼付したＢＧテープを剥離した際の剥離帯電が発生しにくく、帯電防止性に優れたＢＧテープであるといえる。 Next, the items shown below were evaluated for the BG tapes of Examples 1 to 9 and Comparative Examples 1 to 4.
<Measurement of surface resistivity>
The BG tape was cut into a size of 120 mm in length and 120 mm in width, and left for 3 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH for humidity control. After that, the peeling PET film is peeled off to expose the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is used under the condition of an applied voltage of 100 V × 60 seconds using a high resistivity meter (High Restor-UX manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The surface resistivity on the side was measured. Then, it was evaluated according to the following criteria. It can be said that the smaller the surface resistivity, the less likely it is that peeling charge is generated when the BG tape attached to the semiconductor wafer is peeled off, and the BG tape has excellent antistatic properties.
＜表面抵抗率の測定＞
ＢＧテープを縦１２０ｍｍ、横１２０ｍｍの大きさに切り取り、温度２３℃、相対湿度５０％ＲＨの環境下に３時間放置して調湿した。その後、剥離ＰＥＴフィルムを剥がして粘着剤層を露出させ、印加電圧１００Ｖ×６０秒の条件で、高抵抗率計（株式会社三菱化学アナリテック製、ハイレスタ－ＵＸ）を使用して、粘着剤層側の表面抵抗率を測定した。そして、以下の基準で評価した。表面抵抗率が小さいほど、半導体ウエハに貼付したＢＧテープを剥離した際の剥離帯電が発生しにくく、帯電防止性に優れたＢＧテープであるといえる。 Next, the items shown below were evaluated for the BG tapes of Examples 1 to 9 and Comparative Examples 1 to 4.
<Measurement of surface resistivity>
The BG tape was cut into a size of 120 mm in length and 120 mm in width, and left for 3 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH for humidity control. After that, the peeling PET film is peeled off to expose the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is used under the condition of an applied voltage of 100 V × 60 seconds using a high resistivity meter (High Restor-UX manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The surface resistivity on the side was measured. Then, it was evaluated according to the following criteria. It can be said that the smaller the surface resistivity, the less likely it is that peeling charge is generated when the BG tape attached to the semiconductor wafer is peeled off, and the BG tape has excellent antistatic properties.
評価基準
◎（優）：表面抵抗率が１×１０１０Ω／□未満
○（良）：表面抵抗率が１×１０１０Ω／□以上であり１×１０１１Ω／□未満
△（可）：表面抵抗率が１×１０１１Ω／□以上であり１×１０１２Ω／□未満
×（不可）：表面抵抗率が１×１０１２Ω／□以上 Evaluation Criteria ◎ (Excellent): Surface resistivity is less than 1 × 10 10 Ω / □ ○ (Good): Surface resistivity is 1 × 10 10 Ω / □ or more and less than 1 × 10 11 Ω / □ △ (Yes) : Surface resistivity is 1 x 10 11 Ω / □ or more and less than 1 x 10 12 Ω / □ x (impossible): Surface resistivity is 1 x 10 12 Ω / □ or more
◎（優）：表面抵抗率が１×１０１０Ω／□未満
○（良）：表面抵抗率が１×１０１０Ω／□以上であり１×１０１１Ω／□未満
△（可）：表面抵抗率が１×１０１１Ω／□以上であり１×１０１２Ω／□未満
×（不可）：表面抵抗率が１×１０１２Ω／□以上 Evaluation Criteria ◎ (Excellent): Surface resistivity is less than 1 × 10 10 Ω / □ ○ (Good): Surface resistivity is 1 × 10 10 Ω / □ or more and less than 1 × 10 11 Ω / □ △ (Yes) : Surface resistivity is 1 x 10 11 Ω / □ or more and less than 1 x 10 12 Ω / □ x (impossible): Surface resistivity is 1 x 10 12 Ω / □ or more
＜剥離力（剥離強度）＞
ＢＧテープを縦２５ｍｍ、横１５０ｍｍの大きさに切り取り、セパレーターを剥がして粘着剤層を露出させた。その後、露出した粘着剤層の全面を、ガラス板にラミネートして、その上を、質量２ｋｇ（荷重１９．６Ｎ）のゴムローラー（直径：８５ｍｍ、幅：５０ｍｍ）を１往復させることにより、測定用サンプルを得た。得られた測定用サンプルを、温度２３℃および相対湿度５０％ＲＨの環境下に３０分間放置した。その後、ＪＩＳ Ｋ ６８５４－２に準じて、剥離速度０．３ｍ／ｍｉｎ．で１８０°方向の引張試験を行って、ガラス板に対する剥離強度（ｇｆ／２５ｍｍ）を測定した。その結果を表１に示す。 <Peeling force (peeling strength)>
The BG tape was cut into a size of 25 mm in length and 150 mm in width, and the separator was peeled off to expose the adhesive layer. Then, the entire surface of the exposed adhesive layer is laminated on a glass plate, and a rubber roller (diameter: 85 mm, width: 50 mm) having a mass of 2 kg (load 19.6 N) is reciprocated once on the glass plate for measurement. I got a sample for. The obtained measurement sample was left for 30 minutes in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH. Then, according to JIS K 6854-2, the peeling speed was 0.3 m / min. A tensile test in the 180 ° direction was performed in the glass plate to measure the peel strength (gf / 25 mm) with respect to the glass plate. The results are shown in Table 1.
ＢＧテープを縦２５ｍｍ、横１５０ｍｍの大きさに切り取り、セパレーターを剥がして粘着剤層を露出させた。その後、露出した粘着剤層の全面を、ガラス板にラミネートして、その上を、質量２ｋｇ（荷重１９．６Ｎ）のゴムローラー（直径：８５ｍｍ、幅：５０ｍｍ）を１往復させることにより、測定用サンプルを得た。得られた測定用サンプルを、温度２３℃および相対湿度５０％ＲＨの環境下に３０分間放置した。その後、ＪＩＳ Ｋ ６８５４－２に準じて、剥離速度０．３ｍ／ｍｉｎ．で１８０°方向の引張試験を行って、ガラス板に対する剥離強度（ｇｆ／２５ｍｍ）を測定した。その結果を表１に示す。 <Peeling force (peeling strength)>
The BG tape was cut into a size of 25 mm in length and 150 mm in width, and the separator was peeled off to expose the adhesive layer. Then, the entire surface of the exposed adhesive layer is laminated on a glass plate, and a rubber roller (diameter: 85 mm, width: 50 mm) having a mass of 2 kg (load 19.6 N) is reciprocated once on the glass plate for measurement. I got a sample for. The obtained measurement sample was left for 30 minutes in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH. Then, according to JIS K 6854-2, the peeling speed was 0.3 m / min. A tensile test in the 180 ° direction was performed in the glass plate to measure the peel strength (gf / 25 mm) with respect to the glass plate. The results are shown in Table 1.
＜凹凸吸収性＞
ＢＧテープを縦２５ｍｍ、横５０ｍｍの大きさに切り取り、セパレーターを剥がして粘着剤層を露出させた。その後、露出した粘着剤層の表面と、バンプ付きウエハ（ウォルツ社製、ＷＡＬＴＳ－ＴＥＧ ＦＣ１５０ＳＣＪＹ ＬＦ（ＰＩ）、バンプ高さ：７５μｍ、バンプサイズ：直径９０μｍ）のバンプとを対向させて設置した。そして、ＢＧテープの基材上に、質量２ｋｇ（荷重１９．６Ｎ）のゴムローラー（直径：８５ｍｍ、幅：５０ｍｍ）を、速度１０ｍｍ／ｓｅｃで３往復させて、ＢＧテープとバンプ付きウエハとを貼り合わせた。 <Unevenness absorption>
The BG tape was cut into a size of 25 mm in length and 50 mm in width, and the separator was peeled off to expose the adhesive layer. Then, the surface of the exposed pressure-sensitive adhesive layer and the bumps of a wafer with bumps (WALTS-TEG FC150SCJY LF (PI) manufactured by Waltz, bump height: 75 μm, bump size: diameter 90 μm) were placed facing each other. Then, a rubber roller (diameter: 85 mm, width: 50 mm) having a mass of 2 kg (load 19.6 N) is reciprocated three times at a speed of 10 mm / sec on the base material of the BG tape to transfer the BG tape and the bumped wafer. I pasted them together.
ＢＧテープを縦２５ｍｍ、横５０ｍｍの大きさに切り取り、セパレーターを剥がして粘着剤層を露出させた。その後、露出した粘着剤層の表面と、バンプ付きウエハ（ウォルツ社製、ＷＡＬＴＳ－ＴＥＧ ＦＣ１５０ＳＣＪＹ ＬＦ（ＰＩ）、バンプ高さ：７５μｍ、バンプサイズ：直径９０μｍ）のバンプとを対向させて設置した。そして、ＢＧテープの基材上に、質量２ｋｇ（荷重１９．６Ｎ）のゴムローラー（直径：８５ｍｍ、幅：５０ｍｍ）を、速度１０ｍｍ／ｓｅｃで３往復させて、ＢＧテープとバンプ付きウエハとを貼り合わせた。 <Unevenness absorption>
The BG tape was cut into a size of 25 mm in length and 50 mm in width, and the separator was peeled off to expose the adhesive layer. Then, the surface of the exposed pressure-sensitive adhesive layer and the bumps of a wafer with bumps (WALTS-TEG FC150SCJY LF (PI) manufactured by Waltz, bump height: 75 μm, bump size: diameter 90 μm) were placed facing each other. Then, a rubber roller (diameter: 85 mm, width: 50 mm) having a mass of 2 kg (load 19.6 N) is reciprocated three times at a speed of 10 mm / sec on the base material of the BG tape to transfer the BG tape and the bumped wafer. I pasted them together.
ＢＧテープと貼り合わせたバンプ付きウエハを、ＢＧテープの基材側からデジタル光学顕微鏡（株式会社配合ハイロックス社製、ＲＨ－２０００）により観察し、以下の基準により、バンプへの凹凸吸収性を評価した。その結果を表１に示す。
「基準」
○（良）：ＢＧテープの粘着剤層とバンプ付きウエハのバンプ周辺との間に空隙がない。
×（不可）：ＢＧテープの粘着剤層とバンプ付きウエハのバンプ周辺との間に空隙がある。 Observe the wafer with bumps bonded to the BG tape from the base material side of the BG tape with a digital optical microscope (RH-2000 manufactured by Hirox Co., Ltd.), and determine the unevenness absorption to the bumps according to the following criteria. evaluated. The results are shown in Table 1.
"Standard"
◯ (Good): There is no gap between the adhesive layer of the BG tape and the periphery of the bump of the bumped wafer.
X (impossible): There is a gap between the adhesive layer of the BG tape and the periphery of the bump of the bumped wafer.
「基準」
○（良）：ＢＧテープの粘着剤層とバンプ付きウエハのバンプ周辺との間に空隙がない。
×（不可）：ＢＧテープの粘着剤層とバンプ付きウエハのバンプ周辺との間に空隙がある。 Observe the wafer with bumps bonded to the BG tape from the base material side of the BG tape with a digital optical microscope (RH-2000 manufactured by Hirox Co., Ltd.), and determine the unevenness absorption to the bumps according to the following criteria. evaluated. The results are shown in Table 1.
"Standard"
◯ (Good): There is no gap between the adhesive layer of the BG tape and the periphery of the bump of the bumped wafer.
X (impossible): There is a gap between the adhesive layer of the BG tape and the periphery of the bump of the bumped wafer.
＜糊残り・イオン液体による汚染＞
ＢＧテープを縦２５ｍｍ、横５０ｍｍの大きさに切り取り、セパレーターを剥がして粘着剤層を露出させた。その後、露出した粘着剤層の表面と、バンプ付きウエハ（ウォルツ社製、ＷＡＬＴＳ－ＴＥＧ ＦＣ１５０ＳＣＪＹ ＬＦ（ＰＩ）、バンプ高さ：７５μｍ、バンプサイズ：直径９０μｍ）のバンプと対向させて設置した。そして、ＢＧテープの基材上に、質量２ｋｇ（荷重１９．６Ｎ）のゴムローラー（直径：８５ｍｍ、幅：５０ｍｍ）を、速度１０ｍｍ／ｓｅｃで３往復させて、ＢＧテープとバンプ付きウエハとを貼り合わせた。 <Contaminated with adhesive residue / ionic liquid>
The BG tape was cut into a size of 25 mm in length and 50 mm in width, and the separator was peeled off to expose the adhesive layer. Then, the surface of the exposed pressure-sensitive adhesive layer was placed facing the bumps of a wafer with bumps (WALTS-TEG FC150SCJY LF (PI) manufactured by Waltz, bump height: 75 μm, bump size: diameter 90 μm). Then, a rubber roller (diameter: 85 mm, width: 50 mm) having a mass of 2 kg (load 19.6 N) is reciprocated three times at a speed of 10 mm / sec on the base material of the BG tape to transfer the BG tape and the bumped wafer. I pasted them together.
ＢＧテープを縦２５ｍｍ、横５０ｍｍの大きさに切り取り、セパレーターを剥がして粘着剤層を露出させた。その後、露出した粘着剤層の表面と、バンプ付きウエハ（ウォルツ社製、ＷＡＬＴＳ－ＴＥＧ ＦＣ１５０ＳＣＪＹ ＬＦ（ＰＩ）、バンプ高さ：７５μｍ、バンプサイズ：直径９０μｍ）のバンプと対向させて設置した。そして、ＢＧテープの基材上に、質量２ｋｇ（荷重１９．６Ｎ）のゴムローラー（直径：８５ｍｍ、幅：５０ｍｍ）を、速度１０ｍｍ／ｓｅｃで３往復させて、ＢＧテープとバンプ付きウエハとを貼り合わせた。 <Contaminated with adhesive residue / ionic liquid>
The BG tape was cut into a size of 25 mm in length and 50 mm in width, and the separator was peeled off to expose the adhesive layer. Then, the surface of the exposed pressure-sensitive adhesive layer was placed facing the bumps of a wafer with bumps (WALTS-TEG FC150SCJY LF (PI) manufactured by Waltz, bump height: 75 μm, bump size: diameter 90 μm). Then, a rubber roller (diameter: 85 mm, width: 50 mm) having a mass of 2 kg (load 19.6 N) is reciprocated three times at a speed of 10 mm / sec on the base material of the BG tape to transfer the BG tape and the bumped wafer. I pasted them together.
ＢＧテープと貼り合わされたバンプ付きウエハを、２３℃で２４時間放置した後、ＢＧテープをおおよそ２ｍ／ｍｉｎ．程度の速度で手で剥離した。そして、バンプ付きウエハの表面をデジタル光学顕微鏡（株式会社ハイロックス社製、ＲＨ－２０００）により観察し、糊残りやイオン液体による汚染の有無を、以下の基準で評価した。その結果を表１に示す。なお、「糊残り」とは、粘着剤層自体がウエハ表面に付着した状態で残り、ウエハ表面がべたついている状態であることを意味する。「イオン液体による汚染」とは、粘着剤層からブリードアウトしたイオン液体がウエハ表面に付着し、ウエハ表面が濡れている状態であることを意味する。
「基準」
○（良）：バンプ周辺に糊残りおよびイオン液体による汚染がない。
×（不可）：バンプ周辺に糊残りおよび／またはイオン液体による汚染がある。 The bumped wafer bonded to the BG tape was left at 23 ° C. for 24 hours, and then the BG tape was applied at approximately 2 m / min. It was peeled off by hand at a moderate speed. Then, the surface of the bumped wafer was observed with a digital optical microscope (RH-2000 manufactured by Hirox Co., Ltd.), and the presence or absence of adhesive residue and contamination by ionic liquid was evaluated according to the following criteria. The results are shown in Table 1. The “adhesive residue” means that the adhesive layer itself remains attached to the wafer surface and the wafer surface is sticky. The “contamination by the ionic liquid” means that the ionic liquid bleeding out from the pressure-sensitive adhesive layer adheres to the wafer surface and the wafer surface is wet.
"Standard"
○ (Good): There is no adhesive residue or contamination by ionic liquid around the bump.
× (impossible): There is adhesive residue and / or contamination with ionic liquid around the bump.
「基準」
○（良）：バンプ周辺に糊残りおよびイオン液体による汚染がない。
×（不可）：バンプ周辺に糊残りおよび／またはイオン液体による汚染がある。 The bumped wafer bonded to the BG tape was left at 23 ° C. for 24 hours, and then the BG tape was applied at approximately 2 m / min. It was peeled off by hand at a moderate speed. Then, the surface of the bumped wafer was observed with a digital optical microscope (RH-2000 manufactured by Hirox Co., Ltd.), and the presence or absence of adhesive residue and contamination by ionic liquid was evaluated according to the following criteria. The results are shown in Table 1. The “adhesive residue” means that the adhesive layer itself remains attached to the wafer surface and the wafer surface is sticky. The “contamination by the ionic liquid” means that the ionic liquid bleeding out from the pressure-sensitive adhesive layer adheres to the wafer surface and the wafer surface is wet.
"Standard"
○ (Good): There is no adhesive residue or contamination by ionic liquid around the bump.
× (impossible): There is adhesive residue and / or contamination with ionic liquid around the bump.
＜ゲル分率の測定＞
厚さ７５μｍの剥離ＰＥＴフィルム（東山フィルム株式会社製、商品名：クリーンセパ（商標）ＨＹ－Ｓ１０－２）上に、アプリケーターを用いて硬化後の厚さが１５０μｍとなるように、粘着剤組成物を塗布した。なお、比較例４については硬化後の厚さが３０μｍとなるように調整した。次いで、粘着剤組成物の塗布面を、厚さ７５μｍのシリコーン系の超軽剥離ＰＥＴフィルム（東洋紡株式会社製、品名：Ｅ７００６）で覆った。 <Measurement of gel fraction>
Adhesive composition on a 75 μm-thick peeling PET film (manufactured by Higashiyama Film Co., Ltd., trade name: Clean Sepa (trademark) HY-S10-2) so that the thickness after curing is 150 μm using an applicator. I applied the thing. In Comparative Example 4, the thickness after curing was adjusted to 30 μm. Next, the coated surface of the pressure-sensitive adhesive composition was covered with a silicone-based ultra-light peeling PET film (manufactured by Toyobo Co., Ltd., product name: E7006) having a thickness of 75 μm.
厚さ７５μｍの剥離ＰＥＴフィルム（東山フィルム株式会社製、商品名：クリーンセパ（商標）ＨＹ－Ｓ１０－２）上に、アプリケーターを用いて硬化後の厚さが１５０μｍとなるように、粘着剤組成物を塗布した。なお、比較例４については硬化後の厚さが３０μｍとなるように調整した。次いで、粘着剤組成物の塗布面を、厚さ７５μｍのシリコーン系の超軽剥離ＰＥＴフィルム（東洋紡株式会社製、品名：Ｅ７００６）で覆った。 <Measurement of gel fraction>
Adhesive composition on a 75 μm-thick peeling PET film (manufactured by Higashiyama Film Co., Ltd., trade name: Clean Sepa (trademark) HY-S10-2) so that the thickness after curing is 150 μm using an applicator. I applied the thing. In Comparative Example 4, the thickness after curing was adjusted to 30 μm. Next, the coated surface of the pressure-sensitive adhesive composition was covered with a silicone-based ultra-light peeling PET film (manufactured by Toyobo Co., Ltd., product name: E7006) having a thickness of 75 μm.
続いて、紫外線照射装置（アイグラフィックス株式会社製、ＵＶ照射装置３ｋＷ、高圧水銀ランプ）を使用して、照射距離２５ｃｍ、ランプ移動速度１．０ｍ／分、照射量１０００ｍＪ／ｃｍ２の条件で、超軽剥離ＰＥＴフィルムを介して紫外線を照射し、粘着剤組成物を硬化させて硬化物（粘着剤層）を得た。
Subsequently, using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., UV irradiation device 3 kW, high-pressure mercury lamp), the irradiation distance is 25 cm, the lamp moving speed is 1.0 m / min, and the irradiation amount is 1000 mJ / cm 2 . , Ultraviolet rays were irradiated through the ultra-light peeling PET film, and the pressure-sensitive adhesive composition was cured to obtain a cured product (adhesive layer).
次に、硬化物（粘着剤層）を約１ｇとなるサイズに切り出し、両面のＰＥＴフィルムを剥離して測定用サンプルとし、その質量を測定した。続いて、測定用サンプルを５０ｍｌのトルエンに浸漬し、室温で７２時間静置した。その後、測定用サンプルをトルエン中から取り出し、８０℃で５時間乾燥し、再び質量を測定した。そして、下記式に基づいて、ゲル分率を測定した。
ゲル分率（％）＝［Ａ／Ｂ］×１００
Ａ：トルエンに浸漬した後の測定用サンプルの質量（トルエンの質量は含まない）
Ｂ：トルエンに浸漬する前の測定用サンプルの質量 Next, the cured product (adhesive layer) was cut out to a size of about 1 g, and the PET films on both sides were peeled off to prepare a sample for measurement, and the mass thereof was measured. Subsequently, the measurement sample was immersed in 50 ml of toluene and allowed to stand at room temperature for 72 hours. Then, the measurement sample was taken out from toluene, dried at 80 ° C. for 5 hours, and the mass was measured again. Then, the gel fraction was measured based on the following formula.
Gel fraction (%) = [A / B] x 100
A: Mass of measurement sample after immersion in toluene (mass of toluene is not included)
B: Mass of measurement sample before immersion in toluene
ゲル分率（％）＝［Ａ／Ｂ］×１００
Ａ：トルエンに浸漬した後の測定用サンプルの質量（トルエンの質量は含まない）
Ｂ：トルエンに浸漬する前の測定用サンプルの質量 Next, the cured product (adhesive layer) was cut out to a size of about 1 g, and the PET films on both sides were peeled off to prepare a sample for measurement, and the mass thereof was measured. Subsequently, the measurement sample was immersed in 50 ml of toluene and allowed to stand at room temperature for 72 hours. Then, the measurement sample was taken out from toluene, dried at 80 ° C. for 5 hours, and the mass was measured again. Then, the gel fraction was measured based on the following formula.
Gel fraction (%) = [A / B] x 100
A: Mass of measurement sample after immersion in toluene (mass of toluene is not included)
B: Mass of measurement sample before immersion in toluene
表１に示すように、イオン液体を０．４～６質量％含有する粘着剤組成物を用いた実施例１～実施例９のＢＧテープは、いずれも粘着剤層の表面抵抗率が１×１０１１Ω／□未満であり、帯電防止性に優れていた。また、実施例１～実施例９のＢＧテープは、いずれも１０ｇｆ／２５ｍｍ以上の十分な剥離強度を有し、かつ凹凸吸収性および糊残り・汚染の評価が「〇（良）」であった。
As shown in Table 1, the BG tapes of Examples 1 to 9 using the pressure-sensitive adhesive composition containing 0.4 to 6% by mass of the ionic liquid all have a surface resistivity of the pressure-sensitive adhesive layer of 1 ×. It was less than 10 11 Ω / □ and had excellent antistatic properties. In addition, the BG tapes of Examples 1 to 9 all had sufficient peel strength of 10 gf / 25 mm or more, and the evaluation of unevenness absorption and adhesive residue / contamination was "○ (good)". ..
これに対し、イオン液体を含有しない粘着剤組成物を用いた比較例１のＢＧテープは、粘着剤層の表面抵抗率の評価が「×（不可）」であった。また、イオン液体を７．０質量％含有する粘着剤組成物を用いた比較例２のＢＧテープは、糊残り・汚染の評価が「×（不可）」であった。
また、連鎖移動剤を含有しない粘着剤組成物を用いた比較例３のＢＧテープおよび粘着剤層の厚みが３０μｍの比較例４のＢＧテープは、剥離力が１０ｇｆ／２５ｍｍ未満であり、凹凸吸収性の評価が「×（不可）」であった。 On the other hand, in the BG tape of Comparative Example 1 using the pressure-sensitive adhesive composition containing no ionic liquid, the evaluation of the surface resistivity of the pressure-sensitive adhesive layer was "x (impossible)". Further, in the BG tape of Comparative Example 2 using the pressure-sensitive adhesive composition containing 7.0% by mass of the ionic liquid, the evaluation of adhesive residue / contamination was “x (impossible)”.
Further, the BG tape of Comparative Example 3 using the pressure-sensitive adhesive composition containing no chain transfer agent and the BG tape of Comparative Example 4 having a thickness of the pressure-sensitive adhesive layer of 30 μm have a peeling force of less than 10 gf / 25 mm and absorb unevenness. The evaluation of sex was "x (impossible)".
また、連鎖移動剤を含有しない粘着剤組成物を用いた比較例３のＢＧテープおよび粘着剤層の厚みが３０μｍの比較例４のＢＧテープは、剥離力が１０ｇｆ／２５ｍｍ未満であり、凹凸吸収性の評価が「×（不可）」であった。 On the other hand, in the BG tape of Comparative Example 1 using the pressure-sensitive adhesive composition containing no ionic liquid, the evaluation of the surface resistivity of the pressure-sensitive adhesive layer was "x (impossible)". Further, in the BG tape of Comparative Example 2 using the pressure-sensitive adhesive composition containing 7.0% by mass of the ionic liquid, the evaluation of adhesive residue / contamination was “x (impossible)”.
Further, the BG tape of Comparative Example 3 using the pressure-sensitive adhesive composition containing no chain transfer agent and the BG tape of Comparative Example 4 having a thickness of the pressure-sensitive adhesive layer of 30 μm have a peeling force of less than 10 gf / 25 mm and absorb unevenness. The evaluation of sex was "x (impossible)".
本発明によれば、十分な凹凸吸収性、帯電防止性、粘着力を有し、かつ糊残りが生じにくく、しかも少ない製造工程で製造可能なバックグラインドテープが提供される。該バックグラインドテープは、半導体ウエハ加工工程において、半導体ウエハ表面を保護し、加工工程後に剥離する用途として、好ましく用いることができる。
According to the present invention, there is provided a backgrind tape that has sufficient unevenness absorption, antistatic property, adhesive strength, is less likely to cause adhesive residue, and can be manufactured with a small number of manufacturing steps. The back grind tape can be preferably used as an application for protecting the surface of a semiconductor wafer in the semiconductor wafer processing process and peeling it off after the processing process.
Claims (15)
- シート状の基材と、前記基材の片面に形成された粘着剤層とを有するバックグラインドテープであって、
前記粘着剤層が、粘着剤組成物の硬化物からなり、厚みが５０～５００μｍであり、
前記粘着剤組成物が、ポリウレタン（Ａ）と、（メタ）アクリレートモノマー（Ｂ）と、連鎖移動剤（Ｃ）と、光重合開始剤（Ｄ）と、イオン液体（Ｅ）とを含み、
前記ポリウレタン（Ａ）が、ポリオキシアルキレンポリオール由来の構造およびポリイソシアネート由来の構造を含む骨格を有し、複数の末端に（メタ）アクリロイル基を有するポリウレタン（ａ１）を含み、
前記粘着剤組成物がイオン液体（Ｅ）を０．４～６質量％含有することを特徴とするバックグラインドテープ。 A back grind tape having a sheet-like base material and an adhesive layer formed on one side of the base material.
The pressure-sensitive adhesive layer is made of a cured product of the pressure-sensitive adhesive composition and has a thickness of 50 to 500 μm.
The pressure-sensitive adhesive composition contains a polyurethane (A), a (meth) acrylate monomer (B), a chain transfer agent (C), a photopolymerization initiator (D), and an ionic liquid (E).
The polyurethane (A) contains a polyurethane (a1) having a skeleton containing a structure derived from a polyoxyalkylene polyol and a structure derived from a polyisocyanate, and having a (meth) acryloyl group at a plurality of ends.
A back grind tape, wherein the pressure-sensitive adhesive composition contains 0.4 to 6% by mass of an ionic liquid (E). - 前記粘着剤層が、単層構造である請求項１に記載のバックグラインドテープ。 The back grind tape according to claim 1, wherein the pressure-sensitive adhesive layer has a single-layer structure.
- 前記（メタ）アクリレートモノマー（Ｂ）が、単官能（メタ）アクリレートおよび多官能（メタ）アクリレートを含有する、請求項１または２に記載のバックグラインドテープ。 The back grind tape according to claim 1 or 2, wherein the (meth) acrylate monomer (B) contains a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate.
- 前記イオン液体（Ｅ）が、第四級アンモニウムイオン、イミニウムイオン、およびスルホニウムイオンからなる群から選択される有機カチオンを含む化合物である、請求項１～３のいずれか１項に記載のバックグラインドテープ。 The bag according to any one of claims 1 to 3, wherein the ionic liquid (E) is a compound containing an organic cation selected from the group consisting of a quaternary ammonium ion, an iminium ion, and a sulfonium ion. Grind tape.
- 前記イオン液体（Ｅ）が、フッ素含有有機アニオンを含む化合物である、請求項１～４のいずれか１項に記載のバックグラインドテープ。 The backgrinding tape according to any one of claims 1 to 4, wherein the ionic liquid (E) is a compound containing a fluorine-containing organic anion.
- 前記イオン液体（Ｅ）が、１－エチル－３－メチルイミダゾリウムカチオンおよび／または４－メチル－１－オクチルピリジニウムカチオンと、ビス（フルオロスルホニル）イミドアニオン（（ＦＳＯ２）２Ｎ－）とを含む化合物である請求項１～５のいずれか１項に記載のバックグラインドテープ。 The ionic liquid (E) is a 1-ethyl-3-methylimidazolium cation and / or 4-methyl-1-octyl pyridinium cation, bis (fluorosulfonyl) imide anion - and ((FSO 2) 2 N) The back grind tape according to any one of claims 1 to 5, which is a compound containing the same.
- 前記連鎖移動剤（Ｃ）が、多官能チオールである、請求項１～６のいずれか１項に記載のバックグラインドテープ。 The back grind tape according to any one of claims 1 to 6, wherein the chain transfer agent (C) is a polyfunctional thiol.
- 前記粘着剤層のゲル分率が５０～６５質量％である、請求項１～７のいずれか１項に記載のバックグラインドテープ。 The back grind tape according to any one of claims 1 to 7, wherein the gel fraction of the pressure-sensitive adhesive layer is 50 to 65% by mass.
- 前記粘着剤層の表面抵抗率が１×１０１１Ω／□未満である、請求項１～８のいずれか１項に記載のバックグラインドテープ。 The back grind tape according to any one of claims 1 to 8, wherein the surface resistivity of the pressure-sensitive adhesive layer is less than 1 × 10 11 Ω / □.
- 前記（メタ）アクリレートモノマー（Ｂ）の合計を１００モル％としたときに、前記単官能（メタ）アクリレートを８５～９９モル％、前記多官能（メタ）アクリレートを１～１５モル％含有する、請求項３～９のいずれか１項に記載のバックグラインドテープ。 When the total of the (meth) acrylate monomer (B) is 100 mol%, the monofunctional (meth) acrylate is contained in an amount of 85 to 99 mol% and the polyfunctional (meth) acrylate is contained in an amount of 1 to 15 mol%. The back grind tape according to any one of claims 3 to 9.
- 前記粘着剤組成物が、
前記ポリウレタン（Ａ）を２０～５０質量％、
前記（メタ）アクリレートモノマー（Ｂ）を３５～７９質量％、
前記連鎖移動剤（Ｃ）を０．５～８．０質量％、
前記光重合開始剤（Ｄ）を０．０１～５．０質量％、
前記イオン液体（Ｅ）を０．４～６．０質量％含む、請求項１～１０のいずれか１項に記載のバックグラインドテープ。 The pressure-sensitive adhesive composition
20 to 50% by mass of the polyurethane (A),
35-79% by mass of the (meth) acrylate monomer (B),
0.5 to 8.0% by mass of the chain transfer agent (C),
0.01 to 5.0% by mass of the photopolymerization initiator (D),
The back grind tape according to any one of claims 1 to 10, which contains 0.4 to 6.0% by mass of the ionic liquid (E). - 前記粘着剤組成物が、更に脂肪酸エステル（Ｆ）を含有する、請求項１～１１のいずれか１項に記載のバックグラインドテープ。
The back grind tape according to any one of claims 1 to 11, wherein the pressure-sensitive adhesive composition further contains a fatty acid ester (F).
- 前記イオン液体（Ｅ）が、有機カチオンと無機アニオン、もしくは有機カチオンと有機アニオンとを組み合わせた、融点が１００℃以下の有機塩化合物からなる、請求項１～１２のいずれか１項に記載のバックグラインドテープ。 The method according to any one of claims 1 to 12, wherein the ionic liquid (E) is composed of an organic salt compound having a melting point of 100 ° C. or lower, which is a combination of an organic cation and an inorganic anion, or an organic cation and an organic anion. Back grind tape.
- 前記ポリウレタン（Ａ）が前記ポリウレタン（ａ１）のみからなり、
前記ポリウレタン（ａ１）は全ての末端に（メタ）アクリロイルオキシ基を含む、請求項１～１３のいずれか１項に記載のバックグラインドテープ。 The polyurethane (A) is composed of only the polyurethane (a1).
The back grind tape according to any one of claims 1 to 13, wherein the polyurethane (a1) contains a (meth) acryloyloxy group at all ends. - 前記粘着剤層の前記基材と反対側の表面に直接設けられた、透明なセパレーターを有し、
前記粘着剤組成物中における溶剤の含有量が０～１．０質量％であり、
前記粘着剤層は、前記セパレーターを介した前記粘着剤組成物への紫外線照射により光硬化された硬化物層である、請求項１～１４のいずれか１項に記載のバックグラインドテープ。 It has a transparent separator provided directly on the surface of the pressure-sensitive adhesive layer opposite to the substrate.
The content of the solvent in the pressure-sensitive adhesive composition is 0 to 1.0% by mass.
The back grind tape according to any one of claims 1 to 14, wherein the pressure-sensitive adhesive layer is a cured product layer photocured by irradiating the pressure-sensitive adhesive composition with ultraviolet rays via the separator.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202080045154.6A CN113993663B (en) | 2019-09-05 | 2020-08-17 | Back grinding belt |
| JP2021543681A JPWO2021044833A1 (en) | 2019-09-05 | 2020-08-17 | |
| KR1020217041627A KR102589564B1 (en) | 2019-09-05 | 2020-08-17 | backgrind tape |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-162092 | 2019-09-05 | ||
| JP2019162092 | 2019-09-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2021044833A1 true WO2021044833A1 (en) | 2021-03-11 |
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ID=74852464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2020/030939 WO2021044833A1 (en) | 2019-09-05 | 2020-08-17 | Back grinding tape |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2021044833A1 (en) |
| KR (1) | KR102589564B1 (en) |
| TW (1) | TW202112998A (en) |
| WO (1) | WO2021044833A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012077726A1 (en) * | 2010-12-08 | 2012-06-14 | 旭硝子株式会社 | Adhesive-layer-equipped transparent surface material, display device, and methods for producing same |
| WO2019069746A1 (en) * | 2017-10-05 | 2019-04-11 | 昭和電工株式会社 | Adhesive composition and adhesive sheet |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5572487B2 (en) * | 2010-09-01 | 2014-08-13 | 日東電工株式会社 | Viscoelastic body and method for producing the same |
| JP2013247163A (en) * | 2012-05-23 | 2013-12-09 | Furukawa Electric Co Ltd:The | Radiation curable adhesive tape for semiconductor processing |
| WO2014046096A1 (en) * | 2012-09-24 | 2014-03-27 | リンテック株式会社 | Back grinding sheet |
| KR102528633B1 (en) * | 2015-04-30 | 2023-05-03 | 린텍 가부시키가이샤 | Adhesive tape for workpiece processing |
| JP6715109B2 (en) | 2016-06-30 | 2020-07-01 | 三井化学東セロ株式会社 | Adhesive film for semiconductor wafer processing |
-
2020
- 2020-08-17 KR KR1020217041627A patent/KR102589564B1/en active IP Right Grant
- 2020-08-17 JP JP2021543681A patent/JPWO2021044833A1/ja active Pending
- 2020-08-17 WO PCT/JP2020/030939 patent/WO2021044833A1/en active Application Filing
- 2020-08-19 TW TW109128179A patent/TW202112998A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012077726A1 (en) * | 2010-12-08 | 2012-06-14 | 旭硝子株式会社 | Adhesive-layer-equipped transparent surface material, display device, and methods for producing same |
| WO2019069746A1 (en) * | 2017-10-05 | 2019-04-11 | 昭和電工株式会社 | Adhesive composition and adhesive sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202112998A (en) | 2021-04-01 |
| KR102589564B1 (en) | 2023-10-16 |
| KR20220011155A (en) | 2022-01-27 |
| CN113993663A (en) | 2022-01-28 |
| JPWO2021044833A1 (en) | 2021-03-11 |
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