JPH0569859B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a thermoplastic elastomer composition that has excellent fluidity and gives a molded product a good appearance. More specifically, (A) a specific ethylene copolymer with extremely low density obtained by copolymerizing ethylene and α-olefin using a specific catalyst, (B) ethylene-α-olefin-nonconjugated diene copolymer. This relates to a thermoplastic elastomer composition obtained by sulfur vulcanization of a composition consisting of a composite rubber and (C) an ethylene-unsaturated monocarboxylic acid ester copolymer, and has particularly excellent permanent deformability, fluidity and moldability. The object of the present invention is to provide a thermoplastic elastomer composition with improved appearance. [Prior art] Polyolefin thermoplastic elastomers include
Ethylene-propylene copolymer rubber (EPR) and ethylene-propylene-nonconjugated diene copolymer rubber (FPDM) are produced using crystalline polyolefins such as polyethylene and polypropylene as hard segments.
Compositions using amorphous copolymer rubbers such as, for soft segments, or partially crosslinked compositions of these compositions are known. In addition, a method of synthesizing a hard segment and a soft segment by a multi-stage polymerization method is also known. By changing the ratio of each of these segments, various grades of products are manufactured, from those with high flexibility to those with high rigidity. Flexible grades are attracting a lot of attention because they can be widely used as rubber-like materials in automobile parts, hoses, wire coatings, packing materials, etc. When manufacturing such flexible grades, the proportion of soft segments (such as EPR or EPDM) is increased and the proportion of hard segments (such as polyethylene or polypropylene) is decreased in order to impart rubber-like flexibility. There is a need to. [Problems to be solved by the invention] However, soft segments such as EPR and EPDM have low tensile strength and poor heat resistance, fluidity, and
Due to poor oil resistance, flexible thermoplastic elastomer compositions containing a large amount of such soft segments still have the above-mentioned drawbacks and cannot be used in a wide variety of applications. If the proportion of hard segments is increased in order to improve these problems, flexibility is lost and physical properties such as permanent set are also reduced, impairing functionality as a flexible thermoplastic elastomer. In addition, when synthesizing flexible grades by multi-stage polymerization, it is necessary to polymerize hard segments and soft segments separately, which makes the polymerization equipment extremely complex, and the properties and proportions of each segment are control is extremely difficult, and defective products may also occur when switching grades. Furthermore, it is very difficult to recover the produced polymer because it contains a large amount of rubber-like substances. As described above, there are many problems that must be solved in order to produce flexible thermoplastic elastomers of excellent quality. [Means for Solving the Problems] As a result of intensive studies in order to solve these problems, the present inventors have found that they use a specific ethylene-α-olefin copolymer, and that the composition is free from sulfur or sulfur. It has been discovered that these problems can be solved by crosslinking using a thermoplastic elastomer composition, and a highly flexible thermoplastic elastomer composition with excellent performance can be obtained. That is, the present invention provides (A) ethylene obtained by copolymerizing ethylene and an α-olefin having 3 to 12 carbon atoms in the presence of a solid component containing at least magnesium and titanium and a catalyst consisting of an organoaluminum compound. -α-olefin copolymer, () melt index
0.01-50g/10min, () Density 0.860-0.910g/ ^cm3 , () Maximum peak temperature measured by differential scanning calorimetry (DSC) is 100℃ or higher () Boiling n-hexane insoluble content is 10% by weight or higher (B) 40 to 65% by weight of an ethylene-α-olefin copolymer rubber having The present invention relates to a thermoplastic elastomer composition obtained by crosslinking a composition comprising 10 to 40% by weight of an ethylene-unsaturated monocarboxylic acid ester copolymer containing 2 to 10% by mole per monomer unit with sulfur or a sulfur-based compound. [Preferred embodiments for carrying out the invention] (1) Ethylene-α-olefin copolymer (A) In the ethylene-α-olefin copolymer (A) used in the present invention, α copolymerized with ethylene
- The olefin has 3 to 12 carbon atoms. Specifically, propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1, etc. can be mentioned. Among these, particularly preferable ones have a carbon number of 3
-6 propylene, butene-1, 4-methylpentene-1 and hexene-1. Also,
Dienes such as butadiene as comonomers,
1,4-hexadiene and the like can also be used in combination. α- in ethylene-α-olefin copolymer
The olefin content is preferably 5 to 40 mol%. The ethylene-α-olefin copolymer (A) used in the present invention can be produced as follows. First, the catalyst system used is a combination of a solid catalyst component containing at least magnesium and titanium and an organoaluminium compound. Examples of the solid catalyst component include metal magnesium; magnesium hydroxide; magnesium oxide; magnesium salts such as magnesium carbonate and magnesium chloride; double salts and double oxides containing a metal selected from silicon, aluminum, and calcium and a magnesium atom. , carbonates, chlorides, or hydroxides; and inorganic solids containing magnesium, such as those obtained by treating or reacting these inorganic solid compounds with oxygen-containing compounds, sulfur-containing compounds, aromatic hydrocarbons, or halogen-containing substances. Examples include compounds in which a titanium compound is supported by a known method. Examples of the above oxygen-containing compounds include organic oxygen-containing compounds such as water, alcohol, phenol, ketone, aldehyde, carboxylic acid, ester, alkoxysilane, polysiloxane, and acid amide, and inorganic compounds such as metal alkoxides and metal oxychlorides. Examples include oxygen-containing compounds. Examples of the sulfur-containing compound include organic sulfur-containing compounds such as thiol and thioether, and inorganic sulfur-containing compounds such as sulfur dioxide, sulfur trioxide, and sulfuric acid. Examples of aromatic hydrocarbons include various monocyclic and polycyclic aromatic hydrocarbon compounds such as benzene, toluene, xylene, anthracene, and phenanthrene. Examples of halogen-containing substances include compounds such as chlorine, hydrogen chloride, metal chlorides, and organic halides. On the other hand, examples of the titanium compound supported on the magnesium-containing inorganic solid compound include titanium halides, alkoxy halides, alkoxides, and halogenated oxides.
Preferred titanium compounds are tetravalent titanium compounds and trivalent titanium compounds, and specific examples of tetravalent titanium compounds include the general formula Ti(OR) _o X _4-o (where R is 1 carbon number) ~20 alkyl, aryl, or aralkyl groups, X represents a halogen atom, and n is an integer of 0≦n≧4), and titanium tetrachloride, titanium tetrabromide, titanium tetrabromide, Titanium iodide, monomethoxytrichlorotitanium,
Dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, Tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium,
Examples include diphenoxydichlorotitanium, triphenoxymonochlorotitanium, and tetraphenoxytitanium. Examples of trivalent titanium compounds include titanium trihalides obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium, or organometallic compounds of group metals of the periodic table. Can be mentioned. In addition, the general formula _Ti (OR) _n
Trivalent titanium obtained by reducing tetravalent halogenated alkoxytitanium represented by X represents a halogen atom and m is an integer of 0<m<4 with an organometallic compound of a metal of group ~ of the periodic table. Examples include compounds. Among these titanium compounds, tetravalent titanium compounds are particularly preferred. Specific examples of these catalyst systems include, for example, the Mgo-RX-TiCl ₄ system (Japanese Patent Publication No. 51-3514), the Mg-SiCl ₄ -ROH-TiCl ₄ system (Japanese Patent Publication No. 51-3514),
23864), MgCl ₂ −Al(OR) ₃ −TiCl ₄ system (Japanese Patent Publication No. 51-152, Japanese Patent Publication No. 52-15111),
MgCl ₂ −SiCl ₄ −ROH−TiCl ₄ system (Japanese Patent Application Laid-open No. 1983
106581), Mg(OOCR) ₂ −Al(OR) ₃ −TiCl ₄
system (Japanese Patent Publication No. 52-11710), Mg−POCl ₃ −
TiCl ₄ system (Special Publication No. 153/1983), MgCl ₂ −
AlOCl-TiCl ₄ system (Special Publication No. 54-15316),
A solid catalyst component such _as MgCl ₂ -Al(OR) _o X _{3-o -Si} (OR _' ) n An example of a preferable catalyst system is one in which R' is an organic residue and X is a halogen atom) in combination with an organoaluminium compound. Examples of other catalyst systems include solid catalyst components such as
An example is a catalyst system in which a reaction product of an organomagnesium compound such as a so-called Grignard compound and a titanium compound is used in combination with an organoaluminum compound. Examples of organomagnesium compounds include general formula RMgX,
Organomagnesium compounds such as R ₂ Mg, RMg (OR) (where R is an organic residue having 1 to 20 carbon atoms,
represents a halogen atom) and their ether complexes, or these organomagnesium compounds are further combined with other organometallic compounds such as organosodium, organolithium, organopotassium, organoboron, organocalium, organozinc, etc. In addition, modified ones can be used. Specific examples of these catalyst systems include, for example:
RMgX-TiCl ₄ system (Special Publication No. 50-39470),
RMgX-Phenol-TiCl ₄ system (Special Publication 1984-
12953), RMgX-halogenated phenol-TiCl ₄ system (Japanese Patent Publication No. 12954-1987), RMgX-
Examples include those in which an organoaluminum compound is combined with a solid catalyst component such as a CO ₂ -TiCl ₄ system (Japanese Unexamined Patent Publication No. 57-73009). Further, as an example of another catalyst system, a solid substance obtained by contacting an organic oxide such as SiO ₂ or Al ₂ O ₃ with the solid catalyst component containing at least magnesium and titanium is used as a solid catalyst component, A combination of this and an organoaluminum compound can be exemplified. As inorganic oxides,
In addition to SiO ₂ and Al ₂ O ₃ , CaO, B ₂ O ₃ , SnO ₃ and the like can be used, and double oxides of these oxides can also be used without any problem. Any known method can be used to bring these various inorganic oxides into contact with the solid catalyst component containing magnesium and titanium. That is, a method of reacting in the presence or absence of an inert solvent at a temperature of 20 to 400°C, preferably 50 to 300°C for usually 5 minutes to 20 hours, a method of co-pulverization, or a combination of these methods as appropriate. Alternatively, the reaction may be carried out. Specific examples of these catalyst systems include, for example, the SiO ₂ -ROH-MgCl ₂ -TiCl ₄ system (Japanese Patent Application Laid-open No.
47407), SiO ₂ -R-O-R'-MgO-AlCl ₃
−TiCl ₄ system (JP-A-57-187305), SiO ₂ −
MgCl ₂ −Al(OR) ₃ −TiCl ₄ −Si(OR′) ₄ series (JP-A-Sho
58-21405) (in the above formula, R and R' represent hydrocarbon residues), in combination with an organic aluminum compound. In these catalyst systems, a titanium compound can be used as an adduct with an organic carboxylic acid ester, or the above-described magnesium-containing inorganic solid compound can be used after being brought into contact with an organic carboxylic acid ester. Further, there is no problem in using the organoaluminum compound as an adduct with an organic carboxylic acid ester, an organosilicon compound, or the like. A specific example of an organoaluminum compound to be combined with the above-mentioned solid catalyst component is the general formula
R ₃ Al, R ₂ AlX, RAlX ₂ , R ₂ AlOR, RAl(OR)
An organoaluminum compound of X and R ₃ Al ₂ X ₃ (where R is an alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms,
(R may be the same or different) Compounds represented by triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diethylaluminum ethoxide, ethylaluminum sesquichloride, and mixtures thereof are preferred. etc. can be mentioned. The amount of organoaluminum compound used is not particularly limited, but it is usually 0.1 to 1000% of the titanium compound.
Molar times can be used. In addition, by bringing the catalyst system into contact with an α-olefin and then using it in the polymerization reaction, the polymerization activity can be greatly improved and the system can be operated more stably than in the case of no treatment. During the α-olefin treatment, the entire amount of the organoaluminum compound used may be combined with the solid catalyst component and then brought into contact with the α-olefin, or a part of the organoaluminum compound used may be combined with the solid catalyst component. After combining with α
- The polymerization reaction may be carried out by contacting with olefin and adding the remaining organoaluminum compound separately during polymerization. Further, when the catalyst system and the α-olefin are brought into contact, there is no problem even if hydrogen gas coexists, and there is no problem even if other inert gases such as nitrogen, argon, helium, etc. coexist. The polymerization reaction is carried out in the same manner as the polymerization reaction of olefins using ordinary Ziegler type catalysts. That is, all reactions are carried out in a gas phase, in the presence of an inert solvent, or using the monomer itself as a solvent in a state substantially free of oxygen, water, etc. Olefin polymerization conditions are temperature 20-300℃, preferably 40-200℃
The pressure is normal pressure to 70Kg/cm ² ·G, preferably 2OKg/cm ² ·G to 6OKg/cm ² ·G.
Although the molecular weight can be controlled to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, a two-stage or more multi-stage polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problem. Melt index (MI,
According to JIS K6760) is 0.01 to 50 g/10 min, preferably 0.1 to 0.20 g/100 min. Density (JIS
K6760) is 0.860 to 0.910 g/cm ³ , preferably 0.870 to 0.905 g/cm ³ , more preferably 0.870 to
It is 0.900g/ ^cm3 . Differential scanning calorimetry (DSC)
The maximum peak temperature (Tm) is 100°C or higher, preferably 110°C or higher. Boiling n-hexane insoluble content is 10% by weight or more, preferably 20 to 95% by weight,
More preferably, it is 20 to 90% by weight. The MI of ethylene-α-olefin copolymer (A) is
If it is less than 0.01 g/10 min, the MI of the thermoplastic elastomer composition will decrease too much and the fluidity will deteriorate. Moreover, if MI exceeds 50 g/10 min, tensile strength etc. will decrease, which is not desirable. Density is 0.860g/ ^cm3
If it is less than that, the tensile strength decreases and the surface of the composition becomes sticky, impairing the appearance. Also, the density
If it exceeds 0.910 g/cm ³ , flexibility and transparency will decrease, which is not desirable. Maximum peak temperature by DSC is 100℃
If it is less than this, the tensile strength will decrease, the surface of the composition will become sticky, and the heat resistance and oil resistance will also decrease, which is undesirable. If the content insoluble in boiling n-hexane is less than 10% by weight, the tensile strength will decrease and the surface of the composition will become sticky, which is not desirable. (2) Ethylene-α-olefin-nonconjugated diene copolymer rubber (B) The α-olefin in the ethylene-α-olefin-nonconjugated diene copolymer rubber (B) used in the present invention includes propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1
1, octene-1, etc. Particularly preferred is propylene. Examples of the non-conjugated diene include 1,4-hexadiene, 1,6-octadiene, dicyclopentadiene, vinylnorbornene, and ethylidene norbornene. Preferably. These are 1,4-hexadiene and ethyldenorbornene. The Mooney viscosity (ML ₁₊₄ , 100℃) of ethylene-α-olefin-nonconjugated diene copolymer rubber is 10
~95 is preferred. If the Mooney viscosity of the ethylene-α-olefin-nonconjugated diene copolymer rubber is less than 10, the tensile strength of the thermoplastic elastomer composition will decrease or the surface will become sticky, which is undesirable. If the Mooney viscosity exceeds 95, the flowability of the thermoplastic elastomer composition will deteriorate, which is undesirable. In the present invention, a mixture of ethylene-α-olefin-nonconjugated diene copolymer rubber and ethylene-α-olefin copolymer rubber can also be used. Ethylene-α-olefin copolymer (A) and ethylene-α-olefin-nonconjugated diene copolymer rubber, which are constituent components of the thermoplastic elastomer of the present invention
It is easily distinguished from (B). Even if the constituent monomers and densities of both are the same, the maximum peak temperature (Tm) by DSC is the same as that of component (A).
is much higher, and even if component (B) has a maximum peak temperature (Tm), it is at most about 30 to 50°C.
Also, regarding boiling n-hexane insoluble matter, component (B)
There is no insoluble matter, or even if there is, it is in very small amounts. Furthermore, the manufacturing methods for the two components are also significantly different. As mentioned above, component (A) is produced using a catalyst containing magnesium and titanium,
Component (B) is usually produced using a panadium-based catalyst. (3) Ethylene-unsaturated monocarboxylic ester copolymer (C) α,β-ethylenically unsaturated carboxylic ester unit in the ethylene-unsaturated monocarboxylic ester copolymer (C) used in the present invention The content of
The amount is 10 mol%, preferably 3 to 10 mol%. If the carboxylic acid unit exceeds 10 mol %, the tensile strength of the resulting elastomer will decrease and the surface will become sticky, which is undesirable. If the carboxylic acid unit content is less than 2 mol %, the elastomer will lack flexibility and will have a large permanent strain, which is not preferable. Further, a wide range of melt indexes can be used, but a melt index of 0.2 to 20 g/min is preferable. The unsaturated monocarboxylic acid ester, which is a monomer of the copolymer, is obtained from acrylic acid or methacrylic acid and an alcohol having 1 to 6 carbon atoms, and specifically, methyl acrylate, acrylic acid, etc. Examples include ethyl, butyl acrylate, methyl methacrylate, and ethyl methacrylate. (4) Composition ratio (composition ratio) Ethylene-α-olefin copolymer (A) and ethylene-α-olefin-nonconjugated diene copolymer rubber occupy in the thermoplastic elastomer composition of the present invention
The composition ratio of (B) and the ethylene-unsaturated monocarboxylic acid ester copolymer (C) is 10 to 40% by weight of component (A), preferably 20 to 30% by weight, and 40 to 65% by weight of component (B). %, preferably 45-60% by weight, component (C) 10-40
% by weight, preferably 20-30% by weight. If component (A) exceeds 40% by weight, flexibility will be insufficient,
Permanent distortion also worsens. Moreover, if it is less than 10% by weight, the strength will be insufficient and the heat resistance will decrease, which is not preferable. If component (B) exceeds 65% by weight, strength and heat resistance will decrease, and if it is less than 40% by weight, flexibility will decrease and permanent set will worsen. If component (C) exceeds 40% by weight, flexibility and heat resistance will decrease, and if it is less than 10% by weight, fluidity will deteriorate and the appearance of the molded product will deteriorate. (5) Production of thermoplastic elastomer composition To produce the thermoplastic elastomer composition of the present invention, the above-mentioned components (A), (B), and (C) are uniformly mixed in a predetermined composition ratio. and crosslinked with sulfur or sulfur-based compounds. Any known technique for compounding and sulfur crosslinking can be used. A typical example is a method in which sulfur or a sulfur-based compound is added to the above compound and mechanically melt-kneaded, and crosslinking is performed using a single-screw or twin-screw press, a Banbury mixer, various kneaders, rolls, etc. I can do it. The melt-kneading temperature is usually in the range of 100 to 250°C. In addition to sulfur, vulcanizing agents include thiurams represented by tetramethylthium disulfide, thiazoles represented by mercaptobenzothiazole and dibenzothiazyl disulfide, and imidazoles represented by 2-mercaptoimidazole. and mixtures thereof. Furthermore, it is preferable to use generally known vulcanization accelerators such as oxides such as zinc and magnesium, and fatty acids such as stearic acid. The amount of vulcanizing agent used is 0.005 to 5% by weight, preferably 0.05 to 3% by weight. The amount of the vulcanizing agent to be used is determined depending on the performance required of the crosslinked composition and is not necessarily limited to these values. The boiling xylene insoluble fraction (gel fraction) measured by extracting the thermoplastic elastomer composition of the present invention obtained by crosslinking with sulfur or a sulfur-based compound for 5 hours with boiling xylene is 0.5 to
60% by weight, preferably 2-50% by weight. If the gel fraction is less than 0.5% by weight, heat resistance and oil resistance will decrease, and if the gel fraction exceeds 60% by weight, fluidity will decrease, which is not preferred. In addition, various fillers such as carbon black, calcium carbonate, silica, metal fibers, and carbon fibers, as well as additives such as antioxidants, flame retardants, and colorants, may be used before, during, or during crosslinking (especially during melt-kneading). ,
Furthermore, paraffinic, naphthenic, or aromatic mineral oils may be added, if necessary, for the purpose of aiding filler dispersion and increasing flexibility and elasticity. Furthermore, crystalline polyolefins such as high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, natural rubber, various synthetic rubbers, and styrene may be used within a range that does not change the performance of the thermoplastic elastomer composition of the present invention. Various resins and rubbers such as thermoplastic elastomers may be blended as necessary. [Effects of the Invention] The thermoplastic elastomer composition obtained by the present invention has the following characteristics. (a) Permanent elongation is small and it is difficult to deform. (b) Excellent flexibility. (c) It is easy to mold due to its excellent flexibility;
Excellent appearance of molded products. (d) Excellent heat resistance and oil resistance. (e) It has low density and is extremely lightweight. Since the thermoplastic elastomer composition of the present invention has the above-mentioned excellent properties, its application range is extremely wide. Examples of uses of the thermoplastic elastomer composition of the present invention include (a) Automobile interior sheets, mudguards, moldings, and covers (b) Materials for covering electric wires (c) Parts of various electrical appliances (d) Examples include hoses (E), various gaskets (F), window frame sealants (G), sound insulation materials (H), and various polymer modification materials. [Examples of the Invention] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. The physical properties in each Example and Comparative Example were measured by the following method. [Measurement method using DSC] A hot press-molded film with a thickness of 100 μm is used as a sample, heated to 170°C, held at that temperature for 15 minutes, and then cooled to 0°C at a cooling rate of 25°C/min. Next, from this state, increase the temperature at a rate of 10℃/min.
Measurement is performed by raising the temperature to 170℃. The maximum peak temperature (Tm) is defined as the position of the highest peak of the peaks that appear during the temperature increase from 0°C to 170°C. [Method for measuring insoluble content in boiling n-hexane] A sheet with a thickness of 200 μm was formed using a heat press, and three sheets of 20 mm x 30 mm in length and width were cut out from it, and they were extracted using a double-tube Soxhlet extractor. , extraction is carried out with boiling n-hexane for 5 hours. After taking out the n-hexane insoluble matter and vacuum drying (7 hours, under vacuum, 50°C), boiling n-hexane was removed using the following formula.
- Calculate the hexane insoluble content (C ₆ insoluble content). Boiling n-hexane insoluble content (weight %) = Extracted sheet weight / unextracted sheet weight x 100 (weight %) [Creation of test sheet] The resin composition was placed in a sheet with a thickness of 2 mm and a length x width of 150 mm x 150 mm.
After preheating at 210℃ for 5 minutes, press molding at 150Kg/cm ² for 5 minutes at the same temperature, then 30℃.
It was cooled for 10 minutes under a pressure of 150 Kg/cm ² . 50 it
After annealing at ℃ for 20 hours, it was left at room temperature for 24 hours and its physical properties were measured. [Tensile test] According to JIS K6301, a test piece was prepared using a No. 3 damper and measured at a tensile speed of 50 mm/min. [Permanent elongation] A test piece was prepared using a No. 3 damper according to JIS K6301. With the specimen stretched 100%
It was held for 10 minutes, suddenly contracted, and was determined from the elongation rate after being left for 10 minutes. [Vikat Softening Point] A sample with a thickness of 3 mm was prepared according to the test sheet preparation method and used for measurement. While applying a load of 250g through a needle indenter placed vertically on the test piece in a heating bath, the heat transfer medium was heated at a rate of 50℃/60 minutes, and the heat transfer medium was heated when the needle indenter penetrated 1 mm. The temperature was taken as the Vikato softening point. [Hardness] A test piece was prepared according to JIS K6301 and measured using an A-type testing machine. [Gel fraction] 200μ thick using heat press (200℃ x 5 minutes)
Cut out three sheets of 40 mm x 20 mm, put each in a 120-mesh wire mesh bag, and extract with boiling xylene for 5 hours using a double-tube Soxhlet extractor. . The boiling xylene insoluble matter is taken out and vacuum dried (7 hours, 80°C), and the boiling xylene insoluble matter is determined as a gel fraction. [Appearance of extrudate] The surface condition of the extrudate was visually observed during melt flow rate (MFR) measurement at 230°C and a load of 21.6 kg. ◎ Very good ○ Good △ Fairly bad × Bad Components (A) to (C) used in Examples and Comparative Examples
This is described below. [Production of component (A-1)] Ethylene and butene-1 are produced using a solid catalyst component obtained from substantially anhydrous magnesium chloride, 1,2-dichloroethane and titanium tetrachloride, and a catalyst consisting of triethylaluminum. Copolymerization was performed to obtain an ethylene-butene-1 copolymer (A-1). The ethylene content of component (A-1) is 88.3 mol%, melt index (MI; 190°C), 216 kg
Load) is 0.9g/min, density is 0.896g/cm ³ , DSC
The maximum peak temperature was 119.8°C, and the content insoluble in boiling n-hexane was 82% by weight. [Production of component (A-2)] Ethylene and propylene are copolymerized using a solid catalyst component obtained from substantially anhydrous magnesium chloride, anthracene, and titanium tetrachloride and a catalyst consisting of triethylaluminum to produce ethylene-
A propylene copolymer (A-2) was obtained. Ingredients (A
-2) has an ethylene content of 85.5 mol% and an MI of 1.0
g/10 min, density is 0.890 g/cm ³ , maximum peak temperature of DSC is 121.6°C, boiling n-hexane insoluble content is 58
It was in weight%. [Component (B)] The used ethylene-α-olefin-nonconjugated diene copolymer rubber (component (B-1)) (manufactured by Japan Synthetic Rubber Co., Ltd., EP57P) and the ethylene-α-olefin copolymer rubber component ( The physical properties of B-2) (manufactured by Japan Synthetic Rubber Co., Ltd., EP02P) are shown in the table below.

[Component (C)]

Two types of ethylene-ethyl acrylate copolymers using ethyl acrylate as an unsaturated monocarboxylic acid ester (components (C-1) and (C-1), respectively)
−2). ) are shown in the table below. Ethyl acrylate content (g/10min) (mol%) (C-1) 5 7.0 (C-2) 10 8.4 Examples 1 to 4 and Comparative Examples 1 to 4 The compositions shown in Tables 1 and 2 are obtained. Ingredients as shown
Each component (A), (B), and (C), 0.5 parts by weight of tetramethylthiuram disulfide as a vulcanizing agent, 2 parts by weight of zinc white as a vulcanization accelerator, 1 part by weight of stearic acid, and Irganox 1010 (oxidized inhibitor, Ciba Geigy product) 0.1 part by weight (Here, parts by weight are the proportions based on 100 parts by weight of the resin component. The same applies hereinafter)
After dry blending, kneading was performed for 15 minutes at a rotation speed of 40 rpm in a Banbury mixer preheated to 170°C to obtain a thermoplastic elastomer composition. The physical property evaluation results are shown in Tables 1 and 2. Examples 5, 6 and Comparative Example 5 Components (A), (B), Example 1 except that (C) was added, 3 parts by weight of tetramethylthiuram disulfide (vulcanizing agent), and 5 parts by weight and 3 parts by weight of zinc white and stearic acid (vulcanization accelerator), respectively. A thermoplastic elastomer composition was obtained in the same manner as in 4. The physical property evaluation results are shown in Tables 1 and 2. Example 7 Components (A), (B), and (C) were blended to have the composition shown in Table 1, and 15 parts by weight of paraffinic process oil, 0.01 part by weight of sulfur powder as a vulcanizing agent, and tetramethylthiuram were added. 0.3 parts by weight of monosulfide and 0.1 parts by weight of 2-mercaptobenzothiazole, and 0.1 parts by weight of zinc white and 0.2 parts by weight of stearic acid as vulcanization accelerators were added in a dry blend system in a Banbury mixer preheated to 170°C. The mixture was kneaded for 15 minutes at a rotational speed of 40 rpm to obtain a thermoplastic elastomer composition. Table 1 shows the physical property evaluation results. Comparative Examples 6 and 7 Example 1 except that component (C) was not used and only components (A) and (B) were used so as to have the composition shown in Table 2.
A thermoplastic elastomer composition was obtained in the same manner as in steps 4 to 4. Table 2 shows the physical property evaluation results. Comparative Example 8 Example 1~ except that component (A) was not used and only components (B) and (C) were used so as to have the composition shown in Table 2.
A thermoplastic elastomer composition was obtained in the same manner as in 4. Table 2 shows the physical property evaluation results. Comparative Example 9 The same procedure as in Example 7 was carried out except that the vulcanizing agent and vulcanization accelerator were not added. Table 2 shows the physical property evaluation results. Comparative Example 10 The component (A-1) of Example 1 was mixed with linear low-density polyethylene (Japan Petrochemical Co., Ltd. product, Linirex).
AF2320; MI1.0g/10min, density 0.922g/ ^cm3 ,
The same procedure as in Example 1 was conducted except that the DSC maximum peak temperature was 122.1° C. and the insoluble content in boiling n-hexane was 98.8% by weight. The results are shown in Table 2.

【table】

【table】

【table】

[Table] *: Linear low-density polyethylene

Claims (1)

[Claims] 1(A) In the presence of a solid component containing at least magnesium and titanium and a catalyst consisting of an organoaluminium compound,
An ethylene-α-olefin copolymer obtained by copolymerizing 12 α-olefins, which has a melt index of
0.01-50g/10min, () Density 0.860-0.910g/ ^cm3 , () Maximum peak temperature measured by differential scanning calorimetry (DSC) of 100°C or higher, and () Boiling n-hexane insoluble content of 10% by weight or higher. 10 to 40% by weight of an ethylene-α-olefin copolymer having the following properties, (B) 40 to 65% by weight of an ethylene-α-olefin-nonconjugated diene copolymer rubber, and (C) an unsaturated monocarboxylic acid ester unit. Ethylene-unsaturated monocarboxylic acid ester copolymer containing 2 to 10 mol% of the total monomer units
A thermoplastic elastomer composition obtained by crosslinking a composition consisting of 40% by weight with sulfur or a sulfur-based compound.