JP3289571B2 - Method for producing norbornene-based polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a light emitting diode,
The present invention relates to a norbornene-based polymer composition having excellent properties such as moldability and mechanical properties of optical materials such as optical fibers and optical films.

[0002]

2. Description of the Related Art Norbornene resin is an excellent optical resin having high glass transition temperature (high heat resistance), low water absorption and transparency, and is applied to optical films, various lenses, optical fibers, light emitting diodes and the like. Is being promoted. However, a norbornene-based resin has a high glass transition temperature and thus requires a high molding temperature, and there is a need for improvement in fluidity due to problems such as thermal decomposition. Norbornene-based resins are generally brittle compared to polycarbonate resins and the like, and there is a problem that the strength of the weld portion of the molded product is particularly weak. Regarding these problems, it is effective to increase the molecular weight in order to improve the weld strength,
When the molecular weight is increased, there is a problem that the fluidity is deteriorated, and it has been difficult to improve both the strength and the fluidity.

[Problems to be solved by the invention]

In view of the above problems, the present inventors have proposed a composition obtained by mixing a norbornene resin having a specific intrinsic viscosity in order to obtain a resin having an excellent balance between strength and fluidity. The balance between the two is excellent, and it has been found that both the weld strength and the fluidity are improved as compared with the case of using the norbornene resin alone, and the present invention has been achieved. That is, the present invention relates to (A) a ring-opened (co) polymer of a norbornene derivative represented by the following general formula 1 (hereinafter, referred to as “specific monomer”) or a hydrogenated product thereof, having an intrinsic viscosity of 0.1. At least one polymer having a weight ratio of 58 to 1.5 dl / g, and (B ) a component represented by the following general formula 1 and the component (A)
Is mixed with at least one polymer having a ring-opening (co) polymer of the same norbornene derivative as the norbornene derivative or a hydrogenated product thereof and having an intrinsic viscosity in the range of 0.35 to 0.55 dl / g. And a method for producing a norbornene-based polymer composition.

[0004]

Embedded image

Wherein A and B are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y are a hydrogen atom or a monovalent organic group, and at least one of X and Y is A group having a polar group other than a hydrogen atom or a hydrocarbon group, and m is 0 or 1)

In the present invention, when the tetracyclododecene derivative represented by the general formula 1 has a polar group, the polar group is-(CH ₂ ) _n COOR.
³ (wherein, R ³ is a hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 0 to 10), so that the obtained hydrogenated polymer has a high glass transition temperature. Is preferred. In particular, this-(CH ₂ ) _n COOR
It is preferable that one polar substituent represented by ³ is contained in one molecule of the tetracyclododecene derivative of the general formula 1. In the general formula 1, R ¹ has 1 to 20 carbon atoms.
Is preferred in that the greater the number of carbon atoms, the lower the hygroscopicity of the obtained hydrogenated polymer becomes. However, from the viewpoint of the balance with the glass transition temperature of the obtained hydrogenated polymer, the number of carbon atoms is 1 It is preferably a chain alkyl group having 4 to 4 carbon atoms or a (poly) cyclic alkyl group having 5 or more carbon atoms, particularly preferably a methyl group, an ethyl group or a cyclohexyl group. Furthermore, - (CH ₂₎ carbon atom of the polar substituent is bonded, represented by _n COOR ^3, carbon atoms at the same time to 10
The tetracyclododecene derivative of the general formula 1 in which the hydrocarbon group of formula (1) is bonded as a substituent is preferable because it reduces the hygroscopicity. In particular, the tetracyclododecene derivative of the general formula 1 in which the substituent is a methyl group or an ethyl group is preferable in that the synthesis is easy.

Specific monomers that can be used in the present invention include 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene and 5-methyl-5-methoxycarbonylbicyclo [2.2. 1] Hept-2-
Ene, 5-cyanobicyclo [2.2.1] hept-2-
Ene, 8-methoxycarbonyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene, 8-n-propyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
n-butyloxycarbonyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8
-Methoxycarbonyltetracyclo [4.4.0.1
^2,5 . 1 ^{7,1 0]} -3-dodecene, 8-methyl-8-ethoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1
^{7,1 0]} -3-dodecene, 8-methyl -8-n-propyl-oxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.}
1 ^7,10 ] -3-dodecene, 8-methyl-8-isopropyloxycarbonyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-n
-Butyloxycarbonyltetracyclo [4.4.0.
1 ^{2, 5.} 1 ^7,10 ] -3-dodecene pentacyclo [7.4.0.1 ^2,5 . ^19,12 . 0 ^8,13 ]
-3-pentadecene and the like. From the viewpoints of heat resistance and optical properties of the obtained polymer,
-Methyl-8-methoxycarbonyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene is most preferred. The above-mentioned specific monomers do not necessarily need to be used alone, and a ring-opening copolymerization reaction can be performed using two or more kinds. Further, a norbornene derivative other than the general formula 1 can be copolymerized with the norbornene derivative of the general formula 1. Specific examples of the norbornene derivative other than the general formula 1 include tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene, 8-ethylidenetetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene, pentacyclo [6.5.1.1]
^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene, hexacyclo [6.6.1.13,6.110,13.02,7.
09,14] -4-heptadecene, heptacyclo [8.
7.0.1 ^2,9 . ^14,7 . 1 ^11,17 . 0 ^3,8 . 0 ^12,16 ] −
5-eicosene, octacyclo [8.8.0.1 ^2,9 .
^14,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene, pentacyclo [7.4.0.1 ^2,5 . ^19,12 .
0 ^8,13 ] -3-pentadecene 5-phenylbicyclo [2.2.1] -2-heptene,
5-methyl-5-phenylbicyclo [2.2.1] -2
-Heptene, 5- (2,4,6-trimethylphenyl)
Bicyclo [2.2.1] -2-heptene, 5- (ethylphenyl) bicyclo [2.2.1] -2-heptene, 5
-(Isopropylphenyl) bicyclo [2.2.1]-
2-heptene, 5- (biphenyl) bicyclo [2.2.
1] -2-Heptene, 5- (β-naphthyl) bicyclo [2.2.1] -2-heptene, 5- (α-naphthyl)
Bicyclo [2.2.1] -2-heptene, 5- (anthracenyl) bicyclo [2.2.1] -2-heptene,
5,6-diphenylbicyclo [2.2.1] -2-heptene, cyclopentadiene-acenaphthylene adduct, 2
Molecule cyclopentadiene and one molecule acenaphthylene adduct, 1,4-methano-1,4,4a, 5,10,10
a-Hexahydroanthracene, 8-phenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-phenyl-tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (2,
4,6-trimethylphenyl) -tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (ethylphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene, 8- (isopropylphenyl)
-Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene, 8,9-diphenyl-tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (biphenyl) -tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene, 8- (β-naphthyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (α-naphthyl) -tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (anthracenyl) -tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene, 11,12-benzo-pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, 11,12-benzo-pentacyclo [6.
6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene,
11-phenyl-hexacyclo [6.6.1.1 ^3,6 .
1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 14,
15-benzo-heptacyclo [8.7.0.1 ^2,9 . 1
^4,7 . 1 ^11,17 . 0 ^{3 , 8} . 0 ^12,16 ] -5-eicosene.

In the production of the polymer of the present invention, the ring-opening polymerization reaction is carried out in the presence of a metathesis catalyst. The metathesis catalyst comprises (a) at least one selected from compounds of W, Mo, and Re; (b) an element of Group IA of the Periodic Table of Deming (eg, Li, Na, K, etc.);
Group elements (eg, Mg, Ca, etc.), Group IIB elements (eg, Zn, Cd, Hg, etc.), Group IIIA elements (eg, B, Al, etc.), Group IVA elements (eg, Si, Sn, P, etc.)
b) or IVB group element (eg, Ti, Zr, etc.)
And a catalyst comprising a combination of at least one selected from compounds having at least one element-carbon bond or element-hydrogen bond. In this case, in order to increase the activity of the catalyst, an additive (c) described below may be added. Representative examples of compounds of W, Mo or Re suitable as the component (a) include compounds described in JP-A-1-240517, such as WCl ₆ , MoCl ₅ and ReOCl ₃ . As a specific example of the component (b), nC ₄ H ₉ L
i, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl,
(C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlC
JP-A Nos. 1-24 such as l ₂ , methylalumoxane and LiH
Compounds described in JP-A-0517 can be mentioned.
As typical examples of the component (c), which is an additive, alcohols, aldehydes, ketones, amines and the like can be suitably used, and further, compounds described in JP-A-1-240517 are used. be able to.

The amount of the metathesis catalyst used is such that the molar ratio of the component (a) to the specific monomer is such that the ratio of the component (a) to the specific monomer is usually 1: 500 to 1: 50000. , Preferably in the range of 1: 1000 to 1: 10000. The ratio of the component (a) to the component (b) is such that (a) :( b) is in the range of 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atom ratio. The molar ratio of the component (a) to the component (c) is such that (c) :( a) is 0.1.
005: 1 to 15: 1, preferably 0.05: 1 to 7:
1 range.

The solvent (solvent constituting the molecular weight modifier solution, solvent of the specific monomer and / or metathesis catalyst) used in the ring-opening polymerization reaction includes, for example, pentane, hexane, heptane, octane, nonane, decane and the like. Alkanes, cyclohexane, cycloheptane, cyclooctane, decalin, cycloalkanes such as norbornane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide , Chlorobenzene, chloroform,
Compounds such as halogenated alkanes and aryls such as tetrachloroethylene, saturated carboxylic esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate and dimethoxyethane; ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane And the like, and these can be used alone or as a mixture. Of these, aromatic hydrocarbons are preferred. As the amount of the solvent used, "solvent:
The “specific monomer (weight ratio)” is usually in an amount of 1: 1 to 10: 1, and preferably in an amount of 1: 1 to 5: 1.

The molecular weight of the norbornene-based polymer can be adjusted by adjusting the polymerization temperature, the type of catalyst, and the type of solvent. In the production of the polymer constituting the composition of the present invention, the adjustment of the molecular weight is performed by adjusting the molecular weight. It is adjusted by allowing the agent to coexist in the reaction system. Here, suitable molecular weight regulators include, for example, ethylene, propene, 1-butene, 1-butene.
Examples thereof include α-olefins such as pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene, and styrene.
Butene and 1-hexene are particularly preferred. These molecular weight regulators can be used alone or in combination of two or more. The amount of the molecular weight modifier used is 0.005 to 1 mol of the specific monomer subjected to the ring-opening polymerization reaction.
0.6 mol, preferably 0.02 to 0.5 mol.

The ring-opened polymer obtained as described above is
Hydrogenation can be performed using a hydrogenation catalyst. The hydrogenation reaction is carried out in a usual manner, that is, a hydrogenation catalyst is added to a solution of the ring-opening polymer, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm is added at 0 to 200 ° C., preferably It is performed by operating at 20 to 180 ° C. As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used. As the hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst are known. As the heterogeneous catalyst, palladium,
A solid catalyst in which a noble metal catalyst substance such as platinum, nickel, rhodium and ruthenium is supported on a carrier such as carbon, silica, alumina and titania can be used. Examples of homogeneous catalysts include nickel / triethylaluminum naphthenate, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, and chlorotris (triphenylphosphine) rhodium. , Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like. The form of the catalyst may be powdery or granular. However, in the hydrogenation of the copolymer of the present invention, a hydrogenation catalyst and conditions under which the aromatic ring is subjected to nucleus hydrogenation cannot be used. These hydrogenation catalysts have a ring-opening polymer: hydrogenation catalyst (weight ratio) of 1: 1 × 10 −6 to
Used at a ratio of 1: 2. As described above, the hydrogenated polymer obtained by hydrogenation has excellent thermal stability, and its properties are not deteriorated by heating at the time of molding or use as a product. Here, the hydrogenation rate is usually 50% or more, preferably 70%
Above, more preferably 90% or more. Further, in the present invention, polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-non-conjugated diene polymer, unsaturated hydrocarbon-based polymer containing a carbon-carbon double bond in the main chain such as polynorbornene, etc. The specific monomer may be subjected to ring-opening polymerization in the presence. The hydrogenated product of the ring-opening copolymer obtained in this case is useful as a raw material for a resin having high impact resistance.

In the method of the present invention, (A) a ring-opening (co) polymer of the specific monomer represented by the above general formula 1 or a hydrogenated product thereof, having an intrinsic viscosity of 0.58 to 1.5 dl /
g, at least one polymer (hereinafter, referred to as “component A”), (B) represented by the above general formula 1 , and (A)
A ring-opening (co) polymer of the same specific monomer as the specific monomer constituting the component or a hydrogenated product thereof, wherein the polymer has an intrinsic viscosity in the range of 0.35 to 0.55 dl / g ( (Hereinafter, referred to as "component B").
In the present invention, the intrinsic viscosity is measured in chloroform at 30 ° C. In the present invention, the preferred intrinsic viscosity of the component (A) is 0.6 to 1.2 dl / g, and the preferred intrinsic viscosity of the component (B) is 0.4 to 0.52 dl / g. If the intrinsic viscosity of the component (A) exceeds 1.5 dl / g, the resulting composition will have low fluidity, and if the intrinsic viscosity of the component (B) is less than 0.35 dl / g, the resulting composition will have a low strength. Not enough. In the present invention, each of the component (A) and the component (B) may be used in combination of two or more. In the present invention, the intrinsic viscosity of the component (B) is preferably smaller than the intrinsic viscosity of the component (A) by 0.1 or more. (A)
When the difference between the intrinsic viscosities of the component and the component (B) is less than 0.1 dl / g, it is difficult to obtain the effects of improving the weld strength, film impact strength, and fluidity of the obtained composition.
The mixing ratio of the components (A) and (B) is 95 /
It is used at 5 to 5/95, preferably 90/10 to 10/90. The use ratio of the component (A) and the component (B) is 5
When the amount is less than the weight%, the effect of improving the weld strength, the film impact strength and the fluidity is poor. In the present invention, the components (A) and (B) can be mixed before hydrogenation and then hydrogenated, or they can be mixed after hydrogenation of the components (A) and (B), respectively. . The composition obtained by the method of the present invention has a number average molecular weight (Mn) in terms of polystyrene of 10,000 to 5 as measured by gel permeation chromatography (GPC).
0000, weight average molecular weight (Mw) 30,000-
200,000 and a molecular weight distribution (Mw / Mn) of 3
As mentioned above, it is preferably 3 to 5.

The composition obtained by the method of the present invention contains a known antioxidant such as 2,6-di-tert-butyl-4-methylphenol, 2,2'-dioxy-3,3'-. Jee
t-butyl-5,5'-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate] methane; can be stabilized by adding an ultraviolet absorber such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone. Further, an additive such as a lubricant may be added for the purpose of improving workability. The composition obtained by the method of the present invention,
Optical lenses such as optical disks, magneto-optical disks, pickup lenses, laser beam printer lenses, camera lenses, etc., eyeglass lenses, optical films (cast, extruded films) for liquid crystal displays, optical fibers, light emitting diodes, photocouplers, pharmaceuticals, etc. Can be used for containers, medical instruments, sealing materials, etc.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.
The method for preparing a sample and the method for measuring various physical properties in the present invention are described below. (1) Intrinsic Viscosity (ηinh) A chloroform solution having a concentration of 5 g / l was prepared and measured at 30 ° C. using an Ubelod viscometer. (2) Molecular weight (Mn, Mw) and molecular weight distribution (Mw /
Mn) The molecular weight was measured in terms of polystyrene using HLC-8020 manufactured by Tosoh Corporation. (3) MFR 260 ° C, load 1 according to the method of JIS K-6719
It was measured under the condition of 0 kg. (4) Weld strength and weld strength retention Using ASTM No. 1 dumbbell mold using injection molding machine 350-90-270H manufactured by Aburg Co., Ltd., test with weld (both side gates) and no weld (one point side gate) Pieces were made. Molding conditions: cylinder temperature 330 ° C, mold temperature 13
In the evaluation at 0 ° C., the test pieces were conditioned at 23 ° C. and 60% humidity, and then the tensile strength was measured by the method of ASTM D638. The weld strength retention was evaluated as (tensile strength (with ゛) ゛ / tensile strength (without ゛)) × 100%. (5) Film impact strength Using tetrahydrofuran as a casting solvent, about 10
A cast film having a thickness of 0 μm was prepared. Using this cast film, a film impact was measured using a YASUDA film impact tester without load.

Reference Example 1 As a specific monomer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.
^12.5 . 100 parts of [ ^17,10 ] -3-dodecene, 3.6 parts of 1-hexene as a molecular weight regulator and 200 parts of toluene were charged into a reaction vessel purged with nitrogen, and heated to 80 ° C. To this were added 0.17 part of a toluene solution of triethylaluminum (1.5 mol / l) as a polymerization catalyst, and t
Denaturation of WCl ₆ with butanol and methanol, t
1.0 part of a WCl ₆ solution (concentration of 0.05 mol / l) in which the molar ratio of butanol to methanol and tungsten is 0.35: 0.3: 1 is added, and the mixture is heated and stirred at 80 ° C. for 3 hours. Thus, a polymer solution A was obtained. The polymerization conversion in this polymerization reaction was 97%. 4000 parts of the obtained polymer solution A was put into an autoclave, and RuHCl was added thereto.
0.48 parts of (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added, and the mixture was heated and stirred for 3 hours at a hydrogen gas pressure of 100 kg / cm 2 and a reaction temperature of 165 ° C. to carry out a hydrogenation reaction. After cooling the obtained reaction solution, the hydrogen gas was released to obtain a hydrogenated polymer solution B. This hydrogenated polymer solution B was coagulated in a large amount of methanol and dried to isolate the hydrogenated polymer. The glass transition temperature of this hydrogenated polymer is 170
° C and the hydrogenation rate were substantially 100%. The resulting hydrogenated polymer is referred to as polymer (a). Next, 0.3 parts of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate as an antioxidant was added to 100 parts of the polymer (a), and 300 parts were added using an extruder. Pelleted at 0 ° C. Ηin of the obtained pellet
h was 0.85, and the molecular weight in terms of polystyrene measured by GPC was Mn = 54500 and Mw = 158000.

Reference Examples 2 to 7 The same procedures as in Reference Example 1 were carried out except that the amount of 1-hexene of the molecular weight regulator was changed from Reference Example 1 to (b) to (g) shown in Table 1. ) Was prepared. Table 1 shows ηinh of the prepared polymer and the molecular weight in terms of polystyrene measured by GPC.

Example 1 90 parts by weight of the polymer (d) was mixed with 10 parts by weight of the polymer (a) prepared in Reference Example 1, and melt-blended at 300 ° C. using a twin-screw extruder. Pelletized. The ηinh of the obtained pellet is 0.
The molecular weight in terms of polystyrene measured by GPC was Mn = 27300 and Mw = 84500. Further, MFR and weld strength were measured using the obtained pellets. Table 1 shows the results. [Examples 2 to 5 and Comparative Examples 1 to 7] A composition was prepared in the same manner as in Example 1 except that the mixing ratio of the polymer was changed, and the obtained composition was pelletized. A test piece was prepared using the obtained pellet, and the physical properties were evaluated. The results are shown in Tables 1 and 2.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

According to the composition obtained by the present invention, a molding material excellent in weld strength, film impact strength and fluidity can be obtained as compared with the norbornene (co) polymer alone. Furthermore, the composition obtained in the present invention is a molded product in which welds such as light-emitting diodes occur, in which the strength of the weld is important, optical fibers, while maintaining the strength of the film, etc., while suppressing the deterioration during extrusion molding. Suitable for applications that require improved fluidity.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-228380 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 65/00

Claims (1)

(57) [Claims] (A) A ring-opened (co) polymer of a norbornene derivative represented by the following general formula 1 or a hydrogenated product thereof, which has an intrinsic viscosity of 0.58 to 1.5 dl / g. At least one kind and (B) represented by the following general formula 1,
The same as the norbornene derivative constituting the component (A)
A ring-opened (co) polymer of a norbornene derivative or a hydrogenated product thereof having an intrinsic viscosity of 0.35 to 0.55 dl /
g, at least one kind of polymer having a weight ratio of (A) / (B) in a ratio of 95/5 to 5/95 by weight. Manufacturing method. Embedded image (Where A and B are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y are a hydrogen atom or a monovalent organic group, and at least one of X and Y is a hydrogen atom or A group having a polar group other than a hydrocarbon group;
Is 0 or 1. )