JP2005239740A - Thermoplastic resin composition - Google Patents

Abstract

An object of the present invention is to provide a cyclic olefin resin excellent in ultraviolet resistance without coloring a molded product.
A thermoplastic resin composition comprising the following (A) and (B), or (A), (B) and (C).
(A) Cyclic olefin-based thermoplastic resin (B) Oxanilide compound (C) Hydrocarbon resin having a polystyrene-equivalent weight average molecular weight of 200 to 20,000 and solid at room temperature [Selection] None

Description

  The present invention relates to a thermoplastic resin composition having excellent ultraviolet resistance. More specifically, a cyclic olefin-based thermoplastic resin, or a thermoplastic resin excellent in UV resistance without coloring a molded product, obtained by blending an oxanilide compound with a specific thermoplastic resin composition containing the resin. Relates to the composition.

Cyclic olefin-based thermoplastic resins have many tertiary carbons in their molecules, so they tend to be deteriorated by radicals generated by irradiation with ultraviolet rays and the like, and may have a problem with ultraviolet resistance. Many. For this reason, for the purpose of improving the ultraviolet resistance, a compound that absorbs a problem ultraviolet ray is generally added. For example, in Patent Document 1 (Japanese Patent Laid-Open No. 4-154862) and Patent Document 2 (Japanese Patent Laid-Open No. 2001-72839), a cyclic olefin-based thermoplastic resin composition excellent in ultraviolet light resistance blended with a benzotriazole-based compound. Things are disclosed. Also, it is described in Patent Document 3 (Japanese Patent Application Laid-Open No. 1-132626) that a benzophenone-based compound can be added to improve ultraviolet resistance.
However, the above-mentioned benzotriazole compounds or benzophenone compounds, which are generally used, have excellent ultraviolet light absorption performance over a wide range, but the absorption includes the visible light region, resulting in coloring of the molded product, causing hue problems. In use, there were restrictions on use.
JP-A-4-154862 JP 2001-72839 A JP-A-1-132626

  The present invention is a thermoplastic resin that retains various properties of a conventionally known cyclic olefin-based thermoplastic resin or a thermoplastic resin composition containing the resin, and is excellent in stability to ultraviolet rays without coloring a molded product. It is to provide a composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have colored a molded product by blending an oxanilide compound with a cyclic olefin-based thermoplastic resin or a thermoplastic resin composition containing the resin. As a result, it was found that a thermoplastic resin composition excellent in UV resistance was obtained, and the present invention was completed. Further, the present inventors have found that an optical component using the thermoplastic resin composition of the present invention is excellent in optical properties such as transparency, heat resistance and moisture resistance, and is useful. Furthermore, it discovered that the said optical component was obtained by shape | molding the thermoplastic resin composition of this invention by injection molding, melt extrusion, or a solution casting method.

  The thermoplastic resin composition of the present invention can provide a cyclic olefin resin having excellent ultraviolet resistance without coloring a molded product.

Hereinafter, the thermoplastic resin composition of the present invention will be described in detail.
Examples of the cyclic olefin-based thermoplastic resin of the present invention include the following (co) polymers.
(1) A ring-opening polymer of a specific monomer represented by the following general formula (I).
(2) A ring-opening copolymer of a specific monomer represented by the following general formula (I) and a copolymerizable monomer.
(3) A hydrogenated (co) polymer of the ring-opening (co) polymer of (1) or (2) above.
(4) A (co) polymer obtained by cyclizing the ring-opening (co) polymer of the above (1) or (2) by Friedel-Craft reaction and then hydrogenating it.
(5) A saturated copolymer of a specific monomer represented by the following general formula (I) and an unsaturated double bond-containing compound.
(6) Addition type (co) of one or more monomers selected from a specific monomer represented by the following general formula (I), a vinyl-based cyclic hydrocarbon-based monomer, and a cyclopentadiene-based monomer Polymers and their hydrogenated (co) polymers.
(7) An alternating copolymer of a specific monomer represented by the following general formula (I) and an acrylate.

[Wherein, R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or another monovalent organic group, and may be the same or different. R ¹ and R ² or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ are bonded to each other to form a single ring or A polycyclic structure may be formed. m is 0 or a positive integer, and p is 0 or a positive integer. However, when m is 0, p is also 0. ]

<Specific monomer>
Specific examples of the specific monomer include the following compounds, but the present invention is not limited to these specific examples.
Bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.1 ^2,5 ] -3-decene,
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
5-phenylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-phenyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,

5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2-ene,
5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,
8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-difluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9,9-tetrafluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8-heptafluoroiso-propyl-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-chloro-8,9,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene.
These can be used alone or in combination of two or more.

Among the specific monomers, in general formula (I), R ¹ and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 2 carbon atoms. R ² and R ⁴ are a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ represents a polar group having a polarity other than a hydrogen atom or a hydrocarbon group, and m is 0 An integer of ˜3, p is an integer of 0 to 3, more preferably m + p = 0 to 4, more preferably 0 to 2, particularly preferably m = 1 and p = 0. The specific monomer having m = 1 and p = 0 is preferable in that the obtained cyclic olefin-based thermoplastic resin has a high glass transition temperature and excellent mechanical strength.

  Examples of the polar group of the specific monomer include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group. These polar groups are connected via a linking group such as a methylene group. May be combined. In addition, a hydrocarbon group in which a divalent organic group having a polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, or an imino group is bonded as a linking group can also be exemplified. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group or an allyloxycarbonyl group is preferable, and an alkoxycarbonyl group or an allyloxycarbonyl group is particularly preferable.

In addition, a monomer in which at least one of R ² and R ⁴ is a polar group represented by the formula — (CH ₂ ) _n COOR is such that the obtained cyclic olefin-based thermoplastic resin has a high glass transition temperature and a low hygroscopicity, It is preferable at the point which has the outstanding adhesiveness with various materials. In the formula relating to the specific polar group, R is a hydrocarbon group having 1 to 12, preferably 1 to 6, more preferably 1 or 2, and particularly preferably an alkyl group. In addition, n is usually 0 to 5, but the smaller the value of n, the higher the glass transition temperature of the resulting cyclic olefin-based thermoplastic resin, which is preferable, and the specific monomer in which n is 0. Is preferred because of its easy synthesis.

In the general formula (I), R ¹ or R ³ is preferably an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, particularly a methyl group. In particular, it is preferable that the alkyl group is bonded to the same carbon atom as the carbon atom to which the specific polar group represented by the formula — (CH ₂ ) _n COOR is bonded. This is preferable in that the hygroscopicity of the plastic resin can be lowered.

<Copolymerizable monomer>
Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene. The number of carbon atoms of the cycloolefin is preferably 4-20, and more preferably 5-12. These can be used alone or in combination of two or more.
A preferred use range of the specific monomer / copolymerizable monomer is 100/0 to 50/50, more preferably 100/0 to 60/40, in weight ratio.

<Ring-opening polymerization catalyst>
In the present invention, (1) a ring-opening polymer of a specific monomer, and (2) a ring-opening polymerization reaction for obtaining a ring-opening copolymer of a specific monomer and a copolymerizable monomer are metathesis It is carried out in the presence of a catalyst.
This metathesis catalyst comprises (a) at least one selected from W, Mo and Re compounds, (b) Deming periodic table group IA elements (for example, Li, Na, K, etc.), IIA group elements (for example, , Mg, Ca, etc.), Group IIB elements (eg, Zn, Cd, Hg, etc.), Group IIIA elements (eg, B, Al, etc.), Group IVA elements (eg, Si, Sn, Pb, etc.), or Group IVB A catalyst comprising a combination of at least one element selected from compounds having elements (for example, Ti, Zr, etc.) and having at least one element-carbon bond or the element-hydrogen bond. In this case, in order to increase the activity of the catalyst, an additive (c) described later may be added.

Representative examples of W, Mo or Re compounds suitable as component (a) include WCl ₆ , MoCl ₆ , ReOCl _3, etc. JP-A-1-132626, page 8, lower left column, line 6 to page 8, upper right page. The compounds described in column 17th line can be mentioned.
(B) Specific examples of the _{component, n-C 4 H 9 Li} , (C 2 H 5) 3 Al, (C 2 H 5) 2 AlCl, (C 2 H 5) 1.5 AlCl 1.5, (C 2 H ₅ ) AlCl ₂ , methylalumoxane, LiH and the like can be mentioned compounds described in JP-A No. 1-132626, page 8, upper right column, line 18 to page 8, lower right column, line 3.
As typical examples of the component (c) which is an additive, alcohols, aldehydes, ketones, amines and the like can be suitably used, but further, JP-A-1-132626, page 8, lower right column, The compounds shown in line 16 to page 9, upper left column, line 17 can be used.

The amount of the metathesis catalyst used is a range in which “(a) component: specific monomer” is usually 1: 500 to 1: 50,000 in terms of the molar ratio of the component (a) to the specific monomer. The range is preferably 1: 1,000 to 1: 10,000.
The ratio of the component (a) to the component (b) is such that (a) :( b) is 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atomic ratio.
The ratio of the component (a) to the component (c) is such that the molar ratio (c) :( a) is in the range of 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1. The

<Solvent for polymerization reaction>
Examples of the solvent used in the ring-opening polymerization reaction (solvent constituting the molecular weight modifier solution, solvent for the specific monomer and / or metathesis catalyst) include alkanes such as pentane, hexane, heptane, octane, nonane, decane, Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, Compounds such as halogenated alkanes and aryl halides such as chloroform and tetrachloroethylene, saturated carbohydrates such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, and dimethoxyethane Esters, dibutyl ether, tetrahydrofuran, and the like can be illustrated ethers such as dimethoxyethane, they can be used singly or in combination. Of these, aromatic hydrocarbons are preferred.
As the amount of the solvent used, “solvent: specific monomer (weight ratio)” is usually in an amount of 1: 1 to 10: 1, preferably in an amount of 1: 1 to 5: 1. The

<Molecular weight regulator>
The molecular weight of the resulting ring-opening (co) polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight is adjusted by allowing the molecular weight regulator to coexist in the reaction system. To do.
Here, suitable molecular weight regulators include, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Styrene can be mentioned, and among these, 1-butene and 1-hexene are particularly preferable.
These molecular weight regulators can be used alone or in admixture of two or more.
The amount of the molecular weight regulator used is 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per 1 mol of the specific monomer subjected to the ring-opening polymerization reaction.

  (2) In order to obtain a ring-opening copolymer, a specific monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization in the ring-opening polymerization step, and further, polybutadiene, polyisoprene, etc. In the presence of unsaturated hydrocarbon polymers such as conjugated diene compounds, styrene-butadiene copolymers, ethylene-nonconjugated diene copolymers, polynorbornene and the like containing two or more carbon-carbon double bonds in the main chain. The specific monomer may be subjected to ring-opening polymerization.

The ring-opening (co) polymer obtained as described above can be used as it is, but (3) the hydrogenated (co) polymer obtained by further hydrogenation is a resin having a high impact resistance. Useful as a raw material.
<Hydrogenation catalyst>
In the hydrogenation reaction, a hydrogenation catalyst is added to a usual method, that is, a solution of a ring-opening polymer, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is added thereto at 0 to 200 ° C., preferably 20 It is carried out by operating at ~ 180 ° C.
As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. Examples of the hydrogenation catalyst include heterogeneous catalysts and homogeneous catalysts.

  Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. The homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium. Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. The form of the catalyst may be powder or granular.

These hydrogenation catalysts are used in such a ratio that the ring-opening (co) polymer: hydrogenation catalyst (weight ratio) is 1: 1 × 10 ⁻⁶ to 1: 2.
As described above, the hydrogenated (co) polymer obtained by hydrogenation has excellent thermal stability, and its characteristics deteriorate due to heating during molding and use as a product. There is no.
The hydrogenation rate of the hydrogenated (co) polymer is 50% or more, preferably 90% or more, more preferably 98% or more, and most preferably 99% or more, as measured by 500 MHz and ¹ H-NMR. The higher the hydrogenation rate, the better the stability to heat and light.
In the present invention, hydrogenation means hydrogenation of an olefinically unsaturated bond in the molecule, and when an aromatic group is present in the molecule, it does not mean hydrogenation of the aromatic group. . That is, such an aromatic group may have an advantageous effect on the refractive index and birefringence. Therefore, in the present invention, the aromatic group in the molecule does not necessarily need to be hydrogenated. Depending on the desired properties, it is necessary to select conditions under which such aromatic groups are not substantially hydrogenated.

  In the present invention, the gel content contained in a ring-opening (co) polymer used as a cyclic olefin-based thermoplastic resin or a hydrogenated product thereof is preferably 5% by weight or less, and more preferably 1% by weight or less. It is particularly preferred that

Further, as the cyclic olefin-based thermoplastic resin of the present invention, (4) a (co) polymer obtained by cyclization of the ring-opening (co) polymer of the above (1) or (2) by Friedel-Craft reaction and then hydrogenation Can also be used.
<Cyclization by Friedel-Craft reaction>
The method for cyclizing the ring-opened (co) polymer of (1) or (2) by Friedel-Craft reaction is not particularly limited, but the acidic compound described in JP-A-50-154399 is used. Any known method can be employed. Specific examples of the acidic compound include Lewis acids such as AlCl ₃ , BF ₃ , FeCl ₃ , Al ₂ O ₃ , HCl, CH ₃ ClCOOH, zeolite, activated clay, and Bronsted acid.
The cyclized ring-opening (co) polymer is preferably hydrogenated in the same manner as the ring-opening (co) polymer (1) or (2).

Further, as the cyclic olefin-based thermoplastic resin of the present invention, (5) a saturated copolymer of the specific monomer and an unsaturated double bond-containing compound can also be used.
<Unsaturated double bond-containing compound>
As an unsaturated double bond containing compound, ethylene, propylene, butene etc., Preferably it is C2-C12, More preferably, C2-C8 olefin type compound can be mentioned.
The preferred use range of the specific monomer / unsaturated double bond-containing compound is 90/10 to 40/60, more preferably 85/15 to 50/50, in weight ratio.

In the present invention, in order to obtain a saturated copolymer of (5) a specific monomer and an unsaturated double bond-containing compound, a usual addition polymerization method can be used.
<Addition polymerization catalyst>
As the catalyst for synthesizing the (5) saturated copolymer, at least one selected from a titanium compound, a zirconium compound and a vanadium compound and an organoaluminum compound as a promoter are used.
Here, examples of the titanium compound include titanium tetrachloride and titanium trichloride, and examples of the zirconium compound include bis (cyclopentadienyl) zirconium chloride and bis (cyclopentadienyl) zirconium dichloride.

Furthermore, as a vanadium compound, general formula VO (OR) _a X _b or V (OR) _c X _d
[Wherein R is a hydrocarbon group, X is a halogen atom, and 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ (a + b) ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3, ≦ (c + d) ≦ 4. ]
Or an electron-donating adduct of these compounds.
Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, amines, Examples thereof include nitrogen-containing electron donors such as nitrile and isocyanate.

Furthermore, as the organoaluminum compound as the promoter, at least one selected from those having at least one aluminum-carbon bond or aluminum-hydrogen bond is used.
In the above, for example, when the vanadium compound is used, the ratio of the vanadium compound to the organoaluminum compound is such that the ratio of aluminum atom to vanadium atom (Al / V) is 2 or more, preferably 2 to 50, particularly preferably 3 to 20. Range.

  As the solvent for the polymerization reaction used for the addition polymerization, the same solvent as that used for the ring-opening polymerization reaction can be used. Moreover, adjustment of the molecular weight of the (5) saturated copolymer obtained is normally performed using hydrogen.

Further, as the cyclic olefin-based thermoplastic resin of the present invention, (6) one or more monomers selected from the above specific monomer and a vinyl-based cyclic hydrocarbon monomer or a cyclopentadiene monomer. Addition copolymers and their hydrogenated copolymers can also be used.
<Vinyl cyclic hydrocarbon monomer>
Examples of the vinyl cyclic hydrocarbon monomer include vinyl cyclopentene monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene, 4-vinylcyclopentane, 4-isopropenylcyclopentane and the like. Vinylated 5-membered hydrocarbon monomers such as vinylcyclopentane monomers, 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-vinyl Vinylcyclohexene monomers such as cyclohexene and 2-methyl-4-isopropenylcyclohexene, vinylcyclohexane monomers such as 4-vinylcyclohexane and 2-methyl-4-isopropenylcyclohexane, styrene, α-methylstyrene, 2-methylstyrene, 3- Styrenic monomers such as styrene styrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylstyrene, p-methoxystyrene, d-terpene, 1-terpene, diterpene, d-limonene, 1- Terpene monomers such as limonene and dipentene, vinylcycloheptene monomers such as 4-vinylcycloheptene and 4-isopropenylcycloheptene, 4-vinylcycloheptane, 4-isopropenylcycloheptane, etc. And vinyl cycloheptane monomers. Styrene and α-methylstyrene are preferable. These can be used alone or in combination of two or more.

<Cyclopentadiene monomer>
Examples of the cyclopentadiene monomer used as the monomer of the addition copolymer (6) of the present invention include, for example, cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, Examples include 5-methylcyclopentadiene and 5,5-methylcyclopentadiene. Cyclopentadiene is preferred. These can be used alone or in combination of two or more.

The addition type (co) polymer of at least one monomer selected from the above specific monomer, vinyl cyclic hydrocarbon monomer and cyclopentadiene monomer is the above (5) specific monomer. It can be obtained by the same addition polymerization method as the saturated copolymer of the unsaturated double bond-containing compound.
The hydrogenated (co) polymer of the addition type (co) polymer can be obtained by the same hydrogenation method as the hydrogenated (co) polymer of the above (3) ring-opening (co) polymer. .

Furthermore, as the cyclic olefin-based thermoplastic resin of the present invention, (7) an alternating copolymer of the specific monomer and acrylate can also be used.
<Acrylate>
Examples of the acrylate used in the production of the (7) alternating copolymer of the specific monomer and acrylate of the present invention include straight chain having 1 to 20 carbon atoms such as methyl acrylate, 2-ethylhexyl acrylate and cyclohexyl acrylate. C2-C20 heterocyclic group-containing acrylates such as chain, branched or cyclic alkyl acrylates, glycidyl acrylates, 2-tetrahydrofurfuryl acrylates, and aromatic ring groups containing 6-20 carbons such as benzyl acrylates Examples thereof include acrylates having a polycyclic structure having 7 to 30 carbon atoms such as acrylate, isobornyl acrylate, and dicyclopentanyl acrylate.

In the present invention, (7) In order to obtain an alternating copolymer of the specific monomer and acrylate, when the total of the specific monomer and acrylate is 100 mol in the presence of Lewis acid, The specific monomer is 30 to 70 mol, the acrylate is 70 to 30 mol, preferably the specific monomer is 40 to 60 mol, and the acrylate is 60 to 40 mol, particularly preferably the specific monomer. The polymer is radically polymerized at a ratio of 45 to 55 mol and acrylate of 55 to 45 mol.
(7) The amount of Lewis acid used to obtain the alternating copolymer of the specific monomer and acrylate is 0.001 to 1 mol per 100 mol of acrylate. Also, known organic peroxides or azobis radical polymerization initiators that generate free radicals can be used, and the polymerization reaction temperature is usually -20 ° C to 80 ° C, preferably 5 ° C to 60 ° C. . Moreover, the same solvent as used for the ring-opening polymerization reaction can be used as the solvent for the polymerization reaction.
The “alternate copolymer” as used herein refers to a structure in which the structural unit derived from the specific monomer is not adjacent, that is, the structural unit derived from the acrylate is always adjacent to the structural unit derived from the specific monomer. It means a copolymer having a structure as a unit, and does not deny a structure in which structural units derived from acrylate are adjacent to each other.

The preferred molecular weight of the cyclic olefin-based thermoplastic resin used in the present invention is 0.2 to 5 dl / g, more preferably 0.3 to 3 dl / g, particularly preferably 0.4 to 1 in terms of intrinsic viscosity [η] _inh. The polystyrene-reduced number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 8,000 to 100,000, more preferably 10,000 to 80,000, particularly preferably. The weight average molecular weight (Mw) is in the range of 20,000 to 300,000, more preferably 30,000 to 250,000, and particularly preferably 40,000 to 200,000. Is preferred.
When the intrinsic viscosity [η] _inh , number average molecular weight and weight average molecular weight are in the above ranges, the heat resistance, water resistance, chemical resistance, mechanical properties and molding processability of the cyclic olefin thermoplastic resin are improved. .

  The glass transition temperature (Tg) of the cyclic olefin-based thermoplastic resin used in the present invention is usually 120 ° C. or higher, preferably 120 to 350 ° C., more preferably 130 to 250 ° C., and particularly preferably 140 to 200 ° C. is there. When Tg is less than 120 ° C., for example, in applications requiring heat resistance such as in-vehicle applications, the obtained film or sheet may be thermally deformed, which may be a problem. On the other hand, when Tg exceeds 350 ° C., melt extrusion processing becomes difficult, and the possibility that the resin deteriorates due to heat during the processing is not preferable.

<Specific cyclic olefin-based thermoplastic resin composition>
The specific cyclic olefin-based thermoplastic resin composition used in the present invention is, for example, a thermoplastic resin containing a specific hydrocarbon resin described in JP-A-9-221575 and JP-A-10-287732. It is a resin composition and contains the following specific hydrocarbon resin <(C) component> in addition to the said cyclic olefin type thermoplastic resin <(A component)>.

<(C) component>
The hydrocarbon resin of component (C) used in the present invention has a polystyrene equivalent weight average molecular weight of 100 to 20,000, preferably 200 to 10,000, more preferably 300 to 5,000. And solid at room temperature.
Specific examples of (C) hydrocarbon resin include, for example, C ₅ resin, C ₉ resin, C ₅ / C ₉ mixed resin, cyclopentadiene resin, polymer resin of vinyl substituted aromatic compound, olefin / vinyl substitution Examples thereof include copolymer resins of aromatic compounds, copolymer resins of cyclopentadiene compounds / vinyl-substituted aromatic compounds, and hydrogenated products of the above resins.
Among these, C ₅ resins, C ₉ resins, C ₅ / C ₉ mixed resin, cyclopentadiene resin, polymer-based resin of a vinyl-substituted aromatic compounds, and mixtures thereof are preferred. The C ₅ resin is preferably aliphatic, and the C ₉ resin is preferably alicyclic.
Among these, C ₉ resin, cyclopentadiene resin, and a mixture thereof are particularly preferable.

  If the polystyrene-converted weight average molecular weight of these (C) hydrocarbon resins is too low, the strength of the resin tends to be reduced and the resin surface tends to bleed. On the other hand, if it is too high, the cyclic olefin having a polar group This is not preferable because the compatibility with the thermoplastic resin deteriorates and the transparency is reduced. (C) The blending ratio of the hydrocarbon resin is 0.1 to 100 parts by weight, preferably 1 to 60 parts by weight, more preferably 2 to 50 parts by weight with respect to 100 parts by weight of the (A) cyclic olefin-based thermoplastic resin. , Particularly preferably 5 to 45 parts by weight.

  As a method for obtaining the thermoplastic resin composition used in the present invention, known apparatuses used for processing thermoplastic resins, for example, a twin screw extruder, a single screw extruder, a continuous kneader, a roll kneader, a pressure kneader And a method of melt-kneading using a Banbury mixer, and dissolving and blending the component (C) in the solution of the component (A) and pelletizing.

The cyclic olefin-based thermoplastic resin of the present invention or a specific thermoplastic resin composition containing the resin is required to have few foreign matters that cause visual defects and abnormal bright spots when used as an optical material. It is preferable that it does not exist.
The content of such foreign matter should be at least 0/10 g of foreign matter of 50 μm or more, preferably 0/10 g of foreign matter of 30 μm or more, and particularly preferably 0/10 g of foreign matter of 20 μm or more.
The amount of foreign matter is measured by dissolving the resin in a solvent having solubility such as toluene and cyclohexane, filtering with a filter, and observing with a microscope to count the size and number. It is also possible to measure the resin solution using a commercially available fine particle counter based on the principle of light scattering and to count the amount of foreign matter.
Moreover, it is preferable to suppress the content of the fine powder of the cyclic olefin thermoplastic resin of the present invention or the specific cyclic olefin thermoplastic resin composition as much as possible. A large amount of fine powder is not preferable because it appears as optical fluctuations and results in performance defects such as bright spots and blurred focus.

<(B) component: Oxanilide compound>
The oxanilide compound used in the present invention is represented by the following general formula (II).

[Wherein, R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms or other monovalent organic group, and may be the same or different. good. ]

  In the general formula (II), the hydrocarbon group having 1 to 30 carbon atoms or other monovalent organic group is, for example, an alkyl group having 1 to 15 carbon atoms such as a methyl group, an ethyl group or an isobutyl group; a cyclopentyl group or a cyclohexyl group. A cycloalkyl group having 5 to 12 carbon atoms such as a group; an aromatic group having 6 to 20 carbon atoms such as a phenyl group, a biphenyl group, a naphthyl group, an ethylphenyl group and a t-butylphenyl group; a methoxy group, an ethoxy group, an iso C1-C15 alkoxy groups such as propoxy groups; C6-C20 allyloxy groups such as phenoxy groups and naphthoxy groups; C2-C15 alkoxycarbonyls such as methoxycarbonyl groups, ethoxycarbonyl groups and cyclohexylcarbonyl groups Group: aryloxy having 7 to 20 carbon atoms such as phenoxycarbonyl group and naphthoxycarbonyl group Carbonyl group; or a portion thereof those substituted by a halogen atom.

Specific examples of the oxanilide compound include, for example,
2-chloro-oxanilide,
2-methyl-oxanilide,
2-ethyl-oxanilide,
2-cyclohexyl-oxanilide,
2-phenyl-oxanilide,
2-methoxy-oxanilide,
2-phenoxy-oxanilide,
2-methoxycarbonyl-oxanilide,
2-trichloromethyl-oxanilide,
2,2′-dimethyl-oxanilide,
2-methyl-2'-methoxy-oxanilide 2-methyl-2'-ethoxy-oxanilide 2-ethyl-2'-ethoxy-oxanilide 2-isopropyl-2'-isopropoxy-oxanilide 2-isobutyl-2'-isobutoxy- And oxanilide.
In the present invention, among these, compounds in which R ⁵ and R ⁶ are different substituents are preferred, and compounds having an alkyl group and an alkoxy group are preferred. In particular, those in which R ⁵ is an ethyl group and R ⁶ is an ethoxy group, that is, 2-ethyl-2′-ethoxy-oxanilide is preferred because it is easily available industrially.

The component (B) is blended with (A) a cyclic olefin thermoplastic resin or a cyclic olefin thermoplastic resin composition comprising the components (A) and (C).
(B) The preferable addition amount of a component is 10-50,000 ppm with respect to the sum total of (A) in a composition and the (C) component mix | blended as needed, More preferably, 100-10,000 ppm, Particularly preferably, it is 500 to 5,000 ppm. When the added amount of the component (B) is less than 10 ppm, the effect of improving the ultraviolet resistance of the composition may not be recognized. On the other hand, when it exceeds 50,000 ppm, the composition becomes turbid and the transparency is deteriorated. There are things to do.

(B) As a blending method of a component, the method of adding in the manufacturing process of cyclic olefin type thermoplastic resin or cyclic olefin type thermoplastic resin composition, cyclic olefin type thermoplastic resin, or cyclic olefin type thermoplastic resin composition The method of blending after manufacture is mentioned.
When blending in the production process of the cyclic olefin-based thermoplastic resin or cyclic olefin-based thermoplastic resin composition, the method is not particularly limited, but a method of blending with a monomer, a method of blending after ring-opening polymerization, hydrogen The method of blending after additive manufacture, the method of blending after catalyst separation, the method of blending after concentration, the method of blending at the time of pelletization, the method of blending with component (C), etc. are mentioned.

When blending after the production of the cyclic olefin-based thermoplastic resin or cyclic olefin-based thermoplastic resin composition, known equipment used for processing the thermoplastic resin, such as a twin-screw extruder, single-screw extruder, continuous kneader, roll kneading And a blending method using a press, a pressure kneader, and a Banbury mixer. Alternatively, the pellet may be re-dissolved in one or more solvents selected from a solvent group that can be used in ring-opening polymerization, and the solvent may be separated and re-pelletized by the method described above.
Furthermore, you may blend in the process of shape | molding a cyclic olefin type thermoplastic resin or a cyclic olefin type thermoplastic resin composition by the method of the below-mentioned.

The component (B) may be blended with the cyclic olefin-based thermoplastic resin or the cyclic olefin-based thermoplastic resin composition in a powder state, or may be added as a master batch.
Resin or solvent is used as the base material of the masterbatch.
The resin used as the base material is usually a cyclic olefin-based thermoplastic resin or a cyclic olefin-based thermoplastic resin composition to be blended, but is a known thermoplastic resin as long as it does not impair the desired properties when formed into a molded body. Alternatively, a thermoplastic elastomer may be used.
In the production of the masterbatch, an apparatus used for processing the above-described known thermoplastic resin is used. The concentration of the preferred component (B) in the master batch is usually 0.01 to 90% by weight, preferably 0.1 to 60% by weight.
When the solvent-based masterbatch is used, the solvent used is not particularly limited as long as it dissolves the cyclic olefin-based thermoplastic resin or the cyclic olefin-based thermoplastic resin composition of the present invention, but the solvent used in the production thereof. When is used, post-processing may be facilitated, which may be preferable. The component (B) is preferably dissolved in the solution to form a uniform layer. However, it may be in the form of a suspension or paste as long as it is dispersed without impairing the uniformity. The concentration of the component (B) in the solution is usually 0.01 to 90% by weight, preferably 0.1 to 60% by weight.

In the composition of the present invention, a known antioxidant or light stabilizer can be used for the purpose of further improving heat resistance and ultraviolet resistance. These can be used alone or in combination as long as the effects of the present invention are not impaired.
Specific examples are given below, but the present invention is not limited thereto.
Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol, 4,4′-thiobis- (6-tert-butyl-3-methylphenol), 1,1′-bis ( 4-hydroxyphenyl) cyclohexane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 3,9-bis- [2- [3- (3-t-butyl -4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxpiro [5,5 '] undecane, 2,2'-dioxy-3, 3'-di-t-butyl-5,5'-dimethylphenylmethane, 2,2'-dioxy-3,3'-t-butyl-5,5'-diethylphenylmethane, 2,2'-methylenebis ( 4-ethyl-6-t-butylphenol), 2,5-di-t-butylhydroquinone, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate] methane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Phenolic antioxidants such as butyl-4-hydroxybenzyl) benzene, hydroquinone antioxidants, tris (4-methoxy-3,5-diphenyl) phosphite, tris (2,4-t-butylphenyl) phosphite , Tris (nonylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol di Hos Examples thereof include phosphorus-based antioxidants such as phyte and bis (2,4-di-cumylphenyl) pentaerythritol diphosphite.

As the light stabilizer, for example, hindered amines are preferable. Specifically, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4- Diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-hyperidyl) imino}], N, N′-bis (3-Aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5- A triazine condensate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate and the like can be preferably used.
These antioxidants and light stabilizers can be added in the same manner as the component (B) of the present invention.

  The thermoplastic resin composition of the present invention includes other known thermoplastic resins, thermoplastic elastomers, rubber polymers, organic fine particles, inorganic fine particles, and antistatic agents as long as the transparency and heat resistance of the composition are not impaired. A lubricant may be blended.

  The thermoplastic resin composition of the present invention can be molded by a known method. For example, an injection molding method, a profile extrusion method, fiber spinning, a blow molding method, an inflation molding method, a rotational molding method, a melt casting method, a solution casting method and the like can be employed.

Preferred optical components for use in the thermoplastic resin composition of the present invention include optical components of image display devices, information recording / reproducing devices, information recording media, image photographing devices, and image reproducing devices.
Examples of the optical components of the image display device include a liquid crystal cell, a polarizing plate, a retardation plate, a light guide plate, a light guide, a surface protection plate, and a transparent electrode plate. Examples of optical components of the information recording / reproducing apparatus include a pickup lens, a diffraction grating, and a collimating lens. Examples of the optical component of the information recording medium include optical disks such as CD, MD, MO, and DVD, and protective films used for them. Examples of the optical components of the image photographing apparatus include an imaging system lens, a finder prism, a protective cap and a protective film for a CCD element, and a sealing material for a photosensitive element. Examples of the parts of the image reproducing apparatus include an fθ lens and a pickup lens.

  The molded body obtained from the thermoplastic resin composition of the present invention can be subjected to secondary processing by a known method. For example, antireflection treatment using known organic or inorganic materials, coating with known organic or inorganic materials or surface hardening treatment using electron beam, radiation, etc., compounding with film or sheet, metalizing, specific wavelength Coating with an organic or inorganic material that absorbs water, cutting treatment, adhesion to a deformed material by a known method, and fusion.

The thermoplastic resin composition of the present invention can be processed into an optical component by injection molding.
The injection molding machine used for injection molding is not particularly specified. For example, the cylinder method is an inline method, the pre-plastic method, the drive method is hydraulic, electric, hybrid, and the clamping method is direct pressure, toggle, injection. For the direction, horizontal, vertical, etc. can be used. For mold clamping, it may be possible to use injection compression. Cylinder diameter and clamping force are determined by the shape of the target molded product. Generally, the larger the projected area of the molded product, the larger the clamping force. When the molded product has a large capacity, it is preferable to select a cylinder with a larger cylinder diameter. .
The molding conditions should be selected optimally depending on the shape of the molded product, and are not particularly limited.

In addition, the inventive field thermoplastic resin composition can be used as an optical component because a film or sheet-like molded product can be obtained by a melt casting method or a solution casting method. That is, an optical component can be obtained by surface-treating a film or sheet by a known method to be described later or by cutting into a desired shape.
The application of the film or sheet-like molded product obtained with the thermoplastic resin composition of the present invention is not particularly limited, but preferred applications include polarizing plates, retardation plates, and liquid crystal cells for liquid crystal display devices. And polarizing plates, touch panels, diffusion plates, light guide plates, protective plates, information recording media, protective films or sheets for various optical devices, and the like used in various display devices.

  The film or sheet obtained from the thermoplastic resin composition of the present invention can be subjected to secondary processing by a known method. For example, condensing or imparting light diffusion function by heat embossing using a known device, antireflection treatment by coating a known organic or inorganic material, known organic or inorganic material coating or electron beam, radiation irradiation Surface hardening treatment by metallizing, metallizing, adhesion and fusion with known shapes molded by known methods, uniaxial or biaxial or multi-directional stretching treatment, printing of various electrodes, specific wavelength For example, a coating of an organic or inorganic material that absorbs water, printing using a known paint, and the like.

A film or a sheet-like molded product obtained from the thermoplastic resin composition of the present invention is molded by a melt casting method or a solution casting method.
Here, the melt casting method is a method of obtaining a film or sheet by extruding a thin melt from a film or sheet die attached to the tip of an extruder, and cooling and solidifying with various rolls or belts. is there. The extruder used for the solution casting method is not particularly limited, and known ones can be used. Usually, a single-screw or twin-screw extruder is used, and preferably a single-screw extruder is used. The cylinder diameter of the extruder is usually 10 to 100 mm. A known screw is used. For example, in the case of a single shaft, a combination of full flight and subflight, a combination of dull images, and a screw whose pitch or groove depth changes in the same screw can be mentioned. In the case of two shafts, in the case of two or three screws, different direction or same direction rotation, and a system in which screw parts are freely combined, the screw part shape is screw type, reverse feed screw, paddle type screw, helical paddle It is possible to select and incorporate it more freely than a type screw or the like. Although one extruder can be operated, a combination of two or more extruders or a combination of continuous and batch kneaders may be used.

  The solution casting method is a method in which the thermoplastic resin composition of the present invention is dissolved in a soluble solvent of the thermoplastic resin composition of the present invention, and the solution is stretched into a film or a sheet. Can be produced by a method disclosed in, for example, JP-A-5-148413. Examples of the solvent used in the solution casting method include those generally used as solvents such as aromatic compounds such as benzene, toluene and xylene, butyl acetate, tetrahydrofuran dimethoxyethane, chloroform, methylene dichloride and methyl ethyl ketone. As a method for casting the solution, the above solution is extruded onto a metal drum, a steel belt, a polyester film, a Teflon belt or the like from a die having a certain width, and dried over a temperature and time. It is also possible to produce a film having a uniform thickness by applying the solution by spraying, brushing, rolls, spin coating, dipping, etc., and arbitrarily applying temperature and time.

  The thermoplastic composition of the present invention is excellent in ultraviolet light resistance and can be used as various optical components.

Examples of the present invention will be described below, but the present invention is not limited by these examples. In the following, “part” means “part by weight”, and the molecular weight is a weight average molecular weight in terms of polystyrene unless otherwise specified. In addition, various measurement methods in this example are shown below.
<Glass transition temperature: Tg>
Using a DSC6200 manufactured by Seiko Instruments Inc., the temperature increase rate was measured at 20 ° C. per minute under a nitrogen stream.
<Weight average molecular weight and molecular weight distribution>
Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of polystyrene were measured using HLC-8020 gel permeation chromatography (GPC) manufactured by Tosoh Corporation and using a tetrahydrofuran (THF) solvent. In addition, Mn represents the number average molecular weight of polystyrene conversion.
<Intrinsic viscosity ([η] _inh )>
A chloroform solvent or a cyclohexane solvent was used as the solvent, and the measurement was performed with an Ubbelohde viscometer at a polymer concentration of 0.5 g / dl at 30 ° C.
In the examples, the components (A-3) and (A-4) were measured in a cyclohexane solvent, and the other components A were measured in a chloroform solvent.

<(A) component>
(A-1) Component synthesis method:
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (specific monomer) 250 parts, 1-hexene (molecular weight regulator) 41 parts, toluene (ring-opening polymerization solvent) 750 parts in a reaction vessel in which nitrogen was substituted The solution was heated to 60 ° C. Next, 0.62 parts of a toluene solution of triethylaluminum (1.5 mol / l) and tungsten hexachloride modified with t-butanol / methanol (t-butanol: methanol: tungsten = 0.20) were added to the solution in the reaction vessel. 37 parts of a toluene solution (concentration 0.05 mol / l) of 35 mol: 0.3 mol: 1 mol) was added, and this system was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction. Thus, a ring-opening polymer solution was obtained. The polymerization conversion rate in this polymerization reaction was 97%.

The autoclave was charged with 4,000 parts of the ring-opening polymer solution thus obtained, and RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] 30.48 parts was added to the ring-opening polymer solution. The hydrogenation reaction was carried out by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. The hydrogenation rate of the thus obtained hydrogenated polymer (A-1) measured by 60 MHz and ¹ H-NMR was substantially 100%. Moreover, Mw was 75,000, Mw / Mn was 3.5, η _inh was 0.50, and the glass transition temperature (Tg) was 163 ° C.

Using the specific monomers shown in Table 1, the hydrogenated products (A-2) to (A-8) of the ring-opening (co) polymer were obtained in the same manner as the hydrogenated polymer (A-1). Obtained. The hydrogenation rate of the olefinically unsaturated bonds (A-2) to (A-8) measured by 60 MHz and ¹ H-NMR was substantially 100%. However, the aromatic rings of (A-7) and (A-8) were not substantially hydrogenated.
Table 1 shows η _inh , Mw, Mw / Mn, and Tg of (A-1) to (A-8). The molecular weights (η _inh ) of (A-1) to (A-8) were adjusted by appropriately selecting the amount of 1-hexene added as a molecular weight regulator.

<(B) component>
2-Ethyl-2′-ethoxy-oxanilide was used.
<"UV absorber": UV absorber outside the scope of the present invention>
(1) 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole (2) 2-hydroxy-4-n-octoxybenzophenone <(C) component>
Hydrogenated C ₉ petroleum resin, molecular weight 1,590, softening point 100 ° C.
<Other additives>
(1) Phenol antioxidant: Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (2) Phosphorous antioxidant: Tris (2,4-t -Butylphenyl) phosphite (3) Light stabilizer: Poly-2,2,4,4-tetramethyl-7-oxa-2,20-diaza-20 (2,3-epoxy-propyl) -dispiro- [ 5.1.11.2] -Heneikosan-21-on

Preparation Method of Composition After a solution of component (A) or a solution obtained by adding a predetermined amount of component (B) to component (A), a large amount of methanol was added to coagulate. Thereafter, the component (C) was further granulated with further additives as necessary to obtain pellets.

Test piece molding method and evaluation method <Injection molding>
-Molding method of test piece The sample used in the following test was performed by injection molding. The molding machine was SG75M-S manufactured by Sumitomo Heavy Industries, Ltd., and the molding conditions were a resin temperature of 260 to 300 ° C and a mold temperature of 80 to 140 ° C.
About the characteristic required as an optical component shape | molded by injection molding, it measured by the following method.
* A test piece of hue 230mm x 15mm, 3mm thick, with both end faces (15mm side) mirror-finished by injection molding, light from a cold cathode tube enters from one end face, and exits from the opposite end face The hue of the emitted light was measured with a color difference meter (Minolta CS100). The hue is indicated by yellowness: YI.
* Durability (Hue)
The test was conducted using a sunshine fade meter at 63 ° C. without rain, and YI was measured by the above method after 300 hours and after 500 hours.
* Durability (crack)
Using a sunshine fade meter, the test was conducted at 63 ° C. without rain, and the surface state after 500 hours was observed.
○: No change Δ: Within 10 mm × 100 mm field of view, no more than 10 microcracks have occurred.
X: Remarkable cracks are generated.

<Sheet by melt casting method>
A T-die having a width of 600 mm is attached to the tip of a single-screw extruder having a diameter of 50 mm, and the composition shown in the following examples is extruded, cooled on a roll and a belt to obtain a sheet-like molded product having a thickness of 0.8 mm. It was.
* Hue Yellowness: YI was measured with a spectrophotometer (manufactured by Suga Test Instruments).
* UV resistance Using a sunshine fade meter, the test was conducted at 63 ° C with no rain, and the surface condition after 500 hours was observed.
○: No change Δ: Within 10 mm × 100 mm field of view, no more than 10 microcracks have occurred.
X: Remarkable cracks are generated.

<Film by solution casting method>
The composition of the present invention shown in the following examples was adjusted in THF so that the concentration of the composition was 30%, and a film was prepared using an applicator bar having a clearance of 0.3 mm. Further, this membrane was dried in a vacuum dryer maintained at 60 ° C. for 24 hours to obtain a film having a thickness of 100 μm. The amount of residual solvent of the obtained film was measured by a heat loss method (120 ° C. × 3 hours), and all were 0.5% or less.
* Hue Yellowness: YI was measured with a spectrophotometer (manufactured by Suga Test Instruments).
* Durability (Hue)
The test was conducted using a sunshine fade meter at 63 ° C. without rain, and YI was measured by the above method after 300 hours and after 500 hours.
* Durability (crack)
Using a sunshine fade meter, the test was conducted at 63 ° C. without rain, and the surface state after 500 hours was observed.
○: No change Δ: Within 10 × 100 mm field of view, no more than 10 microcracks have occurred.
X: Remarkable cracks are generated.

Examples 1-16, Comparative Examples 1-3
<Manufacture of injection molded products>
The composition shown in Table 2 was used to evaluate the colorability and ultraviolet resistance of an injection molded article using the thermoplastic resin composition of the present invention. From the comparison of Examples 1-16 and Comparative Examples 1-3, the injection-molded article containing the thermoplastic resin composition of the present invention has no coloring immediately after molding, and the hue after ultraviolet irradiation is stable, and the surface It can be seen that there are no cracks.

Examples 17 to 34, Comparative Examples 4 to 13
<Manufacture of film or sheet by melt casting method or solution casting method>
With the compositions shown in Table 3 (melt casting method) and Table 4 (solution casting method), the colorability and ultraviolet resistance of the film or sheet using the thermoplastic resin composition of the present invention were evaluated. From comparison between Examples 17 to 34 and Comparative Examples 4 to 13, the film or sheet containing the thermoplastic resin composition of the present invention is not colored immediately after molding, and the hue of the film or sheet after UV irradiation is also stable. It can be seen that there is no occurrence of cracks on the surface.

The thermoplastic resin composition of the present invention is preferably used for applications of image display devices, information recording / reproducing devices, information recording media, image photographing devices, and optical components of image reproducing devices.
Here, examples of the optical component of the image display device include a liquid crystal cell, a polarizing plate, a retardation plate, a light guide plate, a light guide, a surface protection plate, and a transparent electrode plate. Examples of optical components of the information recording / reproducing apparatus include a pickup lens, a diffraction grating, and a collimating lens. Examples of the optical component of the information recording medium include optical disks such as CD, MD, MO, and DVD, and protective films used for them. Examples of the optical components of the image photographing apparatus include an imaging system lens, a finder prism, a protective cap and a protective film for a CCD element, and a sealing material for a photosensitive element. Examples of the parts of the image reproducing apparatus include an fθ lens and a pickup lens.
Further, the use of the film and sheet-shaped molded product obtained from the thermoplastic resin composition of the present invention is not particularly limited, but preferred applications include polarizing plates for liquid crystal display devices, retardation plates, Examples include a polarizing plate, a touch panel, a diffusion plate, a light guide plate, a protective plate, an information recording medium, and protective films or sheets for various optical devices used in liquid crystal cells and various display devices.

Claims (6)

The thermoplastic resin composition containing the following (A) and (B).
(A) Cyclic olefin-based thermoplastic resin (B) Oxanilide compound A thermoplastic resin composition containing the following (A), (B) and (C).
(A) Cyclic olefin-based thermoplastic resin (B) Oxanilide compound (C) A polystyrene-reduced weight average molecular weight of 200 to 20,000 and a solid hydrocarbon resin at room temperature   (A) The thermoplastic resin composition of Claim 1 or Claim 2 in which a cyclic olefin type thermoplastic resin contains a 1 or more types of polar group in a molecule | numerator.   An optical component comprising the thermoplastic resin composition according to any one of claims 1 to 3.   An injection-molded article comprising the thermoplastic resin composition according to any one of claims 1 to 3. A film or sheet obtained by molding the thermoplastic resin composition according to any one of claims 1 to 3 by a melt extrusion method or a solution casting method.