WO1999038918A1 - Composition de resine cycloolefinique thermoplastique et objet moule - Google Patents

Composition de resine cycloolefinique thermoplastique et objet moule Download PDF

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WO1999038918A1
WO1999038918A1 PCT/JP1999/000416 JP9900416W WO9938918A1 WO 1999038918 A1 WO1999038918 A1 WO 1999038918A1 JP 9900416 W JP9900416 W JP 9900416W WO 9938918 A1 WO9938918 A1 WO 9938918A1
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group
thermoplastic resin
weight
resin composition
repeating unit
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PCT/JP1999/000416
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English (en)
Japanese (ja)
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Kenji Otoi
Teruhiko Suzuki
Kazuyuki Obuchi
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Nippon Zeon Co., Ltd.
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Publication of WO1999038918A1 publication Critical patent/WO1999038918A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Definitions

  • 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.
  • Cyclic olefin thermoplastic resins have excellent properties such as chemical resistance, and are used in a wide range of applications, including medical materials.
  • materials with higher resistance to deterioration especially for plastic films used outdoors.
  • 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.
  • 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.
  • polymers containing no halogen atoms such as chlorine atoms have been used.
  • Alternatives are desired.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • hydrocarbon group examples 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.
  • hydrocarbon group substituted with a functional group examples include an ester group-containing alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms.
  • 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.
  • 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.
  • 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.
  • 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 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).
  • 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.
  • 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]
  • 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).
  • ⁇ ⁇ to ⁇ 2 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.
  • 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.
  • hydrocarbon group examples 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.
  • hydrocarbon group substituted with a functional group examples include an ester group-containing alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms.
  • 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.
  • 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)
  • 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.
  • R 49 to R 62 in the formula (5) are the same as those of R 21 in the formula (1).
  • R 21 in the formula (1) 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)
  • R 63 to R 66 in the formula (6) are the same as those of R 21 in the formula (1).
  • R 21 in the formula (1) 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.
  • Dode force 3-ene and tetracyclo [4. 4. ⁇ . ⁇ . 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.
  • chain-like repeating unit (D) for example, a unit represented by the formula (7) is used.
  • 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.
  • linear repeating unit (D) represented by the formula (7) examples include ⁇ -olefins such as ethylene, propylene, 1-butene, and 11-pentene; aromatic vinyls such as styrene and ⁇ -methylstyrene;
  • the repeating unit examples 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.
  • GPC gel permeation chromatography
  • 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.
  • the content is preferably 10% by weight or less, more preferably 5% by weight or less, mechanical strength ⁇ 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.
  • 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.
  • the production of the cyclic olefinic thermoplastic resin (I) used in the present invention can be carried out according to a conventional method.
  • 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.
  • 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 (9) R 2I to R 34 and d are the same as the symbols in the formula (1). Equation (9)
  • 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.
  • 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).
  • 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).
  • 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)
  • 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 is 70 to 100% by weight, Preferably it is in the range from 80 to 100% by weight, most preferably 100% by weight.
  • chain monomer (d) for example, the one represented by the formula (14) is used.
  • R 67 ⁇ R 7 (1 is the same as in Formula (7) t
  • 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.
  • 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.
  • W tungsten
  • 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_ ⁇ 2, H 2 W0 4, NaWO 4, K 2 WO physician (NH 4) 2 W_ ⁇ physician CaW0 4, CuW_ ⁇ 4, MgW_ ⁇ 4, ( (CO) 5 WC (OCH 3 ) (CH 3 ), (C0 5 ) WC (OC 2 H 5 ) (CH 3 ), (C0 5 ) WC ( ⁇ 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_ ⁇ _F j: etc.
  • 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.
  • 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.
  • a co-catalyst is used together with the above-mentioned metathesis catalyst.
  • the co-catalyst include an organic aluminum compound and an organic tin compound, and an organic aluminum compound is preferable.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • ether examples 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.
  • ester examples 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.
  • ketone examples include acetone, methyl ethyl ketone, getyl ketone, methyl phenyl ketone, diphenyl ketone, and the like, and among them, acetone-methyl methyl ketone is preferable.
  • nitriles examples include acetonitrile, benzonitrile, t-butylonitrile, and the like. Of these, benzonitrile and t_butylonitrile are preferable.
  • regulators can be used alone or in combination of two or more.
  • 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.
  • 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.
  • 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.
  • heterogeneous catalyst examples 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.
  • 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.
  • the 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.
  • 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.
  • a homogeneous catalyst is used as the hydrogenation catalyst
  • 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.
  • 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.
  • 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) UV absorber
  • 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.
  • 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.
  • benzophenone-based ultraviolet absorber examples 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.
  • benzotriazole-based UV absorber examples 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-
  • salicylic acid-based ultraviolet absorber examples 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.
  • acrylate ultraviolet absorber examples 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.
  • 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 ⁇ after infrared irradiation (weather resistance).
  • 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.
  • antioxidant (Z) to be used examples 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.
  • phenolic antioxidant conventionally known ones can be used.
  • 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.
  • 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
  • monophosphite compounds are preferred, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, and tris (2,4-di-t-phenylphenyl) phosphite are particularly preferred.
  • zeo-based antioxidants examples include dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thiodipropionate.
  • Pionate pen erythritol lute tetrakis-(
  • 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.
  • 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. .
  • the inorganic fine particles can be used as the lubricant.
  • 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.
  • 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
  • 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
  • Liquid hydrocarbon poly a linear or branched liquid hydrocarbon polymer having no hydrocarbon ring in the main chain is preferable.
  • 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.
  • squalane liquid paraffin
  • liquid paraffin liquid paraffin
  • polyisobutene hydrogenated polybutadiene
  • hydrogenated polyisoprene hydrogenated polyisoprene
  • pigments examples 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.
  • 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
  • the near-infrared absorbing agent examples 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
  • antistatic agent examples include alkyl sulfonates such as alkyl sulfonate sodium salt and alkyl sulfonate phosphonium salt; and dariserine ester of stearic acid.
  • 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.
  • the rubbery polymer examples 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 ⁇ ⁇ -olefin copolymer such as ethylene ⁇ propylene copolymer, propylene ⁇ Other ⁇ -olefin copolymers Saturated polyolefin rubbers such as ethylene-propylene-gen copolymer, ⁇ -olefin-gen copolymer, isobutylene-isoprene copolymer, ⁇ -olefin-gen copolymer such as isobutylene-gen copolymer Polymer rubber
  • 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.
  • polyolefins such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, polypropylene, syndiotactic polypropylene, polybutene, and poly
  • 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.
  • 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.
  • a suitable good solvent for example, hexane, heptane, decane, cyclohexane, benzene, toluene, xylene, methylene chloride, chlor
  • 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.
  • melt extrusion method such as an inflation method, a calendar method, a hot press method, and an injection molding method.
  • 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.
  • the resin temperature is appropriately selected within a range from a glass transition temperature to a decomposition temperature.
  • 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.
  • 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.
  • a suitable carrier support
  • 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.
  • 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.
  • 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.
  • 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.
  • drying is usually performed in two or more stages.
  • 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.
  • Tg glass transition temperature
  • 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.
  • a thin film of a metal, a metal oxide, a semiconductor, or the like, a foil, or the like may be stacked.
  • a laminated material include conductive polymer films such as polyacetylene, polypyrrol, polypyridine, polythiophene, and polyaniline, polyvinyl benzyl trimethyl ammonium chloride, and oligo (poly).
  • 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
  • L is 50 ⁇ m
  • excellent mechanical strength, elongation, weather resistance, and chemical resistance are preferred.
  • the obtained film can be used as it is without stretching, or can be stretched uniaxially or biaxially.
  • 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.
  • the hydrogenation rate was measured by 1 H-NMR.
  • the glass transition temperature was measured by the DSC method. (5) Mechanical strength
  • ⁇ 5% or more, less than 10%
  • ⁇ 1% or more and less than 5%
  • the weather resistance test of the film was evaluated by the following method.
  • the reduction rate of the total light transmittance is less than 1%.
  • the reduction rate of the total light transmittance is 1% or more and less than 10%.
  • the reduction rate of the total light transmittance is 10% or more and less than 50%.
  • the reduction rate of the total light transmittance is 50% or more.
  • 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 ⁇ I of the test piece before and after the test was measured, and judged based on the following four grade test evaluation criteria.
  • ⁇ : ⁇ 1 is 0.3 or more and less than 1.
  • ⁇ 1 is 1 or more and less than 2.
  • X: ⁇ I is 2 or more.
  • 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.
  • 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.
  • 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.
  • This polymerization reaction solution was transferred to a 1-liter autoclave, and 160 g of cyclohexane was added.
  • 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.
  • 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).
  • 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).
  • 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).
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • a hindered phenol-based antioxidant Irg anox 1010 was used as an antioxidant (Z).
  • 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.
  • 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.

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Abstract

Composition de résine qui comprend: une résine cyclooléfinique thermoplastique, constituée d'au moins 70 % en poids d'unités répétées ayant une structure alicyclique qui n'est pas une structure norbornane; un photostabilisant; et, éventuellement, un agent absorbant les ultraviolets et/ou un antioxydant. Cette composition, qui présente une résistance mécanique, un allongement, une résistance chimique et une résistance aux intempéries satisfaisants, est particulièrement utile comme film.
PCT/JP1999/000416 1998-02-01 1999-02-01 Composition de resine cycloolefinique thermoplastique et objet moule WO1999038918A1 (fr)

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Cited By (6)

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JP2002284971A (ja) * 2001-03-23 2002-10-03 Jsr Corp 熱可塑性樹脂組成物およびその用途
WO2004035688A1 (fr) * 2002-10-03 2004-04-29 Sekisui Chemical Co., Ltd. Film de resine a base de norbornene sature thermoplastique et son procede de production
JP2008208357A (ja) * 2007-02-02 2008-09-11 Jsr Corp 光学フィルムの製造方法、光学フィルム、位相差フィルム、および偏光板
JP2011195623A (ja) * 2010-03-17 2011-10-06 Jsr Corp 光学用熱可塑性樹脂組成物および成形品
WO2017006600A1 (fr) * 2015-07-09 2017-01-12 日本ゼオン株式会社 Composition de résine, article moulé en résine et élément optique
JP2017170894A (ja) * 2016-03-17 2017-09-28 日本ポリエチレン株式会社 易引裂性多層フィルム

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JP2002284971A (ja) * 2001-03-23 2002-10-03 Jsr Corp 熱可塑性樹脂組成物およびその用途
WO2004035688A1 (fr) * 2002-10-03 2004-04-29 Sekisui Chemical Co., Ltd. Film de resine a base de norbornene sature thermoplastique et son procede de production
JP2008208357A (ja) * 2007-02-02 2008-09-11 Jsr Corp 光学フィルムの製造方法、光学フィルム、位相差フィルム、および偏光板
JP2011195623A (ja) * 2010-03-17 2011-10-06 Jsr Corp 光学用熱可塑性樹脂組成物および成形品
WO2017006600A1 (fr) * 2015-07-09 2017-01-12 日本ゼオン株式会社 Composition de résine, article moulé en résine et élément optique
JPWO2017006600A1 (ja) * 2015-07-09 2018-04-19 日本ゼオン株式会社 樹脂組成物、樹脂成形体、及び光学部材
JP2017170894A (ja) * 2016-03-17 2017-09-28 日本ポリエチレン株式会社 易引裂性多層フィルム

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