KR20210016506A - Adhesive tape - Google Patents
Adhesive tape Download PDFInfo
- Publication number
- KR20210016506A KR20210016506A KR1020207025674A KR20207025674A KR20210016506A KR 20210016506 A KR20210016506 A KR 20210016506A KR 1020207025674 A KR1020207025674 A KR 1020207025674A KR 20207025674 A KR20207025674 A KR 20207025674A KR 20210016506 A KR20210016506 A KR 20210016506A
- Authority
- KR
- South Korea
- Prior art keywords
- pressure
- sensitive adhesive
- weight
- adhesive tape
- adhesive layer
- Prior art date
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- 239000002390 adhesive tape Substances 0.000 title claims abstract description 55
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 103
- 239000010410 layer Substances 0.000 claims abstract description 47
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 238000003860 storage Methods 0.000 claims abstract description 22
- 239000011521 glass Substances 0.000 claims abstract description 18
- 238000005259 measurement Methods 0.000 claims abstract description 15
- 239000012790 adhesive layer Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 67
- 229920001296 polysiloxane Polymers 0.000 claims description 65
- 229920000578 graft copolymer Polymers 0.000 claims description 43
- 125000000524 functional group Chemical group 0.000 claims description 34
- 230000001070 adhesive effect Effects 0.000 claims description 30
- 239000000853 adhesive Substances 0.000 claims description 29
- 239000003431 cross linking reagent Substances 0.000 claims description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229920000058 polyacrylate Polymers 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 117
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 37
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- 238000006116 polymerization reaction Methods 0.000 description 22
- 238000010526 radical polymerization reaction Methods 0.000 description 22
- -1 telluride compound Chemical class 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000011109 contamination Methods 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 9
- 229910052714 tellurium Inorganic materials 0.000 description 9
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 5
- JPIIVHIVGGOMMV-UHFFFAOYSA-N ditellurium Chemical compound [Te]=[Te] JPIIVHIVGGOMMV-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 125000002560 nitrile group Chemical group 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003498 tellurium compounds Chemical class 0.000 description 4
- 230000002087 whitening effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- SFLRURCEBYIKSS-UHFFFAOYSA-N n-butyl-2-[[1-(butylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound CCCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCCC SFLRURCEBYIKSS-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- DRAQBUIVUGPBEB-UHFFFAOYSA-N (ethylditellanyl)ethane Chemical compound CC[Te][Te]CC DRAQBUIVUGPBEB-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- LCMDQKIQBKULEI-UHFFFAOYSA-N dimethyl ditelluride Chemical compound C[Te][Te]C LCMDQKIQBKULEI-UHFFFAOYSA-N 0.000 description 2
- VRLFOXMNTSYGMX-UHFFFAOYSA-N diphenyl ditelluride Chemical compound C=1C=CC=CC=1[Te][Te]C1=CC=CC=C1 VRLFOXMNTSYGMX-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000004772 tellurides Chemical class 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- VPIMDGCETSZFGC-UHFFFAOYSA-N 2-(propan-2-ylditellanyl)propane Chemical compound CC(C)[Te][Te]C(C)C VPIMDGCETSZFGC-UHFFFAOYSA-N 0.000 description 1
- MJGLWGBXQWRFCX-UHFFFAOYSA-N 2-[(1-imino-2-methyl-1-pyrrolidin-1-ylpropan-2-yl)diazenyl]-2-methyl-1-pyrrolidin-1-ylpropan-1-imine;dihydrochloride Chemical compound Cl.Cl.C1CCCN1C(=N)C(C)(C)N=NC(C)(C)C(=N)N1CCCC1 MJGLWGBXQWRFCX-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
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- CKSAKVMRQYOFBC-UHFFFAOYSA-N 2-cyanopropan-2-yliminourea Chemical compound N#CC(C)(C)N=NC(N)=O CKSAKVMRQYOFBC-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- WMRNGPYHLQSTDL-UHFFFAOYSA-N n-cyclohexyl-2-[[1-(cyclohexylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound C1CCCCC1NC(=O)C(C)(C)N=NC(C)(C)C(=O)NC1CCCCC1 WMRNGPYHLQSTDL-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 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]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- 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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/10—Block or graft copolymers containing polysiloxane sequences
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Organic Insulating Materials (AREA)
Abstract
본 발명은, 고온에 의한 접착 항진을 저감시킬 수 있음과 함께, 광을 투과시키지 않는 재료에도 사용할 수 있는 점착 테이프를 제공하는 것을 목적으로 한다.
본 발명은, 점착제층을 갖는 점착 테이프로서, 상기 점착제층은, 동적 점탄성 측정으로 평가한 25 ℃ 에 있어서의 전단 저장 탄성률이 4.0 × 104 ∼ 2.0 × 106 Pa 이고, 상기 점착제층은, 상기 점착 테이프의 상기 점착제층 측을 유리에 첩부하여 220 ℃ 에서 120 분간 가열하고, 박리한 후의 대수 접촉각이 80°이상인, 점착 테이프이다.An object of the present invention is to provide an adhesive tape that can reduce adhesion enhancement due to high temperature and can also be used for materials that do not transmit light.
The present invention is an adhesive tape having a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer has a shear storage modulus of 4.0 × 10 4 to 2.0 × 10 6 Pa at 25° C. evaluated by dynamic viscoelasticity measurement, and the pressure-sensitive adhesive layer comprises: It is an adhesive tape having a logarithmic contact angle of 80° or more after affixing the adhesive layer side of the adhesive tape to glass, heating at 220°C for 120 minutes, and peeling off.
Description
본 발명은, 점착 테이프에 관한 것이다.The present invention relates to an adhesive tape.
반도체 칩의 제조 공정에 있어서, 웨이퍼나 반도체 칩의 가공시의 취급을 용이하게 하고, 파손을 방지하기 위해서 점착 테이프가 사용되고 있다. 예를 들어, 고순도의 실리콘 단결정 등으로부터 잘라낸 후막 웨이퍼를 소정의 두께로까지 연삭하여 박막 웨이퍼로 하는 경우, 후막 웨이퍼에 점착 테이프를 첩합 (貼合) 시킨 후에 연삭이 실시된다.In a semiconductor chip manufacturing process, an adhesive tape is used to facilitate handling during processing of wafers or semiconductor chips and to prevent damage. For example, when a thick-film wafer cut from a high-purity silicon single crystal or the like is ground to a predetermined thickness to form a thin-film wafer, grinding is performed after bonding an adhesive tape to the thick-film wafer.
이와 같은 점착 테이프에는, 가공 공정 중에 웨이퍼나 반도체 칩 등의 피착체를 강고하게 고정시킬 수 있을 만큼의 높은 접착성과 함께, 공정 종료 후에는 웨이퍼나 반도체 칩 등의 피착체를 손상시키지 않고 박리할 수 있는 것이 요구된다 (이하, 「고접착 박리 용이」라고도 한다).Such an adhesive tape has a high adhesive property that can firmly fix an adherend such as a wafer or semiconductor chip during the processing process, and can be peeled off without damaging the adherend such as a wafer or semiconductor chip after the process is completed. It is required to be present (hereinafter also referred to as "easy to peel off").
고접착 박리 용이를 실현한 점착 테이프로서, 특허문헌 1 에는 자외선 등의 광을 조사함으로써 경화되어 점착력이 저하되는 광경화형 점착제를 사용한 점착 테이프가 개시되어 있다. 점착제로서 광경화형 점착제를 사용함으로써, 가공 공정 중에는 확실하게 피착체를 고정시킬 수 있음과 함께, 자외선 등을 조사함으로써 용이하게 박리할 수 있다.As an adhesive tape realizing high adhesion and easy peeling, Patent Document 1 discloses an adhesive tape using a photocurable adhesive that is cured by irradiation with light such as ultraviolet rays to reduce adhesive strength. By using a photocurable pressure-sensitive adhesive as the pressure-sensitive adhesive, the adherend can be reliably fixed during the processing step, and can be easily peeled off by irradiation with ultraviolet rays or the like.
반도체 칩 등의 전자 부품의 제조 공정에서는 200 ℃ 이상의 열을 가하는 고온 처리가 실시되는 경우가 있고, 그러한 제조 공정에서 사용되는 점착 테이프에는 내열성과, 고온하에서도 접착 항진하지 않는 내접착 항진성이 요구된다. 종래에는, 고온에 의한 접착 항진을 저감시키기 위해서 특허문헌 1 과 같은 광경화형의 점착 테이프가 사용되어 왔다. 한편, 전자 부품의 제조에서는, 양면 점착 테이프를 개재하여 웨이퍼나 기판 등을 지지판에 고정시키고, 배선 등의 처리를 실시하는 경우가 있다. 그러나, 최근, 비용이나 취급성의 관점에서 구리, 알루미늄, 유리 에폭시 등의 불투명한 소재가 지지판으로서 사용되는 경우가 많아지고 있고, 이와 같은 불투명한 지지판에서는 종래의 광경화형 점착제를 사용한 점착 테이프를 경화시킬 수 없다는 문제가 있다.In the manufacturing process of electronic components such as semiconductor chips, high-temperature treatment is sometimes performed by applying heat of 200°C or higher, and the adhesive tape used in such manufacturing processes requires heat resistance and adhesion resistance that does not increase adhesion even at high temperatures. do. Conventionally, in order to reduce adhesion promotion due to high temperature, a photocurable adhesive tape such as Patent Document 1 has been used. On the other hand, in the manufacture of an electronic component, a wafer or a substrate is fixed to a support plate via a double-sided adhesive tape, and processing such as wiring is sometimes performed. However, in recent years, from the viewpoint of cost and handling properties, opaque materials such as copper, aluminum, and glass epoxy are often used as a support plate, and such an opaque support plate can cure an adhesive tape using a conventional photocurable adhesive. There is a problem that you cannot.
본 발명은, 고온에 의한 접착 항진을 저감시킬 수 있음과 함께, 광을 투과시키지 않는 재료에도 사용할 수 있는 점착 테이프를 제공하는 것을 목적으로 한다.An object of the present invention is to provide an adhesive tape that can reduce adhesion enhancement due to high temperature and can also be used for materials that do not transmit light.
본 발명은, 점착제층을 갖는 점착 테이프로서, 상기 점착제층은, 동적 점탄성 측정으로 평가한 25 ℃ 에 있어서의 전단 저장 탄성률이 4.0 × 104 ∼ 2.0 × 106 Pa 이고, 상기 점착제층은, 상기 점착 테이프의 상기 점착제층 측을 유리에 첩부하여 220 ℃ 에서 120 분간 가열하고, 박리한 후의 대수 (對水) 접촉각이 80°이상인, 점착 테이프이다.The present invention is an adhesive tape having a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer has a shear storage modulus of 4.0 × 10 4 to 2.0 × 10 6 Pa at 25° C. evaluated by dynamic viscoelasticity measurement, and the pressure-sensitive adhesive layer comprises: It is an adhesive tape having a logarithmic contact angle of 80° or more after the adhesive layer side of the adhesive tape is affixed to glass, heated at 220°C for 120 minutes, and peeled off.
이하에 본 발명을 상세히 서술한다.The present invention is described in detail below.
본 발명의 일 실시양태인 점착 테이프는, 점착제층을 갖는다.The adhesive tape which is an embodiment of the present invention has an adhesive layer.
본 발명의 일 실시양태인 점착 테이프는, 점착제층을 가지고만 있으면, 다른 층을 가지고 있어도 된다. 또, 본 발명의 일 실시양태인 점착 테이프는, 기재를 갖는 서포트 타입이어도 되고, 기재를 갖지 않는 논서포트 타입이어도 된다. 본 발명의 일 실시양태인 점착 테이프가 기재를 갖는 경우에는, 기재의 적어도 편면에 점착제층을 가지고 있으면 되고, 편면 점착 테이프여도 되고 양면 점착 테이프여도 된다.The adhesive tape as an embodiment of the present invention may have other layers as long as it has an adhesive layer. Moreover, the adhesive tape which is an embodiment of this invention may be a support type which has a base material, and may be a non-support type which does not have a base material. When the adhesive tape according to an embodiment of the present invention has a base material, it is sufficient to have an adhesive layer on at least one side of the base material, and may be a single-sided adhesive tape or a double-sided adhesive tape.
상기 점착제층은, 동적 점탄성 측정으로 평가한 25 ℃ 에 있어서의 전단 저장 탄성률이 4.0 × 104 ∼ 2.0 × 106 Pa 이다.The pressure-sensitive adhesive layer has a shear storage modulus of 4.0 × 10 4 to 2.0 × 10 6 Pa at 25°C evaluated by dynamic viscoelasticity measurement.
점착제층의 전단 저장 탄성률이 4.0 × 104 Pa 이상임으로써, 점착 테이프에 적합한 경도의 점착제층으로 할 수 있다. 또, 점착제층의 전단 저장 탄성률이 2.0 × 106 Pa 이하임으로써, 점착제층이 지나치게 딱딱해지지 않아, 점착 테이프의 고착을 막아 풀 잔존을 억제할 수 있다. 상기와 동일한 관점에서, 상기 전단 저장 탄성률의 바람직한 하한은 8.0 × 104 Pa, 보다 바람직한 하한은 1.0 × 105 Pa 이다. 상기 전단 저장 탄성률의 바람직한 상한은 1.5 × 106 Pa, 보다 바람직한 상한은 1.3 × 106 Pa, 더욱 바람직한 상한은 1.0 × 106 Pa, 특히 바람직한 상한은 7.0 × 105 Pa, 가장 바람직한 상한은 2.0 × 105 Pa 이다.When the shear storage modulus of the pressure-sensitive adhesive layer is 4.0 × 10 4 Pa or more, it can be set as a pressure-sensitive adhesive layer having a hardness suitable for an adhesive tape. In addition, when the shear storage modulus of the pressure-sensitive adhesive layer is 2.0 × 10 6 Pa or less, the pressure-sensitive adhesive layer does not become too hard, the sticking of the pressure-sensitive adhesive tape is prevented, and the residual of the glue can be suppressed. From the same viewpoint as above, the preferable lower limit of the shear storage modulus is 8.0 × 10 4 Pa, and a more preferable lower limit is 1.0 × 10 5 Pa. A preferable upper limit of the shear storage modulus is 1.5 × 10 6 Pa, a more preferable upper limit is 1.3 × 10 6 Pa, a more preferable upper limit is 1.0 × 10 6 Pa, a particularly preferable upper limit is 7.0 × 10 5 Pa, and the most preferable upper limit is 2.0 × It is 10 5 Pa.
상기 전단 저장 탄성률은 동적 점탄성 측정 장치 (예를 들어, 아이티 계측 제어사 제조, DVA-200) 를 사용하여 동적 점탄성 측정의 전단 모드, 각주파수 10 Hz 에서 승온 속도 5 ℃/min 로 -50 ℃ 에서 200 ℃ 까지 측정을 실시하여 얻은 측정값 중, 25 ℃ 에서의 저장 탄성률의 값으로서 구할 수 있다.The shear storage elastic modulus is a shear mode of dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring device (for example, DVA-200 manufactured by Haiti Instrumentation and Control), a heating rate of 5°C/min at -50°C at an angular frequency of 10 Hz. It can be calculated|required as the value of the storage modulus at 25 degreeC among the measured values obtained by carrying out measurement to 200 degreeC.
또한, 상기 전단 저장 탄성률은, 온도에 의한 변동이 작다. 그 때문에, 본 발명의 일 실시양태인 점착 테이프가 25 ℃ 에 있어서 상기 범위의 전단 저장 탄성률을 가지고 있으면, 220 ℃ 정도의 고온하에 있어서도 상기 효과가 발휘된다.In addition, the shear storage modulus has a small variation due to temperature. Therefore, if the adhesive tape as an embodiment of the present invention has a shear storage modulus in the above range at 25°C, the above effect is exhibited even under a high temperature of about 220°C.
상기 점착제층은, 상기 점착 테이프의 상기 점착제층 측을 유리에 첩부하여 220 ℃ 에서 120 분간 가열하고, 박리한 후의 대수 접촉각 (이하, 간단히 가열 후의 대수 접촉각이라고 한다) 이 80°이상이다.The pressure-sensitive adhesive layer has a logarithmic contact angle (hereinafter, simply referred to as a logarithmic contact angle after heating) of 80° or more after affixing the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive tape to glass, heating at 220°C for 120 minutes, and peeling.
점착 테이프를 유리에 첩부하여 가열하고, 박리한 후의 점착제층이 상기 범위의 대수 접촉각을 가지고 있음으로써, 표면이 소수적이 되어, 피착체와 상호 작용하기 어려워지는 점에서, 가열에 의한 접착 항진을 저감시킬 수 있다. 동일한 관점에서, 상기 가열 후의 대수 접촉각의 바람직한 하한은 81°, 보다 바람직한 하한은 81.5°, 더욱 바람직한 하한은 82°이다. 상기 가열 후의 대수 접촉각의 바람직한 상한은 110°, 보다 바람직한 상한은 105°, 더욱 바람직한 상한은 103°, 보다 더 바람직한 상한은 100°, 특히 바람직한 상한은 97°, 특히 바람직한 상한은 95°, 매우 바람직한 상한은 92°, 한층 바람직한 상한은 91°이다.Since the adhesive tape is affixed to glass and heated, and the adhesive layer after peeling has a logarithmic contact angle within the above range, the surface becomes hydrophobic, making it difficult to interact with the adherend, thereby reducing the adhesion promotion caused by heating. I can make it. From the same viewpoint, the preferable lower limit of the logarithmic contact angle after heating is 81°, the more preferable lower limit is 81.5°, and the further preferable lower limit is 82°. A preferable upper limit of the logarithmic contact angle after heating is 110°, a more preferable upper limit is 105°, a more preferable upper limit is 103°, a more preferable upper limit is 100°, a particularly preferable upper limit is 97°, a particularly preferable upper limit is 95°, and very preferable The upper limit is 92°, and the more preferable upper limit is 91°.
상기 가열 후의 대수 접촉각은, JIS R 3257 : 1999 에 준거한 방법으로 측정할 수 있고, 구체적으로는 이하의 방법으로 측정할 수 있다.The logarithmic contact angle after the heating can be measured by a method conforming to JIS R 3257:1999, and specifically, it can be measured by the following method.
점착 테이프를 25 ㎜ 폭으로 재단한다. 재단한 점착 테이프를 유리 피착체 (예를 들어, 마츠나미 유리 공업사 제조, 대형 슬라이드 글래스 백연마 (白緣磨) No.2) 에 실온 23 ℃, 상대 습도 50 ％ 에서, 2 ㎏ 의 압착 고무 롤러를 사용하여 10 ㎜/SEC 의 속도로 첩부한다. 이어서, 220 ℃, 120 분의 가열 처리를 실시한다. 방랭 후, 점착 테이프를 유리 피착체로부터 박리하고, JIS R 3257 : 1999 에 준하여, 접촉각 측정 장치 (예를 들어, KSV 사 제조, CAM 200) 를 사용하여 점착제층의 대수 접촉각을 측정한다. 구체적으로는, 실온 25 ℃, 습도 40 ％ 의 환경하에서, 수평하게 둔 점착 테이프의 점착제층 표면에, 물방울 2 ㎕ (초순수) 를 적하한다. 적하하고 나서 5 초 후의 순수와 점착제층 표면이 이루는 각도를 대수 접촉각으로 한다.The adhesive tape is cut into 25 mm width. The cut adhesive tape was put on a glass adherend (e.g., Matsunami Glass Co., Ltd. make, large-sized slide glass whitening No.2) at a room temperature of 23°C and a relative humidity of 50%, and a 2 kg compression rubber roller It affixes at a speed of 10 mm/SEC using. Next, heat treatment at 220°C for 120 minutes is performed. After standing to cool, the adhesive tape is peeled from the glass adherend, and the logarithmic contact angle of the adhesive layer is measured using a contact angle measuring device (for example, CAM 200 manufactured by KSV) according to JIS R 3257:1999. Specifically, 2 µl of water droplets (ultrapure water) is dripped onto the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape placed horizontally in an environment at room temperature of 25°C and humidity of 40%. The angle formed by the pure water 5 seconds after dropping and the surface of the pressure-sensitive adhesive layer is taken as the logarithmic contact angle.
본 발명의 일 실시양태인 점착 테이프는, 상기 점착제층의 25 ℃ 에 있어서의 대수 접촉각이 103°이하인 것이 바람직하다.In the pressure-sensitive adhesive tape according to an embodiment of the present invention, it is preferable that the logarithmic contact angle of the pressure-sensitive adhesive layer at 25°C is 103° or less.
점착제층의 25 ℃ 에 있어서의 대수 접촉각이 103°이하임으로써, 보다 적당한 점착력 (초기 점착력) 으로 피착체에 첩부할 수 있다. 동일한 관점에서, 상기 점착제층의 25 ℃ 에 있어서의 대수 접촉각의 보다 바람직한 상한은 102°, 더욱 바람직한 상한은 100°이다. 상기 점착제층의 25 ℃ 에 있어서의 대수 접촉각의 하한은 특별히 한정되지 않지만, 80°인 것이 바람직하다. 상기 점착제층의 25 ℃ 에 있어서의 대수 접촉각은, 가열 처리를 실시하지 않는 것 이외에는 상기 가열 후의 대수 접촉각과 동일한 방법으로 측정할 수 있다.When the logarithmic contact angle at 25°C of the pressure-sensitive adhesive layer is 103° or less, it can be affixed to the adherend with a more appropriate adhesive force (initial adhesive force). From the same viewpoint, a more preferable upper limit of the logarithmic contact angle at 25° C. of the pressure-sensitive adhesive layer is 102°, and a further preferable upper limit is 100°. The lower limit of the logarithmic contact angle at 25° C. of the pressure-sensitive adhesive layer is not particularly limited, but it is preferably 80°. The logarithmic contact angle at 25°C of the pressure-sensitive adhesive layer can be measured in the same manner as the logarithmic contact angle after heating, except that no heat treatment is performed.
상기 점착제층은, 가교성 관능기를 갖는 점착제와, 가교성 관능기를 갖는 실리콘계 그래프트 공중합체와, 상기 점착제 및 상기 실리콘계 그래프트 공중합체와 반응하여 가교시킬 수 있는 가교제를 함유하는 것이 바람직하다.The pressure-sensitive adhesive layer preferably contains a pressure-sensitive adhesive having a crosslinkable functional group, a silicone-based graft copolymer having a crosslinkable functional group, and a crosslinking agent capable of crosslinking by reacting with the pressure-sensitive adhesive and the silicone-based graft copolymer.
점착제층이 가교제를 함유함으로써, 점착제를 가교하여 전단 저장 탄성률을 상기 범위로 조절하기 쉽게 할 수 있다. 또, 점착제층이 실리콘계 그래프트 공중합체를 함유하면, 실리콘계 그래프트 공중합체가 가열에 의해 점착제층 표면으로 블리드 아웃함으로써, 점착제층의 표면이 소수적이 되기 때문에, 가열 후의 대수 접촉각을 상기 범위로 조절하기 쉽게 할 수 있다. 또, 점착제층의 표면이 소수 적이 됨으로써, 점착제층과 피착체가 상호 작용하기 어려워져, 접착력이 감소하는 점에서, 접착 항진을 저감시킬 수 있다. 또한, 실리콘계 그래프트 공중합체가 가교성 관능기를 가짐으로써, 가교제를 개재하여 실리콘계 그래프트 공중합체를 점착제와 결합할 수 있는 점에서, 피착체의 오염을 억제할 수 있다.When the pressure-sensitive adhesive layer contains a crosslinking agent, it is possible to easily adjust the shear storage modulus in the above range by crosslinking the pressure-sensitive adhesive. In addition, when the pressure-sensitive adhesive layer contains a silicone-based graft copolymer, the silicone-based graft copolymer bleeds out to the surface of the pressure-sensitive adhesive layer by heating, so that the surface of the pressure-sensitive adhesive layer becomes hydrophobic, making it easy to adjust the logarithmic contact angle after heating within the above range. can do. In addition, since the surface of the pressure-sensitive adhesive layer becomes hydrophobic, it becomes difficult for the pressure-sensitive adhesive layer and the adherend to interact with each other, and the adhesive strength decreases, so that the adhesion promotion can be reduced. In addition, since the silicone-based graft copolymer has a crosslinkable functional group, since the silicone-based graft copolymer can be bonded to the pressure-sensitive adhesive through a crosslinking agent, contamination of the adherend can be suppressed.
상기 점착제는 특별히 한정되지 않고, 경화형이어도 되고 비경화형이어도 된다.The pressure-sensitive adhesive is not particularly limited, and may be a curable type or a non-curable type.
경화 점착제란, 예를 들어 이중 결합 등의 중합성 관능기를 가짐으로써, 열이나 광 등의 자극에 의해 경화되는 것이고, 비경화형 점착제란, 중합성 관능기를 실질적으로 갖지 않는 것이다. 제조 프로세스를 간략화할 수 있는 점과, 광경화를 실시할 수 없는 불투명한 재료에 대해서도 사용할 수 있는 점에서, 상기 점착제는 비경화형 점착제인 것이 바람직하다. 비경화형 점착제로는, 예를 들어 비광경화형 점착제, 비열경화형 점착제, 비에너지 경화형 점착제를 들 수 있다.A cured pressure-sensitive adhesive is one that is cured by stimulation such as heat or light by having a polymerizable functional group such as a double bond, and a non-cured pressure-sensitive adhesive is one that has substantially no polymerizable functional group. The pressure-sensitive adhesive is preferably a non-curable pressure-sensitive adhesive from the point that the manufacturing process can be simplified and that it can also be used for an opaque material that cannot be photocured. As a non-curable adhesive, a non-photocurable adhesive, a non-thermosetting adhesive, and a non-energy curable adhesive are mentioned, for example.
상기 점착제로는, 예를 들어, 아크릴계 점착제, 실리콘계 점착제, 우레탄계 점착제, 고무계 점착제 등을 들 수 있다. 그 중에서도, 상기 가열 후의 대수 접촉각과 상기 전단 저장 탄성률을 조절하기 쉬운 점에서 비실리콘계 점착제가 바람직하고, 아크릴계 점착제인 것이 보다 바람직하다.Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, and rubber-based pressure-sensitive adhesives. Among them, a non-silicone pressure-sensitive adhesive is preferred, and an acrylic pressure-sensitive adhesive is more preferred from the viewpoint of easy adjustment of the logarithmic contact angle after heating and the shear storage modulus.
상기 점착제 및 실리콘계 그래프트 공중합체에 존재하는 가교성 관능기로는, 각각 독립적으로, 예를 들어, 카르복실기, 수산기, 글리시딜기, 아미노기, 아미드기, 니트릴기 등을 들 수 있다. 그 중에서도, 상기 전단 저장 탄성률의 범위로의 조절이 용이한 점에서, 카르복실기가 바람직하다.The crosslinkable functional groups present in the pressure-sensitive adhesive and the silicone-based graft copolymer may each independently include, for example, a carboxyl group, a hydroxyl group, a glycidyl group, an amino group, an amide group, a nitrile group, and the like. Among them, a carboxyl group is preferable because it is easy to adjust to the range of the shear storage modulus.
상기 점착제는, 분자량 분포 (Mw/Mn) 1.05 ∼ 2.5 의 아크릴계 폴리머인 것이 바람직하고, 리빙 라디칼 중합에 의해 얻어진 분자량 분포 (Mw/Mn) 1.05 ∼ 2.5 의 아크릴계 폴리머 (이하, 간단히 「리빙 라디칼 중합 아크릴계 폴리머」라고도 한다) 인 것이 보다 바람직하다.The pressure-sensitive adhesive is preferably an acrylic polymer having a molecular weight distribution (Mw/Mn) of 1.05 to 2.5, and an acrylic polymer having a molecular weight distribution (Mw/Mn) of 1.05 to 2.5 obtained by living radical polymerization (hereinafter simply referred to as ``living radical polymerization acrylic polymer Also referred to as "polymer") is more preferable.
상기 리빙 라디칼 중합 아크릴계 폴리머는, (메트)아크릴산에스테르나 (메트)아크릴산 등의 아크릴계 모노머를 원료로 하여, 리빙 라디칼 중합, 바람직하게는 유기 텔루륨 중합 개시제를 사용한 리빙 라디칼 중합에 의해 얻어진 아크릴계 폴리머이다. 리빙 라디칼 중합은, 중합 반응이 정지 반응 또는 연쇄 이동 반응 등의 부반응에 의해 방해되지 않고 분자 사슬이 생장해 가는 중합이다. 리빙 라디칼 중합에 의하면, 예를 들어 프리 라디칼 중합 등과 비교하여 보다 균일한 분자량 및 조성을 갖는 폴리머가 얻어지고, 저분자량 성분 등의 생성을 억제할 수 있기 때문에, 고온 처리를 실시한 경우라도 풀 잔존을 억제할 수 있다. 또, 상기 전단 저장 탄성률을 상기 범위로 조절하기 쉽게 할 수 있다. 보다 풀 잔존을 억제하는 관점에서, 리빙 라디칼 중합 아크릴계 폴리머의 상기 분자량 분포의 보다 바람직한 하한은 1.1, 보다 바람직한 상한은 2.0 이다.The living radical polymerization acrylic polymer is an acrylic polymer obtained by living radical polymerization, preferably living radical polymerization using an organic tellurium polymerization initiator, using an acrylic monomer such as (meth)acrylic acid ester or (meth)acrylic acid as a raw material. . Living radical polymerization is a polymerization in which molecular chains grow without the polymerization reaction being disturbed by side reactions such as a stop reaction or a chain transfer reaction. According to living radical polymerization, for example, compared to free radical polymerization, a polymer having a more uniform molecular weight and composition can be obtained, and generation of low molecular weight components, etc. can be suppressed, so even when high-temperature treatment is performed, the residual of the grass is suppressed. can do. In addition, the shear storage modulus can be easily adjusted within the above range. From the viewpoint of further suppressing the residual grass, the lower limit of the molecular weight distribution of the living radically polymerized acrylic polymer is 1.1, and the upper limit is 2.0.
상기 리빙 라디칼 중합에 있어서는, 여러 가지의 중합 방식을 채용해도 된다. 예를 들어, 철, 루테늄이나 구리 촉매 및 할로겐계 개시제를 사용해도 되고 (ATRP), TEMPO 를 사용해도 되고, 유기 텔루륨 중합 개시제를 사용해도 된다. 그 중에서도, 유기 텔루륨 중합 개시제를 사용하는 것이 바람직하다. 유기 텔루륨 중합 개시제를 사용한 리빙 라디칼 중합은, 다른 리빙 라디칼 중합과는 달리, 수산기나 카르복실기와 같은 극성 관능기를 갖는 라디칼 중합성 모노머를 모두 보호하지 않고, 동일한 개시제로 중합하여 균일한 분자량 및 조성을 갖는 폴리머를 얻을 수 있다. 이 때문에, 극성 관능기를 갖는 라디칼 중합성 모노머를 용이하게 공중합할 수 있다.In the living radical polymerization, various polymerization methods may be employed. For example, an iron, ruthenium or copper catalyst and a halogen-based initiator may be used, (ATRP), TEMPO may be used, or an organic tellurium polymerization initiator may be used. Among them, it is preferable to use an organic tellurium polymerization initiator. Living radical polymerization using an organic tellurium polymerization initiator, unlike other living radical polymerizations, does not protect all radical polymerizable monomers having polar functional groups such as hydroxyl groups or carboxyl groups, but polymerizes with the same initiator to have a uniform molecular weight and composition. Polymers can be obtained. For this reason, a radical polymerizable monomer having a polar functional group can be easily copolymerized.
상기 유기 텔루륨 중합 개시제는, 리빙 라디칼 중합에 일반적으로 사용되는 것이면 특별히 한정되지 않고, 예를 들어, 유기 텔루륨 화합물, 유기 텔루라이드 화합물 등을 들 수 있다.The organic tellurium polymerization initiator is not particularly limited as long as it is generally used for living radical polymerization, and examples thereof include organic tellurium compounds and organic telluride compounds.
상기 유기 텔루륨 화합물로서, 예를 들어, (메틸텔라닐-메틸)벤젠, (1-메틸텔라닐-에틸)벤젠, (2-메틸텔라닐-프로필)벤젠, 1-클로로-4-(메틸텔라닐-메틸)벤젠, 1-하이드록시-4-(메틸텔라닐-메틸)벤젠, 1-메톡시-4-(메틸텔라닐-메틸)벤젠, 1-아미노-4-(메틸텔라닐-메틸)벤젠, 1-니트로-4-(메틸텔라닐-메틸)벤젠, 1-시아노-4-(메틸텔라닐-메틸)벤젠, 1-메틸카르보닐-4-(메틸텔라닐-메틸)벤젠, 1-페닐카르보닐-4-(메틸텔라닐-메틸)벤젠, 1-메톡시카르보닐-4-(메틸텔라닐-메틸)벤젠, 1-페녹시카르보닐-4-(메틸텔라닐-메틸)벤젠, 1-술포닐-4-(메틸텔라닐-메틸)벤젠, 1-트리플루오로메틸-4-(메틸텔라닐-메틸)벤젠, 1-클로로-4-(1-메틸텔라닐-에틸)벤젠, 1-하이드록시-4-(1-메틸텔라닐-에틸)벤젠, 1-메톡시-4-(1-메틸텔라닐-에틸)벤젠, 1-아미노-4-(1-메틸텔라닐-에틸)벤젠, 1-니트로-4-(1-메틸텔라닐-에틸)벤젠, 1-시아노-4-(1-메틸텔라닐-에틸)벤젠, 1-메틸카르보닐-4-(1-메틸텔라닐-에틸)벤젠, 1-페닐카르보닐-4-(1-메틸텔라닐-에틸)벤젠, 1-메톡시카르보닐-4-(1-메틸텔라닐-에틸)벤젠, 1-페녹시카르보닐-4-(1-메틸텔라닐-에틸)벤젠, 1-술포닐-4-(1-메틸텔라닐-에틸)벤젠, 1-트리플루오로메틸-4-(1-메틸텔라닐-에틸)벤젠, 1-클로로-4-(2-메틸텔라닐-프로필)벤젠, 1-하이드록시-4-(2-메틸텔라닐-프로필)벤젠, 1-메톡시-4-(2-메틸텔라닐-프로필)벤젠, 1-아미노-4-(2-메틸텔라닐-프로필)벤젠, 1-니트로-4-(2-메틸텔라닐-프로필)벤젠, 1-시아노-4-(2-메틸텔라닐-프로필)벤젠, 1-메틸카르보닐-4-(2-메틸텔라닐-프로필)벤젠, 1-페닐카르보닐-4-(2-메틸텔라닐-프로필)벤젠, 1-메톡시카르보닐-4-(2-메틸텔라닐-프로필)벤젠, 1-페녹시카르보닐-4-(2-메틸텔라닐-프로필)벤젠, 1-술포닐-4-(2-메틸텔라닐-프로필)벤젠, 1-트리플루오로메틸-4-(2-메틸텔라닐-프로필)벤젠, 2-(메틸텔라닐-메틸)피리딘, 2-(1-메틸텔라닐-에틸)피리딘, 2-(2-메틸텔라닐-프로필)피리딘, 2-메틸텔라닐-에탄산메틸, 2-메틸텔라닐-프로피온산메틸, 2-메틸텔라닐-2-메틸프로피온산메틸, 2-메틸텔라닐-에탄산에틸, 2-메틸텔라닐-프로피온산에틸, 2-메틸텔라닐-2-메틸프로피온산에틸, 2-메틸텔라닐아세토니트릴, 2-메틸텔라닐프로피오니트릴, 2-메틸-2-메틸텔라닐프로피오니트릴 등을 들 수 있다. 이들 유기 텔루륨 화합물 중의 메틸텔라닐기는, 에틸텔라닐기, n-프로필텔라닐기, 이소프로필텔라닐기, n-부틸텔라닐기, 이소부틸텔라닐기, t-부틸텔라닐기, 페닐텔라닐기 등이어도 되고, 또, 이들 유기 텔루륨 화합물은, 단독으로 사용해도 되고, 2 종 이상을 병용해도 된다.As the organic tellurium compound, for example, (methyltellanyl-methyl)benzene, (1-methyltellanyl-ethyl)benzene, (2-methyltelanyl-propyl)benzene, 1-chloro-4-(methyl Telanyl-methyl)benzene, 1-hydroxy-4-(methyltelanyl-methyl)benzene, 1-methoxy-4-(methyltelanyl-methyl)benzene, 1-amino-4-(methyltelanyl- Methyl)benzene, 1-nitro-4-(methyltelanyl-methyl)benzene, 1-cyano-4-(methyltelanyl-methyl)benzene, 1-methylcarbonyl-4-(methyltelanyl-methyl) Benzene, 1-phenylcarbonyl-4-(methyltelanyl-methyl)benzene, 1-methoxycarbonyl-4-(methyltelanyl-methyl)benzene, 1-phenoxycarbonyl-4-(methyltelanyl -Methyl)benzene, 1-sulfonyl-4-(methyltelanyl-methyl)benzene, 1-trifluoromethyl-4-(methyltelanyl-methyl)benzene, 1-chloro-4-(1-methyltel) Ranyl-ethyl)benzene, 1-hydroxy-4-(1-methyltellanyl-ethyl)benzene, 1-methoxy-4-(1-methyltelanyl-ethyl)benzene, 1-amino-4-(1 -Methyltellanyl-ethyl)benzene, 1-nitro-4-(1-methyltelanyl-ethyl)benzene, 1-cyano-4-(1-methyltelanyl-ethyl)benzene, 1-methylcarbonyl- 4-(1-Methyltellanyl-ethyl)benzene, 1-phenylcarbonyl-4-(1-methyltelanyl-ethyl)benzene, 1-methoxycarbonyl-4-(1-methyltelanyl-ethyl) Benzene, 1-phenoxycarbonyl-4-(1-methyltelanyl-ethyl)benzene, 1-sulfonyl-4-(1-methyltelanyl-ethyl)benzene, 1-trifluoromethyl-4-( 1-Methyltellanyl-ethyl)benzene, 1-chloro-4-(2-methyltelanyl-propyl)benzene, 1-hydroxy-4-(2-methyltelanyl-propyl)benzene, 1-methoxy- 4-(2-methyltellanyl-propyl)benzene, 1-amino-4-(2-methyltelanyl-propyl)benzene, 1-nitro-4-(2-methyltelanyl-propyl)benzene, 1-cya No-4-(2-methyltelanyl-propyl)benzene, 1-methylcarbonyl-4-(2-methyltelanyl-propyl)benzene, 1-phenylcarbonyl-4-(2-methyltelanyl-propyl )Benzene, 1-methoxycarbonyl-4-(2-methyltelanyl-propyl)benzene, 1-phenoxycarbonyl-4-(2-methyltelanyl-propyl)benzene, 1-sulfonyl-4- (2-Methyltellanyl-propyl)benzene, 1-trifluoromethyl-4-(2-methyltelanyl-propyl)benzene, 2-(methyltelanyl-methyl)pyri Dine, 2-(1-methyltellanyl-ethyl)pyridine, 2-(2-methyltelanyl-propyl)pyridine, 2-methyltelanyl-methyl ethanate, 2-methyltelanyl-methyl propionate, 2-methyl Tellanyl-2-methylpropionate methyl, 2-methyltellanyl-ethyl ethanate, 2-methyltellanyl-ethyl propionate, 2-methyltellanyl-2-methylpropionate ethyl, 2-methyltelanylacetonitrile, 2- Methyltellanylpropionitrile, 2-methyl-2-methyltelanylpropionitrile, and the like. The methyltellanyl group in these organic tellurium compounds may be an ethyltellanyl group, an n-propyltelanyl group, an isopropyltelanyl group, an n-butyltelanyl group, an isobutyltelanyl group, a t-butyltelanyl group, a phenyltelanyl group, and the like, In addition, these organic tellurium compounds may be used alone or in combination of two or more.
상기 유기 텔루라이드 화합물로서, 예를 들어, 디메틸디텔루라이드, 디에틸디텔루라이드, 디-n-프로필디텔루라이드, 디이소프로필디텔루라이드, 디시클로프로필디텔루라이드, 디-n-부틸디텔루라이드, 디-sec-부틸디텔루라이드, 디-tert-부틸디텔루라이드, 디시클로부틸디텔루라이드, 디페닐디텔루라이드, 비스-(p-메톡시페닐)디텔루라이드, 비스-(p-아미노페닐)디텔루라이드, 비스-(p-니트로페닐)디텔루라이드, 비스-(p-시아노페닐)디텔루라이드, 비스-(p-술포닐페닐)디텔루라이드, 디나프틸디텔루라이드, 디피리딜디텔루라이드 등을 들 수 있다. 이들 유기 텔루라이드 화합물은, 단독으로 사용해도 되고, 2 종 이상을 병용해도 된다. 그 중에서도, 디메틸디텔루라이드, 디에틸디텔루라이드, 디-n-프로필디텔루라이드, 디-n-부틸디텔루라이드, 디페닐디텔루라이드가 바람직하다.As the organic telluride compound, for example, dimethylditelluride, diethylditelluride, di-n-propylditelluride, diisopropylditelluride, dicyclopropylditelluride, di-n-butyl Ditelluride, di-sec-butylditelluride, di-tert-butylditelluride, dicyclobutylditelluride, diphenylditelluride, bis-(p-methoxyphenyl)ditelluride, bis- (p-aminophenyl) ditelluride, bis-(p-nitrophenyl) ditelluride, bis-(p-cyanophenyl) ditelluride, bis-(p-sulfonylphenyl) ditelluride, dinaph Tylditelluride, dipyridylditelluride, etc. are mentioned. These organic telluride compounds may be used alone or in combination of two or more. Among them, dimethylditelluride, diethylditelluride, di-n-propylditelluride, di-n-butylditelluride, and diphenylditelluride are preferable.
또한, 본 발명의 효과를 저해하지 않는 범위 내에서, 상기 유기 텔루륨 중합 개시제에 추가하여, 중합 속도의 촉진을 목적으로 하여 중합 개시제로서 아조 화합물을 사용해도 된다.In addition, an azo compound may be used as a polymerization initiator for the purpose of accelerating the polymerization rate in addition to the organic tellurium polymerization initiator within a range not impairing the effect of the present invention.
상기 아조 화합물은, 라디칼 중합에 일반적으로 사용되는 것이면 특별히 한정되지 않고, 예를 들어, 2,2'-아조비스(이소부티로니트릴), 2,2'-아조비스(2-메틸부티로니트릴), 2,2'-아조비스(2,4-디메틸발레로니트릴), 2,2'-아조비스(4-메톡시-2,4-디메틸발레로니트릴), 1,1-아조비스(시클로헥산-1-카르보니트릴), 1-[(1-시아노-1-메틸에틸)아조]포름아미드, 4,4'-아조비스(4-시아노발레리안산), 디메틸-2,2'-아조비스(2-메틸프로피오네이트), 디메틸-1,1'-아조비스(1-시클로헥산카르복실레이트), 2,2'-아조비스{2-메틸-N-[1,1'-비스(하이드록시메틸)-2-하이드록시에틸]프로피온아미드}, 2,2'-아조비스[2-메틸-N-(2-하이드록시에틸)프로피온아미드], 2,2'-아조비스[N-(2-프로페닐)-2-메틸프로피온아미드], 2,2'-아조비스(N-부틸-2-메틸프로피온아미드), 2,2'-아조비스(N-시클로헥실-2-메틸프로피온아미드), 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판]2염산염, 2,2'-아조비스{2-[1-(2-하이드록시에틸)-2-이미다졸린-2-일]프로판}2염산염, 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판], 2,2'-아조비스(2-아미디노프로판)2염산염, 2,2'-아조비스[N-(2-카르복시에틸)-2-메틸프로피온아미딘]4수화물, 2,2'-아조비스(1-이미노-1-피롤리디노-2-메틸프로판)2염산염, 2,2'-아조비스(2,4,4-트리메틸펜탄) 등을 들 수 있다. 이들 아조 화합물은, 단독으로 사용해도 되고, 2 종 이상을 병용해도 된다.The azo compound is not particularly limited as long as it is generally used for radical polymerization, and, for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile) ), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1-azobis ( Cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, 4,4'-azobis(4-cyanovaleric acid), dimethyl-2,2' -Azobis (2-methylpropionate), dimethyl-1,1'-azobis (1-cyclohexanecarboxylate), 2,2'-azobis {2-methyl-N-[1,1' -Bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis [N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2 -Methylpropionamide), 2,2'-azobis[2-(2-imidazolin-2-yl)propane]2 hydrochloride, 2,2'-azobis {2-[1-(2-hydroxy) Ethyl)-2-imidazolin-2-yl]propane}2 hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis( 2-amidinopropane) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate, 2,2'-azobis(1-imino-1 -Pyrrolidino-2-methylpropane) dihydrochloride, 2,2'-azobis (2,4,4-trimethylpentane), and the like. These azo compounds may be used alone or in combination of two or more.
상기 점착제는 가교성 관능기를 갖는 점에서, 리빙 라디칼 중합 아크릴계 폴리머에는 중합하는 모노머로서, 가교성 관능기를 갖는 모노머를 배합한다.Since the pressure-sensitive adhesive has a crosslinkable functional group, a monomer having a crosslinkable functional group is added to the living radically polymerized acrylic polymer as a monomer to be polymerized.
상기 가교성 관능기가 카르복실기인 경우, 카르복실기를 갖는 모노머로는, 예를 들어, (메트)아크릴산을 들 수 있다.When the said crosslinkable functional group is a carboxyl group, as a monomer which has a carboxyl group, (meth)acrylic acid is mentioned, for example.
상기 가교성 관능기가 수산기인 경우, 수산기를 갖는 모노머로는, 예를 들어, 4-하이드록시부틸(메트)아크릴레이트, 2-하이드록시에틸(메트)아크릴레이트 등의 수산기를 갖는 (메트)아크릴산에스테르를 들 수 있다.When the crosslinkable functional group is a hydroxyl group, as a monomer having a hydroxyl group, for example, (meth)acrylic acid having a hydroxyl group such as 4-hydroxybutyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate Esters are mentioned.
상기 가교성 관능기가 글리시딜기인 경우, 글리시딜기를 갖는 모노머로는, 예를 들어, 글리시딜(메트)아크릴레이트를 들 수 있다.When the crosslinkable functional group is a glycidyl group, the monomer having a glycidyl group includes, for example, glycidyl (meth)acrylate.
상기 가교성 관능기가 아미드기인 경우, 아미드기를 갖는 모노머로는, 예를 들어, 하이드록시에틸아크릴아미드, 이소프로필아크릴아미드, 디메틸아미노프로필아크릴아미드 등을 들 수 있다.When the crosslinkable functional group is an amide group, examples of the monomer having an amide group include hydroxyethylacrylamide, isopropylacrylamide, dimethylaminopropylacrylamide, and the like.
상기 가교성 관능기가 니트릴기인 경우, 니트릴기를 갖는 모노머로는, 예를 들어, 아크릴로니트릴 등을 들 수 있다.When the crosslinkable functional group is a nitrile group, examples of the monomer having a nitrile group include acrylonitrile.
상기 카르복실기를 갖는 아크릴계 모노머를 사용하는 경우, 그 함유량은 특별히 한정되지 않지만, 상기 리빙 라디칼 중합에 있어서 중합하는 라디칼 중합성 모노머 중의 바람직한 하한은 0.1 중량％, 바람직한 상한은 10 중량％ 이다. 상기 함유량이 0.1 중량％ 이상이면, 리빙 라디칼 중합 아크릴계 폴리머가 상기 실리콘계 그래프트 공중합체와 상기 가교제를 개재하여 충분히 결합할 수 있기 때문에, 피착체의 오염을 저감시킬 수 있다. 상기 함유량이 10 중량％ 이하이면, 상기 점착제가 지나치게 딱딱해지지 않아, 점착 테이프의 풀 잔존을 억제할 수 있다.When the acrylic monomer having a carboxyl group is used, the content thereof is not particularly limited, but the preferred lower limit of the radical polymerizable monomer to be polymerized in the living radical polymerization is 0.1% by weight, and the preferred upper limit is 10% by weight. When the content is 0.1% by weight or more, since the living radical polymerization acrylic polymer can be sufficiently bonded through the silicone graft copolymer and the crosslinking agent, contamination of the adherend can be reduced. When the content is 10% by weight or less, the pressure-sensitive adhesive does not become too hard, so that the glue remaining of the pressure-sensitive adhesive tape can be suppressed.
상기 수산기를 갖는 (메트)아크릴산에스테르를 사용한 경우, 그 함유량은 특별히 한정되지 않지만, 상기 리빙 라디칼 중합에 있어서 중합하는 라디칼 중합성 모노머 중의 바람직한 상한은 30 중량％ 이다. 상기 함유량이 30 중량％ 이하임으로써, 상기 점착제의 내열 접착성을 보다 향상시킬 수 있다.When the (meth)acrylic acid ester having a hydroxyl group is used, its content is not particularly limited, but the preferred upper limit of the radical polymerizable monomer to be polymerized in the living radical polymerization is 30% by weight. When the content is 30% by weight or less, the heat-resistant adhesiveness of the pressure-sensitive adhesive can be further improved.
상기 리빙 라디칼 중합에 있어서 중합하는 아크릴계 모노머는, 가교성 관능기를 갖는 아크릴계 모노머 이외의 다른 라디칼 중합성 모노머를 사용해도 된다. 상기 다른 라디칼 중합성 모노머로는, 예를 들어, 다른 (메트)아크릴산에스테르를 들 수 있다. 또, 아미노기, 아미드기 및 니트릴기 등의 다른 극성 관능기를 갖는 아크릴계 모노머도 사용할 수 있다. 또한, 상기 아크릴계 모노머에 추가하여, 비닐 화합물을 모노머로서 사용해도 된다.As the acrylic monomer to be polymerized in the living radical polymerization, radical polymerizable monomers other than the acrylic monomer having a crosslinkable functional group may be used. As said other radically polymerizable monomer, another (meth)acrylic acid ester is mentioned, for example. Further, an acrylic monomer having other polar functional groups such as an amino group, an amide group and a nitrile group can also be used. Further, in addition to the acrylic monomer, a vinyl compound may be used as a monomer.
상기 다른 (메트)아크릴산에스테르는 특별히 한정되지 않고, 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, 프로필(메트)아크릴레이트, n-부틸(메트)아크릴레이트, tert-부틸(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, n-옥틸(메트)아크릴레이트, 이소옥틸(메트)아크릴레이트, 이소노닐(메트)아크릴레이트, 이소미리스틸(메트)아크릴레이트, 스테아릴(메트)아크릴레이트 등의 (메트)아크릴산알킬에스테르나, 시클로헥실(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트, 벤질(메트)아크릴레이트, 2-부톡시에틸(메트)아크릴레이트, 2-페녹시에틸(메트)아크릴레이트, 글리시딜(메트)아크릴레이트, 테트라하이드로푸르푸릴(메트)아크릴레이트, 폴리프로필렌글리콜모노(메트)아크릴레이트 등을 들 수 있다. 이들 (메트)아크릴산에스테르는, 단독으로 사용해도 되고, 2 종 이상을 병용해도 된다.The other (meth)acrylic acid ester is not particularly limited, and methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylic Rate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isomirithyl (meth)acrylate, stearyl (meth) )(Meth)acrylate alkyl esters such as acrylates, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2- Phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, polypropylene glycol mono (meth)acrylate, and the like may be mentioned. These (meth)acrylic acid esters may be used alone or in combination of two or more.
상기 비닐 화합물은 특별히 한정되지 않고, 예를 들어, N,N-디메틸아크릴아미드, N,N-디에틸아크릴아미드, N-이소프로필아크릴아미드, N-하이드록시에틸아크릴아미드, 아크릴아미드 등의 (메트)아크릴아미드 화합물, N-비닐피롤리돈, N-비닐 카프로락탐, N-비닐아세트아미드, N-아크릴로일모르폴린, 아크릴로니트릴, 스티렌, 아세트산비닐 등을 들 수 있다. 이들 비닐 화합물은, 단독으로 사용해도 되고, 2 종 이상을 병용해도 된다.The vinyl compound is not particularly limited, for example, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N-hydroxyethylacrylamide, acrylamide ( Meth)acrylamide compounds, N-vinylpyrrolidone, N-vinyl caprolactam, N-vinylacetamide, N-acryloylmorpholine, acrylonitrile, styrene, vinyl acetate, and the like. These vinyl compounds may be used alone or in combination of two or more.
상기 리빙 라디칼 중합에 있어서는, 분산 안정제를 사용해도 된다. 상기 분산 안정제로서, 예를 들어, 폴리비닐피롤리돈, 폴리비닐알코올, 메틸셀룰로오스, 에틸셀룰로오스, 폴리(메트)아크릴산, 폴리(메트)아크릴산에스테르, 폴리에틸렌글리콜 등을 들 수 있다.In the living radical polymerization, a dispersion stabilizer may be used. As the dispersion stabilizer, for example, polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose, ethylcellulose, poly(meth)acrylic acid, poly(meth)acrylic acid ester, polyethylene glycol, and the like can be mentioned.
상기 리빙 라디칼 중합의 방법으로서, 종래 공지된 방법이 사용되고, 예를 들어, 용액 중합 (비점 중합 또는 정온 (定溫) 중합), 유화 중합, 현탁 중합, 괴상 중합 등을 들 수 있다.As the method of living radical polymerization, a conventionally known method is used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, and bulk polymerization.
상기 리빙 라디칼 중합에 있어서 중합 용매를 사용하는 경우, 그 중합 용매는 특별히 한정되지 않는다. 상기 중합 용매로는, 예를 들어, 헥산, 시클로헥산, 옥탄, 톨루엔, 자일렌 등의 비극성 용매나, 물, 메탄올, 에탄올, 프로판올, 부탄올, 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 테트라하이드로푸란, 디옥산, N,N-디메틸포름아미드 등의 고극성 용매를 사용할 수 있다. 이들 중합 용매는, 단독으로 사용해도 되고, 2 종 이상을 병용해도 된다.In the case of using a polymerization solvent in the living radical polymerization, the polymerization solvent is not particularly limited. Examples of the polymerization solvent include non-polar solvents such as hexane, cyclohexane, octane, toluene, and xylene, and water, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, and tetrahydro. High polarity solvents, such as furan, dioxane, and N,N-dimethylformamide, can be used. These polymerization solvents may be used alone or in combination of two or more.
또, 중합 온도는, 중합 속도의 관점에서 0 ∼ 110 ℃ 가 바람직하다.Moreover, the polymerization temperature is preferably 0 to 110°C from the viewpoint of the polymerization rate.
상기 리빙 라디칼 중합 아크릴계 폴리머는, 분자량의 바람직한 하한이 50 만, 보다 바람직한 하한이 80 만, 바람직한 상한이 150 만, 보다 바람직한 상한이 120 만이다. 상기 리빙 라디칼 중합 아크릴계 폴리머의 분자량이 상기 범위임으로써, 상기 가열 후의 대수 접촉각과 상기 전단 저장 탄성률을 상기 범위로 조절하기 쉽게 할 수 있다.The living radical polymerization acrylic polymer has a preferable lower limit of molecular weight of 500,000, a more preferable lower limit of 800,000, a preferable upper limit of 1.5 million, and a more preferable upper limit of 1.2 million. When the molecular weight of the living radical polymerization acrylic polymer is within the above range, it is possible to easily adjust the logarithmic contact angle after heating and the shear storage modulus within the above range.
상기 실리콘계 그래프트 공중합체는, 가교성 관능기를 갖는 한, 특별히 한정되지 않는다. 가교성 관능기는, 그래프트 사슬에 존재해도 되고, 주사슬에 존재해도 되고, 그래프트 사슬 및 주사슬에 존재해도 된다.The silicone-based graft copolymer is not particularly limited as long as it has a crosslinkable functional group. The crosslinkable functional group may exist in a graft chain, may exist in a main chain, and may exist in a graft chain and a main chain.
피착체에 대한 오염을 저감시키는 관점에서, 상기 실리콘계 그래프트 공중합체는, 극성 관능기 함유 모노머, 및 실리콘 매크로 모노머에서 유래하는 구조 단위를 함유하는 것이 바람직하다. 피착체에 대한 오염을 저감시키는 관점에서, 상기 실리콘계 그래프트 공중합체는, 실리콘을 갖는 측사슬을 갖는 그래프트 공중합체인 것이 바람직하다. 상기 극성 관능기 함유 모노머로는, 하이드록실기 함유 모노머, 아미노기 함유 모노머, 하이드록실기 함유 모노머를 들 수 있다. 그 중에서도, 점착력의 제어를 실시하기 쉬운 관점에서, 극성 관능기 함유 모노머는 카르복실기 함유 모노머인 것이 바람직하다.From the viewpoint of reducing contamination to an adherend, the silicone graft copolymer preferably contains a polar functional group-containing monomer and a structural unit derived from a silicone macromonomer. From the viewpoint of reducing contamination to an adherend, the silicone-based graft copolymer is preferably a graft copolymer having a side chain having silicone. Examples of the polar functional group-containing monomer include a hydroxyl group-containing monomer, an amino group-containing monomer, and a hydroxyl group-containing monomer. Among them, it is preferable that the polar functional group-containing monomer is a carboxyl group-containing monomer from the viewpoint of easy control of adhesive force.
상기 극성 관능기 함유 모노머가 카르복실기 함유 모노머인 경우, 초기 점착력과 가열 후의 점착력을 더욱 양화 (良化) 할 수 있는 관점에서, 상기 실리콘계 그래프트 공중합체는, 바람직하게는 0.1 중량％ 이상, 바람직하게는 90 중량％ 이하의 카르복실기 함유 모노머를 함유하는 혼합 모노머를 공중합하여 이루어지는 것인 것이 바람직하다. 상기 카르복실기 함유 모노머의 함유량은, 보다 바람직하게는 0.5 중량％ 이상, 더욱 바람직하게는 1 중량％ 이상이다. 또, 상기 카르복실기 함유 모노머의 함유량은, 보다 바람직하게는 80 중량％ 이하, 더욱 바람직하게는 70 중량％ 이하이며, 보다 더 바람직하게는 60 중량％ 이하, 특히 바람직하게는 50 중량％ 이하, 특히 바람직하게는 40 중량％ 이하, 특히 바람직하게는 30 중량％ 이하, 매우 바람직하게는 20 중량％ 이하이다.When the polar functional group-containing monomer is a carboxyl group-containing monomer, the silicone-based graft copolymer is preferably 0.1% by weight or more, preferably 90 from the viewpoint of further improving the initial adhesive strength and the adhesive strength after heating. It is preferable that it is obtained by copolymerizing a mixed monomer containing not more than a weight% carboxyl group-containing monomer. The content of the carboxyl group-containing monomer is more preferably 0.5% by weight or more, and still more preferably 1% by weight or more. Further, the content of the carboxyl group-containing monomer is more preferably 80% by weight or less, still more preferably 70% by weight or less, even more preferably 60% by weight or less, particularly preferably 50% by weight or less, particularly preferably It is preferably 40% by weight or less, particularly preferably 30% by weight or less, and very preferably 20% by weight or less.
본 발명의 바람직한 실시양태에 있어서, 상기 실리콘계 그래프트 공중합체는, 카르복실기 함유 모노머 (카르복실산 함유 모노머) 0.1 ∼ 2.5 중량％, 실리콘 매크로 모노머 1 ∼ 90 중량％ 를 함유하는 혼합 모노머를 공중합하여 이루어지는 것인 것이 바람직하다.In a preferred embodiment of the present invention, the silicone graft copolymer is obtained by copolymerizing a mixed monomer containing 0.1 to 2.5% by weight of a carboxyl group-containing monomer (carboxylic acid-containing monomer) and 1 to 90% by weight of a silicone macromonomer. It is preferable to be.
카르복실기 함유 모노머는, 실리콘계 그래프트 공중합체의 가교성 관능기의 기초가 되는 것으로, 상기 범위의 함유량으로 배합함으로써, 가교제를 개재하여 실리콘계 그래프트 공중합체와 점착제를 결합시킬 수 있어, 피착체의 오염을 억제할 수 있다. 실리콘 매크로 모노머는, 실리콘계 그래프트 공중합체에 블리드제로서의 성능을 부여하는 것으로, 상기 범위의 함유량으로 배합함으로써 고온에 의한 접착 항진을 저감시킬 수 있다. 특히, 상기 점착제와, 상기 가교제와, 상기 혼합 모노머를 공중합하여 이루어지는 실리콘계 그래프트 공중합체를 사용함으로써, 보다 더 고온에 의한 접착 항진을 저감시킬 수 있어, 피착체의 오염을 억제할 수 있다. 또한, 상기 가열 후의 대수 접촉각을 상기 범위로 조절하기 위해서는, 카르복실기 함유 모노머의 함유량이 특히 중요하다. 카르복실기 함유 모노머가 0.1 중량％ 이상이면, 얻어지는 실리콘계 그래프트 공중합체가 점착제와 충분히 결합할 수 있다. 카르복실기 함유 모노머가 2.5 중량％ 이하이면, 점착제와의 결합에 사용되지 않는 카르복실기가 감소함으로써 점착제층 표면이 친수적이 되는 것을 억제할 수 있기 때문에, 가열 후의 대수 접촉각을 상기 범위로 조정하기 쉬워, 접착 항진을 저감시킬 수 있다. 상기의 관점에서 상기 카르복실기 함유 모노머의 함유량의 보다 바람직한 하한은 1.0 중량％, 더욱 바람직한 하한은 1.5 중량％, 보다 바람직한 상한은 2.0 중량％, 더욱 바람직한 상한은 1.7 중량％ 이다. 또, 가열 후의 대수 접촉각을 상기 범위로 하여 보다 접착 항진을 저감시키는 관점에서, 상기 실리콘 매크로 모노머의 함유량의 보다 바람직한 하한은 2 중량％ 이다. 상기 실리콘 매크로 모노머의 함유량의 더욱 바람직한 하한은 2.5 중량％, 보다 더 바람직한 하한은 3 중량％, 특히 바람직한 하한은 3.5 중량％, 특히 바람직한 하한은 4 중량％, 매우 바람직한 하한은 4.5 중량％, 가장 바람직한 하한은 5 중량％ 이다. 상기 실리콘 매크로 모노머의 함유량의 보다 바람직한 상한은 80 중량％, 더욱 바람직한 상한은 60 중량％, 보다 더 바람직한 상한은 50 중량％, 특히 바람직한 상한은 40 중량％, 특히 바람직한 상한은 30 중량％, 매우 바람직한 상한은 25 중량％, 가장 바람직한 상한은 20 중량％ 이다.The carboxyl group-containing monomer is the basis for the crosslinkable functional group of the silicone-based graft copolymer, and by blending in an amount within the above range, the silicone-based graft copolymer and the adhesive can be bonded to each other through a crosslinking agent, thereby suppressing contamination of the adherend. I can. The silicone macromonomer imparts the performance as a bleed agent to the silicone-based graft copolymer, and by blending it in an amount within the above range, it is possible to reduce adhesion enhancement due to high temperature. In particular, by using a silicone-based graft copolymer obtained by copolymerizing the pressure-sensitive adhesive, the crosslinking agent, and the mixed monomer, it is possible to reduce adhesion enhancement due to higher temperatures, and thus to suppress contamination of the adherend. Further, in order to adjust the logarithmic contact angle after heating within the above range, the content of the carboxyl group-containing monomer is particularly important. When the carboxyl group-containing monomer is 0.1% by weight or more, the resulting silicone-based graft copolymer can be sufficiently bonded to the pressure-sensitive adhesive. If the carboxyl group-containing monomer is 2.5% by weight or less, it is possible to suppress the surface of the pressure-sensitive adhesive layer from becoming hydrophilic by reducing the carboxyl group not used for bonding with the pressure-sensitive adhesive, so it is easy to adjust the logarithmic contact angle after heating to the above range, and adhesion is promoted. Can be reduced. From the above viewpoint, a more preferable lower limit of the content of the carboxyl group-containing monomer is 1.0% by weight, a further preferable lower limit is 1.5% by weight, a more preferable upper limit is 2.0% by weight, and a further preferable upper limit is 1.7% by weight. In addition, from the viewpoint of further reducing adhesion promotion by making the logarithmic contact angle after heating within the above range, a more preferable lower limit of the content of the silicone macromonomer is 2% by weight. A more preferable lower limit of the content of the silicone macromonomer is 2.5% by weight, a more preferable lower limit is 3% by weight, a particularly preferable lower limit is 3.5% by weight, a particularly preferable lower limit is 4% by weight, a very preferable lower limit is 4.5% by weight, the most preferable The lower limit is 5% by weight. A more preferable upper limit of the content of the silicone macromonomer is 80% by weight, a more preferable upper limit is 60% by weight, an even more preferable upper limit is 50% by weight, a particularly preferable upper limit is 40% by weight, a particularly preferable upper limit is 30% by weight, very preferable The upper limit is 25% by weight, and the most preferable upper limit is 20% by weight.
본 발명의 바람직한 실시양태에 있어서, 상기 실리콘계 그래프트 공중합체는, 극성 관능기 함유 모노머 및 실리콘 매크로 모노머 이외에, (메트)아크릴산에스테르를 함유하는 혼합 모노머를 공중합하여 이루어지는 것이어도 된다.In a preferred embodiment of the present invention, the silicone graft copolymer may be formed by copolymerizing a mixed monomer containing a (meth)acrylic acid ester in addition to a polar functional group-containing monomer and a silicone macromonomer.
상기 (메트)아크릴산에스테르로는, 특별히 한정되지 않고, 예를 들어 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, 프로필(메트)아크릴레이트, n-부틸(메트)아크릴레이트, tert-부틸(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, n-옥틸(메트)아크릴레이트, 이소옥틸(메트)아크릴레이트, 이소노닐(메트)아크릴레이트, 이소미리스틸(메트)아크릴레이트, 스테아릴(메트)아크릴레이트 등의 (메트)아크릴산알킬에스테르나, 시클로헥실(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트, 벤질(메트)아크릴레이트, 2-부톡시에틸(메트)아크릴레이트, 2-페녹시에틸(메트)아크릴레이트, 글리시딜(메트)아크릴레이트, 테트라하이드로푸르푸릴(메트)아크릴레이트, 폴리프로필렌글리콜모노(메트)아크릴레이트 등을 들 수 있다. 이들 (메트)아크릴산에스테르는, 단독으로 사용해도 되고, 2 종 이상을 병용해도 된다.The (meth)acrylic acid ester is not particularly limited, and for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (Meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isomirystyl (meth)acrylate, (Meth)acrylate alkyl esters such as stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, 2-butoxyethyl (meth)acrylic Rate, 2-phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, polypropylene glycol mono (meth)acrylate, and the like. These (meth)acrylic acid esters may be used alone or in combination of two or more.
상기 혼합 모노머가 (메트)아크릴산에스테르를 함유하는 경우, (메트)아크릴산에스테르의 함유량은, 바람직하게는 1 중량％ 이상, 바람직하게는 99 중량％ 이하이다. 상기 (메트)아크릴산에스테르의 함유량은, 보다 바람직하게는 5 중량％ 이상, 더욱 바람직하게는 7.5 중량％ 이상, 보다 더 바람직하게는 10 중량％ 이상이고, 보다 바람직하게는 95 중량％ 이하, 더욱 바람직하게는 90 중량％ 이하, 보다 더 바람직하게는 80 중량％ 이하이다.When the mixed monomer contains a (meth)acrylic acid ester, the content of the (meth)acrylic acid ester is preferably 1% by weight or more, and preferably 99% by weight or less. The content of the (meth)acrylic acid ester is more preferably 5% by weight or more, still more preferably 7.5% by weight or more, even more preferably 10% by weight or more, more preferably 95% by weight or less, still more preferably It is preferably 90% by weight or less, and even more preferably 80% by weight or less.
상기 실리콘계 그래프트 공중합체의 가교성 관능기로는, 상기 점착제의 가교성 관능기와 동일한 것을 사용할 수 있다. 또, 상기 실리콘계 그래프트 공중합체의 가교성 관능기는, 상기 점착제의 가교성 관능기와 동일해도 되고 상이해도 된다.As the crosslinkable functional group of the silicone-based graft copolymer, the same crosslinkable functional group of the pressure-sensitive adhesive may be used. In addition, the crosslinkable functional group of the silicone-based graft copolymer may be the same as or different from the crosslinkable functional group of the pressure-sensitive adhesive.
상기 실리콘 매크로 모노머는 중량 평균 분자량이 500 이상인 것이 바람직하고, 1000 이상인 것이 보다 바람직하다.The silicone macromonomer preferably has a weight average molecular weight of 500 or more, and more preferably 1000 or more.
실리콘 매크로 모노머의 중량 평균 분자량이 상기 하한 이상임으로써, 실리콘계 그래프트 공중합체에 의해 형성되는 소수적인 표면층이 두꺼워지는 점에서, 접착 항진을 보다 저감시킬 수 있다. 동일한 관점에서 상기 실리콘 매크로 모노머의 중량 평균 분자량의 보다 바람직한 상한은 50000 이고, 통상 20000 이하이다.When the weight average molecular weight of the silicone macromonomer is greater than or equal to the above lower limit, the hydrophobic surface layer formed by the silicone-based graft copolymer is thickened, and thus adhesion enhancement can be further reduced. From the same viewpoint, a more preferable upper limit of the weight average molecular weight of the silicone macromonomer is 50000, and usually 20000 or less.
상기 실리콘계 그래프트 공중합체는, 피착체의 오염 억제, 초기 점착력 및 가열 후 점착력의 제어의 관점에서, 산가가 바람직하게는 0.5 ㎎KOH/g 이상, 보다 바람직하게는 1 ㎎KOH/g 이상, 더욱 바람직하게는 3 ㎎KOH/g 이상, 특히 바람직하게는 5 ㎎KOH/g 이상, 가장 바람직하게는 10 ㎎KOH/g 이상이다. 또, 상기 산가가, 바람직하게는 22 ㎎KOH/g 이하, 보다 바람직하게는 20 ㎎KOH/g 이하, 더욱 바람직하게는 19 ㎎KOH/g 이하이다.The silicone-based graft copolymer has an acid value of preferably 0.5 mgKOH/g or more, more preferably 1 mgKOH/g or more, even more preferably from the viewpoint of suppression of contamination of the adherend, control of initial adhesion and adhesion after heating. Preferably it is 3 mgKOH/g or more, particularly preferably 5 mgKOH/g or more, and most preferably 10 mgKOH/g or more. Further, the acid value is preferably 22 mgKOH/g or less, more preferably 20 mgKOH/g or less, and still more preferably 19 mgKOH/g or less.
상기 실리콘 매크로 모노머로는, 측사슬에 실록산 결합 함유기를 갖는 모노머이면 되고, 예를 들어, 실리콘기 함유 아크릴계 모노머, 실록산 결합 함유 스티렌계 모노머 등을 들 수 있다. 그 중에서도, 내열성, 내후성이 우수한 점에서, 실록산 결합 함유 아크릴계 모노머가 바람직하다. 상기 실록산 결합 함유 아크릴계 모노머로는, 예를 들어, 이하의 일반식 (1) 또는 일반식 (2) 와 같은 구조식을 갖는 모노머를 들 수 있다.The silicone macromonomer may be a monomer having a siloxane bond-containing group in the side chain, and examples thereof include a silicone group-containing acrylic monomer, a siloxane bond-containing styrene monomer, and the like. Among them, a siloxane bond-containing acrylic monomer is preferable from the viewpoint of excellent heat resistance and weather resistance. As the siloxane bond-containing acrylic monomer, a monomer having a structural formula such as the following general formula (1) or general formula (2) can be mentioned, for example.
[화학식 1][Formula 1]
여기서, R 은 (메트)아크릴로일기 함유 관능기를 나타내고, X 및 Y 는, 각각 독립적으로, 0 이상의 정수를 나타내고, 통상 5000 이하, 특히 500 이하의 정수를 나타낸다.Here, R represents a (meth)acryloyl group-containing functional group, and X and Y each independently represent an integer of 0 or more, and usually 5000 or less, particularly 500 or less.
본 발명의 실리콘계 그래프트 공중합체의 원료 모노머 중에 있어서의 상기 실리콘 매크로 모노머의 함유량은, 1 중량％ 이상 90 중량％ 이하인 것이 바람직하다. 실리콘 매크로 모노머의 함유량이 상기 범위임으로써, 고온하에서의 접착 항진을 보다 억제할 수 있다. 고온하에서의 접착 항진을 더욱 억제하는 관점에서, 상기 실리콘 매크로 모노머의 함유량의 보다 바람직한 하한은 5 중량％, 더욱 바람직한 하한은 10 중량％, 보다 바람직한 상한은 80 중량％, 더욱 바람직한 상한은 60 중량％ 이다.It is preferable that the content of the silicone macromonomer in the raw material monomer of the silicone graft copolymer of the present invention is 1% by weight or more and 90% by weight or less. When the content of the silicone macromonomer is within the above range, the adhesion promotion under high temperature can be further suppressed. From the viewpoint of further suppressing adhesion promotion under high temperature, a more preferable lower limit of the content of the silicone macromonomer is 5% by weight, a more preferable lower limit is 10% by weight, a more preferable upper limit is 80% by weight, and a further preferable upper limit is 60% by weight. .
상기 카르복실기 함유 모노머 및 상기 실리콘 매크로 모노머 이외의 모노머로는 예를 들어, (메트)아크릴산에스테르를 들 수 있다. 또, 수산기, 아미노기, 아미드기 및 니트릴기 등의 다른 극성 관능기를 갖는 아크릴계 모노머도 사용할 수 있다. 또한, 상기 아크릴계 모노머에 추가하여, 비닐 화합물을 모노머로서 사용해도 된다.As a monomer other than the said carboxyl group-containing monomer and said silicone macromonomer, (meth)acrylic acid ester is mentioned, for example. In addition, acrylic monomers having other polar functional groups such as a hydroxyl group, an amino group, an amide group and a nitrile group can also be used. Further, in addition to the acrylic monomer, a vinyl compound may be used as a monomer.
상기 실리콘계 그래프트 공중합체는, 중량 평균 분자량이 40 만 이하인 것이 바람직하다.The silicone-based graft copolymer preferably has a weight average molecular weight of 400,000 or less.
실리콘계 그래프트 공중합체의 중합 평균 분자량이 40 만 이하이면, 점착제층 내에서 움직이기 쉬워지는 점에서, 실리콘계 그래프트 공중합체가 점착제층 표면에 모이기 쉬워져, 접착 항진을 보다 저감시킬 수 있다. 상기 실리콘계 그래프트 공중합체의 중합 평균 분자량의 보다 바람직한 상한은 30 만, 더욱 바람직한 상한은 25 만, 특히 바람직한 상한은 20 만이고, 통상 1 만 이상이다.When the polymerization average molecular weight of the silicone-based graft copolymer is 400,000 or less, the silicone-based graft copolymer tends to accumulate on the surface of the pressure-sensitive adhesive layer because it becomes easy to move in the pressure-sensitive adhesive layer, and adhesion promotion can be further reduced. A more preferable upper limit of the polymerization average molecular weight of the silicone-based graft copolymer is 300,000, a more preferable upper limit is 250,000, and a particularly preferable upper limit is 200,000, and is usually 10,000 or more.
상기 실리콘계 그래프트 공중합체의 함유량은, 상기 점착제 100 중량부에 대해 0.1 ∼ 30 중량부인 것이 바람직하다.The content of the silicone graft copolymer is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the pressure-sensitive adhesive.
실리콘계 그래프트 공중합체의 함유량이 0.1 중량부 이상임으로써, 접착 항진을 보다 저감시킬 수 있다. 실리콘계 그래프트 공중합체의 함유량이 30 중량부 이하임으로써, 실리콘계 그래프트 공중합체가 점착제와 충분히 결합할 수 있어, 피착체의 오염을 보다 억제할 수 있다. 동일한 관점에서, 점착제 100 중량부에 대한 상기 실리콘계 그래프트 공중합체의 함유량의 보다 바람직한 하한은 0.5 중량부, 더욱 바람직한 하한은 1 중량부, 보다 바람직한 상한은 10 중량부, 더욱 바람직한 상한은 5 중량부이다.When the content of the silicone-based graft copolymer is 0.1 parts by weight or more, the adhesion promotion can be further reduced. When the content of the silicone-based graft copolymer is 30 parts by weight or less, the silicone-based graft copolymer can be sufficiently bonded with the pressure-sensitive adhesive, and contamination of the adherend can be further suppressed. From the same viewpoint, a more preferable lower limit of the content of the silicone-based graft copolymer relative to 100 parts by weight of the pressure-sensitive adhesive is 0.5 parts by weight, a more preferable lower limit is 1 part by weight, a more preferable upper limit is 10 parts by weight, and a more preferable upper limit is 5 parts by weight. .
상기 가교제는, 상기 점착제와 상기 실리콘계 그래프트 공중합체가 갖는 가교성 관능기와 결합할 수 있는 것을 적절히 선택할 수 있다. 상기 가교제로는, 예를 들어, 에폭시계 가교제, 이소시아네이트계 가교제 등을 들 수 있다. 그 중에서도, 상기 전단 저장 탄성률의 범위로의 조절이 용이한 점에서, 에폭시계 가교제가 바람직하다.The crosslinking agent may be appropriately selected from those capable of bonding with the crosslinkable functional group of the pressure-sensitive adhesive and the silicone-based graft copolymer. Examples of the crosslinking agent include an epoxy crosslinking agent and an isocyanate crosslinking agent. Among them, an epoxy-based crosslinking agent is preferable because it is easy to adjust to the range of the shear storage modulus.
상기 점착제 100 중량부에 대한 상기 가교제의 함유량은, 바람직한 하한이 0.5 중량부, 보다 바람직한 하한이 1 중량부, 바람직한 상한이 5 중량부, 보다 바람직한 상한이 3 중량부이다. 상기 가교제의 함유량이 상기 범위임으로써, 상기 점착제와 상기 실리콘계 그래프트 공중합체를 충분히 가교시킬 수 있어, 상기 가열 후의 대수 접촉각과 상기 전단 저장 탄성률을 상기 범위로 조절하기 쉽게 할 수 있다.As for the content of the crosslinking agent with respect to 100 parts by weight of the pressure-sensitive adhesive, a preferable lower limit is 0.5 parts by weight, a more preferable lower limit is 1 part by weight, a preferable upper limit is 5 parts by weight, and a more preferable upper limit is 3 parts by weight. When the content of the crosslinking agent is within the above range, the pressure-sensitive adhesive and the silicone-based graft copolymer can be sufficiently crosslinked, so that the logarithmic contact angle after heating and the shear storage modulus can be easily adjusted within the above range.
상기 점착제층은, 흄드 실리카 등의 무기 필러, 가소제, 수지, 계면 활성제, 왁스, 미립자 충전제, 산화 방지제, 가스 발생제 등의 공지된 첨가제를 함유해도 된다.The pressure-sensitive adhesive layer may contain known additives such as inorganic fillers such as fumed silica, plasticizers, resins, surfactants, waxes, particulate fillers, antioxidants, and gas generators.
상기 점착제층의 두께는 특별히 한정되지 않지만, 하한이 5 ㎛, 상한이 100 ㎛ 인 것이 바람직하다. 점착제층의 두께가 상기 범위이면 충분한 점착력으로 피착체에 첩부할 수 있고, 또한 박리시의 풀 잔존을 억제할 수도 있다. 상기 점착제층의 두께의 보다 바람직한 하한은 10 ㎛, 보다 바람직한 상한은 60 ㎛ 이다.The thickness of the pressure-sensitive adhesive layer is not particularly limited, but it is preferable that the lower limit is 5 µm and the upper limit is 100 µm. When the thickness of the pressure-sensitive adhesive layer is within the above range, it can be affixed to the adherend with sufficient adhesive force, and the remaining of the glue upon peeling can be suppressed. A more preferable lower limit of the thickness of the pressure-sensitive adhesive layer is 10 µm, and a more preferable upper limit is 60 µm.
본 발명의 일 실시양태인 점착 테이프를 제조하는 방법은 특별히 한정되지 않고, 종래 공지된 방법을 사용할 수 있다. 예를 들어, 이형 처리를 실시한 필름 상에 상기 점착제 성분의 용액을 도공, 건조시킴으로써 제조할 수 있다.A method of manufacturing the adhesive tape according to an embodiment of the present invention is not particularly limited, and a conventionally known method may be used. For example, it can be produced by coating and drying a solution of the pressure-sensitive adhesive component on a film subjected to a release treatment.
본 발명의 일 실시양태인 점착 테이프의 용도는 특별히 한정되지 않지만, 예를 들어, 반도체 칩, 표시 장치 (OLED, 액정 표시 장치 등) 등의 전자 부품의 제조 등을 들 수 있는데, 고온에 의한 접착 항진을 저감시킬 수 있고, 불투명한 재료에도 적용할 수 있는 점에서, 반도체 칩 등의 전자 부품의 제조에 있어서의 보호 테이프로서 특히 바람직하게 사용할 수 있다.The use of the adhesive tape, which is an embodiment of the present invention, is not particularly limited, but includes, for example, the manufacture of electronic components such as semiconductor chips and display devices (OLED, liquid crystal display devices, etc.). It can be used particularly preferably as a protective tape in the manufacture of electronic components such as semiconductor chips, since it can reduce the acceleration and can be applied to opaque materials.
본 발명의 다른 실시양태에 있어서는, 전자 부품의 제조에 있어서의 상기 점착 테이프의 사용도 제공된다. 특히 불투명한 재료를 사용하는 전자 부품, 예를 들어 반도체 칩의 제조에 있어서, 상기 점착 테이프는 보호 테이프로서 유리하게 사용할 수 있다.In another embodiment of the present invention, the use of the adhesive tape in manufacturing an electronic component is also provided. In particular, in the manufacture of electronic components using opaque materials, for example semiconductor chips, the adhesive tape can be advantageously used as a protective tape.
본 발명에 의하면, 고온에 의한 접착 항진을 저감시킬 수 있음과 함께, 광을 투과시키지 않는 재료에도 사용할 수 있는 점착 테이프를 제공할 수 있다.ADVANTAGE OF THE INVENTION According to this invention, while being able to reduce adhesion promotion by high temperature, it can provide the adhesive tape which can also be used for a material which does not transmit light.
이하에 실시예를 들어 본 발명의 양태를 더욱 상세하게 설명하지만, 본 발명은 이들 실시예에만 한정되는 것은 아니다.Hereinafter, embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(점착제 A 의 합성)(Synthesis of adhesive A)
Tellurium (40 메시, 금속 텔루륨, 알드리치사 제조) 6.38 g (50 m㏖) 을 테트라하이드로푸란 (THF) 50 ㎖ 에 현탁시키고, 이것에 1.6 ㏖/ℓ 의 n-부틸리튬/헥산 용액 (알드리치사 제조) 34.4 ㎖ (55 m㏖) 를, 실온에서 천천히 적하하였다. 이 반응 용액을 금속 텔루륨이 완전히 소실될 때까지 교반하였다. 이 반응 용액에, 에틸-2-브로모-이소부틸레이트 10.7 g (55 m㏖) 을 실온에서 첨가하고, 2 시간 교반하였다. 반응 종료 후, 감압하에서 용매를 농축시키고, 계속해서 감압 증류하여, 황색 유상물의 2-메틸-2-n-부틸텔라닐-프로피온산에틸을 얻었다.Tellurium (40 mesh, metal tellurium, manufactured by Aldrich) 6.38 g (50 mmol) was suspended in 50 ml of tetrahydrofuran (THF), and 1.6 mol/L of n-butyllithium/hexane solution (Aldrich Co., Ltd.) Production) 34.4 ml (55 mmol) was slowly added dropwise at room temperature. This reaction solution was stirred until the metal tellurium disappeared completely. To this reaction solution, 10.7 g (55 mmol) of ethyl-2-bromo-isobutyrate was added at room temperature, and the mixture was stirred for 2 hours. After completion of the reaction, the solvent was concentrated under reduced pressure and then distilled under reduced pressure to obtain 2-methyl-2-n-butyltelanyl-ethyl propionate as a yellow oil.
아르곤 치환한 글로브 박스 내에서, 반응 용기 중에, 얻어진 2-메틸-2-n-부틸텔라닐-프로피온산에틸 19 ㎕, V-60 (2,2'-아조비스이소부티로니트릴, 후지 필름 와코 순약사 제조) 34 ㎎, 아세트산에틸 1 ㎖ 를 투입한 후, 반응 용기를 밀폐하고, 반응 용기를 글로브 박스로부터 꺼냈다. 계속해서, 반응 용기에 아르곤 가스를 유입시키면서, 반응 용기 내에, 표 1 에 나타내는 혼합 모노머의 합계 100 g, 중합 용매로서 아세트산에틸 66.5 g 을 투입하고, 60 ℃ 에서 20 시간 중합 반응을 실시하여, 리빙 라디칼 중합된 아크릴계 폴리머 (점착제 A) 함유 용액을 얻었다.In an argon-substituted glove box, in a reaction vessel, the obtained 2-methyl-2-n-butyltelanyl-ethyl propionate 19 µl, V-60 (2,2'-azobisisobutyronitrile, Fujifilm Wako in order Pharmacopoeia) 34 mg and 1 ml of ethyl acetate were added, the reaction vessel was sealed, and the reaction vessel was taken out from the glove box. Subsequently, while argon gas was introduced into the reaction vessel, 100 g of the total of the mixed monomers shown in Table 1 and 66.5 g of ethyl acetate were added as a polymerization solvent in the reaction vessel, and polymerization reaction was carried out at 60°C for 20 hours. A solution containing a radically polymerized acrylic polymer (adhesive A) was obtained.
이어서, 얻어진 점착제 A 함유 용액을 테트라하이드로푸란 (THF) 에 의해 50 배로 희석시켰다. 얻어진 희석액을 필터로 여과하고, 여과액을 겔 퍼미에이션 크로마토그래프에 공급하여, 샘플 유량 1 밀리리터/min, 칼럼 온도 40 ℃ 의 조건에서 GPC 측정을 실시하고, 점착제 A 의 폴리스티렌 환산 분자량을 측정하여, 중량 평균 분자량 (Mw) 및 분자량 분포 (Mw/Mn) 를 구하였다. 또한, 겔 퍼미에이션 크로마토그래프는, Waters 사 제조, 2690 Separations Model 을 사용하였다. 필터는, 폴리테트라플루오로에틸렌제, 포어 직경 0.2 ㎛ 인 것을 사용하였다. 칼럼으로는 GPC KF-806L (쇼와 전공사 제조) 을 사용하고, 검출기로는 시차 굴절계를 사용하였다.Then, the obtained adhesive A-containing solution was diluted 50 times with tetrahydrofuran (THF). The obtained diluted solution was filtered through a filter, and the filtrate was supplied to a gel permeation chromatograph, GPC measurement was performed under conditions of a sample flow rate of 1 milliliter/min and a column temperature of 40° C., and the molecular weight of the pressure-sensitive adhesive A in terms of polystyrene was measured, The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) were obtained. In addition, as a gel permeation chromatograph, the 2690 Separations Model manufactured by Waters was used. A filter made of polytetrafluoroethylene and a pore diameter of 0.2 µm was used. GPC KF-806L (made by Showa Electric Corporation) was used as a column, and a differential refractometer was used as a detector.
(점착제 B, C, F 의 합성)(Synthesis of adhesives B, C, F)
혼합 모노머의 조성을 표 1 과 같이 한 것 이외에는 점착제 A 의 합성과 동일하게 하여 점착제 B, C, F 함유 용액을 얻어, 중량 평균 분자량 (Mw) 및 분자량 분포 (Mw/Mn) 를 구하였다.Except having made the composition of the mixed monomer as shown in Table 1, a solution containing pressure-sensitive adhesives B, C, and F was obtained in the same manner as in the synthesis of the pressure-sensitive adhesive A, and the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) were calculated.
(점착제 D 의 합성)(Synthesis of adhesive D)
온도계, 교반기, 냉각관을 구비한 반응기를 준비하고, 이 반응기 내에, 모노머로서 2-에틸헥실아크릴레이트 100 중량부, 아크릴산 3 중량부, 하이드록시에틸아크릴레이트 0.1 중량부, 아세트산에틸 80 중량부를 첨가하였다. 이 반응기를 가열하여 환류를 개시하였다. 계속해서, 상기 반응기 내에, 중합 개시제로서 V-60 (2,2'-아조비스이소부티로니트릴, 후지 필름 와코 순약사 제조) 0.01 중량부를 투입하고, 60 ℃ 에서 8 시간 중합 반응을 실시하여, 점착제 D 의 아세트산에틸 용액을 얻었다. 점착제 A 의 합성과 동일하게 하여, 중량 평균 분자량 (Mw) 및 분자량 분포 (Mw/Mn) 를 구하였다.A reactor equipped with a thermometer, agitator, and a cooling tube was prepared, and as monomers, 100 parts by weight of 2-ethylhexyl acrylate, 3 parts by weight of acrylic acid, 0.1 parts by weight of hydroxyethyl acrylate, and 80 parts by weight of ethyl acetate were added to the reactor. I did. The reactor was heated to initiate reflux. Subsequently, 0.01 parts by weight of V-60 (2,2'-azobisisobutyronitrile, manufactured by Fujifilm Wako Pure Pharmaceutical Co., Ltd.) as a polymerization initiator was added into the reactor, and a polymerization reaction was performed at 60°C for 8 hours, An ethyl acetate solution of the pressure-sensitive adhesive D was obtained. It carried out similarly to the synthesis of adhesive A, and calculated|required the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn).
(점착제 E, G 의 합성)(Synthesis of adhesives E and G)
모노머의 조성을 표 1 과 같이 한 것 이외에는 점착제 C 의 합성과 동일하게 하여 점착제 E, G 의 아세트산에틸 용액을 얻어, 중량 평균 분자량 (Mw) 및 분자량 분포 (Mw/Mn) 를 구하였다.Except having made the composition of a monomer as shown in Table 1, it carried out similarly to the synthesis of the adhesive C, and obtained the ethyl acetate solution of adhesives E and G, and the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) were calculated|required.
(블리드제 A 의 합성)(Synthesis of bleed agent A)
온도계, 교반기, 냉각관을 구비한 반응기를 준비하였다. 이 반응기 내에, 모노머로서 2-에틸헥실아크릴레이트 39.9 중량부, 실리콘 매크로 모노머 (신에츠 화학사 제조, KF-2012, 메타크릴로일 변성 실리콘, 중량 평균 분자량 4600) 60 중량부, 아크릴산 0.1 중량부, n-도데칸티올 0.2 중량부, 아세트산에틸 80 중량부를 첨가하였다. 이 반응기를 가열하여 환류를 개시하였다. 계속해서, 상기 반응기 내에, 중합 개시제로서 2,2'-아조비스이소부티로니트릴 (후지 필름 와코 순약사 제조, V-60) 0.1 중량부를 첨가하고, 환류하에서 중합을 개시시켰다. 다음으로, 중합 개시로부터 1 시간 후에도, 2,2'-아조비스이소부티로니트릴 (후지 필름 와코 순약사 제조, V-60) 을 0.1 중량부씩 첨가하고, 추가로, 중합 개시로부터 6 시간 후에 2,2'-아조비스이소부티로니트릴 (후지 필름 와코 순약사 제조, V-60) 을 0.2 중량부 첨가하여 중합 반응을 계속시켰다. 그리고, 중합 개시로부터 7 시간 후에, 실리콘계 그래프트 공중합체인 블리드제 A 의 아세트산에틸 용액을 얻었다. 점착제 A 의 합성과 동일하게 하여, 중량 평균 분자량 (Mw) 및 분자량 분포 (Mw/Mn) 를 구하였다. 또, 산가는, 모노머의 주입량으로부터 산출하였다. 또한, 블리드제 A 의 유리 전이 온도 (Tg) 를, 다음의 FOX 식에 의해 구해지는 이론 계산값으로서 구하였다.A reactor equipped with a thermometer, a stirrer, and a cooling tube was prepared. In this reactor, as a monomer, 39.9 parts by weight of 2-ethylhexyl acrylate, a silicone macromonomer (manufactured by Shin-Etsu Chemical Co., Ltd., KF-2012, methacryloyl-modified silicone, weight average molecular weight 4600) 60 parts by weight, acrylic acid 0.1 parts by weight, n -0.2 parts by weight of dodecanethiol and 80 parts by weight of ethyl acetate were added. The reactor was heated to initiate reflux. Subsequently, 0.1 part by weight of 2,2'-azobisisobutyronitrile (manufactured by Fujifilm Wako Pure Pharmaceutical Co., Ltd., V-60) was added to the reactor as a polymerization initiator, and polymerization was initiated under reflux. Next, even 1 hour after the initiation of polymerization, 2,2'-azobisisobutyronitrile (manufactured by Fujifilm Wako Pure Pharmaceutical Co., Ltd., V-60) was added by 0.1 parts by weight, and further 6 hours after the polymerization initiation, 2 0.2 parts by weight of 2'-azobisisobutyronitrile (manufactured by Fujifilm Wako Pure Chemical Industries, V-60) was added, and the polymerization reaction was continued. And after 7 hours from the start of polymerization, an ethyl acetate solution of the bleed agent A which is a silicone-based graft copolymer was obtained. It carried out similarly to the synthesis of adhesive A, and calculated|required the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn). In addition, the acid value was calculated from the injection amount of the monomer. In addition, the glass transition temperature (Tg) of the bleed agent A was determined as a theoretical calculated value determined by the following FOX equation.
1/Tg ＝ W1/Tg1 ＋ W2/Tg2 ＋ ··· ＋ Wn/Tgn 1/Tg = W1/Tg1 + W2/Tg2 + ··· + Wn/Tgn
(식 중, Tg 는, 블리드제 A 의 유리 전이 온도 (K) 이고, W1, W2,···, Wn은, 각 모노머의 중량 분율이며, Tg1, Tg2,···, Tgn 은, 각 모노머의 호모폴리머의 유리 전이 온도이다). 상기 계산에 사용하는 호모폴리머의 유리 전이 온도는, 문헌에 기재되어 있는 값을 사용할 수 있다.(In the formula, Tg is the glass transition temperature (K) of the bleed agent A, W1, W2, ..., Wn are the weight fractions of each monomer, Tg1, Tg2, ..., Tgn are each monomer Is the glass transition temperature of the homopolymer). The glass transition temperature of the homopolymer used in the above calculation can be a value described in the literature.
(블리드제 B ∼ X 의 합성)(Synthesis of bleed agents B to X)
모노머의 조성을 표 2, 3 과 같이 한 것 이외에는 블리드제 A 의 합성과 동일하게 하여, 실리콘계 그래프트 공중합체인 블리드제 B ∼ X 의 아세트산에틸 용액을 얻어, 중량 평균 분자량 (Mw) 및 분자량 분포 (Mw/Mn) 를 구하였다.Except having made the composition of the monomer as shown in Tables 2 and 3, in the same manner as the synthesis of bleed agent A, ethyl acetate solutions of the bleed agents B to X, which are silicone graft copolymers, were obtained, and the weight average molecular weight (Mw) and molecular weight distribution (Mw/ Mn) was calculated.
(실시예 1)(Example 1)
얻어진 점착제 A 함유 용액에, 그 불휘발분 100 중량부에 대해 아세트산에틸을 첨가하여 교반하고, 표 4 에 나타낸 종류 및 배합량으로 블리드제 A 와 에폭시계 가교제를 첨가하고 교반하여, 불휘발분 30 중량％ 의 점착제 조성물의 아세트산에틸 용액을 얻었다.To the obtained pressure-sensitive adhesive A-containing solution, ethyl acetate was added and stirred with respect to 100 parts by weight of the non-volatile content, and a bleed agent A and an epoxy-based crosslinking agent were added and stirred in the kind and amount shown in Table 4, followed by stirring. An ethyl acetate solution of the pressure-sensitive adhesive composition was obtained.
얻어진 점착제 조성물의 아세트산에틸 용액을, 편면에 코로나 처리를 실시한 두께 50 ㎛ 의 투명한 폴리에틸렌나프탈레이트 필름의 코로나 처리면 상에, 건조 피막의 두께가 40 ㎛ 가 되도록 닥터 나이프로 도공하고, 110 ℃, 5 분간 가열하여 도공 용액을 건조시켰다. 그 후, 40 ℃, 3 일간 정치 (靜置) 양생을 실시하여, 점착 테이프를 얻었다. 또한, 에폭시계 가교제로는, 미츠비시 가스 화학사 제조, 테트라드 C 를 사용하였다.The ethyl acetate solution of the obtained pressure-sensitive adhesive composition was coated with a doctor knife so that the thickness of the dry film was 40 µm on the corona-treated side of a 50 µm-thick transparent polyethylene naphthalate film subjected to corona treatment on one side, and then, at 110°C, 5 The coating solution was dried by heating for a minute. Then, it statically cured at 40 degreeC for 3 days, and obtained the adhesive tape. In addition, as an epoxy crosslinking agent, Mitsubishi Gas Chemical Co., Ltd. product, tetrad C was used.
(25 ℃ 대수 접촉각의 측정)(Measurement of logarithmic contact angle at 25 ℃)
JIS R 3257 : 1999 에 준하여, 접촉각 측정 장치 (KSV 사 제조, CAM 200) 를 사용하여 대수 접촉각을 측정하였다.In accordance with JIS R 3257:1999, a logarithmic contact angle was measured using a contact angle measuring device (manufactured by KSV, CAM 200).
구체적으로는, 점착 테이프를 25 ㎜ 폭으로 재단하여 측정에 사용하였다. 실온 25 ℃, 습도 40 ％ 의 환경하에서 수평하게 둔 점착 테이프의 점착제층 표면에 물방울 2 ㎕ (초순수) 를 적하하였다. 적하하고 나서 5 초 후의 순수와 점착제층 표면이 이루는 각도를 대수 접촉각으로 하였다.Specifically, the adhesive tape was cut to a width of 25 mm and used for measurement. 2 µl (ultra pure water) of water droplets was added dropwise to the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape placed horizontally in an environment at room temperature of 25°C and humidity of 40%. The angle formed by the pure water 5 seconds after dripping and the surface of the pressure-sensitive adhesive layer was taken as the logarithmic contact angle.
(가열 후 대수 접촉각의 측정)(Measurement of logarithmic contact angle after heating)
점착 테이프를 25 ㎜ 폭으로 재단하였다. 재단한 점착 테이프를 유리 피착체 (마츠나미 유리 공업사 제조, 대형 슬라이드 글래스 백연마 No.2) 에 실온 23 ℃, 상대 습도 50 ％ 에서, 2 ㎏ 의 압착 고무 롤러를 사용하여 10 ㎜/SEC 의 속도로 첩부하였다. 이어서, 220 ℃, 120 분의 가열 처리를 1 회 실시하였다. 방랭 후, 점착 테이프를 유리 피착체로부터 박리하고, JIS R 3257 : 1999 에 준하여, 접촉각 측정 장치 (KSV 사 제조, CAM 200) 를 사용하여 대수 접촉각을 측정하였다.The adhesive tape was cut into 25 mm width. The cut adhesive tape was applied to a glass adherend (manufactured by Matsunami Glass Industry Co., Ltd., large-sized slide glass whitening No.2) at a room temperature of 23°C and a relative humidity of 50%, at a rate of 10 mm/SEC using a 2 kg compression rubber roller. Attached with. Subsequently, a heat treatment at 220° C. for 120 minutes was performed once. After standing to cool, the adhesive tape was peeled from the glass adherend, and the logarithmic contact angle was measured using a contact angle measuring device (manufactured by KSV, CAM 200) according to JIS R 3257:1999.
구체적으로는, 실온 25 ℃, 습도 40 ％ 의 환경하에서 수평하게 둔 점착 테이프의 점착제층 표면에 물방울 2 ㎕ (초순수) 를 적하하였다. 적하하고 나서 5 초 후의 순수와 점착제층 표면이 이루는 각도를 대수 접촉각으로 하였다.Specifically, 2 µl of water droplets (ultrapure water) was dripped on the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape placed horizontally in an environment at room temperature of 25°C and humidity of 40%. The angle formed by the pure water 5 seconds after dripping and the surface of the pressure-sensitive adhesive layer was taken as the logarithmic contact angle.
(전단 저장 탄성률의 측정)(Measurement of shear storage modulus)
동적 점탄성 측정 장치 (아이티 계측 제어사 제조, DVA-200) 를 사용하여 동적 점탄성 측정의 전단 모드, 각주파수 10 Hz, 승온 속도 5 ℃/min 로 -50 ℃ 에서 200 ℃ 까지 측정을 실시하여, 얻어진 측정값 중, 25 ℃ 에서의 저장 탄성률의 값을 측정하였다.Using a dynamic viscoelasticity measuring device (manufactured by Haiti Measurement and Control Co., Ltd., DVA-200), measurement was performed from -50°C to 200°C at a shear mode of dynamic viscoelasticity measurement, angular frequency of 10 Hz, and a heating rate of 5°C/min. Among the measured values, the value of the storage modulus at 25°C was measured.
(실시예 2 ∼ 25, 비교예 1 ∼ 12)(Examples 2 to 25, Comparative Examples 1 to 12)
사용하는 점착제, 블리드제, 가교제의 종류 및 배합량을 표 4 ∼ 6 과 같이 한 것 이외에는 실시예 1 과 동일하게 하여 점착 테이프를 제조하여, 가열 전 대수 접촉각, 가열 후 대수 접촉각 및 전단 저장 탄성률을 측정하였다. 또한, 이소시아네이트계 가교제로는 토소사 제조, 콜로네이트 L 을 사용하였다. 에폭시 변성 실리콘으로는, 신에츠 화학사 제조, X-22-163C 를 사용하였다. 또, 이소시아네이트계 가교제로는, 닛폰 폴리우레탄 공업사 제조, 콜로네이트 L45 를 사용하였다.A pressure-sensitive adhesive tape was prepared in the same manner as in Example 1, except that the type and amount of the pressure-sensitive adhesive, bleed agent, and crosslinking agent used were as shown in Tables 4-6, and the logarithmic contact angle before heating, the logarithmic contact angle after heating, and shear storage modulus were measured. I did. In addition, as an isocyanate-based crosslinking agent, Tosoh Corporation make, colonate L was used. As the epoxy-modified silicone, Shin-Etsu Chemical Co., Ltd. product, X-22-163C was used. Moreover, as an isocyanate-type crosslinking agent, the Nippon Polyurethane Industrial Co., Ltd. make, colonate L45 was used.
＜평가＞<Evaluation>
실시예 및 비교예에서 얻은 점착 테이프에 대해, 이하의 방법에 의해 평가를 실시하였다. 결과를 표 4 ∼ 6 에 나타냈다.The adhesive tapes obtained in Examples and Comparative Examples were evaluated by the following method. The results were shown in Tables 4-6.
(초기 점착력의 평가)(Evaluation of initial adhesion)
점착 테이프를 25 ㎜ 폭으로 재단하였다. 재단한 점착 테이프를 유리 피착체 (마츠나미 유리 공업사 제조, 대형 슬라이드 글래스 백연마 No.2) 에, 실온 23 ℃, 상대 습도 50 ％ 에서, 2 ㎏ 의 압착 고무 롤러를 사용하여 10 ㎜/SEC 의 속도로 첩부하였다. 30 분간 방치한 후, JIS Z 0237 에 준거하여, 표면 보호 필름을 300 ㎜/min 의 속도로 박리하여 180 도 박리 강도를 측정하고, 이것을 초기 점착력으로 하였다.The adhesive tape was cut into 25 mm width. The cut adhesive tape was applied to a glass adherend (manufactured by Matsunami Glass Co., Ltd., large-sized slide glass whitening No.2) at a room temperature of 23°C and a relative humidity of 50%, using a 2 kg crimping rubber roller of 10 mm/SEC. Attached at speed. After allowing to stand for 30 minutes, in accordance with JIS Z 0237, the surface protective film was peeled at a rate of 300 mm/min, and the 180 degree peel strength was measured, and this was used as the initial adhesive strength.
(가열 후 점착력의 평가)(Evaluation of adhesion after heating)
점착 테이프를 25 ㎜ 폭으로 재단하였다. 재단한 점착 테이프를 유리 피착체 (마츠나미 유리 공업사 제조, 대형 슬라이드 글래스 백연마 No.2) 에, 실온 23 ℃, 상대 습도 50 ％ 에서, 2 ㎏ 의 압착 고무 롤러를 사용하여 10 ㎜/SEC 의 속도로 첩부하였다. 이어서, 220 ℃, 120 분의 가열 처리를 1 회 실시하였다. 방랭 후, JIS Z 0237 에 준거하여, 표면 보호 필름을 300 ㎜/min 의 속도로 박리하여 180 도 박리 강도를 측정하고, 이것을 가열 후 점착력으로 하였다.The adhesive tape was cut into 25 mm width. The cut adhesive tape was applied to a glass adherend (manufactured by Matsunami Glass Co., Ltd., large-sized slide glass whitening No.2) at a room temperature of 23°C and a relative humidity of 50%, using a 2 kg crimping rubber roller of 10 mm/SEC. Attached at speed. Subsequently, a heat treatment at 220° C. for 120 minutes was performed once. After standing to cool, according to JIS Z 0237, the surface protection film was peeled at a rate of 300 mm/min, and the 180 degree peel strength was measured, and this was made into adhesive force after heating.
(오염성의 평가)(Evaluation of contamination)
가열 후 점착력의 측정 후의 유리판을 육안으로 관찰하고, 하기 기준으로 잔류물을 평가하였다.The glass plate after the measurement of the adhesive force after heating was visually observed, and the residue was evaluated based on the following criteria.
A : 잔류물 없음A: No residue
B : 일부에 잔류물 있음 (잔류물이 있는 부위가 차지하는 면적이 10 ％ 이하)B: There is residue in part (the area occupied by the part with residue is 10% or less)
C : 전체면에 잔류물 있음 (잔류물이 있는 부위가 차지하는 면적이 10 ％ 를 초과한다)C: There is a residue on the whole surface (the area occupied by the part with the residue exceeds 10%)
산업상 이용가능성Industrial availability
본 발명에 의하면, 고온에 의한 접착 항진을 저감시킬 수 있음과 함께, 광을 투과시키지 않는 재료에도 사용할 수 있는 점착 테이프를 제공할 수 있다.ADVANTAGE OF THE INVENTION According to this invention, while being able to reduce adhesion promotion by high temperature, it can provide the adhesive tape which can also be used for a material which does not transmit light.
Claims (11)
상기 점착제층은, 동적 점탄성 측정으로 평가한 25 ℃ 에 있어서의 전단 저장 탄성률이 4.0 × 104 ∼ 2.0 × 106 Pa 이고,
상기 점착제층은, 상기 점착 테이프의 상기 점착제층 측을 유리에 첩부하여 220 ℃ 에서 120 분간 가열하고, 박리한 후의 대수 (對水) 접촉각이 80°이상인, 점착 테이프.As an adhesive tape having an adhesive layer,
The pressure-sensitive adhesive layer has a shear storage modulus at 25° C. evaluated by dynamic viscoelasticity measurement of 4.0×10 4 to 2.0×10 6 Pa,
The pressure-sensitive adhesive layer is an adhesive tape having a logarithmic contact angle of 80° or more after affixing the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive tape to glass, heating at 220°C for 120 minutes, and peeling off.
상기 점착제층은, 상기 점착 테이프의 상기 점착제층 측을 유리에 첩부하여 220 ℃ 에서 가열하고, 박리한 후의 대수 접촉각이 110°이하인, 점착 테이프.The method of claim 1,
The pressure-sensitive adhesive layer has a logarithmic contact angle of 110° or less after affixing the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive tape to glass, heating at 220° C., and peeling off.
상기 점착제층은 25 ℃ 에 있어서의 대수 접촉각이 103°이하인, 점착 테이프.The method according to claim 1 or 2,
The adhesive tape, wherein the pressure-sensitive adhesive layer has a logarithmic contact angle of 103° or less at 25°C.
상기 점착제층을 구성하는 점착제는 비경화형 점착제인, 점착 테이프.The method of claim 1, 2 or 3,
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is a non-curable pressure-sensitive adhesive, an adhesive tape.
상기 점착제층은, 가교성 관능기를 갖는 점착제와, 가교성 관능기를 갖는 실리콘계 그래프트 공중합체와, 상기 점착제 및 상기 실리콘계 그래프트 공중합체와 반응하여 가교시킬 수 있는 가교제를 함유하는, 점착 테이프.The method of claim 1, 2, 3 or 4,
The pressure-sensitive adhesive layer contains a pressure-sensitive adhesive having a crosslinkable functional group, a silicone-based graft copolymer having a crosslinkable functional group, and a crosslinking agent capable of crosslinking by reacting with the pressure-sensitive adhesive and the silicone-based graft copolymer.
상기 실리콘계 그래프트 공중합체는, 산가가 0.5 ㎎KOH/g 이상, 20 ㎎KOH/g 이하인, 점착 테이프.The method of claim 1, 2, 3, 4 or 5,
The silicone-based graft copolymer has an acid value of 0.5 mgKOH/g or more and 20 mgKOH/g or less.
상기 실리콘계 그래프트 공중합체는, 카르복실기 함유 모노머 0.1 ∼ 2.5 중량％, 실리콘 매크로 모노머 1 ∼ 90 중량％ 를 함유하는 혼합 모노머를 공중합하여 이루어지는 것이고, 중량 평균 분자량이 40 만 이하인, 점착 테이프.The method of claim 5 or 6,
The silicone-based graft copolymer is obtained by copolymerizing a mixed monomer containing 0.1 to 2.5% by weight of a carboxyl group-containing monomer and 1 to 90% by weight of a silicone macromonomer, and having a weight average molecular weight of 400,000 or less.
상기 가교제는 에폭시계 가교제인, 점착 테이프.The method of claim 5,
The crosslinking agent is an epoxy-based crosslinking agent, adhesive tape.
상기 실리콘계 그래프트 공중합체의 함유량은, 점착제 100 중량부에 대해 0.1 ∼ 30 중량부인, 점착 테이프.The method of claim 5, 6 or 7,
The adhesive tape, wherein the content of the silicone-based graft copolymer is 0.1 to 30 parts by weight based on 100 parts by weight of the adhesive.
상기 점착제는, 분자량 분포 (Mw/Mn) 1.05 ∼ 2.5 의 아크릴계 폴리머인, 점착 테이프.The method of claim 5, 8 or 9,
The adhesive tape is an acrylic polymer having a molecular weight distribution (Mw/Mn) of 1.05 to 2.5.
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| JP6856799B1 (en) * | 2019-12-06 | 2021-04-14 | 積水化学工業株式会社 | Silicone-based graft copolymers, adhesive compositions and adhesive tapes |
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| CN104520974B (en) * | 2012-08-10 | 2016-02-10 | 积水化学工业株式会社 | The processing method of wafer |
| JP5950869B2 (en) | 2013-06-20 | 2016-07-13 | 古河電気工業株式会社 | Adhesive tape for semiconductor wafer surface protection |
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| JP2015124270A (en) * | 2013-12-26 | 2015-07-06 | 日立化成株式会社 | Temporary-fixing resin composition, temporary-fixing resin film, and temporary-fixing resin film sheet |
| KR101687062B1 (en) * | 2014-03-05 | 2016-12-15 | 제일모직주식회사 | Adhesive film and optical display comprising the same |
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