JPS63277257A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent permanent set, heat-resistance, appearance of molded article, etc., and suitable as a sheet for interior trim of automobile, etc., by crosslinking a specific ethylene-alpha-olefin copolymer, etc., with a phenolic curing agent. CONSTITUTION:The objective composition can be produced by crosslinking (I) a composition composed of (A) 25-70wt.% of an ethylene-alpha-olefin copolymer having a melt flow rate of 0.01-50g/10min, a density of 0.86-0.91g/cm<3> and a maximum peak temperature of >=100 deg.C determined by differential scanning calorimetry, etc., and produced by copolymerizing ethylene with a 3-12C alpha- olefin in the presence of a catalyst composed of an organoaluminum compound and a solid component containing magnesium and titanium, (B) 30-75wt.% of an ethylene-alpha-olefin-nonconjugated diene copolymer rubber and (C) 0-35wt.% of an ethylene-unsaturated carboxylic acid ester copolymer containing 2-12mol.% of carboxylic acid unit with (II) a phenolic curing agent in combination with a metallic compound crosslinking accelerator.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a thermoplastic elastomer composition that has excellent permanent deformability and a good appearance of molded products. For more details (
A) A specific ethylene copolymer with extremely low density obtained by copolymerizing ethylene and α-olefin/fin using a specific catalyst, (B) °ethylene-a-olefin-nonconjugated diene copolymer It relates to a thermoplastic nidistomer composition obtained by crosslinking a composition consisting of a combined comb and an ethylene-unsaturated monocarboxylic acid ester copolymer using a phenolic curing agent, and as a crosslinking agent, A thermoplastic elastomer composition with an excellent balance of physical properties such as particularly superior permanent set properties and heat resistance, as well as good oil resistance, fluidity, and appearance of molded products compared to those using organic peroxides. It provides:

[Conventional technology]

Polyolefin thermoplastic elastomers include crystalline polyolefins such as polyethylene and polypropylene as hard segments, and non-commercial materials such as ethylene-propylene copolymer rubber (EPR) and ethylene-propylene-nonconjugated diene copolymer rubber (EPDM). Compositions using polyester copolymer rubbers for the soft segments, or partially crosslinked compositions of these compositions are known. others,
Hard segment and soft segment i by multi-stage polymerization method
Methods of synthesis are 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 used as rubber-like materials for automotive parts,
It is attracting a lot of attention because it can be widely applied to hoses, line separation coatings, backing materials, etc. When manufacturing such flexibility grades, soft segment 1-(EPR or EPD) is used to impart rubber-like flexibility.
It is necessary to increase the proportion of M, etc.) and reduce the proportion of hard segments (polyethylene, polypropylene, etc.).

[Problem that the invention seeks to solve]

However, soft segments such as EPR and EPDM have low tensile strength and poor heat resistance, fluidity, oil resistance, etc., so flexible thermoplastic elastomer compositions containing multiple soft segments are difficult to use. However, it still has 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 problems]

As a result of intensive studies in order to solve these problems, the present inventors have found that they can solve these problems by using a specific ethylene-olefin covalent polymer and by crosslinking the composition with a phenolic curing agent. It has been found that this problem can be solved, and a thermoplastic elastomer composition can be obtained which has excellent permanent deformation properties and heat resistance, especially compared to crosslinked products using organic peroxides.

That is, the present invention provides (A) the following ( I)～
(IV) (I) Melt flow rate 0.01-5
0f710min.

■Density 0.860-0.910t 7cm” (2)
Ethylene-〇-olefin copolymer 25~ having the following properties: a maximum peak temperature measured by differential scanning calorimetry (DSC) of 100°C or higher, and (IV) a boiling n-hexane insoluble content of 10 times higher or higher.
70% by weight, (B) 30 to 75% by weight of ethylene-α-olefin-nonconjugated diene copolymer, and (C) ethylene-unsaturated monocarboxylic acid ester containing 2 to 12 moles of carboxylic acid units. Copolymer 0-3
The present invention relates to a thermoplastic elastomer composition obtained by crosslinking a composition consisting of 5% by weight and t% using a phenolic curing agent.

[Preferred mode for carrying out the invention]

(1) Ethylene-a-olefin copolymer (4) Ethylene-〇-olefin copolymer used in the present invention (
In A), the α-olefin copolymerized with ethylene has 3 to 12 carbon atoms. Specific examples include propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1, and the like. Among these, particularly preferred are:
They are propylene, butene-1,4-methylpentene-1, and hexene-1, each having 3 to 6 carbon atoms. The a-olefin content in the ethylene-α-ol/fin copolymer is preferably 5 to 40 mol.

The ethylene-〇-olefin copolymer (A) used in the present invention can be produced as follows.

First, the catalyst system used is a combination of a solid component containing at least magnesium and titanium and an organoaluminum compound. Examples of the solid component include magnesium metal; 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, hydroxides, etc.; and inorganic solid compounds 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 those in which a titanium compound is supported by a known method.

Examples of the above oxygen-containing compounds include water, alcohol,
Organic oxygen-containing compounds such as phenols, ketones, aldehydes, carboxylic acids, esters, polysiloxanes, acid amides,
Examples include inorganic oxygen-containing compounds such as metal alkosites and metal oxychlorides. As sulfur-containing compounds,
Examples include organic sulfur-containing compounds such as thiol and thioether, and inorganic sulfur compounds such as sulfur dioxide, sulfur dioxide, and sulfuric acid. Examples of aromatic hydrocarbons include 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 T i (O
R) nX4-n' where R represents an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, X represents a halogen atom, and n is an integer of O≦n≦4). Preferred are titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium,
Tetramethoxytitanium, monoethoxytrichlorotitanium, jetoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetrainpropoquine titanium, monobutoxytrichlorotitanium , dibutoxydichlorotitanium, monopentoxytrichlorotitanium,
Examples include monophenoxydichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, and tetraphenoxytitanium. Trivalent titanium compounds include trihalides obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium, or organometallic compounds of metals from groups I to II of the periodic table. Titanium is ready. Also, the general formula T'(OR)mX4-m' where R has 1 to 2 carbon atoms
0 represents an alkyl group, an aryl group, or an aralkyl group, X represents a halogen atom, and m is an integer of O<m<4. Examples include trivalent titanium compounds obtained by reducing metals with organometallic compounds.

Among these titanium compounds, tetravalent titanium compounds are particularly preferred.

Specific examples of these catalyst systems include, for example, MgO
-Rx-'riciJ system (Japanese Patent Publication No. 51-3514), Mg-8iC1Mg-8iC14-RO system (Japanese Patent Publication No. 50-23864), MgCh -AI (OR
) 3-TiC1s system (Japanese Patent Publication No. 152/1982, Japanese Patent Publication No. 15111/1983), MgC1°-8iC14
-ROH-TiC1s system (JP-A-49-106581), Mg(OOCR)z-AI(OR)s-TiC
14 series c% Publication No. 52-11710), Mg-PO
Cl3-TiC14 system (4! Publication No. 51-153)
, Mg01=-AIOCI-7iC14 series (% Kosho 54
-15316), MgClt-AI(OR)nX
, -8i(OR')mX, -m-TiC14 system (JP-A-56-95909) and other solid components (in the above formula, R and R' are organic residues, and An example of a preferable catalyst system is a combination of an organoaluminum compound and an organoaluminum compound.

Another example of a catalyst system 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 as a solid component, and an organoaluminum compound is combined therewith.

As the organomagnesium compound, for example, the general formula R
MgX.

Organomagnesium compounds such as RzMgs RMg (OR), where R is an organic residue having 1 to 20 carbon atoms, and X is a halogen atom) and their ether complexes, and these organomagnesium compounds are further Organometallic compounds modified by adding various compounds such as organic sodium hydroxide, organic lithium, organic potassium, organic boron, organic calcium, and organic zinc can be used.

Specific examples of these catalyst systems include, for example, RMgX
-TiC14 series (Special Publication No. 50-39470), R
MgX-Phenol-TiC14 system (Special Publication Publication No. 54-12
953), RMgX-halogenated phenol-T
iCI4 series (Special Publication No. 54-12954), RM
gX -CO2-T IC14 series (JP-A-57-730
Examples include those in which an organoaluminum compound is combined with a solid component, such as (No. 09).

Other examples of catalyst systems include 5i02 as a solid component.
, AI, O, etc., and a solid material obtained by contacting the above-mentioned solid component containing at least magnesium and titanium, which is combined with an organic aluminum compound can be exemplified. Inorganic oxides include 5i02, Al2O3, Cab, B2
O3, SnO2, etc. can be mentioned, 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 component containing magnesium and titanium. That is, in the presence or absence of an inert solvent at a temperature of 20 to 400 °C, preferably 50 to 3
The reaction may be carried out by a method of reacting at 00° C. for usually 5 minutes to 20 hours, a method of co-pulverization, or a suitable combination of these methods.

Specific examples of these catalyst systems include, for example, 5i0
2-ROH-MgClx-T iC14 system (JP-A-56-47407), S 1o2-R, -0-R
'-MgO-AICIs-TrC14 system c% Established in 1987-
187305), S i Ox -MgC12-
AI (OR) 3-TiC14-8i (OR') 4 system (Japanese Patent Application Laid-open No. 58-21405) (R,
R' indicates the hydrocarbon residual fund. ) and the like 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, the organic carboxylic acid esters include various aliphatic,
Alicyclic or aromatic carboxylic acid esters are used, and aromatic carboxylic acid 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.

Specific examples of organoaluminum compounds to be combined with the solid components described above include general formulas R3Al, R,A
IX.

RAIXz, RzAIOR, RAI(OR)X and R
3Al2X3 (7) Compounds represented by organoaluminum compounds (where R is an alkyl group having 1 to 2 carbon atoms, an aryl group is an aralkyl group, X is a halogen atom, and R may be the same or different) Preferred are triethylaluminum, triimbutylaluminum, trihexylaluminum, trioctylaluminum,
Examples include diethylaluminum chloride, diethylaluminum ethoxide, ethylaluminum sesquichloride, and mixtures thereof.

The amount of the organoaluminum compound to be used is not particularly limited, but it can usually be used in an amount of 0.1 to 100 times the amount of the titanium compound.

Furthermore, by bringing the catalyst system into contact with an a-olefin and subsequently using it in the polymerization reaction, the polymerization can be carried out more stably than in the case of no treatment.

The polymerization reaction is carried out in the same manner as the usual polymerization reaction of olefins using a Ziegler type catalyst. That is, all reactions are carried out substantially in the absence of oxygen, water, etc., in the gas phase, in the presence of an inert solvent, or using Mono i- itself as a solvent.

The polymerization conditions for the olefin are a temperature of 20 to 300°C, preferably 40 to 200°C, and a pressure of normal pressure to 9A-.
G1 preferably 2Ki10n2 〇 to 60, z搦2・G.

Although the molecular weight can be adjusted 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, two different polymerization conditions such as hydrogen concentration and polymerization temperature are used.
There is no problem with polymerization reactions in one step or more.
Can be implemented.

Melt 70-rate (MFR, JIS
K7210 test condition 4 (190°C, Z16Kff) is 0.01 to 50 r/10 rnin, preferably 0.1 to 20 r/10 rnin. Density (JIS
K7112) is 0.860-0.910 V
/cyr”, preferably 06870~0,905t
7cm”, more preferably o, 87o to 0.90
0t 7cm”.Differential scanning calorimetry (DSC)
) is at least 100°C, preferably at least 110°C. The content insoluble in boiling n-hexane is 10% by weight or more, preferably 20 to 95% by weight, and more preferably 20 to 90% by weight.

MFR of ethylene-a-olefin copolymer (A)
．． If it is less than 710 min, the MF'R of the thermoplastic elastomer composition will be too low and the fluidity will be poor. Moreover, if MFR exceeds 50y/10m1n, tensile strength etc. will decrease, which is not desirable. Density is 0.860 f
If it is less than 7 m'', the tensile strength decreases and the surface of the composition becomes sticky, impairing its appearance.

Also, the density is 0.910? If it is 7 cm or more, flexibility and transparency will decrease, which is undesirable. If the maximum peak temperature measured by DSC is less than 100°C, the tensile strength will decrease, the surface of the composition will become sticky, and the heat resistance and oil resistance will also decrease. 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 undesirable.

(2) Ethylene-a-olefin-nonconjugated diene copolymer rubber (B) The α-olefin in the ethylene-α-olefin-nonconjugated diene copolymer rubber (B) component used in the present invention includes propylene, Examples include butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1, and the like.

Particularly preferred is propylene.

Examples of the non-conjugated diene include L4-hexadiene, L6-octadiene, dicyclopentadiene, vinylnorbornene, and ethylidenenorbornene. Preferred are L4-hexadiene and ethylidene norbornene.

Mooney viscosity (ML1+4.
(100°C) is preferably about 10 to 95. A Mooney viscosity of less than 10 is undesirable because the tensile strength of the thermoplastic nidistomer composition decreases and the surface becomes sticky.

If the Mooney viscosity exceeds 95, the flowability of the thermoplastic elastomer composition will deteriorate, which is not preferable.

Further, the iodine value of the ethylene-a-olefin-nonconjugated diene copolymer rubber (B) is preferably in the range of 5 to 30; if the iodine value is less than 5, it is difficult to obtain a thermoplastic elastomer composition with good physical properties; If it is 30 or more, fluidity and heat aging resistance deteriorate, which is not preferable.

(3) Ethylene-unsaturated monocarboxylic acid ester copolymer (C) The content of carboxylic acid units in the ethylene-unsaturated monocarboxylic acid ester copolymer (C) used in the present invention is 2 to 12 mol. Reeds, preferably 5 to 12 molt. If the number of carboxylic acid units exceeds 12 molty, the tensile strength of the resulting elastomer decreases and stickiness occurs on the surface, which is undesirable. 2 carboxylic acid units
If it is less than 100 ml, the elastomer will lack flexibility and will have a large permanent strain, which is not preferable.

Also, melt flow rate (MFR, JIS K 72
10 (according to test conditions 4) can be used in a wide range, but preferably 01 to 30 r710m1n.

The unplated 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 acid, butyl acrylate, methyl methacrylate, and ethyl methacrylate.

(4) Composition ratio Ethylene-〇-olefin copolymer (A) (hereinafter referred to as component (A)) and ethylene-α-olefin-nonconjugated diene copolymer rubber (hereinafter referred to as component (A)) occupy in the thermoplastic elastomer composition of the present invention B) The composition ratio of component C (hereinafter referred to as component (B)) and ethylene-unsaturated monocarboxylic acid ester copolymer (C) (hereinafter referred to as component (C)) is such that component A) is 25 to 70% by weight, preferably is 30-65
% by weight, component (B) is 30-75% by weight, preferably 3
5 to 70% by weight, and component (C) 0 to 35% by weight, preferably 5 to 30% by weight.

If component (A) exceeds 70% by weight, the resulting elastomer will lack flexibility and will have a large permanent elongation. 25 again
If it is less than % by weight, strength and fluidity will decrease.

When component (B) exceeds 75% by weight, strength and fluidity decrease. If the weight is less than 30%, the flexibility will decrease and the permanent elongation will increase.

When component (C) exceeds 35% by weight, strength and heat resistance decrease. Moreover, by adding component (C), the appearance of the molded product becomes even better.

(5) Production of thermoplastic elastomer composition In order to produce the thermoplastic elastomer composition of the present invention, the above-mentioned components (A
), component (B), and optionally component (C) are uniformly blended in a predetermined composition ratio, and crosslinked using a phenolic curing agent. Any known technique can be used for compounding and crosslinking. A typical example is a method in which a phenolic curing agent is added to the above-mentioned compound and mechanical melt mixing is performed, and crosslinking is carried out using a -screw and twin-screw extruder, a Banbury mixer, various kneaders, rolls, etc. can be done. The temperature of melt-kneading is usually 100 to 250°C.

As the phenolic curing agent, a resol type phenolic resin that is normally used for crosslinking rubber is used, and specifically, tertiary-butylmethylolphenol, α, a, γ,
Examples include 2 to 411 types, such as γ-tetramethylbutylmethylolphenol, nonylmethylolphenol, dodecylmethylolphenol, and eicosylmethylolphenol.

In addition, when crosslinking is performed in combination with a crosslinking accelerator such as metal oxides such as zinc oxide, titanium oxide, and magnesium oxide, and metal chlorides such as stannous chloride and ferric chloride, crosslinking can be carried out more effectively. This is preferable.

The amount of the phenolic curing agent used can be changed as appropriate depending on the performance required of the thermoplastic nidistomer composition. Usually, it is 0.5 to 10% by weight based on the total amount of components (A), (B) and (C). , preferably 1 to 5% by weight.

Note that even if an organic peroxide is used in place of the phenolic curing agent, the effects of the present invention cannot be obtained.

The boiling xylene insoluble fraction (gel fraction) measured by extracting the thermoplastic elastomer composition of the present invention obtained by crosslinking with a phenolic curing agent for 5 hours with boiling xylene is 3 to 60 weight tons. h, preferably 10 to 50
Weight%. If the gel fraction is less than 3% by weight, heat resistance will decrease, and if the gel fraction exceeds 60% by weight, fluidity and elongation will decrease, which is not desirable.

In addition, fillers such as carbon black, calcium carbonate, silica, clay, talc, metal fibers, carbon fibers,
Additives such as antioxidants, flame retardants, and colorants, as well as
Paraffinic, naphthenic, or aromatic mineral oils may be added, if necessary, for the purpose of aiding the dispersion of the filler and increasing flexibility and elasticity. Furthermore, crystalline polyolefins such as polypropylene, high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, natural rubber, and various synthetic resins may be used within the range that does not change the performance of the thermoplastic nidistomer composition of the present invention. Various resins and rubbers such as rubber and styrene thermoplastic elastomer may be blended as necessary.

〔Effect of the invention〕

The thermoplastic elastomer composition obtained by the present invention has the following properties.

(b) Excellent fluidity makes molding easy and the appearance of molded products is excellent.

(b) Excellent heat resistance and oil resistance.

(c) Low permanent elongation and difficult to deform.

(d) Excellent flexibility.

(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 for various electrical appliances (d) Examples include hoses (E), various gaskets (F), window frame sealants (G), sound insulation materials (H), and various polymer modification materials.

[Embodiments of the invention]

EXAMPLES 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 CD5C] A hot press-molded film with a thickness of 100 μm was used as a sample, and after raising the temperature to 170°C and holding it at that temperature for 15 ml,
Cool to 0°C at a cooling rate of 2.5°C/min. next,
From this state, the temperature is raised to 170° C. at a heating rate of 10° C./min, and measurement is performed. The position of the apex of the maximum peak that appeared during the temperature increase from 0° C. to 170° C. is defined as the maximum peak temperature (Tm).

[Method for measuring insoluble matter in boiling n-hexane]

A sheet 1 with a thickness of 200 μm is formed using a hot press, and three sheets each measuring 20 m x 30 u in length and width are cut out from the sheet, and extracted with boiling n-hexane for 5 hours using a double-tube Soxhlet extractor. After taking out the n-hexane insoluble content and vacuum drying (7 hours under vacuum, 50°C), the boiling sn-hexane insoluble content (Cs non-copper content) is calculated using the following formula.

(Creation of test sheet) The resin composition was made into a sheet with a thickness of 2jlJ1 and a width of 150ia
Put it in a 50m mold and heat 5 molecules at 210℃, then 150Kf/'cr at the same temperature! It was press-molded for 12.5 minutes, and then cooled for 10 minutes at 30° C. under a pressure of 150 Ky/2. After annealing it at 50℃ for 20 hours, it was heated to room temperature for 2 hours.
It was left to stand for 4 hours and its physical properties were measured.

[Melt flow rate]

JIS K 7210 test conditions 14 (230℃, 2
．． 16Kff>, but measurements were also made under conditions of 230°C and 21.6Kff, which are closer to the shear rate during molding. This measured value is preferred as a measure of fluidity in practical terms.

[Tensile test]

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

[Permanent elongation]

A test piece was prepared using a No. 3 dumbbell according to JIS K6301. 10 with the test piece stretched 100 inches
It was held for 1 minute, then suddenly shrunk, and the elongation rate was determined from the elongation rate after being left for 10 minutes.

[Vicat softening point]

A sample with a thickness of 3I was prepared according to the test sheet preparation method.
This was used for measurement. While applying a load of 2501 through a needle indenter placed vertically on the test piece in the heating bath,
The temperature of the heat transfer medium is raised at a rate of °C/60 minutes, and the needle indenter reaches I
The temperature of the heat transfer medium when U penetrated was defined as the softening point.

〔hardness〕

A test piece was prepared according to JIS K6301 and measured using a doll testing machine.

[Gel fraction]

200μm thick using heat press (200℃ x 5 minutes)
Three sheets of 40w x 20MJ1 were cut out, and each of them was placed in a 120-mesh all-mesh bag, and extracted 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.

[Extrusion appearance]

The surface condition of the extrudate was visually observed when the melt flow rate was measured at 230° C. and a load of 216°.

◎ Very good O Good Δ Slightly bad × Bad Component (A) and component (B) used in Examples and Comparative Examples
, component (C) will be described below.

[Production of component (A-1)] Copolymerization of ethylene and butene-1 using a solid catalyst component obtained from substantially anhydrous magnesium chloride, L2-dichloroethane, and titanium tetrachloride, and a catalyst consisting of triethylaluminum. In this way, an ethylene-butene-1 copolymer (A-1) was obtained.

The ethylene content of component (A-1) is 88.3 mole, MF
R is 0.9. y/10m1n, density is 0.896t
7cm", Tm is 119.8℃, C6 insoluble content is 82 F
It was Chi.

[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- Propylene copolymer (A-2
) was obtained. The ethylene content of component (A-2) is 85.5
Molch, MFR is 1.0 r/10m1n, density is 0.
890 Rino-1Tm was 1216°C and the C6 insoluble content was 58% by weight.

[Component CB] The two types of ethylene-a-olefin-nonconjugated diene copolymer rubbers used (EP57P and EP27P (both products of Nippon Synthetic Rubber), respectively component (B-1), (
B-2)) and ethylene-〇-olefin copolymer rubber (EP02P (Japanese Synthetic Rubber ■Products, components (B-2)
The physical properties of -3) are shown in the table below.

[Component (C)] The physical properties of two ethylene-ethyl acrylate copolymers (referred to as components (C-1) and (C-2), respectively) are shown in the table below.

Examples 1 to 4 Components (A), (B),
(C) and a phenolic curing agent were kneaded in a triblend ffl and a Banbury mixer preheated to 200° C. at a rotor rotation speed of 4 Q rpm for 20 minutes to obtain a thermoplastic borostomer composition. . Table 1 shows the physical property evaluation results.

Comparative Examples 1 and 2 Comparative Examples 1 and 4 were carried out in the same manner as in Examples 1 and 4, except that 0.1% by weight of ditertiary-butylperoxydiisopropylbenzene (organic peroxide) was used in place of the phenolic curing agent. Table 2 shows the physical property evaluation results.

Comparative Examples 3 to 5 As shown in Table 2, components (A), (B), (C)
and a phenolic curing agent, and the same procedure as in Example 1 was carried out to obtain a composition. Table 2 shows the physical property evaluation results.

Examples 5 to 9 and Comparative Examples 6 to 8 Component (A) so as to have the composition shown in Tables 1 and 2,
(B).

After tri-blending (C) and a phenolic curing agent,
The mixture was kneaded for 5 minutes at a rotor rotation speed of 4° rpm in a Banbury mixer preheated to 200°C, and then 5% by weight of titanium oxide and 1.5% by weight of stannous chloride (both crosslinking accelerators) were added. Mixing was performed again for 15 minutes to obtain a thermoplastic elastomer composition.

The physical property evaluation results are shown in Tables 1 and 2.

Examples 10 and 11 Components (A), (B),
(C), phenolic curing agent and 20 parts by weight of clay (
Components (A), (B) and (C) (based on a total of 100 parts by weight) were tri-blended, and then mixed with 60 parts by weight of process oil (with respect to a total of 100 parts by weight of components (A), (B) and (C)) while kneading at a rotor rotation speed of 4 Qrpm in a Banbury mixer preheated to 200°C. Nippon Oil ■ Product, Komorex 300; Ingredient (A).

(based on 100 parts by weight of (B) and (C)))
After injection for 1 minute, kneading was continued for 15 minutes to obtain a thermoplastic nidistomer composition. Table 1 shows the physical property evaluation results.

Claims (2)

[Claims] (1) (A) The following (I ) ~ (IV) (I) Melt flow rate 0.01 ~ 50g/10
min, (II) Density 0.860-0.910g/cm
^3 (III) Ethylene-α-olefin copolymer 25 having the following properties: the maximum peak temperature measured by differential scanning calorimetry (DSC) is 100°C or higher, and (IV) the boiling n-hexane insoluble content is 10% by weight or higher. ~7
0% by weight, (B) 30 to 75% by weight of ethylene-α-olefin-nonconjugated diene copolymer rubber, and (C) ethylene-unsaturated monocarboxylic acid ester copolymer containing 2 to 12 mol% of carboxylic acid units. A thermoplastic elastomer composition obtained by crosslinking a composition comprising 0 to 35% by weight of a polymer using a phenolic curing agent. (2) The thermoplastic elastomer composition according to claim (1), which is obtained by using a metal compound-based crosslinking accelerator at the time of crosslinking.