JP3465421B2 - Thermoplastic elastomer composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic elastomer composition, and more particularly to an olefin-based thermoplastic elastomer composition capable of providing a molded article having excellent scratch resistance and abrasion resistance.

[0002]

BACKGROUND OF THE INVENTION Olefin-based thermoplastic elastomers are lightweight and easy to recycle, so they are used as energy-saving and resource-saving type elastomers, especially as substitutes for vulcanized rubber for automobile parts, industrial machinery parts, electric
Widely used in electronic parts and building materials.

In recent years, from the viewpoint of protecting the global environment, in place of vinyl chloride resin, which emits harmful gas when incinerated,
Olefin-based thermoplastic elastomers that do not generate harmful gas have been used.

However, the conventional molded article made of an olefinic thermoplastic elastomer has a drawback that it is inferior in scratch resistance and abrasion resistance as compared with a molded article made of a vinyl chloride resin, and its improvement is strongly desired. ing.

Therefore, the inventors of the present invention have conducted diligent research in order to obtain an olefinic thermoplastic elastomer having excellent scratch resistance and abrasion resistance, and to obtain a polyolefin composition comprising an ultrahigh molecular weight polyolefin and a low molecular weight or high molecular weight polyolefin. It was found that a thermoplastic elastomer composition capable of providing a molded article having excellent scratch resistance and abrasion resistance can be obtained by blending a styrene-based block copolymer in a specific ratio, and completed the present invention. Came to do.

[0006]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, is lightweight, is easy to recycle, and does not generate harmful gas even when incinerated. It is an object of the present invention to provide a thermoplastic elastomer composition capable of imparting a molded product excellent in sticking property and abrasion resistance.

[0007]

SUMMARY OF THE INVENTION The first thermoplastic elastomer composition according to the present invention is [I] an ultra high molecular weight polyolefin having an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. within the range of 7 to 40 dl / g. (A) and a low to high molecular weight polyolefin (b) having an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. in the range of 0.1 to 5 dl / g.
A polyolefin composition consisting essentially of: the ultrahigh molecular weight polyolefin (a) is 15 per 100% by weight of the total weight of the ultrahigh molecular weight polyolefin (a) and the low molecular weight or high molecular weight polyolefin (b). 10 to 50 parts by weight of a polyolefin composition (A) present in an amount of ˜40% by weight and having an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. in the range of 3.5 to 8.3 dl / g. ,
And [II] a polymer block (c) of styrene or a derivative thereof and an isoprene polymer block or an isoprene-butadiene copolymer block, which are bonded at 1,2-position and 3,4-position with respect to all isoprene units. 90-50 parts by weight of an optionally hydrogenated block copolymer (B) consisting of a polymer or copolymer block (d) having an isoprene unit content of 40% or more [component (A) And the total amount of (B) is 100 parts by weight].

The second thermoplastic elastomer composition according to the present invention is [I] an ultrahigh molecular weight polyolefin having an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. within the range of 7 to 40 dl / g. (A) and the intrinsic viscosity [η] measured in a solvent of decalin at 135 ° C. is 0.1 to 5 dl / g
A polyolefin composition consisting essentially of a low molecular weight to high molecular weight polyolefin (b) in the range of, wherein the ultra high molecular weight polyolefin (a) comprises the ultra high molecular weight polyolefin (a) and the low molecular weight to high molecular weight polyolefin ( 15-4 based on 100% by weight of total weight with b)
It exists in a proportion of 0% by weight and has an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. of 3.5 to 8.3 dl / g.
In the range of 10 to 50 parts by weight of the polyolefin composition (A), a polymer block (c) of [II] styrene or a derivative thereof, and an isoprene polymer block or an isoprene-butadiene copolymer block. An optionally hydrogenated block copolymer consisting of a polymer or copolymer block (d) having a content of isoprene units bonded at 1,2- and 3,4-positions of the unit of 40% or more. 90 to 25 parts by weight of polymer (B),
And [III] a polymer block (e) of styrene or a derivative thereof and an isoprene polymer block or an isoprene-butadiene copolymer block, which are bonded at 1,2-position and 3,4-position with respect to all isoprene units. An optionally hydrogenated block copolymer (C) consisting of a polymer or copolymer block (f) having an isoprene unit content of 30% or less, or a butadiene polymer block (g) To 30 parts by weight, olefinic rubber (D) 0 to 40 parts by weight, softening agent (E) 0 to 40 parts by weight, and partially or completely cross-linked with a crystalline polyolefin resin and an olefinic rubber. At least one component selected from the group consisting of 0 to 50 parts by weight of the thermoplastic elastomer (F) [component (A),
The total amount of (B), (C), (D), (E) and (F) is 100 parts by weight], and the components (A), (B), (C), (D), (E) and (F)
The ratio of the total amount of the components (A), (B), (C) and (D) to the total amount of is 100 to 40% by weight.

Furthermore, in the first or second thermoplastic elastomer composition according to the present invention, the components (A), (B),
In addition to (C), (D), (E) and (F), if necessary, silicone oil (G), ester (H) of aliphatic alcohol and dicarboxylic acid or fatty acid, and fluoropolymer ( I), at least one component selected from the group consisting of the components (A), (B),
0.01 to 10 parts by weight can be added to 100 parts by weight of the total amount of (C), (D), (E) and (F).

In the first or second thermoplastic elastomer composition according to the present invention as described above, the higher fatty acid amide is added to the components (A), (B), (C), (D),
With respect to 100 parts by weight of the total amount of (E) and (F),
It can be mixed in an amount of 0.1 to 10 parts by weight.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The first and second thermoplastic elastomer compositions according to the present invention will be specifically described below.

The first thermoplastic elastomer composition according to the present invention comprises a polyolefin composition (A) and a block copolymer (B). Moreover, the 2nd thermoplastic elastomer composition which concerns on this invention is a polyolefin composition (A) and a block copolymer (B) in the 1st thermoplastic elastomer composition which concerns on this invention as needed. In addition to the above, a composition comprising at least one component selected from the group consisting of a block copolymer (C), an olefin rubber (D), a softening agent (E) and a thermoplastic elastomer (F). is there.

In the first or second thermoplastic elastomer composition according to the present invention, if necessary, the component (A),
In addition to (B), (C), (D), (E) and (F), silicone oil (G), ester (H) of aliphatic alcohol and dicarboxylic acid or fatty acid, and fluoropolymer (I At least one component selected from the group consisting of 1) and / or higher fatty acid amide can be blended.

Polyolefin Composition (A) The polyolefin composition (A) used in the present invention is 1
Intrinsic viscosity [η] measured in decalin solvent at 35 ° C is 7-
Ultra high molecular weight polyolefin (a) in the range of 40 dl / g and low molecular weight or high molecular weight polyolefin (b) having an intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. of 0.1 to 5 dl / g. And a total weight of the ultrahigh molecular weight polyolefin (a) of the ultrahigh molecular weight polyolefin (a) and the low molecular weight or high molecular weight polyolefin (b) is 10).
It exists in a proportion of 15 to 40% by weight with respect to 0% by weight,
Moreover, the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is in the range of 3.5 to 8.3 dl / g.

In the above-mentioned polyolefin composition (A), 1 to 20% by weight of liquid or solid lubricating oil can be blended with respect to the polyolefin composition (A). The ultra high molecular weight polyolefin (a) as described above is, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-.
It is composed of a homopolymer or a copolymer of α-olefin such as pentene and 3-methyl-1-pentene. In the present invention, ethylene homopolymers and copolymers of ethylene and 50 mol% or less of other α-olefin are preferable.

As the liquid lubricating oil, petroleum-based lubricating oil,
Synthetic lubricating oil is used. As a petroleum-based lubricating oil,
Specifically, liquid paraffin, spindle oil, refrigerating machine oil, dynamo oil, turbine oil, machine oil, cylinder oil and the like are used.

Specific examples of the synthetic lubricating oil include synthetic hydrocarbon oil, polyglycol oil, polyphenyl ether oil, ester oil, phosphate ester oil, polychlorotrifluoroethylene oil, fluoroester oil and chlorinated biphenyl. Oil, silicone oil, etc. are used.

As the solid lubricating oil, specifically, graphite and molybdenum disulfide are mainly used, but in addition, boron nitride, tungsten disulfide, lead oxide, glass powder,
Metal soap and the like can also be used.

Solid lubricating oils can be used alone or in combination with liquid lubricating oils,
For example, the solid lubricating oil and the liquid lubricating oil can be blended with the polyolefin composition (A) in the form of powder, sol, gel, suspenseoid, or the like.

The above polyolefin composition (A) contains
If necessary, additives such as mineral oil-based softeners, heat stabilizers, antistatic agents, weather resistance stabilizers, antiaging agents, fillers, colorants, lubricants, etc. are blended within a range not impairing the object of the present invention. can do.

Polyolefin composition (A) as described above
Is 100 parts by weight in total of the polyolefin composition (A), the block copolymer (B), the block copolymer (C), the olefin rubber (D), the softening agent (E) and the thermoplastic elastomer (F). To 10 to 50 parts by weight, preferably 15 to 40 parts by weight.
However, the above components (C), (D), (E) and (F)
Is an optional component, so these components may be 0 parts by weight.

Block Copolymer (B) The block copolymer (B) used in the present invention comprises a polymer block (c) of styrene or a derivative thereof and a specific isoprene polymer or a specific isoprene-butadiene copolymer. It is composed of a block (d) composed of a united body and may be hydrogenated.

The polymer component constituting the block (c) is styrene or its derivative. As the styrene derivative, specifically, α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene,
4-dodecylstyrene, 2-ethyl-4-benzylstyrene,
4- (phenylbutyl) styrene and the like can be mentioned. As the polymer component constituting the block (c), styrene,
α-Methylstyrene is preferred.

The polymer or copolymer constituting the block (d) is an isoprene polymer or an isoprene-butadiene copolymer, and is in the 1,2-position and 3,4-position with respect to the whole isoprene unit shown below. Content of isoprene unit bonded at position 40% or more, preferably 45
% Or more.

[0025]

[Chemical 1]

[0026]

[Chemical 2]

In the present invention, when the content of isoprene units bonded at the 1,2-position and the 3,4-position with respect to all isoprene units is 40% or more, a molded article having excellent scratch resistance is provided. The resulting thermoplastic elastomer composition can be obtained.

The proportion of the polymer block (c) of styrene or its derivative in the block copolymer (B) is preferably 5 to 50% by weight, more preferably 10 to 45%.
It is in the range of% by weight. That is, the proportion of the above isoprene polymer block or isoprene-butadiene copolymer block (d) is preferably in the range of 95 to 50% by weight, more preferably 90 to 55% by weight.

In the present invention, the hydrogenated block copolymer (B) is preferred. When the hydrogenated block copolymer (B) is used, a thermoplastic elastomer composition capable of providing a molded article having excellent weather resistance and heat resistance can be obtained.

The melt flow rate (MFR; ASTM D 1) of the block copolymer (B) used in the present invention.
238, 230 ° C., 2.16 kg load) is preferably 0.01 to 30 g / 10 minutes, more preferably 0.01
It is in the range of -10 g / 10 minutes. When the block copolymer (B) having a melt flow rate in the above range is used, a thermoplastic elastomer capable of providing a molded article having excellent scratch resistance can be obtained.

The block form of the block copolymer (B) used in the present invention is most preferably block (c) -block (d) -block (c).
It is not limited to this.

Such a block copolymer (B) can be produced, for example, by the following method. (1) A method of sequentially polymerizing styrene or a derivative thereof, isoprene, or an isoprene-butadiene mixture using an alkyllithium compound as an initiator. (2) A method in which styrene or a derivative thereof, and then isoprene or a mixture of isoprene and butadiene are polymerized, and this is coupled with a coupling agent. (3) A method of sequentially polymerizing isoprene or an isoprene-butadiene mixture, and then styrene or a derivative thereof using a dilithium compound as an initiator.

Details of the method for producing the block copolymer (B) are described in, for example, JP-A-2-300250. Further, when the block copolymer (B) obtained by the above method is subjected to hydrogenation treatment, a hydrogenated block copolymer (B) can be obtained. The block to be hydrogenated is an isoprene polymer block or an isoprene-butadiene copolymer block (d).

In the first thermoplastic elastomer composition according to the present invention, the block copolymer (B) is added to the polyolefin composition (A) and the block copolymer (B) in an amount of 100 parts by weight. 90 to 50 parts by weight, preferably 85 to 60 parts by weight.

In the second thermoplastic elastomer composition according to the present invention, the block copolymer (B) is
Based on 100 parts by weight of the total amount of the polyolefin composition (A), the block copolymer (B), the block copolymer (C), the olefin rubber (D), the softening agent (E) and the thermoplastic elastomer (F). 90 to 25 parts by weight, preferably 85 to 30 parts by weight.
However, the above components (C), (D), (E) and (F)
Is an optional component, so these components may be 0 parts by weight.

When the block copolymer (B) is used in the above proportion, a thermoplastic elastomer composition which can provide a molded article having excellent heat resistance and scratch resistance and abrasion resistance can be obtained.

Block Copolymer (C) The block copolymer (C) optionally used in the present invention includes a polymer block (e) of styrene or a derivative thereof and a specific isoprene polymer or a specific isoprene. A block (f) composed of a butadiene copolymer,
Alternatively, it may consist of a butadiene polymer block (g) and may be hydrogenated.

The polymer component constituting the block (e) is styrene or its derivative. Specific examples of the styrene derivative include the same compounds as those exemplified in the section of the copolymer (B). As the polymer component forming the block (e), styrene and α-methylstyrene are preferable.

The polymer or copolymer forming the block (f) is an isoprene polymer or an isoprene-butadiene copolymer, and is bonded at the 1,2-position and the 3,4-position with respect to all isoprene units. The isoprene unit content is 30% or less, preferably 25% or less.

In the present invention, when the content of isoprene units bonded at the 1,2-position and the 3,4-position with respect to all isoprene units is 30% or less, a molded product having a good appearance can be provided. A thermoplastic elastomer composition can be obtained.

The block copolymer (C) used in the present invention may be composed of the block (e) and the block (f), or the block (g) composed of the block (e) and the butadiene polymer. ) And may consist of

The proportion of the polymer block (e) of styrene or its derivative in the block copolymer (C) is preferably 5 to 50% by weight, more preferably 10 to 45%.
It is in the range of% by weight. That is, the ratio of the isoprene polymer block or the isoprene-butadiene copolymer block (f) or the butadiene polymer block (g) is preferably 95 to 50% by weight, more preferably 90 to 55% by weight. Is.

In the present invention, the hydrogenated block copolymer (C) is preferred. When the hydrogenated block copolymer (C) is used, a thermoplastic elastomer composition which can provide a molded article having excellent weather resistance and heat resistance can be obtained.

The melt flow rate (MFR; ASTM D 1) of the block copolymer (C) used in the present invention.
238, 230 ° C., 2.16 kg load) is preferably 0.01 to 100 g / 10 minutes, more preferably 0.0.
It is in the range of 1 to 50 g / 10 minutes. When the block copolymer (C) having a melt flow rate in the above range is used, a thermoplastic elastomer composition capable of providing a molded article having excellent scratch resistance can be obtained.

The block form of the block copolymer (C) used in the present invention is most preferably block (e) -block (f) or (g) -block (e), but is not limited thereto. Not a thing.

The optionally hydrogenated block copolymer (C) can be produced, for example, by the same method as the method for producing the block copolymer (B) described above.

When the hydrogenated block copolymer is prepared, the hydrogenated block is an isoprene polymer block, an isoprene-butadiene copolymer block (f) or a butadiene polymer block (g). is there.

In the present invention, the block copolymer (C) is a polyolefin composition (A), a block copolymer (B), a block copolymer (C), an olefin rubber (D), a softening agent ( 0 to 30 parts by weight, preferably 0 to 25 parts by weight, and more preferably 0 to 100 parts by weight of the total amount of E) and the thermoplastic elastomer (F).
It is used in a proportion of 20 parts by weight. However, since the above components (C), (D), (E) and (F) are optional components, these components may be 0 parts by weight.

When the block copolymer (C) is used in the above proportion, a thermoplastic elastomer composition is obtained which is excellent in scratch resistance and abrasion resistance and can provide a molded article having an excellent appearance.

Olefin-based rubber (D) The olefin-based rubber (D) optionally used in the present invention is an amorphous random elastic copolymer having an α-olefin content of 2 to 20 carbon atoms of 50 mol% or more. Polymers may be mentioned. In the present invention, the olefin rubber (D) and a rubber other than the olefin rubber (D) such as styrene-
Butadiene rubber (SBR), nitrile rubber (NBR),
A diene rubber such as natural rubber (NR) or butyl rubber (IIR), or polyisobutylene rubber may be used in combination.

As the amorphous random elastic copolymer having an α-olefin content of 2 to 20 carbon atoms of 50 mol% or more, an α-olefin copolymer composed of two or more kinds of α-olefins, 2 There is an α-olefin / non-conjugated diene copolymer composed of at least one α-olefin and a non-conjugated diene, and specific examples thereof include the following rubbers. (1) Ethylene / α-olefin copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10
50/50] (2) Ethylene / α-olefin / non-conjugated diene copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10
-50/50] (3) Propylene / α-olefin copolymer rubber [propylene / α-olefin (molar ratio) = about 90/1
0-50 / 50] (4) Butene / α-olefin copolymer rubber [butene / α-olefin (molar ratio) = about 90/10
50/50] As the α-olefin, specifically, ethylene,
Propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like can be mentioned.

Specific examples of the non-conjugated diene include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and ethylidene norbornene.

The iodine value of the ethylene / α-olefin / non-conjugated diene copolymer rubber of the above (2) in which such a non-conjugated diene is copolymerized is preferably 25 or less. Mooney viscosity [ML] of the copolymer rubber of the above (1) to (4)
_{1 + 4} (100 ° C)] is 10 to 250, especially 30
~ 150 is preferred.

In the present invention, the olefin rubber (D) is a polyolefin composition (A), a block copolymer (B), a block copolymer (C), an olefin rubber (D), a softening agent (E). ) And the total amount of thermoplastic elastomer (F) of 100 parts by weight, 0 to 40 parts by weight, preferably 0 to 30 parts by weight, and more preferably 0 to 30 parts by weight.
It is used in a proportion of 25 parts by weight. However, since the above components (C), (D), (E) and (F) are optional components, these components may be 0 parts by weight.

When the olefin rubber (D) is used in the above proportion, a thermoplastic elastomer composition which is excellent in scratch resistance and can provide a molded article excellent in flexibility is obtained.

Softener (E) As the softener (E) optionally used in the present invention, a softener usually used for rubber is suitable, and specifically, a process oil, a lubricating oil and a paraffin. , Liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, petroleum-based substances such as petrolatum;
Coal tars such as coal tar and coal tar pitch; fatty oils such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; tall oil, beeswax, carnauba wax, lanolin and other waxes, ricinoleic acid, palmitic acid , Stearic acid, 12-hydroxy stearic acid, montanic acid, oleic acid, erucic acid and other fatty acids or metal salts thereof; petroleum resin, coumarone indene resin, synthetic polymer such as atactic polypropylene; dioctyl phthalate, dioctyl adipate, Other examples include ester plasticizers such as dioctyl sebacate; microcrystalline wax, liquid polybutadiene or its modified products or hydrogenated products, and liquid thiochol.

In the present invention, the softening agent (E) is a polyolefin composition (A), a block copolymer (B), a block copolymer (C), an olefin rubber (D), a softening agent (E). And total amount of thermoplastic elastomer (F) 1
0 to 40 parts by weight, preferably 0 to 0 parts by weight
It is used in an amount of 30 parts by weight, more preferably 0 to 20 parts by weight. However, the above components (C), (D), (E)
Since (F) is an optional component, these components are 0
It may be part by weight.

When the softening agent (E) is used in the above proportion, a thermoplastic elastomer composition having excellent fluidity during molding can be obtained. A molded article made of this thermoplastic elastomer composition has good scratch resistance.

Thermoplastic Elastomer (F) The thermoplastic elastomer (F) optionally used in the present invention is composed of a crystalline polyolefin resin and an olefin rubber.

As the above crystalline polyolefin resin,
Examples thereof include homopolymers or copolymers of α-olefins having 2 to 20 carbon atoms. Specific examples of the crystalline polyolefin resin include the following polymers or copolymers. (1) Ethylene homopolymer (manufacturing method may be either low pressure method or high pressure method) (2) Copolymerization of ethylene with 10 mol% or less of other α-olefin or vinyl monomer such as vinyl acetate or ethyl acrylate Polymer (3) Propylene homopolymer (4) Random copolymer of propylene and 10 mol% or less of other α-olefin (5) Propylene and 30 mol%
The following block copolymers with other α-olefins (6) 1-butene homopolymer (7) Random copolymers of 1-butene with 10 mol% or less of other α-olefins (8) 4- Methyl-1-pentene homopolymer (9) 4-methyl-1-pentene and 20% by mole or less of other α
-Random copolymer with olefin As the above α-olefin, specifically, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-
Examples include hexene and 1-octene.

Among the above crystalline polyolefin resins, the propylene homopolymer and the propylene content are 5
A propylene / α-olefin copolymer of 0 mol% or more is particularly preferable.

The above crystalline polyolefin resins can be used alone or in combination. The crystalline polyolefin resin used in the present invention is
Melt flow rate (MFR; ASTM D 1238,
230 ° C, 2.16 kg load), preferably 0.01
~ 100g / 10 minutes, more preferably 0.3-70g
/ 10 minutes.

The crystallinity of the crystalline polyolefin resin determined by the X-ray method is usually 5 to 100%, preferably 20 to 80%. The crystalline polyolefin resin constituting the thermoplastic elastomer (F) is the total amount of the crystalline polyolefin resin and the olefin rubber is 1
10 to 90 parts by weight, preferably 1
It is used in an amount of 0 to 80 parts by weight, more preferably 20 to 70 parts by weight.

When the thermoplastic elastomer (F) containing the crystalline polyolefin resin in the above proportion is used, it is possible to provide a molded article which is excellent in scratch resistance and heat resistance and which is excellent in moldability. A plastic elastomer composition is obtained.

As the olefin rubber, the above-mentioned olefin rubber (D) can be used. Olefin-based rubber is a thermoplastic elastomer (F)
It exists in a partially crosslinked state or a completely crosslinked state. In the present invention, it is preferable that the olefin rubber is in a partially crosslinked state.

Further, in the present invention, an olefin rubber and a rubber other than the olefin rubber may be used in combination within a range not impairing the object of the present invention. Examples of rubbers other than such olefin rubbers include styrene-butadiene rubber (SBR), nitrile rubber (NBR), natural rubber (NR) and butyl rubber (IIR).
And the like, such as diene rubber and polyisobutylene rubber.

In the thermoplastic elastomer (F), the olefinic rubber is 10 to 9 relative to 100 parts by weight of the total amount of the crystalline polyolefin resin and the olefinic rubber.
It is used in an amount of 0 part by weight, preferably 20 to 90 parts by weight, more preferably 30 to 80 parts by weight.

When the olefin rubber and the rubber other than the olefin rubber are used in combination, the rubber other than the olefin rubber is 100 parts by weight of the total amount of the crystalline polyolefin resin and the olefin rubber. Four
It is used in an amount of 0 parts by weight or less, preferably 5 to 20 parts by weight.

The thermoplastic elastomer (F) in which the olefin rubber is blended in the above proportion, or the thermoplastic elastomer (F) in which the olefin rubber and a rubber other than the olefin rubber are blended in the above proportion is used. Thus, a thermoplastic elastomer composition which can provide a molded article having excellent scratch resistance and flexibility is obtained.

In the thermoplastic elastomer (F) used in the present invention, if necessary, a mineral oil type softener, a heat resistance stabilizer, an antistatic agent, a weather resistance stabilizer, an antiaging agent, a filler, a colorant, Additives such as lubricants can be added within a range that does not impair the object of the present invention.

The thermoplastic elastomer (F) preferably used in the present invention is a crystalline polypropylene resin and an ethylene / α-olefin copolymer rubber or ethylene / α.
-Consisting of olefin / non-conjugated diene copolymer rubber,
In the thermoplastic elastomer (F), these components are present in a partially crosslinked state, and the weight mixing ratio of the crystalline polypropylene resin and the olefin rubber (crystalline polypropylene resin / olefin rubber) is 70 / Thirty
Within the range of 10/90.

More specific examples of the thermoplastic elastomer (F) preferably used in the present invention include 60 to 10 parts by weight of a crystalline polypropylene resin and an ethylene / propylene copolymer rubber or ethylene / propylene as an olefin rubber. 40 to 90 parts by weight of diene copolymer rubber [total amount of crystalline polypropylene resin and olefinic rubber is 100 parts by weight], and 5 to 40 parts by weight of rubber other than olefinic rubber and / or mineral oil type The thermoplastic elastomer is composed of 5 to 100 parts by weight of a softening agent, and the olefin rubber is partially crosslinked.

The thermoplastic elastomer (F) used in the present invention can be obtained by dynamically heat treating a blend containing a crystalline polyolefin resin and an olefin rubber in the presence of an organic peroxide. it can.

Specific examples of the organic peroxide include:
Dicumyl peroxide, di-tert-butyl peroxide,
2,5-Dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert- Butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-
4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl carbonate, diacetyl Examples thereof include peroxides, lauroyl peroxide, and tert-butyl cumyl peroxide.

Among these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di-from the viewpoint of odor and scorch stability. (Tert-Butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4 1,4-bis (tert-butylperoxy) valerate is preferred, and among them, 1,3-bis (tert-butylperoxyisopropyl) benzene is most preferred.

In the present invention, the organic peroxide is 0.05 to 3% by weight, preferably 0.1 to 1% by weight, based on 100% by weight of the total amount of the crystalline polyolefin resin and the olefin rubber. Used in proportion.

In the present invention, during the partial crosslinking treatment with the above organic peroxide, sulfur, p-quinonedioxime, p,
Peroxy crosslinking aids such as p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide; Alternatively, polyfunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate, vinyl butyrate, vinyl stearate and other polyfunctional methacrylate monomers. Functional vinyl monomers can be included. By using the above compounds, a uniform and mild crosslinking reaction can be expected. Particularly, divinylbenzene is most preferred in the present invention. Divinylbenzene is easy to handle, has good compatibility with the crystalline polyolefin resin and the olefinic rubber system which are the main components of the above-mentioned substance to be crosslinked, and has the action of solubilizing the organic peroxide. Since it functions as a dispersant for organic peroxides, a thermoplastic elastomer having a uniform cross-linking effect by heat treatment and a good balance of fluidity and physical properties can be obtained.

In the present invention, the above-mentioned crosslinking aid or polyfunctional vinyl monomer is contained in an amount of 0.1 to 2% by weight, particularly 0.3 to 1% by weight, based on the total amount of the above-mentioned article to be crosslinked. It is preferable to use it in a ratio of. When the mixing ratio of the crosslinking aid or the polyfunctional vinyl monomer is within the above range,
In the obtained thermoplastic elastomer, since the crosslinking aid and the polyfunctional vinyl monomer do not remain as unreacted monomers in the elastomer, there is no change in physical properties due to heat history during processing and molding, and It has excellent fluidity.

The above-mentioned "dynamically heat-treating" means kneading each of the above components in a molten state. The dynamic heat treatment is carried out using a kneading device such as a mixing roll, an intensive mixer (for example, Banbury mixer, kneader), a single-screw or twin-screw extruder, and preferably in a non-open type kneading device. The dynamic heat treatment is preferably performed in an inert gas such as nitrogen.

The kneading is preferably carried out at a temperature at which the half-life of the organic peroxide used is less than 1 minute.
The kneading temperature is usually 150 to 280 ° C., preferably 170
˜240 ° C., and the kneading time is 1 to 20 minutes, preferably 1 to 5 minutes. The shearing force applied at the time of kneading is usually determined within the range of 10 to 10 ⁴ sec ^-1 , preferably 10 ² to 10 ⁴ sec ^-1 in terms of shear rate.

As described above, the thermoplastic elastomer (F) in which the olefin rubber is partially or completely crosslinked can be obtained. Here, "partially crosslinked" means that the gel content (cyclohexane insoluble content) measured by the following method is, for example, 10% or more, and particularly 20% or more and less than 98%. In the present invention, the gel content is preferably 30% or more. In addition, "completely crosslinked" means that the gel content (cyclohexane insoluble content) measured by the following method is 98% or more and 100%. When the thermoplastic elastomer (F) in the above range is used, the resulting thermoplastic elastomer composition has good fluidity at the time of molding and can provide a molded product excellent in mechanical strength and heat resistance.

[Method for measuring gel content (insoluble in cyclohexane)] About 100 mg of a thermoplastic elastomer sample was weighed and cut into 0.5 mm × 0.5 mm × 0.5 mm strips, which were then obtained. 30m in a closed container
Immerse in 1 liter of cyclohexane at 23 ° C. for 48 hours.

Next, this sample is taken out on a filter paper and dried at room temperature for 72 hours or more until a constant weight is obtained. The value obtained by subtracting the weight of the cyclohexane-insoluble component (fibrous filler, filler, pigment, etc.) other than the polymer component from the weight of the dry residue is defined as "corrected final weight (Y)".

On the other hand, the value obtained by subtracting the weight of the cyclohexane-soluble component other than the polymer component (for example, the softening agent) and the weight of the cyclohexane-insoluble component other than the polymer component (fibrous filler, filler, pigment, etc.) from the weight of the sample,
The corrected initial weight (X) is used.

Here, the gel content (cyclohexane insoluble content) is determined by the following equation. Gel content [% by weight] = [corrected final weight (Y)] ÷
[Corrected initial weight (X)] × 100 In the present invention, the thermoplastic elastomer (F) is the above-mentioned polyolefin composition (A), block copolymer (B), block copolymer (C), 0 to 50 parts by weight, preferably 0 to 40 parts by weight, and more preferably 0 to 100 parts by weight of the total amount of the olefin rubber (D), the softening agent (E) and the thermoplastic elastomer (F).
It is used in a proportion of 30 parts by weight. However, since the above components (C), (D), (E) and (F) are optional components, these components may be 0 parts by weight.

When the thermoplastic elastomer (F) is used in the above proportion, a thermoplastic elastomer composition which can provide a molded article having excellent heat resistance and scratch resistance is obtained.

Silicone oil (G), ester (H)
And the fluorine-based polymer (I) The silicone oil (G) optionally used in the present invention is specifically dimethyl silicone oil, phenylmethyl silicone oil, fluorosilicone oil, tetramethyltetraphenyltrisiloxane, modified Silicone oil etc. are mentioned. Among them, dimethyl silicone oil and phenylmethyl silicone oil are preferably used.

The kinematic viscosity of this silicone oil (G) [J
IS K 2283, 25 ° C] is 10 to 30,000c
St, preferably 50 to 10,000 cSt, and more preferably 100 to 5,000 cSt.

The ester (H) optionally used in the present invention is an ester of an aliphatic alcohol and a dicarboxylic acid or a fatty acid. As such ester (H), specifically, an ester of cetyl alcohol and acetic acid, an ester of cetyl alcohol and propionic acid, an ester of cetyl alcohol and butyric acid,
Ester of tallow alcohol and acetic acid, ester of tallow alcohol and propionic acid, ester of tallow alcohol and butyric acid, ester of stearyl alcohol and acetic acid,
Esters of stearyl alcohol and propionic acid, esters of stearyl alcohol and butyric acid, esters of distearyl alcohol and phthalic acid, glycerin monooleate, glycerin monostearate, 12-hydroxy stearate, glycerin tristearate, trimethylol Propane tristearate, pentaerythritol tetrastearate, butyl stearate, isobutyl stearate, stearic acid ester, oleic acid ester, behenic acid ester, calcium soap-containing ester, isotridecyl stearate, cetyl palmitate, cetyl stearate, Stearyl stearate,
Examples thereof include behenyl behenate, montanic acid ethylene bricol ester, montanic acid glycerin ester, montanic acid pentaerythritol ester, and calcium-containing montanic acid ester. Among them, esters of distearyl alcohol and phthalic acid, glycerin monooleate, glycerin monostearate, stearic acid ester, montanic acid glycerin ester are preferable, and particularly esters of distearyl alcohol and phthalic acid, glycerin monostearate, montanic acid Glycerin ester is preferred.

Further, as the fluorine-based polymer (I) optionally used in the present invention, specifically,
Examples thereof include polytetrafluoroethylene and vinylidene fluoride copolymer. Among them, polytetrafluoroethylene is preferable.

In the present invention, at least one component selected from the group consisting of the above silicone oil (G), ester (H) and fluoropolymer is used as the polyolefin composition (A), the block copolymer (B). ), The block copolymer (C), the olefin rubber (D), the softening agent (E) and the thermoplastic elastomer (F) in a total amount of 10).
It is used in a proportion of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, relative to 0 parts by weight. However, since the above components (C), (D), (E) and (F) are optional components, these components may be 0 parts by weight.

When the above silicone oil (G), ester (H) or fluoropolymer (I) is used in the above proportion, a thermoplastic elastomer composition having excellent scratch resistance can be obtained. .

Higher fatty acid amide (J) The higher fatty acid amide (J) optionally used in the present invention is specifically saturated lauric acid amide, palmitic acid amide, stearic acid amide, behemic acid amide, or the like. Fatty acid amides; unsaturated fatty acid amides such as erucic acid amide, oleic acid amide, brassic acid amide, and elaidic acid amide; methylenebisstearic acid amide, methylenebisstearic acid amide, ethylenebisstearic acid amide, ethylenebisoleic acid amide, etc. Examples thereof include bis fatty acid amide. Of these, erucic acid amide, oleic acid amide, and ethylenebisoleic acid amide are preferable.

The higher fatty acid amide (J) as described above is
Based on 100 parts by weight of the total amount of the polyolefin composition (A), the block copolymer (B), the block copolymer (C), the olefin rubber (D), the softening agent (E) and the thermoplastic elastomer (F). 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight. However, since the above components (C), (D), (E) and (F) are optional components, these components may be 0 parts by weight.

When the above-mentioned higher fatty acid amide (J) is used in the above proportion, an olefinic thermoplastic elastomer composition excellent in scratch resistance is obtained due to the surface improving effect.

Other Components In the present invention, in the thermoplastic elastomer composition,
As far as the object of the present invention is not impaired, if necessary, known inorganic fillers, heat stabilizers, antioxidants, weather stabilizers,
Additives such as antistatic agents, metallic soaps, and lubricants such as waxes can be added.

Specific examples of such an inorganic filler include calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, barium sulfate, aluminum sulfate, calcium sulfate and carbonic acid. Magnesium, molybdenum disulfide, glass fiber, glass sphere, shirasu balloon, graphite, alumina and the like can be mentioned.

Examples of known heat stabilizers, antiaging agents and weathering stabilizers include phenol type, sulfite type, phenylalkane type, phosphite type and amine type stabilizers.

Thermoplastic Elastomer Composition In the thermoplastic elastomer composition according to the present invention,
A polymer component based on the total amount of the polyolefin composition (A), the block copolymer (B), the block copolymer (C), the olefin rubber (D), the softener (E) and the thermoplastic elastomer (F), That is, the ratio of the total amount of the polyolefin composition (A), the block copolymer (B), the block copolymer (C), and the olefin rubber (D) is 100 to 40% by weight.

Preparation of Thermoplastic Elastomer Composition The first thermoplastic elastomer composition according to the present invention comprises a polyolefin composition (A) and a block copolymer (B).
And can be prepared by blending them in the above-mentioned proportions and performing a dynamic heat treatment in the absence of an organic peroxide.

The second thermoplastic elastomer composition according to the present invention comprises a polyolefin composition (A), a block copolymer (B), a block copolymer (C) and an olefin rubber (D). , A softening agent (E) and at least one component selected from the group consisting of a thermoplastic elastomer (F) in the above-mentioned proportions and performing a dynamic heat treatment in the absence of an organic peroxide. Can be prepared by

Further, in the preparation of the first and second thermoplastic elastomer compositions according to the present invention, when the above-mentioned respective components are blended, silicone oil (G), ester (H) and Fluorine-based polymer (I)
At least one component selected from the group consisting of and / or higher fatty acid amide (J) can be blended.

As the dynamic heat treatment method, the dynamic heat treatment method described above in the preparation of the thermoplastic elastomer (F) is desirable. However, this dynamic heat treatment is performed in the absence of organic peroxide.

[0104]

Since the thermoplastic elastomer composition according to the present invention contains the polyolefin composition (A) and the block copolymer (B) in a specific ratio, it is lightweight and easy to recycle. It is possible to provide a molded body that does not generate harmful gas even when incinerated and has excellent scratch resistance and abrasion resistance.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. The raw materials used in the production of the thermoplastic elastomer composition in the examples are described below. Polyolefin composition (A) (A-1) Polyethylene composition: 23% by weight of ultrahigh molecular weight polyethylene having an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. of 28 dl / g,
Polyethylene composition consisting of 77% by weight of low molecular weight polyethylene having an intrinsic viscosity [η] of 0.73 dl / g measured in a decalin solvent at 135 ° C. [Intrinsic viscosity [η] measured in a decalin solvent at 135 ° C .: 7 0.0 dl / g, density:
0.965 g / cm ³ ] block copolymer (B) (B-1) Hydrogenated product of styrene / isoprene / styrene block copolymer 1) Styrene content: 20% by weight 2) 1,2 relative to all isoprene units -Position and 3,4
Content of isoprene unit bonded at -position: 55% 3) MFR (ASTM D 1238-65T, 230 ° C, 2.16 kg load):
2.0 g / 10 min Block Copolymer (C) (C-1) Hydrogenated product of styrene / butadiene / styrene block copolymer 1) Styrene content: 40 wt% 2 ) MFR (ASTM D 1238-65T, 230 ℃, 2.16kg load):
15 g / 10 min Olefin rubber (D) (D-1) Ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber 1) Ethylene content: 70 mol% 2) Iodine value: 14 3) Mooney viscosity [ ML1 + 4 (100 ° C.)]: 62 Softening agent (E) (E-1) Mineral oil-based process oil: PW-380 thermoplastic elastomer (F) (F-1) manufactured by Idemitsu Kosan Co., Ltd. Olefin thermoplastic elastomer produced by: Polypropylene as crystalline polyolefin resin [MFR: 13 g / 10 min, crystallinity determined by X-ray method: 72%] 20 parts by weight, and olefin rubber as ethylene / propylene. 5-ethylidene-2-
Norbornene copolymer rubber [ethylene content: 70 mol%, iodine value: 12, Mooney viscosity (ML _{1 + 4} , 100
C.): 120] 80 parts by weight using a Banbury mixer in a nitrogen atmosphere at 180 ° C. for 5 minutes,
The obtained kneaded product was passed through a roll to form a sheet, which was cut with a sheet cutter to produce a square pellet.

Then, 100 parts by weight of the square pellets,
After 0.3 parts by weight of 1,3-bis (tert-butylperoxyisopropyl) benzene and 0.5 parts by weight of divinylbenzene were mixed with stirring with a Henschel mixer, the resulting mixture was mixed with L / D = 30, screw. Using a uniaxial extruder having a diameter of 50 mm, the pellets of the thermoplastic elastomer (F-1) were produced by extruding at 220 ° C in a nitrogen atmosphere.

Obtained thermoplastic elastomer (F-1)
Had a gel content of 84%. Silicone oil (G) (G-1) Silicone oil Toray Silicone, SH200Ester (H) (H-1) distearyl phthalateFluorine-based polymer (I) (I-1) Polyvinylidene fluoride resin: Kureha
Made, KF polymer W-1000Higher fatty acid amide (J) (J-1) Erucamide (J-2) Oleic acid amide (J-3) Ethylenebisoleic acid amide

[0108]

Example 1 After thoroughly mixing 40 parts by weight of the pellets of the polyethylene composition (A-1) and 60 parts by weight of the pellets of the block copolymer (B-1), L / D = 30, screw diameter 50 mm. Using a single screw extruder in a nitrogen atmosphere,
Extrusion at 220 ° C produced pellets of the thermoplastic elastomer composition.

Next, a square plate (150 mm x 150 mm x) was formed from the pellets of the thermoplastic elastomer composition using an injection molding machine.
150 mm × 3 mm) was molded at 220 ° C. And
Place a 30 mm square cotton cloth on the obtained square plate, put a weight on it so that a pressure of 200 g / cm ² is applied, and reciprocate 100 times on the square plate. The state was observed with the naked eye, and the scratch resistance and abrasion resistance were evaluated according to the surface state according to the following 5 grades.

[Five-step evaluation] 5: No scratches or wear observed 4 …… Scratches are recognized but wear is not recognized 3 ... Slight wear is observed 2 ・ ・ ・ A considerable amount of wear is observed 1 ・ ・ ・ Remarkable wear is observed The results are shown in Table 1.

[0111]

Example 2 In Example 1, the blending amount of the polyethylene composition (A-1) and the hydrogenated product of the styrene / isoprene / styrene block copolymer (B-1) was 1 respectively.
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1 except that 5 parts by weight and 85 parts by weight were used.
Further, a square plate was formed in the same manner as in Example 1.

The obtained square plate was evaluated for scratch resistance and wear resistance. The results are shown in Table 1.

[0113]

Example 3 In Example 1, the polyethylene composition (A-1) and the styrene / isoprene / styrene block copolymer hydrogenated product (B-1) were mixed in amounts of 3 and 3, respectively.
0 parts by weight, 40 parts by weight, and 30 parts by weight of the thermoplastic elastomer (F-1) were further mixed to prepare pellets of the thermoplastic elastomer composition in the same manner as in Example 1, and further, as in Example 1. A rectangular plate was formed in the same manner.

The obtained square plate was evaluated for scratch resistance and wear resistance. The results are shown in Table 1.

[0115]

Example 4 30 parts by weight of a polyethylene composition (A-1), 40 parts by weight of a hydrogenated product of a styrene / isoprene / styrene block copolymer (B-1), and a styrene / butadiene / styrene block copolymer. Hydrogenated product (C-
1) Using a Banbury mixer, 10 parts by weight, 10 parts by weight of ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (D-1), and 10 parts by weight of mineral oil type process oil (E-1) were used. Using a nitrogen atmosphere, 180 ℃
After kneading for 5 minutes, the obtained kneaded product was passed through a roll to form a sheet, which was cut with a sheet cutter to produce square pellets.

Then, this square pellet was mixed with L / D = 30,
Using a uniaxial extruder with a screw diameter of 50 mm, the pellets of the thermoplastic elastomer composition were produced by extruding at 220 ° C. in a nitrogen atmosphere.

Further, a square plate was molded from the pellets of the thermoplastic elastomer composition in the same manner as in Example 1. The obtained square plate was evaluated for scratch resistance and wear resistance.

The results are shown in Table 1.

[0119]

Example 5 In Example 4, a polyethylene composition (A-1), a styrene / isoprene / styrene block copolymer hydrogenated product (B-1), and a styrene / butadiene / styrene block copolymer hydrogenated product. Thing (C-
1), ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (D-1) and mineral oil-based process oil (E-1) in an amount of 15 parts by weight and 85 parts by weight, respectively.
Parts by weight, 0 parts by weight, 0 parts by weight, 0 parts by weight, and 3 parts by weight of the silicone oil (G-1) were added to produce pellets of the thermoplastic elastomer composition in the same manner as in Example 4, A rectangular plate was formed in the same manner as in Example 1.

The obtained square plate was evaluated for scratch resistance and wear resistance. The results are shown in Table 1.

[0121]

Example 6 In Example 1, the blending amount of the polyethylene composition (A-1) and the hydrogenated product of the styrene / isoprene / styrene block copolymer (B-1) was 1 respectively.
Example 1 except that 5 parts by weight, 85 parts by weight, and 0.3 part by weight of distearyl phthalate (H-1) were further added.
Pellets of the thermoplastic elastomer composition were produced in the same manner as in, and a square plate was formed in the same manner as in Example 1.

The obtained square plate was evaluated for scratch resistance and wear resistance. The results are shown in Table 1.

[0123]

Example 7 In Example 1, the blending amount of the polyethylene composition (A-1) and the hydrogenated product of the styrene / isoprene / styrene block copolymer (B-1) was 1 respectively.
5 parts by weight, 85 parts by weight, and 5 parts by weight of the polyvinylidene fluoride resin (I-1) were blended to produce pellets of the thermoplastic elastomer composition in the same manner as in Example 1, and A square plate was formed in the same manner as in 1.

The obtained square plate was evaluated for scratch resistance and wear resistance. The results are shown in Table 1.

[0125]

Comparative Example 1 In Example 1, the blending amount of the polyethylene composition (A-1) and the hydrogenated product of the styrene / isoprene / styrene block copolymer (B-1) was 1 each.
5 parts by weight and 0 parts by weight, and further hydrogenated product of styrene / butadiene / styrene block copolymer (C-1) 8
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1 except that 5 parts by weight were compounded, and further, a square plate was formed in the same manner as in Example 1.

The obtained rectangular plate was evaluated for scratch resistance and abrasion resistance. The results are shown in Table 1.

[0127]

Comparative Example 2 In Example 1, the blending amount of the polyethylene composition (A-1) and the hydrogenated product of the styrene / isoprene / styrene block copolymer (B-1) was 5 respectively.
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1 except that the amount was 95 parts by weight, and the square plate was formed in the same manner as in Example 1.

The obtained square plate was evaluated for scratch resistance and wear resistance. The results are shown in Table 1.

[0129]

Comparative Example 3 In Example 1, the blending amount of the polyethylene composition (A-1) and the hydrogenated product of the styrene / isoprene / styrene block copolymer (B-1) was 1 respectively.
5 parts by weight and 15 parts by weight, and further hydrogenated product of styrene / butadiene / styrene block copolymer (C-1)
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1 except that 70 parts by weight were blended.
A square plate was formed in the same manner as in Example 1.

The obtained square plate was evaluated for scratch resistance and wear resistance. The results are shown in Table 1.

[0131]

[Comparative Example 4] In Example 1, the blending amount of the polyethylene composition (A-1) and the hydrogenated product of the styrene / isoprene / styrene block copolymer (B-1) was 1 each.
5 parts by weight and 15 parts by weight, and ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (D-
1) Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1 except that 70 parts by weight were blended, and further, a square plate was formed in the same manner as in Example 1.

The obtained rectangular plate was evaluated for scratch resistance and abrasion resistance. The results are shown in Table 1.

[0133]

Comparative Example 5 A square plate was molded in the same manner as in Example 1 from 100 parts by weight of pellets of the thermoplastic elastomer (F-1).

The obtained square plate was evaluated for scratch resistance and wear resistance. The results are shown in Table 1.

[0135]

[Table 1]

[0136]

Example 8 In addition to 40 parts by weight of pellets of the polyethylene composition (A-1) and 60 parts by weight of the block copolymer (B-1) in Example 1, erucic acid amide (J-1) was used. A thermoplastic elastomer composition pellet was produced in the same manner as in Example 1 except that 3.0 parts by weight of was added, and further, a square plate was formed in the same manner as in Example 1.

Then, a 30 mm square cotton cloth was placed on the obtained square plate, and a weight was placed thereon so that a pressure of ² kg / cm ² was applied, and the cloth was reciprocated 100 times on the square plate.
The surface condition after the reciprocating operation was visually observed, and the scratch resistance and abrasion resistance were evaluated according to the surface condition according to the following five-grade evaluation.

[Five-step evaluation] 5: No scratches or wear observed 4 …… Scratches are recognized but wear is not recognized 3 ... Slight wear is observed 2 ・ ・ ・ A considerable amount of wear is observed 1 ・ ・ ・ Remarkable wear is observed The results are shown in Table 2.

[0139]

Example 9 In Example 8, erucic acid amide (J-
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 8 except that the compounding amount of 1) was 0.7 parts by weight, and further, a square plate was formed in the same manner as in Example 1.

The obtained square plate was evaluated for scratch resistance and abrasion resistance in the same manner as in Example 8. The results are shown in Table 2.

[0141]

Example 10 In Example 8, the erucic acid amide (J
Example 8 except that the compounding amount of -1) was 8.0 parts by weight.
Pellets of the thermoplastic elastomer composition were produced in the same manner as in, and a square plate was formed in the same manner as in Example 1.

The obtained square plate was evaluated for scratch resistance and abrasion resistance in the same manner as in Example 8. The results are shown in Table 2.

[0143]

Example 11 In Example 8, erucic acid amide (J
-1) except that oleic acid amide (J-2) (3.0 parts by weight) was used, pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 8, and further, the same as in Example 1. Then, a square plate was formed.

With respect to the obtained rectangular plate, scratch resistance and abrasion resistance were evaluated in the same manner as in Example 8. The results are shown in Table 2.

[0145]

Example 12 In Example 8, erucic acid amide (J
-1) instead of ethylene bisoleic acid amide (J-
3) Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 8 except that 3.0 parts by weight was used, and further, a square plate was formed in the same manner as in Example 1.

The obtained square plate was evaluated for scratch resistance and wear resistance in the same manner as in Example 8. The results are shown in Table 2.

[0147]

Example 13 In Example 8, the blending amount of the polyethylene composition (A-1) and the hydrogenated product of the styrene / isoprene / styrene block copolymer (B-1) was 3 respectively.
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 8 except that the amount was 0 parts by weight, 40 parts by weight, and 30 parts by weight of the thermoplastic elastomer (F-1) were further compounded. A square plate was molded in the same manner as in.

The obtained square plate was evaluated for scratch resistance and wear resistance in the same manner as in Example 8. The results are shown in Table 2.

[0149]

[Example 14] In Example 4, a polyethylene composition (A-1), a styrene / isoprene / styrene block copolymer hydrogenated product (B-1), and a styrene / butadiene / styrene block copolymer hydrogenated product. Thing (C-
1), ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (D-1), and mineral oil-based process oil (E-1), erucic acid amide (J-
1) A pellet of a thermoplastic elastomer composition was produced in the same manner as in Example 4 except that 3.0 parts by weight was blended.
Further, a square plate was formed in the same manner as in Example 1.

The obtained square plate was evaluated for scratch resistance and wear resistance in the same manner as in Example 8. The result is the second
Shown in the table.

[0151]

Comparative Example 6 In Example 8, the blending amount of the polyethylene composition (A-1) and the hydrogenated product (B-1) of the styrene / isoprene / styrene block copolymer was 4 respectively.
0 parts by weight, 0 parts by weight, and 60 parts by weight of the styrene-butadiene-styrene block copolymer hydrogenated product (C-1) was blended in the same manner as in Example 8 to prepare a thermoplastic elastomer composition. Manufacture pellets,
A square plate was formed in the same manner as in Example 1.

The obtained square plate was evaluated for scratch resistance and wear resistance in the same manner as in Example 8. The result is the second
Shown in the table.

[0153]

Comparative Example 7 From 100 parts by weight of the thermoplastic elastomer (F-1) and 3.0 parts by weight of the erucic acid amide (J-1),
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1, and then square plates were formed in the same manner as in Example 1.

The obtained square plate was evaluated for scratch resistance and wear resistance in the same manner as in Example 8. The result is the second
Shown in the table.

[0155]

[Table 2]

Claims (6)

(57) [Claims] 1. An ultrahigh molecular weight polyolefin (a) [I] having an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent in the range of 7 to 40 dl / g, and an ultimate viscosity measured in a 135 ° C. decalin solvent. Low molecular weight or high molecular weight polyolefin (b) having a viscosity [η] in the range of 0.1 to 5 dl / g
A polyolefin composition consisting essentially of: wherein the ultrahigh molecular weight polyolefin (a) is 15% by weight based on 100% by weight of the total weight of the ultrahigh molecular weight polyolefin (a) and the low molecular weight or high molecular weight polyolefin (b). 10 to 50 parts by weight of a polyolefin composition (A) present in an amount of ˜40% by weight and having an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. in the range of 3.5 to 8.3 dl / g. , And [II] a polymer block (c) of styrene or a derivative thereof and an isoprene polymer block or an isoprene-butadiene copolymer block at 1,2- and 3,4-positions based on all isoprene units. An optionally hydrogenated block comprising a polymer or copolymer block (d) having a bound isoprene unit content of 40% or more. Copolymer (B) 90-50 parts by weight [the component (A) and the total amount is 100 parts by weight of (B)] The thermoplastic elastomer composition characterized in that it consists of. 2. Silicone oil (G), ester (H) of aliphatic alcohol and dicarboxylic acid or fatty acid,
And at least one component selected from the group consisting of the fluoropolymer (I) and the components (A) and (B)
The thermoplastic elastomer composition according to claim 1, which is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of 3. A higher fatty acid amide (J) is added to 100 parts by weight of the total amount of the components (A) and (B).
The thermoplastic elastomer composition according to claim 1 or 2, wherein the thermoplastic elastomer composition contains 0.1 to 10 parts by weight. 4. [I] an ultrahigh molecular weight polyolefin (a) having an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent within the range of 7 to 40 dl / g, and an ultimate viscosity measured in a 135 ° C. decalin solvent. Low molecular weight or high molecular weight polyolefin (b) having a viscosity [η] in the range of 0.1 to 5 dl / g
A polyolefin composition consisting essentially of: wherein the ultrahigh molecular weight polyolefin (a) is 15% by weight based on 100% by weight of the total weight of the ultrahigh molecular weight polyolefin (a) and the low molecular weight or high molecular weight polyolefin (b). 10 to 50 parts by weight of a polyolefin composition (A) present in an amount of ˜40% by weight and having an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. in the range of 3.5 to 8.3 dl / g. , [II] a polymer block (c) of styrene or a derivative thereof, and an isoprene polymer block or an isoprene-butadiene copolymer block, which bonds at 1,2-position and 3,4-position with respect to all isoprene units. Optionally copolymerized block copolymer having an isoprene unit content of 40% or more and a copolymer or copolymer block (d) 90 to 25 parts by weight of the polymer (B), and [III] a polymer block (e) of styrene or a derivative thereof, and an isoprene polymer block or an isoprene-butadiene copolymer block, wherein 1,2 to all isoprene units are included. Hydrogenated consisting of a polymer or copolymer block (f) or a butadiene polymer block (g) having a isoprene unit content of 30% or less bonded at the-and 3,4-positions, Block copolymer (C) 0 to 30 parts by weight, olefin rubber (D) 0 to 40 parts by weight, softening agent (E) 0 to 40 parts by weight, and crystalline polyolefin resin and olefin rubber Partially or completely crosslinked thermoplastic elastomer (F) 0
To at least 50 parts by weight selected from the group consisting of [parts (A), (B), (C), (D), (E) and (F) are 100 parts by weight] And containing components (A), (B), (C), (D),
The component (A) with respect to the total amount of (E) and (F),
The ratio of the total amount of (B), (C) and (D) is 100 to
40% by weight of a thermoplastic elastomer composition. 5. Silicone oil (G), ester (H) of aliphatic alcohol and dicarboxylic acid or fatty acid,
And at least one component selected from the group consisting of the fluoropolymer (I), the components (A), (B),
The thermoplastic elastomer according to claim 4, wherein 0.01 to 10 parts by weight is contained with respect to 100 parts by weight of the total amount of (C), (D), (E) and (F). Composition. 6. A higher fatty acid amide (J) is added to the components (A), (B), (C), (D), (E) and (F).
0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the thermoplastic elastomer composition according to claim 4 or 5.