JP2000273254A - Thermoplastic elastomer and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer which is excellent in profile extrusion moldability, gloss and scratch resistance, and has excellent compatibility with various olefinic materials, and is advantageous for recycling. SOLUTION: Crystalline chlorinated polyethylene (a) 100
Parts by weight and an ethylene / α-olefin copolymer (b) obtained by copolymerization using a metallocene catalyst (b)
And 0 parts by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an extruded mold,
The present invention relates to a thermoplastic elastomer having excellent gloss and scratch resistance and excellent compatibility with various olefin-based materials, and a method for producing the same.

[0002]

2. Description of the Related Art Thermoplastic elastomers have rubber-like elasticity,
Excellent in colorability and design, injection molding, extrusion molding, blow molding, sheet molding,
Since it can be easily molded by various molding methods such as vacuum molding, it is used in a wide range of fields as molding materials for automobiles, packing materials for building materials, interior and exterior materials of automobiles, parts for building materials, miscellaneous goods, etc. Is expanding. In particular,
BACKGROUND ART Olefin-based thermoplastic elastomers have been widely used in recent years because they are lightweight, easy to recycle, and have high cost performance.

On the other hand, recently, in the field of automobiles, improvement of fuel efficiency has become an important issue in order to reduce carbon dioxide emissions, and therefore, there is a demand for weight reduction of materials. In particular, there is a strong demand for the development of an alternative material to vinyl chloride resin with a large specific gravity, and as a candidate, an olefin-based material that has excellent compatibility with olefin-based materials often used as molding materials for bumpers and is advantageous for recycling Thermoplastic elastomers are expected.

[0004]

However, conventional olefin-based thermoplastic elastomers are difficult to form a molded article having a complicated shape in extrusion molding, especially in profile extrusion molding, and are inferior in smoothness of the surface of the molded article. There was a problem that it was difficult to obtain a high gloss. In addition, the resulting molded article has poor scratch resistance, and there is a problem that even if the surface is lightly scratched, it is easily scratched. Attempts have been made to increase the hardness and harden the material as a means of increasing the scratch resistance, but in this case, bending marks remain when bent,
There are problems such as whitening and the like, and there is a problem in that the hardening of the composition makes it more difficult to carry out profile extrusion.

For this reason, conventional olefin-based thermoplastic elastomers cannot be used as a substitute for vinyl chloride resin.

The present invention solves the problems of the above-mentioned conventional olefin-based thermoplastic elastomers, and provides a profile extrusion moldability, gloss,
An object of the present invention is to provide a thermoplastic elastomer which is excellent in scratch resistance, has excellent compatibility with various olefin-based materials, and is advantageous for recycling.

[0007]

The thermoplastic elastomer of the present invention is an ethylene / α-olefin copolymer obtained by copolymerizing 100 parts by weight of crystalline chlorinated polyethylene (a) with a metallocene catalyst. (B) 10 to 1000 parts by weight.

The method for producing a thermoplastic elastomer of the present invention comprises the steps of: providing 100 parts by weight of crystalline chlorinated polyethylene (a);
Ethylene obtained by copolymerization using a metallocene catalyst
It is characterized by heating and kneading 10 to 1000 parts by weight of the α-olefin copolymer (b).

That is, the inventor of the present invention has proposed an extruded moldability, gloss,
As a result of intensive studies to obtain a thermoplastic elastomer that has excellent scratch resistance and is compatible with olefin-based materials, a thermoplastic resin containing crystalline chlorinated polyethylene and an ethylene / α-olefin copolymer polymerized by a metallocene catalyst It has been found that the above object can be achieved with an elastomer, and the present invention has been completed.

The thermoplastic elastomer of the present invention may further contain 10 to 1000 parts by weight of a crystalline polyolefin resin (c) in addition to the main components.

In the following, crystalline chlorinated polyethylene (a) constituting the thermoplastic elastomer of the present invention will be described.
And the ethylene / α-olefin copolymer (b) are collectively referred to as “main constituents”.

In the present invention, the term “polyethylene”
"Polyethylene" refers to polyethylene in a broad sense that includes not only "a homopolymer of ethylene" but also "a copolymer of ethylene and another monomer". "And" copolymer of propylene and other monomers ".

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the thermoplastic elastomer of the present invention and a method for producing the same will be described below in detail.

The crystalline chlorinated polyethylene (a), which is one of the main components of the thermoplastic elastomer of the present invention, comprises:
High density polyethylene (HDPE), linear low density polyethylene (LLDPE), branched polyethylene (LDPE)
In addition to chlorinated polyethylene obtained by post-chlorination of ethylene homopolymer, ethylene and monomers copolymerizable therewith, for example, propylene, butene-1,1,4-hexadiene, 1,5-hexadiene, octene-1 Chlorinated polyethylene in a broad sense including a chlorinated ethylene copolymer obtained by post-chlorination of a copolymer with 1,7-octadiene, 1,9-decadiene or the like.

The weight average molecular weight of the polyethylene used for the post-chlorination of the crystalline chlorinated polyethylene (a) is 10 to 75.
It is desirable to be in the range of 10,000, especially 150,000 to 600,000. The polyethylene having a small weight average molecular weight before chlorination is inferior in mechanical properties such as tensile strength of the obtained thermoplastic elastomer, and has poor absorbency of a plasticizer described later, and bleed out easily occurs. . Conversely, if the weight average molecular weight is too large, uniform mixing cannot be performed because the melt viscosity of the obtained thermoplastic elastomer becomes large, and the appearance of a molded product obtained by molding such a thermoplastic elastomer also becomes poor. become.

The chlorination degree (chlorine content) of the crystalline chlorinated polyethylene (a) is from 20 to 45% by weight, especially 2%.
It is desirably in the range of 5 to 40% by weight. If the degree of chlorination of the crystalline chlorinated polyethylene (a) is less than 20% by weight, the compatibility with the plasticizer described later is poor, and the plasticizer tends to bleed. Decrease.

Furthermore, crystalline chlorinated polyethylene (a)
Is the crystallinity, that is, D indicating the residual amount of polyethylene crystal.
It is desirable that the heat of crystal fusion by the SC method be in the range of 5 to 35 cal / g, particularly 5 to 25 cal / g. If the crystal heat of fusion is too large, the hardness increases and lacks elasticity, and if it is too small, the rubber elasticity decreases. Where DSC
The heat of crystal fusion by the (differential scanning calorimetry) method is DS measured at a heating rate of 10 ° C./min using a differential calorimeter.
It indicates the value calculated from the total crystal peak area of the C chart.
In addition, the DSC crystal melting point described below is a temperature at which the highest peak among all the crystal peaks is measured at the time of the DSC crystal melting heat measurement, and the crystalline chlorinated polyethylene having the crystal melting heat suitable for the present invention ( The crystal melting point of a) is generally 1
It will be in the range of 10 to 140C.

The crystalline chlorinated polyethylene (a) used in the present invention preferably has an oil absorption of di-2-ethylhexyl phthalate (DOP) of 25 or more.
If the DOP oil absorption is less than 25, the plasticizer tends to bleed after molding, which is not preferable. Here, the DOP oil absorption refers to 100 g of crystalline chlorinated polyethylene (a) powder at a temperature of 23 ° C. according to JIS K5101.
The amount of DOP added is expressed in ml, and the chlorinated polyethylene (a) powder is agitated while adding DOP little by little. The DOP oil absorption of 25 or more is defined as Even after adding 25 ml, it does not clump,
It means that it is in the form of a powder or that it disperses with a slight force or impact even though it appears to be hardened.

The α-olefin of the ethylene / α-olefin copolymer (b) copolymerized using the metallocene catalyst, which is one of the main components of the thermoplastic elastomer of the present invention, has 3 to 20 carbon atoms. Α-olefins, for example, propylene, 1-butene, 1-pentene,
1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-
Tridecene, 1-tetradecene, 1-pentadecene, 1
-Hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1
-Butene, 3-methyl-1-pentene, 3-ethyl-1
-Pentene, 4-methyl-1-pentene, 4-methyl-
1-hexene, 4,4-dimethyl-1-hexene, 4,
4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-
One or more of tetradecene and the like can be mentioned. α-
As the olefin, preferably an α-olefin having 4 to 10 carbon atoms is used.
Olefin is mentioned, and 1-butene, 1-hexene, 1-octene and 1-decene are particularly preferably used.

The ethylene / α-olefin copolymer (b) has a melt flow rate (MFR, condition: 19).
0 ° C, 2.16 kg load) is 0.01 to 50 g / 10
Min, particularly preferably in the range of 0.01 to 30 g / 10 min. If the MFR is less than 0.01 g / 10 min, dispersion is difficult and the desired physical properties are not exhibited. If the MFR exceeds 50 g / 10 min, the mechanical properties are inferior.

In the present invention, examples of the metallocene catalyst used for the polymerization of the ethylene / α-olefin copolymer (b) include JP-A-3-1630088 and JP-A-7-191.
Examples of the catalyst include a metallocene-based transition metal complex and an organoaluminum compound as disclosed in JP-A-18431 and JP-A-7-148895, and the catalyst may be supported on an inorganic substance. Examples of the metallocene-based transition metal compound of the metallocene catalyst include, for example, a transition metal (titanium, zirconium, hafnium) selected from Group 4B of the periodic table, a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, or a substituted indenyl. A group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluoro group or a substituted fluoro group coordinated as one or two ligands, or a bridged structure of two of these groups coordinated And those having a ligand such as a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an acetylacetonate group.

Further, as the organoaluminum compound,
Examples include alkylaluminums and chain or cyclic aluminoxanes. Examples of the alkylaluminums include triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride , Diethyl aluminum hydride, ethyl aluminum sesquichloride and the like. The chain or cyclic aluminoxane can be produced by bringing the above-mentioned alkylaluminum into contact with water. For example, the alkylaluminum is added during polymerization and then water is added, or water of crystallization of a complex salt or organic or inorganic water is added. It can be obtained by reacting the water adsorbed by the compound with the alkyl aluminum.

Examples of the carrier used for supporting the metallocene catalyst include silica gel, zeolite, and diatomaceous earth.

The ethylene / α-olefin copolymer (b) obtained by the polymerization reaction using such a metallocene catalyst has advantages such as high gloss and excellent scratch resistance.

The thermoplastic elastomer of the present invention may further contain a crystalline polyolefin resin (c).
Examples of the crystalline polyolefin resin (c) include a homopolymer or a copolymer of an α-olefin having 2 to 20 carbon atoms. Specific examples of the crystalline polyolefin resin (c) include ethylene homopolymers, copolymers of ethylene with α-olefins or vinyl monomers such as vinyl acetate and ethylene acrylate, propylene homopolymers, and propylene and α-olefins. Block copolymer, random copolymer of propylene and α-olefin, 1-butene homopolymer, random copolymer of 1-butene and α-olefin, 4-methyl-1-pentene homopolymer, 4-
Random copolymers of methyl-1-pentene and α-olefins, where other α-olefins as comonomer
Examples of the olefin include ethylene, 1-butene, 4
Any one kind or two or more kinds of -methyl-1-pentene, 1-hexene, 1-octene and the like can be mentioned.

These crystalline polyolefin resins (c)
Among them, crystalline polypropylene resin is particularly preferred,
A propylene homopolymer, a block copolymer of propylene and an α-olefin, and a random copolymer of propylene and an α-olefin can be used, and a particularly preferred example is a random copolymer of propylene and the α-olefin. .

As the crystalline polyolefin resin (c), the above-mentioned resins can be used alone or in combination of two or more. The melt flow rate (MFR, condition: 230 ° C., 2 ° C.) of the crystalline polyolefin resin (c) can be used. .16k
g load) is in the range of 0.01 to 10 g / 10 min, preferably 0.1 to 70 g / min. If the MFR is less than 0.01 g / 10 minutes, it is difficult to disperse at the time of kneading, and the appearance of the molded article becomes poor. If it exceeds 100 g / 10 minutes, the scratch resistance becomes poor.

The thermoplastic elastomer of the present invention contains the above main constituent components in the following proportions.

Crystalline chlorinated polyethylene (a): 100
Parts by weight ethylene / α-olefin copolymer (b): 10 to 10
00 parts by weight The ratio of the ethylene / α-olefin copolymer (b) to 10 parts by weight of the crystalline chlorinated polyethylene (a) is 10
If the amount is less than 100 parts by weight, it is difficult to obtain a high gloss.

Further, when the resin composition contains the crystalline polyolefin resin (c), an effect of obtaining more excellent profile extrusion moldability is exhibited. In this case, 100 parts by weight of the crystalline chlorinated polyethylene (a) is obtained. If the proportion of the crystalline polyolefin resin (c) is less than 10 parts by weight, a sufficient effect cannot be obtained, and if it exceeds 1000 parts by weight, it is difficult to obtain high gloss.

The thermoplastic elastomer of the present invention preferably contains the above components in the following proportions.

Crystalline chlorinated polyethylene (a): 100
Parts by weight ethylene / α-olefin copolymer (b): 10 to 10
00 parts by weight crystalline polyolefin resin (c): 10 to 1000 parts by weight The thermoplastic elastomer of the present invention has flexibility,
A softener may be added for the purpose of improving moldability. As the softening agent, a softening agent usually used for rubber is suitable, and specifically, process oil, lubricating oil, paraffin,
Liquid paraffin, polyethylene wax, polypropylene wax, petroleum-based substances such as petroleum asphalt, petrolatum, coal tars such as coal tar and coal tar pitch, fatty acids such as castor oil, linseed oil, rapeseed oil, soybean oil, coconut oil, and tall Oils, beeswax, carnauba wax, waxes such as lanolin, di-2-ethylhexyl phthalate,
Phthalate plasticizers such as di-n-octyl phthalate, diisodecyl phthalate, dibutyl phthalate and dihexyl phthalate; dioctyl adipate; and linear dibasic ester plasticizers such as dioctyl sebacate;
Trimellitic acid ester plasticizers, polyester polymer plasticizers, phosphate ester plasticizers such as triphenyl phosphate, trixylyl phosphate, tricresyl phosphate, etc., may be used alone or in combination of two or more. These can be used in combination.

The amount of the softening agent to be added is appropriately determined according to the type and amount of the main constituents or other additives described above, the hardness of the target product, and the like. However, if the content is too large, other properties are adversely affected. Therefore, the content is preferably in the range of 1 to 200 parts by weight, particularly 3 to 150 parts by weight, based on 100 parts by weight of the total of the main constituent components.

It is desirable to add a silicone oil and / or a higher fatty acid amide to the thermoplastic elastomer of the present invention for the purpose of improving scratch resistance.

Specific examples of the silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, fluorosilicone oil, tetramethyltetraphenyltrisiloxane, and modified silicone oil. Particularly, dimethyl silicone oil and phenylmethyl silicone oil are exemplified. preferable. If the kinematic viscosity (JIS K2283, 25 ° C.) of the silicone oil used is large, stickiness tends to occur and dust and the like easily adhere to the surface of the molded product.
s, particularly preferably in the range of 50 to 10,000 cs.

If the amount of the silicone oil is too small, the effect of adding the silicone oil is not sufficiently obtained, and if the amount is too large, other properties are adversely affected. 01 to 10 parts by weight, especially 0.1 to 5 parts
It is preferred to use parts by weight.

Specific examples of the higher fatty acid amide include saturated higher fatty acid amides such as lauric acid amide, palmitic acid amide, stearic acid amide, and behenic acid amide, erucic acid amide, oleic acid amide, brassic acid amide, and elaidin. Unsaturated fatty acid amides such as acid amides, methylene bisstearic acid amides, bis fatty acid amides such as ethylene bisoleic acid amide, and the like.
Among them, erucamide, oleamide, and ethylenebisoleamide are preferred.

If the amount of the higher fatty acid amide is too small, the effect of the addition is not sufficiently obtained, and if the amount is too large, other properties are adversely affected. 0.01 to 10 parts by weight, especially 0.1 to 5 parts by weight
It is preferred to use parts by weight.

The thermoplastic elastomer of the present invention may further contain a stabilizer, if necessary. An excellent stabilizing effect can be obtained by using a hydrotalcite, an epoxy compound and a phosphite compound together as a stabilizer.

The hydrotalcites are double salts of magnesium and aluminum, and are obtained by pulverizing natural ore such as manasenite or obtained by synthesis. The following general formula (1) It is represented by

[0041]

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These hydrotalcites may be surface-treated with metal salts of higher fatty acids such as sodium stearate and sodium oleate, wax, titanium or silane coupling agents.

Epoxy compounds are compounds having an epoxy group (oxirane ring) in the molecule, and include epoxidized vegetable oils, epoxidized animal oils, epoxidized fatty acid esters,
Epoxidized alicyclic compounds, bisphenol A diglycidyl ether, epoxidized polybutadiene, and the like, particularly, epoxidized soybean oil, epoxidized linseed oil, epoxidized safflower oil, epoxidized sunflower oil, epoxidized corn oil and the like Epoxidized vegetable oils are preferred, and among them, epoxidized soybean oil and epoxidized linseed oil are suitably used.

The phosphite compound is a monophosphite represented by the following general formula (2),
Wherein two substituents of a compound represented by the formula form a ring,
Alternatively, an oligophosphite which is a compound having an oligomer structure in which a substituent is intermolecularly bonded may be mentioned.

[0045]

Embedded image

As such a phosphite compound,
For example, triphenyl phosphite, tris nonyl phenyl phosphite, tris (o-cyclohexyl phenyl) phosphite, tris (p-nonyl phenyl) phosphite, tri (monononyl / dinonyl phenyl) phosphite, phenyl-p-nonyl phenyl Triaryl phosphites such as phosphite, tris (2,4-di-t-butylphenyl) phosphite, isooctyl diphenyl phosphite, isodecyl diphenyl phosphite, lauryl diphenyl phosphite, phenyl diisodecyl phosphite, phenyl diphenyl Alkylaryl phosphites such as lauryl phosphite, trialkyl phosphites such as triisooctyl phosphite, triisodecyl phosphite, trilauryl phosphite, and trioleyl phosphite Aito include bisphenol A tetra C _12-15 alkyl diphosphite (number of carbon atoms in the alkyl group is 12 to 15), distearyl pentaerythritol diphosphite, 2-t-butyl-.alpha. (3-t-butyl-4 -Hydroxyphenyl) p-cumenylbis (p
Oligophosphites such as -nonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, and dinonylphenyldipentaerythritol diphosphite.

Each of these hydrotalcites, epoxy compounds and phosphite compounds may be used alone or in combination of two or more. A suitable addition amount for obtaining an excellent stabilizing effect is obtained. Is 0.1 to 20 parts by weight, particularly 0.5 to 15 parts by weight, of the epoxy compound 0.1 to 20 parts by weight, based on 100 parts by weight of the total of the main constituent components.
5 parts by weight, especially 0.5 to 5 parts by weight, 0.01 to 5 parts by weight, especially 0.1 to 3 parts by weight of the phosphite compound.

The amount of the hydrotalcites added is 0.
If the amount is less than 1 part by weight, a sufficient stabilizing effect cannot be obtained. If the amount exceeds 20 parts by weight, foaming tends to occur during molding. If the amount of the epoxy compound is less than 0.1 part by weight, a sufficient stabilizing effect cannot be obtained, and if it exceeds 5 parts by weight, bleeding is liable to occur. If the amount of the phosphite compound is less than 0.01 part by weight, a sufficient stabilizing effect cannot be obtained. If the amount exceeds 5 parts by weight, bleeding is likely to occur.

The thermoplastic elastomer of the present invention may further contain, if necessary, a stabilizer other than those described above, a lubricant, an antioxidant,
Various additives such as an ultraviolet absorber, a foaming agent, a flame retardant, a colorant, and a filler may be blended.

The thermoplastic elastomer of the present invention may be partially crosslinked. In this case, the thermoplastic elastomer of the present invention can be obtained by melting and kneading a blend containing the main constituent components and other additives in a predetermined ratio in the presence of a crosslinking agent, for example, an organic peroxide. it can.

As the organic peroxide to be used, specifically, dimethyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethylperoxide, Dimethyl-2,5-di-
(T-butylperoxy) hexyne-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,
1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t
-Butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, t-butylcumyl peroxide and the like. No. Preferably, 2,5-dimethyl-2,5-di- (t
-Butylperoxy) hexane, 2,5-dimethyl-
2,5-di- (t-butylperoxy) hexyne-3,
1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,
3,5-trimethylcyclohexane, n-butyl-4,
4-bis (t-butylperoxy) valerate.

These organic peroxides are preferably used in an amount of 0.01 to 3 parts by weight, particularly 0.05 to 2 parts by weight, based on 100 parts by weight of the main constituent components.

In the crosslinking treatment with the organic peroxide, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenyl Guanidine, a peroxy crosslinking auxiliary such as trimethylolpropane-N, N'-m-phenylenedimaleimide, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate,
Polyfunctional methacrylate monomers such as trimethylolpropane trimethacrylate and allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl acetate may be blended. Of these, divinylbenzene is particularly preferably used.

The crosslinking aid, polyfunctional methacrylate or polyfunctional vinyl polymer is used in a total amount of 100
0.01 to 5 parts by weight, especially 0.03 to 3 parts by weight,
It is preferred to use in the range of parts by weight.

The thermoplastic elastomer of the present invention comprises a crystalline chlorinated polyethylene (a) and an ethylene / α-olefin copolymer (b), and if necessary, a crystalline polyolefin resin (c) and the softener. It can be produced by heating and kneading a crosslinking agent, a crosslinking assistant and other various additives at a predetermined ratio.

In the production of this thermoplastic elastomer, at least crystalline chlorinated polyethylene (a) among the constituent components is heated and kneaded to form a gel, and then an ethylene / α-olefin copolymer (b) is formed. ) Is added and heated and kneaded. More preferably, the crystalline chlorinated polyethylene (a) and, if necessary, a softener and other various additives are heated and kneaded. When crosslinking the olefin copolymer (b), and possibly the crystalline polyolefin resin (c), and further the thermoplastic elastomer, it is desirable to add a crosslinking agent or a crosslinking assistant as necessary and uniformly heat and knead. . Thus, by extruding the crystalline chlorinated polyethylene (a) and the softening agent and various additives in advance, adding other main components, and uniformly heating and kneading the mixture, the extrudability is improved. And a thermoplastic elastomer having more excellent tensile strength can be obtained.

In this case, the heating temperature during the heating and kneading is 15
The temperature is preferably in the range of 0 to 220 ° C, particularly 170 to 210 ° C. At a temperature higher than this range, the crystalline chlorinated polyethylene (a) may decompose.

The heating and kneading can be carried out by using an extruder type processing equipment, for example, a single screw extruder, a twin screw extruder, a co-kneader, a batch-type heating kneader or a Banbury mixer.

The thermoplastic elastomer of the present invention can be prepared by using an injection molding machine, a single screw extruder, a twin screw extruder, a compression molding machine,
Using a molding machine such as a calendering machine, it can be molded in accordance with a conventional method, and gaskets (packing, joints, etc.) for interior and exterior materials for vehicles such as automobiles, interior and exterior materials for construction, vehicles such as automobiles, electric equipment, buildings, etc. Agents, sealing materials), and various molded products such as miscellaneous goods.

In particular, since the thermoplastic elastomer of the present invention is excellent in profile extrusion moldability, it is effective for profile extrusion molded products among these.

[0061]

The thermoplastic elastomer of the present invention will be described more specifically with reference to the following examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. .

The raw materials used in the following Examples and Comparative Examples are as follows.

<Raw materials used> [Crystalline chlorinated polyethylene (a)] CPE-1: chlorinated high-density polyethylene Chlorine content: 30% by weight, heat of crystal fusion: 7 cal /
g, crystal melting point; 110 ° C., DOP oil absorption; 100, polyethylene weight before chlorination: 350,000 [ethylene / α-olefin copolymer (b)] EP-1: ethylene copolymerized using a metallocene catalyst -1-hexene copolymer (Mitsubishi Chemical Co., Ltd. product name "Kernel KE-028") MFR: 0.2 g / 10 min (190 ° C, 2.16 kg) EP-2: Copolymerization using metallocene catalyst Ethylene / 1-octene copolymer (trade name “Engage 8150” manufactured by DuPont Dow Elastomer Co., Ltd.) MFR: 0.5 g / 10 min (190 ° C., 2.16 kg) [Ethylene / α-olefin / non-conjugated Diene Copolymer] EP-3: Ethylene-propylene copolymer not using a metallocene catalyst (trade name “EP07” manufactured by JSR Corporation)
P ”) MFR; 0.7 g / 10 min (230 ° C., 2.16 kg) [Crystalline polyolefin resin (c)] PP-1: Propylene / ethylene random copolymer Ethylene content; 3.2% by weight, MFR 5 g / 10 min (230 ° C., 2.16 kg) [Softener] Softener-1: DOP (di-2-ethylhexyl phthalate) manufactured by Mitsubishi Chemical Corporation Softener-2: Mineral manufactured by Idemitsu Kosan Co., Ltd. Oil-based process oil “PW-380” [Cross-linking agent] POX: 2,5-dimethyl-2,5-di (t-butylperoxy) hexane DVB: Divinylbenzene [Silicone oil] Dimethyl silicone oil Kinematic viscosity: 100 cs [Higher fatty acid amide] Oleic acid amide [Hydrotalcites] Kyowa Chemical Co., Ltd. product name “Alkanuiser 1” (composition formula: Mg ₄ Al ₂₎ (OH) ₁₂ CO ₃ .3H ₂ O) [Epoxy compound] Epoxidized soybean oil manufactured by Asahi Denka Kogyo Co., Ltd. “Adeka Sizer O-130P” [Phosphite compound] Bisphenol A tetra manufactured by Asahi Denka Kogyo Co., Ltd. C _12-15 alkyl diphosphite trade name “MARK 1500” The physical properties were evaluated by the following methods. In addition, the thermoplastic elastomer was compression-molded at a temperature of 180 ° C. to prepare a predetermined test piece. In the deformability extrusion test, pelletized thermoplastic elastomer was used as it was.

<Test Method> Gloss: A flat shape having a width of 20 mm and a thickness of 2 mm was converted to a flat shape of 40 mmφ.
An extruded product is molded using a full flight screw extruder with L / D = 22 at a die temperature of 190 ° C., and the gloss of the molded surface is measured with a gloss meter (“GP-60” manufactured by Tokyo Denshoku Co., Ltd.).
It measured using.

Scratch resistance: An extruded product molded in the same manner and under the same conditions as in the gloss test was subjected to a surface tester (Haydon “HEIDON-14”) with a load of 200 g and a cloth (denim) at a speed of 100 mm. After 10 reciprocations at / min, the surface of the molded article was observed for damage and evaluated according to the following evaluation criteria. ：: scar scarcely seen △: scar slightly noticeable ×: scar largely noticeable Irregular extrusion property: 40 mmφ, L / D = 22 equipped with an extrusion die having the molded product cross-sectional shape shown in FIG. Using a full flight screw extruder, a die temperature of 19
An extruded product was manufactured at 0 ° C., and the cross-sectional shape of the molded product with respect to the die shape was observed and evaluated according to the following evaluation criteria. ○: Same shape △: Cross-sectional shape close to die shape ×: Deformation Examples 1 to 5 <Preparation of thermoplastic elastomer> Crystal chlorinated polyethylene 100 parts by weight, hydrotalcites 5 parts by weight, epoxy compound 3 parts by weight, 1 part by weight of the phosphite compound and 1 part by weight of stearic acid were charged into a Banbury mixer, kneaded under the conditions of a jacket temperature of 150 ° C. and a rotation speed of 80 rpm, and discharged at a resin temperature of 160 ° C .. 2 parts by weight of silicone oil and 2 parts by weight of higher fatty acid amide, excluding the crystalline chlorinated polyethylene, and 2 parts by weight of higher fatty acid amide were charged into a Banbury, kneaded again at a jacket temperature of 150 ° C. and a rotation speed of 80 rpm, and the resin was kneaded. Kneading was performed until the temperature reached 200 ° C., to obtain a uniform kneaded product. The kneaded material was transferred to a mill roll to form a sheet, and pelletized by a sheet cutting method to obtain a thermoplastic elastomer.

Physical properties of the obtained thermoplastic elastomer were evaluated, and the results are shown in Table 1.

Comparative Examples 1 and 3 5 parts by weight of hydrotalcite, 3 parts by weight of an epoxy compound, 1 part by weight of a phosphite compound and 1 part by weight of stearic acid were added to each component having the composition shown in Table 1 into a Banbury mixer. Kneading was performed under the conditions of a jacket temperature of 150 ° C. and a rotation speed of 80 rpm, and kneading was performed until the resin temperature reached 200 ° C. to obtain a uniform kneaded product. The kneaded material was transferred to a mill roll to form a sheet, and pelletized by a sheet cutting method to obtain a thermoplastic elastomer.

Physical properties of the obtained thermoplastic elastomer were evaluated, and the results are shown in Table 1.

Comparative Example 2 Each component was blended as shown in Table 1 and a twin screw extruder “BT-30” (L / D = 30, isotropic rotation) manufactured by Plastic Engineering Laboratory Co., Ltd.
And extruded at 220 ° C. to obtain a thermoplastic elastomer.

Physical properties of the obtained thermoplastic elastomer were evaluated, and the results are shown in Table 1.

[0071]

[Table 1]

Table 1 shows that the thermoplastic elastomer of the present invention is excellent in gloss, scratch resistance, and profile extrusion moldability.

[0073]

As described in detail above, according to the thermoplastic elastomer of the present invention and the method for producing the same, the molded article has excellent extrudability, gloss, and scratch resistance, and has good compatibility with olefin-based materials and can be recycled. Also advantageous thermoplastic elastomers are provided.

The thermoplastic elastomer of the present invention can be used to mold automobile window parts, exterior parts such as window moldings and flash mount moldings, interior parts such as door skins and grips, electric parts, building materials, industrial gaskets and the like. It is extremely useful as a material, exhibits its excellent effects over a long period of time, and is effectively recycled as an olefin-based material after use.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an extruded shape of an extrusion die used in an extrudability test in Examples and Comparative Examples.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) // (C08L 23/28 83:04 63:00) F term (reference) 4J002 AE035 AE055 BB033 BB035 BB05X BB053 BB063 BB073 BB123 BB15X BB173 BB24W BP023 CD165 CP034 CP084 DE288 EH097 EH147 EP016 EP026 EW068 EW088 FD025 FD027 FD035 FD038 FD204 FD206

Claims (12)

[Claims] 1. A crystalline chlorinated polyethylene (a) 100
Parts by weight and an ethylene / α-olefin copolymer (b) obtained by copolymerization using a metallocene catalyst (b)
And 0 parts by weight. 2. Crystalline chlorinated polyethylene (a) 100
Parts by weight and an ethylene / α-olefin copolymer (b) obtained by copolymerization using a metallocene catalyst (b)
0 parts by weight and the crystalline polyolefin resin (c) 10-1
000 parts by weight. 3. The total of crystalline chlorinated polyethylene (a) and ethylene / α-olefin copolymer (b) is 100
3. The thermoplastic elastomer according to claim 1, comprising 1 to 200 parts by weight of a softening agent based on parts by weight. 4. 4. A total of 100 parts of the crystalline chlorinated polyethylene (a) and the ethylene / α-olefin copolymer (b)
The thermoplastic elastomer according to any one of claims 1 to 3, further comprising 0.01 to 10 parts by weight of a silicone oil having a kinematic viscosity of 1 to 100,000 cs based on parts by weight. 5. A total of crystalline chlorinated polyethylene (a) and ethylene / α-olefin copolymer (b) of 100
The thermoplastic elastomer according to any one of claims 1 to 4, comprising 0.01 to 10 parts by weight of the higher fatty acid amide based on part by weight. 6. The crystalline chlorinated polyethylene (a) is obtained by post-chlorinating polyethylene having a weight average molecular weight of 100,000 to 750,000, and has a chlorine content of 20 to 45% by weight.
The thermoplastic elastomer according to any one of claims 1 to 5, having a heat of crystal fusion of 5 to 35 cal / g according to a DSC method. 7. The thermoplastic elastomer according to claim 2, wherein the crystalline polyolefin resin (c) is a crystalline polypropylene resin. 8. A total of 100 of crystalline chlorinated polyethylene (a) and ethylene / α-olefin copolymer (b)
8. The composition according to claim 1, wherein the hydrotalcites are contained in an amount of 0.1 to 20 parts by weight, an epoxy compound in an amount of 0.1 to 5 parts by weight, and a phosphite compound in an amount of 0.01 to 5 parts by weight.
The thermoplastic elastomer according to any one of the above. 9. The method according to claim 1, wherein the crystalline chlorinated polyethylene (a) is heated and kneaded to form a gel, and then the ethylene / α-olefin copolymer (b) is added and heated and kneaded. 9. The thermoplastic elastomer according to any one of items 1 to 8. 10. The thermoplastic elastomer according to claim 1, which is partially crosslinked. 11. A crystalline chlorinated polyethylene (a) 10
0 parts by weight and an ethylene / α-olefin copolymer (b) obtained by copolymerization using a metallocene catalyst (b) 10 to 10
A method for producing a thermoplastic elastomer in which 100 parts by weight is kneaded with heat. 12. The thermoplastic resin according to claim 11, wherein the crystalline chlorinated polyethylene (a) is heated and kneaded to form a gel, and then the ethylene / α-olefin copolymer (b) is added and heated and kneaded. A method for producing an elastomer.