JPH0711125A - Thermoplastic polyurethane-containing resin composition - Google Patents

Abstract

(57) [Summary] [Structure] In the presence of an olefin polymer in a molten state, an aromatic vinyl monomer is preferably used in combination with a functional group-containing vinyl monomer, and a radical initiator is used for a melt-kneading polymerization reaction. A thermoplastic polyurethane-containing resin composition comprising a modified olefin polymer and a thermoplastic polyurethane resin, or in the presence of a molten olefin polymer and a thermoplastic polyurethane resin, an aromatic vinyl monomer preferably containing a functional group A thermoplastic polyurethane-containing resin composition obtained by melt-kneading and polymerization using a radical initiator in combination with a vinyl monomer. [Effect] The thermoplastic polyurethane-containing resin composition of the present invention is excellent in tensile strength and low-temperature characteristics and exhibits almost no water absorption, so that it is used for electric wire coating materials, industrial products, automobile parts, shoe soles, synthetic leather, sports products, etc. It is applicable and very useful.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic polyurethane-containing resin composition having excellent low-temperature properties, tensile strength, moldability and excellent non-water absorbability.

[0002]

2. Description of the Related Art Thermoplastic polyurethane resin (hereinafter TPU
Abbreviated as) is flexibility, tensile strength, low temperature characteristics, oil resistance,
Since it is excellent in bending fatigue resistance and abrasion resistance, it is widely used as a thermoplastic elastomer for sports shoe soles, ski boots, various hoses, tubes, films and the like. However, TPU does not have sufficient heat resistance and moldability,
In addition, it has drawbacks such as high density, high water absorption, and high price compared to other thermoplastic elastomers. In particular, water absorption is a problem, and TPU that has absorbed water is not preferable because it tends to whiten with bubbles when molding is performed. Also, hydrolysis occurs due to water absorption and not only the mechanical strength decreases significantly. However, problems such as dimensional change and deformation also occur. Since TPU has such drawbacks, its application as a thermoplastic elastomer is limited, and the excellent properties inherent to TPU cannot be fully utilized in many cases.

On the other hand, the olefin polymer has many excellent points such as excellent heat resistance, hydrolysis resistance, solvent resistance, low water absorption and low cost. Therefore, attempts have been made to combine TPU and olefin polymers.

However, even if a highly polar TPU and an olefin polymer having a low polarity are simply blended by melt kneading or the like, the compatibility between the two is poor, so that delamination occurs and the mechanical strength thereof can be put to practical use. is not.

Therefore, in order to improve the compatibility with TPU, an olefin polymer is melt-kneaded and polymerized with an unsaturated carboxylic acid such as maleic acid, maleic anhydride or acrylic acid in the presence of a radical initiator. Compositions using modified olefin-based polymers have been proposed.
(JP-A-2-120358 and JP-A-3-2319)
(Gazette No. 63)

[0006]

However, when an olefin polymer is melt-kneaded and polymerized with an unsaturated carboxylic acid in the presence of a radical initiator, a crosslinking reaction or a decomposition reaction of the olefin polymer by the radical initiator is unavoidable. There is a problem that the original physical properties are degraded. That is,
When the amount of unsaturated carboxylic acids is increased in order to improve the compatibility with TPU, it is necessary to increase the amount of the radical initiator, and the crosslinking reaction and decomposition reaction of the olefinic polymer accompanying this increase the molding processability and mechanical strength. Deterioration becomes a problem. On the contrary, if the addition amount of the radical initiator is reduced in order to suppress the crosslinking reaction or the decomposition reaction of the olefin polymer, the addition amount of the unsaturated carboxylic acid will decrease, and TP
There is a problem that the compatibility with U is insufficient. That is, even if the compatibility with TPU is improved by the olefin polymer modified with carboxylic acids, the effect of improving mechanical strength, low temperature characteristics, moldability, etc. was not always sufficient.

Therefore, if a thermoplastic polyurethane-containing resin composition excellent in water absorption and molding processability can be obtained while maintaining various properties of TPU such as low temperature properties and tensile strength, its application will be dramatically expanded. Can be very useful. The problem to be solved by the present invention is to solve the problems of the conventional composition, further improve the compatibility between TPU and an olefin polymer, have excellent low temperature properties and tensile strength, and have low water absorption and the like. It is to provide a thermoplastic polyurethane-containing resin composition.

[0008]

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have melt-kneaded an aromatic vinyl monomer in the presence of a molten olefin polymer and TPU. Thermoplastic polyurethane-containing resin composition obtained by polymerization, or modified olefin polymer obtained by melt-kneading polymerization reaction of aromatic vinyl monomer, and TP
We have found that a thermoplastic polyurethane-containing resin composition comprising U solves the above problems, and has completed the present invention.

That is, the present invention is: (1) In the presence of the olefin polymer (A) in a molten state,
Aromatic vinyl monomer, preferably modified olefin polymer obtained by melt-kneading polymerization reaction of aromatic vinyl monomer and functional group-containing vinyl monomer using radical initiator, and thermoplastic polyurethane A thermoplastic polyurethane-containing resin composition comprising a resin (B).

(2) In the presence of the olefin polymer (A) and the thermoplastic polyurethane resin (B) in a molten state,
A thermoplastic polyurethane-containing resin composition comprising a melt-kneading polymerization reaction of an aromatic vinyl monomer, preferably an aromatic vinyl monomer and a functional group-containing vinyl monomer, using a radical initiator.

[0011]

The present invention will be described in detail. (Constitution) As the olefin polymer (A) in the present invention, at least 50 mol%, preferably 70 mol% or more of 1-olefin, such as ethylene, propylene, butene-1, isobutene, pentene-1, and hexene-1. ,
Polymers of decene-1,4-methylbutene-1,4-methylpentene-1,4,4-dimethylpentene-1, or mixtures of the above olefins are mentioned. Among them, copolymers obtained from propylene and butene-1, and propylene and ethylene are preferable, and a propylene content of 22% by weight or more and a resin-modifying grade are particularly preferable. Further, other polymers may be used within the range that does not impair the properties of the olefin polymer.

As the thermoplastic polyurethane resin (B) in the present invention, a polyurethane resin obtained by reacting a polyisocyanate compound (isocyanate component) with a polyhydroxyl compound (high molecular weight polyol and / or low molecular weight polyol component) can be used. .

The polyisocyanate used for producing such a polyurethane resin includes aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates and modified products of these diisocyanates. Specific examples of such a diisocyanate include JP-A-53-53
-42234 publication can be used. For example, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, cyclohexane diisocyanate, pyridine diisocyanate, toluidine diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, p-phenylene diisocyanate, m -Phenylene diisocyanate, 1,
Included are 5-naphthylene diisocyanates and mixtures thereof.

As the polymer polyol used as a polyhydroxyl compound for the production of polyurethane, polyester polyol, polyether polyol, polybutadiene diol, polycarbonate polyol, polyester polyether polyol and a mixture thereof are suitable.

The polyester polyol mentioned here means
Examples thereof include a condensation product of a polyhydric alcohol and a polybasic carboxylic acid, a condensation product of a hydroxycarboxylic acid and a polyhydric alcohol, and the polyhydric alcohol includes, for example, ethylene glycol, 1,2-propylene glycol, and 1,3. -Propylene glycol, 2,3-butylene glycol, 1,4
-Butylene glycol, 2,2'-dimethyl-1,3-
Examples include glycols such as propanediol, diethylene glycol, 1,5-pentamethylene glycol, 1,6-hexamethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, and mixtures thereof. it can. Examples of polybasic carboxylic acids include succinic acid, maleic acid, adipic acid, glutanoic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid. And the like dibasic acid. As a condensate of a hydroxycarboxylic acid and a polyhydric alcohol, castor oil, a reaction product of castor oil and ethylene glycol, propylene glycol or the like is also useful.

As the low molecular weight polyol, the above diols can be used.

Further, as the polyester polyol,
Polycaprolactone diols obtained by ring-opening addition polymerization of a lactone such as ε-caprolactone in the presence of glycol or the like can also be used. As the polycaprolactone diols, any of those obtained by addition-polymerizing one or more of ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone and the like to the polyhydric alcohols described above is used. Can be used.

The polyether polyol is a product obtained by addition-polymerizing one or more kinds of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran with a compound having two or more active hydrogens, Examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like. Examples of the compound having two or more active hydrogens include polyhydric alcohols described above, polybasic carboxylic acids, amines such as ethylenediamine and hexamethylenediamine,
Examples thereof include resorcin, polyphenols such as bisphenol, castor oil and the like.

The polybutadiene polyol is a diene-based polymer or copolymer having a number average molecular weight of 500 to 25,000 and a carbon number of 4 to 12, and further, these diene monomer and an olefinic addition polymer monomer having a carbon number of 2 to 22. There are copolymers with, for example, polybutadiene homopolymer, polyisoprene homopolymer, butadiene isoprene copolymer, butadiene styrene copolymer, butadiene acrylonitrile copolymer and the like.

Polycarbonate polyols include polyhydric alcohols such as 1,6-hexanediol and 1,4.
-Butanediol, neopentyl glycol, 1,5-
It has a number average molecular weight of about 300 to 15,000 obtained by condensation of pentanediol with phosgene, chloroacetic acid ester, dialkyl carbonate or diallyl carbonate.

The proportions of the olefin polymer (A) and the thermoplastic polyurethane resin (B) in the composition of the present invention vary widely from 2 to 98 parts by weight of the olefin polymer and 98 to 2 parts by weight of the thermoplastic polyurethane resin. be able to.

Examples of the aromatic vinyl monomer used in the melt-kneading polymerization include styrene, methylstyrene, vinyltoluene, vinylxylene, ethylvinylbenzene, and the like.
Isopropyl styrene, chlorostyrene, dichlorostyrene, bromostyrene, etc. are mentioned, and they are used individually or in mixture. Of these, styrene is preferably used. Further, a small amount of other monomers copolymerizable with an aromatic vinyl monomer, for example, various vinyl cyanides such as acrylonitrile, various vinyl esters such as vinyl acetate, acrylic acid or methacrylic acid, or their You may use together alkyl ester or glycidyl ester, and also maleic acid and its ester. In particular, it is preferable to use a vinyl monomer having a functional group capable of reacting with the -NCO group or the -OH group which is a terminal functional group of TPU together with the aromatic vinyl monomer while increasing the polarity of the graft polymer. The polar functional group-containing vinyl monomer used in combination, copolymerizable epoxy group-containing vinyl monomer, hydroxyl group-containing vinyl monomer, carboxyl group-containing vinyl monomer, oxazoline group-containing vinyl monomer, silyl Examples include group-containing vinyl monomers. It is preferably an epoxy group-containing vinyl monomer or a carboxyl group vinyl monomer.

Examples of the epoxy group-containing vinyl monomer include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and methacryl glycidyl ether, which may be used alone or in combination.
Glycidyl methacrylate is particularly preferable. Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl methacrylate, which may be used alone or in combination. .

The carboxyl group-containing vinyl monomer includes, for example, acrylic acid, methacrylic acid, maleic anhydride, maleic acid and the like and alkyl esters thereof, and these are used alone or as a mixture. Examples of the silyl group-containing vinyl monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, vinyltris (2-methoxyethoxy). ) Silane and the like can be used alone or in combination.

The vinyl monomer containing an oxazoline group includes 2-vinyl-2-oxazoline and 2-vinyl-4-.
Methyl-2-oxazoline, 2-isopropenyl-2-
Examples thereof include oxazoline and 2-isopropenyl-4-oxazoline.

The amount of the aromatic vinyl monomer added is 50% by weight based on the thermoplastic polyurethane-containing resin composition of the present invention.
Below, it is preferably 1 to 30% by weight. If it exceeds 50% by weight, the performance of TPU is impaired, which is not preferable.

The amount of the functional group-containing vinyl monomer added is 10% by weight or less, preferably 0.1 to 5 parts by weight, based on the thermoplastic polyurethane-containing resin composition. If it exceeds 10% by weight, not only unreacted monomer increases but also various physical properties of the product are adversely affected, which is not preferable. Further, when the aromatic vinyl monomer and the functional group-containing vinyl monomer are used in combination, the addition amount of the aromatic vinyl monomer is at least the same amount or more as the addition amount of the functional group-containing vinyl monomer, preferably It is preferable to add 1 to 5 times the amount.

The radical initiator is 1 in order to carry out polymerization at the melt-kneading temperature of the olefin polymer and TPU.
Decomposition temperature to obtain half-life of minutes 130-250 ℃
Is preferred. Specific examples include tertiary butyl peroctoate, benzoyl peroxide, 1,1-ditertiary butyl peroxy-3,
5,5-Trimethylcyclohexane, cyclohexanone peroxide, tertiary butyl perbenzoate, dicumyl peroxide, 1,3-bis (tert-butyl peroxyisopropyl) benzene, 2,5
-Dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3 and the like. The amount of the organic peroxide added is 10
It is usually 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, relative to 0 parts by weight.

In the thermoplastic polyurethane-containing resin composition of the present invention, various stabilizers (antioxidants,
Light stabilizer, antistatic agent, antiblocking agent, lubricant),
Inorganic fillers, pigments, other thermoplastic resins, rubbers, etc. can be added.

Various known methods can be applied to the production of the composition of the present invention. For example, a closed mixer such as a Banbury mixer or a continuous kneader such as an extruder can be used. Extruders are preferable when considering industrial production such as granulation, and among them, twin-screw extruders are excellent in terms of supply of reactants, kneading, reaction temperature, control of polymerization time, and the like. preferable.

As a specific method, a radical initiator is added to the powdery or pelletized olefin polymer and TPU and the aromatic vinyl monomer, or the aromatic vinyl monomer and the functional group-containing vinyl monomer. After addition and mixing, the mixture is fed to a twin-screw extruder and heated to 130 to 250 ° C. under pressure to carry out a melt-kneading polymerization reaction, and the extrudate is pelletized or pulverized and then subjected to molding.

As another method, a powdery or pelletized olefin polymer and an aromatic vinyl monomer, or an aromatic vinyl monomer and a functional group-containing vinyl monomer,
After a radical initiator is added to and mixed with, the mixture is fed to a twin-screw extruder and heated to 130 to 250 ° C. under pressure to carry out a melt-kneading polymerization reaction to obtain a modified olefin polymer as an extrudate. Then, the modified olefin polymer and TP
After U is mixed and melt-kneaded with a twin-screw extruder, a Banbury mixer or the like to pelletize or pulverize, it can be molded. The aromatic vinyl monomer and the functional group-containing vinyl monomer may be added to a molten olefin polymer or TPU using a liquid feeder to carry out a polymerization reaction.
Regarding the radical initiator, it may be dissolved in an aromatic vinyl monomer in advance and then added, or the polymerization reaction may be performed by adding the aromatic vinyl monomer to the olefin polymer or TPU using a liquid feeder. You can go.

As the molding method, general molding methods such as injection molding, hollow molding, extrusion molding, blow molding and the like can be applied.

The thermoplastic polyurethane-containing resin composition of the present invention thus obtained has excellent tensile strength, low temperature characteristics,
It has non-water absorbency and can be used for a wide range of purposes.

[0036]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples. However, the following examples and comparative examples do not limit the present invention in any way.

(Example 1) Propylene-butene 1 copolymer "Toughmer P-0180" as an olefin polymer
(Mitsui Petrochemical Industry Co., Ltd.) 920 parts by weight, aromatic vinyl monomer as styrene 80 parts by weight and perhexin 25
2.4 parts by weight of B (radical initiator manufactured by NOF CORPORATION) was added and thoroughly mixed with a Henschel mixer. A roller mixer of Brabender Plastograph manufactured by Brabender of Germany was set so that the temperature of the mixer section was 200 ° C. 45 parts by weight of a mixture of "Tufmer P-0180", styrene and a radical initiator was supplied to the mixer, and a melt-kneading polymerization reaction was carried out at a rotation speed of 40 rpm for 6 minutes to obtain a modified olefin polymer. 13.5 parts by weight of the obtained modified olefin polymer and "Pandex T-1190".
(Thermoplastic polyurethane resin manufactured by Dainippon Ink and Chemicals, Inc.) 31.5 parts by weight was supplied to the mixer, and the rotation speed was 40.
Melt kneading was performed for 6 minutes at rpm. The obtained melt-kneaded product was heated at 190 ° C. and 150 kg / c using a hydraulic press.
Molding was performed under the condition of m ² to obtain a test piece having a thickness of 1 mm. At that time, the appearance of the molded article (∘: good mixed state, Δ: slightly mixed state with layered peeling, slightly bad, ×: poor layered state with mixed layer) was visually confirmed. Further, the test piece was punched out with JIS No. 3 dumbbell to obtain an autograph IM-10.
0 (manufactured by Shimadzu Corporation) using a pulling speed of 50 mm / mi
Elongation at break (%), tensile strength at break (kg)
/ Cm ² ) and 100% modulus (kg / cm ² ). Further, a low temperature flexible temperature was measured by a Crashberg flexible temperature measurement test according to JIS K-6745. Next, in order to evaluate the water absorption, 20
After punching into a size of mm × 50 mm × 1 mm and immersing in distilled water at 23 ° C. for 24 hours, the water absorption rate was calculated by the following formula. The above results are shown in Table 1.

[0038]

Example 2 Propylene-butene 1 copolymer "Toughmer P-0180" as an olefin polymer
220 parts by weight (manufactured by Mitsui Petrochemical Co., Ltd.), 700 parts by weight of "Pandex T-1190" (manufactured by Dainippon Ink and Chemicals, Inc.), 80 parts by weight of styrene as an aromatic vinyl monomer, and 2 parts of perhexin. .5B
2.4 parts by weight of radical initiator (Nippon Yushi Co., Ltd.) was added and thoroughly mixed with a Henschel mixer. A roller mixer of Brabender Plastograph manufactured by Brabender of Germany was set so that the temperature of the mixer section was 200 ° C. "Toughmer P-0180", "Pandex T-1
190 ", 45 parts by weight of a mixture of styrene and a radical initiator was supplied to the mixer, and a melt-kneading polymerization reaction was performed for 6 minutes at a rotation speed of 40 rpm. The obtained melt-kneaded product was molded using a hydraulic press in the same manner as in Example 1 to obtain a test piece. Then, physical properties were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Example 3) Instead of using "Tufmer P-0180" in Example 1, an ethylene-propylene copolymer "JSR EP91" was used as an olefin polymer.
2P "(manufactured by Japan Synthetic Rubber Co., Ltd.), except that 50 parts by weight of styrene as an aromatic vinyl monomer and 30 parts by weight of methacrylic acid as a vinyl monomer containing a functional group were used instead of 80 parts by weight of styrene. The same operation as in Example 1 was performed. Then, physical properties were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Example 4) Instead of using "Tufmer P-0180" in Example 2, an ethylene-propylene-diene copolymer "Mitsui 30" was used as an olefin polymer.
12P ”(manufactured by Mitsui Petrochemical Industry Co., Ltd.) and styrene 8
The same operation as in Example 1 was performed except that 50 parts by weight of styrene as an aromatic vinyl monomer and 30 parts by weight of glycidyl methacrylate as a functional group-containing vinyl monomer were used instead of 0 part by weight. Then, physical properties were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0042]

[Table 1]

(Comparative Example 1) A roller mixer of Brabender Plastograph manufactured by Brabender of Germany was set so that the temperature of the mixer section was 200 ° C. 45 parts by weight of "Pandex T-1190" (thermoplastic polyurethane resin, manufactured by Dainippon Ink and Chemicals, Inc.) was supplied to the mixer and melt-kneaded at a rotation speed of 40 rpm for 6 minutes.
In the same manner as in Example 1, a hydraulic press was used for molding to obtain a test piece. The physical properties were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

(Comparative Example 2) A roller mixer of Brabender Plastograph manufactured by Brabender of Germany was set so that the temperature of the mixer section was 200 ° C. 31.5 parts by weight of "Pandex T-1190" (a thermoplastic polyurethane resin manufactured by Dainippon Ink and Chemicals, Inc.) and 13.5 parts by weight of "Tufmer P-0180" (manufactured by Mitsui Petrochemicals, Ltd.) as an olefin polymer. Was supplied to the mixer, and melt kneading was performed for 6 minutes at a rotation speed of 40 rpm. Example 1
In the same manner as described above, a hydraulic press was used for molding to obtain a test piece. The physical properties were evaluated in the same manner as in Example 1, and the results are shown in Table 2.
It was shown to.

(Comparative Example 3) A roller mixer of Brabender Plastograph manufactured by Brabender of Germany was set so that the temperature of the mixer section was 200 ° C. 31.5 parts by weight of "Pandex T-1190" (a thermoplastic polyurethane resin manufactured by Dainippon Ink and Chemicals, Inc.) and 13.5 parts by weight of "Mitsui 3012P" (manufactured by Mitsui Petrochemicals, Ltd.) as an olefin polymer Supply to mixer, rotation speed 4
Melt kneading was carried out at 0 rpm for 6 minutes. In the same manner as in Example 1, a hydraulic press was used for molding to obtain a test piece. The physical properties were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

(Comparative Example 4) Propylene-butene 1 copolymer "Toughmer P-0180" as an olefin polymer
270 parts by weight (manufactured by Mitsui Petrochemical Industry Co., Ltd.), 700 parts by weight of "Pandex T-1190" (thermoplastic polyurethane resin manufactured by Dainippon Ink and Chemicals Co., Ltd.), an aromatic vinyl monomer was not used, and a functional group was used. The same operation as in Example 2 was performed except that 30 parts by weight of methacrylic acid was used as the contained vinyl monomer. The physical properties were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

[0047]

[Table 2] From the results shown in Tables 1 and 2, it is clear that the thermoplastic polyurethane-containing resin composition of the present invention has excellent tensile strength, low temperature characteristics, and low water absorption.

Example 5 An ethylene-propylene-diene copolymer "Mitsui 3012" was used as the olefin polymer.
P ”(manufactured by Mitsui Petrochemical Co., Ltd.), 920 parts by weight, and 80 parts by weight of styrene as an aromatic vinyl monomer and 2 parts of perhexin
2.4 parts by weight of 5B (radical initiator manufactured by NOF CORPORATION) was added and thoroughly mixed with a Henschel mixer. A roller mixer of Brabender Plastograph manufactured by Brabender of Germany was set so that the temperature of the mixer section was 200 ° C. 45 parts by weight of a mixture of "Mitsui 3012P", styrene and a radical initiator was supplied to the mixer and the rotation speed was 4
A melt-kneading polymerization reaction was performed at 0 rpm for 6 minutes to obtain a modified olefin polymer. 27 parts by weight of the obtained modified olefin polymer and 18 parts by weight of "Pandex T-2190" (a lactone thermoplastic polyurethane resin manufactured by Dainippon Ink and Chemicals, Inc.) were supplied to the mixer, and the rotation speed was 40r.
Melt kneading was performed for 6 minutes at pm. The obtained melt-kneaded product was molded using a hydraulic press in the same manner as in Example 1 to obtain a test piece. Then, the physical properties are evaluated in the same manner as in Example 1,
The results are shown in Table 3.

(Example 6) Propylene-butene 1 copolymer "Tufmer P-0180" as an olefin polymer
(Mitsui Petrochemical Industry Co., Ltd.) 530 parts, "Pandex T
-2190 "(Lactone-based thermoplastic polyurethane resin
(Manufactured by Dainippon Ink and Chemicals, Inc.) 400 parts by weight, 70 parts by weight of styrene as an aromatic vinyl monomer and perhexine
2.1 parts by weight of 5B (radical initiator manufactured by NOF CORPORATION) was added and thoroughly mixed with a Henschel mixer. A roller mixer of Brabender Plastograph manufactured by Brabender of Germany was set so that the temperature of the mixer section was 200 ° C. "Toughmer P-0180", "Pandex T-
2190 ", a mixture of styrene and a radical initiator 45
Part by weight is fed to the mixer and the speed is 6 rpm at 40 rpm.
A melt-kneading polymerization reaction was carried out for one minute. The obtained melt-kneaded product was molded using a hydraulic press in the same manner as in Example 1 to obtain a test piece. The physical properties were evaluated in the same manner as in Example 1, and the results are shown in Table 3.

(Comparative Example 5) As an olefin polymer, an ethylene-propylene-diene copolymer "Mitsui 3012" was used.
P ”(manufactured by Mitsui Petrochemical Industry Co., Ltd.), 920 parts by weight of aromatic vinyl monomer is not used, 80 parts by weight of methacrylic acid and Perhexin 25B (radical initiator manufactured by NOF Corporation) are used as vinyl monomers containing functional groups 2.4 parts by weight were added and thoroughly mixed with a Henschel mixer. A roller mixer of Brabender Plastograph manufactured by Brabender of Germany was set so that the temperature of the mixer section was 200 ° C. 45 parts by weight of a mixture of "Mitsui 3012P", a functional group-containing vinyl monomer and a radical initiator was supplied to the mixer, and a melt-kneading polymerization reaction was performed at a rotation speed of 40 rpm for 6 minutes to obtain a modified olefin polymer. 27 parts by weight of the obtained modified olefin polymer and 18 parts by weight of "Pandex T-2190" (a lactone thermoplastic polyurethane resin manufactured by Dainippon Ink and Chemicals, Inc.) were supplied to the mixer, and the rotation speed was 40.
Melt kneading was performed for 6 minutes at rpm. The obtained melt-kneaded product was molded using a hydraulic press in the same manner as in Example 1 to obtain a test piece. The physical properties were evaluated in the same manner as in Example 1, and the results are shown in Table 4.

(Comparative Example 6) A Brabender Plastograph roller mixer manufactured by Brabender of Germany was set so that the temperature of the mixer section was 200 ° C. 18 parts by weight of "Pandex T-2190" (a lactone thermoplastic polyurethane resin manufactured by Dainippon Ink and Chemicals, Inc.) and a propylene-butene 1 copolymer as an olefin polymer "Tufmer P-0180" (Mitsui Petrochemical Industry Co., Ltd. 2)
7 parts by weight were supplied to the mixer, and melt kneading was performed at a rotation speed of 40 rpm for 6 minutes. In the same manner as in Example 1, a hydraulic press was used for molding to obtain a test piece. The physical properties were evaluated in the same manner as in Example 1, and the results are shown in Table 4.

[0052]

[Table 3]

[0053]

[Table 4]

[0054]

Industrial Applicability According to the present invention, it has become possible to provide a thermoplastic polyurethane-containing resin composition which is excellent in tensile strength and low temperature characteristics and exhibits almost no water absorption. The obtained thermoplastic polyurethane-containing resin composition is very useful because it can be applied to electric wire coating materials, industrial products, automobile parts, shoe soles, synthetic leather, sports products, paints, adhesives and the like.

Claims (6)

[Claims] 1. A modified olefin polymer obtained by melt-kneading and polymerizing an aromatic vinyl monomer with a radical initiator in the presence of a molten olefin polymer (A), and a thermoplastic polyurethane resin (B. A thermoplastic polyurethane-containing resin composition comprising: 2. A melt-kneading polymerization reaction of an aromatic vinyl monomer using a radical initiator in the presence of an olefin polymer (A) and a thermoplastic polyurethane resin (B) in a molten state. A thermoplastic polyurethane-containing resin composition. 3. A modified thermoplastic polyurethane resin composition, wherein a functional group-containing vinyl monomer is used in combination in the melt-kneading polymerization reaction according to any one of claims 1 and 2. 4. The thermoplastic polyurethane-containing resin composition according to claim 1, wherein the aromatic vinyl monomer is styrene. 5. The thermoplastic polyurethane-containing resin composition according to claim 3, wherein the functional group-containing vinyl monomer is an epoxy group-containing vinyl monomer. 6. The thermoplastic polyurethane-containing resin composition according to claim 3, wherein the functional group-containing vinyl monomer is a carboxyl group-containing vinyl monomer.