WO1999038918A1 - Thermoplastic cycloolefin resin composition and molded object - Google Patents

Abstract

A resin composition which comprises: a thermoplastic cycloolefin resin comprising at least 70 wt.% repeating units having an alicyclic structure which is not a norbornane structure; a light stabilizer; and an ultraviolet absorber and/or an antioxidant as an optional ingredient. The composition is satisfactory in mechanical strength, elongation, chemical resistance, and weatherability and is useful especially as a film.

Description

 Description Cyclic olefinic thermoplastic resin composition and molded article

 The present invention relates to a cyclic olefin-based thermoplastic resin composition having excellent mechanical strength, elongation, chemical resistance, and weather resistance.

 The present invention also relates to a molded article comprising a cyclic olefin-based thermoplastic resin composition having excellent mechanical strength, elongation, chemical resistance, and weather resistance. Background art

 Cyclic olefin thermoplastic resins have excellent properties such as chemical resistance, and are used in a wide range of applications, including medical materials. However, with the progress of technology, there is a demand for improvements to materials with higher resistance to deterioration, especially for plastic films used outdoors. For example, vinyl chloride resin has long been used as a material for plastic films used outdoors, such as agricultural films. That is, vinyl chloride resin films used outdoors have been frequently used because of their excellent properties such as mechanical strength, elongation, chemical resistance, and weather resistance. However, in recent years, halogen-containing resins such as vinyl chloride resin have become a problem as a cause of toxic gases generated during incineration and cause environmental damage.Therefore, polymers containing no halogen atoms such as chlorine atoms have been used. Alternatives are desired. Among them, cyclic olefin-based thermoplastic resins are expected because they do not generate toxic gas during incineration and have excellent mechanical strength and elongation characteristics, but they are still insufficient in weather resistance and chemical resistance. There was a problem that substitution was not progressing easily. Disclosure of the invention

In view of the above situation, an object of the present invention is to provide a cyclic olefin-based thermoplastic resin composition having excellent mechanical strength, elongation, chemical resistance, and weather resistance. . Another object of the present invention is to provide a molded article comprising a cyclic olefin-based thermoplastic resin composition having excellent properties in mechanical strength, elongation, chemical resistance and weather resistance.

 The inventors of the present invention have conducted intensive studies to solve the problems of the prior art, and as a result, a cyclic amine olefin-based thermoplastic resin containing a specific repeating unit having no norpornan structure has a hindered amine-based photostable. A resin composition having excellent mechanical strength, elongation, chemical resistance, and weather resistance by blending an agent or a metal complex-based ultraviolet absorber, and a resin composition formed by molding the resin composition The inventors have found that a molded article such as a film can be obtained, and have completed the present invention.

 Thus, according to the present invention, a cyclic olefin comprising a cyclic olefin thermoplastic resin (I) containing 70% by weight or more of the repeating unit (A) represented by the following formula (1) and a light stabilizer (X): A thermoplastic resin composition is provided.

Equation (1)

式 （1) において、 R²¹〜R³⁴は、 それぞれ独立に、 水素原子、 炭化水素基 、 水酸基、 エステル基、 アルコキシ基、 シァノ基、 イミド基、 シリル基、 または 官能基 （水酸基、 エステル基、 アルコキシ基、 シァノ基、 イミド基およびシリル 基の中から選ばれる少なくとも一つの官能基） で置換された炭化水素基を表す。 ただし、 R²⁵と R²⁷、 または R²⁶と R²⁸とが一緒になつて不飽和結合を形成し てもよく、 また、 R²⁵と R²⁶、 または R²⁷と R²⁸とで、 アルキリデン基を形成 していてもよい。 dは 0または 1である。 は炭素一炭素の単結合または二 重結合を表す。 さらに、 本発明によれば、 上記環状ォレフィン系熱可塑性樹脂組成物を成形し てなる成形体が提供される。 発明を実施するための最良の形態

In the formula (1), R ^{21 to} R ³⁴ each independently represent a hydrogen atom, a hydrocarbon group, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an imide group, a silyl group, or a functional group (hydroxyl group, ester group, Represents a hydrocarbon group substituted with at least one functional group selected from an alkoxy group, a cyano group, an imide group and a silyl group. However, R ²⁵ and R ²⁷ , or R ²⁶ and R ²⁸ may be combined to form an unsaturated bond, and an alkylidene group may be formed by R ²⁵ and R ²⁶ or R ²⁷ and R ^28. It may be formed. d is 0 or 1. Represents a carbon-carbon single bond or a double bond. Further, according to the present invention, there is provided a molded article obtained by molding the above-mentioned cyclic olefin-based thermoplastic resin composition. BEST MODE FOR CARRYING OUT THE INVENTION

 Cyclic olefinic thermoplastic resin (I)

 The cyclic olefinic thermoplastic resin (I) used in the present invention is characterized by containing a repeating unit (A) represented by the above formula (1) containing an alicyclic structure having no norbornane structure. .

 The alicyclic structure having no norbornane structure in the repeating unit (A) may be contained in any of the main chain and / or the side chain. However, when particularly high mechanical strength is required, Those contained in the chains are preferred. The alicyclic structure having no norbornane structure may be either saturated or unsaturated, and when high mechanical strength and weather resistance are required, a saturated alicyclic structure is preferred.

In the formula (1), R ^{21 to} R ³⁴ each independently represent a hydrogen atom, a hydrocarbon group, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an imide group, a silyl group, or a functional group (hydroxyl group). , An ester group, an alkoxy group, a cyano group, an imide group and a silyl group), and is preferably a hydrogen atom or a hydrocarbon group, More preferably, it is a hydrogen atom. The number of carbon atoms of the hydrocarbon group is usually in the range of 1 to 20, preferably 1 to 10, and more preferably 1 to 6. Specific examples of the hydrocarbon group include an alkyl group and an alkenyl group, preferably an alkyl group, and among them, an alkyl group having 1 to 6 carbon atoms is particularly preferable. Examples of the hydrocarbon group substituted with a functional group include an ester group-containing alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms.

Further, R ²⁵ and R ²⁷ or R ²⁶ and R ²⁸ in the formula (1) may form an unsaturated bond together, and R ²⁵ and R ²⁶ , or R ²⁷ and R ²⁸ With the above, an alkylidene group may be formed. The number of carbon atoms of the alkylidene group is usually in the range of 1 to 20, preferably 1 to 10, and more preferably 1 to 6.

D in the formula (1) is 0 or 1, and is preferably 0. Also, in equation (1) 'Represents a carbon-carbon single bond or a double bond.

When it is 95% or more, preferably 98% or more, and more preferably 99% or more, it is particularly excellent in weather resistance, elongation and chemical resistance, and is suitable.

 Among the repeating units (A) having no norbornane structure represented by the above formula (1), those represented by the following formula (2) are the best.

Equation (2)

式 （2) 中の' は炭素一炭素の単結合または二重結合を表すが、 通常、 単 結合の割合が 95%以上、 好ましくは 98%以上、 より好ましくは 99%以上の 場合に、.特に耐候性、 伸びおよび耐薬品性に優れ、 好適である。

'In the formula (2) represents a carbon-carbon single bond or a double bond, and is usually obtained when the ratio of the single bond is 95% or more, preferably 98% or more, more preferably 99% or more. In particular, it has excellent weather resistance, elongation and chemical resistance and is suitable.

 The repeating unit (A) represented by the formula (1) containing an alicyclic structure having no norbornane structure may be used alone or in combination of two or more.

 Specific examples of the repeating unit (A) represented by the formula (1) containing an alicyclic structure having no norbornane structure in the cyclic olefinic thermoplastic resin (I) include dicyclopentadiene and dihydrodicyclo. Examples include repeating units derived from pentadiphenyl, dimethyldicyclopentadiene, and methyldicyclopentadiene. The content of the repeating unit (A) represented by the formula (1) containing an alicyclic structure having no norbornane structure in the cyclic olefinic thermoplastic resin (I) is from 70 to 100% by weight, preferably from 100 to 100% by weight. It is in the range of 80 to 100% by weight, more preferably 90 to 100% by weight. If the amount of the repeating unit (A) represented by the formula (1) in the cyclic olefin-based thermoplastic resin (I) is excessively small, any of the mechanical strength, elongation, chemical resistance, and weather resistance can be reduced. Inferior in characteristics and not preferred.

The norbornane structure in the cyclic olefin thermoplastic resin (I) used in the present invention. The remainder other than the repeating unit (A) represented by the formula (1) containing an alicyclic structure having no structure is not particularly limited. Examples of such a unit include a repeating unit (B) having an alicyclic structure having no norbornane structure, an alicyclic group having a norbornane structure, other than the repeating unit (A) represented by the formula (1). And a repeating unit (C) having a structure and a chain-like repeating unit (D). Among these, other than the repeating unit (A) represented by the formula (1), a repeating unit (B) containing an alicyclic structure having no norbornane structure and a repeating unit containing an alicyclic structure having a norbornane structure Unit (B) is preferred. All repeating units having an alicyclic structure in the cyclic olefinic thermoplastic resin (I) [Repeating units having an alicyclic structure without a norbornane structure (A) and (B) and an alicyclic structure having a norpolnanan structure With the repeating unit containing (C)] is 70% by weight or more, preferably 80% by weight or more, and most preferably 100% by weight. At this time, properties such as mechanical strength, elongation, and chemical resistance are highly balanced.

 Further, all repeating units having an alicyclic structure [the repeating units (A) and (B) containing an alicyclic structure having no norbornane structure and the repeating unit (C) containing an alicyclic structure having a norpolnanic structure] Of the repeating unit (A) containing an alicyclic structure having no norbornane structure in the (A) / C (A) + (B) + (C)] is also preferably 70% by weight or more. Is 80% by weight or more. At this time, properties such as mechanical strength, elongation, and chemical resistance are highly balanced.

Examples of the repeating unit (B) containing an alicyclic structure having no norbornane structure other than the repeating unit (A) represented by the formula (1) include a repeating unit represented by the following formula (3). Can be

Equation (3)

In the formula (3), Ι ^ to Ι2 ⁽⁾ each independently represent a hydrogen atom, a hydrocarbon group, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an imide group, a silyl group, or a functional group (hydroxyl group, At least one functional group selected from an ester group, an alkoxy group, a cyano group, an imide group and a silyl group), and is preferably a hydrogen atom or a hydrocarbon group. Preferably it is a hydrogen atom. The number of carbon atoms of the hydrocarbon group is usually in the range of 1 to 20, preferably 1 to 10, and more preferably 1 to 6. Specific examples of the hydrocarbon group include an alkyl group and an alkenyl group, preferably an alkyl group, and among them, an alkyl group having 1 to 6 carbon atoms is particularly preferable. Examples of the hydrocarbon group substituted with a functional group include an ester group-containing alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms.

In addition, R ⁸ and R ^1Q or R ⁹ and R ¹¹ in the formula (3) may form an unsaturated bond together, and R ⁸ and R ⁹ , or R ^1Q and R 1 ^{And 11} may form an alkylidene group. The carbon number of the alkylidene group is usually in the range of 1 to 20, preferably 1 to 10, and more preferably 1 to 6.

A in the formula (3) is 0 or 1, and is preferably 0. B in the formula (3) is 0 or 1, and is preferably 1. C in Equation (3) is c = 0 or 2 when b = 0, and c = 1 or 2 when b = 1. Specific examples of the repeating unit (B) having an alicyclic structure having no norbornane structure represented by the formula (3) include 5-ethylidene-bicyclo [2.2.1] - E down, 5- Echirupishikuro [2.2.1] into single hept - 2 E down, terrorist Rashikuro [7.4.2 0.0 ² '. ⁷ 1 ^{10' 13]} Tetoradeka one 11 one E down, Tetorashi black ^{[7. 4. 0. 0 2 '7 I} 10 · 13] -. trideca one 2, 4, 6, 1 1-tetraene include units derived from such.

 The repeating unit (C) having an alicyclic structure having a norpornan structure is not particularly limited, and examples thereof include a repeating unit represented by the following formula (4). Equation (4)

式 （4) 中の R³⁵~R⁴⁸の例示および好ましい範囲は、 式 （1) 中の R²¹〜 R³⁴と同様である。 式 （4) 中の eは 1〜3の整数であり、 好ましくは 1であ る。 式 （4) 中の は炭素一炭素の単結合または二重結合を表すが、 通常、 単結合の割合が 95 %以上、 好ましくは 98%以上、 より好ましくは 99%以上 の場合に、 特に耐候性、 伸びおよび耐薬品性に優れ、 好適である。

Examples and preferred ranges of R ³⁵ to R ⁴⁸ in the formula (4) are the same as those of R ²¹ to R ³⁴ in the formula (1). E in the formula (4) is an integer of 1 to 3, and is preferably 1. In the formula (4), represents a carbon-carbon single bond or a double bond. Usually, when the ratio of the single bond is 95% or more, preferably 98% or more, and more preferably 99% or more, the weather resistance is particularly high. Excellent in properties, elongation and chemical resistance.

Among the repeating units (C) having a norpornan structure represented by the formula (4), preferred are represented by the following formula (5), and more preferred are represented by the following formula (6). Equation (5)

式 （5) 中の R⁴⁹〜R⁶²の例示および好ましい範囲は、 式 （1) 中の R²¹の ものと同様である。 式 （5) 中の は炭素一炭素の単結合または二重結合を 表すが、 単結合の割合が通常 95 %以上、 好ましくは 98%以上、 より好ましく は 99%以上の場合に、 特に耐候性、 伸びおよび耐薬品性に優れ、 好適である。 式 （6)

Examples and preferred ranges of R ^{49 to} R ⁶² in the formula (5) are the same as those of R ²¹ in the formula (1). In the formula (5), represents a carbon-carbon single bond or a double bond, and when the ratio of the single bond is usually 95% or more, preferably 98% or more, more preferably 99% or more, particularly weather resistance Excellent in elongation and chemical resistance. Equation (6)

Examples and preferred ranges of R ^{63 to} R ⁶⁶ in the formula (6) are the same as those of R ²¹ in the formula (1). In the formula (6), represents a carbon-carbon single bond or a double bond, and when the ratio of the single bond is usually 95% or more, preferably 98% or more, more preferably 99% or more, particularly weather resistance Excellent in elongation and chemical resistance. Specific examples of the repeating unit (C) having a norbornane structure represented by formula (4), 8 E Chiru tetracyclo ^{[4.4.0.1 2 · 5 .1 7 ·} 10.] - dodeca one 3-E down, 8 Echiriden one tetracyclo ^{[4.4.0.1 2 · 5 .1 7.} '-. de de force one 3-E down, 8-methylcarbamoyl Lou tetracyclo ^{[4.4.0.1 2 · 5 .1 7'} 1 ()] - Dode force 3-ene and tetracyclo [4. ^{4.Ο.Ι. 2 · 5 .1 7 '1} ()] - de de force - include repeating units derived from such a 3-E down. These repeating units (B) having a norbornane structure may be used alone or in combination of two or more.

 As the chain-like repeating unit (D), for example, a unit represented by the formula (7) is used.

式 （7) 中の R⁶⁷〜R^7eは、 式 （1) 中の R²¹と同様であり、 好ましくは水 素原子である。 Equation (7)

R ^{67 to} R ^7e in the formula (7) are the same as R ²¹ in the formula (1), and are preferably a hydrogen atom.

 Specific examples of the linear repeating unit (D) represented by the formula (7) include α-olefins such as ethylene, propylene, 1-butene, and 11-pentene; aromatic vinyls such as styrene and α-methylstyrene; Examples of the repeating unit include cycloolefins such as cyclobutene, cyclopentene and cyclohexene, and non-conjugated gens such as 1,4-hexadiene.

 The molecular weight of the cyclic olefinic thermoplastic resin (I) used in the present invention is appropriately selected according to the purpose of use, but cyclohexane (or toluene when not dissolved in cyclohexane) is used as a solvent. 5,000-500,000, preferably 7,000-300,000, and more preferably 10,000-, as a weight average molecular weight in terms of polyisoprene measured by gel permeation chromatography (GPC). When it is in the range of 100,000, properties such as mechanical strength, elongation and chemical resistance of the film are highly balanced and suitable.

 The proportion of the component having a molecular weight of 1,000 or less measured by GPC in the cyclic thermoplastic resin (I) used in the present invention is not particularly limited, but is usually 20% by weight or less. When the content is preferably 10% by weight or less, more preferably 5% by weight or less, mechanical strength ゃ chemical resistance is particularly enhanced, which is suitable.

The cyclic olefin thermoplastic resin (I) used in the present invention has a low gel content and exhibits good processability. That is, the cyclic olefin system represented by the following formula (8) Nomer or a cyclic olefin monomer mixture containing 70% by weight or more of the monomer is subjected to solution polymerization, and then the obtained polymer is dissolved in the same solvent as used in the polymerization to obtain a 0.5% by weight concentration. to obtain a resin solution, the solution when was filtered through a pore size 0. 5 / zm of Po Li tetrafluoropropoxy O b ethylene filter made one, amounts filters one side 1 cm ² per resin solution passing through the filter, usually and a l cm ³ or more, preferred properly is 2 cc or more, more preferably 3 cc or more. Thus, when the gel content is small, the molding processability of a molded article such as a film is improved, and molding defects such as surface roughness and turbidity of the molded article are less likely to occur.

 (Formulation method)

 The production of the cyclic olefinic thermoplastic resin (I) used in the present invention can be carried out according to a conventional method. For example, an olefinic monomer having an alicyclic structure is polymerized in the presence of a catalyst. If necessary, a method of performing a hydrogenation reaction can be employed.

 As the olefin monomer (a) forming the repeating unit (A) containing an alicyclic structure having no norbornane structure, the olefin monomer represented by the following formula (8), preferably the following formula (9): One is used. The formation of the repeating unit (A) containing an alicyclic structure having no norbornane structure by metathesis polymerization of these olefinic monomers (a) is described in, for example, Japanese Patent No. 2534086 and It is publicly known in, for example, JP-A-7-121981.

Equation (8)

式 （8) 中、 R^2I~R³⁴および dは式 （1) における記号と同じである。 式 （9)

In the formula (8), R ^2I to R ³⁴ and d are the same as the symbols in the formula (1). Equation (9)

これらの式 （8) または式 (9) で表されるォレフィン系モノマー （a) は、 単独で、 あるいは 2種以上を組み合わせて用いることができる。 全モノマー中の 式 （8) または式 （9) で表されるォレフィン系モノマー （a) の割合は、 通常 70〜100重量％、 好ましくは 80〜 100重量％、 より好ましくは 90〜1 00重量％の範囲である。

These olefin monomers (a) represented by the formula (8) or (9) can be used alone or in combination of two or more. The proportion of the olefin monomer (a) represented by the formula (8) or (9) in all the monomers is usually 70 to 100% by weight, preferably 80 to 100% by weight, more preferably 90 to 100% by weight. % Range.

 If desired, the monomer copolymerized with the olefin monomer (a) represented by the formula (8) or (9) is not particularly limited, but is usually a repeating unit (A) represented by the formula (1). Other than the above, an olefin monomer (b) forming a repeating unit (B) containing an alicyclic structure having no norbornane structure and a repeating unit (C) containing an alicyclic structure having a norbornane structure And a monomer (d) which forms a chain-like repeating unit (D). Of these, Olefin monomer (b) and Olefin monomer (c) are preferred.

The olefin monomer (b) that forms the repeating unit (B) containing an alicyclic structure having no norbornane structure other than the repeating unit (A) represented by the formula (1) includes, for example, the following formula ( 10).

Equation (10)

式 （10) において、 R' R²° a bおよび cは式 （3) における記号と 同じである。

In the formula (10), R ′ R ² ° ab and c are the same as the symbols in the formula (3).

 Examples of the olefin monomer (c) forming the repeating unit (C) having an alicyclic structure having a norpolnanane structure include the following formula (11), preferably the following formula (12), and more preferably the following formula (12) 13) is used. Equation (11)

In the formula (11), R ³⁵ R ⁴⁸ and e are the same as the symbols in the formula (4). Equation (12)

式 （12) において、 R⁴⁹〜R⁶²は式 （5) における記号と同じである。 式 （13)

In the formula (12), R ^{49 to} R ⁶² are the same as the symbols in the formula (5). Equation (13)

式 （13) において、 R⁶³~R⁶⁶は式 （6) における記号と同じである。 これらのノルポルナン構造を有する脂環式構造を含有する繰返し単位 （C) を 形成するォレフイン系モノマ一 （c) は、 それぞれ単独で、 あるいは 2種以上を 組み合わせて用いることができる。 全モノマ一中の脂環構造を有するォレフィン 系モノマー [ォレフイン系モノマ一 （a) +ォレフィン系モノマ一 （b) +ォレ フィン系モノマ一 （c) ] の割合は、 70〜100重量％、 好ましくは 80〜1 00重量％の範囲、 最も好ましくは 100重量％である。

In the formula (13), R ⁶³ to R ⁶⁶ are the same as the symbols in the formula (6). These olefin monomers (c) forming the repeating unit (C) containing an alicyclic structure having a norpolnanane structure can be used alone or in combination of two or more. The proportion of the alecyclic monomer having an alicyclic structure in all the monomers [olefin monomer (a) + olefin monomer (b) + olefin monomer (c)] is 70 to 100% by weight, Preferably it is in the range from 80 to 100% by weight, most preferably 100% by weight.

 As the chain monomer (d), for example, the one represented by the formula (14) is used.

Equation (14)

In the formula ^{(14), R 67 ~R 7} (1 is the same as in Formula (7) _t Examples of suitable monomer combinations include (1) dicyclopentene monomer [olefin monomer (a)] + 8-ethyltetracyclododecene [olefin monomer (c) 、, (2) dicyclopentene monomer [ Orefuin monomer (a)] + E chill norbornene [Orefuin based monomer (b)], (3) Jishikuropen evening Zhen [Orefuin monomer (a)] + tetracyclo ^{[7.4.0.0 2 13] '7.} ' - trideca one 2,4,6,11-tetraene [olefin monomer (b)] + ethyltetracyclododecene [olefin monomer (c)], and (4) dicyclopentene [olefin monomer (a)] + 8 Tyltetracyclododecene [olefin monomer (c)] + tetracyclododecene [olefin monomer (c)].

 As the metathesis catalyst, for example, a compound of a Group VI metal such as tungsten (W) or molybdenum (Mo) or a compound of a Group IV metal such as titanium (Ti) can be used. It is a compound or a molybdenum (Mo) compound, and more preferably, a tungsten (W) compound is used.

Specific examples of the tungsten (W) _{compounds, WB r 2, WB r 3} , WB r 6, WC 1 2, WC 1 4, WC 1 5, WC 1 6, WF 2 WF have WF _6, WI _2, WI _{4, WI 6, WOB r 4} , WOC, WOF 4, W_〇 _{2, H 2 W0 4, NaWO} 4, K 2 WO physician (NH _{4) 2} W_〇 physician CaW0 _4, CuW_〇 _4, MgW_〇 _4, ( (CO) ₅ WC (OCH ₃ ) (CH ₃ ), (C0 ₅ ) WC (OC ₂ H ₅ ) (CH ₃ ), (C0 ₅ ) WC (〇C ₂ H ₅ ) (C ₄ H ₅ ) is but, WB r ₂ of _{these, WB r 3, WB r 6} , WC 1 2, WC 1 4, WC 1 5, WC 1 6, WF 2, WF 4, WF 6, WI 2, WI 4, WI There WOB r _4, WOC l _4, W_〇_F j: etc. are _{preferred, WB r 2, WB r 3} , WB r 6, WC 1 2, WC 1 4, WC 1 5, WC 1 6, WF 2, WF ₄ , tungsten halides such as WF ₆ , WI WI ₄ and W ₁₆ are more preferred.

 These metathesis catalysts can be used alone or in combination of two or more. The amount of the catalyst used is usually 0.1 to 1.5 parts by weight, preferably 0.1 to 1.0 parts by weight, more preferably 0.1 to 0 parts by weight, per 100 parts by weight of the total monomers. 5 parts by weight.

When conducting metathesis polymerization, a co-catalyst is used together with the above-mentioned metathesis catalyst. Is common. Examples of the co-catalyst include an organic aluminum compound and an organic tin compound, and an organic aluminum compound is preferable. Specific examples of the organic aluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum and triisobutylaluminum, and alkyls such as getylaluminumdimethylchloride and ethylaluminumdichloride. Examples thereof include aluminum halide and the like, with preference given to triethylaluminum, triisobutylaluminum and getylaluminum chloride.

 These cocatalysts can be used alone or in combination of two or more. The amount of the cocatalyst used is usually from 0.0 l to 30 mol, preferably from 0.1 l to 20 mol, and more preferably from 1 l to 10 mol per lmo of the metathesis catalyst. And high molecular weight is easily obtained, which is preferable.

 In the combination of the metathesis catalyst and the cocatalyst, a combination of a tungsten (W) compound and an organoaluminum compound is particularly preferable. While having a repeating unit (A) having no norpornan structure suitable for the present invention, it has a high molecular weight (specifically, a weight average molecular weight of 5,000 to 500,000, It is preferably 7,000 to 300,000, more preferably 10,000 to: L 00, 000) and has a low low molecular weight component (specifically, the proportion of the component having a molecular weight of 1,000 or less). 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less.) In the case of producing the cyclic olefin-based thermoplastic resin (I), the tantasten (W) -based compound and the organic aluminum compound In addition, it is preferable to use a regulator.

As the modifier, at least one polar compound selected from polar compounds containing active hydrogen such as alcohol and amine and polar compounds not containing active hydrogen such as ether, ester, ketone and nitrile can be used. . The polar compound containing active hydrogen is effective for preventing gelation and obtaining a high molecular weight polymer, and among them, alcohol is preferable. In addition, the polar compound containing no active hydrogen is effective in suppressing the formation of low molecular weight components in the polymer. —Tel, ester and ketone are preferred, and ketone is more preferred.

 Examples of the alcohol include saturated alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, isopenol, hexanol and cyclohexanol, phenol and benzyl. Examples thereof include unsaturated alcohols such as alcohol, and preferred are propanol, isopropanol, butanol, and isobutanol.

 Examples of the ether include dimethyl ether, getyl ether, dibutyl ether, ethylene glycol dibutyl ether and triethylene glycol dibutyl ether. Of these, diisopropyl ether and methyl ether are preferable.

 Examples of the ester include methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, and the like. Of these, methyl acetate / ethyl acetate is preferred.

 Examples of the ketone include acetone, methyl ethyl ketone, getyl ketone, methyl phenyl ketone, diphenyl ketone, and the like, and among them, acetone-methyl methyl ketone is preferable.

 Examples of nitriles include acetonitrile, benzonitrile, t-butylonitrile, and the like. Of these, benzonitrile and t_butylonitrile are preferable.

 These regulators can be used alone or in combination of two or more. In particular, in the present invention, it is preferable to combine a polar compound containing active hydrogen with a polar compound having no active hydrogen, and particularly a combination of alcohol and ketone, alcohol and nitrile, alcohol and ether, and alcohol and ester. preferable. The amount of the adjusting agent to be used is usually in the range of 0.01 to 20 mo, preferably in the range of 0.1 to 1.0 mol, more preferably in the range of 1 to 5 mol, per 1 mo 1 of the catalyst. .

The polymerization reaction is usually performed in the presence of a solvent. Solvents include, for example, benzene, Aromatic hydrocarbons such as benzene and xylene; aliphatic hydrocarbons such as n-pentane, hexane and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclooctane; and the like. Examples thereof include toluene, cyclohexane, and cyclooctane, and more preferred are toluene and cyclohexane. Each of these solvents can be used alone or in combination of two or more. The amount of the solvent used is usually 100 to 1,000 parts by weight, preferably 100 to 1,000 parts by weight, per 100 parts by weight of the monomer. The range is from 500 to 700 parts by weight, more preferably from 100 to 500 parts by weight.

 The polymerization conditions are such that the polymerization temperature is usually in the range of 10 to 200, preferably 0X: to 100, more preferably 10 to 80, and the polymerization time is usually 30 minutes. -10 hours, preferably 1-7 hours, more preferably 2-5 hours. If the polymerization temperature is too high, components having a molecular weight of 1,000 or less increase, and if the polymerization temperature is too low, the reaction rate is too slow to increase the reaction rate.

 After the completion of the polymerization reaction, a hydrogenation catalyst can be added to continue the hydrogenation reaction. The hydrogenation catalyst is not particularly limited as long as it is generally used in hydrogenating an olefin compound, and a heterogeneous catalyst or a homogeneous catalyst is usually used.

 Examples of the heterogeneous catalyst include nickel, palladium, platinum, or a solid catalyst in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina, or titanium oxide: nickel / silica, nickel Z Examples include diatomaceous earth, nickel / alumina, palladium Z-carbon, palladium silica, palladium diatomaceous earth, and palladium alumina.

As the homogeneous catalyst, for example, a catalyst composed of a combination of a transition metal compound and an alkylaluminum compound or an alkyllithium, for example, cobalt acetate triethylaluminum, cobalt acetate Z triisobutylaluminum, nigger acetate / triethylaluminum, Nickel triisobutylaluminum acetate, nickel acetylacetonate Z triethylaluminum, nickel acetylacetonate triisobutylaluminum whim, titanocene chloride Zn-butyllithium, zirconocene chloride Zn-butyl From a combination such as lithium Catalyst.

 These hydrogenation catalysts can be used alone or in combination of two or more. The amount of the hydrogenation catalyst used is usually in the range of 0.1 to 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight, per 100 parts by weight of the polymer.

The hydrogenation reaction is usually carried out under a hydrogen pressure of 1 to 150 kg / cm ² , at a temperature of 0 to 250, preferably at a temperature of 20 to 200, and a reaction time of 1 to 20 hours. After the above-mentioned hydrogenation reaction, the cyclic olefin-based thermoplastic resin (I) used in the present invention is obtained by filtering the reaction solution to remove the hydrogenation catalyst, and then dropping the filtrate into a poor solvent such as alcohol. The resin can be obtained by coagulating the resin and drying the obtained resin. When a homogeneous catalyst is used as the hydrogenation catalyst, after the hydrogenation reaction, alcohol or water is added to the reaction solution to deactivate the catalyst, the catalyst is insolubilized in a solvent, and then filtered to remove the hydrogenation catalyst. It can be obtained by removing, followed by filtration, coagulation and drying.

 Light stabilizer (X)

 The cyclic olefin-based thermoplastic resin composition of the present invention is characterized by containing a light stabilizer (X).

 The light stabilizer (X) can be used without any particular limitation as long as it is generally used in the resin industry, but a hindered amine light stabilizer is particularly preferably used.

The hindered amine light stabilizer is not particularly limited, but has 3,5-di-t-butyl-4-hydroxyphenyl group and 2,2,6,6-methylenepiperidyl in the structure. A compound having a group or a 1,2,2,6,6-pentenemethyl-4-piperidyl group is preferably used. Specific examples thereof include 1- [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] —4 -— [3--3,5-di-tbutyl— 4-hydroxyphenyl) propionyloxy] _2,2,6,6-tetramethylpiperidine (eg, Sanol LS 2626, manufactured by Sankyo)), 2- (3,5-di-t-butyl) -4 —Hydroxybenzyl) — 2-n-Butylmalonic acid—bis— (1, 2, 2, 6, 6- Pentamethyl-4-piperidyl) [For example, Tinuv in 144 (manufactured by Nippon Ciba Geigy Corporation), Adecastab LA-94 (manufactured by Asahi Denki Chemical), Adecastab LA A-63P (manufactured by Asahi Denki Chemical) Can be

 These hindered amine light stabilizers can be used alone or in combination of two or more. The amount of these light stabilizers (X) is usually 0.0001 to 5.0 parts by weight, preferably 0.001 to 1.0 parts by weight per 100 parts by weight of the cyclic olefin-based thermoplastic resin (I). Parts, more preferably 0.01 to 0.5 parts by weight.

 UV absorber (Y)

 It is preferable that the cyclic olefin-based thermoplastic resin composition of the present invention contains an ultraviolet absorber (Y) in addition to the light stabilizer (X).

 The ultraviolet absorber (Y) can be used without any particular limitation as long as it is generally used in the resin industry. Examples thereof include metal complex salts, benzophenones, salicylsans, and benzotriazols. And acrylate UV absorbers. Among these, it is preferable to select from metal complex salt-based, benzophenone-based and benzotriazole-based UV absorbers. The metal complex salt-based UV absorber alone, or the metal complex salt-based UV absorber and another UV absorber It is more preferable to use a combination with an agent.

 As the metal complex-based ultraviolet absorber, a complex salt of nickel-cobalt is preferably used. Specific examples include nickel [2, 2'-thiobis (4-t-one-octyl) phenol] normal ptyramine, nickel dibutyldithiocarbamate, nickel'bis [o-ethyl-3,5-( Di-t-butyl-4-hydroxybenzyl)] phosphate, cobalt 'dicyclohexyldithiophosphate, [1-phenyl, 3-methyl, 4-decanoyl, pyrazolate (5) 2] nickel, and the like.

Examples of the benzophenone-based ultraviolet absorber include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-14-methoxybenzophenone-15-sulfonic acid trihydrate, 2-hydrate Hydroxy-4-octoxybenzophenone, 4-dodecaroxy-2-hydroxybenzopheno , 4-benzyloxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, and the like.

 Examples of the benzotriazole-based UV absorber include 2- (2-hydroxy-5-methylphenyl) 2 H-benzotriazole, 2- (3-t-butyl-2-hydroxy-15-methylphenyl) -15-chloro-2H —Benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro-2H-benzotriazole, 2_ (3,5-di-t-butyl-2-hydroxy) Phenyl) 1 2 H-benzotriazole, 5-chloro-2- (3,5-dibutyl-1-hydroxyphenyl) 12 H-benzotriazole, 2- (3,5-di-t —Amyl— 2-hydroxyphenyl) — 2H—Benzotriazole, 2— (2-Hydroxy-5-t-octylphenyl) — 2H—Venzotriazole, 21—2-Hydroxy—41 (Cutylphenol) — 2 H-benzoto Azole, 2- (2H-benzotriazolyl-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2,2'-methylenebis [4- (1,1,3,3, -tetramethylbutyl) -16-[(2H-benzotriazol-2-yl) phenol]].

 Examples of the salicylic acid-based ultraviolet absorber include phenylsulcylate, 4-t-butylphenyl-12-hydroxybenzoate, phenyl-12-hydroxybenzoate, 2,4-di-tert-butylphenyl-3,5 —Di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like.

 Examples of the acrylate ultraviolet absorber include ethyl-2-cyano-3,3-diphenylacrylate, 2′-ethylhexyl-2-cyano-1,3,3-diphenylacrylate, and the like.

These ultraviolet absorbers (Y) can be used alone or in combination of two or more. The amount of these ultraviolet absorbers (Y) is usually 0.0001 to 5.0 parts by weight, preferably 0.001 to 1.0 parts by weight, per 100 parts by weight of the cyclic olefin thermoplastic resin (I). Parts, more preferably 0.01 to 0.5 parts by weight Range.

 When the ultraviolet stabilizer (Y) is used in combination with the light stabilizer (X), the weather resistance of the cyclic olefin-based thermoplastic resin composition of the present invention is dramatically increased. That is, as shown in Examples (Table 1) described later, the weather resistance of the molded article was evaluated by the reduction rate of the total light transmittance (weather resistance A), and the weather resistance was evaluated by ΔΥ after infrared irradiation (weather resistance). When the light stabilizer (X) is blended without blending the UV absorber (Y) with the light stabilizer (B), both the weather resistance A and the weather resistance B are reasonably good (Example 1) and the light stabilizer (X) When the ultraviolet ray absorbing agent (Y) was blended without blending, the weather resistance A was fairly good, but the weather resistance B was poor (Comparative Example 6). However, when both the light stabilizer (X) and the ultraviolet absorber (Y) are blended, the weather resistance A and the weather resistance B increase dramatically due to a synergistic effect (Example 2).

 Antioxidant (Z)

 In addition to the light stabilizer (X) or the light stabilizer (X) and the ultraviolet absorber (Y), an antioxidant (Z) is added to the cyclic olefin-based thermoplastic resin composition of the present invention. Can be included. By combining the antioxidant (Z), the weather resistance of the resin composition is further improved.

 Examples of the antioxidant (Z) to be used include a phenolic antioxidant, a phosphorus antioxidant, and a zeolite antioxidant. Of these, a phenolic antioxidant is preferable. Alkyl-substituted phenolic antioxidants are particularly preferred.

As the phenolic antioxidant, conventionally known ones can be used. For example, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, JP-A-63-179953, such as 4-diamyl-1-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate Gazette: An acrylate phenol compound described in Japanese Patent Application Laid-Open No. 1-166864; 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenylphenol, Coudecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-1-6-t-butylphenol), 4,4 ' —Butylidene-bis (6-t-butyl-m-cresol), 4,4′-thiopis (3-methyl-6-t-butylphenol), bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) —1,1-dimethylethyl) —2,4,8,10-tetraoxaspiro [5 , 5] didecane, 1,1,3-tris (2-methyl-4-hydroxy-1-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5- Di-t-butyl-1-hydroxybenzyl) benzene, tetrakis (methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenylpropionate) methane [namely, Penno erythrimethyl- Tetrakis (3— (3, 5 Alkyl-substituted phenolic compounds such as —di-t-butyl-4-hydroxyphenylpropionate), triethylene glycol bis (3_ (3-t-butyl-4-hydroxy-5-methylphenyl) propionate), and tocophenol; 6— (4-Hydroxy-1,3,5-di-tert-butylanilino) 1,2,4-Bisoctylthio-1,3,5-triazine, 6— (4-Hydroxy-1,3,5-dimethylanilino) -2,4-bisoctylthio 1,3,5-triazine, 6- (4-hydroxy-3-methyl-5-t-butylanilino) 1,2,4-bisoctylthio-1,3,5-triazine, 2-octylthio-4,6-bis — (3,5-di-butylamine 4-year-old xianilino) — phenolic compounds containing triazine groups, such as 1,3,5-triazine; However, acrylate phenol compounds and alkyl-substituted phenol compounds are preferred, and alkyl-substituted phenol compounds are particularly preferred.

 These phenolic antioxidants can be used alone or in combination of two or more. The amount of the phenolic antioxidant is usually 0.0001 to 5.0 parts by weight, preferably 0.001 to 1.0 parts by weight, per 100 parts by weight of the cyclic olefinic thermoplastic resin (I). It is more preferably in the range of 0.01 to 0.5 parts by weight.

The phosphorus-based antioxidant is not particularly limited as long as it is generally used in the general resin industry. For example, triphenyl phosphite, diphenyl isodecyl phosphite Phyto, phenyldiisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) ) Phosphite, tris (cyclohexylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9, Monophosphite compounds such as 10-dihydro-9-oxa-10-phosphaphenanthrene; 4, 4'-butyl 1,4-bis (3-methyl-6-t-butylphenyl-tridecylphosphite), 4,4'-Isopropylidene-bis (phenyloxyalkyl (C12-C15) phosphite), 4,4 '-Isopropylidene-bis (diphenylmonoalkyl (C12-C15) phosphite), 1,1,3-tris (2-methyl-4-di-tridecyl phosphite-5-t-butylphenyl) butane, Tetrakis (2,4-di-t-butylphenyl) -1,4'-biphenylenediphosphite, cyclic neopenin tetraylbis (isodecyl phosphite), cyclic neopen evening tetraylbis (nonylphenyl) Phosphite), cyclic neopentanetetraylbis (2,4-di-t-butylphenylphosphite), cyclic neopentane Torairubisu (2, 4-dimethyl-phenylalanine phosphite), cyclic neopentane pen evening integrators tri bis (2, 6-di-one t one Buchirufueniruho Sufuai Bok), and the like diphosphite compounds such as. Of these, monophosphite compounds are preferred, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, and tris (2,4-di-t-phenylphenyl) phosphite are particularly preferred.

Examples of the zeo-based antioxidants include dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thiodipropionate. Pionate, pen erythritol lute tetrakis-(| 3-lauryl-thio-propionate), 3 , 9-Bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspi [5,5] pandecan.

 These phosphorus antioxidants and zeolite antioxidants can be used alone or in combination of two or more, but it is preferable to use them in combination with a phenolic antioxidant. . The compounding amount of these antioxidants is usually from 0.001 to 5.0 parts by weight, preferably from 0.001 to 1.0 parts by weight per 100 parts by weight of the cyclic olefin-based thermoplastic resin (I). 0 parts by weight, more preferably in the range of 0.01 to 0.5 parts by weight.

 Other compounding agents

 Other compounding agents can be added to the cyclic olefin-based thermoplastic resin composition of the present invention, if necessary. The other compounding agents are not particularly limited as long as they are generally used in the resin industry, and examples thereof include a lubricant, a plasticizer, a pigment, a near-infrared absorber, and an antistatic agent. .

 As the lubricant, for example, inorganic fine particles can be used. Here, the inorganic fine particles refer to the elements of group 1, 2, 4, 6, 7, 8, 10 to 10, 11, 12, 13 and 14 of the periodic table. Oxides, hydroxides, sulfides, nitrides, halides, carbonates, sulfates, acetates, phosphates, phosphites, organic carboxylate, silicates, titanates, borates, and the like And compounds such as hydrated compounds, composite compounds centered on them, and natural minerals.

Specifically, Group 1 element compounds such as borax (sodium borate hydrate); magnesium carbonate, magnesium phosphate, magnesium oxide (magnesia), magnesium chloride, magnesium acetate, magnesium fluoride, magnesium titanate, magnesium silicate, Magnesium silicate hydrate (talc), calcium carbonate, calcium phosphate, calcium phosphite, calcium sulfate (gypsum), calcium acetate, calcium terephthalate, calcium hydroxide, calcium silicate, calcium fluoride, calcium titanate, titanium Group 2 element compounds such as strontium oxide, barium titanate, zinc titanate, lanthanum titanate, bismuth titanate, lead titanate, barium carbonate, barium phosphate, barium sulfate, barium phosphite; Tan (titania), titanium monoxide, titanium nitride, zirconium dioxide (zirconia), Group 4 element compounds such as zirconium oxide; Group 6 element compounds such as molybdenum dioxide, molybdenum trioxide, and molybdenum sulfide; Group 7 element compounds such as manganese chloride and manganese acetate; Group 8-10 elements such as cobalt chloride and cobalt acetate Compounds: Group 1 element compounds such as cuprous iodide; Group 1 element compounds such as zinc oxide and zinc acetate; aluminum oxide (alumina); aluminum hydroxide; aluminum fluoride; aluminosilicate (alumina silicate, kaolin) , Kaolinite) and other Group 13 element compounds, silicon oxide (silica, silica gel), graphite, carbon, graphite, glass, etc., Group 14 element compounds, carnalite, kainite, mica (my power, kindommo) And particles of natural minerals such as bi-ores. The average particle size of the inorganic fine particles used here is not particularly limited, but is preferably in the range of 0.01 to 3 zm.

 Plasticizers include, for example, tricresyl phosphate, trixylyl phosphate, triphenyl phosphate, triethylphenyl phosphate, diphenyl cresyl phosphate, monophenyl dicresyl phosphate, dicresyl monoxoxy Renyl phosphate, arylalkyl phosphate, diphenyl monoxylenyl phosphate, monophenyl dixylenyl phosphate, tributyl phosphate, triethyl phosphate, trichloroethyl phosphate, trioctyl Phosphate, tris (isopropylphenyl) phosphate and other phosphate triester plasticizers such as dimethyl phthalate, dimethyl phthalate, dibutyl phthalate, diheptyl phthalate, diheptyl phthalate, diphenyl phthalate Phthalate plasticizers such as tyl, di-1-ethylhexyl phthalate, diisononyl phthalate, octyldecyl phthalate and butylbenzyl phthalate; monobasic fatty acids such as butyl butyl oleate and dariserin monooleate Acid ester plasticizers; dibutyl adipate, di-n-adipate fatty acid dibasic acid ester plasticizers; dihydric alcohol ester plasticizers; oxyester ester plasticizers can be used. Phosphoric acid triester plasticizers are preferred, and tricresyl phosphate and trixylyl phosphate are particularly preferred.

Further, as the softening agent or plasticizer, a hydrocarbon polymer which is liquid at room temperature and whose main skeleton is mainly a C—C or C = C structure is preferably used. Liquid hydrocarbon poly Among these, a linear or branched liquid hydrocarbon polymer having no hydrocarbon ring in the main chain is preferable. Further, since the obtained composition has excellent weather resistance, it is preferable that the composition does not have a c = c structure. The molecular weight of the liquid hydrocarbon polymer is preferably below 10,000, more preferably between 200 and 8,000, particularly preferably between 300 and 4,000.

Specific examples of the liquid hydrocarbon polymer, squalane _{(C 3 .H 62, Mw =} 42 2. 8), liquid paraffin (white oil, I SO VG10 as defined in JIS K2231, I SO VG15, I SO VG32, ISO VG68, ISO VG100, VG 8 and VG 12), polyisobutene, hydrogenated polybutadiene, hydrogenated polyisoprene, and the like. Of these, squalane, liquid paraffin and polyisobutene are preferred.

 Examples of pigments include garylide pigments such as Pigment Red 38; azo lake pigments such as Pigment Red 48: 2, Pigment Red 53, and Pigment Red 57: 1; Pigment Red 144, Pigment Red 166, and Pigment Red 220. , Pigment red 221 and pigment red 248; condensed azo pigments such as pigment red 171, pigment red 175, pigment tread 176, pigment red 185, pigment red 208 and the like; pigment red 122; Quinacridone pigments such as pigment red 149, pigment red 178 and pigment red 179; and anthraquinone pigments such as pigment red 177.

Examples of the near-infrared absorbing agent include cyanine-based near-infrared absorbing agent; pyrylium-based infrared-absorbing agent; squarylium-based near-infrared absorbing agent; croconium-based infrared absorbing agent; azulhenium-based near-infrared absorbing agent; Metal complex-based near-infrared absorber; naphthoquinone-based near-infrared absorber; anthraquinone-based near-infrared absorber; indophenol-based near-infrared absorber; azimuth-based near-infrared absorber; In addition, commercially available near infrared absorbers SIR-103, SIR-114, SIR-128, SIR-130, SIR-132, SIR-152, SIR-159, SIR-162 (all manufactured by Mitsui Toatsu Dye) ), Kayasor b IR-750, Ka yasorb I RG—002, Kaya sorb IRG—003, IR-820 B, Kaya sorb I RG-022, Ka yasorb I RG—023, Kay asorb CY—2, Kaya sorb CY 1-4 , Kay asorb CY-9 (all manufactured by Nippon Kayaku).

 Examples of the antistatic agent include alkyl sulfonates such as alkyl sulfonate sodium salt and alkyl sulfonate phosphonium salt; and dariserine ester of stearic acid.

 These other compounding agents can be used alone or in combination of two or more. The amount of other compounding agents is appropriately selected within a range that does not impair the purpose of the present invention.

 Other polymer components

 Other polymers can be added to the cyclic olefin-based thermoplastic resin composition of the present invention, if desired. Other polymers include, for example, rubbery polymers and other thermoplastic resins.

Examples of the rubbery polymer include gen-based rubbers such as natural rubber, polybutadiene rubber, polyisoprene rubber, acrylonitrile'butadiene copolymer rubber; styrene / butadiene copolymer rubber, styrene / isoprene copolymer rubber, styrene · Butadiene · Isoprene terpolymer rubber; hydrogenated product of Jen-based rubber; Ethylene · α-olefin copolymer such as ethylene · propylene copolymer, propylene · Other α-olefin copolymers Saturated polyolefin rubbers such as ethylene-propylene-gen copolymer, α-olefin-gen copolymer, isobutylene-isoprene copolymer, α-olefin-gen copolymer such as isobutylene-gen copolymer Polymer rubber; urethane rubber, silicone rubber, polyether rubber, rubber Special rubbers such as Ril rubber, propylene oxide rubber and ethylene acrylic rubber; thermoplastic elastomers such as styrene / butadiene / styrene block copolymer rubber, styrene / isoprene / styrene block copolymer rubber; hydrogenated thermoplastic elastomer Urethane-based thermoplastic elastomers; polyamide-based thermoplastic elastomers; 1,2-polybutadiene-based thermoplastic elastomers; Can be

 Other thermoplastic resins include, for example, polyolefins such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, polypropylene, syndiotactic polypropylene, polybutene, and polypentene; Polyesters such as polybutylene terephthalate; polyamides such as nylon 6 and nylon 66; ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, polystyrene, syndiotactic polystyrene, polyphenylene sulfide, polyphenylene Examples include ether, polyamide, polyester, and polycarbonate.

 These other polymers can be used alone or in combination of two or more. The blending amount of the other polymer is usually 100 parts by weight or less, preferably 70 parts by weight or less, more preferably 50 parts by weight, based on 100 parts by weight of the cyclic olefin-based thermoplastic resin (I). Or less, most preferably 30 parts by weight or less.

 Cyclic olefinic thermoplastic resin composition

 The cyclic olefin-based thermoplastic resin composition of the present invention can be prepared according to a conventional method. Specifically, a method of mechanically blending the cyclic olefin-based thermoplastic resin (I), the light stabilizer (X), and other desired components as required with an extruder, a kneader, a roll, or the like; Dissolve the components in a suitable good solvent, for example, hexane, heptane, decane, cyclohexane, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, etc. After that, a method of mixing and removing the solvent, and a method of combining these methods can be cited.

 Molded body

The molded article of the present invention is obtained by molding the above-mentioned cyclic olefin-based thermoplastic resin composition. Since the molded article of the present invention is excellent in mechanical strength, elongation, chemical resistance and weather resistance, it is used as various forms of molded articles, but films, sheets and plates are preferably used. In particular, it is suitable as a film for agriculture, medical care, food packaging and the like. The molding method may be a conventional method. For example, in the case of a film, a method such as a melt molding method or a solution casting method can be used, and the melt molding method is preferably employed. When a film or the like is prepared by a melt molding method, there are a method using a T-die, a melt extrusion method such as an inflation method, a calendar method, a hot press method, and an injection molding method. Above all, a melt extrusion method using a T die that can reduce thickness unevenness is preferable. The conditions of the melt molding method are appropriately selected according to the molding method.For example, in the melt molding method using a T-die, the resin temperature is appropriately selected within a range from a glass transition temperature to a decomposition temperature. Usually in the range of 100 to 400, preferably in the range of 150 to 350, more preferably in the range of 200 to 300, and the temperature of the bow I scraping roll is usually 0 to The range is 200, preferably 30 to 180 t :, more preferably 50 to 150. When a film or the like is prepared by the solution casting method, it can be performed according to a conventional method. For example, a liquid composition in which each component is dissolved or dispersed in a solvent is applied to a suitable carrier (support). And then removing the solvent by drying. There are no particular restrictions on the type of carrier, and those used in general solution casting methods are used.For example, glass plates, metal drums, steel belts, polyester films, PVC films, fluororesin belts, metal foils, etc. Examples include a flat plate, a belt or a roll. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; alicyclic hydrocarbons such as cyclohexane; esters such as butyl acetate; ethers such as tetrahydrofuran and dimethoxyethane; Alcohols such as methanol, ethanol, and isopropanol; ketones such as methylethyl ketone; halogenated solvents such as methylene chloride, chloroform, carbon tetrachloride, and ethylene dichloride can be used. These solvents can be used alone or in combination of two or more. The concentration of the cyclic olefinic thermoplastic resin (I) in the solvent is appropriately selected according to the thickness of the film to be produced, but is usually 0.1 to 60% by weight, preferably 1 to 50% by weight, more preferably Ranges from 5 to 45% by weight. When the concentration of the cyclic olefin-based thermoplastic resin (I) is in this range, the film thickness can be easily adjusted and the film-forming property is excellent and suitable.

The method for casting the liquid composition on the carrier is not particularly limited, but is, for example, an example. For example, Barcoder, T-die, T-die with bar, Doc Yuichi Knife, Meir 'Bar

, Roll-coating, die-coating, etc. The liquid composition may be cast by spraying, brushing, rolling, spin coating, diving, or the like. If the desired film thickness cannot be obtained by one coating, the coating can be repeated.

 There is no particular limitation on the removal of the solvent by drying, and it can be performed according to a conventional method.

In order to reduce the residual solvent concentration to 5% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less, and most preferably 0.5% by weight or less, drying is usually performed in two or more stages. Let it. First, in the first stage of drying, the film on a flat plate or a roll is dried at room temperature to 100, preferably at room temperature to 80, and the residual solvent concentration is 10% by weight or less, preferably 5% by weight or less. Dry to less than weight%. In this case, if the drying temperature is too high, the film foams as the solvent evaporates. The film is then peeled off from the plate or roll, and the second stage of drying is carried out by raising the temperature from room temperature to above 60, preferably from 70 to the glass transition temperature (Tg) of the resin, Dry until the residual solvent concentration is 2% by weight or less, more preferably 1% by weight or less, more preferably 0.5% by weight or less.

 If the drying temperature is too high, drying does not proceed, and if the temperature is too high, foaming is likely to occur. The first-stage drying may be performed, and after the drying is completed, the film may be peeled off from a flat plate or a roll, and the second-stage drying may be performed. Drying of the solvent can be performed under reduced pressure, if necessary.

 The resulting film can be laminated alone or with a film of some other polymer. The type of polymer to be laminated is not particularly limited, and is appropriately selected depending on the application. The method of laminating the polymer film is not particularly limited, but generally, an extrusion lamination method, a dry lamination method, a hot melt lamination method, a solventless lamination method, a coextrusion lamination method, or the like is employed.

Further, a thin film of a metal, a metal oxide, a semiconductor, or the like, a foil, or the like may be stacked. Specifically, examples of such a laminated material include conductive polymer films such as polyacetylene, polypyrrol, polypyridine, polythiophene, and polyaniline, polyvinyl benzyl trimethyl ammonium chloride, and oligo (poly). styrene Films of polymer electrolytes such as sulfonates, films of metals such as Au, Ag, Cu, Pt, A 1, Ni, Cr, indium tin oxide [In ₂ 〇 ₃ (Sn)], Sn 〇 ₂ (S b), S n0 ₂ (F e), C dO, Cd ₂ O ₃ , C d S n0 ₄ , T i 0 ₂ , Z r0 ₂ , Cu I etc. Thin film of semiconductor, T i OxZAgZT i Ox (x≤2). These are adhered as a film or foil, or are laminated by means such as plasma polymerization, sputtering, vapor deposition, and plating. The film of the present invention can be laminated not only on one side but also on both the front and back sides, and can be formed into a multilayer composite of three or more layers, including formation on the inside of the film.

 The thickness of the film made of the cyclic olefin-based thermoplastic resin composition of the present invention is a force appropriately selected depending on the purpose of use, usually 1 to 500 jLtm, preferably 10 to 300 uL, more preferably 20 to 300 uL. 200 / m, most preferably 50 to: L When L is 50 μm, excellent mechanical strength, elongation, weather resistance, and chemical resistance are preferred. Further, the obtained film can be used as it is without stretching, or can be stretched uniaxially or biaxially.

 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. Parts and percentages are by weight unless otherwise specified. The measurement method followed the following method.

 (1) Weight average molecular weight

 The weight average molecular weight in terms of polyisoprene was calculated by gel permeation chromatography (GPC) using cyclohexane (toluene when insoluble in cyclohexane) as a solvent.

 (2) Low molecular weight components

 Gel permeation chromatography (GPC) using cyclohexane (toluene when insoluble in cyclohexane) as a solvent calculated the ratio of polyisoprene-equivalent molecular weight of 1,000 or less.

 (3) Hydrogenation rate

 The hydrogenation rate was measured by 1 H-NMR.

 (4) Glass transition temperature

The glass transition temperature was measured by the DSC method. (5) Mechanical strength

 In the mechanical strength test of the film, a test piece of 30 cm x 30 cm and thickness of 100 // m was spread on a specially made jig, fixed horizontally, and vertically stretched from a height of 1.2 m to a height of 60 g. The iron ball was dropped and the test film was observed for tearing. The mechanical strength was determined based on the following four grades.

：: It cannot be broken even once in 10 tests.

〇: Breaks 1-3 times out of 10 tests.

△: 4 to 6 times out of 10 tests.

X: The test breaks 7 to 10 out of 10 times.

 (6) Tensile elongation

 It was measured in accordance with JIS 7127, and judged according to the following four grades.

◎: 10% or more

〇: 5% or more, less than 10%

△: 1% or more and less than 5%

: 1b

 (7) Weather resistance

The weather resistance test of the film was evaluated by the following method.

 (A) According to JIS 5400, a test specimen (10 cm x 10 cm, thickness of 100 zm) was rotated at a black panel temperature of 83 using a sunshine ザ ezalome overnight while rotating once a minute around the light source. Exposure to carbon arc for 300 hours. The weather resistance was evaluated by the reduction rate of the total light transmittance of the film after the test. Judgment was based on the following four-grade evaluation criteria.

 A: The reduction rate of the total light transmittance is less than 1%.

 〇: The reduction rate of the total light transmittance is 1% or more and less than 10%.

 Δ: The reduction rate of the total light transmittance is 10% or more and less than 50%.

 X: The reduction rate of the total light transmittance is 50% or more.

(B) The test piece (10 cm x 10 cm, thickness 100 ^ m) was irradiated with an infrared lamp (500 W) at a distance of 30 cm for one week. The ΔΥI of the test piece before and after the test was measured, and judged based on the following four grade test evaluation criteria. A: ΔYI is less than 0.3.

〇: 丫 1 is 0.3 or more and less than 1.

 : 丫 1 is 1 or more and less than 2.

X: ΔΥI is 2 or more.

 (8) Chemical resistance

 A test piece (10 cm X 10 cm, thickness 100 m) is placed on a cloth moistened with salad oil, held for 80 minutes, and then visually inspected, and the chemical resistance is determined based on the following four grades. did.

 :: No whitening or cracking occurred in any of the test pieces during the 10 times test.

〇: Whitening or cracking occurs 1-2 times during 10 tests.

Δ: Whitening or cracking occurs 3 to 5 times during 10 tests.

 X: Whitening or cracking occurs 6 times or more during 10 tests.

 (9) Gel content

 The polymer was dissolved in the same solvent used during the polymerization to prepare a 0.5% by weight polymer solution, and this solution was filtered through a polytetrafluoroethylene filter with a pore diameter of 0.5 m. At this time, the amount (cc) of the polymer solution passing through the filter was measured. As the amount of filtration increases, the amount of gel decreases, and consequently, the moldability of a film or the like is improved, and molded article defects such as surface roughness and turbidity are reduced.

 (10) Film appearance

A 10 cm ² fragment was cut from an arbitrary portion of the film, and 100 film fragment samples were visually observed to determine the occurrence of spots due to surface roughness and turbidity. The evaluation results were expressed in terms of the number of samples having these defects.

 Reference example 1

To a 1-liter flask purged with nitrogen, 5 g of an 85:15 mixed monomer of dicyclopentene and methyltetracyclododecene and 120 g of cyclohexane were added, and tri-butyl aluminum [i Bu ₃ Al] was used as a polymerization catalyst. 0.57 mmol, 0.57 mol of isobutyl alcohol as a reaction regulator, 0.189 mmol of acetone, and 3.79 mmol of 1-hexene as a molecular weight regulator were added. Here, add 0.76 mmol of tungsten hexachloride, and use 601: for 5 minutes Stirred. Then, while maintaining the reaction system at 60 ° C, 45 g of a 85:15 mixed monomer of dicyclopentene and methyltetracyclododecene was mixed with 0.114 mmol of hexachlorochloride and 0.114 mmol of cyclohexane. The solutions were each continuously dropped into the system. After the completion of the dropwise addition, the mixture was further stirred for 30 minutes to terminate the ring-opening polymerization. The weight average molecular weight (Mw) of the ring-opened polymer thus obtained was 26,300. As a result of gas chromatography analysis of the reaction solution, no peak of unreacted monomer was detected, and it was confirmed that the reaction rate was 100%. This polymerization reaction solution was transferred to a 1-liter autoclave, and 160 g of cyclohexane was added. As a hydrogenation catalyst, 2.5 g of diatomaceous earth-supported nickel catalyst and activated alumina (surface area: 320 cm ² / g, pore volume: 0.8 cm ³ / g, average particle size: 15 zm, manufactured by Mizusawa Chemical) , Neobead D powder), and the inside of the reactor was replaced with hydrogen. Then, the pressure was increased to about 10 kgZ cm ² , and the temperature was increased to 160 while stirring. When the temperature was stabilized, the hydrogen pressure was maintained at 40 kgZcm ² , and the reaction was carried out for 8 hours while replenishing the hydrogen consumed in the reaction process. After completion of the hydrogenation reaction, the hydrogenation catalyst and activated alumina were filtered off, and then the hydrogenation reaction solution was poured into 3 liters of isopropyl alcohol to precipitate out, and collected by filtration. The recovered resin was dried with 100 at 1 Torr or less for 48 hours. The polymer thus obtained is referred to as a polymer (a). The weight average molecular weight (Mw) of the polymer (a) was 52,600, and the ratio of components having a molecular weight of 1,000 or less was 0.5% by weight. Further, the hydrogenation ratio of the polymer (a) was 99.9%, and the glass transition temperature was 103 t :. The proportion of repeating units without a norpornan ring was 85% (calculated value).

 Reference example 2

A ring-opened polymer was synthesized and hydrogenated in the same manner as in Reference Example 1 except that the monomer was changed to a 50:50 mixed monomer of dicyclopentene and methyltetracyclododecene. The polymer thus obtained is referred to as a polymer (b). The weight average molecular weight (Mw) of the polymer (b) was 53,500, and the ratio of components having a molecular weight of 1,000 or less was 0.45% by weight. The hydrogenation ratio of the polymer (b) was 99.9%, and the glass transition temperature was 118. The proportion of the repeating unit without a norpolnan ring was 50% (calculated value). Reference example 3

 A ring-opened polymer was synthesized and hydrogenated in the same manner as in Reference Example 1 except that the monomer was changed to a 35:65 mixture of dicyclopentene and methyltetracyclododecene. The polymer thus obtained is referred to as a polymer (c). The weight average molecular weight (Mw) of the polymer (c) was 53,500, and the ratio of components having a molecular weight of 1,000 or less was 0.5% by weight. The hydrogenation rate of the polymer (c) was 99.9%, and the glass transition temperature was 127. The proportion of the repeating unit having no norbornane ring was 35% (calculated value).

 Comparative Examples 1-3

 In the polymers (a) to (c) obtained in Reference Examples 1 to 3, with respect to 100 parts by weight of the resin component, a hindered phenol-based antioxidant (Z) Irgano 1 010 (Ciba-Geigy Co., Ltd.) was used as an antioxidant. 0.2 parts by weight, and extruded from a 400 mm wide T-die at a resin temperature of 260 using an extruder with a screw diameter of 65 mm. A) to (C) were prepared.

 Example 1, Comparative Examples 4, 5

 In the polymers (a) to (c) obtained in Reference Examples 1 to 3, a hindered phenol-based antioxidant Irganox 1010 (Ciba-Geigy Co., Ltd.) was used as an antioxidant (Z) for 100 parts by weight of the resin component. 0.2 parts by weight and 0.2 parts by weight of hindered amine light stabilizer Cy asoeb UV3346 (manufactured by Shiraishi Calcium Co., Ltd.) as the light stabilizer (X), except that Comparative Examples 1-3 were added. Resin films were prepared, and resin films (D) to (F) were obtained.

 Comparative Examples 6 to 8

In the polymers (a) to (c) obtained in Reference Examples 1 to 3, the hindered phenol-based antioxidant Irg anox 1010 was used as an antioxidant (Z) based on 100 parts by weight of the resin component. 0.2 parts by weight) and 0.2 parts by weight of a benzophenone-based ultraviolet absorber 2,4-dihydroxybenzophenone (SEESO RB 100, manufactured by Shiraishi Calcium Co.) as an ultraviolet absorber (Y) Prepared resin films in the same manner as in Comparative Examples 1 to 3, and obtained resin films (G) to (I). Example 2, Comparative Examples 9, 10

 In the polymers (a) to (c) obtained in Reference Examples 1 to 3, 100 parts by weight of the resin component was used as an antioxidant (Z) as a hindered phenol-based antioxidant Irganox. 0.2 parts by weight, hindered amine light stabilizer as light stabilizer (X) Cy asoeb UV3346 (manufactured by Shiraishi Calcium Co.) 0.2 parts by weight, benzophenone UV absorber as ultraviolet absorber (Y) A resin film was prepared in the same manner as in Comparative Examples 1 to 3, except that 0.2 parts by weight of 2,4-dihydroxybenzophenone (SEESORB 100, manufactured by Shiraishi Calcium Co., Ltd.) was added. L) was obtained.

 The mechanical strength, elongation, chemical resistance and light resistance of the produced films (A) to (L) were measured and are shown in Table 1.

 table 1

 Weather resistance A Reduction rate of total light transmittance

 Weather resistance B ΔΥ I value after infrared irradiation

 Gel content Filter permeation amount (c c)

Film appearance: number of defective films From Table 1, it can be seen that films obtained from the resin composition containing the cyclic olefin-based thermoplastic resin of the present invention show good results in all tests. In addition, those having a large number of repeating units without a norpornan structure (Comparative Examples 1 to 3, Example 1> Comparative Examples 4 to 7> Example 2, Comparative Example 8 to: L0) Force Mechanical strength, elongation and It can be seen that it has excellent chemical resistance. The cyclic olefin-based thermoplastic resin used in the present invention may further include a hindered phenol-based antioxidant (Z) and a hindered amine-based light stabilizer ( X) or a film formed by adding a hindered phenol-based antioxidant (Z) and a benzophenone-based ultraviolet absorber (Y) (Comparative Example 2, 5, Example 2, or Comparative Example 3, From 6 and 9), a film formed by adding a hindered phenol-based antioxidant (Z), a hindered amine-based light stabilizer (X) and a benzophenone-based ultraviolet absorber (Y) (Example 4) Is particularly excellent in weather resistance Reference Example 4

 A polymer was synthesized and hydrogenated in the same manner as in Reference Example 1 except that the monomer was changed to dicyclopentene. The polymer thus obtained is referred to as a polymer (e). The weight average molecular weight (Mw) of the polymer (e) was 53,000, and the proportion of components having a molecular weight of 1,000 or less was 2.5% by weight. The hydrogenation ratio of the polymer (e) was 99.9%, and the glass transition temperature was 97. The repeating unit having no norbornane ring was 100% (calculated value).

 Reference example 5

 A polymer was synthesized and hydrogenated in the same manner as in Reference Example 4 except that the reaction modifier, acetone, was not used. The polymer obtained in this manner is referred to as a polymer (（). The weight average molecular weight (Mw) of the polymer (f) is 52,800, and the proportion of components having a molecular weight of 1,000 or less is 5.0% by weight. The hydrogenation ratio of the polymer (f) was 99.9%, and the glass transition temperature was 97.

 Reference example 6

 A polymer was synthesized and hydrogenated in the same manner as in Reference Example 4, except that acetone as a reaction modifier was not used and the reaction temperature was 70. The polymer thus obtained is referred to as polymer (g). The weight average molecular weight (Mw) of the polymer (g) was 52,600, and the component having a molecular weight of 1,000 or less was 10.0% by weight. The hydrogenation ratio of the polymer (g) was 99.9%, and the glass transition temperature was 97 ° C.

 Examples 3 to 5

Polymers (e) to (g) obtained in Reference Examples 4 to 6 Hindered phenol-based antioxidant Irganox 1010 (Ciba-Geigi-I) as an antioxidant (Z) based on 100 parts by weight of the resin and the resin component 0.2 parts by weight, hindered as light stabilizer (X) Amine light stabilizer Cya soeb UV3346 (manufactured by Shiraishi Calcium Co.) 0.2 parts by weight, benzophenone UV absorber 2,4 dihydroxybenzophenone (SEESORB 100, manufactured by Shiraishi Calcium Co.) A resin film was prepared in the same manner as in Comparative Examples 1 to 3, except that 0.2 part by weight was added, to obtain resin films (M) to (〇).

 The mechanical strength, elongation, chemical resistance and light resistance of the produced films (M) to (III) were measured, and the results are shown in Table 2.

 Table 2

環状ォレフィン系熱可塑性樹脂中の全ての繰り返し単位が脂環構造を有し、 か つ、 該繰り返し単位の全てがノルボルナン構造を有さないものであるものに、 ヒ ンダードフエノール系酸化防止剤、 ヒンダードアミン系光安定剤およびべンゾフ エノン系紫外線吸収剤を添加し、 成形してなるフィルムは、 全ての試験において 良好な結果を示した。 中でも、 環状ォレフィン系熱可塑性樹脂中の分子量が、 1 , 000以下の成分の割合が少ないもの （実施例 3 <実施例 4 <実施例 5) が、 耐薬品性、 耐薬品性、 機械的強度および伸びが高度にバランスされ、 特に良好で あった。

All the repeating units in the cyclic olefin-based thermoplastic resin have an alicyclic structure, and all of the repeating units have no norbornane structure, a hindered phenol-based antioxidant, a hindered amine Films formed by adding a light stabilizer and a benzophenone UV absorber showed good results in all tests. Among them, those having a small proportion of components having a molecular weight of 1,000 or less in the cyclic olefin-based thermoplastic resin (Example 3 <Example 4 <Example 5) have higher chemical resistance, chemical resistance, and mechanical strength. And elongation were highly balanced and especially good.

 Examples 6 to 8

In the polymers (e) to (g) obtained in Reference Examples 4 to 6, with respect to 100 parts by weight of the resin component, a hindered phenol-based antioxidant Irg anox 1010 was used as an antioxidant (Z). 0.5 parts by weight, hindered amine light stabilizer as light stabilizer (X) TI NUV IN 944 (manufactured by Ciba-Geigy Corporation) 0.25 parts by weight, benzotriazole-based ultraviolet light as ultraviolet absorber (Y) Absorbent 2- (2'-Hydroxy-t-butyl-5,1-methylphenyl) -15-chloro mouth'Benzotriazole (SEESORB 703, manufactured by Shiraishi Calcium Co.) 0.2 parts by weight Resin films were prepared in the same manner as in Comparative Examples 1 to 3, except that the resin films (P) to (R) were obtained.

 The mechanical strength, elongation, chemical resistance and light resistance of the prepared films (P) to (R) were measured. Table 3 shows the results.

 Table 3

Industrial applicability

 The resin composition of the present invention, which is obtained by blending a light stabilizer with a cyclic olefin-based thermoplastic resin containing a repeating unit having an alicyclic structure without a norpolnan structure, has excellent and well-balanced mechanical strength. It has excellent elongation, chemical resistance, and weather resistance. Particularly, those containing a hindered amine-based light stabilizer and a 7 or metal complex salt-based UV absorber have more excellent properties. Further, those having a small proportion of components having a molecular weight of 1,000 or less in the cyclic olefin-based thermoplastic resin have a high balance of these properties. Furthermore, the addition of an antioxidant further improves the weather resistance.

 Further, since the resin composition of the present invention does not contain a halogen atom, there is no problem that toxic gas is generated at the time of incineration to cause environmental damage.

Molded articles molded from the cyclic olefin-based thermoplastic resin composition of the present invention are not particularly limited, but films, sheets and plates are particularly excellent in mechanical strength, chemical resistance, water vapor barrier properties and gas barrier properties. So, packaging materials such as food, medicine, tobacco, electronic parts, daily necessities, miscellaneous goods; low transparency and advanced optical properties such as for polarizing film, retardation film, liquid crystal substrate, light diffusion film, prism film etc. for liquid crystal display Demands for film; strength of automotive window materials, roof materials, aircraft windows, vending machine windows, show windows, show cases, etc. Optical sheets, such as transparent glass sheets that can be used as substitutes for glass sheets; Materials for resist solution bags, medical solution bags, infusion bags, etc .; Electrical films, such as electrical insulating films and film capacitors; Exterior materials, building materials, such as roofing materials Used as architectural films and sheets.

 The cyclic olefin-based thermoplastic resin molded article of the present invention is excellent in light resistance, and thus is suitable as a molded article used outdoors. Particularly, it is suitable as an agricultural film such as a house film for cultivating a house, a film for a tunnel, and a film for mulching.

Claims

The scope of the claims 1. Cyclic olefin-based heat containing a cyclic olefin-based thermoplastic resin (I) containing 70% by weight or more of the repeating unit (A) represented by the following formula (1) and a light stabilizer (X). Plastic resin composition. Equation (1)

In the formula (1), R ^{21 to} R ³⁴ each independently represent a hydrogen atom, a hydrocarbon group, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an imide group, a silyl group, or a functional group (hydroxyl group, ester group, Represents a hydrocarbon group substituted with at least one functional group selected from an alkoxy group, a cyano group, an imide group and a silyl group. However, R ²⁵ and R ²⁷ , or R ²⁶ and R ²⁸ may be combined to form an unsaturated bond, and an alkylidene group may be formed by R ²⁵ and R ²⁶ or R ²⁷ and R ^28. It may be formed. d is 0 or 1. Represents a carbon-carbon single bond or a double bond.  2. The cyclic olefin-based thermoplastic resin composition according to claim 1, further comprising an ultraviolet absorber (Y).  3. The cyclic olefin-based thermoplastic resin composition according to claim 1, further comprising an antioxidant (Z). 4. The cyclic olefinic thermoplastic resin composition according to any one of claims 1 to 3, wherein the composition of the cyclic olefinic thermoplastic resin (I) having a molecular weight of 1,000 or less is 20% by weight or less. 5. The cyclic olefinic thermoplastic resin composition according to any one of claims 1 to 4, wherein the cyclic olefinic thermoplastic resin (I) has a weight average molecular weight of 5,000 to 500,000. 6. The cyclic olefinic thermoplastic resin (I) is subjected to solution polymerization of a cyclic olefinic monomer represented by the following formula (8) or a cyclic olefinic monomer mixture containing at least 70% by weight of the monomer. The obtained polymer was dissolved in the same solvent as used in the polymerization to obtain a resin solution having a concentration of 0.5% by weight, and this solution was filled with a polytetrafluoroethylene filter having a pore diameter of 0.5 im. cyclic Orefin based thermoplastic resin composition according to any amount of resin solution through a該Fu Iruta Phil evening one surface 1 cm ² per 1 cm ³ or more der Ru claim 1-5 when filtered in one . Equation (8)

In equation (8), shaku2 ^| ~ 1 ^ ³⁴ぉ 3 is the same as the symbol in equation (1) 7. The cyclic olefinic thermoplastic resin (I) has a norpolnanan structure other than the repeating unit (A) represented by the formula (1) in an amount of 70% by weight or more and the repeating unit (A) represented by the formula (1). A repeating unit having an alicyclic structure having no alicyclic structure (B) and a repeating unit having an alicyclic structure having a norpolnanane structure (C), and at least one selected from the group consisting of 30% by weight or less. 7. The cyclic olefin-based thermoplastic resin composition according to any one of 1 to 6.  8. The cyclic olefinic thermoplastic resin composition according to claim 7, wherein the repeating unit (B) is a repeating unit represented by the following formula (3). Equation (3)

In the formula (3), R ′ R ² ″ ¹ independently represents a hydrogen atom, a hydrocarbon group, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an imide group, a silyl group, or a functional group (hydroxyl group, ester group) , An alkoxy group, a cyano group, an imide group, and a silyl group), and represents a hydrocarbon group substituted by R ⁸ and R ^ID , or R ⁹ and R ^U May combine to form an unsaturated bond, or R ⁸ and R ⁹ , or R ^IQ and R ^11, may form an alkylidene group, and a is 0 or 1. And b is 0 or 1 and c is c = b = 0 0 or 2, and when b = 1, c = 1 or 2. Represents a carbon-carbon single bond or a double bond.  9. The cyclic olefinic thermoplastic resin composition according to claim 7, wherein the repeating unit (C) is a repeating unit represented by the following formula (4). Equation (4)

In the formula (4), R ^{35 to} R ⁴⁸ each independently represent a hydrogen atom, a hydrocarbon group, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an imide group, a silyl group, or a functional group (hydroxyl group, ester group) , An alkoxy group, a cyano group, an imide group and a silyl group). However, R ³⁸ and R ^4G , or R ³⁹ and R ⁴¹ may be combined to form an unsaturated bond, and an alkylidene group may be formed by R ³⁸ and R ³⁹ or R ^4Q and R ^41. May be formed. e is an integer of 1-3. Represents a carbon-carbon single bond or a double bond.  10. The cyclic olefinic thermoplastic resin composition according to any one of claims 1 to 9, wherein the repeating unit (A) is a repeating unit represented by the following formula (2). Equation (2)

In the formula, represents a carbon-carbon single bond or a double bond.  11. The cyclic olefinic thermoplastic resin composition according to claim 10, wherein the light stabilizer (X) is a hindered amine light stabilizer.  12. The cyclic olefin-based thermoplastic resin composition according to claim 1, wherein the ultraviolet absorber (Y) is selected from metal complex salt-based, benzophenone-based, and benzotriazole-based ultraviolet absorbers. object.  13. The method according to any one of claims 1 to 11, wherein the ultraviolet absorbent (Y) comprises a metal complex-based ultraviolet absorbent alone or a combination of a metal complex-based ultraviolet absorbent and another ultraviolet absorbent. The cyclic olefinic thermoplastic resin composition according to the above.  14. The cyclic olefinic thermoplastic resin composition according to any one of claims 1 to 13, wherein the antioxidant (Z) is a phenolic antioxidant. 15. The cyclic olefinic thermoplastic resin set according to any one of claims 1 to 14. A molded article formed by molding a product.  16. The molded article according to claim 15, which is molded into a film shape or a sheet shape. 17. The molded article according to claim 16, which is a laminate in which another polymer is laminated. 18. The molded article according to claim 16, which is a laminate in which a metal, a metal oxide, or a semiconductor is laminated. 19. The molded article according to claim 16, wherein indium tin oxide [In ₂ 〇 ₃ (Sn)] is laminated.  20. The molded body according to any one of claims 16 to 19, wherein the molded body has a thickness of 1 to 500 zm.