KR20200105261A - Adhesive Sheet - Google Patents
Adhesive Sheet Download PDFInfo
- Publication number
- KR20200105261A KR20200105261A KR1020190024201A KR20190024201A KR20200105261A KR 20200105261 A KR20200105261 A KR 20200105261A KR 1020190024201 A KR1020190024201 A KR 1020190024201A KR 20190024201 A KR20190024201 A KR 20190024201A KR 20200105261 A KR20200105261 A KR 20200105261A
- Authority
- KR
- South Korea
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive sheet
- weight
- acrylic copolymer
- Prior art date
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 36
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 36
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 12
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 91
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 21
- 239000011521 glass Substances 0.000 claims description 12
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- -1 isocyanate compound Chemical class 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 13
- 239000010408 film Substances 0.000 description 27
- 239000010410 layer Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000003851 corona treatment Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- RNOOHTVUSNIPCJ-UHFFFAOYSA-N butan-2-yl prop-2-enoate Chemical compound CCC(C)OC(=O)C=C RNOOHTVUSNIPCJ-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000001029 thermal curing Methods 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 description 1
- ZEWLHMQYEZXSBH-UHFFFAOYSA-N 4-[2-(2-methylprop-2-enoyloxy)ethoxy]-4-oxobutanoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)CCC(O)=O ZEWLHMQYEZXSBH-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 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
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 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
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction 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
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Abstract
Description
본 발명은 점착 시트에 관한 것으로, 보다 상세하게는 박막이면서도 우수한 내구성 및 리워크성을 갖는 점착 시트에 관한 것이다.The present invention relates to an adhesive sheet, and more particularly, to an adhesive sheet having excellent durability and rework property while being a thin film.
고투명성을 갖는 광학용 투명 점착 시트(optically clear adhesive, OCA)는 디스플레이 장치에서 부품들을 적층하는 층간 접착에 사용되고 있다. 이러한 광학용 투명 점착 시트는 높은 투과율과 낮은 헤이즈가 요구되며, 다양한 기재와의 밀착성, 내열 및 내습열 내구성, 및 리워크성과 같은 물성을 만족시켜야 한다.An optically clear adhesive (OCA) having high transparency is used for interlayer bonding to laminate components in a display device. Such an optically transparent adhesive sheet is required to have high transmittance and low haze, and must satisfy physical properties such as adhesion to various substrates, heat resistance and moisture resistance durability, and rework property.
최근에는 접었다 펼쳐도 표시 성능을 그대로 유지할 수 있는 폴더블(foldable) 디스플레이 장치가 차세대 디스플레이 장치로 급부상하면서, 폴더블 디스플레이 장치에 적용하기에 적합하도록 박막이면서도 내구성 및 리워크성이 우수한 점착 시트의 개발이 요구되고 있다.In recent years, as foldable display devices capable of maintaining display performance even when folded and unfolded are rapidly emerging as a next-generation display device, development of a thin-film, durable and reworkable adhesive sheet suitable for application to foldable display devices. Is being demanded.
대한민국 공개특허 제2014-0044269호에는 탄소수 12 이상의 알킬기 함유 (메타)아크릴레이트, 탄소수 1 이상 8 이하의 알킬기 함유 (메타)아크릴레이트 및 히드록시기 함유 모노머를 포함하는 (메타)아크릴 공중합체를 포함하는 점착제 조성물이 가교 반응하여 형성된 가교 구조를 포함하는 점착제층을 갖는 점착 시트가 개시되어 있다. 그러나, 상기 점착 시트는 박막인 경우, 내구성 및 리워크성을 확보하기 어려운 문제점이 있다.Korean Patent Application Publication No. 2014-0044269 discloses a pressure-sensitive adhesive comprising a (meth)acrylate containing an alkyl group having 12 or more carbon atoms, a (meth)acrylate containing an alkyl group having 1 or more and 8 or less carbon atoms, and a (meth)acrylic copolymer containing a hydroxy group-containing monomer. A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer including a crosslinked structure formed by a crosslinking reaction of the composition is disclosed. However, when the pressure-sensitive adhesive sheet is a thin film, it is difficult to secure durability and rework property.
따라서, 박막이면서도 내구성 및 리워크성이 우수한 점착 시트에 대한 기술 개발이 요구되고 있다.Therefore, there is a need for technology development for a pressure-sensitive adhesive sheet having excellent durability and reworkability while being a thin film.
본 발명의 한 목적은 박막이면서도 우수한 내구성 및 리워크성을 갖는 점착 시트를 제공하는 것이다.One object of the present invention is to provide a pressure-sensitive adhesive sheet having excellent durability and rework property while being a thin film.
한편으로, 본 발명은 아크릴 공중합체 및 열경화제를 포함하는 점착제 조성물로부터 형성된 점착 시트로서, 상기 점착 시트의 두께는 5㎛ 이하이며, 상기 점착 시트의 두께가 A이고, 상온 점착력이 B일 때, B/A가 1.5 내지 2인 점착 시트를 제공한다.On the other hand, the present invention is a pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition comprising an acrylic copolymer and a thermosetting agent, the thickness of the pressure-sensitive adhesive sheet is 5 μm or less, the thickness of the pressure-sensitive adhesive sheet is A, and the room temperature adhesive strength is B, A pressure-sensitive adhesive sheet having a B/A of 1.5 to 2 is provided.
본 발명의 일 실시형태에서, 상기 점착 시트의 두께는 1 내지 5㎛일 수 있다.In one embodiment of the present invention, the thickness of the adhesive sheet may be 1 to 5㎛.
본 발명의 일 실시형태에서, 상기 아크릴 공중합체는 탄소수 4-12의 알킬기를 갖는 (메타)아크릴레이트 85 내지 99 중량% 및 2-카르복시에틸아크릴레이트 1 내지 15 중량%를 포함하는 단량체 혼합물로부터 형성되는 것일 수 있다.In one embodiment of the present invention, the acrylic copolymer is formed from a monomer mixture comprising 85 to 99% by weight of (meth)acrylate and 1 to 15% by weight of 2-carboxyethyl acrylate having an alkyl group having 4 to 12 carbon atoms It can be.
본 발명의 일 실시형태에서, 상기 아크릴 공중합체는 중량평균분자량이 50만 내지 90만인 것일 수 있다.In one embodiment of the present invention, the acrylic copolymer may have a weight average molecular weight of 500,000 to 900,000.
본 발명의 일 실시형태에서, 상기 열경화제는 이소시아네이트 화합물을 포함하는 것일 수 있다.In one embodiment of the present invention, the thermosetting agent may include an isocyanate compound.
본 발명의 일 실시형태에서, 상기 열경화제는 아크릴 공중합체 전체 100 중량부에 대하여 0.1 내지 1 중량부의 양으로 포함될 수 있다.In one embodiment of the present invention, the thermosetting agent may be included in an amount of 0.1 to 1 part by weight based on 100 parts by weight of the acrylic copolymer.
본 발명의 일 실시형태에 따른 점착 시트는, 상기 점착 시트 한 면을 50㎛의 환상 올레핀 중합체 필름과 접합하고 90㎜×170㎜ 크기로 절단한 후, 다른 한 면을 유리 기판에 부착한 다음, 100℃의 온도에서 500시간 동안 방치한 후에 기포나 박리가 5개 미만일 수 있다.In the pressure-sensitive adhesive sheet according to an embodiment of the present invention, one side of the pressure-sensitive adhesive sheet is bonded to a 50 μm cyclic olefin polymer film, cut into a size of 90 mm×170 mm, and then the other side is attached to a glass substrate, After standing at a temperature of 100° C. for 500 hours, there may be fewer than 5 bubbles or peeling.
본 발명의 일 실시형태에 따른 점착 시트는 상기 점착 시트 한 면을 50㎛의 환상 올레핀 중합체 필름과 접합하고 90㎜×170㎜ 크기로 절단한 후, 다른 한 면을 유리 기판에 부착한 다음, 85℃의 온도 및 85%RH의 조건 하에서 500시간 동안 방치한 후에 기포나 박리가 5개 미만일 수 있다.In the pressure-sensitive adhesive sheet according to an embodiment of the present invention, one side of the pressure-sensitive adhesive sheet is bonded to a 50 μm cyclic olefin polymer film, cut into a size of 90 mm×170 mm, and the other side is attached to a glass substrate, and then 85 After leaving for 500 hours under conditions of a temperature of °C and 85%RH, there may be less than 5 bubbles or peeling.
본 발명의 일 실시형태에서, 상기 점착 시트는 폴더블 디스플레이에 사용될 수 있다.In one embodiment of the present invention, the pressure-sensitive adhesive sheet may be used for a foldable display.
본 발명에 따른 점착 시트는 두께가 5㎛ 이하이며, 상기 점착 시트의 두께가 A이고, 상온 점착력이 B일 때, B/A가 1.5 내지 2가 되도록 조절되어 박막이면서도 우수한 내구성 및 리워크성을 갖는다.The pressure-sensitive adhesive sheet according to the present invention has a thickness of 5 μm or less, and when the thickness of the pressure-sensitive adhesive sheet is A and the adhesive strength at room temperature is B, B/A is adjusted to be 1.5 to 2, so that it is a thin film but has excellent durability and rework property Have.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 일 실시형태는 아크릴 공중합체 및 열경화제를 포함하는 점착제 조성물로부터 형성된 점착 시트로서, One embodiment of the present invention is a pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition containing an acrylic copolymer and a thermosetting agent,
상기 점착 시트의 두께는 5㎛ 이하이며, The thickness of the pressure-sensitive adhesive sheet is 5 μm or less,
상기 점착 시트의 두께가 A이고, 상온 점착력이 B일 때, B/A가 1.5 내지 2인 점착 시트에 관한 것이다.When the thickness of the pressure-sensitive adhesive sheet is A and the adhesive strength at room temperature is B, it relates to a pressure-sensitive adhesive sheet having a B/A of 1.5 to 2.
본 발명의 일 실시형태에 따른 점착 시트는 두께가 5㎛ 이하인 박막 점착 시트이다. 예컨대, 상기 점착 시트의 두께는 1 내지 5㎛일 수 있다. 상기 점착 시트의 두께가 1㎛ 미만이면 점착력 발현이 어려울 수 있고, 5㎛ 초과이면 박막 구현이 어렵다.The adhesive sheet according to an embodiment of the present invention is a thin film adhesive sheet having a thickness of 5 μm or less. For example, the thickness of the pressure-sensitive adhesive sheet may be 1 to 5 μm. If the thickness of the pressure-sensitive adhesive sheet is less than 1 μm, it may be difficult to express adhesion, and if it exceeds 5 μm, it is difficult to implement a thin film.
본 발명의 일 실시형태에 따른 점착 시트는 점착 시트의 두께가 A(㎛)이고, 상온 점착력이 B(N/25㎜)일 때, B/A를 1.5 내지 2로 조절함으로써 박막 조건 하에서도 우수한 내구성 및 리워크성을 가질 수 있다. 상기 B/A가 1.5 미만이면 점착 시트의 내구성이 떨어질 수 있고, 2 초과이면 리워크성이 떨어질 수 있다.The pressure-sensitive adhesive sheet according to an embodiment of the present invention is excellent even under thin film conditions by adjusting B/A to 1.5 to 2 when the thickness of the pressure-sensitive adhesive sheet is A (㎛) and the room temperature adhesive strength is B (N/25 mm). It can have durability and rework property. If the B/A is less than 1.5, the durability of the pressure-sensitive adhesive sheet may decrease, and if it is more than 2, the rework property may decrease.
상기 상온 점착력은 상온에서 피착체가 부착되어 있는 강도를 의미한다. 본 발명에서 점착 시트의 상온 점착력을 측정하는 방법은 특별히 제한되지 않으며, 예를 들면 후술하는 실험예에 제시된 방법으로 측정할 수 있다.The room temperature adhesion refers to the strength at which the adherend is attached at room temperature. In the present invention, a method of measuring the adhesive force at room temperature of the pressure-sensitive adhesive sheet is not particularly limited, and may be measured, for example, by the method shown in the experimental examples described later.
본 발명의 일 실시형태에서, 상기 점착 시트는 아크릴 공중합체(A) 및 열경화제(B)를 포함하는 점착제 조성물로부터 형성된다.In one embodiment of the present invention, the pressure-sensitive adhesive sheet is formed from a pressure-sensitive adhesive composition containing an acrylic copolymer (A) and a thermosetting agent (B).
아크릴 공중합체(A)Acrylic copolymer (A)
본 발명의 일 실시형태에서, 상기 아크릴 공중합체(A)는 점착제 조성물의 점성 대 탄성 균형을 조절하는 역할을 하는 성분으로서, 탄소수 4-12의 알킬기를 갖는 (메타)아크릴레이트 85 내지 99 중량% 및 2-카르복시에틸아크릴레이트 1 내지 15 중량%를 포함하는 단량체 혼합물로부터 형성되는 것일 수 있다. 여기서, (메타)아크릴레이트는 아크릴레이트 및/또는 메타크릴레이트를 의미한다.In one embodiment of the present invention, the acrylic copolymer (A) is a component that serves to adjust the viscosity versus elastic balance of the pressure-sensitive adhesive composition, and 85 to 99% by weight of (meth)acrylate having an alkyl group having 4-12 carbon atoms And 2-carboxyethyl acrylate may be formed from a monomer mixture comprising 1 to 15% by weight. Here, (meth)acrylate means acrylate and/or methacrylate.
상기 탄소수 4-12의 알킬기를 갖는 (메타)아크릴레이트로는, n-부틸(메타)아크릴레이트, 2-부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 펜틸(메타)아크릴레이트, n-옥틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 노닐(메타)아크릴레이트, 데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트 등을 들 수 있으며, 이들 중에서 n-부틸(메타)아크릴레이트가 바람직하다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.As the (meth)acrylate having an alkyl group having 4-12 carbon atoms, n-butyl (meth)acrylate, 2-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth) )Acrylate, pentyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, etc. And among these, n-butyl (meth)acrylate is preferred. These can be used alone or in combination of two or more.
상기 탄소수 4-12의 알킬기를 갖는 (메타)아크릴레이트는 아크릴 공중합체의 제조에 사용되는 총 단량체 100 중량%에 대하여 85 내지 99 중량%, 바람직하게는 90 내지 97 중량%로 포함되는 것이 바람직하다. 상기 탄소수 4-12의 알킬기를 갖는 (메타)아크릴레이트의 함량이 85 중량% 미만인 경우에는 점착제 조성물의 점도가 상승할 수 있고, 99 중량% 초과인 경우에는 점착력 발현이 어려울 수 있다.The (meth)acrylate having an alkyl group having 4-12 carbon atoms is preferably contained in an amount of 85 to 99% by weight, preferably 90 to 97% by weight, based on 100% by weight of the total monomers used in the preparation of the acrylic copolymer. . When the content of the (meth)acrylate having an alkyl group having 4-12 carbon atoms is less than 85% by weight, the viscosity of the pressure-sensitive adhesive composition may increase, and when it is more than 99% by weight, it may be difficult to develop adhesive strength.
상기 2-카르복시에틸아크릴레이트는 점착 시트가 박막인 경우에도 점착력을 발현시키는 역할을 할 수 있다.The 2-carboxyethyl acrylate may serve to express adhesive strength even when the adhesive sheet is a thin film.
상기 2-카르복시에틸아크릴레이트는 아크릴 공중합체의 제조에 사용되는 총 단량체 100 중량%에 대하여 1 내지 15 중량%, 바람직하게는 3 내지 10 중량%로 포함되는 것이 바람직하다. 상기 2-카르복시에틸아크릴레이트의 함량이 1 중량% 미만인 경우에는 점착 시트가 박막인 경우에 점착력 발현이 어려울 수 있고, 15 중량% 초과인 경우에는 점착제 조성물의 점도가 상승할 수 있다.The 2-carboxyethyl acrylate is preferably contained in an amount of 1 to 15% by weight, preferably 3 to 10% by weight, based on 100% by weight of the total monomers used in the preparation of the acrylic copolymer. When the content of the 2-carboxyethyl acrylate is less than 1% by weight, it may be difficult to express adhesion when the pressure-sensitive adhesive sheet is a thin film, and when it is more than 15% by weight, the viscosity of the pressure-sensitive adhesive composition may increase.
상기 아크릴 공중합체의 제조방법은 특별히 한정되지 않으며, 당해 분야에서 통상적으로 사용되는 괴상중합, 용액중합, 유화중합 또는 현탁중합 등의 방법을 이용하여 제조할 수 있으며, 용액중합이 바람직하다. 또한, 중합 시 통상 사용되는 용매, 중합개시제, 분자량 제어를 위한 연쇄이동제 등을 사용할 수 있다.The method for preparing the acrylic copolymer is not particularly limited, and may be prepared by using a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization commonly used in the art, and solution polymerization is preferred. In addition, a solvent commonly used during polymerization, a polymerization initiator, a chain transfer agent for molecular weight control, and the like may be used.
상기 아크릴 공중합체는 겔투과크로마토그래피(Gel permeation chromatography, GPC)에 의해 측정된 중량평균분자량(폴리스티렌 환산, Mw)이 통상 50만 내지 90만이며, 바람직하게는 50만 내지 60만일 수 있다. 중량평균분자량이 50만 미만인 경우 공중합체 간의 응집력이 부족하여 점착 내구성에 문제를 야기할 수 있고, 90만 초과인 경우 도공 시 공정성을 확보하기 위하여 다량의 희석 용매를 필요로 할 수 있다.The acrylic copolymer has a weight average molecular weight (in terms of polystyrene, Mw) measured by gel permeation chromatography (GPC) of 500,000 to 900,000, preferably 500,000 to 600,000. If the weight average molecular weight is less than 500,000, cohesive strength between the copolymers may be insufficient, which may cause a problem in adhesion durability, and if it is more than 900,000, a large amount of dilute solvent may be required to secure fairness during coating.
열경화제Heat curing agent (B)(B)
본 발명의 일 실시형태에서, 상기 열경화제(B)는 밀착성 및 내구성을 향상시킬 수 있고, 고온에서의 신뢰성 및 점착제의 형상을 유지시킬 수 있는 성분으로서, 이소시아네이트 화합물, 에폭시 화합물, 과산화물, 금속킬레이트 화합물, 옥사졸린 화합물 등이 사용될 수 있으며, 1종 또는 2종 이상을 혼합 사용할 수 있다. 이 중 이소시아네이트 화합물이 바람직하다.In one embodiment of the present invention, the thermosetting agent (B) is a component capable of improving adhesion and durability, maintaining reliability at high temperature and the shape of the pressure-sensitive adhesive, as an isocyanate compound, an epoxy compound, a peroxide, and a metal chelate. Compounds, oxazoline compounds, and the like may be used, and one type or two or more types may be used in combination. Among these, isocyanate compounds are preferred.
구체적으로, 상기 열경화제로는 톨릴렌디이소시아네이트, 크실렌디이소시아네이트, 헥사메틸렌디이소시아네이트, 2,4- 또는 4,4-디페닐메탄디이소시아네트 등의 디이소시아네이트 화합물; 및 디이소시아네이트의 트리메틸올프로판 등의 다가 알코올계 화합물의 어덕트체 등이 사용될 수 있다.Specifically, examples of the thermal curing agent include diisocyanate compounds such as tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, and 2,4- or 4,4-diphenylmethane diisocyanate; And adducts of polyhydric alcohol-based compounds such as trimethylolpropane of diisocyanate, and the like can be used.
상기 열경화제는 아크릴 공중합체 전체 100 중량부에 대하여 0.1 내지 1 중량부의 양으로 함유될 수 있다. 상기 열경화제의 함량이 0.1 중량부 미만이면 부족한 가교도로 인해 응집력이 작게 되어 점착 내구성 및 절단성의 물성을 해칠 수 있으며, 1 중량부를 초과할 경우에는 과다 가교반응에 의한 잔류응력 완화에 문제가 발생할 수 있다.The thermosetting agent may be contained in an amount of 0.1 to 1 part by weight based on 100 parts by weight of the acrylic copolymer. If the content of the thermosetting agent is less than 0.1 part by weight, the cohesive strength becomes small due to insufficient crosslinking degree, which may impair adhesion durability and cutting properties, and if it exceeds 1 part by weight, a problem may occur in relieving residual stress due to excessive crosslinking reaction. have.
본 발명의 일 실시형태에서, 상기 점착제 조성물은 상기와 같은 성분 이외에, 용도에 따라 요구되는 점착력, 응집력, 점성, 탄성률, 유리전이온도 등을 조절하기 위하여, 실란 커플링제, 점착성 부여 수지, 산화방지제, 부식방지제, 레벨링제, 표면윤활제, 염료, 안료, 소포제, 충전제, 광안정제 등의 첨가제를 더 포함할 수 있다.In one embodiment of the present invention, the pressure-sensitive adhesive composition is a silane coupling agent, a tackifier resin, an antioxidant in order to control the adhesive force, cohesive force, viscosity, elastic modulus, glass transition temperature, etc. required according to the use in addition to the above components. , Corrosion inhibitors, leveling agents, surface lubricants, dyes, pigments, antifoaming agents, fillers, may further include additives such as light stabilizers.
본 발명의 일 실시형태에 따른 점착 시트는 상술한 점착제 조성물을 이용하여 형성됨으로써 박막 조건 하에서도 우수한 내구성 및 리워크성을 가질 수 있다.The pressure-sensitive adhesive sheet according to an embodiment of the present invention may have excellent durability and rework property even under thin film conditions by being formed using the pressure-sensitive adhesive composition described above.
구체적으로, 본 발명의 일 실시형태에 따른 점착 시트는, 상기 점착 시트 한 면을 50㎛의 환상 올레핀 중합체 필름과 접합하고 90㎜×170㎜ 크기로 절단한 후, 다른 한 면을 유리 기판에 부착한 다음, 100℃의 온도에서 500시간 동안 방치한 후에 기포나 박리가 5개 미만일 수 있다.Specifically, in the pressure-sensitive adhesive sheet according to an embodiment of the present invention, one side of the pressure-sensitive adhesive sheet is bonded to a 50 μm cyclic olefin polymer film, cut into a size of 90 mm×170 mm, and then the other side is attached to a glass substrate. Then, after leaving for 500 hours at a temperature of 100°C, there may be fewer than 5 bubbles or peeling.
또한, 본 발명의 일 실시형태에 따른 점착 시트는 상기 점착 시트 한 면을 50㎛의 환상 올레핀 중합체 필름과 접합하고 90㎜×170㎜ 크기로 절단한 후, 다른 한 면을 유리 기판에 부착한 다음, 85℃의 온도 및 85%RH의 조건 하에서 500시간 동안 방치한 후에 기포나 박리가 5개 미만일 수 있다.In addition, in the pressure-sensitive adhesive sheet according to an embodiment of the present invention, one side of the pressure-sensitive adhesive sheet is bonded to a 50 μm cyclic olefin polymer film, cut into a size of 90 mm×170 mm, and then the other side is attached to a glass substrate. , After leaving for 500 hours under the conditions of a temperature of 85°C and 85%RH, there may be less than 5 bubbles or peeling.
본 발명의 일 실시형태에 따른 점착 시트는 2매의 기재 필름 사이에 상기 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 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, and these are silicone-based, fluorine-based, and silica-based films. It may have been suitably molded out by powder or the like.
점착제층은 1매의 기재 필름 상에 상술한 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, 점착제층은 1매의 기재 필름 상에 점착제 조성물을 도포하고, 30 내지 150℃에서 1초 내지 2시간, 바람직하게는 5초 내지 1시간 동안 건조하여 경화시켜 형성할 수 있다. 이후 상기 점착제층 상에 다른 1매의 기재 필름을 접합시킬 수 있다.The pressure-sensitive adhesive layer can be formed by coating the pressure-sensitive adhesive composition described above on a single 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, the pressure-sensitive adhesive layer may be formed by coating the pressure-sensitive adhesive composition on one base film, drying at 30 to 150° C. for 1 second to 2 hours, preferably 5 seconds to 1 hour, and curing. Thereafter, another base film may be bonded to the pressure-sensitive adhesive layer.
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 통상의 평판 디스플레이 및 플렉서블 디스플레이뿐만 아니라 폴더블 디스플레이에 적용 가능하며, 구체적으로 표시패널, 편광자, 터치패널, 커버 윈도우, 베젤, 고분자 필름 등 다양한 디스플레이 소재의 접합에 적용될 수 있다. 특히, 본 발명의 일 실시형태에 따른 점착 시트는 폴더블 디스플레이에 적용될 수 있다.The pressure-sensitive adhesive sheet according to an embodiment of the present invention can be applied to a foldable display as well as a general flat panel display and a flexible display, and specifically, a display panel, a polarizer, a touch panel, a cover window, a bezel, a polymer film, etc. Can be applied to bonding. In particular, the pressure-sensitive adhesive sheet according to an embodiment of the present invention can be applied to a foldable display.
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.
제조예Manufacturing example : 아크릴 공중합체의 제조: Preparation of acrylic copolymer
제조예Manufacturing example 1: 아크릴 공중합체(A1) 1: Acrylic copolymer (A1)
질소가스가 환류되고 온도조절이 용이하도록 냉각장치를 설치한 1L의 반응기에 2-부틸아크릴레이트(2-BA) 97 중량부 및 2-카르복시에틸아크릴레이트 (2-CEA) 3.0 중량부로 이루어진 단량체 혼합물을 투입한 후, 용제로 에틸아세테이트(EAc) 100 중량부를 투입하였다. 그 다음 산소를 제거하기 위하여 질소가스를 1시간 동안 퍼징한 후, 80℃로 유지하였다. 상기 혼합물을 균일하게 혼합한 후, 반응개시제로 아조비스이소부티로니트릴(AIBN) 0.1 중량부를 투입하고, 8시간 동안 반응시켜 아크릴 공중합체(A1)를 제조하였다(중량평균분자량: 54만).A monomer mixture consisting of 97 parts by weight of 2-butyl acrylate (2-BA) and 3.0 parts by weight of 2-carboxyethyl acrylate (2-CEA) in a 1 L reactor equipped with a cooling device to facilitate nitrogen gas reflux and temperature control After adding, 100 parts by weight of ethyl acetate (EAc) was added as a solvent. Then, nitrogen gas was purged for 1 hour to remove oxygen, and then maintained at 80°C. After uniformly mixing the mixture, 0.1 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator and reacted for 8 hours to prepare an acrylic copolymer (A1) (weight average molecular weight: 540,000).
제조예Manufacturing example 2-6: 아크릴 공중합체(A2-A6) 2-6: acrylic copolymer (A2-A6)
상기 제조예 1과 동일하게 실시하되, 하기 표 1의 조성으로 아크릴 공중합체를 제조하였다(단위: 중량부).It was carried out in the same manner as in Preparation Example 1, but an acrylic copolymer was prepared with the composition shown in Table 1 below (unit: parts by weight).
(단위: 만)Weight average molecular weight
(Unit: 10,000)
2-BA: 2-부틸아크릴레이트(2-butyl acrylate)2-BA: 2-butyl acrylate
2-CEA: 2-카르복시에틸아크릴레이트(2-carboxyethyl acrylate)2-CEA: 2-carboxyethyl acrylate
AA: 아크릴산(acrylic acid)AA: acrylic acid
MES: 모노-2-(메타크릴로일옥시)에틸숙시네이트(mono-2-(methacryloyloxy)ethyl succinate)MES: mono-2-(methacryloyloxy)ethyl succinate
2-HEA: 2-히드록시에틸아크릴레이트(2-hydroxyethyl acrylate)2-HEA: 2-hydroxyethyl acrylate
실시예Example 1 내지 5 및 1 to 5 and 비교예Comparative example 1 내지 5: 점착 시트의 제조 1 to 5: Preparation of adhesive sheet
하기 표 2의 조성으로 각 성분들을 혼합하여 점착제 조성물을 제조하였다(단위: 중량부).To prepare a pressure-sensitive adhesive composition by mixing each component in the composition shown in Table 2 (unit: parts by weight).
(N/25㎜) (B)Room temperature adhesion
(N/25㎜) (B)
열경화제: 톨릴렌디이소시아네이트Thermal curing agent: Tolylene diisocyanate
상기에서 제조된 점착제 조성물을 실리콘 이형제가 코팅된 이형필름 상에 도포하고 100℃에서 1분 동안 건조시켜 상기 표 2의 두께를 갖는 점착제층을 형성하고 그 위에 이형필름을 접합하여 점착 시트를 완성하였다.The pressure-sensitive adhesive composition prepared above was applied on a release film coated with a silicone release agent and dried at 100° C. for 1 minute to form a pressure-sensitive adhesive layer having the thickness of Table 2 above, and the release film was bonded thereon to complete the pressure-sensitive adhesive sheet. .
제조된 점착 시트 한 면의 이형필름을 박리하고 점착제면에 코로나 처리를 한 후 38㎛의 PET 필름과 접합한 다음, 폭이 25 mm이고, 길이가 100mm가 되도록 재단하여 시편을 제조하였다. 이어서, 다른 한 면에 부착된 이형필름을 박리하고, JIS Z 0237의 규정에 따라 2 kg의 롤러를 사용하여 점착 시트를 알칼리 유리에 부착하였다. 점착 시트가 부착된 알칼리 유리를 오토클레이브(50℃, 5 기압)에서 약 20분 동안 압착 처리하고, 항온 항습 조건(23℃, 50% 상대습도)에서 1시간 동안 보관한 다음, TA 장비(Texture Analyzer, 영국 스테이블 마이크로 시스템사제)를 사용하여, 상기 점착 시트를 알칼리 유리로부터 300mm/min의 박리 속도 및 180도의 박리 각도로 박리하면서 박리력을 측정하여 상온 점착력을 평가하였다. 상기 점착제층의 두께(A)와 상온 점착력(B)을 이용하여 B/A 값을 계산하여 표 2에 나타내었다.The release film on one side of the prepared pressure-sensitive adhesive sheet was peeled off, corona treatment was performed on the pressure-sensitive adhesive side, and then bonded with a 38 μm PET film, and then cut to have a width of 25 mm and a length of 100 mm to prepare a specimen. Subsequently, the release film adhered to the other side was peeled off, and the pressure-sensitive adhesive sheet was attached to the alkali glass using a 2 kg roller according to the regulations of JIS Z 0237. The alkali glass to which the adhesive sheet is attached is compressed for about 20 minutes in an autoclave (50°C, 5 atm), and stored for 1 hour in a constant temperature and humidity condition (23°C, 50% relative humidity), and then TA equipment (Texture Analyzer (manufactured by Stable Microsystems, UK) was used to measure the peel force while peeling the pressure-sensitive adhesive sheet from the alkali glass at a peel rate of 300 mm/min and a peel angle of 180 degrees to evaluate the room temperature adhesive force. The B/A values were calculated using the thickness (A) of the pressure-sensitive adhesive layer and the room temperature adhesive strength (B), and are shown in Table 2.
실험예Experimental example 1: One:
상기 실시예 및 비교예에서 제조된 점착 시트의 물성을 하기의 방법으로 측정하고, 그 결과를 하기 표 3에 나타내었다.The physical properties of the pressure-sensitive adhesive sheets prepared in the Examples and Comparative Examples were measured by the following method, and the results are shown in Table 3 below.
(1) 내구성(내열, (1) Durability (heat resistance, 내습열Moist heat resistance ))
점착 시트의 한 면의 이형필름을 박리하고 점착제면에 코로나 처리를 한 후 50㎛의 환상 올레핀 중합체(COP) 필름과 접합하였다. 상기 점착 시트를 90㎜×170㎜ 크기로 절단하고, 다른 한 면의 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 동안 방치한 후에 기포나 박리의 발생 여부를 관찰하였다. 관찰 결과를 하기 평가 기준에 따라 하기 표 3에 나타내었다.The release film on one side of the pressure-sensitive adhesive sheet was peeled off, corona treatment was performed on the pressure-sensitive adhesive side, and then bonded with a 50 μm cyclic olefin polymer (COP) film. The adhesive sheet was cut into a size of 90 mm×170 mm, the release film on the other side was peeled off, 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 being left at a temperature of 100°C for 500 hours, and moisture and heat resistance was observed for 500 hours under conditions of 85°C and 85%RH, followed by bubbles or peeling. Was observed. The observation results are shown in Table 3 below according to the following evaluation criteria.
<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
(2) (2) 리워크성Rework
점착 시트의 한 면의 이형필름을 박리하고 점착제면에 코로나 처리를 한 후 50㎛의 환상 올레핀 중합체(COP) 필름과 접합하였다. 상기 점착 시트를 90㎜×170㎜ 크기로 절단하고, 다른 한 면의 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. 상기 시편을 80℃에서 10 시간 동안, 60℃, 90% RH 조건에서 12 시간 동안 에이징한 후 유리에서 박리시켜 하기의 평가기준에 따라 리워크성을 측정하였다.The release film on one side of the pressure-sensitive adhesive sheet was peeled off, corona treatment was performed on the pressure-sensitive adhesive side, and then bonded with a 50 μm cyclic olefin polymer (COP) film. The adhesive sheet was cut into a size of 90 mm×170 mm, the release film on the other side was peeled off, 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. The specimen was aged at 80° C. for 10 hours, 60° C., and 90% RH for 12 hours, and then peeled off the glass to measure the rework property according to the following evaluation criteria.
<평가 기준><Evaluation criteria>
○: 재박리시 점착제가 남김없이 떨어지는 경우○: When the adhesive falls off completely when peeling again
×: 재박리시 점착제가 떨어지지 않고 남음×: The adhesive does not fall off and remains when peeled again
상기 표 3에서 볼 수 있는 바와 같이, 본 발명에 따라 점착제층, 즉 점착 시트의 두께가 A이고, 상온 점착력이 B일 때, B/A가 1.5 내지 2인 실시예 1 내지 5의 점착 시트는, 점착제층의 두께가 5㎛ 이하인 박막임에도 내구성과 리워크성이 모두 우수한 것을 확인할 수 있었다. 반면, B/A가 1.5 미만인 비교예 1 내지 4의 점착 시트는 내열 및 내습열 내구성이 불량하였고, B/A가 2를 초과하는 비교예 5의 점착 시트는 내열 및 내습열 내구성이 떨어지고 리워크성도 불량한 것을 확인할 수 있었다.As can be seen in Table 3, according to the present invention, when the thickness of the pressure-sensitive adhesive layer, that is, the pressure-sensitive adhesive sheet is A, and the adhesive strength at room temperature is B, the pressure-sensitive adhesive sheets of Examples 1 to 5 in which B/A is 1.5 to 2 , It was confirmed that both durability and rework property were excellent even though the thickness of the pressure-sensitive adhesive layer was 5 μm or less. On the other hand, the pressure-sensitive adhesive sheets of Comparative Examples 1 to 4 with a B/A of less than 1.5 had poor heat resistance and moisture-heat resistance, and the pressure-sensitive adhesive sheet of Comparative Example 5 with a B/A of greater than 2 had poor heat and moisture-heat resistance and rework It was confirmed that the castle was also poor.
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 (9)
상기 점착 시트의 두께는 5㎛ 이하이며,
상기 점착 시트의 두께가 A이고, 상온 점착력이 B일 때, B/A가 1.5 내지 2인 점착 시트.A pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition comprising an acrylic copolymer and a thermosetting agent,
The thickness of the pressure-sensitive adhesive sheet is 5 μm or less,
When the thickness of the pressure-sensitive adhesive sheet is A and the adhesive strength at room temperature is B, the pressure-sensitive adhesive sheet having a B/A of 1.5 to 2.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102444641B1 (en) * | 2021-06-08 | 2022-09-20 | 티와이코퍼레이션(주) | adhesive film using foldable display |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130066571A (en) * | 2010-03-31 | 2013-06-20 | 린텍 가부시키가이샤 | Adhesive sheet |
| JP2013189562A (en) * | 2012-03-14 | 2013-09-26 | Lintec Corp | Adhesive sheet |
| KR20140044269A (en) | 2012-10-04 | 2014-04-14 | 닛뽕 카바이도 고교 가부시키가이샤 | Adhesive composition, adhesive sheet and laminated sheet for optical applications |
| KR20150076150A (en) * | 2012-10-19 | 2015-07-06 | 린텍 가부시키가이샤 | Adhesive agent composition and adhesive sheet |
| KR20150122507A (en) * | 2014-04-23 | 2015-11-02 | 동우 화인켐 주식회사 | Adhesive composition |
| KR20180031330A (en) * | 2016-09-20 | 2018-03-28 | 동우 화인켐 주식회사 | Optically Clear Adhesive Composition, and Optically Clear Adhesive Film comprising the Same, and Flat Panel Display |
| KR101940550B1 (en) * | 2017-08-10 | 2019-01-22 | 애경화학 주식회사 | Thin film acrylic pressure sensitive adhesive composition having high adhesive and the method of manufacturing the same |
-
2019
- 2019-02-28 KR KR1020190024201A patent/KR102609849B1/en active IP Right Grant
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130066571A (en) * | 2010-03-31 | 2013-06-20 | 린텍 가부시키가이샤 | Adhesive sheet |
| JP2013189562A (en) * | 2012-03-14 | 2013-09-26 | Lintec Corp | Adhesive sheet |
| KR20140044269A (en) | 2012-10-04 | 2014-04-14 | 닛뽕 카바이도 고교 가부시키가이샤 | Adhesive composition, adhesive sheet and laminated sheet for optical applications |
| KR20150076150A (en) * | 2012-10-19 | 2015-07-06 | 린텍 가부시키가이샤 | Adhesive agent composition and adhesive sheet |
| KR20150122507A (en) * | 2014-04-23 | 2015-11-02 | 동우 화인켐 주식회사 | Adhesive composition |
| KR20180031330A (en) * | 2016-09-20 | 2018-03-28 | 동우 화인켐 주식회사 | Optically Clear Adhesive Composition, and Optically Clear Adhesive Film comprising the Same, and Flat Panel Display |
| KR101940550B1 (en) * | 2017-08-10 | 2019-01-22 | 애경화학 주식회사 | Thin film acrylic pressure sensitive adhesive composition having high adhesive and the method of manufacturing the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102444641B1 (en) * | 2021-06-08 | 2022-09-20 | 티와이코퍼레이션(주) | adhesive film using foldable display |
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| KR102609849B1 (en) | 2023-12-04 |
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