JP2672079B2 - Method for producing thermoplastic elastomer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] FIELD OF THE INVENTION The present invention is excellent in moldability and rubber elasticity.
A method for producing a thermoplastic elastomer
You. [0002] 2. Description of the Related Art Thermoplastic elastomers are energy-saving
ー, especially as vulcanized rubber as resource saving type elastomer
Alternatively, automotive parts (bellows, tubes, interiors)
Sheets, mudguards, industrial machine parts (pressure hoses, gaskets)
Used for electronic and electrical equipment parts, building materials, etc.
Have been used. Fully cross-linked ethylene-propylene-non
Conjugated diene copolymer rubber (EPDM) and polyolefin
Olefinic thermoplastic elast consisting of blend with resin
Tomer-shaped compositions are disclosed in Japanese Patent Publication No. 58-46138 and Japanese Patent Publication No.
It is known from JP-B-55-18448. this
The composition has various excellent properties, but rubber elasticity
Since it lacks moldability and moldability, it is a constant substitute for vulcanized rubber
There is a limit, and improvement is needed. [0004] [Problems to be Solved by the Invention] Olefinic thermoplasticity
As a general method to improve the rubber elasticity of elastomers
Is Increase the amount of cross-linked rubber component, Increase the amount of process oil used as a softening agent
You Means such as are known. However, rubber elasticity is
Although improved, the strength of the thermoplastic elastomer decreases.
There is a problem that In addition, the olefinic thermoplastic elastomer
As a general method for improving moldability, Increase the blending amount of polyolefin resin, Increase the amount of process oil used as a softening agent
You Means such as are known. However, the former has low rubber elasticity.
The latter causes lowering of the strength as described above.
Problem. Therefore, an object of the present invention is to heat olefins.
Excellent heat resistance, weather resistance and strength of plastic elastomer
Moldability and rubber elasticity are significantly improved without impairing the properties.
To provide a method for producing a thermoplastic elastomer
It is in. According to the present invention, particulate cross-linked ethylene
α-olefin copolymer rubber and crystalline polyolefin resin
For producing a thermoplastic elastomer composed of a blend with
At 135 ° C in a decahydronaphthalene solution
Ethylene / α whose limiting viscosity is in the range of 0.5 to 3.0 dl / g
-Olefin copolymer rubber and low molecular weight α-olefin copolymer
Polymer and / or modified low molecular weight α-olefin copolymer
And (i) Disperse it uniformly in an aqueous medium in the presence of a surfactant.
Forming a copolymer rubber latex, (ii) Crosslinked rubber latex in a latex state
Forming a composition, (iii) by drying the crosslinked rubber latex composition
Fine particle cross-linked ethylene / α-olefin copolymer rubber
And the crystalline polyolefine to be blended with
Resin in the copolymer rubber latex formation step (i) above.
Mixing or aqueous in the cross-linked rubber latex formation step (ii)
Crystalline polyolefin resin dispersed in fine particles in a medium
In advance with the crosslinked rubber latex composition together with an aqueous medium.
Either mixed or obtained in the drying step (iii)
The fine particle cross-linked ethylene / α-olefin copolymer rubber
The resulting fine particle cross-linked ethylene / α-olefin was mixed with
Blends of in-line copolymer rubber and crystalline polyolefin resin
Thermoplastic elastomer characterized by melting and kneading materials
A method of making a mer is provided. [0008] The thermoplastic elastomer obtained by the method of the present invention
-For, fine particles of ethylene / α-olefin copolymer rubber
Since crystalline cross-linked products are used, crystalline polyolefin
The resin was present as a sea-like continuous phase and was crosslinked
Fine spherical particles of ethylene / α-olefin copolymer rubber
It exists as an island phase uniformly dispersed in the. like this
Due to its dispersed structure, it has excellent moldability, weather resistance and
It has various properties such as impact resistance, and is also excellent in rubber elasticity.
It is being done. [0009] DESCRIPTION OF THE PREFERRED EMBODIMENTS Basic ingredients: (A) Ethylene / α-olefin copolymer rubber In the present specification, ethylene / α-olefin copolymer rubber
Mums are only completely amorphous materials such as so-called rubber
And the crystallinity measured by X-ray diffraction method is 15% or less.
It is a concept that includes a polymer having a low crystallinity. Ethylene / α-olefin used in the present invention
Copolymer rubbers include ethylene and α-olefins such as propylene.
Pyrene, 1-butene, 1-pentene, 1-hexene, 4
-Methyl-1-pentene, 1-octene, 1-decene, etc.
At least one α-olefin having 3 to 10 carbon atoms
And a copolymer of Its ethylene content is usually 50
To 87 mol%, preferably 63 to 82 mol%.
And a pole with decahydronaphthalene solution at 135 ° C
Viscosity is 0.5 to 3.0 dl / g, especially 0.7 to 1.5 dl / g
Those in the range of are preferably used. The ethylene / α-olefin copolymerization
Synthetic rubber contains one or more polyene components.
You may. As the polyene component, specifically, 1,4
-Hexadiene, 1,6-octadiene, 2-methyl-
1,5-hexadiene, 6-methyl-1,5-heptadi
Chains such as ene and 7-methyl-1,6-octadiene
Non-conjugated diene, cyclohexadiene, dicyclopentadiene
Ene, methyltetrahydroindene, 5-vinyl-2-
Norbornene, 5-ethylidene-2-norbornene, 5
-Methylene-2-norbornene, 5-isopropylidene
-2-norbornene, 6-chloromethyl-5-isoprone
Cyclic non-conjugated dienes such as penyl-2-norbornene,
2,3-diisopropylidene-5-norbornene, 2-
Ethylidene-3-isopropylidene-5-norbornene
2-propenyl-2,2-norbornadiene, 1,
Of 3,7-octatriene and 1,4,9-decatriene
Such a triene can be illustrated as a typical example.
Suitable polyenes include cyclic non-conjugated dienes and 1,4-hexenes.
Sadiene, especially dicyclopentadiene, 5-ethyl
It is den-2-norbornene. These polyene components
Is a maximum of 30 in terms of iodination in the produced copolymer,
The copolymerization is preferably 20 or less. The above-mentioned ethylene / α-olefin copolymerization
For example, synthetic rubber processing technology "Ethylene Pro"
As described in "Pyrene rubber" (Taisei)
It can be produced by a known method. Soluble Banadiu, for example
Ziegler touch of aluminum compounds and organoaluminum compounds
Medium, ethylene, α-olefin with 3 to 10 carbon atoms
As a polyene, if necessary, as a molecular weight regulator
The hydrogen gas of the
And is obtained by Examples of the medium include pentane and hexa.
Aliphatic hydrocarbons such as methane, heptane, octane, and kerosene
Element, alicyclic hydrocarbon such as cyclohexane, benze
Aromatic hydrocarbons such as methane, toluene, xylene,
Rubenzene, carbon tetrachloride, tetrachloroethylene, tri
Chlorethylene, ethyl chloride, methylene chloride, dichloro
Halogenated hydrocarbons such as ethane, alone or in combination of two or more
It can be used in the above combination. As the soluble vanadium compound, for example,
Vanadium tetrachloride, vanadyl trichloride, vanadium
Triacetyl acetonate, vanadyl acetylacetone
To , The following formula: VO (OR)_Three [Here, R represents an aliphatic hydrocarbon group] Vanadyl trialkoxide represented by the following formula: VO (OR)_nX_3-n [Where R is an aliphatic hydrocarbon group, X is a halogen, 0 <n
Halogenated vanadyl alkoxy represented by <3>
Can be used alone or in combination of two or more.
Can be. The organic aluminum compound is as follows:
formula: R_mAlX_3-m [Wherein R is an aliphatic hydrocarbon group, X is a halogen, 1 ≦ m
≦ 3], for example, triethylaluminum
Aluminum, diethyl aluminum, ethyl aluminum
Lolid, ethyl aluminum sesquichloride, ethyl
Luminium dichloride, etc., alone or in combination of two or more
Can be used in combination. (B) Crystalline polyolefin resin The crystalline polyolefin resin used in the present invention is
1-of an olefin homopolymer or a copolymer of two or more
Yes, the crystallinity by X-ray diffraction method is usually 40% or more,
It is preferably 60% or more. The polymerization type is run
Either dam polymerization or block polymerization may be used. Random weight
In combination, the lesser 1-olefin unit is
It is usually 40 mol% or less, preferably 30% or less.
No. Examples of the 1-olefin include ethylene and propylene.
Ropylene, 1-butene, 1-pentene, 1-hexene,
4-methyl-1-pentene, 1-octene, 1-decene
And 1-dodecene. This crystalline polyolefin resin is
Not limited to polymer or copolymer, other olefin polymer
May be contained in an amount of 40% by weight or less based on the composition.
No. In the present invention, particularly isotactic polypropylene is used.
Of propylene or other small amount of α-olefin
Using a copolymer is a group that has excellent moldability and heat resistance.
It is preferable for obtaining a product. Method for producing elastomer: In the present invention, the above-mentioned (A) ethylene / α-olefin
Prepare a latex of copolymer rubber and place it in the latex state.
Crosslinking is carried out and the resulting crosslinked latex composition is used in various embodiments.
Melt-kneading with (B) crystalline polyolefin resin with
To produce a thermoplastic elastomer. (I) Ethylene / α-olefin copolymer rubber
Latex of This latexing is performed, for example, with ethylene / α-olefin.
Dissolve the copolymer rubber in an organic solvent such as toluene or hexane.
However, after emulsifying in water in which the surfactant is dispersed,
This is done by removing the organic solvent. Emulsion in water
Homomixer with high-speed stirring blades and high-speed pipe
It can be carried out by a known means such as using an emulsifying machine.
Wear. In addition, in this latexing, the above-mentioned copolymerization
The dispersed average particle size of rubber is 0.1 to 10 μm, especially 0.2
Adjust to a maximum of 5 μm and a maximum particle size of 20 μm or less.
It is better to control the cross-linking in the resulting composition.
The dispersed particle size of the rubber particles can be adjusted to the same range. For example,
If the dispersion average particle size of is less than 0.1 μm, the
The rubber elasticity of the stoma becomes insufficient, and it exceeds 10 μm.
If so, the moldability and strength become unsatisfactory. Even more
Even if the large particle size exceeds 20 μm,
The strength becomes unsatisfactory. When the latex is formed, a low molecular weight is used.
α-olefin-based copolymer (hereinafter, simply referred to as an olefin-based copolymer
Sometimes referred to as polymer) or modified low molecular weight α-ole
Fin-based copolymer (hereinafter, simply referred to as modified copolymer
2) to 100 parts by weight of the copolymer rubber.
Use in an amount of 50 parts by weight, especially 5 to 40 parts by weight
Is preferred. This olefin-based copolymer and modified copolymer
The use of the body prevents the coagulation of the co-polymer rubber from being obtained and
Advantageous in improving moldability of thermoplastic elastomers
It is. Among these, as an olefin-based copolymer
Are both waxy and liquid at room temperature
Can be used, or both can be used together
You. As a waxy olefin-based copolymer,
Ethylene-propylene copolymer and / or ethylene-
A 1-butene copolymer is used. Especially advantageous are:
Density is 0.90g / cm^ThreeAs mentioned above, the Vicat softening point is 90 ° C or lower.
Above, especially above 95 ° C. Also liquid olfi
Polymers useful as polymer-based copolymers are
Intrinsic viscosity in cahydronaphthalene solution is 0.01 to 0.3
dl / g. These wax-like or liquid
Polymer grafted with the following unsaturated carboxylic acid compounds
It can also be used in the form of a modified product contained as a copolymerization component. The modified copolymer may be an unsaturated carboxylic acid.
Modified polyethylene resin graft-modified with a base compound
And modified ethylene / α-olefin copolymers are used.
Used. Unsaturated carboxylic acid system used as modifier
The compound is the same as an unsaturated carboxylic acid having 3 to 10 carbon atoms.
And its acid anhydride, amide, imide and ester.
At least one of, for example, acrylic acid,
Taacrylic acid, maleic acid, fumaric acid, itaconic acid,
Citraconic acid, norbornene dicarboxylic acid, tetrahydr
Lophthalic acid, bicyclo [2,2,1] hept-2-ene
Unsaturated carboxylic acids such as -5,6-dicarboxylic acid;
Leic acid, itaconic anhydride, citraconic anhydride, tetra
Hydrophthalic anhydride, bicyclo [2,2,1] hept-
Unsaturated calcium such as 2-ene-5,6-dicarboxylic acid anhydride
Boric acid anhydride; maleic acid monoamide, maleic acid dia
Amides or imides such as amide and maleimide; acrylic acid
Methyl, methyl methacrylate, dimethyl maleate, ma
Monomethyl maleate, diethyl maleate, fumaric acid
Diethyl, dimethyl itaconate, diethyl citraconic acid
Le, tetrahydrodimethyl phthalic anhydride, bicyclo
[2,2,1] hept-2-ene-5,6-dicarboxylic
Fatigue of dimethyl acid, glycidyl (meth) acrylate, etc.
A carboxylic acid ester etc. can be mentioned. Among them
Preferred are maleic anhydride and maleic acid monoacetic acid.
Amide, maleic diamide, maleimide, maleic acid
Nomethyl, diethyl maleate, glycidyl (meth) a
For example, clearate. The above modifiers are based on the weight of the modified copolymer.
And usually 0.2 to 50%, preferably 0.2 to 20%
Used in an amount to be included. With a content rate of 20% or less
Hardly changes the softening point of the modified copolymer. Also
As a modified copolymer, modified ethylene / α-olefin
When using a random copolymer, the temperature at 135 ° C
Intrinsic viscosity in cahydronaphthalene solution is 0.01 to
A value of 0.3 dl / g is preferable. The above-mentioned olefin-based copolymer or modification
The copolymer may be blended in the latex by, for example, adding the polymer to the latex.
It was dissolved in a solvent such as n-hexane and the solution was added as described above.
Solution of ethylene / α-olefin copolymer rubber
, While mixing in an aqueous medium containing an appropriate amount of surfactant with stirring.
The mixture may be dispersed and then heated to remove the solvent. this
At this time, if no solvent is used,
Kneading with an aqueous medium containing a surfactant and an extruder, etc.
By doing so, latex formation can also be performed. As a surfactant for latex formation
Is an anionic activator, cationic activator, nonionic activator
Can be used, but fatty acid sodium or fat
Anion activators such as potassium fatty acid are preferably used.
The amount of surfactant used depends on the type of polymer component used.
However, it is generally 0,0 per 100 parts by weight of the copolymer rubber.
The preferred range is 2 to 20 parts by weight. The amount of the aqueous medium used is the above-mentioned copolymerization.
From the viewpoint of controlling the particle size of rubber, the solid content concentration in the latex
Is preferably selected to be 5 to 65% by weight.
You. (Ii) Crosslinking of latex In the present invention, ethylene / α prepared as described above
-Using olefin copolymer rubber latex,
Then, the copolymer rubber is crosslinked. This cross-linking is
The hot toluene insoluble content of the aluminum is 30 to 95% by weight,
Is performed in a range of 40 to 90% by weight.
preferable. By performing such crosslinking, strength is improved.
To obtain a thermoplastic elastomer having particularly excellent formability
Can be. The hot toluene insoluble content is as follows.
Can be quantified in this way. That is, the finally obtained thermoplastic
Approximately 0.5 g of elastomer is weighed (W₀g) 5
Extraction with boiling toluene of 00cc for 6 hours, 0.05μm
After filtering with a filter and drying the residuals, weigh (W₁
It is calculated by the following formula. Hot toluene insoluble content = [100 x W₁-W₀× X] /
(W₀× Y) In the formula, X is a boiling torque other than the crosslinked rubber in the elastomer.
% Of the non-extracted ene component, Y in the elastomer
The copolymer rubber weight% is shown. The above-mentioned cross-linking results in a multifunctional module in the latex.
Nominer is blended, for example, cross-linked by organic peroxide or
It is effectively carried out by crosslinking with an electron beam. Multifunctional used
Examples of the polymerizable monomer include, for example, 2 or more ethylenically unsaturated
Monomers having bonds, especially vinyl bonds, are preferred,
Specifically, divinylbenzene, tetramethylene di (me
A) acrylate, glyceryl triacrylate, ethi
Lenglycol dimethacrylate, 1,2,4-tribi
Examples include nylcyclohexane, tetraallyloxyethane, etc.
can do. This multifunctional monomer is a copolymer
1 to 20 parts by weight, particularly 0.3 to 100 parts by weight
It is desirable to use within the range of 5 parts by weight. As an organic peroxide, latex stability
Property, stability of cross-linking reaction operation and economic efficiency, 10 hours
A half-life temperature of 0 ° C to 100 ° C is preferable.
Specifically, the following can be exemplified. 1,1-bis (t-butylperoxy) si
Crohexane t-butyl peroxyviparate t-Butylperoxy-2-ethylhexanoate t-butyl peroxyisopropyl carbonate 2,5-dimethyl-2,5-bis (t-butylperoxy)
Shi) Hexin-3 2,5-dimethyl-2,5-bis (t-butylperoxy)
H) hexene-3 2,5-dimethyl-2,5-bis (t-butylperoxy)
Si) Hexane 3,5,5-Trimethylhexanoyl peroxide Benzoyl peroxide p-chlorobenzoyl peroxide 2,4-dichlorobenzoyl peroxide 1,3-bis (t-butylperoxyisopropyl) be
Nzen Isobutyl peroxide Diisopropyl peroxydicarbonate Di (2-ethylhexyl) peroxycarbonate Acetyl cyclohexyl sulfonyl peroxide 1,1-bis (t-butylperoxy) -3,3,5-
Trimethylcyclohexane The amount of organic peroxide used depends on the required crosslinking.
In the present invention, ethylene.α
-Normally 3 x 1 per 100 parts by weight of olefin copolymer rubber
0^-FourThrough 5 × 10^-2Moles, especially 10^-3Through 3 × 10^-2Mo
The range of heat torque
The amount of insoluble matter can be adjusted. In addition, in crosslinking with an organic peroxide
Is preferably used in combination with a crosslinking aid. As a crosslinking aid, sulfur
Yellow, quinonedioxime system such as p-quinonedioxime,
Methac such as polyethylene glycol dimethacrylate
Relate type, diallyl phthalate, trillyl lucia
Allyl type such as nurate, maleimide type, etc.
Can be illustrated. Such crosslinking aids (vulcanization aids) are used
The amount of organic peroxide used is usually 1/2 to 2 mol.
, Preferably about equimolar. These organic peroxides and crosslinking aids are
It may be blended in advance before the production of Tex, or it may be made of latex.
You may mix after manufacturing. As heating time for crosslinking
Is usually preferred to be 5-10 times the half-life
Moreover, it can be carried out either under normal pressure or under pressure. In electron beam cross-linking, α rays, β rays, γ
Ray, electron beam, X-ray, etc. may be used and is required
The absorbed dose is selected according to the degree of crosslinking, but in the case of the present invention
Is usually 1 to 50 Mrad, preferably 5 to 3
It is controlled in the range of 0 Mrad. Such electron beam
Even in the case of cross-linking, it is effective to add a cross-linking aid in advance.
The rate can be improved. (Iii) Cross-linked ethylene / α-olefin copolymerization
Drying of rubber latex In the present invention, the crosslinked rubber latex obtained in the above step
It is dried to separate and remove the aqueous medium. As this method
Is a known drying method such as a spray drying method or a freeze drying method.
Can be used. In the present invention,
The ethylene / α-olefin copolymer rubber is crosslinked in
As a result, there is almost no agglomeration of rubber particles during this drying.
First, by the melt-kneading described below, the dispersed particle size of the crosslinked rubber particles
Can be obtained within the target range. (Iv) Melt kneading In the present invention, fine particles obtained by the above-mentioned steps
Cross-linking copolymer rubber and crystalline polyolefin resin
Target thermoplasticity by melting and kneading
Produce an elastomer. The resulting thermoplastic elastomer
-The polyolefin resin exists as a sea-like continuous phase
Then, the substantially spherical cross-linked copolymer rubber particles are uniformly dispersed in an island shape.
The machine has a unique structure and has excellent moldability, weather resistance and strength.
The rubber elasticity is also excellent. In this case, ethylene α-olefin
Incopolymer rubber (A) and crystalline polyolefin resin
(B) is A: B = 90: 10 to 50:50, especially 80:20
To 60:40 Used in a weight ratio of. The amount of copolymer rubber used is in the above range
If it is larger than the above range, the moldability and strength will be unsatisfactory and
When it is less than the above range, the rubber elasticity is extremely low.
Down. The melt-kneading is performed by using a Banbury mixer or the like.
Use a closed mixer or single or multi-screw extruder
Can be. The kneading temperature depends on the crystalline polyolefin resin used.
Although it depends on the melting point of the fat, it is generally 150 ° C.
A range of up to 260 ° C is selected. Further, in the present invention, fine particle cross-linking copolymerization
Blending of crystalline polyolefin resin to be blended with rubber
Is to be performed in any of the above steps (i) to (iii)
Can be. For example, ethylene / α-olefin copolymer
The polyolefin resin is treated with water to form a latex.
After mixing with a reactive medium and uniformly dispersing, cross-linking,
Then, after drying, melt kneading may be carried out, or
Cross-linked latex composition of styrene / α-olefin copolymer rubber
And mix the polyolefin resin with an aqueous medium to obtain a uniform mixture.
After dispersing, it may be dried and melt-kneaded. Of course,
Dry the crosslinked rubber latex to remove the crosslinked copolymer rubber particles.
After it is obtained, it is added with crystalline polyolefin in the form of pellets or powder.
The fin resin may be mixed and melt-kneaded. In the thermoplastic elastomer thus obtained
The crosslinked copolymer rubber fine particles of are
By adjusting the particle size, the average particle size and the maximum particle size in the above range
It is desirable to have this average particle size and maximum
The particle size can be measured by the following method. An injection-molded sheet having a thickness of 2 mm was freeze-cut,
The cut surface is dyed with osmium tetroxide to dye dispersed rubber particles.
After coloring, the number of dispersed rubber particles is 50 to 1 with an electron microscope.
Arbitrarily select three consecutive areas including 00, and
And calculate the major axis and number of dispersed rubber particles,
The average value is taken as the average particle size. That is, the number average of the areas 1, 2 and 3
Particle size is A₁, A_Two, A_Three, And the maximum particle size is L₁, L_Two,
L_ThreeThen, the average particle size and maximum particle size are calculated by the following formula.
It is. Average particle size = 1/3 (A₁+ A_Two+ A_Three) Maximum particle size = 1/3 (L₁+ L_Two+ L_Three) Optional component In the present invention, in addition to the components described above, thermoplastic
Remarkably impairs the strength, moldability and rubber elasticity of the elastomer
Unless otherwise specified, mineral oil-based softeners known per se,
Various rubber compounding agents can be compounded at any stage.
Wear. For example, a mineral oil type softening agent is usually a rubber softener.
During processing, weakens the intermolecular attractive force of rubber and facilitates processing
Carbon black and sili
Promote the dispersion of fillers such as mosquitoes, or use vulcanized rubber molds.
Blended for the purpose of lowering the elasticity and increasing the flexibility and rubber elasticity.
It is a high boiling point petroleum fraction that is
It is categorized into aromatic type and aromatic type. In the present invention
Is especially effective when using paraffinic process oils.
It is. Such a mineral oil-based softener is ethylene / α-olefin.
200 parts by weight or less per 100 parts by weight of the copolymerized rubber
May be used in quantity. It is advantageous to use more than this range.
The strength of the elastomer is reduced or the softening agent is exuded.
However, there is an inconvenience such as taking out and impairing the appearance. As the compounding agent for rubber, for example, filling
Agent, colorant, anti-aging agent, antioxidant, cross-linking agent, cross-linking aid
Agent, light resistance or light resistance stabilizer, processing aid, antistatic agent,
Other physical property improvers can be appropriately used. As a filler,
Carbon black, clay, talc, heavy calcium carbonate
Mu, kaolin, diatomaceous earth, silica, alumina, asbestos
Examples include strikes, graphite and glass fibers. Oxidation
As the inhibitor, phenyl-α-naphthylamine, p-
Isopropoxy diphenylamine, N, N'-dife
Nyl / ethylenediamine, nonylated diphenylamine, etc.
Amine Antioxidant, 2,6-di-t-butylpheno
, Styrenated phenol, butylhydroxyanisole
4,4'-hydroxydiphenyl, 2,2-methyle
N-bis (4-methyl-6-cyclohexylphenone
), Tetrakis- [methylene-3- (3 ', 5'-di
t-butyl-4'-hydroxyphenyl) propione
G] methane, tris- (2-methyl-hydroxy-5-
Phenol-based antioxidant such as di-t-butylphenyl) butane
A stopping agent can be illustrated. Thermoplastic elastomer thus obtained
Is a mechanical property such as moldability, rubber elasticity, weather resistance and strength.
It is excellent in bellows, tubes and interior
Auto parts such as shoes, mudguards, boots, pressure hoses,
Industrial machinery parts such as gaskets and diaphragms, electronic
Electrical equipment parts, electric cables, covering materials, building materials, footwear saws
It is extremely useful in various fields such as [0048] 【Example】 (Example 1) Ethylene / α-olefin copolymer rubber
Ethylene, propylene, ethylidene norbornene
Polymerized rubber (ethylene unit content 72 mol%, polyene component
As a 5-ethylidene norbornene unit with an iodine value
15-containing, 135 ° C in decahydronaphthalene
Degree [η] is 1.1 dl / g, abbreviated as "EPT" below)
did. As the low molecular weight α-olefin, modified poly (olefin)
Ethylene wax (maleic anhydride unit content: 3 weight
%, Density: 0.93 g / cc, softening point: 111 ° C)
Was. The above-mentioned EPT (100 g) and modified polyester
Tylene wax (11 g) and n-hexane (900
g) and stirred until homogeneous. Then interactivity
Potassium oleate (5 g) was added as water (900
g) and then using a homomixer,
The solution was mixed for 60 minutes at a rotation speed of 10,000 rpm. Get
The emulsion thus prepared is heated to a temperature of 60 to 80 ° C. to produce n-hexene.
The sun was distilled off to obtain a latex. Get in this way
The hot latex insoluble components shown in Table 1
P-divinylbenzene and di-t-butylper
Add an appropriate amount of oxytrimethylcyclohexane and
After dispersing, transfer the latex to an autoclave and mix.
3 kg / cm for raw gas^ThreeG Pressurized at 120 ℃ for 2 hours
It was heated and crosslinked. The obtained crosslinked latex was sprayed onto a disc.
Disk rotation speed 25,000 rpm
Bridge latex feed rate 10kg / hr, feed gas temperature
200 ℃, gas flow 8m^Three/ Hr treatment, cross-linking copolymer
Fine rubber particles were obtained. Average particle size of the obtained crosslinked rubber particles
Etc. and hot toluene insoluble matter are shown in Table 1. Next, the cross-linked copolymer rubber fine particles obtained above
Child and crystalline polypropylene [MFR (230 ℃, 2.1
6 kg): 11 g / 10 min, density: 0.91 g / cc]
So that the weight ratio of the rubber to the polypropylene is 70:30
Melt-mix in an extruder at an extrusion temperature of 230 ° C.
A let-like thermoplastic elastomer was obtained. This thermoplastic elastomer was injected at a temperature of 24
Injection molding at 0 ° C to form a 2mm thick sheet,
The measurement was performed, and the results are shown in Table 1. The measurement conditions are as follows.
It is as below.     Moldability: MFR (230 ° C, 2.16kg) ASTM D-1238     Rubber elasticity: PS% (adds 100% strain) JIS K-6301     Strength: TB (kg / cm^Three) JIS K-6301 Example 2 Intrinsic viscosity [η] is 0.8 dl / g
70g of EPT and crystalline polypropylene
30 g and 21 g of modified polyethylene wax were added to n-hex
A thermoplastic resin was prepared in the same manner as in Example 1 except that it was dissolved in sun.
Rustomer was prepared and the same measurement as in Example 1 was performed.
Table 1 shows the results. Example 3 Intrinsic viscosity [η] is 1.3 dl / g
EPT was used, and crosslinked rubber latex was used in the same manner as in Example 1.
Was prepared. Next, the EPT (100 g) of Example 1
Instead of the crystalline polypropylene 100 used in Example 1.
g in the same manner as in Example 1
Of latex was prepared. With the above crosslinked rubber latex
Polypropylene latex and EPT and polypropylene
Mix so that the weight ratio with ren is 70:30.
Drying is performed in the same manner as in Example 1 to obtain a thermoplastic elastomer.
After the preparation, the same measurement as in Example 1 was performed. The results are shown in Table 1.
Show. (Examples 4 to 11) Examples 4 to 11 except for the following points
A thermoplastic elastomer was prepared in the same manner as in Example 1 and
The same measurement was performed. The results are shown in Tables 2 to 4. Incidentally, the real
In Example 8, used in place of the modified polyethylene wax
The wax has a density of 0.92 g / cc and a softening point of 113 ° C.
Is an unmodified polyethylene wax. [0056] [0057] (Comparative Example 1) Bonding with the EPT used in Example 1
Crystalline polypropylene at a weight ratio of 70:30.
Use, mix with a Banbury mixer for 5 minutes, then use a brabender
-Using a mixer, a mixture of EPT and polypropylene
0.2 parts dicumyl peroxide to 100 parts by weight
And 0.2 parts by weight of divinylbenzene are mixed, and the oil bath temperature is adjusted.
Dynamic cross-linking blur for 7 minutes at 180 ℃ and 60 rpm.
To produce a thermoplastic elastomer. This heat
The same measurement as in Example 1 was performed on the plastic elastomer.
The results are shown in Table 1. Comparative Example 2 Brabender Miki of Comparative Example 1
Comparative Example 1 except that the rotation speed of the sir was changed to 150 rpm
A thermoplastic elastomer is produced in the same manner as
Was measured. The results are shown in Table 1. (Comparative Examples 3 to 6) Example 1 was repeated except for the following points.
A thermoplastic elastomer was prepared in the same manner as in
Such measurement was performed. The results are shown in Table 3 or 4. [0061][0062] [Table 1] [0063] [Table 2][0064] [Table 3] [0065] [Table 4][0066] According to the present invention, heat resistance, weather resistance and strength are high.
Moldability and go
To obtain a thermoplastic elastomer with significantly improved elastic modulus.
Can be.

Claims (1)

(57) [Claims] In a method for producing a thermoplastic elastomer comprising a blend of fine particle cross-linked ethylene / α-olefin copolymer rubber and a crystalline polyolefin resin, the intrinsic viscosity in a decahydronaphthalene solution at 135 ° C is 0.
An ethylene / α-olefin copolymer rubber in the range of 5 to 3.0 dl / g and a low molecular weight α-olefin copolymer and / or a modified low molecular weight α-olefin copolymer, (i) a surfactant To form a copolymer rubber latex by uniformly dispersing it in an aqueous medium in the presence of (ii) crosslinking in a latex state to form a crosslinked rubber latex composition, and (iii) drying the crosslinked rubber latex composition. To obtain a particulate cross-linked ethylene / α-olefin copolymer rubber, and the crystalline polyolefin resin to be blended is premixed in the copolymer rubber latex forming step (i), or
The crystalline polyolefin resin finely dispersed in the aqueous medium in the crosslinked rubber latex forming step (ii) is mixed with the aqueous medium in advance with the crosslinked rubber latex composition, or is obtained in the drying step (iii). And a fine particle crosslinked ethylene / α-olefin copolymer rubber, and the obtained fine particle crosslinked ethylene / α-olefin copolymer rubber and a crystalline polyolefin resin are melt-kneaded. Method for producing a plastic elastomer. 2. The low-molecular-weight α-olefin copolymer or modified low-molecular-weight α-olefin copolymer is used in an amount of 2 to 50 parts by weight per 100 parts by weight of ethylene / α-olefin copolymer rubber, and the fine particle crosslinked ethylene is used. -The manufacturing method of Claim 1 which manufactures an (alpha)-olefin copolymer rubber.