JPH09123211A - Manufacture of composite of foamed extrusion of thermoplastic elastomer and rubber molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide flexibility in perfectly meeting the complicated profile of a car body panel such as a curved face or a corner by easily vulcanizing and bonding a deformed foamed extrusion obtained by water-foaming an olefin thermoplastic elastomer and a rubber molding for accessory into a monolithic composite. SOLUTION: A rubber mixture based on a tricopolymer rubber of ethylene, propylene and diene for the manufacture of a rubber molding for accessory is prepared. Next, a foamed extrusion of a thermoplastic elastomer is cut to the specified length, then one of the end parts of each of two same types or two different types of foamed extrusion is inserted into a molding die, and the rubber mixture based on the tricopolymer rubber of ethylene, propylene and diene for the manufacture of a rubber molding for accessory is injected into the molding die. Finally, a composite is manufactured by integrally binding two pieces of the thermoplastic elastomer foamed extrusion and the rubber molding for accessory by vulcanization at specified temperatures and for a specified period of time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a composite of a foamed extrudate of a thermoplastic elastomer and a rubber molded article, and a composite produced by the method. INDUSTRIAL APPLICABILITY The present invention is used for manufacturing a weather strip for automobiles, or a gasket which is a sealing material for civil engineering and construction.

[0002]

2. Description of the Related Art The present inventors have conducted research and development to establish a technique for producing a composite multiple-profile foamed extrudate of a thermoplastic elastomer (hereinafter abbreviated as TPE), and have already patented one of those results. Filed (Japanese Patent Application No. 6-7627)
5). Incidentally, TPE has been known for a long time since it was developed and has been known in many documents.

The main applications of the composite multi-profile foam extruded product of TPE contemplated by the present inventors are weather strips for automobiles, and gaskets which are civil engineering and construction sealing materials. Weather strips for automobiles are parts that are assembled to the car body and glass of automobiles and have sealing properties.
The purpose is to prevent slight vibration of the vehicle body and rocking of the glass, and also to cushion the vehicle body part. Further, it is required that the dimensional variations of automobiles and the variations in building are absorbed to facilitate the workability of assembling. In addition, gaskets for construction and civil engineering are used for harmful gaps, joints,
It is used for cracked parts, around sashes, etc. to provide an airtight and honey-like seal.

When the composite multiple-profile foamed extrudate of TPE is put to practical use as a weather strip for automobiles, or a gasket which is a sealing material for civil engineering and construction, it must be adapted to a complicated shape such as sheet metal. For example,
Door weather strips, which are the main components of weather strips, absorb variations in the clearance between the door and body, variations in component dimensions, etc., and the door circumference is approximately 3.
Since 5 meters are sealed with a constant cross section, depending on the body panel, it is necessary to completely follow the curved surface and the inverted portion. However, complicated curved surfaces or corners,
Alternatively, since it is impossible to insert along a portion such as a T-shape that cannot be accommodated by an ordinary extrudate, conventionally, members at these portions are separately manufactured by a mold and vulcanized and bonded to the extrudate. It was integrated.

In the present invention, a molded product manufactured by a mold separately from the extruded product is used as a member applied to a complicated curved surface, a corner, or a portion such as a T-shape that cannot be accommodated by a normal extruded product. It is called a "feature." The term "goods" is a term that is commonly used in the building industry. For example, the architectural dictionary published by Shokokusha Inc. defines it as an outline, a material used in a special place that cannot be stored in a flat object.

The present inventors have developed a method for producing a multi-profile foam extrudate by using TPE as a main raw material and water as a foaming agent in view of environmental problems and recovery and recycling of scraps. Applied for the above patent.

[0007] By the way, it has been impossible to vulcanize and bond a profiled foamed extrudate produced by using TPE as a main raw material and water as a foaming agent so that the rubber is integrated.
The technology to widely put TPE foam extruded by water foaming (atypical foamed extruded product, which is not a simple shape in general) into weather strips for automobiles, where many parts are used, or various gaskets, has not progressed easily. .

Incidentally, as a conventional technique related to the present invention, for example, Japanese Patent Application No. 59-59, filed by Toyoda Gosei Co., Ltd.
-272622 (JP-A-61-148012) or Japanese Patent Application No. 3-3 filed by Yokohama Rubber Co., Ltd.
There is an invention described in the specification of Japanese Patent No. 41284 (Japanese Patent Laid-Open No. 5-170934).
A method for vulcanizing and adhering a PE solid molded article and rubber, which comprises vulcanizing and adhering a TPE profiled foam extrudate and rubber.
It does not disclose vulcanization adhesion between a rubber foam and a shaped foam extrudate of TPE.

[0009]

The problem to be solved by the present invention is that it was not possible to vulcanize and bond the deformed foam extruded product of the thermoplastic elastomer and the rubber molded product.

Another problem to be solved by the invention is to vulcanize and bond a profiled extruded product produced by using an olefinic thermoplastic elastomer as a main raw material and water as a foaming agent, and a rubber molded product for an accessory. It was not possible to be united.

Further problems and advantages to be solved by the invention will be made clear successively below.

[0012]

The present inventors have examined the adaptability of various thermoplastic elastomers. As a result, as a thermoplastic elastomer which is a raw material of the foamed extrudate in the present invention, a thermoplastic resin polypropylene is used as a matrix component, and an ethylene / propylene / diene terpolymer rubber (hereinafter abbreviated as EPDM) is a polymer blend. It was found that the above-mentioned so-called olefinic thermoplastic elastomer (hereinafter referred to as TPO), particularly the completely crosslinked olefinic thermoplastic elastomer is preferable.

The present invention is a method for producing a composite of a foamed extrudate of a thermoplastic elastomer and a rubber molded article; one kind having the same cross section size or two or more kinds having different cross section sizes Producing a foamed extrudate of a thermoplastic elastomer; Preparing a mold for producing a rubber molded product for a accessory having a predetermined shape; Ethylene for producing a rubber molded product for an accessory;
Providing a rubber compound containing propylene / diene terpolymer rubber as a main raw material; cutting the foamed extrudate of the thermoplastic elastomer into a predetermined length to obtain two foamed extrudates of the same type or different types. One end of each of the products is inserted into the mold, and then a rubber compound containing ethylene / propylene / diene terpolymer rubber as a main raw material for producing the rubber molded product for the accessory is injected. Then, vulcanization is performed at a predetermined temperature for a predetermined time to vulcanize and bond the foamed extruded products of the two thermoplastic elastomers and the rubber molded product for the accessory to be integrated with each other. The present invention relates to a method for producing a composite of a foam extrudate and a rubber molded product.

As the TPE, for example, AES
Product name "Santoprene 101-6" from Japan Co., Ltd.
8W228 ″. If a completely crosslinked olein-based thermoplastic elastomer such as Santoprene is not used, there is a risk that it may be deformed when it is released from the mold, or may lose its shape after vulcanization.

The present inventors have made a rubber for producing a material for vulcanizing and adhering a TPO profiled foam extrudate excellent in weather resistance, ozone resistance and aging resistance, and to a vehicle body and the like. It was selected as a requirement that it is not contaminated, that the change in tensile stress with temperature is small, and that it is low cost. As a result, EPDM was selected.

Therefore, the means for solving the problem is T
That is, EPDM is used as a raw material rubber of a molded article for accessory that is vulcanized and adhered to the odd-shaped foam extrudate of PO.

EP used in the present invention as a raw material rubber for a molded article for accessory that is vulcanized and adhered to a profiled extruded product of TPO
DM is mainly the type and amount of the diene component (third component),
Those having various characteristics depending on the distribution, the molecular weight of the polymer, the molecular weight distribution, etc. are commercially available, and the selection may be made according to the desired requirements, and there is no particular limitation. For example, if a high vulcanization rate is desired in a sulfur vulcanization system, EPDM using ethylidene norbornene (ENB) as the third component is the fastest even considering the molecular weight and iodine value, and conversely dicyclopentadiene. (DCPD) is slow, while in the peroxide vulcanization system there is almost no difference in the third component. Therefore, it is not technically significant to select EPDM only by the type of the third component. Vulcanization speed in sulfur vulcanization system, Mooney viscosity,
It can be said that the most preferable EPDM of the present invention in which the iodine value, processability, application and the like are taken into consideration is that the third component is ENB. These are, for example, Sumitomo Chemical Co., Ltd.
Available from Japan Synthetic Rubber Co., Ltd.

The rubber content of the EPDM compound used in the present invention is 10 to 70%, the minimum Mooney viscosity of the EPDM compound is 20 to 30 at 121 ° C. L rotor, and the scorch time is 20 to 30 minutes. preferable.

A compounding example of an EPDM compound for producing a rubber molded product for an accessory used in the present invention is exemplified below: compounding component compounding ratio (parts by weight) EPDM (ENB type) 100 carbon black 0 100 Stearic acid 1 to 3 Zinc oxide 4 to 10 Sulfur 1 to 3 Vulcanization accelerator 2 to 5 Foaming agent 0 to 7 Process oil 0 to 50 Softening agent 0 to 20 Calcium carbonate 0 to 100 Various desired values within the above range. It is appropriately set in consideration of the conditions such as the minimum Mooney viscosity and the scorch time.

According to the present invention, a foamed extruded product of TPO produced in advance is cut into a predetermined length according to the use, and the cut end is fitted into a mold formed into a shape of an accessory,
The EPDM compound is injected into a mold and vulcanized at a predetermined mold temperature for a predetermined time to vulcanize and bond the foamed extrudate and the accessory EPDM molded product.

In carrying out the present invention, the foaming agent used for foaming TPO in the production of the foamed extrudate of TPO is not particularly limited, but in consideration of the above-mentioned development idea of the inventors, water is used. Foaming is the most ideal.

The vulcanization temperature and vulcanization time for carrying out the present invention are determined depending on various conditions such as the type and amount of EPDM used and the vulcanization method. In the case of sulfur vulcanization, The mold temperature is selected in the range of 140 to 200 ° C. and the vulcanization time is in the range of 2 to 10 minutes.

The present invention has a high elongation and a low hardness EPD.
Since the M compound is used, it is possible to easily vulcanize and integrate the foamed extruded product of TPO having a hollow portion using a core and the rubber compound for accessory materials such as the corners. No problems such as breakage occur when removing the child.

Hereinafter, the present invention will be described specifically with reference to examples.

[0025]

[Example 1] Production of water-foamed extrudate using TPO as a raw material (1) TPO used AES Japan Co., Ltd. "Santoprene 101"
-68W228 "(2) Extruder used Extruder mainly composed of TPO water foaming extruder, cooling water tank, and take-off machine having the following specifications was used; TPO water foaming extruder specifications Extruder screw Diameter: 90 mm Extruder L / D: 30 Screw rotation speed: 30 rpm The cylinder part of the extruder for TPO water foaming is divided into four zones, each of which is set to a temperature of 170 ° C to 175 ° C, and the head part and the soybean part are set. It was set to 185 ° C. and 183 ° C. The compounded mixture for TPO water foaming was put into an extruder for TPO water foaming, and the TPO compounding was carried out at a position of about 12D from the cylinder rear part, that is, from the hopper side. About 0.4
While injecting water at a rate of T, T at a rate of about 51 kg / Hr
Extruded PO formulation with specific gravity 0.45 with U-shaped cross section
Foamed extrudates were produced.

[0026] were prepared EPDM blends character object for EPDM formulation in blend ratio of production following; Ingredients Ratio (parts by weight) EPDM (ENB system) 100 Carbon black 60 Stearic acid 1.5 Zinc oxide 5 Sulfur 1 .5 Vulcanization accelerator 2 Foaming agent 5 Process oil 45 Softening agent 5 Calcium carbonate 50 Kneader kneading the above composition for 5 minutes at 50 ° C to give 1
A kneaded product having a Mooney viscosity of 25 at 21 ° C. was produced.

The foamed extruded product of TPO is cut into a predetermined length, and both ends thereof are put into a preformed L-shaped accessory mold, and the kneaded product of the EPDM compound is molded into a mold. , Set the mold temperature to 190 ° C, vulcanize for 5 minutes,
The foamed extrudate of TPO was vulcanized and bonded to the L-shaped rubber foam to be integrated.

The adhesive strength of the composite body obtained by vulcanizing and adhering the foamed extruded product of TPO and the L-shaped rubber foam was measured by a peeling test to find that it was 20.5 kgf / c.
The foam material broke at m ² .

[0029]

Example 2 The same procedure as in Example 1 was repeated, except that the blowing agent was removed from the EPDM formulation used in Example 1, to vulcanize the TPO foam extrudate and the L-shaped EPDM solid molding. A bonded and integrated composite was produced.

The adhesive strength of the composite body in which the foamed extruded product of TPO and the solid molded product of L-shaped EPDM adhered and integrated was measured by a peeling test to be 20.0.
The foam material was destroyed by peeling at kg / cm ² .

[0031]

Comparative Example A solid extrudate made from the TPO used in Example 1 was prepared. The same procedure as in Example 1 was repeated except that the solid extrudate of TPO was used.
A solid extruded product of PO and a foamed product of L-shaped EPDM were vulcanized and bonded to each other to produce a composite.

The adhesive strength of the composite obtained by vulcanizing and adhering the solid extruded product of TPO and the foamed molded product of L-shaped EPDM measured by a peel test was 10.0 kg / cm ² . The interface between the two was peeled by peeling.

From the results of the above Examples and Comparative Examples,
It is understood that when the extruded product of TPO is solid, the effect of the present invention is not effective, and when the EPDM molded product as a role is a foam or a solid, the effect of the present invention is effective.

Therefore, the most preferred embodiment of the present invention is: Shaped foam extrusion by completely foaming a completely catenary type olefinic thermoplastic elastomer obtained by polymer blending polypropylene and ethylene propylene diene terpolymer rubber (EPDM). A method for producing a composite of a molded article and a molded article of EPDM; using water as a foaming agent to produce a modified foam extrudate of the thermoplastic elastomer; Preparing a mold for manufacturing; E as a material for manufacturing the accessory molding
Preparing an EPDM compound containing PDM as a main raw material, a rubber content of 10 to 70%, a minimum Mooney viscosity of 20 to 30 at L rotor 121 ° C., and a scour time of 20 to 20 minutes; Cutting the extrudate into a predetermined length, inserting both ends of the extrudate into the mold, and then injecting the EPDM compound for producing the shaped product for the accessory; and then a mold temperature of 140 to 200. A polypropylene obtained by vulcanizing at a temperature of 2 ° C. for 2 to 10 minutes and vulcanizing and adhering the shaped foam extruded product of the thermoplastic elastomer by water foaming and the EPDM molded product for accessory. EPDM and odd-shaped foam extruded product by water-expanding of completely overhead line type olefin-based thermoplastic elastomer obtained by polymer blending ethylene / propylene / diene terpolymer rubber A method for producing a complex of moldings.

[0035]

As described above, according to the present invention,
Since it is possible to easily vulcanize and bond a deformed foam extruded product of TPO with water and a rubber molded product for an accessory to form an integrated composite, for example, a complicated curved surface or a corner portion of a vehicle body panel. Etc. can be made to completely follow, and T
The application of the shaped foam extrudate by the water foaming of PO is significantly expanded.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B60J 5/00 501 B60J 5/00 501G B60R 13/06 B60R 13/06 C09K 3/10 C09K 3 / 10 C E04B 1/66 E04B 1/66 // B29K 23:00 105: 04 B29L 9:00 31:10 31:30 (72) Inventor Kenji Kuroda 2-2-11 Matsuhama-cho, Fukuyama City, Hiroshima Prefecture Hiroshima Chemical Co., Ltd. Inside the company (72) Fumihiko Sato 2-21-11 Matsuhama-cho, Fukuyama City, Hiroshima Prefecture Hiroshima Kasei Co., Ltd. ) Inventor Isamu Terasawa 5-3-8-3 Shiba, Minato-ku, Tokyo Within Mitsubishi Motors Corporation (72) Inventor Tomonori Hamada 5-33-8 Shiba, Minato-ku, Tokyo Mitsubishi Motors Corporation Within the corporation

Claims (4)

[Claims] 1. A method for producing a composite of a foamed extruded product of a thermoplastic elastomer and a rubber molded product; one kind of thermoplastic resin having the same sectional size or two or more thermoplastic resins having different sectional sizes. Producing a foamed extrudate of an elastomer; Preparing a mold for producing a rubber molded product for a accessory having a predetermined shape; Ethylene for producing the rubber molded product for an accessory;
Providing a rubber compound containing propylene / diene terpolymer rubber as a main raw material; cutting the foamed extrudate of the thermoplastic elastomer into a predetermined length, and extruding two foamed extrudates of the same type or different types. One end of each of the products is inserted into the mold, and then a rubber compound containing ethylene / propylene / diene terpolymer rubber as a main raw material for producing the rubber molded product for the accessory is injected. Then, vulcanization is performed at a predetermined temperature for a predetermined time to vulcanize and bond the foamed extruded products of the two thermoplastic elastomers and the rubber molded product for the accessory to be integrated with each other. A method for producing a composite of a foamed extrudate and a rubber molding. 2. The method for producing a foamed extrudate of a thermoplastic elastomer, wherein water is used as a foaming agent.
The method described in. 3. The thermoplastic elastomer is a completely crosslinked olefinic thermoplastic elastomer obtained by polymer blending polypropylene and an ethylene / propylene / diene terpolymer rubber. The method described in. 4. A composite of a foam extrudate of a thermoplastic elastomer produced by the method of claim 1 and a rubber product.