CA2171575A1 - Composite molded product - Google Patents
Composite molded productInfo
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- CA2171575A1 CA2171575A1 CA 2171575 CA2171575A CA2171575A1 CA 2171575 A1 CA2171575 A1 CA 2171575A1 CA 2171575 CA2171575 CA 2171575 CA 2171575 A CA2171575 A CA 2171575A CA 2171575 A1 CA2171575 A1 CA 2171575A1
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Abstract
The present invention relates to a composite molded product in which a molded crosslinked rubber (I) is integrally bonded with a molded product (II), the base material thereof comprising (a) a thermoplastic polymer containing a polar group and/or (b) a thermoplastic polymer containing an inorganic filler. The composite molded product of the present invention can be produced by placing the crosslinked rubber molded product (I) in an injection molding die, and injecting (a) a thermoplastic polymer containing a polar group or (b) a thermoplastic polymer containing an inorganic filler into the molding die. The composite molded body of the present invention can be used, for example, for wind shield gaskets for cars and for weatherstrips.
Description
A COMPOSITE MOLDED PRODUCT
Background of the Invention ~ield of the Invention The present invention relates to a composite molded product in which a molded crosslinked rubber is integrally laminated with a molded thermoplastic polymer and to a production method thereof.
Description of the ~elated Art Conventionally, a crosslinked rubber product with a simple shape has been produced by an extrusion crosslinking method. However, a molded product with a complicated shape cannot be produced by the extrusion crosslinking method alone.
For this reason, methods are known wherein the portion having a simple shape is first molded by an extrusion crosslinking method, and the portion having a complicated shape is produced by injection molding of a crosslinkable rub~er and at the same time curing the crosslinkable rubber, or alternatively by injection molding a thermoplastic resin instead of the crosslinkable rubber. For example, it is described in Japanese Patent Laid-Open No.6-47816 that a thermoplastic resin powder is first adhered on a surface of the crosslinked rubber to be joined with a thermoplastic resin, then the thermoplastic resin is bonded to the crosslinked rubber by injection molding.
However, since the adhesion between injected crosslinkable rubber or uncrosslinked thermoplastic resin and the crosslinked rubber is insufficient when using such an injection molding method, it is proposed that the joint surface of the crosslinked rubber should be subjected to a blast treatment with sandpaper, before adhering an adhesive and a thermoplastic resin powder thereon it and then carrying out injection molding. Since such a complicated step as a blast treatment is required, this is not an efficient process.
It is also proposed that a primer treatment be carried on the joint surface of the crosslinked rubber. But even by this process, the manual labor can not be sufficiently simplified enough, and problems in terms of the product cost are not alleviated.
Summary of the Invention Object of the Invention An object of the present invention is to provide a composite molded product in which a molded crosslinked rubber is firmly bonded and laminated with a molded thermoplastic polymer by heat fusing and an injection molding method by which even a composite injection molded product having a high bond strenght, a complicated shape and a relatively large size can be produced.
Brief Summary of the Invention According to one aspect of the present invention, there is provided a composite molded product in which a molded crosslinked rubber (I) is integrally bonded with a molded product (II~, the base material thereof comprising (a) a thermoplastic polymer containing a polar group and/or (b) a thermoplastic polymer containing an inorganic filler.
According to another aspect of the present invention, there is provided a method of producing a composite molded product, comprising placing a molded crosslinked rubber (I) in an injection molding die, injecting (a) a thermoplastic polymer containing a polar group, and/or (b) a thermoplastic polymer containing an inorganic filler into the molding die, thereby producing a molded product (II), and integrally bonding the product (Il) onto the molded crosslinked rubber (I).
lIl Raw materials (1) Molded crosslinked rubber <1> Rubber Examples of rubber used as a raw material for producing a molded crosslinked rubber include natural rubber (NR), derivatives thereof, synthesized rubbers and the like.
Background of the Invention ~ield of the Invention The present invention relates to a composite molded product in which a molded crosslinked rubber is integrally laminated with a molded thermoplastic polymer and to a production method thereof.
Description of the ~elated Art Conventionally, a crosslinked rubber product with a simple shape has been produced by an extrusion crosslinking method. However, a molded product with a complicated shape cannot be produced by the extrusion crosslinking method alone.
For this reason, methods are known wherein the portion having a simple shape is first molded by an extrusion crosslinking method, and the portion having a complicated shape is produced by injection molding of a crosslinkable rub~er and at the same time curing the crosslinkable rubber, or alternatively by injection molding a thermoplastic resin instead of the crosslinkable rubber. For example, it is described in Japanese Patent Laid-Open No.6-47816 that a thermoplastic resin powder is first adhered on a surface of the crosslinked rubber to be joined with a thermoplastic resin, then the thermoplastic resin is bonded to the crosslinked rubber by injection molding.
However, since the adhesion between injected crosslinkable rubber or uncrosslinked thermoplastic resin and the crosslinked rubber is insufficient when using such an injection molding method, it is proposed that the joint surface of the crosslinked rubber should be subjected to a blast treatment with sandpaper, before adhering an adhesive and a thermoplastic resin powder thereon it and then carrying out injection molding. Since such a complicated step as a blast treatment is required, this is not an efficient process.
It is also proposed that a primer treatment be carried on the joint surface of the crosslinked rubber. But even by this process, the manual labor can not be sufficiently simplified enough, and problems in terms of the product cost are not alleviated.
Summary of the Invention Object of the Invention An object of the present invention is to provide a composite molded product in which a molded crosslinked rubber is firmly bonded and laminated with a molded thermoplastic polymer by heat fusing and an injection molding method by which even a composite injection molded product having a high bond strenght, a complicated shape and a relatively large size can be produced.
Brief Summary of the Invention According to one aspect of the present invention, there is provided a composite molded product in which a molded crosslinked rubber (I) is integrally bonded with a molded product (II~, the base material thereof comprising (a) a thermoplastic polymer containing a polar group and/or (b) a thermoplastic polymer containing an inorganic filler.
According to another aspect of the present invention, there is provided a method of producing a composite molded product, comprising placing a molded crosslinked rubber (I) in an injection molding die, injecting (a) a thermoplastic polymer containing a polar group, and/or (b) a thermoplastic polymer containing an inorganic filler into the molding die, thereby producing a molded product (II), and integrally bonding the product (Il) onto the molded crosslinked rubber (I).
lIl Raw materials (1) Molded crosslinked rubber <1> Rubber Examples of rubber used as a raw material for producing a molded crosslinked rubber include natural rubber (NR), derivatives thereof, synthesized rubbers and the like.
Examples of the above-mentioned synthesized rubber include diene type rubbers such as butadiene rubber (BR), styrene-butadiene rubber (SBR), nitrile rubber (acrylonitrile-butadiene rubber, NBR), isoprene rubber (IR), and chloroprene rubber (CR); and olefin type rubbers such as butyl rubber (isobutylene-isoprene copolymer, IIR), ethylene-propylene rubber (EPM), ethylene-propylene-nonconjugated diene rubber (EPDM), ethylene-butene rubber (EBM), ethylene-propylene-butene copolymer rubber, chlorosulfonated polyethylene (CSM), and chlorinated polyethylene (CPE).
These rubbers can be used alone or in an admixture of two or more components.
These rubber can be blended with a thermoplastic resin such as polypropylene and polyethylene if necessary. If necessary, these rubbers can be also blended with a filler such as talc and calcium carbonate, a plasticizer such as paraffin oil and liquid polybutene, and other various additives including a vulcanizing accelerator, peroxide, crosslinking assistant, mastication accelerator, antiscorching agent, foaming agent, antioxidant, thermal stabilizer, light stabilizer, UV absorbing agent, neutralization agent, slip additive, lubricant, anti--fogging agent, anti-blocking agent, dispersing agent, coloring agent, antibacterial agent, and fluorescent whitener.
<2> Molded crosslinked rubber A molded crosslinked rubber can be obtained by adding 0.1 to 10% by weight, preferably 0.1 to 5% by weight of a crosslinking agent to the above-mentioned rubber, followed by heating and molding.
Examples of a crosslinking agent to crosslink the above-mentioned rubber include sulfur and aromatic or aliphatic peroxides such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane-3,tert-butylperoxy benzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butylcumyl peroxide, diisopropyl ` 21 71 575 benzohydroperoxide, benzoylperoxide, and di-tert-butylperoxide, the above can be used alone or in admixtures.
Among these crosslinking agents, sulfur is preferably employed.
The molded crosslinked rubber can be produced by blending the above crosslinkable rubber material with sulfur or a peroxide, molding the blend into a desired shape by such molding methods as extrusion molding, injection molding or vacuum molding, followed by heat treatment at 100 to 200 ~ for 1 to 10 minutes so that the crosslinkable rubber material is crosslinked or cured by the sulfur or the peroxide contained therein. Among the molded crosslinked rubber products, those produced by the extrusion molding method are particularly preferred.
In one method of laminating the molded crosslinked rubber with the below-mentioned thermoplastic polymer, the molded crosslinked rubber may be first produced in an injection molding die which the thermoplastic polymer is then injected and molded to provide a composite injection molded product in the die, or alternatively, the molded crosslinked rubber may be previously produced in a separate place, and then inserted into the die and the thermoplastic polymer is injected in the die.
Degree of crosslinking The crosslinked rubber has little or no flowability, and has a melt flow rate (MFR:230 ~, ~ kg load) according to JIS-K7210 (ASTM D1238~ of 0 to 0.01 g110 min. As it does not have flowability, the crosslinked rubber is distinguished from the below-mentioned thermoplastic polymer having flowability.
(2) Thermoplastic polymer <1> Thermoplastic polymers Appropriate examples of thermoplastic polymers as a raw material for the thermoplastic polymer used for the injection molding according to the present invention include those having a melt flow rate (MFR:230 ~, 2.16 kg load) according to ASTM D1238 of 0.01 to 1000 g/10 min, preferably0.01 to 300 g/10 minutes, more preferably 0.1 to 100 g/10 min, and even more preferably 0.1 to 50 g/10 min from the view point of flowability which makes the injection molding possible.
When the below-mentioned inorganic fillers are included, it is appropriate to use a thermoplastic polymer having a high melt flow rate.
When it is necessary that the thermoplastic polymer to have the same level of flexibility and rubber elasticity as those of a crosslinked rubber, a thermoplastic polymer having a JIS-A hardness according to a JIS-K6301 lASTM D2240 (Type A)] of 98 or less is generally used, but a thermoplastic polymer having the hardness of 95 or less is preferably used and a thermoplastic polymer having the hardness of 90 to 20 is most preferably used.
The above-mentioned thermoplastic polymers can be thermoplastic resins or thermoplastic elastomers.
Examples of the thermoplastic resin include olefin-type thermoplastic resins such as polyethylene, polypropylene, polybutene-1, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer; soft vinyl chloride polymer, styrene type resin, polyester type resin and polyamide-type resin and the like.
Examples of the thermoplastic elastomer include a copolymer of 15 to 90% by weight of ethylene and 85 to 10% by weight of an alkene having 3 or more carbon atoms, preferably a copolymer of ethylene and an alkene having 3 to 10 carbon atoms.
Illustrative examples of the thermoplastic elastomer include an olefin-type elastomer such as ethylene-propylene copolymer rubber (EPM), ethylene-butene copolymer rubber (EBM), ethylene-hexene copolymer, ethylene-octene copolymer and ethylene-propylene-nonconjugated diene copolymer rubber (EPDM) or ethylene-propylene-butene copolymer and the like wherein 5-21715~5 ethylidenenorbornene, 5-methylnorbornene, 5-vinylnorbornene, dicyclopentadiene and butene and the like are used as the third component; styrene-type elastomer; polyester-type elastomer;
polyamide-type elastomer and the like.
These thermoplastic polymers can be used alone or in admixtures of two or more components.
Among them, preferably used are olefin type elastomers, and a mixture of an olefin type thermoplastic resin and an olefin type elastomer which are mixed at the ratio of 10:90 to 90:10 are preferably used. A ratio of 20:80 to 80:20 (~ by weight) is particularly preferable used since the defining process can be omitted.
The term resin refers to a thermoplastic polymer having a crystallinity index by an x-ray diffraction method of 30 to 70%, and the term elastomer refers to a noncrystalline thermoplastic polymer or a thermoplastic polymer having a crystallinity index of less than 30%.
As the above-mentioned olefin elastomers, those having a Mooney viscosity at 100 ~ (MLl I 4 (100 ~) ) of 10 to 400 according to JIS K6300, particularly those having a Mooney viscosity of 15 to 350 are preferable. Elastomers having a Mooney viscosity exceeding the above-mentioned range tend to have an inferior appearance when they are molded, and those having a Mooney viscosity below that range tend to exhibit an inferior rubber elasticity.
The production methods and the forms of such olefin elastomers are not particularly limited. They can be produced by, for example, mixing an olefin type elastomer and an olefin type thermoplastic resin, and heating the resulting mixture in the presence of an organic peroxide to carry out partial or complete crosslinking mainly by radicals. The product produced by such a crosslinking treatment is different from the a~ove-mentioned crosslinked rubber (1) since it has flowability.
For use as the above-mentioned olefin-type elastomers are the commercially available "JSR EP" and "JSR EBM" produced by Japan Synthetic Rubber Co., Ltd., "MITSUI EPT" and "TAFMER"
produced by Mitsui Petrochemical Industries, Ltd., "ESPRENE"
produced by Sumitomo Chemical Company, Ltd., "ENGAGE" produced by Dow Chemical Japan ~td.
Examples of the partially or completely crosslinked products include "Thermorun" produced by Mitsubishi Chemical Corporation, "MILASTOMER" produced by Mitsui Petrochemical Industries, Ltd., "Sumitomo TPE" produced by Sumitomo Chemical Company, Ltd., and "Santoprene" produced by Advanced Elastomer System, L.P..
<2> Other components The above-mentioned thermoplastic polymer may be blended with a polymer component including a resin other than the above-mentioned resins and an elastomer, as well as other additives including a plasticizer such as paraffin oil and liquid polybutene; an antioxidant, light stabilizer, UV
absorbing agent, antiblocking agent such as silicone oil, a neutralizing agent, lubricant, dispersing agent, antibacterial agent, coloring agent, flame retardant, and fluorescent whitener in amounts that do not remarkably detract from the effects of the present invention.
(3) Thermoplastic polymer having a polar group <1> Polar groups According to the present invention, a thermoplastic polymer described in the above-mentioned paragraph ~2) may have a polar group such as a hydroxyl group, carboxyl group, epoxy group, amino group, carboxylic acid anhydride group, thiol group, and silanol group. Among these, the hydroxyl group, carboxyl group, carboxylic acid anhydride group are preferable from the view point of adhesion with the molded crosslinked rubber.
<2> Process for introducing a polar group (modification of a thermoplastic polymer) Methods for introducing a polar group into a thermoplastic polymer are basically divided into two groups, i.e. (i) a method in which the above-mentioned thermoplastic polymer is blended with a copolymer wherein a polar group has already-been introduced (the copolymer may be the same as the above-mentioned thermoplastic polymer) to carry out modification, or (ii) a method in which the above-mentioned thermoplastic polymer and a compound having a polar group are directly subjected to graft reaction to carry out modification.
(i) Method for blending a copolymer wherein a polar group has been introduced (i-1) A copolymer wherein a polar group has been introduced Preferable examples of the copolymer wherein a polar group has already been introduced include the following compounds.
(a) A diene polymer having a terminal hydroxyl group or a hydrogenated product thereof.
Among the diene polymers having a terminal hydroxyl group and the hydrogenated product thereof, an illustrative example of the diene polymer having a terminal hydroxyl group is polyhydroxy polybutadiene.
Illustrative examples of the diene polymer include a polymer which has at least one terminal hydroxyl group, whose molecular weight is in the range of 200 to 100,000, preferably 500 to 50,000, more preferably 800 to 10,000, and which is liquid, semi-solid or solid at normal temperatures. The average number of hydroxyl groups per molecule of such a diene polymer is generally in the range of 1 to 10, preferably 1.5 to 5, and those having a hydroxyl value generally in the range of 15 to 250, preferably 25 to 125 (KOHmg/g) are particularly preferable.
Illustrative examples of the diene polymer include polyhydroxy polybutadiene.
The diene polymer having a terminal hydroxyl group can be produced from 1,3-diene by a ~nown method such as a radical polymerization process or an anion polymerization process. An illustrative example of such a method is described in Japanese Patent Laid-Open No.51-71391, wherein a compound such as a functional hydrocarbon polymer containing an aromatic ring is catalytically hydrogenated by using molecular hydrogen.
It can also be produced by carrying out reaction between a monoepoxy compound, formaldehyde, acetoaldehyde, acetone, halogenoalkylene oxide or polyepoxide and a living polymer having an al~ali metal bonded to at least one of its terminals, which is produced by anionic polymerization of a conjugated diene monomer according to a known method, using an anionic polymerization catalyst such as an al~ali metal or an organic alkali metal compound.
As the raw material monomer for producing these polymers, at least one kind of conjugated diene monomer is used.
Examples of the conjugated diene monomer include 1,3-butadiene, 1,3-pentadiene, isoprene, chloroprene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene and the like.
Next, a hydrogenated product of the diene polymer having a terminal hydroxyl group can be produced by hydrogenating the above-mentioned diene polymer having the terminal hydroxyl group by an ordinary method such as a method described in Japanese Patent Laid-Open No. 51-71391 .
As for the degree of hydrogenation, the double bonds contained in a polymer may be completely or partially hydrogenated. A polymer normally having an iodine value of generally 0 to 20 (g/100 g) is preferable; more preferable is a polymer having an iodine value of O to S (g/100 g).
The diene polymer having a terminal hydroxyl group and the hydrogenated product thereof can be used alone or in admixtures of two or more compounds.
Among the diene polymer having a terminal hydroxyl group, and the hydrogenated product thereof, the hydrogenated product is preferable since it gives further improved weather-_g_ 21 7 l 51 5 resistance and adhesion.
Such a hydrogenated product is available form Mitsubishi Chemical Corpration as "Polytail H"(trade name).
(b) Copolymer of ethylene and an unsaturated compound containing carboxyl group (including a carboxylic acid anhydride group).
An illustrative example of the copolymer of ethylene and an unsaturated compound containing carboxyl group (including a carboxylic acid anhydride group) is a polymer wherein, for example, ethylene and acrylic acid are copolymerized randomly or at certain set intervals. Here, from the structural point of view, this refers to all polymers having a structure wherein an unsaturated compound containing carboxyl group, that is an unsaturated carboxylic acid compound or its anhydride is copolymerized randomly or regularly in a branched or linear carbon chain.
Examples of such a copolymer include a polymer in the form of a liquid, semi-solid or solid at normal temperatures, wherein the content of the unsaturated carboxylic acid compound or the anhydride thereof is 0.1 to 40% by weight, preferably 0.5 to 35 % by weight, more preferably 1 to 30% by weight, and the melt flow rate measured according to ASTM D1238 (190 ~ and 2.16 kg load) is 0.1 to 1,000 g/10 min, preferably 0.5 to 700 g/10 min, particularly preferably 1 to 500 g/10 min.
The copolymer of ethylene and an unsaturated carboxylic acid compound or an anhydride thereof may be produced from ethylene and the unsaturated carboxylic acid compound or anhydride thereof, by a known method such as a high pressure radical polymerization process. In the case of the high pressure radical polymerization process, ethylene, an unsaturated carboxylic acid or an anhydride thereof and a radical reaction initiator are continuously inserted at the ethylene-to unsaturated carboxylic acid compound or its anhydride ratio of 10,000:1 to 100:2, into a reaction zone which is kept under such ~l 7 1 $7~
conditions as, for example, a pressure of 1,000 to 3,000 atm, and a temperature of 90 to 300 ~. Thereby 3 to 20% of the ethylene is changed to a copolymer and the copolymer is continuously taken out from the reaction zone.
Examples of such an unsaturated carboxylic acid compound and the anhydride thereof include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, norbornene-5,6-dicarboxylic acid and an anhydride thereof.
They can be also used in the form of a terpolymer or a multi component copolymer wherein in addition to ethylene and an unsaturated carboxylic acid compound component, an unsaturated carboxylate such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate; a vinyl aromatic compound such as styrene, a-methylstyrene and vinyl toluene; a nitrile compound such as acrylonitrile and methacrylonitrile; a vinylpyridine such as 2-vinylpyridine and 4-vinylpyridine; a vinyl ether such as methyl vinyl ether, 2-chloroethyl vinyl ether; a vinyl halide such as vinyl chloride and vinyl bromide; a vinyl ester such as vinyl acetate; or acryl amide are used as a third copolymer component.
These copolymers can be used alone or in admixture of two or more compounds.
One of the copolymers is available form Mitsubishi Petrochemical Co. LTD.,as "YUKALON EAA A500W".
(c) Copolymer of ethylene and an unsaturated compound containing hydroxyl group An illustrative example of the copolymer of ethylene and an unsaturated compound containing hydroxyl group is a polymer wherein, for example, ethylene and 2-hydroxyethylmethacrylate are copolymerized randomly or at certain set intervals. Here, from the structural point of view, this refers to all polymers having a structure wherein an unsaturated compound containing hydroxyl group is copolymerized .
randomly or regularly in a branched or linear carbon chain.
Examples of such a copolymer include a polymer in theform of a liquid, semi-solid or solid at normal temperatures, having a content of the unsaturated compound containing hydroxyl group of 0.1 to 50 % by weight, preferably 0.5 to 45 % by weight, more preferably 1 to 40 % by weight, and a molecular - weight of 200 to 200,000, preferably 500 to 150,000, and more preferably 800 to 100,000.
The copolymer of ethylene and an unsaturated compound containing hydroxyl group may be produced from ethylene and the unsaturated compound containing hydroxyl group, by a known method such as a high pressure radical polymerization process.
In the case of a high pressure radical polymerization process, ethylene, an unsaturated compound containing hydroxyl group and a radical reaction initiator are continuously inserted at the ethylene to unsaturated compound containing hydroxyl group ratio of 1:0.0001 to 1:0.02, into a reaction zone which is kept under such conditions as, for example, a pressure of 1,000 to 3,000 atm, and a temperature of 90 to 280 ~. Thereby 3 to 20% of the ethylene is changed to a copolymer and the copolymer is continuously taken out from the reaction zone.
Examples of such an unsaturated compound containing hydroxyl group include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxylpropyl methacrylate, poly(ethyleneglycol)monomethacrylate and the like.
They can be also used in the form of a terpolymer or a multi component copolymer wherein in addition to ethylene and a hydroxyl group containing unsaturated compound component, an unsaturated carboxylate such as methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate; a vinyl aromatic compound such as styrene, a-methylstyrene and vinyl toluene; a nitrile compound such as acrylonitrile and methacrylonitrile; a vinylpyridine such as 2-vinylpyridine and 4-vinylpyridine; a vinyl ether such as methyl vinyl ether and 2-chloroethyl vinyl -ether; a vinyl halide such as vinyl chloride and vinyl bromide;
a vinyl ester such as vinyl acetate; and acryl amide or the like are used as a third copolymer component.
These copolymers can be used alone or in admixtures of two or more compounds.
(i-2) Amount of the polymer blended into the above-mentioned thermoplastic polymer The polymer wherein a polar group has already been introduced is blended in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 9 parts by weight, more preferably 0.1 to 8 parts by weight with 100 parts by weight of the above-mentioned thermoplastic polymer. When the amount is below the above-mentioned range, the resulting adhesion becomes inferior and when the amount exceeds the above-mentioned range, the resulting molded product provides inferior mold releasing properties.
(ii) Graft modified polymer Modified polymers obtained by subjecting the following various polymers and compounds containing a polar group to graft reaction can also be used.
(ii-1) Polymers to be modified The polymers to be modified include a main chain a propylene-type polymer such as propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random copolymer;
an ethylene-type polymer such as a low density polyethylene (branched ethylene polymer), medium density, high density polyethylene (linear ethylene polymer), a polyolefin resin such as a copolymer of ethylene and an unsaturated compound such as unsaturated carboxylic acid; ethylene-propylene rubber (EPM), ethylene-propylene-nonconjugated diene rubber (EPDM) wherein 5-ethylidenenorbornene, 5-methylnorbornene, 5-vinylnorbornene and dicyclopentadiene and the like are used as a nonconjugated diene; an olefin type rubber such as ethylene-butene rubber (EBM) and ethylene-propylene-butene copolymer rubber;
-hydrogenated product of styrene butadiene rubber (SBR); a compound having a hydrogenated product of styrene-conjugated diene block copolymer such as a styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-ethylene-propylene styrene copolymer (SEPS), a hydrogenated product of a styrene-isoprene-butylene-styrene block copolymer and the like.
The preferable number average molecular weight of such a polymer is generally 50,000 or less, but polymers having an number average molecular weight of 30,000 or less, particularly those having the number average molecular weight of 1,000 to 30,000 are preferable.
The number average molecular weight corresponds to a value calculated from the number average molecular weight of polystyrene or polypropylene measured by a gel permeation chromatography method (GPC3 under the conditions shown below:
Apparatus: 150C ALC/GPC (Millipore Corp.) Column: AD80M/S (Showa Denko K.K.) Solvent: o-dichlorobenzene Temperature: 140 ~
Flow rate: lml/min.
Chaged amount: 200~1 Concentration: 2 mg/ml (0.2 wt% of 2,6-di-t-butylphenol was added as an antioxidant and the detection of concentration was carried out with a wave length of 3.42 ~m by an infrared spectrophotometer "MIRAN 1A"(FOXBORO
COMPANY)) (ii-2) Compound containing a polar group A compound containing a polar group employed according to the present invention is one or more compounds selected from an unsaturated carboxylic acid or a derivative thereof, and examples of such a compound include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, 3-butenoic acid, `` 2171575 crotonic acid, pentenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, maleic acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, norbornene-5,6-dicarboxylic acid, or a derivative thereof such as an anhydride, ester, amide, imide and metal salt. Among these, acrylic acid, methacrylic acid, maleic acid or an anhydride thereof are preferable. Particularly preferable is the use of maleic anhydride.
(ii-3) Graft reaction Graft reaction can be carried out, speci~ically by the use of 100 parts by weight of the above-mentioned polymer, and 0.01 to 10 parts by weight, preferably O.OS to 9 parts by weight, more preferably 0.1 to 8 parts by weight of at least one compound selected from either the unsaturated carboxylic acid or the derivative thereof, together with an organic peroxide in the presence of an appropriate catalyst or under heating and melting conditions.
Examples of the organic peroxide to be used include dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane; diacylperoxides such as acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, and 2,4-dichlorobenzoyl peroxide;
peroxy esters such as t-butyloxy acetate, t-butylperoxy butylate, t-butylperoxy-2-ethyl hexanote, t-butylperoxy laurylate, t-butylperoxy benzoate, di-t-butylperoxy isophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxy maleic acid, t-butylperoxy isopropyl carbonate, and cumylperoxy octate; peroxy ketals such as 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)octane, and 2,2-bis(t-butylperoxy)butane; and hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-dihydroperoxide. Among these, diacyl peroxides and peroxy esters are preferable, and particularly preferable are diacyl peroxides.
The organic peroxide is used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, most preferably 0.1 to 10 parts by weight for 100 parts by weight of the polymer.
The graft modified polymer is available, for example, from Sanyo Chemical Industries, Ltd. as "YOUMEX 1210"(trade name).
(4) Thermoplastic polymer containing an inorganic filler <1> Anorganic filler Examples of an inorganic filler of the present invention to be blended with the above-mentioned thermoplastic polymer for the injection molding described in paragraph (2) include talc, mica, glass fiber, whisker, carbon fiber, calcium carbonate, titanium oxide, carbon black, glass balloon and the like.
Among these, calcium carbonate and plate-shaped inorganic fillers such as talc and mica are preferable from the point of view of heat fusion properties.
Particularly preferable is talc which has an average particle size of 1 to 20 microns, more preferably it has a substantial length of 1 to 15 microns, and a particularly preferable average aspect ratio is 5 to 10.
"Substantial" length of the talc means that most of the talc particles have a length within that range.
The above-mentioned talc is produced by, for example, grinding a raw talc ore by an impact grinder or a micro-type grinder, followed by pulverization by a micron mill and a jet type pulverizer and classification by a cyclone or micron separator.
The average particle size is the value measured by a particle-size distribution analyzer by using a laser beam diffraction method, and as a measuring apparatus, for example, the LA-500 type apparatus produced by Horiba, Ltd. is desirable due to its high measurement precision. The diameter, length and aspect ratio are the values measured by a microscope etc.
As a preferable calcium carbonate, that having a specific surface area of 40,000 cm2/g or less is generally used, that having a specific surface area of 30,000 cm2/g or less, particularly of 5,000 to 30,000-cm2/g is more preferably used with that having an average particle size of 0.5 to 20.0 ~m being generally used, and that having an average particle size of 1.0 to 2.5 microns is preferably used.
These inorganic fillers are used generally in an amount of 1 to 40 parts by weight, preferably 3 to 3~ parts by weight, and more preferably 5 to 30 parts by weight for 100 parts by weight of the above-mentioned thermoplastic polymer.
When the amount of the filler blended is below the above-mentioned range, the resulting adhesive strength and dimensional stability (molding shrinkage) tend to be poor, and when it exceeds the above-mentioned range, the resulting moldability tends to be inferior.
The thermoplastic polymer described in the above-mentioned paragraph (2) can be used as a raw material for the thermoplastic polymer containing an inorganic filler according to the present invention. However, in order to improve adhesion with the molded crosslinked rubber, which is an effect of the present invention, it is preferable to replace a part or all of the thermoplastic polymer described in the above-mentioned paragraph (3) with a thermoplastic polymer wherein a polar group has been introduced.
From the view point of improving adhesion, it is preferable to replace all the thermoplastic polymers by the thermoplastic polymer wherein a polar group has been introduced, however, from the view point of mold releasing properties, the amount should be in the range of 0.01 to 20% by weight, preferably 0.05 to 10~ by weight, more preferably 0.05 to 8%, even more preferably 0.1 to 7% by weight.
The inorganic filler can be incorporated into the composition in an amount of 1 to 40 parts by weight based on 100 parts by weight of the thermoplastic polymer.
<2~ Production of a thermoplastic polymer containing an inorganic filler A thermoplastic polymer containing an inorganic filler to be used according to the production of the composite injection molded body of the present invention is produced by mixing and blending the above-mentioned thermoplastic polymer with an inorganic filler in the above-mentioned ratio by a kneader currently used for mixing thermoplastic polymers such as a Banbury mixer, kneader, single-screw extruder, and double-screw extruder.
(5) Others In order to further improve the adhesion of a molded crosslinked rubber with a thermoplastic polymer, it is preferable to coat the following primer on the portions of the surface of the molded crosslinked rubber that are in contact with the injected thermoplastic soft polymer, in a thickness of 0.01 to 100 ~m, preferably 0.1 to 80 ~m, by a spray, brush, coater or printing machine.
Preferable examples of such a primer include a hydrogenated styrene-butadiene-styrene block copolymer (SEBS) which is graft modified by maleic anhydride, similarly modified hydrogenated styrene-isoprene-styrene block copolymer (SEPS), similarly modified ethylene-propylene copolymer and similarly modified chlorinated polypropylene dissolved in a solvent such as toluene, xylene and methyl ethyl ketone.
[II3 Production of a composite injection molded product A composite injection molded product of the present invention can be produced by inserting and fixing a molded crosslinked rubber in a cavity of an injection molding die, and injecting a molten thermoplastic polymer onto the molded crosslinked rubber so that a composite resin molded product isformed wherein the injected thermoplastic polymer having a polar group is adhered on the surface of the molded crosslinked rubber. Also by inserting and fixing a molded crosslinked rubber in a cavity of an injection molding die, and injecting a molten thermoplastic polymer onto the molded crosslinked rubber, a composite resin molded product wherein the injected thermoplastic polymer containing an inorganic filler is adhered -and coated on the surface of the molded crosslinked rubber can be produced.
As for the conditions for the injection molding, the resin temperature is generally in the range of 180 to 280 ~, preferably 200 to 280 ~, the injection molding die temperature is generally in the range of 30 to 80 ~, preferably 40 to 80 ~, the injection molding pressure is generally in the range of 300 to 800 kgf/cm2, preferably 400 to 800 kgf/cm2, the holding pressure is generally in the range of 300 to 800 kgf/cm2, preferably 400 to 800 kgf/cm2, and the retention time is generally in the range of 15 to 60 seconds, preferably 20 to ~0 seconds.
According to the present invention, a composite injection molded product having a complex shape and a relatively large size can be produced, thus the composite injection molded product of the present invention is useful for a wind shield gasket, or for weatherstrip of an automoble, or for various gaskets used as building materials.
Brief Description of the Drawings Fig.1 is a plan view of a part of an automobile weatherstrip.
Fig.2 is a plan view of an automobile weatherstrip.
Description of the Preferred Embodiments The method for producing the composite injection 217i575 molded product of the present invention will be illustrated by the following Examples and Comparative Examples.
The raw materials and the evaluation method employed in the Examples and Comparative Examples are as follows.
Example group A
(Corresponding to "containing a polar group" of the present invention) [I] ~aw materials (1) Thermoplastic polymer <1> Thermoplastic elastomer component TPE-1:
"Thermorun 3801B" produced by Mitsubishi Chemical Corporation (partially crosslin~ed olefin type thermoplastic elastomer, ASTM D2240(Type A) hardness: 87) TPE-2:
"Thermorun 2920B" produced by Mitsubishi Chemical Corporation (uncrosslinked olefin type thermoplastic elastomer, ASTM D2240(Type A) hardness: 96) TPE-3:
A mixture of "Thermorun 3551B" produced by Mitsubishi Chemical Corporation (partially crosslinked olefin type thermoplastic elastomer, ASTM D2240(Type A): 55) and "RABALON
T3314B" produced by Mitsubishi Chemicai Corporation (styrene type thermoplastic elastomer, ASTM D2240(Type A) hardness: 30) blended at 7:3 ASTM D2240 (Type A) hardness: 43).
<2> Modification method Method 1 (M1):
A Propylene-ethylene random copolymer containing 3~ by weight of ethylene was subjected to thermal oxidation at 300 to 350 ~, and maleic anhydride groups were grafted to both ends of the main chain as well as into the main chain of the polymer in an amount of 10% by weight of the whole polymer using 1,1'-azobis(cyclohexane-1-carbonitrile) which is an azo type free-radical initiator. The maleic anhydride groups were then neutralized with ethanol amine to give a modified propylene polymer. The modified propylene polymer having a MFR (230 t, 2.16 kg load) of 50 g/10 min, a number average molecular weight in terms of polypropylene of 7,000, was used.
Method 2 (M2):
Into an autoclave having a capacity of 500 ml, were added 100 g of 1,3-butadiene, 70 g of isopropyl alcohol and 10 g of 60~ aqueous hydrogen peroxide solution, and polymerization was carried out in argon atmosphere at 90 ~ for 5 hours. After the reaction was finished, unreacted monomers were removed and the resulting butadiene polymer was dried. The hydroxyl value of the resulting polymer was about 44.5 KOHmg/g.
Into an autoclave having a capacity of 200 ml, were added 50 g of thus obtained butadiene polymer, 50 g of cyclohexane and 5 g of 5% by weight ruthenium catalyst supported on carbon and the system was purged with argon gas. Then hydrogen gas was introduced until the pressure of the hydrogen reached 50 kg/cm2. The system was heated to 100 ~, and reaction was carried out for 10 hours while the hydrogen gas was supplied so that the total pressure was kept at 50 kg/cm2. After the reaction was finished, hydrogen was removed and the catalyst was removed by filtration and the resulting hydrogenated product was precipitated in methanol, filtered out and dried. The hydrogenated butadiene polymer product thus obtained was used, i.e., a waxy polyolefin polyol having hydroxyl groups at both ends (with an iodine value of 1.0 g/100 g, a hydroxyl value of 44 KOHmg/g, and a number average molecular weight in terms of polystyrene of 5,400) was used.
Method 3 (M3):
An ethylene acrylic acid copolymer having an acrylic acid content of 20 % by weight, an MFR (190 ~, 2.16 kg load) of 300 g/10 min, and a number average molecular weight in terms of polystyrene of 25,000, was used.
i 2171 575 Method 4 (M4):
Maleic anhydride in an amount of 40 g and benzoyl peroxide in an amount of 40 g were dry blended with 5 kg of TPE-1 and melted and kneaded to carry out graft modification in a double-screw extruder which was set at the preset temperature of 160 to 200 ~, the rotation number of 300 rpm, and the discharge rate of 10 kg/h, to give a modified TPE-1 wherein 0.6% by weight of maleic anhydride was added.
(2) Molded crosslinked rubber EP-1:
A sheet made of crosslinked EPDM (crosslinked by sulfur, ASTM D2240 (Type A) hardness of 74, carbon concentration of 40~ and crosslinking degree of 95%) was used.
Example A1 A crosslinked rubber sheet EP-1 ~thickness: 3 mm) was cut to a width of 30 mm and a length of 100 mm to produce an insert molded product. Then the surface of the insert molded product to be joined with an injection molding material was wiped with isopropyl alcohol to remove dust and dirt.
Then, the insert molded product was placed and fixed into the movable half of the cavity of a die for forming a sheet of 100 mm x 100 mm x 3 mm, and a thermoplastic polymer comprising 100 parts by weight of TPE-1 and 5 parts by weight of the modified propylene polymer obtained in the modification method 1 (M1) was injected to produce an injection molded, double layer test piece.
As for the conditions of the injection molding, an inline screw type injection molding machine (a small injection molding machine produced by Toshiba Machine Co., Ltd. : IS9OB) was used, the resin temperature was 240 ~, the die temperature was 40 ~, the injection pressure was 600 kgf/cm2, the retaining pressure was 600 kgf/cm2, and the pressure retaining time was 30 seconds.
Three sample chips (75 mm x 2~ mm x 3 mm) for evaluation were cut out from the double layer test piece and the sample chips for evaluation were sub~ected to measurement of adhesion strength using a tension testing machine (tension speed 500 mm/min). The average values are given in Table A1.
Examples A2-A7, Comparative Examples A1-A3 Double layer test pieces were obtained in a manner similar to that of Example Al except that the thermoplastic polymer laminated by injection molding was changed to the compositions given in Table A1.
The adhesive strength between the two layers is given in the Table.
Table Al - Example No. Comparative Example No.
Al A2 A3 A4 A5 A6 A7Al A2 A3 Thermoplastic polymer Elastomer TPE-l TPE-l TPE-l TPE-l TPEl TPE-2 TPE-3 TPE-l TPE-2 TPE-3 Amount of elastomer(pbw) 100 100 100 100 100 100 100 100 100 100 Modification method Ml M2 M3 M4 Ml Ml Ml Amount of modified elastomer(pbw) 5 5 5 5 3 5 5 Molded product of crosslinked rubber EP-l EP-l EP-l EP-l EP-l EP-l EP-l EP-l EP-l EP-l Adhesion strength ~kg/cm2) 45 40 42 40 38 48 30 30 35 20 Example group B
(Corresponding to "containing an inorganic filler" of the ` 2171575 present invention) lI] Raw materials (1) Thermoplastic polymer <1> Thermoplastic elastomer component TPE-4;
50% by weight of ethylene-propylene-nonconjugated diene rubber (EPDM, wherein 5-ethylidenenorbornene was used as a nonconjugated diene, obtained from Japan Synthetic Rubber Co., Ltd. under the trade name of "EP 98"), 10% by weight of paraffin oil (process oil "PW 380" produced by Idemitsu Kosan Co., Ltd.) and 40% by weight of polypropylene ("BC2" produced by Mitsubishi Chemical Corporation) were put in a Banbury mixer having a capacity of 4 liters and kneaded for about 5 minutes at 170~ and 60 rpm, it was then made into sheeting using rollers, and the sheeting was subjected to a sheet cutter to produce pellets.
100 parts by weight of the pellets produced, 1.0 part by weight of l1,3-bis(tert-butylperoxyisopropyl)]benzene obtained from KAYAKU AKZO COPPOPATION under the trade name of "Perkadox 14/40", 0.4 parts by weight of divinyl benzene, 0.8 parts by weight of carbon black, 0.1 parts by weight of Irganox 1010 produced by Ciba-Geigy AG, and 0.1 parts by weight of Sanol 770 produced by Sanyo Company Limited were blended together and mixed by a Henschel mixer at a normal temperature for 1 minute, then subjected to dynamic crosslinking at 200 ~ and 210 rpm by a double-screw extruder (PCM 45 produced by Ikegai Corporation) to obtain a partially crosslinked olefin type thermoplastic elastomer (ASTM D2400 (Type A) hardness: 85).
TPE-5:
40% by weight of ethylene-propylene-nonconjugated diene rubber (EPDM, wherein 5-ethylidene norbornene was used as a nonconjugated diene, obtained from Japan Synthetic Rubber Co., Ltd. under the trade name of "EP 98"), 10% by weight of paraffin oil (process oil "PW 380" produced by Idemitsu Kosan Co., Ltd.) and 50% by weight of polypropylene ("BC2" produced by Mitsubishi `` 2171575 Chemical Corporation) were put in a Banbury mixer having acapacity of 4 liters and kneaded for about 5 minutes at 170 ~
and 60 rpm. Then it was made into sheeting by rollers, and the sheeting was subjected to a sheet cutter to produce pellets.
100 parts by weight of the pellets produced, 0.8 parts by weight of carbon black, 0.1 parts by weight of Irganox 1010, and 0.1 parts by weight of Sanol 770 were blended together and mixed by a Henschel mixer at room temperature for 1 minute, then subjected to kneading at 200 ~ and 210 rpm by a double-screw extruder (PCM 45 produced by Ikegai Corporation) to obtain a noncrosslinked olefin type thermoplastic elastomer ASTM D2400 (Type A) hardness: 95).
TPE-6:
100 parts by weight of a mixture comprising 70% by weight of TPE-1, 15% by weight of styrene-ethylene-butylene-styrene copolymer (SEBS, "Kraton G1651" produced by Shell Japan Ltd.), and 15% by weight of paraffin oil (process oil "PW 380"
produced by Idemitsu Kosan Co., Ltd.), 0.8 parts by weight of carbon black, 0.1 parts by weight of Irganox 1010, and 0.1 parts by weight of Sanol 770, were blended together and mixed by a Henschel mixer at normal temperature for 1 minute, and then subjected to kneading at 200 ~ and 210 rpm by a double-screw extruder (PCM 45 produced by Ikegai Corporation) to obtain a thermoplastic elastomer (ASTM D2240 (Type A) hardness: 45).
<2> Inorganic fillers Filler 1 (F1):
Talc having a specific surface area of 38,000 cm2/g, an average particle size of 2.8 ~m, and an average aspect ratio of 6.
Filler 2 (F2~:
Calcium carbonate having a specific surface area of 11,000 cm2/g, and an average particle size of 3.5 ~m.
<3> Modification method Method 5 (M5):
A propylene-ethylene random copolymer containing 3% by weight of ethylene, having an MFR (230 ~, 2.16 kg load) of 50 g/10 min, and a number average molecular weight in terms of polypropylene of 7,000 was subjected to thermal oxidation, and maleic anhydride was grafted to both ends of the main chain as well as into the main chain of the polymer in an amount of 10 by weight of the whole polymer by using azoisobutyronitrile which was an azo type free-radical initiator. The maleic anhydride was then neutralized with ethanol amine to give a modified propylene polymer. The resulting modified propylene polymer was used.
Method 6 (M6):
A waxy polyolefin polyol having a terminal hydroxyl group (wherein the iodine value was 1.0 g/100 g, the hydroxyl value was 44 KOHmg/g, and the number average molecular weight in terms of polystyrene was 5,400) was used.
Method 7 (M7):
An ethylene-acrylic acid copolymer having an acrylic acid content of 20% by weight, a MFR (190 ~, 2.16 kg load) of 300 g/10 min, and a number average molecular weight in terms of polystyrene of 25,000 was used.
Method 8 (M8):
Maleic anhydride in an amount of 40 g and benzoyl peroxide in an amount of 40 g were dry-blended with 5 kg of TPE-4 and melted and kneaded to carry out graft modification in a double-screw extruder which was set at the preset temperature of 160 to 200 ~, a rotation of 300 rpm, and a discharge rate of 10 kg/h, to give a modified TPE-4 wherein 0.6% by weight of maleic anhydride was added.
(2) Molded crosslinked rubber EP-2:
A sheet made of crosslinked EPDM (crosslinked by sulfur, ASTM D2240 (Type A) hardness of 74, a carbon concentration of 40% and a crosslinking degree of 95% or more) -~6-was used.
[II] Experiment examples Examples B1-B2 A crosslinked rubber sheet ~thickness: 3 mm) obtained by crosslinking EPDM with sulfur was precisely cut to a width of 30 mm and a length of 100 mm to produce an insert molded product.
The surface of the insert molded product to be joined with an injection molding material was then wiped with isopropyl alcohol to remove dust and dirt.
Next, the insert molded product was placed and fixed in the movable half of a cavity of a die for forming a sheet (internal dimensions: 100 mm x 100 mm x 3 mm) and a thermoplastic polymer comprising 100 parts by weight of TPE-4 and 30 parts by weight of filler-1 as shown in Table B1 was injected to produce an injection molded, double layer test piece having a thickness of 3 mm.
As for the conditions of the injection molding, an inline screw type injection molding machine (a small injection molding machine produced by Toshiba Machine Co., Ltd.:IS 90 B) was used, the resin temperature was 240 ~, the die temperature was 40 ~, the injection pressure was 600 kgf/cm2, the retaining pressure was 600 kgf/cm2, and the pressure retaining time was 30 seconds.
Three sample chips for evaluation [length: 75 mm, width: 25 mm, and thickness: 3 mm, comprising an injection molded part (length: 45 mm, width: 25 mm and thickness: 3 mm) and a crosslinked rubber part (length: 30 mm, width: 25 mm, thickness: 3 mm) bonded by a joint surface of 25 mm x 3 mml were cut out of each of the double layer test pieces (length: 100 mm, width: 100 mm, and thickness: 3 mm) and these sample chips for evaluation were subjected to measurement of adhesion strength and a degree of material breakdown using a tension testing machine (tension speed 500 mm/min). The average values are - 2 l 7 1 57 5 given in Table B1.
Examples B3 The crosslinked rubber sheet (thickness of 3 mm) used in Example B1 was precisely cut to a width of 30 mm and a length of 100 mm to produce an insert molded product.
The surface of the insert molded product to be joined with an injection molding material was then wiped with isopropyl alcohol to remove dust and dirt.
Next, the insert molded product was placed and fixed in the movable half of a cavity of a die for forming a sheet (100 mm x 100 mm x 3 mm) and a thermoplastic polymer comprising 100 parts by weight of TPE-4, 5 parts ~y weight of the modified propylene polymer obtained in modification method 1 and 30 parts by weight of filler 1, as shown in Table B1, was injected to produce an injection molded, double layer test piece.
As for conditions of the injection molding, an inline screw type injection molding machine (a small injection molding machine produced by Toshiba Machine Co., Ltd.:IS 90 B) was used, the resin temperature was 240 ~, the injection molding die temperature was 40 ~, the injection pressure was 600 kgf/cm2, the retaining pressure was 600 kgf/cm2, and the pressure retaining time was 30 seconds.
Three sample chips for evaluation llength: 75 mm, width: 25 mm, and thickness: 3 mm, comprising an injection molded part (length: 45 mm, width: 25 mm and thickness: 3 mm) and a crosslinked ru~ber part (length: 30 mm, width: 25 mm, thickness: 3 mm) ~onded with a joint surface of 25 mm x 3 mm]
were cut out of one double layer test piece shown in Fig.1 (length: 100 mm, width: 100 mm, and thickness: 3 mm) and su~jected to measurement of adhesion strength using a tension testing machine (tension speed 500 mm/minutes). The average values are given in Ta~le B1.
Examples B4-B12 and Comparative Examples Bl-B3 Double layer test pieces were obtained in a manner similar to that of Example Bl or B3 except that the thermoplastic polymer to be by injected and molded was changed to the compositions given in Table B1.
The adhesive strength between the two layers is shown in Table Bl.
.
Table Bl Example No.
Bl B2 B3 B4 B5 B6 B7 B8 Thermoplastic polymer Elastomer TPE-4 TPE-4 TPE-4 TPE-4 TPE-4 TPE-4 TPE-4 TPE-5 Amount of elastomer(pbw) 100 100 100 100 100 100 100 100 Filler Fl F2 Fl Fl Fl Fl Fl Fl Amount of filler (pbw) 30 30 30 30 30 30 30 30 Modification method - - M5 M6 M7 M8 M5 Amount of modified elastomer (pbw) - - 5 5 . 5 5 3 Molded product of crosslinked rubberEP-2 EP-2 EP-2 EP-2 EP-2 EP-2 EP-2 EP-2 Adhesion strength (kg/cm2) 39 38 46 42 43 43 42 43 Degree of material breakdown (~) 70-80 50-60 290 290 290 290 290 70-80 Table B1 (continued) Example No. Comparative Ex. No B9 B10 Bl 1 B12 Bl B2 B3 Thermoplastic polymer Elastomer TPE-5 TPE-6 TPE-6 TPE-6 TPE-4 TPE-5 TPE-6 Amount of elastomer(pbw) 100 100 100 100 100 100 100 Filler Fl Fl Fl Fl Amount of filler (pbw) 30 30 30 15 - _ _ Modification method M5 - M5 M5 Amount of modified elastomer (pbw) Molded product of crosslinked rubberEP-2 EP-2 EP-2 EP-2 EP-2 EP-2 EP-2 Adhesion strength (kg/cm2) 50 26 32 40 30 35 20 Degree of material breakdown(X) - ~90 70-80 290 50-60 20-30 20-30 20-30
These rubbers can be used alone or in an admixture of two or more components.
These rubber can be blended with a thermoplastic resin such as polypropylene and polyethylene if necessary. If necessary, these rubbers can be also blended with a filler such as talc and calcium carbonate, a plasticizer such as paraffin oil and liquid polybutene, and other various additives including a vulcanizing accelerator, peroxide, crosslinking assistant, mastication accelerator, antiscorching agent, foaming agent, antioxidant, thermal stabilizer, light stabilizer, UV absorbing agent, neutralization agent, slip additive, lubricant, anti--fogging agent, anti-blocking agent, dispersing agent, coloring agent, antibacterial agent, and fluorescent whitener.
<2> Molded crosslinked rubber A molded crosslinked rubber can be obtained by adding 0.1 to 10% by weight, preferably 0.1 to 5% by weight of a crosslinking agent to the above-mentioned rubber, followed by heating and molding.
Examples of a crosslinking agent to crosslink the above-mentioned rubber include sulfur and aromatic or aliphatic peroxides such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane-3,tert-butylperoxy benzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butylcumyl peroxide, diisopropyl ` 21 71 575 benzohydroperoxide, benzoylperoxide, and di-tert-butylperoxide, the above can be used alone or in admixtures.
Among these crosslinking agents, sulfur is preferably employed.
The molded crosslinked rubber can be produced by blending the above crosslinkable rubber material with sulfur or a peroxide, molding the blend into a desired shape by such molding methods as extrusion molding, injection molding or vacuum molding, followed by heat treatment at 100 to 200 ~ for 1 to 10 minutes so that the crosslinkable rubber material is crosslinked or cured by the sulfur or the peroxide contained therein. Among the molded crosslinked rubber products, those produced by the extrusion molding method are particularly preferred.
In one method of laminating the molded crosslinked rubber with the below-mentioned thermoplastic polymer, the molded crosslinked rubber may be first produced in an injection molding die which the thermoplastic polymer is then injected and molded to provide a composite injection molded product in the die, or alternatively, the molded crosslinked rubber may be previously produced in a separate place, and then inserted into the die and the thermoplastic polymer is injected in the die.
Degree of crosslinking The crosslinked rubber has little or no flowability, and has a melt flow rate (MFR:230 ~, ~ kg load) according to JIS-K7210 (ASTM D1238~ of 0 to 0.01 g110 min. As it does not have flowability, the crosslinked rubber is distinguished from the below-mentioned thermoplastic polymer having flowability.
(2) Thermoplastic polymer <1> Thermoplastic polymers Appropriate examples of thermoplastic polymers as a raw material for the thermoplastic polymer used for the injection molding according to the present invention include those having a melt flow rate (MFR:230 ~, 2.16 kg load) according to ASTM D1238 of 0.01 to 1000 g/10 min, preferably0.01 to 300 g/10 minutes, more preferably 0.1 to 100 g/10 min, and even more preferably 0.1 to 50 g/10 min from the view point of flowability which makes the injection molding possible.
When the below-mentioned inorganic fillers are included, it is appropriate to use a thermoplastic polymer having a high melt flow rate.
When it is necessary that the thermoplastic polymer to have the same level of flexibility and rubber elasticity as those of a crosslinked rubber, a thermoplastic polymer having a JIS-A hardness according to a JIS-K6301 lASTM D2240 (Type A)] of 98 or less is generally used, but a thermoplastic polymer having the hardness of 95 or less is preferably used and a thermoplastic polymer having the hardness of 90 to 20 is most preferably used.
The above-mentioned thermoplastic polymers can be thermoplastic resins or thermoplastic elastomers.
Examples of the thermoplastic resin include olefin-type thermoplastic resins such as polyethylene, polypropylene, polybutene-1, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer; soft vinyl chloride polymer, styrene type resin, polyester type resin and polyamide-type resin and the like.
Examples of the thermoplastic elastomer include a copolymer of 15 to 90% by weight of ethylene and 85 to 10% by weight of an alkene having 3 or more carbon atoms, preferably a copolymer of ethylene and an alkene having 3 to 10 carbon atoms.
Illustrative examples of the thermoplastic elastomer include an olefin-type elastomer such as ethylene-propylene copolymer rubber (EPM), ethylene-butene copolymer rubber (EBM), ethylene-hexene copolymer, ethylene-octene copolymer and ethylene-propylene-nonconjugated diene copolymer rubber (EPDM) or ethylene-propylene-butene copolymer and the like wherein 5-21715~5 ethylidenenorbornene, 5-methylnorbornene, 5-vinylnorbornene, dicyclopentadiene and butene and the like are used as the third component; styrene-type elastomer; polyester-type elastomer;
polyamide-type elastomer and the like.
These thermoplastic polymers can be used alone or in admixtures of two or more components.
Among them, preferably used are olefin type elastomers, and a mixture of an olefin type thermoplastic resin and an olefin type elastomer which are mixed at the ratio of 10:90 to 90:10 are preferably used. A ratio of 20:80 to 80:20 (~ by weight) is particularly preferable used since the defining process can be omitted.
The term resin refers to a thermoplastic polymer having a crystallinity index by an x-ray diffraction method of 30 to 70%, and the term elastomer refers to a noncrystalline thermoplastic polymer or a thermoplastic polymer having a crystallinity index of less than 30%.
As the above-mentioned olefin elastomers, those having a Mooney viscosity at 100 ~ (MLl I 4 (100 ~) ) of 10 to 400 according to JIS K6300, particularly those having a Mooney viscosity of 15 to 350 are preferable. Elastomers having a Mooney viscosity exceeding the above-mentioned range tend to have an inferior appearance when they are molded, and those having a Mooney viscosity below that range tend to exhibit an inferior rubber elasticity.
The production methods and the forms of such olefin elastomers are not particularly limited. They can be produced by, for example, mixing an olefin type elastomer and an olefin type thermoplastic resin, and heating the resulting mixture in the presence of an organic peroxide to carry out partial or complete crosslinking mainly by radicals. The product produced by such a crosslinking treatment is different from the a~ove-mentioned crosslinked rubber (1) since it has flowability.
For use as the above-mentioned olefin-type elastomers are the commercially available "JSR EP" and "JSR EBM" produced by Japan Synthetic Rubber Co., Ltd., "MITSUI EPT" and "TAFMER"
produced by Mitsui Petrochemical Industries, Ltd., "ESPRENE"
produced by Sumitomo Chemical Company, Ltd., "ENGAGE" produced by Dow Chemical Japan ~td.
Examples of the partially or completely crosslinked products include "Thermorun" produced by Mitsubishi Chemical Corporation, "MILASTOMER" produced by Mitsui Petrochemical Industries, Ltd., "Sumitomo TPE" produced by Sumitomo Chemical Company, Ltd., and "Santoprene" produced by Advanced Elastomer System, L.P..
<2> Other components The above-mentioned thermoplastic polymer may be blended with a polymer component including a resin other than the above-mentioned resins and an elastomer, as well as other additives including a plasticizer such as paraffin oil and liquid polybutene; an antioxidant, light stabilizer, UV
absorbing agent, antiblocking agent such as silicone oil, a neutralizing agent, lubricant, dispersing agent, antibacterial agent, coloring agent, flame retardant, and fluorescent whitener in amounts that do not remarkably detract from the effects of the present invention.
(3) Thermoplastic polymer having a polar group <1> Polar groups According to the present invention, a thermoplastic polymer described in the above-mentioned paragraph ~2) may have a polar group such as a hydroxyl group, carboxyl group, epoxy group, amino group, carboxylic acid anhydride group, thiol group, and silanol group. Among these, the hydroxyl group, carboxyl group, carboxylic acid anhydride group are preferable from the view point of adhesion with the molded crosslinked rubber.
<2> Process for introducing a polar group (modification of a thermoplastic polymer) Methods for introducing a polar group into a thermoplastic polymer are basically divided into two groups, i.e. (i) a method in which the above-mentioned thermoplastic polymer is blended with a copolymer wherein a polar group has already-been introduced (the copolymer may be the same as the above-mentioned thermoplastic polymer) to carry out modification, or (ii) a method in which the above-mentioned thermoplastic polymer and a compound having a polar group are directly subjected to graft reaction to carry out modification.
(i) Method for blending a copolymer wherein a polar group has been introduced (i-1) A copolymer wherein a polar group has been introduced Preferable examples of the copolymer wherein a polar group has already been introduced include the following compounds.
(a) A diene polymer having a terminal hydroxyl group or a hydrogenated product thereof.
Among the diene polymers having a terminal hydroxyl group and the hydrogenated product thereof, an illustrative example of the diene polymer having a terminal hydroxyl group is polyhydroxy polybutadiene.
Illustrative examples of the diene polymer include a polymer which has at least one terminal hydroxyl group, whose molecular weight is in the range of 200 to 100,000, preferably 500 to 50,000, more preferably 800 to 10,000, and which is liquid, semi-solid or solid at normal temperatures. The average number of hydroxyl groups per molecule of such a diene polymer is generally in the range of 1 to 10, preferably 1.5 to 5, and those having a hydroxyl value generally in the range of 15 to 250, preferably 25 to 125 (KOHmg/g) are particularly preferable.
Illustrative examples of the diene polymer include polyhydroxy polybutadiene.
The diene polymer having a terminal hydroxyl group can be produced from 1,3-diene by a ~nown method such as a radical polymerization process or an anion polymerization process. An illustrative example of such a method is described in Japanese Patent Laid-Open No.51-71391, wherein a compound such as a functional hydrocarbon polymer containing an aromatic ring is catalytically hydrogenated by using molecular hydrogen.
It can also be produced by carrying out reaction between a monoepoxy compound, formaldehyde, acetoaldehyde, acetone, halogenoalkylene oxide or polyepoxide and a living polymer having an al~ali metal bonded to at least one of its terminals, which is produced by anionic polymerization of a conjugated diene monomer according to a known method, using an anionic polymerization catalyst such as an al~ali metal or an organic alkali metal compound.
As the raw material monomer for producing these polymers, at least one kind of conjugated diene monomer is used.
Examples of the conjugated diene monomer include 1,3-butadiene, 1,3-pentadiene, isoprene, chloroprene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene and the like.
Next, a hydrogenated product of the diene polymer having a terminal hydroxyl group can be produced by hydrogenating the above-mentioned diene polymer having the terminal hydroxyl group by an ordinary method such as a method described in Japanese Patent Laid-Open No. 51-71391 .
As for the degree of hydrogenation, the double bonds contained in a polymer may be completely or partially hydrogenated. A polymer normally having an iodine value of generally 0 to 20 (g/100 g) is preferable; more preferable is a polymer having an iodine value of O to S (g/100 g).
The diene polymer having a terminal hydroxyl group and the hydrogenated product thereof can be used alone or in admixtures of two or more compounds.
Among the diene polymer having a terminal hydroxyl group, and the hydrogenated product thereof, the hydrogenated product is preferable since it gives further improved weather-_g_ 21 7 l 51 5 resistance and adhesion.
Such a hydrogenated product is available form Mitsubishi Chemical Corpration as "Polytail H"(trade name).
(b) Copolymer of ethylene and an unsaturated compound containing carboxyl group (including a carboxylic acid anhydride group).
An illustrative example of the copolymer of ethylene and an unsaturated compound containing carboxyl group (including a carboxylic acid anhydride group) is a polymer wherein, for example, ethylene and acrylic acid are copolymerized randomly or at certain set intervals. Here, from the structural point of view, this refers to all polymers having a structure wherein an unsaturated compound containing carboxyl group, that is an unsaturated carboxylic acid compound or its anhydride is copolymerized randomly or regularly in a branched or linear carbon chain.
Examples of such a copolymer include a polymer in the form of a liquid, semi-solid or solid at normal temperatures, wherein the content of the unsaturated carboxylic acid compound or the anhydride thereof is 0.1 to 40% by weight, preferably 0.5 to 35 % by weight, more preferably 1 to 30% by weight, and the melt flow rate measured according to ASTM D1238 (190 ~ and 2.16 kg load) is 0.1 to 1,000 g/10 min, preferably 0.5 to 700 g/10 min, particularly preferably 1 to 500 g/10 min.
The copolymer of ethylene and an unsaturated carboxylic acid compound or an anhydride thereof may be produced from ethylene and the unsaturated carboxylic acid compound or anhydride thereof, by a known method such as a high pressure radical polymerization process. In the case of the high pressure radical polymerization process, ethylene, an unsaturated carboxylic acid or an anhydride thereof and a radical reaction initiator are continuously inserted at the ethylene-to unsaturated carboxylic acid compound or its anhydride ratio of 10,000:1 to 100:2, into a reaction zone which is kept under such ~l 7 1 $7~
conditions as, for example, a pressure of 1,000 to 3,000 atm, and a temperature of 90 to 300 ~. Thereby 3 to 20% of the ethylene is changed to a copolymer and the copolymer is continuously taken out from the reaction zone.
Examples of such an unsaturated carboxylic acid compound and the anhydride thereof include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, norbornene-5,6-dicarboxylic acid and an anhydride thereof.
They can be also used in the form of a terpolymer or a multi component copolymer wherein in addition to ethylene and an unsaturated carboxylic acid compound component, an unsaturated carboxylate such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate; a vinyl aromatic compound such as styrene, a-methylstyrene and vinyl toluene; a nitrile compound such as acrylonitrile and methacrylonitrile; a vinylpyridine such as 2-vinylpyridine and 4-vinylpyridine; a vinyl ether such as methyl vinyl ether, 2-chloroethyl vinyl ether; a vinyl halide such as vinyl chloride and vinyl bromide; a vinyl ester such as vinyl acetate; or acryl amide are used as a third copolymer component.
These copolymers can be used alone or in admixture of two or more compounds.
One of the copolymers is available form Mitsubishi Petrochemical Co. LTD.,as "YUKALON EAA A500W".
(c) Copolymer of ethylene and an unsaturated compound containing hydroxyl group An illustrative example of the copolymer of ethylene and an unsaturated compound containing hydroxyl group is a polymer wherein, for example, ethylene and 2-hydroxyethylmethacrylate are copolymerized randomly or at certain set intervals. Here, from the structural point of view, this refers to all polymers having a structure wherein an unsaturated compound containing hydroxyl group is copolymerized .
randomly or regularly in a branched or linear carbon chain.
Examples of such a copolymer include a polymer in theform of a liquid, semi-solid or solid at normal temperatures, having a content of the unsaturated compound containing hydroxyl group of 0.1 to 50 % by weight, preferably 0.5 to 45 % by weight, more preferably 1 to 40 % by weight, and a molecular - weight of 200 to 200,000, preferably 500 to 150,000, and more preferably 800 to 100,000.
The copolymer of ethylene and an unsaturated compound containing hydroxyl group may be produced from ethylene and the unsaturated compound containing hydroxyl group, by a known method such as a high pressure radical polymerization process.
In the case of a high pressure radical polymerization process, ethylene, an unsaturated compound containing hydroxyl group and a radical reaction initiator are continuously inserted at the ethylene to unsaturated compound containing hydroxyl group ratio of 1:0.0001 to 1:0.02, into a reaction zone which is kept under such conditions as, for example, a pressure of 1,000 to 3,000 atm, and a temperature of 90 to 280 ~. Thereby 3 to 20% of the ethylene is changed to a copolymer and the copolymer is continuously taken out from the reaction zone.
Examples of such an unsaturated compound containing hydroxyl group include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxylpropyl methacrylate, poly(ethyleneglycol)monomethacrylate and the like.
They can be also used in the form of a terpolymer or a multi component copolymer wherein in addition to ethylene and a hydroxyl group containing unsaturated compound component, an unsaturated carboxylate such as methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate; a vinyl aromatic compound such as styrene, a-methylstyrene and vinyl toluene; a nitrile compound such as acrylonitrile and methacrylonitrile; a vinylpyridine such as 2-vinylpyridine and 4-vinylpyridine; a vinyl ether such as methyl vinyl ether and 2-chloroethyl vinyl -ether; a vinyl halide such as vinyl chloride and vinyl bromide;
a vinyl ester such as vinyl acetate; and acryl amide or the like are used as a third copolymer component.
These copolymers can be used alone or in admixtures of two or more compounds.
(i-2) Amount of the polymer blended into the above-mentioned thermoplastic polymer The polymer wherein a polar group has already been introduced is blended in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 9 parts by weight, more preferably 0.1 to 8 parts by weight with 100 parts by weight of the above-mentioned thermoplastic polymer. When the amount is below the above-mentioned range, the resulting adhesion becomes inferior and when the amount exceeds the above-mentioned range, the resulting molded product provides inferior mold releasing properties.
(ii) Graft modified polymer Modified polymers obtained by subjecting the following various polymers and compounds containing a polar group to graft reaction can also be used.
(ii-1) Polymers to be modified The polymers to be modified include a main chain a propylene-type polymer such as propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random copolymer;
an ethylene-type polymer such as a low density polyethylene (branched ethylene polymer), medium density, high density polyethylene (linear ethylene polymer), a polyolefin resin such as a copolymer of ethylene and an unsaturated compound such as unsaturated carboxylic acid; ethylene-propylene rubber (EPM), ethylene-propylene-nonconjugated diene rubber (EPDM) wherein 5-ethylidenenorbornene, 5-methylnorbornene, 5-vinylnorbornene and dicyclopentadiene and the like are used as a nonconjugated diene; an olefin type rubber such as ethylene-butene rubber (EBM) and ethylene-propylene-butene copolymer rubber;
-hydrogenated product of styrene butadiene rubber (SBR); a compound having a hydrogenated product of styrene-conjugated diene block copolymer such as a styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-ethylene-propylene styrene copolymer (SEPS), a hydrogenated product of a styrene-isoprene-butylene-styrene block copolymer and the like.
The preferable number average molecular weight of such a polymer is generally 50,000 or less, but polymers having an number average molecular weight of 30,000 or less, particularly those having the number average molecular weight of 1,000 to 30,000 are preferable.
The number average molecular weight corresponds to a value calculated from the number average molecular weight of polystyrene or polypropylene measured by a gel permeation chromatography method (GPC3 under the conditions shown below:
Apparatus: 150C ALC/GPC (Millipore Corp.) Column: AD80M/S (Showa Denko K.K.) Solvent: o-dichlorobenzene Temperature: 140 ~
Flow rate: lml/min.
Chaged amount: 200~1 Concentration: 2 mg/ml (0.2 wt% of 2,6-di-t-butylphenol was added as an antioxidant and the detection of concentration was carried out with a wave length of 3.42 ~m by an infrared spectrophotometer "MIRAN 1A"(FOXBORO
COMPANY)) (ii-2) Compound containing a polar group A compound containing a polar group employed according to the present invention is one or more compounds selected from an unsaturated carboxylic acid or a derivative thereof, and examples of such a compound include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, 3-butenoic acid, `` 2171575 crotonic acid, pentenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, maleic acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, norbornene-5,6-dicarboxylic acid, or a derivative thereof such as an anhydride, ester, amide, imide and metal salt. Among these, acrylic acid, methacrylic acid, maleic acid or an anhydride thereof are preferable. Particularly preferable is the use of maleic anhydride.
(ii-3) Graft reaction Graft reaction can be carried out, speci~ically by the use of 100 parts by weight of the above-mentioned polymer, and 0.01 to 10 parts by weight, preferably O.OS to 9 parts by weight, more preferably 0.1 to 8 parts by weight of at least one compound selected from either the unsaturated carboxylic acid or the derivative thereof, together with an organic peroxide in the presence of an appropriate catalyst or under heating and melting conditions.
Examples of the organic peroxide to be used include dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane; diacylperoxides such as acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, and 2,4-dichlorobenzoyl peroxide;
peroxy esters such as t-butyloxy acetate, t-butylperoxy butylate, t-butylperoxy-2-ethyl hexanote, t-butylperoxy laurylate, t-butylperoxy benzoate, di-t-butylperoxy isophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxy maleic acid, t-butylperoxy isopropyl carbonate, and cumylperoxy octate; peroxy ketals such as 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)octane, and 2,2-bis(t-butylperoxy)butane; and hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-dihydroperoxide. Among these, diacyl peroxides and peroxy esters are preferable, and particularly preferable are diacyl peroxides.
The organic peroxide is used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, most preferably 0.1 to 10 parts by weight for 100 parts by weight of the polymer.
The graft modified polymer is available, for example, from Sanyo Chemical Industries, Ltd. as "YOUMEX 1210"(trade name).
(4) Thermoplastic polymer containing an inorganic filler <1> Anorganic filler Examples of an inorganic filler of the present invention to be blended with the above-mentioned thermoplastic polymer for the injection molding described in paragraph (2) include talc, mica, glass fiber, whisker, carbon fiber, calcium carbonate, titanium oxide, carbon black, glass balloon and the like.
Among these, calcium carbonate and plate-shaped inorganic fillers such as talc and mica are preferable from the point of view of heat fusion properties.
Particularly preferable is talc which has an average particle size of 1 to 20 microns, more preferably it has a substantial length of 1 to 15 microns, and a particularly preferable average aspect ratio is 5 to 10.
"Substantial" length of the talc means that most of the talc particles have a length within that range.
The above-mentioned talc is produced by, for example, grinding a raw talc ore by an impact grinder or a micro-type grinder, followed by pulverization by a micron mill and a jet type pulverizer and classification by a cyclone or micron separator.
The average particle size is the value measured by a particle-size distribution analyzer by using a laser beam diffraction method, and as a measuring apparatus, for example, the LA-500 type apparatus produced by Horiba, Ltd. is desirable due to its high measurement precision. The diameter, length and aspect ratio are the values measured by a microscope etc.
As a preferable calcium carbonate, that having a specific surface area of 40,000 cm2/g or less is generally used, that having a specific surface area of 30,000 cm2/g or less, particularly of 5,000 to 30,000-cm2/g is more preferably used with that having an average particle size of 0.5 to 20.0 ~m being generally used, and that having an average particle size of 1.0 to 2.5 microns is preferably used.
These inorganic fillers are used generally in an amount of 1 to 40 parts by weight, preferably 3 to 3~ parts by weight, and more preferably 5 to 30 parts by weight for 100 parts by weight of the above-mentioned thermoplastic polymer.
When the amount of the filler blended is below the above-mentioned range, the resulting adhesive strength and dimensional stability (molding shrinkage) tend to be poor, and when it exceeds the above-mentioned range, the resulting moldability tends to be inferior.
The thermoplastic polymer described in the above-mentioned paragraph (2) can be used as a raw material for the thermoplastic polymer containing an inorganic filler according to the present invention. However, in order to improve adhesion with the molded crosslinked rubber, which is an effect of the present invention, it is preferable to replace a part or all of the thermoplastic polymer described in the above-mentioned paragraph (3) with a thermoplastic polymer wherein a polar group has been introduced.
From the view point of improving adhesion, it is preferable to replace all the thermoplastic polymers by the thermoplastic polymer wherein a polar group has been introduced, however, from the view point of mold releasing properties, the amount should be in the range of 0.01 to 20% by weight, preferably 0.05 to 10~ by weight, more preferably 0.05 to 8%, even more preferably 0.1 to 7% by weight.
The inorganic filler can be incorporated into the composition in an amount of 1 to 40 parts by weight based on 100 parts by weight of the thermoplastic polymer.
<2~ Production of a thermoplastic polymer containing an inorganic filler A thermoplastic polymer containing an inorganic filler to be used according to the production of the composite injection molded body of the present invention is produced by mixing and blending the above-mentioned thermoplastic polymer with an inorganic filler in the above-mentioned ratio by a kneader currently used for mixing thermoplastic polymers such as a Banbury mixer, kneader, single-screw extruder, and double-screw extruder.
(5) Others In order to further improve the adhesion of a molded crosslinked rubber with a thermoplastic polymer, it is preferable to coat the following primer on the portions of the surface of the molded crosslinked rubber that are in contact with the injected thermoplastic soft polymer, in a thickness of 0.01 to 100 ~m, preferably 0.1 to 80 ~m, by a spray, brush, coater or printing machine.
Preferable examples of such a primer include a hydrogenated styrene-butadiene-styrene block copolymer (SEBS) which is graft modified by maleic anhydride, similarly modified hydrogenated styrene-isoprene-styrene block copolymer (SEPS), similarly modified ethylene-propylene copolymer and similarly modified chlorinated polypropylene dissolved in a solvent such as toluene, xylene and methyl ethyl ketone.
[II3 Production of a composite injection molded product A composite injection molded product of the present invention can be produced by inserting and fixing a molded crosslinked rubber in a cavity of an injection molding die, and injecting a molten thermoplastic polymer onto the molded crosslinked rubber so that a composite resin molded product isformed wherein the injected thermoplastic polymer having a polar group is adhered on the surface of the molded crosslinked rubber. Also by inserting and fixing a molded crosslinked rubber in a cavity of an injection molding die, and injecting a molten thermoplastic polymer onto the molded crosslinked rubber, a composite resin molded product wherein the injected thermoplastic polymer containing an inorganic filler is adhered -and coated on the surface of the molded crosslinked rubber can be produced.
As for the conditions for the injection molding, the resin temperature is generally in the range of 180 to 280 ~, preferably 200 to 280 ~, the injection molding die temperature is generally in the range of 30 to 80 ~, preferably 40 to 80 ~, the injection molding pressure is generally in the range of 300 to 800 kgf/cm2, preferably 400 to 800 kgf/cm2, the holding pressure is generally in the range of 300 to 800 kgf/cm2, preferably 400 to 800 kgf/cm2, and the retention time is generally in the range of 15 to 60 seconds, preferably 20 to ~0 seconds.
According to the present invention, a composite injection molded product having a complex shape and a relatively large size can be produced, thus the composite injection molded product of the present invention is useful for a wind shield gasket, or for weatherstrip of an automoble, or for various gaskets used as building materials.
Brief Description of the Drawings Fig.1 is a plan view of a part of an automobile weatherstrip.
Fig.2 is a plan view of an automobile weatherstrip.
Description of the Preferred Embodiments The method for producing the composite injection 217i575 molded product of the present invention will be illustrated by the following Examples and Comparative Examples.
The raw materials and the evaluation method employed in the Examples and Comparative Examples are as follows.
Example group A
(Corresponding to "containing a polar group" of the present invention) [I] ~aw materials (1) Thermoplastic polymer <1> Thermoplastic elastomer component TPE-1:
"Thermorun 3801B" produced by Mitsubishi Chemical Corporation (partially crosslin~ed olefin type thermoplastic elastomer, ASTM D2240(Type A) hardness: 87) TPE-2:
"Thermorun 2920B" produced by Mitsubishi Chemical Corporation (uncrosslinked olefin type thermoplastic elastomer, ASTM D2240(Type A) hardness: 96) TPE-3:
A mixture of "Thermorun 3551B" produced by Mitsubishi Chemical Corporation (partially crosslinked olefin type thermoplastic elastomer, ASTM D2240(Type A): 55) and "RABALON
T3314B" produced by Mitsubishi Chemicai Corporation (styrene type thermoplastic elastomer, ASTM D2240(Type A) hardness: 30) blended at 7:3 ASTM D2240 (Type A) hardness: 43).
<2> Modification method Method 1 (M1):
A Propylene-ethylene random copolymer containing 3~ by weight of ethylene was subjected to thermal oxidation at 300 to 350 ~, and maleic anhydride groups were grafted to both ends of the main chain as well as into the main chain of the polymer in an amount of 10% by weight of the whole polymer using 1,1'-azobis(cyclohexane-1-carbonitrile) which is an azo type free-radical initiator. The maleic anhydride groups were then neutralized with ethanol amine to give a modified propylene polymer. The modified propylene polymer having a MFR (230 t, 2.16 kg load) of 50 g/10 min, a number average molecular weight in terms of polypropylene of 7,000, was used.
Method 2 (M2):
Into an autoclave having a capacity of 500 ml, were added 100 g of 1,3-butadiene, 70 g of isopropyl alcohol and 10 g of 60~ aqueous hydrogen peroxide solution, and polymerization was carried out in argon atmosphere at 90 ~ for 5 hours. After the reaction was finished, unreacted monomers were removed and the resulting butadiene polymer was dried. The hydroxyl value of the resulting polymer was about 44.5 KOHmg/g.
Into an autoclave having a capacity of 200 ml, were added 50 g of thus obtained butadiene polymer, 50 g of cyclohexane and 5 g of 5% by weight ruthenium catalyst supported on carbon and the system was purged with argon gas. Then hydrogen gas was introduced until the pressure of the hydrogen reached 50 kg/cm2. The system was heated to 100 ~, and reaction was carried out for 10 hours while the hydrogen gas was supplied so that the total pressure was kept at 50 kg/cm2. After the reaction was finished, hydrogen was removed and the catalyst was removed by filtration and the resulting hydrogenated product was precipitated in methanol, filtered out and dried. The hydrogenated butadiene polymer product thus obtained was used, i.e., a waxy polyolefin polyol having hydroxyl groups at both ends (with an iodine value of 1.0 g/100 g, a hydroxyl value of 44 KOHmg/g, and a number average molecular weight in terms of polystyrene of 5,400) was used.
Method 3 (M3):
An ethylene acrylic acid copolymer having an acrylic acid content of 20 % by weight, an MFR (190 ~, 2.16 kg load) of 300 g/10 min, and a number average molecular weight in terms of polystyrene of 25,000, was used.
i 2171 575 Method 4 (M4):
Maleic anhydride in an amount of 40 g and benzoyl peroxide in an amount of 40 g were dry blended with 5 kg of TPE-1 and melted and kneaded to carry out graft modification in a double-screw extruder which was set at the preset temperature of 160 to 200 ~, the rotation number of 300 rpm, and the discharge rate of 10 kg/h, to give a modified TPE-1 wherein 0.6% by weight of maleic anhydride was added.
(2) Molded crosslinked rubber EP-1:
A sheet made of crosslinked EPDM (crosslinked by sulfur, ASTM D2240 (Type A) hardness of 74, carbon concentration of 40~ and crosslinking degree of 95%) was used.
Example A1 A crosslinked rubber sheet EP-1 ~thickness: 3 mm) was cut to a width of 30 mm and a length of 100 mm to produce an insert molded product. Then the surface of the insert molded product to be joined with an injection molding material was wiped with isopropyl alcohol to remove dust and dirt.
Then, the insert molded product was placed and fixed into the movable half of the cavity of a die for forming a sheet of 100 mm x 100 mm x 3 mm, and a thermoplastic polymer comprising 100 parts by weight of TPE-1 and 5 parts by weight of the modified propylene polymer obtained in the modification method 1 (M1) was injected to produce an injection molded, double layer test piece.
As for the conditions of the injection molding, an inline screw type injection molding machine (a small injection molding machine produced by Toshiba Machine Co., Ltd. : IS9OB) was used, the resin temperature was 240 ~, the die temperature was 40 ~, the injection pressure was 600 kgf/cm2, the retaining pressure was 600 kgf/cm2, and the pressure retaining time was 30 seconds.
Three sample chips (75 mm x 2~ mm x 3 mm) for evaluation were cut out from the double layer test piece and the sample chips for evaluation were sub~ected to measurement of adhesion strength using a tension testing machine (tension speed 500 mm/min). The average values are given in Table A1.
Examples A2-A7, Comparative Examples A1-A3 Double layer test pieces were obtained in a manner similar to that of Example Al except that the thermoplastic polymer laminated by injection molding was changed to the compositions given in Table A1.
The adhesive strength between the two layers is given in the Table.
Table Al - Example No. Comparative Example No.
Al A2 A3 A4 A5 A6 A7Al A2 A3 Thermoplastic polymer Elastomer TPE-l TPE-l TPE-l TPE-l TPEl TPE-2 TPE-3 TPE-l TPE-2 TPE-3 Amount of elastomer(pbw) 100 100 100 100 100 100 100 100 100 100 Modification method Ml M2 M3 M4 Ml Ml Ml Amount of modified elastomer(pbw) 5 5 5 5 3 5 5 Molded product of crosslinked rubber EP-l EP-l EP-l EP-l EP-l EP-l EP-l EP-l EP-l EP-l Adhesion strength ~kg/cm2) 45 40 42 40 38 48 30 30 35 20 Example group B
(Corresponding to "containing an inorganic filler" of the ` 2171575 present invention) lI] Raw materials (1) Thermoplastic polymer <1> Thermoplastic elastomer component TPE-4;
50% by weight of ethylene-propylene-nonconjugated diene rubber (EPDM, wherein 5-ethylidenenorbornene was used as a nonconjugated diene, obtained from Japan Synthetic Rubber Co., Ltd. under the trade name of "EP 98"), 10% by weight of paraffin oil (process oil "PW 380" produced by Idemitsu Kosan Co., Ltd.) and 40% by weight of polypropylene ("BC2" produced by Mitsubishi Chemical Corporation) were put in a Banbury mixer having a capacity of 4 liters and kneaded for about 5 minutes at 170~ and 60 rpm, it was then made into sheeting using rollers, and the sheeting was subjected to a sheet cutter to produce pellets.
100 parts by weight of the pellets produced, 1.0 part by weight of l1,3-bis(tert-butylperoxyisopropyl)]benzene obtained from KAYAKU AKZO COPPOPATION under the trade name of "Perkadox 14/40", 0.4 parts by weight of divinyl benzene, 0.8 parts by weight of carbon black, 0.1 parts by weight of Irganox 1010 produced by Ciba-Geigy AG, and 0.1 parts by weight of Sanol 770 produced by Sanyo Company Limited were blended together and mixed by a Henschel mixer at a normal temperature for 1 minute, then subjected to dynamic crosslinking at 200 ~ and 210 rpm by a double-screw extruder (PCM 45 produced by Ikegai Corporation) to obtain a partially crosslinked olefin type thermoplastic elastomer (ASTM D2400 (Type A) hardness: 85).
TPE-5:
40% by weight of ethylene-propylene-nonconjugated diene rubber (EPDM, wherein 5-ethylidene norbornene was used as a nonconjugated diene, obtained from Japan Synthetic Rubber Co., Ltd. under the trade name of "EP 98"), 10% by weight of paraffin oil (process oil "PW 380" produced by Idemitsu Kosan Co., Ltd.) and 50% by weight of polypropylene ("BC2" produced by Mitsubishi `` 2171575 Chemical Corporation) were put in a Banbury mixer having acapacity of 4 liters and kneaded for about 5 minutes at 170 ~
and 60 rpm. Then it was made into sheeting by rollers, and the sheeting was subjected to a sheet cutter to produce pellets.
100 parts by weight of the pellets produced, 0.8 parts by weight of carbon black, 0.1 parts by weight of Irganox 1010, and 0.1 parts by weight of Sanol 770 were blended together and mixed by a Henschel mixer at room temperature for 1 minute, then subjected to kneading at 200 ~ and 210 rpm by a double-screw extruder (PCM 45 produced by Ikegai Corporation) to obtain a noncrosslinked olefin type thermoplastic elastomer ASTM D2400 (Type A) hardness: 95).
TPE-6:
100 parts by weight of a mixture comprising 70% by weight of TPE-1, 15% by weight of styrene-ethylene-butylene-styrene copolymer (SEBS, "Kraton G1651" produced by Shell Japan Ltd.), and 15% by weight of paraffin oil (process oil "PW 380"
produced by Idemitsu Kosan Co., Ltd.), 0.8 parts by weight of carbon black, 0.1 parts by weight of Irganox 1010, and 0.1 parts by weight of Sanol 770, were blended together and mixed by a Henschel mixer at normal temperature for 1 minute, and then subjected to kneading at 200 ~ and 210 rpm by a double-screw extruder (PCM 45 produced by Ikegai Corporation) to obtain a thermoplastic elastomer (ASTM D2240 (Type A) hardness: 45).
<2> Inorganic fillers Filler 1 (F1):
Talc having a specific surface area of 38,000 cm2/g, an average particle size of 2.8 ~m, and an average aspect ratio of 6.
Filler 2 (F2~:
Calcium carbonate having a specific surface area of 11,000 cm2/g, and an average particle size of 3.5 ~m.
<3> Modification method Method 5 (M5):
A propylene-ethylene random copolymer containing 3% by weight of ethylene, having an MFR (230 ~, 2.16 kg load) of 50 g/10 min, and a number average molecular weight in terms of polypropylene of 7,000 was subjected to thermal oxidation, and maleic anhydride was grafted to both ends of the main chain as well as into the main chain of the polymer in an amount of 10 by weight of the whole polymer by using azoisobutyronitrile which was an azo type free-radical initiator. The maleic anhydride was then neutralized with ethanol amine to give a modified propylene polymer. The resulting modified propylene polymer was used.
Method 6 (M6):
A waxy polyolefin polyol having a terminal hydroxyl group (wherein the iodine value was 1.0 g/100 g, the hydroxyl value was 44 KOHmg/g, and the number average molecular weight in terms of polystyrene was 5,400) was used.
Method 7 (M7):
An ethylene-acrylic acid copolymer having an acrylic acid content of 20% by weight, a MFR (190 ~, 2.16 kg load) of 300 g/10 min, and a number average molecular weight in terms of polystyrene of 25,000 was used.
Method 8 (M8):
Maleic anhydride in an amount of 40 g and benzoyl peroxide in an amount of 40 g were dry-blended with 5 kg of TPE-4 and melted and kneaded to carry out graft modification in a double-screw extruder which was set at the preset temperature of 160 to 200 ~, a rotation of 300 rpm, and a discharge rate of 10 kg/h, to give a modified TPE-4 wherein 0.6% by weight of maleic anhydride was added.
(2) Molded crosslinked rubber EP-2:
A sheet made of crosslinked EPDM (crosslinked by sulfur, ASTM D2240 (Type A) hardness of 74, a carbon concentration of 40% and a crosslinking degree of 95% or more) -~6-was used.
[II] Experiment examples Examples B1-B2 A crosslinked rubber sheet ~thickness: 3 mm) obtained by crosslinking EPDM with sulfur was precisely cut to a width of 30 mm and a length of 100 mm to produce an insert molded product.
The surface of the insert molded product to be joined with an injection molding material was then wiped with isopropyl alcohol to remove dust and dirt.
Next, the insert molded product was placed and fixed in the movable half of a cavity of a die for forming a sheet (internal dimensions: 100 mm x 100 mm x 3 mm) and a thermoplastic polymer comprising 100 parts by weight of TPE-4 and 30 parts by weight of filler-1 as shown in Table B1 was injected to produce an injection molded, double layer test piece having a thickness of 3 mm.
As for the conditions of the injection molding, an inline screw type injection molding machine (a small injection molding machine produced by Toshiba Machine Co., Ltd.:IS 90 B) was used, the resin temperature was 240 ~, the die temperature was 40 ~, the injection pressure was 600 kgf/cm2, the retaining pressure was 600 kgf/cm2, and the pressure retaining time was 30 seconds.
Three sample chips for evaluation [length: 75 mm, width: 25 mm, and thickness: 3 mm, comprising an injection molded part (length: 45 mm, width: 25 mm and thickness: 3 mm) and a crosslinked rubber part (length: 30 mm, width: 25 mm, thickness: 3 mm) bonded by a joint surface of 25 mm x 3 mml were cut out of each of the double layer test pieces (length: 100 mm, width: 100 mm, and thickness: 3 mm) and these sample chips for evaluation were subjected to measurement of adhesion strength and a degree of material breakdown using a tension testing machine (tension speed 500 mm/min). The average values are - 2 l 7 1 57 5 given in Table B1.
Examples B3 The crosslinked rubber sheet (thickness of 3 mm) used in Example B1 was precisely cut to a width of 30 mm and a length of 100 mm to produce an insert molded product.
The surface of the insert molded product to be joined with an injection molding material was then wiped with isopropyl alcohol to remove dust and dirt.
Next, the insert molded product was placed and fixed in the movable half of a cavity of a die for forming a sheet (100 mm x 100 mm x 3 mm) and a thermoplastic polymer comprising 100 parts by weight of TPE-4, 5 parts ~y weight of the modified propylene polymer obtained in modification method 1 and 30 parts by weight of filler 1, as shown in Table B1, was injected to produce an injection molded, double layer test piece.
As for conditions of the injection molding, an inline screw type injection molding machine (a small injection molding machine produced by Toshiba Machine Co., Ltd.:IS 90 B) was used, the resin temperature was 240 ~, the injection molding die temperature was 40 ~, the injection pressure was 600 kgf/cm2, the retaining pressure was 600 kgf/cm2, and the pressure retaining time was 30 seconds.
Three sample chips for evaluation llength: 75 mm, width: 25 mm, and thickness: 3 mm, comprising an injection molded part (length: 45 mm, width: 25 mm and thickness: 3 mm) and a crosslinked ru~ber part (length: 30 mm, width: 25 mm, thickness: 3 mm) ~onded with a joint surface of 25 mm x 3 mm]
were cut out of one double layer test piece shown in Fig.1 (length: 100 mm, width: 100 mm, and thickness: 3 mm) and su~jected to measurement of adhesion strength using a tension testing machine (tension speed 500 mm/minutes). The average values are given in Ta~le B1.
Examples B4-B12 and Comparative Examples Bl-B3 Double layer test pieces were obtained in a manner similar to that of Example Bl or B3 except that the thermoplastic polymer to be by injected and molded was changed to the compositions given in Table B1.
The adhesive strength between the two layers is shown in Table Bl.
.
Table Bl Example No.
Bl B2 B3 B4 B5 B6 B7 B8 Thermoplastic polymer Elastomer TPE-4 TPE-4 TPE-4 TPE-4 TPE-4 TPE-4 TPE-4 TPE-5 Amount of elastomer(pbw) 100 100 100 100 100 100 100 100 Filler Fl F2 Fl Fl Fl Fl Fl Fl Amount of filler (pbw) 30 30 30 30 30 30 30 30 Modification method - - M5 M6 M7 M8 M5 Amount of modified elastomer (pbw) - - 5 5 . 5 5 3 Molded product of crosslinked rubberEP-2 EP-2 EP-2 EP-2 EP-2 EP-2 EP-2 EP-2 Adhesion strength (kg/cm2) 39 38 46 42 43 43 42 43 Degree of material breakdown (~) 70-80 50-60 290 290 290 290 290 70-80 Table B1 (continued) Example No. Comparative Ex. No B9 B10 Bl 1 B12 Bl B2 B3 Thermoplastic polymer Elastomer TPE-5 TPE-6 TPE-6 TPE-6 TPE-4 TPE-5 TPE-6 Amount of elastomer(pbw) 100 100 100 100 100 100 100 Filler Fl Fl Fl Fl Amount of filler (pbw) 30 30 30 15 - _ _ Modification method M5 - M5 M5 Amount of modified elastomer (pbw) Molded product of crosslinked rubberEP-2 EP-2 EP-2 EP-2 EP-2 EP-2 EP-2 Adhesion strength (kg/cm2) 50 26 32 40 30 35 20 Degree of material breakdown(X) - ~90 70-80 290 50-60 20-30 20-30 20-30
Claims (9)
1. A composite molded product in which a molded crosslinked rubber (I) is integrally bonded with a molded product (II), the base material thereof comprising (a) a thermoplastic polymer containing a polar group or (b) a thermoplastic polymer containing an inorganic filler.
2. A composite molded product according to claim 1, wherein the polar group of the thermoplastic polymer containing a polar group is selected from the group consisting of a hydroxyl group, carboxyl group and carboxylic acid anhydride group.
3. A composite molded product according to claim 1, wherein the inorganic filler is blended in an amount of 1 to 40 parts by weight for 100 parts by weight of the thermoplastic polymer.
4. A composite molded product according to claim 1, wherein the thermoplastic polymer comprises an olefin-type thermoplastic polymer and an olefin type elastomer used in a ratio of 10:90 to 90:10 (% by weight).
5. A composite molded product according to claim 1 wherein the hardness of the composite product (II) according to ASTM D2240 (Type A) is 20 to 98.
6. A composite molded product according to claim 3, wherein said thermoplastic polymer is a composition containing (i) 0.01 to 20% by weight of a thermoplastic polymer containing a polar group, and (ii) 80 to 99.99% by weight of a thermoplastic polymer containing no polar group.
7. A composite molded product according to claim 1, wherein the inorganic filler is talc having an aspect ratio of 5 to 10.
8. A composite molded product according to claim 1, wherein the composite molded product is a wind shield gasket of a car, or a weatherstrip.
9. A composite molded product according to claim 1, which is produced by placing a molded crosslinked rubber (I) in an injection molding die, injecting (a) a thermoplastic polymer containing a polar group and/or (b) a thermoplastic polymer containing an inorganic filler into the molding die by fusion injection, thereby producing a molded prduct (II), and integrally bonding the product (II) onto the molded crosslinked rubber (I).
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-55582 | 1995-03-15 | ||
| JP5558295A JPH08244068A (en) | 1995-03-15 | 1995-03-15 | Manufacture of combined injection molding |
| JP7-290077 | 1995-11-08 | ||
| JP29007795A JPH09131751A (en) | 1995-11-08 | 1995-11-08 | Manufacture of composite injection molded body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2171575A1 true CA2171575A1 (en) | 1996-09-16 |
Family
ID=26396472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2171575 Abandoned CA2171575A1 (en) | 1995-03-15 | 1996-03-12 | Composite molded product |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2171575A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6777498B2 (en) | 2001-08-31 | 2004-08-17 | Mitsui Chemicals, Inc. | Olefin thermoplastic elastomer, process for producing the same and use thereof |
| WO2014171905A1 (en) * | 2013-04-18 | 2014-10-23 | Conta Elastik Urunler San. Ve Tic. A.S. | A coated and foamed sealing member |
-
1996
- 1996-03-12 CA CA 2171575 patent/CA2171575A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6777498B2 (en) | 2001-08-31 | 2004-08-17 | Mitsui Chemicals, Inc. | Olefin thermoplastic elastomer, process for producing the same and use thereof |
| WO2014171905A1 (en) * | 2013-04-18 | 2014-10-23 | Conta Elastik Urunler San. Ve Tic. A.S. | A coated and foamed sealing member |
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