JPS63225644A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:To obtain the title composition useful for automobile parts, industrial parts, electronic and electric parts and components, etc. excellent in oil resistance, mechanical strengths and thermal aging resistance, by mixing a partially crosslinked graft-modified polyolefin elastomer with a polyamide. CONSTITUTION:A thermoplastic elastomer composition prepared by mixing 50-95pts.wt. graft-modified polyolefin elastomer (A) formed by dynamically heat-treating a blend containing 100-10pts.wt. peroxide-crosslinkable olefin copolymer rubber (a), 0-90pts.wt. olefin polymer (b) [the total amount of components (a) and (b) is 100pts.wt.] and 0.01-10pts.wt. at least one monomer selected from among an unsaturated carboxylic acid (derivative), an unsaturated epoxy monomer and an unsaturated hydroxy monomer (c) in the presence of an organic peroxide and 5-50pts.wt. polyamide (B).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a thermoplastic elastomer composition, and more specifically to a thermoplastic elastomer composition comprising a partially crosslinked modified polyolefin elastomer and a polyamide, which has a property of having oil properties, mechanical strength, and heat resistance. This invention relates to a thermoplastic elastomer composition with excellent aging properties.

(Prior art and its problems) Thermoplastic elastomers are energy-saving and resource-saving elastomers that are particularly used as substitutes for vulcanized rubber for automobile parts (bellows, tubes, interior sheets, mudguards, etc.).
Used in industrial machinery parts (pressure hoses, gaskets, diaphragms), electronic/electromechanical parts, building materials, etc.

As a thermoplastic elastomer, a composition of a crystalline thermoplastic polyolefin resin and a vulcanized ethylene-propylene-polyene copolymer rubber is disclosed, for example, in Japanese Patent Publication No. 58-4
It is described in Japanese Patent Publication No. 6138 and Japanese Patent Publication No. 55-18448. This composition has the disadvantage of having a poor balance between rubber elasticity and mechanical strength.

Additionally, a thermoplastic elastomer composition comprising a blend of crosslinked ethylene-propylene-polyene copolymer rubber, acrylonitrile-butadiene copolymer rubber, and polypropylene resin or nylon resin is disclosed in U.S. Pat. No. 43384.
No. 13. Although this composition has various properties including oil resistance, it has the fatal drawback of poor heat aging resistance and poor weather resistance.

Furthermore, a composition comprising a polyolefin resin, an α,β unsaturated carboxylic acid modified product of an ethylene/α-olefin copolymer mixture, and a polyamide is known from JP-A-57-8246. Although this composition has excellent mechanical strength, it has poor flexibility, which is one of the important properties for a thermoplastic elastomer.

Thus, to the best of the knowledge of the present inventors, a thermoplastic elastomer composition that is excellent in oil resistance, mechanical strength, and heat aging resistance is not yet known.

(Means for solving the problems) According to the present invention, (a) Peroxide crosslinked olefin copolymer rubber 1
00 to 10 parts by weight, (b) 0 to 90 parts by weight of olefin plastic, (
(The total amount of components (a) and (b) is 100 parts by weight) (c) at least one selected from the group consisting of unsaturated carboxylic acids or derivatives thereof, unsaturated epoxy monomers, and unsaturated hydroxy monomers; A graft-modified polyolefin elastomer (A) in which a blend containing 0.01 to 10 parts by weight of one type of monomer is partially crosslinked by dynamic heat treatment in the presence of an organic peroxide. , polyamide (B) is blended in a proportion of (A) of more than 50 to 95 and (8) of from 5 to less than 50, on a weight basis. Ru.

According to the present invention, the blend further includes (d) 0 to 100 parts by weight of a peroxide non-crosslinked rubbery substance, based on 100 parts by weight of the total amount of components (a) and (b). and/or (e) 0 to 200 parts by weight of a mineral oil softener.

(Function) In the thermoplastic elastomer composition of the present invention, the component (
Since the modified polyolefin elastomer A) is composed of a partially crosslinked olefin copolymer rubber and an olefin plastic, preferably a peroxide-decomposed olefin plastic, it has excellent fluidity and heat resistance.
It maintains heat aging resistance and imparts rubber elasticity.

The polyamide of component (3) imparts oil resistance and fluidity at high temperatures, and thereby the elastomer composition maintains predetermined oil resistance and moldability.

The reason why the thermoplastic elastomer composition of the present invention fully exhibits the advantages of component (A) and component (B) is that component (A) is an unsaturated carbonaceous compound that easily forms a physical or chemical bond with component (B). Uniformly modified with at least one monomer selected from the group consisting of acids or derivatives thereof, unsaturated epoxy monomers, and unsaturated hydroxy monomers, and when component (A) is unmodified. This is because the blend interface is greatly strengthened compared to the case where a third component having segments that are compatible with component (A) and component (B) is added.

Thus, according to the present invention, a thermoplastic elastomer composition with excellent oil resistance, mechanical strength, and heat aging resistance is provided due to the effects of the above-mentioned components.

(Preferred Embodiment of the Invention) (a) Peroxide crosslinked olefin copolymer rubber used in the present invention includes, for example, ethylene-brobylene copolymer rubber, ethylene -propylene non-conjugated diene rubber,
Ethylene-butadiene copolymer rubber is an amorphous elastic copolymer mainly composed of olefin, and when mixed with organic peroxide and kneaded under heat, it crosslinks and reduces fluidity. Or rubber that no longer flows.

In addition, non-conjugated diene is dicyclopentadiene, 1.4
- Refers to hexadiene, dicyclooctadiene, methylene norbornene, ethylidene norbornene, etc.

In the present invention, among these copolymer rubbers, ethylene-propylene copolymer rubber, ethylene-propylene-
Non-conjugated diene rubbers are preferably used, with a molar ratio of ethylene units to propylene units (ethylene/propylene) of 5.
0150 to 90/10, particularly 55/45 to 85/15, are preferably used, especially ethylene-propylene-nonconjugated diene copolymer rubber, especially ethylene-propylene-5-ethylidene-2 -Norbornene copolymer rubber and ethylene-propylene-5-ethylidene-2-norbornene-dicyclopentadiene quaternary copolymer are preferred in that thermoplastic elastomers with excellent heat resistance, tensile properties, and impact resilience can be obtained. .

Also, the Mooney viscosity ML of this copolymer rubber.

(at 100° C.) is preferably 10 to 250, particularly 40 to 150. When the Mooney viscosity is within this range, a composition with excellent tensile properties and fluidity can be obtained.

Further, the iodine value (degree of unsaturation) of the copolymer rubber is preferably 2.5 or less, and within this range, a thermoplastic elastomer with well-balanced fluidity and rubber properties can be obtained.

(b) Olefinic Plastics The olefinic plastics contemplated by the present invention consist of crystalline, high molecular weight solid products obtained from the polymerization of one or more monoolefins by either high-pressure or low-pressure processes. Examples of such resins include isotactic and syndiotactic monoolefin homo- or copolymer resins, representative of which are commercially available.

, J Examples of suitable raw material olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1- Examples include pentene, 5-methyl-1-hexene, l-octene, 1-decene, and mixtures of two or more of these polymers.The polymerization mode can be random or block, and a resin-like product can be obtained. If so, you can adopt it.

Among these, preferred olefin plastics are peroxide decomposition type olefin plastics and polyethylene.

The peroxide-decomposable olefin plastic in the present invention refers to an olefin plastic that is thermally decomposed by mixing with peroxide and kneading under heating to reduce the molecular weight and increase the fluidity of the resin, such as isotactic plastic. Polypropylene and copolymers of propylene and small amounts of other α-olefins, such as propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers, propylene-4-methyl-1 -pentene copolymers and the like. Melt index of olefin plastic to be mixed (ASTM-D-1238-657.V230℃)
is 0.1 to 50. In the present invention, the olefin plastic has a role of improving fluidity and heat resistance of the composition.

(c) \Saturated carboxylic acid is its derivation ・The unsaturated carboxylic acid A or its derivative used as one of the components (c) in the saturated water invention specifically includes acrylic acid, methacrylic acid, and maleic acid. , α,β unsaturated carboxylic acids such as fumaric acid, itaconic acid, citraconic acid, and tetrahydrophthalic acid, and unsaturated carboxylic acids such as bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid. , anhydrides of α, β unsaturated carboxylic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2,2,1]hept-2
Anhydrides of unsaturated carboxylic acids such as -ene-5,6-dicarboxylic anhydride, methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconate, tetrahydrocarbon Dimethyl phthalate anhydride, bicyclo[
Examples include esters of unsaturated carboxylic acids such as dimethyl 2,2,1]hept-2-ene-5,6 dicarboxylate. Among these, maleic acid, bicyclo[2
, 2,1]hept-2-ene-5,6-dicarboxylic acid or anhydrides thereof are preferred.

Further, in the present invention, the unsaturated epoxy monomer which is another component (c) includes, for example, glycidyl esters of unsaturated monocarboxylic acids such as glycidyl acrylate, glycidyl methacrylate, and glycidyl p-styrylcarboxylate; Maleic acid, itaconic acid, citraconic acid, butenetricarboxylic acid, endo-cis-bicyclo[2
,2,11hept-5-ene-2,3-dicarboxylic acid,
Monoglycidyl ester or polyglycidyl ester of unsaturated polycarboxylic acids such as endo-cis-bicyclo[2,2,1]hept-5-ene-2-methyl-2,3-dicarboxylic acid; allyl glycidyl ether, 2-
Methylallyl glycidyl ether, 0-allylphenol glycidyl ether, m-allylylphenol glycidyl ether, p-allylylphenol glycidyl ether, isopropenylphenol glycidyl ether, O-vinylphenol glycidyl ether, m- Glycidyl ether of vinylphenol, p-
Unsaturated glycidyl ethers such as glycidyl ether of vinylphenol; 2-(0-vinylphenyl)ethylene oxide, 2-(p-vinylphenyl)ethylene oxide%2-('-vinylphenyl)propylene oxide, 2-(p-vinylphenyl) ) Propylene oxide %2-('-arylphenyl)ethylene oxide, 2
-(p-allylphenyl)ethylene oxide%2-(
0-arylphenyl)propylene oxide, 2-(p
-arylphenyl)propylene oxide, p-glycidylstyrene, 3.4-epoxy-1-butene, 3.4
-Epoxy-3-methyl-1-butene, 3.4-epoxy-1-pentene, 3.4-epoxy-3-methyl-1
-pentene, 5,6-epoxy-l-hexene, vinylcyclohexene monoxide, aldyl-2,3-epoxycyclobentyl ether, and the like are preferred.

Furthermore, the unsaturated hydroxy monomer, which is another component (c) of the present invention, refers to a monomer having one or more ethylenically unsaturated bonds and one or more hydroxyl groups, such as hydroxyethyl acrylate, hydroxypropyl Examples include acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, and hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate are particularly preferred.

These component (c) can be used alone or in combination, and act as a graft modifier during the dynamic heat treatment described below, and serve to strengthen the blend interface between the polyamide and the graft-modified polyolefin elastomer. It improves the oil resistance, strength, etc. of molded products made from thermoplastic elastomer compositions.

The graft-modified polyolefin elastomer in the present invention may further contain (d) a peroxide non-crosslinked rubbery substance and/or (e) a mineral oil softener.

(d) Peroxide crosslinked rubber The peroxide non-crosslinked rubbery substance of component (d) is, for example, polyisobutylene, butyl rubber (IIR),
Hydrocarbon-based rubbery substances that do not crosslink or reduce fluidity even when mixed with peroxide and kneaded under heat, such as propylene-ethylene copolymer rubber containing 70 mol% or more of propylene, atactic polypropylene, etc. Among these, polyisobutylene and butyl rubber (IIR)
However, it is also preferable in terms of performance and handling.

Such components improve the fluidity of the elastomer composition, and those having a Mooney viscosity of 60 or less are particularly suitable.

Component (d) also improves the permanent set of the thermoplastic elastomer composition.

(e) Mineral oil softener (component) (a) is usually used when rolling rubber to weaken the intermolecular force of the rubber, making it easier to process, and is also incorporated as a filler. It is a high boiling point petroleum distillate that is used to assist in the dispersion of carbon black, white carbon, etc., or to reduce the hardness of vulcanized rubber and increase its flexibility and elasticity.
They are classified into aromatic types, etc.

Graft polyolefin, elastomer (A) The partially crosslinked graft-modified polyolefin elastomer (A) in the present invention comprises (a) 100 to 10 parts by weight of the peroxide crosslinked olefin copolymer rubber,
Especially 95 to 60 parts by weight, (b) olefinic plastic 0 to 9o11 parts by weight, especially 5 to 40 parts by weight (where (a) + (b) is selected so as to be 100 parts by weight)
, and (c) 0.01 to 1 of at least one monomer selected from the group consisting of unsaturated carboxylic acids or derivatives thereof, unsaturated epoxy monomers, and unsaturated hydroxy monomers.
It is produced by blending 0 parts by weight, especially 0.1 to 5 parts by weight, and dynamically heat-treating the mixture in the presence of an organic peroxide to partially crosslink it.

In addition, in the present invention, when blending the above-mentioned components, it is preferable to blend the component (d) and/or the component (e). from 100 parts by weight, preferably from 5 to 100 parts by weight, particularly preferably from 5 to 50 parts by weight, and from 0 to 200 parts by weight, preferably from 3 to 100 parts by weight, particularly preferably from 0 to 200 parts by weight of the mineral oil softener of component (e). is 5 to 8
It is preferable to mix it in an amount of 0 parts by weight.

By blending component (a) in the above range, a composition with excellent rubber properties such as rubber elasticity and excellent moldability can be obtained.

By blending components (b), (d), and (e) within the above ranges, a composition with excellent rubber properties such as rubber elasticity, as well as excellent fluidity and moldability can be obtained.

By blending component (c) within the above range, moldability and thermal adhesion to resins and metals will be excellent.

Also, the fluidity (moldability) of the elastomer composition produced
, fillers such as calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, within a range that does not impair rubber properties and oil resistance.
Asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass bulbs, shirasu balloons, carbon fiber, etc. or coloring agents, such as carbon black, titanium oxide, zinc oxide , bengara,
Ultramarine blue, navy blue, azo pigments, nitroso pigments, lake pigments, phthalocyanine pigments, etc. can be blended.

The present invention also includes known heat stabilizers, anti-aging agents, weathering stabilizers such as phenolic, sulfide, phenylalkane, phosphite or amine stabilizers;
Antistatic agents, metal soaps, lubricants such as wax, etc. can be added to the olefin plastic.

In the present invention, a modified polyolefin elastomer is produced by dynamically heat-treating a blend of the above-mentioned components in the presence of an organic peroxide to partially crosslink it.

Dynamic heat treatment means kneading in a molten state.

Examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tart-butyl peroxide, and 2,5-dimethyl-2,5-di(tert-butyl peroxide).
butylperoxy)hexane, 2,5-dimethyl-2,
5-di(tart-butylperoxy)hexyne-3,
1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-
Butyl-4,4-bis(tert-butylperoxy)
Valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tart-butylberbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide etc. can be mentioned.

Among these, it ranks 2.5 in terms of odor and scorch stability.
-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane,
-butylperoxy)hexyne-3,1,3-bis(t
ert-butylperoxyisopropyl)benzene, 1
．． 1-bis(tart-butylperoxy)-3,3,
5-trimethylcyclohexane, and n-butyl-4,
4-bis(tert-butylperoxy)valerate is preferred, and 1,3-bis(tert-butylperoxyisopropyl)benzene is most preferred.

The amount of organic peroxide to be blended is selected to be in the range of 0.05 to 3% by weight, preferably 0.1 to 1% by weight, based on the total amount of components (a), (b) and (c).

By setting the blending amount within the above range, the thermoplastic elastomer obtained will have sufficient rubber properties such as heat resistance, tensile properties, elastic recovery and rebound properties, and strength, and will also have excellent moldability.

As the mixing device, conventionally known devices such as an open type mixing roll, a closed type Banbury mixer 1 extruder, and a kneader 1 continuous mixer are used. Among these, it is preferable to use a closed type device, and it is preferable to knead in an inert gas atmosphere such as nitrogen or carbon dioxide.
The crosstalk may be carried out for 1 to 20 minutes, preferably 3 to 10 minutes at a temperature of less than 1 minute, usually from 150 to 280°C, preferably from 0 to 240°C.

In the present invention, in the partial crosslinking treatment with the organic peroxide, sulfur, p-quinonedioxime, p, p'
-dibenzoylquinone dioxime, N-methyl-N,4
- peroxy crosslinking coagents such as dinitrosoaniline, nitrobenzene, diphenylguanidine, trimethylolpropane-N,N'-m-fuynylene dimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, Multifunctional methacrylate monomers such as polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, and multifunctional vinyl monomers such as vinyl butyrad or vinyl stearate can be incorporated. With such a compound, a uniform and mild crosslinking reaction can be expected.

In particular, in the present invention, when divinylbenzene is used,
It is easy to handle, has good compatibility with olefin rubber and olefin plastic, which are the main components of the treated material, and has an organic peroxide solubilizing effect and acts as a peroxide dispersion aid, so it can be crosslinked by heat treatment. In the present invention, the blending amount of such a crosslinking aid or polyfunctional vinyl chloride is the most preferable because a composition with a homogeneous effect and a well-balanced flowability and physical properties can be obtained. It is preferably in the range of 0.1 to 2% by weight, particularly 0.3 to 1% by weight, based on the total weight.By blending in this range, the composition has excellent fluidity and has a better thermal history during processing and molding. The composition can be changed without causing any change in physical properties.

In addition, in order to promote the decomposition of organic peroxides, tertiary amines such as triethylamine, tributylamine, 2,4゜6-tris(dimethylamino)phenol, aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, Decomposition accelerators such as naphthenates of magnesium, lead, mercury, etc. can also be used.

The kneading is preferably carried out in a closed type apparatus, preferably under an inert gas atmosphere such as nitrogen or carbon dioxide, at a temperature such that the half-life of the organic peroxide used is less than 1 minute; Usually 150-280℃, preferably 1
The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. The shearing force to be applied is usually selected at a shear rate of 10-10'sec'''11, preferably 102-10'5eC-'.

As the kneading device, a mixing roll, an intensive mixer, such as a Banbury mixer, a kneader, 5-screw extruder, or a twin-screw extruder can be used, but a non-open type is preferred.

Dynamic heat treatment in the presence of organic peroxides, as described above, results in partial crosslinking (c
) A graft-modified polyolefin elastomer is obtained.

In the present invention, partially crosslinked graft-modified polyolefin elastomer (A) means that the gel content measured by the following method is 20% or more, preferably 20%.
It refers to a case where it is in the range of 99.5% to 99.5%, particularly preferably 45 to 98%.

Take 100 mg of a thermoplastic elastomer sample and cut it into strips of 0.5 x o, 5 x - xo, and 5 m + a. After 48 hours of immersion in cyclohexane at 23°C, the sample is taken out onto a filter paper and dried at room temperature for 72 hours or more until it reaches a constant weight.

The weight of all cyclohexacine-soluble components other than the polymer component (fibrous fillers, fillers, pigments, etc.) and the weight of the olefinic plastic component in the sample before immersion in cyclohexane are subtracted from the weight of this dried residue. of,"
corrected final weight (Y).

On the other hand, the weight of the peroxide crosslinked olefin copolymer rubber in the sample, [i.e., from the weight of the sample, ■cyclohexane-soluble components other than the peroxide crosslinked olefin copolymer rubber (e.g., mineral oil and plasticizer) and ■olefin The weight of the cyclohexane-insoluble components (fibrous filler, filler, pigment, etc.) other than the polymer component] is defined as the "corrected initial weight (x)".

Here, the gel content is determined by the following formula.

The thermoplastic elastomer composition of the present invention has a graft-modified polyolefin elastomer (A) of more than 50 and 95
up to 60 to 90, preferably from 60 to 90
It is obtained by blending B) in a ratio of 50 to 5, preferably 40 to 10 (based on weight).

By blending components (A) and (B) in the above proportions, a thermoplastic elastomer composition with excellent oil resistance, mechanical strength, and heat aging resistance can be obtained.

In a thermoplastic elastomer composition, the grafted (
c) The content of the component is measured by infrared absorbance analysis or chemical analysis.

Polyamide (B) The polyamide (B) in the present invention includes hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2.4- or 2,4.4-trimethylhexamethylene diamine, 1.3- or 1. Aliphatic, alicyclic, aromatic diamines such as 4-bis(aminomethyl)cyclohexane, bis(p-aminocyclohexylmethane), m- or p-xylylenediamine, adipic acid, speric acid, sebacin polyamide obtained by polycondensation with aliphatic, alicyclic, aromatic dicarboxylic acids such as acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, etc.; aminocarboxylic acids such as ε-aminocaproic acid and 11-amine undecanoic acid; Examples include polyamides obtained by condensation of lactams such as C-caprolactam and ω-laurolactam, copolyamides made of these components, and mixtures of these polyamides. Specifically, nylon 6, nylon 66, nylon 610, nylon 9, and nylon 11.
, nylon 12, nylon 6/66, nylon 66/6
Examples include 101 nylon 6/11. Among these, nylon 6 and nylon 66 are preferred because the thermoplastic elastomer composition has good mechanical strength and heat resistance.

The method for mixing modified polyolefin-based neatstomer (A) and polyamide (B) is to first mix them using a Henschel mixer, V-type blender, ribbon blender, tumbler blender, etc., and then further mix them at a temperature higher than the melting point of the polyamide. Extruder, twin screw extruder, kneader,
Examples include a method of melt-mixing using a Banbury mixer or the like, followed by granulation or pulverization.

Further, the composition of the present invention may contain the above-mentioned fillers that can be blended into the partially crosslinked graft-modified thermoplastic elastomer composition.

(Effects) The thermoplastic elastomer composition of the present invention thus obtained has excellent moldability, can be molded with equipment used for ordinary thermoplastics, and can be used in extrusion molding, calendar molding, injection molding, etc. Are suitable.

Furthermore, the thermoplastic elastomer composition of the present invention contains at least one type of unsaturated carboxylic acid such as maleic anhydride or a derivative thereof, an unsaturated epoxy monomer, and an unsaturated hydroxy monomer. The composition has a significantly strengthened blend interface between a modified polyolefin thermoplastic elastomer graft-modified with a monomer and a polyamide, so it has excellent oil resistance and mechanical strength, and is suitable for use in automobile parts (bellows, channels, etc.). , interior sheets, mudguards, etc.), industrial parts (pressure-resistant hoses, gaskets, diaphragms, etc.), electronic/electrical equipment parts, and building materials.

In the present invention, (a
The content ratio of component ) and component (b) can be measured by the 0-5-C method and/or infrared absorbance analysis method,
The content of components d) and (@) can be measured by a solvent extraction method (Soxhlet extraction method (solvent: acetone)) and/or an infrared absorbance analysis method.

1 Feng ■1 Ethylene content 70 mol%, iodine number 12, Mooney viscosity ML1-a (100°C) 120 (F)! 80 parts by weight of tyrene/propylene/5-ethylidene-2-norbornene copolymer rubber (hereinafter abbreviated as EPDM (1)), MF
R (ASTM 01238-65T, 230°C) 13
, 20 parts by weight of polypropylene (hereinafter abbreviated as PP) with a density of 0.91 g7cm" was kneaded in a Banbury mixer at 180°C in a nitrogen atmosphere for 5 minutes, passed through a roll to form a sheet, and cut into a square pellet with a sheet cutter. 6 Next, this square pellet was mixed with 0.3 parts by weight of 1,3-bis(tart-butylperoxyisopropyl)benzene (hereinafter abbreviated as peroxide (A)) and 0.5 parts by weight of divinylbenzene (hereinafter abbreviated as DVB). and 0.5 parts by weight of maleic anhydride (hereinafter abbreviated as MAR) were stirred and mixed in a Henschel mixer.Then, this mixture was mixed in a nitrogen atmosphere using an LZD-30 single-screw extruder with a screw diameter of 50 mm.
A graft-modified polyolefin elastomer (A) was produced by extrusion at t. Then, the gel content of the copolymer rubber in the modified polyolefin elastomer (A) was measured by the method described above, and the measured values are shown in Table 1.

Next, this modified polyolefin elastomer (A) 85
Weight part and polyamide (B) (Unitika nylon 6A1
030BRF) was extruded at 250° C. under a nitrogen atmosphere using an LZD-30 single screw extruder with a screw diameter of 50 mm. The obtained thermoplastic elastomer was compression molded at 250°C to prepare a sheet for measuring physical properties, and the following physical properties were measured. The results are shown in Table 1.

Oil resistance: Δv% Based on JIS 63012, the sample was immersed in JIS No. 3 oil at 50°C for 7 days, and the volume increase rate (percentage) after immersion compared to before immersion was measured.

Strength: T B kgf/cm' The tensile strength at the breaking point was measured at a tensile speed of 200 mm/win in accordance with JIS 6301.

Flexibility: Twisting stiffness kgf/cm” ASTM 010
Formability according to 43: MFRg/l 0 min ASTM D 123
Based on B 230℃, 2.16kg Heat aging physical properties: AR (EB)%Based on JIS K 6301, put in a gear oven at 135℃ for 7 days and calculated the ratio (retention rate/%) to the elongation at break before aging. It was measured.

Example 1 except that the blended amount of maleic anhydride was zero.
I did the same thing.

The same procedure as in Example 1 was carried out except that the amount of Aizoku DVB was zero, the modified polyolefin elastomer (A) was 70 parts by weight, and the polyamide (B) was 30 parts by weight.

5. Ethylene content 70 mol%, iodine value 12, Mooney viscosity M
L, or (100℃) 120 pellet-shaped ethylene.
80 parts by weight of propylene/5-ethylidene-2-norbornene copolymer rubber (hereinafter abbreviated as EPDM (2)), PP
20 parts by weight, peroxide (A) 0.3 parts by weight, M
A: 5 parts by weight of R0.5 parts by weight and 5 parts by weight of DVBO were stirred and mixed in a Henschel mixer.
A modified polyolefin elastomer (A) was produced at 220°C in a nitrogen atmosphere using a twin-screw extruder with a screw diameter of 53 mm.
The same procedure as in Example 1 was carried out except that A) was changed to 55 parts by weight and polyamide (B) was changed to 45 parts by weight.

4.5. 2 The blending amounts of heheroxide (A) were 0.6 parts by weight, 1 part by weight, and 1.5 parts by weight, respectively, and the blending amounts of MAR1 modified polyolefin elastomer (A) and polyamide (B) were as shown in Table 1. The same procedure as in Example 1 was carried out except for the following.

16, 7. 8. 9. Hi
The same procedure as in Example 3 was conducted except that the blending amounts of 3EPDM (1) and PP were as shown in Table 1.

When producing the industrially modified polyolefin elastomer (A), in addition to EPDM (1) and PP, butyl rubber (IIR-065 manufactured by Esso, unsaturation level 0.8 mol%, hereinafter referred to as IIR) is used.
Example 1 was carried out in the same manner as in Example 1, except that the modified polyolefin elastomer (A) and polyamide (B) were mixed in the amounts shown in Table 1. .

The same procedure as in Example 10 was carried out except that 0.5 parts by weight of glycidyl methacrylate was added instead of 0.5 parts by weight of East Ml Upper M A R 0.5 parts by weight.

Example except that the amounts of EPDM (1), PP% IIR, paraffin process oil, MAH, modified polyolefin elastomer (A), and polyamide (B) were as shown in Table 1. The same procedure as in 10 was carried out.

叉偼ヱ1〉Executed except that the blending amounts of EPDM (1), PP, IIR, paraffin process oil, glycidyl methacrylate, modified polyolefin elastomer (A), and polyamide (B) were as shown in Table 1. The same procedure as in Example 11 was carried out.

The same procedure as in Example 10 was carried out except that hydroxypropyl methacrylate was used instead of maleic anhydride.

The same procedure as in Example 14 was conducted except that hydroxypropyl methacrylate was used instead of maleic anhydride.

Claims (3)

[Claims] (1) (a) 100 to 10 parts by weight of peroxide crosslinked olefin copolymer rubber, (b) 0 to 90 parts by weight of olefin plastic, (the total amount of components (a) and (b) is 100 parts by weight) ) (c) Contains 0.01 to 10 parts by weight of at least one monomer selected from the group consisting of unsaturated carboxylic acids or derivatives thereof, unsaturated epoxy monomers, and unsaturated hydroxy monomers. A blend of a graft-modified polyolefin elastomer (A) which has been dynamically heat-treated in the presence of an organic peroxide and is partially crosslinked, and a polyamide (B), on a weight basis, and (A) has a content of 50% by weight. Up to 95, (B) is 5
1. A thermoplastic elastomer composition, characterized in that it is blended in a ratio of from 50 to less than 50. (2) The blend further contains (d) 0 to 100 parts by weight of a peroxide non-crosslinked rubbery substance, based on 100 parts by weight of the total amount of components (a) and (b), and/or ( The thermoplastic elastomer composition according to claim 1, characterized in that it contains e) 0 to 200 parts by weight of a mineral oil-based softener. (3) The (a) peroxide crosslinked olefin copolymer rubber is 95 to 60 parts by weight, and the (b) olefin plastic is 5 to 40 parts by weight (total of components (a) and (b)). The thermoplastic elastomer composition according to claim 1 or 2, characterized in that the amount is 100 parts by weight).