WO2013118951A1 - Highly heat-resistant transparent cyclic olefin copolymers having excellent flexibility, and flexible substrate produced therefrom - Google Patents

Highly heat-resistant transparent cyclic olefin copolymers having excellent flexibility, and flexible substrate produced therefrom Download PDF

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WO2013118951A1
WO2013118951A1 PCT/KR2012/006274 KR2012006274W WO2013118951A1 WO 2013118951 A1 WO2013118951 A1 WO 2013118951A1 KR 2012006274 W KR2012006274 W KR 2012006274W WO 2013118951 A1 WO2013118951 A1 WO 2013118951A1
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carboxylic acid
cyclic olefin
ester
formula
norbornene carboxylic
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PCT/KR2012/006274
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French (fr)
Korean (ko)
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전승호
박창규
박종
이종성
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주식회사 폴리사이언텍
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    • H—ELECTRICITY
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03926—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/152—Side-groups comprising metal complexes
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/59—Stability
    • C08G2261/592—Stability against heat
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/91—Photovoltaic applications
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/95—Use in organic luminescent diodes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a novel high heat-transparent transparency cyclic olefin copolymer and a flexible substrate suitable for use in displays, solar cells and the like prepared therefrom.
  • TFT-LCD thin film transistor-liquid crystal displays
  • OLED organic light emitting diodes
  • flexible solar cells etc. are thinner, lighter, more impact-resistant, and more portable than conventional glass-based flat panels.
  • the demand is increasing more and more in that it is relatively free from constraints of form and shape, and thus various applications can be secured.
  • a high heat-resistant transparent flexible substrate manufacturing technology In order to implement such a flexible display and a flexible solar cell, many technologies such as a high heat-resistant transparent flexible substrate manufacturing technology, a high blocking technology for moisture and oxygen, and a transparent electrode forming technology are required in combination.
  • Representative methods for providing high barrier properties include, for example, forming a thin layer of silica oxide, aluminum oxide, etc. on a flexible substrate by vacuum deposition, sputtering, or the like, and coating the thermosetting resin again, thereby repeating a high barrier layer having a multilayer structure.
  • oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO) are usually formed into thin films by vacuum deposition, sputtering, or the like.
  • the processes such as vacuum deposition and sputtering, which are essential for the process of imparting high barrier resistance and forming transparent electrodes, are unfortunately required to be performed at a high temperature of 200 ° C. or higher, so that the heat resistance of the natural flexible substrate is extremely demanded.
  • the heat resistance of the flexible substrate is increasingly required because the process temperature for implementing the thin film transistor array on the flexible substrate is extremely high above 250 ° C.
  • This heat resistance is currently evaluated as a glass transition temperature and coefficient of thermal expansion, in order to manufacture a high heat resistant flexible substrate, a high glass transition temperature of at least 250 °C, preferably at least 300 °C and at least 20ppm / °C, preferably 10ppm Plastic materials with low coefficients of thermal expansion below / ° C are needed.
  • a plastic material suitable for such a flexible substrate is required to have various physical properties such as heat resistance having a high glass transition temperature and a low coefficient of thermal expansion, excellent transparency of 90% or more based on light transmittance, and isotropy of 10 nm or less based on birefringence.
  • Plastic materials for flexible substrates which have been the main targets of conventional research and development, include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethersulfone, polynorbornene, polyimide and the like.
  • polyimide Since polyimide has a high glass transition temperature of 360 ° C. and a low thermal expansion coefficient of 17 ppm / ° C., polyimide has great advantages in terms of heat resistance, but is not preferable because of its high raw material and manufacturing cost and yellow color.
  • Polyester resins such as polyethylene terephthalate and polyethylene naphthalate have relatively low thermal expansion coefficients of 13 to 15 ppm / ° C, but have a very low glass transition temperature of 80 to 120 ° C. and high birefringence of 150 nm or more. Plastic material is excluded from the target.
  • 10-1991-0016790 proposes a method for efficiently preparing cyclic olefin random copolymers by copolymerizing ethylene and cyclic olefins at high concentration, but the glass transition temperature of the random copolymer is only 20 to 200 ° C. There is a disadvantage that does not reach the glass transition temperature condition of 250 °C.
  • cyclic olefin resin substrates such as Pronorus' polynorbornene substrate (trade name Appear 3000) have high heat resistance of glass transition temperature of 330 ° C, excellent transparency of 92% and excellent isotropy of birefringence of less than 10nm. It is a great expectation as a strong candidate material suitable for a flexible substrate.
  • such cyclic olefin resin substrates have a problem that the flexibility of the basic properties of the flexible substrate is very insufficient, and the thermal expansion coefficient, which is another measure of heat resistance, is very high at a level of 100 to 200 ppm / ° C. It is requested.
  • the present invention is a novel cyclic olefin copolymer to solve the high thermal expansion coefficient and low transparency, glass transition temperature below 250 °C, low flexibility which is a disadvantage of the plastic material for manufacturing a high heat-resistant flexible substrate and from It is an object to provide the provided flexible substrate.
  • the present invention relates to a carbon number of an alkyl group in a cyclic olefin homopolymer composed of norbornene carboxylic acid alkyl ester units or a cyclic olefin copolymer composed of norbornene carboxylic acid alkyl ester units composed of two or more alkyl groups. While controlling, the long-chain structure with the flexibility in the molecule can be expressed to adjust the flexibility to the desired level.
  • hydrolysis and electrostatic forces of carboxylic acid group or metal carboxylate salt period are generated by generating a novel cyclic olefin copolymer having a carboxylic acid group or a metal carboxylate group as a continuous treatment of the hydrolysis reaction and the neutralization reaction by metal ion.
  • a novel cyclic olefin copolymer having a carboxylic acid group or a metal carboxylate group as a continuous treatment of the hydrolysis reaction and the neutralization reaction by metal ion.
  • the present invention relates to a highly heat-resistant transparent cyclic olefin copolymer having excellent flexibility and a flexible substrate prepared therefrom.
  • the present invention relates to a cyclic olefin copolymer comprising a cyclic olefin unit comprising one or two or more alkyl groups selected from the following general formula (1) and a carboxylic acid group-containing cyclic olefin unit of the following general formula (2).
  • R is (C 1 -C 20 ) alkyl.
  • another embodiment of the present invention includes a part in which some or all of the hydrogen in the carboxylic acid group of the formula (2) is substituted with a metal salt in the cyclic olefin copolymer. That is, the present invention relates to a cyclic olefin copolymer further comprising a carboxylic acid metal base-containing cyclic olefin unit such as the following formula (3).
  • X is any one metal ion selected from alkali metals, alkaline earth metals and transition metals.
  • the metal ions are ion-bonded with neighboring carboxylic acid groups or carboxylic acid groups of neighboring molecular chains to exist in the form of salts and improve physical properties of the substrate.
  • the present invention is to provide any one of an electric device selected from a flexible display and a solar cell using a flexible substrate and a flexible substrate obtained by the solvent casting method or melt extrusion method of the cyclic olefin copolymer.
  • It relates to a cyclic olefin copolymer production method comprising a.
  • the present invention not only exhibits excellent flexibility due to the specificity of the structure of the polymer and the chemical and physical properties obtained therefrom, but can also be easily conceived by those skilled in the art, and also includes hydrogen bonds between the carboxylic acid groups or the carboxylic acid metal bases, and electrostatic forces.
  • the pseudo-crosslinking structure By expressing the pseudo-crosslinking structure by the differential bonding force, the free volume is greatly reduced, thereby exhibiting extremely low coefficient of thermal expansion and simultaneously having high glass transition temperature, excellent transparency, and isotropy, which are advantages of the conventional cyclic olefin resin. It exhibits physical properties, and the flexible substrate obtained from the resin of the present invention can be usefully used in various fields such as a flexible display and a flexible solar cell.
  • the present invention provides a cyclic olefin copolymer comprising a cyclic olefin unit represented by the following formula (1) and a carboxylic acid group-containing cyclic olefin unit represented by the following formula (2).
  • R is (C One To C 20 Alkyl)
  • the carboxylic acid group content of the formula (2) is to provide a cyclic olefin copolymer containing 0.01 to 20% by weight in 100% by weight of the total cyclic olefin copolymer.
  • the present invention provides a cyclic olefin copolymer wherein the cyclic olefin copolymer further comprises a cyclic olefin unit containing a metal carboxylate group of the formula (3).
  • X is any one metal ion selected from alkali metals, alkaline earth metals and transition metals.
  • the substituted metal ion of the carboxylic acid metal base may be selected from lithium ions, sodium ions, potassium ions, magnesium ions, calcium ions, barium ions, nickel ions, copper ions, and zinc ions. If it belongs to the category of X, it is not limited.
  • the content of the metal carboxylate group is not particularly limited in 100% by weight of the cyclic olefin copolymer, but the cyclic olefin air is 0.05 to 40% by weight
  • the copolymerization is good and a part of hydrogen in the carboxylic acid group is substituted with a metal salt, it is not particularly limited, but the total content of the carboxylic acid group and the metal carboxylate group in 100% by weight of the cyclic olefin copolymer is 0.02 to It is better if the cyclic olefin copolymer is 30% by weight because it is suitable for achieving flexibility and various physical properties required by the present invention.
  • Method for producing the polymer in the present invention comprises the steps of: a) preparing a first polymer comprising a compound comprising one or two or more alkyl groups selected from Formula 1 as a repeating unit; b) partially hydrolyzing the first polymer to prepare a second polymer including the carboxylic acid group of Chemical Formula 2; and providing a method of preparing a cyclic olefin copolymer.
  • the salt when the salt is substituted in the present invention is prepared by further comprising a neutralization step of substituting some or all of the hydrogen in the carboxylic acid group with a metal salt.
  • the method of manufacturing a substrate using the cyclic cyclic olefin copolymer of the present invention is not particularly limited if it is conventionally used in the art, but for example, the flexible substrate may be manufactured by a solvent casting method or a melt extrusion method. have.
  • the term "copolymer” or “polymer” basically refers to the norbornene carboxylic acid alkyl ester-based cyclic olefin unit of Formula 1, and a carboxylic acid group and / or a metal carboxylate-containing cyclic olefin unit of Formula 2. It is a cyclic olefin copolymer composed of the above, and also includes all used as a comonomer of two or more different units of the formula (1) polymerized two or more monomers belonging to the formula (1).
  • norbornene carboxylic acid alkyl ester-based cyclic olefin unit in the present invention may be used one or two or more if it belongs to the category of the formula (1).
  • the cyclic olefin represented by Formula 1 is a norbornene carboxylic acid alkyl ester, and specific examples thereof include norbornene carboxylic acid methyl ester, norbornene carboxylic acid ethyl ester, and norbornene carboxylic acid n.
  • norbornene carboxylic acid iso-propyl ester, norbornene carboxylic acid n-butyl ester, norbornene carboxylic acid t-butyl ester, norbornene carboxylic acid n-pentyl ester, norbornene N-carboxylic acid n-hexyl ester, norbornene carboxylic acid cyclohexyl ester, norbornene carboxylic acid n-heptyl ester, norbornene carboxylic acid 1,4-dimethylpentyl ester, norbornene carboxylic acid n-octyl ester, norbornene carboxylic acid 2-ethylhexyl ester, norbornene carboxylic acid myristyl ester, norbornene carboxylic acid palmityl ester,
  • the various norbornene carboxylic acid alkyl ester which has a C1-C20 alkyl group, such
  • Such cyclic olefins are usually obtained by esterification of norbornene carboxylic acid with an alcohol having an alkyl group having 1 to 20 carbon atoms, and in order to improve reactivity, norbornene carboxylic acid is reacted with thionyl chloride to make norbornene.
  • a catalyst such as triethylamine Alcohol, cyclohexyl alcohol, n-heptyl alcohol, 1,4-dimethylpentyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, etc.
  • the cyclic olefin polymer having a cyclic olefin unit represented by Formula 1 is a cyclic olefin which may be a cyclic olefin homopolymer of Formula 1 or a copolymer of two or more monomers contained in the unit of Formula 1 as a first step.
  • a polymer (first polymer) Such cyclic olefin copolymers are described, for example, in J. Polym. Sci. Polym. As described in Chem., Vol 45, 3042-3052 (2007), a cyclic olefin represented by Formula 1, ie, norbornene carboxylic acid alkylester, is obtained by polymerization in the presence of a catalyst.
  • the catalyst is not particularly limited, but is a paradite composite catalyst. Nickel composite catalysts are preferred, and co-catalysts such as methylaluminoxane are more preferred in terms of reaction rate, molecular weight, and yield.
  • the polymerization is preferably a solution polymerization method which proceeds under a solvent such as saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, toluene, and any of these may be continuous polymerization or batch polymerization. Polymerization temperature is 0-200 degreeC temperature.
  • the carbon number of the alkyl group is 1 to 20, preferably 1 to 8 carbon atoms
  • the flexibility is more than 20
  • the glass transition temperature may be too low.
  • the cyclic olefin homopolymer or copolymer composed of the cyclic olefin unit represented by the formula (1) is ethers such as tetrahydrofuran, dibutyl ether, dimethoxyethane, chlorobutane, bromohexane, Organic such as saturated carboxylic acid esters such as halogenated alkanes such as methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform and tetrachloroethylene, ethyl acetate, n-butyl acetate, iso-butyl acetate and methyl propionate
  • an aqueous solution such as hydrochloric acid or sulfuric acid is added to perform a partial hydrolysis reaction in a solution state to form a cyclic olefin copolymer comprising a cyclic olefin unit of Formula
  • the degree of hydrolysis reaction may be adjusted so that the carboxylic acid group content contains 0.01 to 20% by weight, preferably 0.1 to 5% by weight in 100% by weight of the total high heat-transparent cyclic olefin copolymer.
  • the carboxylic acid group content is less than 0.01% by weight, it is difficult to secure a desired low coefficient of thermal expansion due to the lack of functional groups capable of expressing a similar crosslinked structure, and when the content exceeds 20% by weight, the glass transition temperature may be too low.
  • the cyclic olefin copolymer (second polymer) composed of the cyclic olefin unit represented by the formula (1) and the carboxylic acid group-containing cyclic olefin unit represented by the formula (2) is partially or completely neutralized with metal ions.
  • a third polymer can be prepared.
  • metal ions used for neutralization include alkali metal ions such as lithium ions, sodium ions and potassium ions, alkaline earth metal ions such as magnesium ions, calcium ions and barium ions, and transition metal ions such as nickel ions, copper ions and zinc ions.
  • the metal ion may include a form in which a (+) ion and a ( ⁇ ) ion form a complex.
  • sodium ions, zinc ions and the like Preferably sodium ions, zinc ions and the like.
  • the neutralization reaction is carried out using tetrahydrofuran, dibutyl ether, dimethoxyethane, or a cyclic olefin copolymer (second polymer) composed of a cyclic olefin unit represented by Formula 1 and a carboxylic acid group-containing cyclic olefin unit represented by Formula 2.
  • second polymer a cyclic olefin copolymer composed of a cyclic olefin unit represented by Formula 1 and a carboxylic acid group-containing cyclic olefin unit represented by Formula 2.
  • Ethers such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, halogenated alkanes such as chloroform, tetrachloroethylene, ethyl acetate, n-butyl acetate, iso-butyl acetate and propionic acid It is dissolved in an organic solvent such as saturated carboxylic acid esters such as methyl, and then reacted in a solution state by adding a compound containing metal ions such as water or a metal hydroxide, a metal oxide, a metal carbonate or a metal sulfur oxide dissolved in the organic solvent.
  • a compound containing metal ions such as water or a metal hydroxide, a metal oxide, a metal carbonate or a metal sulfur oxide dissolved in the organic solvent.
  • a cyclic olefin unit represented by Formula 1 and represented by Formula 2 The cyclic olefin copolymer (second polymer) composed of the carboxylic acid group-containing cyclic olefin unit is added to a long L / D extruder which can give a sufficient reaction time, and melted, and a compound containing a metal ion is added to neutralize the reaction. There is a way to make it.
  • the neutralization reaction according to the present invention corresponds to all or partial neutralization reactions, and a third polymer can be obtained by carrying out this reaction.
  • the content of the metal carboxylate base in the third polymer obtained by the total neutralization reaction is 0.05 to 40% by weight. Preferably, it is adjusted to contain 0.5 to 20% by weight.
  • the content of the metal carboxylate base is less than 0.05% by weight, it is difficult to secure a desired low coefficient of thermal expansion due to the lack of functional groups capable of expressing a similar crosslinked structure, and if the content exceeds 40% by weight, the glass transition temperature may be too low. .
  • the total content of the carboxylic acid group and the metal carboxylate group in the third polymer obtained by the partial neutralization reaction may be adjusted to contain 0.02 to 30% by weight, preferably 0.2 to 15% by weight.
  • the content of carboxylic acid group and metal carboxylate base is less than 0.02% by weight, it is difficult to secure a desired low coefficient of thermal expansion due to the lack of functional groups capable of expressing a similar crosslinked structure, and the glass transition temperature is too high if it exceeds 30% by weight. It may be lowered.
  • the weight average molecular weight of the cyclic olefin copolymer according to the present invention is excellent in film properties and moldability in the range of 1,000 to 1,000,000, preferably 10,000 to 500,000, more preferably 50,000 to 300,000.
  • additives such as inorganic particles, antioxidants, sunscreens, lubricants, and the like may be added to the cyclic olefin copolymer according to the present invention without departing from the object of the present invention.
  • the film-like flexible substrate according to the present invention can be produced by a conventional solvent casting method or a melt extrusion method. That is, first, the cyclic olefin copolymer resin according to the present invention is dissolved in a solvent, bubbles are removed, cast on a suitable substrate, and the solvent is dried to complete a film-type flexible substrate, or the cyclic olefin copolymer resin pellet according to the present invention is hopper. The film is poured into an extruder, melt-extruded through a cylinder, and passed through a T-die to cool the film on a casting cooling roll and wound on a take-up roll, thereby completing a final film-like flexible substrate.
  • the cyclic olefin copolymer according to the present invention has some long branches in the molecule and thus exhibits excellent flexibility, and also has strong secondary bonding strength such as hydrogen bonding and electrostatic force in the carboxylic acid group or carboxylate metal salt period.
  • the pseudo-crosslinked structure By expressing the pseudo-crosslinked structure by molecular association, the free volume is greatly reduced, resulting in extremely low coefficient of thermal expansion as well as high glass transition temperature, excellent transparency, and isotropy, which are advantages of conventional cyclic olefin resins.
  • the flexible substrate obtained from such a resin can be usefully used in various fields such as a flexible display and a flexible solar cell.
  • the weight average molecular weight of the cyclic olefin copolymer resins prepared according to the following Examples and Comparative Examples and the flexibility, thermal expansion coefficient, glass transition temperature, transparency, isotropy and the like of the film-like substrates obtained from these resins were measured as follows.
  • the weight average molecular weight for the resin was measured at 140 ° C. using GPC (Waters 150C), using o-dichlorobenzene as solvent and polystyrene as standard.
  • the glass transition temperature (° C.) of the film-type substrate was measured in a DSC (Differential Scanning Calorimeter, DuPont 910) under a nitrogen atmosphere and a cooling rate of 10 ° C./min.
  • the light transmittance (%) of the film-type substrate was measured using a Hazemeter (Toyoseiki, Direct Reading Hazemeter) according to ASTM D1003.
  • birefringence (nm) of the film-type substrate specimens was evaluated using a polarized microscope (Oji Scientific Instruments, Automatic Birefringence Analyzer Kobra-WR) by the parallel nicols method.
  • paradigm (II) acetate 7.9 g of paradigm (II) acetate, 7.7 g of tricyclohexylphosphine and 8 L of solvent chlorobenzene were added to the catalyst preparation flask and stirred. Thereafter, 19.5 g of phenylcarbenicit tetrakis (pentafluorophenyl) borate was added thereto, followed by stirring to prepare a paradigm complex catalyst solution.
  • the obtained norbornene carboxylic acid methyl ester-norbornene carboxylic acid copolymer (B) resin was dissolved in a solvent tetrahydrofuran to make a 20% by weight solution, cast on a glass substrate by a solvent casting method, and dried to obtain a final thickness of 80 Film-like flexible substrate specimens were obtained, and the flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated for the specimens, and the results are shown in Table 2.
  • Example 1 The partial hydrolysis reaction on the norbornene carboxylic acid methyl ester homopolymer (A) resin obtained in Example 1 was extended for 24 hours to produce a norbornene carboxylic acid having 7.1% by weight of a carboxylic acid group content and a weight average molecular weight of 192,000.
  • the methyl ester-norbornene carboxylic acid copolymer (C) resin was obtained.
  • the obtained norbornene carboxylic acid methyl ester-norbornene carboxylic acid copolymer (C) resin was dissolved in a solvent tetrahydrofuran to make a 20% by weight solution, cast on a glass substrate by a solvent casting method, dried and the final thickness 80 Film-like flexible substrate specimens were obtained, and the flexibility, thermal expansion coefficient, glass transition temperature, light transmittance and birefringence were evaluated for the specimens and the results are shown in Table 2.
  • Norbornene carboxylic acid was carried out in the same manner as in Example 1 by adjusting the composition ratio of 80 mol% of norbornene carboxylic acid methyl ester as a monomer and 20 mol% of norbornene carboxylic acid n-hexyl ester as a comonomer.
  • the methyl ester-norbornene carboxylic acid n-hexyl ester copolymer (D) resin was obtained, and partial hydrolysis reaction was carried out in the same manner as in Example 1 to obtain methyl norbornene carboxylic acid having a carboxylic acid group content of 7.8% by weight.
  • Ester-norbornene carboxylic acid n-hexyl ester-norbornene carboxylic acid copolymer (E) resin was obtained.
  • Resin 1Kg of the obtained copolymer (E) resin was dissolved in 2L of a mixed solvent of tetrahydrofuran / water (9/1, volume ratio) and 120 g of zinc acetate was added, followed by partial neutralization with stirring at 50 ° C. for 10 hours. The precipitate was filtered and dried in vacuo for 12 hours to obtain a cyclic olefin copolymer (F) resin having a carboxylic acid group content of 5.6 wt%, a zinc carboxylate base content of 3.6 wt% and a weight average molecular weight of 270,000.
  • the obtained cyclic olefin copolymer (F) resin was dissolved in a solvent tetrahydrofuran to make a 20 wt% solution, cast on a glass substrate by a solvent casting method, and dried to obtain a film-like flexible substrate specimen having a final thickness of 80 ⁇ m.
  • the flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated. The results are shown in Table 2.
  • the obtained cyclic olefin copolymer (G) resin was dissolved in a solvent tetrahydrofuran to make a 20 wt% solution, cast on a glass substrate by a solvent casting method, and dried to obtain a film-like flexible substrate specimen having a final thickness of 80 ⁇ m.
  • the flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated. The results are shown in Table 2.
  • Norbornene carboxylic acid was carried out in the same manner as in Example 1 by adjusting the composition ratio of 90 mol% of norbornene carboxylic acid methyl ester as a monomer and 10 mol% of norbornene carboxylic acid n-octyl ester as a comonomer.
  • the methyl ester-norbornene carboxylic acid n-octyl ester copolymer (H) resin was obtained.
  • the obtained cyclic olefin copolymer (J) resin was dissolved in a solvent tetrahydrofuran to make a 20 wt% solution, cast on a glass substrate by a solvent casting method, and dried to obtain a film-like flexible substrate specimen having a final thickness of 80 ⁇ m.
  • the flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated. The results are shown in Table 2.
  • a composition of norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-octyl ester-norbornene carboxylic acid copolymer (I) resin obtained in Example 5 was mixed with 30 parts by weight of resin and 70 parts by weight of zinc oxide. The mixture was kneaded in an L / D 40 twin screw extruder to prepare a zinc oxide masterbatch pellet (A).
  • the obtained cyclic olefin copolymer (K) resin pellet was introduced into a hopper, injected into an extruder having a screw diameter of 70 mm and L / D 36, and melt-extruded to obtain a film-shaped flexible substrate specimen having a thickness of 80 ⁇ m through a Ti die.
  • the flexibility, thermal expansion coefficient, glass transition temperature, light transmittance and birefringence of the specimens were evaluated and the results are shown in Table 2.
  • Example 1 1 kg of the norbornene carboxylic acid methyl ester-norbornene carboxylic acid copolymer (B) resin having a carboxylic acid group content of 3.9% by weight in Example 1 was mixed with a tetrahydrofuran / water (9/1, volume ratio) mixed solvent. It was dissolved in 2L and 50g of zinc acetate was added, followed by partial neutralization with stirring at 50 ° C. for 8 hours to precipitate the resulting resin, followed by filtration and drying in vacuo for 12 hours to carboxylic acid group content of 2.8% by weight and zinc carboxylic acid.
  • a cyclic olefin copolymer (L) resin having a base content of 2.5 wt% and a weight average molecular weight of 230,000 was obtained.
  • the obtained cyclic olefin copolymer (L) resin was dissolved in a solvent tetrahydrofuran to make a 20 wt% solution, cast on a glass substrate by a solvent casting method, and dried to obtain a film-like flexible substrate specimen having a final thickness of 80 ⁇ m.
  • the flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated. The results are shown in Table 2.
  • Norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-hexyl ester-norbornene carboxylic acid copolymer (E) resin of 7.8 weight% of carboxylic acid group contents obtained in Example 3 is a solvent tetrahydrofuran Was dissolved in a 20% by weight solution, cast on a glass substrate by a solvent casting method, and dried to obtain a film-like flexible substrate specimen having a final thickness of 80 ⁇ m. The flexibility, thermal expansion coefficient, glass transition temperature, light transmittance and birefringence of the specimen were obtained. Was evaluated and the results are shown in Table 2.
  • the obtained cyclic olefin copolymer (M) resin was dissolved in a solvent tetrahydrofuran to make a 20 wt% solution, cast on a glass substrate by a solvent casting method, and dried to obtain a film-like flexible substrate specimen having a final thickness of 80 ⁇ m.
  • the flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated. The results are shown in Table 2.
  • a cyclic olefin copolymer (N) resin having an acid group content of 6.1 wt%, a lithium carboxylate base content 1.9 wt%, and a weight average molecular weight of 260,000 was obtained.
  • the obtained cyclic olefin copolymer (N) resin was dissolved in a solvent tetrahydrofuran to make a 20 wt% solution, cast on a glass substrate by a solvent casting method, and dried to obtain a film-shaped flexible substrate specimen having a final thickness of 80 ⁇ m.
  • the flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated. The results are shown in Table 2.
  • the norbornene carboxylic acid methyl ester homopolymer (A) resin obtained in Example 1 was dissolved in a solvent tetrahydrofuran without partial hydrolysis to make a 20% by weight solution, and cast on a glass substrate by a solvent casting method. After drying, a film-like flexible substrate specimen having a final thickness of 80 ⁇ m was obtained. The flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated for the specimen, and the results are shown in Table 2.
  • the norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-hexyl ester copolymer (D) resin obtained in Example 3 was dissolved in a solvent tetrahydrofuran without partial hydrolysis reaction to a 20 wt% solution. After casting on a glass substrate by the solvent casting method and drying, a film-like flexible substrate specimen having a final thickness of 80 ⁇ m was obtained. The flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated for the specimen. 2 is shown.
  • the carboxylic acid group or metal carboxylate-containing cyclic olefin copolymer not only has excellent flexibility and extremely low coefficient of thermal expansion, but also conventional cyclic olefin It can be seen that it has both heat resistance, excellent transparency and isotropy due to the high glass transition temperature, which are advantages of the resin.
  • Example 6 Example 8, and Example 9 were compared, the Examples 8 and 9, which were not neutralized with metal ions, were not suitable for use as substrate materials due to their relatively high thermal expansion coefficient or low glass transition temperature. You can see that.

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Abstract

The present invention relates to cyclic olefin copolymers consisting of norbornene carboxylic acid alkyl ester cyclic olefin units and cyclic olefin units that contain a carboxylic acid group or a carboxylic acid metal base. The present invention also relates to a flexible substrate obtained by processing said copolymers by solvent casting or hot-melt extrusion. The resin and the flexible substrate according to the present invention have not only excellent flexibility, but also excellent heat-resistance and transparency, and therefore can be effectively used in various fields, such as flexible displays and flexible solar cells.

Description

유연성이 우수한 고내열투명성 환상올레핀계 공중합체 및 이로부터 제조된 플렉시블 기판High heat resistance transparent cyclic olefin copolymer having excellent flexibility and flexible substrate prepared therefrom
본 발명은 유연성이 우수한 고내열투명성 신규의 환상올레핀계 공중합체 및 이로부터 제조된 디스플레이, 태양전지 등의 용도에 적합한 플렉시블 기판에 관한 것이다.The present invention relates to a novel high heat-transparent transparency cyclic olefin copolymer and a flexible substrate suitable for use in displays, solar cells and the like prepared therefrom.
박막트랜지스터-액정디스플레이(TFT-LCD), 유기발광다이오드(OLED) 등 플렉시블 디스플레이, 플렉시블 태양전지 등은 기존의 유리 기반 평판형 제품에 비해서 박형 및 경량이고 충격에 강하며 휴대가 간편하다는 장점이외에 공간상, 형태상의 제약에서 상대적으로 자유로워 다양한 응용성을 확보할 수 있다는 점에서 더욱더 그 수요가 급증하고 있다.Flexible displays such as thin film transistor-liquid crystal displays (TFT-LCD), organic light emitting diodes (OLED), flexible solar cells, etc. are thinner, lighter, more impact-resistant, and more portable than conventional glass-based flat panels. The demand is increasing more and more in that it is relatively free from constraints of form and shape, and thus various applications can be secured.
이러한 플렉시블 디스플레이, 플렉시블 태양전지 등을 구현하기 위해서는 고내열투명성 플렉시블 기판 제조기술, 수분 및 산소에 대한 고차단성 부여기술, 투명전극 형성기술 등 많은 기술들이 복합적으로 필요하다. 대표적으로 고차단성을 부여하는 방법으로서는 가령 실리카계 산화물, 알루미늄계 산화물 등을 플렉시블 기판위에 진공증착, 스퍼터링 등 방법을 통해 박막으로 형성하고 다시 열경화성 수지를 코팅하는 작업을 반복함으로써 다층구조의 고차단성층을 형성시키는 방법이 있으며 투명전극 경우는 통상 인튬 틴 옥사이드(ITO), 인튬 징크 옥사이드(IZO) 등 산화물을 진공증착, 스퍼터링 방법 등에 의해 박막으로 형성시키고 있다. In order to implement such a flexible display and a flexible solar cell, many technologies such as a high heat-resistant transparent flexible substrate manufacturing technology, a high blocking technology for moisture and oxygen, and a transparent electrode forming technology are required in combination. Representative methods for providing high barrier properties include, for example, forming a thin layer of silica oxide, aluminum oxide, etc. on a flexible substrate by vacuum deposition, sputtering, or the like, and coating the thermosetting resin again, thereby repeating a high barrier layer having a multilayer structure. In the case of the transparent electrode, oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO) are usually formed into thin films by vacuum deposition, sputtering, or the like.
고차단성 부여 및 투명전극을 형성시키는 공정에 필수적인 진공증착, 스퍼터링 등 공정은 불행히도 200℃이상의 높은 온도에서 실행되어야 하므로 자연 플렉시블 기판의 내열성이 극도로 요구되고 있다. 가령 플렉시블 기판의 주요 용도중 하나인 박막트랜지스터-액정디스플레이 생산 시 박막트랜지스터 어레이를 플렉시블 기판위에 구현하는 공정온도가 250℃이상 극히 고온이기 때문에 플렉시블 기판의 내열성은 더더욱 요청되고 있다. 이러한 내열성은 현재 유리전이온도 및 열팽창계수로서 이를 평가하고 있는데, 고내열성 플렉시블 기판을 제조하기 위해서는 최소 250℃이상, 바람직하게는 300℃이상의 높은 유리전이온도 및 최소 20ppm/℃이하, 바람직하게는 10ppm/℃이하의 낮은 열팽창계수를 가진 플라스틱 소재가 필요하다. The processes such as vacuum deposition and sputtering, which are essential for the process of imparting high barrier resistance and forming transparent electrodes, are unfortunately required to be performed at a high temperature of 200 ° C. or higher, so that the heat resistance of the natural flexible substrate is extremely demanded. For example, in the production of thin film transistor-liquid crystal display, which is one of the main uses of the flexible substrate, the heat resistance of the flexible substrate is increasingly required because the process temperature for implementing the thin film transistor array on the flexible substrate is extremely high above 250 ° C. This heat resistance is currently evaluated as a glass transition temperature and coefficient of thermal expansion, in order to manufacture a high heat resistant flexible substrate, a high glass transition temperature of at least 250 ℃, preferably at least 300 ℃ and at least 20ppm / ℃, preferably 10ppm Plastic materials with low coefficients of thermal expansion below / ° C are needed.
또한 이러한 플렉시블 기판에 적합한 플라스틱 소재는 상기 높은 유리전이 온도 및 낮은 열팽창계수를 가지는 내열성뿐만 아니라 광투과도 기준 90% 이상 우수한 투명성, 복굴절 기준 10㎚이하의 등방성 등 여러 물성이 요구되고 있다. In addition, a plastic material suitable for such a flexible substrate is required to have various physical properties such as heat resistance having a high glass transition temperature and a low coefficient of thermal expansion, excellent transparency of 90% or more based on light transmittance, and isotropy of 10 nm or less based on birefringence.
종래 연구개발의 유력한 대상이 되어온 플렉시블 기판용 플라스틱 소재로서는 폴리에틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 폴리카보네이트, 폴리에테르설폰, 폴리노르보르넨, 폴리이미드 등이 있다.Plastic materials for flexible substrates, which have been the main targets of conventional research and development, include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethersulfone, polynorbornene, polyimide and the like.
폴리이미드는 360℃ 수준의 높은 유리전이온도 및 17ppm/℃ 수준의 낮은 열팽창계수를 가지므로 내열성 측면에서 큰 장점을 가지고 있으나 원료 및 제조원가가 높고 노란색을 띄고 있어 바람직하지 않다. 폴리에틸렌테레프탈레이트, 폴리에틸렌나프탈레이트 등 폴리에스테르 수지는 열팽창계수는 13 내지 15ppm/℃로서 비교적 낮은 편이나 유리전이온도가 80 내지 120℃ 수준으로 매우 낮고, 150nm이상 높은 복굴절을 가지기 때문에 결국 플렉시블 기판에 적합한 플라스틱 소재 대상 에서 제외되고 있다. 폴리카보네이트 경우 광투과도 90%의 투명성, 10㎚이하 낮은 복굴절 측면에선 긍정적이나 유리전이온도가 150 내지 200℃ 수준으로 매우 낮아 역시 바람직하지 않다. 또한 폴리에테르설폰 경우 가령 스미토모배이크라이트사의 폴리에테르설폰 기판(상품명 Sumilite FS-1300)은 광투과도 89%의 투명성, 10㎚이하의 낮은 복굴절을 가지는 장점이 있으나 유리전이온도가 223℃로서 폴리카보네이트 대비 우수하지만 역시 요구하는 250℃이상의 유리전이온도 조건에는 부합하지 못한 단점이 있다. 또한 대한민국 공개특허 10-2010-0091624에서는 환상올레핀계 고분자 화합물 및 그 제조 방법에서는 기존에 사용된 수지인 1,4,5,8-디메타노-1,2,3,4,4a,5,8,8a-옥타하이드로나프탈렌이 가지고 있는 제조공정의 비 용이성과 높은 비용문제를 해결하기 위해 보다 간단한 방법으로 동일한 물성을 낼 수 있는 환상올레핀계 고분자 화합물을 제시하였으나 유리전이온도가 64 내지 177℃로 고내열성 플렉시블 기판을 제조하기 위한 최소의 유리전이온도인 250℃에 못 미치는 단점이 있다. 마찬가지로 대한민국 공개특허 10-1991-0016790에서 에틸렌과 환상올레핀을 공중합하여 환상올레핀계 랜덤공중합체를 고농도로 효율적으로 제조하는 방법을 제시하였으나 랜덤공중합체의 유리전이온도가 20 내지 200℃에 불과하여 요구하는 250℃의 유리전이온도 조건에 미치지 못하는 단점이 있다. Since polyimide has a high glass transition temperature of 360 ° C. and a low thermal expansion coefficient of 17 ppm / ° C., polyimide has great advantages in terms of heat resistance, but is not preferable because of its high raw material and manufacturing cost and yellow color. Polyester resins such as polyethylene terephthalate and polyethylene naphthalate have relatively low thermal expansion coefficients of 13 to 15 ppm / ° C, but have a very low glass transition temperature of 80 to 120 ° C. and high birefringence of 150 nm or more. Plastic material is excluded from the target. In the case of polycarbonate, light transmittance is positive in terms of transparency of 90% and low birefringence of less than 10 nm, but the glass transition temperature is very low, such as 150 to 200 ° C. In addition, in the case of polyether sulfone, for example, Sumitomo Bakelite's polyether sulfone substrate (trade name Sumilite FS-1300) has the advantage of having 89% transparency of light and low birefringence of less than 10 nm, but the glass transition temperature is 223 ° C. Compared with the excellent glass transition temperature conditions of 250 ℃ or more, but also has the disadvantage that does not meet. In addition, the Republic of Korea Patent Publication No. 10-2010-0091624 In the cyclic olefin polymer compound and its manufacturing method 1,4,5,8-dimethano-1,2,3,4,4a, 5, In order to solve the inefficiency and high cost of the manufacturing process of 8,8a-octahydronaphthalene, a cyclic olefin polymer compound having the same physical properties can be proposed in a simpler method, but the glass transition temperature is 64 to 177 ° C. There is a disadvantage that is less than 250 ℃, the minimum glass transition temperature for producing a high heat-resistant flexible substrate. Likewise, Korean Patent Publication No. 10-1991-0016790 proposes a method for efficiently preparing cyclic olefin random copolymers by copolymerizing ethylene and cyclic olefins at high concentration, but the glass transition temperature of the random copolymer is only 20 to 200 ° C. There is a disadvantage that does not reach the glass transition temperature condition of 250 ℃.
반면 프로메러스사의 폴리노르보르넨 기판(상품명 Appear 3000)과 같은 환상올레핀계 수지 기판 경우 유리전이온도 330℃의 높은 내열성, 광투과도 92%의 우수한 투명성, 10㎚이하 복굴절의 우수한 등방성을 가지고 있어 플렉시블 기판에 적합한 강력한 후보 소재로서 큰 기대를 모으고 있다. 그러나 불행히도 이러한 환상올레핀계 수지 기판 경우 플렉시블 기판의 기본 물성이라 할 수 있는 유연성이 매우 부족한 문제점이 있고 또한 내열성의 또 하나의 척도인 열팽창계수가 100 내지 200ppm/℃수준으로 매우 높아 그 해결이 매우 절실히 요청되고 있다. On the other hand, cyclic olefin resin substrates such as Pronorus' polynorbornene substrate (trade name Appear 3000) have high heat resistance of glass transition temperature of 330 ° C, excellent transparency of 92% and excellent isotropy of birefringence of less than 10nm. It is a great expectation as a strong candidate material suitable for a flexible substrate. Unfortunately, however, such cyclic olefin resin substrates have a problem that the flexibility of the basic properties of the flexible substrate is very insufficient, and the thermal expansion coefficient, which is another measure of heat resistance, is very high at a level of 100 to 200 ppm / ° C. It is requested.
본 발명은 기존의 고내열성 플렉시블 기판을 제조하기 위한 플라스틱 소재가 가지고 있는 단점인 높은 열팽창계수와 낮은 투명성, 250℃이하의 유리전이온도, 낮은 유연성을 해결하기 위한 신규의 환상올레핀 공중합체 및 이로부터 제공된 플렉시블 기판을 제공하는 것을 그 목적으로 한다.The present invention is a novel cyclic olefin copolymer to solve the high thermal expansion coefficient and low transparency, glass transition temperature below 250 ℃, low flexibility which is a disadvantage of the plastic material for manufacturing a high heat-resistant flexible substrate and from It is an object to provide the provided flexible substrate.
구체적으로 본 발명은 노르보르넨 카르복실산 알킬에스테르 단위로 구성된 환상올레핀계 단독중합체 또는 2종 이상의 알킬기로 된 노르보르넨 카르복실산 알킬에스테르 단위들로 구성된 환상올레핀계 공중합체에서 알킬기의 탄소수를 조절하면서 분자 내 유연성을 가진 긴가지를 가진 구조를 발현해 유연성을 원하는 수준으로 조절할 수 있으며 노르보르넨 카르복실산 알킬에스테르 단위로 구성된 환상올레핀 단독중합체 또는 공중합체를 부분가수분해반응을 시키거나 부분가수분해반응 및 금속이온에 의한 중화반응을 연속처리함에 따라 카르복실산기 또는 카르복실산금속염기를 가진 신규의 환상올레핀 공중합체를 생성함으로서 카르복실산기 또는 카르복실산금속염기간의 수소결합, 정전기력 등 강한 2차결합력에 의한 유사가교구조를 발현함으로서 극히 낮은 열팽창계수를 갖는 환상올레핀 공중합체 및 이로부터 제조된 플렉시블 기판에 관한 것이다. Specifically, the present invention relates to a carbon number of an alkyl group in a cyclic olefin homopolymer composed of norbornene carboxylic acid alkyl ester units or a cyclic olefin copolymer composed of norbornene carboxylic acid alkyl ester units composed of two or more alkyl groups. While controlling, the long-chain structure with the flexibility in the molecule can be expressed to adjust the flexibility to the desired level. The hydrophobic or partial hydrolysis of the cyclic olefin homopolymer or copolymer composed of norbornene carboxylic acid alkyl ester units Hydrolysis and electrostatic forces of carboxylic acid group or metal carboxylate salt period are generated by generating a novel cyclic olefin copolymer having a carboxylic acid group or a metal carboxylate group as a continuous treatment of the hydrolysis reaction and the neutralization reaction by metal ion. Expresses similar cross-linked structure by strong secondary binding force As relates to a cyclic olefin copolymer, and a flexible substrate prepared therefrom has an extremely low coefficient of thermal expansion.
본 발명은 유연성이 우수한 고내열투명성 환상올레핀 공중합체 및 이로부터 제조된 플렉시블 기판에 관한 것이다.The present invention relates to a highly heat-resistant transparent cyclic olefin copolymer having excellent flexibility and a flexible substrate prepared therefrom.
본 발명은 하기 화학식 1에서 선택되는 1종 또는 2종 이상의 알킬기를 포함하는 환상올레핀 단위와, 하기 화학식 2의 카르복실산기 함유 환상올레핀 단위를 포함하는 환상올레핀 공중합체에 관한 것이다. The present invention relates to a cyclic olefin copolymer comprising a cyclic olefin unit comprising one or two or more alkyl groups selected from the following general formula (1) and a carboxylic acid group-containing cyclic olefin unit of the following general formula (2).
[화학식 1][Formula 1]
Figure PCTKR2012006274-appb-I000001
Figure PCTKR2012006274-appb-I000001
(상기 화학식 1에서, 상기 R은 (C1-C20)알킬이다)(In Formula 1, R is (C 1 -C 20 ) alkyl.)
[화학식 2][Formula 2]
Figure PCTKR2012006274-appb-I000002
Figure PCTKR2012006274-appb-I000002
또한 본 발명의 또다른 양태는, 상기 환상올레핀 공중합체에서 상기 화학식 2의 카르복실산기 중 수소의 일부 또는 전부가 금속염으로 치환한 것도 포함한다. 즉, 하기 화학식 3과 같은 카르복실산금속염기 함유 환상올레핀 단위를 더 포함하는 것인 환상올레핀 공중합체에 관한 것이다.Further, another embodiment of the present invention includes a part in which some or all of the hydrogen in the carboxylic acid group of the formula (2) is substituted with a metal salt in the cyclic olefin copolymer. That is, the present invention relates to a cyclic olefin copolymer further comprising a carboxylic acid metal base-containing cyclic olefin unit such as the following formula (3).
[화학식 3][Formula 3]
Figure PCTKR2012006274-appb-I000003
Figure PCTKR2012006274-appb-I000003
(상기 화학식 3에서, 상기 X는 알칼리금속, 알칼리토금속, 전이금속에서 선택되는 어느 하나의 금속이온이다.)(In Formula 3, X is any one metal ion selected from alkali metals, alkaline earth metals and transition metals.)
상기의 금속이온은 이웃하는 카르복실산기 또는 이웃하는 분자쇄의 카르복실산기와 이온결합하여 염의 형태로 존재하며 기판의 물성을 향상시킨다.The metal ions are ion-bonded with neighboring carboxylic acid groups or carboxylic acid groups of neighboring molecular chains to exist in the form of salts and improve physical properties of the substrate.
또한 본 발명은 상기 환상올레핀계 공중합체를 용매캐스팅방법 또는 용융 압출방법에 의해 얻어지는 플렉시블 기판과 플렉시블 기판을 사용한 플렉시블 디스플레이 또는 태양전지 중에서 선택된 어느 하나의 전기소자를 제공하는 것이다. In another aspect, the present invention is to provide any one of an electric device selected from a flexible display and a solar cell using a flexible substrate and a flexible substrate obtained by the solvent casting method or melt extrusion method of the cyclic olefin copolymer.
또한 본 발명은 In addition, the present invention
a) 상기 화학식 1에서 선택되는 1종 또는 2종 이상의 알킬기를 포함한 화합물을 반복단위로 포함하는 제 1중합체를 제조하는 단계;a) preparing a first polymer including a compound including one or two or more alkyl groups selected from Formula 1 as a repeating unit;
b) 상기 제 1중합체를 부분가수분해 반응시켜 하기 화학식 2의 카르복실산기를 포함하는 제 2중합체를 제조하는 단계;b) partially hydrolyzing the first polymer to prepare a second polymer including a carboxylic acid group represented by Formula 2 below;
c) 상기 제 2중합체 중 상기 화학식 2의 카르복실산기 중 수소의 일부 또는 전부를 금속염으로 치환하는 중화반응단계를 더 포함하여, 상기 화학식 3의 카르복실산금속염기 함유 환상올레핀 단위를 더 포함하는 제 3 중합체를 제조하는 단계;c) further comprising a neutralization step of substituting a part or all of hydrogen in the carboxylic acid group of Formula 2 with a metal salt in the second polymer, further comprising a carboxylate group-containing cyclic olefin unit of Formula 3 Preparing a third polymer;
를 포함하는 환상올레핀계 공중합체 제조방법에 관한 것이다.It relates to a cyclic olefin copolymer production method comprising a.
본 발명은 중합체의 구조의 특이성과 그로부터 얻어지는 화학적 및 물리적 특성으로 인하여 당업자가 용이하게 상도할 수 없는 탁월한 유연성을 발휘할 뿐만 아니라 함유된 카르복실산기 또는 카르복실산 금속염기 간의 수소결합, 정전기력 등의 2차결합력에 의한 유사가교구조를 발현함으로써 자유부피가 크게 감소해, 극히 낮은 열팽창계수를 발휘함은 물론, 종래 환상올레핀계 수지의 장점인 높은 유리전이온도 및 우수한 투명성, 등방성 등을 동시에 가지는 실로 획기적인 물성을 나타내며, 본 발명의 수지로 부터 얻어진 플렉시블 기판은 플렉시블 디스플레이, 플렉시블 태양전지 등 여러 분야에 유용하게 사용될 수 있다.The present invention not only exhibits excellent flexibility due to the specificity of the structure of the polymer and the chemical and physical properties obtained therefrom, but can also be easily conceived by those skilled in the art, and also includes hydrogen bonds between the carboxylic acid groups or the carboxylic acid metal bases, and electrostatic forces. By expressing the pseudo-crosslinking structure by the differential bonding force, the free volume is greatly reduced, thereby exhibiting extremely low coefficient of thermal expansion and simultaneously having high glass transition temperature, excellent transparency, and isotropy, which are advantages of the conventional cyclic olefin resin. It exhibits physical properties, and the flexible substrate obtained from the resin of the present invention can be usefully used in various fields such as a flexible display and a flexible solar cell.
이하 본 발명에 대하여 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail.
본발명은 하기 화학식 1의 환상올레핀 단위와, 하기 화학식 2의 카르복실산기 함유 환상올레핀 단위를 포함하는 환상올레핀 공중합체를 제공하는 것이다.The present invention provides a cyclic olefin copolymer comprising a cyclic olefin unit represented by the following formula (1) and a carboxylic acid group-containing cyclic olefin unit represented by the following formula (2).
[화학식 1][Formula 1]
Figure PCTKR2012006274-appb-I000004
Figure PCTKR2012006274-appb-I000004
(상기 화학식 1에서, 상기 R은 (C1 내지 C20)알킬이다)(In Formula 1, R is (COneTo C20Alkyl)
[화학식 2][Formula 2]
Figure PCTKR2012006274-appb-I000005
Figure PCTKR2012006274-appb-I000005
본 발명에 있어서, 상기 화학식 2의 카르복실산기 함유량은 전체 환상올레핀계 공중합체 100 중량% 중에서 0.01 내지 20 중량%를 함유한 환상올레핀 공중합체를 제공하는 것이다. In the present invention, the carboxylic acid group content of the formula (2) is to provide a cyclic olefin copolymer containing 0.01 to 20% by weight in 100% by weight of the total cyclic olefin copolymer.
또한 본 발명은 상기 환상올레핀 공중합체가 하기 화학식 3의 카르복실산금속염기를 함유하는 환상올레핀 단위를 더 포함하는 것인 환상올레핀 공중합체을 제공한다.In another aspect, the present invention provides a cyclic olefin copolymer wherein the cyclic olefin copolymer further comprises a cyclic olefin unit containing a metal carboxylate group of the formula (3).
[화학식 3][Formula 3]
Figure PCTKR2012006274-appb-I000006
Figure PCTKR2012006274-appb-I000006
(상기 화학식 3에서, 상기 X는 알칼리금속, 알칼리토금속, 전이금속에서 선택되는 어느 하나의 금속이온이다.)(In Formula 3, X is any one metal ion selected from alkali metals, alkaline earth metals and transition metals.)
더욱 구체적으로는 상기 카르복실산 금속염기의 치환 금속이온은 리튬이온, 나트륨이온, 칼륨이온, 마그네슘이온, 칼슘이온, 바륨이온, 니켈이온, 구리이온, 아연이온 중 어느 하나를 선택할 수 있지만, 상기 X의 범주에 속하는 것이라면 제한되지 않는다. 본 발명에 있어서 상기 카르복실산기 중 수소의 전부가 금속염으로 치환되는 경우, 카르복실산금속염기의 함량은 상기 환상올레핀 공중합체 100 중량% 중 특별히 한정하고 있지는 않지만 0.05 내지 40 중량%인 환상올레핀 공중합체가 좋으며, 상기 카르복실산기 중 수소의 일부가 금속염으로 치환되는 경우에는, 특별히 한정하는 것은 아니지만, 상기 환상올레핀 공중합체 100 중량% 중 카르복실산기 및 카르복실산금속염기의 총함유량이 0.02 내지 30 중량%인 환상올레핀 공중합체라면 더욱 좋은데, 이는 유연성과 본 발명에서 요구하는 다양한 물성을 달성하기에 적합하기 때문이다.More specifically, the substituted metal ion of the carboxylic acid metal base may be selected from lithium ions, sodium ions, potassium ions, magnesium ions, calcium ions, barium ions, nickel ions, copper ions, and zinc ions. If it belongs to the category of X, it is not limited. In the present invention, when all of the hydrogen in the carboxylic acid group is substituted with a metal salt, the content of the metal carboxylate group is not particularly limited in 100% by weight of the cyclic olefin copolymer, but the cyclic olefin air is 0.05 to 40% by weight When the copolymerization is good and a part of hydrogen in the carboxylic acid group is substituted with a metal salt, it is not particularly limited, but the total content of the carboxylic acid group and the metal carboxylate group in 100% by weight of the cyclic olefin copolymer is 0.02 to It is better if the cyclic olefin copolymer is 30% by weight because it is suitable for achieving flexibility and various physical properties required by the present invention.
본 발명에서 상기 중합체를 제조하는 방법은 a) 상기 화학식 1에서 선택되는 1종 또는 2종 이상의 알킬기를 포함하는 화합물을 반복단위로 포함하는 제1중합체를 제조하는 단계; b) 상기 제 1중합체를 부분가수분해 반응시켜 상기 화학식 2의 카르복실산기를 포함하는 제2중합체를 제조하는 단계;를 포함하는 환상올레핀 공중합체의 제조방법을 제공한다. Method for producing the polymer in the present invention comprises the steps of: a) preparing a first polymer comprising a compound comprising one or two or more alkyl groups selected from Formula 1 as a repeating unit; b) partially hydrolyzing the first polymer to prepare a second polymer including the carboxylic acid group of Chemical Formula 2; and providing a method of preparing a cyclic olefin copolymer.
또한 본 발명에서 염을 치환하는 경우에는 상기 카르복실산기 중 수소의 일부 또는 전부를 금속염으로 치환하는 중화반응단계를 더 포함하여 제조한다. In addition, when the salt is substituted in the present invention is prepared by further comprising a neutralization step of substituting some or all of the hydrogen in the carboxylic acid group with a metal salt.
본 발명의 상기 환상 환상올레핀 공중합체를 이용하여 기판을 제조하는 방법은 당업계에 통상적으로 사용하는 것이라면 큰 제한을 하는 것은 아니지만 예를 들면 용매캐스팅방법 또는 용융압출방법에 의해 플렉시블 기판을 제조할 수 있다.The method of manufacturing a substrate using the cyclic cyclic olefin copolymer of the present invention is not particularly limited if it is conventionally used in the art, but for example, the flexible substrate may be manufactured by a solvent casting method or a melt extrusion method. have.
이하 본 발명의 각 구성성분 및 그의 제조방법에 대한 각 단계에 대하여 더욱 구체적으로 살피면 다음과 같다. Hereinafter, the respective components of the present invention and each step for the preparation method thereof will be described in more detail.
먼저 본 발명에서 공중합체는 또는 중합체라는 용어는 기본적으로 화학식 1의 상기 노르보르넨 카르복실산 알킬에스테르계 환상올레핀 단위와, 화학식 2의 카르복실산기 및/또는 카르복실산금속염기 함유 환상올레핀 단위로 구성된 환상올레핀계 공중합체인 것이고, 또한 상기 화학식 1에 속하는 2이상의 단량체를 중합한 2이상의 서로 상이한 화학식 1의 단위를 공단량체로 사용한 것도 모두 포함한다. First, in the present invention, the term "copolymer" or "polymer" basically refers to the norbornene carboxylic acid alkyl ester-based cyclic olefin unit of Formula 1, and a carboxylic acid group and / or a metal carboxylate-containing cyclic olefin unit of Formula 2. It is a cyclic olefin copolymer composed of the above, and also includes all used as a comonomer of two or more different units of the formula (1) polymerized two or more monomers belonging to the formula (1).
또한 본 발명에서 노르보르넨 카르복실산 알킬에스테르계 환상올레핀 단위는 상기 화학식 1의 범주에 속하는 것이라면 1종 또는 2종 이상을 사용할 수 있다.In addition, the norbornene carboxylic acid alkyl ester-based cyclic olefin unit in the present invention may be used one or two or more if it belongs to the category of the formula (1).
본 발명에 있어서 상기 화학식 1로 표시되는 환상올레핀은 노르보르넨카르복실산알킬에스테르로서 구체적인 예로서 노르보르넨 카르복실산 메틸에스테르, 노르보르넨 카르복실산 에틸에스테르, 노르보르넨 카르복실산 n-프로필에스테르, 노르보르넨 카르복실산 iso-프로필에스테르, 노르보르넨 카르복실산 n-부틸에스테르, 노르보르넨 카르복실산 t-부틸에스테르, 노르보르넨 카르복실산 n-펜틸에스테르, 노르보르넨 카르복실산 n-헥실에스테르, 노르보르넨 카르복실산 시클로헥실에스테르, 노르보르넨 카르복실산 n-헵틸에스테르, 노르보르넨 카르복실산 1,4-디메틸펜틸에스테르, 노르보르넨 카르복실산 n-옥틸에스테르, 노르보르넨 카르복실산 2-에틸헥실에스테르, 노르보르넨 카르복실산 미리스틸에스테르, 노르보르넨 카르복실산 팔미틸에스테르, 노르보르넨 카르복실산 스테아릴에스테르 등의 탄소수 1 내지 20의 알킬기를 가지는 각종 노르보르넨 카르복실산 알킬에스테르를 말한다. In the present invention, the cyclic olefin represented by Formula 1 is a norbornene carboxylic acid alkyl ester, and specific examples thereof include norbornene carboxylic acid methyl ester, norbornene carboxylic acid ethyl ester, and norbornene carboxylic acid n. -Propyl ester, norbornene carboxylic acid iso-propyl ester, norbornene carboxylic acid n-butyl ester, norbornene carboxylic acid t-butyl ester, norbornene carboxylic acid n-pentyl ester, norbornene N-carboxylic acid n-hexyl ester, norbornene carboxylic acid cyclohexyl ester, norbornene carboxylic acid n-heptyl ester, norbornene carboxylic acid 1,4-dimethylpentyl ester, norbornene carboxylic acid n-octyl ester, norbornene carboxylic acid 2-ethylhexyl ester, norbornene carboxylic acid myristyl ester, norbornene carboxylic acid palmityl ester, The various norbornene carboxylic acid alkyl ester which has a C1-C20 alkyl group, such as norbornene carboxylic acid stearyl ester, is meant.
이러한 환상올레핀은 통상 노르보르넨 카르복실산과 탄소수 1 내지 20의 알킬기를 가지는 알코올과의 에스테르화 반응에 의해 얻어지는데, 반응성을 좋게 하기 위해 노르보르넨 카르복실산을 티오닐클로라이드로 반응시켜 노르보르넨 카르복실산 염화물로 전환시킨 뒤 트리에틸아민 등 촉매 존재 하에서 메틸알코올, 에틸알코올, n-프로필알코올, iso-프로필알코올, n-부틸알코올, t-부틸알코올, n-펜틸알코올, n-헥실알코올, 시클로헥실알코올, n-헵틸알코올, 1,4-디메틸펜틸알코올, n-옥틸알코올, 2-에틸헥실알코올, 미리스틸알코올, 팔미틸알코올, 스테아릴알코올 등 탄소수 1 내지 20의 알킬기를 가지는 알코올과 반응시켜서 얻을 수 있다.Such cyclic olefins are usually obtained by esterification of norbornene carboxylic acid with an alcohol having an alkyl group having 1 to 20 carbon atoms, and in order to improve reactivity, norbornene carboxylic acid is reacted with thionyl chloride to make norbornene. After conversion to n-carboxylic acid chloride, methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, t-butyl alcohol, n-pentyl alcohol, n-hexyl in the presence of a catalyst such as triethylamine Alcohol, cyclohexyl alcohol, n-heptyl alcohol, 1,4-dimethylpentyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, etc. Can be obtained by reacting with alcohol.
구체적으로 본 발명에 의한 환상올레핀계 공중합체를 얻는 방법에 대하여 설명한다.Specifically, the method for obtaining the cyclic olefin copolymer according to the present invention will be described.
먼저 첫 단계로 상기 화학식 1로 표시되는 환상올레핀 단위를 가지는 환상올레핀 중합체는 상기 화학식 1의 환상올레핀 단독중합체 또는 상기 화학식 1의 단위에 포함되는 단량체를 2이상 사용한 이들의 공중합체일 수 있는 환상올레핀 중합체(제1중합체)를 제조한다. 이러한 환상올레핀계 공중합체는 가령 J. Polym. Sci. Polym. Chem., Vol 45, 3042-3052 (2007)에 기재된 바와 같이 상기 화학식 1로 표시되는 환상올레핀 즉, 노르보르넨 카르복실산 알킬에스테르를 촉매 존재 하에서 중합시킴에 따라 얻어진다.  First, the cyclic olefin polymer having a cyclic olefin unit represented by Formula 1 is a cyclic olefin which may be a cyclic olefin homopolymer of Formula 1 or a copolymer of two or more monomers contained in the unit of Formula 1 as a first step. Prepare a polymer (first polymer). Such cyclic olefin copolymers are described, for example, in J. Polym. Sci. Polym. As described in Chem., Vol 45, 3042-3052 (2007), a cyclic olefin represented by Formula 1, ie, norbornene carboxylic acid alkylester, is obtained by polymerization in the presence of a catalyst.
촉매는 특별히 한정되지 않지만 파라디윰 복합체계 촉매. 니켈 복합체계 촉매 등이 좋고 메틸알루미녹산 등 조촉매를 함께 사용할 경우 반응속도, 분자량, 수율 측면에서 더욱 바람직하다. 중합은 헥산, 헵탄, 펜탄, 시클로헥산, 벤젠, 톨루엔 등의 포화 지방족 또는 방향족 탄화수소 등 용매 하에서 진행되는 용액중합법이 바람직하고 연속식 중합, 회분식 중합 등 그 어느 것도 가능하다. 중합온도는 0 내지 200℃ 온도이다. The catalyst is not particularly limited, but is a paradite composite catalyst. Nickel composite catalysts are preferred, and co-catalysts such as methylaluminoxane are more preferred in terms of reaction rate, molecular weight, and yield. The polymerization is preferably a solution polymerization method which proceeds under a solvent such as saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, toluene, and any of these may be continuous polymerization or batch polymerization. Polymerization temperature is 0-200 degreeC temperature.
또한 본 발명에 있어 상기 화학식 1로 표시되는 환상올레핀 단위로 구성된 환상올레핀계 단독중합체 또는 공중합체에서 알킬기의 탄소수는 1 내지 20, 바람직하게는 탄소수 1 내지 8이며, 탄소수가 20을 초과하면 유연성은 우수해지지만 유리전이온도가 너무 낮아질 우려가 있다. 또한 단독 중합체보다는 내열성면에서 유리한 탄소수가 작은 알킬기를 가진 환상올레핀과 유연성 면에서 유리한 탄소수가 큰 환상올레핀을 선택하여 적당하게 혼합비를 조절하여 중합하는 것이 내열성과 유연성을 동시에 부여하기에 용이하다.In the present invention, in the cyclic olefin homopolymer or copolymer composed of the cyclic olefin unit represented by the formula (1), the carbon number of the alkyl group is 1 to 20, preferably 1 to 8 carbon atoms, the flexibility is more than 20 Although excellent, the glass transition temperature may be too low. In addition, it is easy to provide heat resistance and flexibility at the same time by selecting a cyclic olefin having an alkyl group having a lower carbon number advantageous in terms of heat resistance than a homopolymer and a cyclic olefin having a higher carbon number in terms of flexibility and controlling the mixing ratio appropriately.
두 번째 단계로는, 상기 얻어진 화학식 1로 표시되는 환상올레핀 단위로 구성된 환상올레핀계 단독중합체 또는 공중합체를 테트라히드로푸란, 디부틸에테르, 디메톡시에탄 등의 에테르류, 클로로부탄, 브로모헥산, 염화메틸렌, 디클로로에탄, 헥사메틸렌 디브로마이드, 클로로벤젠, 클로로포름, 테트라클로로에틸렌 등의 할로겐화 알칸, 아세트산에틸, 아세트산 n-부틸, 아세트산 iso-부틸, 프로피온산 메틸 등의 포화 카르복실산 에스테르류와 같은 유기용매에 녹인 후 염산, 황산 등 수용액을 첨가하여 용액상태에서 부분가수분해반응을 진행하여 상기 화학식 1의 환상올레핀 단위와 상기 화학식 2의 카르복실산기 함유 환상올레핀 단위를 포함하는 환상올레핀 공중합체(제 2중합체)를 제조한다. 가수분해반응 정도는 카르복실산기 함유량은 전체 고내열투명성 환상올레핀계 공중합체 100 중량% 중에서 0.01 내지 20 중량%, 바람직하게는 0.1 내지 5 중량%를 함유하도록 조절하는 것이 좋다. 카르복실산기 함유량이 0.01 중량% 미만으로 포함될 경우 유사가교구조를 발현할 수 있는 관능기의 부족으로 원하는 낮은 열팽창계수 확보가 곤란하고 20 중량%를 초과할 경우 유리전이온도가 너무 낮아질 우려가 있다. In a second step, the cyclic olefin homopolymer or copolymer composed of the cyclic olefin unit represented by the formula (1) is ethers such as tetrahydrofuran, dibutyl ether, dimethoxyethane, chlorobutane, bromohexane, Organic such as saturated carboxylic acid esters such as halogenated alkanes such as methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform and tetrachloroethylene, ethyl acetate, n-butyl acetate, iso-butyl acetate and methyl propionate After dissolving in a solvent, an aqueous solution such as hydrochloric acid or sulfuric acid is added to perform a partial hydrolysis reaction in a solution state to form a cyclic olefin copolymer comprising a cyclic olefin unit of Formula 1 and a carboxylic acid group-containing cyclic olefin unit of Formula 2 Dipolymer). The degree of hydrolysis reaction may be adjusted so that the carboxylic acid group content contains 0.01 to 20% by weight, preferably 0.1 to 5% by weight in 100% by weight of the total high heat-transparent cyclic olefin copolymer. When the carboxylic acid group content is less than 0.01% by weight, it is difficult to secure a desired low coefficient of thermal expansion due to the lack of functional groups capable of expressing a similar crosslinked structure, and when the content exceeds 20% by weight, the glass transition temperature may be too low.
세 번째 단계로는, 상기 화학식 1로 표시되는 환상올레핀 단위와 상기 화학식 2로 표시되는 카르복실산기 함유 환상올레핀 단위로 구성된 환상올레핀계 공중합체(제 2중합체)를 금속이온으로 부분 또는 전부 중화시켜 제 3중합체를 제조할 수 있다. 중화에 사용되는 금속이온으로서는 리튬이온, 나트륨이온, 칼륨이온 등과 같은 알칼리금속이온, 마그네슘이온, 칼슘이온, 바륨이온 등과 같은 알칼리토금속이온, 니켈이온, 구리이온, 아연이온 등과 같은 전이금속이온 등의 금속이온을 포함하며, 상기 금속이온은 (+)이온과 (-)이온이 복합체(complex)를 이룬 형태를 포함할 수 있다. 바람직하게는 나트륨이온, 아연이온 등이 좋다. In the third step, the cyclic olefin copolymer (second polymer) composed of the cyclic olefin unit represented by the formula (1) and the carboxylic acid group-containing cyclic olefin unit represented by the formula (2) is partially or completely neutralized with metal ions. A third polymer can be prepared. Examples of metal ions used for neutralization include alkali metal ions such as lithium ions, sodium ions and potassium ions, alkaline earth metal ions such as magnesium ions, calcium ions and barium ions, and transition metal ions such as nickel ions, copper ions and zinc ions. Including a metal ion, the metal ion may include a form in which a (+) ion and a (−) ion form a complex. Preferably sodium ions, zinc ions and the like.
중화반응은 상기 화학식 1로 표시되는 환상올레핀 단위와 상기 화학식 2로 표시되는 카르복실산기 함유 환상올레핀 단위로 구성된 환상올레핀계 공중합체(제 2중합체)를 테트라히드로푸란, 디부틸에테르, 디메톡시에탄 등의 에테르류, 클로로부탄, 브로모헥산, 염화메틸렌, 디클로로에탄, 헥사메틸렌 디브로마이드, 클로로벤젠, 클로로포름, 테트라클로로에틸렌 등의 할로겐화 알칸, 아세트산에틸, 아세트산 n-부틸, 아세트산 iso-부틸, 프로피온산 메틸 등의 포화 카르복실산 에스테르류와 같은 유기용매에 녹인 후 물 또는 상기 유기용매에 녹인 금속수산화물, 금속산화물, 금속탄산화물, 금속황산화물 등 금속이온을 함유하는 화합물을 첨가하여 용액상태에서 반응시키는 방법이 있고, 상기 화학식 1로 표시되는 환상올레핀 단위와 상기 화학식 2로 표시되는 카르복실산기 함유 환상올레핀 단위로 구성된 환상올레핀계 공중합체(제 2중합체)를 충분한 반응시간을 줄 수 있는 L/D가 긴 압출기에 투입하여 용융시키고 금속이온을 함유한 화합물을 첨가하여 중화반응을 시키는 방법이 있다. 본 발명에 의한 중화반응은 전부 또는 부분 중화반응 모두 해당되며 이 반응을 시킴으로써 제 3중합체를 얻을 수 있는데, 전부 중화반응을 시켜 얻어진 제 3중합체내에서 카르복실산금속염기 함유량은 0.05 내지 40 중량%, 바람직하게는 0.5 내지 20 중량%를 함유하도록 조절하는 것이 좋다. 카르복실산금속염기 함유량이 0.05 중량% 미만으로 포함될 경우 유사가교구조를 발현할 수 있는 관능기의 부족으로 원하는 낮은 열팽창계수 확보가 곤란하고 40 중량%를 초과할 경우 유리전이 온도가 너무 낮아질 우려가 있다. 또한 부분 중화반응을 시켜 얻어진 제 3중합체내에서 카르복실산기 및 카르복실산금속염기 총함유량은 0.02 내지 30 중량%, 바람직하게는 0.2 내지 15 중량%를 함유하도록 조절하는 것이 좋다. 카르복실산기 및 카르복실산금속염기 함유량이 0.02 중량% 미만으로 포함될 경우 유사가교구조를 발현할 수 있는 관능기의 부족으로 원하는 낮은 열팽창계수 확보가 곤란하고 30 중량%를 초과할 경우 유리전이 온도가 너무 낮아질 우려가 있다. The neutralization reaction is carried out using tetrahydrofuran, dibutyl ether, dimethoxyethane, or a cyclic olefin copolymer (second polymer) composed of a cyclic olefin unit represented by Formula 1 and a carboxylic acid group-containing cyclic olefin unit represented by Formula 2. Ethers such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, halogenated alkanes such as chloroform, tetrachloroethylene, ethyl acetate, n-butyl acetate, iso-butyl acetate and propionic acid It is dissolved in an organic solvent such as saturated carboxylic acid esters such as methyl, and then reacted in a solution state by adding a compound containing metal ions such as water or a metal hydroxide, a metal oxide, a metal carbonate or a metal sulfur oxide dissolved in the organic solvent. And a cyclic olefin unit represented by Formula 1 and represented by Formula 2 The cyclic olefin copolymer (second polymer) composed of the carboxylic acid group-containing cyclic olefin unit is added to a long L / D extruder which can give a sufficient reaction time, and melted, and a compound containing a metal ion is added to neutralize the reaction. There is a way to make it. The neutralization reaction according to the present invention corresponds to all or partial neutralization reactions, and a third polymer can be obtained by carrying out this reaction. The content of the metal carboxylate base in the third polymer obtained by the total neutralization reaction is 0.05 to 40% by weight. Preferably, it is adjusted to contain 0.5 to 20% by weight. If the content of the metal carboxylate base is less than 0.05% by weight, it is difficult to secure a desired low coefficient of thermal expansion due to the lack of functional groups capable of expressing a similar crosslinked structure, and if the content exceeds 40% by weight, the glass transition temperature may be too low. . In addition, the total content of the carboxylic acid group and the metal carboxylate group in the third polymer obtained by the partial neutralization reaction may be adjusted to contain 0.02 to 30% by weight, preferably 0.2 to 15% by weight. If the content of carboxylic acid group and metal carboxylate base is less than 0.02% by weight, it is difficult to secure a desired low coefficient of thermal expansion due to the lack of functional groups capable of expressing a similar crosslinked structure, and the glass transition temperature is too high if it exceeds 30% by weight. It may be lowered.
본 발명에 의한 환상올레핀계 공중합체의 중량평균분자량은 1,000 내지 1,000,000, 바람직하게는 10,000 내지 500,000, 더욱 바람직하게는 50,000 내지 300,000인 범위에서 필름 물성 및 성형성이 우수하다. The weight average molecular weight of the cyclic olefin copolymer according to the present invention is excellent in film properties and moldability in the range of 1,000 to 1,000,000, preferably 10,000 to 500,000, more preferably 50,000 to 300,000.
또한 본 발명의 목적을 손상시키지 않는 범위에서 본 발명에 의한 환상올레핀계 공중합체내에 무기입자, 산화방지제, 자외선차단제, 윤활제 등 통상의 첨가제를 추가할 수 있다. In addition, conventional additives such as inorganic particles, antioxidants, sunscreens, lubricants, and the like may be added to the cyclic olefin copolymer according to the present invention without departing from the object of the present invention.
또한 본 발명에 의한 필름형 플렉시블 기판은 통상의 용매캐스팅방법 또는 용융압출방법에 의해 제조될 수 있다. 즉 먼저 본 발명에 의한 환상올레핀계 공중합체 수지를 용매에 녹이고 기포를 제거한 다음 적정 기재 위에 캐스팅하고 용매를 건조함으로서 필름형 플렉시블 기판이 완성되거나 또는 본 발명에 의한 환상올레핀계 공중합체 수지 펠렛을 호퍼를 통해 압출기에 투입하고, 실린더를 통해 용융압출하여 티다이로 통과시켜 나오는 필름을 캐스팅 냉각롤에서 냉각하고 권취롤에 권취하여 최종 필름형 플렉시블 기판이 완성된다. In addition, the film-like flexible substrate according to the present invention can be produced by a conventional solvent casting method or a melt extrusion method. That is, first, the cyclic olefin copolymer resin according to the present invention is dissolved in a solvent, bubbles are removed, cast on a suitable substrate, and the solvent is dried to complete a film-type flexible substrate, or the cyclic olefin copolymer resin pellet according to the present invention is hopper. The film is poured into an extruder, melt-extruded through a cylinder, and passed through a T-die to cool the film on a casting cooling roll and wound on a take-up roll, thereby completing a final film-like flexible substrate.
전술한 바와 같이 본 발명에 의한 환상올레핀계 공중합체는 분자 내 일부 긴 가지를 가지고 있어 탁월한 유연성을 발휘할 뿐만 아니라 함유된 카르복실산기 또는 카르복실산금속염기간의 수소결합, 정전기력 등 강한 2차 결합력에 의한 분자회합에 따른 유사가교구조를 발현함으로써 자유부피가 크게 감소해 극히 낮은 열팽창계수를 발휘함은 물론 종래 환상올레핀계 수지의 장점인 높은 유리전이온도 및 우수한 투명성, 등방성 등을 동시에 가지는 실로 획기적인 것으로 이러한 수지로 부터 얻어진 플렉시블 기판은 플렉시블 디스플레이, 플렉시블 태양전지 등 여러 분야에 유용하게 사용될 수 있다.As described above, the cyclic olefin copolymer according to the present invention has some long branches in the molecule and thus exhibits excellent flexibility, and also has strong secondary bonding strength such as hydrogen bonding and electrostatic force in the carboxylic acid group or carboxylate metal salt period. By expressing the pseudo-crosslinked structure by molecular association, the free volume is greatly reduced, resulting in extremely low coefficient of thermal expansion as well as high glass transition temperature, excellent transparency, and isotropy, which are advantages of conventional cyclic olefin resins. The flexible substrate obtained from such a resin can be usefully used in various fields such as a flexible display and a flexible solar cell.
이하, 실시예 및 비교예를 들어 본 발명을 구체적으로 설명하는데, 본 발명이 이들 실시예에 한정되는 것은 아니다.Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these Examples.
하기 실시예 및 비교예에 따라 제조된 환상올레핀계 공중합체 수지의 중량평균분자량 및 이러한 수지로부터 얻어진 필름형 기판에 대한 유연성, 열팽창계수, 유리전이온도, 투명성, 등방성 등을 다음과 같이 측정하였다.The weight average molecular weight of the cyclic olefin copolymer resins prepared according to the following Examples and Comparative Examples and the flexibility, thermal expansion coefficient, glass transition temperature, transparency, isotropy and the like of the film-like substrates obtained from these resins were measured as follows.
(중량평균분자량)(Weight average molecular weight)
수지에 대한 중량평균분자량은 GPC(Waters 150C)를 이용하여 140℃하에서, 용매로 o-디클로로벤젠을 사용하고 표준물로는 폴리스티렌을 사용하여 측정하였다.The weight average molecular weight for the resin was measured at 140 ° C. using GPC (Waters 150C), using o-dichlorobenzene as solvent and polystyrene as standard.
(유연성)(flexibility)
유연성에 대한 척도로서 25mm(폭), 150mm(길이) 크기의 필름형 기판 시편을MIT형 굴곡시험기(TMI, MIT type Folding Endurance Tester)에 장착한 후 ASTM-D2176에 의거하여 굴곡각 135도, 굴곡반복속도 50mm/분 조건하에서 굴곡시킨 후에도 손상이 없을 때의 최대 횟수(cycles)를 기준하여 유연성의 평가기준을 만들어 그 결과를 [표 1]에 나타내었다.As a measure of flexibility, a 25mm (width) and 150mm (length) sized film-type substrate was mounted on an MIT type folding endurance tester (TMI), and the bending angle was 135 degrees according to ASTM-D2176. The evaluation criteria for flexibility were made based on the maximum number of cycles when there was no damage even after bending under the repetition rate of 50 mm / min. The results are shown in [Table 1].
[표 1]TABLE 1
Figure PCTKR2012006274-appb-I000007
Figure PCTKR2012006274-appb-I000007
(열팽창계수)(Coefficient of Thermal Expansion)
내열성에 대한 척도로서 TMA(Thermomechanical analyzer, Perkin Elmer TMA-7)에서 ASTM E831에 근거하여 3mm(폭), 30mm(세로), 80㎛(두께) 크기의 필름형 기판 시편에 대한 열팽창계수(ppm/℃)를 측정하였다.Thermal expansion coefficient (ppm / ppm) for film-type substrate specimens of 3 mm (width), 30 mm (length), and 80 μm (thickness) sizes, based on ASTM E831, on the Thermomechanical Analyzer (TMA) (Perkin Elmer TMA-7) as a measure for heat resistance. ℃) was measured.
(유리전이온도)(Glass transition temperature)
내열성에 대한 척도로서 DSC(Differential Scanning Calorimeter, DuPont 910)에서 질소 분위기, 냉각속도 10℃/분 조건으로 필름형 기판 시편에 대한 유리전이온도(℃)를 측정하였다.As a measure of heat resistance, the glass transition temperature (° C.) of the film-type substrate was measured in a DSC (Differential Scanning Calorimeter, DuPont 910) under a nitrogen atmosphere and a cooling rate of 10 ° C./min.
(투명성)(Transparency)
투명성에 대한 척도로서 ASTM D1003에 준하여 Hazemeter(Toyoseiki, Direct Reading Hazemeter)를 이용하여 필름형 기판 시편에 대한 광투과도(%)를 측정하였다.As a measure of transparency, the light transmittance (%) of the film-type substrate was measured using a Hazemeter (Toyoseiki, Direct Reading Hazemeter) according to ASTM D1003.
(등방성)(Isotropic)
등방성에 대한 척도로서 Parallel nicols 방법에 의한 편광현미경(Oji Scientific Instruments, Automatic Birefringence Analyzer Kobra-WR)을 이용해 필름형 기판 시편에 대한 복굴절(㎚)를 평가하였다. As a measure for isotropy, birefringence (nm) of the film-type substrate specimens was evaluated using a polarized microscope (Oji Scientific Instruments, Automatic Birefringence Analyzer Kobra-WR) by the parallel nicols method.
[실시예 1]Example 1
촉매제조용 플라스크에 파라디윰(II)아세테이트 7.9g, 트리시클로헥실포스핀 7.7g 및 용매 클로로벤젠 8L를 넣고 교반하였다. 이후 여기에 페닐카르베니윰 테트라키스(펜타플루오르페닐)보레이트 19.5g을 넣고 교반해서 파라디윰 복합체계 촉매 용액을 제조하였다. 7.9 g of paradigm (II) acetate, 7.7 g of tricyclohexylphosphine and 8 L of solvent chlorobenzene were added to the catalyst preparation flask and stirred. Thereafter, 19.5 g of phenylcarbenicit tetrakis (pentafluorophenyl) borate was added thereto, followed by stirring to prepare a paradigm complex catalyst solution.
한편 교반기가 장착된 반응기에 노르보르넨 카르복실산 메틸에스테르 4.98kg과 용매 톨루엔 5L를 투입하고 교반하다가 미리 준비한 상기 파라디윰 복합체계 촉매 용액 전체를 투입하고 100℃, 1시간 동안 교반하면서 중합반응을 진행하였다. 중합반응을 종결한 후 약 400L 메틸알코올에 생성된 수지를 침전시키고 여과한 뒤 12시간 진공건조 함으로써 노르보르넨 카르복실산 메틸에스테르 단독 중합체(A)수지를 얻었다. Meanwhile, 4.98 kg of norbornene carboxylic acid methyl ester and 5 L of solvent toluene were added to a reactor equipped with a stirrer, followed by stirring. Then, the entire paradigm complex catalyst solution prepared in advance was added thereto, followed by polymerization at 100 ° C. for 1 hour. Proceeded. After completion of the polymerization reaction, the resin produced in about 400 L methyl alcohol was precipitated, filtered, and vacuum dried for 12 hours to obtain norbornene carboxylic acid methyl ester homopolymer (A) resin.
얻어진 노르보르넨 카르복실산 메틸에스테르 단독 중합체(A)수지 1Kg를 테트라히드로푸란/물(9/1, 부피비) 혼합용매 2L에 녹이고 염산 0.2L를 첨가한 후 50℃에서 10시간 교반하면서 부분가수분해반응을 진행시켜 생성된 수지를 메틸알코올에 침전시키고 여과한 뒤 12시간 진공건조 함으로써 카르복실산기 함량 3.9 중량%, 중량평균분자량 220,000의 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 공중합체(B)수지를 얻었다. 1 Kg of the obtained norbornene carboxylic acid methyl ester homopolymer (A) resin was dissolved in 2 L of a mixed solvent of tetrahydrofuran / water (9/1, volume ratio), 0.2 L of hydrochloric acid was added, followed by stirring at 50 ° C. for 10 hours. The resin produced by the decomposition reaction was precipitated in methyl alcohol, filtered, and vacuum dried for 12 hours. The norbornene carboxylic acid methyl ester-norbornene carboxylic acid having a carboxylic acid group content of 3.9% by weight and a weight average molecular weight of 220,000 was obtained. Copolymer (B) resin was obtained.
얻어진 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 공중합체(B)수지를 용매 테트라히드로푸란에 녹여 20 중량% 용액으로 만들었고 용매캐스팅 방법에 의해 유리기판위에 캐스팅하고 건조하여 최종 두께 80㎛의 필름형 플렉시블 기판 시편을 얻었고, 이 시편에 대한 유연성, 열팽창계수, 유리전이온도, 광투과도 및 복굴절을 평가하여 그 결과를 표 2에 나타내었다.The obtained norbornene carboxylic acid methyl ester-norbornene carboxylic acid copolymer (B) resin was dissolved in a solvent tetrahydrofuran to make a 20% by weight solution, cast on a glass substrate by a solvent casting method, and dried to obtain a final thickness of 80 Film-like flexible substrate specimens were obtained, and the flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated for the specimens, and the results are shown in Table 2.
[실시예 2]Example 2
실시예 1에서 얻어진 노르보르넨 카르복실산 메틸에스테르 단독 중합체(A)수지에 대한 부분가수분해반응을 24시간 연장 실시하여 카르복실산기 함량 7.1 중량%, 중량평균분자량 192,000의 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 공중합체(C)수지를 얻었다. The partial hydrolysis reaction on the norbornene carboxylic acid methyl ester homopolymer (A) resin obtained in Example 1 was extended for 24 hours to produce a norbornene carboxylic acid having 7.1% by weight of a carboxylic acid group content and a weight average molecular weight of 192,000. The methyl ester-norbornene carboxylic acid copolymer (C) resin was obtained.
얻어진 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 공중합체(C)수지를 용매 테트라히드로푸란에 녹여 20 중량% 용액으로 만들고 용매캐스팅 방법에 의해 유리기판위에 캐스팅하고 건조하여 최종 두께 80㎛의 필름형 플렉시블 기판 시편을 얻었고, 이 시편에 대한 유연성, 열팽창계수, 유리전이온도, 광투과도 및 복굴절을 평가하였고 그 결과를 표 2에 나타내었다.The obtained norbornene carboxylic acid methyl ester-norbornene carboxylic acid copolymer (C) resin was dissolved in a solvent tetrahydrofuran to make a 20% by weight solution, cast on a glass substrate by a solvent casting method, dried and the final thickness 80 Film-like flexible substrate specimens were obtained, and the flexibility, thermal expansion coefficient, glass transition temperature, light transmittance and birefringence were evaluated for the specimens and the results are shown in Table 2.
[실시예 3] Example 3
단량체로서 노르보르넨 카르복실산 메틸에스테르 80몰%와 공단량체인 노르보르넨 카르복실산 n-헥실에스테르 20몰%의 조성비로 조절해 실시예 1과 동일한 방법으로 실시하여 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 n-헥실에스테르 공중합체(D)수지를 얻었고 실시예 1과 같은 방법으로 부분가수분해반응을 실시하여 카르복실산기 함량 7.8 중량%의 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 n-헥실에스테르-노르보르넨 카르복실산 공중합체(E)수지를 얻었다. Norbornene carboxylic acid was carried out in the same manner as in Example 1 by adjusting the composition ratio of 80 mol% of norbornene carboxylic acid methyl ester as a monomer and 20 mol% of norbornene carboxylic acid n-hexyl ester as a comonomer. The methyl ester-norbornene carboxylic acid n-hexyl ester copolymer (D) resin was obtained, and partial hydrolysis reaction was carried out in the same manner as in Example 1 to obtain methyl norbornene carboxylic acid having a carboxylic acid group content of 7.8% by weight. Ester-norbornene carboxylic acid n-hexyl ester-norbornene carboxylic acid copolymer (E) resin was obtained.
얻어진 공중합체(E)수지 1Kg를 테트라히드로푸란/물(9/1, 부피비) 혼합용매 2L에 녹였고 아연아세테이트 120g를 첨가한 후 50℃에서 10시간 교반하면서 부분중화반응을 진행시켜 생성된 수지를 침전시키고 여과한 뒤 12시간 진공건조 함으로써 카르복실산기 함량 5.6 중량%, 카르복실산아연염기 함량 3.6 중량%, 중량평균분자량 270,000의 환상올레핀계 공중합체(F)수지를 얻었다. 얻어진 환상올레핀계 공중합체(F)수지를 용매 테트라히드로푸란에 녹여 20 중량% 용액으로 만들고 용매캐스팅 방법에 의해 유리기판위에 캐스팅하고 건조하여 최종 두께 80㎛의 필름형 플렉시블 기판 시편을 얻었고, 이 시편에 대한 유연성, 열팽창계수, 유리전이온도, 광투과도 및 복굴절을 평가하여 그 결과를 표 2에 나타내었다.Resin 1Kg of the obtained copolymer (E) resin was dissolved in 2L of a mixed solvent of tetrahydrofuran / water (9/1, volume ratio) and 120 g of zinc acetate was added, followed by partial neutralization with stirring at 50 ° C. for 10 hours. The precipitate was filtered and dried in vacuo for 12 hours to obtain a cyclic olefin copolymer (F) resin having a carboxylic acid group content of 5.6 wt%, a zinc carboxylate base content of 3.6 wt% and a weight average molecular weight of 270,000. The obtained cyclic olefin copolymer (F) resin was dissolved in a solvent tetrahydrofuran to make a 20 wt% solution, cast on a glass substrate by a solvent casting method, and dried to obtain a film-like flexible substrate specimen having a final thickness of 80 μm. The flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated. The results are shown in Table 2.
[실시예 4] Example 4
실시예 3에서 얻어진 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 n-헥실에스테르-노르보르넨 카르복실산 공중합체(E)수지 1Kg를 테트라히드로푸란/물(9/1, 부피비) 혼합용매 2L에 녹였고 아연아세테이트 240g를 첨가한 후 50℃에서 36시간 교반하여 완전중화를 시켜 생성된 수지를 침전시키고 여과한 뒤 12시간 진공건조 함으로써 카르복실산아연염기 함량 12.8 중량%, 중량평균분자량 235,000의 환상올레핀계 공중합체(G)수지를 얻었다. 1 kg of norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-hexyl ester-norbornene carboxylic acid copolymer (E) resin obtained in Example 3 is added tetrahydrofuran / water (9/1, volume ratio) ) Dissolved in 2L of mixed solvent and added 240g of zinc acetate, stirred at 50 ℃ for 36 hours to completely neutralize the precipitated resin, precipitated and filtered and vacuum dried for 12 hours to give 12.8% by weight of zinc carboxylate. A cyclic olefin copolymer (G) resin having an average molecular weight of 235,000 was obtained.
얻어진 환상올레핀계 공중합체(G)수지를 용매 테트라히드로푸란에 녹여 20 중량% 용액으로 만들었고 용매캐스팅 방법에 의해 유리기판위에 캐스팅하고 건조하여 최종 두께 80㎛의 필름형 플렉시블 기판 시편을 얻었고, 이 시편에 대한 유연성, 열팽창계수, 유리전이온도, 광투과도 및 복굴절을 평가하여 그 결과를 표 2에 나타내었다.The obtained cyclic olefin copolymer (G) resin was dissolved in a solvent tetrahydrofuran to make a 20 wt% solution, cast on a glass substrate by a solvent casting method, and dried to obtain a film-like flexible substrate specimen having a final thickness of 80 μm. The flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated. The results are shown in Table 2.
[실시예 5] Example 5
단량체로서 노르보르넨 카르복실산 메틸에스테르 90몰%와 공단량체인 노르보르넨 카르복실산 n-옥틸에스테르 10몰%의 조성비로 조절하여 실시예 1과 동일한 방법으로 실시하여 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 n-옥틸에스테르 공중합체(H)수지를 얻었다. Norbornene carboxylic acid was carried out in the same manner as in Example 1 by adjusting the composition ratio of 90 mol% of norbornene carboxylic acid methyl ester as a monomer and 10 mol% of norbornene carboxylic acid n-octyl ester as a comonomer. The methyl ester-norbornene carboxylic acid n-octyl ester copolymer (H) resin was obtained.
이어서 실시예 1과 같은 방법으로 부분가수분해반응을 실시하여 카르복실산기 함량 10.2 중량%의 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 n-옥틸에스테르-노르보르넨 카르복실산 공중합체(I)수지를 얻은 뒤 이를 실시예 3과 같은 방법으로 부분중화반응을 실시하여 최종적으로 카르복실산기 함량 8.9 중량%, 카르복실산아연염기 함량 2.1 중량%, 중량평균분자량 295,000의 환상올레핀계 공중합체(J)수지를 얻었다. 얻어진 환상올레핀계 공중합체(J)수지를 용매 테트라히드로푸란에 녹여 20 중량% 용액으로 만들었고 용매캐스팅 방법에 의해 유리기판위에 캐스팅하고 건조하여 최종 두께 80㎛의 필름형 플렉시블 기판 시편을 얻었고, 이 시편에 대한 유연성, 열팽창계수, 유리전이온도, 광투과도 및 복굴절을 평가하여 그 결과를 표 2에 나타내었다.Subsequently, the partial hydrolysis reaction was carried out in the same manner as in Example 1 to form norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-octyl ester-norbornene carboxylic acid having a carboxylic acid group content of 10.2% by weight. After obtaining the copolymer (I) resin, it was subjected to partial neutralization reaction in the same manner as in Example 3, and finally, a cyclic olefin system having a content of 8.9% by weight of carboxylic acid group, 2.1% by weight of zinc carboxylate group, and a weight average molecular weight of 295,000. Copolymer (J) resin was obtained. The obtained cyclic olefin copolymer (J) resin was dissolved in a solvent tetrahydrofuran to make a 20 wt% solution, cast on a glass substrate by a solvent casting method, and dried to obtain a film-like flexible substrate specimen having a final thickness of 80 μm. The flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated. The results are shown in Table 2.
[실시예 6] Example 6
먼저 실시예 5에서 얻어진 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 n-옥틸에스테르-노르보르넨 카르복실산 공중합체(I)수지 30중량부와 산화아연 70중량부로 혼합한 조성물을 L/D 40인 이축압출기에서 혼련시켜 산화아연 마스터뱃치 펠렛(A)을 준비하였다.  First, a composition of norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-octyl ester-norbornene carboxylic acid copolymer (I) resin obtained in Example 5 was mixed with 30 parts by weight of resin and 70 parts by weight of zinc oxide. The mixture was kneaded in an L / D 40 twin screw extruder to prepare a zinc oxide masterbatch pellet (A).
이어서 상기 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 n-헥실에스테르-노르보르넨 카르복실산 공중합체(I)수지 펠렛 100중량부에 대해 산화아연 마스터뱃치 펠렛(A) 10중량부를 혼합한 조성물을 호퍼에 투입하여 스크류 직경 70㎜이고, L/D 40인 이축 압출기에 주입하고 용융 압출 중화반응을 시켜 최종적으로 카르복실산기 함량 6.4 중량%, 카르복실산아연염기 함량 6.1 중량%, 중량평균분자량 295,000의 환상올레핀계 공중합체(K)수지를 얻었다. 10 weight parts of zinc oxide masterbatch pellets (A) to 100 parts by weight of the norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-hexyl ester-norbornene carboxylic acid copolymer (I) resin pellets. The mixed composition was added to a hopper and injected into a twin screw extruder having a screw diameter of 70 mm and L / D 40, followed by melt extrusion neutralization to finally give a carboxylic acid group content of 6.4 wt% and a zinc carboxylate base content of 6.1 wt%. And cyclic olefin copolymer (K) resin having a weight average molecular weight of 295,000 were obtained.
얻어진 환상올레핀계 공중합체(K)수지 펠렛을 호퍼에 투입하여 스크류 직경 70㎜이고, L/D 36인 압출기에 주입하였고 용융 압출시켜 티다이를 통해 두께 80㎛의 필름형 플렉시블 기판 시편을 얻었고, 이 시편에 대한 유연성, 열팽창계수, 유리전이온도, 광투과도 및 복굴절을 평가하여 그 결과를 표 2에 나타내었다.The obtained cyclic olefin copolymer (K) resin pellet was introduced into a hopper, injected into an extruder having a screw diameter of 70 mm and L / D 36, and melt-extruded to obtain a film-shaped flexible substrate specimen having a thickness of 80 μm through a Ti die. The flexibility, thermal expansion coefficient, glass transition temperature, light transmittance and birefringence of the specimens were evaluated and the results are shown in Table 2.
[실시예 7] Example 7
실시예 1에서 얻어진 카르복실산기 함량 3.9 중량%의 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 공중합체(B)수지 1Kg를 테트라히드로푸란/물(9/1, 부피비) 혼합용매 2L에 녹였고 아연아세테이트 50g를 첨가한 후 50℃에서 8시간 교반하면서 부분중화반응을 진행시켜 생성된 수지를 침전시키고 여과한 뒤 12시간 진공건조 함으로써 카르복실산기 함량 2.8 중량%, 카르복실산아연염기 함량 2.5 중량%, 중량평균분자량 230,000의 환상올레핀계 공중합체(L)수지를 얻었다. 얻어진 환상올레핀계 공중합체(L)수지를 용매 테트라히드로푸란에 녹여 20 중량% 용액으로 만들고 용매캐스팅 방법에 의해 유리기판위에 캐스팅하고 건조하여 최종 두께 80㎛의 필름형 플렉시블 기판 시편을 얻었고, 이 시편에 대한 유연성, 열팽창계수, 유리전이온도, 광투과도 및 복굴절을 평가하여 그 결과를 표 2에 나타내었다.1 kg of the norbornene carboxylic acid methyl ester-norbornene carboxylic acid copolymer (B) resin having a carboxylic acid group content of 3.9% by weight in Example 1 was mixed with a tetrahydrofuran / water (9/1, volume ratio) mixed solvent. It was dissolved in 2L and 50g of zinc acetate was added, followed by partial neutralization with stirring at 50 ° C. for 8 hours to precipitate the resulting resin, followed by filtration and drying in vacuo for 12 hours to carboxylic acid group content of 2.8% by weight and zinc carboxylic acid. A cyclic olefin copolymer (L) resin having a base content of 2.5 wt% and a weight average molecular weight of 230,000 was obtained. The obtained cyclic olefin copolymer (L) resin was dissolved in a solvent tetrahydrofuran to make a 20 wt% solution, cast on a glass substrate by a solvent casting method, and dried to obtain a film-like flexible substrate specimen having a final thickness of 80 μm. The flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated. The results are shown in Table 2.
[실시예 8] Example 8
실시예 3에서 얻어진 카르복실산기 함량 7.8 중량%의 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 n-헥실에스테르-노르보르넨 카르복실산 공중합체(E)수지를 용매 테트라히드로푸란에 녹여 20 중량% 용액으로 만들고 용매캐스팅 방법에 의해 유리기판위에 캐스팅하고 건조하여 최종 두께 80㎛의 필름형 플렉시블 기판 시편을 얻었고, 이 시편에 대한 유연성, 열팽창계수, 유리전이온도, 광투과도 및 복굴절을 평가하여 그 결과를 표 2에 나타내었다.Norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-hexyl ester-norbornene carboxylic acid copolymer (E) resin of 7.8 weight% of carboxylic acid group contents obtained in Example 3 is a solvent tetrahydrofuran Was dissolved in a 20% by weight solution, cast on a glass substrate by a solvent casting method, and dried to obtain a film-like flexible substrate specimen having a final thickness of 80 μm. The flexibility, thermal expansion coefficient, glass transition temperature, light transmittance and birefringence of the specimen were obtained. Was evaluated and the results are shown in Table 2.
[실시예 9] Example 9
실시예 5에서 얻어진 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 n-옥틸에스테르 공중합체(H)수지를 부분가수분해반응을 실시하여 카르복실산기 함량 25.3 중량%, 중량평균분자량 310,000의 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 n-옥틸에스테르-노르보르넨 카르복실산 공중합체(M)수지를 얻었다. 얻어진 환상올레핀계 공중합체(M)수지를 용매 테트라히드로푸란에 녹여 20 중량% 용액으로 만들었고 용매캐스팅 방법에 의해 유리기판위에 캐스팅하고 건조하여 최종 두께 80㎛의 필름형 플렉시블 기판 시편을 얻었고, 이 시편에 대한 유연성, 열팽창계수, 유리전이온도, 광투과도 및 복굴절을 평가하여 그 결과를 표 2에 나타내었다.Partial hydrolysis reaction of the norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-octyl ester copolymer (H) resin obtained in Example 5 was carried out to give a carboxylic acid group content of 25.3% by weight and a weight average molecular weight of 310,000. The norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-octyl ester-norbornene carboxylic acid copolymer (M) resin was obtained. The obtained cyclic olefin copolymer (M) resin was dissolved in a solvent tetrahydrofuran to make a 20 wt% solution, cast on a glass substrate by a solvent casting method, and dried to obtain a film-like flexible substrate specimen having a final thickness of 80 μm. The flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated. The results are shown in Table 2.
[실시예 10] Example 10
실시예 3에서 얻어진 카르복실산기 함량 7.8 중량%의 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 n-헥실에스테르-노르보르넨 카르복실산 공중합체(E)수지 1Kg를 테트라히드로푸란/물(9/1, 부피비) 혼합용매 2L에 녹였고 리튬아세테이트 80g를 첨가한 후 50℃에서 10시간 교반하면서 부분중화반응을 진행시켜 생성된 수지를 침전시키고 여과한 뒤 12시간 진공건조 함으로써 카르복실산기 함량 6.1 중량%, 카르복실산리튬염기 함량 1.9 중량%, 중량평균분자량 260,000의 환상올레핀계 공중합체(N)수지를 얻었다. 얻어진 환상올레핀계 공중합체(N)수지를 용매 테트라히드로푸란에 녹여 20 중량% 용액으로 만들고 용매캐스팅 방법에 의해 유리기판위에 캐스팅하고 건조하여 최종 두께 80㎛의 필름형 플렉시블 기판 시편을 얻었고, 이 시편에 대한 유연성, 열팽창계수, 유리전이온도, 광투과도 및 복굴절을 평가하여 그 결과를 표 2에 나타내었다.1 kg of norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-hexyl ester-norbornene carboxylic acid copolymer (E) resin of the carboxylic acid group content 7.8 weight% obtained in Example 3 was made into tetrahydrofuran. / Water (9/1, volume ratio) was dissolved in 2L of mixed solvent, and 80 g of lithium acetate was added, followed by partial neutralization reaction with stirring at 50 ° C. for 10 hours to precipitate the resulting resin, filtered and dried under vacuum for 12 hours. A cyclic olefin copolymer (N) resin having an acid group content of 6.1 wt%, a lithium carboxylate base content 1.9 wt%, and a weight average molecular weight of 260,000 was obtained. The obtained cyclic olefin copolymer (N) resin was dissolved in a solvent tetrahydrofuran to make a 20 wt% solution, cast on a glass substrate by a solvent casting method, and dried to obtain a film-shaped flexible substrate specimen having a final thickness of 80 μm. The flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated. The results are shown in Table 2.
[비교예 1]Comparative Example 1
상기 실시예 1에서 얻어진 노르보르넨 카르복실산 메틸에스테르 단독 중합체(A)수지를 사용하여 부분가수분해반응 없이 용매 테트라히드로푸란에 녹여 20 중량%용액으로 만들었고 용매캐스팅 방법에 의해 유리기판위에 캐스팅하고 건조하여 최종 두께 80㎛의 필름형 플렉시블 기판 시편을 얻었고, 이 시편에 대한 유연성, 열팽창계수, 유리전이온도, 광투과도 및 복굴절을 평가하여 그 결과를 표 2에 나타내었다. The norbornene carboxylic acid methyl ester homopolymer (A) resin obtained in Example 1 was dissolved in a solvent tetrahydrofuran without partial hydrolysis to make a 20% by weight solution, and cast on a glass substrate by a solvent casting method. After drying, a film-like flexible substrate specimen having a final thickness of 80 μm was obtained. The flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated for the specimen, and the results are shown in Table 2.
[비교예 2]Comparative Example 2
상기 실시예 3에서 얻어진 노르보르넨 카르복실산 메틸에스테르-노르보르넨 카르복실산 n-헥실에스테르 공중합체(D)수지를 사용하여 부분가수분해반응 없이 용매 테트라히드로푸란에 녹여 20 중량% 용액으로 만들었고 용매캐스팅 방법에 의해 유리기판위에 캐스팅하고 건조하여 최종 두께 80㎛의 필름형 플렉시블 기판 시편을 얻었고, 이 시편에 대한 유연성, 열팽창계수, 유리전이온도, 광투과도 및 복굴절을 평가하여 그 결과를 표 2에 나타내었다. The norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-hexyl ester copolymer (D) resin obtained in Example 3 was dissolved in a solvent tetrahydrofuran without partial hydrolysis reaction to a 20 wt% solution. After casting on a glass substrate by the solvent casting method and drying, a film-like flexible substrate specimen having a final thickness of 80 µm was obtained. The flexibility, thermal expansion coefficient, glass transition temperature, light transmittance, and birefringence were evaluated for the specimen. 2 is shown.
[표 2]TABLE 2
Figure PCTKR2012006274-appb-I000008
Figure PCTKR2012006274-appb-I000008
상기 표 2에서 보이는 바와 같이, 실시예 1 내지 실시예 10을 살펴볼 때, 카르복실산기 또는 카르복실산금속염기 함유 환상올레핀계 공중합체는 탁월한 유연성 및 극히 낮은 열팽창계수를 가질 뿐 만 아니라 종래 환상올레핀계 수지의 장점인 높은 유리전이온도에 의한 내열성, 우수한 투명성 및 등방성을 동시에 가짐을 알 수 있다. As shown in Table 2, when looking at Examples 1 to 10, the carboxylic acid group or metal carboxylate-containing cyclic olefin copolymer not only has excellent flexibility and extremely low coefficient of thermal expansion, but also conventional cyclic olefin It can be seen that it has both heat resistance, excellent transparency and isotropy due to the high glass transition temperature, which are advantages of the resin.
특히 실시예 3 내지 실시예 6과 비교예 1을 비교해 볼 때 유리전이온도, 투명성 및 등방성면에서는 상호 유사하지만 유연성 및 열팽창계수에 있어서 매우 큰 차이가 있음을 알 수 있다. In particular, when comparing Examples 3 to 6 and Comparative Example 1, it can be seen that the glass transition temperature, transparency and isotropy are similar to each other, but there are very large differences in flexibility and coefficient of thermal expansion.
또한 실시예 3, 실시예 4 및 비교예 2와 비교해 볼 때 유리전이온도, 투명성, 등방성, 유연성 면에서는 상호 유사하지만 카르복실산기 또는 카르복실산금속염기 도입에 따라 유연성이 더욱 개선되고 열팽창계수에 있어서는 극명한 차이를 볼 수 있다. In addition, compared with Examples 3, 4 and Comparative Example 2, the glass transition temperature, transparency, isotropy and flexibility are similar to each other, but the flexibility is further improved by the introduction of a carboxylic acid group or a metal carboxylate base and the coefficient of thermal expansion You can see the difference.
또한 실시예 6과 실시예 8, 실시예 9을 비교하였을 때 금속이온으로 중화하지 않은 실시예 8, 실시예 9의 경우 열팽창계수가 비교적 높거나 유리전이온도가 떨어져 기판용 재료로 사용하기에 부적합하다는 것을 알 수 있다.In addition, when Example 6, Example 8, and Example 9 were compared, the Examples 8 and 9, which were not neutralized with metal ions, were not suitable for use as substrate materials due to their relatively high thermal expansion coefficient or low glass transition temperature. You can see that.

Claims (15)

  1. 하기 화학식 1의 환상올레핀 단위와, 하기 화학식 2의 카르복실산기 함유 환상올레핀 단위를 포함하는 환상올레핀 공중합체.The cyclic olefin copolymer containing the cyclic olefin unit of following formula (1), and the carboxylic acid group containing cyclic olefin unit of following formula (2).
    [화학식 1][Formula 1]
    Figure PCTKR2012006274-appb-I000009
    Figure PCTKR2012006274-appb-I000009
    (상기 화학식 1에서, 상기 R은 (C1 내지 C20)알킬이다)(In Formula 1, R is (COneTo C20Alkyl)
    [화학식 2][Formula 2]
    Figure PCTKR2012006274-appb-I000010
    Figure PCTKR2012006274-appb-I000010
  2. 제 1항에 있어서,The method of claim 1,
    상기 화학식 2의 카르복실산기 함유량이 전체 환상올레핀계 공중합체 100 중량% 중에서 0.01 내지 20 중량%를 함유한 환상올레핀 공중합체.The cyclic olefin copolymer in which the carboxylic acid group content of the said Formula (2) contains 0.01-20 weight% in 100 weight% of all the cyclic olefin copolymers.
  3. 제 1항에 있어서, The method of claim 1,
    상기 환상올레핀 공중합체는 하기 화학식 3의 카르복실산금속염기를 함유하는 환상올레핀 단위를 더 포함하는 것인 환상올레핀 공중합체.The cyclic olefin copolymer is a cyclic olefin copolymer further comprising a cyclic olefin unit containing a metal carboxylate group of the formula (3).
    [화학식 3][Formula 3]
    Figure PCTKR2012006274-appb-I000011
    Figure PCTKR2012006274-appb-I000011
    (상기 화학식 3에서, 상기 X는 알칼리금속, 알칼리토금속, 전이금속에서 선택되는 어느 하나의 금속이온이다.)(In Formula 3, X is any one metal ion selected from alkali metals, alkaline earth metals and transition metals.)
  4. 제 1항 내지 제 3항에서 선택되는 어느 한 항에 있어서, The method according to any one of claims 1 to 3,
    상기 환상올레핀계 공중합체는 중량평균분자량이 1,000 내지 1,000,000인 환상올레핀계 공중합체.The cyclic olefin copolymer has a weight average molecular weight of 1,000 to 1,000,000 cyclic olefin copolymer.
  5. 제 3항에 있어서,The method of claim 3,
    상기 카르복실산금속염기의 금속염은 리튬이온, 나트륨이온, 칼륨이온, 마그네슘이온, 칼슘이온, 바륨이온, 니켈이온, 구리이온, 아연이온 중 어느 하나의 금속이온을 포함하는 것인 환상올레핀계 공중합체.The metal salt of the metal carboxylate base is cyclic olefin-based air containing any one metal ion of lithium ions, sodium ions, potassium ions, magnesium ions, calcium ions, barium ions, nickel ions, copper ions, zinc ions coalescence.
  6. 제 3항에 있어서,The method of claim 3,
    상기 화학식 2의 카르복실산기 중 수소의 전부가 금속염으로 치환되어 상기 환상올레핀 공중합체 100 중량% 중 카르복실산금속염기의 함유량이 0.05 내지 40 중량%인 환상올레핀 공중합체.The cyclic olefin copolymer in which all of the hydrogen in the carboxylic acid group of Formula 2 is substituted with a metal salt so that the content of the metal carboxylate group in 100% by weight of the cyclic olefin copolymer is 0.05 to 40% by weight.
  7. 제 3항에 있어서,The method of claim 3,
    상기 화학식 2의 카르복실산기 중 수소의 일부가 금속염으로 치환되어 상기 환상올레핀 공중합체 100 중량% 중 카르복실산기 및 카르복실산금속염기의 총함유량이 0.02 내지 30 중량%인 환상올레핀 공중합체.A cyclic olefin copolymer in which a part of hydrogen in the carboxylic acid group of Formula 2 is substituted with a metal salt so that the total content of the carboxylic acid group and the metal carboxylate group in 100% by weight of the cyclic olefin copolymer is 0.02 to 30% by weight.
  8. 제 1항에 있어서, The method of claim 1,
    상기 화학식 1의 환상올레핀 단위는 노르보르넨 카르복실산 메틸에스테르, 노르보르넨 카르복실산 에틸에스테르, 노르보르넨 카르복실산 n-프로필에스테르, 노르보르넨 카르복실산 iso-프로필에스테르, 노르보르넨 카르복실산 n-부틸에스테르, 노르보르넨 카르복실산 t-부틸에스테르, 노르보르넨 카르복실산 n-펜틸에스테르, 노르보르넨 카르복실산 n-헥실에스테르, 노르보르넨 카르복실산 시클로헥실에스테르, 노르보르넨 카르복실산 n-헵틸에스테르, 노르보르넨 카르복실산 1,4-디메틸펜틸에스테르, 노르보르넨 카르복실산 n-옥틸에스테르, 노르보르넨 카르복실산 2-에틸헥실에스테르, 노르보르넨 카르복실산 미리스틸에스테르, 노르보르넨 카르복실산 필미틸에스테르, 노르보르넨 카르복실산 스테아릴에스테르에서 선택되는 어느 하나 또는 둘 이상인 환상올레핀 공중합체.The cyclic olefin unit of Formula 1 may be norbornene carboxylic acid methyl ester, norbornene carboxylic acid ethyl ester, norbornene carboxylic acid n-propyl ester, norbornene carboxylic acid iso-propyl ester, norbornene N-butyl ester of carboxylic acid, t-butyl ester of norbornene carboxylic acid, n-pentyl ester of norbornene carboxylic acid, n-hexyl ester of norbornene carboxylic acid, norbornene carboxylic acid cyclohexyl norbornene Ester, norbornene carboxylic acid n-heptyl ester, norbornene carboxylic acid 1,4-dimethylpentyl ester, norbornene carboxylic acid n-octyl ester, norbornene carboxylic acid 2-ethylhexyl ester, Any one or two or more selected from norbornene carboxylic acid myristyl ester, norbornene carboxylic acid filmyl ester, norbornene carboxylic acid stearyl ester Cyclic olefin copolymer.
  9. a) 하기 화학식 1에서 선택되는 1종 또는 2종 이상의 알킬기를 포함하는 화합물을 반복단위로 포함하는 제1중합체를 제조하는 단계;a) preparing a first polymer including a compound including one or two or more alkyl groups selected from Formula 1 as repeating units;
    b) 상기 제 1중합체를 부분가수분해 반응시켜 하기 화학식 2의 카르복실산기를 포함하는 제2중합체를 제조하는 단계;b) partially hydrolyzing the first polymer to prepare a second polymer including a carboxylic acid group represented by Formula 2 below;
    를 포함하는 환상올레핀 공중합체의 제조방법.Method for producing a cyclic olefin copolymer comprising a.
    [화학식 1][Formula 1]
    Figure PCTKR2012006274-appb-I000012
    Figure PCTKR2012006274-appb-I000012
    (상기 화학식 1에서, 상기 R은 (C1 내지 C20)알킬이다)(In Formula 1, R is (COneTo C20Alkyl)
    [화학식 2][Formula 2]
    Figure PCTKR2012006274-appb-I000013
    Figure PCTKR2012006274-appb-I000013
  10. 제 9항에 있어서,The method of claim 9,
    상기 화학식 2의 카르복실산기 중 수소의 일부 또는 전부를 금속염으로 치환하는 중화반응단계를 더 포함하여, 하기 화학식 3의 카르복실산금속염기 함유 환상올레핀 단위를 더 포함하는 제 3 중합체를 제조하는 환상올레핀 공중합체의 제조방법.Further comprising a neutralization step of substituting a part or all of the hydrogen in the carboxylic acid group of Formula 2 with a metal salt, to form a third polymer further comprising a carboxylate group containing cyclic olefin unit of the formula (3) Method for producing an olefin copolymer.
    [화학식 3][Formula 3]
    Figure PCTKR2012006274-appb-I000014
    Figure PCTKR2012006274-appb-I000014
    (상기 화학식 3에서, 상기 X는 알칼리금속, 알칼리토금속, 전이금속에서 선택되는 어느 하나의 금속이온이다.)(In Formula 3, X is any one metal ion selected from alkali metals, alkaline earth metals and transition metals.)
  11. 제 9항에 있어서, The method of claim 9,
    상기 a)단계에서 제1중합체는 노르보르넨 카르복실산 메틸에스테르, 노르보르넨 카르복실산 에틸에스테르, 노르보르넨 카르복실산 n-프로필에스테르, 노르보르넨 카르복실산 iso-프로필에스테르, 노르보르넨 카르복실산 n-부틸에스테르, 노르보르넨 카르복실산 t-부틸에스테르, 노르보르넨 카르복실산 n-펜틸에스테르, 노르보르넨 카르복실산 n-헥실에스테르, 노르보르넨 카르복실산 시클로헥실에스테르, 노르보르넨 카르복실산 n-헵틸에스테르, 노르보르넨 카르복실산 1,4-디메틸펜틸에스테르, 노르보르넨 카르복실산 n-옥틸에스테르, 노르보르넨 카르복실산 2-에틸헥실에스테르, 노르보르넨 카르복실산 미리스틸에스테르, 노르보르넨 카르복실산 필미틸에스테르, 노르보르넨 카르복실산 스테아릴에스테르에서 선택되는 어느 하나 또는 둘 이상의 단량체와, 촉매를 용매하에서 반응시킨 것인 환상올레핀 공중합체의 제조방법.In step a), the first polymer is norbornene carboxylic acid methyl ester, norbornene carboxylic acid ethyl ester, norbornene carboxylic acid n-propyl ester, norbornene carboxylic acid iso-propyl ester, nordene Borneen carboxylic acid n-butyl ester, norbornene carboxylic acid t-butyl ester, norbornene carboxylic acid n-pentyl ester, norbornene carboxylic acid n-hexyl ester, norbornene carboxylic acid cyclo Hexyl ester, norbornene carboxylic acid n-heptyl ester, norbornene carboxylic acid 1,4-dimethylpentyl ester, norbornene carboxylic acid n-octyl ester, norbornene carboxylic acid 2-ethylhexyl ester Any one or two or more selected from norbornene carboxylic acid myristyl ester, norbornene carboxylic acid filmyl ester, norbornene carboxylic acid stearyl ester And a method for producing a cyclic olefin copolymer that was the reaction catalyst in the solvent.
  12. 제 9항에 있어서, The method of claim 9,
    상기 b)단계의 부분가수분해 반응은 상기 제 1중합체를 유기용매에 녹인 후, 염산 또는 황산 수용액에 첨가하여 부분가수분해반응을 시키는 것인 환상올레핀 공중합체의 제조방법.The partial hydrolysis reaction of step b) is to dissolve the first polymer in an organic solvent, and then added to hydrochloric acid or sulfuric acid aqueous solution to perform a partial hydrolysis reaction.
  13. 제 10항에 있어서, The method of claim 10,
    상기 중화반응은 리튬이온, 나트륨이온, 칼륨이온, 마그네슘이온, 칼슘이온, 바륨이온, 니켈이온, 구리이온, 아연이온 중 어느 하나의 금속이온을 포함하는 화합물을 첨가하여 반응시킨 것인 환상올레핀 공중합체의 제조방법.The neutralization reaction is a cyclic olefin air which is reacted by adding a compound including any one of metal ions of lithium ions, sodium ions, potassium ions, magnesium ions, calcium ions, barium ions, nickel ions, copper ions and zinc ions. Method for preparing coalescing.
  14. 제 1항 내지 제 3항중 어느 한 항의 환상올레핀 공중합체를 이용하여 용매캐스팅방법 또는 용융압출방법에 의해 가공된 플렉시블 기판.The flexible substrate processed by the solvent casting method or the melt extrusion method using the cyclic olefin copolymer of any one of Claims 1-3.
  15. 제 14항에 의해 얻어진 플렉시블 기판을 사용한 플렉시블 디스플레이 또는 태양전지 중에서 선택된 어느 하나의 전기소자.Any one of an electric element selected from a flexible display or a solar cell using the flexible substrate obtained in claim 14.
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