JP2001234056A - Urethane elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To inexpensively obtain both a thermoplastic elastomer composition having excellent flexibility, weather resistance, heat resistance, low-temperature characteristics, strength, moldability and processability and an elastomer member having excellent scratch resistance comprising the composition, not requiring surface coating. SOLUTION: This thermoplastic elastomer composition comprises (A) 100 pts.wt. of polyurethane elastomer and (B) 10-900 pts.wt. of a copolymerized metallocene polyolefin of 10-40 wt.% of a 3-12C α-olefin comonomer and ethylene, having 0.86-0.94 density and 1.5-5.0 molecular weight distribution (Mw/Mn).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to various molded articles having excellent scratch resistance (scratch resistance) on the surface of molded articles, and excellent flexibility, heat resistance, low-temperature properties, weather resistance, strength, and moldability. The present invention relates to a thermoplastic elastomer composition that can be used as a material.

[0002]

2. Description of the Related Art Thermoplastic elastomers having excellent productivity have been increasingly used for automotive parts, home electric parts, medical parts and miscellaneous goods, for which vulcanized rubber has hitherto been mainly used. Examples thereof include olefin-based elastomers composed of an ethylene-propylene copolymer and polypropylene, polyurethane elastomers, and soft polyvinyl chloride.

However, at present, these molding materials have drawbacks in terms of scratch resistance, flexibility, workability, economy, and recyclability. That is, olefin-based elastomers are relatively inexpensive and have excellent weather resistance and heat resistance, but are inferior in flexibility and scratch resistance. Polyurethane elastomers have excellent scratch resistance, but have the disadvantage that they have a large specific gravity and are expensive. Soft vinyl chloride is relatively inexpensive and has excellent weather resistance and scratch resistance, but has the drawback of poor flexibility at low temperatures and poor recyclability.

Some proposals have also been made for elastomer compositions using hydrogenated derivatives of vinyl aromatic compound-conjugated diene compound block copolymers (hereinafter abbreviated as hydrogenated block copolymers). . For example, JP-A-50-14742, JP-A-52-65551,
JP-A-58-206644 discloses compositions in which a hydrogenated block copolymer is blended with a rubber softener and an olefin resin. However, these compositions, like the olefin-based elastomers, also had poor scratch resistance.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional technical problems, and a thermoplastic elastomer having excellent flexibility, weather resistance, heat resistance, low-temperature properties, strength, and moldability. Another object of the present invention is to provide an inexpensive elastomer member having excellent scratch resistance which does not require coating of the surface of the composition.

[0006]

That is, the present invention relates to a thermoplastic elastomer composition comprising the following components (A) and (B). (A) polyurethane elastomer: 100 parts by weight (B) density 0.86 to 0.94, molecular weight distribution (Mw /
Copolymerized metallocene polyolefin of 10 to 40% by weight of an α-olefin comonomer having 3 to 12 carbon atoms having an Mn of 1.5 to 5.0 and ethylene, and
0 to 900 parts by weight

Hereinafter, the present invention will be described in detail. The polyurethane elastomer (hereinafter abbreviated as TPU) as the component (A) of the present invention is classified according to the linear polyol used, and includes polyester (caprolactone, adipate), polycarbonate, and polyether types. Both can be used. Of these, polycarbonates having high mechanical strength and a good balance of heat aging resistance and hydrolysis resistance are desirable.

The polycarbonate-based polyurethane elastomers have a Shore D hardness of 20 to 70 obtained by copolymerizing the following components (a) and (b) and, if necessary, component (c).
Are preferred.

(A) A polycarbonate diol comprising a repeating unit represented by the following formula (1) and having a terminal group of a hydroxyl group (wherein R represents an aliphatic or alicyclic hydrocarbon group having 2 to 10 carbon atoms) .

[0010]

Embedded image

(B) Polyisocyanate (c) Chain extender having two active hydrogens capable of reacting with polyisocyanate

The polycarbonate diol used as the component (a) of the polyurethane elastomer of the present invention comprises:
Schell, Polymer Review No. 9
, Pages 9-20 (1964), from aliphatic and / or cycloaliphatic diols. Preferred diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 2,3 -Butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like.

In order to obtain a steering wheel having a good balance of hydrolysis resistance (sweat resistance), weather resistance and softness, it is necessary to use 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. Is preferred.

Particularly preferred polycarbonate diols are 1,4-butanediol and / or 1,5-butanediol.
A copolymerized polycarbonate diol synthesized from pentanediol and 1,6-hexanediol is preferred because the resulting thermoplastic elastomer composition has excellent low-temperature properties and rebound resilience. A repeating unit in the polymer,
The ratio of 1,4-butanediol and / or 1,5-pentanediol to 1,6-hexanediol is 1
0/90 to 90/10, preferably 20/80 to 80
/ 20, more preferably 30/70 to 70/30.

The average molecular weight of the polycarbonate diol used in the present invention is usually in the range of number average molecular weight of 500.
~ 5000, preferably 1000 ~ 3000,
More preferably, those having a molecular weight of 1500 to 2500 are used, and it is desirable that the terminal of the polymer is substantially all hydroxyl groups.

In the present invention, in addition to the above-mentioned diols, compounds having three or more hydroxyl groups in one molecule, such as trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol,
Polyurethane using a polycarbonate which has been polyfunctionalized by using a small amount such as the above is also included.

Next, as the polyisocyanate used as the component (b) of the polyurethane elastomer of the present invention, for example, 2,4-tolylene diisocyanate, 2,6
-Tolylene diisocyanate and mixtures thereof (TD
I), diphenylmethane-4,4′-diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3′-dimethyl-4,4′-biphenylene diisocyanate, crude TDI, polymethylene polyphenylisocyanate, Known aromatic diisocyanates such as crude MDI; xylylene diisocyanate (XD
I), known aromatic alicyclic diisocyanates such as phenylene diisocyanate; 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), cyclohexane diisocyanate (hydrogenated XDI) Known aliphatic diisocyanates, such as
And modified isocyanurates, carbodiimidations and biurets of these isocyanates.

Suitable chain extenders used as necessary as the copolymer component (c) of the polyurethane elastomer of the present invention include those commonly used in the polyurethane industry. Supervised by Keiji Iwata Recent polyurethane application technology CMC 1985, pp. 25-27, including known water, low molecular polyol, polyamine and the like.
A known polyol may be used in combination with the aliphatic polycarbonate used in the present invention, depending on the use of the polyurethane, as long as the effects of the present invention are not impaired. Known polyols include known polyols such as polyester and polyether carbonate described in Yoshio Imai, Polyurethane Form Polymer Publishing Association, 1987, pp. 12-23.

Specifically, a diol having a molecular weight of 300 or less is usually used as the low-molecular polyol. For example, aliphatic diols such as ethylene glycol, 1,3-propylene diol, 1,4-butane diol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol and the like can be mentioned.

Also, alicyclic diols such as 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and tricyclodecanedimethanol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxy Phenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4 (2-hydroxy) phenyl] sulfone,
1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane and the like. Preferably, ethylene glycol and 1,4-butanediol are used.

As a method for producing the polyurethane elastomer of the present invention, a urethane-forming reaction technique known in the polyurethane industry is used. For example, an NCO-terminated polyurethane prepolymer is produced by reacting the polyol with an organic polyisocyanate at room temperature to 200 ° C.

A thermoplastic polyurethane elastomer can be produced using the polyol, polyisocyanate and, if necessary, a chain extender. In the production of these, known polymerization catalysts represented by organic metal salts such as tertiary amines, tin, and titanium are described, for example, by Keiji Yoshida (polyurethane resin), published by Nihon Kogyo Shimbun, pp. 23-32 (1).
969) can be used. These reactions may be carried out using a solvent, and preferred solvents include dimethylformamide, diethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, methylisobutylketone, dioxane, cyclohexanone, benzene, toluene, and ethylcellosolve. is there.

In producing the polyurethane elastomer of the present invention, a compound containing only one active hydrogen which reacts with an isocyanate group, for example, a monohydric alcohol such as ethyl alcohol and propyl alcohol, and a compound such as diethylamine and di-n-propylamine Secondary amines and the like can be used as terminal terminators.

The polyurethane elastomer using the polycarbonate diol of the present invention is not only excellent in flexibility and elastic recovery but also extremely good in hydrolyzability as compared with other polyurethane elastomers. When used as a member, it is suitable because of its excellent sweat resistance.

Next, the metallocene polyolefin as the component (B) of the present invention is produced using a metallocene catalyst as described in US Pat. Nos. 5,322,728 and 5,272,236. Polyolefin.
The copolymerized metallocene polyolefin obtained by polymerization using the metallocene catalyst of the present invention is ethylene and having 3 to 12 carbon atoms, for example, propylene, butene-1, pentene-1, hexene-1, heptene-1, Octene-1,
It is a copolymer with one or more α-olefins such as 4-methyl-pentene-1 and decene-1. α-
The copolymerization ratio of the olefin is in the range of 10 to 40% by weight, preferably 15 to 30% by weight, and more preferably 20 to 30% by weight. α-olefin copolymerization ratio is 10% by weight
If it is less than 10, the resulting elastomer composition is inferior in soft feeling, rubber elasticity, and low-temperature characteristics, which is not preferable. Also, α-
When the copolymerization ratio of the olefin exceeds 40% by weight. It is not preferable because the strength, heat resistance and scratch resistance of the obtained elastomer composition decrease.

The ethylene-α-olefin copolymer polymerized using a metallocene catalyst has rubber elasticity, flexibility, mechanical strength, and the like as compared with a Ziegler catalyst or a polyolefin-based copolymer polymerized using a solid catalyst or the like. Excellent heat sealability. If the density of the ethylene-α-olefin copolymer is 0.86 to 0.94 g / cm ³ , preferably 0.865 to 0.90 g / cm ³ , the flexibility is extremely excellent. If the density exceeds 0.94 g / cm ³ , the resulting elastomer composition is insufficient in flexibility, which is not preferable. The density is 0.86
When the amount is less than g / cm ³ , the heat resistance of the obtained elastomer composition is unfavorably deteriorated.

A melt index based on ASTM D-1238 (hereinafter abbreviated as MI, condition; 190)
C, 2.16 kgf) is 0.1 to 10 g / 10 min, preferably 0.5 to 5 g / 10 min. MI is 10g / 10
If the amount exceeds the above range, the heat resistance of the obtained elastomer composition deteriorates, which is not preferable. In addition, MI is 0.1 g / 1.
If the time is 0 minute or less, the moldability of the obtained elastomer composition deteriorates, which is not preferable.

The molecular weight distribution measured by GPC, that is, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), Mw
/ Mn is 1.5 to 5.0, preferably 2.0 to 3.0. If the molecular weight distribution exceeds 5.0, the strength, heat resistance and rubber elasticity of the obtained elastomer composition are undesirably deteriorated. On the other hand, if the molecular weight distribution is less than 1.5, the moldability of the obtained elastomer composition is unfavorably deteriorated.

The metallocene catalyst is also called a single-site catalyst or a Kaminsky catalyst.
No. 88, JP-A-7-118431, JP-A-7-118431
A catalyst comprising a metallocene-based transition metal complex and an organoaluminum compound as disclosed in JP-A-148895 and the like, and may be used by being supported on an inorganic substance. Examples of the metallocene-based transition metal compound include a transition metal (titanium, zirconium, hafnium) selected from Group 4B of the periodic table, a cyclopentadienyl group,
A substituted cyclopentadienyl group, a dicyclopentadienyl group, a substituted dicyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is a ligand; Or two or more of these groups are covalently cross-linked to form a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group, or an alkoxy group. , An aryl group, an acetylacetonate group and the like.

Further, as the organoaluminum compound,
Alkyl aluminum and chain or cyclic aluminoxane are mentioned, as alkyl aluminum, triethyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, Diethylaluminum hydride, ethylaluminum sesquichloride and the like can be exemplified, and the chain or cyclic aluminoxane can be produced by contacting the above-mentioned alkylaluminum with water, for example, adding alkylaluminum during polymerization, Water is added later, or water of crystallization of the complex salt or water adsorbed by organic or inorganic compounds It can be obtained by reacting aluminum. Examples of the carrier for supporting the metallocene catalyst include silica gel, zeolite, and diatomaceous earth.

Such copolymerized metallocene polyolefins are available from Dow Chemical Company as A
Trademarks of FFINITY or ENGAGE (ethylene / octene copolymer) and Exxon Chemical
It is commercially available from al Company under the trademark EXACT (ethylene / butene copolymer).

The amount of the metallocene polyolefin copolymerized as the component (B) in the thermoplastic elastomer composition of the present invention is 10 to 900 parts by weight, preferably 20 to 500 parts by weight, per 100 parts by weight of the polyurethane elastomer component (A).
Parts by weight, more preferably 50 to 200 parts by weight.
If the compounding amount of the copolymerized metallocene polyolefin of the component (B) exceeds 900 parts by weight, the scratch resistance and heat resistance are lowered, and the low-temperature characteristics are unfavorably deteriorated. If the amount of the copolymerized metallocene polyolefin of the component (B) is less than 10 parts by weight, the appearance of the molded thermoplastic elastomer composition is deteriorated (flow marks are generated), and the specific gravity is high.

Further, the elastomer composition of the present invention comprises:
If necessary, a polyolefin-based resin can be added. Specific examples of polyolefin resins that can be added include polyethylene resins and polypropylene resins. Examples of the polyethylene resin include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms. In the case of a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms, the α-olefin in the copolymer may be propylene, butene-1, isobutene, pentene-
1, hexene-1, 4-methylpentene-1, octene-1 and the like. The ratio of α-olefin is 3
What is 0% by weight or less is used.

The polypropylene resin is a propylene homopolymer or a copolymer of propylene and an α-olefin having 2 to 8 carbon atoms (hereinafter abbreviated as propylene resin). In the case of a copolymer of propylene and an α-olefin having 2 to 8 carbon atoms, the α-olefin in the copolymer may be ethylene, butene-1, isobutene, pentene-
1, hexene-1, 4-methylpentene-1, octene-1 and the like. The ratio of α-olefin is 3
What is 0% by weight or less is used. These propylene-based resins can be synthesized by a conventionally known method, for example, a propylene homopolymer synthesized using a Ziegler-Natta type catalyst, or a copolymer of random or block propylene and an α-olefin. Is raised.

As additives used in the present invention, it is desirable to use at least an antioxidant, a light stabilizer and a heat stabilizer. Examples of these antioxidants include aliphatic, aromatic or alkyl-substituted aromatic esters of phosphoric acid and phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkylpentaerythritol diacids. Phosphite,
Phosphorus compounds such as dialkylbisphenol A diphosphite; phenol derivatives, especially compounds containing sulfur such as hindered phenol compounds, thioethers, dithioates, mercaptobenzimidazoles, thiocarbanilides, thiodipropionates; tinmalate, dibutyltin mono Tin compounds such as oxides can be used.

These may be used alone or in combination of two or more. The addition amount of these stabilizers is based on 100 parts by weight of the polyetherester block copolymer.
0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, more preferably 0.2 to 2 parts by weight. Generally, antioxidants can be divided into primary, secondary and tertiary antiaging agents. Particularly, as a hindered phenol compound as a primary anti-aging agent, Irganox 1010 (trade name:
Ciba-Geigy), Irganox 1520 (trade name: Ciba-Geigy) and the like are preferable. Phosphorus compounds as secondary aging inhibitors are PEP-36, PEP-24G,
HP-10 (all trade names: manufactured by Asahi Denka Co., Ltd.)
afos168 (trade name: Ciba-Geigy) is preferred. Further, as the sulfur compound as the tertiary aging inhibitor, thioether compounds such as dilauryl thiopropionate (DLTP) and distearyl thiopropionate (DSTP) are preferable.

[0037] Examples of the ultraviolet absorber and light stabilizer include benzotriazole compounds and benzophenone compounds. As the light stabilizer, a radical scavenging light stabilizer such as a hindered amine compound is suitably used.

Further, the composition of the present invention may optionally contain a plasticizer. Examples of such a plasticizer include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, diundecyl phthalate, diisononyl phthalate: tricresyl phosphate, triethyl phosphate, Tributyl phosphate, tri-2-ethylhexyl phosphate, trimethylhexyl phosphate, tris-chloroethyl phosphate, tris-
Phosphates such as dichloropropyl phosphate: octyl trimellitate, isodecyl trimellitate, trimellitate, dipentaerythritol esters, dioctyl adipate, dimethyl adipate, di-2-ethylhexyl azelate,
Dioctyl azelate, dioctyl sebacate, di-2
Fatty acid esters such as ethylhexyl sebacate and methylacetyl ricinocate: pyromellitic esters such as octyl pyromellitic acid: epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized fatty acid alkyl esters: Polyether plasticizers such as adipic acid ether ester and polyether: liquid N
Liquid rubbers such as BR, liquid acrylic rubber and liquid polybutadiene: non-aromatic paraffin oils and the like.

These plasticizers can be used alone or in combination of two or more. The addition amount of the plasticizer is appropriately selected according to the required hardness and physical properties, but is preferably 0 to 50 parts by weight per 100 parts by weight of the composition.

The elastomer composition may contain an inorganic filler, a lubricant, a coloring agent, a silicone oil, a foaming agent, a flame retardant, and the like. Examples of the inorganic filler include calcium carbonate, talc, magnesium hydroxide, mica, barium sulfate, silicic acid (white carbon), titanium oxide,
And carbon black.

Shore D of the thermoplastic elastomer of the present invention
The hardness is preferably from 20 to 70, more preferably from 25 to 70.
The range is 50. If the Shore D hardness is less than 20, heat resistance and scratch resistance are inferior. On the other hand, if the Shore D hardness exceeds 70, the obtained low-temperature performance and soft feeling are insufficient, which is not preferable.

Further, the melt flow rate of the thermoplastic elastomer of the present invention (at 230 ° C., under a load of 2.16 kg,
(Hereinafter abbreviated as MFR) is 0.5 to 100 g / 10 min, preferably 5 to 50 g / 10 min, more preferably 10 to 3 g.
0 g / 10 minutes. If the MFR is less than 0.5 g / 10 minutes, the injection moldability is poor and short shots are caused, which is not preferable. On the other hand, if the MFR exceeds 100 g / 10 minutes, not only are mechanical properties (breaking strength, breaking elongation, etc.) and wear properties inferior, but also low-temperature performance is unfavorably deteriorated.

In general, any method known in the art for blending polymer components may be used to prepare the elastomer composition of the present invention.
In order to obtain the most homogeneous blend, a method of melt-kneading using various kinds of kneading machines such as commonly used mixing rolls, kneaders, Banbury mixers and extruders is desirable. Before melt-kneading, these compounds are dry-blended in advance using a mixer such as a Henschel mixer, tumbler or ribbon blender, and the mixture is melt-kneaded to obtain a homogeneous elastomer composition.

As the molding method of the elastomer composition of the present invention, injection molding, extrusion molding, compression molding and the like can be applied, but it has a feature that it is particularly excellent in moldability at the time of injection molding. When performing injection molding, a normal plastic molding machine can be used, and an injection molded product can be obtained in a short time. In addition, the elastomer composition has an advantage that the sprue portion and the runner portion can be recycled because of its excellent thermal stability.

[0045]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the examples and comparative examples, the test methods used for various evaluation methods are as follows. (1) Shore D hardness [-]: ASTM D2240, D
Type, measured at 23 ° C. (2) Melt flow rate (MFR) [g / 10 min]:
ASTM D1238 was measured at 230 ° C. under a load of 2.16 kg. (3) Tensile strength [kgf / cm ² ]: JIS K625
No. 1 and No. 3 dumbbells and 2 mm thick pressed sheets were used as samples. (4) Elongation [%]: JIS K6251, No. 3 dumbbell, 2 mm thick pressed sheet was used as a sample. (5) Rebound resilience [%]: JIS K6255, Lupke pendulum, 23 ° C. (6) Embrittlement temperature [° C.]: JIS K6261, Gehman torsion test, t100 temperature

(7) Scratch resistance and gloss retention [%]: A flat plate having a smooth surface was formed by injection molding. A flat plate is placed horizontally, and a cotton cloth to which a load of 40 g / cm ² is applied is placed.
Reciprocated twice. The glossiness of the friction surface is determined according to JIS K7105.
(E1), and the retention ratio from the glossiness (E0) before friction; (E1 / E0) × 100 (%) was determined.

(8) Crack drop test: A flat plate having a grained surface (matte, edging depth of about 20 microns) was formed by injection molding. The plate was left in an oven at 100 ° C. for 168 hours. After being taken out of the oven, the surface condition was visually observed, and those having no change were evaluated as ○, slightly glossy as Δ, and glossy as ×.

(9) Formability: A flat plate having a length of 150 mm, a width of 100 mm and a thickness of 2 mm was molded by an injection molding machine under the following conditions (gate; side gate having a cross section of 10 × 2 mm). Observe the appearance of the molded product, such as flow mark and gloss, by visual observation.
Poor ones were marked as x. Cylinder temperature C1: 200
° C, C2: 210 ° C, C3: 210 ° C, nozzle temperature: 2
00 ° C, injection speed: low, mold temperature: 40 ° C

(10) Evaluation of Peelability A flat plate was molded in the same manner except that the injection speed was increased under the above-mentioned injection molding conditions. The case where the peeling phenomenon occurred in the gate portion was visually evaluated as poor, and the case where the peeling phenomenon was not observed was evaluated as good.

(11) Sweat resistance test The injection test piece was subjected to artificial sweat (artificial sweat composition; 7 g of NaCl,
It was immersed in 500 cc of methyl alcohol, 1 g of urea, 4 g of lactic acid, and 500 cc of distilled water at room temperature for 30 days. The test piece was taken out and subjected to an abrasion test (JIS K7
204 after wear test) was rated on a scale of 3. 3: no scratches due to worn wheels were observed at all 2: scratches due to worn wheels were slightly observed 1: scratches caused by worn wheels were clearly observed

The components used in the examples and comparative examples are as follows. Component (A): Polyurethane Elastomer A method for synthesizing an aliphatic copolycarbonate diol is shown below as a reference example.

Reference Example 1 970 g of ethylene carbonate (EC) was placed in a 3 liter flask equipped with a 10 mm diameter and 300 mm length distillation column filled with Dickson packing 3φ and having a thermometer and a stirrer.
(11 mol), 1,6-hexanediol (HDL) 6
50 g (5.5 mol) and 570 g (5.5 mol) of 1,5-pentanediol (PDL) were added, and 20 torr was added.
The mixture was heated and stirred under reduced pressure, and the internal temperature was controlled to 150 ° C. The reaction was carried out for 20 hours while distilling EC having an azeotropic composition and ethylene glycol (hereinafter abbreviated as EG) from the top of the distillation column. Next, the distillation column was removed, the degree of vacuum was reduced to 7 torr, and unreacted EC and diol were recovered. After the completion of the distillation of unreacted substances, the internal temperature is set to 190 ° C,
By distilling out the diol while maintaining the temperature, a self-condensation reaction was performed to increase the molecular weight. Four hours later, G
A polymer having a molecular weight of 2000 was obtained by PC analysis. The yield was 740 g and the hydroxyl value was 56 mgKOH / g. This polymer is abbreviated as pc-a.

Reference Examples 2 and 3 1,4-butanediol (BDL) as the diol,
Aliphatic copolycarbonate diol (pc-pc) was prepared in the same manner as in Reference Example 1 except that 1,5-pentanediol and 1,6-hexanediol were used and the amounts shown in Table 1 were used.
b, pc-c). Table 1 shows the respective molecular weights.

[0054]

[Table 1]

Raw materials used in Examples and Comparative Examples,
And the evaluation method is as follows. 1. Polyurethane elastomer (hereinafter abbreviated as TPU) component Component (A) -1 (TPU-1): pc- obtained in Reference Example 1
a 200 g, hexamethylene diisocyanate 67.2
g was charged into a reactor equipped with a stirrer, thermometer and cooling tube, and reacted at 100 ° C. for 4 hours to obtain a prepolymer having terminal NCO. 30 g of 1,4-butanediol as a chain extender and 0.006 g of dibutyltin dilaurate as a catalyst are added to the prepolymer, and a universal extruder for a laboratory with a built-in kneader (a universal extruder for LABO manufactured by Kasamatsu Chemical Industry Laboratory Co., Ltd.). KR-
(Type 35) at 140 ° C. for 60 minutes, and then pelletized by an extruder. Shore D hardness of urethane elastomer is 3
9, MFR was 24.

Component (A) -2 (TPU-2): TP was used except that pc-b was used as the polycarbonate diol.
Polymerization was carried out in the same manner as in the synthesis method of U-1 to obtain a urethane elastomer. The Shore D hardness of the obtained urethane elastomer was 40, and the MFR was 20.

Component (A) -3 (TPU-3): TP was used except that pc-c was used as the polycarbonate diol.
Polymerization was carried out in the same manner as in the synthesis method of U-1 to obtain a urethane elastomer. The resulting urethane elastomer had a Shore D hardness of 43 and an MFR of 23.

Component (A) -4 (TPU-4): Polycaprolactone polyol (manufactured by Daicel, Placcel 220, molecular weight of 2.0) was used instead of polycarbonate diol.
Compound (00) was synthesized in the same manner as in the synthesis method of TPU-1. The resulting urethane elastomer had a Shore D hardness of 45 and an MFR of 27.

Component (A) -5 (TPU-5): Miractran E190 (manufactured by Nippon Miractran Co., Ltd., MDI / adipate TPU), Shore D hardness 45, MFR: 28

(B): Copolymerized metallocene polyolefin Component (B) -1: Ethylene-octene-1 copolymer (Engage EG8100, octene-1 manufactured by Dow Chemical Co.)
Content: 24% by weight, density: 0.870 g / cm ³ , M
I: 1.0 g / 10 min, Mw / Mn = 2.3, hardness (J
(IS-A): 75, tensile strength: 105 kg / cm ² , elongation at break: 800%)

Component (B) -2: ethylene-octene-1
Copolymer (manufactured by Dow Chemical, Engage EG8200,
Octene-1 content: 24% by weight, density: 0.870 g
/ Cm ³ , MI: 5.0 g / 10 min, Mw / Mn = 2.
2. Hardness (JIS-A): 75, tensile strength: 77 kg /
cm ² , elongation at break: 950%)

Component (B) -3: ethylene-octene-1
Copolymer (Affinity FW165 manufactured by Dow Chemical)
0, octene-1 content: 15% by weight, density: 0.90
2 g / cm ³ , MI: 3.0 g / 10 min, Mw / Mn =
2.2, hardness (JIS-A): 88, tensile strength: 240
kg / cm ² , elongation at break: 600%)

Examples 1 to 10 (A) -1, (A)-
2, (A) -3, (A) -4, and (A) -5 were used as copolymerized metallocene polyolefins (B) -1,
After using (B) -2 and (B) -3 and blending at a ratio shown in Tables 2 to 4 with a Henschel mixer, 45 mm
The mixture was melt-kneaded at 220 ° C. in a twin screw extruder having the same diameter to obtain pellets of the elastomer composition. Tables 2 to 4 show the results of physical properties and molding processability.

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

Comparative Examples 1-4 As the polyetherester block copolymer (A)-
1 and kneaded in the same manner as in Example 1 at the respective ratios shown in Table 3 using the copolymerized metallocene polyolefin and (B) -2, and evaluated. In place of the copolymerized metallocene polyolefin of the present invention, a nonmetallocene copolymerized polyolefin (Nippon Synthetic Rubber Co., Ltd.)
Manufactured by T7711SP, ethylene-propylene copolymer,
Density: 0.87 g / cm ³ , MFR: 2.5 g / 10
Min, Mw / Mn = 2.3, Hardness (JISA): 70)
And kneaded at the respective ratios shown in Table 5 in the same manner as in the method of Example 1 and evaluated. Table 5 shows the results. From this result, it is clear that the composition outside the range of the present invention has any bad physical properties.

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[Table 5]

[0069]

The elastomer composition obtained by the present invention is excellent in scratch resistance, strength, heat resistance, flexibility, and moldability, so that it can be suitably used in the fields of automobile parts, home electric parts, toys, miscellaneous goods and the like. Although it can be used, it is particularly suitable for automotive interior parts such as instrument panels, armrests, handles, horn pads, etc., and interior and exterior parts for automobiles such as window moldings and bumpers, which require a product appearance due to its excellent scratch resistance. Can be. Further, since the surface of the molded article is excellent in scratch resistance and molding workability, the coating step which has been conventionally required can be eliminated, so that high productivity and low cost can be realized.

Claims (4)

[Claims] 1. A thermoplastic elastomer composition comprising the following components (A) and (B): (A) polyurethane elastomer: 100 parts by weight (B) density 0.86 to 0.94, molecular weight distribution (Mw /
Copolymerized metallocene polyolefin of 10 to 40% by weight of an α-olefin comonomer having 3 to 12 carbon atoms having an Mn of 1.5 to 5.0 and ethylene, and
0 to 900 parts by weight 2. The thermoplastic elastomer according to claim 1, wherein the polyurethane elastomer is a polyurethane elastomer obtained by copolymerizing the following components (a), (b) and, if necessary, component (c). Composition. (A) a polycarbonate diol comprising a repeating unit represented by the following formula (1) and having a terminal group of a hydroxyl group (wherein R
Represents an aliphatic or alicyclic hydrocarbon group having 2 to 10 carbon atoms). Embedded image (B) Polyisocyanate (c) Chain extender having two active hydrogens capable of reacting with polyisocyanate 3. The polycarbonate diol comprises a repeating unit of the following formulas (2) and (3), and includes an aliphatic polycarbonate diol having a hydroxyl group as a terminal group,
The ratio of the above (2) and (3) is (2) / (3) = 10/9
3. The thermoplastic elastomer according to claim 2, wherein the polyol is a high molecular weight polyol (where n is an integer of 4 and / or 5), which is 0 to 90/10 (molar ratio). Composition. Embedded image Embedded image 4. The elastomer composition according to claim 1, wherein the comonomer in the copolymerized metallocene polyolefin is octene.