KR102156082B1 - Heat resistant acrylic pressure sensitive adhesive composition having early law adhesion and high wettability - Google Patents
Heat resistant acrylic pressure sensitive adhesive composition having early law adhesion and high wettability Download PDFInfo
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- KR102156082B1 KR102156082B1 KR1020180128765A KR20180128765A KR102156082B1 KR 102156082 B1 KR102156082 B1 KR 102156082B1 KR 1020180128765 A KR1020180128765 A KR 1020180128765A KR 20180128765 A KR20180128765 A KR 20180128765A KR 102156082 B1 KR102156082 B1 KR 102156082B1
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- South Korea
- Prior art keywords
- acrylate
- meth
- heat
- adhesion
- sensitive adhesive
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 61
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 49
- 239000000853 adhesive Substances 0.000 claims abstract description 30
- 230000001070 adhesive effect Effects 0.000 claims abstract description 30
- 238000009736 wetting Methods 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- 239000002202 Polyethylene glycol Substances 0.000 claims description 18
- 229920001223 polyethylene glycol Polymers 0.000 claims description 18
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 14
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 9
- 229940093499 ethyl acetate Drugs 0.000 claims description 8
- 235000019439 ethyl acetate Nutrition 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 229920000578 graft copolymer Polymers 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 23
- 230000008569 process Effects 0.000 abstract description 23
- 230000001681 protective effect Effects 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- -1 triethylhexyl Chemical group 0.000 description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 11
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 150000002433 hydrophilic molecules Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- 239000003522 acrylic cement Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 description 1
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- JKRZOJADNVOXPM-UHFFFAOYSA-N Oxalic acid dibutyl ester Chemical compound CCCCOC(=O)C(=O)OCCCC JKRZOJADNVOXPM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002270 phosphoric acid ester group Chemical group 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- 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
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
본 발명은 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물 및 그 제조방법에 관한 것으로, 더욱 상세하게는 공중합 가능한 아크릴 모노머와; 하이드록실기 함유 모노머와; 카르복실기 함유 모노머와; 비이온계 (메트)아크릴레이트 모노머를 혼합, 그라프트 공중합시켜 중량평균분자량이 40~50만으로 기존 고분자보다 분자량이 낮은 반면, 점도가 높고, 초기 부착 시 낮은 접착력과 보호기재에 대한 높은 웨팅성을 나타내며, 내열 공정 후 점착력의 낮은 증가 폭을 나타내고, 내열 공정 후 박리 시 전사 및 소음이 없는 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물에 관한 것이다.The present invention relates to a heat-resistant acrylic pressure-sensitive adhesive composition having initial low tack and high wettability, and a method of manufacturing the same, and more particularly, to an acrylic monomer capable of copolymerization; A hydroxyl group-containing monomer; A carboxyl group-containing monomer; Nonionic (meth)acrylate monomers are mixed and graft-copolymerized to have a weight average molecular weight of 40 to 500,000, but have a lower molecular weight than existing polymers, but have a high viscosity, low adhesion and high wettability to the protective substrate during initial attachment. And shows a low increase in adhesive strength after the heat-resistant process, and relates to a heat-resistant acrylic pressure-sensitive adhesive composition having initial low-adhesion and high-wetting properties without transfer and noise during peeling after the heat-resistant process.
Description
본 발명은 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물에 관한 것으로, 더욱 상세하게는 공중합 가능한 아크릴 모노머와; 하이드록실기 함유 모노머와; 카르복실기 함유 모노머와; 비이온계 (메트)아크릴레이트 모노머를 혼합, 그라프트 공중합시켜 중량평균분자량이 40~50만으로 기존 고분자보다 분자량이 낮은 반면, 점도가 높고, 초기 부착 시 낮은 접착력과 보호기재에 대한 높은 웨팅성을 나타내며, 내열 공정 후 점착력의 낮은 증가 폭을 나타내고, 내열 공정 후 박리 시 전사 및 소음이 없는 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물에 관한 것이다.The present invention relates to a heat-resistant acrylic pressure-sensitive adhesive composition having initial low tack and high wettability, and more particularly, to a copolymerizable acrylic monomer; A hydroxyl group-containing monomer; A carboxyl group-containing monomer; Nonionic (meth)acrylate monomers are mixed and graft-copolymerized to have a weight average molecular weight of 40 to 500,000, but have a lower molecular weight than existing polymers, but have a high viscosity, low adhesion and high wettability to the protective substrate during initial attachment. And shows a low increase in adhesive strength after the heat-resistant process, and relates to a heat-resistant acrylic pressure-sensitive adhesive composition having initial low-adhesion and high-wetting properties without transfer and noise during peeling after the heat-resistant process.
일반적으로 표면 보호필름은 보호필름 측에 도포되는 점착제 층을 이용하여, 피보호체, 즉 피착체에 부착되어 피착체의 가공, 또는 반송시에 발생하는 상처나 오염을 방지하는 목적으로 사용된다.In general, the surface protective film is used for the purpose of preventing scratches or contamination that occur during processing or transportation of the adherend by using an adhesive layer applied to the protective film side.
예를 들어, 액정 디스플레이의 패널에 사용되는 편광판은 표면 보호필름의 점착제층과의 부착 면이 표면 보호필름에 의해 보호를 받고 있다가 추후에 검사 공정시 상기 보호필름을 박리하여 제거한다. For example, in a polarizing plate used for a panel of a liquid crystal display, the surface of the surface protective film with the adhesive layer is protected by the surface protective film, and then the protective film is peeled off and removed during a later inspection process.
그러나, 상기와 같은 전자소재 공정 중 내열공정 후, 점착제의 전사 오염 및 박리력(점착력) 증가, 박리시 소음 등으로 인하여 공정 불량으로 고가인 소재를 폐기하여 비용 부담 및 생산단가가 상승하는 결과를 초래하고 있다. However, after the heat-resistant process during the electronic material process as described above, the cost burden and production cost increase by discarding expensive materials due to process defects due to transfer contamination of the adhesive, increase in peeling force (adhesion), noise during peeling, etc. Is causing.
이에 따라, 최근 점착제에 관련된 부품 소재산업의 중요한 연구방향 중의 하나는 낮은 생산 단가 및 공정 프로세스 단축, 생산성 향상 및 고품질을 추구하고 있으며, 특히, 현재 아크릴 점착제는 내열공정 후의 점착력이 증가하여 박리력이 상승하므로 문제가 발생하고 있어 내열공정 전후의 박리력(점착력)의 경시변화가 거의 없어야 할 것을 요구하고 있다. Accordingly, one of the most important research directions in the parts and materials industry related to adhesives in recent years is to pursue low production costs, shortened process processes, improved productivity, and high quality. In particular, the current acrylic adhesives have increased adhesive strength after heat-resistant process, resulting in increased peel strength. As it rises, there is a problem, and it is required that there is little change over time in the peeling force (adhesive force) before and after the heat-resistant process.
아크릴 점착에 관한 종래기술로는 한국등록특허 10-0995510에 3a) 아크릴계 공중합체; b) 에테르기, 케톤기, 에스테르기, -OH, -NH2, -SO3H, 아미드기, 및 인산 에스테르기로 이루어진 군으로부터 선택되는 하나 이상을 가지는 친수성 가소제; 및 c) 디부틸 프탈레이트, 디-2-에틸헥실 프탈레이트, 디아이소노닐 프탈레이트, 디아이소데실 프탈레이트, 디-2-에틸헥실 아디페이트, 디아이소노닐 아디페이트, 트리에틸헥실 트리메리테이트, 트리크레실 포스페이트 및 디-부틸 옥살레이트로 이루어진 군으로부터 선택되는 하나 이상인 소수성 가소제를 포함하는 아크릴계 점착제 조성물이 공지되어 있는데, 상기 아크릴계 점착제 조성물은 내습열 조건에서 무라가 없어 피착체의 내오염성이 우수하고, 피착제의 표면특성이 친수성 또는 소수성인지와 무관하게, 젖음성, 내구신뢰성, 투명성, 및 접착신뢰성이 우수한 효과가 있는 것으로 알려지고 있다.As a prior art for acrylic adhesion, Korean Patent Registration No. 10-0995510 3a) acrylic copolymer; b) a hydrophilic plasticizer having at least one selected from the group consisting of an ether group, a ketone group, an ester group, -OH, -NH2, -SO3H, an amide group, and a phosphoric ester group; And c) dibutyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, di-2-ethylhexyl adipate, diisononyl adipate, triethylhexyl trimeritate, tricresyl There is known an acrylic pressure-sensitive adhesive composition comprising one or more hydrophobic plasticizers selected from the group consisting of phosphate and di-butyl oxalate.The acrylic pressure-sensitive adhesive composition has excellent stain resistance of the adherend because there is no mura under moist heat resistance conditions. Regardless of whether the surface property of the agent is hydrophilic or hydrophobic, it is known to have excellent effects in wettability, durability reliability, transparency, and adhesion reliability.
또한, 한국등록특허 10-1084033에는 아크릴계 공중합체 100 중량부에 대하여, 친수성 화합물을 0.01 내지 0.5중량부를 함유하는 것으로서, 상기 친수성 화합물의 함량을 최적화하여 물성을 제어함으로써, 내습열 조건에서 피착체 특성에 대한 영향이나 컬 발생이 거의 없으며, 피착체에 내오염성이 우수하고, 신뢰성 박리력, 박리시 대전방지성이 우수한 아크릴계 점착제 조성물이 공지되어 있으며, 상기 친수성 화합물은 -COOH, -COOM (M은 1가, 2가 또는 3가의 금속이온 또는 치환 또는 비치환된 암모늄 이온), -OH, -NH2, -SO3H, 아미드기 및 인산 에스테르기로 이루어진 군에서 선택되는 극성기를 구조말단에 함유하는 화합물을 사용하는 아크릴계 점착제 조성물이 공지되어 있다.In addition, Korean Patent Registration No. 10-1084033 contains 0.01 to 0.5 parts by weight of a hydrophilic compound based on 100 parts by weight of the acrylic copolymer, and by optimizing the content of the hydrophilic compound to control physical properties, the properties of the adherend under moist heat resistance There is almost no effect or curl on the adherend, excellent stain resistance, reliable peeling power, and excellent antistatic properties during peeling, acrylic pressure-sensitive adhesive compositions are known, and the hydrophilic compounds are -COOH, -COOM (M is A compound containing a polar group selected from the group consisting of monovalent, divalent or trivalent metal ions or substituted or unsubstituted ammonium ions), -OH, -NH2, -SO3H, amide group and phosphoric acid ester group at the end of the structure An acrylic pressure-sensitive adhesive composition is known.
또한, 한국공개특허 10-2015-0025838에는 에폭시기를 갖는 아크릴계 공중합체, 및 하기 화학식 1 내지 3으로 이루어진 군에서 선택된 1종 이상의 화합물을 함유하는 아크릴계 공중합체를 사용하여, 공중합체에 도입된 이온성 작용기에 의해 점착 내구성을 향상시킬 수 있고 별도로 부식방지제 성분을 함유하지 않고 금속층의 부식을 효과적으로 억제할 수 있는 점착제 조성물이 공지되어 있다.In addition, Korean Patent Laid-Open Publication No. 10-2015-0025838 uses an acrylic copolymer having an epoxy group and an acrylic copolymer containing at least one compound selected from the group consisting of the following Chemical Formulas 1 to 3, and the ionicity introduced into the copolymer A pressure-sensitive adhesive composition capable of improving adhesion durability by a functional group and capable of effectively suppressing corrosion of a metal layer without separately containing a corrosion inhibitor component is known.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
(상기 화학식 1 내지 3중, R1, R2, R3, R4 및 R5는 각각 독립적으로 C1 내지 C6의 알킬기 또는 C5 내지 C8의 방향족탄화수소기이고, X는 불소함유 유기염, 불소함유 무기염 또는 요오드 이온임).(In Formulas 1 to 3, R1, R2, R3, R4 and R5 are each independently a C1 to C6 alkyl group or a C5 to C8 aromatic hydrocarbon group, and X is a fluorine-containing organic salt, a fluorine-containing inorganic salt, or an iodine ion. being).
또한, 본 출원인이 발명하여 특허받은 한국등록특허 10-1810921(2017년12월14일)에는 공중합 가능한 아크릴 모노머 및 하이드록시 아크릴 모노머와 에틸아세테이트(EA)를 혼합, 그라프트 공중합시킨 그라프트 공중합체를 포함하여 조성되되, 상기 공중합 가능한 아크릴 모노머는 2-에틸헥실아크릴레이트(2-EHA)이고, 하이드록시 아크릴 모노머는 4-하이드록시부틸아크릴레이트(4-HBA)인 아크릴 점착제 조성물로서, 상기 아크릴 점착제 조성물은 유리전이온도(Tg)가 -80℃ ~ -63℃이고, 중량평균분자량이 85~95만이며, 코팅두께 10㎛에서의 내열 후 점착력 증가율이 190~230%인 것을 특징으로 하는 고웨팅성을 갖는 내열 아크릴 점착제 조성물이 공지된 바 있다.In addition, in Korean Patent Registration 10-1810921 (December 14, 2017) invented and patented by the present applicant, a graft copolymer obtained by mixing copolymerizable acrylic monomers, hydroxy acrylic monomers, and ethyl acetate (EA) A composition comprising, but the copolymerizable acrylic monomer is 2-ethylhexyl acrylate (2-EHA), and the hydroxy acrylic monomer is 4-hydroxybutyl acrylate (4-HBA) as an acrylic pressure-sensitive adhesive composition, wherein the acrylic The pressure-sensitive adhesive composition has a glass transition temperature (Tg) of -80°C to -63°C, a weight average molecular weight of 850,000 to 950,000, and an adhesive strength increase rate of 190 to 230% after heat resistance at a coating thickness of 10 μm. Heat-resistant acrylic pressure-sensitive adhesive compositions having tinting properties have been known.
그러나, 상기한 바와 같은 종래 특허기술들은 아크릴계 화합물에 가소제를 사용하거나, 친수성 극성기 함유 화합물을 사용하거나, 에폭시기를 사용함에 따라 반응물질과 제조방법이 복잡하고 그 점착제 조성물도 전자소재 공정에 사용하기에는 전사오염, 점착력의 증가, 박리시 소음 등의 물성이 만족스럽지 못한 문제점이 있었다. However, conventional patented technologies as described above are complicated by the use of a plasticizer for an acrylic compound, a compound containing a hydrophilic polar group, or an epoxy group, and the reaction material and manufacturing method are complicated, and the pressure-sensitive adhesive composition is also difficult to use in the electronic material process. There was a problem that physical properties such as contamination, increase in adhesion, and noise during peeling were not satisfactory.
특히, 상기 본 출원인의 한국등록특허 10-1810921(2017년12월14일)는 중량평균분자량이 85~95만으로서 고분자량이고 초기 점착력 및 내열 후 점착력이 높아 내열공정에 사용하기에는 불안정한 문제점이 있었다.In particular, the Korean Patent Registration No. 10-1810921 (December 14, 2017) of the applicant has a high molecular weight with a weight average molecular weight of 850,000 to 950,000, and has high initial adhesion and high adhesion after heat resistance, so it is unstable for use in a heat-resistant process. .
따라서 본 발명자들은 상기 문제점을 해결하기 위해 연구한 결과, 공중합 가능한 아크릴 모노머와; 하이드록실기 함유 모노머와; 카르복실기 함유 모노머와; 비이온계 (메트)아크릴레이트 모노머를 혼합, 그라프트 공중합시켜 중량평균분자량이 40~50만으로 기존 고분자보다 분자량이 낮은 반면, 점도가 높고, 초기 부착시 낮은 접착력과 보호기재에 대한 높은 웨팅성을 나타내며, 내열공정 후 점착력의 낮은 증가 폭을 나타내고, 내열 공정 후 박리 시 전사 및 소음이 없는 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물을 제조하고 본 발명을 완성하게 되었다.Accordingly, the present inventors have studied to solve the above problems, and as a result, a copolymerizable acrylic monomer; A hydroxyl group-containing monomer; A carboxyl group-containing monomer; Nonionic (meth)acrylate monomers are mixed and grafted to copolymerize, so that the weight average molecular weight is 40~500,000, but the molecular weight is lower than that of the existing polymer, while the viscosity is high, and at the time of initial attachment, low adhesion and high wettability to the protective substrate. The present invention was completed by preparing a heat-resistant acrylic pressure-sensitive adhesive composition having initial low-adhesion and high-wetting properties without transfer and noise when peeling after the heat-resistant process and exhibits a low increase in adhesive strength after the heat-resistant process.
본 발명은 상기한 문제점을 해결하기 위하여, 공중합 가능한 아크릴 모노머와; 하이드록실기 함유 모노머와; 카르복실기 함유 모노머와; 비이온계 (메트)아크릴레이트 모노머를 혼합, 그라프트 공중합시켜 중량평균분자량이 40~50만으로 기존 고분자보다 분자량이 낮은 반면, 점도가 높고, 초기 부착시 낮은 접착력과 보호기재에 대한 높은 웨팅성을 나타내며, 내열공정 후 점착력의 낮은 증가 폭을 나타내고, 내열 공정 후 박리 시 전사 및 소음이 없는 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물을 제공하는 것을 해결하고자 하는 과제로 한다.The present invention, in order to solve the above problems, and a copolymerizable acrylic monomer; A hydroxyl group-containing monomer; A carboxyl group-containing monomer; Nonionic (meth)acrylate monomers are mixed and grafted to copolymerize, so that the weight average molecular weight is 40~500,000, but the molecular weight is lower than that of the existing polymer, while the viscosity is high, and at the time of initial attachment, low adhesion and high wettability to the protective substrate. It is a subject to solve the problem of providing a heat-resistant acrylic pressure-sensitive adhesive composition having an initial low-adhesion and high-wetting property that exhibits a low increase in adhesive strength after the heat-resistant process and does not transfer and noise when peeling after the heat-resistant process.
본 발명은 상기 과제의 해결을 위하여, 공중합 가능한 아크릴 모노머와; 하이드록실기 함유 모노머와; 카르복실기 함유 모노머와; 비이온계 (메트)아크릴레이트 모노머를 혼합, 그라프트 공중합시킨 그라프트 공중합체를 포함하여 조성되는 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물을 과제의 해결수단으로 한다.In order to solve the above problems, the present invention includes a copolymerizable acrylic monomer; A hydroxyl group-containing monomer; A carboxyl group-containing monomer; A heat-resistant acrylic pressure-sensitive adhesive composition comprising a graft copolymer obtained by mixing and graft copolymerizing a nonionic (meth)acrylate monomer having initial low tack and high wetting properties is used as a solution to the problem.
상기 공중합 가능한 아크릴 모노머는 2-에틸헥실아크릴레이트(2-EHA)이고, 하이드록실기 함유 모노머는 4-하이드록시부틸아크릴레이트(4-HBA)이며, 카르복실기 함유 모노머는 에틸아세테이트(EA), (메트)아크릴산, 말레익산, 푸마르산, 이타콘산, 무수말레산으로 이루어진 군에서 선택되는 1종 이상이고, 비이온계 (메트)아크릴레이트 모노머는 페녹시에틸(메트)아크릴레이트, 폴리에틸렌글리콜(메트)아크릴레이트, 에톡시에톡시에틸아크릴레이트, 페녹시폴리에틸렌글리콜(메트)아크릴레이트, 노닐페놀폴리에틸렌글리콜(메트)아크릴레이트, 메톡시폴리에틸렌글리콜(메트)아크릴레이트, 폴리에틸렌글리콜모노(메트)아크릴레이트, 폴리프로필렌글리콜모노(메트)아크릴레이트, 폴리테트라메틸렌글리콜모노(메트)아크릴레이트, 폴리에틸렌글리콜폴리테트라메틸렌글리콜모노(메트)아크릴레이트, 폴리프로필렌글리콜폴리테트라메틸렌글리콜모노(메트)아크릴레이트로 이루어진 군에서 선택되는 1종 이상인 것을 과제의 해결수단으로 한다.The copolymerizable acrylic monomer is 2-ethylhexyl acrylate (2-EHA), the hydroxyl group-containing monomer is 4-hydroxybutyl acrylate (4-HBA), and the carboxyl group-containing monomer is ethyl acetate (EA), ( At least one selected from the group consisting of meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, and maleic anhydride, and nonionic (meth)acrylate monomers are phenoxyethyl (meth)acrylate, polyethylene glycol (meth) Acrylate, ethoxyethoxyethyl acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenol polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, Group consisting of polypropylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, polyethylene glycol polytetramethylene glycol mono(meth)acrylate, and polypropylene glycol polytetramethylene glycol mono(meth)acrylate At least one selected from is used as a means of solving the problem.
상기 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물은 유리전이온도(Tg)가 -63℃이하이고, 중량평균분자량이 40~50만인 것을 과제의 해결수단으로 한다.The heat-resistant acrylic pressure-sensitive adhesive composition having an initial low-adhesion and high-wetting property has a glass transition temperature (Tg) of -63°C or less, and a weight average molecular weight of 400,000 to 500,000 as a solution to the problem.
상기 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물은 점도가 1100~1200cps인 것을 과제의 해결수단으로 한다.The heat-resistant acrylic pressure-sensitive adhesive composition having an initial low tack and high wetting property has a viscosity of 1100 to 1200 cps as a solution to the problem.
상기 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물은 코팅두께 10㎛에서 상온 초기점착력이 2.0 gf/inch 인 것을 과제의 해결수단으로 한다.The heat-resistant acrylic pressure-sensitive adhesive composition having initial low tack and high wettability has an initial adhesive strength of 2.0 at room temperature at a coating thickness of 10 μm. What is gf/inch is the solution to the problem.
본 발명의 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물은 공중합 가능한 아크릴 모노머와; 하이드록실기 함유 모노머와; 카르복실기 함유 모노머와; 비이온계 (메트)아크릴레이트 모노머를 혼합, 그라프트 공중합시켜 중량평균분자량이 40~50만으로 기존 고분자보다 분자량이 낮은 반면, 점도가 높고, 초기 부착시 낮은 접착력과 보호기재에 대한 높은 웨팅성을 나타내며, 내열공정 후 점착력의 낮은 증가 폭을 나타내고, 내열 공정 후 박리 시 전사 및 소음이 없는 우수한 효과가 있다.The heat-resistant acrylic pressure-sensitive adhesive composition having an initial low-adhesion and high-wetting property of the present invention comprises a copolymerizable acrylic monomer; A hydroxyl group-containing monomer; A carboxyl group-containing monomer; Nonionic (meth)acrylate monomers are mixed and grafted to copolymerize, so that the weight average molecular weight is 40~500,000, but the molecular weight is lower than that of the existing polymer, while the viscosity is high, and at the time of initial attachment, low adhesion and high wettability to the protective substrate. It shows a low increase in adhesive strength after the heat-resistant process, and has excellent effects without transfer and noise when peeling after the heat-resistant process.
본 발명은, 공중합 가능한 아크릴 모노머와; 하이드록실기 함유 모노머와; 카르복실기 함유 모노머와; 비이온계 (메트)아크릴레이트 모노머를 혼합, 그라프트 공중합시킨 그라프트 공중합체를 포함하여 조성되는 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물을 기술구성의 특징으로 한다.The present invention is a copolymerizable acrylic monomer; A hydroxyl group-containing monomer; A carboxyl group-containing monomer; A heat-resistant acrylic pressure-sensitive adhesive composition comprising a graft copolymer obtained by mixing and graft copolymerizing a nonionic (meth)acrylate monomer having initial low tack and high wettability is characterized by the technical configuration.
상기 공중합 가능한 아크릴 모노머는 2-에틸헥실아크릴레이트(2-EHA)이고, 하이드록실기 함유 모노머는 4-하이드록시부틸아크릴레이트(4-HBA)이며, 카르복실기 함유 모노머는 에틸아세테이트(EA), (메트)아크릴산, 말레익산, 푸마르산, 이타콘산, 무수말레산으로 이루어진 군에서 선택되는 1종 이상이고, 비이온계 (메트)아크릴레이트 모노머는 페녹시에틸(메트)아크릴레이트, 폴리에틸렌글리콜(메트)아크릴레이트, 에톡시에톡시에틸아크릴레이트, 페녹시폴리에틸렌글리콜(메트)아크릴레이트, 노닐페놀폴리에틸렌글리콜(메트)아크릴레이트, 메톡시폴리에틸렌글리콜(메트)아크릴레이트, 폴리에틸렌글리콜모노(메트)아크릴레이트, 폴리프로필렌글리콜모노(메트)아크릴레이트, 폴리테트라메틸렌글리콜모노(메트)아크릴레이트, 폴리에틸렌글리콜폴리테트라메틸렌글리콜모노(메트)아크릴레이트, 폴리프로필렌글리콜폴리테트라메틸렌글리콜모노(메트)아크릴레이트로 이루어진 군에서 선택되는 1종 이상인 것을 기술구성의 특징으로 한다.The copolymerizable acrylic monomer is 2-ethylhexyl acrylate (2-EHA), the hydroxyl group-containing monomer is 4-hydroxybutyl acrylate (4-HBA), and the carboxyl group-containing monomer is ethyl acetate (EA), ( At least one selected from the group consisting of meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, and maleic anhydride, and nonionic (meth)acrylate monomers are phenoxyethyl (meth)acrylate, polyethylene glycol (meth) Acrylate, ethoxyethoxyethyl acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenol polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, Group consisting of polypropylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, polyethylene glycol polytetramethylene glycol mono(meth)acrylate, and polypropylene glycol polytetramethylene glycol mono(meth)acrylate At least one selected from is characterized by the technology configuration.
상기 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물은 유리전이온도(Tg)가 -63℃이하이고, 중량평균분자량이 40~50만인 것을 기술구성의 특징으로 한다.The heat-resistant acrylic pressure-sensitive adhesive composition having an initial low-adhesion and high-wetting property has a glass transition temperature (Tg) of -63°C or less, and a weight average molecular weight of 400,000 to 500,000.
상기 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물은 점도가 1100~1200cps인 것을 기술구성의 특징으로 한다.The initial low-adhesion and high-wetting heat-resistant acrylic pressure-sensitive adhesive composition is characterized in that the viscosity is 1100 ~ 1200cps.
상기 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물은 코팅두께 10㎛에서 상온 초기점착력이 2.0 gf/inch 인 것을 기술구성의 특징으로 한다.The heat-resistant acrylic pressure-sensitive adhesive composition having initial low tack and high wettability has an initial adhesive strength of 2.0 at room temperature at a coating thickness of 10 μm. It is gf/inch as a feature of the technology configuration.
이하에서는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예를 통하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구형될 수 있으며, 여기에서 설명하는 실시예에 한정되지 않는다.Hereinafter, it will be described in detail through embodiments of the present invention so that those of ordinary skill in the art can easily implement the present invention. However, the present invention may be spherical in various different forms, and is not limited to the embodiments described herein.
먼저, 본 발명의 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물은 공중합 가능한 아크릴 모노머와; 하이드록실기 함유 모노머와; 카르복실기 함유 모노머와; 비이온계 (메트)아크릴레이트 모노머를 혼합, 그라프트 공중합시킨 그라프트 공중합체를 포함하여 조성된다.First, the heat-resistant acrylic pressure-sensitive adhesive composition having an initial low-adhesion and high-wetting property of the present invention comprises a copolymerizable acrylic monomer; A hydroxyl group-containing monomer; A carboxyl group-containing monomer; It is composed of a graft copolymer obtained by mixing and graft copolymerizing a nonionic (meth)acrylate monomer.
여기서, 상기 공중합 가능한 아크릴 모노머는 필름에 점착력을 부여하는 기능을 하는데, 아크릴 모노머로는 특별한 제한이 없으나, 2-에틸헥실메타크릴레이트, 이소옥틸아크릴레이트, 2-에틸헥실아크릴레이트, 에틸아크릴레이트, n-부틸아크릴레이트, iso-부틸아크릴레이트 및 옥타데실메타크릴레이트로 이루어진 군으로부터 선택될 수 있으나, 2-에칠헥실아크릴레이트(2-EHA)를 사용하는 것이 바람직하다.Here, the copolymerizable acrylic monomer functions to impart adhesion to the film, but there is no particular limitation as an acrylic monomer, but 2-ethylhexyl methacrylate, isooctyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate , n-butyl acrylate, iso-butyl acrylate, and may be selected from the group consisting of octadecyl methacrylate, but it is preferable to use 2-ethylhexyl acrylate (2-EHA).
또한, 하이드록실기 함유 모노머는 특별한 제한이 있는 것은 아니지만, 2-하이드록시에틸메타아크릴레이트, 하이드록시에틸아크릴레이트, 4-하이드록시부틸아크릴레이트, 하이드록시프로필(메타)아크릴레이트 및 비닐카프로락탐으로 이루어진 군으로부터 선택되며, 4-하이드록시부틸아크릴레이트(4-HBA)를 사용하는 것이 바람직하다.In addition, the hydroxyl group-containing monomer is not particularly limited, but 2-hydroxyethyl methacrylate, hydroxyethyl acrylate, 4-hydroxybutyl acrylate, hydroxypropyl (meth) acrylate, and vinyl caprolactam It is selected from the group consisting of, and it is preferable to use 4-hydroxybutyl acrylate (4-HBA).
이때, 상기 아크릴 모노머는 낮은 경화 밀도, linear 한 구조를 가지고 있어 상대적으로 더 좋은 유동성을 가지므로 기재에 대한 웨팅성을 향상시키고, 상기 하이드록시 아크릴 모노머는 속건성이고 경화성이 우수하므로 미경화로 인한 점착력 증가를 억제하게 된다.At this time, since the acrylic monomer has a low curing density and a linear structure, it has relatively better fluidity, thus improving the wettability to the substrate, and the hydroxyacryl monomer is quick-drying and has excellent curing properties, so the adhesive strength due to uncuring is increased. Is suppressed.
또한, 본 발명의 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물은 카르복실기 함유 모노머로서 에틸아세테이트(EA), (메트)아크릴산, 말레익산, 푸마르산, 이타콘산, 무수말레산으로 이루어진 군에서 선택되는 1종 이상 사용하여 초기 저점착력을 나타내며, 내수성, 내용제성을 개선하였다.In addition, the heat-resistant acrylic pressure-sensitive adhesive composition having initial low tack and high wettability of the present invention is selected from the group consisting of ethyl acetate (EA), (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride as a carboxyl group-containing monomer. By using more than one type, it shows low initial adhesive strength, and improves water resistance and solvent resistance.
한편, 본 발명의 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물은 상기 공중합 가능한 아크릴 모노머와; 하이드록실기 함유 모노머와; 카르복실기 함유 모노머와 함께 비이온계 (메트)아크릴레이트 모노머를 혼합, 그라프트 공중합시켜 제조되며, 상기 비이온계 (메트)아크릴레이트 모노머는 분산안정성 및 친수성을 높이며, 공중합반응시 저분자량화 작용을 함과 동시에 공중합과정에서 3차원적 그물망모습의 고분자 조직을 형성하여 저분자량이면서도 공중합체의 고점도를 나타내도록 한다.On the other hand, the heat-resistant acrylic pressure-sensitive adhesive composition having an initial low-adhesion and high-wetting property of the present invention comprises the copolymerizable acrylic monomer; A hydroxyl group-containing monomer; It is prepared by mixing and graft copolymerizing a nonionic (meth)acrylate monomer with a carboxyl group-containing monomer, and the nonionic (meth)acrylate monomer increases dispersion stability and hydrophilicity, and has a low molecular weight effect during the copolymerization reaction. At the same time, in the process of copolymerization, a three-dimensional network-like polymer structure is formed to exhibit a low molecular weight and high viscosity of the copolymer.
특히, 상기 비이온계 (메트)아크릴레이트 모노머는 수산기가를 낮춤으로써, 당량 이상의 경화제 첨가에도 불구하고 후경화로 인한 내열 전후의 분자들의 움직임을 최소화하여 초기 점착성과 내열 후 점착성의 변화를 최소화한다.In particular, the nonionic (meth)acrylate monomer lowers the hydroxyl value, thereby minimizing the movement of molecules before and after heat resistance due to post-curing despite the addition of an equivalent or more curing agent, thereby minimizing changes in initial adhesion and adhesion after heat resistance. .
본 발명에서는 상기 비이온계 (메트)아크릴레이트 모노머로서, 페녹시에틸(메트)아크릴레이트, 폴리에틸렌글리콜(메트)아크릴레이트, 에톡시에톡시에틸아크릴레이트, 페녹시폴리에틸렌글리콜(메트)아크릴레이트, 노닐페놀폴리에틸렌글리콜(메트)아크릴레이트, 메톡시폴리에틸렌글리콜(메트)아크릴레이트, 폴리에틸렌글리콜모노(메트)아크릴레이트, 폴리프로필렌글리콜모노(메트)아크릴레이트, 폴리테트라메틸렌글리콜모노(메트)아크릴레이트, 폴리에틸렌글리콜폴리테트라메틸렌글리콜모노(메트)아크릴레이트, 폴리프로필렌글리콜폴리테트라메틸렌글리콜모노(메트)아크릴레이트로 이루어진 군에서 선택되는 1종 이상 사용할 수 있다.In the present invention, as the nonionic (meth)acrylate monomer, phenoxyethyl (meth)acrylate, polyethylene glycol (meth)acrylate, ethoxyethoxyethylacrylate, phenoxypolyethylene glycol (meth)acrylate, Nonylphenol polyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, One or more selected from the group consisting of polyethylene glycol polytetramethylene glycol mono(meth)acrylate and polypropylene glycol polytetramethylene glycol mono(meth)acrylate may be used.
아울러, 본 발명의 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물은 경화 후의 적절한 초기 점착력을 얻기 위해 -80~-40℃의 유리전이온도, 바람직하게는 -70~-50℃, 특히 바람직하게는 -63℃이하의 유리전이온도를 가지는데, 유리전이 온도가 약 -40℃를 초과하는 경우, 초기 점착력이 낮은 문제점이 있고, -80℃ 미만인 경우 경화전 높은 점착력에 의해 경화 후에도 점착력(박리력)이 높아지는 단점이 있다.In addition, the heat-resistant acrylic pressure-sensitive adhesive composition of the present invention having an initial low tack and high wetting property has a glass transition temperature of -80 to -40°C, preferably -70 to -50°C, particularly preferably in order to obtain an appropriate initial adhesive strength after curing. Has a glass transition temperature of -63°C or less, but when the glass transition temperature exceeds about -40°C, the initial adhesive strength is low, and if it is less than -80°C, the adhesive strength (peelable) after curing due to high adhesion before curing There is a disadvantage of increasing power).
또한, 본 발명의 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물은 평균분자량이 40~50만의 범위에서 가장 우수한 점착력을 나타내게 된다..In addition, the heat-resistant acrylic pressure-sensitive adhesive composition having an initial low-adhesion and high-wetting property of the present invention exhibits the best adhesive strength in the range of 40 to 500,000 average molecular weight.
상기와 같은 본 발명의 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물은 낮은 경화 밀도, linear 한 구조를 가지고 있어 좋은 유동성을 가지므로 웨팅성을 높일 수 있고, 속건성이며 경화성이 우수한 4-HBA를 사용하여 미경화로 인한 접착현상을 개선하였으며, 공중합후 저분자량화 및 고점도 효과를 나타내는 비이온계 (메트)아크릴레이트를 사용하여 열공정 테스트 전후의 수지와 피착면의 밀착정도 차이를 줄여주는 역할을 하여 열공정 후 점착력 증가폭이 줄어드는 성능을 발휘하게 된다.The heat-resistant acrylic pressure-sensitive adhesive composition of the present invention as described above has a low curing density and a linear structure, so it has good fluidity, so it is possible to increase the wetting property, and to use 4-HBA having excellent quick-drying and curing properties. It was used to improve the adhesion phenomenon due to uncured, and a nonionic (meth)acrylate that exhibits low molecular weight and high viscosity effects after copolymerization was used to reduce the difference in adhesion between the resin and the adherend before and after the thermal process test. Therefore, it exhibits the performance of reducing the increase in the adhesive strength after the thermal process.
질소 가스 도입관, 교반 장치, 온도계 및 콘트롤 장치, 비드컨덴서, 적하 깔대기, 맨틀등이 장착된 1리터의 4구 플라스크에 300 미리 리터 적하 깔대기를 장착하였다. 그리고 EAc, MeOH, 2-EHA, 4-HBA 및 페녹시폴리에틸렌글리콜(메트)아크릴레이트를 넣고 교반 후, 40oC로 승온 시켰다. 40oC 에서 개시제로서 아조비스이소부티로니트릴(2,2-Azobisisobutyronitrile(AIBN)을 투입시킨 뒤 온도를 더 승온 시켰다. 자체 발열이 형성 시 냉각수를 통해 온도조절을 하여 끓어 넘치지 않도록 하고, 중합이 진행되어 점도가 증가하는 것을 확인하며 온도를 유지시켰다. 반응 8시간 후 가열을 중지하고 냉각시킨 뒤 에틸아세테이트(EAc)를 넣어 점도와 NVM를 조정하여 본 발명의 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물을 수득하였다. 수득된 조성물의 유리전이온도(Tg)는 -63℃이고, 평균분자량이 40~50만, 점도는 1,180cps 였다.A 300 ml dropping funnel was attached to a 1 liter four-necked flask equipped with a nitrogen gas inlet tube, a stirring device, a thermometer and a control device, a bead condenser, a dropping funnel, and a mantle. And EAc, MeOH, 2-EHA, 4-HBA, and phenoxy polyethylene glycol (meth) acrylate were added and stirred, and the temperature was raised to 40 o C. Azobisisobutyronitrile (2,2-Azobisisobutyronitrile (AIBN) was added as an initiator at 40 ° C. Then, the temperature was further raised. When self-heating is formed, the temperature is controlled through cooling water so that it does not boil over, and polymerization does not occur. After 8 hours of reaction, heating was stopped and cooled, and the viscosity and NVM were adjusted by adding ethyl acetate (EAc) to ensure the initial low tack and high wetting resistance of the present invention. An acrylic pressure-sensitive adhesive composition was obtained, The glass transition temperature (Tg) of the obtained composition was -63°C, the average molecular weight was 400,000 to 500,000, and the viscosity was 1,180 cps.
[비교예 1][Comparative Example 1]
질소 가스 도입관, 교반 장치, 온도계 및 콘트롤 장치, 비드컨덴서, 적하 깔대기, 맨틀등이 장착된 1리터의 4구 플라스크에 300 미리 리터 적하 깔대기를 장착하였다. 그리고 EAc, MeOH, 2-EHA, 4-HBA를 넣고 교반 후, 40oC로 승온 시켰다. 40oC 에서 개시제로서 아조비스이소부티로니트릴(2,2-Azobisisobutyronitrile(AIBN)을 투입시킨 뒤 온도를 더 승온 시켰다. 자체 발열이 형성 시 냉각수를 통해 온도조절을 하여 끓어 넘치지 않도록 하고, 중합이 진행되어 점도가 증가하는 것을 확인하며 온도를 유지시켰다. 반응 8시간 후 가열을 중지하고 냉각시킨 뒤 에틸아세테이트(EAc)를 넣어 점도와 NVM를 조정하여 기존의 비교대상 점착제를 수득하였다. 수득된 조성물의 유리전이온도(Tg)는 -63℃이고, 평균분자량이 70~80만, 점도는 1,000cps였다.A 300 ml dropping funnel was attached to a 1 liter four-necked flask equipped with a nitrogen gas inlet tube, a stirring device, a thermometer and a control device, a bead condenser, a dropping funnel, and a mantle. Then, EAc, MeOH, 2-EHA, and 4-HBA were added and stirred, and the temperature was raised to 40 o C. Azobisisobutyronitrile (2,2-Azobisisobutyronitrile (AIBN) was added as an initiator at 40 ° C. Then, the temperature was further raised. When self-heating is formed, the temperature is controlled through cooling water so that it does not boil over, and polymerization does not occur. After 8 hours of reaction, heating was stopped and cooled, and the viscosity and NVM were adjusted by adding ethyl acetate (EAc) to obtain a conventional pressure-sensitive adhesive for comparison. The glass transition temperature (Tg) of was -63°C, the average molecular weight was 700,000 to 800,000, and the viscosity was 1,000 cps.
[시편제작][Prototype production]
[실시예 1]과 [비교예 1]에서 수득한 본 발명의 아크릴 점착조성물과 비교대상 아크릴 점착조성물을 다음 [표 1]에 나타난 바와 같이 CCL필름에 코팅하여 시편을 제작하였다.The acrylic adhesive composition of the present invention and the comparative acrylic adhesive composition obtained in [Example 1] and [Comparative Example 1] were coated on a CCL film as shown in the following [Table 1] to prepare a specimen.
[점착제의 상온 점착력 측정][Measurement of adhesive strength at room temperature of adhesive]
코팅된 CCL필름을 SUS304 시편에 2Kg Roll 압력으로 1회 왕복 부착하고 상온에서 20분 방치 후, 0-100N 범위 내에서 측정이 가능한 Shimadzu EZTest/CE(Japan) 제품을 사용하여 1인치 폭으로 절단되고 점착제가 코팅된 필름의 180도 박리력을 측정하여 그 결과를 [표 2]에 나타내었다.After attaching the coated CCL film to the SUS304 specimen with a 2Kg roll pressure once and leaving it for 20 minutes at room temperature, it is cut into 1 inch width using Shimadzu EZTest/CE (Japan) product that can be measured within the range of 0-100N. The 180 degree peeling force of the adhesive-coated film was measured and the results are shown in Table 2.
[점착제의 [Adhesive 내열후After heat resistance 점착력 측정] Adhesive force measurement]
코팅된 CCL필름을 SUS304 시편에 2Kg Roll 압력으로 1회 왕복 부착하고 상온에서 20분 방치 후, 오븐에서 150℃조건으로 30분 후 0-100N 범위 내에서 측정이 가능한 Shimadzu EZTest/CE(Japan) 제품을 사용하여 1인치 폭으로 절단되고 점착제가 코팅된 필름의 180도 박리력을 측정하여 그 결과를 [표 2]에 나타내었다.Shimadzu EZTest/CE(Japan) product that can measure within the range of 0-100N after attaching the coated CCL film to the SUS304 specimen at 2Kg Roll pressure once and leaving it at room temperature for 20 minutes and then 30 minutes at 150℃ in an oven. The peeling force of the film was cut to 1 inch width and coated with an adhesive was measured at 180 degrees, and the results are shown in Table 2.
(gf/inch)Room temperature adhesion
(gf/inch)
(gf/inch)Adhesion after resistance
(gf/inch)
상기 [표 2]에 나타난 바와 같이, 본 발명의 초기 저점착 및 고웨팅성을 갖는 내열 아크릴 점착제 조성물은 초기 점착력이 기존 제품보다 낮고, 내열 후 점착력 증가가 기존 제품 점착력 증가보다 낮은 것으로 나타났고, 박리시 소음도 없는 것을 확인 할 수 있다.As shown in [Table 2], the heat-resistant acrylic pressure-sensitive adhesive composition of the present invention having initial low-adhesion and high-wetting properties was found to have lower initial adhesive strength than existing products, and the increase in adhesive strength after heat resistance was lower than that of existing products. It can be confirmed that there is no city noise.
이상의 설명은 본 발명의 기술 사상을 예시적으로 설명한 것에 불과한 것으로서, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위 내에서 다양한 수정, 변경 및 치환이 가능할 것이다. 따라서, 본 발명에 개시된 실시예는 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 기술 사상의 범위가 한정되는 것은 아니다. 본 발명의 보호범위는 아래의 청구 범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술 사상은 본 발명의 권리 범위에 포함되는 것으로 해석되어야 할 것이다.The above description is merely illustrative of the technical idea of the present invention, and those of ordinary skill in the technical field to which the present invention belongs can make various modifications, changes, and substitutions within the scope not departing from the essential characteristics of the present invention. will be. Accordingly, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention, but to explain the technical idea, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be interpreted by the following claims, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of the present invention.
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