KR20140045786A - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
- Publication number
- KR20140045786A KR20140045786A KR1020120111970A KR20120111970A KR20140045786A KR 20140045786 A KR20140045786 A KR 20140045786A KR 1020120111970 A KR1020120111970 A KR 1020120111970A KR 20120111970 A KR20120111970 A KR 20120111970A KR 20140045786 A KR20140045786 A KR 20140045786A
- Authority
- KR
- South Korea
- Prior art keywords
- group
- weight
- acrylic copolymer
- adhesive composition
- sensitive adhesive
- Prior art date
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 239000000853 adhesive Substances 0.000 title abstract description 23
- 230000001070 adhesive effect Effects 0.000 title abstract description 23
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 36
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 30
- 125000000075 primary alcohol group Chemical group 0.000 claims abstract description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 aromatic isocyanate Chemical class 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 15
- 125000000524 functional group Chemical group 0.000 claims abstract description 15
- 239000012948 isocyanate Substances 0.000 claims abstract description 12
- 229920006243 acrylic copolymer Polymers 0.000 claims description 67
- 239000000178 monomer Substances 0.000 claims description 41
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 125000001174 sulfone group Chemical group 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 150000003623 transition metal compounds Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 abstract description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 23
- 238000004519 manufacturing process Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000000149 penetrating effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 206010040844 Skin exfoliation Diseases 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- AAUXVPAKDMCMMN-UHFFFAOYSA-N 2-[(4-ethenylphenoxy)methyl]oxirane Chemical compound C1=CC(C=C)=CC=C1OCC1OC1 AAUXVPAKDMCMMN-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- MGGVALXERJRIRO-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-2-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-1H-pyrazol-5-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)O MGGVALXERJRIRO-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000004260 weight control Methods 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
- 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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
본 발명은 응력 집중에 의한 빛샘 현상 방지와 동시에 내구성이 우수한 점착제 조성물에 관한 것이다.
The present invention relates to a pressure-sensitive adhesive composition with excellent durability while preventing light leakage due to stress concentration.
일반적으로 액정표시장치(Liquid crystal display device, LCD)는 액정을 포함하고 있는 액정셀과 편광판이 구비되며, 이를 접합하기 위한 적절한 점착제층이 사용된다.In general, a liquid crystal display device (LCD) is provided with a liquid crystal cell and a polarizing plate containing a liquid crystal, and an appropriate pressure-sensitive adhesive layer for bonding them is used.
편광판은 편광자와 상기 편광자를 보호하기 위하여 양면에 트리아세틸셀룰로오스계(TAC) 등의 보호필름이 적층된다. 또한, 광시야각 보상필름 및 기능성 필름을 부가적으로 포함할 수 있다.In order to protect the polarizer and the polarizer, the polarizing plate is laminated with protective films such as triacetyl cellulose (TAC). In addition, it may additionally include a wide viewing angle compensation film and a functional film.
이때, 각 필름들은 서로 다른 분자구조 및 조성을 가지는 재료로 만들어지므로 상이한 물리적 특성을 갖는다. 특히 고온 또는 고온 다습한 조건하에서는 일방성 분자 배열을 가진 재료들의 수축 또는 팽창에 따른 치수안정성이 부족하다. 따라서, 편광판이 점착제에 의해 고정되면 고온 또는 고온 다습한 조건하에서 편광판의 수축 또는 팽창에 의하여 TAC층에 응력이 집중되어, 편광판이 휘어지게 되므로 빛샘현상이 발생하는 단점이 있다.At this time, each film is made of a material having a different molecular structure and composition and thus have different physical properties. In particular, under high temperature or high temperature and high humidity conditions, dimensional stability due to shrinkage or expansion of materials having a unidirectional molecular arrangement is insufficient. Therefore, when the polarizing plate is fixed by the pressure-sensitive adhesive, stress is concentrated in the TAC layer by contraction or expansion of the polarizing plate under high temperature or high temperature and high humidity conditions, and thus the polarizing plate is bent, which causes a light leakage phenomenon.
이러한 휨은 편광판에 고정된 점착제의 응력완화 특성을 조절하여 잔류응력이 남지 않도록 함으로써 억제할 수 있으며, 이는 점착제가 미가교인 경우에 달성 가능하다. Such warpage can be suppressed by adjusting the stress relaxation property of the pressure-sensitive adhesive fixed to the polarizing plate so that residual stress does not remain, which can be achieved when the pressure-sensitive adhesive is uncrosslinked.
이에, 가교성 공중합체, 비가교성 공중합체 및 가교제가 함유하여, SEMI-INTER PENETRATING NETWORK 구조를 갖는 점착제가 제시되고 있다[한국등록특허 제948,778호]. 상기 점착제는 유동성 및 응력완화 특성이 우수하나, 최근 편광판의 대형화 및 박막화 경향에 적합한 내구성을 나타내지 못하는 한계가 있었다. Accordingly, a crosslinkable copolymer, a noncrosslinkable copolymer, and a crosslinking agent are contained, and an adhesive having a SEMI-INTER PENETRATING NETWORK structure has been proposed [Korean Patent No. 948,778]. The pressure-sensitive adhesive is excellent in fluidity and stress relaxation characteristics, but recently there was a limit that does not show the durability suitable for the trend of the size of the polarizing plate and thinning.
또한, 가교성 공중합체, 가교제, 다관능 아크릴레이트계 단량체 및 광개시제를 함유하여, INTER PENETRATING NETWORK 구조를 갖는 점착제가 제시되고 있다[한국등록특허 제983,026호]. 상기 점착제는 최근 경향을 만족할 수 있는 내구성의 구현은 가능하나, 응력완화성의 확보가 어려워 휨이 발생하는 한계가 있었다.
In addition, a pressure-sensitive adhesive having an INTER PENETRATING NETWORK structure containing a crosslinkable copolymer, a crosslinking agent, a polyfunctional acrylate monomer and a photoinitiator has been proposed [Korean Patent No. 983,026]. The pressure-sensitive adhesive is able to implement the durability that can satisfy the recent trend, but it is difficult to secure the stress relaxation property there was a limit that warpage occurs.
본 발명은 응력 완화로 휨 발생을 저하시켜 빛샘 현상을 방지할 뿐만 아니라 내구성이 우수한 점착제 조성물을 제공하는 데 그 목적이 있다.
The present invention is to provide a pressure-sensitive adhesive composition excellent in durability as well as preventing light leakage phenomenon by reducing the occurrence of warpage by stress relaxation.
상기 목적을 달성하기 위하여, 본 발명은 1차 알코올기를 갖는 아크릴계 공중합체, 에폭시기를 갖는 아크릴계 공중합체, 방향족 이소시아네이트계 가교제, 및 카르복시기, 페놀기 또는 이들의 혼합 작용기 함유 가교제를 함유하는 점착제 조성물을 제공한다. In order to achieve the above object, the present invention provides an adhesive composition containing an acrylic copolymer having a primary alcohol group, an acrylic copolymer having an epoxy group, an aromatic isocyanate crosslinking agent, and a carboxyl group, a phenol group or a mixed functional group-containing crosslinking agent. do.
상기 1차 알코올기를 갖는 아크릴계 공중합체는 하기 화학식 1 내지 5중에서 선택된 1종 이상의 단량체를 함유할 수 있다.The acrylic copolymer having a primary alcohol group may contain at least one monomer selected from the following formulas (1) to (5).
(식 중, R1은 수소원자 또는 메틸기이고, n은 2 내지 12의 정수임)(Wherein R 1 is a hydrogen atom or a methyl group, n is an integer from 2 to 12)
(식 중, R1은 수소원자 또는 메틸기이고, n은 1 내지 12의 정수임)(Wherein R 1 is a hydrogen atom or a methyl group, n is an integer from 1 to 12)
(식 중, R1은 수소원자 또는 메틸기이고, n은 1 내지 10의 정수임)(Wherein R 1 is a hydrogen atom or a methyl group, n is an integer from 1 to 10)
(식 중, R1은 수소원자 또는 메틸기임)Wherein R 1 is a hydrogen atom or a methyl group
(식 중, R1은 수소원자 또는 메틸기임).(Wherein R 1 is a hydrogen atom or a methyl group).
상기 1차 알코올기를 갖는 아크릴계 공중합체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 및 상기 화학식 1 내지 5중에서 선택된 1종 이상의 단량체를 함유할 수 있다.The acrylic copolymer having a primary alcohol group may contain a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and at least one monomer selected from Formulas 1 to 5.
상기 화학식 1 내지 5중에서 선택된 1종 이상의 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 0.1 내지 10중량부 함유할 수 있다.The at least one monomer selected from Formulas 1 to 5 may contain 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms.
상기 에폭시기를 갖는 아크릴계 공중합체는 하기 화학식 6 내지 8중에서 선택된 1종 이상의 단량체를 함유할 수 있다.The acrylic copolymer having the epoxy group may contain one or more monomers selected from the following Chemical Formulas 6 to 8.
(식 중, R1은 수소원자 또는 메틸기임)Wherein R 1 is a hydrogen atom or a methyl group
(식 중, R1은 수소원자 또는 메틸기임)Wherein R 1 is a hydrogen atom or a methyl group
상기 에폭시기를 갖는 아크릴계 공중합체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 및 상기 화학식 6 내지 8중에서 선택된 1종 이상의 단량체를 함유할 수 있다.The acrylic copolymer having the epoxy group may contain a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and at least one monomer selected from Formulas 6 to 8.
상기 화학식 6 내지 8중에서 선택된 1종 이상의 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 0.01 내지 5중량부 함유할 수 있다.The at least one monomer selected from Chemical Formulas 6 to 8 may contain 0.01 to 5 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms.
상기 카르복시기, 페놀기 또는 이들의 혼합 작용기 함유 가교제는 하기 화학식 9 내지 15중에서 선택된 1종 이상일 수 있다.The carboxyl group, phenol group or a mixed functional group-containing crosslinking agent thereof may be at least one selected from formulas (9) to (15).
(식 중, R1은 직접결합, 탄소수 1 내지 12의 지방족 탄화수소기, 카르보닐기, 술폰기, 탄소수 2 내지 6의 불소함유 지방족 탄화수소기 또는 산소원자임)(Wherein R 1 is a direct bond, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a carbonyl group, a sulfone group, a fluorine-containing aliphatic hydrocarbon group having 2 to 6 carbon atoms or an oxygen atom)
(식 중, R1은 직접결합, 탄소수 1 내지 12의 지방족 탄화수소기, 카르보닐기, 슬폰기, 탄소수 2 내지 6의 불소함유 지방족 탄화수소기 또는 산소원자임)(Wherein R 1 is a direct bond, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a carbonyl group, a sulfone group, a fluorine-containing aliphatic hydrocarbon group having 2 to 6 carbon atoms or an oxygen atom)
(식 중, R1은 탄소수 1 내지 12의 지방족 탄화수소기, 또는 산소원자, 질소원자 또는 황원자임)(Wherein R 1 is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an oxygen atom, a nitrogen atom, or a sulfur atom)
상기 점착제 조성물은 4차 암모늄염, 3차 아민 및 전이금속 화합물 중에서 선택된 1종 이상의 촉매를 추가로 함유할 수 있다.The pressure-sensitive adhesive composition may further contain at least one catalyst selected from quaternary ammonium salts, tertiary amines and transition metal compounds.
상기 1차 알코올기를 갖는 아크릴계 공중합체 60 내지 95중량%와 에폭시기를 갖는 아크릴계 공중합체 5 내지 40중량%를 함유하는 아크릴계 공중합체와, 상기 아크릴계 공중합체 100중량부에 대하여 방향족 이소시아네이트계 가교제 0.1 내지 5중량부 및 카르복시기, 페놀기 또는 이들의 혼합 작용기 함유 가교제 0.01 내지 0.5중량부를 함유할 수 있다.
Acrylic copolymer containing 60 to 95% by weight of the acrylic copolymer having the primary alcohol group and 5 to 40% by weight of the acrylic copolymer having an epoxy group, and 0.1 to 5 aromatic isocyanate crosslinking agent based on 100 parts by weight of the acrylic copolymer. It can contain a weight part and 0.01-0.5 weight part of carboxyl group, phenol group, or mixed functional group containing crosslinking agent.
본 발명의 점착제 조성물은 응력 완화로 휨 발생을 저하시켜 응력집중으로 인한 빛샘 현상을 방지할 뿐만 아니라 내구성이 우수한 이점이 있어 편광판 및 액정표시장치 등의 분야에 유용하게 활용될 수 있다.
The pressure-sensitive adhesive composition of the present invention can be usefully used in fields such as polarizing plates and liquid crystal display devices because the pressure-reduced warpage lowers the occurrence of warpage and prevents light leakage due to stress concentration.
본 발명은 응력 집중에 의한 빛샘 현상 방지와 동시에 내구성이 우수한 점착제 조성물에 관한 것이다.
The present invention relates to a pressure-sensitive adhesive composition with excellent durability while preventing light leakage due to stress concentration.
이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명의 점착제 조성물은 1차 알코올기를 갖는 아크릴계 공중합체, 에폭시기를 갖는 아크릴계 공중합체, 방향족 이소시아네이트계 가교제, 및 카르복시기, 페놀기 또는 이들의 혼합 작용기 함유 가교제를 함유한다.The pressure-sensitive adhesive composition of the present invention contains an acrylic copolymer having a primary alcohol group, an acrylic copolymer having an epoxy group, an aromatic isocyanate-based crosslinking agent, and a carboxyl group, a phenol group or a mixed functional group-containing crosslinking agent.
본 발명은 1차 알코올기를 갖는 아크릴계 공중합체와 에폭시기를 갖는 아크릴계 공중합체가 상호침투 가교(Inter penetrating network, IPN) 구조를 형성한다. According to the present invention, an acrylic copolymer having a primary alcohol group and an acrylic copolymer having an epoxy group form an inter penetrating network (IPN) structure.
구체적으로 본 발명은 아크릴계 공중합체와 가교제의 상대적인 입체장애 정도와 가교제의 반응속도 차이에 의해 단일 종류의 아크릴계 공중합체 사이에 가교반응이 수행되며 이들은 가교된 아크릴계 공중합체들 상호간에 침투하여 IPN 구조를 형성한다.Specifically, in the present invention, a crosslinking reaction is performed between a single type of acryl-based copolymer based on the relative degree of steric hindrance between the acryl-based copolymer and the crosslinking agent and the difference in the reaction rate of the crosslinking agent. Form.
상기 방향족 이소시아네이트계 가교제는 1차 알코올기를 갖는 아크릴계 공중합체의 가교반응, 카르복시기 또는 페놀기 함유 가교제는 에폭시기를 갖는 아크릴계 공중합체의 가교반응에 관여한다.The aromatic isocyanate crosslinking agent is involved in the crosslinking reaction of the acrylic copolymer having a primary alcohol group, and the carboxyl group or phenol group-containing crosslinking agent is involved in the crosslinking reaction of the acrylic copolymer having an epoxy group.
다만, 가교제들 사이에 반응이 수행될 수 있으나 이는 소량이므로 상기 공중합체들은 대부분 상호침투 가교(Inter penetrating network, IPN) 구조를 형성하고, IPN 구조에 의한 물리 화학적 특성을 갖는다.However, the reaction may be carried out between the crosslinking agents, but since the reaction is small, most of the copolymers form an inter penetrating network (IPN) structure and have physicochemical properties due to the IPN structure.
본 발명은 기존의 IPN구조 형성을 위한 다관능 아크릴레이트의 라디칼 가교를 이용하지 않고, 가교 관능기수가 적고 가교길이가 상대적으로 긴 우레탄 및 에스테르 가교의 이중 가교 시스템을 적용하여 IPN구조를 형성함으로써, 종래의 IPN 구조의 점착제 조성물에 비해 응력 완화성이 향상되고 동시에 내구성이 우수하다.
The present invention does not use radical crosslinking of a multifunctional acrylate for forming an existing IPN structure, and forms an IPN structure by applying a double crosslinking system of urethane and ester crosslinking having a small number of crosslinking functional groups and a relatively long crosslinking length. Compared with the pressure-sensitive adhesive composition of the IPN structure, the stress relaxation property is improved and at the same time, the durability is excellent.
1차 알코올기를 갖는 아크릴계 공중합체는 하기 화학식 1 내지 5중에서 선택된 1종 이상의 단량체를 함유하여 공중합된다. 화학식 1 내지 5중에서 선택된 1종 이상의 단량체는 화학결합에 의해 점착제 조성물의 응집력 또는 점착 강도를 보강하여 내구성과 절단성을 부여하는 가교성 단량체 성분이다. The acrylic copolymer having a primary alcohol group is copolymerized by containing at least one monomer selected from the following formulas (1) to (5). At least one monomer selected from Formulas 1 to 5 is a crosslinkable monomer component that enhances cohesive force or adhesive strength of the pressure-sensitive adhesive composition by chemical bonding to impart durability and cutability.
[화학식 1][Chemical Formula 1]
(식 중, R1은 수소원자 또는 메틸기이고, n은 2 내지 12의 정수임)(Wherein R 1 is a hydrogen atom or a methyl group, n is an integer from 2 to 12)
[화학식 2](2)
(식 중, R1은 수소원자 또는 메틸기이고, n은 1 내지 12의 정수임)(Wherein R 1 is a hydrogen atom or a methyl group, n is an integer from 1 to 12)
[화학식 3](3)
(식 중, R1은 수소원자 또는 메틸기이고, n은 1 내지 10의 정수임)(Wherein R 1 is a hydrogen atom or a methyl group, n is an integer from 1 to 10)
[화학식 4][Chemical Formula 4]
(식 중, R1은 수소원자 또는 메틸기임)Wherein R 1 is a hydrogen atom or a methyl group
[화학식 5][Chemical Formula 5]
(식 중, R1은 수소원자 또는 메틸기임).(Wherein R 1 is a hydrogen atom or a methyl group).
이 중 점착제 조성물의 내구성, 응력완화성 등을 동시에 고려하면, 2-하이드록시에틸(메타)아크릴레이트, 4-하이드록시부틸(메타)아크릴레이트, 2-하이드록시에틸(메타)아크릴아미드, 히드록시메틸(메타)아크릴아미드 및 상기 화학식 4의 화합물을 사용하는 것이 바람직하다.Considering the durability, stress relaxation property, etc. of an adhesive composition at the same time, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylamide, a hydride Preference is given to using oxymethyl (meth) acrylamide and the compound of formula (4).
본 발명의 1차 알코올기를 갖는 아크릴계 공중합체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 및 상기 화학식 1 내지 5중에서 선택된 1종 이상의 단량체를 함유하는 것이 바람직하다. 본 발명에 있어서, (메타)아크릴레이트는 아크릴레이트 및 메타크릴레이트를 의미한다.It is preferable that the acryl-type copolymer which has a primary alcohol group of this invention contains the (meth) acrylate monomer which has a C1-C12 alkyl group, and 1 or more types of monomers chosen from the said Formula (1-5). In the present invention, (meth) acrylate means acrylate and methacrylate.
상기 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체로는 n-부틸(메타)아크릴레이트, 2-부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 에틸(메타)아크릴레이트, 메틸(메타)아크릴레이트, n-프로필(메타)아크릴레이트, 프로필(메타)아크릴레이트, 펜틸(메타)아크릴레이트, n-옥틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 노닐(메타)아크릴레이트, 데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트 등을 들 수 있으며, 이들 중에서 n-부틸아크릴레이트, 2-에틸헥실아크릴레이트 또는 이들의 혼합물이 바람직하다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms include n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth). ) Acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, propyl (meth) acrylate, pentyl (meth) acrylate, n-octyl (meth) acrylate, Isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and the like, among which n-butyl acrylate, 2-ethylhexyl acrylate or Mixtures of these are preferred. These may be used alone or in combination of two or more.
상기 화학식 1 내지 5중에서 선택된 1종 이상의 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 0.1 내지 10중량부로 포함되는 것이 바람직하고, 보다 바람직하게는 0.5 내지 2중량부인 것이 좋다. 함량이 0.1중량부 미만인 경우 점착제의 응집력이 작아지게 되어 내구성이 저하될 수 있으며, 10중량부 초과인 경우 높은 겔분율에 의해 점착력이 떨어지고 내구성에 문제를 야기할 수 있다.The at least one monomer selected from Formulas 1 to 5 may be included in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms. Madam is good. When the content is less than 0.1 part by weight, the cohesive force of the pressure-sensitive adhesive becomes small and durability may be deteriorated. When the content is more than 10 parts by weight, a high gel fraction may deteriorate the adhesive strength and cause durability problems.
또한, 본 발명의 아크릴계 공중합체는 상기 단량체들 이외에 다른 중합성 단량체를 점착력을 저하시키지 않는 범위, 예컨대 총량에 대하여 10중량부 이하로 더 함유할 수 있다.The acrylic copolymer of the present invention may further contain other polymerizable monomers other than the above monomers in a range not lowering the adhesive force, for example, 10 parts by weight or less based on the total amount.
공중합체의 제조방법은 특별히 한정되지 않으며, 당 분야에서 통상적으로 사용되는 괴상중합, 용액중합, 유화중합 또는 현탁중합 등의 방법을 이용하여 제조할 수 있으며, 용액중합이 바람직하다. 또한, 중합 시 통상 사용되는 용매, 중합개시제, 분자량 제어를 위한 연쇄이동제 등을 사용할 수 있다.The method for producing the copolymer is not particularly limited and can be produced by methods such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, which are commonly used in the art, and solution polymerization is preferable. In addition, a solvent, a polymerization initiator, a chain transfer agent for molecular weight control and the like which are usually used in polymerization can be used.
아크릴계 공중합체는 겔투과크로마토그래피(Gel permeation chromatography, GPC)에 의해 측정된 중량평균분자량(폴리스티렌 환산, Mw)이 5만 내지 200만인 것이 바람직하며, 보다 바람직하기로는 40만 내지 200만인 것이 좋다. 중량평균분자량이 5만 미만인 경우 공중합체 간의 응집력이 부족하여 점착 내구성에 문제를 야기할 수 있고, 200만 초과인 경우 도공 시 공정성을 확보하기 위하여 다량의 희석 용매를 필요로 할 수 있다. The acrylic copolymer preferably has a weight average molecular weight (polystyrene conversion, Mw) of 50,000 to 2,000,000, more preferably 400,000 to 2,000,000 as measured by Gel Permeation Chromatography (GPC). When the weight-average molecular weight is less than 50,000, cohesion between co-polymers may be insufficient, which may cause problems in adhesion durability. If the weight average molecular weight is more than 2,000,000, a large amount of a diluting solvent may be required in order to ensure fairness in coating.
이러한 1차 알코올기를 갖는 아크릴계 공중합체는 60 내지 95중량% 함유하는 것이 바람직하며, 70 내지 90중량%가 보다 바람직하다. 함량이 60중량% 미만이면 내구성이 부족할 수 있고, 95중량%를 초과하는 경우에는 응력완화 특성이 부족할 수 있다.
It is preferable to contain 60-95 weight% of acrylic copolymers which have such a primary alcohol group, and 70-90 weight% is more preferable. If the content is less than 60% by weight may be insufficient durability, when it exceeds 95% by weight may be insufficient stress relaxation characteristics.
에폭시기를 갖는 아크릴계 공중합체는 하기 화학식 6 내지 8중에서 선택된 1종 이상의 단량체를 함유하여 공중합된다. 이때, 상기 화학식 6 내지 8의 단량체도 가교성 단량체의 역할을 한다.The acrylic copolymer having an epoxy group is copolymerized by containing at least one monomer selected from the following formulas (6) to (8). At this time, the monomer of Formula 6 to 8 also serves as a crosslinkable monomer.
[화학식 6][Chemical Formula 6]
(식 중, R1은 수소원자 또는 메틸기임)Wherein R 1 is a hydrogen atom or a methyl group
[화학식 7][Formula 7]
(식 중, R1은 수소원자 또는 메틸기임)Wherein R 1 is a hydrogen atom or a methyl group
[화학식 8][Chemical Formula 8]
이 중 점착제 조성물의 내구성, 응력완화성 등을 동시에 고려하면, 글리시딜메타아크릴레이트, 4-글리시독시스티렌이 바람직하며, 글리시딜메타아크릴레이트가 보다 바람직하다.Among them, glycidyl methacrylate and 4-glycidoxy styrene are preferable, and glycidyl methacrylate is more preferable in consideration of durability, stress relaxation property, and the like of the pressure-sensitive adhesive composition.
본 발명의 에폭시기를 갖는 아크릴계 공중합체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 및 상기 화학식 6 내지 8중에서 선택된 1종 이상의 단량체를 함유하는 것이 바람직하다. It is preferable that the acryl-type copolymer which has an epoxy group of this invention contains the (meth) acrylate monomer which has a C1-C12 alkyl group, and 1 or more types of monomers chosen from the said Formulas 6-8.
상기 화학식 6 내지 8중에서 선택된 1종 이상의 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 0.01 내지 5중량부로 포함되는 것이 바람직하고, 보다 바람직하게는 0.05 내지 2중량부인 것이 좋다. 함량이 0.01중량부 미만이면 점착제의 응집력이 작아지게 되어 내구성이 저하될 수 있으며, 5중량부 초과이면 응력완화성의 부족이 우려될 수 있다. The at least one monomer selected from Chemical Formulas 6 to 8 is preferably included in an amount of 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms. Madam is good. If the content is less than 0.01 parts by weight, the cohesive force of the pressure-sensitive adhesive may be reduced, the durability may be lowered.
이외에 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체의 종류, 중합방법, 제조된 아크릴계 공중합체의 중량평균분자량 등은 상기 1차 알코올기를 갖는 공중합체와 동일하다. In addition, the kind of the (meth) acrylate monomer which has a C1-C12 alkyl group, the polymerization method, the weight average molecular weight of the produced acrylic copolymer, etc. are the same as the copolymer which has the said primary alcohol group.
이러한 에폭시기를 갖는 아크릴계 공중합체는 5 내지 40중량% 함유하는 것이 바람직하며, 10 내지 30중량%가 보다 바람직하다. 함량이 5 중량% 미만이면 응력완화성능이 부족할 수 있고, 40중량%를 초과하는 경우에는 내구성이 저하될 수 있다.
It is preferable to contain 5-40 weight% of acrylic copolymers which have such an epoxy group, and 10-30 weight% is more preferable. If the content is less than 5% by weight may be insufficient stress relaxation performance, if the content exceeds 40% by weight may endurance.
방향족 이소시아네이트계 가교제, 및 카르복시기, 페놀기 또는 이들의 혼합 작용기 함유 가교제는 아크릴계 공중합체를 적절히 가교함으로써 점착제의 응집력을 강화하는 성분이다.An aromatic isocyanate type crosslinking agent, and a carboxyl group, a phenol group, or these mixed functional group containing crosslinking agents are components which strengthen the cohesion force of an adhesive by appropriately crosslinking an acrylic copolymer.
방향족 이소시아네이트계 가교제는 1차 알코올기를 갖는 아크릴계 공중합체의 가교반응에 관여한다. 구체적으로 톨릴렌 디이소시아네이트, 이의 이소시아누레이트 또는 다가알코올의 어덕트 형태일 수 있다.The aromatic isocyanate crosslinking agent is involved in the crosslinking reaction of the acrylic copolymer having a primary alcohol group. Specifically, it may be in the form of an adduct of tolylene diisocyanate, isocyanurate thereof or polyhydric alcohol.
이러한 방향족 이소시아네이트계 가교제는 1차 알코올기를 갖는 아크릴계 공중합체와 에폭시기를 갖는 아크릴계 공중합체의 총 함량 100중량부에 대하여 0.1 내지 5중량부 함유하는 것이 바람직하며, 0.8 내지 1.5중량부가 보다 바람직하다. 함량이 0.1중량부 미만이면 내구성 저하가 우려될 수 있고, 5중량부를 초과하는 경우에는 내구성 및 응력완화성의 동시 저하가 우려될 수 있다.Such an aromatic isocyanate-based crosslinking agent is preferably contained in an amount of 0.1 to 5 parts by weight, more preferably 0.8 to 1.5 parts by weight, based on 100 parts by weight of the total content of the acrylic copolymer having a primary alcohol group and the acrylic copolymer having an epoxy group. If the content is less than 0.1 part by weight may be a decrease in durability, if the content exceeds 5 parts by weight may be a concern of simultaneous degradation of durability and stress relaxation properties.
상기 카르복시기, 페놀기 또는 이들의 혼합 작용기 함유 가교제는 에폭시기를 갖는 아크릴계 공중합체의 가교반응에 관여한다. 구체적으로 한 분자 내에 카르복시산기 또는 페놀기 2개 이상 함유하거나, 한 분자 내에 각각 카르복시산과 페놀기를 1개 이상 동시에 함유하는 형태일 수 있다. The carboxyl group, phenol group or a mixed functional group-containing crosslinking agent thereof is involved in the crosslinking reaction of the acrylic copolymer having an epoxy group. Specifically, two or more carboxylic acid groups or phenol groups may be contained in one molecule, or one or more carboxylic acid and phenol groups may be simultaneously contained in one molecule.
상기 한 분자 내에 카르복시산기를 2개 이상 함유한 가교제는 일례로하기 화학식 9 내지 12중에서 선택된 1종 이상일 수 있다.The crosslinking agent containing two or more carboxylic acid groups in one molecule may be at least one selected from Formulas 9 to 12 as an example.
[화학식 9][Chemical Formula 9]
[화학식 10][Chemical formula 10]
[화학식 11](11)
[화학식 12][Chemical Formula 12]
(식 중, R1은 직접결합, 탄소수 1 내지 12의 지방족 탄화수소기, 카르보닐기, 술폰기, 탄소수 2 내지 6의 불소함유 지방족 탄화수소기 또는 산소원자임)(Wherein R 1 is a direct bond, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a carbonyl group, a sulfone group, a fluorine-containing aliphatic hydrocarbon group having 2 to 6 carbon atoms or an oxygen atom)
이때, 상기 화학식 12는 예컨대,
상기 한 분자 내에 페놀기를 2개 이상 함유한 가교제는 일례로 하기 화학식 13 또는 14일 수 있다.The crosslinking agent containing two or more phenol groups in one molecule may be, for example, the following Chemical Formula 13 or 14.
[화학식 13][Chemical Formula 13]
(식 중, R1은 직접결합, 탄소수 1 내지 12의 지방족 탄화수소기, 카르보닐기, 슬폰기, 탄소수 2 내지 6의 불소함유 지방족 탄화수소기 또는 산소원자임)(Wherein R 1 is a direct bond, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a carbonyl group, a sulfone group, a fluorine-containing aliphatic hydrocarbon group having 2 to 6 carbon atoms or an oxygen atom)
상기 화학식 13은 예컨대,
[화학식 14][Chemical Formula 14]
(식 중, R1은 탄소수 1 내지 12의 지방족 탄화수소기, 또는 산소원자, 질소원자 또는 황원자임)(Wherein R 1 is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an oxygen atom, a nitrogen atom, or a sulfur atom)
상기 한 분자 내에 각각 카르복시산과 페놀기를 1개 이상 동시에 함유한 가교제는 하기 화학식 15일 수 있다.The crosslinking agent containing at least one carboxylic acid and at least one phenol group simultaneously in one molecule may be represented by Formula 15 below.
[화학식 15][Chemical Formula 15]
이러한 카르복시기, 페놀기 또는 이들의 혼합 작용기 함유 가교제는 1차 알코올기를 갖는 아크릴계 공중합체와 에폭시기를 갖는 아크릴계 공중합체의 총 함량 100중량부에 대하여 0.01 내지 0.5중량부 함유하는 것이 바람직하며, 0.02 내지 0.05중량부가 보다 바람직하다. 함량이 0.01중량부 미만이면 내구성 저하가 우려될 수 있고, 0.5중량부를 초과하는 경우에는 응력완화성의 저하가 우려될 수 있다.
Such a carboxyl group, a phenol group or a mixed functional group-containing crosslinking agent thereof is preferably 0.01 to 0.5 parts by weight based on 100 parts by weight of the total content of the acrylic copolymer having a primary alcohol group and the acrylic copolymer having an epoxy group, and 0.02 to 0.05. A weight part is more preferable. If the content is less than 0.01 parts by weight may be a decrease in durability, if the content is more than 0.5 parts by weight may be a reduction in stress relaxation properties.
본 발명의 점착제 조성물은 양생속도를 감소시키기 위하여 촉매를 추가로 함유할 수 있다. 촉매는 가교제의 작용기인 카르복시기 또는 페놀기와, 공중합체의 에폭시기 사이의 반응속도를 향상시킬 수 있는 것으로, 예를 들면 4차 암모늄염, 3차 아민 및 전이금속 화합물 중에서 선택된 1종 이상일 수 있다.The pressure-sensitive adhesive composition of the present invention may further contain a catalyst in order to reduce the curing speed. The catalyst is capable of improving the reaction rate between the carboxyl group or the phenol group, which is a functional group of the crosslinking agent, and the epoxy group of the copolymer, and may be, for example, at least one selected from quaternary ammonium salts, tertiary amines, and transition metal compounds.
이러한 촉매는 1차 알코올기를 갖는 아크릴계 공중합체와 에폭시기를 갖는 아크릴계 공중합체의 총 함량 100중량부에 대하여 0.001 내지 1중량부 함유하는 것이 바람직하다. 함량이 0.001중량부 미만이면 그 양이 미미하여 목적으로 하는 효과 달성이 어려울 수 있으며, 1중량부를 초과하는 경우에는 촉매의 블리드 아웃에 의한 내구성의 저하가 우려될 수 있다Such a catalyst is preferably contained 0.001 to 1 parts by weight based on 100 parts by weight of the total content of the acrylic copolymer having a primary alcohol group and the acrylic copolymer having an epoxy group. If the content is less than 0.001 parts by weight, the amount may be insignificant, and thus, it may be difficult to achieve the desired effect. If the content is more than 1 part by weight, the durability of the catalyst by bleeding out may be a concern.
상기와 같은 성분 이외에, 점착제 조성물은 용도에 따라 요구되는 점착력, 응집력, 점성, 탄성률, 유리전이온도 등을 조절하기 위하여, 실란커플링제, 점착성 부여 수지, 산화방지제, 레벨링제, 표면윤활제, 염료, 안료, 소포제, 충전제, 광안정제, 대전방지제 등의 첨가제를 더 함유할 수 있다. In addition to the above components, the pressure-sensitive adhesive composition may further contain various additives such as a silane coupling agent, a tackifier resin, an antioxidant, a leveling agent, a surface lubricant, a dye, an antioxidant, and the like in order to control the adhesion, cohesion, viscosity, A pigment, a defoaming agent, a filler, a light stabilizer, an antistatic agent, and the like.
이중 실란커플링제는 점착제와 기재와의 밀착력을 향상시키는 역할을하므로 이를 함유하는 것이 바람직하며, 아미노기, 에폭시기, 아세토아세틸기, 폴리알킬렌글리콜기, 아크릴기, 알킬기 등의 관능기를 함유하는 알콕시실란을 사용할 수 있다.The double silane coupling agent serves to improve the adhesion between the pressure-sensitive adhesive and the substrate. Therefore, it is preferable that the double silane coupling agent contains an alkoxysilane containing an amino group, an epoxy group, an acetoacetyl group, a polyalkylene glycol group, an acryl group, Can be used.
이러한 첨가제는 본 발명의 효과를 저해하지 않는 범위내에서 적절히 함량을 조절할 수 있으며, 일례로 실란커플링제는 밀착력 및 내구성 등을 고려하여 아크릴계 공중합체 100중량부에 대하여 0.1 내지 2중량부 함유할 수 있다. The amount of such an additive may be suitably controlled within a range that does not impair the effect of the present invention. For example, the silane coupling agent may be contained in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the acrylic copolymer in consideration of adhesion strength and durability have.
본 발명의 점착제 조성물은 특히 액정셀과의 접합을 위한 편광판용 점착제, 표면보호필름용 점착제로 사용할 수 있다. 또한, 보호필름, 반사시트, 구조용 점착시트, 사진용 점착시트, 차선표시용 점착시트, 광학용 점착제품, 전자부품용 점착제뿐만 아니라 일반 상업용 점착시트제품으로도 사용 가능하다.
In particular, the pressure-sensitive adhesive composition of the present invention can be used as a pressure-sensitive adhesive for polarizing plates and a surface protective film for bonding to liquid crystal cells. In addition, it can be used as a general commercial adhesive sheet product as well as a protective film, a reflective sheet, a structural adhesive sheet, a photographic adhesive sheet, a lane marking adhesive sheet, an optical adhesive product, an adhesive for electronic parts, and the like.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.
제조예Manufacturing example : 아크릴계 공중합체 제조 : Acrylic copolymer preparation
제조예Manufacturing example A: 1차 A: 1st 알코올기를Alcohol groups 갖는 아크릴계 공중합체 Acrylic copolymer
제조예Manufacturing example A-1 A-1
질소가스가 환류되고 온도조절이 용이하도록 냉각장치를 설치한 1 L의 반응기에 n-부틸아크릴레이트(BA) 92중량부, 메틸아크릴레이트(MA) 7중량부, 2-하이드록시에틸아크릴레이트 1.0중량부로 이루어진 단량체 혼합물을 투입한 후, 용제로 아세톤 100중량부를 투입하였다. 그 다음 산소를 제거하기 위하여 질소가스를 1시간 동안 퍼징한 후, 55℃로 유지하였다. 상기 혼합물을 균일하게 한 후, 반응개시제로 아조비스이소부티로니트릴(AIBN) 0.02중량부를 투입하고, 12시간 동안 반응시켜 중량평균분자량이 약 150만인 1차 알코올기를 갖는 아크릴계 공중합체를 제조하였다.
92 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), 2-hydroxyethyl acrylate 1.0 in a 1 L reactor equipped with a refrigeration system to allow nitrogen gas to reflux and facilitate temperature control. After adding the monomer mixture consisting of parts by weight, 100 parts by weight of acetone was added as a solvent. Then, after purging nitrogen gas for 1 hour to remove oxygen, it was maintained at 55 ℃. After homogenizing the mixture, 0.02 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator, and reacted for 12 hours to have a primary alcohol group having a weight average molecular weight of about 1.5 million. Acrylic copolymer.
제조예Manufacturing example A-2 A-2
상기 제조예 A-1과 동일하게 실시하되, 2-하이드록시에틸아크릴레이트 대신에 화학식 4(식 중, R1은 수소 임)를 사용하여 1차 알코올기를 갖는 아크릴계 공중합체를 제조하였다.
The same procedure as in Preparation Example A-1, except that 2-hydroxyethyl acrylate has a primary alcohol group using Chemical Formula 4 (wherein R 1 is hydrogen). Acrylic copolymer.
제조예Manufacturing example A-3 A-3
상기 제조예 A-1과 동일하게 실시하되, 2-하이드록시에틸아크릴레이트 대신에 4-하이드록시부틸아크릴레이트 사용하여 1차 알코올기를 갖는 아크릴계 공중합체를 제조하였다.
In the same manner as in Preparation Example A-1, using 4-hydroxybutyl acrylate instead of 2-hydroxyethyl acrylate having a primary alcohol group Acrylic copolymer.
제조예Manufacturing example A-4 A-4
상기 제조예 A-1과 동일하게 실시하되, 2-하이드록시에틸아크릴레이트 대신에 4-하이드록시부틸비닐에테르를 사용하여 1차 알코올기를 갖는 아크릴계 공중합체를 제조하였다.
The same procedure as in Production Example A-1, except that 4-hydroxybutyl vinyl ether is used instead of 2-hydroxyethyl acrylate to have a primary alcohol group. Acrylic copolymer.
제조예Manufacturing example A-5 A-5
상기 제조예 A-1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 92중량부와 2-하이드록시에틸아크릴레이트 1중량부 대신에 n-부틸아크릴레이트(BA) 92.5중량부와 2-하이드록시에틸아크릴레이트 0.5중량부를 사용하여 1차 알코올기를 갖는 아크릴계 공중합체를 제조하였다.
In the same manner as in Preparation Example A-1, 92.5 parts by weight of n-butyl acrylate (BA) and 2-instead of 92 parts by weight of n-butyl acrylate (BA) and 1 part by weight of 2-hydroxyethyl acrylate. 0.5 parts by weight of hydroxyethyl acrylate having a primary alcohol group Acrylic copolymer.
제조예Manufacturing example A-6 A-6
상기 제조예 A-1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 92중량부와 2-하이드록시에틸아크릴레이트 1중량부 대신에 n-부틸아크릴레이트(BA) 90중량부와 2-하이드록시에틸아크릴레이트 3중량부를 사용하여 1차 알코올기를 갖는 아크릴계 공중합체를 제조하였다.
In the same manner as in Preparation Example A-1, 90 parts by weight of n-butyl acrylate (BA) and 2-instead of 92 parts by weight of n-butyl acrylate (BA) and 1 part by weight of 2-hydroxyethyl acrylate. Using 3 parts by weight of hydroxyethyl acrylate having a primary alcohol group Acrylic copolymer.
제조예Manufacturing example B: 에폭시기를 갖는 아크릴계 공중합체 B: acrylic copolymer having an epoxy group
제조예Manufacturing example B-1 B-1
질소가스가 환류되고 온도조절이 용이하도록 냉각장치를 설치한 1 L의 반응기에 n-부틸아크릴레이트(BA) 99.9중량부, 글리시딜메타아크릴레이트 0.1중량부로 이루어진 단량체 혼합물을 투입한 후, 용제로 아세톤 100중량부를 투입하였다. 그 다음 산소를 제거하기 위하여 질소가스를 1시간 동안 퍼징한 후, 65℃로 유지하였다. 상기 혼합물을 균일하게 한 후, 반응개시제로 아조비스이소부티로니트릴(AIBN) 0.1중량부를 투입하고, 6시간 동안 반응시켜 중량평균분자량이 약 40만인 에폭시기를 갖는 아크릴계 공중합체를 제조하였다.
After the nitrogen mixture was refluxed and a monomer mixture composed of 99.9 parts by weight of n-butyl acrylate (BA) and 0.1 part by weight of glycidyl methacrylate was added to a 1 L reactor equipped with a cooling device, and then a solvent. 100 parts by weight of acetone was added thereto. Then, after purging nitrogen gas for 1 hour to remove oxygen, it was maintained at 65 ℃. After uniformizing the mixture, 0.1 part by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator, and reacted for 6 hours to have an epoxy group having a weight average molecular weight of about 400,000. Acrylic copolymer.
제조예Manufacturing example B-2 B-2
상기 제조예 B-1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 99.9중량부와 글리시딜메타아크릴레이트 0.1중량부 대신에 n-부틸아크릴레이트(BA) 99.98중량부와 글리시딜메타아크릴레이트 0.02중량부를 사용하여 에폭시기를 갖는 아크릴계 공중합체를 제조하였다.
In the same manner as in Preparation Example B-1, 99.9 parts by weight of n-butyl acrylate (BA) and 99.98 parts by weight of n-butyl acrylate (BA) and glycidyl instead of 0.1 part by weight of glycidyl methacrylate. 0.02 part by weight of methacrylate to have an epoxy group Acrylic copolymer.
제조예Manufacturing example B-3 B-3
상기 제조예 B-1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 99.9중량부와 글리시딜메타아크릴레이트 0.1중량부 대신에 n-부틸아크릴레이트(BA) 99.7중량부, 글리시딜메타아크릴레이트 0.3중량부를 사용하여 에폭시기를 갖는 아크릴계 공중합체를 제조하였다.
The same process as in Preparation Example B-1, 99.9 parts by weight of n-butyl acrylate (BA) and 99.7 parts by weight of n-butyl acrylate (BA) instead of 0.1 part by weight of glycidyl methacrylate, glycidyl 0.3 parts by weight of methacrylate to have an epoxy group Acrylic copolymer.
제조예Manufacturing example B-4 B-4
상기 제조예 B-3과 동일하게 실시하되, 글리시딜메타아크릴레이트 0.1중량부 대신에 글리시딜알릴에테르(화학식 8) 0.3중량부를 사용하여 에폭시기를 갖는 아크릴계 공중합체를 제조하였다.
Doing the same as in Preparation Example B-3, but instead of 0.1 parts by weight of glycidyl methacrylate having 0.3 parts by weight of glycidyl allyl ether (Formula 8) having an epoxy group Acrylic copolymer.
제조예Manufacturing example C-1: 반응성 C-1: Reactivity 관능기Functional group 미함유 아크릴계 공중합체 Free Acrylic Copolymer
상기 제조예 B-1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 100중량부를 사용하여 아크릴계 공중합체를 제조하였다.
The same procedure as in Preparation Example B-1, except that 100 parts by weight of n-butyl acrylate (BA) was used to prepare an acrylic copolymer.
실시예Example 1-15 및 1-15 and 비교예Comparative Example 1-4 1-4
하기 표 1과 같이, 1차 알코올기를 갖는 아크릴계 공중합체, 에폭시기를 갖는 아크릴계 공중합체, 방향족 이소시아네이트계 가교제, 카르복시기 또는 페놀기 함유 가교제를 및 실란커플링제(3-글리시독시프로필트리메톡시실란, KBM-403제품, 신에츠사)와 테트라부틸암모늄브로마이드를 아크릴계 공중합체 100중량부에 대하여 각각 0.5중량부와 0.01중량부를 혼합한 후, 유기용매에 희석하여 점착제 조성물을 제조하였다.
As shown in Table 1 below, an acrylic copolymer having a primary alcohol group, an acrylic copolymer having an epoxy group, an aromatic isocyanate crosslinking agent, a carboxyl group or a phenol group-containing crosslinking agent and a silane coupling agent (3-glycidoxypropyltrimethoxysilane, KBM-403, Shin-Etsu Co., Ltd.) and tetrabutylammonium bromide were mixed with 0.5 parts by weight and 0.01 parts by weight with respect to 100 parts by weight of the acrylic copolymer, respectively, and then diluted in an organic solvent to prepare an adhesive composition.
(중량부)division
(Parts by weight)
D-1:
D-2:
D-3:
D-1:
D-2:
D-3:
비교예Comparative Example 5 5
상기 실시예 1과 동일하게 실시하되, 상기 제조예 B-1의 에폭시기를 갖는 아크릴계 공중합체 대신에 제조예 C-1의 아크릴계 공중합체를 사용하여 점착제 조성물을 제조하였다.
In the same manner as in Example 1, but having the epoxy group of Preparation Example B-1 An adhesive composition was prepared using the acrylic copolymer of Preparation Example C-1 instead of the acrylic copolymer.
비교예Comparative Example 6 6
제조예 A-1의 1차 알코올기를 갖는 아크릴계 공중합체 100중량부와 트리메틸올프로판의 톨리렌디이소시아네이트 부가물(TDI-1) 1.0중량부의 혼합물에, 1,6-헥산디올 디아크릴레이트(HDDA) 10중량부 및 a,a-메톡시-a-하이드록시아세토페논(Irgacure#-651) 1중량부를 넣은 후 충분히 교반하여 점착제 조성물을 제조하였다.
1,6-hexanediol diacrylate (HDDA) in a mixture of 100 parts by weight of the acrylic copolymer having a primary alcohol group of Production Example A-1 and 1.0 part by weight of tolylene diisocyanate adduct (TDI-1) of trimethylolpropane 10 parts by weight and 1 part by weight of a, a-methoxy-a-hydroxyacetophenone (Irgacure # -651) were added thereto, followed by sufficiently stirring to prepare an adhesive composition.
시험예Test Example
상기 실시예 및 비교예에서 제조된 점착제 조성물, 점착제 부착 편광판의 물성을 하기의 방법으로 측정하고, 그 결과를 하기 표 2에 나타내었다.
The physical properties of the pressure-sensitive adhesive composition and pressure-sensitive adhesive polarizing plate prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 2 below.
1.휨 1.Bending
상기의 제조된 점착제 부착 편광판을 17인치 코닝글라스의 일면에 접합하고, 오토크레이브 처리하였다, 이후에 80℃에서 100시간 열처리하고 상온에서 24시간 방치한 후, 평평한 면에 올려 놓고 가장 평면에서 높게 휜 변까지의 거리를 측정하여 휨 특성을 확인하였다. 이때, 높이가 10mm이하이면 휨 특성이 양호한 것으로 판단한다.
The prepared pressure-sensitive adhesive polarizing plate was bonded to one surface of 17-inch Corning glass and autoclaved. Then, the resultant was heat-treated at 80 ° C. for 100 hours, left at room temperature for 24 hours, and then placed on a flat surface to have a high flatness. The bending characteristic was confirmed by measuring the distance to a side. At this time, when the height is 10 mm or less, it is determined that the bending property is good.
2. 점착 내구성2. Adhesive durability
점착제 부착 편광판의 이형필름을 박리하고 점착제층 표면과 코닝글라스를 접합한 후, 60℃에서 300시간 방치한 후 외관을 확인하였다(내열시험). The release film of the polarizing plate with pressure-sensitive adhesive was peeled off, the surface of the pressure-sensitive adhesive layer was bonded to Corning glass, and after standing at 60 ° C. for 300 hours, the appearance was confirmed (heat resistance test).
<평가기준><Evaluation Criteria>
기포와 박리현상 시인됨: ×Bubbles and peeling phenomenon are observed: x
기포와 박리현상 미시인됨: ○
Bubbles and Peelings Unidentified: ○
상기 표 2와 같이, 본 발명에 따라 1차 알코올기를 갖는 아크릴계 공중합체, 에폭시기를 갖는 아크릴계 공중합체, 방향족 이소시아네이트계 가교제, 및 카르복시기, 페놀기 또는 이들의 혼합 작용기 함유 가교제를 함유한 실시예 1 내지 15의 점착제 조성물은 비교예 1 내지 6과 비교하면 휨 발생이 적고 내구성을 동시에 만족할 수 있음을 확인할 수 있었다.As shown in Table 2, Examples 1 to 1 containing an acrylic copolymer having a primary alcohol group, an acrylic copolymer having an epoxy group, an aromatic isocyanate-based crosslinking agent, and a carboxyl group, a phenol group or a mixed functional group-containing crosslinking agent according to the present invention. Compared with the comparative examples 1 to 6, the pressure-sensitive adhesive composition of 15 was confirmed that the generation of less warpage and durability can be satisfied at the same time.
Claims (10)
Acrylic copolymers having a primary alcohol group; Acrylic copolymer which has an epoxy group; Aromatic isocyanate crosslinking agents; And a carboxyl group, a phenol group or a mixed functional group-containing crosslinking agent thereof.
[화학식 1]
(식 중, R1은 수소원자 또는 메틸기이고, n은 2 내지 12의 정수임)
[화학식 2]
(식 중, R1은 수소원자 또는 메틸기이고, n은 1 내지 12의 정수임)
[화학식 3]
(식 중, R1은 수소원자 또는 메틸기이고, n은 1 내지 10의 정수임)
[화학식 4]
(식 중, R1은 수소원자 또는 메틸기임)
[화학식 5]
(식 중, R1은 수소원자 또는 메틸기임).
The pressure-sensitive adhesive composition of claim 1, wherein the acrylic copolymer having a primary alcohol group contains at least one monomer selected from the following Chemical Formulas 1-5:
[Chemical Formula 1]
(Wherein R 1 is a hydrogen atom or a methyl group, n is an integer from 2 to 12)
(2)
(Wherein R 1 is a hydrogen atom or a methyl group, n is an integer from 1 to 12)
(3)
(Wherein R 1 is a hydrogen atom or a methyl group, n is an integer from 1 to 10)
[Chemical Formula 4]
Wherein R 1 is a hydrogen atom or a methyl group
[Chemical Formula 5]
(Wherein R 1 is a hydrogen atom or a methyl group).
The pressure-sensitive adhesive composition of claim 2, wherein the acrylic copolymer having a primary alcohol group contains a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and at least one monomer selected from Formulas 1 to 5.
The pressure-sensitive adhesive composition of claim 3, wherein the at least one monomer selected from Formulas 1 to 5 contains 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms.
[화학식 6]
(식 중, R1은 수소원자 또는 메틸기임)
[화학식 7]
(식 중, R1은 수소원자 또는 메틸기임)
[화학식 8]
The pressure-sensitive adhesive composition of claim 1, wherein the acrylic copolymer having an epoxy group contains at least one monomer selected from Chemical Formulas 6 to 8.
[Chemical Formula 6]
Wherein R 1 is a hydrogen atom or a methyl group
(7)
Wherein R 1 is a hydrogen atom or a methyl group
[Chemical Formula 8]
The pressure-sensitive adhesive composition of claim 5, wherein the acrylic copolymer having an epoxy group contains a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and at least one monomer selected from Formulas 6 to 8.
The pressure-sensitive adhesive composition of claim 6, wherein the at least one monomer selected from Formulas 6 to 8 contains 0.01 to 5 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms.
[화학식 9]
[화학식 10]
[화학식 11]
[화학식 12]
(식 중, R1은 직접결합, 탄소수 1 내지 12의 지방족 탄화수소기, 카르보닐기, 술폰기, 탄소수 2 내지 6의 불소함유 지방족 탄화수소기 또는 산소원자임)
[화학식 13]
(식 중, R1은 직접결합, 탄소수 1 내지 12의 지방족 탄화수소기, 카르보닐기, 슬폰기, 탄소수 2 내지 6의 불소함유 지방족 탄화수소기 또는 산소원자임)
[화학식 14]
(식 중, R1은 탄소수 1 내지 12의 지방족 탄화수소기, 또는 산소원자, 질소원자 또는 황원자임)
[화학식 15]
The pressure-sensitive adhesive composition of claim 1, wherein the carboxyl group, phenol group, or mixed functional group-containing crosslinking agent is at least one selected from Formulas 9 to 15:
[Chemical Formula 9]
[Chemical formula 10]
(11)
[Chemical Formula 12]
(Wherein R 1 is a direct bond, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a carbonyl group, a sulfone group, a fluorine-containing aliphatic hydrocarbon group having 2 to 6 carbon atoms or an oxygen atom)
[Chemical Formula 13]
(Wherein R 1 is a direct bond, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a carbonyl group, a sulfone group, a fluorine-containing aliphatic hydrocarbon group having 2 to 6 carbon atoms or an oxygen atom)
[Chemical Formula 14]
(Wherein R 1 is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an oxygen atom, a nitrogen atom, or a sulfur atom)
[Chemical Formula 15]
The pressure-sensitive adhesive composition of claim 1, wherein the pressure-sensitive adhesive composition further contains at least one catalyst selected from quaternary ammonium salts, tertiary amines, and transition metal compounds.
상기 아크릴계 공중합체 100중량부에 대하여 방향족 이소시아네이트계 가교제 0.1 내지 5중량부 및 카르복시기, 페놀기 또는 이들의 혼합 작용기 함유 가교제 0.01 내지 0.5중량부를 함유하는 점착제 조성물. The acrylic copolymer according to claim 1, comprising 60 to 95% by weight of the acrylic copolymer having a primary alcohol group and 5 to 40% by weight of the acrylic copolymer having an epoxy group,
Pressure-sensitive adhesive composition containing 0.1 to 5 parts by weight of aromatic isocyanate-based crosslinking agent and 0.01 to 0.5 parts by weight of carboxyl group, phenol group or mixed functional group-containing crosslinking agent based on 100 parts by weight of the acrylic copolymer.
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| KR20170059158A (en) * | 2015-11-20 | 2017-05-30 | 동우 화인켐 주식회사 | Flexible touch-screen panel module and flexible display device comprising the same |
| KR20210034896A (en) * | 2019-09-23 | 2021-03-31 | 주식회사 엘지화학 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer and polarizing plate comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060047363A (en) * | 2004-04-22 | 2006-05-18 | 닛토덴코 가부시키가이샤 | Pressure-sensitive adhesive composition and manufacturing method and its use |
| KR20090011403A (en) * | 2007-07-26 | 2009-02-02 | 동우 화인켐 주식회사 | Adhesive composition and polarizing plate including same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20060047363A (en) * | 2004-04-22 | 2006-05-18 | 닛토덴코 가부시키가이샤 | Pressure-sensitive adhesive composition and manufacturing method and its use |
| KR20090011403A (en) * | 2007-07-26 | 2009-02-02 | 동우 화인켐 주식회사 | Adhesive composition and polarizing plate including same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20170059158A (en) * | 2015-11-20 | 2017-05-30 | 동우 화인켐 주식회사 | Flexible touch-screen panel module and flexible display device comprising the same |
| KR20210034896A (en) * | 2019-09-23 | 2021-03-31 | 주식회사 엘지화학 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer and polarizing plate comprising the same |
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