WO2007100223A1 - Norbornene-ester polymer containing bulky substituents - Google Patents

Norbornene-ester polymer containing bulky substituents Download PDF

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WO2007100223A1
WO2007100223A1 PCT/KR2007/001047 KR2007001047W WO2007100223A1 WO 2007100223 A1 WO2007100223 A1 WO 2007100223A1 KR 2007001047 W KR2007001047 W KR 2007001047W WO 2007100223 A1 WO2007100223 A1 WO 2007100223A1
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norbornene
substrate
methyl
intensity
determined
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Soo Min Baek
Hyun Jin Kim
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Kolon Industries Inc
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Kolon Industries Inc
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    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • 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
    • 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
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/127—Acids containing aromatic rings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to a norbornene-ester polymer having an ester group, and more particularly, to a norbornene-ester polymer, which is obtained from a norbornene monomer having a bulky substituent.
  • inorganic material such as silicon oxide or silicon nitride
  • inorganic material such as silicon oxide or silicon nitride
  • polyimide or BCB bis-benzocyclobutene
  • BCB bis-benzocyclobutene
  • polyimide suffers because it has problems related to element corrosion and an increase in dielectric constant due to high moisture absorption, anisotropic electric properties, a need for pretreatment to decrease its reactivity with copper lines, and adhesion to metal.
  • BCB has lower hygroscopicity and a lower dielectric constant than polyimide, it also has problems in which metal adhesion is poor and a curing process should be conducted at high temperatures . Therefore, attempts to use cyclic olefin polymers have been made.
  • Cyclic olefin polymers which are polymers obtained through the polymerization of a cyclic olefin monomer, such as norbornene, have superior transparency, heat resistance, and chemical resistance, and furthermore, have much lower birefringence and moisture absorption, compared to conventional olefin polymers. Accordingly, this polymer may be used for insulating films of semiconductors or TFT-LCDs, protecting films for polarizing plates, multi-chip modules, ICs, printed circuit boards, sealants for electronic materials, or low dielectric coating materials, films, and packages for flat panel displays or optics, and may also be used as material for plastic substrates for flexible displays .
  • the norbornene polymer which is presently commercially available, has light transmittance of about 80-90% and a glass transition temperature (Tg) of 100 ⁇ 180 ° C, which does not satisfy the requirements for properties for realizing the above end uses .
  • the cyclic olefin monomer contains a polar functional group, such as an ester group
  • this polar functional group plays a role in increasing intermolecular packing and increasing adhesion to metal substrates or other polymers, and may be efficiently used for information electronic materials, and therefore, polymerization or copolymerization of norbornene, having an ester group, is steadily receiving increasing attention (US Patent No.
  • Korean Unexamined Patent Publication No. 2004-5593 discloses a norbornene-ester addition polymer having a low dielectric constant, low hygroscopicity, a high. glass transition temperature, excellent thermal stability and oxidation stability, and high chemical resistance and metal adhesion, and a method of preparing the same.
  • the norbornene-ester addition polymer comprises at least 50 mol% of norbornene-ester monomer, which is an exo isomer, as a repeating unit, and has a molecular weight of at least 20,000.
  • a norbornene-ester polymer in which a norbornene-ester monomer comprises a bulky substituent to thereby increase a glass transition temperature, and thus an optical material comprising the same provides exhibit excellent optical properties and thermal properties.
  • An object of the present invention is to provide a norbornene-ester polymer, which is able to increase thermal stability and light transmittance and to minimize moisture absorption.
  • the invention provides a norbornene-ester polymer, i) comprising a repeating unit of a norbornene-ester compound having a total number of carbons of the ranges from 19 to 80, represented by Formula 1 below; and ii) having light transmittance of 0.9 or higher which is determined in a manner such that the polymer is formed into a casting film, which is then measured for intensity of normal incident light on a substrate, light absorption intensity to the substrate, and light reflection intensity from the substrate at a wavelength ranging from 400 nm to 800 nm using a hazemeter, and then the light transmittance is determined according to Equation 1 below:
  • Formula 1 Formula 1
  • R 1 , R 2 and R 3 which are the same as or different from each other, are each a hydrogen atom, a Ci ⁇ io linear or branched alkyl group, or a C 5 ⁇ 12 cyclic alkyl group, at least one of R 1 , R 2 and R 3 is not a hydrogen atom, and R4
  • R 5 is a hydrogen
  • n is an integer of 0 or more,- and Equation 1
  • the norbornene- ester polymer may have a glass transition temperature (Tg) ranging from 200 ° C to 3OQ " C.
  • the norbornene-ester polymer may have a number average molecular weight (Mh) of 10,000 or more and a molecular weight distribution of 1.0-4.0.
  • the present invention provides an optical material, comprising the norbornene-ester polymer.
  • the optical material is characterized in that it has light transmittance of 0.9 or higher which is determined according to Equation 1.
  • the optical material may be a film.
  • a norbornene-ester polymer has a high glass transition temperature, to thus exhibit excellent thermal stability, has good metal adhesion, has increased light transmittance, to thus realize superior optical properties, and has minimal moisture absorption, thus making it easy to prepare electronic material.
  • the norbornene-ester polymer of the present invention is obtained by polymerizing a norbornene-ester monomer having from 19 to 80 carbons, represented by Formula 1, which is intruduced an ester group and a bulky substituent to a cyclic norbornene monomer.
  • the polymer of the present invention is characterized in that the monomer itself, constituting the repeating unit, is added with the bulky substituent, and thereby the chains of the resultant polymer are stacked less extensively, or stacking spaces are increased, thus preventing a tangling phenomenon and leading to increased light transmittance.
  • 'norbornene-ester monomer means a monomer containing at least one norbornene (bicyclo[2, 2, l]hept-2-ene) unit represented by Formula 2 below:
  • the norbornene-ester monomer represented by Formula 1 may be obtained by subjecting an alkyl group-substituted or unsubstituted cyclopentadiene (CPD) , dicyclopentadiene
  • DCPD DC-substituted or unsubstituted CPD, DCPD or mixture thereof and alkylacrylate having an adamantyl group, to Diels-Alder reaction.
  • an alkyl group-substituted or unsubstituted CPD, DCPD or mixture thereof and alkylacrylate having an adamantyl group are reacted at a molar ratio of
  • reaction temperature is set to 180-220 ° C and the reaction pressure is set to atmospheric pressure or higher.
  • a polymerization inhibitor may be added in order to adjust n of
  • Formula 1 to a desired numerical value.
  • the polymerization inhibitor include, but are not limited to, aniline, cyclohexane, phenol, 4-epoxyphenol, nitrobenzene, hydroquinone, benzoquinone, copper dichloride, and 2,2-di(4- tert-octylphenyl) -1-picrylhydrazyl, and hydroquinone or benzoquinone is preferably used.
  • the polymerization inhibitor is added so that the molar ratio of the alkyl group-substituted or unsubstituted CPD, DCPD or mixture thereof to the polymerization inhibitor is 1:0.001-0.05, and preferably 1 : 0.002-0.04.
  • the monomer thus obtained is represented by Formula 1, and preferably may have a structure in which, in Formula 1, at least one of Ri to R 3 , in particular, R 1 is not a hydrogen atom.
  • R 1 is not a hydrogen atom.
  • Such a structure is included as the repeating unit in the polymer to thus function to increase the amorphous properties of the polymer, leading to increased light transmittance .
  • a polymerizable monomer and a catalyst are mixed with an organic solvent according to a typical norbornene polymerization process, and furthermore, a cocatalyst may be added, if necessary.
  • alcohol may be used alone, or may be used in combination with water or an organic solvent other than alcohol, such as tetrahydrofuran, examples of alcohol including methanol, ethanol, isopropanol, and butanol .
  • the catalyst examples include transition metal catalysts, such as nickel and palladium, as well as metallocene compounds.
  • the norbornene-ester polymer having bulky substituents thus prepared has a number average molecular weight (Mn) of 10,000 or more. Under typical polymerization conditions, Mn ranges from 20,000 to 1,000,000, and the molecular weight distribution is 1.0-4.0.
  • the norbornene-ester polymer has a glass transition temperature of 200 ⁇ 300 ° C, it is able to be applied to highly thermally stable materials, and also has metal adhesion equal to or higher than conventional norbornene- ester polymers.
  • the norbornene-ester polymer having bulky substituents is dissolved in a solvent, and is then prepared into a film or a sheet through a solvent casting process.
  • the polymer may be used in mixtures of one or more.
  • the prepared film has a thickness of 50-500 ⁇ m and has light transmittance of 0.9 or higher, which is determined according to Equation 1 below: Equation 1
  • I 0 is the intensity of normal incident light on a substrate
  • l a is the light absorption intensity to the substrate
  • l r is the light reflection intensity from the substrate.
  • the film or the sheet has low moisture absorption, and therefore superior dimensional stability is realized.
  • DCPD dicyclopentadiene, Aldrich, 10.2 in£, 0.0757 mol
  • DCPD dicyclopentadiene
  • DCPD dieye1opentadiene, Aldrich, 10.2 ml, 0.0757 mol
  • 2-ethyl-2- adamantylmethacrylate 44.3 g, 0.18 mol
  • DCPD dieye1opentadiene, Aldrich, 5.1 ml, 0.0379 mol
  • reaction product was cooled, transferred into a distillation apparatus, and then distilled at a reduced pressure of 1 torr using a vacuum pump, thus obtaining a final product at 117 ° C (yield: 34%) .
  • This product had a molar ratio (mol%) of exo isomer to endo isomer of 50.1:49.9.
  • the second precipitate was filtered, and was then dried in a vacuum oven at 60 ° C for 24 hours, yielding a 5-norbornene-2-carboxylic acid methyl ester homopolymer.
  • the obtained polymer was purified through vacuum drying.
  • the yield of the resultant polymer was determined to be 12 g (60%)
  • the molecular weight thereof was determined to be 35,000
  • the molecular weight distribution thereof was determined to be 2.0.
  • Example 2 Polymerization was conducted in the same manner as in Example 1, with the exception that 20 g (6.99 mmol) of 1- adamantyl-5-norbornene-2-methyl-2-carboxylate, synthesized in Synthesis Example 4, was used, instead of 2-methyl-2- adamantyl-5-norbornene-2-methyl-2-carboxylate.
  • the catalyst and the monomer were used in the same molar ratio as in Example 1.
  • the yield of the resultant polymer was determined to be 16 g (80%) , the molecular weight thereof was determined to be 26,000, and the molecular weight distribution thereof was determined to be 1.42.
  • Example 5 2-Methyl-2-Adamantyl-9-Tetracyclododecene- 4-Methyl-4-Carboxylate H ⁇ mopolymer Polymerization was conducted in the same manner as in Example 1, with the exception that 20 g (5.46 mmol) of 2- methyl-2-adamantyl-9-tetracyclododecene-4-methyl-4- carboxylate, synthesized in Synthesis Example 5, was used, instead of 2-methyl-2-adamantyl-5-norbornene-2-methyl-2- carboxylate. The catalyst and the monomer were used in the same molar ratio as in Example 1. As the results of the present example, the yield of the resultant polymer was determined to be 15 g (81%) , the molecular weight thereof was determined to be 31,500, and the molecular weight distribution thereof was determined to be 1.92.
  • Example 7 Polymerization was conducted in the same manner as in Example 1, with the exception that 20 g (5.26 mmol) of 2- methyl-2-adamantyl-9-tetracyclododecene-4-ethyl-4- carboxylate, synthesized in Synthesis Example 7, was used, instead of 2-methyl-2-adamantyl-5-norbornene-2-methyl-2- carboxylate.
  • the catalyst and the monomer were used in the same molar ratio as in Example 1.
  • the yield of the resultant polymer was determined to be 12 g (60%) , the molecular weight thereof was determined to be 27,000, and the molecular weight distribution thereof was determined to be 1.27.
  • Example 8 l-Adamantyl-9-Tetracyclododecene-4-Methyl- 4-Carbo. ⁇ ylate H ⁇ mppolymer Polymerization was conducted in the same manner as in Example 1, with the exception that 20 g (5.68 mmol) of 1- adamantyl-9-tetracyclododecene-4-methyl-4-carboxylate, synthesized in Synthesis Example 8, was used, instead of 2- methyl-2-adamantyl-5-norbornene-2-methyl-2-carboxylate . The catalyst and the monomer were used in the same molar ratio as in Example 1. As the results of the present example, the yield of the resultant polymer was determined to be 9.5 g
  • the molecular weight thereof was determined to be 34,000, and the molecular weight distribution thereof was determined to be 1.53.
  • the temperature of the reactor was decreased to room temperature, and the resultant reaction solution was added in droplets to excess methanol, thus forming a first precipitate that deposited.
  • the first precipitate was dissolved in 5 mi of ethanol, after that the precipitate solution was added in droplets to excess methanol to thus deposit a second precipitate.
  • the second precipitate was filtered, and was then dried in a vacuum oven at 6O0C for 24 hours, yielding a 5-norbornene-2-carboxylic acid methyl ester homopolymer .
  • the obtained polymer was purified through vacuum drying.
  • the yield of the resultant polymer was determined to be 62%, the molecular weight thereof was determined to be 42,000, and the molecular weight distribution thereof was determined to be 2.2.
  • the yield of the resultant polymer was determined to be 48%
  • the molecular weight thereof was determined to be 37,600
  • the molecular weight distribution thereof was determined to be 2.53.
  • Example 2 Polymerization was conducted in the same manner as in Example 1, with the exception that 20 g (7.3 mmol) of 2- adamantyl-5-norbornene-2-carboxylate, synthesized in Comparative Synthesis Example 2, was used, instead of 2- methyl-2-adamantyl-5-norbornene-2-methyl-2-carboxylate .
  • the catalyst and the monomer were used in the same molar ratio as in Example 1.
  • the yield of the resultant polymer was determined to be 8.8 g (44%), the molecular weight thereof was determined to be 23,000, and the molecular weight distribution thereof was determined to be 2.1.
  • the polymer was dissolved in 10 wt% of toluene and was then applied to a thickness of 1 jtrni on each of glass plates which had been coated with chromium, aluminum and tungsten patterns.
  • the thin film was cross-cut in the form of a grid of squares, each square having a width of 5 mm x a length of 5 mm, and was then subjected to a 180°tape test. As the results, no squares of the test pieces of Examples 1-10 and Comparative Examples 1 and 2 were separated from the glass plate coated with the pattern.
  • the norbornene-ester polymer having an adamantyl group as a bulky substituent, has a glass transition temperature of 200 ° C or higher to thus exhibit high thermal stability, and therefore is suitable for use in electronic materials, and also has good metal adhesion.
  • the film which is prepared with the use of the norbornene-ester polymer having an adamantyl group as a bulky substituent, can be seen to have further increased light transmittance, compared to films prepared without the use thereof.
  • the film has low moisture absorption, and consequently, superior dimensional stability is realized.

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Abstract

This invention provides a norbornene- ester polymer, obtaining by a norbornene- ester monomer having a total number of carbons of the ranges from 19 to 80, having a bulky substituent.

Description

[DESCRIPTION] [invention Titlel
NORBORNENE-ESTER POLYMER CONTAINING BULKY SUBSTITUENTS
[Technical Field]
The present invention relates to a norbornene-ester polymer having an ester group, and more particularly, to a norbornene-ester polymer, which is obtained from a norbornene monomer having a bulky substituent.
[Background Art]
In general, as material for insulating elements, inorganic material, such as silicon oxide or silicon nitride, has been mainly used. However, the increased demand for smaller devices having high efficiency has led to the requirement for polymers that are low in dielectric constant and hygroscopicity and are superior in metal adhesion, strength, thermal stability, and light transmittance, and have a high glass transition temperature. Presently, polyimide or BCB (bis-benzocyclobutene) has been used as a low dielectric substance for electronic materials . Polyimide has excellent thermal stability and oxidation stability, a high glass transition temperature, and superior mechanical properties, and thus has been widely used for electronic materials. However, polyimide suffers because it has problems related to element corrosion and an increase in dielectric constant due to high moisture absorption, anisotropic electric properties, a need for pretreatment to decrease its reactivity with copper lines, and adhesion to metal. Further, although BCB has lower hygroscopicity and a lower dielectric constant than polyimide, it also has problems in which metal adhesion is poor and a curing process should be conducted at high temperatures . Therefore, attempts to use cyclic olefin polymers have been made.
Cyclic olefin polymers, which are polymers obtained through the polymerization of a cyclic olefin monomer, such as norbornene, have superior transparency, heat resistance, and chemical resistance, and furthermore, have much lower birefringence and moisture absorption, compared to conventional olefin polymers. Accordingly, this polymer may be used for insulating films of semiconductors or TFT-LCDs, protecting films for polarizing plates, multi-chip modules, ICs, printed circuit boards, sealants for electronic materials, or low dielectric coating materials, films, and packages for flat panel displays or optics, and may also be used as material for plastic substrates for flexible displays . However, in order to apply the norbornene polymer to the above end uses, high optical properties and thermal stability must be assured. The norbornene polymer, which is presently commercially available, has light transmittance of about 80-90% and a glass transition temperature (Tg) of 100~180°C, which does not satisfy the requirements for properties for realizing the above end uses .
In the case where the cyclic olefin monomer contains a polar functional group, such as an ester group, this polar functional group plays a role in increasing intermolecular packing and increasing adhesion to metal substrates or other polymers, and may be efficiently used for information electronic materials, and therefore, polymerization or copolymerization of norbornene, having an ester group, is steadily receiving increasing attention (US Patent No.
3,330,815, EP 0445755A2, US Patent No. 5,705,503, US Patent
No. 6,455,650) .
However, even though such a polar functional group is contained, there are problems in which optical properties and thermal stability are not assured.
Korean Unexamined Patent Publication No. 2004-5593 discloses a norbornene-ester addition polymer having a low dielectric constant, low hygroscopicity, a high. glass transition temperature, excellent thermal stability and oxidation stability, and high chemical resistance and metal adhesion, and a method of preparing the same. The norbornene-ester addition polymer comprises at least 50 mol% of norbornene-ester monomer, which is an exo isomer, as a repeating unit, and has a molecular weight of at least 20,000.
Whereas the metal adhesion and surface tension of the addition polymer and the adhesion and birefringence of the film using the addition polymer are measured, hygroscopicity, stability, including thermal stability, and optical properties are not mentioned in the above patent. Ultimately, the above patent is unsuitable for solving the above-described problems. Further, although the norbornene- ester monomer, which is an exo isomer, should be used in an amount of 50 mol% or more, it is difficult to assure this amount of monomer.
[Disclosure]
[Technical Problem] According to an embodiment of the present invention, there is provided a norbornene-ester polymer, in which a norbornene-ester monomer comprises a bulky substituent to thereby increase a glass transition temperature, and thus an optical material comprising the same provides exhibit excellent optical properties and thermal properties.
An object of the present invention is to provide a norbornene-ester polymer, which is able to increase thermal stability and light transmittance and to minimize moisture absorption.
[Technical Solution]
According to an embodiment of the present invention, the invention provides a norbornene-ester polymer, i) comprising a repeating unit of a norbornene-ester compound having a total number of carbons of the ranges from 19 to 80, represented by Formula 1 below; and ii) having light transmittance of 0.9 or higher which is determined in a manner such that the polymer is formed into a casting film, which is then measured for intensity of normal incident light on a substrate, light absorption intensity to the substrate, and light reflection intensity from the substrate at a wavelength ranging from 400 nm to 800 nm using a hazemeter, and then the light transmittance is determined according to Equation 1 below: Formula 1
Figure imgf000007_0001
wherein R1, R2 and R3, which are the same as or different from each other, are each a hydrogen atom, a Ci~io linear or branched alkyl group, or a C5^12 cyclic alkyl group, at least one of R1, R2 and R3 is not a hydrogen atom, and R4
has a structure selected from among
Figure imgf000007_0002
Figure imgf000007_0003
and , in which R5 is a hydrogen
atom, a Ci~io linear or branched alkyl group, or a C5_i2 cyclic alkyl group, and n is an integer of 0 or more,- and Equation 1
Figure imgf000007_0004
wherein I0 is the intensity of normal incident light on a substrate, la is the light absorption intensity to the substrate, and lr is the light reflection intensity from the substrate. According to the present invention, the norbornene- ester polymer may have a glass transition temperature (Tg) ranging from 200°C to 3OQ"C.
The norbornene-ester polymer may have a number average molecular weight (Mh) of 10,000 or more and a molecular weight distribution of 1.0-4.0.
In addition, the present invention provides an optical material, comprising the norbornene-ester polymer. The optical material is characterized in that it has light transmittance of 0.9 or higher which is determined according to Equation 1.
The optical material may be a film.
[Advantageous Effects] According to the present invention, a norbornene-ester polymer has a high glass transition temperature, to thus exhibit excellent thermal stability, has good metal adhesion, has increased light transmittance, to thus realize superior optical properties, and has minimal moisture absorption, thus making it easy to prepare electronic material.
[Best Mode]
Hereinafter, the present invention is described in detail . The norbornene-ester polymer of the present invention is obtained by polymerizing a norbornene-ester monomer having from 19 to 80 carbons, represented by Formula 1, which is intruduced an ester group and a bulky substituent to a cyclic norbornene monomer.
If polymer chains become tangled with each other or become stacked, light transmittance may be decreased. The polymer of the present invention is characterized in that the monomer itself, constituting the repeating unit, is added with the bulky substituent, and thereby the chains of the resultant polymer are stacked less extensively, or stacking spaces are increased, thus preventing a tangling phenomenon and leading to increased light transmittance.
The term 'norbornene-ester monomer' means a monomer containing at least one norbornene (bicyclo[2, 2, l]hept-2-ene) unit represented by Formula 2 below:
Formula 2
Figure imgf000009_0001
The norbornene-ester monomer represented by Formula 1 may be obtained by subjecting an alkyl group-substituted or unsubstituted cyclopentadiene (CPD) , dicyclopentadiene
(DCPD) , or mixture thereof, and alkylacrylate, having an adamantyl group, to Diels-Alder reaction. Specifically, an alkyl group-substituted or unsubstituted CPD, DCPD or mixture thereof and alkylacrylate having an adamantyl group are reacted at a molar ratio of
1:0.5-10, and preferably 1:0.5-4, yielding the norbornene- ester monomer.
As such, the reaction temperature is set to 180-220°C and the reaction pressure is set to atmospheric pressure or higher.
When the monomer of Formula 1 is synthesized, a polymerization inhibitor may be added in order to adjust n of
Formula 1 to a desired numerical value. Specific examples of the polymerization inhibitor include, but are not limited to, aniline, cyclohexane, phenol, 4-epoxyphenol, nitrobenzene, hydroquinone, benzoquinone, copper dichloride, and 2,2-di(4- tert-octylphenyl) -1-picrylhydrazyl, and hydroquinone or benzoquinone is preferably used.
The polymerization inhibitor is added so that the molar ratio of the alkyl group-substituted or unsubstituted CPD, DCPD or mixture thereof to the polymerization inhibitor is 1:0.001-0.05, and preferably 1 : 0.002-0.04.
The monomer thus obtained is represented by Formula 1, and preferably may have a structure in which, in Formula 1, at least one of Ri to R3, in particular, R1 is not a hydrogen atom. Such a structure is included as the repeating unit in the polymer to thus function to increase the amorphous properties of the polymer, leading to increased light transmittance .
When the above monomer is polymerized to a polymer, a polymerizable monomer and a catalyst are mixed with an organic solvent according to a typical norbornene polymerization process, and furthermore, a cocatalyst may be added, if necessary.
As the organic solvent, alcohol may be used alone, or may be used in combination with water or an organic solvent other than alcohol, such as tetrahydrofuran, examples of alcohol including methanol, ethanol, isopropanol, and butanol .
Examples of the catalyst include transition metal catalysts, such as nickel and palladium, as well as metallocene compounds.
While the polymerization temperature, which varies depending on the type of solvent, is maintained at 20-100"C, the reaction is conducted for 1-24 hours, thus preparing a norbornene-ester polymer.
The norbornene-ester polymer having bulky substituents thus prepared has a number average molecular weight (Mn) of 10,000 or more. Under typical polymerization conditions, Mn ranges from 20,000 to 1,000,000, and the molecular weight distribution is 1.0-4.0.
Since the norbornene-ester polymer has a glass transition temperature of 200~300°C, it is able to be applied to highly thermally stable materials, and also has metal adhesion equal to or higher than conventional norbornene- ester polymers.
Further, the norbornene-ester polymer having bulky substituents is dissolved in a solvent, and is then prepared into a film or a sheet through a solvent casting process. As such, the polymer may be used in mixtures of one or more. The prepared film has a thickness of 50-500 μm and has light transmittance of 0.9 or higher, which is determined according to Equation 1 below: Equation 1
Figure imgf000012_0001
wherein I0 is the intensity of normal incident light on a substrate, la is the light absorption intensity to the substrate, and lr is the light reflection intensity from the substrate.
Moreover, the film or the sheet has low moisture absorption, and therefore superior dimensional stability is realized. [Mode for Invention]
A better understanding of the present invention may be obtained through the following examples, which are set forth to illustrate, but are not to be construed as the limit of the present invention.
Synthesis of Norbornene-Ester Monomer (Synthesis Examples 1~8, Comparative Synthesis Examples 1~2)
<Synthesis Example 1> Synthesis of 2-Methyl-2- Adamantyl-5-Norbornene-2-Methyl-2-Carboxylate
Into a 0.25 L autoclave, DCPD (dieye1opentadiene, Aldrich, 10.2 ml, 0.0757 mol) , 2-methyl-2-adamantylmethacrylate (42.6 g, 0.18 mol) , and hydroquinone (0.83 g, 0.1 mol) were added, and were then allowed to react at 180°C for 12 hours, after that the reaction product was cooled, transferred into a distillation apparatus, and then distilled at a reduced pressure of 1 torr using a vacuum pump, thus obtaining a final product at 110°C (yield: 25%) . This product had a molar ratio (mol%) of exo isomer to endo isomer of 48.5:51.5. 1H-NMR (500MHz, CDCl3), endo: 56.20 (dd, IH), 6.18 (dd, IH) ; exo: δ 6.12 (m, 2H)
<Synthesis Example 2> Synthesis of 2-Ethyl-2- Adamantyl-5-Norbornene-2-Methyl-2-Carboxylate Into a 0.25 L autoclave, DCPD (dicyclopentadiene,
Aldrich, 10.2 mi, 0.0757 mol) , 2-ethyl-2-adamantγlmethacrγlate
(44.3 g, 0.18 mol), and hydroquinone (0.83 g, 0.1 mol) were added, and were then allowed to react at 200"C for 12 hours, after that the reaction product was cooled, transferred into a distillation apparatus, and then distilled at a reduced pressure of 1 torr using a vacuum pump, thus obtaining a final product at 120°C (yield: 27%) . This product had a molar ratio (mol%) of exo isomer to endo isomer of 45.5:54.2. 1H-NMR ( 500MHz , CDCl3) , endo : 56 . 22 (dd, IH) , 6 . 19 (dd,
IH) ; exo : δ 6 . 18 (m, 2H)
<Synthesis Example 3> Synthesis of 2-Methyl-2- Adamanty1-5-Norbornene-2-Ethyl-2-Carboxylate
Into a 0.25 L autoclave, DCPD (dicyclopentadiene, Aldrich, 10.2 in£, 0.0757 mol), 2-methyl-2-adamantylethacrylate
(44.3 g, 0.18 mol), and hydroquinone (0.83 g, 0.1 mol) were added, and were then allowed to react at 210°C for 12 hours, after that the reaction product was cooled, transferred into a distillation apparatus, and then distilled at a reduced pressure of 1 torr using a vacuum pump, thus obtaining a final product at 117°C (yield: 34%) . This product had a molar ratio (mol%) of exo isomer to endo isomer of 40.2:59.5.
1H-NMR ( 500MHz , CDCl3 ) , endo : 56 . 20 (dd, IH) , 6 . 18 (dd, IH) ; exo : 56 . 14 (m, 2H) <Synthesis Example 4> Synthesis of l-Adamantyl-5- Norbornene-2-Methyl-2-Carboxylate
Into a 0.25 L autoclave, DCPD (dicyclopentadiene, Aldrich, 10.2 mi, 0.0757 mol) , 1-adamantγlmethacrylate (40.0 g, 0.18 mol), and hydroqμinone (0.83g, 0.1 mol) were added, and were then allowed to react at 200°C for 12 hours, after that the reaction product was cooled, transferred into a distillation apparatus, and then distilled at a reduced pressure of 1 torr using a vacuum pump, thus obtaining a final product at 100°C (yield: 85%) . This product had a molar ratio (mol%) of exo isomer to endo isomer of 40.0:59.1.
1H-NMR (500MHz, CDCl3), endo: δβ.18 (dd, IH), 6.04 (dd, IH); exo: 56.12 (dd, IH), 6.04 (dd, IH)
<Synthesis Example 5> Synthesis of 2-Methyl-2- Adamantyl-9-Tetracyclododecene-4-Methyl-4-Carboxylate
Into a 0.25 L autoclave, DCPD (dicyclopentadiene,
Aldrich, 10.2 mi, 0.0757 mol) and 2-methyl-2- adamantylmethacrylate (42.6 g, 0.18 mol) were added, and were then allowed to react at 180°C for 12 hours, after that the resultant reaction solution was added with DCPD
(dicyclopentadiene, Aldrich, 5.1 mi, 0.0379 mol), and was then allowed to react at 200°C for 8 hours. The reaction product was cooled, transferred into a distillation apparatus, and then distilled at a reduced pressure of 1 torr using a vacuum pump, thus obtaining a final product at 110°C (yield: 25%) . This product had a molar ratio (mol%) of exo isomer to endo isomer of 47.5 : 52.5.
1H-NMR (500MHz, CDCl3), endo: 56.30 (dd, IH), 6.18 (dd, IH), 2.32 (dd, 2H); exo: 56.20 (m, 2H), 2.40 (dd, 2H)
<Synthesis Example 6> Synthesis of 2-Ethyl-2- Adamantyl-9-Tetracyclododβcene-4-Methyl-4-Carboxylate
Into a 0.25 L autoclave, DCPD (dieye1opentadiene, Aldrich, 10.2 ml, 0.0757 mol) and 2-ethyl-2- adamantylmethacrylate (44.3 g, 0.18 mol) were added and were then allowed to react at 200°C for 12 hours, after that the resultant reaction solution was added with DCPD (dieye1opentadiene, Aldrich, 5.1 ml, 0.0379 mol), and was then allowed to react at 200°C for 8 hours. The reaction product was cooled, transferred into a distillation apparatus, and then distilled at a reduced pressure of 1 torr using a vacuum pump, thus obtaining a final product at 120°C (yield: 27%) . This product had a molar ratio (mol%) of exo isomer to endo isomer of 43.7:56.3. 1H-NMR (500MHz, CDCl3), endo: 56.32 (dd, IH), 6.20 (dd, IH), 2.32 (dd, 2H); exo: 56.25 (m, 2H), 2.40 (dd, 2H)
<Synthesis Example 7> Synthesis of 2-Methyl-2- Aaaτnantyl-9-Tetracyclododecene-4-Ethyl-4-Carboxylate Into a 0.25 L autoclave, DCPD (dicyclopentadiene, Aldrich, 10.2 mi, 0.0757 mol) and 2-methyl-2- adaπnantγlethacrγlate (44.3 g, 0.18 mol) were added and were then allowed to react at 210°C for 12 hours, after that the resultant reaction solution was added with DCPD (dicyclopentadiene, Aldrich, 5.1 mi, 0.0379 mol), and was then allowed to react at 210"C for 8 hours. The reaction product was cooled, transferred into a distillation apparatus, and then distilled at a reduced pressure of 1 torr using a vacuum pump, thus obtaining a final product at 117°C (yield: 34%) . This product had a molar ratio (mol%) of exo isomer to endo isomer of 50.1:49.9.
1H-NMR (500MHz, CDCl3), endo: 56.31 (dd, IH) , 6.23 (dd, IH), 2.30 (dd, 2H); exo: 56.27 (m, 2H), 2.39 (dd, 2H) <Synthesis Example 8> Synthesis of l-Adamantyl-9- Tetracyclododecene-4-Methyl-4-Carbo2cylate
Into a 0.25 L autoclave, DCPD (dicyclopentadiene, Aldrich, 10.2 mi, 0.0757 mol) and 1-adamantylmethacrylate (40.0 g, 0.18 mol) were added and were then allowed to react at 200°C for 12 hours, after that the resultant reaction solution was added with DCPD (dicyclopentadiene, Aldrich, 5.1 mi, 0.0379 mol), and was then allowed to react at 200°C for 8 hours . The reaction product was cooled, transferred into a distillation apparatus, and then distilled at a reduced pressure of 1 torr using a vacuum pump, thus obtaining a final product at 100°C (yield: 75%) . This product had a molar ratio (mol%) of exo isomer to endo isomer of 45.2:54.8.
1H-NMR ( 500MHz , CDCl3 ) , endo : 56 . 34 (dd, IH) , 6 . 27 (dd, IH) , 2 . 32 (dd, 2H) ; exo : 56 . 31 (m, 2H) , 2 . 34 (dd, 2H)
<Cαmparative Synthesis Example 1> Synthesis of Norbornene-2-Carboxylic Acid Methyl Ester
Into a 0.5 L autoclave, DCPD (dicyclopentadiene, Aldrich, 67 ml, 0.5 mol) , methylacrylate (Aldrich, 94.6 mi, 1.05 mol), and hydroquinone (2.3 g, 0.02 mol) were added, and were then allowed to react at 200°C for 12 hours, after that the reaction product was cooled, transferred into a distillation apparatus, and then distilled at a reduced pressure of 1 torr using a vacuum pump, thus obtaining a final product at 50°C (yield: 89%) . This product had a molar ratio (mol%) of exo isomer to endo isomer of 52.8:47.2.
1H-NMR (500MHz, CDCl3), endo: 56.17 (dd, IH) , 5.91 (dd,
IH), 3.60 (s, 3H), 3.17 (b, IH) , 2.91 (m, IH), 2.88 (b, IH),
1.28 (m,lH); exo: 56.09 (m, 2H), 3.67 (s, 3H), 3.01 (b, IH), 2.88 (b, IH), 2.20 (m, IH), 1.88 (m, IH), 1.51 (d,lH), 1.34
(m, 2H)
<Cαmparative Synthesis Example 2> Synthesis of 2- Adamantyl-5- Norbornene-2-Carboκylate Into a 0.25 L autoclave, DCPD (dieye1opentadiene, Aldrich, 10.2 mi, 0.0757 mol) , 2-adamantylacrylate (37.1 g, 0.18 mol), and hydroquinone (0.83 g, 0.1 mol) were added, and were then allowed to react at 200°C for 12 hours, after that the reaction product was cooled, transferred into a distillation apparatus, and then distilled at a reduced pressure of 1 torr using a vacuum pump, thus obtaining a final product at 120°C (yield: 40%) . This product had a molar ratio (mol%) of exo isomer to endo isomer of 50.2:49.8. 1H-NMR (500MHz, CDCl3), endo: 56.22 (dd, IH), 6.19 (dd, IH); exo: 56.17 (m, 2H)
Synthesis of Norbornene-Ester Polymer (Examples 1-10, Comparative Examples 1-2)
<Example 1> 2-Methyl-2-Adamantyl-5-Norbornene-2- Methyl-2-Carboxylate Hαmopolymer
0.13 g (1.0 mmol) of nickel chloride (NiCl2) was added with 3 ml of ethanol, after that 20 g (6.73 mmol) of 2- methyl-2-adamantyl-5-norbornene-2-methyl-2-carboxylate, synthesized in Synthesis Example 1, was added thereto while the temperature was maintained at 60oC, to thus conduct the reaction for 12 hours. After the completion of the reaction, the temperature of the reactor was decreased to room temperature, and the resultant reaction solution was added in droplets to excess methanol, thus forming a first precipitate that deposited. The first precipitate was dissolved in 5 ιύ of ethanol, after that the precipitate solution was added in droplets to excess methanol to thus deposit a second precipitate. The second precipitate was filtered, and was then dried in a vacuum oven at 60°C for 24 hours, yielding a 5-norbornene-2-carboxylic acid methyl ester homopolymer. The obtained polymer was purified through vacuum drying. As the results of the present example, the yield of the resultant polymer was determined to be 12 g (60%) , the molecular weight thereof was determined to be 35,000, and the molecular weight distribution thereof was determined to be 2.0.
<Example 2> 2-Ethyl-2-Adamantyl-5-Norbornene-2-Methyl- 2-Carboxylate Hαmopolymer
Polymerization was conducted in the same manner as in Example 1, with the exception that 20 g (6.47 iranol) of 2- ethyl-2-adamantyl-5-norbornene-2-methyl-2-carboxylate, synthesized in Synthesis Example 2, was used, instead of 2- methyl-2-adamantyl-5-norbornene-2-methyl-2-carboxylate. The catalyst and the monomer were used in the same molar ratio as in Example 1. As the results of the present example, the yield of the resultant polymer was determined to be 10 g
(50%) , the molecular weight* thereof was determined to be
22,000, and the molecular weight distribution thereof was determined to be 1.48. <Exaiηple 3> 2-Methyl-2-Adamantyl-5-Norbornene-2-Ethyl- 2-Carboxylate Hαmopolymer
Polymerization was conducted in the same manner as in Example 1, with the exception that 20 g (6.47 mmol) of 2- methyl-2-adamantγl-5-norbornene-2-ethyl-2-carboxylate, synthesized in Synthesis Example 3, was used, instead of 2- methyl-2-adamantyl-5-norbornene-2-methyl-2-carboxylate. The catalyst and the monomer were used in the same molar ratio as in Example 5. As the results of the present example, the yield of the resultant polymer was determined to be 9.2 g (46%) , the molecular weight thereof was determined to be 21,000, and the molecular weight distribution thereof was determined to be 1.72.
<Exaiηple 4> l-Adamantyl-5-Norbornene-2-Methyl-2- Carboxylate Hαmopolymer
Polymerization was conducted in the same manner as in Example 1, with the exception that 20 g (6.99 mmol) of 1- adamantyl-5-norbornene-2-methyl-2-carboxylate, synthesized in Synthesis Example 4, was used, instead of 2-methyl-2- adamantyl-5-norbornene-2-methyl-2-carboxylate. The catalyst and the monomer were used in the same molar ratio as in Example 1. As the results of the present example, the yield of the resultant polymer was determined to be 16 g (80%) , the molecular weight thereof was determined to be 26,000, and the molecular weight distribution thereof was determined to be 1.42.
<Example 5> 2-Methyl-2-Adamantyl-9-Tetracyclododecene- 4-Methyl-4-Carboxylate Hαmopolymer Polymerization was conducted in the same manner as in Example 1, with the exception that 20 g (5.46 mmol) of 2- methyl-2-adamantyl-9-tetracyclododecene-4-methyl-4- carboxylate, synthesized in Synthesis Example 5, was used, instead of 2-methyl-2-adamantyl-5-norbornene-2-methyl-2- carboxylate. The catalyst and the monomer were used in the same molar ratio as in Example 1. As the results of the present example, the yield of the resultant polymer was determined to be 15 g (81%) , the molecular weight thereof was determined to be 31,500, and the molecular weight distribution thereof was determined to be 1.92.
<Exainple 6> 2-Ethyl-2-Adamantyl-9-Tetracyclododecene- 4-Methyl-4-Carboxylate Hαmopolymer
Polymerization was conducted in the same manner as in Example 1, with the exception that 20 g (5.26 mmol) of 2- ethyl-2-adamantyl-9-tetracyclododecene-4-methyl-4- carboxylate, synthesized in Synthesis Example 6, was used, instead of 2-methyl-2-adamantyl-5-norbornene-2-methyl-2- carboxylate. The catalyst and the monomer were used in the same molar ratio as in Example 1. As the results of the present example, the yield of the resultant polymer was determined to be 9 g (45%) , the molecular weight thereof was determined to be 14,000, and the molecular weight distribution thereof was determined to be 1.83. <Example 7> 2-Methyl-2-Ax5amantyl-9-Tetracyclcxa.odecene- 4-Ethyl-4-Carboxylate Hαmopolymer
Polymerization was conducted in the same manner as in Example 1, with the exception that 20 g (5.26 mmol) of 2- methyl-2-adamantyl-9-tetracyclododecene-4-ethyl-4- carboxylate, synthesized in Synthesis Example 7, was used, instead of 2-methyl-2-adamantyl-5-norbornene-2-methyl-2- carboxylate. The catalyst and the monomer were used in the same molar ratio as in Example 1. As the results of the present example, the yield of the resultant polymer was determined to be 12 g (60%) , the molecular weight thereof was determined to be 27,000, and the molecular weight distribution thereof was determined to be 1.27.
<Example 8> l-Adamantyl-9-Tetracyclododecene-4-Methyl- 4-Carbo.κylate Hαmppolymer Polymerization was conducted in the same manner as in Example 1, with the exception that 20 g (5.68 mmol) of 1- adamantyl-9-tetracyclododecene-4-methyl-4-carboxylate, synthesized in Synthesis Example 8, was used, instead of 2- methyl-2-adamantyl-5-norbornene-2-methyl-2-carboxylate . The catalyst and the monomer were used in the same molar ratio as in Example 1. As the results of the present example, the yield of the resultant polymer was determined to be 9.5 g
(48%) , the molecular weight thereof was determined to be 34,000, and the molecular weight distribution thereof was determined to be 1.53.
<Example 9> 2-Methyl-2-Adamantyl-5-Norbornene-2- Methyl-2-Carboxylate and 2-Ethyl-2-Adamantyl-9- Tetracyclododecene-4-Methyl-4-Carboxylate Copolymer 1.0 mmol of nickel chloride (NiCl2) was added with 10 mi of ethanol, after that 2-methyl-2-adamantyl-5-norbornene- 2-methyl-2-carboxylate, synthesized in Synthesis Example 1, and 2-ethyl-2-adamantyl-9-tetracyclododecene-4-methyl-4- carboxylate, of Synthesis Example 5, were added at a molar ratio of 1:1 while the temperature was maintained at 60°C, to thus conduct the reaction for 15 hours. After the completion of the reaction, the temperature of the reactor was decreased to room temperature, and the resultant reaction solution was added in droplets to excess methanol, thus forming a first precipitate that deposited. The first precipitate was dissolved in 5 mi of ethanol, after that the precipitate solution was added in droplets to excess methanol to thus deposit a second precipitate. The second precipitate was filtered, and was then dried in a vacuum oven at 6O0C for 24 hours, yielding a 5-norbornene-2-carboxylic acid methyl ester homopolymer . The obtained polymer was purified through vacuum drying. As the results of the present example, the yield of the resultant polymer was determined to be 62%, the molecular weight thereof was determined to be 42,000, and the molecular weight distribution thereof was determined to be 2.2.
<Example 10> l-Adamantyl-5-Norbornene-2-Methyl-2- Carboxylate and 2-Ethyl-2-Adamantyl-9-Tetracyclododecene-4- Methyl-4-Carboxylate Copolymer
Polymerization was conducted in the same manner as in
Example 9, with the exception that l-adamantyl-5-norbornene-
2-methyl-2-carboxylate, synthesized in Synthesis Example 4, and 2-ethyl-2-adamantyl-9-tetracyclododecene-4-methyl-4- carboxylate, synthesized in Synthesis Example 6, were used.
As the results of the present example, the yield of the resultant polymer was determined to be 48%, the molecular weight thereof was determined to be 37,600, and the molecular weight distribution thereof was determined to be 2.53.
<Cαmparative Example 1> Norbornene-2-Carboxylic Acid Methyl Ester Homopolymer
Polymerization was conducted in the same manner as in Example 1, with the exception that 50 g (0.33 mmol) of norbornene-2-carboxylic acid methyl ester, synthesized in Comparative Synthesis Example 1, was used, instead of 2- methyl-2-adamantyl-5-norbornene-2-methyl-2-carboxylate . The catalyst and the monomer were used in the same molar ratio as in Example 1. As the results of the present comparative example, the yield of the resultant polymer was determined to be 40 g (80%) , the molecular weight thereof was determined to be 60,000, and the molecular weight distribution thereof was determined to be 1.7. Comparative Example 2> 2-Adamantyl-5-Norbornene-2- Carboxylate Hαmopolymer
Polymerization was conducted in the same manner as in Example 1, with the exception that 20 g (7.3 mmol) of 2- adamantyl-5-norbornene-2-carboxylate, synthesized in Comparative Synthesis Example 2, was used, instead of 2- methyl-2-adamantyl-5-norbornene-2-methyl-2-carboxylate . The catalyst and the monomer were used in the same molar ratio as in Example 1. As the results of the present comparative example, the yield of the resultant polymer was determined to be 8.8 g (44%), the molecular weight thereof was determined to be 23,000, and the molecular weight distribution thereof was determined to be 2.1. Preparation, of Film <Examples ll~20, Comparative Examples 3~4> Using the polymer of each of Examples 1-10 and Comparative Examples 1 and 2, a film was prepared. Specifically, the polymer of each of Examples 1-10 and Comparative Examples 1 and 2 was mixed with an organic solvent having the composition shown in Table 1 below to thus prepare a coating solution, which was then cast on a glass substrate using an applicator (YOSHMITSU YBA-4) , dried at room temperature for 1 hour, further dried at 100°C for 18 hours in a nitrogen atmosphere, and then allowed to stand at -10°C for 10 sec. Thereafter, the resultant film was removed from the glass substrate using a knife, thus obtaining the transparent film of each of Examples 11-20 and Comparative Examples 3 and 4, having a uniform thickness, with a thickness variation less than 5%, as shown in Table 1 below. [Table l]
Figure imgf000028_0001
<Evaluation of Properties>
(1) Glass Transition Temperature
The glass transition temperature of the polymer of each of Examples 1-10 and Comparative Examples 1 and 2 was measured using TGA (Thermogravimetric Analyzer) and DSC (Differential Scanning Calorimeter) . The results are shown in Table 2 below. [Table 2]
Figure imgf000029_0001
(2) Metal Adhesion
In order to evaluate the metal adhesion of the polymer of each of Examples 1-10 and Comparative Examples 1 and 2, the polymer was dissolved in 10 wt% of toluene and was then applied to a thickness of 1 jtrni on each of glass plates which had been coated with chromium, aluminum and tungsten patterns. The thin film was cross-cut in the form of a grid of squares, each square having a width of 5 mm x a length of 5 mm, and was then subjected to a 180°tape test. As the results, no squares of the test pieces of Examples 1-10 and Comparative Examples 1 and 2 were separated from the glass plate coated with the pattern.
(3) Light Transmittance The film of each of Examples 11-20 and Comparative Examples 3 and 4 was measured for the intensity of normal incident light on the substrate, the light absorption intensity to the substrate, and the light reflection intensity from the substrate at a wavelength ranging from 400 nm to 800 nm using a hazemeter (NIPPON DENSHOKU 30OA) , and then light transmittance was determined according to Equation 1 below. The results are shown in Table 3 below. Equation 1
/ =τ
0
wherein I0 = the intensity of normal incident light on a substrate, la = the light absorption intensity to a substrate, and lr = the light reflection intensity from a substrate. (4) Moisture Absorption The film of each of Examples 11-20 and Comparative Examples 3 and 4 was cut to a size of 10 cm XlO cm, and was then allowed to stand in water at 25°C for 24 hours, after that moisture absorption was determined through weight changes. The results are shown in Table 3 below. [Table 3]
Figure imgf000031_0001
As is apparent from the above evaluation results, the norbornene-ester polymer, having an adamantyl group as a bulky substituent, has a glass transition temperature of 200°C or higher to thus exhibit high thermal stability, and therefore is suitable for use in electronic materials, and also has good metal adhesion.
The film, which is prepared with the use of the norbornene-ester polymer having an adamantyl group as a bulky substituent, can be seen to have further increased light transmittance, compared to films prepared without the use thereof. In addition, the film has low moisture absorption, and consequently, superior dimensional stability is realized.

Claims

[CLAIMS] [Claim l]
A norbornene-ester polymer: i) comprising a repeating unit of a norbornene-ester compound having a total number of carbons of the ranges from 19 to 80, represented by Formula 1 below; and ii) having light transmittance of 0.9 or higher which is determined in a manner such that the polymer is formed into a casting film, which is then measured for intensity of normal incident light on a substrate, light absorption intensity to the substrate, and light reflection intensity from the substrate at a wavelength ranging from 400 nm to 800 nm using a hazemeter, and then the light transmittance is determined according to Equation 1 below: Formula 1
Figure imgf000032_0001
wherein Ri, R2 and R3, which are same as or different from each other, are each a hydrogen atom, a Cno linear or branched alkyl group, or a C5-12 cyclic alkyl group, at least one of Ri, R2 and R3 is not a hydrogen atom, and R4 has a structure selected from among
Figure imgf000033_0001
and
Figure imgf000033_0002
, in which R5 is a hydrogen atom, a Ci~ ■ :10
linear or branched alkyl group, or a Cs-I2 cyclic alkyl group, and n is an integer of 0 or more; and Equation 1
rr
Figure imgf000033_0003
wherein Io is the intensity of normal incident light on a substrate, la is the light absorption intensity to the substrate, and lr is the light reflection intensity from the substrate.
[Claim 2]
The norbornene-ester polymer according to claim 1, which has a glass transition temperature (Tg) ranging from 200°C to 300°C.
[Claim 3] The norbornene-ester polymer according to claim 1, which has a number average molecular weight (Mn) of 10,000 or more and a molecular weight distribution of 1.0-4.0.
[Claim 4]
An optical material, comprising the norbornene-ester polymer of any one of claims 1 to 3.
[Claim 5] The optical material according to claim 4, which has light transmittance of 0.9 or higher which is determined in a manner such that the optical material is measured for the intensity of normal incident light on a substrate, the light absorption intensity to the substrate, and the light reflection intensity from the substrate at a wavelength ranging from 400 nm to 800 nm using a hazemeter, and then the light transmittance is determined according to Equation 1 below:
Equation 1
Figure imgf000034_0001
wherein I0 is the intensity of normal incident light on a substrate, la is the light absorption intensity to the substrate, and lr is the light reflection intensity from the substrate.
[Claim 6] The optical material according to claim 4, wherein the optical material is a film.
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