JPH0689080B2 - Thermoplastic elastomer composition having excellent thermal adhesion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to a thermoplastic elastomer composition which is excellent in thermal adhesiveness to various resins and metals and is also excellent in rubber elasticity, moldability and heat resistance. More specifically, an ethylene-α-olefin-non-conjugated diene copolymer rubber, which is a peroxide-crosslinking olefin-based copolymer rubber, and a crystalline polypropylene, which is a peroxide-decomposing olefin-based plastic, are mixed with an unsaturated epoxy. The present invention relates to a thermoplastic elastomer composition that is partially crosslinked by dynamically heat-treating it together with a monomer or an unsaturated hydroxy monomer in the presence of an organic peroxide.

(Prior Art and Problems Thereof) Thermoplastic elastomers are conventionally known as energy-saving and resource-saving type vulcanized rubber substitutes.

As such a thermoplastic elastomer, for example, an olefin-based thermoplastic elastomer containing ethylene-propylene-non-conjugated diene copolymer rubber as a main component is known, but these are excellent in performance as a thermoplastic elastomer. However, its adhesiveness to various resins, metals, etc. is not sufficient, so that its use is extremely limited.

Further, attempts have been made to graft-modify the above rubber component with maleic anhydride or the like in order to improve the adhesiveness,
In such a case, although the adhesiveness is improved, it is inevitable that the properties such as rubber elasticity and moldability are significantly deteriorated. In the end, various properties such as rubber elasticity and moldability as well as adhesiveness to various resins and metals An excellent thermoplastic elastomer is not yet known.

(Means for Solving the Problems) According to the present invention, (a) 95 to 10 parts by weight of an amorphous ethylene-α-olefin-non-conjugated diene copolymer rubber, (b) a crystalline polypropylene of 5 to 90 Parts by weight (the total amount of the components (a) and (b) is 100 parts by weight) (c) 0.1 to 5 parts by weight of an unsaturated epoxy monomer or an unsaturated hydroxy monomer, A thermoplastic elastomer composition is provided which is dynamically heat treated in the presence of an organic peroxide and is partially cross-linked with a gel content in the range of 45 to 98% by weight.

According to the present invention, further a. In the blended product, (d) 0 to 100 parts by weight of a non-crosslinking peroxide type rubber-like substance, (e) a mineral oil-based softening agent, based on 100 parts by weight of the total of the components (a) and (b) An embodiment containing one or more kinds of compounding agents selected from the group consisting of 0 to 200 parts by weight of the agent, and 0 to 100 parts by weight of (f) the fibrous filler, and b. There is provided a thermoplastic elastomer composition of the aspect in which the (f) fibrous filler is blended with the thermoplastic elastomer composition after partial crosslinking.

(Function) In the thermoplastic elastomer composition of the present invention, the amorphous ethylene-α-olefin-non-conjugated diene copolymer rubber which is the peroxide-crosslinking olefin copolymer rubber of the component (a) imparts rubber elasticity. It also has excellent heat resistance because it is partially crosslinked.

The crystalline polypropylene as the component (b) imparts fluidity at a high temperature, whereby the elastomer has a predetermined moldability.

The unsaturated epoxy monomer or unsaturated hydroxy monomer of the component (c) is a graft modifier and is graft-bonded to the rubber component of the component (a) during the dynamic heat treatment, whereby the elastomer has Thermal adhesion to various resins and metals is provided.

The component (d) or (e) also improves the fluidity of the rubber composition and imparts moldability in the same manner as the olefin plastic as the component (b).

The fibrous filler as the component (f) imparts dimensional stability (low linear expansion coefficient) and shape stability (appropriate rigidity) to the composition.

Thus, according to the present invention, by the action of each of the above components, while maintaining the predetermined rubber elasticity, heat resistance and moldability, the thermal adhesiveness to various resins and metals is remarkably improved, and the fibrous filler. When blended with, it becomes possible to further improve the dimensional and shape stability.

(A) Peroxide-Crosslinking Olefin Copolymer Rubber In the present invention, an amorphous ethylene-α-olefin-non-conjugated diene copolymer rubber is used as the peroxide-crosslinking olefin copolymer.

This copolymer rubber has a property that when it is mixed with an organic peroxide and kneaded under heating, it is crosslinked and the fluidity is lowered or it does not flow.

Incidentally, the non-conjugated diene, dicyclopentadiene, 1,4-
Hexadiene, dicyclooctadiene, methylene norbornene, ethylidene norbornene and the like are referred to.

In the present invention, particularly, those having a molar ratio of ethylene units and propylene units (ethylene / propylene) of 50/50 to 90/10, more preferably 55/45 to 85/15 are preferably used, and among them, Particularly, ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber and ethylene-propylene-5-ethylidene-2-norbornene-dicyclopentadiene quaternary copolymer are excellent in heat resistance, tensile strength and impact resilience. It is preferable in that a thermoplastic elastomer can be obtained.

Also, the Mooney viscosity of the rubber of this copolymer MLl ₊₄ (100 ℃)
Is preferably 10 to 150, and particularly preferably 40 to 120. Within this range, an elastomer composition having excellent tensile properties and fluidity can be obtained.

Further, the iodine value (unsaturation degree) of the copolymer rubber is preferably 16 or less, and in this range, a thermoplastic elastomer having a good balance of fluidity and rubber properties can be obtained.

(B) Crystalline polypropylene The crystalline polypropylene that is the component (b) of the present invention includes
Polypropylene homopolymers such as isotactic and syndiotactic polypropylene, and crystalline polypropylene copolymers containing propylene as a main component and a small amount of another monoolefin copolymerized therein are included.

These polypropylenes used in the present invention have the property that when mixed with peroxide and kneaded under heating, they undergo thermal decomposition to reduce the molecular weight and increase the fluidity of the resin. The crystalline polypropylene used in the present invention has a melt index (ASTM-D-1238-65T, 230 ° C) of 0.1 to 50,
Particularly, those in the range of 5 to 20 are preferable.

In the present invention, the crystalline polypropylene has a role of improving the fluidity and heat resistance of the composition.

(C) Unsaturated Epoxy Monomer or Unsaturated Hydroxy Monomer Examples of the unsaturated epoxy monomer used as the component (c) in the present invention include glycidyl acrylate, glycidyl methacrylate, p-styrylcarboxylic acid glycidyl and the like. Glycidyl ester of unsaturated monocarboxylic acid; maleic acid, itaconic acid, citraconic acid, butenetricarboxylic acid, endo-cis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid, endo-cis- Bicyclo [2.2.1] hept-5-ene-2-methyl-2,3-
Monoglycidyl ester or polyglycidyl ester of unsaturated polycarboxylic acid such as dicarboxylic acid; allyl glycidyl ether, 2-methyl allyl glycidyl ether, o-allyl phenol glycidyl ether, m-allyl phenol glycidyl ether, p
Unsaturated glycidyl ethers such as glycidyl ethers of allylphenol, glycidyl ethers of isopropenylphenol, glycidyl ethers of o-vinylphenol, glycidyl ethers of m-vinylphenol, glycidyl ethers of p-vinylphenol;
(O-Vinylphenyl) ethylene oxide, 2- (p-
Vinylphenyl) ethylene oxide, 2- (o-vinylphenyl) propylene oxide, 2- (p-vinylphenyl) propylene oxide, 2- (o-arlylphenyl) ethylene oxide, 2- (p-allylphenyl)
Ethylene oxide, 2- (o-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-1-hexene, vinylcyclohexene monoxide, allyl-
2,3-Epoxy cyclopentyl ether and the like are preferable, and glycidyl acrylate and glycidyl methacrylate are particularly preferable.

The unsaturated hydroxy monomer is a monomer having at least one ethylenically unsaturated bond and at least one hydroxy group, and examples thereof include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and polyethylene glycol mono. Methacrylate, polypropylene glycol monomethacrylate and the like can be mentioned, with hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate being particularly preferred.

(D) Peroxide non-crosslinking rubber-like substance In the present invention, the peroxide non-crosslinking rubbery substance is
For example, polyisobutylene, butyl rubber (IIR), propylene 70% mol or more propylene-ethylene copolymer rubber, atactic polypropylene, etc. do not crosslink when mixed with peroxide and kneaded under heating, resulting in poor fluidity. Not a hydrocarbon-like substance. Of these, polyisobutylene and butyl rubber (IIR) are the most 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-based softening agent The mineral oil-based softening agent in the present invention is a carbon black to be blended as a filler, which usually weakens the intermolecular action force of the rubber during roll processing and facilitates processing.
It is a high boiling point petroleum fraction used to help disperse white carbon etc. or reduce the hardness of vulcanized rubber to increase flexibility and elasticity, such as paraffin type, naphthene type, aromatic type etc. It is a distinction.

(F) Fibrous filler The fibrous filler in the present invention has a diameter of 0.1 μm.
It is preferably about 15 to 15 μm and a length of about 5 to 10 μm. Specific examples thereof include glass fibers (chopped strands, rovings, milled glass fibers, glass flakes, etc.), wollastonite, cut fibers, rock fibers, microfibers. , Processed mineral fiber, carbon fiber, gypsum fiber, aromatic polyamide fiber,
Examples thereof include potassium titanate fiber. Among these, milled glass fiber, glass flake, and potassium titanate fiber are preferable. Further, the fibrous filler is more preferably treated with various coupling agents such as silane-based, chromium-based and titanium-based in order to improve the wettability with the thermoplastic elastomer serving as the matrix.

The fibrous filler is also compounded at the time of graft bonding or at a subsequent stage.

Further, in the present invention, a polyolefin-based plastic can be blended with the thermoplastic elastomer composition after the partial cross-linking, and in that case, based on the weight, the polyolefin-based plastic (A): thermoplastic elastomer composition (B) is 0: 100 to 75:25, that is,
300 parts by weight to 100 parts by weight of the thermoplastic elastomer,
Particularly, it is preferable to blend the olefin-based plastic in a ratio of up to 200 parts by weight.

Examples of the polyolefin-based plastic to be blended with the thermoplastic elastomer composition include high-, medium- to low-density polyethylene, isotactic polypropylene and copolymers of propylene and a small amount of other α-olefins known per se, such as propylene-. Examples thereof include ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers and propylene-4-methyl-1-pentene copolymers. Melt index of mixed olefinic plastics (ASTM-D-1238-
65T, 230 ° C) is preferably in the range of 0.1 to 50, especially 5 to 20. In the present invention, the olefin-based plastic plays a role of improving the fluidity and heat resistance of the composition.

Production of Elastomer Composition Suitable examples of the thermoplastic elastomer composition in the present invention include the above-mentioned (a) amorphous ethylene-α-olefin-non-conjugated diene copolymer rubber 95 to 10 parts by weight, preferably 95 to 40 parts by weight, (b) crystalline polypropylene 5 to
90 parts by weight, preferably 5 to 60 parts by weight, (the total amount of components (a) and (b) is 100 parts by weight), and (c) unsaturated epoxy monomer or unsaturated hydroxy monomer 0.1. It is prepared by blending 5 to 5 parts by weight, dynamically heat treating in the presence of an organic peroxide, and partially crosslinking.

Another preferred example of the thermoplastic elastomer composition according to the present invention is: (d) a non-crosslinking peroxide-type rubber-like substance 0 to 100 per 100 parts by weight of the total of the components (a) and (b). Parts by weight, preferably 5 to 10 parts by weight, particularly preferably 5 to 50 parts by weight, (e) mineral oil softener 0
To 200 parts by weight, preferably 3 to 100 parts by weight, particularly preferably 3 to 80 parts by weight, and (f) fibrous filler 0 to 100 parts by weight, preferably 1.0 to 100 parts by weight, particularly preferably 4 to 35 parts by weight. Part, and one or more kinds of compounding agents selected from the group consisting of 2 or more kinds are blended, and in the same manner, they are dynamically heat-treated in the presence of an organic peroxide, and partially cross-linked.

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

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

By blending the component (c) within the above range, the moldability and the thermal adhesiveness to the resin or metal become excellent. Further, by blending the component (f) within the above range, the fluidity is excellent and the dimensional and shape stability are improved.

Further, fillers such as calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth are used within a range that does not impair the fluidity (moldability), rubber-like properties and thermal adhesiveness of the produced elastomer composition. ,
Mica powder, asbestos, alumina, barium sulphate, aluminum sulphate, calcium sulphate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fibers, glass spheres, shirasu balloons, carbon fibers, etc. or colorants such as carbon black, titanium oxide. , Zinc flower,
Red iron oxide, ultramarine blue, navy blue, azo pigment, nitroso pigment, lake pigment, phthalocyanine pigment and the like can be added.

In the present invention, known heat stabilizers such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based or amine-based stabilizers, antiaging agents, weathering stabilizers,
Antistatic agents, metal soaps, lubricants such as waxes, and the like can be compounded to the extent of being used in olefin plastics or olefin copolymer rubbers.

In the present invention, the blend of the above components is dynamically heat-treated in the presence of an organic peroxide to partially crosslink.

Dynamically heat treating means kneading in a molten state.

Examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2,5. -Di (tert-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, te
rt-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide,
Examples thereof include lauroyl peroxide and tert-butyl cumyl peroxide.

Among these, odor and scorch stability are 2,5-
Dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-Dimethyl-2,5-di (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene , 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and n-butyl-4,4-bis (tert-butylperoxy)
Valerates are preferred, with 1,3-bis (tert-butylperoxyisopropyl) benzene being most preferred.

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

When the compounding amount is within the above range, the thermoplastic elastomer to be obtained has sufficient rubber properties such as heat resistance, tensile properties, elastic recovery and impact resilience and strength, and also has excellent moldability.

As the kneading device, conventionally known devices such as an open mixing roll, a non-open Banbury mixer, an extruder, a kneader, and a continuous mixer can be used. Among these, it is preferable to use a non-open type apparatus, and it is preferable to knead under an atmosphere of an inert gas such as nitrogen or carbon dioxide. For kneading, the half-life of the organic peroxide used is 1
A temperature of less than a minute, usually 150 to 280 ° C, preferably 17
0 to 240 ° C., 1 to 20 minutes, preferably 3 to 10
Just do it for a minute.

In the present invention, sulfur, p-quinonedioxime, p, p'-is used in the partial crosslinking treatment with the organic peroxide.
Peroxide crosslinking aids such as dibenzoylquinone dioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimeth It is possible to incorporate polyfunctional methacrylate monomers such as methacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, polyfunctional vinyl monomers such as vinyl butyrate or vinyl stearate. With such a compound, a uniform and mild crosslinking reaction can be expected. Particularly in the present invention, when divinylbenzene is used,
It is easy to handle, has good compatibility with the olefin-based rubber and olefin-based plastics that are the main components of the material to be treated, has an organic peroxide solubilizing action, and acts as a dispersion aid for peroxides. It is most preferable because a composition having a uniform effect and a good balance of fluidity and physical properties can be obtained. In the present invention, the content of such a crosslinking aid or polyfunctional vinyl monomer is preferably 0.1 to 2% by weight, more preferably 0.3 to 1% by weight, and more than 2% by weight based on the total amount of the object to be treated. If the compounding amount of the organic peroxide is large, the composition is inferior in fluidity as a result of the progress of the crosslinking reaction.On the other hand, if the compounding amount of the organic peroxide is small, it is present as unreacted monomer in the composition. However, excessive blending should be avoided because the physical properties may change due to the thermal history during processing and molding of the composition.

In order to accelerate the decomposition of organic peroxides, tertiary amines such as triethylamine, tributylamine, 2,4,6-tris (dimethylamino) phenol, and aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium It is also possible to use decomposition accelerators such as naphthenates such as lead, mercury and the like.

The kneading is preferably carried out in a non-open type apparatus, preferably in an inert gas atmosphere such as nitrogen or carbon dioxide gas. The temperature is a temperature at which the half-life of the organic peroxide used is less than 1 minute, usually 150 to 280 ° C, preferably 170 to 240
The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. The shearing force applied is usually 10 to 10 at the shearing rate.
10 ⁴ sec ^-1 , preferably 10 ² to 10 ³ sec ^-1 is selected.

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

According to the present invention, the above-mentioned dynamic heat treatment gives a thermoplastic elastomer composition which is cross-linked and graft-modified in a partial area.

The term “partially crosslinked” in the present invention means that the gel content measured by the following method is within the range of 45 to 98%.

Measurement of gel content Weigh 100 mg of thermoplastic elastomer sample and
What was cut into mm × 0.5 mm × 0.5 mm strips was immersed in 30 ml of cyclohexane in a closed container at 23 ° C for 48 hours, then the sample was taken out on filter paper and kept at room temperature for 72 hours or more at a constant weight. Dry until dry.

The value obtained by subtracting the weight of all cyclohexane-insoluble components (fibrous fillers, fillers, pigments, etc.) other than the polymer component and the weight of the olefin-based plastic component in the sample before dipping in cyclohexane from the weight of this dry residue was corrected. Final weight (Y) ”.

On the other hand, the weight of the peroxide-crosslinking olefin-based copolymer rubber in the sample, [that is, from the weight of the sample, cyclohexane-soluble components (for example, mineral oil and plasticizer) and olefin-based plastics other than the peroxide-crosslinking-type olefin-based copolymer rubber] The component and the cyclohexane-insoluble component other than the polymer component (reducing the weight of the fibrous filler, filler, pigment, etc.) are referred to as "corrected initial weight (X)".

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

(Function and Effect) In the present invention, (a) an amorphous ethylene-α-olefin-non-conjugated diene copolymer rubber, (b) a crystalline polypropylene, and (c) an unsaturated epoxy monomer or unsaturated Hydroxy monomer (further, if necessary, (d) peroxide non-crosslinked rubber-like substance, (e) mineral oil softener,
(F) a fibrous filler component) in a specific proportion, and is dynamically heat-treated and partially crosslinked in the presence of an organic peroxide (that is, when the gel content is in a specific range). First, it is possible to obtain a composition having excellent rubber properties, moldability, adhesiveness to resin metal and the like, strength, and excellent heat resistance and flexibility.

For example, a mere blend (uncrosslinked product) of the above components (a), (b) and (c), or a peroxide crosslinked olefin copolymer rubber component (component a) graft-deformed with an unsaturated carboxylic acid and an olefin plastic. Component (component b)
The composition of the present invention is particularly excellent in heat resistance as compared with the mere blend (uncrosslinked product).

Further, the effect of improving the fluidity when the components (d) and (e) are blended is also particularly exhibited when the gel content is within the above range.

The thermoplastic elastomer composition of the present invention thus obtained is excellent in moldability and can be molded by an apparatus used for ordinary thermoplastics, and is suitable for extraction molding, calender molding, injection molding and the like.

In addition, since the polymer component is graft-modified by blending an unsaturated epoxy monomer or an unsaturated hydroxy monomer, as is apparent from the examples described below, thermal adhesion to various resins, metals, etc. It is remarkably excellent in
Non-primer coating automotive bumpers, soft fascias, fenders, door panels, side steps, and other outer panel materials, and door laminates, instrument panels, malls, home appliance cases, bags, hoses, tubes, building materials, industrial parts, etc. It is preferably used for.

(Example) From the elastomer composition produced in each example,
The molding conditions and the test method for obtaining the test sample are as follows.

(1) Injection molding Machine: Dynamelter (Meiki Seisakusho) Molding temperature: 220 ℃ Injection pressure: Primary pressure 1000kg / cm ² Secondary pressure 700kg / cm ² Injection speed: Maximum molding speed: 90sec / cycle Gate: Direct gate (Land length 10 mm, width 10 mm, thickness 3 mm) Molded product: length 150 mm, width 120 mm, thickness 3 mm (2) Extrusion molding A T die sheet is extrusion molded under the following conditions.

Molding machine: 40mmφ extruder (made by Toshiba Machine) Screw: Full flight type L / D = 28, CR = 3.5 Screen back: 80 mesh x 2 sheets Molding temperature: Hopper side 160 ° C, die side 210 ° C Die: Coat hanger type Die lip: 1.5 mm Pulling speed: 5 m / min (3) Basic physical properties A test piece was punched out from a 3 mm-thick square plate obtained by injection molding by the method of (1), and measured by the following method.

Tensile properties: Measured by the method of JIS K-6301.

(M ₁₀₀ ) Stress at 100% elongation (T _S ) Tensile strength (T _B ) Tensile elongation at break Spring hardness (HS): JIS A type method described in JIS K 6301 or Shore D described in ASTM D2240 It was measured by the type method.

Initial flexural modulus (FM): Measured by the method of ASTM D790.

Permanent elongation (PS): 100%, measured by the method of JIS K-6301
It was indicated by the residual elongation during elongation.

Softening temperature (SP): TAM measuring device manufactured by DuPont was used, the temperature rising rate was 20 ° C / min, the load was 49 g, and the temperature at which a needle having a diameter of 0.8 mm was inserted into the sample by 0.1 mm was expressed.

(4) Adhesive strength A. Preparation of test piece An extruded sheet of elastomer composition (thickness 1.0 mm) and an adherend having a thickness of 0.5 mm formed under the conditions of (2) above were press-molded (clamping pressure 50 ton). , 150 mm × 150 mm test pieces were prepared.

The following adherends were used.

Nylon: Toray, Nylon 6 (Amilan CM1021) Polyurethane: Nippon Polyurethane P26 SRNAT Eval: Kuraray, EP-F101A Steel plate: Nippon Test Panel SS-41 (Sandblast treatment with a surface roughness of 30 microns) B. Peel test specimen: Width 25 mm, 100 mm long punched piece.

Test method: 180 degree peeling Peeling speed: 25 mm / min Adhesive strength: Shown as the value obtained by dividing the peeling load by the width of the test piece (kg / cm).

In addition, when the base material was destroyed, it was described as a material fracture.

In the present invention, the content ratio of the component (a) and the component (b) in the thermoplastic elastomer composition can be measured by the D.S.C method and / or the infrared absorption analysis method. The contents of the components (d) and (e) are determined by a solvent extraction method (Soxhlet extraction method (solvent: acetone)) and / or an infrared absorption analysis method, and the content ratio of the (f) component and the organic component is It can be measured by a thermogravimetric analysis method.

The content of the grafted component (c) was measured by infrared absorption analysis method or chemical analysis method.

Example 1 70 parts by weight of ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber Ethylene content 70 mol%, iodinated 12, Mooney viscosity MLl ₊₄ (100 ° C.) 120 (hereinafter abbreviated as EPDM) Polypropylene 30 parts by weight MFR (ASTM D-1238-65T, 230 ° C) 13g / 10min Density 0.91g / cm ³ (abbreviated as PP below) in a Banbury mixer in a nitrogen atmosphere at 180 ° C for 5 minutes, then roll it through a sheet cutter To produce square pellets.

Next, the square pellets and glycidyl methacrylate (hereinafter abbreviated as GMA) 0.5 parts by weight divinylbenzene (hereinafter abbreviated as DVB) 0.5 parts by weight 1,3-bis (t-butylperoxyisopropyl) benzene 0.3 parts by weight (hereinafter peroxide (A And abbreviated) are stirred and mixed by a Henschel mixer, and the pellets are extruded by an extruder at a temperature of 220 ° C. in a nitrogen atmosphere to prepare a thermoplastic elastomer composition.

The various physical properties of this composition depend on the adhesive strength as well as that of the elastomers prepared in the following Examples and Comparative Examples.
Shown in the table.

Examples 2 and 3 Example 1 except that the amounts of GMA and peroxide were changed.
A thermoplastic elastomer was produced in the same manner as in.

Example 4 A thermoplastic elastomer was produced in the same manner as in Example 2 except that 1.0 part by weight of hydroxypropyl methacrylate (hereinafter abbreviated as HPMA) was used instead of GMA.

Comparative Example 1 A thermoplastic elastomer was prepared in the same manner as in Example 1 except that GMA was not added.

Examples 5 to 7 and Comparative Example 2 A thermoplastic elastomer was produced in the same manner as in Example 1, except that the compounding amount of each component was variously changed.

Example 8 Pelletized ethylene-propylene-5-ethylidene-
2-norbornene copolymer rubber 70 parts by weight Ethylene content 70 mol%, iodine value 10, Mooney viscosity MLl ₊₄ (100 ° C) 70 Oil extension 20 parts by weight (hence, rubber content 50 parts by weight) PP (polypropylene) 50 Parts by weight GMA (glycidyl methacrylate) 0.5 parts by weight DVB (divinylbenzene) 0.5 parts by weight Peroxide (A) 0.3 parts by weight was stirred with a Henschel mixer to prepare a blend.

Next, this blend was extruded at a temperature of 220 ° C. under a nitrogen atmosphere using a twin-screw extruder having L / D = 44 and a screw diameter of 53 mm to prepare a thermoplastic elastomer.

The basic physical properties and adhesive strength of the obtained elastomer are shown in Table 1 together with those of the elastomers produced in the following Examples and Comparative Examples.

Examples 9 and 10 and Comparative Example 3 A thermoplastic elastomer was prepared in the same manner as in Example 8 except that the compounding amounts of the respective components were variously changed.

Examples 11 to 14 Glycidyl methacrylate (GMA), hydroxypropyl methacrylate (HPMA), divinylbenzene (DV
A thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that the blending amounts of B) and peroxide (A) were as shown in Table 1.

Example 15 EPDM 70 parts by weight PP 30 parts by weight Butyl rubber 10 parts by weight Esso IIR-065, degree of unsaturation 0.8 mol% (hereinafter abbreviated as IIR) 30 parts by weight of paraffinic process oil (hereinafter abbreviated as oil) Example 1 Square pellets were produced in the same manner as in.

Next, a thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that the above pellets, 0.5 parts by weight of GMA, 0.5 parts by weight of DVB and 0.3 parts by weight of peroxide (A) were used.

Various physical properties and adhesive strength of this composition are shown in Table 2 together with those of the elastomer compositions prepared in the following Examples and Comparative Examples.

Example 16 A thermoplastic elastomer composition was prepared in the same manner as in Example 15 except that hydroxypropyl methacrylate (hereinafter abbreviated as HPMA) was used instead of GMA.

Comparative Example 4 A thermoplastic elastomer composition was prepared in the same manner as in Example 15 except that GMA was not added.

Comparative Example 5 A thermoplastic elastomer composition was prepared in the same manner as in Example 15 except that no peroxide was added.

Examples 17 to 20 Thermoplastic elastomer compositions were prepared in the same manner as in Example 15 except that the amounts of GMA, DVB and peroxide were changed.

Examples 21 to 30 Thermoplastic elastomer compositions were prepared in the same manner as in Example 15 except that the composition was as shown in Table 2. Second result
It is also shown in the table.

Example 31 20 parts by weight of ethylene-propylene-5-ethylidene-2-norbornene (abbreviated as EPDM (1) below) 70 mol% ethylene content, iodine value 15, Mooney viscosity MLl ₊₄ (100 ° C) 120 PP 60 parts by weight IIR 10 parts by weight Oil 10 parts by weight Milled glass fiber 5 parts by weight Nippon Sheet Glass "Micro Glass Milled Fiber RX-
EMFP "Fiber diameter 11μ, average fiber length 240μ (hereinafter abbreviated as milled glass fiber) The above composition was mixed with a Banbury mixer under nitrogen atmosphere 19
After kneading at 0 ° C. for 5 minutes, it was passed through a roll to produce square pellets with a sheet cutter. (First Step) Next, 0.3 part by weight of peroxide (A), 0.5 part by weight of DVB and 0.5 part by weight of HPMA were mixed with 100 parts by weight of the pellet by stirring with a Henschel mixer.

Then, the pellets were extruded in an extruder at 220 ° C. under a nitrogen atmosphere. (Second Step) Examples 32 to 37 Example 32 to 37 were carried out in the same manner as in Example 31 except that the kind and the amount of the filler were changed as shown in Table 3 in the first step. The fillers used are as follows.

<Glass flakes> Glass for flake-shaped thin films with a thickness of 3μ and a grain size of 325 mesh bath 88% or more (hereinafter abbreviated as "glass microflakes (EF325)" manufactured by Nippon Sheet Glass) <Potassium titanate fiber> Fiber diameter 0.2 .About.0.5 .mu.m, average fiber length 10 to 20 .mu.m potassium titanate fiber (Otiska Chemical Co., Ltd. "Tismo D" abbreviated as potassium titanate hereinafter) Comparative Example 6 Same as Example 32 except that HPMA was removed in the second step. Went to.

The physical properties of the compositions obtained in Examples 31 to 37 and Comparative Example 6 were evaluated as follows.
Shown in the table.

Example 38 Pelletized ethylene-propylene-5-ethylidene-2
-Norbornene copolymer rubber 50 parts by weight (hereinafter abbreviated as EPDM (2)) Ethylene content 78 mol%, iodine value 10, Mooney viscosity l ₊₄ (100 ° C) 160 Oil extension amount 30% by weight (oil content 15 Parts by weight PP 50 parts by weight HPMA 0.5 parts by weight DVB 0.5 parts by weight 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3 0.3 parts by weight (abbreviated as peroxide (B) hereinafter) Was mixed by stirring with a Henschel mixer.

Then, this mixture was mixed with a Warner twin-screw extruder (L / D = 43,
It was extruded at 230 ° C. in a nitrogen atmosphere with a meshing type, the same direction rotation, a triple thread type screw. (First Step) 5 parts by weight of milled glass fiber was kneaded with 100 parts by weight of the above pellets in a Banbury mixer under a nitrogen atmosphere at 200 ° C. for 5 minutes, and then passed through a roll to produce square pellets with a sheet cutter. (Second Step) Examples 39 to 44 The same procedure as in Example 38 was carried out except that the kinds and blending amounts of the fillers shown in Table 4 were used in the second step.

Comparative Example 7 The procedure of Example 40 was repeated except that HPMA was removed in the first step.

The physical properties of the compositions obtained in Examples 38 to 44 and Comparative Example 7 were evaluated as 4th.
Shown in the table.

Example 45 EPDM (2) 70 parts by weight (50 parts by weight of EPDM, 20 parts by weight of oil) PP 30 parts by weight HPMA 0.5 parts by weight DVB 0.5 parts by weight Peroxide (B) 0.3 parts by weight The above composition was used in a Henschel mixer. It was stirred.

Next, this mixture was extruded at 230 ° C. in a nitrogen atmosphere in a Warner twin-screw extruder. (First step) For 100 parts by weight of the above pellets, 5 parts by weight of milled glass fiber was mixed with a Banbury mixer in a nitrogen atmosphere at 200 ° C. for 5 days.
After kneading for a minute, square rolls were produced with a sheet cutter. (Second Step) Examples 46 to 51 The same process as in Example 45 was carried out except that the kind and the blending amount of the filler in the second step were shown in Table 5.

Comparative Example 8 The procedure of Example 45 was repeated except that HPMA was removed in the first step.

The physical properties of the compositions obtained in Examples 45 to 51 and Comparative Example 8 were evaluated as 5th.
Shown in the table.

Example 52 The same operation as in Example 45 was carried out except that in the second step, two kinds of fillers were used together as shown in Table 5. The results are also shown in Table 5.

Examples 53-55 Instead of HPMA, glycidyl methacrylate (GM
A), allyl glycidyl ether (AGE) and hydroxyethyl acrylate (HEA) were used, and the same procedure as in Example 31 was performed. The results are shown in Table 6.

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Claims (3)

[Claims] 1. (a) 95 to 10 parts by weight of an amorphous ethylene-α-olefin-non-conjugated diene copolymer rubber, (b) 5 to 90 parts by weight of crystalline polypropylene, ((a) component and (b)) ) The total amount of the components is 100 parts by weight) (c) A blend comprising 0.1 to 5 parts by weight of an unsaturated epoxy monomer or an unsaturated hydroxy monomer is dynamically heat treated in the presence of an organic peroxide. The modified thermoplastic elastomer composition is characterized in that the gel content is partially crosslinked in the range of 45 to 98% by weight. 2. (a) 95 to 10 parts by weight of an amorphous ethylene-α-olefin-non-conjugated diene copolymer rubber, (b) 5 to 90 parts by weight of crystalline polypropylene, ((a) component and (b)) (C) The total amount of the components is 100 parts by weight) (c) 0.1 to 5 parts by weight of the unsaturated epoxy monomer or unsaturated hydroxy monomer, and the total amount of the components (a) and (b) is 100 parts by weight Selected from the group consisting of (d) 0 to 100 parts by weight of peroxide non-crosslinked rubbery substance, (e) 0 to 200 parts by weight of mineral oil-based softening agent, and (f) 0 to 100 parts by weight of fibrous filler. The blend containing one or more ingredients selected from the above is dynamically heat-treated in the presence of an organic peroxide to partially crosslink the gel content in the range of 45 to 98% by weight. A characteristic modified thermoplastic elastomer composition. 3. (a) 95 to 10 parts by weight of an amorphous ethylene-.alpha.-olefin-non-conjugated diene copolymer rubber, (b) 5 to 90 parts by weight of crystalline polypropylene, ((a) component and (b)). (C) The total amount of the components is 100 parts by weight) (c) 0.1 to 5 parts by weight of the unsaturated epoxy monomer or unsaturated hydroxy monomer, and the total amount of the components (a) and (b) is 100 parts by weight And (d) 0 to 100 parts by weight of non-peroxide rubber-like substance, (e) 0 to 200 parts by weight of mineral oil-based softener, and one or more compounding agents selected from the group consisting of A composition in which the blend is dynamically heat-treated in the presence of an organic peroxide to partially crosslink the gel content in the range of 45 to 98% by weight, and further comprises (a) component and (b) component (F) 0 to 100 parts by weight of the fibrous filler is added to the total amount of 100 parts by weight of Thermoplastic elastomer composition, characterized in that the.