WO2007058239A1 - Norbornene addition polymer, articles molded from the same, and uses thereof - Google Patents

Abstract

[PROBLEMS] To provide a norbornene addition polymer which is improved in the solubility in general-purpose solvents and dimensional stability while keeping the heat resistance and the low water absorption; articles molded from the polymer; and uses of them. [MEANS FOR SOLVING PROBLEMS] A norbornene addition polymer consisting of repeating units derived from norbornene compounds, characterized by containing repeating units represented by the general formula (1) [wherein R1 to R4 are each independently hydrogen, halogeno, or a hydrocarbon group having 1 to 20 carbon atoms] as the essential and having a content of repeating units having polar groups of 40% by mole or below.

Description

 Specification

 Norbornene compound addition polymer, molded article comprising the same, and application

 [0001] The present invention relates to a norbornene compound addition polymer having excellent dimensional stability, a molded product comprising the same, and a use. More specifically, the present invention relates to a norbornene compound addition polymer, a molded article made of the same, and a use that is small in dimensional change even when the use environment temperature and humidity vary, that is, excellent in dimensional stability.

 Background art

 In the field of optical materials such as optical components such as lenses, liquid crystal display elements, display substrates such as color filters and EL display element substrates, knock lights, and light guide plates, inorganic glass has been generally used. Yes. However, inorganic glass has drawbacks such as fragility, lack of flexibility, large specific gravity, poor processability, etc., and it is insufficient to meet the recent demands for light weight, small size and high density. Therefore, there is a strong demand for an alternative with transparent rosin. In order to use transparent resin for optical materials, in addition to transparency, extremely high performance is required in terms of heat resistance, chemical resistance, low water absorption and the like. For example, in the manufacture of a display element substrate, processing at a high temperature is necessary in the process of laminating a metal or metal oxide thin film, but deformation due to heat of the substrate or dimensional variation due to water absorption becomes a serious problem. . However, acrylic resin and polycarbonate resin used for optical materials have a drawback that they have low heat resistance and high water absorption, and thus have not been satisfactory.

 [0003] For this reason, a cyclic olefin addition polymer has been proposed as a resin satisfying transparency, heat resistance, chemical resistance, low water absorption and optical properties, and a liquid crystal display substrate material using this polymer has been proposed. Being! (Patent Document 1).

Cyclic olefin-added polymers, especially polynorbornene, have a high glass transition temperature of 250 ° C. or higher, and are therefore excellent in heat-resistant deformation during high-temperature processing. In addition, polynorbornene has extremely low hygroscopicity, so it has excellent dimensional stability against humidity changes in the environment of use. Furthermore, its linear expansion coefficient is as low as 55 ppmZ ° C, so it has excellent dimensional stability against thermal fluctuations. It has the characteristics. Hereinafter, “ppmZ ° C” is simply referred to as “ppm”. However, polynorbornene has a problem that it cannot be formed into a film by a casting method because of its low solubility in general solvents.

[0004] For this reason, various measures for improving polynorbornene have been studied. (1) Addition copolymers of ethylene and other _a- olefins (Patent Document 2), (2) Substituents having a linear hydrocarbon group Addition copolymer with rubornene (Patent Document 3), (3) Addition copolymer with norbornene compound having specific cyclic saturated hydrocarbon group (Patent Document 4), and (4) Norbornene compound having polar group And addition polymers (Patent Documents 5 and 6) have been proposed.

 However, for norbornene Z ethylene copolymer (1), it is difficult to produce a polymer having a glass transition temperature of 200 ° C or higher, and the linear expansion coefficient is as high as 70 to LOOppm. There was a problem. Similarly, the addition copolymer of (2) with a norbornene compound having a straight-chain hydrocarbon group also has the problems of lowering the glass transition temperature and increasing the linear expansion coefficient. The addition copolymer (3) with a norbornene compound having a specific cyclic saturated hydrocarbon group is troublesome to synthesize such a specific norbornene compound and is not practical. The polar group-containing norbornene copolymer of (4) has a problem that the water absorption becomes high, as is an example of a copolymer with a norbornene compound having an ester group or a silyl group as a polar group. In addition, there is a problem that the linear expansion coefficient is greatly increased.

 Patent Document 1: Japanese Patent Application Laid-Open No. 5-61026

 Patent Document 2: JP-A-6-202091

 Patent Document 3: JP-A-8-198919

 Patent Document 4: Japanese Patent Laid-Open No. 2004 51949 (Pamphlet of International Publication No. 03Z099887) Patent Document 5: Japanese Patent Publication No. 11-505880 (Pamphlet of International Publication No. 96Z037526) Patent Document 6: Japanese Patent Laid-Open No. 2002-114826 US Patent Application Publication No. 2002Z042461)

 Disclosure of the invention

 Problems to be solved by the invention

[0006] Accordingly, an object of the present invention is to provide an optical material excellent in heat resistance and dimensional stability as well as transparency, chemical resistance and optical properties, a molded article comprising the same, and a polymer for obtaining them. More specifically, the glass transition temperature is high and the water absorption is low. The present invention also provides a norbornene compound addition polymer that dissolves in a general solvent having a low linear expansion coefficient, a molded product comprising the same, and uses thereof.

 Means for solving the problem

 [0007] As a result of intensive studies to solve the above problems, the present inventors have found that norbornene compound addition polymers having a repeating unit derived from a specific tetracyclododecene compound have heat resistance and low water absorption. While maintaining the above, it was found that the composition was excellent in solubility in general solvents and further excellent in dimensional stability, and the present invention was completed based on this finding.

 [0008] Forcibly, according to the present invention, there is provided a norbornene compound addition polymer composed only of a repeating unit derived from a norbornene compound, wherein at least the repeating unit (a) represented by the general formula (1) is present. A norbornene compound addition polymer is provided, wherein the content ratio of the repeating unit (b) having a polar group, which is contained and represented by the general formula (2), is 40 mol% or less.

 [0009] [Chemical 1]

(In the general formula (1), I ^ to R ⁴ each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. I ^ to R ⁴ are in any combination. And may be bonded to each other to form a ring, or R ¹ and R ² or R ³ and R ⁴ may be combined to form an alkylidene group.

 [0011] [Chemical 2]

(In general formula (2), R ^{5 to} R ⁸ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a polar group, or a carbon having at least one polar group. a organic group having 1 to 20, at least one of R ⁵ to R ⁸ is a polar group, or an organic group having 1 to 20 carbon atoms and having at least one polar group. R ⁵ to R ⁸ may be bonded together in any combination to form a ring, and m is an integer of 0 to 2.)

 [0013] Further, the present invention is a caropolymer with a norbornene compound that has only a repeating unit derived from a norbornene compound, and contains at least the repeating unit (a) represented by the general formula (1) and represented by the general formula (2). The norbornene compound addition polymer of the present invention, wherein the content ratio of the repeating unit (b) having a polar group is 0 mol% or less, is represented by the general formula (3) The unit may further contain a repeating unit (c) not corresponding to the repeating unit (a).

 [0014] [Chemical 3]

(In the general formula (3), R ^{9 to} R ¹² each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. R ^{9 to} R ¹² may be combined in any combination. They may be bonded to each other to form a ring, and R ⁹ and R ^1C> or R ¹¹ and R ¹² may be combined to form an alkylidene group.

[0016] Then, per cent norbornene compound addition polymers described above, Te is, I ^ to R ⁴ are each independently a hydrogen atom, it is preferable to be a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms Yes.

 Further, in the above norbornene compound addition polymer, the weight average molecular weight (Mw) force in terms of polystyrene is 60,000 to 900,000.

 Further, according to the present invention, there is provided a molded article comprising the above norbornene compound addition polymer.

The molded article is preferably a film or a sheet. The molded article is preferably a film or sheet having a total light transmittance of 70% or more.

 The molded article is preferably a film or sheet having a linear expansion coefficient of 200 ppm or less.

 The molded article is preferably a film or sheet having a water absorption of 0.1% by weight or less.

 The molded article is preferably a film or sheet having a glass transition temperature of 200 ° C or higher.

 The molded article is preferably a laminate of transparent conductive films.

 Moreover, said molded article is used suitably for optics.

 Moreover, said molded article is used suitably for a display element substrate.

 The invention's effect

 [0017] The norbornene compound addition polymer of the present invention is excellent in transparency and optical properties, heat resistance and solubility in general solvents, and has excellent dimensional stability with low water absorption. A molded product obtained by using is useful as an optical material.

 BEST MODE FOR CARRYING OUT THE INVENTION

[Norbornene compound addition polymer]

 The norbornene compound addition polymer of the present invention may be referred to as a repeating unit (a) derived from a tetracyclododecene compound represented by the general formula (1) (“tetracyclododecane structure repeating unit (a)”). .)), A norbornene compound addition polymer consisting only of repeating units derived from norbornene compounds.

[0019] [Chemical 4]

[0020] Here, in the general formula (1), I ^ ~R ⁴ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

 Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

 Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. Alkyl group; alkenyl group having 2 to 20 carbon atoms such as bur group, probe group, iso-propyl group, butur group, isobutur group, pentale group, hexyl group, etc .; A cycloalkyl group having 3 to 20 carbon atoms such as a pentyl group and a cyclohexyl group; a cycloalkenyl group having 3 to 20 carbon atoms such as a cyclopentyl group and a cyclohexyl group; and a phenyl group and a naphthyl group Examples thereof include aromatic hydrocarbon groups having 6 to 20 carbon atoms. These hydrocarbon groups may have their hydrogen atoms replaced by halogen atoms.

[0021] Moreover, I ^ to R ⁴ is to form a monocyclic or condensed ring bonded to each other in any combination! In addition, these single rings or condensed rings may have a double bond.

Specific examples of the monocycle formed by any combination of I ^ to R ⁴ include a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, and a benzene ring. In addition, examples of the condensed ring formed by any combination of I ^ to R ⁴ include those in which a ring structure is further bonded to these single rings.

R ¹ and R ² or R ³ and R ⁴ may be combined to form an alkylidene group such as a methylidene group, an ethylidene group, a propylidene group, or an isopropylidene group.

 [0022] A norbornene compound addition polymer containing a tetracyclododecane structure repeating unit (a) is obtained by addition polymerization of a tetracyclododecene compound represented by the general formula (4). It is done.

 [0023] [Chemical 5]

In general formula (4), I ^ to R ⁴ are the same as in general formula (1).

[0025] Specific examples of tetracyclododecene compound represented by the general formula (4), tetracyclo ^{[6 .2.1 I 3 '6 .0} 2' 7.] Dodeka 4 E emissions; 9-chloro-tetracyclo [6.2. 1. Halogens such as I ³ ' ⁶ .0 ² ' ⁷ ] Dode force 1 and 9 bromotetracyclo [6.2. 1. I ³ ' ⁶ .0 ² ' ⁷ ] Dode force 1 tetracyclododecene I匕合product having atomic; 9-methyl-tetracyclo ^{[. 6.2.1 I 3 '. 6} 0 2' 7] de de force one 4 E down, 9 E chill tetracyclo [6.2.1. ^{I 3 '6 .0 2' 7} ] de de force one 4 E down, 9-butyl tetracyclo ^{[6.2.1. I 3 '6 .0} 2' 7] de de force one 4 E down, Kishiruteto Rashikuro to 9 [ 6.2.1. I ³ ' ⁶ .0 ² ' ⁷ ] Aldehyde groups such as Dode force 4 and 9 Decyltetracyclo [6.2. 1. I ³ '6.0 ² ' ⁷ ] Dode force 1 and 4 tetracyclododecene I匕合product having; 9 bi two Rutetorashikuro ^{[. 6.2.1 I 3 '6 .0} 2' 7] de de force one 4 E down, 9- Purobe - . Tetracyclo ^{[. 6.2.1 I 3 '6 .0} 2' 7] de de force one 4 E emissions etc. Aruke - tetracyclododecene compounds having Le group; 9 cyclohexyl tetramethyl cycloheteroalkyl [6.2.1 I ^{3 '6.0 2' 7]} de de force one 4 E down, 9-cyclopentyl-tetracyclo [6.2. 1. having I ^{3 '6.0 2' 7]} de de force one 4 cycloalkyl Le group such as E down Tetracyclododecene compound; 9-cyclopentyltetracyclo [6.2.1. I ³ ' ⁶ .0 ² ' ⁷ ] dode force 4, 9 cyclohextetracyclo [6.2.1. I ³ ' ⁶ .0 ² ' ⁷ ] tetracyclododecene compounds having a cycloalkenyl group such as dodeca 4-ene; 9-phenoltetracyclo [6.2.1. I ³ ' ⁶ .0 ² ' ⁷ ] dode force - tetracyclododecene I匕合product having an aromatic hydrocarbon group such as 4 E emissions; 9-chloromethyl-tetracyclo ^{[. 6.2.1 I 3 '6 .0} 2' 7] a halogen atom such as dodeca 4 E down Carbonized with Tetracyclo Dodeseni 匕合 product having the original; and the like.

Further, as R ¹ and R ² guilt or R ³ and R ⁴ to form an alkylidene group, 9 Mechiri Den tetracyclo ^{[6 .2. 1. I 3 '} 6 .0 2' 7] dodecane force one 4 E down, 9 E dust Den tetracyclo ^{[6.2.1. I 3 '6 .0} 2' 7] can be exemplified de de force one 4 E down like.

[0026] In the case of using a norbornene compound addition polymer of the present invention as an optical molding material, from the viewpoint of heat resistance and dimensional stability, it said I ^ to R ⁴ is a hydrogen atom, the number a halogen atom or a C 1 It is preferably a hydrocarbon group of ˜6. Specific examples thereof include Tetorashi black ^{[6.2. 1. I 3 '6} .0 2' 7] de de force one 4 E down, 9-chloro-tetracyclo ^{[6.2.1. I 3 '6 .0} 2' 7] Dode force 4, 9 Bromotetracyclo [6.2.1. I ³ ' ⁶ .0 ² ' ⁷ ] Dode force 4, 9 -. Methyl tetracyclo ^{[6. 2. 1. I 3 '.} 6 0 2' 7] de de force one 4-E down, 9-E chill tetracyclo ^{[6. 2. 1. I 3 '6} 0 2 ^'7] de de force one 4-E down, 9-1-butyl tetracyclo ^{[6. 2. 1. I 3' 6} . 0 2 '7] de de force one 4-E down, 9-Bulle tetracyclo [6 ^{. 2. 1. I 3 '. 6} 0 2' 7] de de force one 4-E down, 9 - Purobe - Rutetorashikuro ^{[6. 2. 1. I 3 '.} 6 0 2' 7] de de force one 4-E down, 9- Kuroromechirute Torashikuro ^{[6. 2. 1. I 3 '6} . 0 2' 7] de de force one 4-E down, 9-methylidene-tetracyclo [6. 2. 1. I ^{3 '6.0 2' 7]} de de force one 4-E down, 9-1 E dust Den tetracyclo ^{[6. 2. 1. I 3 '6} . 0 2' 7] de de force one 4- E down Etc.

Of these, I ^ to R ⁴ are more preferably hydrogen atoms or hydrocarbon groups having 1 to ⁴ carbon atoms. I ^ to R ⁴ are hydrogen atoms or hydrocarbon groups having 1 to 2 carbon atoms. Things are particularly preferred.

 [0027] The polymer with norbornene compound of the present invention has a weight average molecular weight force S in terms of polystyrene obtained by measuring by gel permeation chromatography using a solvent such as tetrahydrofuran, chloroform, and toluene. , Usually from 50,000 to 1,000,000, preferably <60,000 to 900,000, more preferably <70,000 to 800,000. If the weight average molecular weight is too small, the mechanical properties are inferior, and if it is too large, the solution viscosity becomes high and handling may be difficult.

 [0028] The norbornene compound addition polymer of the present invention contains a polar group represented by the general formula (2) in addition to the tetracyclododecane structure repeating unit (a) represented by the general formula (1). It may further contain a repeating unit (b) derived from a norbornene compound (hereinafter sometimes referred to as “polar group-containing norbornane structure repeating unit (b)”).

 [0029] [Chemical 6]

(In the general formula (2), R ^{5 to} R ⁸ are each independently a hydrogen atom, a halogen atom, or 1 to 2 carbon atoms. 0 hydrocarbon group, polar group, or organic group having 1 to 20 carbon atoms having at least one polar group, and at least one of R ^{5 to} R ⁸ is a polar group or at least one polar group It is a C1-C20 organic group having a group. R ^{5 to} R ⁸ may be bonded to each other in any combination to form a ring. m is an integer of 0-2. )

 [0031] The polar group is an atomic group containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, and a carbon atom.

 Specific examples of polar groups include polar groups containing oxygen atoms such as hydroxyl groups, alkoxy groups, aryloxy groups, carboxyl groups, acyl groups, ester groups (alkoxycarbol groups, aryloxycarboro groups), and epoxy groups. Groups; polar groups containing nitrogen atoms such as amino, nitrile and amide groups; polar groups containing sulfur atoms such as mercapto groups and thioepoxy groups; polar groups containing phosphorus atoms such as triarylphosphine A polar group containing a silicon atom such as an alkoxysilyl group; In the case where the polar group has a carbon atom, the carbon atom may be further substituted with a polar group, such as a hydroxyethoxycarbon group.

 [0032] The organic group having 1 to 20 carbon atoms and having at least one polar group is not particularly limited, and preferred examples include groups represented by the following general formula (5) or (6).

R ¹³ -X (5)

(Here, R ¹³ is a divalent hydrocarbon group having 1 to 20 carbon atoms. X is a polar group.) Specific examples of the polar group X include those described above.

R ¹⁴ -X ¹ -R ¹⁵ (6)

(Where R ¹⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁵ is a monovalent hydrocarbon group having hydrogen or a carbon number of ~ ^ 20, provided that both carbon numbers are total is 1-21. also, R ¹⁵ is a hydrogen atom may have a Yogu poly Okishiarukiren structure be one substituted with a polar group contained therein. X ¹ is Nitrogen atom, oxygen atom, sulfur atom, and key atom group are divalent groups containing at least one selected atom.)

Specific examples of X ¹ include an oxy group (—0—), a carbo group, a carbo oxy group, a force carboxy group; a thio group (1 S), a thio carbo group; an imino group; an imide Base And so on.

 [0033] In the organic group having 1 to 20 carbon atoms having at least one polar group, the carbon number is preferably 1 to 3. When the carbon number power is within this range, the dimensional stability of the norbornene addition polymer is improved, which is preferable.

 [0034] A norbornene compound addition polymer containing a tetracyclododecane structure repeating unit (a) and a polar group-containing norbornane structure repeating unit (b) is a tetracyclodone represented by the general formula (4). It can be obtained by addition copolymerization of a decene compound and a polar group-containing norbornene compound represented by the general formula (7).

 [0035] [Chemical 7]

In the general formula (7), IT to R ⁸ and m are the same as in the general formula (2).

Specific examples of the norbornene compound represented by the general formula (7) include those having m = 0, such as norbornene having a carboxyl group such as 5-norbornene 2-strong rubonic acid, 5-norbornene 2,3 dicarboxylic acid, etc. Compound: Norbornene compound having a carboxylic acid anhydride group such as 5 norbornene 2,3 dicarboxylic acid anhydride; 5-hydroxy-2 norbornene, 5 hydroxymethyl 1-2 norbornene, 5, 6 di (hydroxymethyl) 2 norbornene, Norbornene compounds having a hydroxyl group, such as 5, 5 di (hydroxymethyl) 2 norbornene, 5- (2-hydroxyethoxycarbol) 2 norbornene, 5-methyl-5- (2 hydroxyethoxycarbol) 2 norbornene; Norbornene 2—Strength Methyl Rubonate, 5 Norbornene 2—Strength Ethyl Rubonate, 2 Methyl 5 Nor Boronene 2 methyl carboxylate, 2 methyl 5-norbornene 2—strong ethyl ethyl sulfonate, acetic acid 5 norbornene 2 yl, acetic acid 2-methyl-5 norbornene 2 yl, acrylic acid 5 norbornene 2 yl, methacrylic acid 5 norbornene 2— Norbornene compounds having an ester group such as ethyl; 3-methoxycarbo -Norbornene compounds having an ester group and a carboxyl group such as 5-norbornene 2 carboxylic acid; norbornene compounds having a -tolyl group such as 5 norbornene 2 carbo-tolyl; 5-methoxy-2-norbornene, 5 ethoxy-2-norbornene, 5 Norbornene compounds having an oxy group such as phenoxy 2 norbornene; 5-norbornene compounds having an alkoxy silyl group such as 5-trimethoxysilyl-2 norbornene, 5 triethoxysilyl-2 norbornene; ₅ ethyleneoxy 2-norbornene, 5- (2 , 3 propyleneoxy) 2 norbornene, 5 norbornene 1 2-strength norbornene compounds having an epoxy group such as glycidyl rubonic acid; 5-norbornene-2,3 dicarboxylic imide, 5 norbornene 2,3 dicarboxylic acid (N-phenol) ) Imido group such as imide That norbornene I 匕合 thereof; or the like can be mentioned.

Examples of those wherein m = l, tetracyclo ^{[6.2 1. I 3 '6 .0} 2' 7.] dodecane force one 9 E down one 4 -. carboxylic acid, tetracyclo [6.2.1 I ^{3 '6} .0 ² ' ⁷ ] Dode force 1 9 1 4, 5 Norbornene compound having a carboxyl group such as dicarboxylic acid; Tetracyclo [6.2.1. I ³ ' ⁶ .0 ² ' ⁷ ] Dodecar 9 , norbornene compound that having a carboxylic acid anhydride group such as 5-dicarboxylic anhydride; 9-hydroxy-tetracyclo ^{[. 6.2.1 I 3 '6 .0} 2' 7] de de force one 4-E down, 9 Hydroxymethyltetracyclo [6.2.1. I ³ ' ⁶ .0 ² ' ⁷ ] Dode force 1, 9, 10

(Hydroxymethyl) tetracyclo [6.2.1. I ³ ' ⁶ .0 ² ' ⁷ ] Dode force 1, 9 1 (2 hydroxyethoxycarbol) tetracyclo [6.2. 1. I ³ ' ⁶ . 0 ^{2 '7]} de de force one 4 E down, 9- methylate Lou 9-. (2-hydroxyethoxy carbo - Le) tetracyclo [6.2.1 I ^3' of the ^{6.0 2 '7]} hydroxyl group such dodeca 4 En norbornene I匕合product having;. tetracyclo ^{[. 6.2.1 I 3 '6 .0} 2' 7] de de force one 9 E down one 4-carboxylate, tetracyclo [6.2.1 I ^{3 '6} .0 ² ' ⁷ ] Dodeca-9-ethyl 4-carboxylate, 4-methyltetracyclo [6.2.1. I ³ ' ⁶ .0 ² ' ⁷ ] Dodec-Force 9-methyl 4-carboxylate, 4 - methyl tetracyclo ^{[. 6.2.1 I 3 '6 .0} 2' 7] de deca one 9 E down one 4-carboxylic acid Echiru, acetic tetracyclo ^{[. 6.2 1. I 3 '6} .0 2' 7] de De force 1 9 4-l, 4-methyltetracycloacetate [6.2.1. I ³ ' ⁶ .0 ² ' ⁷ ] Dode force 9-ene 4-yl, tetracycloacrylate [6.2.1. I ³ ' ⁶ .0 ² ' ⁷ ] Dode force 1 9- 4-yl, tetracyclomethacrylate [ 6.2.1. I ³ ' ⁶ .0 ² ' ⁷ ] Norbornene compound having the ester group; 5- methoxycarbonyl - Rutetorashikuro ^{[. 6. 2 1. I 3 '} . 6 0 2' 7] de de force - 9 E emissions - ester group and a carboxyl group such as 4-carboxylic acid norbornene I匕合product having a preparative; tetracyclo ^{[. 6 2. 1. I 3 '} . 6 0 2' 7] de de force one ⁹ - E down one 4-carbonitrile - a tolyl - norbornene I spoon having a tolyl group compound; 9-1 trimethoxysilyl tetracyclo ^{[6. 2. 1. I 3 '.} 6 0 2' 7] de de force one 4 E down, 9-triethoxysilyl-tetracyclo [6. 2. 1. I ³ ' . ⁶ 0 ^{2. '7]} Dodeka 4 norbornene compound having an alkoxysilyl group such as En; 9 ethylene O carboxymethyl tetracyclo ^{[6. 2. 1. I 3' 6} 0 2 '7] de de force one 4 E down 9- (2, 3 propylene O carboxymethyl) tetracyclo ^{[6. 2. 1. I 3 '} 6. 0 2' 7] de de force one 4 E down, Tetorashi black [6. 2. 1. I ^{3 '6} . 0 ^{2 '7]} de de force one 9 E down Norbornene I匕合product having an epoxy group such as 4-carboxylic acid glycidyl; tetracyclo ^{[6. 2. 1. I 3 '.} 6 0 2' 7] de de force one 9 E down -4 5 dicarboximide, tetracyclo ^{[6. 2. 1. I 3 '.} 6 0 2' 7] de de force one 9 E down one 4, 5 - dicarboxylic acid (N - Hue - Le) norbornene I匕合having an imide group such as an imide The thing; etc. can be mentioned.

 [0038] The polar group-containing norbornane structure repeating unit (b) is a norbornene compound addition polymer containing a tetracyclododecane structure repeating unit (a) or a tetracyclododecane structure repeating unit ( It may be introduced by modifying a norbornene compound addition polymer containing a) and a norbornane structure repeating unit (c) in a narrow sense, which will be described later, with a polar group. For example, a method of epoxidizing an unsaturated hydrocarbon group constituting a tetracyclododecane structure repeating unit (a) or a narrowly defined norbornane structure repeating unit (c) described later, a polar group-containing norbornane structure repeating unit (b) Those obtained by hydrolyzing ester groups to convert them into hydroxyl groups or carboxyl groups are also included in the norbornene compound addition polymer of the present invention.

 For the modification reaction with a polar group, a known method may be employed.For example, the introduction reaction of a polar group such as an epoxy group is performed using a peroxide such as m-peroxybenzoic acid, peracetic acid, hydrogen peroxide, oxygen, etc. The epoxidizing agent or the like may be contacted.

[0039] In the norbornene compound addition polymer of the present invention, the molar ratio of the polar group-containing norbornane structure repeating unit (b) to all repeating units is essential to be 40 mol% or less, but is 30 mol% or less. It is more preferable that it is 25 mol% or less. It is particularly preferably 20 mol% or less. If the proportion of the polar group-containing norbornane structure repeating unit (b) is larger than 40 mol%, the water absorption may increase and the dimensional stability may be lowered.

 [0040] The norbornene compound addition polymer of the present invention is a repeating unit represented by the general formula (3), and does not correspond to the tetracyclododecane repeating unit (a), and is a repeating unit derived from norbornene ( c) (It may be referred to as “norbornane structure repeating unit (c) in a narrow sense)”).

 [0041] [Chemical 8]

Here, in the general formula (3), R ^{9 to} R ¹² each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. R ^{9 to} R ¹² may be bonded to each other in any combination to form a ring. Further, R ⁹ and R ^1C> or R ¹¹ and R ¹² may be combined to form an alkylidene group.

 Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, and dodecyl group. Alkyl group having 2 to 20 carbon atoms such as bur group, probe group, iso probe group, butenyl group, isobutenyl group, pentenyl group, hexyl group; cyclopentyl group, A cycloalkyl group having 3 to 20 carbon atoms such as a cyclohexyl group; a cycloalkyl group having 3 to 20 carbon atoms such as a cyclopentyl group or a cyclohexyl group; and a carbon such as a phenyl group or a naphthyl group. Examples thereof include aromatic hydrocarbon groups of 6 to 20. These hydrocarbon groups may have their hydrogen atoms replaced by halogen atoms.

[0043] Further, R ^{9 to} R ¹² may be bonded together in any combination to form a single ring or condensed ring! /, And these single rings or condensed rings may have a double bond. May be. Specific examples of the monocycle formed by any combination of R ^{9 to} R ¹² include a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, and a benzene ring. Examples of the condensed ring formed by any combination of ^{5 to} R ⁸ include those in which a ring structure is further bonded to these single rings.

 [0044] A norbornene compound addition polymer containing a tetracyclododecane structure repeating unit (a) and a narrowly defined norbornane structure repeating unit (c) is composed of a tetracyclodecene compound represented by the general formula (4): A norbornene compound represented by the general formula (8), which is not a tetracyclododecene compound represented by the general formula (4) (referred to as a “norbornene compound in a narrow sense”). May be obtained by addition copolymerization with a polar group-containing norbornene compound (7) if desired.

 [0045] [Chemical 9]

In the general formula (8), R ^{9 to} R ¹² are the same as those in the general formula (3).

[0047] Specific examples of the narrowly defined norbornene compound represented by the general formula (8) include: 2 norbornene; norbornene compound having a halogen atom such as 5 chloro-2 norbornene, 5 bromo 2 norbornene; 5 methyl-2 -Norbornene compounds having an alkyl group such as norbornene, 5 ethyl 2 norbornene, 5 butyl-2 norbornene, 5 hexyl-2 norbornene, 5 decyl 2 norbornene; 5 bur 2 norbornene, 5 probe 2 norbornene, etc. Norbornene compounds having an alkenyl group; norbornene compounds having a cycloalkyl group such as 5-cyclohexyl-2-norbornene and 5-cyclopentyl 2 norbornene; 5-cyclopentyl-ru 2 norbornene, 5-cyclohexenyl- Norbornene compounds having a cycloalkenyl group such as 2-norbornene Norbornene compounds having an aromatic hydrocarbon group such as 5-phenyl-2-norbornene, p-methyl 5--ferro- 2-norbornene, o-methyl 5--fluoro- 2-norbornene, m-methyl 5-phenyl 2-norbornene, etc. 5-chloromethyl-2-norbornene, p black mouth 1-phenyl-2-norbo And norbornene compounds having a hydrocarbon group substituted with a halogen atom such as runene.

[0048] Further, R ⁹ R ¹² may be bonded to each other in any combination to form a monocyclic ring or condensed ring, and examples thereof include dicyclopentagen, methyldicyclopentagen, dihydrodicyclopentagen ("tricyclo [ 5. 2. 1.0 ^{2 '6]} also called deca one 8 E down ".), tetracyclo [9.2.2 1.0 ^{2" 10.} 0 ^{3' 8]} tetradec one 3, 5, 7, 12 tetraene ( "1, 4-methanol 1, 4, 4a, 9a- Te Torahidoro one 9H-fluoren" also referred to.), tetracyclo [10. 2.1.2 0 ^{2 '11.} 0 ^{4' 9]} pentadecanoyl one 4, 6, 8, 13-tetraene (also referred to as “1, 4-methanoyl 1, 4, 4a, 9, 9a, 10 hexahydroanthracene”).

In addition, R ⁹ and R ^1G or R ¹¹ and R ¹² jointly formed an alkylidene group, which includes 5-methylidene-2 norbornene, 5 ethylidene-2 norbornene, 5 propylidene 2 norbornene, 5 And isopropylidene-2-norbornene.

[0049] In addition to the tetracyclododecane structure repeating unit (a) represented by the general formula (1), the present invention comprises a narrow norbornane structure repeating unit (c) represented by the general formula (3) When the norbornene compound addition polymer is used as an optical molding material, from the viewpoint of heat resistance and low thermal expansion, the above R ⁹ R ¹² is a hydrogen atom, a halogen atom or a hydrocarbon having 16 carbon atoms. A group of forces, or R ⁹ R ¹² is a hydrogen atom or a hydrocarbon group having a carbon number of 14 that preferably combines with each other to form a single ring or a condensed ring. Or R ⁹ R ¹² are bonded together in any combination to form a single ring or condensed ring.

[0050] Preference is given to norbornene compounds in the narrow sense represented by the general formula (8)! /, For example, 2 norbornene, 5 chloro 2 norbornene, 5 bromo 2 norbornene, 5-methyl-2-norbornene, 5 ethyl-2-norbornene, 5 Butyl-2-norbornene, 5—Buyl-2-norbornene, 5-—Probe-l-2 norbornene, 5 Hue-2 norbornene, 5 Chloromethyl-2-norbornene, dicyclopentagen, methyl dicyclopentagen, dihydrodicyclopentagen ( 'also referred to as ^"[6 deca-8 E down.), tetracyclo [9.2.2 1.0 ² tricyclo 5. 2. 1.0 ^{2]" "10.} 0 ^{3' 8]} tetradec one 3, 5, 7, 12 - Tetoraen ( "1, 4-methano one 1, 4, 4a, 9a- tetrahydro one 9H-fluoren" also called;.), Tetracyclo [10. 2.1.2 0 ² '. ¹¹ 0 ^{4' 9]} Pentadeka 4, 6, 8, 13—Tetragen (also referred to as “1, 4 methanol 1, 4, 4a, 9, 9a, 10 hexahydroanthracene!), 5--methylidene-2-norbornene, 5-ethylidene-2-norbornene 5 propylidene-2-norbornene, 5 isopropylidene-2-norbornene, and the like.

[0051] In the norbornene compound addition polymer of the present invention, the norbornane structure repeating unit (c) in the narrow sense includes the tetracyclododecane structure repeating unit (a) and the norbornane structure repeating unit (c) in the narrow sense. Is 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less. If the proportion of the norbornane structure repeating unit (c) in the narrow sense is too large, the polymer may become insoluble in general solvents, or the dimensional stability may deteriorate.

[0052] In the norbornene compound addition polymer of the present invention, since the effect of the present invention becomes more prominent, the repeating unit (a) Z the repeating unit (b) Z the repeating unit (c ) Is preferably (5-60) 7 (0-40) 7 (40-95), particularly preferably (10-60) / (0-20) / (60-90).

[0053] The norbornene compound addition polymer of the present invention has a total light transmittance of preferably 70% or more, more preferably 80% or more, and particularly preferably 85% or more.

 Further, the norbornene compound addition polymer of the present invention preferably has a linear expansion coefficient of 200 ppm or less, more preferably lOO ppm or less, and particularly preferably 70 ppm or less, and thus has excellent stability against thermal fluctuation.

 Furthermore, the norbornene compound addition polymer of the present invention preferably has a glass transition temperature of 200 ° C., more preferably 250 ° C. or more, and particularly preferably 290 ° C. or more. The upper limit of the glass transition point is preferably 500 ° C. or less, particularly preferably 400 ° C. or less.

 Furthermore, the norbornene compound addition polymer of the present invention has a water absorption rate of preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.02% or less on a weight basis.

[Production of Norbornene Compound Addition Polymer]

In order to obtain the norbornene compound addition polymer of the present invention, a tetracyclododecene compound represented by the general formula (4) is an essential component and, if desired, a narrow definition represented by the general formula (8). of A norbornene compound monomer containing a norbornene compound and Z or a polar group-containing norbornene compound represented by the general formula (7) may be polymerized in the presence of a polymerization catalyst.

[0055] The polymerization catalyst is not particularly limited. Specific examples include polymerization catalysts such as [6-Methoxynorbornene-2-ylu-5palladium (cyclooctagen)] hexafluorophosphate described in Japanese Patent Publication No. 11 505880; pamphlet of International Publication No. 2000Z20472 Polymerization catalysts such as (aryl) palladium chloride dimer / tricyclohexylphosphine / lithium tetrakis (pentafluorophenyl) borate '2.5 ether; (Phenol) described in JP 2001-098035 A Polymerization catalysts composed of Group 10 transition metal catalysts such as palladium bis (triphenylphosphine) iodide Z polymerization catalyst such as Z-methylaluminoxane can be mentioned as suitable ones.

 [0056] The norbornene compound addition polymer obtained by the above method may have an olefinic unsaturated bond. A hydrogenated olefinic unsaturated bond is also a norbornene compound of the present invention. Included in addition polymers.

 [0057] The hydrogenation reaction may be performed by a generally known method, that is, by contacting with hydrogen in the presence of a hydrogenation catalyst. As a hydrogenation catalyst, a solid catalyst in which a Group 8-10 transition metal such as nickel, palladium, platinum, cobalt, ruthenium, rhodium or a compound thereof is supported on a porous carrier such as carbon, alumina, silica, silica alumina, diatomaceous earth, etc. ; Combination of group 4-10 metal organic carboxylates, β-diketone compounds such as conoleto, nickel, palladium, etc. and organoaluminum or organolithium; complexes such as ruthenium, rhodium, iridium, etc. A homogeneous catalyst is used.

 [0058] After the addition polymerization reaction, it is preferable to remove the catalyst. The catalyst removal method includes adsorption removal using an adsorbent such as silica, alumina, activated carbon, etc .; removal using ion exchange resin; method of adding a chelating agent to insolubilize the catalyst residue and filtering; polymer And a method of solidifying by adding the solution to a large amount of methanol, acetone or the like.

[0059] Recovery of the norbornene compound addition polymer after the addition polymerization reaction is carried out by a known method such as a method of directly removing the solvent from the polymer solution; a method of coagulating and separating with a poor solvent such as methanol. Can do. Also, the solution after the polymerization reaction and the solution after removing the catalyst are used. Even if it is used for cast molding as it is, the molded product can be produced.

 [0060] [Molded product]

 The norbornene compound addition polymer of the present invention can be molded into a molded product such as an optical component, an electrical insulation component, an electrical / electronic component, an electronic component sealant, a medical device, or a packaging material. I'll do it.

 Although the form of the molded article of the present invention is not particularly limited, a sheet and a film are preferable. The norbornene compound addition polymer of the present invention is a transparent resin that may be used alone as a molded product, for example, cyclic olefin addition polymer, hydrogenated cyclic olefin fin-opening polymer, a-olefin and cyclic olefin. Coated copolymer, crystalline (X-olefin polymer, rubber copolymer of ethylene and α-olefin having 3 or more carbon atoms, hydrogenated butadiene polymer, hydrogenated butadiene · It may be used in combination with a styrene block copolymer, a hydrogenated isoprene polymer, etc. in an arbitrary ratio.

[0061] When molding a molded product from the norbornene compound addition polymer of the present invention, various additives may be blended as necessary.

 Such additives include fillers, antioxidants, phosphors, ultraviolet absorbers, antistatic agents, light stabilizers, near infrared absorbers, colorants such as dyes and pigments, lubricants, plasticizers, difficult additives. A flame retardant, a crosslinking agent, etc. are mentioned.

[0062] Examples of the filler include metal oxides such as silicon, titanium, aluminum, and zirconium.

 Examples of the acid / antioxidant include phenol-based acid / antioxidant, rataton-based antioxidant, phosphorus-based antioxidant, and thioether-based acid / antioxidant.

 The phosphor is excited by receiving light and emits light having a wavelength longer than the excitation wavelength.For example, when sealing an optical element, the wavelength of the blue region to the ultraviolet region in which the optical element emits light. Is used to emit light in the visible region.

 The method of blending these additives is not particularly limited!

 In order to obtain a molded product made of the norbornene compound addition polymer of the present invention, a known molding method may be used.

[Film or sheet] The norbornene compound addition polymer of the present invention is easily dissolved in an organic solvent. Therefore, the organic solvent solution can be coated or cast on a steel belt, carrier film or the like, and then a film or sheet can be obtained by a solution casting method in which a molded product is obtained through a drying step.

 [0064] After impregnating a woven or non-woven fabric such as glass cloth with the organic solvent solution of the norbornene compound addition polymer of the present invention, drying is performed to obtain a film or sheet containing the woven or non-woven fabric. Monkey.

 Further, after swelling the norbornene compound addition polymer of the present invention with an organic solvent, the polymer can be formed into a film or sheet while the solvent is evaporated by an extruder.

 [0065] Alternatively, the organic solvent solution of the norbornene compound addition polymer of the present invention is poured into a mold, and then the solvent is evaporated to form. In addition, after the organic solvent solution is attached to a specific part or substrate, the solvent can be evaporated to form.

 Furthermore, the norbornene compound addition polymer of the present invention is blended with another thermoplastic resin to form a polymer blend composition, and from this, a film or sheet is obtained by a melt extrusion method using a melt extruder or the like. You can also.

 [0066] The thickness of the film or sheet is a force that can be selected depending on the intended use, and is usually 1 to 1,000 ^ m, preferably 2 to 500 / ζ πι. When the thickness of the film or sheet is within this range, the film or sheet obtained with a short time required for forming the film or sheet is excellent in strength.

 [0067] The sheet or film having the norbornene compound addition polymer power of the present invention has a total light transmittance of 70% or more, preferably 80% or more, more preferably 85% or more. It can be suitably used as a filter substrate.

 The norbornene compound addition polymer sheet or film of the present invention has a linear expansion coefficient of preferably 200 ppm or less, more preferably lOO ppm or less, and particularly preferably 70 ppm or less. Therefore, it can be suitably used particularly for optical applications.

Furthermore, the norbornene compound addition polymer sheet or film of the present invention is preferable. It preferably has a glass transition temperature of 200 ° C., more preferably 250 ° C. or more, particularly preferably 290 ° C. or more. The upper limit of the glass transition point is preferably 500 ° C. or less, particularly preferably 400 ° C. or less.

 Furthermore, the norbornene compound addition polymer sheet or film of the present invention is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.02% or less on the basis of weight. Has water absorption.

[Transparent conductive film laminated film or sheet]

 The film or sheet having the strength of the norbornene compound addition polymer of the present invention is a laminate of a transparent conductive film (sometimes referred to as a “transparent conductive film laminated film or sheet”).

 Specifically, inorganic substances such as inorganic oxides, inorganic nitrides or inorganic sulfides, for example, acid indium tin oxide (ITO), acid aluminum, silicon oxide, titanium oxide, zinc oxide, tungsten oxide, Using aluminum nitride, silicon nitride, titanium nitride, nickel cadmium sulfate, zinc zinc, selenium zinc, etc., by vacuum film formation, for example, sputtering, vapor deposition, CVD, etc. A transparent conductive film is laminated.

 The film thickness of the transparent conductive film can be appropriately selected within the range of 50 to 4,000 A.

[0069] The transparent conductive film laminated film or sheet of the present invention has a total light transmittance of 70% or more, preferably 80% or more, more preferably 85% or more, and is therefore preferably used as a color filter substrate. be able to.

[0070] In the transparent conductive film laminated film or sheet of the present invention, smoothness of the film and adhesion between the transparent conductive film and the film or sheet having norbornene-compound-attached caropolymer force. An adhesive layer may be provided for the purpose of improvement. The adhesive layer can be obtained by applying a varnish varnish and removing the solvent by drying. At this time, a resin having film-forming properties after removal of the solvent, that is, a varnish to which a solid resin is added is preferred for uniform application and uniform viewpoint power. Specific examples of the resin for this purpose include photo-curable resins such as epoxy prepolymers such as epoxy diatalylate, urethane diatalylate and polyester diatalylate; o-cresol novolac type, bisphenol type Epoxy, urethane, acrylic, urine And thermosetting resin such as elemental, melamine, and unsaturated polyester; electron beam curable resin; and the like. Of these, photocurable resin is preferable in terms of productivity and cost. As a method for forming the cured resin coating, any method having a gravure coating method, a reverse roll coating method, a kiss roll coating method, or the like may be used.

 [0071] The transparent conductive film laminated film or sheet of the present invention may have a gas barrier layer on the side opposite to the transparent conductive film. The gas noble layer may be formed of an inorganic material or an organic material. Examples of the inorganic material that can be used include silicon oxide, aluminum oxide, indium oxide, and the like, and examples of the organic material include polybutyl alcohol, ethylene butyl alcohol copolymer, and polyamide.

 The film thickness of the gas layer is 100-2, OOOA for inorganic materials and 500 for organic materials.

~ Ιο, 000 A power to s desire.

 These inorganic materials can be formed by known means such as sputtering, ion plating, resistance heating, and CDV. In the case of an organic material, a film can be formed by dissolving it in a solvent, applying it by the coating method as described above, and drying it.

 Further, an adhesive layer may be provided between the film or sheet and the gas nozzle layer. Further, a protective coat layer may be laminated on the gas barrier layer to protect it. The protective coating layer is preferably formed by the same method as the adhesive layer.

 [0072] [Color filter]

 A color filter is obtained by laminating a color filter layer on a sheet or film having the norbornene compound addition polymer power of the present invention or a transparent filter laminated film or sheet of the present invention. be able to. As a lamination method, a known pigment dispersion method, dyeing method, electrodeposition method, printing method, transfer method, or the like can be used.

For example, in the pigment dispersion method, on the color filter substrate of the present invention, using a sputtering method or a vacuum evaporation method, a chromium compound such as chromium metal, chromium oxide, chromium nitride, or a metal such as nickel and tungsten alloy is used. A black matrix is formed by a light-shielding film, and then a photosensitive resin composition (color resist) in which a red pigment is dispersed is spin-coated, Apply over the entire surface by the Yarber method, flow coating method, die coating method, roll coating method, spray coating method, etc., expose through a mask, develop after exposure to form red pixels

. In the same procedure, the blue, green pixels are coated, exposed and developed to form three color pixels. Note that the order in which the three color pixels are formed is arbitrarily selected. If the black matrix between pixels is concave, the surface may be covered with a transparent resin such as epoxy resin or acrylic resin for smoothing. Good. Also, when forming the black matrix, the above-mentioned pigment dispersion method may be employed. Specifically, a photosensitive resin (black resist) in which a black pigment is dispersed may be applied, exposed and developed.

[0073] Constituent components of the color resist and black resist compositions and methods of application, exposure and image formation are described in, for example, JP-A-2004-56151, JP-A-2004-347831, etc. Ingredients and methods can be used. As the printing method, a known method can be used. For example, the ink and the printing method described in JP-A-6-347637, JP-A-11-326622 and JP-A-2004-333971 are used! / I can.

 Since the norbornene compound addition polymer of the present invention has high resistance to chemicals such as resists, inks, and developers, the substrate may be deformed or cracks may be generated in one color filter lamination process. I don't know what to do.

[0074] Thin film formation of various resins such as corona discharge treatment, ozone treatment, silane coupling agent and urethane-based resin is performed on the transparent substrate and the black matrix forming substrate as necessary in order to improve surface properties such as adhesion. You can do some processing! / ヽ. When a thin film forming process of various resins is performed, the film thickness is usually in the range of 0.01 to 10 / ζ πι, preferably 0.05 to 5 m.

[0075] The above color filter can be used as a color filter of a liquid crystal display device, and can also be used as a part of a component such as a color display or a liquid crystal display device.

 [Optical parts]

The film or sheet having the norbornene compound addition polymer power of the present invention is a color film. In addition to filter substrates, light guide plates, protective films, polarizing films, retardation films, touch panels, transparent electrode substrates, optical recording substrates such as CD, MD, DVD, TFT substrates, liquid crystal display substrates, organic EL display substrates, etc. And optical components such as optical transmission waveguides, optical lenses, and sealing materials.

 [0077] The molded article having norbornene compound addition polymer power of the present invention is used not only for optical parts but also for electric insulating parts, electric and electronic parts, electronic component sealants, medical equipment, and packaging materials. Can be used.

 [0078] [Electrical insulation parts]

 The molded product made of the norbornene compound addition polymer of the present invention is excellent in heat resistance and has a low content of Group 10 transition metal atoms, halogen atoms and phosphorus atoms. Since there is no deterioration in mechanical properties due to thermal degradation, it is optimal as an electrical insulation component.

 Examples of electrical insulation parts include wire and cable coating materials, insulation materials for office automation equipment such as computers, printers, and copiers, and insulation parts for flexible printed circuit boards. In particular, an electrically insulating component in the form of a film or sheet is suitably used as a flexible printed board.

 [0079] [Electric 'Electronic Components]

 Electrical / electronic components include containers, trays, carrier tapes, separation films, cleaning containers, pipes, tubes, etc., sealing elements for semiconductor elements, optical elements (light emitting diodes, etc.), sealing elements for integrated circuits, Used for overcoat materials.

 [0080] [Electronic component sealing material]

The norbornene compound addition polymer of the present invention is useful as a sealing material for electronic parts because it has a low water absorption and is excellent in heat resistance, transparency and electrical properties. Electronic components include integrated circuit components including semiconductor chips such as CPU and DRAM; semiconductor components such as diodes, transistors, and light emitting elements (LEDs, etc.); general electronics such as resistors, capacitors, inductors, ceramic filters, and thermistors List the parts. Above all, LED element sealing materials such as blue LED elements, ultraviolet light emitting LED elements and white LED elements are preferred, especially as sealing materials for these surface mount LEDs! [0081] The sealing method of the electronic component can be performed by attaching the organic solvent solution of the norbornene compound addition polymer of the present invention to the electronic component to be sealed and evaporating and removing the solvent. At this time, a conventional sealing method such as a transfer molding method, a potting method, or a coating method can be used. In the case of the transfer molding method, the norbornene compound-added polymer solids containing a small amount of organic solvent are softened by heating, and then injected into a mold equipped with electronic components and molded, and a small amount of the solvent is removed by evaporation. In the case of the potting method, the sealed electronic parts are filled with a high-viscosity norbornene compound addition polymer solution and dried. In the coating method, a norbornene compound addition polymer solution is coated on an electronic component to be sealed, particularly an electronic substrate, by a method such as a roll coating method, a curtain coating method, a screen printing method, a spin coating method, or a dating method. The solvent is removed by evaporation.

 [0082] [Medical equipment]

 As medical equipment, it is used for chemical containers, ampoules, syringes, infusion bags, sample containers, test tubes, blood collection tubes, sterilization containers, pipes, tubes and the like.

 Example

 [0083] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited to these examples. Unless otherwise indicated, parts and% in the examples are based on weight.

 The test and evaluation in an Example and a comparative example were performed with the following method.

[0084] (1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer

 Measured as polystyrene converted value by gel 'permeation' chromatography (GPC) using tetrahydrofuran or black mouth form as solvent.

 (2) Copolymerization ratio of polymer

 1. Obtained by NMR measurement.

 (3) Water absorption

 Obtain the ratio (% by weight) of the weight increase after immersion of the film piece in water at 23 ° C for 24 hours to the weight of the film piece before immersion.

(4) Glass transition temperature Measured at the temperature of the inflection point of the storage elastic modulus E 'measured by dynamic viscoelasticity. Dynamic viscoelasticity is measured using DMS6100 (Seiko Instruments), measuring frequency is 10Hz, heating rate is 5 ° CZ, excitation mode is single waveform, excitation amplitude is 5.0 m. Measure the temperature at the inflection point of the storage elastic modulus E '.

(5) Linear expansion coefficient

 Using TMA (Thermal Mechanical Analysis) / SDTA840 (Metola ^ Toledo), a test piece with a film thickness of about 70 m, length of 15.4 mm, width of 5.95 mm is upright, fixed, and Apply lg weight. In order to remove the thermal history of the film, the temperature was raised from room temperature to 300 ° C at 5 ° CZmin, then lowered to room temperature, and again from room temperature at 5 ° CZmin, 30 ° C to 250 ° C. The linear expansion rate is obtained from the inclination of the elongation of the film piece between ° C. The unit is (ppmZ ° C).

(Example 1)

 (Synthesis of norbornene compound addition polymer (A))

 A nitrogen-substituted glass reactor was charged with 0.77 parts of (aryl) palladium (tricyclohexylphosphine) chloride and 14 parts of lithium tetrakis (pentafluorophenyl) borate, followed by 2 parts of toluene. Was added to prepare a catalyst solution.

Next, a pressure-resistant glass reactor equipped with a nitrogen-replaced stirrer was charged with 1,650 parts of bicyclo [2.2.1] hept-2-ene (molecular weight = 94), 9-ethylidenetetracyclo [6. ^{1. I 3 '6. 0 2} ' 7] Dodeka 4 En (molecular weight = 186) 1, 400 parts of toluene were charged 7, 200 parts of a styrene 521 parts及beauty polymerization solvent as a molecular weight modifier, the above catalyst solution Polymerization was initiated by addition. After reacting at 60 ° C for 1.5 hours, the polymerization reaction solution is poured into a large amount of methanol to completely precipitate the polymer, filtered and washed, and then dried under reduced pressure at 50 ° C for 18 hours to give a copolymer ( A) 2,000 parts were obtained. The obtained copolymer (A) was soluble in toluene, black mouth form and the like. The number average molecular weight of the copolymer (A) (hereinafter sometimes abbreviated as “Mn”) is 171,000, and the weight average molecular weight (hereinafter sometimes abbreviated as “Mw”) is 659,000. bicyclo in the copolymer (a) [2. 2. 1] Heputo 2 E emission unit Z9- E dust Den tetracyclo ^{[6. 2. 1. I 3 '6} . 0 2' 7] de de force The composition ratio of 4-ene units was 76/24 (mol / mol). Table 1 shows the evaluation results of the properties of copolymer (A). [0086] [Table 1]

 [0087] (Example 2)

 (Synthesis of norbornene compound addition polymer (B))

A solution obtained by dissolving 300 parts of the copolymer (A) in 9,000 parts of toluene was placed in a pressure-resistant glass reactor equipped with a stirrer substituted with nitrogen, and heated to 55 ° C. Next, 5 parts of m-chloroperbenzoic acid was added to this solution and reacted at 55 ° C for 3 hours to give 9-ethylidenetetracyclo [6.2.1] in copolymer (A). I ³ ' ^6. 0 ² ' ⁷ ] Ethylidene group in dodecane structural unit was epoxidized. After the reaction, the reaction solution was poured into a large amount of methanol to completely precipitate the polymer, washed by filtration and dried under reduced pressure at 50 ° C. for 18 hours to obtain 278 parts of copolymer (B). The obtained copolymer (B) was soluble in toluene, black mouth form and the like. Copolymer (B) has Mn of 154,000, Mw of 692,000, bicyclo in the copolymer (B) [2.2.1] heptene-2-ene Z 9-ethylidenetetra cyclo ^{[6. 2. 1. I 3 '6} . 0 2' 7] de de force one 4-E emission units / 9-ethylene O carboxymethyl tetracyclo ^{[6. 2. 1. I 3 '6} . 0 2' ⁷ ] The ratio of 4-deoxy units was 76/13/11 (mol Z mol Z mol). Table 1 shows the evaluation results of the properties of the copolymer (B).

 [0088] (Example 3)

 (Synthesis of norbornene compound addition polymer (C))

A nitrogen-substituted glass reactor was charged with (aryl) palladium (tricyclohexylphosphine) A catalyst solution was prepared by adding 0.77 parts of lolide and 14 parts of lithium tetrakis (pentafluorophenyl) borate followed by 2 parts of toluene.

Next, a nitrogen-substituted pressure-resistant glass reactor equipped with a stirrer was charged with 2,100 parts of 5-ethylidenebicyclo [2.2.1] hepto-2-ene (molecular weight = 120), tetracyclo [6.2.1. ^{I 3 '. 6 0 2'} 7] de de force - 4- E emissions (molecular weight = 160) 1, 200 parts of toluene were charged 7, 700 parts of a styrene 521 parts and a polymerization solvent as a molecular weight modifier, the above catalyst The liquid was added to initiate the polymerization. After reacting at 60 ° C for 2 hours, the polymerization reaction solution is poured into a large amount of methanol to completely precipitate the polymer, washed by filtration, dried under reduced pressure at 50 ° C for 18 hours, and then copolymer (C) 2, 0 14 parts were obtained. The resulting copolymer (C) was soluble in toluene, black mouth form and the like. Copolymer (C) has Mn of 158,000, Mw of 355,000, 5-ethylidene bicyclo [2.2.1] hepto-2-ene unit / tetracyclo [6.2 in copolymer (C) 1. I ³ ' ^6. 0 ² ' ⁷ ] The ratio of 4-deoxy units was 73Z27 (mol Z mol). Table 1 shows the evaluation results of the properties of copolymer (C).

(Comparative Example 1)

 (Synthesis of norbornene compound addition polymer (D))

 A nitrogen-replaced glass reactor was charged with 8.2 parts of N, N, -bis- (2-methylphenol) benzamidinetonickel (triphenylphosphine) chloride and 9.0% aluminum aluminoxane. 825 parts of a toluene solution was added, and subsequently 500 parts of toluene was added to prepare a catalyst solution.

Next, in a pressure-resistant glass reactor equipped with a nitrogen-replaced stirrer, 1,175 parts of bicyclo [2.2.1] hept-2-ene, 5-hexylbicyclo [2.2.1] hept-2-ene (Molecular weight = 17 8) 2,230 parts and 4,000 parts of toluene as a polymerization solvent were added, and the above catalyst solution was added to initiate polymerization. After reacting at 60 ° C for 2.5 hours, the polymerization reaction solution is poured into a large amount of methanol to completely precipitate the polymer, washed by filtration, dried under reduced pressure at 50 ° C for 18 hours, and then copolymer (D ) 2,834 parts were obtained. The obtained copolymer (D) was soluble in toluene, black mouth form and the like. Copolymer (D) has Mn of 134,000, Mw of 314,000, and bicyclo [2.2.1] hepto-2-ene unit Z5—hexylbicyclo [2.2 in copolymer (D) 1] The composition ratio of heptoe-2-en units was 5lZ49 (mol Z mol). Evaluation of properties of copolymer (D) The results are shown in Table 1.

[0090] (Comparative Example 2)

 (Synthesis of norbornene compound addition polymer (E))

 A nitrogen-substituted glass reactor was charged with 0.77 parts of (aryl) palladium (tricyclohexylphosphine) chloride and 14 parts of lithium tetrakis (pentafluorophenyl) borate, followed by 2 parts of toluene. Was added to prepare a catalyst solution.

 Next, a nitrogen-substituted pressure-resistant glass reactor equipped with a stirrer was charged with 2,400 parts of 5-ethylidenebicyclo [2.2.1] hept-2-ene (molecular weight = 120), 5-triethoxysilylbicyclo [ 2. 2. 1] Hepto-2-ene (molecular weight = 256) 1,280 parts, styrene 5 21 parts as a molecular weight regulator and toluene 8,600 parts as a polymerization solvent were added, and the above catalyst solution was added and heavy. Started. After reacting at 60 ° C for 3 hours, the polymerization reaction solution is poured into a large amount of methanol to completely precipitate the polymer, washed by filtration, dried under reduced pressure at 50 ° C for 18 hours, and copolymer (E) 2 905 parts were obtained. The obtained copolymer (E) was soluble in toluene, black mouth form and the like. Copolymer (E) has Mn of 195,000, Mw of 475,000, 5-ethylidenebicyclo in copolymer (E) [2.2.1] hept-2-ene units / 5— The composition ratio of triethoxysilylbicyclo [2.2.1] hept-2-ene unit was 88Z12 (mol Z mol). Table 1 shows the evaluation results of the properties of copolymer (E).

[0091] (Examples 4 to 6, Comparative Examples 3 to 4)

 A 10% toluene solution of each polymer obtained in Examples 1 to 3 and Comparative Examples 1 to 2 was cast on a flat polytetrafluoroethylene sheet and allowed to stand at room temperature for 24 hours under an air stream. Toluene was removed by evaporation, followed by vacuum drying at 80 ° C. for 24 hours to obtain 100 μm thick Finolem.

 Table 1 shows the results of measuring the light transmittance, glass transition temperature, water absorption, and linear expansion coefficient of the obtained film piece.

 [0092] From the results in Table 1, repeating structural units derived from tetracyclododecene compound monomers

(Tetracyclododecane structure repeating unit (a))! / Solbornene compound addition polymer has no polar group-containing norbornane structure repeating unit (b). Low temperature (Comparative Example 3), polar group-containing norbornane structure repeating unit ( When b) is present, the glass transition temperature is high, but the water absorption is high (Comparative Example 4). In any case, the linear expansion coefficient is large.

In contrast, a norbornene compound addition polymer having a repeating structural unit derived from a tetracyclododecene compound monomer (tetracyclododecane structural repeating unit ( _a )) as an essential component has a glass transition temperature. It can be seen that the coefficient of linear expansion is small (Examples 4 and 5). In particular, when the proportion of the polar group-containing norbornane structure repeating structural unit (b) is small, the water absorption is also low (Examples 4 and 6).

Claims

What is claimed is a norbornene compound addition polymer comprising only repeating units derived from a norbornene compound, comprising at least the repeating unit (a) represented by the general formula (1), wherein the general formula A norbornene compound addition polymer, characterized in that the content ratio of the repeating unit (b) having a polar group represented by (2) is 0 mol% or less. [Chemical 1]

(In the general formula (1), I ^ to R ⁴ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. I ^ to R ⁴ are bonded to each other in any combination. In addition, R ¹ and R ² or R ³ and R ⁴ may be combined to form an alkylidene group.

[Chemical 2]

(In General Formula (2), R ^{5 to} R ° are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a polar group, or a carbon number having at least one polar group 1 to 20 is an organic group, and at least one of R ^{5 to} R ⁸ is a polar group or an organic group having 1 to 20 carbon atoms having at least one polar group, and R ^{5 to} R ⁸ are optional. And may be combined with each other to form a ring, and m is an integer of 0 to 2.)

Repeating unit represented by general formula (3) that does not fall under repeating unit (a) The norbornene compound addition polymer according to claim 1, further comprising a unit (c)

(In general formula (3), R ^{9 to} R ¹² each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ^{9 to} R ¹² are bonded to each other in any combination. In addition, R ⁹ and R ^1C> or R ¹¹ and R ¹² may be combined to form an alkylidene group.

 [3] The norbornene compound addition polymer according to claim 1 or 2, wherein each is independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.

 [4] The norbornene compound addition polymer has a polystyrene equivalent weight average molecular weight (Mw) of 60,

The norbornene compound addition polymer according to claim 1 or 2, which is 000-900,000.

 [5] The norbornene compound addition polymer described in claim 1 or 2

 [6] The molded article according to claim 5, which is a film or a sheet.

[7] The molded article according to claim 6, which is a film or sheet having a total light transmittance of 70% or more.

 [8] The molded article according to claim 6, which is a film or sheet having a linear expansion coefficient of 200 ppm or less.

 [9] The molded article according to claim 6, which is a film or sheet having a water absorption of 0.1% by weight or less.

 [10] The molded article according to claim 6, which is a film or sheet having a glass transition temperature of 200 ° C or higher.

[11] The composition according to claim 6, wherein the transparent conductive film is a laminated film or sheet. TOo

 The molded article according to claim 5, which is for optical use.

 A display element substrate comprising the molded article according to claim 5.