JP2740248B2 - Thermoplastic elastomer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a thermoplastic elastomer composition, and more specifically, it contains a cyclic olefin component, and has heat resistance, scratch resistance,
And a thermoplastic elastomer composition having excellent shrinkage resistance during molding.

(Prior art)

A cyclic olefin ring-opened polymer represented by the following general formula (I) or (II) or a hydride thereof, or a cyclic olefin represented by the general formula (I) or (II) and an addition polymer of ethylene, For example, it is disclosed in JP-A-58-127728, JP-A-60-26024, JP-A-60-168708 and the like, and is a polymer having excellent heat resistance and high rigidity.

[Object of the invention]

The present inventors surprisingly obtained a thermoplastic elastomer composition having rubbery properties and resinous properties when a specific soft polymer was blended in a specific ratio with the above polymer, and molded from the thermoplastic elastomer. The resulting molded article was found to have high surface hardness and excellent scratch resistance.

That is, an object of the present invention is to provide a novel thermoplastic elastomer composition.

It is a further object of the present invention to provide a thermoplastic elastomer which gives a molded article having a high surface hardness and excellent scratch resistance.

Another object of the present invention is to provide a thermoplastic elastomer having excellent heat resistance.

[Summary of the Invention]

In order to achieve the above object, the thermoplastic elastomer composition according to the present invention comprises an ethylene component, another α-olefin component, and a cyclic olefin component represented by the following general formula (I) or (II). A cyclic olefin polymer (i) having an intrinsic viscosity [η] of 0.01 to 10 dl / g and a glass transition temperature (T _g ) of 0 ° C. or less, measured in decalin at 135 ° C .; Amorphous or low-crystalline α-olefin copolymer (ii) having a glass transition temperature (T _g ) of 0 ° C. or less, comprising at least two α-olefins and at least one non-conjugated diene The glass transition temperature (T _g ) of 0 ° C
The following α-olefin / diene copolymer (ii
i), an aromatic vinyl hydrocarbon / conjugated diene random or block copolymer having a glass transition temperature (T _g ) of 0 ° C. or less or a hydride thereof (iv), isobutylene, or a soft material comprising isobutylene and a conjugated diene A polymer or copolymer (v), a soft polymer [A] composed of at least one member selected from the groups (i) to (v), and a polymer represented by the following general formula [I] or [II]: A ring-opened polymer of a cyclic olefin represented by the formula or a hydride thereof, and / or an addition polymer of a cyclic olefin represented by the following general formula [I] or [II] and ethylene; A cyclic olefin polymer [B] having an intrinsic viscosity [η] of 0.05 to 10 dl / g and a glass transition temperature (T _g ) of at least 60 ° C. The weight ratio of the system polymer [B] is 98/2 It is characterized by being 30/70.

General formula [Wherein, n and m are each 0 or a positive integer, L is an integer of 3 or more, and R ^{1 to} R ¹⁰ each represent a hydrogen atom, a halogen atom, or a hydrocarbon group. [Preferred Embodiment of the Invention] Hereinafter, a preferred embodiment according to the present invention will be described.

Flexible polymer [A] As the flexible polymer [A] according to the present invention, the flexible polymers (i) to (v) are used. Among these soft polymers, those known per se are used as (ii) to (v).

Cyclic olefin-based polymer (i) The cyclic olefin-based polymer (i) as the soft polymer [A] is composed of a cyclic component having a monomer component composed of an ethylene component, another α-olefin component and a specific cyclic olefin component. It is an olefin-based random copolymer.

The cyclic olefin as a component of the cyclic olefin polymer (i) is at least one or more cyclic olefins selected from the group consisting of unsaturated monomers represented by the general formulas [I] and [II]. Become. The cyclic olefin represented by the general formula [I] can be easily produced by subjecting a cyclopentadiene and a corresponding olefin to a Diels-Alder reaction.

Similarly, the cyclic olefin represented by the general formula (II) also includes cyclopentadiene and a corresponding olefin,
It can be easily produced by performing a Diels-Alder reaction.

Specific examples of the polycyclic olefin represented by the general formula [I] include the compounds described in Table 1 or 1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a In addition to octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,
8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-hexyl-1,4,
5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,
4a, 5,8,8a-octahydronaphthalene, 2-methyl-3
-Ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2 , 3,4,4a, 5,8,8a-octahydronaphthalene, 2
-Bromo-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2 , 3,4,4a, 5,8,8a-octahydronaphthalene,
2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8
a-octahydronaphthalene, 2-cyclohexyl-1,
4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-n-butyl-1,4,5,8-dimethano-1,2,
3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, etc. Octahydronaphthalenes, and the compounds shown in Table 2.

Specific examples of the cyclic olefin represented by the general formula [II] include the compounds shown in Tables 3 and 4.

In the cyclic olefin polymer (i), an ethylene component and an α-olefin component are essential components in addition to the cyclic olefin components of the general formulas [I] and [II]. As the α-olefin, for example, propylene,
1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1
-Eicosene and the like. Of these, α-olefins having 3 to 20 carbon atoms are preferred. Further, cyclic olefins such as norbornene, ethylidene norbornene, and dicyclopentadiene, and cyclic dienes can also be used.

In the cyclic olefin polymer (i) as the soft polymer [A], the ethylene component is used in the range of 40 to 98 mol%, preferably 50 to 90 mol%. The α-olefin component is used in the range of 2 to 50 mol%, and the cyclic olefin component is used in the range of 2 to 20 mol%, preferably 2 to 15 mol%.

The cyclic olefin polymer (i) is disclosed in JP-A-60-168708.
JP-A-61-120816, JP-A-61-115912, JP-A-61-115916, JP-A-61-271308, JP-A-61-272216, and JP-A-61-272216. Based on JP-A-62-252406, JP-A-62-252406, etc., it can be produced by appropriately selecting conditions according to the method proposed by the present applicant.

The cyclic olefin-based polymer (i) forms a substantially linear random copolymer in which each component is randomly arranged. The fact that this random copolymer is formed substantially linearly and does not have a gel-like cross-linked structure can be confirmed by the complete dissolution of the ethylene copolymer in decalin at 135 ° C.

The intrinsic viscosity [η] of the cyclic olefin polymer (i) measured in decalin at 135 ° C. is 0.01 to 10 dl / g, preferably 0.8 to 7 dl / g.

The properties of the cyclic olefin polymer (i) are such that the glass transition temperature (T _g ) is 0 ° C. or lower, preferably −10 ° C.
° C or lower, which is different from the cyclic olefin polymer [B] described later in this point. Furthermore, the cyclic olefin polymer (i) has a crystallinity of 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%, as measured by X-ray diffraction.

α-olefin-based copolymer (ii) The α-olefin-based copolymer (ii) as the soft polymer [A] is composed of at least two kinds of α-olefins,
It is an amorphous or low crystalline copolymer. The α-olefin is usually an α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
-Methyl-1-pentene, 1-octene, 1-decene and the like. The copolymer (ii) is composed of at least two kinds of these α-olefins,
The proportion of one type of α-olefin in the copolymer (ii) is preferably 90 mol% or less. Specifically, an ethylene / α-olefin copolymer and a propylene / α-olefin copolymer are used.

As the α-olefin constituting the ethylene / α-olefin copolymer, one having 3 to 20 carbon atoms is usually used, and specifically, propylene, 1-butene, 4-methyl-1-
Examples include pentene, 1-hexene, 1-octene, 1-decene, and the like, or a mixture thereof. Of these, α-olefins having 3 to 10 carbon atoms are particularly preferred.

The molar ratio of the ethylene / α-olefin copolymer (ethylene / α-olefin) varies depending on the type of α-olefin, but is generally preferably 50/50 to 95/5.

Α- constituting propylene / α-olefin copolymer
As the olefin, ethylene or one having 4 to 20 carbon atoms is usually used, and specifically, 1-butene, 4-methyl-1
-Butene, 1-hexene, 1-octene, 1-decene and the like, or a mixture thereof. Among them, ethylene or an α-olefin having 4 to 10 carbon atoms is preferred.

In the propylene / α-olefin copolymer as described above, the molar ratio of propylene to α-olefin (propylene / α-olefin) varies depending on the type of α-olefin, but generally ranges from 50/50 to 95/50. It is preferably 5.

α-olefin / diene copolymer (iii) As the α-olefin / diene copolymer (iii) as the soft polymer [A], ethylene / α-olefin / diene copolymer rubber, propylene / α −Olefin ・
Diene copolymer rubber is used.

Α-olefins constituting these copolymer rubbers are:
Usually, α-olefins having 3 to 20 carbon atoms (ethylene or 4 to 20 carbon atoms in the case of propylene / α-olefin) such as propylene, 1-butene, 1-pentene,
-Methyl-1-pentene, 1-hexene, 1-octene, 1-decene or a mixture thereof. Of these, α-olefins having 3 to 10 carbon atoms are preferred.

The diene components constituting these copolymer rubbers are 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7- Chain non-conjugated dienes such as methyl-1,6-octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5- Isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylenyl-
Examples include cyclic non-conjugated dienes such as 2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,2-norbornadiene.

In the above-mentioned ethylene / α-olefin / diene copolymer rubber, the molar ratio between ethylene and α-olefin (ethylene / α-olefin) varies depending on the type of α-olefin, but is generally 50/50 to 95 /. It is preferably 5.

In the propylene / α-olefin / diene copolymer rubber, similarly to the ethylene copolymer rubber, the molar ratio of propylene to α-olefin (propylene / α-
The olefin) varies depending on the type of the α-olefin, but is generally preferably 50/50 to 95/5.

The content of the diene component in these copolymer rubbers is desirably 1 to 20 mol%, preferably 2 to 15 mol%.

Aromatic vinyl hydrocarbon / conjugated gen soft copolymer (iv) Aromatic vinyl hydrocarbon as soft polymer [A]
The conjugated soft copolymer is an aromatic vinyl hydrocarbon, a conjugated random copolymer, a block copolymer or a hydride thereof. Specifically, styrene-butadiene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene block copolymer rubber, styrene-isoprene-
Styrene block copolymer rubber, hydrogenated styrene / butadiene / styrene block copolymer, hydrogenated styrene / isoprene / styrene block copolymer rubber, styrene / butadiene random copolymer rubber, and the like are used.

In these copolymer rubbers, the molar ratio of aromatic vinyl hydrocarbon to conjugated diene (aromatic vinyl hydrocarbon / conjugated diene) is generally preferably from 10/90 to 70/30. The hydrogenated copolymer rubber is a copolymer rubber obtained by hydrogenating a part or all of the double bonds remaining in the above-mentioned copolymer rubber.

Soft polymer or copolymer (v) comprising isobutylene or isobutylene / conjugated diene The isobutylene-based soft polymer or copolymer (v) as the soft polymer [A] is specifically a polyisobutylene rubber, a polyisoprene. Rubber, polybutadiene rubber, isobutylene / isoprene copolymer rubber and the like are used.

The properties of the copolymers (ii) to (v) as the soft polymer [A] are the same as the properties of the cyclic olefin polymer (i), and the intrinsic viscosity measured in decalin at 135 ° C. [η] of 0.01 to 10 dl / g, preferably in the range of 0.08 to 7 dl / g, a glass transition temperature (T _g) 0 ℃ less, preferably -10 ° C. or less, particularly preferably at -20 ° C. or less is there.
The crystallinity measured by the X-ray diffraction method is 0 to 10
%, Preferably 0 to 7%, particularly preferably 0 to 5%
Is preferable.

Cyclic olefin polymer [B] The cyclic olefin polymer [B] blended in the thermoplastic elastomer composition according to the present invention is a soft polymer [A].
The cyclic olefin polymer (i) has the same physical properties as those of the cyclic olefin component (cyclic olefin represented by the general formula [I] or [II]).

The cyclic olefin component has been described in detail in the cyclic olefin-based polymer (i), and the description thereof will be omitted. Also, the synthesis of a copolymer of a cyclic olefin component and an α-olefin component can be produced by appropriately selecting conditions according to the method proposed by the present applicant based on the above-mentioned known publication.

Examples of the cyclic olefin polymer [B] include (1) a ring-opened polymer of a cyclic olefin represented by the general formula [I] and / or [II] and a hydrogenated product thereof; Copolymers obtained by addition polymerization of the cyclic olefin represented by [I] and / or [II] with ethylene can be mentioned.

(1) Cyclic olefin ring-opening polymer and hydrogenated product thereof The cyclic olefin ring-opening polymer is obtained by subjecting the cyclic olefin represented by the general formulas [I] and [II] to ring-opening polymerization by a method known per se. And homopolymerized or copolymerized. For example, 1,4,5,8-dimethano-1,2,
A copolymer of 3,4,4a, 5,8,8a, -octahydronaphthalenes or a copolymer of norbornene (bicyclo [2.2.1] hept-2-ene) shown in Table 1 above. It may be something.

Further, the ring-opened polymer can easily hydrogenate the remaining double bond by a method known per se, and the hydrogenated product is a resin material having more excellent thermal stability and weather resistance.

In the case of ring-opening polymerization, other cyclic olefins can be subjected to ring-opening copolymerization within a range that does not impair the physical properties of the cyclic olefin polymer represented by the above [I] and [II]. As the olefin, cyclobutene,
Cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, 2,3,3a, 7a-tetrahydro-4,7-methano-1H-indene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene and the like can be mentioned.

(2) Copolymer obtained by addition polymerization of cyclic olefin and ethylene (sometimes referred to as cyclic olefin addition polymer) In the cyclic olefin addition polymer, the ethylene component is
It is used in the range of 40 to 85 mol%, preferably 50 to 75 mol%. The cyclic olefin component is used in the range of 15 to 60 mol%, preferably 25 to 50 mol%.

In addition, in the cyclic olefin addition polymer, in addition to the cyclic olefin component and the ethylene component, an α-olefin component and / or a cyclic olefin other than the general formulas (I) and (II), as long as the properties of the polymer are not impaired. Those obtained by addition polymerization of components may be used.

The α-olefin is linear or branched, and includes, for example, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-octene.
Α-olefins having 3 to 20 carbon atoms such as decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene can be exemplified. Among them, those having 3 to 15 carbon atoms, particularly 3 to 15 carbon atoms
Ten α-olefins are preferred.

The cyclic olefin components other than the general formulas [I] and [II] are represented by a broad concept including unsaturated polycyclic hydrocarbon compounds.

More specifically, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-
Cyclohexene, styrene, α-methylstyrene, 2,3,
3a, 7a-tetrahydro-4,7-methano-1H-indene, 3
a, 5,6,7a-Tetrahydro-4,7-methano-1H-indene and the like can be mentioned.

When a cyclic olefin other than the formulas [I] and [II] has two or more double bonds in the molecule, it can be used by hydrogenation for the purpose of improving weather resistance.

The above-mentioned (1) cyclic olefin ring-opening polymer and its hydrogenated product and (2) cyclic olefin addition polymer [B] form a substantially linear random copolymer in which each component is randomly arranged. Things. The fact that this random copolymer is formed substantially linearly and does not have a gel-like cross-linked structure can be confirmed by the complete dissolution of the ethylene copolymer in decalin at 135 ° C.

The cyclic olefin polymer [B] has an intrinsic viscosity [η] of 0.05 to 10 dl / g, preferably 0.8 to 5 dl / g measured in decalin at 135 ° C.

The properties of the cyclic olefin polymer [B] are such that the softening temperature (TMA) measured with a thermomechanical analyzer is 70 ° C or higher, preferably 90 to 250 ° C, particularly preferably 100 to 200 ° C. And a glass transition temperature (T _g ) of 60 to 240 ° C., preferably 70 to 230 ° C. The degree of crystallinity measured by the X-ray diffraction method is in the range of 0 to 10%, preferably 0 to 7%, and particularly preferably 0 to 5%.

Blending composition of soft polymer [A] and cyclic olefin polymer [B] First, the components of soft polymers [A] (i) to (v) are as follows:
One type may be used alone, or two or more types may be used in combination in the thermoplastic elastomer composition.

In the thermoplastic elastomer composition according to the present invention,
The weight ratio of the soft polymer [A] / the cyclic olefin polymer [B] is in the range of 98/2 to 30/70, preferably 95/5 to 40 /.
It is in the range of 60, particularly preferably in the range of 90/10 to 50/50. If the amount of the soft polymer [A] is less than 30% by weight, rubber-like properties are undesirably lowered. On the other hand, if it exceeds 98% by weight, the heat resistance and the scratch resistance are not effective, which is not preferable.

Addition of components other than the soft polymer [A] and the cyclic olefin polymer [B] The thermoplastic elastomer composition according to the present invention essentially includes the soft polymer [A] and the cyclic olefin polymer [B]. As a component, an organic peroxide [C] can be blended to further improve heat resistance and scratch resistance. Furthermore,
If necessary, a radical polymerizable compound [D] having two or more radical polymerizable functional groups in the molecule can be blended. After blending these, the soft polymer [A], the cyclic olefin polymer [B] and the radical polymerizable compound [D] are partially crosslinked by a radical reaction.

Examples of the organic peroxide [C] include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, and 1,1-bis (t-butylperoxy) cyclohexane 2,2-bis (t-butylperoxy) octane. Such as peroxyketals, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, etc. Hydroxy peroxides, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t
Dibutyl peroxides such as -butylperoxy) hexine-3, diacyl peroxides such as lauroyl peroxide and benzoyl peroxide, t-butylperoxyacetate, t-butylperoxybenzoate;
Examples thereof include peroxyesters such as 2,5-dimethyl-2,5-di (benzoylperoxy) hexane.

The radical polymerizable compound [D] has two or more radical polymerizable functional groups in the molecule, and specific examples thereof include divinylbenzene, vinyl acrylate, and vinyl methacrylate.

The amount of the organic peroxide [C] is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the total of the components [A] and [B]. Further, the radical polymerizable compound [D] is not more than 1 part by weight, preferably not more than 1 part by weight based on 100 parts by weight of the total amount of the components (A) and (B).
0.1 to 0.5 parts by weight.

Furthermore, in addition to the copolymers (A) and (D) components, heat stability, weather stability, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, Synthetic oils, waxes, organic or inorganic fillers and the like can be compounded, and the mixing ratio is an appropriate amount.

For example, as a stabilizer blended as an optional component, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane,
β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-oxamidobis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Phenolic antioxidants such as propionate, zinc stearate, calcium stearate, fatty acid metal salts such as calcium 1,2-hydroxystearate, glycerin monostearate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate And polyhydric alcohol fatty acid esters such as pentaerythritol tristearate. These may be blended alone or in combination. For example, tetrakis [methylene-3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] A combination of methane, zinc stearate, and glycerin monostearate can be exemplified.

In addition, as an organic or inorganic filler, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dowamite, calcium sulfate, titanium Potassium silicate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass peas, calcium silicate, montmorillonite, pentonite, graphite, aluminum powder molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene Fiber, polypropylene fiber,
Examples thereof include polyester fibers and polyamide fibers.

Method for Producing Thermoplastic Elastomer Composition As a method for producing the thermoplastic elastomer composition according to the present invention, a known method can be applied. For example, a method in which a flexible polymer [A] and a cyclic olefin polymer [B] are separately produced and blended by an extruder to produce a flexible polymer [A] or a cyclic olefin polymer [B]. The components are converted to a suitable solvent such as heptane, hexane, decane, saturated hydrocarbons such as cyclohexane, toluene, benzene,
A polymer solution obtained by dissolving an aromatic hydrocarbon such as xylene in a solution blending method, and further by synthesizing a soft polymer [A] component and a cyclic olefin polymer [B] component in separate polymerization vessels. Can be produced by a method of blending in a separate container.

The thus obtained composition of the soft polymer [A] and the cyclic olefin polymer [B] component may, if necessary, be continued with the organic peroxide [C] component, and further, the radical polymerizable compound [ The crosslinked thermoplastic elastomer composition can be obtained by adding and blending the component [D] and performing the reaction at a temperature at which the organic peroxide [C] component decomposes.

The thermoplastic elastomer composition according to the present invention is molded by a known method. For example, single-screw extruder, vented extruder, twin-screw extruder, conical twin-screw extruder, co-kneader, plasticizer, mixtruder, twin-screw conical screw extruder, planetary screw extruder, gear-type extruder Extrusion molding, injection molding, blow molding, rotational molding and the like can be performed using a screwless extruder or the like. The molded article of the thermoplastic elastomer composition obtained in this manner has excellent heat resistance and scratch resistance, and can be applied to a wide range of uses.

〔The invention's effect〕

As described above, the thermoplastic elastomer composition according to the present invention is composed of a soft polymer and a cyclic olefin copolymer, so that the thermoplastic elastomer composition has a high Shore D hardness and a high pencil hardness, and the surface thereof has a high hardness. Since the hardness of the molded article is increased, the scratch resistance of the surface is improved, and the appearance of the molded article can be maintained for a long time.

In addition, the thermoplastic elastomer composition has improved heat resistance, and in particular, is further improved in heat resistance by crosslinking polymerization of an organic peroxide or the like, and can be applied to a wide range of applications.

〔Example〕

 Hereinafter, the present invention will be described specifically with reference to Examples.

The methods for measuring and evaluating various physical properties according to the present invention are described below.

(1) using the Create Toshiba Machine Co., Ltd. injection molding machine IS-50EP and predetermined specimen mold test pieces were molded sheet of 120 × 130 × 2 ^t mm under the following molding conditions. The test pieces were left for 48 hours at room temperature after molding and then subjected to measurement.

Molding conditions: cylinder temperature 220 ° C, mold temperature 60 ° C, injection pressure primary / secondary = 1000 / 800Kg / cm ² , injection speed (primary) 30mm
/ Sec (2) Tensile rupture strength (Tb) and Tensile rupture elongation (Eb) The tensile strength at break was measured in accordance with JISK6301 using the test pieces prepared above.

Test piece shape; JIS No. 3 dumbbell Test temperature; 23 ° C. Test speed; 200 mm / min (3) Permanent strain (PS) Measured according to JISK6301. That is, the above test piece was
(S1 dumbbell) was held for 10 minutes after 100% elongation at the distance between the marked lines.

Test temperature: 23 ° C. (4) Shore D hardness Measured using a TipeD Schlometer hardness meter according to JIS K7215.

Test temperature: 23 ° C Load: 50N (5) Pencil hardness Measured according to JISK5401.

Test temperature: 23 ° C (6) Glass transition temperature (T _g ) Temperature rise rate 10 using DSC-20 manufactured by SEIKO Electronic Industries Co., Ltd.
Measured in ° C / min.

(Example 1) As a soft polymer [A] component, an ethylene-propylene-ethylidene norbornene random copolymer (ethylene content of 77 mol% and ethylidene norbornene content of 1.5 mol%,
Glass transition temperature (T _g ) -41 ° C, intrinsic viscosity [η] 3.2dl /
g), 2 kg of pellets, and ethylene and 1,4,5,8-dimetano-1,2,3,4,4a, 5,8,8a, -octahydronaphthalene ( Structural formula; With an ethylene content of 62 mol% measured by ¹³ C-NMR, MFR ₂₆₀ · c 35 g / min, 135
° C. intrinsic viscosity measured in decalin at [η] 0.47 dl / g, a softening temperature (TMA) 148 ° C., after mixing pellets 2 kg, the glass transition temperature (T _g) 137 ℃), twin-screw extruder (Ikegai PCM4 manufactured by Iron Works Co., Ltd.
The mixture was melt-blended at a cylinder temperature of 220 ° C according to 5) and pelletized with a pelletizer.

Using the obtained pellets, test pieces were prepared by the method described above, and their physical properties were measured. Table 5 shows the results.

Example 2 Pellets of an ethylene / propylene random copolymer (ethylene content: 80 mol%; glass transition temperature (T _g ) -55 ° C., intrinsic viscosity [η]: 2.4 dl / g) as the soft polymer [A] component Example 1 2 kg, as a cyclic olefin polymer [B] component
Pellets of ethylene / DMON random copolymer similar to 2k
g, after mixing, twin screw extruder (PCM4 manufactured by Ikegai Iron Works Co., Ltd.)
The mixture was melt-blended at a cylinder temperature of 220 ° C according to 5) and pelletized with a pelletizer.

Using the obtained pellets, test pieces were prepared by the method described above, and their physical properties were measured. Table 5 shows the results.

Example 3 As a soft polymer [A] component, an ethylene / propylene / DMON random copolymer (ethylene content 66 mol%, DMON
2 kg of pellets having a glass transition temperature (T _g ) of −35 ° C. and an intrinsic viscosity [η] of 2.5 dl / g, and the same ethylene / DMON random as in Example 1 as a cyclic olefin polymer [B] component Copolymer pellet 2k
g, after mixing, twin screw extruder (PCM4 manufactured by Ikegai Iron Works Co., Ltd.)
The mixture was melt-blended at a cylinder temperature of 220 ° C according to 5) and pelletized with a pelletizer.

Using the obtained pellets, test pieces were prepared by the method described above, and their physical properties were measured. Table 5 shows the results.

(Example 4) soft polymer as component [A], a hydrogenated product of a styrene-isoprene-styrene block copolymer (styrene content 30 wt%; glass transition temperature (T _g) -58 ° C., the intrinsic viscosity [η] 0.65 dl / g) 2 kg of pellets, as the cyclic olefin polymer [B] component,
Pellets of ethylene / DMON random copolymer similar to 2k
g, after mixing, twin screw extruder (PCM4 manufactured by Ikegai Iron Works Co., Ltd.)
The mixture was melt-blended at a cylinder temperature of 220 ° C according to 5) and pelletized with a pelletizer.

Using the obtained pellets, test pieces were prepared by the method described above, and their physical properties were measured. Table 5 shows the results.

(Example 5) soft polymer component [A], a styrene-butadiene-styrene random copolymer (styrene content 24 wt%; glass transition temperature (T _g) -57 ° C., the intrinsic viscosity [η] 1.5 dl / g)
1 kg of the pellets of Example 1 as the cyclic olefin polymer [B] component
Pellets of ethylene / DMON random copolymer similar to 2k
g, after mixing, twin screw extruder (PCM4 manufactured by Ikegai Iron Works Co., Ltd.)
The mixture was melt-blended at a cylinder temperature of 220 ° C according to 5) and pelletized with a pelletizer.

Using the obtained pellets, test pieces were prepared by the method described above, and their physical properties were measured. Table 5 shows the results.

(Example 6) soft polymers as (A) component, polyisobutylene (glass transition temperature (T _g) -80 ° C., the intrinsic viscosity [η] 2.1 dl / g)
1 kg of the pellets of Example 1 as the cyclic olefin polymer [B] component
Pellets of ethylene / DMON random copolymer similar to 2k
g, after mixing, twin screw extruder (PCM4 manufactured by Ikegai Iron Works Co., Ltd.)
The mixture was melt-blended at a cylinder temperature of 220 ° C according to 5) and pelletized with a pelletizer.

Test pieces were prepared by the above-described method using the obtained pellets, and the physical properties were measured. Table 5 shows the results.

(Example 7) The flexible polymer [A] is the same as that in Example 1, and the cyclic olefin polymer [B] is ethylene-DMON of Example 1.
Instead of the random copolymer, MFR ₂₆₀ · c 20 g / min, intrinsic viscosity [η] measured in decalin at 135 ° C. 0.60 dl / g, softening temperature (TMA) 115 ° C., glass transition temperature (T _g ) 98 ° C. Random copolymer of ethylene and DMON (ethylene content 71mol%)
Was performed in the same manner as in Example 1 except that

Using the obtained pellets, test pieces were prepared by the method described above, and their physical properties were measured. Table 5 shows the results.

(Reference Example 1) The soft polymer [A] is the same as in Example 1, and MFR ₂₃₀ • is used in place of the ethylene / DMON random copolymer which is the cyclic olefin polymer of Example 1 as the component [B]. c25g /
The procedure was performed in the same manner as in Example 1 except that the amount of polypropylene used was 1.

Using the obtained pellets, test pieces were prepared by the method described above, and their physical properties were measured. Table 5 shows the results.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 65/00 C08L 65/00

Claims (1)

(57) [Claims] 1. An intrinsic viscosity [η] measured in decalin at 135 ° C. comprising an ethylene component, another α-olefin component, and a cyclic olefin component represented by the following general formula [I] or [II]. Is 0.01 to 10 dl / g, glass transition temperature [T _g ]
Is a cyclic olefin polymer (i) having a glass transition temperature (T _g ) of at least 2 α-olefins having a glass transition temperature (T _g ) of 0 ° C. or lower. Coalescing (ii), an α-olefin / diene copolymer (iii) comprising at least two kinds of α-olefins and at least one kind of non-conjugated diene and having a glass transition temperature (T _g ) of 0 ° C. or lower, An aromatic vinyl hydrocarbon / conjugated diene random or block copolymer having a glass transition temperature (T _g ) of 0 ° C. or lower or a hydride thereof (iv), isobutylene, or a soft polymer comprising isobutylene and a conjugated diene; or A soft polymer [A] composed of at least one selected from the group (i) to (v) of the copolymer (v), and represented by the following general formula [I] or [II] Ring opening of cyclic olefins A polymer or a hydride thereof, and / or an addition polymer of a cyclic olefin represented by the following general formula [I] or [II] and ethylene, and an intrinsic viscosity [η] measured in decalin at 135 ° C. Is 0.05 to 10 dl / g, and the glass transition temperature (T _g ) is 60 ° C. or higher.
Wherein the weight ratio of soft polymer [A] / cyclic olefin polymer [B] is 98/2 to 30/70. General formula [Wherein, n and m are each 0 or a positive integer, L is an integer of 3 or more, and R ^{1 to} R ¹⁰ each represent a hydrogen atom, a halogen atom, or a hydrocarbon group. ]