KR20220087673A - Multi-layer stretchable substrate for stretchable display - Google Patents
Multi-layer stretchable substrate for stretchable display Download PDFInfo
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- KR20220087673A KR20220087673A KR1020200177891A KR20200177891A KR20220087673A KR 20220087673 A KR20220087673 A KR 20220087673A KR 1020200177891 A KR1020200177891 A KR 1020200177891A KR 20200177891 A KR20200177891 A KR 20200177891A KR 20220087673 A KR20220087673 A KR 20220087673A
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- stretchable
- substrate
- stretchable substrate
- polymer
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
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Abstract
본 발명은 스트레처블 디스플레이 장치에 사용되는 내오염, 내스크래치성을 가지는 스트레처블 디스플레이용 연신기판에 관한 것이다. 본 발명의 조성물 및 제조방법을 이용하면, 한 번의 코팅으로 2개의 층을 가진 스트레처블 디스플레이용 연신기판을 쉽게 제조할 수 있고, 연신 기판의 최외곽 표면에 코팅된 퍼플루오로 폴리머 코팅층에 의해 내오염성 및 내스크래치성이 도입되어 스트레처블 디스플레이 터치에 의한 표면의 손상을 막을 수 있다.The present invention relates to a stretchable substrate for a stretchable display having stain resistance and scratch resistance used in a stretchable display device. Using the composition and manufacturing method of the present invention, it is possible to easily manufacture a stretched substrate for a stretchable display having two layers by one coating, and by a perfluoropolymer coating layer coated on the outermost surface of the stretched substrate By introducing stain resistance and scratch resistance, it is possible to prevent damage to the surface of the stretchable display by touch.
Description
본 발명은 스트레처블 디스플레이 장치에 사용되는 내오염, 내스크래치성을 가지는 스트레처블 디스플레이용 연신기판에 관한 것이다.The present invention relates to a stretchable substrate for a stretchable display having stain resistance and scratch resistance used in a stretchable display device.
최근에는 LCD, OLED등의 평판 디스플레이 관련 기술이 발달하고 있으며, 접었다 펼 수 있는 폴더블 디스플레이 롤 형태로 감을 수 있는 롤러블 디스플레이와 더불어 늘리거나 줄일 수 있으며 자유로운 형태로 변화 가능한 스트레처블 디스플레이 장치에 대한 연구가 활발히 진행되고 있다. 스트레처블 디스플레이를 구현하기 위해서는 먼저 스트레처블 기판 제작에 대한 선행연구가 진행되어야 하며, 주로 PDMS(polydimethylsiloxane), PU(polyurethane)과 같은 소재들로 연구가 진행되고 있다. 최근 어플리케이션에 대한 개발이 다양화되면서 디스플레이에 터치센서를 도입하게 되면서 디스플레이 표면에 대한 내오염 및 내스크래치성의 중요성이 커지고 있다.Recently, flat-panel display-related technologies such as LCD and OLED have been developed, and in addition to the rollable display that can be rolled up in the form of a foldable display that can be folded and unfolded, stretchable display devices that can be increased or decreased and can be freely changed are used. Research is being actively conducted. In order to realize a stretchable display, prior research on the fabrication of a stretchable substrate should be conducted first, and research is mainly conducted on materials such as PDMS (polydimethylsiloxane) and PU (polyurethane). Recently, as the development of applications is diversified and touch sensors are introduced into displays, the importance of contamination resistance and scratch resistance on the display surface is increasing.
최근 어플리케이션에 대한 개발이 다양화되면서 디스플레이에 터치센서를 도입하게 되면서 터치에 의한 디스플레이의 오염 혹은 스크래치에 의한 손상이 발생하여 성능이 저하되거나 디스플레이에 영구적인 고장을 일으킬 수 있다는 문제가 있었다. 이에 본 발명자들은 디스플레이 표면에 대한 내오염성 및 내스크래치성을 가진 스트레처블 디스플레이용 연신기판을 개발하고자 예의 연구 노력하였다. 그 결과, 퍼플루오로 폴리머와 연신기판 제조용 폴리머를 혼합하여 코팅을 하면, 두 가지 폴리머의 비중 차이에 의하여 한 번의 코팅으로 2층의 연신기판이 쉽게 제조될 수 있음을 규명함으로써, 본 발명을 완성하게 되었다. Recently, as the development of applications has been diversified, as a touch sensor is introduced into the display, there has been a problem that the display may be damaged due to contamination or scratches by touch, which may result in deterioration of performance or permanent failure of the display. Accordingly, the present inventors made intensive research efforts to develop a stretchable substrate for a stretchable display having stain resistance and scratch resistance on the display surface. As a result, when a perfluoro polymer and a polymer for manufacturing a stretched substrate are mixed and coated, the present invention was completed by identifying that a two-layer stretched substrate can be easily manufactured with one coating due to the difference in specific gravity between the two polymers. did it
따라서, 본 발명의 목적은 퍼플루오로 폴리머를 포함하는 코팅층; 및 연신성(stretchable)을 갖는 연신성 기판을 포함하는, 스트레처블 디스플레이용 연신기판을 제공하는 것이다. Accordingly, an object of the present invention is a coating layer comprising a perfluoro polymer; And to provide a stretchable substrate for a stretchable display, including a stretchable substrate having a stretchable (stretchable).
본 발명의 다른 목적은 퍼플루오로 폴리머 및 연신성 기판 제조용 폴리머를 포함하는, 스트레처블 연신기판 제조용 조성물을 제공하는 것이다.Another object of the present invention is to provide a composition for manufacturing a stretchable stretchable substrate, comprising a perfluoropolymer and a polymer for manufacturing a stretchable substrate.
본 발명의 또 다른 목적은 스트레처블 디스플레이용 연신기판의 제조방법을 제공하는 것이다. Another object of the present invention is to provide a method for manufacturing a stretched substrate for a stretchable display.
본 발명의 일 양태에 따르면, 본 발명은 퍼플루오로 폴리머를 포함하는 코팅층; 및 연신성(stretchable)을 갖는 연신성 기판을 포함하는, 스트레처블 디스플레이용 연신기판을 제공한다. According to one aspect of the present invention, the present invention is a coating layer comprising a perfluoro polymer; And it provides a stretchable substrate for a stretchable display, comprising a stretchable substrate having a stretchable (stretchable).
본 발명의 일 구현예에 있어서, 상기 퍼플루오로 폴리머는 (a) 퍼플루오로 다이올; 불소계 용제; 유기용매; 모노이소시아네이트 아크릴레이트 모노머, 다이이소시아네이트 모노머, 또는 이들의 조합을 포함하는 반응 혼합물을 형성시키는 단계; 및 (b) 촉매제를 첨가하고 가열하는 중합반응 단계에 의해 생성된다. In one embodiment of the present invention, the perfluoro polymer is (a) perfluoro diol; fluorine-based solvents; organic solvents; forming a reaction mixture comprising monoisocyanate acrylate monomers, diisocyanate monomers, or combinations thereof; and (b) a polymerization reaction step of adding and heating a catalyst.
상기 퍼플루오로 폴리머의 생성 공정 (a) 및 (b) 단계는 1 내지 5회의 범위 내에서 반복 실시 가능하다. 예를 들어, 상기 공정이 1회만 실시될 경우는 1차 중합반응에 의해 퍼플루오로 폴리머가 형성되고, 상기 공정이 2회 실시될 경우에는 1차 및 2차 중합반응에 의해 퍼플루오로 폴리머가 형성된다.Steps (a) and (b) of the perfluoropolymer production process can be repeated within the range of 1 to 5 times. For example, when the above process is performed only once, the perfluoro polymer is formed by the primary polymerization reaction, and when the above process is performed twice, the perfluoro polymer is formed by the primary and secondary polymerization reactions. is formed
상기 (a) 단계의 반응혼합물은 100 내지 500 rpm, 또는 200 내지 300 rpm의 교반속도로 교반함으로써 형성되고, 교반 온도는 실온 또는 상온이다.The reaction mixture of step (a) is formed by stirring at a stirring speed of 100 to 500 rpm, or 200 to 300 rpm, and the stirring temperature is room temperature or room temperature.
상기 (b) 단계의 가열은 상온에서 시작하여 50 내지 150℃, 50 내지 120℃, 50 내지 100℃, 70 내지 150℃, 70 내지 120℃, 70 내지 100℃, 80 내지 150℃, 80 내지 120℃, 80 내지 100℃의 온도로 이루어진다.The heating in step (b) is started at room temperature, 50 to 150 ℃, 50 to 120 ℃, 50 to 100 ℃, 70 to 150 ℃, 70 to 120 ℃, 70 to 100 ℃, 80 to 150 ℃, 80 to 120 ℃, consisting of a temperature of 80 to 100 ℃.
상기 퍼플루오로 폴리머의 중합반응에는 퍼플루오로 다이올 5 내지 40 중량부; 불소계 용제 30 내지 60 중량부; 모노이소시아네이트 아크릴레이트 모노머 5 내지 35 중량부 및/또는 다이이소시아네이트 모노머 5내지 35 중량부; 촉매제 0.005 내지 0.1 중량부; 및 유기용매 5 내지 15 중량부를 포함할 수 있다. In the polymerization reaction of the perfluoro polymer, 5 to 40 parts by weight of perfluoro diol; 30 to 60 parts by weight of a fluorine-based solvent; 5 to 35 parts by weight of monoisocyanate acrylate monomer and/or 5 to 35 parts by weight of diisocyanate monomer; 0.005 to 0.1 parts by weight of a catalyst; and 5 to 15 parts by weight of an organic solvent.
상기 퍼플루오로 폴리머의 중합반응에는 모노이소시아네이트 아크릴레이트 모노머 25 중량부에 대하여 퍼플루오로 다이올 10 내지 40 중량부; 불소계 용제 35 내지 55 중량부; 다이이소시아네이트 모노머 5내지 30 중량부; 촉매제 0.005 내지 0.1 중량부; 및 유기용매 5 내지 15 중량부를 포함할 수 있다. In the polymerization reaction of the perfluoro polymer, 10 to 40 parts by weight of perfluorodiol based on 25 parts by weight of monoisocyanate acrylate monomer; 35 to 55 parts by weight of a fluorine-based solvent; 5 to 30 parts by weight of diisocyanate monomer; 0.005 to 0.1 parts by weight of a catalyst; and 5 to 15 parts by weight of an organic solvent.
본 발명의 일 구현예에 있어서, 상기 퍼플루오로 폴리머의 중합반응에는 모노이소시아네이트 아크릴레이트 모노머 25 중량부에 대하여 퍼플루오로 다이올 10 내지 30 중량부; 불소계 용제 45 중량부; 다이이소시아네이트 모노머 5내지 25 중량부; 촉매제 0.01 내지 0.05 중량부; 및 유기용매 10 중량부를 포함한다.In one embodiment of the present invention, in the polymerization reaction of the perfluoro polymer, 10 to 30 parts by weight of perfluorodiol based on 25 parts by weight of monoisocyanate acrylate monomer; 45 parts by weight of a fluorine-based solvent; 5 to 25 parts by weight of diisocyanate monomer; 0.01 to 0.05 parts by weight of a catalyst; and 10 parts by weight of an organic solvent.
본 발명의 특정 구현예에 있어서, 상기 퍼플루오로 폴리머의 중합반응에는 모노이소시아네이트 아크릴레이트 모노머 25 중량부에 대하여 퍼플루오로 다이올 20 중량부; 불소계 용제 45 중량부; 다이이소시아네이트 모노머 12 중량부; 촉매제 0.02 중량부; 및 유기용매 10 중량부를 포함한다.In a specific embodiment of the present invention, in the polymerization of the perfluoro polymer, 20 parts by weight of perfluorodiol based on 25 parts by weight of the monoisocyanate acrylate monomer; 45 parts by weight of a fluorine-based solvent; 12 parts by weight of diisocyanate monomer; 0.02 parts by weight of a catalyst; and 10 parts by weight of an organic solvent.
본 발명의 일 구현예에 있어서, 상기 유기용매는 상기 고형분 성분들을 용해하기에 적합한 것이라면 제한되지 않고 사용될 수 있으며, 프로필렌글리콜 모노메틸 에테르 아세테이트(PGMEA), 프로필렌글리콜 모노메틸 에테르(PGME), 부틸셀로솔브(BC), 메틸셀로솔부(MC), 에틸렌글리콜(EG), 프로필렌글리콜(PG), N-메틸-2-피롤리돈(NMP), 디메틸아세트아미드(DMAc), 프로필렌 글리콜 디아세테이트(PGDA), 프로필렌 글리콜 노멀프로필에테르(PnP), 테트라하이드로퓨란, 톨루엔, 자일렌, 부틸아세테이트, 에틸아세테이트, 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 메탄올, 에탄올, n-프로판올, 이소프로판올, 부탄올, 부톡시에탄올, 펜탄올, 옥탄올, 헥산, 헵탄, 에테르, 케톤 및 이들의 조합물로 구성되는 군에서 선택될 수 있고, 예를 들어, 메틸에틸케톤, 메틸아이소부틸케톤, 아세톤, 에틸아세테이트, 또는 이들의 혼합물일 수 있다.In one embodiment of the present invention, the organic solvent may be used without limitation as long as it is suitable for dissolving the solid components, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), butyl cell Rosolv (BC), methyl cellosolve (MC), ethylene glycol (EG), propylene glycol (PG), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), propylene glycol diacetate (PGDA), propylene glycol normal propyl ether (PnP), tetrahydrofuran, toluene, xylene, butyl acetate, ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, isopropanol, butanol , butoxyethanol, pentanol, octanol, hexane, heptane, ether, ketone and combinations thereof, for example, methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate , or a mixture thereof.
본 발명의 구체적인 구현예에 있어서, 상기 유기용매는 메틸에틸케톤, 메틸아이소부틸케톤, 아세톤, 에틸아세테이트를 5:3:1:1 또는 6:2:2:1 중량부를 포함하는 것일 수 있다. In a specific embodiment of the present invention, the organic solvent may include 5:3:1:1 or 6:2:2:1 parts by weight of methyl ethyl ketone, methyl isobutyl ketone, acetone, or ethyl acetate.
상기 퍼플루오로 다이올은 하기 화학식 1로 표시되는 화합물에서 선택되는 것일 수 있다. The perfluorodiol may be selected from compounds represented by the following formula (1).
[화학식 1] [Formula 1]
(상기 화학식 1에서 R은 -CH2(CF2)nCH2-, -CH2CF2(OCF2CF2)mOCF2CH2-, (In Formula 1, R is -CH 2 (CF 2 )nCH 2 -, -CH 2 CF 2 (OCF 2 CF 2 )mOCF 2 CH 2 -,
-CH2CF2O(CF2CF2O)nCF2CH2-, -CH2CF2O(CF2O)mCF2CH2-, 또는 —CH 2 CF 2 O(CF 2 CF 2 O)nCF 2 CH 2 —, —CH 2 CF 2 O(CF 2 O)mCF 2 CH 2 —, or
-CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-이며, 상기 n과 m은 독립적으로, 상기 n은 1 내지 8에서 선택되는 정수이고, m은 1 내지 5 에서 선택되는 정수이다).-CH 2 CF 2 O(CF 2 CF 2 O)n(CF 2 O)mCF 2 CH 2 -, wherein n and m are independently, wherein n is an integer selected from 1 to 8, and m is 1 to It is an integer selected from 5).
본 발명의 일 구현예에 있어서, 상기 화학식 1에서 R은 -CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-이고, 상기 n은 8이며, m은 5이다. In one embodiment of the present invention, in Formula 1, R is -CH 2 CF 2 O(CF 2 CF 2 O)n(CF 2 O)mCF 2 CH 2 -, wherein n is 8, m is 5 to be.
본 발명의 일 구현예에 있어서, 상기 퍼플루오로 다이올은 perfluoropolyether-diol(PFPE-diol)이다.In one embodiment of the present invention, the perfluorodiol is perfluoropolyether-diol (PFPE-diol).
상기 불소계 용제는 트리플루오로노난올, 트리플루오로데칸올, 테트라플루오로노난올, 테트라플루오로데칸올, 메톡시―노나플루오로부탄 및 에톡시-노나플루오로부탄으로 이루어진 군으로부터 선택되는 하나 이상일 수 있다. The fluorine-based solvent is one selected from the group consisting of trifluorononanol, trifluorodecanol, tetrafluorononanol, tetrafluorodecanol, methoxy-nonafluorobutane and ethoxy-nonafluorobutane may be more than
본 발명의 일 구현예에 있어서, 상기 불소계 용제는 에톡시-노나플루오로부탄이다. In one embodiment of the present invention, the fluorine-based solvent is ethoxy-nonafluorobutane.
본 발명의 일 구현예에 있어서, 상기 모노이소시아네이트 아크릴레이트 모노머는 하기 화학식 2로 표시되는 화합물인 것인, 스트레처블 디스플레이용 연신기판:In one embodiment of the present invention, the monoisocyanate acrylate monomer is a compound represented by the following formula (2), a stretchable substrate for a stretchable display:
[화학식 2][Formula 2]
(상기 화학식 2에서 R1은 하기 화학식 1로 표시되는 화합물에서 선택되고, X1은 하기 화학식 3 내지 6으로 표시되는 치환기로부터 선택된다);(In Formula 2, R 1 is It is selected from the compounds represented by the following Chemical Formula 1, and X 1 is selected from the substituents represented by the following Chemical Formulas 3 to 6);
[화학식 1] [Formula 1]
(상기 화학식 1에서 R은 -CH2(CF2)nCH2-, -CH2CF2(OCF2CF2)mOCF2CH2-, (In Formula 1, R is -CH 2 (CF 2 )nCH 2 -, -CH 2 CF 2 (OCF 2 CF 2 )mOCF 2 CH 2 -,
-CH2CF2O(CF2CF2O)nCF2CH2-, -CH2CF2O(CF2O)mCF2CH2-, 또는—CH 2 CF 2 O(CF 2 CF 2 O)nCF 2 CH 2 —, —CH 2 CF 2 O(CF 2 O)mCF 2 CH 2 —, or
-CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-이며, 상기 n과 m은 독립적으로, 상기 n은 1 내지 8에서 선택되는 정수이고, m은 1 내지 5 에서 선택되는 정수이다);-CH 2 CF 2 O(CF 2 CF 2 O)n(CF 2 O)mCF 2 CH 2 -, wherein n and m are independently, wherein n is an integer selected from 1 to 8, and m is 1 to It is an integer selected from 5);
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
; 및; and
[화학식 6][Formula 6]
본 발명의 일 구현예에 있어서, 상기 모노이소시아네이트 아크릴레이트 모노머는 2-이소시아네이트에틸 메타아크릴레이트 또는 이소시아네이트에틸 아크릴레이트이다. In one embodiment of the present invention, the monoisocyanate acrylate monomer is 2-isocyanateethyl methacrylate or isocyanateethyl acrylate.
본 발명의 일 구현예에 있어서, 상기 다이이소시아네이트 모노머는 하기 화학식 7로 표시되는 화합물에서 선택되는 것일 수 있다:In one embodiment of the present invention, the diisocyanate monomer may be selected from compounds represented by the following formula (7):
[화학식 7][Formula 7]
(상기 화학식 7에서 R2는 하기 화학식 1로 표시되는 화합물에서 선택되고, X1은 하기 화학식 3 내지 6으로 표시되는 치환기로부터 선택되며, Y1 은 하기 화학식 8 내지 23으로 표시되는 치환기로부터 선택된다);(In Formula 7, R 2 is selected from the compounds represented by Formula 1, X 1 is selected from the substituents represented by the following Formulas 3 to 6, Y 1 is selected from the substituents represented by the following Formulas 8 to 23);
[화학식 1] [Formula 1]
(상기 화학식 1에서 R은 -CH2(CF2)nCH2-, -CH2CF2(OCF2CF2)mOCF2CH2-, (In Formula 1, R is -CH 2 (CF 2 )nCH 2 -, -CH 2 CF 2 (OCF 2 CF 2 )mOCF 2 CH 2 -,
-CH2CF2O(CF2CF2O)nCF2CH2-, -CH2CF2O(CF2O)mCF2CH2-, 또는—CH 2 CF 2 O(CF 2 CF 2 O)nCF 2 CH 2 —, —CH 2 CF 2 O(CF 2 O)mCF 2 CH 2 —, or
-CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-이며, 상기 n과 m은 독립적으로, 상기 n은 1 내지 8에서 선택되는 정수이고, m은 1 내지 5 에서 선택되는 정수이다);-CH 2 CF 2 O(CF 2 CF 2 O)n(CF 2 O)mCF 2 CH 2 -, wherein n and m are independently, wherein n is an integer selected from 1 to 8, and m is 1 to It is an integer selected from 5);
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 8] [Formula 8]
[화학식 9][Formula 9]
[화학식 10][Formula 10]
[화학식 11][Formula 11]
[화학식 12][Formula 12]
[화학식 13][Formula 13]
[화학식 14][Formula 14]
[화학식 15][Formula 15]
[화학식 16][Formula 16]
[화학식 17][Formula 17]
[화학식 18][Formula 18]
[화학식 19][Formula 19]
[화학식 20][Formula 20]
[화학식 21][Formula 21]
[화학식 22][Formula 22]
[화학식 23][Formula 23]
본 발명의 일 구현예에 있어서, 상기 다이이소시아네이트 모노머는 이소포론 다이이소시아네이트(isophorone isocyanate)이다.In one embodiment of the present invention, the diisocyanate monomer is isophorone diisocyanate (isophorone isocyanate).
본 발명의 일 구현예에 있어서, 상기 촉매제는 당업계에서 통상적으로 사용하는 촉매제라면 특별히 제한되지 않으며, 예를 들어 아민계촉매, 유기 티탄 화합물계 및 유기 주석 화합물계 촉매에서 선택되는 어느 하나 또는 둘 이상을 사용할 수 있고, 예를 들어, 바람직하게는 유기 주석 화합물계 촉매로 디부틸 주석 디라우레이트(dibutyl tin dilaurate) 또는 디-n-부틸비스(도데실싸이오)주석(di-n-butylbis(dodecylthio)tin)을 사용할 수 있다.In one embodiment of the present invention, the catalyst is not particularly limited as long as it is a catalyst commonly used in the art, for example, any one or two selected from an amine-based catalyst, an organic titanium compound-based catalyst and an organic tin compound-based catalyst The above can be used, for example, preferably dibutyl tin dilaurate or di-n-butylbis(dodecylthio)tin (di-n-butylbis) as an organotin compound-based catalyst (dodecylthio)tin) may be used.
본 발명의 일 구현예에 있어서, 본 발명의 디스플레이용 연신기판의 퍼플루오로 폴리머 코팅층은 20 ㎛ 내지 1 mm의 두께를 가지고, 보다 구체적으로는 20 ㎛ 내지 800 ㎛, 20 ㎛ 내지 700 ㎛, 20 ㎛ 내지 600 ㎛, 20 ㎛ 내지 500 ㎛, 20 ㎛ 내지 350 ㎛, 20 ㎛ 내지 300 ㎛, 20 ㎛ 내지 200 ㎛, 20 ㎛ 내지 150 ㎛, 20 ㎛ 내지 100 ㎛의 두께를 가질 수 있으나, 이에 한정되는 것은 아니다.In one embodiment of the present invention, the perfluoropolymer coating layer of the stretched substrate for display of the present invention has a thickness of 20 μm to 1 mm, more specifically 20 μm to 800 μm, 20 μm to 700 μm, 20 It may have a thickness of μm to 600 μm, 20 μm to 500 μm, 20 μm to 350 μm, 20 μm to 300 μm, 20 μm to 200 μm, 20 μm to 150 μm, 20 μm to 100 μm, but is limited thereto it is not
본 발명의 일 구현예에 있어서, 본 발명의 디스플레이용 연신기판을 구성하는 상기 연신성 기판은 열경화성 폴리 우레탄, 열가소성 폴리 우레탄, 실리콘, 폴리 염화 비닐, 천연 고무, PDMS(폴리디메틸실옥산) 및 에틸렌 프로필렌 고무, 또는 이들의 조합으로 형성되는 것이나, 이에 한정되는 것은 아니다. In one embodiment of the present invention, the stretchable substrate constituting the stretched substrate for display of the present invention is thermosetting polyurethane, thermoplastic polyurethane, silicone, polyvinyl chloride, natural rubber, PDMS (polydimethylsiloxane) and ethylene. It is formed of propylene rubber, or a combination thereof, but is not limited thereto.
본 발명의 일 구현예에 있어서, 본 발명의 스트레처블 디스플레이용 연신기판은 점착제 층을 추가로 합지(lamination)하여 제조될 수 있다. 이 경우 퍼플루오로 폴리머 코팅층, 연신성 기판, 및 점착제 층의 순서로 이루어진 3층의 스트레처블 디스플레이용 연신기판을 제작할 수 있다. In one embodiment of the present invention, the stretchable substrate for a stretchable display of the present invention may be manufactured by additionally laminating an adhesive layer. In this case, a stretchable substrate for a three-layer stretchable display consisting of a perfluoropolymer coating layer, a stretchable substrate, and an adhesive layer in this order can be manufactured.
본 발명의 다른 일 양태에 따르면, 본 발명은 퍼플루오로 폴리머 및 연신성 기판 제조용 폴리머를 포함하는, 스트레처블 연신기판 제조용 조성물을 제공한다.According to another aspect of the present invention, the present invention provides a composition for manufacturing a stretchable stretchable substrate comprising a perfluoro polymer and a polymer for manufacturing a stretchable substrate.
본 발명의 일 구현예에 있어서, 상기 퍼플루로오 폴리머는 (a) 퍼플루오로 다이올; 불소계 용제; 유기용매; 모노이소시아네이트 아크릴레이트 모노머, 다이이소시아네이트 모노머, 또는 이들의 조합을 포함하는 반응 혼합물을 형성시키는 단계; 및 (b) 촉매제를 첨가하고 가열하는 중합반응 단계에 의해 생성된다. In one embodiment of the present invention, the perfluoro polymer is (a) perfluoro diol; fluorine-based solvents; organic solvents; forming a reaction mixture comprising monoisocyanate acrylate monomers, diisocyanate monomers, or combinations thereof; and (b) a polymerization reaction step of adding and heating a catalyst.
상기 퍼플루오로 폴리머는 상술한 본 발명의 일 양태에 따른 스트레처블 디스플레이용 연신기판을 구성하는 퍼플로오로 폴리머와 같은 구성이다. The perfluoro polymer has the same configuration as the perfluoro polymer constituting the stretchable substrate for a stretchable display according to an aspect of the present invention.
본 발명의 일 구현예에 있어서, 상기 연신성 기판 제조용 폴리머는 열경화성 폴리 우레탄, 열가소성 폴리 우레탄, 실리콘, 폴리 염화 비닐, 천연 고무, PDMS(폴리디메틸실옥산) 및 에틸렌 프로필렌 고무, 또는 이들의 조합이나, 이에 한정되는 것은 아니다. In one embodiment of the present invention, the polymer for manufacturing a stretchable substrate is thermosetting polyurethane, thermoplastic polyurethane, silicone, polyvinyl chloride, natural rubber, PDMS (polydimethylsiloxane) and ethylene propylene rubber, or a combination thereof. , but is not limited thereto.
본 발명이 일 양태에 따른 조성물을 이용하면, 상기 조성물에 포함된 연신성 기판 제조용 폴리머 및 퍼플루오로 폴리머의 비중차이에 의하여 한번의 코팅으로 두 개의 층이 제조된다. When the composition according to an aspect of the present invention is used, two layers are prepared by one coating due to the difference in specific gravity of the polymer for preparing a stretchable substrate and the perfluoropolymer included in the composition.
본 발명의 상기 일 양태에 따른 스트레처블 디스플레이용 연신기판의 제조용 조성물은 상술한 본 발명의 일 양태에 따른 스트레처블 디스플레이용 연신기판을 제조하기 위하여 사용되는 것으로, 이들 발명 간에는 중복되는 구성이 존재하고 이들은 각 발명마다 동일하게 적용되며, 상기 중복되는 구성에 대해서는 명세서의 복잡성을 피하기 위하여 그 기재를 생략한다.The composition for manufacturing a stretched substrate for a stretchable display according to an aspect of the present invention is used for manufacturing the stretched substrate for a stretchable display according to an aspect of the present invention described above. exists and they are equally applied to each invention, and the description of the overlapping configuration is omitted to avoid the complexity of the specification.
본 발명의 또 다른 일 양태에 따르면, 본 발명은 다음 단계를 포함하는 스트레처블 디스플레이용 연신기판의 제조방법을 제공한다:According to another aspect of the present invention, the present invention provides a method of manufacturing a stretchable substrate for a stretchable display comprising the following steps:
(a) 연신성 기판 제조용 폴리머 및 퍼플루오로 폴리머를 교반하여 혼합하는 단계;(a) mixing a polymer for preparing a stretchable substrate and a perfluoropolymer by stirring;
(b) 상기 혼합물을 평면 필름 상에 코팅한 후 경화시키는 단계.(b) curing the mixture after coating the mixture on a flat film.
본 발명의 일 구현예에 있어서, 상기 연신성 기판 제조용 폴리머는, 모노머와 가교제, 및 경화방지제를 혼합하여 제조된다. In one embodiment of the present invention, the polymer for preparing a stretchable substrate is prepared by mixing a monomer, a crosslinking agent, and a curing inhibitor.
본 발명의 일 구현예에 있어서, 상기 코팅의 두께는 20 ㎛ 내지 1 mm이다.In one embodiment of the present invention, the thickness of the coating is 20 μm to 1 mm.
본 발명의 일 구현예에 있어서, 상기 경화는 100 내지 140℃에서 5 내지 30분간 가열되어 이루어진다. 보다 구체적으로, 상기 경화는 100 내지 130℃, 100 내지 120℃, 110 내지 130℃, 120 내지 130℃, 또는 115 내지 125℃에서 5 내지 30분간 가열되어 이루어질 수 있으나, 이에 한정되는 것은 아니다.In one embodiment of the present invention, the curing is made by heating at 100 to 140 ℃ 5 to 30 minutes. More specifically, the curing may be made by heating at 100 to 130 °C, 100 to 120 °C, 110 to 130 °C, 120 to 130 °C, or 115 to 125 °C for 5 to 30 minutes, but is not limited thereto.
본 발명의 구체적인 구현예에 있어서, 상기 연신성 기판 제조용 폴리머가 PDMS인 경우, 상기 모노머는 비닐폴리실록산이다. 상기 PDMS는 비닐폴리실록산과 가교제, 경화방지제를 혼합하여 약 15분 내지 30분간 교반한 후 백금 소재의 촉매를 넣고 10분간 추가로 교반하여 제조된다.In a specific embodiment of the present invention, when the polymer for manufacturing a stretchable substrate is PDMS, the monomer is vinylpolysiloxane. The PDMS is prepared by mixing a vinyl polysiloxane, a crosslinking agent, and a curing inhibitor and stirring for about 15 to 30 minutes, then adding a platinum catalyst and further stirring for 10 minutes.
본 발명의 일 구현예에 있어서, 상기 연신성 기판 제조용 폴리머 및 퍼플루오로 폴리머는 연신성 기판 제조용 폴리머 100 중량부를 기준으로 퍼플루오로 폴리머 1 내지 20 중량부가 혼합된다. In one embodiment of the present invention, 1 to 20 parts by weight of the perfluoropolymer is mixed based on 100 parts by weight of the polymer for preparing the stretchable substrate and the perfluoropolymer for preparing the stretchable substrate.
본 발명의 구체적인 구현예에 있어서, 상기 연신성 기판 제조용 폴리머가 PDMS인 경우, 상술한 바와 같이 비닐폴리실록산과 가교제, 경화방지제를 혼합하여 약 15분 내지 30분간 교반한 후 백금 소재의 촉매를 첨가하고, 약 5 내지 15분간 추가로 교반한 후, 퍼플루오로 폴리머를 첨가하고 약 5 내지 15분간 추가로 교반하여 연신성 기판 제조용 폴리머와 퍼플루오로 폴리머의 혼합물을 제조한다.In a specific embodiment of the present invention, when the polymer for preparing the stretchable substrate is PDMS, as described above, the vinyl polysiloxane, the crosslinking agent, and the curing inhibitor are mixed and stirred for about 15 to 30 minutes, and then a platinum material catalyst is added, After further stirring for about 5 to 15 minutes, the perfluoro polymer is added and further stirred for about 5 to 15 minutes to prepare a mixture of the polymer for preparing a stretchable substrate and the perfluoro polymer.
본 발명의 일 구현예에 있어서, 상기 연신성 기판 제조용 폴리머와 퍼플루오로 폴리머의 혼합물은 평면 상에 소정의 두께로 코팅된 후 100 내지 140℃에서 5 내지 30분간 가열 및 건조하여 경화된다. 상기 가열 및 건조는 오븐에서 이루어질 수 있으나, 이에 한정되는 것은 아니다.In one embodiment of the present invention, the mixture of the polymer for preparing a stretchable substrate and the perfluoropolymer is coated on a plane to a predetermined thickness, and then cured by heating and drying at 100 to 140° C. for 5 to 30 minutes. The heating and drying may be performed in an oven, but is not limited thereto.
본 발명의 제조방법에 의에 제조된 스트레처블 디스플레이용 연신기판은 상기 연신성 기판 제조용 폴리머 및 퍼플루오로 폴리머의 비중차이에 의하여 한번의 코팅으로 두 개의 층이 제조된다. The stretchable substrate for a stretchable display manufactured by the manufacturing method of the present invention is prepared in two layers by one coating by the difference in specific gravity between the polymer and the perfluoropolymer for manufacturing the stretchable substrate.
예컨대 연신성 기판 제조용 폴리머가 PDMS인 경우 비중이 약 1.9이고, 본 발명 퍼플루오로 폴리머의 비중은 약 1.7이므로, 한 번의 코팅으로 PDMS 층 및 퍼플루오로 폴리머 층, 두 개의 층이 제조된다.For example, when the polymer for preparing a stretchable substrate is PDMS, the specific gravity is about 1.9, and the specific gravity of the perfluoro polymer of the present invention is about 1.7, so two layers, the PDMS layer and the perfluoropolymer layer, are prepared by one coating.
또한, 본 발명의 일 구현예에 있어서, 본 발명의 스트레처블 디스플레이용 연신기판은 상기 제조된 두 개의 층에 있어서, 점착제 층을 추가로 합지(lamination)하여 제조될 수 있다. 이 경우 퍼플루오로 폴리머 코팅층, 연신성 기판, 및 점착제 층의 순서로 이루어진 3층의 스트레처블 디스플레이용 연신기판을 제작할 수 있다. Further, in one embodiment of the present invention, the stretchable substrate for a stretchable display of the present invention may be manufactured by additionally laminating an adhesive layer in the two prepared layers. In this case, a stretchable substrate for a three-layer stretchable display consisting of a perfluoropolymer coating layer, a stretchable substrate, and an adhesive layer in this order can be manufactured.
본 발명의 상기 일 양태에 따른 스트레처블 디스플레이용 연신기판의 제조방법은 상술한 본 발명의 일 양태에 따른 스트레처블 디스플레이용 연신기판을 제조하기 위한 것으로, 상술한 본 발명의 다른 일 양태에 따른 스트레처블 디스플레이용 연신기판 제조용 조성물을 이용한 방법이므로, 이들 발명 간에는 중복되는 구성이 존재하고 이들은 각 발명마다 동일하게 적용되며, 상기 중복되는 구성에 대해서는 명세서의 복잡성을 피하기 위하여 그 기재를 생략한다.The method for manufacturing a stretched substrate for a stretchable display according to the one aspect of the present invention is for manufacturing the stretched substrate for a stretchable display according to the above-described aspect of the present invention, and in another aspect of the present invention, Since it is a method using the composition for manufacturing a stretchable substrate for a stretchable display according to the present invention, overlapping configurations exist between these inventions, and they are equally applied to each invention, and the description of the overlapping configuration is omitted to avoid the complexity of the specification. .
본 발명은 스트레처블 디스플레이 장치에 사용되는 내오염, 내스크래치성을 가지는 스트레처블 디스플레이용 연신기판에 관한 것이다. 본 발명의 조성물 및 제조방법을 이용하면, 한 번의 코팅으로 2개의 층을 가진 스트레처블 디스플레이용 연신기판을 쉽게 제조할 수 있고, 연신 기판의 최외곽 표면에 코팅된 퍼플루오로 폴리머 코팅층에 의해 내오염성 및 내스크래치성이 도입되어 스트레처블 디스플레이 터치에 의한 표면의 손상을 막을 수 있다.The present invention relates to a stretchable substrate for a stretchable display having stain resistance and scratch resistance used in a stretchable display device. Using the composition and manufacturing method of the present invention, it is possible to easily manufacture a stretched substrate for a stretchable display having two layers by one coating, and by a perfluoropolymer coating layer coated on the outermost surface of the stretched substrate By introducing stain resistance and scratch resistance, it is possible to prevent damage to the surface of the stretchable display by touch.
도 1은 본 발명의 3층구조의 스트레처블 디스플레이용 연신기판의 단면도이다. 상기 도 1에 나타낸 바와 같이, 디스플레이의 최외곽면에 퍼플루오로 폴리머층을 위치시켜 내오염 및 내스크래치성을 증가시키고; 연신특성을 가지는 PDMS, PU, 또는 Acryl 소재의 연신성 기판을 중간층에 배치하고; LED 및 배선 등을 고정시킬 수 있는 점착층을 합지하여 디스플레이 내부면에 위치시킨다.1 is a cross-sectional view of a stretchable substrate for a stretchable display having a three-layer structure of the present invention. 1, by placing a perfluoro polymer layer on the outermost surface of the display to increase stain resistance and scratch resistance; disposing a stretchable substrate made of PDMS, PU, or Acryl material having stretch characteristics on the intermediate layer; An adhesive layer capable of fixing LEDs and wires is laminated and placed on the inner surface of the display.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 요지에 따라 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 당업계에서 통상의 지식을 가진 자에 있어서 자명할 것이다.Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples according to the gist of the present invention. .
실시예Example
본 명세서 전체에 걸쳐, 특정 물질의 농도를 나타내기 위하여 사용되는 "%"는 별도의 언급이 없는 경우, 고체/고체는 (중량/중량) %, 고체/액체는 (중량/부피) %, 그리고 액체/액체는 (부피/부피) %이다.Throughout this specification, "%" used to indicate the concentration of a specific substance is (weight/weight) % for solid/solid, (weight/volume) % for solid/liquid, and Liquid/liquid is (volume/volume) %.
제조예: 퍼플루오로 폴리머의 합성Preparation Example: Synthesis of Perfluoropolymer
제조예 1 Preparation Example 1
퍼플루오로 다이올 10 중량부에 불소계 용제(ethoxynonafluorobutane (C4F9OC2H5)) 45 중량부와 메틸에틸케톤, 메틸아이소부틸케톤, 아세톤, 에틸아세테이트를 5:3:1:1 또는 6:2:2:1 중량부를 첨가하고, 2-이소시아네이트에틸 메타아크릴레이트를 25 중량부 첨가하고 질소 가스 분위기에서 촉매제로서 디부틸 주석 디라우레이트 0.01 중량부를 첨가하고 20-50분 동안 상온 교반하였다. 이어서 온도를 최고 100℃까지 천천히 올려 촉매제 0.01 중량부를 첨가하고 반응 시간을 확인하여 우레아 반응이 끝날 때까지 중합을 실시하였다. 상기 중합은 유리반응기에서 200-300 rpm으로 교반시키며 실시하였다.In 10 parts by weight of perfluorodiol, 45 parts by weight of a fluorine-based solvent (ethoxynonafluorobutane (C 4 F 9 OC 2 H 5 )) and methyl ethyl ketone, methyl isobutyl ketone, acetone, or ethyl acetate were mixed in 5:3:1:1 or 6:2:2:1 parts by weight were added, 25 parts by weight of 2-isocyanate ethyl methacrylate was added, and 0.01 parts by weight of dibutyl tin dilaurate as a catalyst was added in a nitrogen gas atmosphere, followed by stirring at room temperature for 20-50 minutes. . Then, the temperature was slowly raised to a maximum of 100° C., 0.01 parts by weight of a catalyst was added, and the reaction time was checked to carry out polymerization until the urea reaction was completed. The polymerization was carried out with stirring at 200-300 rpm in a glass reactor.
제조예 2Preparation 2
퍼플루오로 다이올(Fomblin D2, Solvay) 10 중량부에 불소계 용제(ethoxynonafluorobutane (C4F9OC2H5)) 45 중량부와 메틸에틸케톤, 메틸아이소부틸케톤, 아세톤, 에틸아세테이트를 5:3:1:1 또는 6:2:2:1 중량부를 첨가하고, 다이이소시아네이트 모노머(TCI) 6 중량부 첨가하고 질소 가스 분위기에서 촉매제로서 디부틸 주석디라우레이트 0.01 중량부를 첨가하고 20-50분 동안 상온 교반하였다. 이어서 온도를 최고 100℃까지 천천히 올려 반응 시간을 확인하여 우레아 반응이 끝날 때 까지중합을 실시하였다. 1차 중합 실시 후 2-이소시아네이트에틸 메타아크릴레이트(TCI)를 25 중량부 첨가하고 질소 가스 분위기에서 촉매제 0.01 중량부를 첨가한 다음, 20-50분 동안 상온 교반하였다. 이어서 온도를 최고 100℃까지 천천히 올려 반응 시간을 확인하여 우레아 반응이 끝날 때까지 중합을 실시하였다. 상기 중합은 유리반응기에서 200-300 rpm으로 교반시키며 실시하였다.10 parts by weight of perfluorodiol (Fomblin D2, Solvay) 45 parts by weight of a fluorine-based solvent (ethoxynonafluorobutane (C 4 F 9 OC 2 H 5 )) and methyl ethyl ketone, methyl isobutyl ketone, acetone, and ethyl acetate 5: 3:1:1 or 6:2:2:1 parts by weight are added, 6 parts by weight of diisocyanate monomer (TCI) is added, and 0.01 parts by weight of dibutyl tindilaurate as a catalyst is added in a nitrogen gas atmosphere and 20-50 minutes while stirring at room temperature. Then, the temperature was slowly raised to a maximum of 100° C., the reaction time was checked, and polymerization was carried out until the urea reaction was completed. After the primary polymerization, 25 parts by weight of 2-isocyanate ethyl methacrylate (TCI) was added, and 0.01 parts by weight of a catalyst was added in a nitrogen gas atmosphere, followed by stirring at room temperature for 20-50 minutes. Then, the temperature was slowly raised to a maximum of 100° C., the reaction time was checked, and polymerization was carried out until the urea reaction was completed. The polymerization was carried out with stirring at 200-300 rpm in a glass reactor.
제조예 3Preparation 3
퍼플루오로 다이올(Fomblin D2, Solvay) 20 중량부에 불소계 용제(ethoxynonafluorobutane (C4F9OC2H5)) 45 중량부와 메틸에틸케톤, 메틸아이소부틸케톤, 아세톤, 에틸아세테이트를 5:3:1:1 또는 6:2:2:1 중량부를 첨가하고, 다이이소시아네이트 모노머 12 중량부 첨가하고 질소 가스 분위기에서 촉매제로서 디부틸 주석디라우레이트 0.02 중량부를 첨가하고 20-50분 동안 상온 교반하였다. 이어서 온도를 최고 100℃까지 천천히 올려 반응 시간을 확인하여 우레아 반응이 끝날 때 까지중합을 실시하였다. 1차 중합 실시 후 2-이소시아네이트에틸 메타아크릴레이트를 25 중량부 첨가하고 질소 가스 분위기에서 촉매제 0.02 중량부를 첨가한 다음, 20-50분 동안 상온 교반하였다. 이어서 온도를 천천히 최고 100℃까지 올려 반응 시간을 확인하여 우레아 반응이 끝날 때까지 중합을 실시하였다. 상기 중합은 유리반응기에서 200-300 rpm으로 교반시키며 실시하였다.To 20 parts by weight of perfluorodiol (Fomblin D2, Solvay), 45 parts by weight of a fluorine-based solvent (ethoxynonafluorobutane (C 4 F 9 OC 2 H 5 )) and methyl ethyl ketone, methyl isobutyl ketone, acetone, and ethyl acetate were mixed with 5: 3:1:1 or 6:2:2:1 parts by weight are added, 12 parts by weight of diisocyanate monomer is added, 0.02 parts by weight of dibutyl tin dilaurate as a catalyst is added in a nitrogen gas atmosphere, and the mixture is stirred at room temperature for 20-50 minutes. did Then, the temperature was slowly raised to a maximum of 100° C., the reaction time was checked, and polymerization was carried out until the urea reaction was completed. After the primary polymerization, 25 parts by weight of 2-isocyanate ethyl methacrylate was added, and 0.02 parts by weight of a catalyst was added in a nitrogen gas atmosphere, followed by stirring at room temperature for 20-50 minutes. Then, the temperature was slowly raised to a maximum of 100° C., the reaction time was checked, and polymerization was carried out until the urea reaction was completed. The polymerization was carried out with stirring at 200-300 rpm in a glass reactor.
제조예 4Preparation 4
퍼플루오로 다이올(Fomblin D2, Solvay) 30 중량부에 불소계 용제(ethoxynonafluorobutane (C4F9OC2H5)) 45 중량부와 메틸에틸케톤, 메틸아이소부틸케톤, 아세톤, 에틸아세테이트를 5:3:1:1 또는 6:2:2:1 중량부를 첨가하고, 다이이소시아네이트 모노머 18 중량부 첨가하고 질소 가스 분위기에서 촉매제로서 디부틸 주석디라우레이트 0.03 중량부를 첨가하고 20-50분 동안 상온 교반하였다. 이어서 온도를 천천히 최고 100℃까지 올려 반응 시간을 확인하여 우레아 반응이 끝날 때까지 중합을 실시하였다. 1차 중합 실시 후 2-이소시아네이트에틸 메타아크릴레이트를 25 중량부 첨가하고 질소 가스 분위기에서 촉매제 0.03 중량부를 첨가한 다음, 20-50분 동안 상온 교반하였다. 이어서 온도를 천천히 최고 100℃까지 올려 반응 시간을 확인하여 우레아 반응이 끝날 때까지 중합을 실시하였다. 상기 중합은 유리반응기에서 200-300 rpm으로 교반시키며 실시하였다.30 parts by weight of perfluorodiol (Fomblin D2, Solvay) 45 parts by weight of a fluorine-based solvent (ethoxynonafluorobutane (C 4 F 9 OC 2 H 5 )) and methyl ethyl ketone, methyl isobutyl ketone, acetone, and ethyl acetate 5: 3:1:1 or 6:2:2:1 parts by weight are added, 18 parts by weight of diisocyanate monomer is added, and 0.03 parts by weight of dibutyl tindilaurate as a catalyst is added in a nitrogen gas atmosphere, followed by stirring at room temperature for 20-50 minutes. did Then, the temperature was slowly raised to a maximum of 100° C., the reaction time was checked, and polymerization was carried out until the urea reaction was completed. After the primary polymerization, 25 parts by weight of 2-isocyanate ethyl methacrylate was added, and 0.03 parts by weight of a catalyst was added in a nitrogen gas atmosphere, followed by stirring at room temperature for 20-50 minutes. Then, the temperature was slowly raised to a maximum of 100° C., the reaction time was checked, and polymerization was carried out until the urea reaction was completed. The polymerization was carried out with stirring at 200-300 rpm in a glass reactor.
상기 중합비(중량비)는 표 1과 같았다.The polymerization ratio (weight ratio) was shown in Table 1.
(Fomblin D2, Solvay)perfluorodiol
(Fomblin D2, Solvay)
(디부틸 주석디라우레이트)catalyst
(dibutyl tin dilaurate)
(TCI)Monoisocyanate Acrylate Monomer
(TCI)
비교예 1: 일반 실리콘 연신기판의 제조(종래 기술)Comparative Example 1: Preparation of a general stretched silicon substrate (prior art)
500 ml 용기에 비닐폴리실록산과 가교제, 경화방지제(1-Ethynyl-1-cyclohexanol)를 투입한 뒤 교반기를 사용하여 500 rpm으로 20 분간 교반하였다. 여기에 백금 촉매를 투입하고 교반기를 사용하여 10분간 교반한 뒤 진공에서 10분간 탈포하여 기판 제조를 위한 실리콘 조성물을 제조한 뒤 폴리에틸렌 필름 위에 코팅바를 사용하여 500 μm 두께로 코팅한 후 120℃ 오븐에서 10분간 경화시켜 스트레처블 연신기판을 제조하였다. In a 500 ml container, vinyl polysiloxane, a crosslinking agent, and a curing inhibitor (1-Ethynyl-1-cyclohexanol) were added, and then stirred at 500 rpm for 20 minutes using a stirrer. Platinum catalyst was put here, stirred for 10 minutes using a stirrer, and then degassed in vacuum for 10 minutes to prepare a silicone composition for substrate production, and then coated on a polyethylene film to a thickness of 500 μm using a coating bar, and then heated in an oven at 120 ° C. It was cured for 10 minutes to prepare a stretchable oriented substrate.
상기에서 사용된 원료의 조성은 하기 표 2과 같았다. The composition of the raw material used above is shown in Table 2 below.
실시예 1 내지 실시예 4: 다층구조의 스트레처블 디스플레이용 연신기판의 제조Examples 1 to 4: Preparation of a stretchable substrate for a stretchable display having a multi-layer structure
상기 비교예 1과 같이 500 ml 용기에 비닐폴리실록산과 가교제, 경화방지제(1-Ethynyl-1-cyclohexanol)를 투입한 뒤 교반기를 사용하여 500 rpm으로 20 분간 교반하였다. 여기에 백금 촉매를 투입하고 교반기를 사용하여 10분간 교반하여 제조한 실리콘 코팅액에 제조예 1 내지 4에서 제조된 퍼플루오로 폴리머 10 중량부를 혼합하여 10분간 교반하여, 본 발명의 스트레처블 디스플레이용 연신기판 제조용 조성물을 제조하였다. 제조된 상기 조성물을 폴리에틸렌 필름 위에 코팅바를 사용하여 500 μm 두께로 코팅하였다. 상기 코팅 층은 본 발명의 스트레처블 디스플레이용 연신기판 제조용 조성물에 포함된 연신기판 제조용 폴리머(PDMS) 및 퍼플루오로 폴리머의 비중차이에 의해 2 층으로 나뉘고, 이를 120℃ 오븐에서 10간 경화시켜 본 발명의 스트레처블 디스플레이용 연신기판을 제조하였다. 상기에서 사용된 원료의 조성은 하기 표 3 같았다.As in Comparative Example 1, vinyl polysiloxane, a crosslinking agent, and a curing inhibitor (1-Ethynyl-1-cyclohexanol) were added to a 500 ml container, and then stirred at 500 rpm for 20 minutes using a stirrer. A platinum catalyst was added thereto, and 10 parts by weight of the perfluoropolymer prepared in Preparation Examples 1 to 4 was mixed with the silicone coating solution prepared by stirring for 10 minutes using a stirrer and stirred for 10 minutes, for a stretchable display of the present invention A composition for manufacturing a stretched substrate was prepared. The prepared composition was coated on a polyethylene film to a thickness of 500 μm using a coating bar. The coating layer is divided into two layers by the difference in specific gravity of the stretchable substrate manufacturing polymer (PDMS) and the perfluoropolymer included in the stretchable substrate manufacturing composition for a stretchable display of the present invention, and it is cured in an oven at 120° C. for 10 hours. A stretched substrate for a stretchable display of the present invention was prepared. The composition of the raw material used above was as shown in Table 3 below.
(Toluene)menstruum
(Toluene)
실험예 1: 투과율(%) 및 헤이즈(%)의 측정Experimental Example 1: Measurement of transmittance (%) and haze (%)
비교예 및 각 실시예에서 제조한 연신기판 필름의 시편을 채취하여 Nippon Denshoku사의 COH-400을 사용하여 투과율과 Haze를 측정하였다. 비교예와 실시예를 통하여 제조한 500 ㎛의 연신기판 필름을 시편의 제조방향 처음으로 300 mm 부분을 잘라내고 다시 그 끝 부분에서 20 mm 안쪽의 부위에서 100 mm X 100 mm 의 사각으로 잘라내었다. 광원이 할로겐 램프인 Nippon Denshoku사의 COH-400을 사용하여 Single 빔 가시광선 전파장의 투과율과 Haze를 측정하였다.Specimens of the stretched substrate films prepared in Comparative Examples and Examples were collected, and transmittance and haze were measured using COH-400 manufactured by Nippon Denshoku. In the 500 μm stretched substrate film prepared in Comparative Examples and Examples, a 300 mm portion was first cut in the production direction of the specimen, and then a 100 mm X 100 mm square was cut from the end 20 mm inside. Transmittance and haze of single-beam visible light wavelength were measured using COH-400 of Nippon Denshoku whose light source is a halogen lamp.
실험예 2: 접촉각Experimental Example 2: Contact angle
물의 부피를 3 ㎕ 크기로 600 ㎕/min 시료 중간에 떨어뜨리고 3초후 접촉각을 측정하였다. 50 mm X 50 mm 크기로 잘라낸 연신기판 위에 물의 부피를 3 ㎕ 크기로 600 ㎕/min 시료 중간에 떨어뜨리고 3초 후 정지된 물방울과 연신기판 필름사이의 접촉각을 Surfacetech사의 GS-Mini 모델을 사용하여 측정하였다.A volume of water was dropped in the middle of a 600 μl/min sample in a size of 3 μl, and the contact angle was measured after 3 seconds. On the stretched substrate cut to 50 mm X 50 mm in size, drop a volume of water in the middle of the 600 μl/min sample at a size of 3 μl, and after 3 seconds, the contact angle between the stopped water droplet and the stretched substrate film was measured using Surfacetech's GS-Mini model. measured.
실험예 3: 코팅 두께의 측정Experimental Example 3: Measurement of Coating Thickness
두께측정기(Mitutoyo, 547 thickness gauge)로 압력 20±0.2 kPa로 5초 동안 가압한 후 제품의 제조방향으로 처음 300 mm 부분은 잘라내고, 다시 그 끝 부분에서 20 mm 안쪽인 부위에서 양끝으로 각각 나비(폭)의 10% 안쪽으로 들어간 지점 2곳과 그 사이를 9등한 지점 8곳을 합한 10곳을 0.01 mm 까지 두께를 측정하여 그 측정치의 평균치를 구하였다. After pressurizing with a pressure of 20±0.2 kPa for 5 seconds with a thickness gauge (Mitutoyo, 547 thickness gauge), cut the first 300 mm part in the direction of product manufacture, and then spread the The thickness was measured up to 0.01 mm at 10 places including 2 points that entered 10% of the (width) and 8 points ranked 9th between them, and the average value of the measurements was obtained.
상기 실험예 1 내지 3의 결과는 표 4에 나타내었다.The results of Experimental Examples 1 to 3 are shown in Table 4.
상기 표 4에 나타낸 바와 같이, 본 발명의 퍼플루오로 폴리머를 포함하는 스트레처블 디스플레이용 연신기판은 물접촉각이 높아져 내오염성 및 내스크래치성이 우수하고, 투과율이 증가하고 헤이즈가 감소하므로 디스플레이로서의 광학적 성능이 우수해짐을 알 수 있다. As shown in Table 4, the stretchable substrate for a stretchable display containing the perfluoropolymer of the present invention has a high water contact angle, so it has excellent stain resistance and scratch resistance, and has an increased transmittance and reduced haze. It can be seen that the optical performance is excellent.
100: 퍼플루오로 폴리머를 포함하는 코팅층
200: 연신성을 갖는 연신성 기판
300: 점착제 층100: a coating layer comprising a perfluoro polymer
200: stretchable substrate having stretchability
300: adhesive layer
Claims (17)
a coating layer comprising a perfluoro polymer; And A stretchable substrate for a stretchable display comprising a stretchable substrate having a stretchable (stretchable).
(a) 퍼플루오로 다이올; 불소계 용제; 유기용매; 모노이소시아네이트 아크릴레이트 모노머, 다이이소시아네이트 모노머, 또는 이들의 조합을 포함하는 반응 혼합물을 형성시키는 단계; 및
(b) 촉매제를 첨가하고 가열하는 중합반응 단계에 의해 생성된 것인, 스트레처블 디스플레이용 연신기판.
According to claim 1, wherein the perfluoro polymer is
(a) perfluoro diols; fluorine-based solvents; organic solvents; forming a reaction mixture comprising monoisocyanate acrylate monomers, diisocyanate monomers, or combinations thereof; and
(b) a stretchable substrate for a stretchable display, which is produced by a polymerization reaction step of adding a catalyst and heating.
[화학식 1]
(상기 화학식 1에서 R은 -CH2(CF2)nCH2-, -CH2CF2(OCF2CF2)mOCF2CH2-,
-CH2CF2O(CF2CF2O)nCF2CH2-, -CH2CF2O(CF2O)mCF2CH2-, 또는
-CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-이며, 상기 n과 m은 독립적으로, 상기 n은 1 내지 8에서 선택되는 정수이고, m은 1 내지 5 에서 선택되는 정수이다).
The stretchable substrate for a stretchable display according to claim 2, wherein the perfluorodiol is selected from compounds represented by the following formula (1):
[Formula 1]
(In Formula 1, R is -CH 2 (CF 2 )nCH 2 -, -CH 2 CF 2 (OCF 2 CF 2 )mOCF 2 CH 2 -,
—CH 2 CF 2 O(CF 2 CF 2 O)nCF 2 CH 2 —, —CH 2 CF 2 O(CF 2 O)mCF 2 CH 2 —, or
-CH 2 CF 2 O(CF 2 CF 2 O)n(CF 2 O)mCF 2 CH 2 -, wherein n and m are independently, wherein n is an integer selected from 1 to 8, and m is 1 to It is an integer selected from 5).
According to claim 2, wherein the fluorine-based solvent is trifluorononanol, trifluorodecanol, tetrafluorononanol, tetrafluorodecanol, methoxy-nonafluorobutane and ethoxy-nonafluorobutane At least one selected from the group consisting of, a stretchable substrate for a stretchable display.
The stretchable substrate for a stretchable display according to claim 2, wherein the organic solvent is methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, or a mixture thereof.
[화학식 2]
(상기 화학식 2에서 R1은 하기 화학식 1로 표시되는 화합물에서 선택되고, X1은 하기 화학식 3 내지 6으로 표시되는 치환기로부터 선택된다);
[화학식 1]
(상기 화학식 1에서 R은 -CH2(CF2)nCH2-, -CH2CF2(OCF2CF2)mOCF2CH2-,
-CH2CF2O(CF2CF2O)nCF2CH2-, -CH2CF2O(CF2O)mCF2CH2-, 또는
-CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-이며, 상기 n과 m은 독립적으로, 상기 n은 1 내지 8에서 선택되는 정수이고, m은 1 내지 5 에서 선택되는 정수이다);
[화학식 3]
[화학식 4]
[화학식 5]
[화학식 6]
[Formula 2]
(In Formula 2, R 1 is It is selected from the compounds represented by the following Chemical Formula 1, and X 1 is selected from the substituents represented by the following Chemical Formulas 3 to 6);
[Formula 1]
(In Formula 1, R is -CH 2 (CF 2 )nCH 2 -, -CH 2 CF 2 (OCF 2 CF 2 )mOCF 2 CH 2 -,
—CH 2 CF 2 O(CF 2 CF 2 O)nCF 2 CH 2 —, —CH 2 CF 2 O(CF 2 O)mCF 2 CH 2 —, or
-CH 2 CF 2 O(CF 2 CF 2 O)n(CF 2 O)mCF 2 CH 2 -, wherein n and m are independently, wherein n is an integer selected from 1 to 8, and m is 1 to It is an integer selected from 5);
[Formula 3]
[Formula 4]
[Formula 5]
[Formula 6]
[화학식 7]
(상기 화학식 7에서 R2는 하기 화학식 1로 표시되는 화합물에서 선택되고, X1은 하기 화학식 3 내지 6으로 표시되는 치환기로부터 선택되며, Y1 은 하기 화학식 8 내지 23으로 표시되는 치환기로부터 선택된다);
[화학식 1]
(상기 화학식 1에서 R은 -CH2(CF2)nCH2-, -CH2CF2(OCF2CF2)mOCF2CH2-,
-CH2CF2O(CF2CF2O)nCF2CH2-, -CH2CF2O(CF2O)mCF2CH2-, 또는
-CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-이며, 상기 n과 m은 독립적으로, 상기 n은 1 내지 8에서 선택되는 정수이고, m은 1 내지 5 에서 선택되는 정수이다);
[화학식 3]
[화학식 4]
[화학식 5]
[화학식 6]
[화학식 8]
[화학식 9]
[화학식 10]
[화학식 11]
[화학식 12]
[화학식 13]
[화학식 14]
[화학식 15]
[화학식 16]
[화학식 17]
[화학식 18]
[화학식 19]
[화학식 20]
[화학식 21]
[화학식 22]
[화학식 23]
The stretched substrate for a stretchable display according to claim 2, wherein the diisocyanate monomer is selected from compounds represented by the following formula (7):
[Formula 7]
(In Formula 7, R 2 is selected from the compounds represented by Formula 1, X 1 is selected from the substituents represented by the following Formulas 3 to 6, Y 1 is selected from the substituents represented by the following Formulas 8 to 23);
[Formula 1]
(In Formula 1, R is -CH 2 (CF 2 )nCH 2 -, -CH 2 CF 2 (OCF 2 CF 2 )mOCF 2 CH 2 -,
—CH 2 CF 2 O(CF 2 CF 2 O)nCF 2 CH 2 —, —CH 2 CF 2 O(CF 2 O)mCF 2 CH 2 —, or
-CH 2 CF 2 O(CF 2 CF 2 O)n(CF 2 O)mCF 2 CH 2 -, wherein n and m are independently, wherein n is an integer selected from 1 to 8, and m is 1 to It is an integer selected from 5);
[Formula 3]
[Formula 4]
[Formula 5]
[Formula 6]
[Formula 8]
[Formula 9]
[Formula 10]
[Formula 11]
[Formula 12]
[Formula 13]
[Formula 14]
[Formula 15]
[Formula 16]
[Formula 17]
[Formula 18]
[Formula 19]
[Formula 20]
[Formula 21]
[Formula 22]
[Formula 23]
The stretchable substrate for a stretchable display according to claim 1, wherein the coating layer has a thickness of 20 μm to 1 mm.
The method of claim 1 , wherein the stretchable substrate is formed of thermosetting polyurethane, thermoplastic polyurethane, silicone, polyvinyl chloride, natural rubber, PDMS (polydimethylsiloxane) and ethylene propylene rubber, or a combination thereof. Stretchable substrate for stretchable display.
The stretchable substrate for a stretchable display according to claim 1, wherein the stretchable substrate further comprises an adhesive layer.
상기 퍼플루로오 폴리머는 (a) 퍼플루오로 다이올; 불소계 용제; 유기용매; 모노이소시아네이트 아크릴레이트 모노머, 다이이소시아네이트 모노머, 또는 이들의 조합을 포함하는 반응 혼합물을 형성시키는 단계; 및
(b) 촉매제를 첨가하고 가열하는 중합반응 단계에 의해 생성된 것인, 스트레처블 연신기판 제조용 조성물.
In the composition for manufacturing a stretchable stretchable substrate comprising a perfluoropolymer and a polymer for manufacturing a stretchable substrate,
The perfluoro polymer comprises (a) a perfluoro diol; fluorine-based solvents; organic solvents; forming a reaction mixture comprising monoisocyanate acrylate monomers, diisocyanate monomers, or combinations thereof; and
(b) a composition for producing a stretchable oriented substrate, which is produced by a polymerization reaction step of adding and heating a catalyst.
12. The strain according to claim 11, wherein the polymer for preparing extensible substrates is thermosetting polyurethane, thermoplastic polyurethane, silicone, polyvinyl chloride, natural rubber, PDMS (polydimethylsiloxane) and ethylene propylene rubber, or a combination thereof. A composition for manufacturing a chubby stretched substrate.
(a) 연신성 기판 제조용 폴리머 및 퍼플루오로 폴리머를 교반하여 혼합하는 단계;
(b) 상기 혼합물을 평면 필름 상에 코팅한 후 경화시키는 단계.
A method for manufacturing a stretched substrate for a stretchable display comprising the steps of:
(a) mixing a polymer for preparing a stretchable substrate and a perfluoropolymer by stirring;
(b) curing the mixture after coating it on a flat film.
The method according to claim 13, wherein the polymer for preparing the stretchable substrate is thermosetting polyurethane, thermoplastic polyurethane, silicone, polyvinyl chloride, natural rubber, PDMS (polydimethylsiloxane) and ethylene propylene rubber, or a combination thereof. .
(b) 촉매제를 첨가하고 가열하는 중합반응 단계에 의해 생성된 것인, 제조방법.
14. The method of claim 13, wherein the perfluoro polymer comprises: (a) a perfluoro diol; fluorine-based solvents; organic solvents; forming a reaction mixture comprising monoisocyanate acrylate monomers, diisocyanate monomers, or combinations thereof; and
(b) a method for producing, which is produced by a polymerization reaction step of adding and heating a catalyst.
The method according to claim 13, wherein the coating has a thickness of 20 μm to 1 mm.
The method of claim 13, wherein the curing is made by heating at 100 to 140°C for 5 to 30 minutes.
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