KR20160117866A - Adhesive composition, adhesive film prepared using the same and optical display apparatus comprising the same - Google Patents
Adhesive composition, adhesive film prepared using the same and optical display apparatus comprising the same Download PDFInfo
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- KR20160117866A KR20160117866A KR1020150045767A KR20150045767A KR20160117866A KR 20160117866 A KR20160117866 A KR 20160117866A KR 1020150045767 A KR1020150045767 A KR 1020150045767A KR 20150045767 A KR20150045767 A KR 20150045767A KR 20160117866 A KR20160117866 A KR 20160117866A
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- 239000000203 mixture Substances 0.000 title claims abstract description 167
- 239000002313 adhesive film Substances 0.000 title claims abstract description 22
- 230000003287 optical effect Effects 0.000 title claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 title description 6
- 239000000853 adhesive Substances 0.000 title description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 144
- 239000000178 monomer Substances 0.000 claims abstract description 102
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 54
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 22
- -1 isostearyl Chemical group 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 125000002723 alicyclic group Chemical group 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 claims 1
- 239000010408 film Substances 0.000 description 64
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000012788 optical film Substances 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000005574 cross-species transmission Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 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
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 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
- 125000003700 epoxy group Chemical group 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 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
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 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
- 239000002070 nanowire Substances 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C09J7/02—
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- C09J2201/622—
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Organic Chemistry (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
중량평균분자량이 60만g/mol 내지 150만g/mol인 (메트)아크릴계 공중합체 및 (메트)아크릴계 단량체를 포함하고, 상기 (메트)아크릴계 공중합체와 상기 (메트)아크릴계 단량체의 합 100중량부 중 상기 (메트)아크릴계 공중합체 5중량부 내지 40중량부, 상기 (메트)아크릴계 단량체 60중량부 내지 95중량부를 포함하는 점착제 조성물이고, 상기 점착제 조성물은 식 1의 경화수축률이 3% 이하이고, 상기 점착제 조성물은 경화 후 신율이 500% 이상인 점착제 조성물, 이로부터 형성된 점착 필름 및 이를 포함하는 광학표시장치가 제공된다.(Meth) acrylic copolymer and a (meth) acrylic monomer having a weight average molecular weight of 600,000 g / mol to 150,000 g / mol, wherein the sum of the (meth) acrylic copolymer and the Wherein the pressure-sensitive adhesive composition is a pressure-sensitive adhesive composition comprising 5 to 40 parts by weight of the (meth) acrylic copolymer and 60 to 95 parts by weight of the (meth) acrylic monomer, , The pressure-sensitive adhesive composition has an elongation after curing of not less than 500%, an adhesive film formed therefrom, and an optical display device comprising the same.
Description
본 발명은 점착제 조성물, 이로부터 형성된 점착필름 및 이를 포함하는 광학표시장치에 관한 것이다.The present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive film formed therefrom, and an optical display device including the same.
액정표시장치는 액정패널, 편광판을 포함한다. 액정패널, 편광판 등은 외부의 충격에 의해 쉽게 파손될 수 있다. 액정패널, 편광판을 외부 충격으로부터 보호하고, 야외 시인성 향상을 위해, 액정표시장치는 전면에 반사방지필름, 눈부심 방지 필름 등의 기능성 필름을 더 포함할 수 있다.The liquid crystal display device includes a liquid crystal panel and a polarizing plate. A liquid crystal panel, a polarizing plate and the like can be easily broken by an external impact. The liquid crystal display device may further include a functional film such as an antireflection film and an anti-glare film on the entire surface in order to protect the liquid crystal panel and the polarizing plate from external impact and improve the outdoor visibility.
액정표시장치 중 편광판, 기능성 필름 사이를 충진하기 위한 방법으로, 액상의 광경화형 점착제 조성물을 도포하고 경화시켜 충진하는 방법이 있다. 그러나, 경화수축률이 큰 액상의 광경화형 점착제 조성물은 편광판, 기능성 필름 간에 들뜸이 생기게 할 수 있다. 그렇다고 경화수축률을 낮출 경우 경화율이 떨어져서 편광판, 기능성 필름 사이를 충분히 충진하지 못할 수도 있다.As a method for filling between a polarizing plate and a functional film in a liquid crystal display device, there is a method of coating a liquid photo-curable pressure-sensitive adhesive composition and curing it. However, in a liquid phase photo-curable pressure sensitive adhesive composition having a high hardening shrinkage ratio, lifting between polarizing plates and functional films may occur. However, if the curing shrinkage ratio is lowered, the curing rate may be lowered, and the polarizing plate or the functional film may not be sufficiently filled.
또한, 유기발광소자표시장치에서도 편광판, 도전체, 윈도우 필름 사이에 액상의 광경화형 점착제 조성물을 도포하고 경화시켜 점착시킬 수 있다. 이 경우도 마찬가지로, 액상의 광경화형 점착제 조성물의 경화수축률이 크고 경화율이 낮을 경우 문제가 될 수 있다.Also, in the organic light emitting element display device, a liquid photo-curable pressure sensitive adhesive composition can be applied between the polarizing plate, the conductor and the window film, and cured to adhere. Also in this case, it may be a problem when the curing shrinkage ratio of the liquid photocurable pressure-sensitive adhesive composition is large and the curing rate is low.
이와 관련한 선행 기술은 한국 공개 특허 제2007-0055363호에 개시되어 있다.Prior art related to this is disclosed in Korean Patent Publication No. 2007-0055363.
본 발명이 해결하고자 하는 과제는 경화수축률이 3% 이하이고 경화 후 신율이 500% 이상인 점착제 조성물을 제공하는 것이다.A problem to be solved by the present invention is to provide a pressure-sensitive adhesive composition having a hardening shrinkage of not more than 3% and an elongation after hardening of not less than 500%.
본 발명이 해결하고자 하는 다른 과제는 광경화율이 높고 내구성이 높은 점착 필름을 구현할 수 있는 점착제 조성물을 제공하는 것이다.Another problem to be solved by the present invention is to provide a pressure-sensitive adhesive composition capable of realizing a pressure-sensitive adhesive film having a high photo-curability and a high durability.
본 발명이 해결하고자 하는 또 다른 과제는 도포시 흘러 넘침이 적은 점착제 조성물을 제공하는 것이다.Another problem to be solved by the present invention is to provide a pressure-sensitive adhesive composition which has little spillover upon application.
본 발명의 점착제 조성물은 중량평균분자량이 60만g/mol 내지 150만g/mol인 (메트)아크릴계 공중합체 및 (메트)아크릴계 단량체를 포함하고, 상기 (메트)아크릴계 공중합체와 상기 (메트)아크릴계 단량체의 합 100중량부 중 상기 (메트)아크릴계 공중합체 5중량부 내지 40중량부, 상기 (메트)아크릴계 단량체 60중량부 내지 95중량부를 포함하고, 상기 점착제 조성물은 하기 식 1의 경화수축률이 3% 이하이고, 상기 점착제 조성물은 경화 후 신율이 500% 이상이 될 수 있다:The pressure sensitive adhesive composition of the present invention comprises a (meth) acrylic copolymer and a (meth) acrylic monomer having a weight average molecular weight of 600,000 g / mol to 1,500,000 g / mol, wherein the (meth) (Meth) acryl-based copolymer and 60 to 95 parts by weight of the (meth) acryl-based monomer in 100 parts by weight of the sum of the acrylic monomer, the pressure-sensitive adhesive composition having a curing shrinkage ratio 3% or less, and the pressure-sensitive adhesive composition may have an elongation after curing of 500% or more:
<식 1><Formula 1>
경화수축률 = (B-A)/B x 100Cure shrinkage ratio = (B-A) / B x 100
(상기 식 1에서, A 및 B는 하기 발명의 상세한 설명에서 정의한 바와 같다).(In the above formula 1, A and B are as defined in the detailed description of the present invention).
본 발명의 점착제 조성물은 중량평균분자량이 60만g/mol 내지 150만g/mol이고 비치환된 C14 내지 C20의 알킬기를 갖는 (메트)아크릴산 에스테르가 중합된 (메트)아크릴계 공중합체 및 (메트)아크릴계 단량체를 포함하고, 상기 (메트)아크릴계 공중합체와 상기 (메트)아크릴계 단량체의 합 100중량부 중 상기 (메트)아크릴계 공중합체는 5중량부 내지 40중량부를 포함되고, 상기 점착제 조성물은 25℃에서 점도가 5,000cps 내지 10,000cps가 될 수 있다.The pressure-sensitive adhesive composition of the present invention comprises a (meth) acrylic copolymer having a weight average molecular weight of 600,000 g / mol to 150,000 g / mol and a (meth) acrylic acid ester polymer having an unsubstituted C14- (Meth) acryl-based copolymer in 100 parts by weight of the sum of the (meth) acrylic copolymer and the (meth) acrylic monomer, and the pressure-sensitive adhesive composition comprises 5 to 40 parts by weight of the The viscosity may be from 5,000 cps to 10,000 cps.
본 발명의 점착 필름은 상기 점착제 조성물로 형성될 수 있다.The pressure-sensitive adhesive film of the present invention may be formed of the pressure-sensitive adhesive composition.
본 발명의 광학표시장치는 상기 점착 필름을 포함할 수 있다.The optical display device of the present invention may include the above-mentioned pressure-sensitive adhesive film.
본 발명은 경화수축률이 3% 이하이고 경화 후 신율이 500% 이상인 점착제 조성물을 제공하였다.The present invention provides a pressure-sensitive adhesive composition having a hardening shrinkage of 3% or less and an elongation after hardening of 500% or more.
본 발명은 경화율이 높고 내구성이 높은 점착 필름을 구현할 수 있는 점착제 조성물을 제공하였다.The present invention provides a pressure-sensitive adhesive composition capable of realizing a pressure-sensitive adhesive film having a high curing rate and high durability.
본 발명은 도포시 흘러 넘침이 적은 점착제 조성물을 제공하였다.The present invention provides a pressure-sensitive adhesive composition having less overflow at the time of application.
본 명세서에서 "(메트)아크릴"은 아크릴 및/또는 메타아크릴을 의미한다.As used herein, "(meth) acrylic" means acrylic and / or methacrylic.
본 명세서에서 "경화수축율"은 비중컵을 사용하여 점착제 조성물 10g에 대해 점착제 조성물의 밀도(A, 단위:g/cm3)를 측정하였다. 점착제 조성물 10g을 이형 필름인 폴리에틸렌테레프탈레이트 필름에 도포하고 UV를 20mW/cm2의 세기로 3분 동안 조사하여 두께 200㎛의 점착 필름을 제조하였다. 비중컵을 사용하여 점착 필름에 대해 점착 필름의 밀도(B, 단위:g/cm3)를 구하였다. 경화수축률은 하기 식 1로 계산한 값이다:As used herein, the "hardening shrinkage ratio" is the density (A, unit: g / cm 3 ) of the pressure-sensitive adhesive composition for 10 g of the pressure-sensitive adhesive composition using a specific weight cup. 10 g of the pressure-sensitive adhesive composition was applied to a polyethylene terephthalate film as a release film and UV was irradiated for 3 minutes at an intensity of 20 mW / cm 2 to produce a pressure-sensitive adhesive film having a thickness of 200 탆. The density (B, unit: g / cm < 3 >) of the pressure-sensitive adhesive film relative to the pressure-sensitive adhesive film was determined using a specific weight cup. The hardening shrinkage ratio is calculated by the following formula 1:
<식 1><Formula 1>
경화수축률 = (B-A)/B x 100Cure shrinkage ratio = (B-A) / B x 100
(상기 식 1에서, A 는 점착제 조성물 10g의 밀도, B는 점착제 조성물 10g을 UV 20mW/cm2의 세기로 3분 동안 경화시켜 제조된 점착 필름의 밀도)(Density of the pressure-sensitive adhesive film prepared by curing 10 g of the pressure-sensitive adhesive composition at an intensity of 20 mW / cm 2 of UV for 3 minutes)
본 명세서에서 "신율"은 점착필름 시편에 대해 ASTM D638 방법으로 측정된 값이다.As used herein, "elongation" is a value measured by the ASTM D638 method for an adhesive film specimen.
이하, 본 발명의 일 실시예에 따른 점착제 조성물을 설명한다.Hereinafter, a pressure-sensitive adhesive composition according to an embodiment of the present invention will be described.
본 발명의 일 실시예에 따른 점착제 조성물은 중량평균분자량이 60만g/mol 내지 150만g/mol인 (메트)아크릴계 공중합체 및 (메트)아크릴계 단량체를 포함하고, 상기 (메트)아크릴계 공중합체와 상기 (메트)아크릴계 단량체의 합 100중량부 중 상기 (메트)아크릴계 공중합체는 5중량부 내지 40중량부로 포함될 수 있다. 또한, 본 발명의 일 실시예에 따른 점착제 조성물은 25℃에서 점도가 5,000cps 내지 10,000cps가 될 수 있다. 상기 중량평균분자량, (메트)아크릴계 공중합체의 함량 및 점도 범위에서, 점착제 조성물을 경화시켰을 때 경화수축률이 3% 이하가 되도록 하면서 점착제 조성물의 광경화율도 높이고 신율이 500% 이상이 될 수 있다. 또한, 상기 중량평균분자량, (메트)아크릴계 공중합체의 함량 및 점도 범위에서, 점착제 조성물을 패널 또는 터치패널 등에 도포하고 경화시켜 제조되는 점착 필름은 들뜸이 없고 경화 수축에 의한 황변이 생기지 않으며 도포시 흘러 넘침이 없을 수 있다. 점착제 조성물의 경화수축률이 3% 이하가 될 때, 점착제 조성물로 형성된 점착 필름은 편광판, 기능성 필름 간에 들뜸이 없게 할 수 있다.The pressure-sensitive adhesive composition according to one embodiment of the present invention comprises a (meth) acrylic copolymer and a (meth) acrylic monomer having a weight average molecular weight of 600,000 g / mol to 1,500,000 g / mol, And the (meth) acrylic monomer may be contained in an amount of 5 to 40 parts by weight, based on 100 parts by weight of the sum of the (meth) acrylic monomer. Also, the pressure-sensitive adhesive composition according to one embodiment of the present invention may have a viscosity of 5,000 cps to 10,000 cps at 25 ° C. When the pressure-sensitive adhesive composition is cured, the curing shrinkage rate may be 3% or less in the weight average molecular weight, the content of the (meth) acrylic copolymer and the viscosity, and the light curing rate of the pressure-sensitive adhesive composition may be increased and the elongation may be 500% or more. In addition, the pressure-sensitive adhesive film prepared by applying and curing the pressure-sensitive adhesive composition to a panel or a touch panel in the weight-average molecular weight, the content of the (meth) acrylic copolymer and the viscosity range is free from yellowing and yellowing due to curing shrinkage, There may be no overflow. When the curing shrinkage ratio of the pressure-sensitive adhesive composition is 3% or less, the pressure-sensitive adhesive film formed from the pressure-sensitive adhesive composition can be free from peeling between the polarizing plate and the functional film.
구체적으로, (메트)아크릴계 공중합체는 중량평균분자량이 70만g/mol 내지 100만g/mol이 될 수 있다. 구체적으로, (메트)아크릴계 공중합체는 상기 (메트)아크릴계 공중합체와 상기 (메트)아크릴계 단량체의 합 100중량부 중 10중량부 내지 20중량부로 포함될 수 있다. 구체적으로, 점착제 조성물은 25℃에서 점도가 6,000cps 내지 9,500cps가 될 수 있다. Specifically, the (meth) acrylic copolymer may have a weight average molecular weight of 700,000 g / mol to 1,000,000 g / mol. Specifically, the (meth) acrylic copolymer may be contained in an amount of 10 to 20 parts by weight based on 100 parts by weight of the sum of the (meth) acrylic copolymer and the (meth) acrylic monomer. Specifically, the pressure-sensitive adhesive composition may have a viscosity of 6,000 cps to 9,500 cps at 25 占 폚.
(메트)아크릴계 공중합체는 선형의(linear) (메트)아크릴계 공중합체를 포함할 수 있다. 본 명세서에서 "선형의 (메트)아크릴계 공중합체"는 가교되지 않은 (메트)아크릴계 공중합체를 의미한다.The (meth) acrylic copolymer may include a linear (meth) acrylic copolymer. As used herein, "linear (meth) acrylic copolymer" means a non-crosslinked (meth) acrylic copolymer.
(메트)아크릴계 공중합체는 유리전이온도(Tg)가 -100℃ 내지 -10℃, 구체적으로 -50℃ 내지 -15℃가 될 수 있다. 상기 범위에서, 우수한 접착력의 효과가 있을 수 있다.(Meth) acrylic copolymer may have a glass transition temperature (Tg) of -100 ° C to -10 ° C, specifically -50 ° C to -15 ° C. Within this range, there can be an effect of excellent adhesion.
(메트)아크릴계 단량체는 점착제 조성물의 경화시 (메트)아크릴계 중합체와 가교되어 점착 필름을 형성하고 점착제 조성물의 경화율을 높이고 점착 필름의 가교도를 높일 수 있다. The (meth) acrylic monomer can crosslink the (meth) acrylic polymer upon curing of the pressure-sensitive adhesive composition to form an adhesive film, thereby increasing the curing rate of the pressure-sensitive adhesive composition and increasing the degree of crosslinking of the pressure-sensitive adhesive film.
(메트)아크릴계 단량체는 (메트)아크릴계 공중합체와 (메트)아크릴계 단량체의 합 100중량부 중 60중량부 내지 95중량부로 포함될 수 있다. 상기 범위에서, 점착제 조성물의 경화수축률이 3% 이하가 되게 하고, 점착제 조성물의 경화율을 높이고 점착 필름의 가교도를 높일 수 있다. 구체적으로, (메트)아크릴계 단량체는 (메트)아크릴계 공중합체와 (메트)아크릴계 단량체의 합 100중량부 중 80중량부 내지 90중량부로 포함될 수 있다.The (meth) acrylic monomer may be contained in an amount of 60 to 95 parts by weight based on 100 parts by weight of the sum of the (meth) acrylic copolymer and the (meth) acrylic monomer. Within this range, the curing shrinkage ratio of the pressure-sensitive adhesive composition is 3% or less, thereby increasing the curing rate of the pressure-sensitive adhesive composition and increasing the degree of crosslinking of the pressure-sensitive adhesive film. Specifically, the (meth) acrylic monomer may be contained in an amount of 80 to 90 parts by weight based on 100 parts by weight of the sum of the (meth) acrylic copolymer and the (meth) acrylic monomer.
(메트)아크릴계 공중합체와 (메트)아크릴계 단량체의 혼합물은 단량체 혼합물을 완전히 중합시키지 않고 부분적으로 중합시켜 제조될 수 있다. 구체적으로, (메트)아크릴계 공중합체를 위한 단량체 혼합물을 중합도 40% 미만, 예를 들면 5% 내지 35%로 중합시켜 제조될 수 있다. 그 결과, (메트)아크릴계 공중합체와 (메트)아크릴계 단량체의 합 100중량부 중 상기 (메트)아크릴계 공중합체 5중량부 내지 40중량부, 상기 (메트)아크릴계 단량체 60중량부 내지 95중량부를 포함하고, 경화수축률이 낮고 경화 후 신율이 500% 이상인 점착제 조성물을 제조할 수 있다. 중합도는 당업자에게 알려진 통상의 방법으로 측정될 수 있다.The mixture of the (meth) acrylic copolymer and the (meth) acrylic monomer can be prepared by partially polymerizing the monomer mixture without completely polymerizing the monomer mixture. Specifically, it can be produced by polymerizing a monomer mixture for a (meth) acrylic copolymer at a polymerization degree of less than 40%, for example, from 5% to 35%. As a result, 5 parts by weight to 40 parts by weight of the (meth) acrylic copolymer and 60 to 95 parts by weight of the (meth) acrylic monomer were contained in 100 parts by weight of the sum of the (meth) acrylic copolymer and the (meth) , A pressure-sensitive adhesive composition having a low hardening shrinkage percentage and a hardening elongation of 500% or higher can be produced. The degree of polymerization can be measured by conventional methods known to those skilled in the art.
(메트)아크릴계 공중합체와 (메트)아크릴계 단량체의 혼합물의 제조 방법은 하기 점착제 조성물의 제조 방법을 참고한다.As a method of producing a mixture of the (meth) acrylic copolymer and the (meth) acrylic monomer, refer to the production method of the pressure-sensitive adhesive composition described below.
(메트)아크릴계 공중합체 및 (메트)아크릴계 단량체의 혼합물을 위한 단량체 혼합물은 비치환된 C14 내지 C20의 알킬기를 갖는 (메트)아크릴산 에스테르를 포함할 수 있다. The monomer mixture for the mixture of the (meth) acrylic copolymer and the (meth) acrylic monomer may comprise a (meth) acrylic acid ester having an unsubstituted C14 to C20 alkyl group.
비치환된 C14 내지 C20의 알킬기를 갖는 (메트)아크릴산 에스테르는 비치환된 C14 내지 C20의 알킬기를 제공함으로써 점착제 조성물의 경화수축률을 3% 이하로 낮출 수 있고, 점착 필름의 신율을 500% 이상으로 할 수 있고, 경화 수축에 의한 황변 현상을 제거할 수 있다. 구체적으로, 비치환된 C14 내지 C20의 알킬기는 분지형(branched form)이 됨으로써, 점착제 조성물의 경화수축률을 더 낮출 수 있다.The (meth) acrylic acid ester having an unsubstituted C14 to C20 alkyl group can lower the curing shrinkage of the pressure-sensitive adhesive composition to 3% or less by providing an unsubstituted C14 to C20 alkyl group, and the elongation of the pressure-sensitive adhesive film to 500% And yellowing due to curing shrinkage can be removed. Specifically, the unsubstituted C14 to C20 alkyl group is branched so that the curing shrinkage ratio of the pressure-sensitive adhesive composition can be further lowered.
비치환된 C14 내지 C20의 알킬기를 갖는 (메트)아크릴산 에스테르는 비치환된 C14의 알킬기를 갖는 (메트)아크릴산 에스테르, 비치환된 C15의 알킬기를 갖는 (메트)아크릴산 에스테르, 비치환된 C16의 알킬기를 갖는 (메트)아크릴산 에스테르, 비치환된 C17의 알킬기를 갖는 (메트)아크릴산 에스테르, 비치환된 C18의 알킬기를 갖는 (메트)아크릴산 에스테르, 비치환된 C19의 알킬기를 갖는 (메트)아크릴산 에스테르, 비치환된 C20의 알킬기를 갖는 (메트)아크릴산 에스테르 중 하나 이상을 포함할 수 있다. 더 구체적으로, 비치환된 C14 내지 C20의 알킬기를 갖는 (메트)아크릴산 에스테르는 이소스테아릴(메트)아크릴레이트가 될 수 있다. 이들은 단독 또는 2종 이상 혼합하여 포함될 수 있다.(Meth) acrylic acid esters having an unsubstituted C14 to C20 alkyl group include (meth) acrylic acid esters having an unsubstituted C14 alkyl group, (meth) acrylic acid esters having an unsubstituted C15 alkyl group, an unsubstituted C16 alkyl group (Meth) acrylic esters having an unsubstituted C17 alkyl group, (meth) acrylic esters having an unsubstituted C18 alkyl group, (meth) acrylic esters having an unsubstituted C18 alkyl group, (Meth) acrylic acid esters having an unsubstituted C20 alkyl group. More specifically, the (meth) acrylic acid ester having an unsubstituted C14 to C20 alkyl group may be isostearyl (meth) acrylate. These may be included singly or in combination of two or more.
비치환된 C14 내지 C20의 알킬기를 갖는 (메트)아크릴산 에스테르는 고형분 기준 상기 단량체 혼합물 중 10중량% 내지 30중량%, 구체적으로 10중량% 내지 20중량%로 포함될 수 있다. 상기 범위에서, 점착제 조성물의 경화수축률이 3% 이하가 될 수 있고, 점착제 조성물의 광경화율이 높아질 수 있다.The (meth) acrylic ester having an unsubstituted C14 to C20 alkyl group may be contained in an amount of 10 to 30% by weight, specifically 10 to 20% by weight, based on the solids content of the monomer mixture. Within this range, the curing shrinkage ratio of the pressure-sensitive adhesive composition may be 3% or less, and the light-curing rate of the pressure-sensitive adhesive composition may be increased.
(메트)아크릴계 공중합체 및 (메트)아크릴계 단량체를 위한 단량체 혼합물은 비치환된 C1 내지 C13의 알킬기를 갖는 (메트)아크릴산 에스테르, 수산기를 갖는 (메트)아크릴계 단량체 및 지환족기를 갖는 (메트)아크릴계 단량체를 더 포함할 수 있다.The monomer mixture for the (meth) acrylic copolymer and the (meth) acrylic monomer is a (meth) acrylic ester having an unsubstituted C1 to C13 alkyl group, a (meth) acrylic monomer having a hydroxyl group, And may further include monomers.
비치환된 C1 내지 C13의 알킬기를 갖는 (메트)아크릴산 에스테르는 점착제 조성물로 제조된 점착필름의 점착 특성을 높일 수 있다. 구체적으로, 비치환된 C1 내지 C13의 알킬기를 갖는 (메트)아크릴산 에스테르는 메틸 (메트)아크릴레이트, 에틸 (메트)아크릴레이트, 프로필 (메트)아크릴레이트, n-부틸 (메트)아크릴레이트, t-부틸 (메트)아크릴레이트, iso-부틸 (메트)아크릴레이트, 펜틸 (메트)아크릴레이트, 헥실 (메트)아크릴레이트, 헵틸 (메트)아크릴레이트, 에틸헥실 (메트)아크릴레이트, 옥틸 (메트)아크릴레이트, 이소옥틸 (메트)아크릴레이트, 노닐 (메트)아크릴레이트, 데실 (메트)아크릴레이트, 라우릴 (메트)아크릴레이트 중 하나 이상을 포함할 수 있다. 이들은 단독 또는 2종 이상 혼합하여 포함될 수 있다. 더 구체적으로, 비치환된 C1 내지 C13의 알킬기를 갖는 (메트)아크릴산 에스테르는 분지형의 (메트)아크릴산 에스테르가 됨으로써, 분지형의 비치환된 C14 내지 C20의 알킬기를 갖는 (메트)아크릴산 에스테르와 상용성이 좋을 수 있다.The (meth) acrylic acid ester having an unsubstituted C1 to C13 alkyl group can improve the adhesive property of the pressure-sensitive adhesive film made of the pressure-sensitive adhesive composition. Specifically, the (meth) acrylic esters having an unsubstituted C1 to C13 alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (Meth) acrylate, isobutyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, (Meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate and lauryl (meth) acrylate. These may be included singly or in combination of two or more. More specifically, the (meth) acrylic acid ester having an unsubstituted C1 to C13 alkyl group is a branched (meth) acrylic acid ester, and thus a (meth) acrylic acid ester having an unsubstituted C14 to C20 alkyl group The compatibility may be good.
비치환된 C1 내지 C13의 알킬기를 갖는 (메트)아크릴산 에스테르는 고형분 기준 상기 단량체 혼합물 중 50중량% 내지 80중량%, 구체적으로 50중량% 내지 75중량%, 더 구체적으로 55중량% 내지 75중량%로 포함될 수 있다. 상기 범위에서, 점착제 조성물의 경화수축률이 3% 이하가 될 수 있고, 점착 필름의 점착 특성이 확보될 수 있다.(Meth) acrylic acid ester having an unsubstituted C1 to C13 alkyl group is contained in an amount of 50 to 80% by weight, specifically 50 to 75% by weight, more specifically 55 to 75% by weight, ≪ / RTI > Within this range, the curing shrinkage ratio of the pressure-sensitive adhesive composition can be 3% or less, and the pressure-sensitive adhesive property of the pressure-sensitive adhesive film can be secured.
수산기를 갖는 (메트)아크릴계 단량체는 하나 이상의 수산기를 제공함으로써 점착제 조성물의 경화시 가교도를 높일 수 있다. 수산기를 갖는 (메트)아크릴계 단량체는 1개 이상의 수산기를 갖는 C1 내지 C20의 알킬기를 갖는 (메트)아크릴산 에스테르를 포함할 수 있다. 구체적으로, 수산기를 갖는 (메트)아크릴계 단량체는 2-히드록시에틸(메트)아크릴레이트, 4-히드록시부틸 (메트)아크릴레이트, 2-히드록시프로필(메트)아크릴레이트, 2-히드록시부틸 (메트)아크릴레이트, 6-히드록시헥실(메트)아크릴레이트 중 하나 이상을 포함할 수 있다. 이들은 단독 또는 2종 이상 혼합하여 포함될 수 있다.The (meth) acrylic monomer having a hydroxyl group can increase the degree of crosslinking upon curing of the pressure-sensitive adhesive composition by providing at least one hydroxyl group. The (meth) acrylic monomer having a hydroxyl group may include a (meth) acrylic acid ester having a C1 to C20 alkyl group having at least one hydroxyl group. Specifically, the (meth) acrylic monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- hydroxypropyl (meth) (Meth) acrylate, 6-hydroxyhexyl (meth) acrylate ≪ / RTI > These may be included singly or in combination of two or more.
수산기를 갖는 (메트)아크릴계 단량체는 고형분 기준 상기 단량체 혼합물 중 5중량% 내지 30중량%, 구체적으로 15중량% 내지 25중량%로 포함될 수 있다. 상기 범위에서, 점착제 조성물의 경화수축률이 3% 이하가 될 수 있고, 점착제 조성물의 경화율을 높일 수 있다.The (meth) acrylic monomer having a hydroxyl group may be contained in an amount of 5% by weight to 30% by weight, specifically 15% by weight to 25% by weight, based on the solids content of the monomer mixture. Within this range, the curing shrinkage ratio of the pressure-sensitive adhesive composition can be 3% or less, and the curing rate of the pressure-sensitive adhesive composition can be increased.
지환족기를 갖는 (메트)아크릴계 단량체는 점착제 조성물의 경화시 점착필름의 접착력을 높일 수 있다. 지환족기를 갖는 (메트)아크릴계 단량체는 비치환된 C3 내지 C10의 지환족기를 갖는 (메트)아크릴계 단량체를 포함할 수 있다. 구체적으로, 지환족기를 갖는 (메트)아크릴계 단량체는 시클로펜틸(메트)아크릴레이트, 시클로헥실(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트 중 하나 이상을 포함할 수 있다. 이들은 단독 또는 2종 이상 혼합하여 포함될 수 있다.The (meth) acrylic monomer having an alicyclic group can increase the adhesive force of the pressure-sensitive adhesive film when the pressure-sensitive adhesive composition is cured. The (meth) acrylic monomer having an alicyclic group may include a (meth) acrylic monomer having an unsubstituted C3 to C10 alicyclic group. Specifically, the (meth) acrylic monomer having an alicyclic group may include at least one of cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate. These may be included singly or in combination of two or more.
지환족기를 갖는 (메트)아크릴계 단량체는 고형분 기준 상기 단량체 혼합물 중 5중량% 내지 25중량%, 구체적으로 10중량% 내지 20중량%로 포함될 수 있다. 상기 범위에서, 점착제 조성물의 경화수축률이 3% 이하가 될 수 있고, 점착필름의 접착력이 좋을 수 있다.The (meth) acrylic monomer having an alicyclic group may be contained in an amount of 5% by weight to 25% by weight, specifically 10% by weight to 20% by weight, based on the solids content of the monomer mixture. Within this range, the curing shrinkage of the pressure-sensitive adhesive composition may be 3% or less, and the adhesive force of the pressure-sensitive adhesive film may be good.
일 구체예에서, 단량체 혼합물은 비치환된 C14 내지 C20의 알킬기를 갖는 (메트)아크릴산 에스테르 10중량% 내지 30중량%, 비치환된 C1 내지 C13의 알킬기를 갖는 (메트)아크릴산 에스테르 50중량% 내지 80중량%, 수산기를 갖는 (메트)아크릴계 단량체 5중량% 내지 30중량%, 및 지환족기를 갖는 (메트)아크릴계 단량체 5중량% 내지 25중량%를 포함할 수 있다.In one embodiment, the monomer mixture comprises 10% to 30% by weight of a (meth) acrylic acid ester having an unsubstituted C14 to C20 alkyl group, 50% to 50% by weight of a (meth) acrylic acid ester having an unsubstituted C1- 5 to 30% by weight of a (meth) acrylic monomer having a hydroxyl group and 5 to 25% by weight of a (meth) acrylic monomer having an alicyclic group.
(메트)아크릴계 공중합체 및 (메트)아크릴계 단량체를 위한 단량체 혼합물은 헤테로지환족기를 갖는 (메트)아크릴계 단량체를 더 포함할 수 있다. The monomer mixture for the (meth) acrylic copolymer and the (meth) acrylic monomer may further comprise a (meth) acrylic monomer having a heteroalicyclic group.
헤테로지환족기를 갖는 (메트)아크릴계 단량체는 점착제 조성물에 포함되어 경화수축율 감소 또는 접착력 상승 효과를 구현할 수 있다. 헤테로지환족기를 갖는 (메트)아크릴계 단량체는 비치환된, 질소, 산소, 또는 황을 갖는 C2 내지 C10의 헤테로지환족기를 갖는 (메트)아크릴산 에스테르를 포함할 수 있다. 구체적으로, 헤테로지환족기를 갖는 (메트)아크릴계 단량체는 (메트)아크릴로일모르폴린을 포함할 수 있다. 이들은 단독 또는 2종 이상 혼합하여 포함될 수 있다.The (meth) acrylic monomer having a hetero-alicyclic group may be included in the pressure-sensitive adhesive composition to reduce the hardening shrinkage or increase the adhesion. The (meth) acrylic monomer having a hetero-alicyclic group may include unsubstituted (meth) acrylic acid esters having a C2 to C10 heteroalicyclic group having nitrogen, oxygen, or sulfur. Specifically, the (meth) acrylic monomer having a hetero-alicyclic group may include (meth) acryloylmorpholine. These may be included singly or in combination of two or more.
헤테로지환족기를 갖는 (메트)아크릴계 단량체는 고형분 기준 상기 단량체 혼합물 중 1중량% 내지 25중량%, 구체적으로 1중량% 내지 10중량%로 포함될 수 있다. 상기 범위에서, 접착력 상승 및 경화 수축 감소 효과가 있을 수 있다.The (meth) acrylic monomer having a hetero-alicyclic group may be contained in an amount of 1 to 25% by weight, specifically 1 to 10% by weight based on the solid content of the monomer mixture. Within this range, there may be an effect of increasing the adhesion and reducing the hardening shrinkage.
일 구체예에서, 단량체 혼합물은 비치환된 C14 내지 C20의 알킬기를 갖는 (메트)아크릴산 에스테르 10중량% 내지 30중량%, 비치환된 C1 내지 C13의 알킬기를 갖는 (메트)아크릴산 에스테르 50중량% 내지 75중량%, 수산기를 갖는 (메트)아크릴계 단량체 5중량% 내지 30중량%, 지환족기를 갖는 (메트)아크릴계 단량체 5중량% 내지 25중량% 및 헤테로지환족기를 갖는 (메트)아크릴계 단량체 1중량% 내지 25중량%를 포함할 수 있다.In one embodiment, the monomer mixture comprises 10% to 30% by weight of a (meth) acrylic acid ester having an unsubstituted C14 to C20 alkyl group, 50% to 50% by weight of a (meth) acrylic acid ester having an unsubstituted C1- (Meth) acrylic monomer having a hydroxyl group, 5 to 30% by weight of a (meth) acrylic monomer having a hydroxyl group, 5 to 25% by weight of a (meth) acrylic monomer having an alicyclic group, By weight to 25% by weight.
(메트)아크릴계 단량체는 상술한 비치환된 C14 내지 C20의 알킬기를 갖는 (메트)아크릴산 에스테르, 비치환된 C1 내지 C13의 알킬기를 갖는 (메트)아크릴산 에스테르, 수산기를 갖는 (메트)아크릴계 단량체, 및 지환족기를 갖는 (메트)아크릴계 단량체의 혼합물을 포함할 수 있다.(Meth) acrylic monomer, the (meth) acrylic acid ester having an unsubstituted C14 to C20 alkyl group, the (meth) acrylic acid ester having an unsubstituted C1 to C13 alkyl group, the (meth) acrylic monomer having a hydroxyl group, and And a mixture of (meth) acrylic monomers having an alicyclic group.
(메트)아크릴계 단량체는 상술한 헤테로지환족기를 갖는 (메트)아크릴계 단량체를 더 포함할 수 있다.The (meth) acrylic monomer may further include a (meth) acrylic monomer having the above-mentioned heteroalicyclic group.
점착제 조성물은 개시제를 더 포함할 수 있다.The pressure-sensitive adhesive composition may further include an initiator.
개시제는 (메트)아크릴계 중합체 및 (메트)아크릴계 단량체를 가교시켜 점착제 조성물을 가교시킬 수 있다. 개시제는 인계, 벤조인계 중 하나 이상을 포함할 수 있다. 이들은 단독 또는 2종 이상 혼합하여 포함될 수 있다.The initiator may crosslink the pressure-sensitive adhesive composition by crosslinking the (meth) acrylic polymer and the (meth) acrylic monomer. The initiator may include one or more of phosphorous, benzoin, and the like. These may be included singly or in combination of two or more.
개시제는 (메트)아크릴계 공중합체와 (메트)아크릴계 단량체의 혼합물(합) 100중량부에 대해 0.1중량부 내지 3중량부, 구체적으로 0.5중량부 내지 2중량부로 포함될 수 있다. 상기 범위에서, (메트)아크릴계 중합체와 (메트)아크릴계 단량체 혼합물이 충분히 경화될 수 있고, 잔량의 개시제가 남아 점착 필름의 투명도가 저하되는 것을 막을 수 있다.The initiator may be included in an amount of 0.1 part by weight to 3 parts by weight, specifically 0.5 parts by weight to 2 parts by weight, based on 100 parts by weight of the mixture (sum) of the (meth) acrylic copolymer and the (meth) acrylic monomer. Within the above range, the mixture of the (meth) acrylic polymer and the (meth) acrylic monomer can be sufficiently cured, and the remaining amount of the initiator can be prevented from lowering the transparency of the adhesive film.
점착제 조성물은 실란커플링제를 더 포함할 수 있다. The pressure-sensitive adhesive composition may further include a silane coupling agent.
실란커플링제는 점착제 조성물로부터 제조된 점착 필름의 점착력을 높일 수 있다. 실란커플링제는 당업자에게 알려진 통상의 점착제를 포함할 수 있다. 구체적으로, 실란커플링제는 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필메틸디메톡시실란 등의 에폭시기 함유 실란 화합물; 비닐트리메톡시실란, (메트)아크릴로일옥시프로필트리메톡시실란 등의 중합성 불포화기 함유 실란 화합물; 3-아미노프로필트리메톡시실란, N-(2-아미노에틸)-3-아미노프로필트리메톡시실란 등의 아미노기 함유 실란 화합물; 3-메르캅토프로필트리메톡시실란 등의 메르캅토기 함유 실란 화합물 중 하나 이상을 포함할 수 있다.The silane coupling agent can increase the adhesive strength of the pressure-sensitive adhesive film produced from the pressure-sensitive adhesive composition. The silane coupling agent may comprise conventional tackifiers known to those skilled in the art. Specifically, the silane coupling agent is an epoxy group-containing silane compound such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane; Silane compounds containing polymerizable unsaturated groups such as vinyltrimethoxysilane and (meth) acryloyloxypropyltrimethoxysilane; Amino group-containing silane compounds such as 3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane; And mercapto group-containing silane compounds such as 3-mercaptopropyltrimethoxysilane.
실란커플링제는 (메트)아크릴계 공중합체와 (메트)아크릴계 단량체의 혼합물(합) 100중량부에 대해 0.01중량부 내지 15중량부, 구체적으로 0.01중량부 내지 5중량부로 포함될 수 있다. 상기 범위에서, 점착제 조성물로 제조된 점착 필름은 접착력이 좋을 수 있다.The silane coupling agent may be contained in an amount of 0.01 to 15 parts by weight, specifically 0.01 to 5 parts by weight, based on 100 parts by weight of the mixture (sum) of the (meth) acrylic copolymer and the (meth) acrylic monomer. In the above range, the pressure-sensitive adhesive film made of the pressure-sensitive adhesive composition may have good adhesion.
점착제 조성물은 점착제 조성물에 포함되는 통상의 첨가제를 더 포함할 수 있다. 첨가제는 소포제, 레벨링제, 대전방지제 등을 포함할 수 있지만, 이에 제한되지 않는다. 첨가제는 (메트)아크릴계 공중합체와 (메트)아크릴계 단량체의 혼합물(합) 100중량부에 대해 0.0001중량부 내지 5중량부, 구체적으로 0.001중량부 내지 1중량부로 포함될 수 있다. 상기 범위에서, 점착제 조성물로 제조된 점착 필름은 접착력이 좋을 수 있다.The pressure-sensitive adhesive composition may further include conventional additives included in the pressure-sensitive adhesive composition. The additives may include, but are not limited to, antifoaming agents, leveling agents, antistatic agents, and the like. The additive may be added in an amount of 0.0001 to 5 parts by weight, specifically 0.001 to 1 part by weight based on 100 parts by weight of the mixture (sum) of the (meth) acrylic copolymer and the (meth) acrylic monomer. In the above range, the pressure-sensitive adhesive film made of the pressure-sensitive adhesive composition may have good adhesion.
점착제 조성물은 용매를 포함하지 않는 무용제형일 수 있다.The pressure-sensitive adhesive composition may be a solvent-free solventless type.
점착제 조성물은 경화수축률이 3% 이하, 구체적으로 0.1% 내지 2%가 될 수 있다. 상기 경화수축률 범위에서, 점착제 조성물을 광학표시장치에 사용시 경화시키더라도 패널, 편광판, 기능성 필름, 또는 도전층 간에 들뜸이 없을 수 있다.The pressure-sensitive adhesive composition may have a hardening shrinkage of 3% or less, specifically 0.1% to 2%. Within the above range of curing shrinkage, even when the pressure-sensitive adhesive composition is cured when used in an optical display device, there may be no peeling between the panel, the polarizing plate, the functional film, or the conductive layer.
이하, 본 발명의 일 실시예에 따른 점착제 조성물의 제조방법을 설명한다.Hereinafter, a method for producing a pressure-sensitive adhesive composition according to an embodiment of the present invention will be described.
본 발명의 일 실시예에 따른 점착제 조성물은 중량평균분자량이 60만g/mol 내지 150만g/mol인 (메트)아크릴계 공중합체와 (메트)아크릴계 단량체의 혼합물을 제조하고, 개시제를 첨가하는 단계에 의해 제조될 수 있다.The pressure-sensitive adhesive composition according to one embodiment of the present invention is prepared by preparing a mixture of a (meth) acrylic copolymer and a (meth) acrylic monomer having a weight average molecular weight of 600,000 g / mol to 1,500,000 g / mol and adding an initiator ≪ / RTI >
중량평균분자량이 60만g/mol 내지 150만g/mol인 (메트)아크릴계 공중합체와 (메트)아크릴계 단량체의 혼합물은 (메트)아크릴계 공중합체 및 (메트)아크릴계 단량체를 위한 상기 단량체 혼합물에, 개시제를 첨가하고, UV 파장에서 0.5mW/cm2 내지 20mW/cm2로 조사하여 상기 단량체 혼합물을 부분 중합시켜 제조될 수 있다. 개시제는 상기 단량체 혼합물 100중량부에 대해 0.01중량부 내지 3중량부, 구체적으로 0.01중량부 내지 1.5중량부로 포함될 수 있다. 상기 UV 세기, 시간 및 개시제 범위에서, 단량체 혼합물이 완전히 중합되지 않고, 60만g/mol 내지 150만g/mol의 중량평균분자량을 갖는 (메트)아크릴계 공중합체와 (메트)아크릴계 단량체 혼합물을 제조할 수 있다. 개시제는 인계, 벤조인계 중 하나 이상을 포함할 수 있다. 이들은 단독 또는 2종 이상 혼합하여 포함될 수 있다.A mixture of a (meth) acrylic copolymer and a (meth) acrylic monomer having a weight average molecular weight of 600,000 g / mol to 150,000 g / mol is added to the monomer mixture for the (meth) acrylic copolymer and the (meth) And then partially polymerizing the monomer mixture by irradiation with an initiator at 0.5 mW / cm 2 to 20 mW / cm 2 at an UV wavelength. The initiator may be included in an amount of 0.01 to 3 parts by weight, specifically 0.01 to 1.5 parts by weight based on 100 parts by weight of the monomer mixture. (Meth) acryl-based monomer mixture having a weight average molecular weight of 600,000 g / mol to 150,000 g / mol without the monomer mixture being completely polymerized in the above UV intensity, time and initiator range can do. The initiator may include one or more of phosphorous, benzoin, and the like. These may be included singly or in combination of two or more.
그런 다음, 중량평균분자량이 60만g/mol 내지 150만g/mol인 (메트)아크릴계 공중합체와 (메트)아크릴계 단량체의 혼합물에 개시제를 첨가하여, 본 발명의 일 실시예에 따른 점착제 조성물을 제조한다. 이때, 점착제 조성물에 실란커플링제, 통상의 첨가제를 더 첨가하는 단계를 더 포함할 수 있다.Then, an initiator was added to a mixture of a (meth) acrylic copolymer and a (meth) acrylic monomer having a weight average molecular weight of 600,000 g / mol to 1,500,000 g / mol to prepare a pressure- . At this time, it may further include adding a silane coupling agent and a conventional additive to the pressure-sensitive adhesive composition.
이하, 본 발명의 일 실시예에 따른 점착 필름을 설명한다.Hereinafter, an adhesive film according to an embodiment of the present invention will be described.
점착 필름은 신율이 500% 이상, 구체적으로 500% 내지 1500%, 더 구체적으로 500% 내지 700%가 될 수 있다. 상기 범위에서, 점착 필름의 수축을 제어하는 효과가 있을 수 있다.The adhesive film may have a elongation of 500% or more, specifically 500% to 1500%, more specifically 500% to 700%. Within this range, there may be an effect of controlling the shrinkage of the adhesive film.
점착 필름은 광학적으로 투명할 수 있다. 구체적으로, 점착 필름은 파장 380nm 내지 파장 780nm에서 광투과도가 90% 이상, 구체적으로 90% 내지 99%가 될 수 있다. 구체적으로, 점착 필름은 파장 380nm 내지 파장 780nm에서 헤이즈(haze)가 1% 이하, 구체적으로 0.1% 내지 1%가 될 수 있다. 상기 광투과도와 헤이즈 범위에서, 광학 표시 장치에 사용될 수 있다.The adhesive film may be optically transparent. Specifically, the adhesive film may have a light transmittance of 90% or more, specifically 90% to 99% at a wavelength of 380 nm to a wavelength of 780 nm. Specifically, the adhesive film may have a haze of 1% or less, specifically 0.1% to 1% at a wavelength of 380 nm to a wavelength of 780 nm. The light transmittance and the haze range can be used in an optical display device.
점착 필름은 본 발명의 일 실시예에 따른 점착제 조성물을 경화시켜 제조될 수 있다. 구체적으로, 점착 필름은 이형 필름(예:폴리에틸렌테레프탈레이트 필름) 또는 유리에 본 발명의 일 실시예에 따른 점착제 조성물을 소정의 두께로 도포하고, UV를 조사하여 제조될 수 있다. UV 조사는 조사량 10mW/cm2 내지 30mW/cm2 에서 2분 내지 6분 동안 수행될 수 있다. 상기 범위에서, 점착제 조성물이 충분히 경화될 수 있고, 과경화로 인한 점착 필름의 표면조도 증가를 억제할 수 있다. UV 조사는 점착제 조성물 위에 이형 필름(예:폴리에틸렌테레프탈레이트 필름) 또는 유리를 덮음으로써 산소의 접촉을 차단하여 경화율을 더 높일 수도 있다.The adhesive film can be prepared by curing the pressure-sensitive adhesive composition according to one embodiment of the present invention. Specifically, the pressure-sensitive adhesive film can be prepared by applying a pressure-sensitive adhesive composition according to one embodiment of the present invention to a release film (e.g., a polyethylene terephthalate film) or a glass to a predetermined thickness and irradiating UV light. UV irradiation can be performed for 2 to 6 minutes at a dose of 10 mW / cm 2 to 30 mW / cm 2 . Within this range, the pressure-sensitive adhesive composition can be sufficiently cured, and the increase in surface roughness of the pressure-sensitive adhesive film due to the hardening can be suppressed. UV irradiation may further increase the curing rate by blocking the contact of oxygen by covering a releasing film (e.g., polyethylene terephthalate film) or glass over the pressure sensitive adhesive composition.
점착 필름은 광학 필름의 일면 또는 양면에 부착되는 점착층으로서, 유리, 기판, 터치패널의 전극, LCD/OLED 모듈과 터치패널, 광학 필름 등을 서로 부착하는데 사용될 수 있다. 광학 필름은 터치패널, 윈도우, 편광판, 칼라필터, 위상차 필름, 타원 편광필름, 반사필름, 반사방지 필름, 보상필름, 휘도 향상필름, 배향막, 광확산 필름, 유리비산 방지 필름, 표면 보호필름, 플라스틱 LCD 기판, ITO(indium tin oxide), FTO(fluorinated tin oxide), AZO(aluminum dopped zinc oxide), CNT(carbon nanotube) 포함 필름, Ag 나노와이어(nanowire) 포함 필름, 또는 그래핀(graphene)의 투명 전극 필름을 포함할 수 있다.The adhesive film is an adhesive layer adhered to one side or both sides of an optical film and can be used for attaching glass, a substrate, an electrode of a touch panel, an LCD / OLED module, a touch panel, an optical film and the like to each other. The optical film may be at least one selected from the group consisting of a touch panel, a window, a polarizing plate, a color filter, a retardation film, an elliptically polarizing film, a reflection film, an antireflection film, a compensation film, a brightness enhancement film, A substrate including an LCD substrate, an indium tin oxide (ITO), a fluorinated tin oxide (FTO), an aluminum doped zinc oxide (AZO), a film containing a carbon nanotube (CNT), a film containing Ag nanowire or a graphene And an electrode film.
이하, 본 발명의 일 실시예에 따른 광학표시장치를 설명한다.Hereinafter, an optical display device according to an embodiment of the present invention will be described.
본 발명의 일 실시예에 따른 광학표시장치는 본 발명의 일 실시예에 따른 점착제 조성물로 형성된 점착 필름을 포함할 수 있다. 구체적으로, 광학표시장치는 액정표시장치, 유기발광소자표시장치 등을 포함할 수 있다.The optical display device according to an embodiment of the present invention may include an adhesive film formed of a pressure-sensitive adhesive composition according to an embodiment of the present invention. Specifically, the optical display device may include a liquid crystal display device, an organic light emitting element display device, and the like.
이하, 본 발명의 바람직한 실시예를 통해 본 발명의 구성 및 작용을 더욱 상세히 설명하기로 한다. 다만, 이는 본 발명의 바람직한 예시로 제시된 것이며 어떠한 의미로도 이에 의해 본 발명이 제한되는 것으로 해석되어서는 안 된다.Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It should be understood, however, that the same is by way of illustration and example only and is not to be construed in any way as limiting the invention.
실시예 1Example 1
반응기에, 2-에틸헥실아크릴레이트 60중량부, 2-히드록시에틸아크릴레이트 20중량부, 이소스테아릴아크릴레이트 10중량부 및 이소보르닐아크릴레이트 10중량부를 혼합하여 단량체 혼합물을 제조하였다. 상기 단량체 혼합물에 개시제 Irgacure 651(Ciba사) 0.04중량부를 첨가하였다. 상기 반응기 내 산소를 질소로 교체하였다. UV 파장에서 10mW/cm2의 세기로 3분 동안 조사하여 상기 단량체 혼합물을 부분 중합시켜, (메트)아크릴계 공중합체 및 중합되지 않고 남아있는 (메트)아크릴계 단량체의 혼합물을 얻었다. 제조한 혼합물에 대해 분석한 결과, 하기 표 1의 (메트)아크릴계 공중합체의 함량을 얻었다.In the reactor, 60 parts by weight of 2-ethylhexyl acrylate, 20 parts by weight of 2-hydroxyethyl acrylate, 10 parts by weight of isostearyl acrylate and 10 parts by weight of isobornyl acrylate were mixed to prepare a monomer mixture. To the monomer mixture was added 0.04 parts by weight of initiator Irgacure 651 (Ciba). The oxygen in the reactor was replaced with nitrogen. The monomer mixture was partially polymerized by irradiation with UV light at an intensity of 10 mW / cm < 2 > for 3 minutes to obtain a mixture of the (meth) acrylic copolymer and the un polymerized (meth) acrylic monomer. The obtained mixture was analyzed. As a result, the content of the (meth) acrylic copolymer in Table 1 was obtained.
그런 다음, 개시제 Irgacure 651(Ciba사) 1.5중량부, 실란커플링제 KBM-403 0.1중량부, 소포제 BYK-A-515 0.01중량부를 더 첨가하여, 점착제 조성물을 제조하였다. Then, 1.5 parts by weight of initiator Irgacure 651 (Ciba), 0.1 part by weight of silane coupling agent KBM-403 and 0.01 part by weight of antifoaming agent BYK-A-515 were further added to prepare a pressure-sensitive adhesive composition.
실시예 2Example 2
반응기에, 2-에틸헥실아크릴레이트 58중량부, 2-히드록시에틸아크릴레이트 20중량부, 이소스테아릴아크릴레이트 10중량부, 이소보르닐아크릴레이트 10중량부 및 아크릴로일모르폴린 2중량부를 혼합하여 단량체 혼합물을 제조하였다. 단량체 혼합물에 개시제 Irgacure 651(Ciba사) 0.04중량부를 더 첨가하였다. 상기 반응기 내 산소를 질소로 교체하였다. UV 파장에서 10mW/cm2의 세기로 3분 동안 조사하여 단량체 혼합물을 부분 중합시켜, (메트)아크릴계 공중합체 및 중합되지 않고 남아있는 단량체의 혼합물을 얻었다. 제조한 혼합물에 대해 분석한 결과, 하기 표 1의 (메트)아크릴계 공중합체의 함량을 얻었다.A reactor was charged with 58 parts by weight of 2-ethylhexyl acrylate, 20 parts by weight of 2-hydroxyethyl acrylate, 10 parts by weight of isostearyl acrylate, 10 parts by weight of isobornyl acrylate and 2 parts by weight of acryloylmorpholine To prepare a monomer mixture. To the monomer mixture, 0.04 parts by weight of initiator Irgacure 651 (Ciba) was further added. The oxygen in the reactor was replaced with nitrogen. The monomer mixture was partially polymerized by irradiation with UV light at an intensity of 10 mW / cm < 2 > for 3 minutes to obtain a mixture of the (meth) acrylic copolymer and the un polymerized monomers. The obtained mixture was analyzed. As a result, the content of the (meth) acrylic copolymer in Table 1 was obtained.
그런 다음, 개시제 Irgacure 651 (Ciba사) 1.5중량부, 실란커플링제 KBM-403 0.1중량부, 소포제 BYK-A-515 0.01중량부를 첨가하여, 점착제 조성물을 제조하였다. Then, 1.5 parts by weight of initiator Irgacure 651 (Ciba), 0.1 part by weight of silane coupling agent KBM-403 and 0.01 part by weight of defoaming agent BYK-A-515 were added to prepare a pressure-sensitive adhesive composition.
비교예 1Comparative Example 1
반응기에, 2-에틸헥실아크릴레이트 25중량부 및 2-히드록시에틸아크릴레이트 75중량부를 혼합하여 단량체 혼합물을 제조하였다. 상기 단량체 혼합물에 개시제 Irgacure 651(Ciba사) 0.04중량부를 더 첨가하였다. 반응기 내 산소를 질소로 교체하였다. UV 파장에서 10mW/cm2의 세기로 3분 동안 조사하여 단량체 혼합물을 부분 중합시켜, (메트)아크릴계 공중합체 및 중합되지 않고 남아있는 단량체의 혼합물을 얻었다. 제조한 혼합물에 대해 분석한 결과, 하기 표 1의 (메트)아크릴계 공중합체의 함량을 얻었다.In the reactor, 25 parts by weight of 2-ethylhexyl acrylate and 75 parts by weight of 2-hydroxyethyl acrylate were mixed to prepare a monomer mixture. To the monomer mixture, 0.04 part by weight of initiator Irgacure 651 (manufactured by Ciba) was further added. The oxygen in the reactor was replaced with nitrogen. The monomer mixture was partially polymerized by irradiation with UV light at an intensity of 10 mW / cm < 2 > for 3 minutes to obtain a mixture of the (meth) acrylic copolymer and the un polymerized monomers. The obtained mixture was analyzed. As a result, the content of the (meth) acrylic copolymer in Table 1 was obtained.
그런 다음, 개시제 Irgacure 651(Ciba사) 1.5중량부, 실란커플링제 KBM-403 0.1중량부, 소포제 BYK-A-515 0.01중량부를 첨가하여, 점착제 조성물을 제조하였다. Then, 1.5 parts by weight of initiator Irgacure 651 (Ciba), 0.1 part by weight of silane coupling agent KBM-403 and 0.01 part by weight of defoaming agent BYK-A-515 were added to prepare a pressure-sensitive adhesive composition.
실시예와 비교예의 점착제 조성물에 대해 하기 표 1의 물성을 평가하였다.The properties of the pressure-sensitive adhesive compositions of Examples and Comparative Examples were evaluated as shown in Table 1 below.
(g/in)Peel strength
(g / in)
상기 표 1에서와 같이, 본 발명의 일 실시예에 따른 점착제 조성물은 경화수축률이 3% 이하로 낮고, 점착제 조성물의 경화 후 휘발분이 적으며, 들뜸 등이 없어 내구성이 좋았다.As shown in Table 1, the pressure-sensitive adhesive composition according to an embodiment of the present invention has a low hardening shrinkage rate of 3% or less, low volatility after curing of the pressure-sensitive adhesive composition, and good durability without lifting.
반면에, 비교예 1은 경화수축률이 높았다. On the other hand, in Comparative Example 1, the hardening shrinkage ratio was high.
또한, 표 1에서 나타나 있지 않지만, 본 발명의 일 실시예에 따른 점착제 조성물은 디스플레이 패널에 합지 후 UV 조사후 경화수축률이 낮아 얼룩(mura)이 생기지 않았다. 반면에, 비교예 1은 경화수축률이 높아 경화 수축에 의한 얼룩(mura) 발생의 문제점이 있다.In addition, although not shown in Table 1, the pressure-sensitive adhesive composition according to an embodiment of the present invention has a low hardening shrinkage after UV irradiation after laminating on a display panel, and no mura is generated. On the other hand, Comparative Example 1 has a high hardening shrinkage ratio, which causes a problem of occurrence of mura due to hardening shrinkage.
<물성평가방법>≪ Property evaluation method &
(1)(메트)아크릴계 공중합체의 중량평균분자량: 점착제 조성물에 대해 테트라히드로푸란을 용매로 하는 겔투과 크로마토그래피를 사용하고, 표준 폴리스티렌의 검량을 사용하여 (메트)아크릴계 공중합체의 중량평균분자량을 측정하였다. (1) Weight average molecular weight of (meth) acrylic copolymer: The gel permeation chromatography using tetrahydrofuran as a solvent was used for the pressure-sensitive adhesive composition, and the weight average molecular weight of the (meth) acrylic copolymer Were measured.
(2)점착제 조성물의 점도: 점착제 조성물에 대해 브룩필드(Brookfield) 점도계 LV-II 장치를 사용하여 25℃에서 측정하였다.(2) Viscosity of the pressure-sensitive adhesive composition: The pressure-sensitive adhesive composition was measured at 25 캜 using a Brookfield viscometer LV-II apparatus.
(3)점착제 조성물의 경화수축률: 점착제 조성물 10g에 대해 비중컵을 사용하여 점착제 조성물의 밀도(A, 단위: g/cm3)를 구하였다. 점착제 조성물 10g을 이형 필름인 폴리에틸렌테레프탈레이트 필름에 도포하고 UV를 20mW/cm2의 세기로 3분 동안 조사하여 두께 200㎛의 점착 필름을 제조하였다. 점착 필름에 대해 비중컵을 사용하여 점착 필름의 밀도(B, 단위:g/cm3)를 구하였다. 경화수축률은 하기 식 1로 계산하였다.(3) Cure shrinkage ratio of pressure-sensitive adhesive composition: The density (A, unit: g / cm 3 ) of the pressure-sensitive adhesive composition was determined using a specific weight cup for 10 g of the pressure-sensitive adhesive composition. 10 g of the pressure-sensitive adhesive composition was applied to a polyethylene terephthalate film as a release film and UV was irradiated for 3 minutes at an intensity of 20 mW / cm 2 to produce a pressure-sensitive adhesive film having a thickness of 200 탆. The density (B, unit: g / cm < 3 >) of the pressure-sensitive adhesive film was determined using a specific gravity cup for the pressure-sensitive adhesive film. The hardening shrinkage was calculated by the following formula 1.
<식 1><Formula 1>
경화수축률 = (B-A)/B x 100Cure shrinkage ratio = (B-A) / B x 100
(상기 식 1에서, A 는 점착제 조성물 10g의 밀도, B는 점착제 조성물 10g을 UV 20m W/cm2의 세기로 3분 동안 경화시켜 제조된 점착 필름의 밀도)(Density of the pressure-sensitive adhesive film prepared by curing 10 g of the pressure-sensitive adhesive composition at an intensity of 20 mW / cm 2 of UV for 3 minutes)
(4)점착 필름의 헤이즈와 광투과도: 점착제 조성물 10g을 이형 필름인 폴리에틸렌테레프탈레이트 필름(두께:50㎛)에 도포하고 UV를 20mW/cm2의 세기로 3분 동안 조사하여 이형 필름 상에 두께 200㎛의 점착 필름을 제조하였다. 제조된 점착 필름에 대해 haze meter(NIPPON DENSHOKU NDH-5000)로 헤이즈와 광투과도를 측정하였다.(4) Haze and light transmittance of the pressure-sensitive adhesive film: 10 g of the pressure-sensitive adhesive composition was applied to a polyethylene terephthalate film (thickness: 50 탆) as a release film and irradiated with UV at an intensity of 20 mW / cm 2 for 3 minutes, An adhesive film having a thickness of 200 mu m was produced. The haze and light transmittance of the resulting adhesive film were measured with a haze meter (NIPPON DENSHOKU NDH-5000).
(5)신율: 폴리에틸렌테레프탈레이트 필름 상에 점착제 조성물을 코팅하고, 코팅된 점착제 조성물 상에 폴리에틸렌테레프탈레이트 필름을 다시 합지하고, UV를 20mW/cm2의 세기로 3분 동안 조사하여 점착제 조성물을 경화시켜, 점착 필름의 두께가 1mm이 되는 시편을 제조하였다. 상기 폴리에틸렌테레프탈레이트 필름을 제외 시킨 점착 필름 시편에 대해 ASTM D638로 측정하였다. (5) Elongation at break: curing the pressure-sensitive adhesive composition is irradiated for 3 minutes for laminating a polyethylene terephthalate coated with a pressure-sensitive adhesive composition on the film, and polyethylene terephthalate film to the coated pressure-sensitive adhesive composition again, and UV in intensity of 20mW / cm 2 To prepare a specimen having a thickness of 1 mm on the adhesive film. The pressure-sensitive adhesive film specimens excluding the polyethylene terephthalate film were measured by ASTM D638.
(6)박리강도: 점착제 조성물 10g을 이형 필름인 폴리에틸렌테레프탈레이트 필름(두께:50㎛)에 도포하고 UV를 20mW/cm2의 세기로 3분 동안 조사하여 이형 필름 상에 두께 200㎛의 점착 필름을 제조하였다. 점착 필름 위에 ITO(indium tin oxide) 필름을 부착하고, 부착한 후 30분이 경과한 시점에 TA.XT_PLUS Texture Analyzer(Stable Micro System)를 사용하여 300mm/min에서 박리강도를 측정하였다.6 Peel Strength: The pressure-sensitive adhesive composition 10g a release film of polyethylene terephthalate film (thickness: 50㎛) UV coating and an adhesive film of 20mW / cm investigated 200㎛ thickness on a release film for 3 minutes to 2 intensity of the . An indium tin oxide (ITO) film was attached on the adhesive film, and the peel strength was measured at 300 mm / min using a TA.XT_PLUS Texture Analyzer (Stable Micro System) 30 minutes after the attachment.
(7)내구성: 점착제 조성물 10g을 유리판 위에 도포하고 다른 유리판을 합지 후 UV를 20mW/cm2의 세기로 3분 동안 조사하여 두께 200㎛의 점착층이 형성된 시편을 얻었다. 상기 시편을 60℃ 및 90% 상대습도에서 500시간 동안 방치하고, 유리판 피착면에서의 들뜸, 기포 발생 여부를 육안으로 평가하였다. 들뜸, 기포 발생이 없는 경우 양호, 들뜸 및/또는 기포 발생이 있는 경우 불량으로 평가하였다.(7) Durability: 10 g of the pressure-sensitive adhesive composition was coated on a glass plate, another glass plate was laminated, and UV was irradiated for 3 minutes at an intensity of 20 mW / cm 2 to obtain a specimen having a thickness of 200 탆. The specimens were allowed to stand at 60 DEG C and 90% relative humidity for 500 hours, and visually evaluated for lifting and bubbling on the glass plate surface. And when the bubbles were not generated, it was evaluated as good, when the bubbles were generated, and when the bubbles were generated.
이상 본 발명의 실시예들을 설명하였으나, 본 발명은 상기 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 제조될 수 있으며, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야 한다.While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.
Claims (18)
상기 (메트)아크릴계 공중합체와 상기 (메트)아크릴계 단량체의 합 100중량부 중 상기 (메트)아크릴계 공중합체 5중량부 내지 40중량부, 상기 (메트)아크릴계 단량체 60중량부 내지 95중량부를 포함하고,
상기 점착제 조성물은 하기 식 1의 경화수축률이 3% 이하이고,
<식 1>
경화수축률 = (B-A)/B x 100
(상기 식 1에서, A 는 점착제 조성물 10g의 밀도, B는 점착제 조성물 10g을 UV 20m W/cm2의 세기로 3분 동안 경화시켜 제조된 점착 필름의 밀도)
상기 점착제 조성물은 경화 후 신율이 500% 이상인, 점착제 조성물.(Meth) acrylic copolymer and a (meth) acrylic monomer having a weight average molecular weight of 600,000 g / mol to 150,000 g / mol,
5 to 40 parts by weight of the (meth) acrylic copolymer and 60 to 95 parts by weight of the (meth) acrylic monomer in 100 parts by weight of the sum of the (meth) acrylic copolymer and the (meth) ,
The pressure-sensitive adhesive composition preferably has a curing shrinkage of 3% or less in the following formula (1)
<Formula 1>
Cure shrinkage ratio = (BA) / B x 100
(Density of the pressure-sensitive adhesive film prepared by curing 10 g of the pressure-sensitive adhesive composition at an intensity of 20 mW / cm 2 of UV for 3 minutes)
Wherein the pressure-sensitive adhesive composition has an elongation after curing of 500% or more.
상기 (메트)아크릴계 공중합체와 상기 (메트)아크릴계 단량체의 합 100중량부 중 상기 (메트)아크릴계 공중합체는 5중량부 내지 40중량부를 포함되고,
상기 점착제 조성물은 25℃에서 점도가 5,000cps 내지 10,000cps인 것인 점착제 조성물.(Meth) acrylic copolymer having a weight average molecular weight of 600,000 g / mol to 150,000 g / mol and (meth) acrylic acid ester polymer having an unsubstituted C14 to C20 alkyl group and a (meth) acrylic monomer Composition,
The amount of the (meth) acrylic copolymer in the total amount of 100 parts by weight of the (meth) acrylic copolymer and the (meth) acrylic monomer is 5 parts by weight to 40 parts by weight,
Wherein the pressure-sensitive adhesive composition has a viscosity of 5,000 cps to 10,000 cps at 25 占 폚.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880800A (en) * | 2017-11-20 | 2018-04-06 | 上海固柯胶带科技有限公司 | A kind of novel solvent-free adhesive tape and preparation method thereof |
| KR20190083480A (en) | 2018-01-04 | 2019-07-12 | 동우 화인켐 주식회사 | Adhesive sheet, optical member and display device using the same |
| WO2022055148A1 (en) * | 2020-09-11 | 2022-03-17 | 주식회사 엘지화학 | Adhesive composition for foldable display and adhesive film for foldable display comprising cured product thereof |
| JP2023051932A (en) * | 2017-09-06 | 2023-04-11 | 日東電工株式会社 | Adhesive composition for organic EL display device, adhesive layer for organic EL display device, polarizing film with adhesive layer for organic EL display device, and organic EL display device |
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2015
- 2015-03-31 KR KR1020150045767A patent/KR20160117866A/en not_active Ceased
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023051932A (en) * | 2017-09-06 | 2023-04-11 | 日東電工株式会社 | Adhesive composition for organic EL display device, adhesive layer for organic EL display device, polarizing film with adhesive layer for organic EL display device, and organic EL display device |
| CN107880800A (en) * | 2017-11-20 | 2018-04-06 | 上海固柯胶带科技有限公司 | A kind of novel solvent-free adhesive tape and preparation method thereof |
| KR20190083480A (en) | 2018-01-04 | 2019-07-12 | 동우 화인켐 주식회사 | Adhesive sheet, optical member and display device using the same |
| WO2022055148A1 (en) * | 2020-09-11 | 2022-03-17 | 주식회사 엘지화학 | Adhesive composition for foldable display and adhesive film for foldable display comprising cured product thereof |
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