KR101265274B1 - Flexible cyclic olefin copolymers with low coefficient of thermal expansion and flexible substrates produced therefrom - Google Patents
Flexible cyclic olefin copolymers with low coefficient of thermal expansion and flexible substrates produced therefrom Download PDFInfo
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- KR101265274B1 KR101265274B1 KR1020110017531A KR20110017531A KR101265274B1 KR 101265274 B1 KR101265274 B1 KR 101265274B1 KR 1020110017531 A KR1020110017531 A KR 1020110017531A KR 20110017531 A KR20110017531 A KR 20110017531A KR 101265274 B1 KR101265274 B1 KR 101265274B1
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Abstract
The present invention provides a carboxylic acid metal base or a sulfonic acid metal base-containing cyclic olefin copolymer obtained by using a cyclic olefin-alkenyldialkylaluminum copolymer having a molecular structure having a long branch as a starting material and a solvent casting method or The present invention relates to a flexible substrate obtained by a melt extrusion method. The resins and flexible substrates according to the present invention are useful in various fields such as flexible displays and flexible solar cells because they have excellent flexibility and low coefficient of thermal expansion, as well as excellent transparency, isotropy and high glass transition temperature.
Description
The present invention relates to cyclic olefin copolymers having excellent flexibility and low coefficient of thermal expansion and to flexible substrates prepared therefrom. More particularly, the present invention relates to a novel cyclic olefin copolymer having not only excellent flexibility and low coefficient of thermal expansion but also excellent transparency, isotropy and high glass transition temperature, and a flexible substrate suitable for use in displays, solar cells, and the like produced therefrom. .
Flexible displays, flexible solar cells, etc. are thinner, lighter, more impact-resistant, and easier to carry than conventional glass-based flat panel products. In that respect, the demand is increasing rapidly.
In order to implement such a flexible display and a flexible solar cell, many technologies such as a transparent high heat-resistant flexible substrate manufacturing technology, a high blocking property 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 a transparent electrode, oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO) are commonly 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 a transparent electrode, are unfortunately required to be performed at a high temperature of 200 ° C. or higher, so the heat resistance of the flexible substrate is extremely required. In particular, in the production of thin film transistor-liquid crystal display (TFT-LCD), one of the main uses of flexible substrates, the process temperature for implementing thin film transistor arrays on flexible substrates is more than 300 ℃. have. This heat resistance is currently evaluated as glass transition temperature and coefficient of thermal expansion. 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.
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 over 90% based on light transmittance, and isotropy below 10 nm based on birefringence. Plastic materials for flexible substrates, which have been the main targets of research and development so far, include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyether sulfone, polynorbornene, polyimide and the like.
Since polyimide has high glass transition temperature of 360 ° C. and low coefficient of thermal expansion of 17ppm / ° C., it has great advantages in terms of heat resistance, but it is not preferable because of high raw materials and manufacturing cost and yellow color. Polyester resins such as polyethylene terephthalate and polyethylene naphthalate have a relatively low thermal expansion coefficient of 13 to 15 ppm / ℃, but have a very low glass transition temperature of 80 to 120 ℃ and have a birefringence higher than 150 nm. The situation is excluded from the plastic material. 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 as 150 ~ 200 ℃ level is also undesirable. 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.
On the other hand, cyclic polyolefin-based resin substrates such as Promerus' polynorbornene substrate (trade name Appear 3000) have excellent transparency of 92% of light transmittance, excellent isotropy of birefringence of less than 10nm, and high heat resistance of glass transition temperature of 330 ℃. As a strong candidate material suitable for a board | substrate, great expectation is gathered. Unfortunately, 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.
In order to solve the above problems, the inventor of the present invention has made intensive studies and has come to the present invention.
It is an object of the present invention to provide a novel cyclic olefin copolymer having not only excellent flexibility and low coefficient of thermal expansion suitable for flexible substrates, but also excellent transparency, isotropy and high glass transition temperature.
It is another object of the present invention to provide a flexible substrate produced from such a novel cyclic olefin copolymer.
The present invention relates to a carboxylic acid base or sulfonic acid metal base-containing cyclic olefin copolymer containing a cyclic olefin unit and an olefin unit containing a metal carboxylate or sulfonic acid base group represented by the following formula (1): The present invention relates to a cyclic olefin copolymer having excellent flexibility and low coefficient of thermal expansion.
[Formula 1]
(In Formula 1, n is an integer of 1 to 20, X is COOM or SO 3 M, M is one or two or more metals selected from the group consisting of alkali metal, alkaline earth metal, transition metal.)
The present invention also relates to a flexible substrate obtained by a solvent casting method or a melt extrusion method using the carboxylic acid metal base or sulfonic acid metal base-containing cyclic olefin copolymer, and an electronic device using the same.
The method for obtaining the carboxylic acid metal base or sulfonic acid metal base-containing cyclic olefin copolymer according to the present invention will be described in more detail.
a) copolymerizing a cyclic olefin with an alkenyldialkylaluminum compound of formula (2) to prepare a cyclic olefin-alkenyldialkylaluminum copolymer comprising a cyclic olefin unit and a unit represented by the following formula (3);
[Formula 2]
(In Formula 2, R 1 , R 2 are each independently an alkyl group having 1 to 20 carbon atoms, n is an integer of 1 to 20.)
(3)
(In Formula 3, R 1 and R 2 are each independently selected from an alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 20.)
b) contacting the cyclic olefin-alkenyldialkylaluminum copolymer of step a) with carbon dioxide or sulfur trioxide to form a carboxylic acid group or sulfonic acid group-containing cyclic olefin copolymer containing a cyclic olefin unit and a unit represented by the following formula (4): Manufacturing step; And
[Formula 4]
(In Formula 4, n is an integer of 1 to 20, Y is COOH or SO 3 H.)
c) neutralizing the carboxylic acid group or sulfonic acid group-containing cyclic olefin copolymer obtained in step b) with metal ions to partially or completely neutralize the cyclic olefin unit and the metal carboxylate or sulfonic acid metal base represented by the following formula (1): Preparing a carboxylic acid metal base or sulfonic acid metal base-containing cyclic olefin copolymer containing an olefin unit;
[Formula 1]
(In Formula 1, n is an integer of 1 to 20, X is COOM or SO 3 M, M is one or two or more metals selected from the group consisting of alkali metal, alkaline earth metal, transition metal.)
.
In the present invention, the core of the technology introduced to obtain a novel resin and a flexible substrate produced therefrom as well as excellent flexibility and low coefficient of thermal expansion, as well as excellent transparency, isotropy and high glass transition temperature can be three major have.
First, cyclic olefin resins having transparency, isotropy and high glass transition temperature are introduced as basic resins.
Secondly, in order to solve the shortcoming of the disadvantage of the conventional cyclic olefin resin, an olefin copolymer having olefin having a long branched molecular structure as a comonomer is adopted.
Third, in order to solve the high thermal expansion coefficient, which is another disadvantage of the conventional cyclic olefin resin, molecular association by secondary bonding force such as electrostatic force, which can act strongly at a long distance to the end of the long branch contained in the copolymer. By expressing pseudo-crosslinking structure, the free volume is greatly reduced, and the cyclic olefin copolymer having molecular structure containing special functional groups that can exert a low thermal expansion coefficient effect can be introduced into the new molecular design. will be.
In more detail, the present inventors have examined the conventional cyclic olefin resins, but the cyclic olefin homopolymers are slightly different depending on the type of the cyclic olefin monomer, but are very excellent in terms of transparency, isotropy and high glass transition temperature, which are suitable as materials for flexible substrates. There is a problem that even if the flexibility is too low when forming into a film and the thermal expansion coefficient is also very high, which is not suitable for use as a flexible substrate material. In contrast, the hydrolysis reaction of the dialkylaluminum groups contained in the copolymer prepared by introducing an alkenyldialkylaluminum compound capable of expressing a long branched structure having a cyclic olefin as a main component as a comonomer It can be seen that the cyclic olefin copolymer obtained by introducing the olefin having the long branched molecular structure as a comonomer obtained as a result of the excellent transparency, isotropy and high glass transition temperature can be improved more than desired level. there was. Unfortunately, however, there is a problem that the coefficient of thermal expansion is higher than that in the case of the cyclic olefin homopolymer due to the increase in free volume due to the long flexible branch. Therefore, the present inventors have intensively studied, and when introducing a metal carboxylate group or a sulfonic acid metal base at the end of a long branch by a comonomer, the present inventors maintain excellent transparency, isotropy, and a high glass transition temperature. Free volume is greatly reduced by expressing pseudo-crosslinked structure according to molecular association of metal carboxylate or sulfonic acid metal salt period by secondary binding force such as electrostatic force that can act powerfully from a long distance without any significant damage of excellent flexibility. The inventors have found that an extremely low coefficient of thermal expansion, which is suitable as a material for flexible substrates, is secured at the same time, thereby completing the present invention.
Hereinafter, the configuration of the present invention will be described in more detail.
The present invention uses a cyclic olefin-alkenyldialkylaluminum copolymer obtained by copolymerizing a cyclic olefin unit and an alkenyldialkylaluminum compound represented by the following formula (2) as a starting material.
[Formula 2]
(In Formula 2, R 1 , R 2 are each independently an alkyl group having 1 to 20 carbon atoms, n is an integer of 1 to 20.)
In the present invention, the cyclic olefin is an olefin compound having a cyclic structure, specifically, for example, norbornene, 5-vinyl-2-norbornene, 5-butyl-2-norbornene, 5-methyl 2-norbornene, 5-hexyl-2-norbornene, 5-dimethylmethoxy norbornene, dicyclo pentadiene, cyclopentadiene, as a pendant functional group oxygen, chlorine, nitrogen, bromine And various norbornene derivatives having polar groups such as fluorine.
In the present invention, the alkenyldialkyl aluminum compound is represented by the following formula (2).
[Formula 2]
(In Formula 2, R 1 , R 2 are each independently an alkyl group having 1 to 20 carbon atoms, n is an integer of 1 to 20.)
In Formula 2, R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. In addition, n is an integer of 1-20, Preferably it is an integer of 2-16, More preferably, it is 4-12. If n is less than 1 it is difficult to secure the desired excellent flexibility, if n exceeds 20 there is a fear that the glass transition temperature is too low.
Specific examples of the alkenyldialkyl aluminum compound include propenyl diethyl aluminum, propenyl diisobutyl aluminum, pentenyl diethyl aluminum, pentenyl diisobutyl aluminum, hexenyl diisobutyl aluminum, hexenyl diethyl aluminum, and octenyl diisobutyl Aluminum, octenyldiethylaluminum, decenyldiisobutylaluminum, dodecenyldiisobutylaluminum, undecenyldiisobutylaluminum, and the like. Preferred are hexenyldiisobutylaluminum, hexenyldiethylaluminum, octenyldiisobutylaluminum, and octenyldiethylaluminum, which are relatively inexpensive compounds.
In the present invention, the cyclic olefin-alkenyldialkylaluminum copolymer is obtained by copolymerizing the cyclic olefin and the alkenyldialkylaluminum compound in the presence of a catalyst, for example, as described in detail in Japanese Patent Application No. 2004-138946. Although the catalyst is not particularly limited, coordination anionic catalysts such as metalocene catalysts and half-methlocene catalysts, which are usually used for cyclic olefin polymerization, may be used, but cyclic olefins and alkenyldialkylaluminum compounds having a bulky molecular structure It is preferable to use a half metalocene catalyst from a viewpoint of copolymerization with. The polymerization may be carried out by solution polymerization carried out in a solvent such as saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or bulk polymerization using cyclic olefins as a solvent. Any polymerization or the like is possible. The polymerization temperature is in the range of 0 to 200 ° C. and hydrogen may be used for molecular weight control.
Further, in the present invention, the cyclic olefin-alkenyldialkylaluminum copolymer may contain 50 to 99 mol%, preferably 60 to 95 mol%, more preferably 70 to 90 mol% of cyclic olefin units, It is preferable to adjust and copolymerize so that an alkenyldialkyl aluminum compound unit may contain 1-50 mol%, Preferably it is 5-40 mol%, More preferably, it is 10-30 mol%. When the alkenyldialkylaluminum compound unit is included in less than 1 mol%, it is difficult to secure excellent flexibility and low coefficient of thermal expansion, and when it exceeds 50 mol%, the glass transition temperature may be too low.
In the present invention, the carboxylic acid group or sulfonic acid group-containing cyclic olefin copolymer is a copolymer containing a cyclic olefin unit and a unit represented by the following formula (4), wherein the cyclic olefin-alkenyldialkylaluminum copolymer is carbon dioxide or sulfur trioxide. It is obtained by the hydrolysis reaction of the dialkyl aluminum group contained in contact with.
[Formula 4]
(In Formula 4, n is an integer of 1 to 20, Y is COOH or SO 3 H.)
More specifically, by contacting with carbon dioxide to convert the dialkylaluminum group to a carboxylic acid group, a carboxyl group-containing cyclic olefin copolymer can be obtained (Ref. K. Zieglar, F.Krupp, K.Weyer and W. Larbig, Ann. Chem., 629, 251 (1960), contacting sulfur trioxide to convert a dialkylaluminum group to a sulfonic acid group to give a sulfonic acid group-containing cyclic olefin copolymer (Ref. US Pat. 3121737).
In the present invention, the carboxylic acid group or sulfonic acid metal base-containing cyclic olefin copolymer is obtained by partially or totally neutralizing the carboxylic acid group or sulfonic acid group-containing cyclic olefin copolymer with metal ions. Here, partial neutralization means that the degree of neutralization of the carboxylic acid group or the sulfonic acid group is 20% or more, and when the degree of neutralization is less than 20%, it is difficult to secure a desired low coefficient of thermal expansion.
The present inventors have completed the present invention by discovering that when the carboxylic acid group or sulfonic acid group is neutralized partially or entirely with metal ions, a low coefficient of thermal expansion can be expressed.
Examples of the metal ions used for the neutralization include alkali metal ions such as lithium ions, sodium ions, potassium ions, alkali metal ions such as magnesium ions, calcium ions, barium ions, transition metal ions such as nickel ions, copper ions, zinc ions, and the like. Among these, sodium ions are advantageous in terms of cost, and zinc ions are preferable in terms of facilitating low thermal expansion coefficient because zinc ions are more likely to express similar crosslinked structures than other ions.
The neutralization reaction may be carried out using a carboxylic acid group or sulfonic acid group-containing cyclic olefin copolymer with ethers such as tetrahydrofuran, dibutyl ether and dimethoxyethane; Halogenated alkanes such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform and tetrachloroethylene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, and the like; and then dissolved in water or metal hydroxides, metal oxides, metal carbonates, and metal sulfates in the organic solvent. There is a method of adding a compound containing a metal ion such as a cargo and reacting it in a solution state, and adding a carboxylic acid group or a sulfonic acid group-containing cyclic olefin copolymer to a long L / D extruder that can give a sufficient reaction time and melt it. And neutralizing reaction by adding a compound containing a metal ion.
The neutralization degree by the neutralization reaction is 20% or more, preferably 30% or more, more preferably 40% or more. If the degree of neutralization is less than 20%, it is difficult to secure a desired low coefficient of thermal expansion due to the lack of functional groups capable of expressing similar network structures.
The weight average molecular weight of the carboxylic acid metal base or sulfonic acid metal base-containing cyclic olefin copolymer according to the present invention is 1,000 to 1,000,000, preferably 10,000 to 500,000, more preferably 50,000 to 300,000 in terms of film properties and moldability. desirable.
In the carboxylic acid metal base or sulfonic acid metal base-containing cyclic olefin copolymer according to the present invention, the carboxylate base or sulfide which makes a decisive contribution to ultimately exhibiting a low coefficient of thermal expansion due to the development of pseudo network structure by electrostatic force. The fonate group-containing olefin unit content is proportional to the alkenyldialkylaluminum compound unit content contained in the cyclic olefin-alkenyldialkylaluminum copolymer as a starting material. In the carboxyl group or sulfonate group-containing olefin unit, it is preferable to adjust the content to 1 to 50 mol%, preferably 5 to 40 mol%, more preferably 10 to 30 mol%. When the metal carboxylate or sulfonic acid base-containing olefin unit is included in less than 1 mol%, it is difficult to secure excellent flexibility and low coefficient of thermal expansion, and when it exceeds 50 mol%, the glass transition temperature may be too low.
More specifically, the method for producing a metal carboxylate or sulfonic acid metal base-containing cyclic olefin copolymer according to the present invention
a) copolymerizing a cyclic olefin with an alkenyldialkylaluminum compound of formula (2) to prepare a cyclic olefin-alkenyldialkylaluminum copolymer comprising a cyclic olefin unit and a unit represented by the following formula (3);
[Formula 2]
(In Formula 2, R 1 , R 2 are each independently an alkyl group having 1 to 20 carbon atoms, n is an integer of 1 to 20.)
(3)
(In Formula 3, R 1 and R 2 are each independently selected from an alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 20.)
b) contacting the cyclic olefin-alkenyldialkylaluminum copolymer of step a) with carbon dioxide or sulfur trioxide to form a carboxylic acid group or sulfonic acid group-containing cyclic olefin copolymer containing a cyclic olefin unit and a unit represented by the following formula (4): Manufacturing step; And
[Formula 4]
(In Formula 4, n is an integer of 1 to 20, Y is COOH or SO 3 H.)
c) neutralizing the carboxylic acid group or sulfonic acid group-containing cyclic olefin copolymer obtained in step b) with metal ions to partially or completely neutralize the cyclic olefin unit and the metal carboxylate or sulfonic acid metal base represented by the following formula (1): Preparing a carboxylic acid metal base or sulfonic acid metal base-containing cyclic olefin copolymer containing an olefin unit;
[Formula 1]
(In Formula 1, n is an integer of 1 to 20, X is COOM or SO 3 M, M is one or two or more metals selected from the group consisting of alkali metal, alkaline earth metal, transition metal.)
.
In addition, conventional additives such as inorganic particles, antioxidants, sunscreens, lubricants, and the like can be prescribed in the cyclic olefin copolymer within the scope of not impairing the object of the present invention.
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, the film-type flexible substrate is completed by first dissolving the carboxylic acid base metal or sulfonic acid base-containing cyclic olefin copolymer resin according to the present invention in a solvent, removing air bubbles, and then casting it on a suitable substrate and drying the solvent. The cyclic olefin copolymer resin pellets containing a metal acid base or a sulfonic acid base are introduced into an extruder through a hopper, melt-extruded through a cylinder, and passed through a Ti-die. The final film-like flexible substrate is completed.
As described above, the carboxylic acid metal base or sulfonic acid metal base-containing cyclic olefin copolymer according to the present invention has some long branches in the molecule and thus exhibits excellent flexibility, and also contains metal carboxylates contained in the long branch ends. It exhibits extremely low coefficient of thermal expansion by expressing pseudo-crosslinking structure according to molecular association of base or sulfonic acid metal salt period, and it is a breakthrough that has excellent transparency, isotropy and high glass transition temperature which are advantages of conventional cyclic olefin resin. The flexible substrate obtained from the resin can be usefully used in various fields such as a flexible display and a flexible solar cell.
The present invention is characterized in that it is a carboxylic acid metal base or sulfonic acid metal base-containing cyclic olefin copolymer obtained by using a cyclic olefin-alkenyldialkylaluminum copolymer having a molecular structure having some long branches as a starting material. It has a long branch to provide excellent flexibility and exhibits a very low thermal expansion coefficient by expressing a similar crosslinking structure according to the molecular association of the metal carboxylate or sulfonic acid salt period contained in the long branch end portion, as well as the conventional ring. Since it has excellent transparency, isotropy and high glass transition temperature which are advantages of olefin resin, it is expected to be useful for various fields such as flexible display and flexible solar cell.
Through the following examples will be described in more detail the present invention. The following examples are merely examples and are not limited to the examples.
Flexibility, thermal expansion coefficient, transparency, isotropy, glass transition temperature, weight average molecular weight, and the like of the cyclic olefin copolymer resins prepared according to the following Examples and Comparative Examples and the film-like substrates obtained therefrom were measured as follows.
(flexibility)
As a measure of flexibility, the film specimens having a thickness of 100 μm were mounted on the bending tester, and then evaluated as follows based on the maximum diameter (mm) without damage even after bending to a constant diameter of 10,000 repetitions.
[Table 1] Evaluation criteria of flexibility
(Coefficient of Thermal Expansion)
As a measure of heat resistance, the coefficient of thermal expansion (ppm / ° C.) of the specimen was measured by a TMA (Thermomechanical Analyzer).
(Transparency)
As a measure of transparency, the light transmittance (%) of the specimen was measured using a Hazemeter according to ASTM D1003.
(Isotropic)
As a measure for isotropy, birefringence (nm) for the specimens was evaluated using a phase difference measuring instrument (OJI measuring instrument, KOBRA-WR).
(Glass transition temperature)
As a measure for heat resistance, the glass transition temperature (° C.) for the specimens was measured in a differential scanning calorimeter (DSC).
(Weight average molecular weight)
The weight average molecular weight of the specimens was measured by gel permeation chromatography (GPC, Waters 150C) using oxo-chlorobenzene as a solvent and polystyrene as a standard.
Example 1
First, norbornene and octenyl diisobutyl aluminum were prepared as monomers. 25 L of toluene was added to a 50 L reactor equipped with a stirrer, and then 25 mmol of [Ph 3 C] [B (C 6 F 5 ) 4 ], a catalyst, 25 mmol of [t-BuNSiMe 2 Flu], and 90 mol% of norbornene as a monomer. And norbornene-octenyldiisobutylaluminum copolymer resin (A-1) in a reactor with a composition ratio of 10 mol% octenyldiisobutylaluminum as a comonomer, followed by polymerization for 30 minutes while maintaining the reaction temperature at 40 ° C. Got. Next, an excessive amount of 10L carbon dioxide was injected into the reactor to proceed with complete hydrolysis of the diisobutylaluminum group contained in the octenyldiisobutylaluminum compound unit, precipitated in methanol, filtered and washed with methanol three times. It dried under reduced pressure at 8 degreeC for 8 hours, and obtained the carboxylic acid group containing cyclic olefin copolymer (A-2). 1 kg of the carboxylic acid group-containing cyclic olefin copolymer (A-2) was added to a 10 L reactor equipped with a stirrer, and 5 L of tetrahydrofuran was added and stirred to dissolve. Subsequently, an excess of 20% aqueous NaOH solution was added to neutralize all the carboxylic acid groups, followed by a predetermined washing process, and drying under reduced pressure at 60 ° C. for 8 hours to obtain a weight average molecular weight of 350,000 sodium carboxylate base-containing cyclic olefin copolymer (A). Got it. The obtained sodium carboxylate base-containing cyclic olefin copolymer (A) resin pellets were introduced into a hopper, injected into an extruder having a screw diameter of 70 mm and L / D 36, melt extruded, and a film-shaped flexible substrate having a thickness of 100 μm through a Ti die. Specimens were obtained and their flexibility, thermal expansion coefficient, light transmittance, birefringence and glass transition temperature were evaluated. The results are shown in Table 2.
[Example 2]
Example 1 except that the norbornene-octenyldiisobutylaluminum copolymer resin (B-1) was obtained by adjusting the composition ratio of 80 mol% of norbornene monomers and 20 mol% of octenyl diisobutyl aluminum comonomers. The same procedure as in Example 1 was conducted to prepare a cyclic olefin-based copolymer (B) resin containing sodium carboxylate. Also, by using the same method as in Example 1, a film-like flexible substrate specimen having a thickness of 100 μm was obtained. Flexibility, coefficient of thermal expansion, light transmittance, birefringence and glass transition temperature were evaluated and the results are shown in Table 2.
[Example 3]
Example 1 except that norbornene-octenyldiisobutylaluminum copolymer resin (C-1) was obtained by adjusting the composition ratio of 70 mol% of norbornene monomers and 30 mol% of octenyl diisobutyl aluminum comonomers. Sodium carboxylate-containing cyclic olefin-based copolymer (C) resin was prepared in the same manner as in Example 1, and a film-like flexible substrate specimen having a thickness of 100 μm was obtained by the same method as in Example 1. Flexibility, coefficient of thermal expansion, light transmittance, birefringence and glass transition temperature were evaluated and the results are shown in Table 2.
Example 4
As in Example 1, norbornene-octenyldiisobutylaluminum copolymer resin (A-1) was obtained, followed by injection of an excess of 10L sulfur trioxide into the reactor, and diisobutylaluminum contained in the octenyldiisobutylaluminum compound unit. After complete hydrolysis of the group, precipitated in methanol, filtered, washed three times with methanol, and dried under reduced pressure at 60 ° C. for 8 hours to obtain a sulfonic acid group-containing cyclic olefin copolymer (D-2). In the same manner as in Example 1, a sulfonic acid base-containing cyclic olefin copolymer (D) resin was prepared. Using this method, a film-like flexible substrate specimen having a thickness of 100 μm was obtained by the same method as in Example 1, and the flexibility, thermal expansion coefficient, light transmittance, birefringence, and glass transition temperature were evaluated for the specimen, and the results are shown in Table 2. It was.
[Example 5]
Example except that norbornene-octenyldiisobutylaluminum copolymer resin (E-1) prepared by adjusting the composition ratio of 75 mol% of norbornene monomer and 25 mol% of octenyldiisobutyl aluminum comonomer was used. In the same manner as in 4, a sulfonic acid salt-containing cyclic olefin copolymer (E) resin was prepared. Using this method, a film-like flexible substrate specimen having a thickness of 100 μm was obtained by the same method as in Example 1, and the flexibility, thermal expansion coefficient, light transmittance, birefringence, and glass transition temperature of the specimen were evaluated. Indicated.
[Example 6]
First, the norbornene-octenyldiisobutylaluminum copolymer resin (A-1) obtained in Example 1 was precipitated in a mixture of hydrochloric acid and methanol, filtered, washed several times with methanol, and then dried under reduced pressure at 60 ° C. for 8 hours. To a norbornene-1-octene copolymer (A). A mixture of 50 parts by weight of the norbornene-1-octene copolymer (A) and 50 parts by weight of zinc oxide was kneaded in a twin screw extruder of L / D 40 to prepare a zinc oxide masterbatch pellet (A). Subsequently, the composition which mixed 2.5 weight part of zinc oxide masterbatch pellets (A) with respect to 100 weight part of said carboxylic acid group containing cyclic olefin type copolymer (A-2) resin pellets was thrown into the hopper, and screw diameter is 70 mm, and L / D It was injected into a 40-screw twin screw extruder and subjected to melt extrusion neutralization to prepare a carboxylic acid zinc base-containing cyclic olefin copolymer (F) resin pellet having a degree of neutralization of 72%. Using this method, a film-like flexible substrate specimen having a thickness of 100 μm was obtained by the same method as in Example 1, and the flexibility, thermal expansion coefficient, light transmittance, birefringence, and glass transition temperature were evaluated for the specimen, and the results are shown in Table 2. It was.
[Example 7]
First, norbornene and hexenyl diethyl aluminum were prepared as monomers. 25L of toluene was added to a 50L reactor equipped with a stirrer, and then 25 mmol of [Ph 3 C] [B (C 6 F 5 ) 4 ] as a catalyst, 25 mmol of [t-BuNSiMe 2 Flu] and 85 mol% of norbornene as a monomer. And norbornene-hexenyldiethylaluminum copolymer resin (G-1) in a reactor with a composition ratio of 15 mol% of hexenyldiethylaluminum as a comonomer, which was subjected to a polymerization reaction for 40 minutes while maintaining the reaction temperature at 40 ° C. Got. Next, an excess of 10L carbon dioxide was injected into the reactor to proceed with a complete hydrolysis reaction of the diethylaluminum group contained in the hexenyldiethylaluminum compound unit, precipitated in acidic methanol, filtered and washed with methanol three times. It dried under reduced pressure at 8 degreeC for 8 hours, and obtained the carboxylic acid group containing cyclic olefin type copolymer (G-2). 1 kg of the carboxylic acid group-containing cyclic olefin copolymer (G-2) was added to a 10 L reactor equipped with a stirrer, and 5 L of tetrahydrofuran was added and stirred to dissolve. Subsequently, an excess of 20% aqueous NaOH solution was added to neutralize all the carboxylic acid groups, and the resultant was washed under reduced pressure at 60 ° C. for 8 hours to obtain a cyclic olefin copolymer (G) containing a sodium carboxylate base having a weight average molecular weight of 350,000. . The obtained sodium carboxylate base-containing cyclic olefin copolymer (G) resin pellets were introduced into a hopper, injected into an extruder with a screw diameter of 70 mm and L / D 36, melt extruded, and a film-shaped flexible substrate having a thickness of 100 μm through a Ti die. Specimens were obtained and their flexibility, thermal expansion coefficient, light transmittance, birefringence and glass transition temperature were evaluated. The results are shown in Table 2.
[Example 8]
First, norbornene and decenyldiisobutylaluminum were prepared as monomers. 25 L of toluene was added to a 50 L reactor equipped with a stirrer, and then 25 mmol of [Ph 3 C] [B (C 6 F 5 ) 4 ], a catalyst, 25 mmol of [t-BuNSiMe 2 Flu], and 92 mol% of norbornene as a monomer. And a comonomer of deshenyldiisobutylaluminum, 8 mol%, was added to the reactor and subjected to a polymerization reaction for 40 minutes while maintaining the reaction temperature at 40 ° C. to norbornene-decenyldiisobutylaluminum copolymer resin (H- 1) was obtained. Next, an excess of 10L carbon dioxide was injected into the reactor to proceed with complete hydrolysis of the diisobutylaluminum group contained in the decenyldiisobutylaluminum compound unit, precipitated in acidic methanol, filtered and washed with methanol three times. It dried under reduced pressure at 60 degreeC for 8 hours, and obtained the carboxylic acid group containing cyclic olefin copolymer (H-2). Subsequently, a composition in which 1.5 parts by weight of the zinc oxide masterbatch pellet (A) obtained in Example 6 was mixed with respect to 100 parts by weight of the carboxylic acid group-containing cyclic olefin copolymer (H-2) resin pellets was introduced into a hopper, and the screw diameter was 70 mm. It injected | poured into the twin screw extruder which is L / D40, and melt extrusion neutralization reaction was carried out, and the carboxylate zinc carboxylate containing cyclic olefin type copolymer (H) resin pellet was prepared. Using this method, a film-like flexible substrate specimen having a thickness of 100 μm was obtained by the same method as in Example 1, and the flexibility, thermal expansion coefficient, light transmittance, birefringence, and glass transition temperature were evaluated for the specimen, and the results are shown in Table 2. It was.
Comparative Example 1
200 parts by weight of toluene was added to a 50 L reactor equipped with a stirrer, and then 0.01 parts by weight of triisobutylaluminum was added to serve as a scavenger, followed by 20 wt% of W (NPh) Cl with a tungsten-imide catalyst as a catalyst. After adding 10 parts by weight of a 4 OEt 2 cyclohexane solution and 5 parts by weight of 15% by weight of triethylaluminum cyclohexane solution, 60 parts by weight of norbornene were injected, and then reacted at 50 ° C. for 3 hours. Norbornene homopolymer was prepared by injecting 10 parts by weight of 0.5% by weight of tungsten chloride cyclohexane at 85% conversion, injecting 1 part by weight of methanol and 1 part by weight of water, respectively, per 100 parts by weight of the polymer to complete the reaction, followed by drying through washing. (A) Resin was prepared. Using this method, a film-like flexible substrate specimen having a thickness of 100 μm was obtained by the same method as in Example 1. Flexibility, thermal expansion coefficient, light transmittance, birefringence and glass transition temperature were evaluated for this specimen and the results are shown in Table 2.
Comparative Example 2
Using the norbornene-1-octene copolymer (A) resin obtained in Example 6, a film-like flexible substrate specimen having a thickness of 100 μm was obtained by the same method as in Example 1, and the flexibility, thermal expansion coefficient, and light for this specimen were obtained. Permeability, birefringence and glass transition temperature were evaluated and the results are shown in Table 2.
[Comparative Example 3]
Using the carboxylic acid group-containing cyclic olefin copolymer (A-2) resin obtained in Example 1, a film-like flexible substrate specimen having a thickness of 100 μm was obtained by the same method as in Example 1, and the flexibility and thermal expansion coefficient of the specimen were obtained. , Light transmittance, birefringence and glass transition temperature were evaluated and the results are shown in Table 2.
TABLE 2 Physical Properties of Substrates Obtained in Examples and Comparative Examples
When looking at Examples 1 to 8, the carboxylic acid base metal or sulfonic acid base-containing cyclic olefin copolymers not only have excellent flexibility and extremely low coefficient of thermal expansion, but also have excellent transparency, which is an advantage of conventional cyclic olefin resins, It can be seen that it has both isotropy and high glass transition temperature. In particular, when comparing Example 1 and Comparative Example 1 it can be seen that there is a very large difference in the flexibility, and the coefficient of thermal expansion, but similar in terms of transparency, isotropy and glass transition temperature. In addition, Comparative Examples 2 and 3 according to the prior art show that the flexibility is excellent, but the coefficient of thermal expansion is very high, and thus it is not suitable for the requirements for flexible substrates.
Claims (15)
[Chemical Formula 4]
(In Formula 4, n is an integer of 1 to 20, Y is COOH or SO 3 H.)
The cyclic olefin copolymer is a cyclic olefin copolymer obtained by copolymerizing a cyclic olefin unit in a range of 50 to 99 mol% and a carboxylate or sulphate-containing olefin unit represented by the formula (1) at 1 to 50 mol%. .
The cyclic olefin copolymer has a weight average molecular weight of 1,000 to 1,000,000 cyclic olefin copolymer.
(2)
(In Formula 2, R 1 , R 2 are each independently an alkyl group having 1 to 20 carbon atoms, n is an integer of 1 to 20.)
(3)
(In Formula 3, R 1 and R 2 are each independently selected from an alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 20.)
b) contacting the cyclic olefin-alkenyldialkylaluminum copolymer of step a) with carbon dioxide or sulfur trioxide to form a carboxylic acid group or sulfonic acid group-containing cyclic olefin copolymer containing a cyclic olefin unit and a unit represented by the following formula (4): Manufacturing step; And
[Chemical Formula 4]
(In Formula 4, n is an integer of 1 to 20, Y is COOH or SO 3 H.)
c) the carboxylic acid group or sulfonic acid group-containing cyclic olefin copolymer obtained in step b) is partially or totally neutralized with any one or two or more metals selected from alkali metals, alkaline earth metals or transition metals to form cyclic olefin units and carboxyl Preparing a carboxylic acid metal base or a sulfonic acid metal base-containing cyclic olefin copolymer containing an acid metal base or a sulfonic acid metal base-containing olefin unit;
Method for producing a cyclic olefin copolymer comprising a.
The alkenyldialkylaluminum compounds include propenyldiethylaluminum, propenyldiisobutylaluminum, pentenyldiethylaluminum, pentenyldiisobutylaluminum, hexenyldiisobutylaluminum, hexenyldiethylaluminum, octenyldiisobutylaluminum, A method for producing a cyclic olefin copolymer comprising at least one selected from octenyl diethyl aluminum, desenyl diisobutyl aluminum, dodecenyl diisobutyl aluminum, and undecenyl diisobutyl aluminum.
The carboxylic acid metal base or the sulfonic acid metal base-containing cyclic olefin copolymer includes 50 to 99 mol% of the cyclic olefin unit, and 1 to 50 olefin unit containing the carboxylic acid metal base or sulfonic acid metal base represented by the formula (1). Method for producing a cyclic olefin copolymer containing in mol%.
The cyclic olefin copolymer has a weight average molecular weight of 1,000 to 1,000,000 cyclic olefin copolymer.
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| KR100501398B1 (en) | 2003-01-15 | 2005-07-18 | 삼성토탈 주식회사 | Long-Chain Branched α-olefin/cycloolefin/diene Copolymers and Method for Preparing the Same |
| KR100620475B1 (en) | 2001-06-28 | 2006-09-13 | 제이에스알 가부시끼가이샤 | Olefinic Thermoplastic Elastomer, Process for Production Thereof, Olefinic Thermoplastic Elastomer Compositions, Process for Producing the Same and Moldings thereof |
| US7595369B2 (en) | 2004-11-10 | 2009-09-29 | Lg Chem, Ltd. | Method of polymerizing cyclic olefins and vinyl olefins, copolymer produced by the method and optical anisotropic film comprising the same |
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| KR100620475B1 (en) | 2001-06-28 | 2006-09-13 | 제이에스알 가부시끼가이샤 | Olefinic Thermoplastic Elastomer, Process for Production Thereof, Olefinic Thermoplastic Elastomer Compositions, Process for Producing the Same and Moldings thereof |
| KR100501398B1 (en) | 2003-01-15 | 2005-07-18 | 삼성토탈 주식회사 | Long-Chain Branched α-olefin/cycloolefin/diene Copolymers and Method for Preparing the Same |
| US7595369B2 (en) | 2004-11-10 | 2009-09-29 | Lg Chem, Ltd. | Method of polymerizing cyclic olefins and vinyl olefins, copolymer produced by the method and optical anisotropic film comprising the same |
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