KR102197328B1 - Adhesive Composition and Adhesive Sheet Using the Same - Google Patents
Adhesive Composition and Adhesive Sheet Using the Same Download PDFInfo
- Publication number
- KR102197328B1 KR102197328B1 KR1020160127477A KR20160127477A KR102197328B1 KR 102197328 B1 KR102197328 B1 KR 102197328B1 KR 1020160127477 A KR1020160127477 A KR 1020160127477A KR 20160127477 A KR20160127477 A KR 20160127477A KR 102197328 B1 KR102197328 B1 KR 102197328B1
- Authority
- KR
- South Korea
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive composition
- polybutadiene
- hydroxy group
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 239000000853 adhesive Substances 0.000 title description 10
- 230000001070 adhesive effect Effects 0.000 title description 10
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 67
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 48
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 48
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 30
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- 239000012948 isocyanate Substances 0.000 claims abstract description 20
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 20
- 239000010954 inorganic particle Substances 0.000 claims description 10
- 239000002841 Lewis acid Substances 0.000 claims description 9
- 150000007517 lewis acids Chemical class 0.000 claims description 9
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 abstract description 15
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- -1 methylene, ethylene, propylene, butylene Chemical group 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000003760 tallow Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000012802 nanoclay Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 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 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 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
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J115/00—Adhesives based on rubber derivatives
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
Abstract
본 발명은 히드록시기 함유 폴리부타디엔 및 다관능 이소시아네이트 가교제를 포함하는 점착제 조성물을 제공한다. 본 발명에 따른 점착제 조성물은 배리어 특성과 내구성이 우수하여 OLED 등의 수분 취약성을 나타내는 유기전자소자를 봉지하여 보호하는데 적용될 수 있다.The present invention provides a pressure-sensitive adhesive composition comprising a hydroxy group-containing polybutadiene and a polyfunctional isocyanate crosslinking agent. The pressure-sensitive adhesive composition according to the present invention has excellent barrier properties and durability and can be applied to encapsulate and protect organic electronic devices exhibiting moisture fragility such as OLEDs.
Description
본 발명은 점착제 조성물 및 그를 이용한 점착 시트에 관한 것으로, 보다 상세하게는 배리어 특성과 내구성이 우수한 점착제 조성물 및 그를 이용한 점착 시트에 관한 것이다.The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet using the same, and more particularly, to a pressure-sensitive adhesive composition excellent in barrier properties and durability, and a pressure-sensitive adhesive sheet using the same.
차세대 평판 디스플레이(flat panel display)로서 주목 받고 있는 유기 발광 다이오드(Organic Light-Emitting Diode, OLED)는 양극과 음극 사이에 유기물을 증착 또는 용액 공정을 통해 필름을 형성하고 적층하여 만들어진 다이오드 형태의 소자이다. OLED는 자체발광형이기 때문에 시야각, 대조비 등이 우수하며 공정의 단순화가 가능하여 경량 박형화가 가능하다.Organic Light-Emitting Diode (OLED), which is attracting attention as a next-generation flat panel display, is a diode-type device made by depositing an organic material between the anode and the cathode or forming a film through a solution process and stacking it. . Since OLED is a self-luminous type, it has excellent viewing angle and contrast ratio, and simplification of the process makes it possible to reduce weight and thickness.
그러나, OLED는 수분 또는 산소 등의 외부적 요인에 취약하다. 특히, OLED는 유기물 층이 전극과의 계면에서 수분의 영향으로 박리되거나, 수분에 의해 전극이 산화하여 저항값이 높아지거나, 유기물 자체가 변질되어서 발광 기능의 상실 또는 휘도의 저하가 발생할 수 있다. 이에 따라, OLED를 외부 환경으로부터 보호하기 위하여 기판에 형성된 OLED를 배리어 특성을 갖는 점착 시트로 고정한 봉지 구조 등이 사용되고 있다.However, OLEDs are vulnerable to external factors such as moisture or oxygen. In particular, in the OLED, the organic material layer may be peeled off under the influence of moisture at the interface with the electrode, or the electrode may be oxidized by moisture to increase the resistance value, or the organic material itself may be deteriorated, resulting in loss of light-emitting function or reduction in brightness. Accordingly, in order to protect the OLED from the external environment, an encapsulation structure in which the OLED formed on the substrate is fixed with an adhesive sheet having barrier properties is used.
따라서, 최근 배리어 특성을 증가시킨 점착 시트에 대한 관심이 증가하고 있다. 예를 들어, 대한민국 특허공개 제10-2015-0079567호에는 폴리이소부틸렌계 수지, 스티렌계 공중합체 및 점착부여제를 포함하는 점착제 조성물로부터 형성되는 배리어 특성을 갖는 점착 시트가 개시되어 있다. 그러나, 상기 점착 시트는 OLED에 적용시 배리어 특성과 함께 내구성을 확보하기 어려운 문제점이 있었다.Therefore, interest in a pressure-sensitive adhesive sheet having increased barrier properties has recently increased. For example, Korean Patent Publication No. 10-2015-0079567 discloses a pressure-sensitive adhesive sheet having a barrier property formed from a pressure-sensitive adhesive composition comprising a polyisobutylene-based resin, a styrene-based copolymer, and a tackifier. However, when the pressure-sensitive adhesive sheet is applied to an OLED, it is difficult to secure durability as well as barrier properties.
본 발명의 한 목적은 배리어 특성과 내구성이 우수한 점착제 조성물을 제공하는 것이다.One object of the present invention is to provide a pressure-sensitive adhesive composition having excellent barrier properties and durability.
본 발명의 다른 목적은 상기 점착제 조성물을 이용하여 형성한 점착 시트를 제공하는 것이다.Another object of the present invention is to provide a pressure-sensitive adhesive sheet formed by using the pressure-sensitive adhesive composition.
한편으로, 본 발명은 히드록시기 함유 폴리부타디엔 및 다관능 이소시아네이트 가교제를 포함하는 점착제 조성물을 제공한다.On the one hand, the present invention provides a pressure-sensitive adhesive composition comprising a hydroxy group-containing polybutadiene and a polyfunctional isocyanate crosslinking agent.
본 발명의 일 실시형태에서, 상기 히드록시기 함유 폴리부타디엔은 하나 이상의 히드록시 말단기를 갖는 폴리부타디엔일 수 있다.In one embodiment of the present invention, the hydroxy group-containing polybutadiene may be a polybutadiene having one or more hydroxy end groups.
본 발명의 일 실시형태에서, 상기 히드록시기 함유 폴리부타디엔은 하기 화학식 1의 구조를 가질 수 있다:In one embodiment of the present invention, the hydroxy group-containing polybutadiene may have a structure represented by Formula 1:
[화학식 1] [Formula 1]
상기 식에서, In the above formula,
R1은 C1-C10의 알킬렌기이고, n은 20 내지 85의 정수이다.
R 1 is a C 1 -C 10 alkylene group, and n is an integer of 20 to 85.
본 발명의 일 실시형태에서, 상기 다관능 이소시아네이트 가교제가 3관능 이소시아네이트 가교제일 수 있다.In one embodiment of the present invention, the polyfunctional isocyanate crosslinking agent may be a trifunctional isocyanate crosslinking agent.
본 발명의 일 실시형태에서, 상기 점착제 조성물은 루이스산을 추가로 포함할 수 있다.In one embodiment of the present invention, the pressure-sensitive adhesive composition may further include Lewis acid.
본 발명의 일 실시형태에서, 상기 점착제 조성물은 판상 무기입자를 추가로 포함할 수 있다.
In one embodiment of the present invention, the pressure-sensitive adhesive composition may further include plate-shaped inorganic particles.
다른 한편으로, 본 발명은 상기 점착제 조성물을 이용하여 형성된 점착 시트를 제공한다.On the other hand, the present invention provides a pressure-sensitive adhesive sheet formed by using the pressure-sensitive adhesive composition.
본 발명에 따른 점착제 조성물은 히드록시기 함유 폴리부타디엔을 포함하여 배리어 특성이 우수할 뿐만 아니라 다관능 이소시아네이트 가교제에 의한 가교로 인해 내구성도 확보할 수 있어 OLED와 같은 수분 취약성 유기전자소자를 봉지하여 보호하는데 적용될 수 있다.The pressure-sensitive adhesive composition according to the present invention not only has excellent barrier properties, including hydroxy group-containing polybutadiene, but can also secure durability due to crosslinking by a multifunctional isocyanate crosslinking agent, and thus can be applied to encapsulate and protect organic electronic devices such as OLEDs. I can.
이하, 본 발명을 보다 상세히 설명한다.
Hereinafter, the present invention will be described in more detail.
본 발명의 일 실시형태는 히드록시기 함유 폴리부타디엔 및 다관능 이소시아네이트 가교제를 포함하는 점착제 조성물에 관한 것이다.
An embodiment of the present invention relates to a pressure-sensitive adhesive composition comprising a hydroxy group-containing polybutadiene and a polyfunctional isocyanate crosslinking agent.
본 발명의 일 실시형태에서, 상기 히드록시기 함유 폴리부타디엔은 하나 이상의 히드록시 말단기를 갖는 폴리부타디엔일 수 있으며, 바인더 수지로서의 역할을 한다.In one embodiment of the present invention, the hydroxy group-containing polybutadiene may be a polybutadiene having one or more hydroxy end groups, and serves as a binder resin.
상기 폴리부타디엔은 모노머로서 1,3-부타디엔을 중합하여 얻어지는 고분자이다. 상기 폴리부타디엔은 수소 첨가된 폴리부타디엔일 수 있다. 수소 첨가된 폴리부타디엔은 이중결합의 농도가 감소하여 배리어 특성면에서 유리하다.The polybutadiene is a polymer obtained by polymerizing 1,3-butadiene as a monomer. The polybutadiene may be hydrogenated polybutadiene. Hydrogenated polybutadiene is advantageous in terms of barrier properties because the concentration of double bonds decreases.
상기 폴리부타디엔은 하기 화학식 2 및 3으로부터 선택되는 1종 이상의 반복 단위를 포함할 수 있다.The polybutadiene may include one or more repeating units selected from Formulas 2 and 3 below.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
상기 식에서, In the above formula,
실선과 점선의 이중선은 단일결합 또는 이중결합을 나타내고,The double line of solid and dotted lines represents a single bond or a double bond,
파선은 이중결합의 경우에, 시스체 또는 트랜스체 중 어느 하나를 나타낸다.
In the case of a double bond, a broken line represents either a cis or a trans form.
상기 실선과 점선의 이중선이 이중결합을 나타내는 경우에는 수소 미첨가 폴리부타디엔이고, 단일결합을 나타내는 경우에는 수소 첨가된 폴리부타디엔이다. 수소 첨가된 폴리부타디엔의 경우, 이중결합은 100％ 수소 첨가되어 있을 필요는 없고, 이중결합의 잔존율은 특별히 한정되지 않는다.When the double line of the solid line and the dotted line represents a double bond, it is hydrogenated polybutadiene, and when it represents a single bond, it is hydrogenated polybutadiene. In the case of hydrogenated polybutadiene, 100% of the double bond does not need to be hydrogenated, and the residual ratio of the double bond is not particularly limited.
상기 화학식 3의 반복 단위가 이중결합을 갖는 경우에는 시스체, 트랜스체 또는 이들의 조합이 존재할 수 있다.
When the repeating unit of Formula 3 has a double bond, a cis form, a trans form, or a combination thereof may exist.
상기 화학식 2의 반복 단위는 1,3-부타디엔의 1,2-결합에 의해 형성되고, 화학식 3의 반복 단위는 1,3-부타디엔의 1,4-결합에 의해 형성된다.The repeating unit of Formula 2 is formed by a 1,2-bond of 1,3-butadiene, and the repeating unit of Formula 3 is formed by a 1,4-bond of 1,3-butadiene.
상기 화학식 2의 반복 단위와 화학식 3의 반복 단위의 비율은 각각 0 내지 100몰%이다. 즉, 상기 폴리부타디엔은 상기 화학식 2의 반복 단위 또는 화학식 3의 반복 단위만을 가지거나, 또는 상기 화학식 2의 반복 단위와 화학식 3의 반복 단위를 둘 다 가질 수 있다.The ratio of the repeating unit of Formula 2 and the repeating unit of Formula 3 is 0 to 100 mol%, respectively. That is, the polybutadiene may have only the repeating unit of Formula 2 or the repeating unit of Formula 3, or both of the repeating unit of Formula 2 and the repeating unit of Formula 3.
상기 화학식 2의 반복 단위와 화학식 3의 반복 단위는 중합시 사용되는 촉매에 따라 비율이 달라질 수 있으며, 특정 반복 단위가 우세하거나 또는 실질적으로 특정 반복 단위로 이루어진 폴리부타디엔이 형성될 수 있다. 예를 들어, 1,3-부타디엔을 지글러 촉매, 리튬 촉매 또는 라디칼 중합 개시제를 사용하여 중합시킬 경우 주로 1,4-결합에 의해 중합된 폴리부타디엔을 얻을 수 있고, 1,3-부타디엔을 나트륨 촉매의 존재 하에 중합시킬 경우 주로 1,2-결합에 의해 중합된 폴리부타디엔을 얻을 수 있다.The ratio of the repeating unit of Formula 2 and the repeating unit of Formula 3 may vary depending on the catalyst used during polymerization, and a specific repeating unit may predominate or polybutadiene may be substantially formed of a specific repeating unit. For example, when 1,3-butadiene is polymerized using a Ziegler catalyst, a lithium catalyst, or a radical polymerization initiator, polybutadiene polymerized mainly by 1,4-bonds can be obtained, and 1,3-butadiene is used as a sodium catalyst. In the case of polymerization in the presence of a polybutadiene polymerized mainly by 1,2-bonds can be obtained.
수소 첨가된 폴리부타디엔은 상기와 같이 중합된 폴리부타디엔을 수소 첨가 반응시켜 얻을 수 있다. 상기 수소 첨가 반응은 라니 니켈(Raney Nickel), 백금, 티타늄 등의 수소화 촉매의 존재 하에 당해 기술분야에 공지된 방법으로 수행할 수 있다.
Hydrogenated polybutadiene can be obtained by hydrogenating polybutadiene polymerized as described above. The hydrogenation reaction may be performed by a method known in the art in the presence of a hydrogenation catalyst such as Raney Nickel, platinum, or titanium.
본 발명의 일 실시형태에서, 상기 히드록시기 함유 폴리부타디엔은 하기 화학식 1의 구조를 가질 수 있다:In one embodiment of the present invention, the hydroxy group-containing polybutadiene may have a structure represented by Formula 1:
[화학식 1][Formula 1]
상기 식에서, In the above formula,
R1은 C1-C10의 알킬렌기이고, n은 20 내지 85의 정수이다.
R 1 is a C 1 -C 10 alkylene group, and n is an integer of 20 to 85.
본 명세서에서 사용되는 C1-C10의 알킬렌기는 탄소수 1 내지 10개로 구성된 직쇄형 또는 분지형의 탄화수소를 의미하며, 예를 들어 메틸렌, 에틸렌, 프로필렌, 부틸렌 등이 포함되나 이에 한정되는 것은 아니다.
The C 1 -C 10 alkylene group used herein refers to a straight-chain or branched hydrocarbon consisting of 1 to 10 carbon atoms, and includes, for example, methylene, ethylene, propylene, butylene, etc., but is limited thereto. no.
상기 히드록시기 함유 폴리부타디엔은 상업적으로 입수하거나, 당해 기술분야에 공지된 방법으로 제조하여 사용할 수 있다. 예를 들어, 상기 히드록시기 함유 폴리부타디엔은 폴리부타디엔을 에폭시 화합물과 반응시켜 제조할 수 있다. 상기 에폭시 화합물로는 에틸렌 옥사이드, 프로필렌 옥사이드 등을 사용할 수 있다. 시판되는 히드록시기 함유 폴리부타디엔으로는 닛폰 소다 사의 GI-1000, GI-2000, GI-3000 등을 예로 들 수 있다.
The hydroxy group-containing polybutadiene can be obtained commercially or can be prepared and used by a method known in the art. For example, the hydroxy group-containing polybutadiene can be prepared by reacting polybutadiene with an epoxy compound. Ethylene oxide, propylene oxide, or the like may be used as the epoxy compound. Examples of commercially available hydroxy group-containing polybutadiene include Nippon Soda's GI-1000, GI-2000, and GI-3000.
상기 히드록시기 함유 폴리부타디엔은 겔투과크로마토그래피(Gel permeation chromatography, GPC)에 의해 측정된 수평균분자량(폴리스티렌 환산)이 1,000 내지 5,000일 수 있다. 상기 히드록시기 함유 폴리부타디엔의 수평균분자량이 1,000 미만이면 수분차단 특성이 저하되거나 내열성이 저하될 수 있고, 5,000 초과이면 점착제 조성물의 점도가 상승하거나 점착력이 저하될 수 있다.
The hydroxy group-containing polybutadiene may have a number average molecular weight (in terms of polystyrene) measured by gel permeation chromatography (GPC) of 1,000 to 5,000. If the number average molecular weight of the hydroxy group-containing polybutadiene is less than 1,000, moisture barrier properties may decrease or heat resistance may decrease, and if it exceeds 5,000, the viscosity of the pressure-sensitive adhesive composition may increase or adhesive strength may decrease.
본 발명의 일 실시형태에서, 상기 다관능 이소시아네이트 가교제는 가교되어 점착제의 내구성을 강화하기 위한 성분으로서, 특히 3관능 이소시아네이트 가교제일 수 있다. 예를 들어, 상기 다관능 이소시아네이트 가교제는 트리메틸올프로판 등의 다가 알코올 화합물 1몰에 디이소시아네이트 화합물 3몰을 반응시킨 부가체, 디이소시아네이트 화합물 3몰을 자기 축합시킨 이소시아누레이트체, 디이소시아네이트 화합물 3몰 중 2몰로부터 얻어지는 디이소시아네이트 우레아에 나머지 1몰의 디이소시아네이트가 축합된 뷰렛체, 트리페닐메탄트리이소시아네이트, 메틸렌비스트리이소시아네이트 등을 들 수 있다.
In one embodiment of the present invention, the polyfunctional isocyanate crosslinking agent is a component for enhancing durability of the pressure-sensitive adhesive by crosslinking, and in particular, may be a trifunctional isocyanate crosslinking agent. For example, the polyfunctional isocyanate crosslinking agent is an adduct obtained by reacting 3 moles of a diisocyanate compound with 1 mole of a polyhydric alcohol compound such as trimethylolpropane, an isocyanurate compound obtained by self-condensing 3 moles of a diisocyanate compound, and a diisocyanate compound. A biuret body, triphenylmethane triisocyanate, methylene bistriisocyanate, and the like in which the remaining 1 mol of diisocyanate is condensed with diisocyanate urea obtained from 2 mol of 3 mol.
상기 다관능 이소시아네이트 가교제는 상기 히드록시기 함유 폴리부타디엔 전체 100 중량부에 대하여 1 내지 20 중량부, 예를 들어 1 내지 10 중량부로 포함될 수 있다. 상기 다관능 이소시아네이트 가교제의 함량이 1 중량부 미만이면 가교될 수 있는 모노머 양이 적으므로 바인더 수지인 히드록시기 함유 폴리부타디엔을 고정화시킬 수 있는 능력이 약해져 내구성이 저하될 수 있고, 20 중량부 초과이면 고경화로 인해 점착력이 저하되어 점착 내구성이 저하되고, 가교에 의해 생성되는 우레탄 관능기의 함량 증가로 인하여 수분차단 특성이 저하될 수 있다.
The polyfunctional isocyanate crosslinking agent may be included in an amount of 1 to 20 parts by weight, for example, 1 to 10 parts by weight, based on 100 parts by weight of the hydroxy group-containing polybutadiene. If the content of the polyfunctional isocyanate crosslinking agent is less than 1 part by weight, the amount of monomer that can be crosslinked is small, so the ability to immobilize the hydroxy group-containing polybutadiene, which is a binder resin, may be weakened, resulting in reduced durability, and if it exceeds 20 parts by weight, high curing As a result, adhesive strength is lowered, adhesive durability is lowered, and moisture barrier properties may be deteriorated due to an increase in the content of urethane functional groups generated by crosslinking.
본 발명의 일 실시형태에 따른 점착제 조성물은 루이스산을 추가로 포함할 수 있다.The pressure-sensitive adhesive composition according to an embodiment of the present invention may further include Lewis acid.
상기 루이스산은 히드록시기 함유 폴리부타디엔의 히드록시기와 가교제에 포함된 이소시아네이트기의 가교반응을 촉진시키는 촉매 역할을 하는 성분으로서, 전자의 수용 특성을 갖는 금속할라이드 또는 유기금속화합물일 수 있다. 예를 들어 디부틸틴 디라우레이트, 디부틸틴 옥시드, 디부틸틴 아세틸아세토네이트, 보론 트리플루오라이드, 알루미늄 트리클로라이드, 티타늄 트리클로라이드 등을 사용할 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.
The Lewis acid is a component that serves as a catalyst for accelerating the crosslinking reaction of the hydroxy group of the hydroxy group-containing polybutadiene and the isocyanate group contained in the crosslinking agent, and may be a metal halide or an organometallic compound having electron-accepting properties. For example, dibutyltin dilaurate, dibutyltin oxide, dibutyltin acetylacetonate, boron trifluoride, aluminum trichloride, titanium trichloride, etc. can be used, and these can be used alone or in combination of two or more. I can.
상기 루이스산은 상기 히드록시기 함유 폴리부타디엔 전체 100 중량부에 대하여 0.0001 내지 1 중량부로 포함될 수 있다. 상기 루이스산의 함량이 0.0001 중량부 미만이면 가교반응을 촉진시키는 효과가 부족할 수 있고, 1 중량부 초과이면 루이스산의 미용해 고형분이 잔류하거나 점착제 조성물의 저장안정성이 나빠질 수 있다.
The Lewis acid may be included in an amount of 0.0001 to 1 part by weight based on 100 parts by weight of the total polybutadiene containing the hydroxy group. If the content of the Lewis acid is less than 0.0001 parts by weight, the effect of promoting the crosslinking reaction may be insufficient, and if it exceeds 1 part by weight, the undissolved solid content of the Lewis acid may remain or the storage stability of the pressure-sensitive adhesive composition may be deteriorated.
본 발명의 일 실시형태에 따른 점착제 조성물은 판상 무기입자를 추가로 포함할 수 있다.The pressure-sensitive adhesive composition according to an embodiment of the present invention may further include plate-shaped inorganic particles.
상기 판상 무기입자는 수분의 이동을 차단하거나 방해하는 성분으로서, 예를 들어 나노 클레이일 수 있다. 상기 나노 클레이로는 층상의 실리케이트를 사용할 수 있으며, 이러한 층상의 실리케이트로는 몬모릴로나이트(montmorillonite), 사포나이트(saponite), 헥토라이트(hectorite), 버미큘라이트(vermiculite), 벤토나이트(bentonite), 아타풀자이트(attapulgite), 세피오라이트(sepiolite), 할로이사이트(halloysite) 등을 예로 들 수 있다. The plate-shaped inorganic particles are a component that blocks or interferes with the movement of moisture, and may be, for example, nanoclay. Layered silicate may be used as the nano-clay, and as such layered silicate, montmorillonite, saponite, hectorite, vermiculite, bentonite, attapulgite ( attapulgite), sepiolite, halloysite, and the like.
상기 나노 클레이는 바인더 수지와의 상용성을 향상시키기 위하여 유기 개질제로 개질된 것을 사용할 수 있다. 상기 유기개질제로는 디메틸 벤질 수소화 탈로우 4차 암모늄 이온, 비스(수소화 탈로우) 디메틸 4차 암모늄 이온, 메틸 탈로우 비스-2-히드록시에틸 4차 암모늄 이온, 디메틸 수소화 탈로우 2-에틸헥실 4차 암모늄 이온 또는 디메틸 탈수소화 탈로우 4차 암모늄 이온 등을 예로 들 수 있다.
The nanoclay may be modified with an organic modifier in order to improve compatibility with a binder resin. The organic modifiers include dimethyl benzyl hydrogenated tallow quaternary ammonium ion, bis (hydrogenated tallow) dimethyl quaternary ammonium ion, methyl tallow bis-2-hydroxyethyl quaternary ammonium ion, dimethyl hydrogenated tallow 2-ethylhexyl Quaternary ammonium ions or dimethyl dehydrogenated tallow quaternary ammonium ions, and the like.
상기 판상 무기입자는 상기 히드록시기 함유 폴리부타디엔 전체 100 중량부에 대하여 1 내지 20 중량부로 포함될 수 있다. 상기 판상 무기입자의 함량이 1 중량부 미만이면 배리어 특성 향상 효과가 부족할 수 있고, 20 중량부 초과이면 점착제 조성물의 점도가 상승하여 코팅 불균일이 발생할 수 있고, 젖음성 저하 및 점착력의 저하로 인해 점착 내구성이 저하될 수 있다.
The plate-shaped inorganic particles may be included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the total polybutadiene containing the hydroxy group. If the content of the plate-shaped inorganic particles is less than 1 part by weight, the effect of improving the barrier properties may be insufficient, and if it exceeds 20 parts by weight, the viscosity of the pressure-sensitive adhesive composition may increase, resulting in coating unevenness, and adhesion durability due to lower wettability and lower adhesive strength. This can be degraded.
본 발명의 일 실시형태에 따른 점착제 조성물들은 상기와 같은 성분 이외에, 용도에 따라 요구되는 점착력, 응집력, 점성, 탄성률, 유리전이온도, 대전방지성 등을 조절하기 위하여, 실란 커플링제, 점착성 부여 수지, 산화방지제, 부식방지제, 레벨링제, 표면윤활제, 염료, 안료, 소포제, 충전제, 광안정제, 대전방지제 등의 첨가제를 더 포함할 수 있다.
In addition to the above components, the pressure-sensitive adhesive composition according to an embodiment of the present invention includes a silane coupling agent, a tackifier resin in order to control adhesive force, cohesive force, viscosity, elastic modulus, glass transition temperature, antistatic properties, etc. , Antioxidants, corrosion inhibitors, leveling agents, surface lubricants, dyes, pigments, antifoaming agents, fillers, light stabilizers, may further include additives such as antistatic agents.
본 발명의 일 실시형태는 상기 점착제 조성물을 이용하여 형성된 점착 시트에 관한 것이다.
One embodiment of the present invention relates to a pressure-sensitive adhesive sheet formed by using the pressure-sensitive adhesive composition.
본 발명의 일 실시형태에 따른 점착 시트는 2매의 기재 필름 사이에 본 발명에 따른 점착제 조성물로부터 형성된 점착제층이 개재된 것일 수 있다.The pressure-sensitive adhesive sheet according to an embodiment of the present invention may be a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present invention interposed between two base films.
상기 기재 필름은 폴리올레핀계 필름, 폴리에스테르계 필름, 아크릴계 필름, 스티렌계 필름, 아미드계 필름, 폴리염화비닐 필름, 폴리염화비닐리덴 필름, 폴리카보네이트 필름 등을 들 수 있으며, 이들은 실리콘계, 불소계, 실리카 분말 등에 의해 적절히 이형 처리된 것일 수도 있다.The base film may be a polyolefin-based film, a polyester-based film, an acrylic film, a styrene-based film, an amide-based film, a polyvinyl chloride film, a polyvinylidene chloride film, a polycarbonate film, and the like, which are silicone-based, fluorine-based, and silica It may have been suitably molded out by powder or the like.
점착제층은 1매의 기재 필름 상에 점착제 조성물을 도공하는 방법으로 형성할 수 있다. 도공방법은 당해 분야에서 공지된 방법이라면 특별히 한정되지 않으며, 예를 들면 바코터, 에어 나이프, 그라비아, 리버스롤, 키스 롤, 스프레이, 블레이드, 다이 코터, 캐스팅, 스핀 코팅 등의 방법을 이용할 수 있다. 구체적으로, 1매의 기재 필름 상에 점착제 조성물을 도포하고, 30 내지 150℃에서 1초 내지 2시간, 바람직하게는 5초 내지 1시간 동안 건조한 후 약 100 내지 2000 mJ/㎠, 바람직하게는 200 내지 1500 mJ/㎠의 자외선 조사량으로 조사하여 경화시켜 형성할 수 있다.
The pressure-sensitive adhesive layer can be formed by coating the pressure-sensitive adhesive composition on one base film. The coating method is not particularly limited as long as it is a method known in the art, and for example, a bar coater, air knife, gravure, reverse roll, kiss roll, spray, blade, die coater, casting, spin coating, etc. may be used. . Specifically, a pressure-sensitive adhesive composition is applied on one base film, dried at 30 to 150° C. for 1 second to 2 hours, preferably 5 seconds to 1 hour, and then about 100 to 2000 mJ/cm 2, preferably 200 It can be formed by curing by irradiation with an ultraviolet irradiation dose of 1500 mJ/cm 2.
상기 점착제층의 두께는 5 내지 200㎛, 바람직하게는 5 내지 100㎛일 수 있다. 상기 점착제층의 두께가 5㎛ 미만이면 배리어 특성이 떨어지거나 외부로부터 발생하는 충격을 완충하기 어려울 수 있고, 200㎛ 초과이면 재료의 사용량 증가에 따른 단가 상승이 발생할 수 있으며, 건조시 용제의 휘발에 의한 표면 불균일이 발생할 수 있다.
The thickness of the pressure-sensitive adhesive layer may be 5 to 200 μm, preferably 5 to 100 μm. If the thickness of the pressure-sensitive adhesive layer is less than 5 μm, the barrier property may be deteriorated or it may be difficult to buffer external impacts. If it exceeds 200 μm, the unit price may increase due to the increase in the amount of material used. Surface unevenness may occur.
본 발명의 일 실시형태에 따른 점착 시트는 접합 전에 점착제층을 표면처리하여 밀착성을 향상시킬 수도 있다.The pressure-sensitive adhesive sheet according to an embodiment of the present invention may improve adhesion by surface-treating the pressure-sensitive adhesive layer before bonding.
표면처리 방법은 특별히 한정되지 않으며, 예컨대 코로나 방전 처리, 플라즈마 처리, 자외선 조사, 전자빔 조사 또는 정착제(anchoring agent) 도포 등과 같은 방법으로 점착제층의 표면을 활성화시킬 수 있다.
The surface treatment method is not particularly limited, and the surface of the pressure-sensitive adhesive layer may be activated by a method such as corona discharge treatment, plasma treatment, ultraviolet irradiation, electron beam irradiation, or application of an anchoring agent.
본 발명의 일 실시형태에 따른 점착 시트는 유기 발광 다이오드(OLED), 태양전지, 이차전지, 터치패널 등에 적용 가능하다. 특히, 본 발명의 일 실시형태에 따른 점착제 조성물은 수분 또는 산소 등의 외부적 요인에 민감한 OLED 등을 봉지(encapsulation)하여 보호하는데 사용될 수 있다.
The pressure-sensitive adhesive sheet according to an embodiment of the present invention can be applied to an organic light emitting diode (OLED), a solar cell, a secondary battery, a touch panel, and the like. In particular, the pressure-sensitive adhesive composition according to an embodiment of the present invention may be used to encapsulate and protect OLEDs that are sensitive to external factors such as moisture or oxygen.
이하, 실시예, 비교예 및 실험예에 의해 본 발명을 보다 구체적으로 설명하고자 한다. 이들 실시예, 비교예 및 실험예는 오직 본 발명을 설명하기 위한 것으로, 본 발명의 범위가 이들에 국한되지 않는다는 것은 당업자에게 있어서 자명하다.
Hereinafter, the present invention will be described in more detail by Examples, Comparative Examples and Experimental Examples. These Examples, Comparative Examples and Experimental Examples are for illustrative purposes only, and it is obvious to those skilled in the art that the scope of the present invention is not limited thereto.
실시예Example 1 내지 5 및 1 to 5 and 비교예Comparative example 1 내지 2: 점착제 조성물 및 점착 시트의 제조 1 to 2: Preparation of pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet
히드록시기 함유 폴리부타디엔, 3관능 이소시아네이트 가교제, 루이스산 및 판상 무기입자를 하기 표 1의 조성으로 혼합한 후(단위: 중량부), 에틸아세테이트에 28중량%의 농도로 희석하여 점착제 조성물을 제조하였다.
Polybutadiene containing a hydroxy group, trifunctional isocyanate crosslinking agent, Lewis acid, and plate-shaped inorganic particles were mixed in the composition shown in Table 1 below (unit: parts by weight), and then diluted to a concentration of 28% by weight in ethyl acetate to prepare a pressure-sensitive adhesive composition.
히드록시기 함유 폴리부타디엔: GI-2000(수평균 분자량: 2,100, 닛폰 소다 사)Hydroxy group-containing polybutadiene: GI-2000 (number average molecular weight: 2,100, Nippon Soda)
폴리부타디엔: BI-2000(수평균 분자량: 2,100, 닛폰 소다 사)Polybutadiene: BI-2000 (number average molecular weight: 2,100, Nippon Soda Corporation)
3관능 이소시아네이트 가교제: 코로네이트-L(톨릴렌디이소시아네이트 부가물, 일본우레탄사)Trifunctional isocyanate crosslinking agent: Coronate-L (Tolylene diisocyanate adduct, Nippon Urethane)
2관능 이소시아네이트 가교제: 톨릴렌디이소시아네이트 단량체(TDI, 알드리치사)Bifunctional isocyanate crosslinking agent: Tolylene diisocyanate monomer (TDI, Aldrich)
루이스산: 디부틸틴 디라우레이트Lewis acid: dibutyltin dilaurate
판상 무기입자: 비스(수소화 탈로우) 디메틸 4차 암모늄 이온으로 개질된 나노 클레이(Cloisite93A, Southern Clay Products)
Plate-shaped inorganic particles: Nano clay modified with bis (hydrogenated tallow) dimethyl quaternary ammonium ion (Cloisite93A, Southern Clay Products)
상기에서 제조된 점착제 조성물을 실리콘 이형제가 코팅된 이형필름 상에 두께가 100㎛가 되도록 도포하고 130℃에서 5분 동안 건조시켜 점착제층을 형성하고, 그 위에 이형필름을 접합한 후 하기의 조건과 같이 UV처리하여 점착 시트를 제작하였다.
The pressure-sensitive adhesive composition prepared above was applied to a thickness of 100 μm on a release film coated with a silicone release agent, and dried at 130° C. for 5 minutes to form a pressure-sensitive adhesive layer, and after bonding the release film thereon, the following conditions were applied. The adhesive sheet was prepared by UV treatment as well.
<자외선 처리 조건><Ultraviolet ray treatment conditions>
자외선 조사기: 고압 수은 램프UV irradiator: high pressure mercury lamp
조사 조건: 광량(UVA) = 1500 mJ/cm2
Irradiation conditions: Light quantity (UVA) = 1500 mJ/cm 2
실험예Experimental example 1: One:
실시예 및 비교예에서 제조된 점착 시트의 물성을 하기의 방법으로 측정하고, 그 결과를 하기 표 2에 나타내었다.
The physical properties of the pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 2 below.
(1) 수분 (1) moisture 배리어Barrier 특성 characteristic
실시예 및 비교예에서 제조된 점착 시트 한 면의 이형필름을 박리하고 점착제면을 다공성 필름과 합지한 후, 나머지 한 면의 이형필름을 박리하여 시편을 준비하였다. 그 다음, 37℃ 및 100%RH의 조건에 상기 시편을 위치시킨 상태에서 상기 시편의 두께 방향에 대한 투습도를 측정하였다. 상기 투습도는 ASTM F1249에 따라서 측정하였다.
A specimen was prepared by peeling the release film on one side of the pressure-sensitive adhesive sheet prepared in Examples and Comparative Examples, laminating the pressure-sensitive adhesive side with a porous film, and then peeling the release film on the other side. Then, the moisture permeability in the thickness direction of the specimen was measured while the specimen was placed under conditions of 37°C and 100%RH. The moisture permeability was measured according to ASTM F1249.
(2) 내구성(내열, (2) Durability (heat resistance, 내습열Moist heat resistance ))
실시예 및 비교예에서 제조된 점착 시트 한 면의 이형필름을 박리하고 점착제면에 코로나 처리한 다음 40 ㎛의 COP 필름과 접합하여 제조된 점착 시트를 90㎜×170㎜ 크기로 절단하고 나머지 이형필름을 박리한 후 유리 기판(110㎜×190㎜×0.7㎜)에 부착하여 시편을 제작하였다. 이때, 가해진 압력은 5㎏/㎠이며 기포나 이물이 생기지 않도록 크린룸 작업을 하였다. 내열 특성은 100℃의 온도에서 500시간 동안 방치한 후에 기포나 박리의 발생 여부를 관찰하였고, 내습열 특성은 85℃의 온도 및 85%RH의 조건 하에서 500시간 방치한 후에 기포나 박리의 발생 여부를 관찰하였다.
The release film on one side of the pressure-sensitive adhesive sheet prepared in Examples and Comparative Examples was peeled off, corona-treated on the pressure-sensitive adhesive side, and then bonded with a 40 μm COP film to cut the prepared pressure-sensitive adhesive sheet into a size of 90 mm×170 mm, and the remaining release film And then attached to a glass substrate (110 mm×190 mm×0.7 mm) to prepare a specimen. At this time, the applied pressure was 5 kg/㎠ and the clean room was performed to prevent bubbles or foreign matter from occurring. Heat resistance was observed for occurrence of bubbles or peeling after leaving for 500 hours at a temperature of 100°C, and moisture and heat resistance was observed for occurrence of bubbles or peeling after leaving for 500 hours under conditions of 85°C and 85%RH. Was observed.
<평가 기준><Evaluation criteria>
ⓞ: 기포나 박리 없음.Ⓞ: No air bubbles or peeling.
○: 기포나 박리 < 5개○: Bubbles or peeling <5
△: 5개 ≤ 기포나 박리 < 10개△: 5 ≤ bubbles or peeling <10
×: 10개 ≤ 기포나 박리
×: 10 ≤ bubbles or peeling
(3) 접착력(3) adhesion
실시예 및 비교예에서 제조된 점착 시트 한 면의 이형필름을 박리하고 점착제면에 코로나 처리한 후 38 ㎛의 PET 필름과 접합한 다음, 폭이 25 mm이고, 길이가 100mm가 되도록 재단하여 시편을 제조하였다. 이어서, 나머지 한 면의 이형필름을 박리하고, JIS Z 0237의 규정에 따라 2 kg의 롤러를 사용하여 점착 시트를 유리에 부착하였다. 그 다음, TA 장비(Texture Analyzer, 영국 스테이블 마이크로 시스템사제)를 사용하여, 상기 점착 시트를 유리로부터 300mm/min의 박리 속도 및 180도의 박리 각도로 박리하여 접착력을 측정하였다.
The release film on one side of the pressure-sensitive adhesive sheet prepared in Examples and Comparative Examples was peeled off, corona-treated on the pressure-sensitive adhesive side, bonded with a 38 µm PET film, and cut to a width of 25 mm and a length of 100 mm to prepare the specimen. Was prepared. Subsequently, the release film on the other side was peeled off, and the pressure-sensitive adhesive sheet was attached to the glass using a 2 kg roller according to the regulations of JIS Z 0237. Then, using a TA equipment (Texture Analyzer, manufactured by Stable Micro Systems, UK), the adhesive sheet was peeled from the glass at a peeling rate of 300 mm/min and a peeling angle of 180 degrees to measure adhesion.
(g/㎡·day)Moisture barrier properties
(g/㎡·day)
상기 표 2에서 볼 수 있는 바와 같이, 히드록시기 함유 폴리부타디엔과 3관능 이소시아네이트 가교제를 사용한 실시예 1 내지 5의 점착제 조성물은 비교예 1 내지 2의 점착제 조성물에 비해 수분 배리어 특성이 우수할 뿐만 아니라 내구성과 접착력도 우수한 것을 확인할 수 있었다.
As can be seen in Table 2, the pressure-sensitive adhesive compositions of Examples 1 to 5 using a hydroxy group-containing polybutadiene and a trifunctional isocyanate crosslinking agent are superior to the pressure-sensitive adhesive compositions of Comparative Examples 1 to 2, as well as durability and It was confirmed that the adhesion was also excellent.
이상으로 본 발명의 특정한 부분을 상세히 기술하였는 바, 본 발명이 속한 기술분야에서 통상의 지식을 가진 자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현예일 뿐이며, 이에 본 발명의 범위가 제한되는 것이 아님은 명백하다. 본 발명이 속한 기술분야에서 통상의 지식을 가진 자라면 상기 내용을 바탕으로 본 발명의 범주 내에서 다양한 응용 및 변형을 행하는 것이 가능할 것이다.As described above, a specific part of the present invention has been described in detail, and it is obvious that this specific technology is only a preferred embodiment for those of ordinary skill in the art to which the present invention belongs, and the scope of the present invention is not limited thereto. Do. Those of ordinary skill in the art to which the present invention belongs will be able to perform various applications and modifications within the scope of the present invention based on the above contents.
따라서, 본 발명의 실질적인 범위는 첨부된 특허청구범위와 그의 등가물에 의하여 정의된다고 할 것이다.Therefore, it will be said that the substantial scope of the present invention is defined by the appended claims and their equivalents.
Claims (10)
상기 히드록시기 함유 폴리부타디엔은 수평균분자량이 1,000 내지 5,000이며, 말단에 (메타)아크릴로일옥시기를 포함하지 않는 점착제 조성물.A hydroxy group-containing polybutadiene and a polyfunctional isocyanate crosslinking agent,
The hydroxy group-containing polybutadiene has a number average molecular weight of 1,000 to 5,000, and does not contain a (meth)acryloyloxy group at the terminal.
[화학식 1]
상기 식에서,
R1은 C1-C10의 알킬렌기이고, n은 20 내지 85의 정수이다.The pressure-sensitive adhesive composition of claim 1, wherein the hydroxy group-containing polybutadiene has a structure represented by the following formula (1):
[Formula 1]
In the above formula,
R 1 is a C 1 -C 10 alkylene group, and n is an integer of 20 to 85.
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