KR102087428B1 - Photo curable adhesive and bonding composition and adhesive film - Google Patents
Photo curable adhesive and bonding composition and adhesive film Download PDFInfo
- Publication number
- KR102087428B1 KR102087428B1 KR1020160038379A KR20160038379A KR102087428B1 KR 102087428 B1 KR102087428 B1 KR 102087428B1 KR 1020160038379 A KR1020160038379 A KR 1020160038379A KR 20160038379 A KR20160038379 A KR 20160038379A KR 102087428 B1 KR102087428 B1 KR 102087428B1
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- acrylate
- acrylic
- adhesive composition
- photocurable
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 239000002313 adhesive film Substances 0.000 title claims description 31
- 239000000853 adhesive Substances 0.000 title claims description 30
- 230000001070 adhesive effect Effects 0.000 title claims description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 72
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000012546 transfer Methods 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 55
- -1 2,4-diphenyl-4-methyl-2- Pentene (2,4-diphenyl-4-methyl-2-pentene) Chemical compound 0.000 claims description 23
- 239000012986 chain transfer agent Substances 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 20
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 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 3
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 claims description 2
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 claims 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 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001421 myristyl 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])[H] 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- FAQJJMHZNSSFSM-UHFFFAOYSA-N phenylglyoxylic acid Chemical compound OC(=O)C(=O)C1=CC=CC=C1 FAQJJMHZNSSFSM-UHFFFAOYSA-N 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 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 1
- 238000001723 curing Methods 0.000 description 13
- 238000005520 cutting process Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000379 polymerizing effect Effects 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- NQUXRXBRYDZZDL-UHFFFAOYSA-N 1-(2-prop-2-enoyloxyethyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCOC(=O)C=C)C(O)=O NQUXRXBRYDZZDL-UHFFFAOYSA-N 0.000 description 1
- YUTHQCGFZNYPIG-UHFFFAOYSA-N 1-[2-(2-methylprop-2-enoyloxy)ethyl]cyclohexane-1,2-dicarboxylic acid Chemical compound CC(=C)C(=O)OCCC1(C(O)=O)CCCCC1C(O)=O YUTHQCGFZNYPIG-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- HDXFJCYSSZDPJG-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)butanedioic acid Chemical compound CC(=C)C(=O)OC(C(O)=O)CC(O)=O HDXFJCYSSZDPJG-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- ZOXFNNYRXYTZKZ-UHFFFAOYSA-N 3-(2-hydroxyethyl)phthalic acid Chemical compound OCCC1=CC=CC(C(O)=O)=C1C(O)=O ZOXFNNYRXYTZKZ-UHFFFAOYSA-N 0.000 description 1
- UXTGJIIBLZIQPK-UHFFFAOYSA-N 3-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCOC(=O)C=C)=C1C(O)=O UXTGJIIBLZIQPK-UHFFFAOYSA-N 0.000 description 1
- DWTKNKBWDQHROK-UHFFFAOYSA-N 3-[2-(2-methylprop-2-enoyloxy)ethyl]phthalic acid Chemical compound CC(=C)C(=O)OCCC1=CC=CC(C(O)=O)=C1C(O)=O DWTKNKBWDQHROK-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 238000011191 terminal modification Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
(메타)아크릴계 모노머, (메타)아크릴계 올리고머, (메타)아크릴계 프리폴리머 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함하는 (메타)아크릴계 광경화성 화합물; 연쇄 이동제; 및 광개시제;를 포함하는 광경화성 점착제 조성물을 제공한다.A (meth) acrylic photocurable compound comprising one selected from the group consisting of (meth) acrylic monomers, (meth) acrylic oligomers, (meth) acrylic prepolymers, and combinations thereof; Chain transfer agents; It provides a photocurable pressure-sensitive adhesive composition comprising; and a photoinitiator.
Description
광경화성 점착제 조성물 및 점착 필름에 관한 것이다.
It relates to a photocurable adhesive composition and an adhesive film.
전기 산업 또는 전자 산업에서 부품을 접착하거나, 고정하는 것은 중요한 문제이고, 특히 2개 이상의 상이한 소재 또는 부품을 서로 접합하기 위해서는 양쪽 모두 접착력이 우수한 접착제를 사용하여야 한다. 구체적으로, 디스플레이는 터치 스크린 패널(TSP, Touch Screen Panel) 및 액정 모듈로 구성되며, 상기 터치 스크린 패널은 도전성 필름 및 투명 기재 등의 적층 구조를 갖는다. 이때, 상기 터치 스크린 패널의 적층 구조에 대해 각 층을 부착하는 경우 접착제가 사용되며, 상기 터치 스크린 패널과 액정 모듈을 부착하는 경우에도 접착제가 사용된다. 이러한 용도의 접착제를 통상적으로 광학 투명 접착제(OCA, Optical Clear Adhesive)로 지칭하며, 상기 광학 투명 접착제는 터치 민감도, 시인성 등의 물성을 저하시키지 않으면서 우수한 접착 성능을 구현해야 한다. 특히, 터치 스크린 또는 터치 패널에 사용되는 접착제는 사용 위치에 따라 단차 흡수성이 중요할 수 있다.
Bonding or fixing parts in the electrical or electronics industry is an important issue, and in order to bond two or more different materials or parts to each other, it is necessary to use an adhesive with good adhesion on both sides. Specifically, the display is composed of a touch screen panel (TSP) and a liquid crystal module, and the touch screen panel has a laminated structure such as a conductive film and a transparent substrate. In this case, an adhesive is used to attach each layer to the laminated structure of the touch screen panel, and an adhesive is also used to attach the touch screen panel and the liquid crystal module. Adhesives for this purpose are commonly referred to as optical clear adhesives (OCAs), and the optical clear adhesives should implement excellent adhesive performance without degrading physical properties such as touch sensitivity and visibility. In particular, adhesives used in touch screens or touch panels may have significant step absorbency depending on the location of use.
본 발명의 일 구현예는 터치 스크린 패널 및 액정 모듈 사이의 직부착(direct bonding)에 사용되는 광경화성 점착제 조성물로서, 단차 흡수성이 우수한 점착제 조성물을 제공한다.One embodiment of the present invention is a photocurable pressure-sensitive adhesive composition used for direct bonding between a touch screen panel and a liquid crystal module, and provides a pressure-sensitive adhesive composition having excellent step absorption.
본 발명의 다른 구현예는 상기 광경화성 점착제 조성물로부터 제조되어 우수한 단차 흡수 성능을 제공하는 점착 필름을 제공한다.
Another embodiment of the present invention provides a pressure-sensitive adhesive film prepared from the photocurable pressure-sensitive adhesive composition provides excellent step absorption performance.
본 발명의 일 구현예에서, (메타)아크릴계 모노머, (메타)아크릴계 올리고머, (메타)아크릴계 프리폴리머 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함하는 (메타)아크릴계 광경화성 화합물; 연쇄 이동제; 및 광개시제;를 포함하는 광경화성 점착제 조성물을 제공한다.In one embodiment of the present invention, a (meth) acrylic monomer, a (meth) acrylic oligomer, a (meth) acrylic prepolymer and a (meth) acrylic photocurable compound including one selected from the group consisting of a combination thereof; Chain transfer agents; It provides a photocurable pressure-sensitive adhesive composition comprising; and a photoinitiator.
본 발명의 다른 구현예에서, 상기 광경화성 점착제 조성물의 경화물을 포함하는 점착 필름을 제공한다.
In another embodiment of the present invention, it provides a pressure-sensitive adhesive film comprising a cured product of the photocurable pressure-sensitive adhesive composition.
상기 광경화성 점착제 조성물 및 점착 필름은 우수한 커팅성과 함께, 향상된 응력 완화와 향상된 단차 흡수성을 구현할 수 있다.
The photocurable pressure-sensitive adhesive composition and pressure-sensitive adhesive film may implement an improved stress relaxation and improved step absorbance with excellent cutting properties.
본 발명의 이점 및 특징, 그리고 그것들을 달성하는 방법은 후술하는 실시예들을 참조하면 명확해질 것이다 그러나, 본 발명은 이하에서 개시되는 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 것이며, 단지 본 실시예들은 본 발명의 개시가 완전하도록 하며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이다.
Advantages and features of the present invention, and methods for achieving the same will be apparent with reference to the following embodiments. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various forms. The present embodiments are merely provided to make the disclosure of the present invention complete, and to fully inform the scope of the invention to those skilled in the art.
본 발명의 일 구현예에서, (메타)아크릴계 모노머, (메타)아크릴계 올리고머, (메타)아크릴계 프리폴리머 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함하는 (메타)아크릴계 광경화성 화합물; 연쇄 이동제; 및 광개시제;를 포함하는 광경화성 점착제 조성물을 제공한다In one embodiment of the present invention, a (meth) acrylic monomer, a (meth) acrylic oligomer, a (meth) acrylic prepolymer and a (meth) acrylic photocurable compound including one selected from the group consisting of a combination thereof; Chain transfer agents; And a photoinitiator; provides a photocurable pressure-sensitive adhesive composition comprising
상기 광경화성 점착제 조성물은 이를 광경화 반응시켜 형성된 점착 필름에 우수한 커팅성과 함께, 향상된 응력 완화와 향상된 단차 흡수성을 부여할 수 있다.The photocurable pressure-sensitive adhesive composition may impart improved stress relaxation and improved step absorbance to the pressure-sensitive adhesive film formed by photocuring reaction thereof.
일반적으로, 터치 패널의 인쇄 단차부에 점착 필름을 부착하는 경우에 기포가 생기기 쉬운 문제가 있다. 예를 들어, 터치 패널에 장식이나 광 차폐를 목적으로 인쇄에 의해 착색층을 형성하는 경우에 약 수십 ㎛의 인쇄 단차가 생기고, 상기 인쇄 단차부에 점착 필름을 부착하는 경우에 기포가 생긴다. Generally, when sticking an adhesive film to the printing step part of a touch panel, there exists a problem which a bubble is easy to produce. For example, when a colored layer is formed by printing for the purpose of decoration or light shielding on a touch panel, a printing step of about several tens of micrometers is generated, and bubbles are generated when an adhesive film is attached to the printing step.
점착 필름의 응력을 감소시켜, 단차 흡수성을 부여함으로써 기포의 발생을 억제할 수 있다. The generation | occurrence | production of a bubble can be suppressed by reducing the stress of an adhesive film and giving a level | step difference absorptivity.
일반적으로, 점착 필름에 우수한 단차 흡수성을 부여하기 위하여, 점착 필름을 이루는 점착제 조성물에 포함되는 프리폴리머의 유리전이온도를 조절하는 방법, 점착제 조성물에 포함되는 개시제 또는 경화제의 함량을 조절하는 방법, 또는 점착필름의 겔 함량을 조절하는 방법 등이 있을 수 있다.In general, in order to impart excellent step absorbency to the pressure-sensitive adhesive film, a method of controlling the glass transition temperature of the prepolymer included in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive film, a method of adjusting the content of an initiator or a curing agent included in the pressure-sensitive adhesive composition, or adhesion There may be a method for adjusting the gel content of the film.
그러나, 이와 같은 방법으로 점착 필름의 응력을 완화하여 단차 흡수성을 부여하는 경우에는, 점착 필름의 유동성이 지나치게 높아지게 되어, 커팅성(cutting)이 나빠지고, 찐(residual adhesive)이 쉽게 발생하며, 또한, 시간의 경과에 따라 점착필름의 물성이 저하되므로, 작업성이 나빠지는 문제가 있다.
However, when the stress of the pressure-sensitive adhesive film is relieved in this manner to impart step difference absorbency, the fluidity of the pressure-sensitive adhesive film becomes excessively high, resulting in poor cutting, and easy development of residual adhesive. As the physical properties of the pressure-sensitive adhesive film decreases with time, workability deteriorates.
상기 광경화성 점착제 조성물은 (메타)아크릴계 광경화성 화합물, 연쇄 이동제 및 광개시제를 포함하는 것으로서, 이를 광경화시켜 점착 필름을 형성함에 있어서, 상기 (메타)아크릴계 광경화성 화합물과 연쇄 이동제가 반응하여, 점착필름에 향상된 응력 완화와 향상된 단차 흡수성을 부여할 수 있다. 또한, 상기 점착 필름은 우수한 커팅성을 동시에 가질 수 있다. 즉, 전술한 바와 같은 프리폴리머의 유리전이온도 등의 조절 없이도, 상기 광경화성 점착제 조성물의 경화물인 점착 필름은 우수한 커팅성과 함께, 향상된 응력 완화와 향상된 단차 흡수성을 가질 수 있다.
The photocurable pressure-sensitive adhesive composition includes a (meth) acrylic photocurable compound, a chain transfer agent, and a photoinitiator, and when the photocurable is formed to form an adhesive film, the (meth) acrylic photocurable compound and the chain transfer agent react to each other. The film can be given improved stress relaxation and improved step absorbency. In addition, the adhesive film may have excellent cutting properties at the same time. That is, the adhesive film, which is a cured product of the photocurable pressure sensitive adhesive composition, may have improved stress relaxation and improved step absorbency without controlling the glass transition temperature of the prepolymer as described above.
상기 광경화성 점착제 조성물에 포함되는 연쇄 이동제는 이미 중합반응을 완료시킨 후에 형성된 상기 (메타)아크릴계 광경화성 화합물에 첨가 되어, 상기 광경화성 점착제 조성물을 경화하여 점착 필름을 형성하는 경화 반응에 사용된다. 이는 일반적으로, 연쇄 이동제를 모노머와 혼합하여 프리폴리머로의 중합시, 즉, 중합 반응에 사용하는 것과 구별되어야 한다. 연쇄 이동제가 모노머의 중합 반응시 사용되면 얻어지는 중합체인 프리폴리머의 분자량을 조절한다. 이에 반해, 상기 광경화성 점착제 조성물에 포함되는 연쇄 이동제는 상기 (메타)아크릴계 광경화성 화합물 즉, (메타)아크릴계 모노머, (메타)아크릴계 올리고머, 또는 (메타)아크릴계 프리폴리머에 대하여 광경화 반응시 사슬 길이를 조절할 수 있다.
The chain transfer agent included in the photocurable pressure-sensitive adhesive composition is added to the (meth) acrylic photocurable compound formed after the polymerization reaction has already been completed, and used in a curing reaction for curing the photocurable pressure-sensitive adhesive composition to form an adhesive film. It should generally be distinguished from the use of a chain transfer agent in admixture with monomers in the polymerization into prepolymers, ie in the polymerization reaction. When a chain transfer agent is used in the polymerization reaction of the monomer, the molecular weight of the prepolymer which is a polymer obtained is controlled. In contrast, the chain transfer agent included in the photocurable pressure-sensitive adhesive composition has a chain length during photocuring reaction with respect to the (meth) acrylic photocurable compound, that is, (meth) acrylic monomer, (meth) acrylic oligomer, or (meth) acrylic prepolymer. Can be adjusted.
상기 연쇄 이동제는 상기 (메타)아크릴계 광경화성 화합물에 포함되는 (메타)아크릴계 모노머, (메타)아크릴계 올리고머, 또는 (메타)아크릴계 프리폴리머의 경화 반응에 작용하여, 상기 광경화성 수지 조성물의 경화물인 점착 필름에 우수한 커팅성과 함께 향상된 응력 완화와 향상된 단차 흡수성을 부여할 수 있다.The said chain transfer agent acts on the hardening reaction of the (meth) acrylic-type monomer, the (meth) acrylic-type oligomer, or the (meth) acrylic-type prepolymer contained in the said (meth) acrylic-type photocurable compound, and is an adhesive film which is a hardened | cured material of the said photocurable resin composition. It can give a better cutting performance and improved stress relaxation and improved step absorption.
상기 (메타)아크릴계 광경화성 화합물은 광에 의해 광경화 반응을 하는 반응 싸이트인 아크릴레이트기를 포함하여 광경화 가능한 화합물을 의미하는 것으로서, (메타)아크릴계 모노머를 중합반응시켜 얻어진 결과물로서 얻을 수 있고, 이러한 (메타)아크릴계 모노머를 중합반응시켜 얻어진 결과물은 중합반응에 의해 얻어진 (메타)아크릴계 올리고머와 (메타)아크릴계 프리폴리머 뿐만 아니라 미반응 (메타)아크릴계 모노머를 포함한다.
The (meth) acrylic photocurable compound means a compound which can be photocurable including an acrylate group which is a reaction site that undergoes photocuring reaction by light, and can be obtained as a result obtained by polymerizing a (meth) acrylic monomer. The result obtained by polymerizing such a (meth) acrylic monomer includes not only the (meth) acrylic oligomer and (meth) acrylic prepolymer obtained by the polymerization reaction, but also the unreacted (meth) acrylic monomer.
상기 연쇄 이동제는 상기 (메타)아크릴계 광경화성 화합물을 포함하는 광경화성 점착제 조성물의 경화 반응에 사용되어, 상기 (메타)아크릴계 광경화성 화합물, 즉, (메타)아크릴계 모노머, (메타)아크릴계 올리고머, 또는 (메타)아크릴계 프리폴리머와 반응하여 경화반응에 참여할 수 있다. 구체적으로, (메타)아크릴계 모노머, (메타)아크릴계 올리고머, 또는 (메타)아크릴계 프리폴리머가 각각 또는 상호 간에 연결되어 3차원의 그물구조를 이루면서 경화 반응을 할 때, 상기 연쇄 이동제가 사슬의 길이를 짧게 조절할 수 있다. 이를 통하여, 상기 점착제 조성물의 경화물인 점착 필름은 향상된 단차 흡수성과, 동시에 우수한 커팅성을 가질 수 있다.
The chain transfer agent is used in the curing reaction of the photocurable pressure-sensitive adhesive composition containing the (meth) acrylic photocurable compound, the (meth) acrylic photocurable compound, that is, (meth) acrylic monomer, (meth) acrylic oligomer, or It may participate in a curing reaction by reacting with a (meth) acrylic prepolymer. Specifically, when the (meth) acrylic monomer, the (meth) acrylic oligomer, or the (meth) acrylic prepolymer are linked to each other or to form a three-dimensional network structure, the chain transfer agent shortens the length of the chain. I can regulate it. Through this, the adhesive film, which is a cured product of the pressure-sensitive adhesive composition, may have improved step absorbability and at the same time excellent cutting properties.
구체적으로, 상기 연쇄 이동제는 라우릴메르캅탄, n-도데실메르캅탄, n-옥틸메르캅탄, 라우릴 메르캅탄으로 이루어진 군으로부터 선택된 하나를 포함하는 메르캅탄계 화합물, 알파-메틸스티렌 다이머, 브로모트리클로로메탄(Bromotrichloromethane) 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함할 수 있다. Specifically, the chain transfer agent is a mercaptan compound including one selected from the group consisting of lauryl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, lauryl mercaptan, alpha-methylstyrene dimer, bro Motrichloromethane (Bromotrichloromethane) may include one selected from the group consisting of a combination thereof.
일 구현예에서, 상기 광경화성 점착제 조성물은 상기 연쇄 이동제로 알파-메틸스티렌 다이머를 포함함으로써, 경화도 및 단차 흡수성을 보다 쉽게 조절할 수 있다. 예를 들어, 상기 알파-메틸스티렌 다이머는 2,4-디페닐-4-메틸-1-펜텐(2,4-diphenyl-4-methyl-1-pentene), 2,4-디페닐-4-메틸-2-펜텐(2,4-diphenyl-4-methyl-2-pentene) 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함할 수 있다.
In one embodiment, the photocurable pressure-sensitive adhesive composition includes alpha-methylstyrene dimer as the chain transfer agent, it is possible to more easily control the degree of cure and step absorption. For example, the alpha-methylstyrene dimer is 2,4-diphenyl-4-methyl-1-pentene, 2,4-diphenyl-4- It may include one selected from the group consisting of methyl-2-pentene (2,4-diphenyl-4-methyl-2-pentene) and combinations thereof.
구체적으로, 상기 알파-메틸스티렌 다이머는 상기 (메타)아크릴계 광경화성 화합물에 포함되는 (메타)아크릴계 모노머, (메타)아크릴계 올리고머, (메타)아크릴계 프리폴리머와 결합하여 사슬 끝에 안정한 구조의 페닐기를 가지도록 하는 바, 우수한 말단 변형(terminal modification)을 나타낼 수 있다. 따라서, 상기 알파-메틸스티렌 다이머를 포함하는 상기 광경화성 점착제 조성물은 고온 고습 하에서 우수한 내구성을 가지고, 높은 저장성을 부여하여 수개월 내지 수년의 시간이 지나도 이로부터 제조된 점착 필름의 물성이 저하되지 않도록 할 수 있다.Specifically, the alpha-methylstyrene dimer is combined with a (meth) acrylic monomer, (meth) acrylic oligomer, and (meth) acrylic prepolymer included in the (meth) acrylic photocurable compound to have a phenyl group having a stable structure at a chain end. As such, excellent terminal modifications can be exhibited. Accordingly, the photocurable pressure sensitive adhesive composition including the alpha-methylstyrene dimer has excellent durability under high temperature and high humidity, and provides high storage so that physical properties of the pressure-sensitive adhesive film prepared therefrom may not be degraded even after several months to several years. Can be.
또한, 상기 알파-메틸스티렌 다이머는 이를 포함하는 광경화성 점착제 조성물로부터 제조된 제품에 음이온 물질 등을 잔존시키지 않을 수 있다. 이에 따라, 제품에 잔존하는 음이온이 열 및 광과 반응하여 제품을 변질시키는 것을 방지할 수 있다. In addition, the alpha-methylstyrene dimer may not remain an anionic material or the like in a product prepared from the photocurable pressure-sensitive adhesive composition comprising the same. Accordingly, it is possible to prevent anions remaining in the product from reacting with heat and light to deteriorate the product.
또한, 전기 신호에 영향을 줄 수 있는 음이온 물질을 잔존시키지 않는 상기 알파-메틸스티렌 다이머를 포함하는 상기 광경화성 점착제 조성물은 전자제품에 사용하는 점착 필름의 이용에 더욱 적합할 수 있다.
In addition, the photocurable pressure-sensitive adhesive composition comprising the alpha-methylstyrene dimer that does not leave an anionic material that may affect the electrical signal may be more suitable for use of the pressure-sensitive adhesive film used in electronic products.
상기 광경화성 점착제 조성물에 포함되는 상기 연쇄 이동제의 함량은 상기 (메타)아크릴계 광경화성 화합물 100중량부에 대하여 약 0.01 내지 약 0.05 중량부일 수 있다. The amount of the chain transfer agent included in the photocurable pressure sensitive adhesive composition may be about 0.01 to about 0.05 parts by weight based on 100 parts by weight of the (meth) acrylic photocurable compound.
상기 광경화성 점착제 조성물은 상기 연쇄 이동제를 상기 범위의 함량으로 포함함으로써, 상기 (메타)아크릴계 광경화성 화합물에 포함된 상기 (메타)아크릴계 모노머, (메타)아크릴계 올리고머, (메타)아크릴계 프리폴리머의 경화 반응을 적절히 조절하고, 적절한 사슬 길이를 가지도록 조정하여, 점착 필름에 적절한 접착성능을 부여하고, 우수한 커팅성과 함께 향상된 응력 완화와 향상된 단차 흡수성을 구현할 수 있다.
The photocurable pressure-sensitive adhesive composition comprises the chain transfer agent in the content of the above range, the curing reaction of the (meth) acrylic monomer, (meth) acrylic oligomer, (meth) acrylic prepolymer contained in the (meth) acrylic photocurable compound By properly adjusting and adjusting to have an appropriate chain length, it is possible to give the adhesive film an appropriate adhesive performance, and to realize improved stress relaxation and improved step absorbance with excellent cutting property.
상기 (메타)아크릴계 광경화성 화합물은 전술한 바와 같이 (메타)아크릴계 모노머를 중합반응시켜 얻어진 결과물로서 사용할 경우, 약 10 내지 약 60%의 전환율로 중합반응시켜 얻어질 미반응 모노머, 올리고머 및 프리폴리머의 혼합물일 수 있다. 즉, 상기 (메타)아크릴계 광경화성 화합물은 상기 범위의 전환율로 (메타)아크릴계 모노머를 중합반응시켜 얻어진 결과물의 혼합물을 사용하여, (메타)아크릴계 모노머, (메타)아크릴계 올리고머, (메타)아크릴계 프리폴리머 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함할 수 있다.When the (meth) acrylic photocurable compound is used as a result obtained by polymerizing the (meth) acrylic monomer as described above, the unreacted monomer, oligomer and prepolymer to be obtained by polymerization at a conversion rate of about 10 to about 60% It may be a mixture. That is, the (meth) acrylic photocurable compound is a (meth) acrylic monomer, a (meth) acrylic oligomer, or a (meth) acrylic prepolymer, using a mixture of the resultant obtained by polymerizing a (meth) acrylic monomer at a conversion ratio in the above range. And combinations thereof may include one selected from the group consisting of.
상기 광경화성 점착제 조성물은 상기 범위의 전환율로 (메타)아크릴계 모노머를 중합반응시켜 얻어진 (메타)아크릴계 모노머, (메타)아크릴계 올리고머, (메타)아크릴계 프리폴리머 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함하는 (메타)아크릴계 광경화성 화합물을 포함함으로써, 적정한 점착력을 유지하고, 타발 공정에서 찐이 발생하지 않아 작업성이 우수하며, 우수한 단차 흡수성을 가질 수 있다.
The photocurable pressure-sensitive adhesive composition comprises one selected from the group consisting of (meth) acrylic monomers, (meth) acrylic oligomers, (meth) acrylic prepolymers, and combinations thereof obtained by polymerizing a (meth) acrylic monomer at a conversion rate in the above range. By including the (meth) acrylic-based photocurable compound, it is possible to maintain an appropriate adhesive force, steam is not generated in the punching process, excellent workability, and excellent step absorption.
상기 (메타)아크릴계 모노머는 C1-C22 알킬기를 갖는 알킬(메타)아크릴레이트, C3-C15 시클로알킬기를 갖는 지환족(메타)아크릴레이트 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함할 수 있다. The (meth) acrylic monomers include one selected from the group consisting of alkyl (meth) acrylates having C 1 -C 22 alkyl groups, alicyclic (meth) acrylates having C 3 -C 15 cycloalkyl groups, and combinations thereof can do.
구체적으로, 상기 C1-C22 알킬기를 갖는 알킬(메타)아크릴레이트는 선형 또는 분지형 C1-C22 알킬기를 갖는 알킬(메타)아크릴레이트일 수 있다. 예를 들어, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, n-프로필(메타)아크릴레이트, n-부틸(메타)아크릴레이트, 펜틸(메타)아크릴레이트, n-옥틸(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 테트라데실(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, t-부틸(메타)아크릴레이트, sec-부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 2-에틸부틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 이소노닐(메타)아크릴레이트 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함할 수 있다.Specifically, the alkyl (meth) acrylate having a C 1 -C 22 alkyl group may be an alkyl (meth) acrylate having a linear or branched C 1 -C 22 alkyl group. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, pentyl (meth) acrylate, n-octyl (meth) acrylic Late, lauryl (meth) acrylate, tetradecyl (meth) acrylate, isopropyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, 2-ethylbutyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and combinations thereof.
또한, 상기 C3-C15 시클로알킬기를 갖는 지환족(메타)아크릴레이트는 이소보닐(메타)아크릴레이트, 테트라하이드로퍼퓨릴(메타)아크릴레이트(tetrahydrofurfuryl(meth)acrylate), 사이클로헥실(메타)크릴레이트(cyclohexyl(metha)crylate) 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함할 수 있다.In addition, the alicyclic (meth) acrylate having the C 3 -C 15 cycloalkyl group is isobonyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate (tetrahydrofurfuryl (meth) acrylate), cyclohexyl (meth) It may include one selected from the group consisting of cyclohexyl (metha) crylate and combinations thereof.
상기 (메타)아크릴계 올리고머 및 상기 (메타)아크릴계 프리폴리머는 상기 (메타)아크릴계 모노머 성분으로부터 중합된 것으로서, 상기 연쇄 이동제와 반응하여 경화물인 점착 필름에 포함된다. The (meth) acrylic oligomer and the (meth) acrylic prepolymer are polymerized from the (meth) acrylic monomer component, and are included in the pressure-sensitive adhesive film that reacts with the chain transfer agent to form a cured product.
상기 (메타)아크릴계 올리고머의 중량평균분자량은 약 50만 이하일 수 있다. 구체적으로, 약 5만 내지 약 30만 일 수 있다. 상기 광경화성 점착제 조성물에 포함되는 상기 (메타)아크릴계 프리폴리머의 중량평균분자량(Mw)은 약 100만 내지 약 350만일 수 있다. 상기 광경화성 점착제 조성물은 상기 범위의 중량평균분자량을 갖는 (메타)아크릴계 프리폴리머를 포함함으로써, 점착 필름에 적절한 점착력을 부여하고, 고온 고습의 환경 하에서도 충분한 점착 유지력을 부여할 수 있다.
The weight average molecular weight of the (meth) acrylic oligomer may be about 500,000 or less. Specifically, it may be about 50,000 to about 300,000. The weight average molecular weight (Mw) of the (meth) acrylic prepolymer included in the photocurable pressure sensitive adhesive composition may be about 1 million to about 3.5 million. The photocurable pressure sensitive adhesive composition includes a (meth) acrylic prepolymer having a weight average molecular weight in the above range, thereby imparting appropriate adhesive force to the adhesive film and providing sufficient adhesive holding force even in an environment of high temperature and high humidity.
상기 광경화성 점착제 조성물에 포함되는 상기 (메타)아크릴계 프리폴리머의 유리전이온도(Tg)는 약 -50℃ 내지 약 -10℃일 수 있다. 구체적으로 약 -40℃ 이상일 수 있으며, 보다 구체적으로 약 -30℃ 이상일 수 있다.The glass transition temperature (Tg) of the (meth) acrylic prepolymer included in the photocurable pressure sensitive adhesive composition may be about −50 ° C. to about −10 ° C. Specifically, it may be about −40 ° C. or more, and more specifically about −30 ° C. or more.
전술한 바와 같이, 점착 필름을 이루는 점착제 조성물에 포함되는 프리폴리머의 유리전이온도를 조절하여, 점착 필름에 단차 흡수성을 부여할 수 있다. 구체적으로, 점착 필름을 이루는 점착제 조성물에 포함되는 프리폴리머의 유리전이온도를 낮게 할수록, 점착 필름은 높은 단차 흡수성을 가질 수 있다. As described above, the glass transition temperature of the prepolymer included in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive film may be adjusted to impart step difference absorbency to the pressure-sensitive adhesive film. Specifically, the lower the glass transition temperature of the prepolymer included in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive film, the pressure-sensitive adhesive film may have a high step absorbency.
그러나, 프리폴리머의 유리전이온도가 너무 낮으면, 이의 경화물인 필름의 단차 흡수성은 좋아질 수 있으나, 커팅성이 떨어지는 등의 문제가 있다.However, if the glass transition temperature of the prepolymer is too low, the step absorption of the cured film thereof may be improved, but there is a problem such as poor cutting property.
상기 광경화성 점착제 조성물은 상기 범위의 유리전이온도를 갖는 상기 (메타)아크릴계 프리폴리머를 포함하고도, 이의 경화물인 점착 필름에 향상된 응력 완화와 향상된 단차 흡수성을 부여할 수 있다. 또한, 상기 점착 필름은 우수한 커팅성을 함께 가질 수 있다.
The photocurable pressure-sensitive adhesive composition may include the (meth) acrylic prepolymer having a glass transition temperature in the above range, and may provide improved stress relaxation and improved step absorbency to the cured adhesive film thereof. In addition, the adhesive film may have excellent cutting properties.
상기 (메타)아크릴계 광경화성 화합물은 상기 (메타)아크릴계 모노머에 추가적으로 가교성 모노머를 더 혼합하여 중합반응시켜 얻어진 미반응 모노머, 올리고머 및 프리폴리머의 혼합물일 수 있다.
The (meth) acrylic photocurable compound may be a mixture of unreacted monomers, oligomers and prepolymers obtained by further polymerizing a crosslinkable monomer in addition to the (meth) acrylic monomer.
상기 가교성 모노머는 히드록시기를 갖는 모노머, 카르복실기를 갖는 모노머, 질소 함유 관능기를 갖는 모노머 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함할 수 있다. 이들은 친수성 관능기를 갖는 모노머로서, 상기 (메타)아크릴계 프리폴리머의 구성 모노머로 사용되어, 접착 성능 및 응집력을 향상시킬 수 있다.The crosslinkable monomer may include one selected from the group consisting of a monomer having a hydroxy group, a monomer having a carboxyl group, a monomer having a nitrogen-containing functional group, and a combination thereof. These are monomers having a hydrophilic functional group, and are used as constituent monomers of the (meth) acrylic prepolymer, thereby improving adhesion performance and cohesion.
상기 히드록시기를 갖는 모노머는 히드록시에틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 5-히드록시펜틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 10-히드록시데실(메타)아크릴레이트, (4-히드록시메틸시클로헥실)메틸(메타)아크릴레이트, 카프로락톤 변성 2-히드록시에틸(메탈)아크릴레이트, 2-아크릴로일옥시에틸-2-히드록실에틸프탈산, N-메틸올(메타)아크릴이미드, N-히드록시에틸(메타)아크릴레이트, 2-히드록시 프로필(메타)아크릴레이트, 2-히드록시-3-프로필(메타)아크릴레이트, 3-클로로-2-히드록시프로필(메타)아크릴레이트, 2-히드록시-3-페녹시프로필(메타)아크릴레이트, 2,2-디메틸-2-히드록시에틸(메타)아크릴레이트 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함할 수 있다. The monomer having a hydroxy group is hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10- Hydroxydecyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, caprolactone modified 2-hydroxyethyl (metal) acrylate, 2-acryloyloxyethyl-2-hydride Oxylethylphthalic acid, N-methylol (meth) acrylimide, N-hydroxyethyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate, 2-hydroxy-3-propyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2,2-dimethyl-2-hydroxyethyl (meth) acrylate, and these It may include one selected from the group consisting of a combination of.
상기 카르복실기를 갖는 모노머는 아크릴산, 메타크릴산, 크로톤산, 말레산, 무수말레산, 이타콘산, 푸마르산, 글리콜산, 계피산, 아크릴산 다이머, 메타아크릴산 다이머, 아크릴산 트라이머, 아크릴산 테트라머, 메타크릴산 테트라머, 2-아크릴로일옥시에틸숙신산모노에스테르, 2-메타크릴로일옥시숙신산모노에스테르, 2-아크릴로일옥시에틸프탈산모노에스테르, 2-메타크릴로일옥시에틸프탈산모노에스테르, 2-아크릴로일옥시에틸헥사히드로프탈산모노에스테르, 2-메타크릴로일옥시에틸헥사히드로프탈산모노에스테르 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함할 수 있다. The monomer having a carboxyl group is acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, glycolic acid, cinnamic acid, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, acrylic acid tetramer, methacrylic acid Tetramer, 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxy succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2- It may include one selected from the group consisting of acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloyloxyethylhexahydrophthalic acid monoester, and combinations thereof.
상기 질소 함유 관능기를 갖는 모노머는 N-비닐피닐리돈, N-비닐카프로락탐, 아크릴로일모르폴린, 아크릴로니트릴, 아크릴아미드, N,N-디메틸아크릴아미드, 디메틸아미노에틸(메타)아크릴레이트 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함할 수 있다.
The monomer having a nitrogen-containing functional group is N-vinylpinyridone, N-vinylcaprolactam, acryloyl morpholine, acrylonitrile, acrylamide, N, N-dimethylacrylamide, dimethylaminoethyl (meth) acrylate And combinations thereof may include one selected from the group consisting of.
상기 광경화성 점착제 조성물은 (메타)아크릴계 광경화성 화합물 및 연쇄 이동제와 함께 광개시제를 포함한다. 상기 광개시제는 일정 광량의 광을 조사할 때 활성 반응을 일으켜 경화 반응을 개시하는 물질이다.The photocurable pressure-sensitive adhesive composition includes a photoinitiator together with a (meth) acrylic photocurable compound and a chain transfer agent. The photoinitiator is a substance that initiates a curing reaction by causing an active reaction when irradiating a certain amount of light.
구체적으로, 상기 광개시제는 알파-히드록시케톤류 개시제, 페닐글리옥실레이트류 개시제, 벤질디메틸-케탈류 개시제, 알파-아미노케톤류 개시제, 모노아실포스핀류 개시제, 비스아실포스핀류 개시제, 포스핀 옥사이드류 개시제, 메탈로센류 개시제, 아이오도늄염류 개시제 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함할 수 있다.
Specifically, the photoinitiator alpha-hydroxy ketone initiator, phenylglyoxylate initiator, benzyldimethyl- ketal initiator, alpha-amino ketone initiator, monoacylphosphine initiator, bisacylphosphine initiator, phosphine oxide initiator It may include one selected from the group consisting of metallocene initiators, iodonium salt initiators and combinations thereof.
또한, 상기 광경화성 점착제 조성물은 상기 (메타)아크릴계 광경화성 화합물 100 중량부에 대하여, 상기 광개시제를 약 0.01 내지 약 5.0 중량부의 함량으로 포함할 수 있다. 상기 광개시제가 상기 범위의 함량으로 포함됨으로써, 적절한 수준의 경화도를 확보할 수 있고, 그 결과 우수한 단차 흡수성을 구현할 수 있다.
In addition, the photocurable pressure-sensitive adhesive composition may include the photoinitiator in an amount of about 0.01 to about 5.0 parts by weight based on 100 parts by weight of the (meth) acrylic photocurable compound. By including the photoinitiator in the content of the above range, it is possible to secure an appropriate level of degree of curing, and as a result it can implement an excellent step absorption.
상기 광경화성 점착제 조성물은 경화제, 가교제, 자외선 안정제, 산화 방지제, 보강제, 충진제, 소포제, 계면 활성제, 가소제, 및 이들의 조합으로 이루어진 군으로부터 선택된 하나 이상의 첨가제를 더 포함할 수 있다. The photocurable pressure sensitive adhesive composition may further include one or more additives selected from the group consisting of a curing agent, a crosslinking agent, an ultraviolet stabilizer, an antioxidant, a reinforcing agent, a filler, an antifoaming agent, a surfactant, a plasticizer, and a combination thereof.
예를 들어, 상기 광경화성 점착제 조성물은 경화제를 더 포함할 수 있고, 이 경우, 상기 경화제는 상기 (메타)아크릴계 광경화성 화합물 100 중량부에 대하여, 약 0.1 내지 약 1.0 중량부 포함될 수 있다.For example, the photocurable pressure-sensitive adhesive composition may further include a curing agent, and in this case, the curing agent may be included in an amount of about 0.1 to about 1.0 parts by weight based on 100 parts by weight of the (meth) acrylic photocurable compound.
전술한 바와 같이, 점착 필름을 이루는 점착제 조성물에 포함되는 경화제의 함량을 조절하여, 점착 필름에 단차 흡수성을 부여할 수 있다. 구체적으로, 경화제의 함량을 낮출수록, 점착 필름은 높은 단차 흡수성을 가질 수 있다. 그러나, 커팅성이 떨어지는 등의 문제가 있다.As described above, by adjusting the content of the curing agent included in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive film, it is possible to impart step difference absorbency to the pressure-sensitive adhesive film. Specifically, as the content of the curing agent is lowered, the adhesive film may have higher step absorbency. However, there is a problem such as poor cutting property.
상기 광경화성 점착제 조성물은 상기 범위의 경화제를 포함하고도, 이의 경화물인 점착 필름에 향상된 응력 완화와 향상된 단차 흡수성을 부여할 수 있다. 또한, 상기 점착 필름은 우수한 커팅성을 함께 가질 수 있다.
The photocurable pressure-sensitive adhesive composition may include a hardening agent in the above range, and may provide improved stress relaxation and improved step absorbency to an adhesive film thereof. In addition, the adhesive film may have excellent cutting properties.
본 발명의 다른 구현예에서, 상기 광경화성 점착제 조성물의 경화물을 포함하는 점착 필름을 제공한다.In another embodiment of the present invention, there is provided an adhesive film comprising a cured product of the photocurable pressure-sensitive adhesive composition.
상기 점착 필름은 상기 광경화성 점착제 조성물을 광경화 반응시킴으로써 형성되는 것으로서, 상기 광경화성 점착제 조성물은 전술한 바와 같이, (메타)아크릴계 광경화성 화합물, 연쇄 이동제 및 광개시제를 포함하며, 상기 (메타)아크릴계 광경화성 화합물과 연쇄 이동제가 반응하여, 점착필름에 향상된 응력 완화와 향상된 단차 흡수성을 부여할 수 있다. 또한, 상기 점착 필름은 우수한 커팅성을 동시에 가질 수 있다.
The pressure-sensitive adhesive film is formed by photocuring the photocurable pressure-sensitive adhesive composition, wherein the photocurable pressure-sensitive adhesive composition includes a (meth) acrylic photocurable compound, a chain transfer agent, and a photoinitiator, as described above. The photocurable compound and the chain transfer agent react to impart improved stress relaxation and improved step absorbency to the adhesive film. In addition, the adhesive film may have excellent cutting properties at the same time.
구체적으로, 상기 점착 필름은 약 40℃의 온도, 약 1rad/sec(=0.1591549 Hz)의 주파수에서 스트레인 약 10%일 때의 손실계수(tanδ)가 약 0.5 내지 약 0.8일 수 있다. 손실계수(tanδ)는 하기 식 1과 같이, 손실 탄성률(G``)을 저장 탄성률(G`)로 나눈 값(G``/G`)으로서, 상기 손실 탄성률 및 저장 탄성률은 ARES(Advanced Rheometric Expansion System)을 사용하여 측정할 수 있다. 구체적으로, 약 40℃의 온도에서 약 1rad/sec(=0.1591549 Hz) 의 주파수에서 스트레인 약 10%일 때의 저장 탄성률 및 손실 탄성율을 측정하여 손실계수를 측정할 수 있다.
Specifically, the adhesive film may have a loss factor (tanδ) of about 0.5% to about 0.8 when the strain is about 10% at a temperature of about 40 ° C. and a frequency of about 1 rad / sec (= 0.1591549 Hz). The loss coefficient tan δ is a value obtained by dividing the loss modulus G`` by the storage modulus G` (G`` / G`), and the loss modulus and storage modulus are ARES (Advanced Rheometric). It can be measured using an Expansion System. Specifically, the loss coefficient may be measured by measuring the storage modulus and the loss modulus when the strain is about 10% at a frequency of about 1 rad / sec (= 0.1591549 Hz) at a temperature of about 40 ° C.
[식 1][Equation 1]
손실계수(tanδ) = 손실 탄성률(G``)/저장 탄성률(G`)
Loss factor (tanδ) = loss modulus (G``) / storage modulus (G`)
상기 점착 필름은 상기 범위의 손실계수(tanδ)를 가질 수 있는 바, 적절한 접착력 및 박리력과 함께 향상된 응력 완화와 향상된 단차 흡수성을 가질 수 있다.
The adhesive film may have a loss factor (tan δ) in the above range, and may have an improved stress relaxation and an improved step absorbency with appropriate adhesive force and peel force.
또한, 상기 점착 필름은 약 25℃의 온도에서 약 10% 신장되어 약 180초간 유지한 때의 응력 완화율이 약 80% 내지 약 95%일 수 있다. 즉, 하기 식 2에 의해 측정된 응력 완화율이 약 80% 내지 약 95%일 수 있다.
In addition, the pressure-sensitive adhesive film may be about 10% elongation at a temperature of about 25 ° C may be about 80% to about 95% of the stress relaxation rate when maintained for about 180 seconds. That is, the stress relaxation ratio measured by Equation 2 may be about 80% to about 95%.
[식 2][Equation 2]
응력 완화율(%) = {(초기 응력-완화 후 응력)/초기 응력}×100
% Stress relaxation = {(initial stress-stress after relaxation) / initial stress} × 100
상기 점착 필름의 응력 완화율이 상기 범위를 만족함으로써, 인쇄 단차부에 상기 점착 필름을 부착하는 경우 향상된 단차 흡수성으로 인하여 기포의 발생을 억제할 수 있다.
Since the stress relaxation rate of the pressure-sensitive adhesive film satisfies the above range, when the pressure-sensitive adhesive film is attached to the printing step, the generation of bubbles may be suppressed due to the improved level absorbency.
이하에서는 본 발명의 구체적인 실시예들을 제시한다. 다만, 하기에 기재된 실시예들은 본 발명을 구체적으로 예시하거나 설명하기 위한 것에 불과하며, 이로서 본 발명이 제한되어서는 아니된다.
The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.
실시예Example 1 One
2-에틸헥실아크릴레이트(EHA) 60 중량%, 이소보닐메타크릴레이트(IBOMA) 15 중량% 및 히드록시에틸아크릴레이트(HEA) 20 중량%를 포함하는 혼합 모노머 성분을 제조하였다. 상기 혼합 모노머 성분을 전환율이 20%가 되도록 열 중합 반응시켜 중량평균분자량(Mw)이 100만인 (메타)아크릴계 프리폴리머(유리전이온도 (-42)℃)를 얻었다. (메타)아크릴계 광경화성 화합물로서, 상기 혼합 모노머 성분을 열중합 반응시킨 결과물을 준비하였고, 상기 (메타)아크릴계 광경화성 화합물은 상기 (메타)아크릴계 프리폴리머와 함께 미반응 모노머 및 올리고머 형태를 함께 포함하는 시럽 형태로 얻었다.A mixed monomer component was prepared comprising 60 weight percent 2-ethylhexyl acrylate (EHA), 15 weight percent isobonyl methacrylate (IBOMA) and 20 weight percent hydroxyethyl acrylate (HEA). The mixed monomer component was thermally polymerized to have a conversion ratio of 20% to obtain a (meth) acrylic prepolymer (glass transition temperature (-42) ° C.) having a weight average molecular weight (Mw) of 1 million. As a (meth) acrylic photocurable compound, a product obtained by thermally polymerizing the mixed monomer component was prepared, and the (meth) acrylic photocurable compound together with the (meth) acrylic prepolymer includes an unreacted monomer and an oligomer form together. Obtained in the form of syrup.
상기 (메타)아크릴계 광경화성 화합물 100중량부에 대하여 알파-메틸스티렌 다이머를 0.01 중량부 포함하고, 광개시제로서 벤질디메틸-케탈류 개시제 0.3 중량부를 혼합하여 광경화성 점착제 조성물을 제조하였다.
0.01 weight part of alpha-methylstyrene dimers were contained with respect to 100 weight part of said (meth) acrylic-type photocurable compounds, and 0.3 weight part of benzyldimethyl- ketal initiators were mixed as a photoinitiator, and the photocurable adhesive composition was prepared.
실시예Example 2 2
(메타)아크릴계 광경화성 화합물 100중량부에 대하여 알파-메틸스티렌 다이머를 0.03 중량부 포함한 것을 제외하고는 실시예 1과 동일한 방법으로 광경화성 점착제 조성물을 제조하였다.
A photocurable pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that 0.03 part by weight of alpha-methylstyrene dimer was included based on 100 parts by weight of the (meth) acrylic photocurable compound.
실시예Example 3 3
(메타)아크릴계 광경화성 화합물 100중량부에 대하여 알파-메틸스티렌 다이머를 0.05 중량부 포함한 것을 제외하고는 실시예 1과 동일한 방법으로 광경화성 점착제 조성물을 제조하였다.
A photocurable pressure-sensitive adhesive composition was manufactured in the same manner as in Example 1, except that 0.05 part by weight of alpha-methylstyrene dimer was included based on 100 parts by weight of the (meth) acrylic photocurable compound.
실시예Example 4 4
(메타)아크릴계 광경화성 화합물 100중량부에 대하여 알파-메틸스티렌 다이머를 0.07 중량부 포함한 것을 제외하고는 실시예 1과 동일한 방법으로 광경화성 점착제 조성물을 제조하였다.
A photocurable pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that 0.07 part by weight of alpha-methylstyrene dimer was included based on 100 parts by weight of the (meth) acrylic photocurable compound.
실시예Example 5 5
(메타)아크릴계 광경화성 화합물 100중량부에 대하여 n-도데실메르캅탄 (n-DDM, n-dodecyl mercaptan)를 0.03 중량부 포함한 것을 제외하고는 실시예 1과 동일한 방법으로 광경화성 점착제 조성물을 제조하였다.
A photocurable pressure-sensitive adhesive composition was manufactured in the same manner as in Example 1, except that 0.03 part by weight of n-dodecyl mercaptan (n-DDM, n-dodecyl mercaptan) was included based on 100 parts by weight of the (meth) acrylic photocurable compound. It was.
실시예Example 6 6
(메타)아크릴계 광경화성 화합물 100중량부에 대하여 브로모트리클로로메탄 (Bromotrichloromethane)를 0.03중량부 포함한 것을 제외하고는 실시예 1과 동일한 방법으로 광경화성 점착제 조성물을 제조하였다.
A photocurable pressure-sensitive adhesive composition was manufactured in the same manner as in Example 1, except that 0.03 part by weight of bromotrichloromethane was included with respect to 100 parts by weight of the (meth) acrylic photocurable compound.
비교예Comparative example 1 One
(메타)아크릴계 광경화성 화합물에 대하여 연쇄 이동제를 포함하지 않는 것을 제외하고는 실시예 1과 동일한 방법으로 광경화성 점착제 조성물을 제조하였다.
A photocurable pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that no chain transfer agent was included for the (meth) acrylic photocurable compound.
(중량부)Photoinitiator
(Part by weight)
<평가><Evaluation>
상기 실시예 1 내지 6 및 비교예 1의 광경화성 점착제 조성물에 2 J/㎠의 광량을 조사하여 광경화물을 형성하였다. 이에, 상기 광경화물을 포함하는 점착 필름을 제조하였다.The photocurable adhesive composition of Examples 1-6 and Comparative Example 1 was irradiated with a light amount of 2 J / cm 2 to form a photocured product. Thus, an adhesive film containing the photocured product was prepared.
1. 손실계수(tanδ) 1. Loss Factor (tanδ)
실시예 1 내지 6 및 비교예 1로부터 제조된 점착 필름에 대하여, TA instrument사의 ARES-G2 장비를 이용하여, 하기 식 1의 손실 계수(tanδ를 측정하였다.About the adhesive films manufactured from Examples 1-6 and Comparative Example 1, the loss coefficient (tanδ) of the following Formula 1 was measured using ARES-G2 equipment from TA instrument.
구체적으로, 상기 점착 필름을 ARES-G2의 평행판(parallel plate)을 사용하여, 40℃의 온도에서, 204gf(=2N)의 수직힘이 되도록 설정한 후, 10%의 스트레인 조건에서, 1rad/sec(=0.1591549 Hz) 에서의 저장 탄성률(G') 및 손실 탄성률(G")을 측정하고, 이를 하기 식 1에 대입하여 손실 계수(tanδ)를 측정하였다. 그 결과를 하기 표 2에 나타내었다.
Specifically, using the ARES-G2 parallel plate (parallel plate), at a temperature of 40 ℃, it was set to a vertical force of 204gf (= 2N), and then in a strain condition of 10%, 1rad / The storage modulus (G ') and loss modulus (G ") at sec (= 0.1591549 Hz) were measured and substituted into Equation 1 to determine the loss factor (tanδ). The results are shown in Table 2 below. .
[식 1][Equation 1]
손실계수(tanδ) = 손실 탄성률(G")/저장 탄성률(G')
Loss factor (tanδ) = loss modulus (G ") / storage modulus (G ')
2. 응력완화율(%)2. Stress relaxation rate (%)
실시예 1 내지 6 및 비교예 1로부터 제조된 점착 필름에 대하여, TA instrument사의 ARES-G2 장비를 이용하여, 하기 식 2의 응력완화율(%)을 측정하였다.About the adhesive films manufactured from Examples 1 to 6 and Comparative Example 1, using the ARES-G2 equipment of TA instrument, the stress relaxation rate (%) of the following formula (2) was measured.
구체적으로, 상기 점착 필름을 25℃의 온도에서 10% 신장되도록 하였다. 이 때의 응력(초기 응력)을 측정하였다. 또한, 상기 상태를 180초간 유지한 때의 응력(완화 후 응력)을 측정하였다. 수득된 초기 응력 및 완화 후 응력 값을 하기 식 2에 대입하여 응력 완화율을 측정하였다. 그 결과를 하기 표 2에 나타내었다.
Specifically, the pressure-sensitive adhesive film was allowed to elongate 10% at a temperature of 25 ℃. The stress (initial stress) at this time was measured. Moreover, the stress (stress after relaxation) when the said state was hold | maintained for 180 second was measured. The stress relaxation rate was measured by substituting the obtained initial stress and the stress value after relaxation into Equation 2 below. The results are shown in Table 2 below.
[식 2][Equation 2]
응력 완화율(%) = {(초기 응력-완화 후 응력)/초기 응력}×100
% Stress relaxation = {(initial stress-stress after relaxation) / initial stress} × 100
3. 3. 단차Step 흡수성 Absorbency
모서리 4 부분에 15㎛의 단차가 인쇄된 커버 윈도우(cover window)에 실시예 1 내지 6 및 비교예 1로부터 제조된 점착 필름을 위치시키고, 이형 폴리에틸렌테레프탈레이트(polyethyleneterephthalate,PET)를 제거하고, 그 위에 0.55T의 유리를 부착하였다. 그 후, 오토클레이브(autoclave) 40℃, 4bar에서 20분 동안 압착을 한 후, 인쇄 단차부에 기포의 형상여부를 육안으로 관찰하여, 하기 평가기준에 따라 평가하였다. 그 결과를 하기 표 2에 나타내었다.
A pressure-sensitive adhesive film prepared in Examples 1 to 6 and Comparative Example 1 was placed in a cover window in which a step of 15 μm was printed at 4 corners of the corner, and the release polyethyleneterephthalate (PET) was removed, and 0.55T of glass was attached on top. Thereafter, after pressing the autoclave at 40 ° C. and 4 bar for 20 minutes, the shape of the bubbles was visually observed on the printing step, and evaluated according to the following evaluation criteria. The results are shown in Table 2 below.
<평가 기준><Evaluation Criteria>
-좋음: 모서리 4부분 중, 3 부분에서 기포가 관찰되지 않음.-Good: No bubbles are observed in 3 of 4 corners.
-양호: 모서리 4부분 중, 2부분에서 기포가 관찰되지 않음.-Good: No bubbles are observed in 2 of 4 corners.
-나쁨: 모서리 4부분 중, 1부분에서 기포가 관찰되지 않음.-Poor: No bubble is observed in 1 of 4 corners.
실시예로부터 제조된 점착 필름은 약 80% 내지 약 95%의 높은 응력 완화율과 약 0.5 내지 약 0.8의 손실계수를 가지고, 향상된 단차 흡수성을 나타내는 것을 확인할 수 있다.
It can be seen that the adhesive film prepared from the example has a high stress relaxation ratio of about 80% to about 95% and a loss factor of about 0.5 to about 0.8, and exhibits improved step absorption.
이상에서 본 발명의 바람직한 실시예들에 대하여 상세하게 설명하였지만 본 발명의 권리 범위는 이에 한정되는 것은 아니고 다음의 청구 범위에서 정의하고 있는 본 발명의 기본 개념을 이용한 당업자의 여러 변형 및 개량 형태 또한 본 발명의 권리 범위에 속하는 것이다.Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of the invention.
Claims (15)
A (meth) acrylic photocurable compound comprising one selected from the group consisting of (meth) acrylic monomers, (meth) acrylic oligomers, (meth) acrylic prepolymers, and combinations thereof; Chain transfer agents that are alpha-methylstyrene dimers; And a photoinitiator; Photocurable pressure-sensitive adhesive composition comprising.
상기 알파-메틸스티렌 다이머는 2,4-디페닐-4-메틸-1-펜텐(2,4-diphenyl-4-methyl-1-pentene), 2,4-디페닐-4-메틸-2-펜텐(2,4-diphenyl-4-methyl-2-pentene) 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함하는
광경화성 점착제 조성물.
The method of claim 1,
The alpha-methylstyrene dimer is 2,4-diphenyl-4-methyl-1-pentene, 2,4-diphenyl-4-methyl-2- Pentene (2,4-diphenyl-4-methyl-2-pentene) and combinations thereof
Photocurable adhesive composition.
상기 연쇄 이동제의 함량은 상기 (메타)아크릴계 광경화성 화합물 100 중량부에 대하여 0.01 내지 0.05 중량부인
광경화성 점착제 조성물.
The method of claim 1,
The content of the chain transfer agent is 0.01 to 0.05 parts by weight based on 100 parts by weight of the (meth) acrylic photocurable compound.
Photocurable adhesive composition.
상기 (메타)아크릴계 광경화성 화합물은 10% 내지 60%의 전환율로 형성된
광경화성 점착제 조성물.
The method of claim 1,
The (meth) acrylic photocurable compound is formed with a conversion rate of 10% to 60%
Photocurable adhesive composition.
상기 (메타)아크릴계 모노머는 C1-C22 알킬기를 갖는 알킬(메타)아크릴레이트, C3-C15 시클로알킬기를 갖는 지환족(메타)아크릴레이트 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함하는
광경화성 점착제 조성물.
The method of claim 1,
The (meth) acrylic monomers include one selected from the group consisting of alkyl (meth) acrylates having C 1 -C 22 alkyl groups, alicyclic (meth) acrylates having C 3 -C 15 cycloalkyl groups, and combinations thereof doing
Photocurable adhesive composition.
상기 C1-C22 알킬기를 갖는 알킬(메타)아크릴레이트는 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, n-프로필(메타)아크릴레이트, n-부틸(메타)아크릴레이트, 펜틸(메타)아크릴레이트, n-옥틸(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 테트라데실(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, t-부틸(메타)아크릴레이트, sec-부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 2-에틸부틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 이소노닐(메타)아크릴레이트 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함하는
광경화성 점착제 조성물.
The method of claim 6,
The alkyl (meth) acrylate having the C 1 -C 22 alkyl group is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, pentyl ( Meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) acrylate, isopropyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and combinations thereof Containing one
Photocurable adhesive composition.
상기 C3-C15 시클로알킬기를 갖는 지환족(메타)아크릴레이트는 이소보닐(메타)아크릴레이트, 테트라하이드로퍼퓨릴(메타)아크릴레이트, 사이클로헥실(메타)크릴레이트 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함하는
광경화성 점착제 조성물.
The method of claim 6,
The cycloaliphatic (meth) acrylate having a C 3 -C 15 cycloalkyl group is a group consisting of isobornyl (meth) acrylate, tetrahydroperfuryl (meth) acrylate, cyclohexyl (meth) acrylate, and combinations thereof Containing one selected from
Photocurable adhesive composition.
상기 (메타)아크릴계 프리폴리머의 중량평균분자량(Mw)은 100만 내지 350만인
광경화성 점착제 조성물.
The method of claim 1,
The weight average molecular weight (Mw) of the (meth) acrylic prepolymer is 1 million to 3.5 million
Photocurable adhesive composition.
상기 (메타)아크릴계 프리폴리머의 Tg가 -50℃ 내지 -10℃인
광경화성 점착제 조성물.
The method of claim 1,
Tg of the (meth) acrylic-based prepolymer is -50 ℃ to -10 ℃
Photocurable adhesive composition.
상기 광개시제는 알파-히드록시케톤류 개시제, 페닐글리옥실레이트류 개시제, 벤질디메틸-케탈류 개시제, 알파-아미노케톤류 개시제, 모노아실포스핀류 개시제, 비스아실포스핀류 개시제, 포스핀 옥사이드류 개시제, 메탈로센류 개시제, 아이오도늄염류 개시제 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함하는
광경화성 점착제 조성물.
The method of claim 1,
The photoinitiator is alpha-hydroxy ketone initiator, phenylglyoxylate initiator, benzyldimethyl- ketal initiator, alpha-amino ketone initiator, monoacylphosphine initiator, bisacylphosphine initiator, phosphine oxide initiator, metallo It includes one selected from the group consisting of a senyu initiator, an iodonium salt initiator and a combination thereof
Photocurable adhesive composition.
상기 광개시제의 함량은 상기 (메타)아크릴계 광경화성 화합물 100 중량부에 대하여 0.01 내지 5.0 중량부인
광경화성 점착제 조성물.
The method of claim 1,
The content of the photoinitiator is 0.01 to 5.0 parts by weight based on 100 parts by weight of the (meth) acrylic photocurable compound.
Photocurable adhesive composition.
The adhesive film containing the hardened | cured material of the photocurable adhesive composition of any one of Claims 1-11.
상기 점착 필름은 40℃의 온도, 1rad/sec의 주파수에서 스트레인 10%일 때의 손실계수(tanδ)가 0.5 내지 0.8인
점착 필름.
The method of claim 13,
The adhesive film has a loss coefficient (tanδ) of 0.5 to 0.8 at a strain of 10% at a temperature of 40 ° C. and a frequency of 1 rad / sec.
Adhesive film.
상기 점착 필름은 25℃의 온도에서 10% 신장되어 180초간 유지한 때의 응력 완화율이 80% 내지 95%인
점착필름.
The method of claim 13,
The pressure-sensitive adhesive film has a stress relaxation rate of 80% to 95% when stretched 10% at a temperature of 25 ℃ maintained for 180 seconds
Adhesive film.
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