JPH056575B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel thermoplastic elastomer composition formed by partially crosslinking a hard segment and a soft segment. More specifically, a blend of an extremely low density ethylene copolymer obtained by copolymerizing ethylene and α-olefin using a specific catalyst and an ethylene-α-olefin copolymer rubber is partially cross-linked. The present invention relates to a thermoplastic elastomer composition which is highly flexible, has excellent fluidity, heat resistance and oil resistance, and has small permanent set. [Prior art] Polyolefin thermoplastic elastomers include
Ethylene-propylene copolymer rubber (EPR) and ethylene-propylene-nonconjugated diene copolymer rubber (EPDM) are produced using crystalline polyolefins such as polyethylene and polypropylene as hard segments.
Blends in which amorphous copolymer rubbers such as 100% rubber are used as soft segments, and compositions in which these blends are partially crosslinked 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 coverings, packing, etc. When manufacturing such flexible grades, the proportion of soft segments (EPR, EPDM, etc.) is increased to give them rubber-like flexibility.
It is necessary to reduce the proportion of hard segments (polyethylene, polypropylene, etc.). [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 many 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 to solve these problems, the present inventors found that using a specific ethylene-α-olefin copolymer as a hard segment,
It has also been found that by partially crosslinking the blend, these problems can be solved and a highly flexible thermoplastic elastomer composition with excellent performance can be obtained. That is, the thermoplastic elastomer composition of the present invention comprises ethylene and carbon atoms having 3 to 12 carbon atoms in the presence of (A) a solid component containing at least magnesium and titanium and a catalyst consisting of an organoaluminum compound.
The following () to () () Melt index 0.01 to 100 g/10 min, () Density 0.860 to 0.905 g/cm ³ , () Differential scanning calorimetry (DSC) obtained by copolymerizing α-olefin with Maximum peak temperature is 100℃ or more, () Boiling n-hexane insoluble content is 10% by weight or more,
It is obtained by partially crosslinking a composition consisting of 10 to 90% by weight of an ethylene-α-olefin copolymer having the following properties and 90 to 10% by weight of (B) ethylene-α-olefin copolymer rubber. be. [Preferred embodiments for carrying out the invention] In the ethylene-α-olefin copolymer (A) used in the present invention, α to be 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% by mole. 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-mentioned oxidizing compounds include organic oxygen-containing compounds such as water, alcohol, phenol, ketone, aldehyde, carboxylic acid, ester, polysiloxane, and acid amide, and inorganic oxygen-containing compounds such as metal alkoxides and metal oxychlorides. can be exemplified. Examples of sulfur-containing compounds include thiol,
Examples include organic sulfur-containing compounds such as thioether, and inorganic sulfur 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.
As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are suitable. Specifically, the tetravalent titanium compound has 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), 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}
A trivalent titanium compound obtained by reducing a tetravalent halogen-valent alkoxytitanium represented by (m<4, an integer) with an organometallic compound of a group metal of the periodic table can be mentioned. Among these titanium compounds, tetravalent titanium compounds are particularly preferred. Specific examples of these catalysts include, for example:
MgO−RX−TiCl ₄ system (Special Publication No. 51-3514),
Mg- _SiCl4 -ROH- _TiCl4 system
Publication No.), MgCl ₂ −Al(OR) ₃ −TiCl ₄ system (Special Publication No. 1973), MgCl 2 −Al(OR) 3 −TiCl 4
-152 Publication, Special Publication No. 52-15111), MgCl ₂
−SiCl ₄ −ROH−TiCl ₄ system (Japanese Patent Application Publication No. 1983-106581), Mg (OOCR) ₂ −Al (OR) ₃ −TiCl ₄ system (Japanese Patent Publication No. 11710/1981), Mg−POCl ₃ − TiCl ₄ system (Japanese Patent Publication No. 51-153), MgCl ₂ -AlOCl-TiCl ₄ system (Japanese Patent Publication No. 54-15316), MgCl ₂ -Al (OR) _o
X _3-o Si(OR′) _n X _4-n −TiCl ₄ system (JP-A-56-95909
A preferred example of a catalyst system is one in which an organic aluminum compound is combined with a solid catalyst component (in the above formula, R and R' are organic residues, and X is a halogen atom) such as JP-A No. 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) and their ether complexes, and these organomagnesium compounds can be further combined with other organometallic compounds such as organosodium,
Those modified by adding various compounds such as organic lithium, organic potassium, organic boron, organic calcium, and organic zinc 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). In addition, as an example of another catalyst system, a solid substance obtained by contacting an inorganic oxide such as SiO ₂ or Al ₂ O ₃ with a 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 ₂ 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 organoaluminum 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. Moreover, there is no problem in using an organoaluminum compound as an adduct with an organic carboxylic acid ester. Furthermore, in all cases it is also possible to use catalyst systems prepared in the presence of organic carboxylic esters without any problems. Here, various aliphatic, alicyclic, and aromatic carboxylic esters are used as the organic carboxylic ester, and aromatic carboxylic esters having 7 to 12 carbon atoms are preferably used. Specific examples include alkyl esters of benzoic acid, anisic acid, toluic acid, such as methyl and ethyl. 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. Further, 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. Various α-olefins can be used as the α-olefin used at this time, but α-olefins having 3 to 12 carbon atoms are preferable, and α-olefins having 3 to 8 carbon atoms are more preferable.
-Olefins are preferred. Examples of these α-olefins include propylene, butene-olefin, etc.
Examples include 1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1, and mixtures thereof. The temperature and time during contact between the catalyst system and the α-olefin can be selected within a wide range, for example, the contact treatment can be carried out at 0 to 200°C, preferably 0 to 110°C, for 1 minute to 24 hours. α− to contact
The amount of olefin can be selected within a wide range, but usually, 1 g to 50,000 g of α-olefin is treated per 1 g of the solid catalyst component, preferably 5 g to 30,000 g, and 1 g to 500 g of α-olefin is treated per 1 g of the solid catalyst component.
- It is desirable to react olefins. At this time, the pressure at the time of contact can be arbitrarily selected, but it is usually desirable to contact under a pressure of -1 to 100 kg/cm ² ·G. 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 the olefin and adding the remaining organoaluminum compound separately during the polymerization. Furthermore, there is no problem even if hydrogen gas coexists during contact between the catalyst system and α-olefin.
Further, there is no problem even if other inert gases such as nitrogen, argon, and helium 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 70 kg/cm ² ·G, preferably 2 kg/cm ² ·G to 60 kg/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 100 g/10 min, preferably 0.1 to 50 g/10 min. Density (JIS
K6760) is 0.860 to 0.905 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℃ or more,
Preferably the temperature is 110°C or higher. The boiling n-hexane insoluble content is 10% by weight or more, preferably 20 to 95% by weight, more preferably 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 100g/10min, 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 0.905 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 boiling n-hexane insoluble content is less than 10% by weight, the tensile strength will decrease and the surface of the composition will become sticky, which is undesirable. The ethylene-α-olefin copolymer rubber (B), which is another component used in the present invention, is
These copolymer rubbers are ethylene-α-olefin copolymer rubber or ethylene-α-olefin-nonconjugated diene copolymer rubber, and these copolymer rubbers are amorphous copolymers. The α-olefin in the ethylene-α-olefin copolymer rubber (B) component includes propylene, butene-1, pentene-1, 4-methyl-pentene-
1, hexane-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. Preferred are 1,4-hexadiene and ethylidene norbornene. Mooney viscosity (ML _l+4 ,
100°C) is preferably about 10 to 95. If the Mooney viscosity of the ethylene-α-olefin 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. Ethylene-α-olefin copolymer (A) and ethylene-α-olefin copolymer rubber (B), which are constituent components of the thermoplastic elastomer of the present invention, can be easily distinguished. Even if the constituent monomers and densities are the same for both components, the maximum peak temperature measured by DSC is much higher for component (A), and for component (B), even if the maximum peak temperature exists, it is at most 30 ~50℃
That's about it. Regarding the insoluble matter in boiling n-hexane, component (B) has no insoluble matter, or even if it exists, it is in a very small amount. 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, whereas component (B) is usually produced using a vanadium-based catalyst. The composition ratio of the ethylene-α-olefin copolymer (A) and the ethylene-α-olefin copolymer rubber (B) in the thermoplastic elastomer composition of the present invention is such that (A)/(B) is from 90 to The ratio is 10/10 to 90 (weight ratio), preferably 75 to 25/25 to 75 (weight ratio). The amount of ethylene-α-olefin copolymer (A) is 90
If it exceeds 10% by weight, flexibility will be lost and permanent elongation will be poor, and if it is less than 10% by weight, tensile strength will decrease and oil resistance will deteriorate, which is not desirable. Furthermore, in producing the thermoplastic elastomer composition of the present invention, the soft segment contains ethylene-α-olefin copolymer rubber and ethylene-α-olefin copolymer rubber.
Mixtures of α-olefin-nonconjugated diene copolymer rubbers can also be used. To produce the thermoplastic elastomer composition of the present invention, the ethylene-α-olefin copolymer
(A) and the ethylene-α-olefin copolymer rubber (B) are uniformly blended so as to have the above-mentioned composition ratio, and partially cross-linked using a cross-linking agent. Any known technique can be used to produce the partially crosslinked product. A typical example is a method in which a crosslinking agent is added to the above compound and mechanical melt-kneading is performed, and partial crosslinking can be performed using single- and twin-screw extruders, Banbury mixers, various kneaders, rolls, etc. can. The temperature of melt kneading is generally
300℃ or less, preferably at a temperature at which the half-life of the crosslinking agent used is 1 minute or less, usually 100 to 300℃
It is. Further, after mixing a crosslinking agent by impregnation or the like, partial crosslinking may be performed by heat or radiation. Organic peroxides are usually used as crosslinking agents. Specifically, 2,5-dimethyl-2,5-di(t-butylperoxy), hexane, di-t-butylperoxide, di(t-butylperoxy)
Diisopropylbenzene, di(t-butylperoxy)diisobutylbenzene, dicumyl peroxide, t-butycumyl peroxide, t-butylperoxybenzoate, 1,1-bis(t-
(butylperoxy)-3,3,5-trimethyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, and the like. Further, a crosslinking aid may be used in combination. Specific examples include liquid polybutadiene, divinylbenzene, ethylene dimethacrylate, and diaryl phthalate. The amount of crosslinking agent used is 0.005 to 3% by weight, preferably 0.05 to 1.0% by weight. The amount of crosslinking agent used is determined by the performance required of the crosslinking composition, and is not necessarily limited to these values. Furthermore, several types of crosslinking agents and crosslinking aids may be used in combination depending on the purpose. The boiling xylene insoluble fraction (gel fraction) measured by extracting the thermoplastic elastomer composition of the present invention obtained by partial crosslinking with boiling xylene for 5 hours is 0.5 to 60% by weight, preferably 2～
50% by weight. If the gel fraction is less than 0.5% by weight, oil resistance etc. will decrease, and if the gel fraction exceeds 60% by weight, tensile strength and elongation will decrease, which is not desirable. In addition, carbon black, calcium carbonate,
Various fillers such as silica, metal fibers, and carbon fibers, and additives such as antioxidants, flame retardants, and colorants may be added as necessary. Furthermore, crystalline polyolefins such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and polypropylene, natural rubber, and various synthetic rubbers 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 styrene thermoplastic elastomers may be blended as necessary. [Effects of the Invention] The partially crosslinked thermoplastic elastomer composition obtained by the present invention has the following properties. (b) It has excellent fluidity and is easy to mold.
Excellent appearance of molded products. (b) Excellent heat resistance and oil resistance compared to non-crosslinked products. (c) Permanent elongation is small and it is difficult to deform. (d) Excellent transparency. (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 seats, mudguards, moldings, and covers (b) materials for covering electric wires (c) parts of various electrical appliances (d) hoses ( E) Various sealants (F) Window frame sealants (G) Sound insulation materials (H) Various polymer modification materials, etc. [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]

Approximately 5 mg of a sample was accurately weighed from a 100 μm thick hot-press film, set in a DSC device, heated to 170°C, held at that temperature for 15 minutes, and then lowered to 0 at a cooling rate of 2.5°C/min. Cool to ℃.
Next, from this state, increase the temperature to 170°C at a rate of 10°C/min.
Measurement is performed by raising the temperature to . The temperature at the top of the maximum peak that appeared during the temperature increase from 0°C to 170°C is defined as Tm.

[Measurement method for boiling n-hexane insoluble matter]

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 from it, and extracted with boiling n-hexane for 5 hours using a double-tube Soxhlet extractor. Do this. After taking out the n-hexane insoluble content and vacuum drying (7 hours under vacuum, 50°C), the boiling n-hexane insoluble content (C ₆ insoluble content) is calculated using the following formula. Boiling n-hexane insoluble content (wt%) =
Extracted sheet weight/unextracted sheet weight x 100 (weight%)

[Creation of test sheet]

The resin composition is 2 mm thick and 150 mm long x 150 mm wide.
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.

[Flow parameter: FP]

FP = 230℃, melt index at 21.6Kg load/230℃,
The larger the melt index FP value at a load of 2.16 kg, the better the flowability during molding.

[Tensile test]

A test piece was prepared using a No. 3 dumbbell according to JIS K6301, and the test piece was measured at a tensile speed of 50 mm/min.

[Permanent elongation]

A test piece was prepared using a No. 3 dumbbell 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.

[Vikatsuto Softening Point]

A sample with a thickness of 3 mm was prepared according to the test sheet preparation method and used for measurement. The temperature of the heat transfer medium is increased at a rate of 50℃/60 minutes while applying a load of 1 kg through a needle indenter placed vertically on the test piece in a heating bath. 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.

【Oil resistance】

A test piece was prepared according to JIS K6301, and the volume change rate was determined using JIS No. 3 oil at 70°C for 22 hours.

[Gel fraction]

200μ thick using heat press (200℃ x 5 minutes)
Cut out three 40mm x 20mm sheets, place 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. Example 1 Ethylene and butene-1 were copolymerized to form ethylene-butene using a solid catalyst component obtained from substantially anhydrous magnesium chloride, 1,2-dichloroethane, and titanium tetrachloride, and a catalyst consisting of triethylaluminum. -1 copolymer was obtained. The ethylene content of this ethylene-butene-1 copolymer is 88.3 mol%, and the melt index is 0.9.
g/10 min, density is 0.896 g/cm ³ , DSC maximum peak temperature is 119.8°C, boiling n-hexane insoluble content is 82
It was in weight%. Separately, using a vanadyl trichloride-ethylaluminum sesquichloride catalyst, ethylene, propylene and ethylidene norbornene (ENB)
was copolymerized to obtain a copolymerized rubber. The copolymer rubber has a Mooney viscosity (ML _l+4 at 100°C) of 90, a propylene content of 27% by weight, and a density of 0.863 g/cm ³
The ENB content in the copolymer rubber was 16 in terms of iodine value. 20 g of these ethylene-butene-1 copolymers,
20g of ethylene-propylene-ENB copolymer rubber,
0.1 part by weight of di(t-butylperoxy)dipropylbenzene as a crosslinking agent, and 0.1 part by weight of Irganox 1010 (trade name, manufactured by Ciba Geigy) as an antioxidant.
Calcium stearate by weight and as lubricant
After dry blending 0.1 part by weight (all parts by weight are based on 100 parts by weight of the total polymer), use a Banbury mixer (Brabender, capacity) preheated to 200°C.
60 ml) and kneaded for 10 minutes at a rotor rotation speed of 40 rpm to obtain a thermoplastic elastomer composition. Table 1 shows the evaluation results of various physical properties. Example 2 An elastomer composition was obtained in exactly the same manner as in Example 1, except that the amount of ethylene-butene-1 copolymer in Example 1 was changed to 10 g and the amount of ethylene-propylene-ENB copolymer rubber was changed to 30 g. . The evaluation results are shown in Table 1. Example 3 An elastomer composition was obtained in exactly the same manner as in Example 1, except that the amount of ethylene-butene-1 copolymer in Example 1 was changed to 30 g and the amount of ethylene-propylene-ENB copolymer rubber was changed to 10 g. . The evaluation results are shown in Table 1. Example 4 An elastomer composition was obtained in exactly the same manner as in Example 1, except that the amount of crosslinking agent in Example 1 was changed to 0.3 parts by weight. The evaluation results are shown in Table 1. Example 5 An elastomer composition was obtained in exactly the same manner as in Example 2, except that the amount of crosslinking agent in Example 2 was changed to 0.3 parts by weight. The evaluation results are shown in Table 1. Example 6 An elastomer composition was obtained in exactly the same manner as in Example 3, except that the amount of crosslinking agent in Example 3 was changed to 0.05 parts by weight. The evaluation results are shown in Table 1. Example 7 An ethylene-propylene copolymer rubber was obtained using a vanadyl trichloride-ethylaluminum sesquichloride catalyst. The copolymer rubber had a Mooney viscosity (ML _l+4 , 100°C) of 73, a propylene content of 26% by weight, and a density of 0.862 g/cm ³ . Ethylene-propylene in Example 1
Example 1 except that the above ethylene-propylene copolymer rubber was used instead of the ENB copolymer rubber.
An elastomer composition was obtained in exactly the same manner. The evaluation results are shown in Table 1. Example 8 Ethylene and propylene were copolymerized using a solid catalyst component obtained from substantially anhydrous magnesium chloride, anthracene and titanium tetrachloride and a catalyst consisting of triethylaluminum to form ethylene-
A propylene copolymer was obtained. The ethylene content of this ethylene-propylene copolymer is 85.5 mol%,
Melt index is 1.0g/10min, density is 0.890
g/cm ³ , the maximum peak temperature of DSC was 121.6°C, and the content insoluble in boiling n-hexane was 58% by weight. An elastomer composition was obtained in exactly the same manner as in Example 1, except that the above ethylene-propylene copolymer was used instead of the ethylene-butene-1 copolymer in Example 1. The evaluation results are shown in Table 1. Comparative Examples 1 and 2 Elastomer compositions were obtained in the same manner as in Examples 1 and 2, except that no crosslinking agent was used. The evaluation results are shown in Table 2. Comparative Example 3 The melt index obtained by copolymerizing ethylene and butene-1 instead of the ethylene-butene-1 copolymer in Example 1 was 1.0 g/10 minutes,
Density is 0.920g/cm ³ , DSC maximum peak temperature is 124
An elastomer composition was obtained in exactly the same manner as in Example 1, except that linear low-density polyethylene having an n-hexane insoluble content of 97% by weight was used.
The evaluation results are shown in Table 2. Comparative Example 4 In Example 1, instead of the ethylene-butene-1 copolymer, the melt index was 0.7 g/10 min,
An elastomer composition was obtained in exactly the same manner as in Example 1, except that a propylene-ethylene block copolymer (ethylene content: 5.9 mol %) was used. The evaluation results are shown in Table 2. As is clear from the above results, the thermoplastic elastomer composition obtained by the present invention is highly flexible and has excellent fluidity and oil resistance.

【table】

【table】

【table】

[Table] *1 and *2 are the same as Table 1

Claims (1)

[Scope of Claims] 1 (A) Ethylene and carbon atoms 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.
The following () to () () Melt index 0.01 to 100 g/10 min () Density 0.860 to 0.905 g/cm ³ () Maximum measured by differential scanning calorimetry (DSC) (B) 10 to 90% by weight of an ethylene-α-olefin copolymer having a peak temperature of 100°C or more and a boiling n-hexane insoluble content of 10% by weight or more; and (B) ethylene-α-olefin copolymer rubber. A thermoplastic elastomer composition obtained by partially crosslinking a composition comprising 90 to 10% by weight. 2. The thermoplastic elastomer composition according to claim 1, wherein the α-olefin as a raw material for the ethylene-α-olefin copolymer (A) has 3 to 6 carbon atoms.