WO2016010171A1 - Polymère de polystyrène réactif ayant un indice de réfraction élevé et procédé de fabrication associé à l'aide d'un dérivé de styrène réactif - Google Patents

Polymère de polystyrène réactif ayant un indice de réfraction élevé et procédé de fabrication associé à l'aide d'un dérivé de styrène réactif Download PDF

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Publication number
WO2016010171A1
WO2016010171A1 PCT/KR2014/006373 KR2014006373W WO2016010171A1 WO 2016010171 A1 WO2016010171 A1 WO 2016010171A1 KR 2014006373 W KR2014006373 W KR 2014006373W WO 2016010171 A1 WO2016010171 A1 WO 2016010171A1
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WO
WIPO (PCT)
Prior art keywords
formula
refractive index
polymer
polymer compound
compound represented
Prior art date
Application number
PCT/KR2014/006373
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English (en)
Korean (ko)
Inventor
김상하
정진권
이종휘
이형종
Original Assignee
(주)켐옵틱스
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Publication of WO2016010171A1 publication Critical patent/WO2016010171A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/30—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur

Definitions

  • the present invention relates to a method for producing the same using a high refractive index reactive polystyrene polymer and a reactive styrene derivative.
  • OLEDs organic light emitting diodes
  • organic EL especially AMOLED
  • the external quantum efficiency of the organic light emitting diode is determined by the internal quantum efficiency and the light extraction efficiency. At present, due to the development of phosphorescent organic materials, the internal quantum efficiency shows a value close to 100%, but the external light efficiency is still low due to the low light extraction efficiency.
  • the high refractive thin film fabrication technology can improve the efficiency of OLED panel by extracting the isolated light to the outside by placing the transparent thin film layer having the refractive index similar to that of the ITO layer to the light loss consumed by the refractive index difference between the ITO layer and the glass layer. will be.
  • the optical film In order to have an optical extraction efficiency, the optical film should have a high refractive index of 1.8 to 2.0, similar to that of ITO, and have stable heat resistance at high temperature according to the process used for device fabrication.
  • the refractive index is higher than 2.0, there are inorganic materials such as TiO 2 and ZrO 2 , but the molding process is very difficult and complicated, and in the case of a polymer material, it is difficult to obtain a refractive index of 1.60 or more due to the electronic properties of the internal constituent molecules.
  • the present applicant has completed the present invention to provide a novel polystyrene polymer having a high refractive index characteristic of 1.80 or more, excellent in transparency, thermal stability and chemical resistance, and which can be crosslinked by reaction with an inorganic material or a self reaction. It was.
  • the present invention has been made to solve the above problems, it is a basic matrix compound for developing a high refractive index organic-inorganic hybrid resin applicable to the flat layer for OLED light extraction having a high light transmittance and transparency by dramatically improving the refractive index
  • the purpose is to provide a high refractive index reactive polystyrene polymer.
  • the present invention provides a high-refractive reactive polystyrene polymer having a high refractive index is easy to cross-linked by the additional reaction by the use of a cyan epoxy styrene compared to the acrylate-based polymer, the reactive cyan epoxy It aims to do it.
  • the present invention provides a polymer compound represented by the following formula (1).
  • R 1 and R 2 are hydrogen or (C 1 -C 30) alkyl
  • X is a single bond, (C1-C20) alkylene or (C2-C20) alkenylene;
  • Y is S, NH or 0;
  • Z is (C6-C30) aryl or (C3-C30) heteroaryl
  • A, b and c are each independently an integer of 0 to 10.
  • the polymer compound represented by Chemical Formula 1 may be R 1 and R 2 are hydrogen or (C 1 -C 10) alkyl, and X may be a single bond, (C 1 -C 10) alkylene.
  • the Y of the polymer compound is S or 0, and Z may be selected from the following structures.
  • the polymer compound may be selected from the following formula.
  • A, b and c are each independently an integer of 0 to 10.
  • the polymer compound represented by Chemical Formula 1 may be one containing 5 to 30 mol% of a cyan epoxy styrene compound represented by Chemical Formula 2 below.
  • the polymer compound represented by Chemical Formula 1 may be a polymer compound having a weight average molecular weight of 500 to 20,000 g / mol.
  • the polymer compound may have a refractive index of 1.8 to 2.0.
  • the present invention is a step of preparing a polymer compound represented by the formula 1 by reacting a thio epoxy styrene compound represented by the formula (2), an acrylate compound represented by the formula (3) and an acrylate compound represented by the formula (4) ; It provides a method for producing a polymer compound comprising a.
  • R 1 and R 2 are hydrogen or (C 1 -C 30) alkyl
  • X is a single bond, (C1-C20) alkylene or (C2-C20) alkenylene;
  • Y is S, NH or 0;
  • Z is (C6-C30) aryl or (C3-C30) heteroaryl
  • A, b and c are each independently an integer of 0 to 10.
  • the high refractive index reactive polystyrene polymer according to the present invention can maximize the refractive index compared to the general acrylate type, and when the polymer according to the present invention is used as a basic matrix compound of the organic-inorganic hybrid composition, it exhibits high refractive index and high light transmittance and transparency of 1.80 or more.
  • the present invention can be applied to a buffer layer such as a light extraction flat layer used to extract light attenuated by the difference in refractive index to the outside.
  • the high refractive-reactive polystyrene polymer is easy to form a thin film using a thermosetting reaction, and because the high refractive index of the polymer itself has a high refractive index even if less additional inorganic sol, it is easy to improve the coating property, yellowing Less, there is an advantage that can improve the transmittance to express excellent optical properties such as lighting or display field.
  • the present invention uses a thio epoxy styrene as a monomer to synthesize a high refractive-reactive polystyrene polymer.
  • Scheme 1 is a chemical structural formula and synthetic route of the thio epoxy styrene (B).
  • an object is to synthesize a polymer represented by the following formula (1) comprising the B monomer.
  • R 1 and R 2 are hydrogen or (C 1 -C 30) alkyl
  • X is a single bond, (C1-C20) alkylene or (C2-C20) alkenylene;
  • Y is S, NH or 0;
  • Z is (C6-C30) aryl or (C3-C30) heteroaryl
  • A, b and c are each independently an integer of 0 to 10.
  • R1 and R2 are hydrogen or (C1-C10) alkyl
  • X is a single bond
  • (C1-C10) alkylene number have.
  • Y is S or 0, and Z is preferably selected from the following structures.
  • the polymer is more preferably selected from the following chemical formula in view of having a high refractive index, but is not limited thereto.
  • A, b and c are each independently an integer of 0 to 10.
  • A, b, and c indicate the constituent ratios of the polymer compound of the present invention.
  • the polymer compound according to one embodiment of the present invention may include 20 to 70 mol% of a cation epoxy styrene compound represented by Formula 2 below.
  • the polymer compound represented by Chemical Formula 1 which is a curable polymer having a high refractive index according to an embodiment of the present invention, may have a weight average molecular weight of 500 to 20,000 g / mol, and the polymer compound has a high refractive index of 1.8 to 2.0.
  • the present invention is prepared by reacting a thio epoxy styrene compound represented by the following Chemical Formula 2, an acrylate compound represented by the following Chemical Formula 3, and an acrylate compound represented by the following Chemical Formula 4 to prepare a polymer compound having a high refractive index.
  • a polymer compound represented by 1 It may include, but is not limited thereto.
  • R 1 and R 2 are hydrogen or (C 1 -C 30) alkyl
  • X is a single bond, (C1-C20) alkylene or (C2-C20) alkenylene;
  • Y is S, NH or 0;
  • Z is (C6-C30) aryl or (C3-C30) heteroaryl
  • A, b and c are each independently an integer of 0 to 10.
  • a polymer compound including an acrylic monomer having a high refractive index and a reactive styrene derivative may be prepared by the following reaction formula.
  • the polymer compound which is a curable polymer, is a polymer compound that can be thermally cured.
  • the polymer compound includes cio epoxy styrene, and has a carboxylic acid functional group to enable chemical reaction with a metal nanosol, and is advantageous for forming a thin film and forming a pattern.
  • the curable polymer preferably has a weight average molecular weight of 500 to 20,000, and more preferably 1,000 to 10,000 in order to improve the compatibility of the reaction solvent or coating and the property of easily dissolving during development in the patterning process. .
  • the unit of the curable polymer in the above formula may include a cation epoxy group at the terminal by radical polymerization of an acryl or methacryl monomer having a high refractive aromatic aromatic structure and a styrene monomer including a cation epoxy.
  • the high refractive aromatic compound has naphthyl, benzene, and heterocyclic structure.
  • the a, b and c is a constituent of the polymer compound a is 0 to 90%, b is 5 to 100% and c may be synthesized in the ratio of 0 to 20%, preferably a is 60 to 90% , b may be synthesized at a ratio of 5 to 30% and c at 5 to 20%.
  • P1 polymer synthesis is as follows.
  • the obtained polymer was found to have a weight average molecular weight of 7,500 through GPC (solvent: 1% THF, 10uL injection) measurement, and the refractive index was confirmed through a prism coupler (thin film thickness of 7.65um), showing 1.6502 @ 830nm. It was.
  • P2 polymer synthesis is as follows.
  • the obtained polymer was found to have a weight average molecular weight of 7,500 through GPC (solvent: 1% THF, 10uL injection) measurement, and the refractive index was confirmed through a prism coupler (thin film thickness of 7.6um), showing 1.6322 @ 830nm. It was.
  • the polymer resins according to the present invention prepared in Examples 1 and 2 had a refractive index of 1.655@550nm and 1.640@550nm, respectively, in the visible region, and showed 91% and 92% of UV spectrometer results, respectively. It was confirmed that the expression of high refractive index and excellent transmittance, which can be applied to the flat layer for light extraction has the advantage that can increase the application potential in the field of lighting or display.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention est applicable à une couche d'aplanissement pour l'extraction de lumière à diodes électroluminescentes organiques (OLED) ayant une transmittance de la lumière et une transparence élevées par la forte augmentation d'un indice de réfraction par le biais de la synthèse d'un polymère durcissable comprenant du styrène 4,2,5 époxyde, facilite le traitement d'un film mince et la formation d'un motif à l'aide d'une réaction de photodurcissement ou de thermodurcissement, et a un potentiel d'application élevé dans le domaine de l'affichage ou de l'éclairage à diodes électroluminescentes organiques, étant donné que l'invention est rarement tournée vers le jaune et, par conséquent, est capable d'augmenter la transmission.
PCT/KR2014/006373 2014-07-14 2014-07-15 Polymère de polystyrène réactif ayant un indice de réfraction élevé et procédé de fabrication associé à l'aide d'un dérivé de styrène réactif WO2016010171A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2014-0088160 2014-07-14
KR20140088160 2014-07-14

Publications (1)

Publication Number Publication Date
WO2016010171A1 true WO2016010171A1 (fr) 2016-01-21

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PCT/KR2014/006373 WO2016010171A1 (fr) 2014-07-14 2014-07-15 Polymère de polystyrène réactif ayant un indice de réfraction élevé et procédé de fabrication associé à l'aide d'un dérivé de styrène réactif

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KR (1) KR101717955B1 (fr)
WO (1) WO2016010171A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4622425A (en) * 1979-08-24 1986-11-11 Rhone-Poulenc Industries Process for the preparation of aqueous solutions of low molecular weight polyacrylic acids or their salts
KR900000976B1 (ko) * 1984-07-11 1990-02-23 아사히가세이고오교가부시끼가이샤 고에너지선에 고감응성을 갖는 상형성 재료
KR910003964B1 (ko) * 1986-09-29 1991-06-17 아사히 가세이 고오교 가부시끼가이샤 광경화성 적층판
US7491441B2 (en) * 2004-12-30 2009-02-17 3M Innovative Properties Company High refractive index, durable hard coats
KR20130016702A (ko) * 2011-08-08 2013-02-18 박문수 용액중합법에 의한 고분자량 폴리메타크릴산의 제조방법
WO2013062170A1 (fr) * 2011-10-27 2013-05-02 제일모직 주식회사 Composition de résine thermoplastique et moulage l'utilisant

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090039612A (ko) * 2007-10-18 2009-04-22 제일모직주식회사 메타크릴계 공중합체, 그 제조방법 및 이를 이용한 메타크릴계 수지 조성물
JP5275849B2 (ja) 2008-04-21 2013-08-28 帝人株式会社 二軸配向多層積層ポリエステルフィルム
KR101469261B1 (ko) * 2011-12-20 2014-12-08 제일모직주식회사 열가소성 (메타)아크릴레이트 공중합체, 이를 포함하는 수지 조성물 및 그 성형품

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4622425A (en) * 1979-08-24 1986-11-11 Rhone-Poulenc Industries Process for the preparation of aqueous solutions of low molecular weight polyacrylic acids or their salts
KR900000976B1 (ko) * 1984-07-11 1990-02-23 아사히가세이고오교가부시끼가이샤 고에너지선에 고감응성을 갖는 상형성 재료
KR910003964B1 (ko) * 1986-09-29 1991-06-17 아사히 가세이 고오교 가부시끼가이샤 광경화성 적층판
US7491441B2 (en) * 2004-12-30 2009-02-17 3M Innovative Properties Company High refractive index, durable hard coats
KR20130016702A (ko) * 2011-08-08 2013-02-18 박문수 용액중합법에 의한 고분자량 폴리메타크릴산의 제조방법
WO2013062170A1 (fr) * 2011-10-27 2013-05-02 제일모직 주식회사 Composition de résine thermoplastique et moulage l'utilisant

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KR101717955B1 (ko) 2017-03-20
KR20160008483A (ko) 2016-01-22

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