WO2015099443A1 - Silsesquioxane ayant une aptitude au formage par extrusion à chaud, substrat en plastique transparent très transparent et très résistant à la chaleur l'utilisant, et son procédé de fabrication - Google Patents

Silsesquioxane ayant une aptitude au formage par extrusion à chaud, substrat en plastique transparent très transparent et très résistant à la chaleur l'utilisant, et son procédé de fabrication Download PDF

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WO2015099443A1
WO2015099443A1 PCT/KR2014/012790 KR2014012790W WO2015099443A1 WO 2015099443 A1 WO2015099443 A1 WO 2015099443A1 KR 2014012790 W KR2014012790 W KR 2014012790W WO 2015099443 A1 WO2015099443 A1 WO 2015099443A1
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formula
transparent substrate
plastic transparent
silsesquioxane
thermosetting
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Korean (ko)
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김두식
유재원
최승석
최지식
오성연
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주식회사 동진쎄미켐
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Priority to CN201480071015.5A priority Critical patent/CN105873983B/zh
Priority to JP2016542763A priority patent/JP6659550B2/ja
Publication of WO2015099443A1 publication Critical patent/WO2015099443A1/fr

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    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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    • C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the present invention relates to a silsesquioxane capable of hot melt-extrusion molding, a highly transparent and high heat-resistant plastic transparent substrate using the same, and a manufacturing method thereof, and more particularly to a thermoplastic ladder-type silsesquioxane capable of hot melt-extrusion.
  • a plastic transparent substrate capable of melt-extrusion molding by high temperature prepared by sequential curing by low temperature firing step by step, and excellent thermal prepared by forming a thermosetting silsesukioxane coating layer prepared separately on the surface of the substrate and sequentially curing
  • the present invention relates to a multilayer plastic transparent substrate having optical properties.
  • Flexible transparent substrates are the most important components that determine the fairness, performance, reliability, and price of a flexible display, and are currently receiving considerable attention in the industry.
  • research on materials and processes of various flexible transparent substrates has been conducted.
  • plastics have been widely studied for practical application due to ease of processing, low weight, and suitability of continuous processes.
  • material / process problems compared to glass which is a typical representative substrate material.
  • the manufacturing process of the display panel is usually subjected to a high temperature process, such as inorganic film sputtering or plasma chemical vapor deposition (PECVD), when applying a general plastic transparent substrate is a deformation caused by heat can be ensured to ensure the dimensional stability none.
  • PECVD plasma chemical vapor deposition
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PES polyethersulphone
  • PI polyimide
  • PEN polyethylene naphthalate
  • silsesquioxane polymer materials are mainly applied as an insulating film, a protective film, and an alignment film of a functional film coating material, a laminate or an electronic material, or are developed to improve properties by blending with other plastic materials as additives or fillers.
  • plastic materials it is difficult to find an example of forming a transparent substrate using itself as a base material.
  • Most silicon materials are mainly in liquid form, and in the solid state, they are usually very low in thermoplasticity and are not suitable for melt-extrusion molding, which is a conventional plastic substrate forming process.
  • Patent Document 1 a polyhedral oligomeric silsesquioxane (POSS) modified with terephthalic acid was added to PET to improve heat resistance, but its improvement is not so large, and thus it is difficult to apply to a plastic transparent substrate.
  • Patent Publication No. 2013-0028626 Patent Document 2 attaches a side chain having a functional group capable of hydrogen bonding with a polysiloxane main chain to impart thermoplasticity properties, and is mainly applicable to an insulating coating, a weatherproof coating, a semiconductor encapsulant, and the like. It does not meet the required characteristics.
  • Patent Document 3 provides thermoplastics by providing a method for preparing a ladder-type polyphenylsilsesuccioxane having a specific molecular weight, but in the case of silsesquioxane having phenyl as a functional group, brittleness It is true that application to a substrate is difficult.
  • the present invention is to produce a silsesquioxane having a completely different thermal properties than the conventional plastic substrate material, by using this method for producing a high transparent, high heat-resistant plastic transparent substrate, the It is an object of the present invention to provide a method for manufacturing a multilayer plastic transparent substrate having improved physical properties such as surface flatness, hardness, flexibility and heat resistance by coating the thermosetting composition on the substrate once more.
  • thermoplastic ladder silsesquioxane of Formula 1 and a thermosetting cage silsesquioxane of Formula 4:
  • Each R ′ 1 independently represents an alkyl group having 1-5 carbon atoms
  • n is an integer from 1 to 200;
  • R 11 and R 12 are each independently selected from the formula 2, the organic functional groups, to the organic functional group of Formula 3 or a hydroxyl group are:
  • R 1 and R 9 each independently represent an alkyl group having 1 to 5 carbon atoms
  • R 2 to R 8 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R 10 is hydrogen or an aromatic, epoxy, acryl or siol group linked to an alkyl group of 1 to 20 carbon atoms;
  • Q is an alkylene group or alkyleneoxy group having 1 to 6 carbon atoms
  • n is an integer of 1-3;
  • n is an integer from 0-4,
  • p 0 or 1.
  • the present invention provides a thermosetting composition
  • a thermosetting composition comprising the thermoplastic ladder silsesquioxane of Formula 1 and the thermosetting cage silsesquioxane of Formula 4.
  • the present invention is a method for manufacturing a plastic transparent substrate (primary plastic transparent substrate) and the plastic transparent substrate prepared according to the step of molding and curing the thermoplastic ladder-type silsesquioxane of the formula (1) by hot melt-extrusion (Primary plastic transparent substrate).
  • thermoplastic ladder-type silsesquioxane of Chemical Formula 1 thermally extruding and molding the thermoplastic ladder-type silsesquioxane of Chemical Formula 1 to prepare a primary plastic transparent substrate;
  • thermosetting composition on the surface of the primary plastic transparent substrate and curing the coating layer and the multilayer plastic transparent substrate manufactured accordingly To provide.
  • the present invention provides an electronic device comprising the plastic transparent substrate.
  • thermoplastic ladder-type silsesquioxane capable of hot melt extrusion may be sequentially cured by low-temperature firing stepwise to produce a plastic transparent substrate (primary plastic transparent substrate) capable of melt-extrusion molding at a high temperature.
  • a thermally curable silsesquioxane coating layer formed using a composition comprising the thermoplastic ladder silsesquioxane and the thermosetting cage silsesquioxane separately prepared on the surface of the substrate, followed by sequential curing.
  • a multilayer plastic transparent substrate (secondary plastic transparent substrate) having optical properties can be produced.
  • the plastic transparent substrate according to the present invention is a flexible display substrate such as a liquid crystal display, an organic light emitting display, an electronic paper, a substrate for a solar cell and a secondary battery, such as a liquid crystal display, an organic light emitting display, an electronic paper, and the like. It can be applied in various ways. In addition, it can be applied to both the hot melt-extrusion method and the solvent caster method, which is a conventional plastic substrate manufacturing process, and can be easily and quickly applied to the industry.
  • Example 3 is a TGA curve of the substrate prepared in Example 4 of the present invention.
  • thermosetting composition of the present invention is a view showing the structure of the silsesquioxane complex in the thermosetting composition of the present invention.
  • the plastic transparent substrate of the present invention includes a thermoplastic ladder-type silsesquioxane alone capable of hot melt extrusion, or a mixture of the thermoplastic ladder-type silsesquioxane and thermosetting cage-type silsesquioxanes on the surface thereof. It characterized in that it comprises a coating layer of the thermosetting composition.
  • thermoplastic ladder silses quoxane is a compound having the structure of Formula 1:
  • Each R ′ 1 independently represents an alkyl group having 1-5 carbon atoms
  • n is an integer from 1 to 200;
  • Each R 11 is independently an organic functional group represented by Formula 2, an organic functional group represented by Formula 3, or a hydroxyl group:
  • R 1 and R 9 represent an alkyl group having 1 to 5 carbon atoms
  • R 2 to R 8 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R 10 is hydrogen or an aromatic, epoxy, acryl or siol group linked to an alkyl group of 1 to 20 carbon atoms;
  • Q is an alkylene group or alkyleneoxy group having 1 to 6 carbon atoms
  • n is an integer of 1-3;
  • n is an integer from 0-4,
  • p 0 or 1.
  • thermoplastic ladder-type silsesquioxane of Chemical Formula 1 may be produced by hydrolyzing the epoxy group-containing alkoxy silane compound of Chemical Formula 2 and the alkoxy silane compound of Chemical Formula 3 under a base catalyst and continuously condensation reaction, preferably Can be synthesized according to the methods already known by the present inventors, for example, the method described in Korean Patent Publication No. 10-2010-0131904.
  • the relationship of 0.3 ⁇ b / a ⁇ 0.6 is preferably satisfied.
  • the number of moles of hydroxy group is c, 0.001 ⁇ c / (a + b) ⁇ 0.3, preferably considering the appropriate plasticizing properties of the material, it is preferable to satisfy the relationship of 0.01 ⁇ c / (a + b) ⁇ 0.1.
  • a resin having excellent thermoplastic properties may be formed instead of forming a liquid resin or a powder of a small phase having lost thermoplastic properties.
  • the weight average molecular weight of the thermoplastic ladder-type silsesquioxane of the formula (1) is 10,000 to 200,000, preferably 30,000 to 100,000.
  • thermosetting cage-type silsesquioxane may be a compound having a structure of Formula 4:
  • R 12 is each independently an organic functional group of Formula 2, an organic functional group of Formula 3 or a hydroxyl group.
  • thermosetting cage-type silsesquioxane of Chemical Formula 4 may be produced by hydrolyzing the epoxy group-containing alkoxy silane compound of Chemical Formula 2 and the alkoxy silane compound of Chemical Formula 3 under a base catalyst and continuously condensation reaction.
  • the number of moles of the compound of formula (2) in formula (4) is d
  • the number of moles of the compound of formula (3) is e
  • the number of moles of the hydroxy group is f , 0.001 ⁇ f / (d + e) ⁇ 0.01.
  • the thermosetting properties are excellent, and the physical and optical properties of the transparent substrate may be further improved.
  • thermosetting cage-type silsesquioxane of Chemical Formula 4 is 1,000 to 10,000, preferably 2,000 to 4,000.
  • the thermosetting composition may include the thermoplastic ladder silsesquioxane of Formula 1 and the thermosetting cage silsesquioxane of Formula 4, wherein the two silsesquioxanes in the composition
  • the complex may be formed to have a structure as shown in FIG. 4.
  • the number of moles of the compound of formula (1) is x
  • the number of moles of the compound of formula (4) is y
  • the thermosetting composition may further include a known curing agent.
  • curing agent contains phenolic compounds, such as a phenol resin, amine compounds, such as diamine, dimethyltriamine, and a polyamine, acid anhydride compounds, such as phthalic anhydride, tetrahydro phthalic anhydride, tetracarboxylic phthalic anhydride, a norbornene anhydride, etc. Although it does not restrict
  • thermosetting composition may further include a curing accelerator.
  • the curing accelerator is not particularly limited as long as it is a compound that accelerates the reaction between the composition and the curing agent, and the amount is not particularly limited as long as the curing accelerator can be exhibited even in the blended amount.
  • the blending amount of the curing accelerator is 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight based on 100 parts by weight of the total weight of the silsesquioxanes of the general formulas (1) and (4). It is good to be a negative range.
  • thermosetting composition may further include a solvent.
  • the solvent that can be used in the present invention is not particularly limited as long as it dissolves the produced curable composition uniformly, but polar organic solvents such as dichloromethane, tetrahydrofuran, methyl ethyl ketone, and dimethylacetamide are preferable.
  • thermosetting composition may further include additives such as a UV absorber, an antioxidant, an antifoaming agent, a leveling agent, a water repellent agent, a flame retardant agent, and an adhesion improving agent for the purpose of improving hardness, strength, durability, moldability, and the like.
  • additives are not particularly limited in use, but may be appropriately added within a range that does not impair the properties of the substrate, that is, properties such as flexibility, light transmittance, heat resistance, hardness, and strength.
  • the present invention also provides a method for producing a plastic transparent substrate (primary plastic transparent substrate) comprising the step of hot melt-extrusion molding and curing the thermoplastic ladder-type silsesquioxane and the plastic transparent substrate produced accordingly .
  • the method for producing the substrate is not particularly limited, and for example, may be produced by a solvent-caster method in addition to the hot melt-extrusion method.
  • the thickness of the substrate may range from 0.1 mm to 2.0 mm, and in consideration of flexibility, it is preferable to have a range of 0.2 mm to 0.5 mm.
  • the curing can be cured using a commonly used method, that is, thermal polymerization curing or photopolymerization curing.
  • thermal polymerization curing or photopolymerization curing There is no restriction
  • One type or two or more types can be used mixing a conventionally used cationic radical hardening
  • the thermal curing when the substrate is thermally cured, the thermal curing may be carried out at a temperature of 40 to 200 °C, preferably by sequential curing by low temperature baking by subdividing the curing temperature and curing time in two or more multi-stage It is good to allow the curing to proceed.
  • the present invention also provides
  • thermoplastic ladder-type silsesquioxane 1) thermally extruding and molding the thermoplastic ladder-type silsesquioxane to prepare a primary plastic transparent substrate;
  • thermosetting composition 1) preparing and curing a coating layer by coating the thermosetting composition on the surface of the primary plastic transparent substrate
  • It provides a method of manufacturing a multilayer plastic transparent substrate (secondary plastic transparent substrate) comprising a and a multilayer plastic transparent substrate (secondary plastic transparent substrate) manufactured accordingly.
  • the manufacturing method of the present invention is characterized in that the secondary plastic transparent substrate including the coating layer is finally manufactured by forming a coating layer of the thermosetting composition as described above on the surface of the prepared primary plastic transparent substrate.
  • the coating layer is to improve the hardness, mechanical strength and heat resistance of the substrate, the thickness of the coating layer is not limited within a range that does not affect the flexible properties of the substrate, but preferably 5 to 30 ⁇ m range .
  • the method of coating the composition may be applied by those skilled in the art arbitrarily selected from known methods such as spin coating, bar coating, slit coating.
  • the curing of the secondary plastic transparent substrate may be performed in the same manner as the curing of the primary plastic transparent substrate described above.
  • the present invention also provides an electronic device comprising the plastic transparent substrate (primary plastic transparent substrate) or the multilayer plastic transparent substrate (secondary plastic transparent substrate).
  • thermoplastic transparent substrate using a thermoplastic ladder-type silsesquioxane capable of hot melt extrusion and sequentially cured by low-temperature firing step by step to perform melt-extrusion molding at a high temperature
  • a multi-layered plastic transparent substrate having excellent thermal and optical properties may be manufactured by forming and sequentially curing a thermosetting silsesquioxane coating layer separately prepared on the surface of the substrate.
  • the plastic transparent substrate according to the present invention is a flexible display substrate such as a liquid crystal display, an organic light emitting display, an electronic paper, a substrate for a solar cell and a secondary battery, such as a liquid crystal display, an organic light emitting display, an electronic paper, and the like. It can be applied in various ways.
  • the stirred solution was washed and fractionated several times with distilled water to remove impurities and finally washed with methanol.
  • the washed liquid was then vacuum dried at room temperature for 20 hours or longer to obtain a solid ladder-type silsesquioxane compound.
  • BPA bisphenol-A epoxy
  • YD-128 methyl phthalic anhydride
  • methyl triphenylphosphonium bromide curing accelerator 100 parts by weight of commercially available bisphenol-A (BPA) epoxy (Kukdo Chemical, trade name YD-128), 80 parts by weight of methyl phthalic anhydride, and 1 part by weight of methyl triphenylphosphonium bromide curing accelerator are added to the stirrer and stirred for at least 3 hours. To obtain a liquid curable composition.
  • BPA bisphenol-A
  • Ladder-type silsesquioxane compound synthesized in Synthesis Example 1 was put into a mold and pressurized at 200 ° C. to perform hot melt molding, and then cooled, followed by 2 hours at 100 ° C., 1 hour at 140 ° C., and complete curing. Curing stepwise at 180 °C for 1 hour to finally produce a 200 ⁇ m thick plastic transparent substrate.
  • the BPA epoxy cured product synthesized in Comparative Synthesis Example 1 was placed in a mold and cured stepwise at 100 ° C. for 1 hour, 120 ° C. for 1 hour, and 150 ° C. for 1 hour to finally prepare a plastic substrate having a thickness of 200 ⁇ m.
  • thermosetting composition prepared in Example 2 Bar-coated the thermosetting composition prepared in Example 2 on the surface of the primary plastic substrate prepared in Example 1 to a thickness of 10 ⁇ m, semi-hardened in an oven at 100 °C, the bar on the opposite side to the same 10 ⁇ m thickness -Coated. After stepwise curing at 120 ° C. for 60 minutes, 140 ° C. for 30 minutes, and 180 ° C. for 30 minutes, a plastic transparent substrate having a thickness of 220 ⁇ m was finally prepared.
  • a plastic transparent substrate was manufactured in the same manner as in Example 4, except that the curable composition prepared in Example 2 was coated on the surface of the first plastic substrate prepared in Comparative Example 1.
  • a 0.5 mm thick polymethylmethacrylate (PMMA, LG MMA) substrate was prepared for comparison with commercially available products.
  • the transmission at 550 nm was measured using a spectrophotometer Cary-4000 (Agilent).
  • the glass transition temperature of 10 mm ⁇ 30 mm ⁇ 0.5 mm (W ⁇ H ⁇ D) size specimens was measured using a viscoelastic analyzer SS6100 (Seiko).
  • the specimen was placed in a 180 ° C. atmosphere for 12 hours to measure a change in transmittance thereto.
  • the primary substrate of the present invention using the thermoplastic ladder-type silsesquioxane compound was superior in light transmittance, glass transition temperature and heat stability compared to the primary substrate of the comparative example.
  • the second substrate of the present invention prepared by coating a composition comprising a mixture of thermoplastic ladder-type silsesquioxane and thermosetting cage-type silsesquioxane compound on the primary substrate of Example 1 is Comparative Examples 2 and 3 The light transmittance, glass transition temperature and thermal stability were superior to those of the substrate.
  • thermoplastic ladder-type silsesquioxane capable of hot melt extrusion may be sequentially cured by low-temperature firing stepwise to produce a plastic transparent substrate (primary plastic transparent substrate) capable of melt-extrusion molding at a high temperature.
  • a thermally curable silsesquioxane coating layer formed using a composition comprising the thermoplastic ladder silsesquioxane and the thermosetting cage silsesquioxane separately prepared on the surface of the substrate, followed by sequential curing.
  • a multilayer plastic transparent substrate (secondary plastic transparent substrate) having optical properties can be produced.
  • the plastic transparent substrate according to the present invention is a flexible display substrate such as a liquid crystal display, an organic light emitting display, an electronic paper, a substrate for a solar cell and a secondary battery, such as a liquid crystal display, an organic light emitting display, an electronic paper, and the like. It can be applied in various ways. In addition, it can be applied to both the hot melt-extrusion method and the solvent caster method, which is a conventional plastic substrate manufacturing process, and can be easily and quickly applied to the industry.

Abstract

La présente invention concerne un silsesquioxane ayant une aptitude au formage par extrusion à chaud, un substrat en plastique transparent très transparent et très résistant à la chaleur l'utilisant, et son procédé de fabrication et, plus particulièrement, un substrat en plastique transparent apte à être façonné par une extrusion à chaud qui est produit par un durcissement séquentiel du silsesquioxane thermoplastique du type en échelle (ayant une aptitude au formage par extrusion à chaud) par un thermodurcissement à basse température par étapes, et un substrat en plastique transparent multicouche présentant de bonnes propriétés thermiques et optiques et fabriqué par le formation d'une couche de revêtement de silsesquioxane thermodurcissable produite séparément sur la surface du substrat et son durcissement séquentiel. Le substrat en plastique transparent selon la présente invention présente peu de déformation à chaud aux températures de traitement utilisées pour les panneaux d'affichage existants, est souple, et présente une bonne transmittance de lumière, de sorte à être utilisé de différentes manières pour des affichages à cristaux liquides, des affichages organiques électroluminescents, des substrats pour des affichages souples tels qu'un papier électronique, ou comme substrats pour des cellules solaires et des piles secondaires.
PCT/KR2014/012790 2013-12-26 2014-12-24 Silsesquioxane ayant une aptitude au formage par extrusion à chaud, substrat en plastique transparent très transparent et très résistant à la chaleur l'utilisant, et son procédé de fabrication WO2015099443A1 (fr)

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CN201480071015.5A CN105873983B (zh) 2013-12-26 2014-12-24 能够热熔融挤压成型的倍半硅氧烷、利用其的高透明及高耐热塑料透明基板及其制造方法
JP2016542763A JP6659550B2 (ja) 2013-12-26 2014-12-24 熱溶融−押出成形が可能なシルセスキオキサン、これを用いた高透明および高耐熱プラスチック透明基板およびその製造方法

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KR1020130163607A KR102170818B1 (ko) 2013-12-26 2013-12-26 열 용융-압출 성형이 가능한 실세스퀴옥산, 이를 이용한 고투명 및 고내열 플라스틱 투명기판 및 이의 제조방법

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CN105873983A (zh) 2016-08-17
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