JP2007063356A - Optical substrate and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical substrate which excels in transparency, heat resistance, moisture resistance, water resistance, solvent resistance, and chemical resistance to an acid, an alkali and the like, has a small coefficient of thermal expansion (coefficient of linear expansion), improved mechanical properties, and toughness, and its manufacturing method. <P>SOLUTION: The optical substrate is composed of a cyclic olefin addition copolymer having a cyclic olefin structural unit (1) having no substituent or only any one of substituents of a halogen atom, a methyl group, and an ethyl group and a cyclic olefin structural unit (2) having a substituent such as a trimethylsilyl group at a specific ratio, and a number average molecular weight (Mn) of 20,000-300,000. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an optically transparent substrate and a method for manufacturing the same. Specifically, the present invention relates to an optical substrate made of a specific cyclic olefin addition copolymer and a method for producing the same.

  As a substrate of display elements such as a liquid crystal substrate, an organic EL (electroluminescence) substrate, a substrate for electronic paper, etc., the glass substrate is excellent in transparency, heat resistance, dimensional stability, etc. Since a substrate that is easy to handle is required, many alternatives to a substrate made of a plastic material have been studied. A substrate made of a plastic material is required to have characteristics such as transparency, heat resistance, and dimensional stability similar to those of a glass material substrate.

  Due to the design of plastic materials, plastic materials with high transparency are those that have alicyclic structural units, because if there are many aromatic structural units, they will absorb light and it will be difficult to obtain a high degree of transparency. Is preferred. However, a plastic having an alicyclic structural unit is inferior in mechanical properties, and an improvement thereof is desired.

  As a plastic material excellent in dimensional stability, a material having a low coefficient of thermal expansion or a coefficient of linear expansion, which is an index related thereto, is preferable. Another factor related to dimensional stability is the hygroscopicity of the material, and the material itself needs to have low hygroscopicity.

  Furthermore, since the substrate of the display element requires high-temperature processing during secondary processing such as lead-free soldering or ITO electrode attachment, the heat resistance of the material is required, for example, it has a glass transition temperature of 220 ° C. or higher. Is required. Further, it is desired that the substrate is a film or sheet that can be easily handled.

As liquid crystal substrate materials which are plastic materials, hydrogenated ring-opening polymers and cyclic olefin addition polymers of cyclic olefins have been proposed as cyclic olefin polymers having excellent optical transparency. (Patent Documents 1 to 3)
However, conventionally known hydrogenated ring-opening polymers of cyclic olefins and addition copolymers of cyclic olefins and ethylene have a glass transition temperature of less than 200 ° C. and a large heat resistance and thermal expansion coefficient, which are not suitable as substrate materials. There are many enough.

  For this reason, various cyclic olefin addition polymers have been proposed as liquid crystal substrate materials. For example, addition copolymers of cyclic olefins having hexyl groups in the side chain substituents (Patent Documents 4 and 5), addition copolymers of cyclic olefins having alkoxysilyl groups in the side chain substituents, and crosslinked products and composites thereof (Patent Documents 6 to 9), cyclic olefin addition copolymers having a silacycloalkylene group in the side chain substituent, and a crosslinked complex thereof (Patent Document 10) have been proposed.

In addition to cyclic olefin polymers, liquid crystal display element substrates and organic EL display element substrate materials include organic materials such as acrylate resins, epoxy resins, polyester resins, and bacterial cellulose, organic materials and glass fillers, and glass fiber cloths. Transparent composites are proposed. (Patent Documents 11 to 20)
When the conventionally proposed cyclic olefin addition polymers are used as substrate materials for glass substitute substrates such as liquid crystal substrates, organic EL substrates, and electronic paper substrates, for example, 5-hexylbicyclo [2.2.1] hepta. A cyclic olefin addition copolymer containing -2-ene has a large thermal expansion coefficient (linear expansion coefficient) and insufficient thermal dimensional stability. That is, an addition copolymer of a cyclic olefin having an alkoxysilyl group in the side chain substituent, and a crosslinked product or composite thereof, or a cyclic olefin addition copolymer having a silacycloalkylene group in the side chain substituent and a crosslinked product thereof In the composite, the water absorption is large and the dimensional stability due to humidity change is insufficient.

  The present inventor has intensively studied in view of such a situation, and as a result, bicyclo [2.2.1] which has no substituent or has only one of a halogen atom, a methyl group and an ethyl group. A copolymer obtained by addition copolymerization of hept-2-ene and bicyclo [2.2.1] hept-2-ene having a substituent of any one of butyl group, trimethylsilyl group and trimethylsilylmethyl group at a specific ratio. The inventors have found that the polymer is particularly suitable for optical substrate materials and have completed the present invention.

Patent Document 21 discloses a palladium system of bicyclo [2.2.1] hept-2-ene and 5-butylbicyclo [2.2.1] hept-2-ene (molar ratio: 50/50). A catalyst addition copolymer is described, which is similar to the addition copolymer used in the present invention, but such a copolymer with a polymerization ratio has other materials that have a large coefficient of thermal expansion. As a material for an optical substrate having processes such as lamination and adhesion, it has undesirable properties. In addition, since the palladium-based catalyst used in Patent Document 21 has insufficient polymerization activity and uses a large amount of palladium, the resulting addition copolymer does not have high optical transparency. Further, this document does not describe the use of an addition copolymer as a substrate material for a display element.
JP-A-5-61026 JP 2001-215482 A JP-A-6-202091 JP 2002-047318 A JP 2002-012624 A JP 2002-114826 A JP 2002-327024 A JP 2003-48998 A JP 2003-105214 A JP 2003-160620 A JP 2004-300433 A JP 2004-168945 A JP 2004-168944 A JP 2004-269727 A JP 2004-307845 A JP 2004-307845 A JP 2002-302539 A JP 2002-173529 A JP 2005-60480 A JP 2005-60680 A Japanese Patent No. 3646334

  The present invention is excellent in transparency, heat resistance, wet water, water resistance, solvent resistance, chemical resistance to acids, alkalis, etc., has a small thermal expansion coefficient (linear expansion coefficient), and has improved mechanical properties. It is an object of the present invention to provide a tough optical substrate and a manufacturing method thereof. Another object of the present invention is to provide an optical substrate suitable for applications such as a liquid crystal substrate, an organic EL (electroluminescence) substrate, and electronic paper, particularly a film or sheet-like optical substrate.

The optical substrate of the present invention is
The structural unit (1) represented by the following formula (1) and the structural unit (2) represented by the following formula (2)
In a total of 100 mol% of the structural unit (1) and the structural unit (2), the proportion of the structural unit (1) is 55 to 98 mol%, the proportion of the structural unit (2) is 2 to 45 mol%,
It is characterized by comprising a cyclic olefin addition copolymer having a number average molecular weight (Mn) of 20,000 to 300,000.

(In formula (1), A ^{1 to} A ⁴ each independently represents an atom or group selected from a hydrogen atom, a halogen atom, a methyl group, and an ethyl group.)

(In Formula (2), ^one of B ^{1 to} B ⁴ is a group selected from a butyl group, a trimethylsilyl group, and a trimethylsilylmethyl group, and the others are independently a hydrogen atom, a halogen atom, a methyl group, and an ethyl group. Indicates the atom or group selected.)

  In the present invention, in the cyclic olefin addition copolymer, the proportion of the structural unit (1) is 80 to 98 mol% in the total of 100 mol% of the structural unit (1) and the structural unit (2). ) Is preferably 2 to 20 mol%.

In this invention, it is preferable that the glass transition temperature of the said cyclic olefin addition copolymer is 220-400 degreeC.
The optical substrate of the present invention preferably has a linear expansion coefficient of 70 ppm / ° C. or less.

In the present invention, the cyclic olefin-based addition copolymer preferably satisfies the following conditions 1) and 2) when the film is formed into a film having a thickness of 100 μm and the wide-angle X-type scattering is measured.
1) Of the two detected peaks, the low-angle peak position (2θ) is 8 ° or more.
2) The ratio of the high angle peak intensity to the low angle peak intensity is 0.5 or more.

The optical substrate of the present invention is preferably in the form of a film or a sheet.
The optical substrate of the present invention is preferably a substrate for a liquid crystal display element, preferably an organic EL substrate, preferably a plasma display panel substrate, and an electronic paper substrate. Is also preferable.

The method for producing an optical substrate of the present invention comprises a monomer (i) represented by the following formula (i) and a monomer (ii) represented by the following formula (ii), Monomer in which the proportion of monomer (i) is 55 to 98 mol% and the proportion of monomer (ii) is 2 to 45 mol% in a total of 100 mol% of i) and monomer (ii) Body composition
An addition copolymerization reaction in the presence of a polymerization catalyst comprising a palladium compound (a) and a phosphine compound (b) having at least two unsubstituted or alkyl-substituted cyclopentyl groups or cyclohexyl groups;
Producing a cyclic olefin addition copolymer having a number average molecular weight of 20,000 to 300,000;
And a step of molding the obtained cyclic olefin addition copolymer.

(In formula (i), A ^{1 to} A ⁴ each independently represents an atom or group selected from a hydrogen atom, a halogen atom, a methyl group, and an ethyl group.)

(In Formula (ii), ^one of B ^{1 to} B ⁴ is a group selected from a butyl group, a trimethylsilyl group, and a trimethylsilylmethyl group, and the others are independently a hydrogen atom, a halogen atom, a methyl group, and an ethyl group. Indicates the atom or group selected.)

In the method for producing an optical substrate of the present invention, the polymerization catalyst is:
(A) a palladium compound selected from an organic acid salt of palladium or a beta-diketone compound of palladium;
(B) a phosphine compound selected from compounds represented by the following formula (3);
P (R ¹ ) ₂ (R ² ) (3)
(In Formula (3), P is a phosphorus atom,
R ¹ is an unsubstituted or alkyl-substituted cyclopentyl group or cyclohexyl group having 5 to 12 carbon atoms,
R ² is selected from an unsubstituted or alkyl-substituted cyclopentyl group or cyclohexyl group having 5 to 12 carbon atoms, an unsubstituted or alkyl-substituted phenyl group having 6 to 12 carbon atoms, and a branched alkyl group having 3 to 6 carbon atoms. Group. ),
(C) at least one compound selected from a Lewis acidic boron compound, a Lewis acidic aluminum compound, an ionic boron compound, and an ionic aluminum compound,
And it is preferable that (d) an organoaluminum compound is included as needed.

In the method for producing an optical substrate of the present invention, it is more preferable that the palladium compound (a) and the phosphine compound (b) form a complex represented by the following formula (4).
Pd (X) ₂ · [P (R ¹ ) ₂ (R ² )] _k (4)
(In Formula (4), Pd is a palladium atom, X is an organic acid anion or a betadiketone anion, R ¹ and R ² are the same as those in Formula (3), and k represents 1 or 2. )
In the method for producing an optical substrate of the present invention, the phosphine compound (b) is preferably an unsubstituted or alkyl-substituted tricyclopentylphosphine compound having 5 to 12 carbon atoms.

  In the method for producing an optical substrate of the present invention, at least one compound (c) selected from a Lewis acidic boron compound, a Lewis acidic aluminum compound, an ionic boron compound, and an ionic aluminum compound is carbenium. It is preferably an ionic boron compound of a cation or a phosphonium cation.

  According to the present invention, transparency, heat resistance, wet water, water resistance, solvent resistance, and chemical resistance to acids, alkalis, etc. are excellent, the thermal expansion coefficient (linear expansion coefficient) is small, and mechanical properties are low. An optical substrate having improved toughness and a method for manufacturing the same can be provided. In the present invention, an optical substrate suitable for applications such as a liquid crystal substrate, an organic EL (electroluminescence) substrate, and electronic paper, particularly a film or sheet-like optical substrate can be provided.

Hereinafter, the present invention will be specifically described.
Cyclic olefin addition copolymer The cyclic olefin addition copolymer which comprises the optical board | substrate of this invention is a structural unit (1) represented by following formula (1), and a structural unit (2) represented by following formula (2) ( 2).

(In formula (1), A ^{1 to} A ⁴ each independently represents an atom or group selected from a hydrogen atom, a halogen atom, a methyl group, and an ethyl group.)

(In Formula (2), ^one of B ^{1 to} B ⁴ is a group selected from a butyl group, a trimethylsilyl group, and a trimethylsilylmethyl group, and the others are independently a hydrogen atom, a halogen atom, a methyl group, and an ethyl group. Indicates the selected atom or group.)
The cyclic olefin addition copolymer which concerns on this invention is 55-98 mol% of structural units (1) with respect to a total of 100 mol% of a structural unit (1) and a structural unit (2), and a structural unit (2). In a proportion of 2 to 45 mol%, preferably 70 to 98 mol% of the structural unit (1), 2 to 30 mol% of the structural unit (2), more preferably the structural unit (1). It has 80 to 98 mol% and the structural unit (2) in a proportion of 2 to 20 mol%. In the cyclic olefin addition copolymer having the structural units (1) and (2), the proportion of the structural unit (1) having high stereoregularity increases as the proportion of the structural unit (1) increases. The mechanical properties of an optical substrate such as a film or sheet obtained from the olefin addition copolymer are improved, and the linear expansion coefficient is reduced.

  When the proportion of the structural unit (1) is less than 55 mol%, that is, the proportion of the structural unit (2) exceeds 45 mol%, the linear expansion coefficient of the film or sheet obtained by molding from the cyclic olefin addition copolymer is large. This is not preferable in terms of dimensional stability.

  Further, when the proportion of the structural unit (1) exceeds 98 mol%, that is, when the proportion of the structural unit (2) is less than 2 mol%, the cyclic olefin addition copolymer is highly aromatic at room temperature to 100 ° C. In some cases, it is difficult to obtain a film or sheet by the solution casting method (casting method) without being dissolved in an aromatic hydrocarbon or alicyclic hydrocarbon solvent.

  The structural unit (1) in the cyclic olefin addition copolymer is formed by addition copolymerization of the monomer (i) represented by the following formula (i), and the structural unit (2) is represented by the following formula ( It is formed by addition copolymerization of the monomer (ii) represented by ii).

(In formula (i), A ^{1 to} A ⁴ are the same as in formula (1), and each independently represents an atom or group selected from a hydrogen atom, a halogen atom, a methyl group, and an ethyl group.)

(In the formula (ii), B ¹ .about.B ⁴ is a similar to Equation (2), one of the B ¹ .about.B ^4, a butyl group, a trimethylsilyl group, a group selected from trimethylsilylmethyl group, others Each independently represents an atom or group selected from a hydrogen atom, a halogen atom, a methyl group, and an ethyl group.)
Specific examples of the monomer (i) represented by the above formula (i) include, for example,
Bicyclo [2.2.1] hept-2-ene,
5-methylbicyclo [2.2.1] hept-2-ene,
5,6-dimethylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-chlorbicyclo [2.2.1] hept-2-ene,
5-fluorobicyclo [2.2.1] hept-2-ene,
And 5-methyl-6-ethylbicyclo [2.2.1] hept-2-ene.

Among these monomers (i), bicyclo [2.2.1] hept-2-ene is particularly preferable from the viewpoint of mechanical strength and toughness of a film or sheet formed from the addition copolymer.
Moreover, as a specific example of the monomer (ii) represented by the above formula (ii), for example,
5-n-butylbicyclo [2.2.1] hept-2-ene,
5-sec-butylbicyclo [2.2.1] hept-2-ene,
5-tert-butylbicyclo [2.2.1] hept-2-ene,
5-trimethylsilylbicyclo [2.2.1] hept-2-ene,
5-trimethylsilylmethylbicyclo [2.2.1] hept-2-ene,
5-trimethylsilyl-6-methylbicyclo [2.2.1] hept-2-ene,
5-n-butyl-6-methylbicyclo [2.2.1] hept-2-ene,
5-methyl-6-n-butylbicyclo [2.2.1] hept-2-ene,
5-ethyl-6-n-butylbicyclo [2.2.1] hept-2-ene,
5-n-butyl-6-chlorobicyclo [2.2.1] hept-2-ene,
Etc.

Among these monomers (ii)
A compound wherein one of B ^{1 to} B ⁴ in formula (ii) is a butyl group, such as 5-butylbicyclo [2.2.1] hept-2-ene,
5-Trimethylsilylbicyclo [2.2.1] hept-2-ene is preferred because it imparts toughness to the film or sheet molded from the resulting cyclic olefin addition copolymer and can reduce the linear expansion coefficient.

In addition to the structural unit (1) and the structural unit (2) described above, the cyclic olefin addition copolymer according to the present invention includes the structural unit (1) and the structural unit for the purpose of imparting adhesion and introducing a crosslinking site. You may have the other cyclic olefin type structural unit (3) which has a polar or a functional group in a side chain substituent in the ratio of 10 mol% or less with respect to a total of 100 mol% with (2). The structural unit (3) is formed by addition polymerization of a cyclic olefin monomer (iii) having a polar group or a functional group selected from an ester group, an acid anhydride group, a carbonimide group, an oxetanyl group, and the like. The

Specific examples of such monomer (iii) include the following compounds.
Methyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
Methyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
T-butyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] methyl dodeca-9-ene-4-carboxylate,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] methyl dodeca-9-ene-4-carboxylate,
4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] t-butyl dodeca-9-ene-4-carboxylate,
Bicyclo [2.2.1] hept-5-ene-2,3-carboxylic anhydride,
Bicyclo [2.2.1] hept-5-ene-2-spiro-3'-exo-succinic anhydride,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-spiro-3′-exo-succinic anhydride,
Bicyclo [2.2.1] hept-5-ene-N-cyclohexyl-2,3-carbonimide,
Bicyclo [2.2.1] hept-5-ene-N- (2 ′, 6′-diethylphenyl) -2,3-carbonimide,
Bicyclo [2.2.1] hept-5-ene-N-cyclohexyl-2-spiro-3'-exo-anhydrous succinimide 5-[(3-ethyl-3-octacenyl) methoxy] bicyclo [2.2.1 ] Hept-2-ene,
5-[(3-oxetanyl) methoxy] bicyclo [2.2.1] hept-2-ene,
Bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-ethyl-3-oxetanyl) methyl.

  The cyclic olefin addition copolymer according to the present invention has a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC), a number average molecular weight (Mn) of 20,000 to 300,000, and a weight average molecular weight (Mw). ) Is 50,000 to 500,000, preferably the number average molecular weight (Mn) is 50,000 to 150,000, and the weight average molecular weight (Mw) is 100,000 to 300,000.

  When the number average molecular weight (Mn) of the cyclic olefin addition copolymer according to the present invention is less than 20,000, the mechanical strength of the molded film or sheet may be lowered and may be easily broken. On the other hand, when the number average molecular weight (Mn) exceeds 300,000, when producing a film or sheet by the solution casting method, the solution viscosity becomes too high, and it becomes difficult to form the film or sheet. Often the flatness of the film or sheet is impaired.

  The glass transition temperature (Tg) of the cyclic olefin addition copolymer according to the present invention is determined by Tanδ (Tanδ = E) derived from storage elastic modulus (E ′) and loss elastic modulus (E ″) measured by dynamic viscoelasticity. "/ E ').

The glass transition temperature of the cyclic olefin addition copolymer according to the present invention is 220 to 400 ° C, preferably 250 to 350 ° C. If the glass transition temperature is less than 220 ° C, the heat resistance is insufficient, the coefficient of linear expansion as a film or sheet material is increased, or the film or sheet is subjected to high temperatures during secondary processing such as with ITO (indium tin oxide) electrodes. This becomes difficult, and the conductive effect as an ITO electrode is reduced.

Further, when the glass transition temperature of the cyclic olefin addition copolymer according to the present invention exceeds 400 ° C., a tough film or sheet is often not obtained.
The cyclic olefin addition copolymer according to the present invention is excellent in transparency, and the light transmittance (wavelength 400 nm) measured with a film having a thickness of 100 μm is usually 85% or more, preferably 88% or more, and the haze value is Usually, it is less than 1.0%, preferably 0.6% or less.

Moreover, when the cyclic olefin type addition copolymer which concerns on this invention is shape | molded into a film with a film thickness of 100 micrometers, and measured wide angle X money scattering, it is preferable to satisfy the following conditions 1) and 2). 1) Of the two detected peaks, the low-angle peak position (2θ) is 8 ° or more.
2) The ratio of the high angle peak intensity to the low angle peak intensity is 0.5 or more.

  In addition, it has the characteristic that the intermolecular distance in a polymer is so small that the peak position (2 (theta)) of a low angle position of a wide angle X-ray-scattering figure is large. The high-angle peak has a feature that the peak intensity increases as the arrangement in the molecule is more regular. That is, the cyclic olefin addition copolymer satisfying the above conditions 1) and 2) has a small intermolecular distance and a regular intramolecular arrangement. As such a cyclic olefin type addition copolymer, the cyclic olefin addition copolymer obtained in the manufacturing method of the optical board | substrate of this invention is mentioned as a suitable thing.

Production of Cyclic Olefin Addition Copolymer The cyclic olefin addition copolymer according to the present invention is a monomer comprising the above-mentioned monomer (i), monomer (ii) and optionally monomer (iii). The body composition can be obtained by addition copolymerization. The monomer composition to be subjected to addition copolymerization has a monomer (i) ratio of 55 to 98 mol%, in a total amount of 100 mol% of monomer (i) and monomer (ii). The proportion of the body (ii) is 2 to 45 mol%, preferably the proportion of the monomer (i) is 70 to 98 mol%, the proportion of the monomer (ii) is 2 to 30 mol%, and more Preferably, the proportion of monomer (i) is 80 to 98 mol%, and the proportion of monomer (ii) is 2 to 20 mol%. The proportion of monomer (iii) in the monomer composition is a proportion of 10 mol% or less with respect to 100 mol% in total of monomer (i) and monomer (ii).

  In the present invention, it is preferable to use a palladium-based catalyst for addition copolymerization of the monomer composition, and it is more preferable to use a specific palladium-based catalyst containing a palladium compound and a specific phosphine compound. When the cyclic olefin addition copolymer is produced using a specific palladium catalyst, the structural unit (1) in the cyclic olefin addition copolymer has high stereoregularity, and the molecular weight of the cyclic olefin addition copolymer is increased. It can be easily controlled within a preferable range. A nickel-based catalyst does not provide a highly stereoregular structural unit (1) and has high solubility in a hydrocarbon solvent at 25 ° C., but the resulting molded article has poor mechanical properties and a linear expansion coefficient. Is also unfavorable because it becomes large.

By the way, since the structural unit (1) obtained by addition polymerization using a specific palladium catalyst exhibits high stereoregularity as described above, the addition polymer containing only the monomer (i) has a temperature of 25 ° C. It is difficult to dissolve in a hydrocarbon solvent, and molding by the solution casting method is difficult. For this reason, the cyclic olefin addition copolymer which concerns on this invention needs to have a structural unit (2), and can shape | mold to the film or sheet | seat by a solution casting method by this.
-Polymerization catalyst In this invention, the polymerization catalyst which manufactures a cyclic olefin addition polymer, Preferably, it is a palladium-type catalyst containing a palladium compound (a) and a phosphine compound (b), More specifically, ( a) a palladium compound, (b) a phosphine compound, (c) at least one compound selected from a Lewis acidic boron compound, a Lewis acidic aluminum compound, an ionic boron compound and an ionic aluminum compound, and Accordingly, (d) a catalyst composed of an organoaluminum compound.
(A) Palladium compound Examples of the palladium compound as the catalyst component (a) include the following groups of compounds.
1) Palladium organic acid salt, palladium beta-diketone compound, palladium halide. Preferably, a carboxylate having 1 to 20 carbon atoms, a sulfonate having 1 to 20 carbon atoms, a phosphate ester salt having 4 to 30 carbon atoms, a beta diketone compound, a halide, palladium (ii) [Beta] -diketone compound having 5 to 15 carbon atoms.
2) Alkyl group, aryl group and / or alkenyl group bonded to Pd atom with π (pi) bond, substituted or unsubstituted cycloalkadienyl group, cycloalkadiene bonded to Pd atom with σ (sigma) bond A palladium complex having at least one substituent selected from the group.

Specific examples of the palladium compound of group 1) include, for example,
Palladium dimethanoate, palladium diethanoate,
Bis (tricyclohexylphosphine) palladium dietanoate,
Bis (tricyclopentylphosphine) palladium dietanoate,
Bis (triphenylphosphine) palladium dietanoate,
Palladium bis (trifluoroethanoate),
Palladium dibutanoate,
Palladium bis (2-ethylhexanoate),
Palladium zidodecano art,
Palladium di (octadeca-9-enato),
Palladium bis (cyclohexanecarboxylate),
Palladium bis (benzenecarboxylate),
Palladium bis (3-methylbenzenecarboxylate),
Palladium bis (4-methylbenzenecarboxylate),
Palladium bis (naphthalenecarboxylate),
Palladium bis (butyl phosphate),
Palladium bis (dibutyl phosphate),
Palladium bis (dihexyl phosphate),
Palladium bis (methanesulfonate),
Palladium bis (trifluoromethanesulfonate),
Palladium bis (p-toluenesulfonate),
Palladium bis (benzenesulfonate),
Palladium bis (naphthalene sulfonate),
Palladium bis (dodecylbenzenesulfonate),
Palladium bis (2,4-pentadionate),
Palladium bis (1-ethoxy-1,3-butanedionate),
Palladium bis (1,1,1-trifluoro-5,5,5-trifluoro-2,4-pentadionate),
Palladium bis (2,2,6,6-tetramethylhepta-3,5-dionate),
Bis (tricyclohexylphosphine) palladium dichloride,
Bis (tricyclohexylphosphine) palladium dibromide,
Bis (tricyclopentylphosphine) palladium dichloride,
Bis [tri (2-methylphenyl) phosphine] palladium dibromide,
Bis [tri (4-methylphenyl) phosphine] palladium dibromide,
1,2-bis (diphenylphosphino) ethane palladium dichloride,
1,3-bis (diphenylphosphino) propane palladium dichloride,
Bis (dimethylglyoxime) palladium dichloride,
Etc.

Specific examples of the palladium compound of the group 2) include, for example,
(1,5-cyclooctadiene) palladium dichloride,
[(Η ³ -crotyl) (1,5-cyclooctadiene) palladium chloride],
[(Η ³ -crotyl) (1,5-cyclooctadiene) palladium bromide],
[(Η ³ -crotyl) (1,5-cyclooctadiene) palladium] [ethanoate],
[(Η ³ -allyl) (tricyclohexylphosphine) palladium] {trifluoroethanoate},
(Cyclopentadienyl) (methyl) (triphenylphosphine) palladium,
[Bis (tricyclohexylphosphine) (methyl) palladium (chloride)],
[Bis (tricyclohexylphosphine) (phenyl) palladium (chloride)],
[2,6- (dimethylaminomethyl) phenyl] palladium chloride,
[2- (dimethylaminomethyl) phenyl] (tricyclohexylphosphine) palladium] [ethanoate],
[2- (dimethylaminomethyl) phenylpalladium ethanolate] ₂ ,
(1,5,9-cyclododecatriene) palladium,
Bis (bicyclo [2.2.1] hepta-2,5-diene) palladium,
Bis (η ³ -allyl palladium chloride),
Bis (dibenzylideneacetone) palladium,
Bis [mu ² - chloro -1η ^2, 5η ¹ -6- ethoxy-exo-5,6-dihydro-dicyclopentadiene palladium (II)]
Etc.

Among these palladium compounds, a compound selected from an organic acid salt of palladium or a beta-diketone compound of palladium, which does not require complicated synthesis and has excellent polymerization activity, is preferably used.
(B) Phosphine Compound The phosphine compound as the catalyst component (b) is preferably a phosphine compound having at least two unsubstituted or alkyl-substituted cyclopentyl groups or cyclohexyl groups, more preferably represented by the following formula (3). A phosphine compound selected from the following compounds is desirable.

P (R ¹ ) ₂ (R ² ) (3)
(In Formula (3), P is a phosphorus atom,
R ¹ is an unsubstituted or alkyl-substituted cyclopentyl group or cyclohexyl group having 5 to 12 carbon atoms,
R ² is selected from an unsubstituted or alkyl-substituted cyclopentyl group or cyclohexyl group having 5 to 12 carbon atoms, an unsubstituted or alkyl-substituted phenyl group having 6 to 12 carbon atoms, and a branched alkyl group having 3 to 6 carbon atoms. Group. )
As a specific example of such a phosphine compound,
Tricyclopentylphosphine,
Dicyclopentyl (cyclohexyl) phosphine,
Dicyclopentyl (3-methylcyclohexyl) phosphine,
Dicyclopentyl (isopropyl) phosphine,
Dicyclopentyl (s-butyl) phosphine,
Dicyclopentyl (t-butyl) phosphine,
Dicyclopentyl (2-methylphenyl) phosphine,
Tricyclohexylphosphine,
Dicyclohexyl (cyclopentyl) phosphine,
Dicyclohexyl (3-methylcyclohexyl) phosphine,
Dicyclohexyl (isopropyl) phosphine,
And dicyclohexyl (2-methylphenyl) phosphine.

Among these phosphine compounds (b), unsubstituted or alkyl-substituted tricyclopentylphosphine having 5 to 12 carbon atoms is particularly preferable.
In the polymerization catalyst according to the present invention, it is more preferable that the palladium compound (a) forms a complex with the phosphine compound (b), and the palladium compound (a) and the phosphine compound (b) are represented by the following formula (4). It is more preferable that the complex represented by this is formed.

Pd (X) ₂ · [P (R ¹ ) ₂ (R ² )] _k (4)
(In Formula (4), Pd is a palladium atom, X is an organic acid anion or a betadiketone anion, R ¹ and R ² are the same as those in Formula (3), and k represents 1 or 2. ).
(C) at least one compound selected from a Lewis acidic boron compound, a Lewis acidic aluminum compound, an ionic boron compound and an ionic aluminum compound. As the catalyst component (c), 1) a Lewis acidic boron compound, Examples thereof include at least one compound selected from 2) Lewis acidic aluminum compounds, 3) ionic boron compounds, and 4) ionic aluminum compounds.
1) Lewis acidic boron compound Examples of the Lewis acidic boron compound include compounds represented by the following formula.

B (R ³ ) ₃・ D
(Wherein B is a boron atom, R ³ is a fluorine atom-substituted or fluorinated alkyl-substituted phenyl group or fluorine atom, D is selected from dialkyl ethers having 1 to 10 carbon atoms, trialkylamines, phenols and alcohols) Electron donating compounds)
As such a Lewis acidic boron compound, specifically, for example,
Tris (pentafluorophenyl) boron,
Tris (3,5-fluorophenyl) boron,
Tris [3,5-bis (trifluoromethyl) phenyl] boron,
Boron trifluoride-diethyl ether complex,
Boron trifluoride / dibutyl ether complex,
Boron trifluoride-triethylamine complex,
And the like.
2) Lewis acidic aluminum compound Examples of the Lewis acidic aluminum compound include compounds represented by the following formulas.

AlR ⁴ _k X _3-k
(In the formula, Al is an aluminum atom, R ⁴ is a fluorine atom-substituted or fluorinated alkyl-substituted phenyl group, an alkyl group having 1 to 10 carbon atoms, or an aryl group, and X is a halogen selected from fluorine, chlorine, and bromine. Atom, k represents an integer of 0 to 3)
As such a Lewis acidic aluminum compound, specifically, for example,
Tris (pentafluorophenyl) aluminum,
Tris (3,5-fluorophenyl) aluminum,
Tris [3,5-bis (trifluoromethyl) phenyl] aluminum,
Aluminum trifluoride, diethyl ether complex,
Ethylaluminum difluoride,
Ethylaluminum dichloride,
Butyl aluminum dibromide,
Diethylaluminum fluoride,
Examples include compounds such as 3,5-dimethylphenylaluminum difluoride.
3) Ionic Boron Compound Examples of the ionic boron compound include compounds represented by the following formula.

[R ⁵ ] ⁺ [B (R ⁶ ) ₄ ] ^-
(Wherein R ⁵ is a carbonium cation, a phosphonium cation,
An organic cation having 1 to 30 carbon atoms selected from an ammonium cation and an anilinium cation, R ⁶ represents a fluorine atom-substituted or fluorinated alkyl-substituted phenyl group, and B represents a boron atom. )
As such an ionic boron compound, specifically, for example,
Triphenylcarbenium tetrakis (pentafluorophenyl) borate,
Tri (p-tolyl) carbenium tetrakis (pentafluorophenyl) borate,
Diphenyl (methyl) carbenium tetrakis (pentafluorophenyl) borate,
Bis (diphenyl) methylcarbenium tetrakis (pentafluorophenyl) borate,
Triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,
Triphenylcarbenium tetrakis (2,4,6-trifluorophenyl) borate,
Triphenylcarbenium tetraphenylborate,
Triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Diphenylphosphonium tetrakis (pentafluorophenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
N, N-diethylanilinium tetrakis (pentafluorophenyl) borate,
N, N-diphenylanilinium tetrakis (pentafluorophenyl) borate,
Lithium tetrakis (pentafluorophenyl) borate,
Lithium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,
Etc.
4) Ionic Aluminum Compound Examples of the ionic aluminum compound include compounds represented by the following formula.

[R ⁵ ] ⁺ [Al (R ⁶ ) ₄ ] ^-
(Wherein R ⁵ is a carbonium cation, a phosphonium cation,
An organic cation having 1 to 30 carbon atoms selected from an ammonium cation and an anilinium cation, R ⁶ represents a fluorine atom-substituted or fluorinated alkyl-substituted phenyl group, and Al represents an aluminum atom. )
As such an ionic aluminum compound, specifically, for example,
Triphenylcarbenium tetrakis (pentafluorophenyl) aluminate,
Triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] aluminate,
Triphenylcarbenium tetrakis (2,4,6-trifluorophenyl) aluminate,
And triphenylcarbenium tetraphenylaluminate.

Among these catalyst components (c), 3) an ionic boron compound is preferable, and an ionic boron compound of a carbenium cation or a phosphonium cation is particularly preferable.
(D) Organoaluminum compound The organoaluminum compound as the catalyst component (d) used as necessary is an aluminum compound having at least one aluminum-alkyl bond.

Specifically, as the organoaluminum compound as such a catalyst component (d), for example,
Alkylalumoxane compounds such as methylalumoxane, ethylalumoxane, butylalumoxane;
Trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum;
Dialkylalkylaluminum hydride compounds such as diisobutylaluminum hydride and diethylaluminum hydride; are preferably used.

  In addition, alkylaluminum compounds having a halogen atom such as diethylaluminum chloride, dibutylaluminum chloride, and ethylaluminum chloride can also be exemplified.

When the palladium compound of the catalyst component (a) has an alkyl group or η ³ -allyl group, or is an organic carboxylate of palladium, or a beta diketone compound of palladium. Although not necessarily a necessary component, there is an action of removing amines and sulfur compounds that inhibit polymerization when present in the polymerization system.

Each of these catalyst components is usually used in an amount within the following range.
The palladium compound of the catalyst component (a) is used in the range of 0.001 to 0.1 mmol, preferably 0.002 to 0.02 mmol, with respect to 1 mol of the monomer.

  The phosphine compound of the catalyst component (b) is used in the range of 0.2 to 2.0 mol, preferably 0.5 to 1.5 mol, per 1 mol of the palladium atom of the palladium compound of the catalyst component (a). It is done. When the palladium compound (a) is a compound that forms a complex with the phosphine compound of the catalyst component (b), the separate catalyst component (b) is not necessarily required.

Lewis acidic boron compound of catalyst component (c), Lewis acidic aluminum compound,
The compound selected from the ionic boron compound or the ionic aluminum compound is 0.1 to 10 mol, preferably 0.5 to 2.0 mol, per 1 mol of the palladium compound of the catalyst component (a).

The organoaluminum compound of the catalyst component (d) is used in an amount of 0.5 to 100 mol, preferably 1 to 10 mol, per mol of the palladium compound of the catalyst component (a).
In the present invention, the method for preparing the catalyst used for addition copolymerization, that is, the method for adding each catalyst component described above is not particularly limited.
1) A catalyst component (a), a mixture of a monomer (i), a monomer (ii) and, if necessary, a cyclic olefin monomer composition comprising a single fluid (iii) and a polymerization solvent, A method in which the catalyst component (b) and the catalyst component (c) are added in the order of the catalyst component (d) as necessary.
2) A method of adding the catalyst component (d), the catalyst component (c), the catalyst component (a) and the catalyst component (b) in this order to the mixture of the monomer composition and the polymerization solvent, if necessary.
3) A method such as a method of previously mixing and contacting the catalyst components (a), (b) and (c) to the monomer composition and the mixture of the polymerization solvent is used.
・ Molecular weight regulator (chain transfer agent)
The following 1), 2) and 3) are mentioned as molecular weight regulators used for the production of the cyclic olefin addition copolymer according to the present invention.
1) Cyclopentene compound having 5 to 15 carbon atoms having a cyclopentene ring Examples include cyclopentene, 3-methylcyclopentene, 3-ethylcyclopentene, 3-isopropylcyclopentene, 4-methylcyclopentene, 4-ethylcyclopentene, 4-isopropylcyclopentene and the like. It is done.
2) An α-olefin compound having 1 to 12 carbon atoms.

Examples include ethene, prop-1-ene, but-1-ene, hexa-1-ene, octa-1-ene, styrene, vinyltrimethylsilane, and the like.
3) A C6-C15 cycloalkadiene compound having a C6-C10 cycloalkadiene ring.

Examples thereof include cycloocta-1,5-diene, cyclo-1,3-diene, cyclohexa-1,4-diene and the like.
The amount of these molecular weight regulators used depends on the desired molecular weight of the cyclic olefin addition copolymer to be produced, the kind of molecular weight regulator, the kind of palladium compound, and the kind of phosphine compound, but usually, per mole of monomer. , 0.001 to 5 mol, preferably 0.01 to 2 mol. Thereby, the number average molecular weight (Mn) of the cyclic olefin addition copolymer obtained can be suitably controlled in the range of 20,000-300,000.
Polymerization In the present invention, examples of the solvent that can be used for the cyclic olefin addition copolymerization include alicyclic hydrocarbon solvents such as cyclohexane, cyclopentane, and methylcyclopentane, and aliphatic hydrocarbons such as hexane, heptane, and octane. Solvents, aromatic hydrocarbon solvents such as toluene, benzene, xylene, ethylbenzene, mesitylene, halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, etc. However, the use of a non-halogen solvent is preferable for safety and health and environmental measures. In the present invention, a mixed solvent using two or more of these solvents can also be used.

The polymerization solvent can be used in the range of 0 to 2000 parts by weight per 100 parts by weight of the monomer.
The polymerization temperature for producing the cyclic olefin addition copolymer according to the present invention is usually in the range of -20 to 120 ° C., and the temperature can be changed with time. In the present invention, the polymerization can be performed under nitrogen, argon, and air as the polymerization atmosphere.

In the present invention, it is possible to adopt a method of charging monomers at once or a method of sequentially adding monomers. When two or more types of monomers are used, the resulting copolymer is controlled from random copolymers with no composition distribution to copolymers with a composition distribution, depending on the difference in copolymerization reactivity and the monomer preparation method. However, it is preferable to minimize the composition distribution. As the polymerization process method, either a batch polymerization method or a continuous polymerization method using a tank reactor, a column reactor, a tube reactor or the like can be employed.
-Recovery of cyclic olefin addition copolymer In the present invention, a solution of the cyclic olefin addition polymer produced by the above polymerization is prepared by using an oxycarboxylic acid such as lactic acid, glycolic acid, oxypropionic acid, oxybutyric acid, triethanolamine, or dialkyl. Extraction and separation using an aqueous solution such as ethanolamine or ethylenediaminetetraacetate, a solution selected from methanol and ethanol, or adsorption and filter using an adsorbent such as diatomaceous earth, silica, alumina, activated carbon or celite The catalyst can be decatalyzed by performing filtration and separation in the above.

  Furthermore, the cyclic olefin can be removed by evaporating and removing the solvent directly from the decatalyzed solution, or coagulating with alcohols such as methanol, ethanol and propanol, or ketones such as acetone and methyl ethyl ketone, and then drying. The addition copolymer can be recovered.

By such a method, the cyclic olefin addition polymer according to the present invention can be adjusted to 5 ppm or less, preferably 1 ppm or less, more preferably 0.1 ppm or less as Pd atoms.
Additive Additives can be added to the cyclic olefin addition polymer according to the present invention as necessary.

As an antioxidant,
2,6-di-t-butyl-4-methylphenol, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,5-di-t-butylhydroquinone, pentaerythrityl tetox [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,1′-bis (4-hydroxyphenyl) cyclohexane, 4,4′-thiobis- (6-tert-butyl-3) -Phenolic and hydroquinone antioxidants such as methylphenol);
Tris (4-methoxy-3,5-diphenyl) phosphite, tris (nonylphenyl) phosphite, tris (isodecyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite bis (2,4 Phosphorus antioxidants such as -di-t-butylphenyl) pentaerythritol diphosphite;
Furthermore, an antioxidant selected from a thioether type and a lactone type is added in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the cyclic olefin addition copolymer according to the present invention to further improve the heat deterioration resistance. Can do.

The cyclic olefin addition copolymer according to the present invention is obtained by adding a condensed phosphate ester compound, typically 1,3-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] benzene or the like. It is also preferable to impart flame retardancy, and when added in the range of 5 to 15 parts by weight per 100 parts by weight of the cyclic olefin addition copolymer, the flame retardancy is V-0 and transparency can be maintained. it can.
Optical Substrate The optical substrate of the present invention is obtained by molding the cyclic olefin addition copolymer according to the present invention or a composition containing the addition copolymer. In addition, the shape of the optical substrate of the present invention is not particularly limited as long as it is suitable for its use, but it is preferably a film or a sheet.

The optical substrate of the present invention has a linear expansion coefficient of usually 70 ppm / ° C. or less, preferably 60 ppm / ° C. or less, and is excellent in heat resistance and dimensional stability.
Further, the optical substrate of the present invention has a breaking strength measured at a pulling speed of 3 mm / min according to JIS K7113, preferably 35 MPa or more, and more preferably 40 to 90 MPa. Such an optical substrate having a breaking strength has a sufficient mechanical strength when used in various display elements and the like.

The method for molding the cyclic olefin addition copolymer or the composition containing the addition copolymer according to the present invention is not particularly limited, but in the case of producing a film-like or sheet-like optical substrate. The cyclic olefin addition copolymer according to the present invention or a composition containing the addition copolymer is dissolved in a solvent and applied to a support, in that the deterioration of the polymer due to heat history can be suppressed. The film is preferably formed by a solution casting method (casting method) for drying the solvent, whereby a thin film, a film, and a sheet having a film thickness of 20 to 300 μm are suitably obtained.

  The solvent used in the solution casting method needs to be a solvent that can dissolve the cyclic olefin addition copolymer to be molded. Many of the cyclic olefin addition copolymers according to the present invention are cycloaliphatic hydrocarbon solvents such as cyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane, toluene, xylene, ethylbenzene, mesitylene, chlorobenzene, o-dichlorobenzene and the like. However, as the proportion of the structural unit (1) increases, the solvent tends to be difficult to dissolve unless the proportion of the alicyclic hydrocarbon solvent is high. The alicyclic hydrocarbon solvent is more soluble than the aromatic solvent in the cyclic olefin addition copolymer according to the present invention, but depending on the film thickness, it is difficult to remove the residual solvent from the film or sheet during drying. There is a case. However, residual solvent can be removed from the film or sheet by treating with steam or solution such as methylene chloride, methanol, ethanol, etc. and drying.

  Since the preferred optical substrate of the present invention is a film or sheet formed by molding the cyclic olefin addition copolymer according to the present invention by a solution casting method, since it has excellent surface smoothness, image distortion is caused. The contrast of the image is excellent because it is small and has excellent optical transparency. Furthermore, since the optical elastic coefficient is small, it can be bent and used like a curved display element display.

  The optical substrate of the present invention can be suitably used as a substrate for various display elements, and is particularly useful as an optical substrate for liquid crystal display elements, for organic EL (electroluminescence), for plasma display panels, and for electronic paper. is there.

  A plastic substrate of a liquid crystal display is usually used with an undercoat film, a gas barrier film, a hard coat film, and a transparent conductive film such as ITO (indium tin oxide). Since the film or sheet-like optical substrate according to the present invention is made of a cyclic olefin addition polymer having a glass transition temperature of 220 ° C. or higher, the thermal expansion is small and the dimensional stability is good. And since heat resistance is good, when providing the electrode by ITO (indium tin oxide) on a board | substrate, it can process at high temperature and the electrode with the outstanding electroconductivity is obtained.

  Furthermore, the film or sheet-like optical substrate according to the present invention is excellent in moisture resistance and water resistance. When moisture passes through the liquid crystal substrate, the liquid crystal and the transparent conductive film may be deteriorated. However, the optical substrate of the present invention is excellent in moisture resistance and water resistance, and has a moisture absorption of 0.05% or less, preferably 0.01%. Since it can be set as the following films or sheets, it is also suitable as a substrate (liquid crystal substrate) for a liquid crystal display element. Also, the birefringence of the film or sheet produced during the production of the film or sheet can be reduced by annealing the film or sheet containing 5 to 20% of the solvent at 50 to 150 ° C.

  The cyclic olefin addition copolymer according to the present invention has chemical resistance to hydrochloric acid, potassium hydroxide, tetramethylammonium hydroxide, and the like, such as dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP). It has solvent resistance to the cleaning solvent used when forming the thin film transistor (TFT) array on the substrate (TFT array process). For this reason, the optical substrate of the present invention can be suitably used as a liquid crystal substrate. Even when the liquid crystal is sealed between two liquid crystal substrates, the optical substrate is resistant to liquid crystal. Excellent.

The optical substrate of the present invention can be applied to an organic EL (electroluminescence) substrate in which a glass substrate is used in addition to a liquid crystal substrate. For organic EL, since a high level of moisture resistance and water resistance is required for extending the life of the light emitting material, oxidation is required for resistance to water vapor and oxygen by sputtering and CVD (vapor phase deposition method). It is necessary to provide a barrier film of silicon, aluminum oxide or silicon nitride. Since the optical substrate of the present invention can be easily treated with plasma, corona, etc. on its surface, there is no problem of adhesion with silicon oxide, aluminum oxide, silicon nitride, etc. when these barrier films are formed.

  Further, the optical substrate of the present invention can also be applied to a microcapsule-type or thin-film organic EL-type electronic paper substrate. The electronic paper is composed of a substrate plastic material, a hard coat layer, a transparent conductive layer, a gas barrier layer, and the like, like the liquid crystal display. As a substrate plastic material, flexibility, dimensional stability, transparency, and adhesion to each layer are required. The optical substrate of the present invention has sufficient flexibility, and in particular, by increasing the proportion of the structural unit (1) of the cyclic olefin addition copolymer, it becomes a film or sheet having excellent flexibility. Adhesion between the undercoat film and the optical substrate of the present invention is improved by using a corona-treated film or sheet.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

The properties of the cyclic olefin addition copolymer, such as the molecular weight, glass transition temperature, composition and film transparency, were determined by the following methods.
(1) Molecular weight A 150C gel permeation chromatography (GPC) apparatus manufactured by WATERS was used at 120 ° C. using o-dichlorobenzene as a solvent, using an H-type column manufactured by Tosoh Corporation. The obtained molecular weight is a standard polystyrene equivalent value.
(2) Glass transition temperature The glass transition temperature is measured at the peak temperature of temperature dispersion of Tan δ (ratio of storage elastic modulus E ′ and loss elastic modulus E ″ Tan δ = E ″ / E ′) measured by dynamic viscoelasticity. did. Measurement of dynamic viscoelasticity using Leo Vibron DDV-01FP (manufactured by Orientec), measuring frequency 10Hz, heating rate 4 ° C / min, excitation mode single waveform, excitation amplitude 2.5μm Was used to measure the peak temperature of Tan δ.
(3) Composition analysis in copolymer A part of the polymer solution after polymerization was collected, tetralin was added as a standard substance, and the polymer was coagulated with excess isopropanol. By using a gas chromatogram (GC-14B manufactured by Shimadzu Corporation) apparatus and a capillary column (film thickness: 1 μm, inner diameter: 0.25 mm, length: 60 m, column temperature: 200 ° C.), the supernatant solution was obtained from the calibration curve. Was analyzed. The composition of the copolymer formed from the residual monomer amount and the charged monomer amount was determined.
(4) Transparency (light transmittance, haze)
Using a visible UV spectrometer HITATI U-2010 Spectrophotometer, the light transmittance at a wavelength of 400 nm was measured according to ASTM-D1003 for a film having a thickness of 100 μm.
Measured according to

The haze was determined according to JIS K7105-1981 using “Haze-gard plus BKY Gardner” manufactured by Big Chemie Japan.
(5) Mechanical properties (breaking strength, elongation)
According to JIS K7113, the test piece is pulled at a speed of 3 mm / min. Measured with
(6) Linear expansion coefficient Using a TMA (Thermal Mechanical Analysis) SS6100 apparatus (manufactured by Seiko Instruments Inc.), a film piece of a test shape having a film thickness of 100 μm, a length of 10 mm, and a width of 10 mm was fixed upright, and 1 g by a probe Apply heavy load. In order to remove the thermal history of the film, from room temperature to 200 ° C., 5 ° C./min. After raising the temperature once at room temperature, the temperature was again increased from room temperature to 5 ° C / min. The linear expansion coefficient was determined from the slope of elongation of the film piece between 50 and 150 ° C.
(7) Water absorption rate The film was immersed in 23 degreeC water for 24 hours, and the water absorption rate was calculated | required from the weight change before and behind immersion. (8) Wide-angle X-ray scattering (WAXS) measurement As a sample, a film with a film thickness of 100 μm and a 2 cm × 2 cm square is used, and the apparatus has an X-ray source of CuKα (λ = 1.54 mm). Using an X-ray diffractometer MXP18 manufactured by Bruker AXS Co., Ltd., measurement was performed by scanning a range of 2θ from 3 ° to 30 ° at 5 ° / min at room temperature.

In a 2000 ml pressure-resistant reactor, under a nitrogen atmosphere, 470 ml of toluene having a water content of 10 ppm, 380 mmol of monomeric 5-n-butylbicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hepta -2-ene (520 mmol) was charged, and the molecular weight regulator cyclopentene (200 mmol) was charged. Next, a compound in which 0.0025 mmol of palladium di (ethanoate) as a catalyst component (a) and 0.0025 mmol of tricyclopentylphosphine as a catalyst component (b) were brought into contact with each other was charged in advance. After another 2 minutes, the catalyst component (c) triphenylcarbenium tetrakis (pentafluorophenyl) borate [Ph ₃ C ·
B (C ₆ F ₅ ) ₄ ] 0.0025 mmol was charged, and addition polymerization was carried out at 50 ° C.

  After 1 hour and 3 hours from the start of polymerization, 50 mmol each of bicyclo [2.2.1] hept-2-ene was added and polymerization was carried out for 6 hours to obtain addition copolymer-1. The conversion rate to addition copolymer-1 was 99.9%.

  The ratio of the structural unit derived from 5-n-butylbicyclo [2.2.1] hept-2-ene in the produced addition copolymer-1 was 38 mol%. Moreover, the number average molecular weight (Mn) of addition copolymer-1 was 65,000, the weight average molecular weight (Mw) was 205,000, and the glass transition temperature was 310 degreeC.

  Subsequently, antioxidant pentaerythrityl tetokis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4-di-) were added to the solution of addition copolymer-1. Each t-butylphenyl) phosphite was added in an amount of 0.3 part by weight per 100 parts by weight of the addition polymer, dissolved, passed through a Celite filter, and further passed through a Teflon (registered trademark) filter having a diameter of 10 μm.

  A polymer solution of this addition copolymer-1 is prepared in a toluene solution having a solid content of 20% by weight, formed into a film by a solution casting method, and then dried at 180 ° C. for 90 minutes to form a film having a thickness of 100 μm. F-1 was obtained.

  Various physical properties and wide-angle X-ray scattering were measured using this film. The results are shown in Table 1 and FIG. From the wide-angle X-ray scattering diagram of FIG. 1, the low-angle peak position (2θ) was 9.0 °, and the high-angle / low-angle peak intensity ratio was 0.59.

  In Example 1, 400 ml of toluene and 70 ml of cyclohexane as a solvent, 200 mmol of monomeric 5-n-butylbicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-2-ene Addition copolymer-2 was obtained in the same manner as in Example 1 except that 700 mmol of ethylene was charged and 10 mmol of ethylene was charged as a molecular weight regulator before the start of polymerization. The conversion rate to addition copolymer-2 was 99.7%.

The proportion of structural units derived from 5-n-butylbicyclo [2.2.1] hept-2-ene in addition copolymer-2 is 19.9 mol%, number average molecular weight (Mn) is 55,000, weight. The average molecular weight (Mw) was 195,000 and the glass transition temperature was 320 ° C.

  Subsequently, it carried out similarly to Example 1, and obtained the film F-2 with a film thickness of 100 micrometers. The evaluation results are shown in Table-1.

In a 100 ml glass pressure bottle, under nitrogen atmosphere, 5 mmol of 5-n-butylbicyclo [2.2.1] hept-2-ene and 95 mmol of bicyclo [2.2.1] hept-2-ene are used as monomers. Then, 50 ml of solvent methylcyclohexane and 1 mmol of molecular weight modifier ethylene were charged and sealed with a perforated crown with a rubber cap. Palladium dichloride (Etanoato) 2.5 × 10 ^-4 mmol as a catalyst, a complex mmol of tricyclohexylphosphine 2.5 × 10 ^-4, triphenylcarbenium tetrakis (pentafluorophenyl) borate _{[Ph 3 C · B (C 6} F 6) 4 Polymerization was carried out at 60 ° C. for 6 hours using 2.5 × 10 ⁻⁴ mmol to obtain addition copolymer-3. The conversion rate to addition copolymer-3 was 99.9%.

  This addition copolymer-3 had a number average molecular weight (Mn) of 52,900, a weight average molecular weight (Mw) of 193,000, and a glass transition temperature of 360 ° C. Moreover, the ratio of the structural unit derived from 5-n-butylbicyclo [2.2.1] hept-2-ene of the addition copolymer-3 was 4.7 mol%.

  Then, in the same manner as in Example 1, the antioxidant pentaerythrityltetox [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4 -Di-t-butylphenyl) phosphite was added in an amount of 0.3 parts by weight per 100 parts by weight of the addition polymer, dissolved, and then decatalyzed through a Celite filter and a Teflon (registered trademark) filter having a diameter of 10 μm. Then, a film was formed by a solution casting method. In order to remove methylcyclohexane remaining on the film, the film was exposed to methylene chloride vapor for 30 minutes and then dried to obtain a film F-3 having a thickness of 100 μm.

  Various physical properties and wide-angle X-ray scattering were measured using this film. The results are shown in Table 1 and FIG. From the wide-angle X-ray scattering diagram of FIG. 2, the low-angle peak position (2θ) was 10.5 °, and the high-angle / low-angle peak intensity ratio was 0.79. Thus, in the film F-3, since the 2θ of the low angle peak (intermolecular interaction) is larger than the measurement result of the film F-1 shown in FIG. It turns out that it is filling.

  This film F-3 is stable and does not swell or become cloudy even when immersed in a solvent or chemical such as N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), isopropanol, hydrochloric acid or tetramethylammonium hydroxide. It was.

In a 100 ml glass pressure bottle under nitrogen atmosphere, 5-trimethylsilylbicyclo [2.2.1] hept-2-ene 5 mmol, bicyclo [2.2.1] hept-2-ene 95 mmol as a monomer, solvent 50 ml of methylcyclohexane and 1 mmol of ethylene as a molecular weight regulator were charged and sealed with a perforated crown with a rubber cap. Palladium bis (2,4-pentadionate) 2.5 × 10 ⁻⁴ mmol, tricyclopentylphosphine 2.5 × 10 ⁻⁴ complex mmol, triphenylcarbenium tetrakis (pentafluorophenyl) borate [Ph ₃ C · B ( C ₆ F ₆ ) ₄ ] 2.5 × 10 ⁻⁴ mmol was used for polymerization at 50 ° C. for 6 hours to obtain addition copolymer-4. The conversion rate to addition copolymer-4 was 99.8%.

The number average molecular weight (Mn) of this addition copolymer-4 is 56,000, and the weight average molecular weight (Mw)
) Was 190,000 and its glass transition temperature was 350 ° C. Moreover, the ratio of the structural unit derived from 5-trimethylsilylbicyclo [2.2.1] hept-2-ene in the addition copolymer-4 was 4.9 mol%.

  Subsequently, in the same manner as in Example 3, the antioxidant pentaerythrityltetox [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and tris (2,4) were added to the polymer solution. -Di-t-butylphenyl) phosphite was added in an amount of 0.3 parts by weight per 100 parts by weight of the addition polymer, dissolved, and then decatalyzed through a Celite filter and a Teflon (registered trademark) filter having a diameter of 10 μm. Then, a film was formed by a solution casting method. In order to remove methylcyclohexane remaining on the film, the film was exposed to methylene chloride vapor for 30 minutes and then dried to obtain a film F-4 having a thickness of 100 μm.

  This film F-4 is stable and does not swell or become cloudy even when immersed in a solvent or chemical such as N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), isopropanol, hydrochloric acid, tetramethylammonium hydroxide, etc. It was.

In a 100 ml glass pressure bottle under a nitrogen atmosphere, 1 mmol of 5-n-butylbicyclo [2.2.1] hept-2-ene and 95 mmol of bicyclo [2.2.1] hept-2-ene are used as monomers. The solvent was charged with 40 ml of methylcyclohexane, 10 ml of methylene chloride and 5 mmol of hexa-1-ene as a molecular weight regulator, and sealed with a perforated crown with a rubber cap. Nickel di (2-ethylhexanoate) modified with antimonic acid (HSbF ₆ ) as a catalyst (HSbF ₆ / Ni = 1 molar ratio) from a hole in the crown to a mixture of these monomers, molecular weight regulator and solvent. 025 mmol, boron trifluoride diethyl ether complex 0.225 mmol, and triethylaluminum 0.25 mmol were sequentially added, and polymerization was performed at 30 ° C. for 2 hours to obtain an addition copolymer-5. The conversion rate to addition copolymer-5 was 96%.

  The polymer solution is coagulated in 1 L of methanol containing 1 mmol of hydrochloric acid, further dissolved in 50 ml of methylcyclohexane, re-coagulated with 1 L of methanol, the addition copolymer is separated, and dried to obtain the addition copolymer-5. It was collected.

  This addition copolymer-5 had a number average molecular weight (Mn) of 80,300, a weight average molecular weight (Mw) of 183,000, and a glass transition temperature of 340 ° C. The ratio of the structural unit derived from 5-n-butylbicyclo [2.2.1] hept-2-ene in the addition copolymer-5 was 4.8 mol%.

  A methylcyclohexane polymer solution having a solid content of 20 wt% was prepared, and the antioxidants pentaerythrityl tetox [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4 -Di-t-butylphenyl) phosphite was added in an amount of 0.3 part by weight per 100 parts by weight of the addition polymer, dissolved, and then formed into a film by a solution casting method. In order to remove methylcyclohexane remaining on the film, the film was exposed to methylene chloride vapor for 30 minutes and then dried to obtain a film F-5 having a thickness of 100 μm.

Various physical properties and wide-angle X-ray scattering were measured using this film. The results are shown in Table 1 and FIG. From the wide-angle X-ray scattering diagram of FIG. 3, the low-angle peak position (2θ) was 9.3 °, and the high-angle / low-angle peak intensity ratio was 0.33.
Comparative Example 1
In Example 1, 500 mmol of 5-n-butylbicyclo [2.2.1] hept-2-ene and 400 mmol of bicyclo [2.2.1] hept-2-ene were charged as monomers, and a molecular weight regulator. 200 mmol of cyclopentene was charged. Next, in advance, 0.0025 mmol of catalyst component (a) palladium di (ethanoate) and 0.0025 mmol of tricyclopentylphosphine of catalyst component (b) were contacted to form a complex. After another 2 minutes, 0.0025 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate [Ph ₃ C · B (C ₆ F ₅ ) ₄ ] as a catalyst component (c) was charged, and addition polymerization was carried out at 50 ° C. It was.

  After 1 hour and 3 hours from the start of polymerization, 50 mmol each of bicyclo [2.2.1] hept-2-ene was added and polymerization was carried out for 6 hours to obtain addition copolymer-6. Conversion to addition copolymer-6 was 99.9%.

  The ratio of the structural unit derived from 5-n-butylbicyclo [2.2.1] hept-2-ene in the addition copolymer-6 was 49 mol%. Moreover, the number average molecular weight (Mn) of addition copolymer-6 was 63,000, the weight average molecular weight (Mw) was 205,000, and the glass transition temperature was 290 degreeC.

Next, a film H-1 having a thickness of 100 μm was obtained in the same manner as in Example 1. Although the evaluation result is shown in Table 1, it was a film having a large linear expansion coefficient.
Comparative Example-2
In Example 1, 400 mmol of 5-n-butylbicyclo [2.2.1] hept-2-ene and 300 mmol of bicyclo [2.2.1] hept-2-ene were charged as monomers, and a molecular weight regulator. 100 mmol of cyclopentene was charged. Next, 0.002 mmol of catalyst component (a) palladium di (ethanoate) was charged in advance, and 0.002 mmol of tricyclopentylphosphine of catalyst component (b) was charged in advance. After another minute, the catalyst component (c) triphenylcarbenium tetrakis (pentafluorophenyl) borate [Ph ₃ C
_{· B (C 6 F 5)} 4 ] 0.0022mmol were charged and subjected to addition polymerization at 50 ° C.. 50 mmol of bicyclo [2.2.1] hept-2-ene was added 1 hour and 3 hours after the start of polymerization, respectively. Polymerization was carried out for 6 hours to obtain an addition copolymer-7. Conversion to addition copolymer-7 was 91%.

  The proportion of the structural unit derived from 5-n-butylbicyclo [2.2.1] hept-2-ene in the addition copolymer-7 was 48 mol%. The number average molecular weight (Mn) of the addition copolymer-7 was 59,000, the weight average molecular weight (Mw) was 189,000, and its glass transition temperature was 290 ° C.

Subsequently, it carried out similarly to Example 1, and obtained the film H-2 with a film thickness of 100 micrometers. The evaluation results are shown in Table 1, but the Haze value of the film was large.
Comparative Example-3
In Example 1, addition copolymerization was performed in the same manner as in Example 1 except that the amount of the molecular weight regulator cyclopentene used was 50 mmol, and an addition copolymer-8 was obtained. The polymerization system at the end of the polymerization was solidified and swollen.

The number average molecular weight (Mn) of the addition copolymer-8 was 335,000, and the weight average molecular weight (Mw) was 1,050,000.
Even if this addition copolymer-8 is diluted and prepared to be a toluene solution having a solid content of 10% by weight, the film H-3 having a flat film thickness of 100 μm is formed by a solution casting method. It was not obtained.
Comparative Example-4
In Example 2, an addition copolymer-9 was obtained in the same manner as in Example 2 except that the amount of ethylene used as the molecular weight modifier was 200 mmol. The conversion rate to the addition copolymer-9 was 98.7%.

  The proportion of the structural unit derived from 5-n-butylbicyclo [2.2.1] hept-2-ene in the addition copolymer-9 is 19.8 mol%, the number average molecular weight (Mn) is 15,000, and the weight. The average molecular weight (Mw) was 45,000 and the glass transition temperature was 290 ° C.

Subsequently, it carried out similarly to Example 2, and obtained the film H-4 with a film thickness of 100 micrometers. Although the evaluation results are shown in Table 1, the film was easily broken.
Comparative Example-5
In Example 2, 200 mmol of 5-n-hexylbicyclo [2.2.1] hept-2-ene was used instead of the monomeric 5-n-butylbicyclo [2.2.1] hept-2-ene. The addition copolymer-10 was obtained in the same manner as in Example-2 except that. The conversion rate to addition copolymer-10 was 99.7%.

  The proportion of structural units derived from 5-n-hexylbicyclo [2.2.1] hept-2-ene in addition copolymer-10 is 19.6 mol%, number average molecular weight (Mn) is 59,000, and weight The average molecular weight (Mw) was 205,000 and the glass transition temperature was 300 ° C.

In the same manner as in Example 1, a film H-5 having a thickness of 100 μm was obtained from the addition copolymer-10. Although an evaluation result is shown in Table-1, compared with the film F-2 of Example 2, the linear expansion coefficient was large and the mechanical property fell.
Comparative Example-6
In Example 3, the amount of bicyclo [2.2.1] hept-2-ene used was 100 mmol, 5-n-butylbicyclo [2.2.1] hept-2-ene was not used, and the solvent was cyclohexane. The addition polymer-11 was obtained in the same manner as in Example 3 except that the addition polymer-11 was changed. As the polymerization progressed, the polymerization system became cloudy and the addition polymer swelled and solidified. The addition rate to the addition polymer-11 was 90%.

  This addition polymer-11 was insoluble in cyclohexane, methylcyclohexane, toluene, xylene, chlorobenzene, methylene chloride, etc. in the temperature range of room temperature to 100 ° C., and could not be molded by the solution casting method.

Corona treatment (100 W · min) for film F-1 of addition copolymer-1 of Example 1
. / M ² ). The wettability of the film surface was measured by the contact angle with pure water.
The contact angle before corona treatment was 100 °, and the contact angle after corona treatment was 50 °. Further, the mechanical properties of the film F-1 were not changed by the corona treatment at a breaking strength of 60 MPa and an elongation of 7.6%.

  The optical substrate according to the present invention can be used as an optical display device substrate such as a liquid crystal display device substrate, an organic EL (electroluminescence) display device substrate, and an electronic paper display device.

FIG. 1 shows a wide-angle X-ray scattering diagram of film F-1 obtained in Example 1. FIG. 2 shows a wide-angle X-ray scattering diagram of the film F-3 obtained in Example 3. FIG. 3 shows a wide-angle X-ray scattering diagram of film F-5 obtained in Example 5. 1 to 3, “cps” is an abbreviation of “counts per second”.

Claims (15)

The structural unit (1) represented by the following formula (1) and the structural unit (2) represented by the following formula (2)
In a total of 100 mol% of the structural unit (1) and the structural unit (2), the proportion of the structural unit (1) is 55 to 98 mol%, the proportion of the structural unit (2) is 2 to 45 mol%,
An optical substrate comprising a cyclic olefin addition copolymer having a number average molecular weight (Mn) of 20,000 to 300,000;

(In formula (1), A ^{1 to} A ⁴ each independently represents an atom or group selected from a hydrogen atom, a halogen atom, a methyl group, and an ethyl group.)

(In Formula (2), ^one of B ^{1 to} B ⁴ is a group selected from a butyl group, a trimethylsilyl group, and a trimethylsilylmethyl group, and the others are independently a hydrogen atom, a halogen atom, a methyl group, and an ethyl group. Indicates the atom or group selected.)   In the cyclic olefin addition copolymer, the proportion of the structural unit (1) is 80 to 98 mol% and the proportion of the structural unit (2) is 100 mol% in total of the structural unit (1) and the structural unit (2). The optical substrate according to claim 1, wherein the content is 2 to 20 mol%.   The optical substrate according to claim 1, wherein the cyclic olefin addition copolymer has a glass transition temperature of 220 to 400 ° C.   The optical substrate according to claim 1, wherein the linear expansion coefficient is 70 ppm / ° C. or less. 2. The optical substrate according to claim 1, wherein the cyclic olefin-based addition copolymer satisfies the following conditions 1) and 2) when the wide-angle X-shaped scattering is measured after being formed into a film having a thickness of 100 μm. ;
1) Among the two detected peaks, the low-angle peak position (2θ) is 8 ° or more,
2) The ratio of the high angle peak intensity to the low angle peak intensity is 0.5 or more.   The optical substrate according to claim 1, wherein the optical substrate is a film or a sheet.   The optical substrate according to claim 1, wherein the optical substrate is a substrate for a liquid crystal display element.   The optical substrate according to claim 1, wherein the optical substrate is an organic EL substrate.   The optical substrate according to claim 1, wherein the optical substrate is a substrate for a plasma display panel.   The optical substrate according to claim 1, wherein the optical substrate is an electronic paper substrate. A monomer (i) represented by the following formula (i) and a monomer (ii) represented by the following formula (ii), the monomer (i) and the monomer (ii): In a total of 100 mol%, a monomer composition in which the proportion of monomer (i) is 55 to 98 mol% and the proportion of monomer (ii) is 2 to 45 mol%,
An addition copolymerization reaction in the presence of a polymerization catalyst comprising a palladium compound (a) and a phosphine compound (b) having at least two unsubstituted or alkyl-substituted cyclopentyl groups or cyclohexyl groups;
Producing a cyclic olefin addition copolymer having a number average molecular weight of 20,000 to 300,000;
A process for producing the obtained cyclic olefin addition copolymer;

(In formula (i), A ^{1 to} A ⁴ each independently represents an atom or group selected from a hydrogen atom, a halogen atom, a methyl group, and an ethyl group.)

(In Formula (ii), ^one of B ^{1 to} B ⁴ is a group selected from a butyl group, a trimethylsilyl group, and a trimethylsilylmethyl group, and the others are independently a hydrogen atom, a halogen atom, a methyl group, and an ethyl group. Indicates the atom or group selected.) The polymerization catalyst is
(A) a palladium compound selected from an organic acid salt of palladium or a beta-diketone compound of palladium;
(B) a phosphine compound selected from compounds represented by the following formula (3);
P (R ¹ ) ₂ (R ² ) (3)
(In Formula (3), P is a phosphorus atom,
R ¹ is an unsubstituted or alkyl-substituted cyclopentyl group or cyclohexyl group having 5 to 12 carbon atoms,
R ² represents an unsubstituted or alkyl-substituted cyclopentyl group or cyclohexyl group having 5 to 12 carbon atoms, an unsubstituted or alkyl-substituted phenyl group having 6 to 12 carbon atoms, and 3 carbon atoms.
A group selected from -6 branched alkyl groups. ),
(C) at least one compound selected from a Lewis acidic boron compound, a Lewis acidic aluminum compound, an ionic boron compound, and an ionic aluminum compound,
The method for producing an optical substrate according to claim 11, further comprising (d) an organoaluminum compound as required. The method for producing an optical substrate according to claim 12, wherein the palladium compound (a) and the phosphine compound (b) form a complex represented by the following formula (4):
Pd (X) ₂ · [P (R ¹ ) ₂ (R ² )] _k (4)
(In Formula (4), Pd is a palladium atom, X is an organic acid anion or a betadiketone anion, R ¹ and R ² are the same as those in Formula (3), and k represents 1 or 2. ).   The method for producing an optical substrate according to claim 12, wherein the phosphine compound (b) is an unsubstituted or alkyl-substituted tricyclopentylphosphine compound having 5 to 12 carbon atoms.   At least one compound (c) selected from a Lewis acidic boron compound, a Lewis acidic aluminum compound, an ionic boron compound and an ionic aluminum compound is an ionic boron compound of a carbenium cation or a phosphonium cation. The method for producing an optical substrate according to claim 12, wherein the method is provided.

Images