KR102339820B1 - Reactive urethane oligomer, preparation method thereof, and adhesive composition comprising same - Google Patents
Reactive urethane oligomer, preparation method thereof, and adhesive composition comprising same Download PDFInfo
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- KR102339820B1 KR102339820B1 KR1020200161635A KR20200161635A KR102339820B1 KR 102339820 B1 KR102339820 B1 KR 102339820B1 KR 1020200161635 A KR1020200161635 A KR 1020200161635A KR 20200161635 A KR20200161635 A KR 20200161635A KR 102339820 B1 KR102339820 B1 KR 102339820B1
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- KR
- South Korea
- Prior art keywords
- formula
- acrylate
- meth
- independently
- urethane oligomer
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000000853 adhesive Substances 0.000 title claims abstract description 58
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title description 16
- 238000000034 method Methods 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 74
- -1 ethylhexyl Chemical group 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 31
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 229920005992 thermoplastic resin Polymers 0.000 claims description 7
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 5
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 235000010292 orthophenyl phenol Nutrition 0.000 claims description 3
- 125000000913 palmityl 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])[H] 0.000 claims description 3
- 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 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 150000002367 halogens Chemical group 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- ZLPORNPZJNRGCO-UHFFFAOYSA-N 3-methylpyrrole-2,5-dione Chemical compound CC1=CC(=O)NC1=O ZLPORNPZJNRGCO-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000003848 UV Light-Curing Methods 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000013034 phenoxy resin Substances 0.000 description 4
- 229920006287 phenoxy resin Polymers 0.000 description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 3
- 125000006833 (C1-C5) alkylene group Chemical group 0.000 description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 3
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920003192 poly(bis maleimide) Polymers 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZEERWUUHFUFJJT-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1.CC(C)(O)C(=O)C1=CC=CC=C1 ZEERWUUHFUFJJT-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005917 3-methylpentyl group Chemical group 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 description 1
- YYJIYUNJTKCRHL-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC(=O)C=C YYJIYUNJTKCRHL-UHFFFAOYSA-N 0.000 description 1
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- AQGZJQNZNONGKY-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(N2C(C=CC2=O)=O)C=C1 AQGZJQNZNONGKY-UHFFFAOYSA-N 0.000 description 1
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- 125000003562 2,2-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003660 2,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- 125000003764 2,4-dimethylpentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical group [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 1
- YJQMXVDKXSQCDI-UHFFFAOYSA-N 2-ethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3SC2=C1 YJQMXVDKXSQCDI-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- 125000004336 3,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- GTYRFVGHYNRSKT-UHFFFAOYSA-N 3-benzylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(CC=2C=CC=CC=2)=C1 GTYRFVGHYNRSKT-UHFFFAOYSA-N 0.000 description 1
- 125000004337 3-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- SEZLVNATVKZSQO-UHFFFAOYSA-N 3-methyl-1-[3-(3-methyl-2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C(C)=CC(=O)N1C1=CC=CC(N2C(C(C)=CC2=O)=O)=C1 SEZLVNATVKZSQO-UHFFFAOYSA-N 0.000 description 1
- SMKMSUCZZOQDGA-UHFFFAOYSA-N 3-methyl-1-[4-(3-methyl-2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C(C)=CC(=O)N1C1=CC=C(N2C(C(C)=CC2=O)=O)C=C1 SMKMSUCZZOQDGA-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- DWHJJLTXBKSHJG-UHFFFAOYSA-N 5-hydroxy-2-methylpent-2-enoic acid Chemical compound OC(=O)C(C)=CCCO DWHJJLTXBKSHJG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- XWUNIDGEMNBBAQ-UHFFFAOYSA-N Bisphenol A ethoxylate diacrylate Chemical compound C=1C=C(OCCOC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCCOC(=O)C=C)C=C1 XWUNIDGEMNBBAQ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XBCFXELSWDAYIW-UHFFFAOYSA-N [4-[2-[4-(prop-2-enoyloxymethoxy)phenyl]propan-2-yl]phenoxy]methyl prop-2-enoate Chemical compound C=1C=C(OCOC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCOC(=O)C=C)C=C1 XBCFXELSWDAYIW-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- KGQLBLGDIQNGSB-UHFFFAOYSA-N benzene-1,4-diol;methoxymethane Chemical compound COC.OC1=CC=C(O)C=C1 KGQLBLGDIQNGSB-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- QDVNNDYBCWZVTI-UHFFFAOYSA-N bis[4-(ethylamino)phenyl]methanone Chemical compound C1=CC(NCC)=CC=C1C(=O)C1=CC=C(NCC)C=C1 QDVNNDYBCWZVTI-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 230000004580 weight loss Effects 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- 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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
본 발명은 반응성 우레탄 올리고머, 이의 제조방법 및 이를 포함하는 접착제 조성물을 제공하는 것으로, 본 발명의 반응성 우레탄 올리고머를 포함하는 접착제 조성물은 광학투명성 및 접착력이 매우 우수하다.The present invention provides a reactive urethane oligomer, a method for preparing the same, and an adhesive composition comprising the same, and the adhesive composition comprising the reactive urethane oligomer of the present invention has very excellent optical transparency and adhesion.
Description
본 발명은 반응성 우레탄 올리고머, 이의 제조방법 및 이를 포함하는 접착제 조성물에 관한 것이다.The present invention relates to a reactive urethane oligomer, a method for preparing the same, and an adhesive composition comprising the same.
세계적인 환경 규제강화로 인해 무용제형, 분체형, 수성형 및 자외선 경화형 등 친환경 접착제에 대한 관심이 높아지고 있다. Due to global strengthening of environmental regulations, interest in eco-friendly adhesives such as solvent-free, powder, water-based and UV-curable adhesives is increasing.
특히 자외선 경화형 접착제는 1970년대 실용화된 이후로 다양한 연구 결과들이 보고되고 있다. In particular, since the UV curing adhesive was put to practical use in the 1970s, various research results have been reported.
자외선 경화형 접착제는 순간 경화성이므로 에너지 소비가 적고, 무용제형으로 친환경적이며, 상대적으로 작은 설비 공간으로 인해 생산비용이 낮으며, 고경도이면서 투명성과 화학적 물성이 우수한 많은 장점을 가지고 있다.UV curable adhesive has many advantages such as low energy consumption because it is instant curing, eco-friendly as a solvent-free type, low production cost due to a relatively small facility space, high hardness, and excellent transparency and chemical properties.
자외선 경화형 접착제 조성물은 반응성 올리고머, 단량체, 광개시제 및 첨가제 등으로 구성된다.The UV-curable adhesive composition is composed of a reactive oligomer, a monomer, a photoinitiator and an additive.
반응성 올리고머 중의 하나로 반응성 우레탄 올리고머는 다양하고 독특한 물성을 가진다. As one of the reactive oligomers, reactive urethane oligomers have various and unique physical properties.
즉, 반응성 우레탄 올리고머는 2개의 이상의 알코올기를 가지는 폴리올과 2개 이상의 이소시아네이트기를 가지는 화합물 등이 우레탄 결합을 형성하며, 분자구조 내에는 소프트 세그먼트(soft segments)와 하드 세그먼트(hard segments)를 동시에 갖고 있어 분자길이를 자유롭게 설계할 수 있기 때문에 우수한 물성을 발현시키기가 용이하다.That is, the reactive urethane oligomer forms a urethane bond between a polyol having two or more alcohol groups and a compound having two or more isocyanate groups, and has soft segments and hard segments at the same time in the molecular structure. Because the molecular length can be freely designed, it is easy to express excellent physical properties.
또한, 우레탄 결합은 N-H, C=O 그룹으로 이루어져 있어, 피접착물에 강한 수소결합과 같은 2차 결합 등을 형성하여 접착제와 피접착제 사이의 접착력 향상을 기대할 수 있는 장점을 가진다.In addition, since the urethane bond consists of N-H and C=O groups, it forms a secondary bond such as a strong hydrogen bond to the adherend, thereby improving the adhesion between the adhesive and the adherend.
한편 현대사회에서 스마트폰, 휴대폰, 웨어러블 액세사리, 스마트 패드, 텔레비전, 데스크탑의 모니터, 네비게이션, 게임기 등 디스플레이를 구성요소로 하는 각종 전자 제품의 사용은 필수불가결한 상황이다. Meanwhile, in modern society, the use of various electronic products including displays such as smartphones, mobile phones, wearable accessories, smart pads, televisions, desktop monitors, navigation devices, and game consoles is indispensable.
또한, 각종 전자 제품은 가벼우면서도 간편한 휴대성은 필수적이며 외부의 물리적 충격에 쉽게 노출되기 때문에 내구성도 요구된다.In addition, various electronic products are required to be light and easy to carry, and durability is also required because they are easily exposed to external physical shocks.
이러한 각종 전자 제품인 스마트폰, 태블릿 PC 등과 같은 모바일 기기의 표시 장치로는 LCD 패널 또는 OLED 패널과 같은 디스플레이 패널이 사용되고, 이는 일반적으로 아크릴계 또는 에폭시 수지계 점착 수지를 통해 금속프레임에 부착되는 구조로 제공이 된다.Display panels such as LCD panels or OLED panels are used as display devices of mobile devices such as smartphones and tablet PCs, which are various electronic products, which are generally provided in a structure that is attached to a metal frame through an acrylic or epoxy resin adhesive resin. do.
이에 접착성이 우수할 뿐만 아니라 투명성 및 내구성이 우수한 접착제에 대한 요구 또한 높아지고 있는 실정이다.Accordingly, the demand for an adhesive having excellent adhesion as well as excellent transparency and durability is also increasing.
본 발명은 접착성 및 투명성이 우수하여 접착제로 유용하게 사용될 수 있는 반응성 우레탄 올리고머 및 이의 제조방법을 제공한다.The present invention provides a reactive urethane oligomer that can be usefully used as an adhesive due to excellent adhesion and transparency, and a method for preparing the same.
또한 본 발명은 본 발명의 반응성 우레탄 올리고머를 포함하는 접착제 조성물을 제공한다.The present invention also provides an adhesive composition comprising the reactive urethane oligomer of the present invention.
본 발명은 접착제로 우수한 물성을 가지는 반응성 우레탄 올리고머를 제공하는 것으로, 본 발명의 반응성 우레탄 올리고머는 하기 화학식 1로 표시된다.The present invention provides a reactive urethane oligomer having excellent physical properties as an adhesive, and the reactive urethane oligomer of the present invention is represented by the following formula (1).
[화학식 1] [Formula 1]
(상기 화학식 1에서(In Formula 1 above
R은 할로겐 또는 할로C1-C10알킬이며;R is halogen or haloC1-C10 alkyl;
A1 내지 A4는 서로 독립적으로 C1-C20알킬렌이며;A 1 to A 4 are each independently C1-C20 alkylene;
R1 및 R-2는 서로 독립적으로 수소 또는 메틸이며;R 1 and R- 2 are each independently hydrogen or methyl;
D1 및 D2는 서로 독립적으로 C1-C10알킬렌 또는 하기 구조에서 선택되는 하나이다.D 1 and D 2 are each independently selected from C1-C10 alkylene or the following structure.
상기 구조식에서, R11 내지 R21은 서로 독립적으로 C1-C10알킬이며;In the above structural formula, R 11 to R 21 are each independently C1-C10 alkyl;
p, q, s 및 t는 서로 독립적으로 0 내지 4의 정수이다.)p, q, s and t are each independently an integer from 0 to 4.)
바람직하게 본 발명의 일 실시예에 따른 화학식 1에서 R은 할로C1-C10알킬이며; A1 및 A2는 서로 독립적으로 C3-C10알킬렌이며; A3 및 A4는 서로 독립적으로 C1-C10알킬렌일 수 있다.Preferably, in Formula 1 according to an embodiment of the present invention, R is haloC1-C10 alkyl; A 1 and A 2 are each independently C3-C10 alkylene; A 3 and A 4 may independently be C1-C10 alkylene.
보다 바람직하게 본 발명의 일 실시예에 따른 화학식 1에서 D1 및 D2는 하기 구조에서 선택될 수 있다.More preferably, in Formula 1 according to an embodiment of the present invention, D 1 and D 2 may be selected from the following structures.
(상기 구조식에서, R11 내지 R17은 서로 독립적으로 C1-C5알킬이며;(In the above structural formula, R 11 to R 17 are each independently C1-C5 alkyl;
p 및 q는 서로 독립적으로 0 내지 1의 정수이다.)p and q are each independently an integer from 0 to 1.)
보다 바람직하게 본 발명의 일 실시예에 따른 화학식 1은 하기 화학식 2로 표시될 수 있다.More preferably, Chemical Formula 1 according to an embodiment of the present invention may be represented by Chemical Formula 2 below.
[화학식 2][Formula 2]
(상기 화학식 2에서(In Formula 2 above
A3 및 A4는 서로 독립적으로 C1-C20알킬렌이며;A 3 and A 4 are each independently C1-C20 alkylene;
R1 및 R-2는 서로 독립적으로 수소 또는 메틸이며;R 1 and R- 2 are each independently hydrogen or methyl;
n은 3 내지 8의 정수이다.)n is an integer from 3 to 8.)
본 발명의 일 실시예에 따른 반응성 우레탄 올리고머는 중량평균분자량이 500 내지 2500g/mol일 수 있다.The reactive urethane oligomer according to an embodiment of the present invention may have a weight average molecular weight of 500 to 2500 g/mol.
또한 본 발명은 본 발명의 반응성 우레탄 올리고머의 제조방법을 제공하는 것으로, 본 발명의 반응성 우레탄 올리고머의 제조방법은 In addition, the present invention provides a method for producing the reactive urethane oligomer of the present invention, the method for producing the reactive urethane oligomer of the present invention
촉매 존재 하 하기 화학식 11의 화합물과 하기 화학식 12의 화합물 및 하기 화학식 13의 화합물을 반응시켜 반응 혼합물을 얻는 단계 및reacting a compound of Formula 11 with a compound of Formula 12 and a compound of Formula 13 in the presence of a catalyst to obtain a reaction mixture; and
상기 반응 혼합물과 하기 화학식 14의 화합물 및 하기 화학식 15의 화합물을 반응시켜 하기 화학식 1의 반응성 우레탄 올리고머를 제조하는 단계를 포함한다. and reacting the reaction mixture with a compound of Formula 14 and a compound of Formula 15 below to prepare a reactive urethane oligomer of Formula 1 below.
[화학식 1] [Formula 1]
[화학식 11][Formula 11]
[화학식 12][Formula 12]
[화학식 13][Formula 13]
[화학식 14][Formula 14]
[화학식 15][Formula 15]
(상기 화학식 1 및 화학식 11 내지 화학식 15에서,(In Formula 1 and Formula 11 to Formula 15,
R은 할로겐 또는 할로C1-C10알킬이며;A1 내지 A4는 서로 독립적으로 C1-C20알킬렌이며;R is halogen or haloC1-C10 alkyl; A 1 to A 4 are each independently C1-C20 alkylene;
R1 및 R-2는 서로 독립적으로 수소 또는 메틸이며;R 1 and R- 2 are each independently hydrogen or methyl;
D1 및 D2는 서로 독립적으로 C1-C10알킬렌 또는 하기 구조에서 선택되는 하나이다.D 1 and D 2 are each independently selected from C1-C10 alkylene or the following structure.
상기 구조식에서, R11 내지 R21은 서로 독립적으로 C1-C10알킬이며;In the above structural formula, R 11 to R 21 are each independently C1-C10 alkyl;
p, q, s 및 t는 서로 독립적으로 0 내지 4의 정수이다.)p, q, s and t are each independently an integer from 0 to 4.)
또한 본 발명은 본 발명의 반응성 우레탄 올리고머; 희석 단량체; 및 광개시제;를 포함하는 접착제 조성물을 제공한다.In addition, the present invention is a reactive urethane oligomer of the present invention; dilute monomer; and a photoinitiator; provides an adhesive composition comprising.
본 발명의 일 실시예에 따른 희석 단량체는 반응성 우레탄 올리고머 100중량부에 대해 희석 단량체는 40 내지 90중량부로 포함되며, 상기 광개시제는 0.5 내지 10중량부로 포함될 수 있다.The diluting monomer according to an embodiment of the present invention may be included in an amount of 40 to 90 parts by weight of the diluting monomer based on 100 parts by weight of the reactive urethane oligomer, and the photoinitiator may be included in an amount of 0.5 to 10 parts by weight.
본 발명의 일 실시예에 따른 희석 단량체는 메틸(메타)아크릴레이트, 에틸(메트)아크릴레이트, 부틸(메트)아크릴레이트, 에틸헥실(메트)아크릴레이트, 이소 옥틸(메트)아크릴레이트, 이소데실(메트)아크릴레이트, 라우릴(메트)아크릴레이트, 세틸(메트)아크릴레이트, 스 테아릴(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트, 테트라하이드로퍼퓨릴(메트)아크릴레이트, 벤질(메트)아크릴레이트, 사이클로헥실(메트)아크릴레이트, 트리메틸사이클로헥실포르말(메트)아크릴레이트, o-페닐페 놀(메트)아크릴레이트, 페놀(EO)(메트)아크릴레이트, 에톡시에톡시에틸(메트)아크릴레이트, 페닐티오에틸(메트)아크릴레이트 및 쿠밀페녹실에틸(메트)아크릴레이트에서 선택되는 하나 또는 둘 이상일 수 있다.The diluting monomer according to an embodiment of the present invention is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, trimethylcyclohexyl formal (meth)acrylate, o-phenylphenol (meth)acrylate, phenol (EO) (meth)acrylate, ethoxyethoxy It may be one or two or more selected from ethyl (meth) acrylate, phenylthioethyl (meth) acrylate, and cumylphenoxyl ethyl (meth) acrylate.
본 발명의 일 실시예에 따른 접착제 조성물은 열가소성 수지, 열가소성 엘라스토머 및 도전입자에서 선택되는 하나 또는 둘 이상의 첨가제를 더 포함할 수 있다.The adhesive composition according to an embodiment of the present invention may further include one or more additives selected from a thermoplastic resin, a thermoplastic elastomer, and conductive particles.
본 발명의 반응성 우레탄 올리고머는 내열성 우수하여 접착제 조성물로 매우 유용하다.The reactive urethane oligomer of the present invention is very useful as an adhesive composition because of its excellent heat resistance.
또한 본 발명의 반응성 우레탄 올리고머의 제조방법은 간단한 공정으로 분자량 및 전이온도의 조절이 가능한 반응성 우레탄 올리고머의 제조가 가능하다.In addition, the method for preparing a reactive urethane oligomer of the present invention can prepare a reactive urethane oligomer capable of controlling molecular weight and transition temperature through a simple process.
또한 본 발명의 접착제 조성물은 본 발명의 반응성 우레탄 올리고머를 포함함으로써 내열성, 내구성 및 투명성이 우수할 뿐만 아니라 접착력 또한 매우 우수하다.In addition, the adhesive composition of the present invention includes the reactive urethane oligomer of the present invention, and thus has excellent heat resistance, durability and transparency, as well as excellent adhesion.
따라서 본 발명의 접착제 조성물은 친환경적 및 경제적으로 다양한 대상에 사용될 수 있다.Therefore, the adhesive composition of the present invention can be used for various objects environmentally and economically.
이하, 본 발명에 대하여 보다 구체적으로 설명한다. 이 때 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다.Hereinafter, the present invention will be described in more detail. If there is no other definition in the technical and scientific terms used at this time, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and may unnecessarily obscure the subject matter of the present invention in the following description. A description of possible known functions and configurations will be omitted.
본 명세서에서 사용된 용어 "알킬"은 (탄소수가 특별히 한정되지 않은 경우) 탄소수 1 내지 20, 바람직하게 탄소수 1 내지 10, 일 양태에서 바람직하게 탄소수 1 내지 5, 일 양태에서 바람직하게 탄소수 2 내지 10, 일 양태에서 바람직하게 탄소수 3 내지 8을 가진 포화된 직쇄상 또는 분지상의 비-고리(cyclic) 탄화수소를 의미한다. "저급 알킬"은 탄소수가 1 내지 7인 일 양태에서 바람직하게 탄소수 1 내지 5인 직쇄상 또는 분지상 알킬을 의미한다. 대표적인 포화 직쇄상 알킬은 -메틸, -에틸, -n-프로필, -n-부틸, -n-펜틸, -n-헥실, -n-헵틸, -n-옥틸, -n-노닐 과 -n-데실을 포함하고, 반면에 포화 분지상 알킬은 -이소프로필, -sec-부틸, -이소부틸, -tert-부틸, 이소펜틸, 2-메틸헥실, 3-메틸부틸, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 2-메틸헥실, 3-메틸헥실, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 2-메틸헥실, 3-메틸헥실, 4-메틸헥실, 5- 메틸헥실, 2,3-디메틸부틸, 2,3-디메틸펜틸, 2,4-디메틸펜틸, 2,3-디메틸헥실, 2,4-디메틸헥실, 2,5-디메틸헥실, 2,2-디메틸펜틸, 2,2-디메틸헥실, 3,3-디메틸펜틸, 3,3-디메틸헥실, 4,4-디메틸헥실, 2-에틸펜틸, 3-에틸펜틸, 2-데틸헥실, 3-에틸헥실, 4-에틸헥실, 2-메틸-2-에틸펜틸, 2-메틸-3-에틸펜틸, 2-메틸-4-에틸펜틸, 2-메틸-2-에틸헥실, 2-메틸-3-에틸헥실, 2-메틸-4-에틸헥실, 2,2-디에틸펜틸, 3,3-디에틸헥실, 2,2-디에틸헥실, 및 3,3-디에틸헥실을 포함한다.As used herein, the term "alkyl" (when the number of carbon atoms is not particularly limited) has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms in one embodiment, preferably 2 to 10 carbon atoms in one embodiment. , preferably in one aspect, refers to a saturated straight-chain or branched acyclic hydrocarbon having 3 to 8 carbon atoms. "Lower alkyl" means straight-chain or branched alkyl having 1 to 7 carbon atoms, preferably 1 to 5 carbon atoms in one aspect. Representative saturated straight chain alkyls are -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl and -n- contains decyl, whereas saturated branched alkyl is -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3- Methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5- Methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 2,2-dimethyl Pentyl, 2,2-dimethylhexyl, 3,3-dimethylpentyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 2-ethylpentyl, 3-ethylpentyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl, 2-methyl-3-ethylpentyl, 2-methyl-4-ethylpentyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2-methyl-4-ethylhexyl, 2,2-diethylpentyl, 3,3-diethylhexyl, 2,2-diethylhexyl, and 3,3-diethylhexyl.
본 명세서에서 "C1-C10"와 같이 기재될 경우 이는 탄소수가 1 내지 10개임을 의미한다. 예를 들어, C1-C10알킬은 탄소 수가 1 내지 10인 알킬을 의미한다.When described as "C1-C10" in the present specification, it means that the number of carbon atoms is 1 to 10. For example, C 1 -C 10 alkyl means alkyl having 1 to 10 carbon atoms.
본 명세서에서 사용된 용어 "할로겐" 및 "할로"는 플루오린, 클로린, 브로민 또는 아이오딘을 의미한다.As used herein, the terms “halogen” and “halo” refer to fluorine, chlorine, bromine or iodine.
본 명세서에서 사용된 용어 "할로알킬"은 하나 이상의 수소 원자가 할로겐으로 치환된 알킬 그룹을 의미한다. 바람직하게 할로알킬은 불소가 치환된 알킬일 수 있으며, 구체적으로 하나이상의 수소 원자가 불소로 치환된 알킬 그룹을 의미한다. 예를 들어, 불소가 치환된 알킬은 -CH2F, -CHF2, -CF3, 및 이와 유사한 것을 포함한다. 여기에서 알킬 및 할로겐은 위에서 정의된 바와 같다.As used herein, the term “haloalkyl” refers to an alkyl group in which one or more hydrogen atoms are replaced by halogen. Preferably, haloalkyl may be an alkyl substituted with fluorine, and specifically refers to an alkyl group in which one or more hydrogen atoms are substituted with fluorine. For example, fluorine-substituted alkyl includes -CH 2 F, -CHF 2 , -CF 3 , and the like. Alkyl and halogen herein are as defined above.
이하, 본 발명의 실시예에 따른 반응성 우레탄 올리고머, 이의 제조방법및 이를 포함하는 접착제 조성물에 대해 상세히 설명한다.Hereinafter, a reactive urethane oligomer according to an embodiment of the present invention, a method for preparing the same, and an adhesive composition comprising the same will be described in detail.
본 발명의 반응성 우레탄 올리고머는 하기 화학식 1로 표시된다.The reactive urethane oligomer of the present invention is represented by the following formula (1).
[화학식 1][Formula 1]
(상기 화학식 1에서(In Formula 1 above
R은 할로겐 또는 할로C1-C10알킬이며;R is halogen or haloC1-C10 alkyl;
A1 내지 A4는 서로 독립적으로 C1-C20알킬렌이며;A 1 to A 4 are each independently C1-C20 alkylene;
R1 및 R-2는 서로 독립적으로 수소 또는 메틸이며;R 1 and R- 2 are each independently hydrogen or methyl;
D1 및 D2는 서로 독립적으로 C1-C10알킬렌 또는 하기 구조에서 선택되는 하나이다. D 1 and D 2 are each independently selected from C1-C10 alkylene or the following structure.
상기 구조식에서, R11 내지 R21은 서로 독립적으로 C1-C10알킬이며;In the above structural formula, R 11 to R 21 are each independently C1-C10 alkyl;
p, q, s 및 t는 서로 독립적으로 0 내지 4의 정수이다.)p, q, s and t are each independently an integer from 0 to 4.)
본 발명의 일 실시예에 따른 반응성 우레탄 올리고머는 특정한 중심골격을 메틸렌으로 연결된 비스(인돌린-1,3디온)(5,5'-(methylene-2,2,diylis(isoindoline-1,3-dione))을 도입함으로써 낮은 전이온도를 가지며, 내열성이 우수하다.Reactive urethane oligomer according to an embodiment of the present invention is bis(indoline-1,3dione)(5,5'-(methylene-2,2,diylis(isoindoline-1,3-) Dione)) has a low transition temperature and excellent heat resistance.
나아가 중심골격으로 도입된 메틸렌으로 연결된 비스(인돌린-1,3디온)의 질소에 치환된 알킬렌기의 탄소수를 조절함으로써 분자량의 조절이 가능하며, 따라서 본 발명의 반응성 우레탄 올리고머는 낮은 전이온도 및 우수한 내열성을 가질 수 있다.Furthermore, the molecular weight can be controlled by controlling the number of carbon atoms of the alkylene group substituted with the nitrogen of the methylene-linked bis(indoline-1,3-dione) introduced into the central skeleton. Therefore, the reactive urethane oligomer of the present invention has a low transition temperature and It may have excellent heat resistance.
바람직하게 본 발명의 일 실시예에 따른 화학식 1에서 R은 할로C1-C10알킬이며; A1 및 A2는 서로 독립적으로 C3-C10알킬렌이며; A3 및 A4는 서로 독립적으로 C1-C10알킬렌일 수 있으며, 좋기로는 R은 할로C1-C5알킬이며; A1 및 A2는 서로 독립적으로 C3-C10알킬렌이며; A3 및 A4는 서로 독립적으로 C1-C5알킬렌일 수 있으며, 보다 좋기로는 R은 플루오로C1-C5알킬이며; A1 및 A2는 서로 독립적으로 C3-C8알킬렌이며; A3 및 A4는 서로 독립적으로 C1-C5알킬렌일 수 있다.Preferably, in Formula 1 according to an embodiment of the present invention, R is haloC1-C10 alkyl; A 1 and A 2 are each independently C3-C10 alkylene; A 3 and A 4 may independently of each other be C 1 -C 10 alkylene, preferably R is haloC 1 -C 5 alkyl; A 1 and A 2 are each independently C3-C10 alkylene; A 3 and A 4 may independently of each other be C 1 -C 5 alkylene, more preferably R is fluoroC 1 -C 5 alkyl; A 1 and A 2 are each independently C3-C8 alkylene; A 3 and A 4 may independently be C1-C5 alkylene.
바람직하게 본 발명의 일 실시예에 따른 화학식 1에서 D1 및 D2는 하기 구조에서 선택될 수 있다. Preferably, in Formula 1 according to an embodiment of the present invention, D 1 and D 2 may be selected from the following structures.
상기 구조식에서, R11 내지 R21은 서로 독립적으로 C1-C10알킬이며;In the above structural formula, R 11 to R 21 are each independently C1-C10 alkyl;
p, q, s 및 t는 서로 독립적으로 0 내지 1의 정수이다.)p, q, s and t are each independently an integer from 0 to 1.)
보다 바람직하게 본 발명의 일 실시예에 따른 화학식 1에서 D1 및 D2는 
바람직하게 본 발명의 일 실시예에 따른 화학식 1은 하기 화학식 1-1로 표시될 수 있다.Preferably, Chemical Formula 1 according to an embodiment of the present invention may be represented by the following Chemical Formula 1-1.
[화학식 1-1] [Formula 1-1]
(상기 화학식 1-1에서,(In Formula 1-1,
R은 할로겐 또는 할로C1-C10알킬이며;R is halogen or haloC1-C10 alkyl;
A1 및 A3는 서로 독립적으로 C1-C20알킬렌이며;A 1 and A 3 are each independently C1-C20 alkylene;
R1은 수소 또는 메틸이며;R 1 is hydrogen or methyl;
D1은 C1-C10알킬렌 또는 하기 구조에서 선택되는 하나이다. D 1 is C1-C10 alkylene or one selected from the following structures.
상기 구조식에서, R11 내지 R21은 서로 독립적으로 C1-C10알킬이며;In the above structural formula, R 11 to R 21 are each independently C1-C10 alkyl;
p, q, s 및 t는 서로 독립적으로 0 내지 4의 정수이다.)p, q, s and t are each independently an integer from 0 to 4.)
바람직하게 본 발명의 일 실시예에 따른 화학식 1-1에서 R은 할로C1-C10알킬이며; A1 및 A3는 서로 독립적으로 C1-C10알킬렌이며; R1은 수소 또는 메틸이며; D1은 하기 구조에서 선택되는 하나일 수 있다.Preferably, in Formula 1-1 according to an embodiment of the present invention, R is haloC1-C10 alkyl; A 1 and A 3 are each independently C1-C10 alkylene; R 1 is hydrogen or methyl; D 1 may be one selected from the following structures.
상기 구조식에서, R11 내지 R21은 서로 독립적으로 C1-C10알킬이며;In the above structural formula, R 11 to R 21 are each independently C1-C10 alkyl;
p, q, s 및 t는 서로 독립적으로 0 내지 4의 정수이다.)p, q, s and t are each independently an integer from 0 to 4.)
보다 바람직하게 본 발명의 일 실시예에 따른 화학식 1-1에서 R은 플루오로C1-C5알킬이며; A1은 C3-C8알킬렌이며; A3은 C1-C5알킬렌이며; R1은 수소 또는 메틸이며; D1은 하기 구조에서 선택되는 하나일 수 있다.More preferably, in Formula 1-1 according to an embodiment of the present invention, R is fluoroC1-C5alkyl; A 1 is C3-C8 alkylene; A 3 is C1-C5 alkylene; R 1 is hydrogen or methyl; D 1 may be one selected from the following structures.
(상기 구조식에서, R11 내지 R17은 서로 독립적으로 C1-C5알킬이며;(In the above structural formula, R 11 to R 17 are each independently C1-C5 alkyl;
p 및 q는 서로 독립적으로 0 내지 1의 정수이다.)p and q are each independently an integer from 0 to 1.)
접착제로서 보다 우수한 물성을 가지기위한 측면에서 바람직하게 본 발명의 일 실시예에 따른 화학식 1의 반응성 우레탄 올리고머는 하기 화학식 2로 표시될 수 있다.Preferably, the reactive urethane oligomer of Chemical Formula 1 according to an embodiment of the present invention in terms of having better physical properties as an adhesive may be represented by Chemical Formula 2 below.
[화학식 2][Formula 2]
(상기 화학식 2에서(In Formula 2 above
A3 및 A4는 서로 독립적으로 C1-C20알킬렌이며;A 3 and A 4 are each independently C1-C20 alkylene;
R1 및 R-2는 서로 독립적으로 수소 또는 메틸이며;R 1 and R- 2 are each independently hydrogen or methyl;
n은 3 내지 8의 정수이다.)n is an integer from 3 to 8.)
본 발명의 일 실시예에 따른 화학식 2에서 A3 및 A4는 서로 독립적으로 C1-C10알킬렌, 바람직하게는 C2-C8알킬렌일 수 있다.In Formula 2 according to an embodiment of the present invention, A 3 and A 4 may be each independently C1-C10 alkylene, preferably C2-C8 alkylene.
본 발명의 일 실시예에 따른 반응성 우레탄 올리고머는 중량평균분자량이 500 내지 2500g/mol, 바람직하게 800 내지 2000g/mol, 보다 바람직하게 1000 내지 1500g/mol일 수 있다.The reactive urethane oligomer according to an embodiment of the present invention may have a weight average molecular weight of 500 to 2500 g/mol, preferably 800 to 2000 g/mol, and more preferably 1000 to 1500 g/mol.
또한 본 발명은 본 발명의 반응성 우레탄 올리고머의 제조방법을 제공하는 것으로, 본 발명의 반응성 우레탄 올리고머의 제조방법은,In addition, the present invention provides a method for producing the reactive urethane oligomer of the present invention, the method for producing the reactive urethane oligomer of the present invention,
촉매 존재 하 하기 화학식 11의 화합물과 하기 화학식 12의 화합물 및 하기 화학식 13의 화합물을 반응시켜 반응 혼합물을 얻는 단계 및reacting a compound of Formula 11 with a compound of Formula 12 and a compound of Formula 13 in the presence of a catalyst to obtain a reaction mixture; and
상기 반응 혼합물에 하기 화학식 14의 화합물 및 하기 화학식 15의 화합물을 반응시켜 하기 화학식 1의 반응성 우레탄 올리고머를 제조하는 단계를 포함하는 반응성 우레탄 올리고머의 제조방법.A method for preparing a reactive urethane oligomer comprising preparing a reactive urethane oligomer of the following Chemical Formula 1 by reacting a compound of the following Chemical Formula 14 and a compound of the following Chemical Formula 15 with the reaction mixture.
[화학식 1] [Formula 1]
[화학식 11][Formula 11]
[화학식 12][Formula 12]
[화학식 13][Formula 13]
[화학식 14][Formula 14]
[화학식 15][Formula 15]
(상기 화학식 1 및 화학식 11 내지 화학식 15에서,(In Formula 1 and Formula 11 to Formula 15,
R은 할로겐 또는 할로C1-C10알킬이며;R is halogen or haloC1-C10 alkyl;
A1 내지 A4는 서로 독립적으로 C1-C20알킬렌이며;A 1 to A 4 are each independently C1-C20 alkylene;
R1 및 R-2는 서로 독립적으로 수소 또는 메틸이며;R 1 and R- 2 are each independently hydrogen or methyl;
D1 및 D2는 서로 독립적으로 C1-C10알킬렌 또는 하기 구조에서 선택되는 하나이다. D 1 and D 2 are each independently selected from C1-C10 alkylene or the following structure.
상기 구조식에서, R11 내지 R21은 서로 독립적으로 C1-C10알킬이며;In the above structural formula, R 11 to R 21 are each independently C1-C10 alkyl;
p, q, s 및 t는 서로 독립적으로 0 내지 4의 정수이다.)p, q, s and t are each independently an integer from 0 to 4.)
본 발명의 일 실시예에 따른 반응성 우레탄 올리고머의 제조방법에서 촉매는 반응성 우레탄 올리고머의 제조에 사용될 수 있으며, 당업자가 인식가능한 촉매라면 모두 가능하나, 바람직하게 주석 촉매일 수 있으며, 구체적인 일례로 주석 (II) 2-에틸헥사노에이트일 수 있다.In the method for preparing a reactive urethane oligomer according to an embodiment of the present invention, the catalyst can be used for the preparation of the reactive urethane oligomer, and any catalyst can be recognized by those skilled in the art, but may preferably be a tin catalyst, and a specific example is tin ( II) 2-ethylhexanoate.
본 발명의 일 실시예에 따른 화학식 12의 화합물 또는 화학식 13의 화합물은 화학식 11의 화합물 1몰에 대하여 0.5 내지 1.5몰, 바람직하게 0.5 내지 1몰로 사용될 수 있으며, 화학식 14의 화합물 또는 화학식 15의 화합물 또한 화학식 11의 화합물 1몰에 대하여 0.5 내지 1.5몰, 바람직하게 0.5 내지 1몰로 사용될 수 있다.The compound of Formula 12 or the compound of Formula 13 according to an embodiment of the present invention may be used in an amount of 0.5 to 1.5 moles, preferably 0.5 to 1 mole, based on 1 mole of the compound of Formula 11, and the compound of Formula 14 or the compound of Formula 15 In addition, 0.5 to 1.5 moles, preferably 0.5 to 1 mole, may be used with respect to 1 mole of the compound of Formula 11.
바람직하게 본 발명의 일 실시예에 따른 반응성 우레탄 올리고머의 제조방법은 화학식 12의 화합물과 화학식 13의 화합물이 동일할 수 있으며, 화학식 14의 화합물과 화학식 15의 화합물이 동일할 수 있다.Preferably, in the method for preparing a reactive urethane oligomer according to an embodiment of the present invention, the compound of Formula 12 and the compound of Formula 13 may be the same, and the compound of Formula 14 and the compound of Formula 15 may be the same.
즉, 바람직하게 본 발명의 일 실시예에 따른 반응성 우레탄 올리고머의 제조방법은 촉매 존재 하 하기 화학식 21의 화합물과 하기 화학식 22의 화합물을 반응시켜 반응 혼합물을 얻는 단계 및That is, preferably, the method for preparing a reactive urethane oligomer according to an embodiment of the present invention comprises the steps of reacting a compound of the following formula (21) with a compound of the following formula (22) in the presence of a catalyst to obtain a reaction mixture;
상기 반응 혼합물에 하기 화학식 23의 화합물을 반응시켜 하기 화학식 1-1의 반응성 우레탄 올리고머를 제조하는 단계를 포함할 수 있다.It may include reacting a compound of Formula 23 with the reaction mixture to prepare a reactive urethane oligomer of Formula 1-1 below.
[화학식 1-1] [Formula 1-1]
[화학식 21][Formula 21]
[화학식 22] [Formula 22]
[화학식 23] [Formula 23]
(상기 화학식 1-1 및 화학식 21 내지 화학식 23에서,(In Formulas 1-1 and 21 to 23,
R은 할로겐 또는 할로C1-C10알킬이며;R is halogen or haloC1-C10 alkyl;
A1 내지 A2는 서로 독립적으로 C1-C20알킬렌이며;A 1 to A 2 are each independently C1-C20 alkylene;
R1은 수소 또는 메틸이며;R 1 is hydrogen or methyl;
D1은 C1-C10알킬렌 또는 하기 구조에서 선택되는 하나이다.D 1 is C1-C10 alkylene or one selected from the following structures.
상기 구조식에서, R11 내지 R21은 서로 독립적으로 C1-C10알킬이며;In the above structural formula, R 11 to R 21 are each independently C1-C10 alkyl;
p, q, s 및 t는 서로 독립적으로 0 내지 4의 정수이다.)p, q, s and t are each independently an integer from 0 to 4.)
본 발명의 일 실시예에 따른 반응성 우레탄 올리고머의 제조방법에서 반응은 한정이 있는 것은 아니나, 20 내지 60℃, 바람직하게 30 내지 50℃에서 30분 내지 4시간, 바람직하게 1시간 내지 3시간동안 수행될 수 있다.In the method for producing a reactive urethane oligomer according to an embodiment of the present invention, the reaction is not limited, but is carried out at 20 to 60° C., preferably at 30 to 50° C., for 30 minutes to 4 hours, preferably 1 hour to 3 hours. can be
또한 본 발명은 접착제 조성물을 제공하는 것으로, 본 발명의 접착제 조성물은 반응성 우레탄 올리고머, 희석 단량체 및 광개시제를 포함한다.The present invention also provides an adhesive composition, wherein the adhesive composition includes a reactive urethane oligomer, a diluent monomer and a photoinitiator.
본 발명의 일 실시예에 따른 희석 단량체는 메틸(메타)아크릴레이트, 에틸(메트)아크릴레이트, 부틸(메트)아크릴레이트, 에틸헥실(메트)아크릴레이트, 이소 옥틸(메트)아크릴레이트, 이소데실(메트)아크릴레이트, 라우릴(메트)아크릴레이트, 세틸(메트)아크릴레이트, 스 테아릴(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트, 테트라하이드로퍼퓨릴(메트)아크릴레이트, 벤질(메트)아크릴레이트, 사이클로헥실(메트)아크릴레이트, 트리메틸사이클로헥실포르말(메트)아크릴레이트, o-페닐페놀(메트)아크릴레이트, 페놀(EO)(메트)아크릴레이트, 에톡시에톡시에틸(메트)아크릴레이트, 페닐티오에틸(메트)아크릴레이트 및 쿠밀페녹실에틸(메트)아크릴레이트에서 선택되는 하나 또는 둘 이상일 수 있으며, 보다 우수한 접착력 및 투명성을 가지기 위한 측면에서 바람직하게 이소보르닐(메트)아크릴레이트, 테트라하이드로퍼퓨릴(메트)아크릴레이트 및 사이클로헥실(메트)아크릴레이트에서 선택되는 하나 또는 둘 이상일 수 있다.The diluting monomer according to an embodiment of the present invention is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, trimethylcyclohexyl formal (meth)acrylate, o-phenylphenol (meth)acrylate, phenol (EO) (meth)acrylate, ethoxyethoxyethyl It may be one or two or more selected from (meth)acrylate, phenylthioethyl (meth)acrylate and cumylphenoxylethyl (meth)acrylate, preferably isobornyl ( It may be one or two or more selected from meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and cyclohexyl (meth) acrylate.
본 발명의 일 실시예에 따른 희석 단량체는 반응성 우레탄 올리고머 100중량부에 대하여 40 내지 95중량부로 포함될 수 있으며, 바람직하게 60 내지 95중량%일 수 있다.The dilution monomer according to an embodiment of the present invention may be included in an amount of 40 to 95 parts by weight, preferably 60 to 95 parts by weight, based on 100 parts by weight of the reactive urethane oligomer.
본 발명의 일 실시예에 따른 광개시제는 광 조사에 의해 유리 라디칼을 발생시키는 것으로, 중합 또는 가교 반응을 개시시킬 수 있는 라디칼 개시제라면 모두 가능하다.The photoinitiator according to an embodiment of the present invention generates free radicals by irradiation with light, and any radical initiator capable of initiating a polymerization or crosslinking reaction is possible.
본 발명의 접착제 조성물에 있어서, 빠른 시간에 접촉이 가능하면서도 우수한 접착력을 얻기위한 측면에서 광개시제의 함유량은 본 발명의 반응성 우레탄 올리고머 100중량부에 대해 0.5 내지 10중량부, 바람직하게는 5 내지 10중량부로 포함될 수 있다. 본 발명의 일 실시예에 따른 광개시제는 예를 들면, 벤조인계, 히드록시케톤 화합물, 아미노케톤 화합물 또는 포스핀 옥시드 화합물 등과 같은 개시제를 사용할 수 있고, 예를 들면, 포스핀 옥시드 화합물 등을 사용할 수 있다. 광개시제로는, 보다 구체적으로는, 벤조인, 벤조인 메틸에테르, 벤조인 에틸에테르, 벤조인 이소프로필에테르, 벤조인 n-부틸에테르, 벤조인 이소부틸에테르, 아세토페논, 디메틸아니노 아세토페논, 2,2-디메톡시-2-페닐아세토페논, 2,2-디에톡시-2-페닐아세토페논, 2-하이드록시-2-메틸 프로피오페논(2-Hydroxy-2-methyl propiophenone), 2-히드록시-2-메틸-1-페닐프로판-1온, 1-히드록시시클로헥실페닐케톤, 2-메틸-1-[4-(메틸티오)페닐]-2-몰포리노-프로판-1-온, 4-(2-히드록시에톡시)페닐-2-(히드록시-2-프로필)케톤, 벤조페논, p-페닐벤조페논, 4,4'-디에틸아미노벤조페논, 디클로로벤조페논, 2-메틸안트라퀴논, 2-에틸안트라퀴논, 2-t-부틸안트라퀴논, 2-아미노안트라퀴논, 2-메틸티오잔톤(thioxanthone), 2-에틸티오잔톤, 2-클로로티오잔톤, 2,4-디메틸티오잔톤, 2,4-디에틸티오잔톤, 벤질디메틸케탈, 아세토페논 디메틸케탈, p-디메틸아미노 안식향산 에스테르, 올리고[2-히드록시-2-메틸-1-[4-(1-메틸비닐)페닐]프로판논], 비스(2,4,6-트리메틸벤조일)-페닐-포스핀옥시드 및 2,4,6-트리메틸벤조일-디페닐-포스핀옥시드 등이 들 수 있으나, 이에 한정이 있는 것은 아니다.In the adhesive composition of the present invention, the content of the photoinitiator is 0.5 to 10 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the reactive urethane oligomer of the present invention in terms of obtaining excellent adhesion while allowing quick contact. may be included as a part. As the photoinitiator according to an embodiment of the present invention, for example, an initiator such as a benzoin-based compound, a hydroxyketone compound, an aminoketone compound, or a phosphine oxide compound may be used. For example, a phosphine oxide compound may be used. can be used As the photoinitiator, more specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethyl anino acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl propiophenone (2-Hydroxy-2-methyl propiophenone), 2- Hydroxy-2-methyl-1-phenylpropan-1one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one , 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2 -Methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4- Dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenone dimethylketal, p-dimethylaminobenzoic acid ester, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl) )phenyl]propanone], bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, but there are limited it is not
본 발명의 일 실시예에 따른 접착제 조성물은 열가소성 수지, 열가소성 엘라스토머 및 도전입자에서 선택되는 하나 또는 둘 이상의 첨가제를 더 포함할 수 있다.The adhesive composition according to an embodiment of the present invention may further include one or two or more additives selected from a thermoplastic resin, a thermoplastic elastomer, and conductive particles.
본 발명의 일 실시예에 따른 열가소성 수지는 일례로 비스페놀 A형 페녹시 수지나 비스페놀 F형 페녹시 수지, 비스페놀 A 비스페놀 F 공중합형 페녹시 수지 등의 범용 페녹시 수지류, 폴리메타크릴레이트류, 폴리아크릴레이트류, 폴리이미드류, 폴리우레탄류, 폴리에스테르류, 폴리비닐부티랄 등을 들 수 있으며, 이들을 단독 또는 2종 이상의 조합으로 사용될 수 있다. 또한 열가소성 수지 중에는 실록산 결합이나 불소 치환기가 포함될 수도 있다. 추가 첨가되는 수지들은 함께 완전히 상용되거나 또는 마이크로 상분리가 생겨 백탁되는 상태이면 보다 바람직하게 사용할 수 있다. 열가소성 수지의 분자량은 특별히 제한을 받지 않지만, 접착제 조성물의 물성의 저하를 막고 다른 성분과의 상용성이 저하되지 않도록 중량평균 분자량으로서는 5,000 내지 150,000g/mol이 바람직하고, 10,000 내지 80,000g/mol이 보다 바람직하다. The thermoplastic resin according to an embodiment of the present invention includes, for example, general-purpose phenoxy resins such as bisphenol A phenoxy resin or bisphenol F phenoxy resin, bisphenol A bisphenol F copolymerization phenoxy resin, polymethacrylates, and polyacrylates, polyimides, polyurethanes, polyesters, polyvinyl butyral, and the like, and these may be used alone or in combination of two or more. In addition, the thermoplastic resin may contain a siloxane bond or a fluorine substituent. The additionally added resins can be used more preferably if they are completely compatible with each other or are in a cloudy state due to micro-phase separation. Although the molecular weight of the thermoplastic resin is not particularly limited, the weight average molecular weight is preferably 5,000 to 150,000 g/mol, and 10,000 to 80,000 g/mol to prevent deterioration of the physical properties of the adhesive composition and not decrease compatibility with other components. more preferably.
본 발명의 일 실시예에 따른 열가소성 엘라스토머로서는, 일례로 SBS 및 그의 에폭시 변성체나, SEBS 및 그의 변성체 등을 들 수 있으며, 이들 단독 또는 2종 이상을 조합하여 사용할 수 있다. 본 발명의 일 실시예에 따른 접착제 조성물에 있어서의 열가소성 수지 또는 열가소성 엘라스토머의 함유량은 유동성이나 접착성이 저하를 막기위한 측면에서 바람직하게 본 발명의 반응성 우레탄 올리고머 100 중량부에 대하여 20 내지 320중량부로 포함할 수 있다.As the thermoplastic elastomer according to an embodiment of the present invention, for example, SBS and its epoxy-modified product, SEBS and its modified product, etc. may be mentioned, and these may be used alone or in combination of two or more. The content of the thermoplastic resin or thermoplastic elastomer in the adhesive composition according to an embodiment of the present invention is preferably 20 to 320 parts by weight based on 100 parts by weight of the reactive urethane oligomer of the present invention in terms of preventing a decrease in fluidity or adhesion. may include
본 발명의 일 실시예에 따른 접착제 조성물은 접착제 조성물의 접속 신뢰성의 향상을 목적으로 라디칼 중합성 물질을 더 첨가할 수 있다. 라디칼 중합성 물질은 라디칼에 의해 중합시키는 관능기를 갖는 물질이고며, 일례로 (메트)아크릴레이트 수지, 말레이미드 수지, 시트라콘이미드 수지, 나디이미드 수지 등의 수지를 들 수 있다. 라디칼 중합성 물질은 단량체, 올리고머 중 어느 상태에도 사용할 수 있고, 단량체와 올리고머를 혼합하여 이용할 수도 있다. (메트)아크릴레이트 수지는 일례로, (메트)아크릴레이트를 라디칼 중합시킴으로써 얻어지는 것이다. (메트)아크릴레이트로서는, 예를 들면 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, 이소프로필(메트)아크릴레이트, 이소부 틸(메트)아크릴레이트, 에틸렌글리콜디(메트)아크릴레이트, 디에틸렌글리콜 디(메트)아크릴레이트, 트리메틸올프로판트리(메트)아크릴레이트, 테트라메틸렌글리콜테트라(메트)아크릴레이트, 2-히드록시-1,3-디아크릴옥시 프로판, 2,2-비스[4-(아크릴옥시메톡시)페닐]프로판, 2,2-비스[4-(아크릴옥시에톡시)페닐]프로판, 디시클로펜테닐(메트)아크릴레이트 트리시클로데카닐(메트)아크릴레이트, 트리스(아크릴옥시에틸)이소시아누레이트, 우레탄 (메트)아크릴레이트, 이소시아누르산 에틸렌옥시드 변성 디아크릴레이트 등을 들 수 있으며, 이들은 단독 또는 2종 이상을 조합하여 사용할 수 있다. The adhesive composition according to an embodiment of the present invention may further add a radical polymerizable material for the purpose of improving the connection reliability of the adhesive composition. The radically polymerizable substance is a substance having a functional group polymerized by radicals, and examples thereof include resins such as (meth)acrylate resins, maleimide resins, citraconimide resins, and nadiimide resins. The radically polymerizable substance can be used in any state of a monomer and an oligomer, and a monomer and an oligomer can also be mixed and used. (meth)acrylate resin is obtained by radical polymerization of (meth)acrylate, for example. As (meth)acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, ethylene glycol di (meth) acrylate, di Ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylene glycol tetra(meth)acrylate, 2-hydroxy-1,3-diacryloxy propane, 2,2-bis[4 -(acryloxymethoxy)phenyl]propane, 2,2-bis[4-(acryloxyethoxy)phenyl]propane, dicyclopentenyl(meth)acrylate tricyclodecanyl(meth)acrylate, tris( Acryloxyethyl) isocyanurate, urethane (meth)acrylate, isocyanuric acid ethylene oxide modified diacrylate, etc. are mentioned, These can be used individually or in combination of 2 or more types.
또한, 본 발명의 일 실시예에 따른 접착제 조성물은 필요에 따라서 히드로퀴논, 메틸에테르히드로퀴논 등의 라디칼 중합 금지제를 경화성이 손상되지 않는 범위에서 사용할 수도 있다. 말레이미드 수지는 분자 중에 말레이미드기를 1개 이상 가지는 것이며, 일례로, 페닐말레이미드, 1-메틸-2,4- 비스말레이미드벤젠, N,N'-m-페닐렌비스말레이미드, N,N'-p-페닐렌비스말레이미드, N,N'-4,4-비페닐렌비스말레 이미드, N,N'-4,4-(3,3-디메틸비페닐렌)비스말레이미드, N,N'-4,4-(3,3-디메틸디페닐메탄)비스말레이미드, N,N4,4-(3,3-디에틸디페닐메탄)비스말레이미드, N,N'-4,4-디페닐메탄비스말레이미드, N,N'-4,4-디페닐프로판비스말 레이미드, N,N'-4,4-디페닐에테르비스말레이미드, N,N'-4,4-디페닐술폰비스말레이미드, 2,2-비스(4-(4-말레이미드페녹시)페닐)프로판, 2,2-비스(3-s-부틸-3,4-(4-말레이미드페녹시)페닐)프로판, 1,1-비스(4-(4-말레이미드페녹시)페닐)데칸, 4,4'-시클로헥실리덴-비스(1-(4-말레이미드페녹시)페녹시)-2-시클로헥실벤젠, 2,2-비스(4-(4-말레이미드페녹시)페닐)헥사플루오로프로판 등을 들 수 있으며, 이들은 단독으로 또는 2종 이상을 혼합 하여 사용할 수 있다. 시트라콘이미드 수지는 분자 중에 시트라콘이미드기를 1개 이상 가지는 시트라콘이미드 화합물을 중합시킨 것으로, 시트라콘이미드 화합물로서는, 일례로 페닐시트라콘이미드, 1-메틸-2,4-비스시트라콘이미드벤젠, N,N'- m-페닐렌비스시트라콘이미드, N,N'-p-페닐렌비스시트라콘이미드, N,N'-4,4-비페닐렌비스시트라콘이미드, N,N'- 4,4-(3,3-디메틸비페닐렌)비스시트라콘이미드, N,N'-4,4-(3,3-디메틸디페닐메탄)비스시트라콘이미드, N,N'-4,4- (3,3-디에틸디페닐메탄)비스시트라콘이미드, N,N'-4,4-디페닐메탄비스시트라콘이미드, N,N'-4,4-디페닐프로판비스시트라콘이미드, N,N'-4,4-디페닐에테르비스시트라콘이미드, N,N'-4,4-디페닐술폰비스시트라콘이미드, 2,2-비스(4-(4-시트라콘이미드페녹시)페닐)프로판, 2,2-비스(3-s-부틸-3,4-(4-시트라콘이미드페녹시)페닐)프로판, 1,1-비스(4-(4-시트라콘이미드페녹시)페닐)데칸, 4,4'-시클로헥실리덴-비스(1-(4-시트라콘이미드페녹시)페녹시)-2-시클로헥실벤젠, 2,2-비스(4-(4-시트라콘이미드페녹시)페닐)헥사플루오로프로판 등을 들 수 있으며, 이들을 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다. 나디이미드 수지는 분자 중에 나디이미드기를 1개 이상 가지는 나디이미드 화합물을 중합시킨 것으로 일례로 페닐나디이미드, 1-메틸-2,4-비스나디이미드벤젠, N,N'-m-페닐렌비스나디이미드, N,N'-p-페닐렌비스나디이미드, N,N'-4,4-비페닐렌비스나디이미드, N,N'-4,4-(3,3-디메틸비페닐렌)비스나디이미 드, N,N'-4,4-(3,3-디메틸디페닐메탄)비스나디이미드, N,N'-4,4-(3,3-디에틸디페닐메탄)비스나디이미드, N,N'- 4,4-디페닐메탐비스나디이미드, N,N'-4,4-디페닐프로판비스나디이미드, N,N'-4,4-디페닐에테르비스나디이미드, N,N'-4,4-디페닐술폰비스나디이미드, 2,2-비스(4-(4-나디이미드페녹시)페닐)프로판, 2,2-비스(3-s-부틸-3,4-(4-나디이미드페녹시)페닐)프로판, 1,1-비스(4-(4-나디이미드페녹시)페닐)데칸, 4,4'-시클로헥실리덴-비스(1-(4-나 디이미드페녹시)페녹시)-2-시클로헥실벤젠, 2,2-비스(4-(4-나디이미드페녹시)페닐)헥사플루오로프로판 등을 들 수 있고, 이들은 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다. 라디칼 중합성 물질의 함유량은 접착제 조성물의 총중량에 대하여 10 내지 50 중량％이고, 보다 바람직하게는 10 내지 20 중량％일 수 있다.In addition, in the adhesive composition according to an embodiment of the present invention, if necessary, a radical polymerization inhibitor such as hydroquinone or methyl ether hydroquinone may be used in a range in which curability is not impaired. The maleimide resin has at least one maleimide group in the molecule, for example, phenylmaleimide, 1-methyl-2,4-bismaleimidebenzene, N,N'-m-phenylenebismaleimide, N, N'-p-phenylenebismaleimide, N,N'-4,4-biphenylenebismaleimide, N,N'-4,4-(3,3-dimethylbiphenylene)bismaleimide , N,N'-4,4-(3,3-dimethyldiphenylmethane)bismaleimide, N,N4,4-(3,3-diethyldiphenylmethane)bismaleimide, N,N'- 4,4-diphenylmethanebismaleimide, N,N'-4,4-diphenylpropanebismaleimide, N,N'-4,4-diphenyletherbismaleimide, N,N'-4 ,4-diphenylsulfonebismaleimide, 2,2-bis(4-(4-maleimidephenoxy)phenyl)propane, 2,2-bis(3-s-butyl-3,4-(4-malei) Midphenoxy)phenyl)propane, 1,1-bis(4-(4-maleimidephenoxy)phenyl)decane, 4,4'-cyclohexylidene-bis(1-(4-maleimidephenoxy) phenoxy)-2-cyclohexylbenzene, 2,2-bis(4-(4-maleimidephenoxy)phenyl)hexafluoropropane, etc. These may be used alone or in combination of two or more. have. The citraconimide resin is obtained by polymerizing a citraconimide compound having one or more citraconimide groups in the molecule. Examples of the citraconimide compound include phenylcitraconimide, 1-methyl-2,4- Biscitraconimidebenzene, N,N'-m-phenylenebiscitraconimide, N,N'-p-phenylenebiscitraconimide, N,N'-4,4-biphenylenebis Citraconimide, N,N'-4,4-(3,3-dimethylbiphenylene)biscitraconimide, N,N'-4,4-(3,3-dimethyldiphenylmethane)bis Citraconimide, N,N'-4,4- (3,3-diethyldiphenylmethane)biscitraconimide, N,N'-4,4-diphenylmethanebiscitraconimide, N ,N'-4,4-diphenylpropanebiscitraconimide, N,N'-4,4-diphenyletherbiscitraconimide, N,N'-4,4-diphenylsulfonebiscitraconimide imide, 2,2-bis(4-(4-citraconimidephenoxy)phenyl)propane, 2,2-bis(3-s-butyl-3,4-(4-citraconimidephenoxy) )phenyl)propane, 1,1-bis(4-(4-citraconimidephenoxy)phenyl)decane, 4,4'-cyclohexylidene-bis(1-(4-citraconimidephenoxy) ) phenoxy)-2-cyclohexylbenzene, 2,2-bis(4-(4-citraconimidephenoxy)phenyl)hexafluoropropane, etc., alone or in combination of two or more can be used by Nadiimide resin is obtained by polymerizing a nadiimide compound having one or more nadiimide groups in the molecule. For example, phenylnadiimide, 1-methyl-2,4-bisnadiimidebenzene, N,N'-m-phenylenebisnadiy Mid, N,N'-p-phenylenebisnadiimide, N,N'-4,4-biphenylenebisnadiimide, N,N'-4,4-(3,3-dimethylbiphenylene) Visnadiimide, N,N'-4,4-(3,3-dimethyldiphenylmethane)bisnadiimide, N,N'-4,4-(3,3-diethyldiphenylmethane)bisnadiy mide, N,N'-4,4-diphenylmethambisnadiimide, N,N'-4,4-diphenylpropanebisnadiimide, N,N'-4,4-diphenyletherbisnadiimide; N,N'-4,4-diphenylsulfonebisnadiimide, 2,2-bis(4-(4-nadiimidephenoxy)phenyl)propane, 2,2-bis(3-s-butyl-3, 4-(4-nadiimidephenoxy)phenyl)propane, 1,1-bis(4-(4-nadiimidephenoxy)phenyl)decane, 4,4'-cyclohexylidene-bis(1-(4) -nadiimidephenoxy)phenoxy)-2-cyclohexylbenzene, 2,2-bis(4-(4-nadiimidephenoxy)phenyl)hexafluoropropane, etc., these alone or 2 More than one species can be mixed and used. The content of the radical polymerizable material may be 10 to 50% by weight, more preferably 10 to 20% by weight, based on the total weight of the adhesive composition.
본 발명의 일 실시예에 따른 접착제 조성물은 도전성 또는 이방 도전성을 부여하는 것을 목적으로 하여 도전 입자를 더 첨가할 수도 있다. 도전 입자로서는, 실리카, 삼산화이안티몬, 금, 은, 구리, 니켈, 알루미늄, 스 테인레스, 카본, 세라믹, 또는 상기 금속, 비도전성 유리, 세라믹, 플라스틱 등을 핵으로 하고, 이 핵에 상기 금속이나 카본을 피복한 것일 수 있으며, 이들을 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다. 본 발명의 일 실시예에 따른 접착제 조성물에 있어서의 도전 입자의 함유량은 접착제 조성물의 총중량에 대하여 0.1 내지 20 중량％일 수 있다.The adhesive composition according to an embodiment of the present invention may further add conductive particles for the purpose of imparting conductivity or anisotropic conductivity. As the conductive particles, silica, antimony trioxide, gold, silver, copper, nickel, aluminum, stainless, carbon, ceramic, or the above-mentioned metal, non-conductive glass, ceramic, plastic, etc. are used as a nucleus, and the above-mentioned metal or It may be one coated with carbon, and these may be used alone or in combination of two or more. The content of the conductive particles in the adhesive composition according to an embodiment of the present invention may be 0.1 to 20% by weight based on the total weight of the adhesive composition.
또한 본 발명의 일 실시예에 따른 접착제 조성물은 적절하게, 연화제, 촉진제, 노화 방지제, 착색제, 난연제, 커플링제, 충전재 등과 같은 첨가제를 더 첨가할 수도 있다. 접착제 조성물은 상온에서 액상인 경우에는 페이스트형으로 사용할 수 있다. 실온에서 고체인 경우에는, 가열 하여 사용하는 것 외에, 용제를 이용하여 페이스트화할 수도 있다. 사용할 수 있는 용제로서는, 상술한 성분과 반응성이 없으면서 충분한 용해성을 나타내는 것이면 특별히 제한은 받지 않지만, 실온에서 방치하면 휘발될 우려가 없으면서도 용제를 휘발이 용이하고, 접착 후의 신뢰성에 악영향을 미칠 우려가 없는 상압에서의 비점이 50 내 지 150℃ 인 것이 바람직하다. 비점이 50℃ 미만인 경우가 바람직하다. In addition, the adhesive composition according to an embodiment of the present invention may further add additives such as a softening agent, an accelerator, an anti-aging agent, a colorant, a flame retardant, a coupling agent, and a filler, as appropriate. When the adhesive composition is liquid at room temperature, it may be used in the form of a paste. In the case of a solid at room temperature, in addition to heating it, it can also be made into a paste using a solvent. The solvent that can be used is not particularly limited as long as it exhibits sufficient solubility without reactivity with the above-mentioned components. It is preferable that the boiling point in the absence of atmospheric pressure is 50 to 150°C. It is preferable that a boiling point is less than 50 degreeC.
본 발명의 일 실시예에 따른 접착제 조성물은 필름형으로 하여 이용할 수도 있다. 이 경우, 접착제 조성물에 필요에 따라서 용제 등을 첨가하거나 한 용액을, 불소 수지 필름, 폴리에틸렌테레프탈레이트 필름, 이형지 등의 박리성 기재 상에 도포하거나, 또는 부직포 등의 기재에 상기 용액을 함침시켜 박리성 기재 상에 배치하고, 용제 등을 제거하여 필름으로서 사용할 수 있다. 필름 형상으로 사용하면 취급성에 있어서 매우 편리하다.The adhesive composition according to an embodiment of the present invention may be used in the form of a film. In this case, a solution obtained by adding a solvent or the like to the adhesive composition as needed is applied onto a releasable substrate such as a fluororesin film, a polyethylene terephthalate film, or a release paper, or a substrate such as a nonwoven fabric is impregnated with the solution and peeled off It can be used as a film by disposing it on a base material and removing the solvent or the like. When used in the form of a film, it is very convenient in terms of handling.
본 발명의 접착제 조성물은 열팽창 계수가 다른 이종의 피착체의 접착제로서 사용될 수 있다. 구체적으로는 은 페이스트, 은 필름, 이방 도전 접착제 등으로 대표되는 회로 접속 재료, CSP용 엘라스토머, CSP용 언더 충전재, LOC 테이프, 다이 본딩용 접착제 등으로 대표되는 반도체 소자용 접착제로서 사용될 수 있다.The adhesive composition of the present invention can be used as an adhesive for different types of adherends having different coefficients of thermal expansion. Specifically, it can be used as an adhesive for a semiconductor device represented by a circuit connection material represented by silver paste, a silver film, an anisotropic conductive adhesive, etc., an elastomer for CSP, an under filler for CSP, an LOC tape, an adhesive for die bonding, and the like.
이하 실시예를 통하여 본 발명을 보다 상세하게 설명한다. 그러나, 이들 실시예들은 예시적인 목적일 뿐 본 발명이 이들 실시예에 한정되는 것은 아니다.The present invention will be described in more detail with reference to the following examples. However, these examples are for illustrative purposes only, and the present invention is not limited to these examples.
[제조예 1] 6FDA-diol 유도체 1의 제조[Preparation Example 1] Preparation of 6FDA-diol derivative 1
아미노알코올(0.081 몰) 및 디메틸포름아마이드(170 mL)를 온도계, 축합기 및 Dean-Stark 트랩이 장착된 250 mL 4-목 둥근 바닥 반응 플라스크에 첨가한 뒤 마그네틱바를 이용해 혼합시켰다. 완전히 용해되면 화합물 1(6FDA)를 첨가한 후 질소 분위기 하에 상온에서 반응시켰다. 이때, 모든 반응 과정은 얇은층 크로마토그래피 (TLC)를 이용해 관찰하였다. 12시간 이후 반응이 종료되었음을 확인한 뒤, 톨루엔(30mL, 282 몰)을 첨가하고 반응혼합물을 120 ℃에서 환류시켜 반응을 진행하였다. 12시간 이후 TLC를 통해 반응이 종료되었음을 확인한 뒤 반응물을 상온으로 냉각하였다. 이후, 잔여 디메틸포름아마이드 제거를 위해 분별깔때기를 이용하여 반응물을 세척하였다. 이때, 0.003N 염화수소 수용액과 1% 탄산수소나트륨 수용액을 번갈아 사용하여 세척을 진행하였으며 염화수소 수용액은 디메틸포름아마이드 염 형성을 위해, 탄산수소나트륨은 잔여 염화수소 제거를 위해 사용되었다. 3번 세척 과정을 거친 후, 유기용매층만 따로 모아 황산 마그네슘 처리를 통해 잔여 물을 제거해줬다. 이후 로토-증발기를 이용해 용매를 제거한 뒤, 얻어진 반응물은 컬럼 크로마토그래피 방법을 통해 정제 후 건조시켜 최종적으로 연노란색의 고체인 6FDA-diol 유도체 1을 얻었다. Aminoalcohol (0.081 mol) and dimethylformamide (170 mL) were added to a 250 mL 4-neck round bottom reaction flask equipped with a thermometer, condenser and Dean-Stark trap and mixed using a magnetic bar. When completely dissolved, compound 1 (6FDA) was added and reacted at room temperature under a nitrogen atmosphere. At this time, all reaction processes were observed using thin layer chromatography (TLC). After confirming that the reaction was completed after 12 hours, toluene (30 mL, 282 mol) was added, and the reaction mixture was refluxed at 120° C. to proceed with the reaction. After 12 hours, after confirming that the reaction was complete through TLC, the reaction product was cooled to room temperature. Thereafter, the reaction product was washed using a separatory funnel to remove residual dimethylformamide. At this time, washing was carried out by alternately using 0.003N aqueous hydrogen chloride solution and 1% aqueous sodium hydrogen carbonate solution. The aqueous hydrogen chloride solution was used to form dimethylformamide salt, and sodium hydrogen carbonate was used to remove residual hydrogen chloride. After washing three times, only the organic solvent layer was collected separately and residual water was removed by treatment with magnesium sulfate. After removing the solvent using a roto-evaporator, the obtained reactant was purified by column chromatography and dried to finally obtain 6FDA-diol derivative 1 as a pale yellow solid.
제조된 6FDA-diol 유도체 1의 특성을 하기 표 1에 나타내었다.The properties of the prepared 6FDA-diol derivative 1 are shown in Table 1 below.
1H-NMR(DMSO-d6) δ 8.03-8.05 (d, 2H; ArH), 7.84-7.86 (d, 2H; ArH), 7.65 (s, 2H; ArH), 4.50-4.52 (t, 2H; -OH), 3.62-3.66 (t, 4H; -N-CH2-), 3.43-3.47 (q, 4H; -CH2-OH), 1.71-1.77 (q, 4H; -CH2-) 1 H-NMR(DMSO-d 6 ) δ 8.03-8.05 (d, 2H; ArH), 7.84-7.86 (d, 2H; ArH), 7.65 (s, 2H; ArH), 4.50-4.52 (t, 2H; -OH), 3.62-3.66 (t, 4H; -N-CH 2 -), 3.43-3.47 (q, 4H; -CH 2 -OH), 1.71-1.77 (q, 4H; -CH 2 -)
[제조예 2 내지 3] 6FDA-diol 유도체 2 및 3의 제조[Preparation Examples 2 to 3] Preparation of 6FDA-diol derivatives 2 and 3
제조예 1에서 아미노알코올을 n=5 또는 n=6을 각각 사용한 것을 제외하고는 제조예 1과 동일하게 실시하여 6FDA-diol 유도체 2와 6FDA-diol 유도체 3을 제조하였으며, 제조된 6FDA-diol 유도체 2 또는 3의 특성을 하기 표 1에 나타내었다.6FDA-diol derivative 2 and 6FDA-diol derivative 3 were prepared in the same manner as in Preparation Example 1 except that n = 5 or n = 6 of amino alcohol was used in Preparation Example 1, respectively, and the prepared 6FDA-diol derivative The characteristics of 2 or 3 are shown in Table 1 below.
6FDA-diol 유도체 2: 1H-NMR(DMSO-d6 δ 7.90-7.92 (t, 2H; ArH), 7.78 (s, 4H; ArH), 8.03-8.05 (d, 2H; ArH), 7.84-7.86 (d, 2H; ArH), 7.66 (s, 2H; ArH), 4.34-4.36 (t, 2H; -OH), 3.55-.3.58 (t, 4H; -N-CH2-), 3.33-3.39 (q, 4H; -CH2-OH-), 1.55-1.62 (m, 4H; -N-CH2-CH2-), 1.39-1.46 (m, 4H; -CH2-CH2-OH), 1.26-1.33 (m, 4H; -CH2-)6FDA-diol derivative 2: 1 H-NMR (DMSO-d 6 δ 7.90-7.92 (t, 2H; ArH), 7.78 (s, 4H; ArH), 8.03-8.05 (d, 2H; ArH), 7.84-7.86 (d, 2H; ArH), 7.66 (s, 2H; ArH), 4.34-4.36 (t, 2H; -OH), 3.55-.3.58 (t, 4H; -N-CH 2 -), 3.33-3.39 ( q, 4H; -CH 2 -OH-), 1.55-1.62 (m, 4H; -N-CH 2 -CH 2 -), 1.39-1.46 (m, 4H; -CH 2 -CH 2 -OH), 1.26 -1.33 (m, 4H; -CH 2 -)
6FDA-diol 유도체 3: 1H-NMR(DMSO-d6 δ 8.03-8.05 (d, 2H; ArH), 7.84-7.86 (d, 2H; ArH), 7.66 (s, 2H; ArH), 4.34-4.36 (t, 2H; -OH), 3.54-.3.58 (t, 4H; -N-CH2-), 3.32-3.38 (q, 4H; -CH2-OH-), 1.56-1.59 (m, 4H; -N-CH2-CH2-), 1.37-1.41 (m, 4H; -CH2-CH2-OH), 1.28-1.29 (m, 8H; -CH2-) 6FDA-diol derivative 3: 1 H-NMR (DMSO-d 6 δ 8.03-8.05 (d, 2H; ArH), 7.84-7.86 (d, 2H; ArH), 7.66 (s, 2H; ArH), 4.34-4.36 (t, 2H; -OH), 3.54-.3.58 (t, 4H; -N-CH 2 -), 3.32-3.38 (q, 4H; -CH 2 -OH-), 1.56-1.59 (m, 4H; -N-CH 2 -CH 2 -), 1.37-1.41 (m, 4H; -CH 2 -CH 2 -OH), 1.28-1.29 (m, 8H; -CH 2 -)
[실시예 1] 반응성 우레탄 올리고머 1의 제조[Example 1] Preparation of reactive urethane oligomer 1
제조예 1에서 제조된 디올 모노머 (0.02 몰)를 온도계 및 축합기가 장착된 50 mL 4-목 둥근 바닥 반응 플라스크에 첨가한 뒤 질소를 퍼지하였다. 이후 질소 분위기 하에 아세톤(10 mL)을 첨가한 뒤 10분 동안 기계적으로 교반시켰다. 용액이 완전히 용해되면 이소포론 디이소시아네이트 (0.04 몰)과 디부틸주석 디라우레이트(0.00016 몰)를 순차적으로 플라스크에 첨가한 뒤, 온도를 45 ℃로 승온하여 반응시켰다. 2시간 동안 반응한 뒤, 반응 플라스크를 냉각시키고 반응액의 온도가 상온으로 되었을 때 2-하이드록시에틸 메타크릴산 (0.04 몰)을 첨가하였다. 이후 온도를 45℃로 승온하여 2시간 동안 반응을 실시하였다. 반응이 종료되면 반응액을 상온으로 냉각시킨 뒤 증류수로 2 내지 3번 세정하고 진공 오븐 내에서 건조시켰다. 건조 후 최종적으로 흰색 고체인 반응성 우레탄 올리머 1을 제조하였다. The diol monomer (0.02 mol) prepared in Preparation Example 1 was added to a 50 mL 4-neck round bottom reaction flask equipped with a thermometer and a condenser, and then nitrogen was purged. Then, acetone (10 mL) was added under a nitrogen atmosphere and mechanically stirred for 10 minutes. When the solution was completely dissolved, isophorone diisocyanate (0.04 mol) and dibutyltin dilaurate (0.00016 mol) were sequentially added to the flask, and then the temperature was raised to 45° C. to react. After reacting for 2 hours, the reaction flask was cooled, and when the temperature of the reaction solution reached room temperature, 2-hydroxyethyl methacrylic acid (0.04 mol) was added. Thereafter, the temperature was raised to 45° C. and the reaction was carried out for 2 hours. When the reaction was completed, the reaction solution was cooled to room temperature, washed 2-3 times with distilled water, and dried in a vacuum oven. After drying, reactive urethane oligomer 1 was finally prepared as a white solid.
제조된 반응성 우레탄 올리머 1의 특성을 하기 표 1에 나타내었다.The properties of the prepared reactive urethane oligomer 1 are shown in Table 1 below.
1H-NMR(DMSO-d6) δ 8.03 (d, 2H; ArH), 7.85 (d, 2H; ArH), 7.66 (d, 2H; ArH), 7.24 (s, 2H; -C-NH-), 6.98 (m, 2H; -CH2-NH-), 5.69,6.03 (s, 4H; -C=C-H2), 4.21-4.25 (d, 8H; -O-CH2-CH2-O-), 3.96 (s, 4H; -N-CH2-), 3.64 (m, 2H, 4H; -CH-NH-, -CH2-COO-), 1.87 (m, 4H, 6H; -HN-CH2-C-, -COO-CH3), 0.78-1.61 (m, 34H; -CH2-, -CH3) 1 H-NMR(DMSO-d 6 ) δ 8.03 (d, 2H; ArH), 7.85 (d, 2H; ArH), 7.66 (d, 2H; ArH), 7.24 (s, 2H; -C-NH-) , 6.98 (m, 2H; -CH 2 -NH-), 5.69,6.03 (s, 4H; -C=CH 2 ), 4.21-4.25 (d, 8H; -O-CH 2 -CH 2 -O-) , 3.96 (s, 4H; -N-CH 2 -), 3.64 (m, 2H, 4H; -CH-NH-, -CH 2 -COO-), 1.87 (m, 4H, 6H; -HN-CH 2 -C-, -COO-CH 3 ), 0.78-1.61 (m, 34H; -CH 2 -, -CH 3 )
[실시예 2] 반응성 우레탄 올리고머 2의 제조[Example 2] Preparation of reactive urethane oligomer 2
상기 실시예 1에서 6FDA-diol 유도체 1 대신에 제조예 2에서 제조된 6FDA-diol 유도체 2를 사용한 것을 제외하고 실시예 1과 동일하게 실시하여 반응성 우레탄 올리머 1을 제조하였으며, 제조된 반응성 우레탄 올리머 2의 특성을 하기 표 1에 나타내었다.In Example 1 above Reactive urethane oligomer 1 was prepared in the same manner as in Example 1 except that 6FDA-diol derivative 2 prepared in Preparation Example 2 was used instead of 6FDA-diol derivative 1, and the properties of the prepared reactive urethane oligomer 2 were evaluated. It is shown in Table 1 below.
1H-NMR(DMSO-d6) δ 8.03 (d, 2H; ArH), 7.85 (d, 2H; ArH), 7.66 (d, 2H; ArH), 7.24 (s, 2H; -C-N-H-), 6.92 (m, 2H; -CH2-NH-), 5.68,6.02 (s, 4H; -C=C-H2), 4.21-4.25 (d, 8H; -O-CH2-CH2-O-), 3.88 (s, 4H; -N-CH2-), 3.64 (m, 2H, 4H; -CH-NH-, -CH2-COO-), 1.87 (m, 4H, 6H; -HN-CH2-C-, -COO-CH3), 0.78-1.61 (m, 50H; -CH2-, -CH3) 1 H-NMR(DMSO-d 6 ) δ 8.03 (d, 2H; ArH), 7.85 (d, 2H; ArH), 7.66 (d, 2H; ArH), 7.24 (s, 2H; -CNH-), 6.92 (m, 2H; -CH 2 -NH-), 5.68,6.02 (s, 4H; -C=CH 2 ), 4.21-4.25 (d, 8H; -O-CH 2 -CH 2 -O-), 3.88 (s, 4H; -N-CH 2 -), 3.64 (m, 2H, 4H; -CH-NH-, -CH 2 -COO-), 1.87 (m, 4H, 6H; -HN-CH 2 -C -, -COO-CH 3 ), 0.78-1.61 (m, 50H; -CH 2 -, -CH 3 )
[실시예 3] 반응성 우레탄 올리고머 3의 제조[Example 3] Preparation of reactive urethane oligomer 3
상기 실시예 1에서 6FDA-diol 유도체 1 대신에 제조예 3에서 제조된 6FDA-diol 유도체 3을 사용한 것을 제외하고 실시예 1과 동일하게 실시하여 반응성 우레탄 올리머 1을 제조하였으며, 제조된 반응성 우레탄 올리머 3의 특성을 하기 표 1에 나타내었다.In Example 1 above Reactive urethane oligomer 1 was prepared in the same manner as in Example 1 except that 6FDA-diol derivative 3 prepared in Preparation Example 3 was used instead of 6FDA-diol derivative 1, and the properties of the prepared reactive urethane olimer 3 were analyzed It is shown in Table 1 below.
1H-NMR(DMSO-d6) δ 8.03 (d, 2H; ArH), 7.85 (d, 2H; ArH), 7.66 (d, 2H; ArH), 7.24 (s, 2H; -C-N-H-), 6.91 (m, 2H; -CH2-NH-), 5.68,6.02 (s, 4H; -C=C-H2), 4.21-4.25 (d, 8H; -O-CH2-CH2-O-), 3.89 (s, 4H; -N-CH2-), 3.56 (m, 2H, 4H; -CH-NH-, -CH2-COO-), 1.87 (m, 4H, 6H; -HN-CH2-C-, -COO-CH3), 0.78-1.87 (m, 58H; -CH2-, -CH3) 1 H-NMR(DMSO-d 6 ) δ 8.03 (d, 2H; ArH), 7.85 (d, 2H; ArH), 7.66 (d, 2H; ArH), 7.24 (s, 2H; -CNH-), 6.91 (m, 2H; -CH 2 -NH-), 5.68,6.02 (s, 4H; -C=CH 2 ), 4.21-4.25 (d, 8H; -O-CH 2 -CH 2 -O-), 3.89 (s, 4H; -N-CH 2 -), 3.56 (m, 2H, 4H; -CH-NH-, -CH 2 -COO-), 1.87 (m, 4H, 6H; -HN-CH 2 -C -, -COO-CH 3 ), 0.78-1.87 (m, 58H; -CH 2 -, -CH 3 )
[비교예 1] 비교 반응성 우레탄 올리고머의 제조[Comparative Example 1] Preparation of comparative reactive urethane oligomer
실시예 1에서 중심골격이 상이하며, 상업적으로 구입가능한 출발물질을 사용한 것을 제외하고는 실시예 1과 동일하게 실시하여 하기 구조의 비교 반응성 우레탄 올리고머(Mw: 5055 g/mol)를 제조하였다. 
1H-NMR (THF-d8):δ 6.51 (s, 2H; -COO-NH-), 6.30 (s, 2H; -CH-NH-), 5.60, 6.10 (s, 4H; -C=C-H2), 4.26-4.31 (m, 8H; -COO-CH2-CH2-COO-), 4.03 (m, 4H; -COO-CH2-), 3.80 (m, 2H; -CH-NH-COO-), 2.88 (m, 4H; -NH-CH2-), 1.94 (s, 6H; -COO-C-CH3), 0.87-1.81 (m, 508H; -CH2-, -CH3) 1 H-NMR (THF-d 8 ): δ 6.51 (s, 2H; -COO-NH-), 6.30 (s, 2H; -CH-NH-), 5.60, 6.10 (s, 4H; -C=C -H2), 4.26-4.31 (m, 8H; -COO-CH2-CH2-COO-), 4.03 (m, 4H; -COO-CH2-), 3.80 (m, 2H; -CH-NH-COO-) , 2.88 (m, 4H; -NH-CH2-), 1.94 (s, 6H; -COO-C-CH3), 0.87-1.81 (m, 508H; -CH2-, -CH3)
[실시예 4] 접착제 조성물[Example 4] Adhesive composition
실시예 1에서 제조된 반응성 우레탄 올리고머 1을 희석 단량체인 아이소보닐 아크릴레이트(IBA) 와 광개시제인 Irgacure 1173와 혼합하여 분산시켜 자외선 경화형 접착제 조성물을 제조하였다. 이때, 조성물의 배합비는 중량비로 실시예 1의 반응성 우레탄 올리고머 : IBA : Irgacure 1173 = 50 : 45 : 5 이며, 씽키 믹서를 이용하여 혼합해 조성물을 제조하였다.The reactive urethane oligomer 1 prepared in Example 1 was mixed and dispersed with isobornyl acrylate (IBA) as a diluting monomer and Irgacure 1173 as a photoinitiator to prepare an ultraviolet curable adhesive composition. At this time, the compounding ratio of the composition was the reactive urethane oligomer of Example 1 by weight: IBA: Irgacure 1173 = 50: 45: 5, and mixed using a thinky mixer to prepare a composition.
[실시예 5 내지 6] 접착제 조성물[Examples 5 to 6] Adhesive composition
실시예 4에서 실시예 1에서 제조된 반응성 우레탄 올리고머 1 대신 실시예 2 및 3에서 제조된 반응성 우레탄 올리고머를 사용한 것을 제외하고는 실시예 4와 동일하게 실시하여 접착제 조성물을 제조하였다.In Example 4, an adhesive composition was prepared in the same manner as in Example 4, except that the reactive urethane oligomer prepared in Examples 2 and 3 was used instead of the reactive urethane oligomer 1 prepared in Example 1.
[비교예 2] 비교 접착제 조성물의 제조[Comparative Example 2] Preparation of comparative adhesive composition
실시예 4에서 실시예 1에서 제조된 반응성 우레탄 올리고머 1 대신 비교예 1에서 제조한 비교 반응성 우레탄 올리고머를 사용한 것을 제외하고는 실시예 4와 동일하게 실시하여 접착제 조성물을 제조하였다.In Example 4, an adhesive composition was prepared in the same manner as in Example 4, except that the comparative reactive urethane oligomer prepared in Comparative Example 1 was used instead of the reactive urethane oligomer 1 prepared in Example 1.
[실시예 7] 접착제 조성물의 평가[Example 7] Evaluation of adhesive composition
실시예 4 내지 6 및 비교예 2에서 제조된 각각의 접착제 조성물을 유리판 (7.5 cm X 5.3 cm)에 0.005g 내지 0.025g 도포한 후 같은 크기의 다른 유리판으로 겹쳐 주었다. 이때, 겹치는 면적의 길이가 4cm가 되도록 했으며, 두께는 갭 테이프를 이용해 200um가 되도록 하였다. 이후, 컨베이어 벨트 형식의 UV 경화장치(Seimyung Vactron Co., LTD, SSCM-M3.6K2)를 이용하여 3000mJ의 자외선을 조사하여 접착력 평가용 경화 샘플을 제조하였다. 제조한 샘플들은 만능재료시험기(UTM, Lloyd, LR5K-PLUS)를 이용하여 상온에서 측정함으로써 접착력을 평가했다.0.005 g to 0.025 g of each of the adhesive compositions prepared in Examples 4 to 6 and Comparative Example 2 was applied to a glass plate (7.5 cm X 5.3 cm), and then overlapped with another glass plate of the same size. At this time, the length of the overlapping area was 4 cm, and the thickness was 200 μm using a gap tape. Then, using a conveyor belt-type UV curing device (Seimyung Vactron Co., LTD, SSCM-M3.6K2) was irradiated with UV light of 3000 mJ to prepare a cured sample for evaluation of adhesion. The prepared samples were evaluated for adhesion by measuring at room temperature using a universal testing machine (UTM, Lloyd, LR5K-PLUS).
그 결과를 하기 표 2에 나타내었다.The results are shown in Table 2 below.
본 발명의 접착제 조성물은 (5,5'-(methylene-2,2,diylis(isoindoline-1,3-dione))을 도입함하지 않은 비교예 2와 대비하여 열특성 및 내열성 측면에서 매우 우수한 효과를 가지며, 접착력 또한 우수함을 알 수 있다.The adhesive composition of the present invention has a very excellent effect in terms of thermal properties and heat resistance compared to Comparative Example 2 in which (5,5'-(methylene-2,2,diylis(isoindoline-1,3-dione)) is not introduced It can be seen that the adhesive strength is also excellent.
구체적으로 본 발명의 접착제 조성물은 높은 투명도를 가지며, 접착력 또한 매우 우수한 값을 가진다.Specifically, the adhesive composition of the present invention has high transparency, and also has a very good adhesive strength.
이상에서 살펴본 바와 같이 본 발명의 실시예에 대해 상세히 기술되었지만, 본 발명이 속하는 기술분야에 있어서 통상의 지식을 가진 사람이라면, 첨부된 청구범위에 정의된 본 발명의 정신 및 범위를 벗어나지 않으면서 본 발명을 여러 가지로 변형하여 실시할 수 있을 것이다. 따라서 본 발명의 앞으로의 실시예들의 변경은 본 발명의 기술을 벗어날 수 없을 것이다.As described above, the embodiments of the present invention have been described in detail, but those of ordinary skill in the art to which the present invention pertains can view the present invention without departing from the spirit and scope of the present invention as defined in the appended claims. The invention may be practiced with various modifications. Accordingly, modifications of future embodiments of the present invention will not depart from the teachings of the present invention.
Claims (10)
[화학식 1]
상기 화학식 1에서
R은 할로겐 또는 할로C1-C10알킬이며;
A1 내지 A4는 서로 독립적으로 C1-C20알킬렌이며;
R1 및 R-2는 서로 독립적으로 수소 또는 메틸이며;
D1 및 D2는 서로 독립적으로 C1-C10알킬렌 또는 하기 구조에서 선택되는 하나이다.
상기 구조식에서, R11 내지 R21은 서로 독립적으로 C1-C10알킬이며;
p, q, s 및 t는 서로 독립적으로 0 내지 4의 정수이다.A reactive urethane oligomer represented by the following formula (1).
[Formula 1]
In Formula 1 above
R is halogen or haloC1-C10 alkyl;
A 1 to A 4 are each independently C1-C20 alkylene;
R 1 and R- 2 are each independently hydrogen or methyl;
D 1 and D 2 are each independently selected from C1-C10 alkylene or the following structure.
In the above structural formula, R 11 to R 21 are each independently C1-C10 alkyl;
p, q, s and t are each independently an integer from 0 to 4.
상기 화학식 1에서,
R은 할로C1-C10알킬이며;
A1 및 A2는 서로 독립적으로 C3-C10알킬렌이며;
A3 및 A4는 서로 독립적으로 C1-C10알킬렌인 반응성 우레탄 올리고머.2. The method of claim 1
In Formula 1,
R is haloC1-C10 alkyl;
A 1 and A 2 are each independently C3-C10 alkylene;
A 3 and A 4 are each independently C1-C10 alkylene reactive urethane oligomer.
상기 화학식 1에서 D1 및 D2는 하기 구조에서 선택되는 반응성 우레탄 올리고머.
상기 구조식에서, R11 내지 R17은 서로 독립적으로 C1-C5알킬이며;
p 및 q는 서로 독립적으로 0 내지 1의 정수이다.2. The method of claim 1
In Formula 1, D 1 and D 2 are a reactive urethane oligomer selected from the following structure.
In the above structural formula, R 11 to R 17 are each independently C1-C5 alkyl;
p and q are each independently an integer from 0 to 1.
상기 화학식 1은 하기 화학식 2로 표시되는 반응성 우레탄 올리고머.
[화학식 2]
상기 화학식 2에서
A3 및 A4는 서로 독립적으로 C1-C20알킬렌이며;
R1 및 R-2는 서로 독립적으로 수소 또는 메틸이며;
n은 3 내지 8의 정수이다.The method of claim 1,
Formula 1 is a reactive urethane oligomer represented by Formula 2 below.
[Formula 2]
In the above formula (2)
A 3 and A 4 are each independently C1-C20 alkylene;
R 1 and R- 2 are each independently hydrogen or methyl;
n is an integer from 3 to 8;
상기 반응성 우레탄 올리고머는 중량평균분자량이 500 내지 2500g/mol인 반응성 우레탄 올리고머.The method of claim 1,
The reactive urethane oligomer is a reactive urethane oligomer having a weight average molecular weight of 500 to 2500 g/mol.
상기 반응 혼합물과 하기 화학식 14의 화합물 및 하기 화학식 15의 화합물을 반응시켜 하기 화학식 1의 반응성 우레탄 올리고머를 제조하는 단계;를 포함하는 반응성 우레탄 올리고머의 제조방법.
[화학식 1]
[화학식 11]
[화학식 12]
[화학식 13]
[화학식 14]
[화학식 15]
상기 화학식 1 및 화학식 11 내지 화학식 15에서,
R은 할로겐 또는 할로C1-C10알킬이며;
A1 내지 A4는 서로 독립적으로 C1-C20알킬렌이며;
R1 및 R-2는 서로 독립적으로 수소 또는 메틸이며;
D1 및 D2는 서로 독립적으로 C1-C10알킬렌 또는 하기 구조에서 선택되는 하나이다.
상기 구조식에서, R11 내지 R21은 서로 독립적으로 C1-C10알킬이며;
p, q, s 및 t는 서로 독립적으로 0 내지 4의 정수이다.reacting a compound of Formula 11 with a compound of Formula 12 and a compound of Formula 13 in the presence of a catalyst to obtain a reaction mixture; and
A method of preparing a reactive urethane oligomer comprising a; reacting the reaction mixture with a compound of Formula 14 and a compound of Formula 15 to prepare a reactive urethane oligomer of Formula 1 below.
[Formula 1]
[Formula 11]
[Formula 12]
[Formula 13]
[Formula 14]
[Formula 15]
In Formula 1 and Formula 11 to Formula 15,
R is halogen or haloC1-C10 alkyl;
A 1 to A 4 are each independently C1-C20 alkylene;
R 1 and R- 2 are each independently hydrogen or methyl;
D 1 and D 2 are each independently selected from C1-C10 alkylene or the following structure.
In the above structural formula, R 11 to R 21 are each independently C1-C10 alkyl;
p, q, s and t are each independently an integer from 0 to 4.
희석 단량체; 및
광개시제;를 포함하는 접착제 조성물.A reactive urethane oligomer of any one of claims 1 to 5;
dilute monomer; and
Adhesive composition comprising; a photoinitiator.
상기 희석 단량체는 반응성 우레탄 올리고머 100중량부에 대해 40 내지 90중량부로 포함되며, 상기 광개시제는 0.5 내지 10중량부로 포함되는 접착제 조성물. 8. The method of claim 7,
The diluent monomer is included in an amount of 40 to 90 parts by weight based on 100 parts by weight of the reactive urethane oligomer, and the photoinitiator is included in an amount of 0.5 to 10 parts by weight.
상기 희석 단량체는 메틸(메타)아크릴레이트, 에틸(메트)아크릴레이트, 부틸(메트)아크릴레이트, 에틸헥실(메트)아크릴레이트, 이소 옥틸(메트)아크릴레이트, 이소데실(메트)아크릴레이트, 라우릴(메트)아크릴레이트, 세틸(메트)아크릴레이트, 스 테아릴(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트, 테트라하이드로퍼퓨릴(메트)아크릴레이트, 벤질(메트)아크릴레이트, 사이클로헥실(메트)아크릴레이트, 트리메틸사이클로헥실포르말(메트)아크릴레이트, o-페닐페 놀(메트)아크릴레이트, 페놀(EO)(메트)아크릴레이트, 에톡시에톡시에틸(메트)아크릴레이트, 페닐티오에틸(메트)아크릴레이트 및 쿠밀페녹실에틸(메트)아크릴레이트에서 선택되는 하나 또는 둘 이상인 접착제 조성물.8. The method of claim 7,
The dilution monomer is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, Uryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, cyclo Hexyl (meth) acrylate, trimethylcyclohexyl formal (meth) acrylate, o-phenylphenol (meth) acrylate, phenol (EO) (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, One or two or more adhesive compositions selected from phenylthioethyl (meth)acrylate and cumylphenoxylethyl (meth)acrylate.
상기 접착제 조성물은 열가소성 수지, 열가소성 엘라스토머 및 도전입자에서 선택되는 하나 또는 둘 이상의 첨가제를 더 포함하는 접착제 조성물.8. The method of claim 7,
The adhesive composition further comprises one or more additives selected from a thermoplastic resin, a thermoplastic elastomer, and conductive particles.
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