JP2000273248A - Thermoplastic elastomer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer having excellent profile extrusion moldability, tensile strength and flaw-resistance, and further miscibility with various olefin-based materials and useful for recycling. SOLUTION: This thermoplastic elastomer is composed of (a) 100 pts.wt. of crystalline chlorinated polyethylene, (b) 5-800 pts.wt. of a crystalline polyolefin resin, 20-1,500 pts.wt. of (c) olefinic rubber having 50-350 Mooney viscosity [ML1+4 (100 deg.C)] and/or (d) hydrogen-added styrenic rubber and (e) 10-600 pts.wt. of an ethylene.α-olefin copolymer obtained by copolymerizing by using a metallocene catalyst.

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 tensile strength and scratch resistance, and also having 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 provide a molded article having excellent surface smoothness. There was a problem that it was difficult to obtain. In addition, since the obtained molded product has a low tensile strength, it cannot be used for parts requiring sufficient strength, has poor scratch resistance, and is easily scratched even if the surface is lightly scratched. Was.

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 is excellent in profile extrusion moldability, tensile strength and scratch resistance, and also excellent in compatibility with various olefin-based materials. It is an object of the present invention to provide a thermoplastic elastomer which is advantageous for recycling.

[0007]

The thermoplastic elastomer of the present invention comprises 100 parts by weight of a crystalline chlorinated polyethylene (a), 5-800 parts by weight of a crystalline polyolefin resin (b), and a Mooney viscosity [ML _{1+. 4} (100 ° C)]
An ethylene / α-olefin copolymer obtained by copolymerizing 20 to 1500 parts by weight of the olefin rubber (c) and / or the hydrogenated styrene rubber (d) in the range of 350 with a metallocene catalyst ( e) 10 to 600 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);
5 to 800 parts by weight of the crystalline polyolefin resin (b);
Mooney viscosity [ML _{1 + 4} (100 ° C)] is 50 to 350
Obtained by copolymerizing 20 to 1500 parts by weight of the olefin rubber (c) and / or the hydrogenated styrene rubber (d) in the range described above with a metallocene catalyst.
It is characterized by heating and kneading 10 to 600 parts by weight of the olefin copolymer (e).

In the following, crystalline chlorinated polyethylene (a) constituting the thermoplastic elastomer of the present invention will be described.
And a crystalline polyolefin resin (b), an olefin rubber (c) and / or a hydrogenated styrene rubber (d)
And the ethylene / α-olefin copolymer (e) are collectively referred to as “main constituents”.

That is, the present inventors have conducted intensive studies to obtain a thermoplastic elastomer which is excellent in profile extrusion moldability, tensile strength and scratch resistance, and is compatible with an olefin material.
Crystalline chlorinated polyethylene, crystalline polyolefin and a specific rubber and a thermoplastic elastomer containing an ethylene-α-olefin copolymer polymerized by a metallocene catalyst, have found that the above object can be achieved,
The present invention has been completed.

In the present invention, "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 ".

[0012]

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 chlorinated ethylene copolymers obtained by post-chlorination of copolymers with 1,7-octadiene, 1,9-decadiene and 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 degree of chlorination (chlorine content) of the crystalline chlorinated polyethylene (a) is from 20 to 45% by weight, particularly 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 heat of crystal fusion is too large, the hardness will be high and the feeling of elasticity will be lacking. If it is too small, the rubber elasticity will be reduced. 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 a DOP oil content of 100 g of crystalline chlorinated polyethylene (a) powder at 23 ° C. in accordance with JIS K5101.
Stirring is performed while adding OP little by little, and the added volume of DOP in which the crystalline chlorinated polyethylene (a) powder becomes a cluster-like lump is expressed in ml. The DOP oil absorption of 25 or more means that DOP is 25 ml. Even if it is added, it does not form a lump, it is in the form of powder, or it looks like a solid,
It means that it is dispersed with a slight force or impact.

The crystalline polyolefin resin (b), which is one of the main components of the thermoplastic elastomer of the present invention, includes a homopolymer or copolymer of an α-olefin having 2 to 20 carbon atoms. Specific examples of the crystalline polyolefin resin (b) include an ethylene homopolymer, a copolymer of ethylene and an α-olefin or a vinyl monomer such as vinyl acetate or ethylene acrylate, a propylene homopolymer, or a mixture of propylene and an α-olefin. 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, Examples include random copolymers of 4-methyl-1-pentene and α-olefins, wherein the other α-olefins as comonomer include, for example, ethylene, 1-butene, 4-methyl-1-pentene, Any one kind or two or more kinds such as -hexene, 1-octene and the like can be mentioned.

These crystalline polyolefin resins (b)
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. .

The crystalline polyolefin resin (b) 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 (b) 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 min, it is difficult to disperse at the time of kneading, so that the appearance of the molded article is inferior. If it exceeds 100 g / 10 min, the mechanical properties are inferior.

The olefin rubber (c), which is one of the main components of the thermoplastic elastomer of the present invention, has a Mooney viscosity [ML _{1 + 4} (100 ° C.)] of 50 to 350. In the case of the olefin rubber (c) having a Mooney viscosity of less than 50, the mechanical properties are poor, and the Mooney viscosity is 3
If the olefin-based rubber (c) exceeds 50, the melt viscosity is large and it is difficult to disperse.

Examples of the olefin rubber (c) include a random copolymer rubber containing 50 mol% or more of an α-olefin having 2 to 20 carbon atoms, for example, a copolymer of two or more α-olefins and a non-conjugated diene. Polymerized rubber can be mentioned. As the α-olefin random copolymer rubber, ethylene / α-olefin copolymer rubber, ethylene / α-
Olefin non-conjugated diene copolymer rubber, 1-butene-α
-Olefin copolymer rubber and the like, and examples of the α-olefin include ethylene, propylene, 1-butene,
4-methyl-1-pentene, 1-pentene, 1-hexene, 1-octene and the like. The non-conjugated diene preferably has 6 to 20 carbon atoms, and examples thereof include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, and ethylidene norbornene.

The hydrogenated styrene rubber (d), which is one of the main components of the thermoplastic elastomer of the present invention, is preferably a block copolymer obtained from a polymer block of styrene or a derivative thereof and a conjugated diene. A hydrogenated copolymer rubber, wherein the styrene derivative includes, for example, α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene,
Propylstyrene, 4-cyclohexylstyrene, 4-
Dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene and the like can be mentioned, but styrene and α-methyl styrene are preferably used. Examples of the conjugated diene include butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene, and combinations thereof. Of these, isoprene or a combination of isoprene and butadiene is preferable,
The hydrogenated styrene rubber (d) is obtained by hydrogenating a part or all of carbon-carbon double bonds of the conjugated diene block.

The melt flow rate (MFR, condition: 230) of the hydrogenated styrene rubber (d) used in the present invention.
° C, 2.16 kg load) is 0.01 to 100 g / 10
Min, particularly preferably in the range of 0.01 to 50 g / 10 min. If the MFR is less than 0.01 g / 10 min, the MFR is difficult to be dispersed microscopically, and the appearance of the molded article is inferior.
If it exceeds a minute, mechanical properties deteriorate.

The α-olefin of the ethylene / α-olefin copolymer (e) polymerized by 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 (e) preferably has a density of 0.86 to 0.94 g / cc. If the density is less than 0.86 g / cc, the mechanical properties decrease, and if it exceeds 0.94 g / cc, the rubbery elasticity decreases.

The ethylene / α-olefin copolymer (e) 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. When the MFR is less than 0.01 g / 10 minutes, dispersion is difficult, and the desired physical properties are not exhibited. When the MFR exceeds 50 g / 10 minutes, the mechanical properties are inferior.

In the present invention, examples of the metallocene catalyst used for the polymerization of the ethylene / α-olefin copolymer (e) include JP-A-3-1630088 and JP-A-7-1.
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 organic aluminum 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.

The carrier used for supporting the metallocene catalyst includes, for example, silica gel, zeolite, and diatomaceous earth.

The ethylene / α-olefin copolymer (e) obtained by the polymerization reaction using such a metallocene catalyst has an advantage of excellent mechanical properties.

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 Crystalline polyolefin resin (b): 5 to 800 parts by weight Olefin rubber (c) and / or hydrogenated styrene rubber (d): 20 to 1500 parts by weight Ethylene / α-olefin copolymer (e): 10-60
If the proportion of the crystalline polyolefin resin (b) is less than 5 parts by weight per 100 parts by weight of the crystalline chlorinated polyethylene (a), the moldability cannot be satisfied, and if it exceeds 800 parts by weight, the thermoplastic elastomer is flexible. Can not be obtained.

When the ratio of the olefin rubber (c) and / or the hydrogenated styrene rubber (d) is less than 20 parts by weight per 100 parts by weight of the crystalline chlorinated polyethylene (a), rubber elasticity is hardly obtained, and 1500 parts by weight If it exceeds 3, the moldability cannot be satisfied.

Ethylene / α-olefin copolymer (e) based on 100 parts by weight of crystalline chlorinated polyethylene (a)
If the proportion is less than 10 parts by weight, the effect of improving the tensile strength is not sufficient, and if it exceeds 600 parts by weight, it becomes difficult to carry out profile extrusion.

The thermoplastic elastomer of the present invention preferably contains the following main components in particular.

Crystalline chlorinated polyethylene (a): 100
Parts by weight crystalline polyolefin resin (b): 20 to 500 parts by weight olefin-based rubber (c) and / or hydrogenated styrene-based rubber (d): 30 to 1200 parts by weight ethylene / α-olefin copolymer (e): 15-50
0 parts by weight The thermoplastic elastomer of the present invention imparts 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 depending on the type and amount of the above-mentioned main constituents or other additives, 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 insufficient, 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.

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

Here, 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

[0046]

Embedded image

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.

[0050]

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. Suitable amounts for obtaining an excellent stabilizing effect are provided. 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.

When the added amount of the hydrotalcites 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- 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.

It is preferable to use these organic peroxides 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 crystalline chlorinated polyethylene (a), crystalline polyolefin resin (b), olefin rubber (c) and / or hydrogenated styrene rubber (d), and ethylene / α. -It can be produced by kneading the olefin copolymer (e) and, if necessary, the above-mentioned softener, cross-linking agent, cross-linking auxiliary agent, and other various additives at a predetermined ratio.

In the production of the thermoplastic elastomer, at least crystalline chlorinated polyethylene (a) among the constituent components is heated and kneaded to form a gel, and then the olefin rubber (c) and / or hydrogen It is preferable to add the styrene-based rubber (d) and knead the mixture by heating, and more preferably, to knead the crystalline chlorinated polyethylene (a), and if necessary, the softening agent and other various additives. The main components other than the crystalline chlorinated polyethylene (a), namely, the crystalline polyolefin resin (b), the olefin rubber (c) and / or the hydrogenated styrene rubber (d), and the ethylene / α-olefin When the polymer (e) is further crosslinked with the thermoplastic elastomer, it is desirable to add a crosslinking agent or a crosslinking assistant as needed and to 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, and a Banbury mixer.

The thermoplastic elastomer of the present invention can be prepared by 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, the thermoplastic elastomer of the present invention is excellent in profile extrusion moldability, and therefore, it is particularly effective for profile extrusion molded products.

[0066]

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 average molecular weight before chlorination: 350,000 [crystalline polyolefin resin (b)] PP-1: propylene / ethylene random copolymer ethylene content: 3.2 % By weight, MFR: 5 g / 10 min [Olefin rubber (c)] EP-1: Ethylene / propylene / ethylidene norbornene copolymer rubber Mooney viscosity [ML _{1 + 4} (100 ° C)]; 60 (process oil 75 phr oil) Exhibition) EP-2: Ethylene / propylene / ethylidene norbornene copolymer rubber Mooney viscosity [ML _{1 + 4} (100 ° C)]; 88 [hydrogenated styrene rubber (d)] SE-1: Styrene / butadiene / styrene block Hydrogenated product MFR of copolymer: 3 g / 10 min [Ethylene / α-olefin copolymer (e)] P-1: Ethylene / 1-hexene copolymer polymerized using a metallocene catalyst (trade name “Kernel KE-028” manufactured by Mitsubishi Chemical Corporation) MFR: 0.2 g / 10 min, density: 0.895 g / Cc MP-2: ethylene / 1-hexene copolymer polymerized using a metallocene catalyst (trade name “Kernel KF360” manufactured by Mitsubishi Chemical Corporation) MFR: 3.5 g / 10 min, density: 0.898 g / Cc [Softener] Softener-1: DOP (di-2-ethylhexyl phthalate) manufactured by Mitsubishi Chemical Corporation Softener-2: Mineral oil-based process oil manufactured by Idemitsu Kosan Co., Ltd. Product name "PW-380" [ Crosslinking agent] POX: 2,5-dimethyl-2,5-di (t-butylperoxy) hexane DVB: divinylbenzene [silicone oil] dimethyl silicone oil kinematic viscosity; 100c s [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 C _12-15 manufactured by Asahi Denka Kogyo Co., Ltd. Alkyl diphosphite trade name "MARK 1500" In addition, 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> Tensile strength: JIS K63
Dumbbell No. 3 shape and tensile speed 5
A tensile test was performed at 00 mm / min to measure the tensile strength.

Scratch resistance test: width 20 mm, thickness 2 mm
40mmφ, L / L equipped with a flat extrusion die of
An extruded product was manufactured using a full flight screw extruder with D = 22 at a die temperature of 190 ° C., the surface of the extruded product was scratched with a nail, and a scratched state was observed. ：: 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 7 <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 to 3 To each component having the composition shown in Table 1, 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 put 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.

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

Comparative Example 4 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.

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

[0076]

[Table 1]

Table 1 shows that the thermoplastic elastomer of the present invention has high tensile strength, and is excellent in scratch resistance and deformability.

[0078]

As described above in detail, according to the thermoplastic elastomer of the present invention and the method for producing the same, excellent extrudability, tensile strength and scratch resistance are excellent, and good compatibility with olefin-based materials. Thus, a thermoplastic elastomer which is advantageous for recycling is provided.

The thermoplastic elastomer of the present invention can be used for packing materials for automobiles, exterior parts such as door moldings, opening trims, glass run channels, weather strips, etc., interior parts such as door skins, grips, etc., electric parts, building materials and industrial use. It is extremely useful as a molding material for gaskets and the like, 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.

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Claims (15)

[Claims] 1. A crystalline chlorinated polyethylene (a) 100
Parts by weight, crystalline polyolefin resin (b) 5 to 800
Parts by weight and Mooney viscosity [ML _{1 + 4} (100 ° C)] of 5
Olefin rubber (c) in the range of 0 to 350 and / or
Or a thermoplastic containing 20 to 1500 parts by weight of a hydrogenated styrene rubber (d) and 10 to 600 parts by weight of an ethylene / α-olefin copolymer (e) obtained by copolymerization using a metallocene catalyst. Elastomer. 2. A crystalline chlorinated polyethylene (a), a crystalline polyolefin resin (b), an olefin rubber (c) and / or a hydrogenated styrene rubber (d), and an ethylene / α-olefin copolymer. 100 in total with coalescence (e)
The thermoplastic elastomer according to claim 1, wherein the thermoplastic elastomer is contained in an amount of 1 to 200 parts by weight based on part by weight. 3. 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 claim 1, which has a heat of crystal fusion of 5 to 35 cal / g according to a DSC method. 4. The thermoplastic elastomer according to claim 1, wherein the crystalline polyolefin resin (b) is a crystalline polypropylene resin. 5. The olefin rubber (c) has 2 to 2 carbon atoms.
The thermoplastic elastomer according to any one of claims 1 to 4, which is an α-olefin random copolymer rubber containing 50 αmol or more of 20 α-olefins. 6. The hydrogenated styrene rubber (d) is a copolymer rubber obtained by hydrogenating a block copolymer obtained from a polymer block of styrene and / or a derivative thereof and a conjugated diene. 6. The thermoplastic elastomer according to any one of 1 to 5. 7. The thermoplastic elastomer according to claim 1, wherein the density of the ethylene / α-olefin copolymer (e) is 0.86 to 0.94 g / cc. 8. A copolymer of crystalline chlorinated polyethylene (a), crystalline polyolefin resin (b), olefin rubber (c) and / or hydrogenated styrene rubber (d), and ethylene / α-olefin copolymer. 100 in total with coalescence (e)
The thermoplastic elastomer according to any one of claims 1 to 7, 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. 9. A crystalline chlorinated polyethylene (a), a crystalline polyolefin resin (b), an olefin rubber (c) and / or a hydrogenated styrene rubber (d), and an ethylene / α-olefin copolymer. 100 in total with coalescence (e)
The thermoplastic elastomer according to any one of claims 1 to 8, comprising 0.01 to 10 parts by weight of the higher fatty acid amide based on part by weight. 10. A crystalline chlorinated polyethylene (a),
A total of 100 of the crystalline polyolefin resin (b), the olefin rubber (c) and / or the hydrogenated styrene rubber (d), and the ethylene / α-olefin copolymer (e)
10. The composition according to claim 1, comprising 0.1 to 20 parts by weight of hydrotalcites, 0.1 to 5 parts by weight of an epoxy compound and 0.01 to 5 parts by weight of a phosphite compound based on parts by weight.
The thermoplastic elastomer according to any one of the above. 11. Crystallized chlorinated polyethylene (a) is heated and kneaded to form a gel, and then the crystalline polyolefin resin (b) is mixed with an olefin rubber (c) and / or a hydrogenated styrene rubber (d). The thermoplastic elastomer according to any one of claims 1 to 10, which is produced by adding an ethylene / α-olefin copolymer (e) and kneading with heat. 12. The thermoplastic elastomer according to claim 1, which is partially crosslinked. 13. A crystalline chlorinated polyethylene (a),
A total of 100 of the crystalline polyolefin resin (b), the olefin rubber (c) and / or the hydrogenated styrene rubber (d), and the ethylene / α-olefin copolymer (e)
13. The thermoplastic elastomer according to claim 12, which is crosslinked with 0.01 to 3 parts by weight of a crosslinking agent based on parts by weight. 14. A crystalline chlorinated polyethylene (a) 10
0 parts by weight and the crystalline polyolefin resin (b) 5 to 80
0 parts by weight, 20 to 1500 parts by weight of an olefin rubber (c) and / or a hydrogenated styrene rubber (d) having a Mooney viscosity [ML _{1 + 4} (100 ° C.)] of 50 to 350, and metallocene A method for producing a thermoplastic elastomer, comprising heating and kneading 10 to 600 parts by weight of an ethylene / α-olefin copolymer (e) obtained by copolymerization using a catalyst. 15. After the crystalline chlorinated polyethylene (a) is heated and kneaded to form a gel, the crystalline polyolefin resin (b) is mixed with the olefin-based rubber (c) and / or the hydrogenated styrene-based rubber (d). The method for producing a thermoplastic elastomer according to claim 14, wherein the ethylene / α-olefin copolymer (e) is added and the mixture is heated and kneaded.