JPH0569858B2 - - 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, we will discuss extremely low-density ethylene copolymers obtained by copolymerizing ethylene and α-olefin using a specific catalyst, ethylene-α-olefin copolymer rubber, and specific ethylene-α,β- It is a partially crosslinked blend with ethylenically unsaturated carboxylic acid ester copolymer, and has features such as high flexibility, excellent heat resistance and oil resistance, and low permanent set, as well as fluidity. The present invention relates to a thermoplastic elastomer composition having extremely good properties. (Conventional technology) 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.). (Problem to be solved by the invention) However, soft segments such as EPR and EPDM have low tensile strength, low heat resistance, fluidity,
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 to improve these problems, flexibility will be lost and
In addition, physical properties such as permanent set are reduced, and functionality as a flexible thermoplastic elastomer is impaired. 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. The present applicant has already proposed a thermoplastic elastomer composition that solved these problems in Japanese Patent Application No. 84393/1983, but further improvements in fluidity and moldability are desired. (Means for Solving the Problem) The present inventors added a specific ethylene-α-olefin copolymer as a hard segment to a composition using an ethylene-α-olefin copolymer rubber as a soft segment, and further We have discovered that by combining a specific ethylene-α,β-ethylenically unsaturated carboxylic acid ester copolymer, fluidity under high shear stress can be greatly improved without reducing flexibility or heat resistance. Ta. That is, the present invention provides (A) a compound 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. An ethylene-α-olefin copolymer, comprising: (I) melt index;
0.01-100g/10min, () Density 0.860-0.910g/ ^cm3 , () Maximum peak temperature by differential scanning calorimetry (DSC) of 100℃ or more, () Boiling n-hexane insoluble content of 10% by weight or more 10 to 90 parts by weight of an ethylene-α-olefin copolymer having the properties of (B) 90 parts by weight of ethylene-α-olefin copolymer rubber
~10 parts by weight (here, (A) + (B) is selected to be 100 parts by weight) and (C) a viscosity average molecular weight of 500 to 20,000, and α, β-
Contains 0.5 to 10 mol% of ethylenically unsaturated carboxylic acid ester units per total monomer unit,
The present invention relates to a thermoplastic elastomer composition obtained by partially crosslinking a composition comprising 5 to 50 parts by weight of an ethylene-α,β-ethylenically unsaturated carboxylic acid ester copolymer. (Preferred embodiment for carrying out the invention) In the ethylene-α-olefin copolymer (A) used in the present invention, α copolymerized with ethylene
- The olefin has 3 to 12 carbon atoms. Specific examples include propylene, butene-1,4-methylpentene-1, hexane-1, octene-1, decene-1, dodecene-1, and the like. 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. As the solid catalyst component, for example, metal magnesium;
Magnesium hydroxide; Magnesium oxide; Magnesium carbonate; Magnesium salts such as magnesium chloride; Double salts, double oxides, carbonates, chlorides, hydroxides, etc. containing magnesium atoms and a metal selected from silicon, aluminum, and calcium. Furthermore, a titanium compound is supported by a known method on an inorganic solid compound containing magnesium, such as one obtained by treating or reacting these inorganic solid compounds with an oxygen-containing compound, a sulfur-containing compound, an aromatic hydrocarbon, or a halogen-containing substance. Examples include things that have been done. Examples of the above oxygen-containing 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.
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), 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 in the periodic table. Can be mentioned. In addition, the general formula Ti(OR _{) n}
A trivalent titanium compound obtained by reducing a tetravalent alkoxy titanium halide represented by m<4 (an integer of 4) 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. 1984-106581), 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
A preferred example of a catalyst system is one in which an organoaluminum 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 Japanese Patent Publication No. 95909). 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 formulas RMgX,
Organomagnesium compounds such as R ₂ Mg, RMg (OR) (where R is an organic residue having 1 to 20 carbon atoms, and X is a halogen), ether complexes thereof, and other organomagnesium compounds. 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. 73009/1983). Further, as an example of another catalyst system, a solid material 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 catalyst 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), _SiO2 -R-O-R'-MgO- _AlCl3
−TiCl ₄ system (JP-A-57-187305), SiO ₂ −
MgCl ₂ -Al-(OR) ₃ -TiCl ₄ -Si(OR') ₄ system (JP-A-58-21405) (In the above formula, R,
R′ represents a hydrocarbon residue. ) 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. 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 acid 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 per 1 g of the solid catalyst component.
It is desirable to react the α-olefin.
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 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 ordinary polymerization reaction of olefins using a Ziegler type catalyst. 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 JISK6760) is 0.01 to 100 g/10 min, preferably 0.1 to 50 g/10 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
~0.900g/ ^cm3 . Maximum peak temperature (Tm) measured by differential scanning calorimetry (DSC) is 100℃
The temperature is preferably 110°C or higher. Boiling n-hexane insoluble content is 10% by weight or more, preferably 20-95%
% 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 mm, the MI of the thermoplastic elastomer composition will be too low, resulting in poor fluidity. 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 0.910 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 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 an ethylene-α-olefin copolymer rubber or an ethylene-α-olefin-nonconjugated diene copolymer rubber. 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, hexene-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 ₁₊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. Ethylene-α,β-ethylenically unsaturated carboxylic acid ester copolymer (C), which is yet another component of the present invention, is a copolymer of ethylene and α,β-ethylenically unsaturated carboxylic acid ester under high pressure. Copolymerization method, or heating degradation of a relatively high molecular weight ethylene-α,β-ethylenically unsaturated carboxylic acid ester copolymer at 150 to 600°C in the presence of water or steam in an inert atmosphere. Manufactured by methods such as The α,β-ethylenically unsaturated carboxylic acid ester in component (C) used in the present invention includes methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, Acrylic acid-2
-ethylhexyl, octyl acrylate, or methyl methacrylate, ethyl methacrylate,
Examples include esters of acrylic acid or methacrylic acid with alcohols having 1 to 12 carbon atoms, such as propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, and octyl methacrylate. and these can also be used in mixtures. The ethylene-α,β-ethylenically unsaturated carboxylic acid ester copolymer used in the present invention has a viscosity average molecular weight of 500 to 20,000, preferably 1,000 to 10,000, and α,β-ethylenically unsaturated carboxylic acid ester 0.5 to 10 mol% of units, preferably 1 to 10 mol%
It contains 5 mol%. Viscosity average molecular weight
If it is less than 500, the resulting composition will become sticky, and if it exceeds 20,000, the fluidity of the resulting composition will not improve. When the α,β-ethylenically unsaturated carboxylic acid ester unit exceeds 10 mol%, the tensile strength of the resulting composition decreases, and 0.5 mol%
If it is less than that, the flexibility will be insufficient and the permanent strain will become large, which is not preferable. In addition, α, β−
When copolymerizing ethylenically unsaturated carboxylic acid esters, a small amount of unsaturated carboxylic acid corresponding to the hydrolyzate of the ester is often copolymerized, but the coexistence of these small amounts of unsaturated carboxylic acid units is permissible. 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 1 part by weight, flexibility will be lost and permanent elongation will be poor, and if it is less than 10 parts by weight, tensile strength will decrease and oil resistance will deteriorate, which is not desirable. The ratio of the ethylene-α,β-ethylenically unsaturated carboxylic acid ester copolymer (C) to the total amount of (A) and (B) is 5 to 50/100, preferably 10 to 100.
40/100 ((C)/(A)+(B)), weight ratio). Ingredients (C)
If it exceeds 50 parts by weight, the tensile strength will decrease and the surface will become sticky, while if it is less than 5 parts by weight, the fluidity of the composition will not improve. To produce the thermoplastic elastomer composition of the present invention, an ethylene-α-olefin copolymer (A),
A method in which the ethylene-α-olefin copolymer (B) and the ethylene-α,β-ethylenically unsaturated carboxylic acid ester copolymer (C) are uniformly blended in the above composition ratio and partially crosslinked. Ingredient (A) and ingredients
Examples include methods of blending component (B) with component (C) after partial crosslinking. Any known technique can be used to produce the partially crosslinked product. A typical example is a method in which a crosslinking example is added to the above-mentioned compound and mechanically melt-kneaded, and partial crosslinking can be performed using single-screw 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-butylcumyl 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 sialylphthalate. 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～
It is 40% by weight. If the gel fraction is less than 0.5% by weight, heat resistance etc. will decrease, and if the gel fraction exceeds 60% by weight, fluidity will decrease, which is not desirable. Various fillers such as carbon black, calcium carbonate, silica, metal fibers, carbon fibers, additives such as antioxidants, flame retardants, colorants, etc. For the purpose of facilitating dispersion of the filler and increasing flexibility and elasticity, paraffinic, naphthenic, or aromatic mineral oils may be blended as necessary. Furthermore, high density polyethylene, low density polyethylene,
Various resins and rubbers such as crystalline polyolefins such as linear low-density polyethylene and polypropylene, natural rubber, various synthetic rubbers, and styrene thermoplastic elastomers may be blended as necessary. (Effects of the Invention) The thermoplastic elastomer composition obtained by the present invention has the following properties. (a) It has excellent fluidity under high shear stress, so it is easy to mold and the appearance of molded products is excellent. (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 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] Accurately weigh approximately 5 mg of a sample from a 100 μm thick hot press-molded film, set it in the DSC device, raise the temperature to 170°C, hold it at that temperature for 15 minutes, and then measure the cooling rate. Cool to 0°C at 2.5°C/min.
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 appears while increasing the temperature from 0°C to 170°C is defined as the maximum peak temperature (Tm). [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 from the sheet, and using a double-tube Soxhlet extractor, , extraction is carried out with boiling n-hexane for 5 hours.
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 (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.
mm mold, preheated at 210℃ for 5 minutes, pressure molded at the same temperature for 5 minutes at 150Kg/cm ² , 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 = Melt flow index at 230℃ and 21.6Kg load/Melt flow index at 230℃ and 2.16Kg load The larger the value of FP, the better the flowability during molding. [Tensile Test] According to JIS K6301, a test piece was prepared using a No. 3 dumbbell and 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. [Vikatto 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 250g 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. [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. . Remove the boiling xylene insoluble matter and vacuum dry (7 hours,
80℃) and determine the boiling xylene insoluble content as the 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 copolymer rubber. The Mooney viscosity (ML ₁₊₄ , 100℃) of the copolymer rubber is 90,
Propylene content is 27% by weight, density is 0.863g/
The ENB content in the cm ³ copolymer rubber was 16 in terms of iodine value. The other component, ethylene-ethyl acrylate copolymer, is a high molecular weight ethylene-ethyl acrylate copolymer (ethyl acrylate content: 4.9
mol%, melt index 9 g/10 min) at 355°C and 130 kg/cm ² in a nitrogen atmosphere in the presence of water vapor.
Obtained by time thermal degradation. The viscosity average molecular weight of the obtained heat-reduced product was 5500, and the contents of ethyl acrylate and acrylic acid were 3.2 mol% and 1.2, respectively.
It was in mol%. 50 parts by weight of these ethylene-butene-1 copolymers, ethylene-propylene-ENB copolymer rubber
50 parts by weight and 20 parts by weight of ethylene-ethyl acrylate copolymer, 0.1% by weight of di(t-butylperoxy)dipropylbenzene (crosslinking agent), and 0.1% by weight of Irganox 1010 (antioxidant; Ciba Geigy brand name). % and calcium stearate (lubricant) 0.1% by weight (both weight% are total polymer)
(based on 100% by weight) was added and mixed, then put into a Banbury mixer preheated to 200°C, and kneaded for 20 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 The same procedure as in Example 1 was conducted except that the amount of the ethylene-ethyl acrylate copolymer was changed to 10 parts by weight. The evaluation results are shown in Table 1. Example 3 The same procedure as in Example 1 was conducted except that the amount of the ethylene-ethyl acrylate copolymer was changed to 40 parts by weight. The evaluation results are shown in Table 1. Example 4 The amount of the ethylene-butene-1 copolymer in Example 1 was changed to 75 parts by weight, ethylene-propylene-1
An elastomer composition was obtained in exactly the same manner as in Example 1, except that the ENB copolymer rubber was used in an amount of 25 parts by weight. The evaluation results are shown in Table 1. Example 5 The amount of the ethylene-butene-1 copolymer in Example 1 was changed to 25 parts by weight, ethylene-propylene-1
An elastomer composition was obtained in exactly the same manner as in Example 1, except that the ENB copolymer rubber was used in an amount of 75 parts by weight. The evaluation results are shown in Table 1. Example 6 Same as Example 1 except that an ethylene-ethyl acrylate copolymer having a viscosity average molecular weight of 9400 and a content of ethyl acrylate and acrylic acid of 2.7 mol% and 0.4 mol%, respectively, was used in Example 1. I went in the same way. The evaluation results are shown in Table 1. Example 7 Ethylene and propylene were copolymerized to form ethylene-
A propylene copolymer was obtained. The ethylene content of this ethylene-propylene copolymer is 85.5 mol%,
Melt index 1.0g/10 minutes, density 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. Example 8 An elastomer composition was obtained by changing the blending order of each component in Example 1. Namely, ethylene-butene-1 copolymer, ethylene-propylene-
After mixing ENB copolymer rubber, crosslinking agent, antioxidant and lubricant, use a Banbury mixer at 200℃.
After kneading for 10 minutes, ethylene-ethyl acrylate copolymer was added and kneading was carried out again for 10 minutes to obtain an elastomer composition. The evaluation results are shown in Table 1.
Note that the mixing ratio of each component is the same as in Example 1. Example 9 In Example 1, ethylene-propylene-
Mooney viscosity of ENB copolymer rubber (ML ₁₊₄ , 100
The same procedure as in Example 1 was carried out except that one having a temperature of 62° C. was used. The evaluation results are shown in Table 1. Comparative Example 1 The same procedure as in Example 1 was conducted except that the ethylene-ethyl acrylate copolymer was not used. The evaluation results are shown in Table 1. Comparative Example 2 The same procedure as in Example 1 was conducted except that 70 parts by weight of the ethylene-ethyl acrylate copolymer was used. The evaluation results are shown in Table 1. Comparative Example 3 The same procedure as Example 2 was carried out except that no crosslinking agent was used in Example 2. The evaluation results are shown in Table 1. Comparative Example 4 In Example 1, instead of the ethylene-butene-1 copolymer, linear low-density polyethylene (Japan Petrochemical Co., Ltd. product, Linirex AF2320; melt index 1.0 g/10 min, density 0.922 g/cm ³ ,
The same procedure as in Example 1 was carried out, except that the maximum peak temperature of DSC was 122.1°C and the insoluble content in boiling n-hexane was 98.8% by weight. The results are shown in Table 1. As is clear from the above results, the thermoplastic elastomer composition obtained by the present invention is highly flexible, has excellent heat resistance and tensile properties, and has extremely good fluidity under high shear stress. be.

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Claims (1)

[Scope of Claims] 1 (A) Ethylene and a catalyst having 3 carbon atoms in the presence of a solid component containing at least magnesium and titanium and a catalyst consisting of an organoaluminum compound.
An ethylene-α-olefin copolymer obtained by copolymerizing ~12 α-olefins, comprising: (I) melt index;
0.01-100g/10min, () Density 0.860-0.910g/ ^cm3 , () Maximum peak temperature by differential scanning calorimetry (DSC) of 10°C or higher, and () Boiling n-hexane insoluble content of 10% by weight or higher. 10 to 90 parts by weight of an ethylene-α-olefin copolymer having the following properties; (B) 90 parts by weight of ethylene-α-olefin copolymer rubber;
~10 parts by weight (here, (A) + (B) is selected to be 100 parts by weight) and (C) a viscosity average molecular weight of 500 to 20,000, and α, β
- containing 0.5 to 10 mol% of ethylenically unsaturated carboxylic acid ester units per total monomer units,
A thermoplastic elastomer composition obtained by partially crosslinking a composition comprising 5 to 50 parts by weight of ethylene-α,β-ethylenically unsaturated carboxylic acid ester copolymer.