JPH11217424A - Durable plate member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a member excellent in all of the properties including mechanical strengths, elongation, chemical resistance, weathering resistance, and light transmittance by using a thermoplastic cycloolefin resin containing a specified or larger amount of repeating units having an alicyclic structure. SOLUTION: A thermoplastic cycloolefin resin containing 30 wt.% or above repeating units having an alicyclic structure is used. The alicyclic structure in the repeating units desirably exist in the main chain and is desirably a saturated alicyclic structure. Among the repeating units having the alicyclic structure, repeating units free from a norbornane structure are desirable. It is desirable that the thermoplastic cycloolefin resin contains at most 20 wt.% component having a molecular weight of 1,000 or below (as determined by GPC). The durable sheety member is a molding which is 50 mm by 50 mm square or larger. Its thickness is usually desirably 0.5-500 mm. It is desirable as an outdoor member having excellent transparency.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a durable plate member excellent in mechanical strength, elongation, chemical resistance, weather resistance and light transmittance, and more particularly, suitable for outdoor use excellent in transparency. And a durable plate member.

[0002]

2. Description of the Related Art Conventionally, as transparent plate materials for outdoor use such as carports, exteriors, windows of vending machines, signs, etc.
A plate material such as an acrylic plate or a polycarbonate plate made of polymethyl methacrylate has been frequently used. However, acrylic plates have excellent light transmittance and weather resistance, but have drawbacks inferior in mechanical strength, elongation, and chemical resistance. In addition, polycarbonate plates have excellent mechanical strength and elongation, but chemical resistance. However, there is a disadvantage that the weather resistance and the light transmittance are inferior.
Thus, the conventional transparent plate material has mechanical strength, elongation,
There is a problem that there is no one in which the properties of chemical resistance, weather resistance and light transmission are balanced.

[0003] The above-mentioned problems of the conventional transparent resin are compensated, and thermoplastic norbornene-based resin is used as a material highly balanced in mechanical strength, elongation, chemical resistance, weather resistance and light transmission characteristics. Cyclic olefin-based resins are known, and JP-A-8-41178, JP-A-6-13657 and the like disclose a sheet or press formed by extruding a thermoplastic norbornene-based resin to 500 μm, a flat plate obtained by injection molding, and the like. Disclosed. However, these sheets and flat plates are for use in specific optical materials and the like, and have not been found to be effective particularly when used as durable plate members outdoors or the like,
Further, the strength of the plate was not sufficiently satisfactory.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a durable plate-like member which is excellent in mechanical strength, elongation, chemical resistance, weather resistance and light transmittance.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, a repeating unit (A) having an alicyclic structure such as cycloalkane or cycloalkene has been obtained. By using a cyclic olefin-based thermoplastic resin (I) containing a specific amount of
The inventors have found that a durable plate-like member excellent in all of the properties of elongation, chemical resistance, weather resistance and light transmittance can be obtained, and have completed the present invention. Thus, according to the present invention,
(1) A cyclic olefin-based thermoplastic resin (I) containing 30% by weight or more of the repeating unit (A) having an alicyclic structure
And a durable plate-shaped member comprising: According to the present invention, (2) the thickness of the plate is 0.5 to 500 mm (1).
There is provided a durable plate-like member as described. According to the present invention,
(3) The maximum deflection of a rectangular test piece having a width of 40 mm and a length of 100 mm when a concentrated load of 5 g is applied to the free end of the cantilever is 80 mm or less (1) or (2). Is provided. According to the present invention, (4) 30% by weight or more of the repeating unit (A) having an alicyclic structure is (A-i) having no norbornane structure (Ai). A durable plate-shaped member according to any of the above is provided. According to the present invention,
(5) The durable plate-like member according to any one of (1) to (4), wherein the proportion of the component having a molecular weight of 1,000 or less in the cyclic olefin-based thermoplastic resin (I) is 20% by weight or less. Is done. According to the present invention, there is provided (6) a durable plate member according to any one of (1) to (5), which is a transparent plate material. According to the present invention, (7) the durable plate-shaped member according to any one of (1) to (6), which is used outdoors. According to the present invention, there is provided (8) a method of forming the durable plate member according to any one of (1) to (7) by a melt extrusion method using a T-die.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Cyclic olefin-based thermoplastic resin
(I) The cyclic olefin-based thermoplastic resin (I) used in the present invention is characterized by containing a repeating unit (A) having an alicyclic structure. The alicyclic structure in the repeating unit (A) may be any of a main chain and / or a side chain,
Especially when high mechanical strength and light transmittance are required,
Those having in the main chain are preferred. The alicyclic structure may be either saturated or unsaturated. When high mechanical strength and weather resistance are required, a saturated alicyclic structure is preferred.
Specific examples include a cycloalkane and a cycloalkene structure, and a cycloalkane structure is preferred. Also,
The number of carbon atoms constituting the alicyclic structure may be appropriately selected according to the purpose of use, but is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15. In particular, the characteristics of mechanical strength and elongation are highly balanced and suitable. These repeating units (A) having an alicyclic structure may be used alone or in combination of two or more. The content of the repeating unit (A) having an alicyclic structure in the cyclic olefin-based thermoplastic resin (I) is 30% by weight or more, 50% by weight or more, and more preferably 70% by weight or more. If the content of the repeating unit (A) having an alicyclic structure in the cyclic olefin-based thermoplastic resin (I) is excessively small, the mechanical strength, elongation and light transmittance are unfavorably poor.

In the present invention, among these repeating units (A) having an alicyclic structure, repeating units (Ai) having no norbornane structure are particularly excellent in mechanical strength and weather resistance and are preferred. It is. The repeating unit (Ai) having no norbornane structure is not particularly limited.

[0008]

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[R ^{1 to} R ²⁰ each independently represent a hydrogen atom, a hydrocarbon group, a hydroxyl group, an ester group, an alkoxy group,
Cyano group, imide group, silyl group, or functional group (hydroxyl group, ester group, alkoxy group, cyano group, imide group,
A silyl group). Where R
⁸ and R ¹⁰ , or R ⁹ and R ¹¹ may together form an unsaturated bond, and R ⁸ and R ⁹ , or R ¹⁰ and R ¹¹
And may form an alkylidene group. a is 0 or 1, b is 0 or 1, and c is 0, 1 or 2. ‥‥‥ represents a carbon-carbon single bond or a double bond. ]. R ^{1 to} R ²⁰ in the formula (1) 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, A hydrocarbon group substituted with an alkoxy group, a cyano group, an imide group, or a silyl group), preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom. The number of carbon atoms of the hydrocarbon group is generally 1 to 20, preferably 1 to 1.
0, 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, for example, those having 1 to 2 carbon atoms.
0, preferably 1 to 10, more preferably 1 to 6, ester group-containing alkyl groups. Further, R ⁸ and R ¹⁰ or R ⁹ and R ¹¹ in the formula (1) may form an unsaturated bond together, and R ⁸ and R ⁹ , or R ¹⁰ and R ¹¹ And may form an alkylidene group. The number of carbon atoms of the alkylidene group is generally 1-20, preferably 1-10, more preferably 1-6.
Range. A in the formula (1) is 0 or 1,
Preferably it is 0. B in the formula (1) is 0 or 1, and preferably 1. C in the formula (1) is 0, 1 or 2, and is preferably 0. ‥‥ in equation (1)
‥ 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, more preferably 99% or more, particularly excellent weather resistance is obtained. Among the repeating units having no norbornane structure represented by the above formula (1), the repeating unit is preferably represented by the formula (2), more preferably the formula (3).

[0010]

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Examples and preferred ranges of R ^{21 to} R ³⁴ in the formula (2) are the same as those of R ¹ in the formula (1). It is also possible to form an unsaturated bond R ⁸ and R ²⁷ in formula (2) or R ⁹ and R ^28, taken together, also, a R ⁸ R
²⁶ , or R ²⁷ and R ²⁸ may form an alkylidene group. The carbon number of the alkylidene group is usually 1
-20, preferably 1-10, more preferably 1-6. D in the formula (2) is 0 or 1, and is preferably 0. In the formula (2), 表 す represents a carbon-carbon single bond or a double bond. Usually, the ratio of the single bond is 95% or more, preferably 98% or more, more preferably 99% or more. In this case, it is particularly excellent in weather resistance and is suitable.

[0012]

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In the formula (3), ‥‥‥ represents a carbon-carbon single bond or a double bond.
5% or more, preferably 98% or more, more preferably 99% or more
% Or more is particularly excellent in weather resistance and is preferable. These repeating units having no norbornane structure (A-
i) may be used alone or in combination of two or more. The proportion of the repeating unit (A-i) having no norbornane structure in the repeating unit (A) having an alicyclic structure is usually 30 to 100% by weight,
Preferably 50 to 100% by weight, more preferably 70 to 100% by weight.
When it is in the range of 100% by weight, mechanical strength, chemical resistance and weather resistance are highly balanced and suitable. The repeating unit other than the repeating unit (A-i) having no norbornane structure in the repeating unit (A) having an alicyclic structure, that is, the repeating unit (A-ii) having a norbornane structure is not particularly limited. Is, for example, the equation (4)

[0014]

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## EQU1 ## Examples and preferred ranges of R ^{35 to} R ⁴⁸ in the formula (4) are the same as those of R ¹ in the formula (1). E in the formula (4) is an integer of 1 to 3, and is preferably 1. In the formula (4), 表 す represents a carbon-carbon single bond or a double bond. Usually, the ratio of the single bond is 95% or more, preferably 98% or more, more preferably 99% or more. In this case, it is particularly excellent in weather resistance and is suitable. Among the repeating units (A-ii) having a norbornane structure represented by the formula (4), they are preferably represented by the formula (5), and more preferably represented by the formula (6).

[0016]

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Examples and preferred ranges of R ^{49 to} R ⁶² in the formula (5) are the same as those of R ¹ in the formula (1). In the formula (5), ‥‥‥ represents a carbon-carbon single bond or a double bond. Usually, the ratio of the single bond is 95% or more, preferably 98% or more, more preferably 99% or more. In this case, it is particularly excellent in weather resistance and is suitable.

[0018]

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Illustrative and preferred ranges of R ^{63 to} R ⁶⁶ in the formula (6) are the same as those of R ¹ in the formula (1). In the formula (6), 表 す represents a carbon-carbon single bond or a double bond. Usually, the ratio of the single bond is 95% or more, preferably 98% or more, more preferably 99% or more. In this case, it is particularly excellent in weather resistance and is suitable.

These repeating units (A-ii) having a norbornane structure may be used alone or in combination of two or more. The content of the repeating unit (A-ii) having a norbornane structure is not particularly limited, but is usually a repeating unit (A-ii) having no norbornane structure.
-70% by weight or less, preferably 50% by weight of the balance of i), that is, 70% by weight or less in the repeating unit (A) having an all-alicyclic structure.
Or less, more preferably 30% by weight or less.

The repeating unit (B) other than the repeating unit (A) having the alicyclic structure in the cyclic olefin-based thermoplastic resin (I) used in the present invention is not particularly limited. And a chain-like repeating unit. As the chain repeating unit, for example, a unit represented by the formula (7) is used.

[0022]

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[0023] R ⁶⁷ to R ⁷⁰ in the formula (7) is the same as R ¹ in formula (1), preferably a hydrogen atom.

The molecular weight of the cyclic olefin-based thermoplastic resin (I) used in the present invention is appropriately selected according to the purpose of use, and gel permeation using cyclohexane (or toluene when not dissolved in cyclohexane) as a solvent. Weight average molecular weight in terms of polyisoprene as measured by cation chromatography (GPC), usually 5,000 to
500,000, preferably 7,000-300,00
When it is in the range of 0, more preferably in the range of 10,000 to 100,000, properties such as mechanical strength, elongation, and chemical resistance of the film are highly balanced, which is preferable.
The proportion of the component having a molecular weight of 1,000 or less measured by GPC in the cyclic olefin-based thermoplastic resin (I) used in the present invention is not particularly limited, but is usually 20% by weight or less, preferably 20% by weight or less. When the content is 10% by weight or less, more preferably 5% by weight or less, mechanical strength and chemical resistance are particularly enhanced, which is preferable.

(Production Method) The method for producing the above-mentioned cyclic olefin-based thermoplastic resin (I) used in the present invention can be carried out according to a conventional method. For example, an alicyclic olefin-based monomer is prepared in the presence of a metathesis catalyst system. And a hydrogenation reaction can be carried out if necessary. As the alicyclic olefin-based monomer (a), those which are a repeating unit having no norbornane structure are preferable, for example, the formula (8), preferably the formula (9), and more preferably the formula (1)
The olefin monomer (ai) represented by 0) is used. The fact that these olefin-based monomers (a-i) become repeating units having no norbornane structure by the metathesis polymerization (the above-mentioned A-i) is disclosed, for example, in Japanese Patent No. 2534.
No. 086 and Japanese Patent Publication No. 7-121981, for example.

[0026]

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Wherein R ^{1 to} R ²⁰ , a, b and c are the same as the symbols in the formula (1). ]

[0028]

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Wherein R ^{21 to} R ³⁴ and d are represented by the formula (2)
Is the same as the symbol in. ]

[0030]

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These equations (8), (9) or (1)
The olefin-based monomers (ai) represented by 0) can be used alone or in combination of two or more. The proportion of the olefin monomer (ai) represented by the formula (8), the formula (9) or the formula (10) in the cyclic olefin monomer (a) having an alicyclic structure is usually 30 to 100% by weight, preferably 50-1
00% by weight, more preferably 70-100% by weight. The remainder of the alicyclic olefin monomer (a) other than the olefin monomer (ai) represented by the formula (8), (9) or (10) is usually represented by the formula (1)
1), preferably formula (12), more preferably formula (1)
The one represented by 3) is used.

[0032]

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Wherein R ^{35 to} R ⁴⁸ and e are represented by the formula (4)
Is the same as the symbol in. ]

[0034]

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

[0036]

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[In the formula, R ^{63 to} R ⁶⁶ are the same as the symbols in the formula (6). These cyclic olefin-based monomers (a) having an alicyclic structure can be used alone or in combination of two or more. The proportion of the cyclic olefin-based monomer (a) having an alicyclic structure in all the monomers is usually in the range of 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 70 to 100% by weight.
Cyclic olefin monomer having alicyclic structure (a)
As the remaining monomer (b) other than, a chain monomer is usually used. The chain monomer is represented, for example, by the formula (14).

[0038]

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[Wherein, R ^{67 to} R ⁷⁰ are the same as the symbols in the formula (7). ]

As the metathesis catalyst, for example, a metal compound such as tungsten (W) or molybdenum (Mo) or a metal compound such as titanium (Ti) can be used. And molybdenum (Mo) compounds, and more preferably a tungsten (W) compound. Specific examples of the tungsten (W) compound include WBr ₂ , WBr ₃ , WBr ₆ , WCl ₂ ,
WCl ₄ , WCl ₅ , WCl ₆ , WF ₂ , WF ₄ , WF ₆ , W
I ₂ , WI ₄ , WI ₆ , WOBr ₄ , WOCl ₄ , WOF ₄ ,
_{WO 2, H 2 WO 4,} NaWO 4, K 2 WO 4, (NH 4) 2 W
O ₄ , CaWO ₄ , CuWO ₄ , MgWO ₄ , (CO) ₅ W
C (OCH ₃ ) (CH ₃ ), (CO ₅ ) WC (OC ₂ H ₅ )
(CH ₃ ), (CO ₅ ) WC (OC ₂ H ₅ ) (C ₄ H ₅ ) and the like. Among them, WBr ₂ , WBr ₃ , WB
r ₆ , WCl ₂ , WCl ₄ , WCl ₅ , WCl ₆ , WF ₂ , W
_{F 4, WF 6, WI 2} , WI 4, WI 6, WOBr 4, WOC
l _4, WOF _4, etc. are preferable, WBr _2, WBr _3, WB
r ₆ , WCl ₂ , WCl ₄ , WCl ₅ , WCl ₆ , WF ₂ , W
F ₄ , WF ₆ , WI ₂ , WI ₄ , WI ₆ are more preferred. These metathesis catalysts can be used alone or in combination.
More than one species can be used in combination. The amount of the metathesis catalyst used is usually per 100 parts by weight of all monomers,
0.1 to 1.5 parts by weight, preferably 0.1 to 1.0 parts by weight, and more preferably 0.1 to 0.5 parts by weight.

When performing metathesis polymerization, it is common to use a co-catalyst together with the above-mentioned metathesis catalyst. 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 organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, and triisobutylaluminum, and alkylaluminum halides such as diethylaluminum chloride and ethylaluminum dichloride. However, preferred are triethylaluminum, triisobutylaluminum and diethylaluminum chloride. These cocatalysts can be used alone or in combination of two or more. The amount of the cocatalyst used is usually 0.01 to 30 mol per 1 mol of the metathesis catalyst,
Preferably 0.1 to 20 mol, more preferably 1 to
When the amount is 10 mol, the generation of a gel is small, the polymerization activity is high, and a high molecular weight product 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 organic aluminum compound is particularly preferable. However, it has a preferred repeating unit (a-i) having no norbornane structure and has a high molecular weight (polymerization average molecular weight of 5,000 to 500,000, preferably 7,000 to
3,000,000, more preferably 10,000 to 10
(000) and a small amount of low molecular weight components (the proportion of components having a molecular weight of 1,000 or less is 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less). When producing I), it is preferable to use a regulator in addition to the tungsten (W) -based compound and the organoaluminum compound. As the modifier, at least one kind of polar compound selected from a polar compound containing active hydrogen such as alcohol and amine; and a polar compound not containing active hydrogen such as ether, ester, ketone and nitrile can be used. The active hydrogen-containing polar compound is effective for preventing gelation and obtaining a high molecular weight polymer, and among them, alcohol is preferable. Further, the polar compound containing no active hydrogen is effective for suppressing the production of low molecular weight components in the polymer,
Among them, ethers, esters and ketones are preferred, and ketones are particularly preferred. Examples of the alcohol include, for example, saturated alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, isopentanol, hexanol and cyclohexanol, and unsaturated alcohols such as phenol and benzyl alcohol. But preferably propanol, isopropanol,
Butanol and isobutanol. Examples of the ether include dimethyl ether, diethyl ether, dibutyl ether, ethylene glycol dibutyl ether, and triethylene glycol dibutyl ether. Of these, diisopropyl ether and diethyl 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, propyl benzoate, isopropyl benzoate, and the like. Of these, methyl acetate and ethyl acetate are preferred. Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone,
Examples thereof include methylphenyl ketone and diphenyl ketone, and among them, acetone and methyl ethyl ketone are preferred. Examples of the nitrile include acetonitrile, benzonitrile, t-butyronitrile and the like, and among these, benzonitrile and t-butyronitrile are preferable. These modifiers can be used alone or in combination of two or more. In particular, in the present invention, it is preferable to combine an active hydrogen-containing polar compound and a polar compound having no active hydrogen, particularly alcohol and ketone, alcohol and nitrile,
Combinations of alcohol and ether and of alcohol and ester are preferred. The amount of the modifier used is usually 0.01 to 20 mol, preferably 0.1 to 10 mol, and more preferably 1 to 5 mol, per 1 mol of the metathesis catalyst.
1 range.

The polymerization reaction is usually performed in the presence of a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, hexane, and heptane; aliphatic alicyclic hydrocarbons such as cyclopentane, cyclohexane, and cyclooctane; And preferably, toluene, cyclohexane,
Cyclooctane and the like, and more preferably toluene and cyclohexane. These solvents can be used alone or in combination of two or more, and the amount of use is usually 10 to 1000 parts by weight, preferably 50 to 700 parts by weight, per 100 parts by weight of the monomer. Preferably it is in the range of 100 to 500 parts by weight. The polymerization conditions are such that the polymerization temperature is usually -10C to 200C.
° C, preferably 0 ° C to 100 ° C, more preferably 10 ° C
To 80 ° C., and the polymerization time is usually 30 minutes to 10 minutes.
Time, preferably from 1 hour to 7 hours, more preferably from 2 hours to 5 hours. If the polymerization temperature is too high, the number of components having a molecular weight of 1,000 or less increases.

After the completion of the polymerization reaction, a hydrogenation catalyst can be added to carry out 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 generally used. As the heterogeneous catalyst, for example, nickel, palladium, platinum, or these metals are carbon, silica, diatomaceous earth, alumina,
Solid catalyst supported on a carrier such as titanium oxide: nickel /
Silica, nickel / diatomaceous earth, nickel / alumina,
Palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like. As the homogeneous catalyst, for example, a catalyst comprising a combination of a transition metal compound and an alkylaluminum metal compound or an alkyllithium, for example, cobalt acetate / triethylaluminum, cobalt acetate / triisobutylaluminum, nickel acetate / triethylaluminum, nickel acetate / triethylaluminum A catalyst comprising a combination of isobutylaluminum, nickel acetylacetonate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene chloride / n-butyllithium, zirconocenechloride / n-butyllithium, and the like. Each of these hydrogenation catalysts is independently performed at 0 to 250 ° C, preferably 20 to 200 ° C. Or in combination of two or more. The amount of the hydrogenation catalyst to be used is generally 0.01 to 100 parts by weight, preferably 0.1 to 100 parts by weight, per 100 parts by weight of the polymer.
It is in the range of 1 to 50 parts by weight, more preferably 1 to 30 parts by weight. The hydrogenation reaction is usually performed under a hydrogen pressure of 1 to 150 kg / cm ² in a temperature range of 0 to 250 ° C and a reaction time of 1 hour to 20 hours. The cyclic olefin-based thermoplastic resin (I) used in the present invention can be obtained by filtration after the above-mentioned hydrogenation reaction to remove the hydrogenation catalyst, followed by coagulation and drying. When a homogeneous catalyst is used as the hydrogenation catalyst, it can be obtained by adding alcohol or water after the hydrogenation reaction to deactivate the catalyst, insolubilizing the solvent, filtering, coagulating, and drying.

Other Resin Component The cyclic olefin-based thermoplastic resin (I) used in the present invention may be blended with other polymers as required. Other polymers include, for example, rubbery polymers and other thermoplastic resins. Examples of the rubbery polymer include diene rubbers such as natural rubber, polybutadiene rubber, polyisoprene rubber, acrylonitrile / butadiene copolymer rubber; styrene / butadiene copolymer rubber; styrene / isoprene copolymer rubber; Butadiene / isoprene terpolymer rubber; hydrogenated diene rubber; ethylene
Ethylene / α-olefin copolymers such as propylene copolymers, saturated polyolefin rubbers such as propylene / other α-olefin copolymers; ethylene / propylene / diene copolymers, α-olefin / diene copolymers, Α-olefin / diene polymer rubber such as isobutylene / isoprene copolymer, isobutylene / diene copolymer; urethane rubber, silicone rubber, polyether rubber, acrylic rubber, propylene oxide rubber,
Special rubbers such as ethylene acrylic rubber; styrene / butadiene / styrene block copolymer rubber, styrene
Thermoplastic elastomers such as isoprene / styrene block copolymer rubber; hydrogenated thermoplastic elastomers;
Urethane-based thermoplastic elastomer; polyamide-based thermoplastic elastomer; 1,2-polybutadiene-based thermoplastic elastomer.

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

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

Compounding Agent The cyclic olefin-based thermoplastic resin (I) used in the present invention may optionally contain a compounding agent. The compounding agent is not particularly limited as long as it is generally used in the resin industry, for example, an antioxidant,
UV absorbers, lubricants, anti-fog agents, anti-fog agents, plasticizers, pigments,
Near-infrared absorbing agents, antistatic agents and the like can be mentioned.

Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Of these, phenol-based antioxidants are preferred, and alkyl-substituted phenol-based oxidants are preferred. Inhibitors are particularly preferred. As the phenolic antioxidant, conventionally known phenolic antioxidants, for example, 2-t-butyl-6
-(3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6- (1- (3,5-di-t-amyl-
JP-A-63-179953 and JP-A-Hei 1-179, such as 2-hydroxyphenyl) ethyl) phenyl acrylate.
Acelay and system compound described in JP-A-168643; 2,6-di-t-butyl-4-methylphenol,
2,6-di-t-butyl-4-ethylphenol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylene-
Bis (4-methyl-6-t-butylphenol), 4,
4'-butylidene-bis (6-t-butyl-m-cresol), 4,4'-thiobis (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] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5 -T-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, tetrakis (methylene-3- (3 ′, 5′-
Di-tert-butyl-4'-hydroxyphenylpropionate) methane [that is, pentaerythrimethyl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenylpropionate)], triethylene glycol Bis (3- (3-t-butyl-4-hydroxy-5
Alkyl-substituted phenolic compounds such as -methylphenyl) propionate) and tocophenol; 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4
-Bisoctylthio-1,3,5-triazine, 6-
(4-hydroxy-3,5-dimethylanilino) -2,
4-bisoctylthio-1,3,5-triazine, 6-
(4-hydroxy-3-methyl-5-t-butylanilino) -2,4-bisoctylthio-1,3,5-triazine, 2-octylthio-4,6-bis- (3,5-di-t -Butyl-4-oxyanilino) -1,3-triazine-containing phenolic compounds such as triazine;
And the like. The phosphorus-based antioxidant is not particularly limited as long as it is a substance generally used in the general resin industry. For example, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl 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, 1
0- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9 Monophosphite compounds such as -oxa-10-phosphaphenanthrene;
4'-butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl phosphite), 4,4'isopropylidene-bis (phenyl-di-alkyl (C1
2-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) -4,4'-biphenylenediphosphite, cyclic neopentanetetraylbis (in Decyl phosphite), cyclic neopentanetetraylbis (nonylphenyl phosphite), cyclic neopentanetetraylbis (2,4-di-t-butylphenylphosphite), cyclic neopentanetetraylbis (2 , 4-dimethylphenylphosphite), cyclic neopentanetetraylbis (2,6-di-
diphosphite-based compounds such as t-butylphenylphosphite). Among these, monophosphite compounds are preferable, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and the like are particularly preferable. Examples of the sulfur-based antioxidant include dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thiodipro Pionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate, 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro
[5, 5] undecane and the like. As the ultraviolet absorber, for example, 2,2,6,6-tetramethyl-
4-piperidyl benzoate, bis (2,2,6,6
-Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2- n-butylmalonate, 4- (3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Hindered amine ultraviolet rays such as propionyloxy) -1- (2- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -2,2,6,6-tetramethylpiperidine Absorbent; 2-
(2-hydroxy-5-methylphenyl) 2H-benzotriazole, 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5- Di-tert-butyl-2-hydroxyphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 5-chloro-
2- (3,5-di-t-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-
benzotriazole ultraviolet absorbers such as t-amyl-2-hydroxyphenyl) -2H-benzotriazole; 4-t-butylphenyl-2-hydroxybenzoate, phenyl-2-hydroxybenzoate, 2,4
-Di-t-butylphenyl-3,5-di-t-butyl-
4-hydroxybenzoate, hexadecyl-3,5-
Di-tert-butyl-4-hydroxybenzoate, 2-
(2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (2-hydroxy-5-t-octylphenyl) -2H -Benzotriazole, 2-
Bezoate UV absorbers such as (2-hydroxy-4-octylphenyl) -2H-benzotriazole;
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Methoxybenzophenone-5-sulfonic acid trihydrate, 2
-Hydroxy-4-octyloxybenzophenone, 4-
Dodecaloxy-2-fodroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,
2 ′, 4,4′-tetrahydroxybenzophenone,
Benzophenone ultraviolet absorbers such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; ethyl-2-cyano-3,3-diphenylacrylate, 2 '
Acrylate UV absorbers such as -ethylhexyl-2-cyano-3,3-diphenylacrylate; [2,
2'-thiobis (4-t-octylphenolate)]-
Examples include a nickel complex ultraviolet absorber such as 2-ethylhexylamine nickel.

As the lubricant, for example, inorganic fine particles can be used. Here, the inorganic fine particles are 1 in the periodic table.
Group 2, group 4, group 4, group 6, group 7, group 8-10, group 11, group 1
Oxides, hydroxides, sulfides, nitrides, carbonates, sulfates, acetates, phosphates, phosphites, organic carboxylates, silicates, titanates of Group 2, 13 and 14 elements Shows salts, borates and their hydrated compounds, composite compounds centered on them, and natural mineral particles. 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 Hydrated salt (talc), calcium carbonate, calcium phosphate, calcium phosphite, calcium sulfate (gypsum), calcium acetate, calcium terephthalate,
Calcium hydroxide, calcium silicate, calcium fluoride, calcium titanate, strontium titanate, barium titanate, zinc titanate, lanthanum titanate, bismuth titanate, lead titanate, barium carbonate, barium phosphate, barium sulfate, phosphorous acid Group 2 element compound such as barium; Group 4 element compound such as titanium dioxide (titania), titanium monoxide, titanium nitride, zirconium dioxide (zirconia), zirconium monoxide; molybdenum dioxide;
Group 6 element compounds such as molybdenum trioxide and molybdenum sulfide; Group 7 element compounds such as manganese chloride and manganese acetate; Group 8 to 10 element compounds such as cobalt chloride and cobalt acetate; Group 11 element compounds such as cuprous iodide Group 12 element compounds such as zinc oxide and zinc acetate, aluminum oxide (alumina), aluminum hydroxide, aluminum fluoride, aluminosilicate (alumina silicate, kaolin,
Group 13 element compounds such as kaolinite), silicon oxide (silica, silica gel), graphite, carbon, graphite,
Group 14 element compounds such as glass, and particles of natural minerals such as kernalite, kainite, mica (mica, kinmo), and virose ore. The average particle size of the inorganic fine particles used here is not particularly limited, but is preferably 0.01
３3 μm.

Examples of the antifogging agent include sorbitan fatty acid esters, sorbitol fatty acid esters, glycerin fatty acid esters, diglycerin fatty acid esters, and compounds obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to these compounds. What is used for a vinyl resin film can be used. Specifically, sorbitan palmitate, sorbitan stearate, sorbitan behenate, sorbitan stearate / ethylene oxide 2 mol adduct, sorbitan stearate / propylene oxide 3 mol adduct, sorbitol stearate, sorbitol stearate / ethylene oxide 3 mol adduct, diglycerin palmitate, diglycerin stearate, glycerin palmitate ethylene oxide 2
Mol adduct, sorbitan stearate adipate / ethylene oxide 3 mol adduct, sorbitol stearate adipate / ethylene oxide 2 mol adduct, diglycerin palmitate sebacate / propylene oxide 3 mol adduct, sorbitol palmitate adipate / ethylene oxide 3 And a molar adduct. As the antifog agent, a fluorine-containing compound generally used for agricultural vinyl chloride resins can be used. In particular,
Fluorinated alkylene oxide compounds described in JP-A-5-163406 and JP-A-5-331339;
162, and the like.

As the plasticizer, for example, tricresyl phosphate, trixylyl phosphate, triphenyl phosphate, triethylphenyl phosphate, diphenylcresyl phosphate, monophenyl dicresyl phosphate, dicresyl monoxylenyl Phosphate, arylalkyl phosphate,
Phosphate triester plasticizers such as diphenyl monoxylenyl phosphate, monophenyl dixylenyl phosphate, tributyl phosphate, triethyl phosphate, trichloroethyl phosphate, trioctyl phosphate, and tris (isopropylphenyl) phosphate Dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, octyl decyl phthalate,
Phthalate ester plasticizers such as butyl benzyl phthalate; fatty acid monobasic acid ester plasticizers such as butyl oleate and glycerol monooleate; dibutyl adipate, di-n-adipate fatty acid dibasic acid ester plasticizer Agents: dihydric alcohol ester-based plasticizers; oxyacid ester-based plasticizers can be used, and among them, phosphate triester-based plasticizers are preferable, and tricresyl phosphate and trixylyl phosphate are particularly preferable. As the pigment, for example, Pigment Red 38
Azo lake-based pigments such as Pigment Red 48: 2, Pigment Red 53, and Pigment Red 57: 1; condensed azos such as Pigment Red 144, Pigment Red 166, Pigment Red 220, Pigment Red 221 and Pigment Red 248; Pigment Red: Pigment Red 171, Pigment Red 17
5, Pigment Red 176, Pigment Red 18
5, penzimidazolone-based pigments such as Pigment Red 208; quinacridone-based pigments such as Pigment Red 122; Pigment Red 149, Pigment Red 17
8, perylene pigments such as Pigment Red 179; and anthraquinone pigments such as Pigment Red 177. The near-infrared absorbing agent is, for example, a cyanine-based near-infrared absorbing agent; a pyrylium-based infrared-absorbing agent; a squarylium-based near-infrared absorbing agent; a croconium-based infrared absorbing agent; an azurenium-based near-infrared absorbing agent; Complex near-infrared absorbers; naphthoquinone-based near-infrared absorbers; anthraquinone-based near-infrared absorbers; indophenol-based near-infrared absorbers; In addition, commercially available near infrared absorbers SIR-103, SIR-114, SIR-12
8, SIR-130, SIR-132, SIR-15
2, SIR-159, SIR-162 (manufactured by Mitsui Toatsu Dye), Kayasorb IR-750, Kaya
Sorb IRG-002, Kayasorb IRG
-003, IR-820B, Kayasorb IRG
-022, Kayasorb IRG-023, Kaya
sorb CY-2, Kayasorb CY-4, K
ayasorb CY-9 (all manufactured by Nippon Kayaku) and the like. Examples of the antistatic agent include alkyl sulfonates such as sodium alkyl sulfonate and phosphonium alkyl sulfonate; and glycerin esters of stearic acid. These compounding agents can be used alone or in combination of two or more. The amount of other ingredients used
It is appropriately selected within a range that does not impair the object of the present invention.

The durable plate member in the present invention is composed of a cyclic olefin-based thermoplastic resin (I) containing 30% by weight or more of the repeating unit (A) having an alicyclic structure. Cyclic olefin-based thermoplastic resin is a transparent durable plate-like member obtained by molding by adding other polymers or compounding agents as necessary, and the durability is, for example, a vehicle, a human, etc. Has sufficient impact resistance or weather resistance to protect the target object from the external environment. The durable plate-shaped member of the present invention has such a size that a partition can be formed in the space between the object and the external environment. Examples of the external environment include (1) dust, dirt, dust, and other external impacts, (2) external environments such as sunlight (ultraviolet rays), rain, and snow, and (3) acids, alkalis, and other chemicals. Can be

As a method of protection by the durable plate-like member of the present invention, such a durable plate-like member is installed at a specific distance from an object, such as a roof or a fence, and is protected from rain, wind and light rays. A method of protecting the object from external factors from a certain fixed method, a method of completely covering the object and protecting it from external factors, and the like. In the case of covering all with only the case, there is a case where a part is covered with the durable plate-like member like a window.

The size of the durable plate-like member in the present invention can be 50 mm square or more, but a larger plate, specifically, a 100 mm square or more plate can be formed. When the size is preferably not less than 300 mm square, particularly preferably not less than 500 mm square, the above-mentioned protective function is more sufficiently exhibited, which is suitable. The thickness of the durable plate member is appropriately selected depending on the purpose of use,
Usually 0.5-500m to have the above protection function
m, preferably 1.0 to 300 mm, more preferably 3.0 to 100 mm, the mechanical strength,
It is excellent in elongation, weather resistance and light transmittance, and is preferable. The shape of the surface of the durable plate-shaped member may be any of a square and a circle. In the case of a square, the second shortest side (Y) is obtained when the shortest side (X) of the plate is defined as the thickness direction. And the ratio (Y / X)
Is 2.0 or more, preferably 3.0 or more, and most preferably 5.0 or more when the mechanical strength, elongation, weather resistance,
It is excellent in light transmittance and is preferable.

The durable plate member of the present invention has a width of 40
The maximum deflection when a concentrated load of 5 g is applied to the free end of a cantilever beam of a strip-shaped test piece having a length of 100 mm and a length of 100 mm is appropriately selected according to the purpose of use, but is usually 80 m.
m or less, preferably 40 mm or less, more preferably 20 mm or less.
When it is at most 5 mm, most preferably at most 5 mm, it is particularly excellent in mechanical strength and weather resistance and is suitable.

The total light transmittance of the durable plate-shaped member in the present invention is appropriately selected according to the purpose of use.
% Or more, preferably 30% or more, more preferably 50%
When it is above, it is suitable and suitable for outdoor use.

The method of forming the durable plate-like member can be carried out according to a conventional method, and can be usually carried out by a melt forming method. When a durable plate member is produced by a melt molding method, there are a melt extrusion method such as a method using a T-die and an inflation method, a calender method, a hot press method, an injection molding method, and the like. Among them, 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 a 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, but usually, 100-4
00 ° C, preferably 150 to 350 ° C, more preferably 200 to 300 ° C, and the temperature of the take-off roll is usually 0 to 200 ° C, preferably 30 to 180 ° C, more preferably 50 to 150 ° C. is there. The durable plate-shaped member of the present invention has a high balance of mechanical strength, elongation, chemical resistance, weather resistance and light transmittance, so a plate material having a protective or protective function, a large-sized for outdoor use. It is useful as a transparent plate. Specifically, as an application for installing or protecting a roof or a partition at a certain distance from an object, for example, an automobile (vehicle) such as a carport or a garage
Roof for storage; windows and partitions for exteriors and glazings (solariums, balconies, terraces, etc.); windows for vending machines to completely cover and protect objects; windows for showcases, showrooms, etc. Useful for applications requiring impact resistance such as mechanical strength and elongation, such as sunroofs, lift hoods, gondola windows, ropeway windows, and other vehicle windows, and where necessary, weather resistance. It is. The size of the durable plate-shaped member of the present invention when used for the above applications is, for example, 300 mm square or more, preferably 5 mm when used for carports, windows, glazing, and the like.
When it is not less than 00 mm square, the function of the durable plate-shaped member of the present invention is more effectively exhibited, which is preferable. For example, when used for a house exterior or the like, a plurality of plate materials having a size of about 50 to 100 mm square can be used in combination. Further, the durable plate-like member of the present invention is useful as an application suitable for outdoor use, particularly for applications requiring weather resistance and chemical resistance, such as signboards, bulletin boards, and signs for highways.

[0058]

The present invention will be described more specifically below with reference to examples and comparative examples. Parts and percentages are by weight unless otherwise specified. The measuring 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 as a solvent. (2) Low molecular weight component A gel having a molecular weight of 1,000 or less in terms of polyisoprene was calculated by gel permeation chromatography (GPC) using cyclohexane as a solvent. (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 A 3/4 inch radius missile-type weight (5
0g) was dropped naturally from a height of 1 m, and cracks and cracks were observed. If no cracks or cracks were found, 0 out of 10 sheets were excellent (very good). 1 to 3 sheets out of 10 sheets The following are ○ (good), 4 or more and 6 or less out of 10 are Δ
(Somewhat defective) 7 or more of 10 sheets were evaluated as x (bad). (6) Tensile elongation Measured according to JIS 7127 and evaluated according to the following criteria. ：: 10% or more ：: 5% or more and less than 10% △: 1% or more and less than 5% ×: less than 1% (7) Light transmittance The total light transmittance was measured with an absorption altimeter and evaluated according to the following criteria. A: Total light transmittance is 90% or more. ：: The total light transmittance is 80% or more and less than 90%. Δ: The total light transmittance is 50% or more and less than 80%. X: Total light transmittance is less than 50%. (8) Weather resistance The weather resistance test of the plate was evaluated by the following method. (A) According to JIS 5400, using a sunshine weatherometer, a black panel temperature of 35 ° C. and rain (18 minutes / 120 minutes), while rotating the test piece around the light source once a minute, It was exposed to a carbon arc for a predetermined time. The weather resistance was evaluated by the reduction rate of the total light transmittance of the plate after the test. The judgment was made according to the following criteria. A: The reduction rate of the total light transmittance is less than 0.1%. Good: The reduction rate of the total light transmittance is 0.1% to 10%. Δ: The reduction rate of the total light transmittance is 10% to 30%. X: The reduction rate of the total light transmittance is 30% or more. (B) The surface condition of the film after 10 months and 20 months of outdoor exposure was visually observed. A: Transparent without turbidity or yellowish color. ：: There is no turbidity and there is yellowish but transparent. Δ: Cloudy and yellowish, but slightly transparent. ×: Turbid, yellowish, and opaque. (9) Chemical Resistance A cloth moistened with salad oil was applied to the test piece, and a solvent crack generated after holding for 60 minutes was visually observed.
The chemical resistance was tested. A sample having no white scratches or discoloration visually was evaluated as good. (10) Maximum deflection A rectangular test piece having a width of 40 mm and a length of 100 mm was prepared, and the maximum deflection (mm) in the vertical direction when a concentrated load of 5 g was applied to the free end of the cantilever was measured.

REFERENCE EXAMPLE 1 5 parts by weight of a 85:15 monomer mixture of dicyclopentadiene and methyltetracyclododecene and 120 parts by weight of cyclohexane were added to a 1-liter flask purged with nitrogen, and tri-i was used as a polymerization catalyst. -Butyl aluminum [iBu ₃ Al] 0.57
mmol equivalent, 0.57 mol equivalent of isobutyl alcohol and 0.189 mmol of acetone as a reaction modifier
1-hexene 3.79 mm as an equivalent and molecular weight regulator
ol equivalents were added. Where tungsten hexachloride
0.076 mmol equivalent was added and stirred at 60 ° C. for 5 minutes. Then, while maintaining the reaction system at 60 ° C, dicyclopentadiene and methyltetracyclododecene at 85:
A mixed solution of 45 parts by weight of the mixed monomer of No. 15, 0.114 mmol equivalent of tungsten hexachloride and cyclohexane was continuously dropped into the system. After dropping,
The ring-opening polymerization was completed by stirring for another 30 minutes. Weight average molecular weight (Mw) of the ring-opened polymer thus obtained
Was 26,300. Since the peak of the unreacted monomer was not detected by gas chromatography analysis of the reaction solution, it was confirmed that the reaction rate was 100%.

This polymerization reaction solution was transferred to a 1-liter autoclave, and 160 parts by weight of cyclohexane was added. As a hydrogenation catalyst, 2.5 parts by weight of diatomaceous earth-supported nickel catalyst and activated alumina (surface area 320 c
^2.5 parts by weight of m ² / parts by weight, pore volume 0.8 cm ³ / parts by weight, average particle size 15 μm, manufactured by Mizusawa Chemical Co., Ltd., and 2.5 parts by weight. c
The pressure was increased at m ² and the temperature was raised to 160 ° C. while stirring. When the temperature was stabilized, the hydrogen pressure was maintained at 40 kg / cm 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 the activated alumina were separated by filtration, and the hydrogenation reaction solution was poured into 3 liters of isopropyl alcohol to precipitate out, and collected by filtration. The recovered resin is treated at 100 ° C. and 1 Torr or less for 48 hours.
Let dry for hours. The polymer thus obtained is referred to as a polymer (A). Weight average molecular weight of polymer (A) (M
w) was 52,600, and the proportion of components having a molecular weight of 1,000 or less was 0.5% by weight. The hydrogenation ratio of the polymer (A) was 99.9%, and the glass transition temperature was 103.
° C. The repeating unit having an alicyclic structure was 100% by weight, and the repeating unit having an alicyclic structure and having no norbornane structure was 85% by weight.

Reference Example 2 Synthesis was performed in the same manner as in Reference Example 1 except that the monomer was changed to a 50:50 mixed monomer of dicyclopentadiene and methyltetracyclododecene.
The polymer thus obtained is referred to as a polymer (B). The weight average molecular weight (Mw) of the polymer (B) is 53,000, and the ratio of components having a weight average molecular weight of 1,000 or less is 0.4% by weight.
Met. The hydrogenation rate of the polymer (B) was 99.9%.
And the glass transition temperature was 118 ° C. The repeating unit having an alicyclic structure was 100% by weight, and the repeating unit having an alicyclic structure and having no norbornane structure was 50% by weight.

Reference Example 3 Synthesis was performed in the same manner as in Reference Example 1, except that the monomer was changed to a mixed monomer of dicyclopentadiene and methyltetracyclododecene at a ratio of 30:70.
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 ratio of the polymer (C) was 99.9%, and the glass transition temperature was 127 ° C. The repeating unit having an alicyclic structure is 100% by weight, and the repeating unit having an alicyclic structure and having no norbornane structure is 3% by weight.
It was 0% by weight.

[Examples 1 to 4] The polymers (A) to (C) obtained in Reference Examples 1 to 3 and the polymer (D) (APL-65)
09T; manufactured by Mitsui Chemicals; 30% by weight of a repeating unit having an alicyclic structure, and the other repeating unit being ethylene), and phenolic antioxidant pentaerythrityl as an antioxidant to 100 parts by weight of a resin component. 0.1 parts by weight of tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate);
0.3 parts by weight of Cyasorb UV-3346 (manufactured by Cipro Kasei Co., Ltd.) as a light stabilizer and 0.2 parts by weight of SEESORB 709 (manufactured by Cipro Kasei Co., Ltd.) as an ultraviolet absorber are added, and a T-die is provided. The resin plate (A) to (D) having a thickness of 10 mm and a width of 1000 mm was produced by extruding through an extrusion polishing roll at an extrusion temperature of 260 ° C. using an extruder. Plates (A) to (D) prepared
Was measured for weather resistance, chemical resistance, mechanical strength, elongation and light transmittance. Incidentally, the maximum deflections of the plates (A) to (D) were all 1 mm or less.

Reference Example 4 A polymer obtained in the same manner as in Reference Example 1 except that the monomer was changed to dicyclopentadiene is referred to as a polymer (E). The weight average molecular weight (Mw) of the polymer (E) was 52,000, and the ratio of components having a molecular weight of 1,000 or less was 2.5% by weight. The hydrogenation rate of the polymer (E) was 99.9%, and the glass transition temperature was 97%.
° C. The repeating unit having an alicyclic structure was 100% by weight, and the repeating unit having an alicyclic structure and having no norbornane structure was also 100% by weight.

Reference Example 5 Synthesis was carried out in the same manner as in Reference Example 4, except that acetone as a reaction modifier was not used. The polymer thus obtained is referred to as a polymer (F). The weight average molecular weight (Mw) of the polymer (F) is 53,500, and the molecular weight is 1,000.
The proportion of the following components was 5.0% by weight. The hydrogenation ratio of the polymer (F) was 99.9%, and the glass transition temperature was 97 ° C. The repeating unit having an alicyclic structure was 100% by weight, and the repeating unit having an alicyclic structure and having no norbornane structure was also 100% by weight.

Reference Example 6 Synthesis was carried out 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 ° C. The polymer thus obtained is referred to as a polymer (G). Weight average molecular weight of polymer (G) (M
w) is 55,300 and the component having a molecular weight of 1000 or less is 1
It was 0.0% by weight. The hydrogenation rate is 99.9%,
The glass transition temperature was 97 ° C. The repeating unit having an alicyclic structure was 100% by weight, and the repeating unit having an alicyclic structure and having no norbornane structure was also 100% by weight.

[Examples 5 to 7] Using the polymers (E) to (G) obtained in Reference Examples 4 and 6, based on 100 parts by weight of the resin component, a phenolic antioxidant pentaerythri as an antioxidant. 0.1 parts by weight of lytyl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and Cyasor as a light stabilizer
b 0.3-3 UV-3346 (manufactured by Cipro Kasei Co., Ltd.)
Parts by weight and SEESORB 709 as an ultraviolet absorber
(Cipro Kasei Co., Ltd.) was added in an amount of 0.2 part by weight.
With an extruder equipped with a die, the resin was passed through an extrusion polishing roll at an extrusion temperature of 260 ° C. to produce resin plates (E) to (G) having a thickness of 10 mm and a width of 1000 mm. The weather resistance, chemical resistance, mechanical strength, elongation and light transmittance of the prepared plates (E) to (G) were measured and are shown in Table 2. Incidentally, the maximum deflections of the plates (E) to (G) were all 1 mm or less.

[0068]

[Table 1]

Table 1 shows that the plate obtained from the cyclic olefin-based thermoplastic resin of the present invention showed good results in all tests. In addition, those having a large amount of repeating units having an alicyclic structure in the all-cyclic olefin-based thermoplastic resin (Examples 1 to 3; 100% by weight) are those having a small number of repeating units having an alicyclic structure ( Example 4;
30% by weight), the results are excellent in all results such as weather resistance, chemical resistance, chemical resistance and light transmittance. Furthermore, compared with the plate (Examples 1 to 3) made of a 100% by weight alicyclic thermoplastic resin having an alicyclic structure, those having many repeating units having no norbornane structure (Examples 1>2>) It can be seen that 3) is particularly excellent.

[0070]

[Table 2]

In the cyclic olefin-based thermoplastic resin, all the repeating units have an alicyclic structure, and all of the repeating units have no norbornane structure. The results are shown. Among them,
Weight average molecular weight in the cyclic olefin-based thermoplastic resin,
Those with a small proportion of components of 1000 or less are chemically resistant,
The chemical resistance, mechanical strength and elongation were highly balanced and particularly good. From Tables 1 and 2 above,
Plate-shaped members having excellent weather resistance (A) and weather resistance (B) are used for outdoor use such as signboards and display boards, and plate-shaped members having excellent mechanical strength and elongation are used for carports, windows and glazing. Is effective as

[0072]

According to the present invention, there is provided a durable plate member excellent in mechanical strength, elongation, chemical resistance, weather resistance, and light transmittance. Further, according to the present invention, there is provided a durable plate-like member having excellent transparency and suitable for outdoor use. The durable plate-shaped member of the present invention has a carport,
It is useful as a board material for housing exteriors.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B29L 31:00

Claims (8)

[Claims] 1. A repeating unit (A) having an alicyclic structure
Durable plate member made of a cyclic olefin-based thermoplastic resin (I) containing at least 30% by weight of 2. The durable plate member according to claim 1, wherein the plate has a thickness of 0.5 to 500 mm. 3. The maximum deflection of a strip-shaped test piece having a width of 40 mm and a length of 100 mm when a concentrated load of 5 g is applied to the free end of the cantilever, is 80 mm or less. Durable plate member. 4. A repeating unit (A) having an alicyclic structure
The durable plate-like member according to any one of claims 1 to 3, wherein 30% by weight or more of the durable plate-like member (A-i) has no norbornane structure. 5. The durable plate member according to claim 1, wherein the proportion of the component having a molecular weight of 1,000 or less in the cyclic olefin-based thermoplastic resin (I) is 20% by weight or less. 6. The durable plate member according to claim 1, which is a transparent plate material. 7. The durable plate member according to claim 1, which is used outdoors. 8. A method for molding the durable plate member according to claim 1 by a melt extrusion method using a T-die.