JPH1160971A - Thermoplastic hydrocarbon polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition, excellent in dielectric dissipation factor or heat resistance, sufficiently excellent in mechanical characteristics such as tensile strength or impact strength and suitable for insulating films or the like by compounding a thermoplastic hydrocarbon polymer having a monocyclic or bicyclic saturated hydrocarbon group with a specific thermoplastic elastomer. SOLUTION: This composition contains (A) a thermoplastic hydrocarbon polymer having a monocyclic or a bicyclic saturated hydrocarbon group in a recurring unit and (B) a thermoplastic elastomer having <=50 g/100 g iodine value and 100,000-1,000,000 weight-average molecular weight Mw . A hydrogenated ring opening polymer of a norbornene-based monomer containing >=50 wt.% norbornenes of a bicyclic and/or a tricyclic substances is preferred as the component A. For example, norbornene is cited as the norbornene of the bicyclic substance. Tricyclo[4.3.1<2> ,<5> .0<1> ,<6> ]deca-3,7-diene is preferred as the tricyclic substance. A hydrogenated aromatic vinyl-conjugated diene block copolymer is preferred as the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic hydrocarbon polymer composition, and more particularly to a thermoplastic hydrocarbon polymer composition having excellent dielectric loss tangent and heat resistance, and also having excellent mechanical properties such as tensile strength, impact strength and elongation. The present invention relates to an excellent thermoplastic hydrocarbon polymer composition suitable for an insulating film. Further, the present invention relates to a film obtained by molding such a thermoplastic hydrocarbon polymer composition, particularly an insulating film, and a film capacitor.

[0002]

2. Description of the Related Art In recent years, plastic insulators have characteristics of high insulation resistance, excellent frequency characteristics, and excellent flexibility, and are therefore used for communication, electronic equipment, electric equipment, power, It is expected to be used as a film capacitor for medium / low pressure phase advance. As a film capacitor,
Wireless communication devices such as aircraft, ships and vehicles; Consumer DC electrical equipment such as radios, televisions and audios; Driving small motors such as air conditioners, washing machines and electric fans; Used to improve the power factor of fluorescent and mercury lamps Can be

[0003] A film capacitor is usually composed of a film having aluminum or zinc deposited on the surface, or a multilayer of aluminum foil and a film.
The film becomes the dielectric and the metal becomes the electrode. In recent years, film capacitors have been increasing in length, and therefore, a method of performing metal deposition by a semi-continuous method or a continuous method has been adopted. When a double-sided vapor deposition device for a capacitor is used, the film passes through more roll groups. When such a vapor deposition device is used, a strong mechanical load is applied to the film, so that the film is required to have sufficient tensile strength and flexibility (elongation).

As a material for such a plastic insulator, a polyethylene terephthalate (PET) film or P
P films and the like have been studied. However,
These conventional plastic materials have various problems. That is, although the PP film has good electrical properties and flexibility, it has a problem that the temperature of the dielectric loss tangent greatly changes, the electrical properties have a temperature dependency, and the heat resistance is not sufficient. PET films are excellent in heat resistance, but have a problem that they have a large dielectric loss tangent and are particularly difficult to use in high-frequency circuits.

On the other hand, a film made of a thermoplastic norbornene resin has good electric characteristics such as dielectric loss tangent and excellent heat resistance, and thus is useful as an insulating film for communication, electronic equipment, and electric equipment. (JP-A-2-102256, JP-A-5-1484)
No. 13). Among the thermoplastic norbornene resins, it has been reported that a hydrogenated product of a ring-opening polymer containing dicyclopentadiene as a main component is particularly excellent in flexibility and mechanical strength and excellent in properties such as moisture permeability (Japanese Patent Application Laid-Open No. 5-9552
No. 0, Japanese Unexamined Patent Publication No. Hei 6-198004, etc.) show that even such a resin is not sufficient for high required characteristics such as resistance to a strong mechanical load and elongation required for producing a film capacitor and the like. Performance.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic hydrocarbon polymer which is excellent in dielectric loss tangent and heat resistance, and which is sufficiently excellent in mechanical properties such as tensile strength, impact strength and elongation. It is to provide a united composition. It is another object of the present invention to provide a thermoplastic hydrocarbon polymer composition suitable as a material for a film capacitor having good physical properties. Still another object of the present invention is to provide a film having the above characteristics, particularly an insulating film, and a film capacitor.

The present inventors have conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, have found that a single ring or two ring
In a thermoplastic hydrocarbon polymer having a ring saturated hydrocarbon group,
By blending a thermoplastic elastomer with a large molecular weight and a small degree of unsaturation, it is excellent in electrical properties such as dielectric loss tangent and heat resistance, and also has excellent tensile strength, impact strength and elongation. Was obtained, and the present invention was completed based on the knowledge.

[0008]

Thus, according to the present invention, there is provided a thermoplastic hydrocarbon polymer having a monocyclic or bicyclic saturated hydrocarbon group in a repeating unit, and an iodine value of 50 g / l.
Weight average molecular weight (Mw) of 100,000 or less at 100 g or less
The present invention provides a thermoplastic hydrocarbon polymer composition containing a thermoplastic elastomer having a molecular weight of about 1,000,000.

Further, according to the present invention, there is provided a film obtained by molding the above-mentioned thermoplastic hydrocarbon polymer composition, particularly an insulating film. Further, according to the present invention, there is provided a film capacitor using the above film.

[0010]

DETAILED DESCRIPTION OF THE INVENTION Thermoplastic Hydrocarbon Polymer The thermoplastic hydrocarbon polymer used in the present invention is a thermoplastic hydrocarbon polymer having a monocyclic or bicyclic saturated hydrocarbon group in a repeating unit. . Examples of such a thermoplastic hydrocarbon polymer include (i) a hydride of a ring-opened polymer of a norbornene-based monomer containing 50% by weight or more of bicyclic and / or tricyclic norbornenes; (ii) (Iii) a hydrocarbon polymer having a saturated cyclic molecular structure of a carbon-carbon 5- to 8-membered ring in which part or all of the repeating units are connected by 1,4-bonds and / or 1,2-bonds; A polymer obtained by polymerizing a vinyl group-containing cyclic hydrocarbon monomer or a hydride thereof is exemplified. Among these thermoplastic polymers, a norbornene-based monomer containing bicyclic and / or tricyclic norbornenes in an amount of 50% by weight or more has a high balance between dielectric loss tangent and dielectric constant and excellent mechanical strength. Preferred is a hydride of the ring-opening polymer of

(I) bicyclic and / or tricyclic nor
Ring-opening polymer of bornenes or hydride thereof Bicycle used for production of hydride of ring-opening polymer of norbornene-based monomer containing 50% by weight or more of bicyclic and / or tricyclic norbornenes Are adducts of substituted or unsubstituted acyclic olefins or acyclic dienes with cyclopentadiene, and specific examples thereof include bicyclo [2.2.1] hept-2-ene (common name norbornene). ), 5-Methyl-bicyclo [2.2.
1] Hept-2-ene, 5,5-dimethyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl- Bicyclo [2.2.1] hepta-2-ene, 5-ethylidene-bicyclo [2.2.1] hepta-2-ene, 5-hexyl-bicyclo [2.2.1] hepta-2-ene, 5-
Octyl-bicyclo [2.2.1] hepta-2-ene,
5-octadecyl-bicyclo [2.2.1] hepta-2
-Ene, 5-ethylidene-bicyclo [2.2.1] hepta-2-ene, 5-methylidene-bicyclo [2.2.
1] Hept-2-ene, 5-vinyl-bicyclo [2.
2.1] norbornene derivatives such as hepta-2-ene, 5-propenyl-bicyclo [2.2.1] hepta-2-ene, and halogens of these norbornene derivatives;
Substitutes (for example, 5-methoxy-carbonyl-bicyclo [2.2.1] hept-2-) substituted by a polar group such as a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, and a silyl group. Ene, 5-cyano-bicyclo [2.2.1] hepta-2-ene, 5-methyl-5
Methoxycarbonyl-bicyclo [2.2.1] hepta
2-ene). Among these, since the dielectric loss tangent and the dielectric constant are highly balanced,
Norbornene derivatives having no polar group are preferred.

The tricyclic norbornenes used in the production of the hydrogenated ring-opened polymer of norbornene-based monomers are substituted or unsubstituted cyclic olefins or adducts of cyclic dienes and cyclopentadiene. , A dimer of cyclopentadiene, tricyclo [4.3.0.1
^2,5 ] deca-3,7-diene (commonly known as dicyclopentadiene), and its partially hydrogenated tricyclo [4.cyclopentadiene and cyclopentene adduct].
3.0.1 ^2,5 ] dec-3-ene; tricyclo [4. An adduct of cyclopentadiene and cyclohexadiene].
4.0.1 ^2,5 ] undeca-3,7-diene or tricyclo [4.4.0.1 ^2,5 ] undeca-3,8-diene or partially hydrogenated products thereof (or cyclopentadiene and cyclohexene) Adduct of tricyclo [4.4.0.1 ^2,5 ] undec-3-ene; 5-cyclopentyl-bicyclo which is an adduct of cyclopentadiene with a vinyl compound having an alicyclic group or an aromatic ring group [2.2.1] Hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5 -Phenyl-bicyclo [2.2.1] hept-2
And tricyclic norbornenes such as -ene. Further, substituted products of these norbornenes substituted with polar groups such as halogen, hydroxyl group, ester group, alkoxy group, cyano group, amide group, imide group and silyl group (for example, 5-methoxycarbonylbicyclo [2.2] .1] Hept-2-ene, 5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1]
Hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-5-enyl-2-methylpropionate, bicyclo [2.2.1] Hept-5-enyl-2-methyloctanoate, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, 5-hydroxymethylbicyclo [2. 2.1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.
2.1] Hept-2-ene, 5-hydroxy-i-propylbicyclo [2.2.1] hept-2-ene, 5,6
Norbornene derivatives having a substituent containing an oxygen atom such as -dicarboxybicyclo [2.2.1] hept-2-ene; 5-cyanobicyclo [2.2.1] hept-2-ene
Ene, bicyclo [2.2.1] hept-2-ene-5,
Norbornene derivatives having a substituent containing a nitrogen atom such as 6-dicarboxylic imide). Among these, those having no polar group are preferable, and tricyclo [4.3.1 ^2,5 . [ ^1,6 ] deca-3,7-diene is particularly preferred.

These bicyclic norbornenes and tricyclic norbornenes are used alone or in combination of two or more. In particular, a tricyclic norbornene alone or a mixture with a bicyclic norbornene containing a large proportion of tricyclic norbornenes is preferable. That is, the amount of tricyclic norbornenes in the total amount of bicyclic and tricyclic norbornenes is preferably 50% by weight or more, more preferably 60% by weight or more, and particularly preferably 70% by weight.
Not less than 100% by weight.

The components other than these bicyclic and / or tricyclic norbornenes in the norbornene monomer are not particularly limited as long as they are copolymerizable monomer components.
Normally, tetracyclic or more norbornenes can be used. Examples of tetracyclic or more norbornenes include tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dode-3-ene (also simply referred to as tetracyclododecene), 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-ethyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-methylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-Dodeca-
3-ene, 8-ethylidenetetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -dodec-3-ene, 8-vinyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodeca-3
-Ene, 8-propenyl-tetracyclo [4.4.0.
^12.5 . 4-cyclic norbornenes having a tetracyclododecene (tetracyclic) structure such as 1 ^7,10 ] -dodec-3-ene; 8-cyclopentyl-tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 .
1 ^{7,1 0]} - dodeca-3-ene, 8-cyclohexenyl -
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . ^Pentacyclic norbornenes having a tetracyclododecene ring structure and an alicyclic or aromatic ring such as ^1,7,10 ] -dode-3-ene; tetracyclo [7.
4.0.1 ^10,13 . 0 ^2,7 ] -Trideca-2,4,6,1
1-tetraene (1,4-methano-1,4,4a, 9a
- also referred tetrahydrofluorene), tetracyclo [8.4.0.1 ^11,14. 0 ^3,8 ] -tetradeca-3,
5,7,12-tetraene (1,4-methano-1,4,4)
Pentacyclic norbornenes having a norbornene ring structure other than a tetracyclododecene ring and an aromatic ring, such as 4a, 5,10,10a-hexahydroanthracene;
Pentacyclo [6.5.1.1 ^3,6 ... Which is a trimer and pentacyclic monomer of cyclopentadiene. 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene and pentacyclo [7.
4.0.1 ^3,6 . 1 ^10,13 . 0 ^2,7 ] pentadeca-4,1
1-diene; cyclopentadiene tetramer or higher adduct, and the like.

The norbornenes having 4 or more rings are the above 4
Derivatives having a cyclic group or more of norbornenes having a polar group (for example, 8-methoxycarbonyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -dodec-3-ene, 8-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
Dodeca-3-ene, 8-carboxytetracyclo [4.
4.0.1 ^2,5 . ^{Tetracyclododecene} derivatives having a substituent containing an oxygen atom such as [ ^17,10 ] -dode-3-ene). Among these tetracyclic or more norbornenes, those having no polar group are preferable because the dielectric loss tangent and the dielectric constant are highly balanced.

Norbornenes (bicyclic and / or 3
Bicyclic and / or tricyclic norbornenes are preferably 50% by weight or more, the sum of the cyclic norbornenes and the optional tetracyclic or more norbornenes).
It is more preferably at least 60% by weight, particularly preferably at least 70% by weight, and at most 100% by weight. When in such a range, properties such as induction tangent, impact resistance, heat resistance and elongation are highly balanced and good.

Among norbornene monomers (total of monomers), norbornenes (bicyclic and / or tricyclic and 4
The combined amount of the ring and the ring) is preferably 70% by weight, more preferably 80% by weight or more, particularly preferably 90% by weight or more and 100% by weight or less. When it is in such a range, the activity of the ring-opening polymerization reaction is high, which is preferable.

The norbornene-based monomer can be copolymerized with another monomer. Other copolymerizable monomers include α-olefins having 2 to 12 carbon atoms, such as ethylene, propylene, 1-butene and 4-methyl-1-pentene; styrene, α-methylstyrene, p- Styrenes such as methylstyrene and p-chlorostyrene;
Linear or branched dienes such as 3-butadiene, 1,4-butadiene and isoprene; ethyl vinyl ether;
Vinyl ethers such as isobutyl vinyl ether; cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene monocyclic cycloolefin monomers; 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, And non-conjugated cyclic diene monomers such as 1,3-cyclooctadiene.

The above norbornene-based monomer is subjected to ring-opening polymerization by a known method using a metathesis ring-opening polymerization catalyst system. The metathesis ring-opening polymerization catalyst system comprises a main catalyst and an activator, and is used in combination with a reaction modifier if necessary.

The norbornene-based ring-opened polymer obtained as a result of the ring-opening polymerization has an unsaturated bond remaining in the molecule, and the unsaturated bond lowers the weather resistance stability and thermal stability of the norbornene-based ring-opened polymer. May be. For the purpose of improving this, 80% or more, preferably 90% or more of the unsaturated bond is saturated and used by hydrogenation. Known hydrogenation methods and hydrogenation catalysts can be employed.

The molecular weight of the hydrogenated product of the norbornene-based ring-opening polymer is appropriately selected. Gel permeation chromatography of a cyclohexane solution (a toluene solution when the hydride of the norbornene-based ring-opening polymer is not dissolved) is used. The number average molecular weight (in terms of polyisoprene) measured by the (GPC) method is usually from 3,000 to 200,000, preferably from 5,000 to 100,000, particularly preferably from 1 to 100,000.
It is in the range of from 000 to 80,000. When the molecular weight is in this range, mechanical strength such as impact resistance and molding workability are excellent, which is preferable.

The glass transition temperature (Tg) of the hydride of the norbornene-based ring-opening polymer may be appropriately selected, but is preferably higher.
The resin is preferably in an appropriate temperature range since the resin becomes hard and mechanical strength such as impact resistance decreases.
The lower limit of the Tg range is usually 30 ° C. or higher, preferably 50 ° C.
° C or higher, more preferably 60 ° C or higher, most preferably 7 ° C or higher.
0 ° C. or higher, and the upper limit of the Tg range is usually 140 ° C. or lower, preferably 120 ° C. or lower, more preferably 110 ° C.
Or less, most preferably 100 ° C. or less. The hydride of the norbornene-based ring-opening polymer can be used alone or in combination of two or more.

(Ii) 5- to 8-membered saturated cyclic in the repeating unit
Hydrocarbon polymer having a molecular structure A part or all of the repeating units are a hydrocarbon having a saturated cyclic molecular structure of a carbon-carbon 5- to 8-membered ring connected by a 1,4-bond and / or a 1,2-bond Examples of the polymer include a polymer hydride described in JP-A-7-258362. Preferred specific examples of such a polymer hydride include 5 to 8 such as 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene and 1,3-cyclooctadiene.
And hydrides of polymers and copolymers of cyclic conjugated dienes having a six-membered carbon ring.

Other monomers copolymerizable with the cyclic conjugated diene having a 5- to 8-membered carbon ring include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3 Chain conjugated diene monomers such as pentadiene and 1,3-hexadiene, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-
tert-butylstyrene, 1,3-dimethylstyrene, divinylbenzene, vinylnaphthalene, diphenylethylene, vinyl aromatic monomers such as vinylpyridine, methyl methacrylate, methyl acrylate, acrylonitrile, methyl vinyl ketone, α-cyano Examples thereof include polar vinyl monomers such as methyl acrylate, and polar monomers such as ethylene oxide, propylene oxide, cyclic lactone, cyclic lactam, and cyclic siloxane, or ethylene monomers and α-olefin monomers.
The proportion of these copolymerizable monomers is at most 50% by weight, preferably at most 60% by weight.

As the hydrogenation method and the hydrogenation catalyst for the above-mentioned polymer and copolymer of the cyclic conjugated diene having a 5- to 8-membered carbon ring, known ones can be employed. The molecular weight of the hydride is usually 5,000 to 1,000,000, preferably 1 as an average molecular weight in terms of polystyrene measured by the GPC method of a 1,2,4-trichlorobenzene solution.
It is between 000 and 500,000.

(Iii) Vinyl group-containing cyclic hydrocarbon monomer
Body polymers hydride addition, other examples of thermoplastic hydrocarbon polymers, JP 6
A polymer of a vinyl group-containing cyclic hydrocarbon monomer described in JP-A-199950 or a hydride thereof.

Examples of the vinyl group-containing cyclic hydrocarbon monomer used to obtain this polymer include vinylcyclopentane monomers such as vinylcyclopentane and isopropenylcyclopentane, 4-vinylcyclopentene, Vinyl group-containing five-membered hydrocarbon-based monomers such as vinylcyclopentene-based monomers such as 2-methyl-4-isopropenylcyclopentene; styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, −
Styrene monomers such as phenylstyrene; vinylcyclohexane monomers such as vinylcyclohexane and 3-methylisopropenylcyclohexane; 4-vinylcyclohexene; 4-isopropenylcyclohexene;
Methyl-4-vinylcyclohexene, 1-methyl-4-
Vinylcyclohexene monomers such as isopropenylcyclohexene, 2-methyl-4-vinylcyclohexene, 2-methyl-4-isopropenylcyclohexene, d-
6-membered ring-containing hydrocarbon monomer containing vinyl group such as terpene monomer such as terpene, 1-terpene and diterpene; vinylcycloheptane monomer such as vinylcycloheptane and isopropenylcycloheptane; 4-vinyl Examples include vinyl group-containing hydrocarbon monomers such as vinylcycloheptene monomers such as cycloheptene and 4-isopropenylcycloheptene. Among them, a six-membered ring hydrocarbon monomer is preferable. However, as described below, a monomer containing no aromatic ring is preferable, and when a styrene-based monomer containing an aromatic ring is used, it is preferable that substantially no aromatic ring remains by a hydrogenation reaction. preferable.

Further, monomers other than the vinyl group-containing cyclic hydrocarbon monomer may be copolymerized in a small proportion (generally, a range in which the repeating unit in the polymer is less than 10% by weight). Examples of the copolymerizable monomer include α, such as ethylene, propylene, isobutene, 2-methyl-1-butene, 2-methyl-1-butene, 2-methyl-1-pentene, and 4-methyl-1-pentene. -Olefinic monomers; cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5-
Cyclopentadiene monomers such as methylcyclopentadiene and 5,5-dimethylcyclopentadiene; cyclic olefin monomers such as cyclobutene, cyclopentene, cyclohexene and dicyclopentadiene; butadiene, isoprene, 1,3-pentadiene, furan, Conjugated diene monomers such as thiophene and 1,3-cyclohexene; cyclic ether monomers such as ethylene oxide, propylene oxide, trimethylene oxide, trioxane, dioxane, cyclohexene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran; methyl vinyl ether , N-vinylcarbazole, N-vinyl-2-pyrrolidone, and other heterocyclic-containing vinyl compound-based monomers.

The polymerization method and the hydrogenation method of the vinyl group-containing cyclic hydrocarbon monomer or the monomer copolymerizable with the vinyl group-containing cyclic hydrocarbon monomer are not particularly limited, and are not particularly limited. It can be done according to the method. Further, the obtained polymer or polymer hydrogenated product is described in JP-A-3-95235.
Α, β by a known method disclosed in
-It may be modified with unsaturated carboxylic acids and / or derivatives thereof, styrenic hydrocarbons, organosilicon compounds having olefinic unsaturated bonds and hydrolyzable groups, unsaturated epoxy monomers and the like.

The molecular weight of the hydride of the polymer of the vinyl group-containing cyclic hydrocarbon monomer can be appropriately selected according to the purpose of use, and the bicyclic and / or tricyclic norbornenes can be selected. Of the ring-opened polymer described above.

If the molecular weight of the thermoplastic hydrocarbon polymer is excessively small, the mechanical strength is not sufficient, and in some cases, the shape of the molded article cannot be maintained. Conversely, if the molecular weight is excessively large, the moldability is insufficient. None is not preferred. The molecular weight distribution of the thermoplastic hydrocarbon polymer is not particularly limited.
Weight average molecular weight (M) in terms of polystyrene measured by permeation chromatography (GPC)
w) and the number average molecular weight (Mn) ratio (Mw / Mn) is
Usually, when it is 4.0 or less, preferably 3.0 or less, and more preferably 2.5 or less, the workability is highly enhanced and suitable.

The glass transition temperature (Tg) of the thermoplastic hydrocarbon polymer may be appropriately selected according to the purpose of use, and is usually 30 to 300 ° C., preferably 50 to 250 ° C.
More preferably, the range is 100 to 200 ° C.
The above thermoplastic hydrocarbon polymers can be used alone or in combination of two or more.

Thermoplastic Elastomer The thermoplastic elastomer used in the present invention has a high molecular weight and a low degree of unsaturation. The molecular weight of the thermoplastic elastomer is determined by
Weight average molecular weight (M) in terms of polystyrene measured by permeation chromatography (GPC)
w), in the range of 100,000 to 1,000,000, preferably 150,000 to 500,000, more preferably 200,000 to 400,000. If the molecular weight of the thermoplastic elastomer is too small, the processing characteristics such as tensile strength and elongation are not sufficient, and if it is too large, the heat resistance is not sufficient, and neither is preferable.

The iodine value of the thermoplastic elastomer is 50
g / 100 g or less, preferably 20 g / 100 g or less,
The value is more preferably 10 g / 100 g or less. If the iodine value of the thermoplastic elastomer is excessively high, electrical properties such as dielectric loss tangent, durability and weather resistance of the resulting composition are undesirably reduced. Specific examples of the thermoplastic elastomer are not particularly limited as long as the above conditions are satisfied. However, aromatic vinyl thermoplastic elastomers are generally preferable because they have excellent compatibility with the thermoplastic hydrocarbon polymer. .

Examples of the aromatic vinyl thermoplastic elastomer include hydrogenated aromatic vinyl-conjugated diene block copolymers such as hydrogenated styrene-butadiene block copolymer and hydrogenated styrene-isoprene block copolymer; Examples thereof include aromatic vinyl-grafted olefin-based rubbers such as a grafted ethylene-propylene elastomer, and a hydrogenated aromatic vinyl-conjugated diene block copolymer is preferable.

The styrene content of the styrene-based thermoplastic elastomer is appropriately selected depending on the purpose of use, but is usually in the range of 5 to 60% by weight, preferably 10 to 50% by weight, more preferably 15 to 40% by weight. It is. When the styrene content of the hydrogenated styrene-based thermoplastic elastomer is in this range, the compatibility with the thermoplastic norbornene-based resin is excellent, and the tensile strength and elongation are highly balanced, which is preferable.

These thermoplastic elastomers are used alone or in combination of two or more. The blending amount of the thermoplastic elastomer is appropriately selected according to the purpose of use, and is usually 5 to 100 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the thermoplastic hydrocarbon polymer.
-60 parts by weight, more preferably 15-40 parts by weight. When the amount of the thermoplastic elastomer is in this range, the dielectric tangent, heat resistance, tensile strength, impact strength, and elongation characteristics are highly balanced and suitable.

Optional Components In addition to the above components, the thermoplastic hydrocarbon polymer composition of the present invention may further contain, if necessary, other thermoplastic resins, lubricants, oxidation stabilizers, ultraviolet absorbers, crystal nucleating agents, Antistatic agents and other compounding agents commonly used in hydrocarbon polymer compositions can be added.

(1) Other thermoplastic resins Examples of other thermoplastic resins include low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, polypropylene, syndiotactic polypropylene, polybutene, and the like. Polyolefins such as polypentene; polyethylene terephthalate,
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 ether, polyamide, polyester, polycarbonate And the like. These other thermoplastic resins can be used alone or in combination of two or more, and the blending amount is appropriately selected within a range not to impair the object of the present invention.

(2) Lubricant As the lubricant, inorganic fine particles can generally be used. Here, as the inorganic fine particles, group 1 of the periodic table,
Tribes, four, six, seven, eight to ten, eleven, twelve,
Oxides, hydroxides, sulfides, nitrides, halides, carbonates, sulfates, acetates, phosphates, phosphites, organic carboxylate, silicate, titanate of Group 13 and 14 elements , Borate and hydrated compounds thereof, composite compounds centered on them, and particles of natural minerals.

Specific examples of the inorganic fine particles include Group 1 element compounds such as thylium fluoride and borax (sodium borate hydrate); magnesium carbonate, magnesium phosphate, magnesium oxide (magnesia), magnesium chloride, magnesium acetate, and 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, Group 2 elements such as calcium titanate, strontium titanate, barium titanate, zinc titanate, lanthanum titanate, bismuth titanate, lead titanate, barium carbonate, barium phosphate, barium sulfate, barium phosphite Compounds; titanium dioxide (titania),
Group 4 element compounds such as titanium monoxide, titanium nitride, zirconium dioxide (zirconia), zirconium monoxide;
Group 6 element compounds such as molybdenum dioxide, molybdenum trioxide and molybdenum sulfide; Group 7 element compounds such as manganese chloride and manganese acetate; Group 8 to 10 element compounds such as cobalt chloride and cobalt acetate; 11 such as cuprous iodide Group 12 element compounds; Group 13 element compounds such as zinc oxide and zinc acetate; aluminum oxide (alumina), aluminum hydroxide, aluminum fluoride, aluminosilicate (alumina silicate, kaolin, kaolinite); silicon oxide (Silica, silica gel), graphite, carbon, graphite, glass and other Group 14 element compounds, kernalite, kainite, mica (mica, kinunmo),
Fine particles of natural minerals such as byrose ore. The average particle size of the inorganic fine particles used here is not particularly limited, but is preferably selected appropriately in the range of 0.01 to 3 μm according to the purpose of use.

These lubricants can be used alone or in combination of two or more. The amount of the lubricant used is appropriately selected according to the purpose of use, but is usually 0.001 parts by weight based on 100 parts by weight of the thermoplastic hydrocarbon polymer.
5 to 5 parts by weight, preferably 0.005 to 3 parts by weight, depending on the purpose of use.

(3) Antioxidant Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Of these, phenol-based antioxidants are preferred. Particularly preferred are alkyl-substituted phenolic antioxidants. As the phenolic antioxidant, conventionally known phenolic antioxidants can be used. For example, 2-t-butyl-6- (3-t
-Butyl-2-hydroxy-5-methylbenzyl) -4
JP-A-63-179953 such as -methylphenyl acrylate and 2,4-di-t-amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate And Japanese Patent Laid-Open No. 1-1
Acrylate compounds described in 68643;
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'-hydroxyphenyl) propionate) methane [that is, pentaerythryl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]], triethylene glycol bis (3- (3-tert-butyl-4-hydroxy-5
Alkyl-substituted phenolic compounds such as -methylphenyl) propionate) and tocopherol; 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4
-Bis-octylthio-1,3,5-triazine, 6-
(4-hydroxy-3,5-dimethylanilino) -2,
4-bis-octylthio-1,3,5-triazine, 6
-(4-hydroxy-3-methyl-5-tert-butylanilino) -2,4-bis-octylthio-1,3,5-triazine, 2-octylthio-4,6-bis- (3,5
-Di-t-butyl-4-oxyanilino) -1,3,5
-A phenolic compound containing a triazine group such as triazine.

The phosphorus-based antioxidant is not particularly limited as long as it is generally used in the general resin industry. For example, triphenyl phosphite, diphenyl isodecyl phosphite, 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 (C
12-C15) phosphite), 4,4'-isopropylidene-bis (diphenylmonoalkyl (C12-C1
5) phosphite), 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, tetrakis (2,4-di-t-butylphenyl)- 4,4′-biphenylene phosphite,
Cyclic neopentanetetraylbis (octadecylphosphite), cyclic neopentanetetraylbis (isodecylphosphite), cyclic neopentanetetraylbis (nonylphenylphosphite), cyclic neopentanetetraylbis (2 ,
4-di-t-butylphenyl phosphite), cyclic neopentanetetraylbis (2,4-dimethylphenylphosphite), cyclic neopentanetetraylbis (2,6-di-t-butylphenylphosphite) ) And the like. Among these, monophosphite compounds are preferable, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, and tris (2,4-
Di-t-butylphenyl) phosphite and the like are particularly preferred.

Examples of the sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3 , 3'-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl)-
2,4,8,10-tetraoxaspiro [5,5] undecane and the like.

These antioxidants are each used alone.
Alternatively, two or more kinds can be used in combination.
The compounding amount of the antioxidant is 100 ppm of the thermoplastic hydrocarbon polymer.
It is usually in the range of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight based on parts by weight.

(4) Ultraviolet ray inhibitor As an ultraviolet ray absorber, for example, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis (2,2)
2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxy) Benzyl) -2-n-butylmalonate, 4-
(3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) -1- (2- (3- (3,
Hindered amine ultraviolet absorbers such as 5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -2,2,6,6-tetramethylpiperidine;
2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3-t-butyl-2-hydroxy-
5- (methylphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3
Benzotriazole ultraviolet absorbers such as 5-di-t-amyl-2-hydroxyphenyl) benzotriazole; 2,4-di-t-butylphenyl-3,5-di-t
Benzoate ultraviolet absorbers such as -butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate;

These ultraviolet absorbers can be used alone or in combination of two or more. The blending amount of the ultraviolet absorber is usually in the range of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the thermoplastic hydrocarbon polymer.

(5) Crystal nucleating agent Examples of the crystal nucleating agent include salts of benzoic acid, dibenzylidene sorbitols, salts of phosphate esters, polyvinylcyclohexane, poly-3-methylbutene, crystalline polystyrenes, trimethylvinylsilane and the like. Polymers having a high melting point are preferred, and talc, kaolin,
Inorganic compounds such as mica can also be preferably used. These nucleating agents can be used alone or in combination of two or more. The amount used is usually in the range of 0.0001 to 1% by weight.

(6) Antistatic agent Examples of the antistatic agent include sodium alkylsulfonate and / or phosphonium alkylsulfonate and fatty acid ester hydroxyamine compounds such as glycerin ester of stearic acid. Can be. These antistatic agents can be used alone or in combination of two or more. The compounding amount of the antistatic agent is 100% of the thermoplastic norbornene resin.
It is usually in the range of 0 to 5 parts by weight with respect to parts by weight.

(7) Other compounding agents Other compounding agents include, for example, hydrochloric acid absorbents such as zinc stearate; pigments; dyes; antiblocking agents; natural oils, synthetic oils, waxes, fatty acid metal salts (stearic acid). Lubricants such as zinc, calcium stearate, calcium 1,2-hydroxystearate, etc., polyhydric alcohol fatty acid esters (glycerin monostearate, glycerin distearate, pentaerythritol distearate, pentaerythritol tristearate, etc.); flame retardants And the like. These compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not to impair the object of the present invention.

Thermoplastic Hydrocarbon Polymer Composition The thermoplastic hydrocarbon polymer composition of the present invention is prepared by mixing a thermoplastic hydrocarbon polymer, a thermoplastic elastomer and, if necessary, the above-mentioned various components according to a conventional method. Obtainable. Specifically, for example, a method of kneading the resin in a molten state using a ribbon blender, a Henschel mixer, a twin-screw kneader, or the like can be given.

The thermoplastic hydrocarbon polymer composition of the present invention can be formed into various molded articles by a usual molding method such as injection molding, press molding, extrusion molding, and rotational molding. Transparent or translucent molded products can be obtained by selecting the compounding agents, etc., which have excellent mechanical strength such as impact resistance, high moisture and water vapor permeability, and excellent permeation solvent resistance. Molded products for medical applications such as through packages, disposable syringes, chemical vials, and infusion bags; Molded products for electric or electronic materials such as wire coatings and wafer shippers; Building materials such as carports and glazings; wrap films, stretch films, shrinks It is suitable for packaging films such as films and blister packs; stationery such as ballpoint pen cores.

The thermoplastic hydrocarbon polymer composition of the present invention can provide a transparent or translucent molded product even when formed into a thin film or sheet, has excellent mechanical strength such as impact resistance, and has excellent water and water vapor. Has low transmittance and excellent solvent permeation resistance. Therefore, it can be used as a press-through package with excellent moisture-proof properties by forming it into a film or sheet by extrusion or the like and then stretching it as necessary, and furthermore, because it can be heat sealed, it can be used as a film for packaging chemicals. is there. In addition, because it has self-adhesiveness, it is used as a wrap film or stretch film, because of its transparency and low birefringence, it is used as a deflecting film and as a different phase difference film, and because it has excellent strength, it is used as a highway translucent plate, vending machine panel, carport Or because of its excellent weather resistance, it is suitable as a reflective film or a marking film.

In particular, the thermoplastic hydrocarbon polymer composition of the present invention has a dielectric loss tangent, dielectric constant, heat resistance, and tensile strength,
Since properties such as impact resistance are good and well-balanced, they are particularly useful as dielectric films and film capacitors. Hereinafter, the dielectric film and the film capacitor will be described.

Dielectric Film There is no particular limitation on the method for producing a dielectric film using the thermoplastic hydrocarbon polymer composition of the present invention. For example, these materials are heated and melted to form a preform. Can be used, for example, by heat-stretching and, if necessary, heat-setting.

The procedure from the heat-melting to the heat-setting is as follows. First, the thermoplastic hydrocarbon polymer composition is used as a molding material, which is usually extruded to obtain a preform for stretching (film, sheet or tube). ). In this molding, it is general to mold the above-mentioned molding material which has been heated and melted into a predetermined shape by an extruder, but it is also possible to mold the molding material in a softened state without being heated and melted. .
The extruder used here may be either a single-screw extruder or a twin-screw extruder, and may be either with or without vent. If an appropriate filter is used for the extruder, impurities and foreign substances can be removed. The shape of the filter can be appropriately selected and used, such as a flat plate shape or a cylindrical shape. The extrusion conditions are not particularly limited and may be appropriately selected according to various situations. Preferably, the temperature is selected from the range of (the melting point of the molding material) to (the temperature 50 ° C. higher than the decomposition temperature), and the Is 5 × 106 dyne /
cm ² or less. Examples of the die used include a T die and a ring die.

After the extrusion molding, the obtained preform for stretching is cooled and solidified. Various refrigerants such as a gas, a liquid, and a metal roll can be used for cooling. When using metal rolls, air knives, air chambers,
According to a method such as a touch roll or electrostatic imprinting, it is effective in preventing thickness unevenness and waving. The temperature for cooling and solidifying is usually 0 ° C. to (30 ° C. below the glass transition temperature of the preform for stretching.
(Temperature lower by 70 ° C. than the glass transition temperature) to (glass transition temperature).
The cooling rate is appropriately selected in the range of 200 ° C./sec to 3 ° C./sec.

The obtained dielectric film is preferably uniaxially or biaxially stretched from the cooled and solidified preform. In the case of biaxial stretching, stretching may be performed simultaneously in the machine direction and the transverse direction, or may be performed sequentially in any order. Stretching may be performed in one step or may be performed in multiple steps. The stretching ratio is 1.2 times or more, preferably 1.5 times or more in terms of area ratio. As a stretching method, various methods such as a method using a tenter, a method of stretching between rolls, a method of bubbling using gas pressure, and a method of rolling can be used, and these may be appropriately selected or combined and applied.
The stretching temperature may generally be set between the glass transition temperature and the melting point of the preform. The stretching speed is usually 1 × 10
１1 × 10 ⁵ % / min, preferably 1 × 103 to 1 × 10 ⁸
% / Min.

When the stretched film obtained by stretching under the above-mentioned conditions requires further dimensional stability at high temperature, heat resistance, and strength balance in the film plane, heat fixing is performed. Is preferred. The heat setting can be carried out by a conventional method. Usually, the stretched film is stretched under a tensioned state, a relaxed state or a limited shrinkage state, in a range of (glass transition temperature) to (melting point), preferably (melting point). More 1
In the range of (00 ° C lower temperature) to (temperature just before the melting point)
This is performed by holding for about 0.5 to 120 seconds. The heat setting can be performed twice or more by changing the conditions within the above range. This heat setting may be performed in an atmosphere of an inert gas such as an argon gas or a nitrogen gas.

The thickness of the dielectric film is not particularly limited. For example, in the case of a film capacitor, it may be appropriately selected according to the specifications such as its type, size, and performance. For example, in the case of a wound-type film capacitor, its thickness is generally in the range of 0.1 to 50 μm, preferably 0.3 to 30 μm, and more preferably 0.5 to 10 μm. When the thickness of the dielectric film is in this range, the size and strength of the capacitor are appropriately balanced,
It is suitable.

The dielectric constant of the dielectric film is appropriately selected according to the purpose of use, but is usually in the range of 0.1 to 100, preferably 1 to 50, and more preferably 2 to 10. When the dielectric constant is in this range, the capacitor capacity and the dielectric loss are highly balanced and suitable. The dielectric loss tangent of the dielectric film is small, usually 0.01 or less, preferably 0.001 and more preferably 0.0005 or less.
If the dielectric loss tangent is too large, the dielectric loss is large, which is not preferable.

The tensile strength and elongation of the dielectric film are highly balanced, and the tensile strength is usually 6 kgf / mm.
² or more, preferably 7 kgf / mm ² or more, and
The elongation is at least 8%, preferably at least 10%. The heat resistance of the dielectric film is sufficiently high and the softening temperature is usually 5
The temperature is in the range of 0 to 300 ° C, preferably 70 to 250 ° C, more preferably 100 to 200 ° C. The water absorption of the dielectric film is sufficiently low, usually 0.1% or less, preferably 0.05% or less, more preferably 0.01% or less. If the water absorption is excessively high, the dielectric loss tangent deteriorates and the dielectric loss increases, which is not preferable.

Film Capacitor A film capacitor can be obtained by laminating an electrode layer on the above dielectric film. Depending on the type of the film capacitor, the electrode layers may be laminated on both sides, or may be laminated on only one side. The film may be laminated on the entire surface or partially. When manufacturing a general wound film capacitor, an electrode layer is laminated on the entire surface of one side of the film.

The electrode layer is not particularly limited, but is generally a layer made of a conductive metal such as aluminum, zinc, gold, platinum, and copper, and is laminated as a metal foil or a vapor-deposited metal film. In the present invention, either the metal foil or the vapor-deposited metal coating may be used, or both may be used in combination. Since the electrode layer can be thinned, the capacity can be increased with respect to the volume, the adhesion to the dielectric is excellent, and the thickness variation is small. Is preferred.

When using a vapor-deposited metal film as the electrode layer,
The method for forming the coating is not particularly limited, and for example, a vacuum evaporation method, a sputtering method, an ion plating method, or the like is employed. The deposited metal film is not limited to a single layer. For example, a method in which a semiconductor aluminum oxide layer is further formed on an aluminum layer to provide moisture resistance to provide an electrode layer (for example, JP-A-2-250306) For example, a multilayer may be used as necessary. The thickness of the deposited metal coating is
Although not particularly limited, it is preferably in the range of 100 to 2,000 angstroms, and more preferably in the range of 200 to 1,000 angstroms. When the thickness of the vapor-deposited metal coating is within this range, the capacity and strength of the capacitor are balanced, which is preferable. Even when using a metal foil as the electrode layer, the thickness of the metal foil is not particularly limited, but usually,
The range is 0.1 to 100 μm, preferably 1 to 50 μm, and more preferably 3 to 15 μm.

As a structure of a film capacitor, for example, a laminated type in which electrode layers and dielectric films are alternately laminated (JP-A-63-181411, JP-A-3-1811)
No. 13) and a wound type in which a tape-shaped dielectric film and an electrode layer are wound (Japanese Patent Application Laid-Open No. Sho 60-262414 where the electrodes are not continuously laminated on the dielectric film). And those disclosed in JP-A-3-286514, in which electrodes are continuously laminated on a dielectric film. The manufacturing method differs depending on each structure. Film capacitors are not limited by structure and manufacturing method.

In the case of a wound type film capacitor having a simple structure and relatively easy to manufacture, in which electrodes are continuously laminated on a dielectric film, a dielectric film generally having electrodes laminated on one side is generally used. Are stacked and wound so that the electrodes do not come into contact with each other. Usually, after getting involved, fix it so that it will not be loosened. The fixing method is not particularly limited. For example, the fixing and the protection of the structure may be performed simultaneously by sealing with a resin or enclosing in an insulating case or the like. The connection method of the lead wire is not limited, and examples include welding, ultrasonic pressure welding, heat pressure welding, and fixing with an adhesive tape. A lead wire may be connected to the electrode before being wound. The opening may be sealed with a thermosetting resin such as a urethane resin or an epoxy resin to prevent oxidative deterioration or the like, if necessary, for example, when enclosing in an insulating case.

When a metal thin film layer is formed on a film,
The surface of the film may be previously subjected to a treatment for improving adhesiveness such as a corona treatment or a plasma treatment. Next, if necessary, an end surface conductive treatment, a lead wire attaching,
A capacitor is formed by forming a jacket. Further, the capacitor may be impregnated with oil, an electrolytic solution, or the like to form a so-called immersion capacitor. The film capacitor obtained as described above has a small temperature dependency of capacitance, is excellent in heat resistance, has a wide operating temperature range, is excellent in volumetric efficiency, and is suitably used as a temperature-compensated capacitor. .

[0070]

EXAMPLES The present invention will be described more specifically with reference to Reference Examples, Examples and Comparative Examples. In addition, the measuring method of physical properties etc. is as follows. (1) Molecular weight and molecular weight distribution The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of a thermoplastic hydrocarbon polymer were measured by gel permeation chromatography (GPC) using cyclohexane as a solvent, unless otherwise specified. ) Method, and was measured as a polyisoprene conversion value. The weight average molecular weight (Mw) of the thermoplastic elastomer was measured as a polystyrene equivalent value by a GPC method using toluene as a solvent, unless otherwise specified.

(2) Glass transition temperature (Tg) The glass transition temperature (Tg, ° C.) was measured using a differential scanning calorimeter (DS).
It measured using C). (3) Hydrogenation rate The hydrogenation rate (%) of carbon-carbon unsaturated bonds in the main chain is ¹
It was measured by 1 H-NMR.

(4) Iodine value The iodine value (g / 100 g) was measured according to JIS K0070B. (5) Amount of bound styrene The amount of bound styrene (% by weight) was measured according to JIS K6383. (6) Refractive index The refractive index was measured at 25 ° C. in accordance with ASTM-D542.

(7) Physical Properties of Film The physical properties of the film were determined according to JIS C2330 [dielectric constant, dielectric loss tangent (1 kHz), tensile strength and elongation], JIS K7
196 (softening temperature), measured at 25 ° C. according to JIS K7209 (water absorption). (8) Physical Properties of Film Capacitor The physical properties of the film capacitor were determined according to JIS C5102 [compensation temperature, dielectric loss tangent (10 kHz), and dielectric loss (85
° C)].

Reference Example 1 In a nitrogen atmosphere, tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (tricyclic norbornenes, common name dicyclopentadiene, manufactured by Zeon Corporation, purity: 95% by weight) % Or more (hereinafter abbreviated as DCP) of 100 parts by weight using a known metathesis ring-opening polymerization catalyst system, followed by hydrogenation by a known method to obtain a hydrogenated product of a DCP ring-opening polymer. This hydrogenated product of the DCP ring-opening polymer is obtained by using G in cyclohexane as a solvent.
The number average molecular weight Mn measured by the PC method in terms of polyisoprene was 13,000. The hydrogenated DCP ring-opening polymer was dried by a known method. Compared before and after the hydrogenation reaction, the hydrogenation rate is 99.8% or more, and Tg is 97
° C and the refractive index was 1.5230). This pellet 1
0.2 parts by weight to 00 parts by weight of the phenolic antioxidant pentaerythritol-tetrakis (3- (3,5
-Di-tert-butyl-4-hydroxyphenyl)
Propionate) was mixed and kneaded with a twin-screw kneader, and a strand (rod-shaped molten resin) was passed through a strand cutter to obtain a pellet (granular) molding material. The glass transition temperature of the pellet was 96 ° C.

Reference Example 2 Instead of 100 parts by weight of DCP, 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (tetracyclic norbornenes, hereinafter abbreviated as MTCD) 5 parts by weight, dicyclo [2.2.1] -hept-2-ene (bicyclic norbornenes, hereinafter NB) Abbreviation) 15 parts by weight and DC
A hydrogenated MTCD / NB / DCP ring-opening copolymer was obtained in the same manner as in Reference Example 1 except that P80 parts by weight (total 100 parts by weight) was used. When the copolymerization ratio of each norbornene in the polymer was calculated from the residual norbornene composition (by gas chromatography) in the solution after polymerization,
MTCD / NB / DCP = 5/15/80 was almost equal to the charged composition. The hydrogenated MTCD / NB / DCP ring-opened polymer had Mn of 14,000, a hydrogenation rate of 99.8% or more, and a glass transition temperature (Tg) of 81.
° C.

Reference Example 3 Instead of 100 parts by weight of DCP, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene (tetracyclic norbornenes, hereinafter abbreviated as ETCD) ETCD / DCP in the same manner as in Reference Example 1 except that 30 parts by weight and DCP 70 parts by weight (total 100 parts by weight) were used. A hydrogenated ring-opening copolymer was obtained. When the copolymerization ratio of each norbornene in the polymer was calculated from the composition of the residual norbornene in the solution after polymerization (by gas chromatography), it was almost equal to the charged composition at ETCD / DCP = 30/70. The hydrogenated ETCD / DCP ring-opening polymer had Mn of 13,000 and had a hydrogenation rate of 99.8%.
As described above, the glass transition temperature (Tg) was 110 ° C.

Example 1 A hydrogenated DCP ring-opening polymer obtained in Reference Example 1 and a hydrogenated styrene-isoprene block copolymer [Septon 4055, manufactured by Kuraray Co., Ltd .; bound styrene content 30% by weight, M
w 280,000, iodine value 4 g / 100 g] at a weight ratio of 100/10 in a twin-screw kneader (manufactured by Toshiba Machine Co., Ltd., TEM35
Using B), the mixture was melted and mixed at 240 ° C. to obtain a resin composition A. This resin composition A was melted at 260 ° C. and extruded into a sheet by an extruder equipped with a T-die at the tip, and cooled to obtain a preform having a thickness of 20 μm. This preform was stretched twice at 140 ° C. in the machine direction and twice in the cross direction to obtain a film having a thickness of 5 μm. The physical properties of this film were measured, and the results are shown in Table 1.

Example 2 A hydrogenated DCP ring-opening polymer obtained in Reference Example 1 and a hydrogenated styrene-isoprene block copolymer [Kuraray Co., Ltd., Septon 4055; bound styrene content 30% by weight, M
w 280,000, iodine value 4 g / 100 g] at a weight ratio of 100/30 in a twin-screw kneader (manufactured by Toshiba Machine Co., Ltd., TEM35
Using B), the mixture was melted and mixed at 240 ° C. to obtain a resin composition B. This resin composition B was melted at 260 ° C. and extruded into a sheet by an extruder equipped with a T-die at the tip, and cooled to obtain a preform having a thickness of 20 μm. This preform was stretched twice at 140 ° C. in the machine direction and twice in the cross direction to obtain a film having a thickness of 5 μm. The physical properties of this film were measured, and the results are shown in Table 1.

Example 3 A hydrogenated product of the DCP ring-opening polymer obtained in Reference Example 1 and a hydrogenated styrene-isoprene block copolymer [Kuraray Co., Ltd., Septon 4055; bound styrene content 30% by weight, M
w 280,000, iodine value 4 g / 100 g] at a weight ratio of 100/50 in a twin-screw kneader (TEM35, manufactured by Toshiba Machine Co., Ltd.).
Using B), the mixture was melted and mixed at 240 ° C. to obtain a resin composition C. This resin composition C was melted at 260 ° C. and extruded into a sheet by an extruder equipped with a T die at the tip, and cooled to obtain a preformed body having a thickness of 20 μm. This preform was stretched twice at 140 ° C. in the machine direction and twice in the cross direction to obtain a film having a thickness of 5 μm. The physical properties of this film were measured, and the results are shown in Table 1.

Example 4 A hydrogenated DCP ring-opening polymer obtained in Reference Example 1 and a hydrogenated styrene-isoprene block copolymer [Septon 2005, manufactured by Kuraray Co., Ltd .; bound styrene content 20% by weight, M
w 270,000, iodine value 6 g / 100 g] at a weight ratio of 100/20 in a twin-screw kneader (manufactured by Toshiba Machine Co., Ltd., TEM35
Using B), the mixture was melted and mixed at 240 ° C. to obtain a resin composition D. This resin composition D was melted at 260 ° C. and extruded into a sheet by an extruder with a T-die attached to the tip, and cooled to obtain a preform having a thickness of 20 μm. This preform was stretched twice at 140 ° C. in the machine direction and twice in the cross direction to obtain a film having a thickness of 5 μm. The physical properties of this film were measured, and the results are shown in Table 1.

Example 5 A hydrogenated DCP ring-opening polymer obtained in Reference Example 1 and a hydrogenated styrene-isoprene block copolymer [Septon 4033, manufactured by Kuraray Co .; bound styrene content 30% by weight, M
w, 100,000, iodine value 5 g / 100 g] by weight ratio of 1
00/20 twin screw kneader (manufactured by Toshiba Machine, TEM35
Using B), the mixture was melted and mixed at 240 ° C. to obtain a resin composition E. This resin composition E was melted at 260 ° C. and extruded into a sheet by an extruder equipped with a T-die at the tip, and cooled to obtain a preform having a thickness of 20 μm. This preform was stretched twice at 140 ° C. in the machine direction and twice in the cross direction to obtain a film having a thickness of 5 μm. The physical properties of this film were measured, and the results are shown in Table 1.

Example 6 A hydrogenated MTCD / NB / DCP ring-opening polymer obtained in Reference Example 2 and a hydrogenated styrene-isoprene block copolymer [Septon 4055, manufactured by Kuraray Co., Ltd .; bound styrene content 30% by weight] , Mw 280,000 Iodine value 4g / 10
0g] at a weight ratio of 100/20 using a twin-screw kneader (manufactured by Toshiba Machine Co., Ltd., TEM35B) at 240 ° C to obtain a resin composition F. This resin composition F was melted at 260 ° C. and extruded into a sheet by an extruder with a T die attached to the tip, and cooled to obtain a 20 μm-thick preform. This preform was stretched twice at 140 ° C. in the machine direction and twice in the cross direction to obtain a film having a thickness of 5 μm. The physical properties of this film were measured, and the results are shown in Table 1.

Example 7 A hydrogenated ETCD / DCP ring-opening polymer obtained in Reference Example 3 and a hydrogenated styrene-isoprene block copolymer [Kuraray Co., Ltd., Septon 4055; bound styrene amount 30
Weight%, Mw 280,000 iodine value 4 g / 100 g]
At a weight ratio of 100/20 by a twin-screw kneader (Toshiba Machine Co., Ltd., T
Using EM35B), the mixture was melted and mixed at 240 ° C. to obtain a resin composition G. This resin composition G was melted at 260 ° C. and extruded into a sheet by an extruder equipped with a T-die at the tip, and cooled to obtain a preform having a thickness of 20 μm. This preform was stretched twice at 140 ° C. in the machine direction and twice in the cross direction to obtain a film having a thickness of 5 μm. The physical properties of this film were measured, and the results are shown in Table 1.

Comparative Example 1 A hydrogenated product of the DCP ring-opening polymer obtained in Reference Example 1 and a hydrogenated styrene-isoprene block copolymer [Septon 2002, manufactured by Kuraray Co., Ltd .; bound styrene content 30% by weight, M
w 24,000, iodine value 6 g / 100 g] by weight ratio of 1
00/20 twin screw kneader (manufactured by Toshiba Machine, TEM35
Using B), the mixture was melted and mixed at 240 ° C. to obtain a resin composition H. This resin composition H was melted at 260 ° C. and extruded into a sheet by an extruder equipped with a T-die at the tip, and cooled to obtain a preform having a thickness of 20 μm. This preform was stretched twice at 140 ° C. in the machine direction and twice in the cross direction to obtain a film having a thickness of 5 μm. The physical properties of this film were measured, and the results are shown in Table 1.

Comparative Example 2 The hydrogenated DCP ring-opening polymer obtained in Reference Example 1 was
With an extruder having a die attached to the tip, it was melted at 260 ° C., extruded into a sheet, and cooled to obtain a preform having a thickness of 20 μm. The preformed body is vertically stretched at 140 ° C. for 2 hours.
The film was stretched twice and twice in the transverse direction to obtain a film having a thickness of 5 μm. The physical properties of this film were measured, and the results are shown in Table 1.

[0086]

[Table 1]

Example 8 The film obtained in Example 2 was formed on a high-frequency induction heating type vacuum heating evaporator (manufactured by Nippon Vacuum Co., Ltd.) to form an aluminum layer having a thickness of 400 Å at a processing speed of 300 m / sec. The film was wound up, compressed at 170 ° C., sprayed with zinc, leaded, and packaged with an epoxy resin to prepare a capacitor. The physical properties of this capacitor were measured, and the results are shown in Table 2.

Comparative Example 3 A polypropylene film was formed with a high-frequency induction heating type vacuum heating evaporator (manufactured by Nippon Vacuum Co., Ltd.) to form an aluminum layer having a thickness of 400 Å at a processing speed of 300 m / sec. A capacitor was prepared by compression at 170 ° C., spraying with zinc, attaching a lead wire, and covering with an epoxy resin. The physical properties of this capacitor were measured, and the results are shown in Table 2.

Comparative Example 4 A polyethylene terephthalate film was treated with a high-frequency induction heating type vacuum heating evaporator (manufactured by Nippon Vacuum Co., Ltd.) to process an aluminum layer having a thickness of 400 angstroms at a processing speed of 300 m / sec.
And then wind up this metallized film,
A capacitor was prepared by compression at 170 ° C., spraying with zinc, attaching a lead wire, and covering with an epoxy resin. The physical properties of this capacitor were measured, and the results are shown in Table 2.

[0090]

[Table 2]

[0091]

According to the present invention, there is provided a thermoplastic hydrocarbon polymer composition excellent in dielectric loss tangent and heat resistance, and excellent in mechanical properties such as impact resistance, tensile strength and elongation.
This resin composition is suitable, for example, for use in a film capacitor.

Preferred Embodiments The thermoplastic hydrocarbon polymer composition of the present invention, that is, a thermoplastic hydrocarbon polymer having a monocyclic or bicyclic saturated hydrocarbon group in a repeating unit, and an iodine value of 50 g / 100 g
Below, the weight average molecular weight (Mw) is from 100,000 to 1,
The preferred embodiments of the thermoplastic hydrocarbon polymer composition containing the thermoplastic elastomer of the present invention are as follows.

(1) The thermoplastic hydrocarbon polymer having a monocyclic or bicyclic saturated hydrocarbon group in the repeating unit is represented by (i)
A hydride of a ring-opened polymer of a norbornene-based monomer containing 50% by weight or more of bicyclic and / or tricyclic norbornenes, (ii) a part or all of the repeating units are 1,4-
Polymerizing a hydrocarbon polymer having a carbon-carbon 5- to 8-membered saturated cyclic molecular structure linked by a bond and / or a 1,2-bond, and (iii) a vinyl group-containing cyclic hydrocarbon-based monomer At least one selected from polymers or hydrides thereof.

(2) A bicyclic norbornene used in the production of a hydrogenated product (i) of a ring-opening polymer of a norbornene-based monomer is substituted with a substituted or unsubstituted non-cyclic olefin or non-cyclic diene and cycloalkyl. It is an adduct of pentadiene, and more preferably has no polar group. (3) The tricyclic norbornenes used in the production of the hydride (i) of the ring-opening polymer of a norbornene-based monomer are substituted or unsubstituted cyclic olefins or adducts of cyclic dienes and cyclopentadiene. Yes, more preferably
No polar groups.

(4) The norbornene-based monomer used in the production of the hydride (i) of the ring-opened polymer of the norbornene-based monomer is a bicyclic and / or tricyclic norbornene.
0-100% by weight, more preferably 60-100% by weight
And 4 to 4 weight% norbornenes 0 to 50% by weight, more preferably 0 to 40% by weight. (5) Of the norbornene-based monomers used for producing the hydride (i) of the ring-opened polymer of the norbornene-based monomer, 2
The proportion of the cyclic norbornene and the tricyclic norbornene is based on the total weight of the two, and the bicyclic norbornene is preferably 0 to 50% by weight, more preferably 0 to 40% by weight,
The tricyclic norbornenes are 50 to 100% by weight, more preferably 60 to 100% by weight.

(6) The molecular weight of the hydride (i) of the ring-opening polymer of norbornene-based monomer is expressed as a number average molecular weight in terms of polyisoprene measured by a GPC method using cyclohexane (when not dissolved, toluene) as a solvent. 3,000-2
00,000, more preferably 5,000 to 100,0
00. (7) The glass transition temperature (Tg) of the hydride (i) of the ring-opening polymer of a norbornene-based monomer is 30 to 140 ° C, more preferably 50 to 120 ° C.

(8) Some or all of the repeating units are
A hydrocarbon polymer (ii) having a saturated cyclic molecular structure of a carbon-carbon 5- to 8-membered ring connected by a 1,4-bond and / or a 1,2-bond is a 1,3-cycloalkadiene (carbon It is a hydride of a homopolymer of Formulas 5 to 8) or a hydride of a copolymer containing 50% by weight or more of the chloroalkadiene. (9) The molecular weight of a hydrocarbon polymer (ii) having a saturated cyclic molecular structure having a carbon-carbon 5- to 8-membered ring is defined as a polystyrene-equivalent number average molecular weight measured by a GPC method of a 1,2,4-trichlorobenzene solution. 5,000 to 1,000,000
0, more preferably 10,000 to 500,000.

(10) A vinyl group-containing cyclic saturated hydrocarbon-based monomer polymer or a vinyl group-containing cyclic unsaturated hydrocarbon-based polymer hydride (iii) used for producing a hydride (iii) The cyclic saturated or unsaturated hydrocarbon monomer is a homopolymer of a 5- to 7-membered carbocyclic hydrocarbon monomer having a vinyl group or a copolymer containing 90% by weight or more of the monomer. (11) The thermoplastic elastomer has a weight average molecular weight in terms of polystyrene measured by GPC of 150,000 or more.
500,000, more preferably 200,000 to 40
0,000, the iodine value is 20 g / 100 g or less,
More preferably, it is 10 g / 100 g or less.

(12) The thermoplastic elastomer is an aromatic vinyl thermoplastic elastomer, more preferably a hydrogenated aromatic vinyl-conjugated diene block copolymer. (13) The amount of the thermoplastic elastomer in the thermoplastic hydrocarbon polymer composition is 5 to 100 with respect to 100 parts by weight of the thermoplastic hydrocarbon polymer having a monocyclic or bicyclic saturated hydrocarbon group in the repeating unit. Parts by weight, preferably from 10 to 60 parts by weight, more preferably from 15 to 40 parts by weight.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Sadaji Ohara 1-2-1, Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture, Japan Zeon Corporation General Development Center

Claims (4)

[Claims] 1. A thermoplastic hydrocarbon polymer having a monocyclic or bicyclic saturated hydrocarbon group in a repeating unit, an iodine value of 50 g / 100 g or less and a weight average molecular weight (Mw) of 10
A thermoplastic hydrocarbon polymer composition comprising a thermoplastic elastomer having a molecular weight of from 0.001 to 1,000,000. 2. A film formed by molding the thermoplastic hydrocarbon polymer composition according to claim 1. 3. An insulating film formed by molding the thermoplastic hydrocarbon polymer composition according to claim 1. 4. A film capacitor comprising the film according to claim 2.