JP2654356B2 - Thermoplastic elastomer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer composition. More specifically, it has excellent flexibility, rubber elasticity over a wide temperature range, high temperature creep performance, low temperature impact resistance, mechanical strength, moldability, and oil resistance and light discoloration resistance despite being a thermoplastic elastomer composition. The present invention relates to a novel thermoplastic elastomer composition which is excellent in color matching property and can be used as a material for various molded articles.

[0002]

2. Description of the Related Art In recent years, thermoplastic elastomers which are rubber-like soft materials which do not require a vulcanization step and have the same moldability as thermoplastic resins have been used in automobile parts, home electric parts, wire covering materials, medical parts. , Miscellaneous goods and footwear. As a typical example of the structure of a thermoplastic elastomer, as disclosed in JP-A-61-34050 and the like, there is a type in which hard segments and soft segments are alternately contained in a copolymer chain. There is something. These elastomers are manufactured in various grades from those having high flexibility to those having rigidity by changing the ratio of each segment. In addition, there are other types of thermoplastic elastomers derived from inexpensive and readily available raw materials. That is, Japanese Patent Publication No. 53-2
No. 1021 as a thermoplastic blend of a monoolefin copolymer rubber and a polyolefin resin partially crosslinked with an organic peroxide as disclosed in JP-A-1021 or as a crosslinking aid for a monoolefin copolymer rubber and a polyolefin resin A composition that has been melt-kneaded using an organic peroxide and partially crosslinked corresponds to this.

However, in the former case of a thermoplastic elastomer having a structure in which hard segments and soft segments are alternately contained in a copolymer chain, a large amount of soft segments is required to obtain a flexible thermoplastic elastomer. Must be included. Usually, the soft segment has low tensile strength, and has poor heat resistance, fluidity, and oil resistance. Therefore, a flexible thermoplastic elastomer composition containing a large amount of such a soft segment still has low tensile strength and heat resistance. It has drawbacks such as poor fluidity and oil resistance, and cannot be used for various applications over a wide range. In addition, when a flexible grade thermoplastic elastomer is synthesized by a multi-stage synthesis method, it is necessary to synthesize the hard segment and the soft segment separately, so that the polymerization apparatus becomes very complicated and each segment in the polymerization stage is increased. It is very difficult to control the properties and proportions of
In addition, defective products may occur when switching grades. Further, it is very difficult to recover the produced polymer because it contains a large amount of rubbery ones. In the latter case, in the case of a thermoplastic elastomer composition having a structure in which a monoolefin copolymer rubber, which is one of the components, is partially crosslinked, oil resistance and shape recovery at a high temperature and the like are due to the partial crosslinkage. It cannot be used for various applications over a wide range because of insufficiency. In addition, since an organic peroxide is used, a polymer chain is cut off by radicals caused by the organic peroxide at the same time as crosslinking, resulting in a decrease in mechanical strength. A means for overcoming this drawback is disclosed in Japanese Patent Publication No. 58-46138. That is, this is a means in which only a crosslink of the monoolefin copolymer rubber is preferentially advanced by using a thermoreactive alkylphenol resin as a crosslinker. The thermoplastic elastomer obtained by this means is fully cross-linked and therefore has sufficient oil resistance and shape recovery properties at high temperatures, but the use of an alkylphenol resin results in extremely poor light discoloration resistance and free color adjustment. It cannot be used for applications such as automobile parts, home appliance parts, and electric wire coating, which require a high degree of reliability.

Further, US Pat. No. 4,803,244 proposes a method using an organic organosiloxane compound instead of an alkylphenol resin as a crosslinking agent. In this method, only the crosslinking of the monoolefin copolymer rubber can be preferentially advanced as in the case of the alkylphenol resin crosslinking, and a material excellent in oil resistance, shape recovery at high temperatures, and light discoloration resistance can be obtained. Therefore, it can be used for applications such as automobile parts, home appliance parts, and electric wire coating, which require a high degree of freedom in toning. However, in this method, the adhesion between rubber and resin is not sufficient because no compatibilizing agent is added, so that low-temperature impact resistance cannot be said to be satisfactory. It cannot be used for materials for airbag covers. Further, since there is no compatibilizer, the rubber is not sufficiently dispersed by the ordinary kneading method, and the extruded appearance of the molded product is extremely poor at present. So, U
2000 / sec as disclosed in SP4594390
A method of dynamically heat treating under high shear of c or more has been proposed to solve the above problem. However, in this method, the material itself is exposed to high shear even though the residence time is short, so that the material itself tends to decompose and deteriorate. Furthermore, in order to achieve high shear, not only the rotational speed during melt kneading, but also the clearance of the kneading machine is about 1/3 to 1 /
It is necessary to be about 5, which is not practical in terms of productivity of the thermoplastic elastomer composition and durability of the kneader. Furthermore, the known technology that has been proposed so far does not solve the essential problem of causing morphological changes such as re-agglomeration of the rubber dispersed by the annealing treatment, and as a result, the long-term reliability of the quality is not improved. At present, it cannot be used in the required automobile field.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve a problem which has been difficult with a conventional thermoplastic elastomer composition, and has an object to maintain good rubber properties over a wide temperature range. Due to its characteristics such as low-temperature impact resistance, wide degree of freedom in coloring, and low residual heavy metals,
An object of the present invention is to provide a thermoplastic elastomer composition that can be used for a wide variety of applications including applications requiring toning, hygiene, and long-term reliability.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to an organosiloxane compound having excellent photo-discoloration resistance and biocompatibility as a cross-linking agent and having two or more SiH groups in a molecule having the property of selectively cross-linking rubber. In addition, by using a hydrosilylation catalyst to perform cross-linking while melt-kneading, selective cross-linking of rubber is performed, and furthermore, a compatibilizer is used to improve the adhesive strength at the interface between the rubber and the thermoplastic resin, Based on the technical idea of highly dispersing crosslinked rubber particles without relying only on shearing force, we have been conducting research, and as a result, have good rubber properties over a wide temperature range, low temperature impact resistance, A thermoplastic elastomer composition that can be applied to various applications over a wide range of colors, including applications in which a good molded appearance is required, can be obtained by a conventional kneader at a shear rate of 100 to 10 It found finding that can be achieved in a very sensible melt kneading conditions such as 0 / sec,
Based on the knowledge, the present inventors have further advanced various studies and completed the present invention. Further, since the thermoplastic elastomer composition produced according to the present invention has been subjected to a compatibilization method, it is difficult for morphological change to occur even if annealing treatment is performed, and as a result, it is very excellent in long-term reliability. I found it. That is, the present invention provides an unsaturated double bond-containing rubber (a), a thermoplastic resin (b), an organosiloxane crosslinking agent having two or more SiH groups in a molecule (c), a hydrosilylation catalyst (d), And a compatibilizing agent (e), and dynamically heat-treated to obtain a thermoplastic elastomer composition. Specifically, based on 100 parts by weight of the unsaturated double bond-containing rubber (a),
5-300 parts by weight of thermoplastic resin (b), SiH in the molecule
Organosiloxane crosslinking agent having two or more groups (c)
0.5 to 30 parts by weight, hydrosilylation catalyst (d)
001 to 20 parts by weight, and compatibilizer (e) 0.5 to 20
Parts by weight, and if necessary, 30 to 300 parts by weight of a paraffinic oil (f), and then dynamically heat-treated to obtain a thermoplastic elastomer composition.

[0007] The unsaturated carbon-containing double bond group-containing rubber (a) used in the present invention is not particularly limited, and is generally commercially available rubber having a main chain and / or a side chain containing an unsaturated carbon double bond. Point to. For example, ethylene-
α-olefin-non-conjugated diene copolymer rubber, polybutadiene, polyisoprene, natural rubber, styrene-butadiene random copolymer rubber, styrene-isoprene random copolymer rubber, styrene-butadiene block copolymer rubber, styrene-isoprene An acrylonitrile-butadiene copolymer rubber most frequently used as a block copolymer rubber or an α, β-unsaturated nitrile-conjugated diene copolymer rubber is exemplified. Further, a partially hydrogenated rubber in which an aliphatic double bond contained in these rubbers is partially hydrogenated to reduce the degree of unsaturation can also be used. For example, a partially hydrogenated rubber having a hydrogenation ratio of less than 80% may be used. These rubbers may be one kind or a blend of two or more kinds. Here, the α-olefin in the ethylene-α-olefin-non-conjugated diene copolymer rubber composed of ethylene, α-olefin and non-conjugated diene preferably has 3 to 15 carbon atoms. As the non-conjugated diene, dicyclopentadiene, 1,4-hexadiene, ethylidene norbornene, methylene norbornene and the like can be used. In the present invention, propylene is suitable as the α-olefin from the viewpoint of easy availability and improvement of impact resistance. That is, EPDM is preferred. Ethylene-α-olefin-
The ethylene / α-olefin ratio of the non-conjugated diene copolymer rubber is preferably 50/50 to 90/10, more preferably 60/40 to 80/20 by weight. Here, the Mooney viscosity, ML1 + 4 (100 ° C.) of the rubber used is 10 to 1
20, preferably in the range of 40 to 100. If the Mooney viscosity is less than 10, preferable crosslinking cannot be obtained, and improvement of compression set at high temperature cannot be expected, which is not preferable. On the other hand, when the ratio exceeds 120, the moldability is remarkably deteriorated, and the appearance of the molded product is further deteriorated. The rubber preferably has an iodine value of 5 to 30, particularly preferably 10 to 20.

Next, the thermoplastic resin (b) used in the present invention is effective for improving the processability and heat resistance of the obtained composition. Here, the thermoplastic resin needs to be relatively inert to the hydrosilylation reaction of the rubber crosslinking reaction. Specific examples include crystalline or non-crystalline polyolefin resins, polystyrene resins such as ABS and polystyrene, vinyl chloride resins, polyamide resins, polyester resins, polycarbonate resins, polyacetal resins, and polyphenylene ethers. Resins and the like can be given. Further, two or more kinds of thermoplastic resins may be used in combination. Here, as the crystalline olefin resin, for example, polyethylene, isotactic polypropylene or propylene and a small amount of α
-Random or block copolymers of olefins,
Specific examples include a polypropylene-ethylene copolymer, a propylene-1-hexene copolymer, a propylene-4-methyl-1-pentene copolymer, and poly-4-methyl-1-pentene, polybutene-1 and the like. . MFR (ASTM-D) when isotactic polypropylene or its copolymer is used as the crystalline olefin resin
(-1238L condition, 230 ° C) is 0.1 ~ 50g / 10min.
Those having a range of 5 to 30 g / 10 minutes can be suitably used.
The amorphous olefin resin is a homopolymer having a cyclic olefin structure or a copolymer of a cyclic olefin and an α-olefin. When a crystalline olefin resin or a vinyl chloride resin is used, workability is particularly good, and when a polyamide resin or a polyester resin is used, heat resistance is good. The blending amount of the thermoplastic resin (b) is preferably from 5 to 300 parts by weight, more preferably from 10 to 200 parts by weight, per 100 parts by weight of the rubber component (a). 30
If the amount exceeds 0 parts by weight, the hardness of the obtained elastomeric composition tends to be high and the flexibility tends to be lost.
If the amount is less than parts by weight, processability tends to be poor.

The rubber crosslinking agent (c) used in the present invention is an organic organosiloxane compound having two or more SiH groups. This crosslinking method utilizes a selective addition reaction (hydrosilylation) of SiH groups to unsaturated hydrocarbons in the rubber component. In order to be a cross-linking agent, it is necessary to add to two or more molecules of rubber, so it is necessary to have two or more SiH groups in the molecule. Specific examples of such compounds are compounds having structures of cyclic polysiloxanes, linear polysiloxanes, and tetrahedral siloxanes as shown below. Further, a compound and / or a polymer derived from the compound may be used. Wherein m is an integer from 3 to 30, n is an integer from 0 to 200, R is hydrogen, an alkyl group, an alkoxy group, an aryl group or an aryloxy group, and (At least one silicon atom in which at least one R is hydrogen is present in two or more molecules in the molecule.) The organoorganosiloxane having the structure described above can selectively crosslink rubber.

The crosslinking reaction catalyst (d) used in the present invention
Refers to all catalysts that promote the hydrosilylation reaction.
Examples of the catalyst include a Group VIII transition metal such as palladium, rhodium, and platinum, or a compound or complex thereof. Also, peroxides, amines and phosphines are used. In addition, ultraviolet rays and γ rays can also be used. The most common catalyst is dicloclobis (acetonitrile)
Palladium (II), chlorotris (triphenylphosphine) rhodium (I), chloroplatinic acid and the like. Further, as the crosslinking reaction catalyst (d) used in the present invention, an organic peroxide-based catalyst can be suitably used. Examples of organic peroxides include 2,5-dimethyl 2,5-di (t-butylperoxy) hexane, 2,5 dimethyl 2,5-di (t-butylperoxy) hexyne-3, , 3-bis (t-butylperoxyisopropyl) benzene, 1,
Examples include 1-di (t-butylperoxy) 3,5,5 trimethylcyclohexane, 2,5 dimethyl 2,5 di (peroxybenzoyl) hexyne 3, and dicumyl peroxide. Further, a system in which an organic peroxide is used in combination with a bismaleimide compound as a promoter may be used as the catalyst. The bismaleimide compound used in the present invention includes N, N'-m-
There are phenylene bismaleimide and toluylene bismaleimide. As N, N'-m-phenylenebismaleimide, commercially available, for example, HVA-2 (manufactured by DuPont),
Succinol BM (manufactured by Sumitomo Chemical) or the like can be used. By using a peroxide catalyst, the thermoplastic elastomer composition obtained in the present invention can be suitably used in applications where residual heavy metals are a problem-for example, in the medical field. In order to further disperse the catalyst, the hydrosilylation catalyst (d) can be dissolved or supported on at least one selected from a liquid component and a solid component. That is, or dissolved in a solvent, or carried on an inorganic filler,
Alternatively, a method of combining both can be used. The solvent used here is not particularly limited, but needs to be relatively inert to the hydrosilylation reaction. Examples of the solvent type include hydrocarbons, alcohols, ketones, and esters. The concentration of the solution to be adjusted is not particularly limited. In addition, the inorganic filler needs to have an adsorption ability, calcium carbonate, carbon black, talc, magnesium hydroxide,
Examples thereof include mica, barium sulfate, natural silicic acid, synthetic silicic acid (white carbon), and titanium oxide. A known method can be used for adjusting the supported catalyst.

Here, the dynamically heat-treated, that is, dynamically vulcanized, thermoplastic elastomer composition is obtained by refluxing 1 g of the composition obtained in the present invention with boiling xylene in a Soxhlet extractor for 10 hours. The residue was filtered through an 80-mesh wire gauze, and the ratio of the dry weight of the insoluble matter remaining on the mesh (g) / the weight of the component a contained in 1 g of the composition was 1
A gel content of at least 30%, indicated by a value of 00,
Preferably, it is vulcanized so as to be 50% or more (however, insoluble components such as inorganic fillers are not included in this), and the vulcanization is performed during melt-kneading of the thermoplastic elastomer composition. It is characterized by the following. In order to obtain such a dynamically vulcanized thermoplastic elastomer composition, the compounding amount of the organic organosiloxane-based crosslinking agent (c) is determined by adjusting the amount of the component (a)
It can be suitably selected from 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight, and its gel content can be adjusted. The catalyst (d) can be arbitrarily added in an amount of 0.001 to 20 parts by weight per 100 parts by weight of the rubber component. The amount of the heavy metal catalyst is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 2 parts by weight. Further, in the case of a peroxide catalyst, the addition amount is 0.01 parts by weight or more.
15 parts by weight is preferred, and more preferably 0.1 to 10 parts by weight.
Parts by weight. Here, when the amount is less than 0.001 part by weight,
Crosslinking does not proceed at a practical rate. If the amount exceeds 20 parts by weight, not only is there no effect of increasing the amount, but the deactivated catalyst becomes blackish and becomes poor in appearance, and undesired side reactions (decomposition of unreacted SiH groups, etc.) tend to be caused by heat treatment. There is.

The compatibilizer (e) used in the present invention includes:
In the same molecule, there is a component having an affinity for each of the rubber and the thermoplastic resin, which acts as a surfactant. As a result, normal kneading conditions (shear rate:
The rubber vulcanized at 100 to 1000 / sec) is finely dispersed to 30 microns or less, and the adhesive strength at the interface between the vulcanized rubber and the thermoplastic resin is improved, thereby significantly improving the low-temperature impact resistance. It is added for the purpose of having it. No particular limitation is imposed on the monomer, oligomer, or polymer having any structure as long as the object is met. As a general structure of the compatibilizer, it is necessary that the rubber (a) and the thermoplastic resin (b) have components that are molecularly compatible with each other in the same molecule. On the other hand, in the case of a polymer of a single monomer, few have an affinity for both components having different molecular structures. Therefore, in general, the compatibilizer is preferably a block copolymer, a random copolymer, or a graft copolymer polymerized from two or more types of monomers. Such a copolymer may be a commercially available product, or may be prepared by oneself. For example, ethylene-propylene-diene terpolymer (EP
DM), examples of commercially available copolymers used as compatibilizers with hydrocarbon-based rubbers such as butyl rubber and thermoplastic resins among polystyrene-based resins, polycarbonate-based resins, polyphenylene ether-based resins, and polyolefin-based resins. Is a styrene-based copolymer. That is, a styrene-butadiene copolymer and a hydrogenated product thereof (including all of a random copolymer, a block copolymer, a graft copolymer, etc.) are mentioned. More specifically, a styrene-butadiene-styrene copolymer is used. Polymer (SBS),
Hydrogenated styrene-butadiene-styrene copolymer (SEB
S), isoprene-styrene copolymer, hydrogenated isoprene-styrene copolymer (SEP), styrene-isoprene-styrene copolymer (SIS), hydrogenated styrene-isoprene-styrene copolymer (SEPS), and the like. Can be Above all, styrene elastomers which significantly improve low-temperature impact resistance and are preferably used are SEBS and SEBS.
P, SEPS, among which the preferred styrene content is
10 to 80% by weight, more preferably 30 to 70% by weight
And most preferably 40 to 70% by weight.

Some typical structures of the compatibilizers are listed below. Combinations of the unsaturated double bond-containing rubber (a) and the thermoplastic resin (b) in which each compatibilizer suitably exerts its effect Is shown. The compatibilizer (e) is the following compatibilizer (e)
-1) or (e-2), when it is at least one compatibilizer selected from the group consisting of ethylene-α-olefin-non-conjugated diene copolymer as unsaturated double bond-containing rubber (a) At least one selected from rubber, vinyl aromatic compound-conjugated diene compound copolymer rubber, butadiene rubber, and butyl rubber, and a polyolefin resin as the thermoplastic resin (b);
It is suitably used in combination with at least one selected from a polystyrene resin, a styrene copolymer, and a polyphenylene ether resin. (E-1) Water obtained by hydrogenating a copolymer containing at least two terminal blocks A mainly composed of a vinyl aromatic compound and at least one intermediate polymer block mainly composed of a conjugated diene compound Addition block copolymer (e-2) Ethylene-α-olefin copolymer The combination of the unsaturated double bond-containing rubber (a) and the thermoplastic resin (b) described above has relatively good compatibility. is there. However, a highly functional thermoplastic elastomer composition can be produced by using, as a compatibilizer, a component having a good affinity for rubber and a thermoplastic resin in the block component as in (e-1). . As the compatibilizing agent (e-2), the unsaturated double bond-containing rubber (a) and the thermoplastic resin (b) are originally compatible with each other, but have a large molecular weight, so that the fluidity during melt-kneading deteriorates. Therefore, when the dispersion is poor, the improvement effect is particularly exhibited.

Next, the compatibilizing agent (e) is modified with the following epoxy group to form the compatibilizing agent (e-3), (e-4), (e-
5) When at least one compatibilizer selected from among the above, ethylene-α is used as the unsaturated double bond-containing rubber (a).
-One or more selected from olefin-non-conjugated diene copolymer rubber, vinyl aromatic compound-conjugated diene compound copolymer rubber, butadiene rubber, and butyl rubber, and a polyolefin-based resin or polyester-based thermoplastic resin (b) It is suitably used for one or more combinations selected from resins, polyamide resins and polycarbonate resins. (E-3) Epoxy obtained by hydrogenating a copolymer containing at least two terminal blocks A mainly composed of a vinyl aromatic compound and at least one intermediate polymer block mainly composed of a conjugated diene compound Modified hydrogenated block copolymer (e-4) Epoxy-modified ethylene-α-olefin (-non-conjugated diene) copolymer rubber (e-5) Epoxy-modified polyolefin resin In this combination, the thermoplastic resin is a polyolefin resin Has a group that reacts with the epoxy group, and has a compatibility with both the unsaturated double bond-containing rubber (a) and the thermoplastic resin (b) by reacting with the epoxy group. A graft copolymer having a property is formed. This graft copolymer allows the vulcanized rubber to be highly dispersed in the thermoplastic resin. If the thermoplastic resin is a polyolefin resin, because the compatibilizer itself has an affinity,
The vulcanized rubber can be highly dispersed in the thermoplastic resin.

Further, the compatibilizing agent (e) is modified with the following maleic anhydride to form a compatibilizing agent (e-6), (e-7),
The one or more compatibilizers selected from (e-8) are selected from the group consisting of ethylene-α-olefin-non-conjugated diene copolymer rubber and vinyl aromatic compound as unsaturated double bond-containing rubber (a). Conjugated diene compound copolymer rubber, butadiene rubber,
It is suitably used in a combination of at least one selected from butyl rubber and at least one selected from a polyolefin-based resin and a polyamide-based resin as the thermoplastic resin (b). (E-6) An anhydride obtained by hydrogenating at least two terminal blocks A mainly composed of a vinyl aromatic compound and at least one copolymer containing an intermediate polymer mainly composed of a conjugated diene compound. Maleic acid-modified hydrogenated block copolymer (e-7) Maleic anhydride-modified ethylene-α-olefin (-non-conjugated diene) copolymer rubber (e-8) Maleic anhydride-modified polyolefin-based resin Except for the polyolefin resin, the plastic resin has a group that reacts with maleic anhydride, and by reacting this with maleic anhydride,
A graft copolymer having an affinity for both the unsaturated double bond-containing rubber (a) and the thermoplastic resin (b) is formed. This graft copolymer allows the vulcanized rubber to be highly dispersed in the thermoplastic resin. When the thermoplastic resin is a polyolefin resin, the vulcanized rubber can be highly dispersed in the thermoplastic resin because the compatibilizer itself has an affinity. This compatibilizer is particularly preferably used when the thermoplastic resin is a polyamide resin.

Further, when the compatibilizer (e-9) is a modified polyolefin resin having an epoxy group and an ester group in the same molecule, the unsaturated double bond-containing rubber (a) may be ethylene-α-olefin. Non-conjugated diene copolymer rubber, vinyl aromatic compound-conjugated diene compound copolymer rubber, butadiene rubber, butyl rubber, α, β-unsaturated nitrile-conjugated diene copolymer rubber, one selected from acrylic rubber The above is suitably used in combination with at least one selected from the group consisting of a polyolefin resin, a polyester resin, a polyamide resin, a polycarbonate resin, a vinyl chloride resin and a methacrylate resin as the thermoplastic resin (b). Since the compatibilizer is a modified polyolefin resin having an epoxy group and an ester group in the same molecule, a wide range of thermoplastic resins that can react with or be compatible with this compatibilizer are available. The combination of the unsaturated double bond-containing rubber (a) and the thermoplastic resin (b) has an improving effect. Further, the compatibilizer (e-1)
0) is at least one compatibilizer selected from a halogenated olefin resin, a vinyl chloride-vinyl acetate copolymer, and a vinyl aromatic compound-α, β-unsaturated nitrile-conjugated diene copolymer; At least one selected from an acrylic rubber and an α, β-unsaturated nitrile-conjugated diene copolymer rubber as the unsaturated double bond-containing rubber (a), and a vinyl chloride resin as the thermoplastic resin (b) , A polyurethane resin and a methacrylate-based resin.

Examples of the compatibilizing agent for the hydrocarbon rubber and the thermoplastic resin with the polyolefin resin include (e-11), (e-12) and (e-13) shown below. Can be (E-11) Polyethylene having an epoxy group-containing polypropylene resin as an essential component and having a carboxylic acid anhydride and / or a carboxylic acid group in a molecule thereof, an ethylene-based copolymer, a styrene block copolymer and / or a hydrogenated product thereof ,
Compatibilizer obtained by melting and reacting at least one selected from carboxylic acid-modified resins such as styrene random copolymer and / or hydrogenated product thereof (e-12) Polypropylene having maleic anhydride group in the molecule Selected from among epoxy-modified resins such as polyethylene having an epoxy group, an ethylene-based copolymer, a styrene block copolymer and / or a hydrogenated product thereof, a styrene random copolymer and / or a hydrogenated product thereof. (E-13) a compatibilizer obtained by causing at least one kind to undergo a melt reaction; (e-13) a polypropylene as an essential component, polyethylene, an ethylene-based copolymer, a styrene block copolymer and / or a hydrogenated product thereof, a styrene random copolymer and Alternatively, a blend with at least one resin selected from hydrogenated products is dynamically added in the presence of a peroxide. The compatibilizer obtained by the treatment The modified resin having a maleic anhydride group and the modified resin having an epoxy group used as a raw material of the compatibilizers (e-11) and (e-12) can be easily obtained by a known technique. Can be.
That is, it can be obtained by a method of graft copolymerization using a peroxide or the like or by copolymerizing a resin monomer component.
These may be commercially available products. Ethylene is used as the modified resin having a maleic anhydride group used in the present invention.
Acrylic acid / maleic anhydride terpolymer, ethylene
Ethyl acrylate / maleic anhydride terpolymer, ethylene / methacrylic acid / maleic anhydride terpolymer,
Maleic anhydride-grafted polypropylene, maleic anhydride-grafted polyethylene, maleic anhydride-grafted ethylene-propylene copolymer, maleic anhydride-grafted styrene-ethylene-butylene-styrene block copolymer, maleic anhydride And a styrene-ethylene-butylene-styrene random copolymer obtained by grafting the above.

The epoxy-modified resin used in the present invention includes ethylene-glycidyl methacrylate copolymer or ethylene-acrylic acid-glycidyl acrylate terpolymer, ethylene acrylate-allyl glycyl ether terpolymer, ethylene Methacrylate
Glycidyl acrylate terpolymer, ethylene / propylene / glycidyl methacrylate terpolymer, polypropylene grafted with glycidyl methacrylate, styrene-ethylene / butylene-styrene block copolymer grafted with glycidyl methacrylate,
Styrene-ethylene-butylene-styrene random copolymer is exemplified. The compatibilizer (e-11) of the present invention (e
-12) is obtained by melting the above-mentioned composition comprising a modified resin having a maleic anhydride group in the molecule and a resin having an epoxy group in a batch-type kneader at 150 to 250 ° C for 5 to 30 minutes. . At the time of melt-kneading, a remarkable increase in torque occurs, and it is considered that some reaction occurs between the modified resin having a maleic anhydride group in the molecule and the resin having an epoxy group. The compatibilizer (e-
11) Examining the infrared absorption spectrum of (e-12), the characteristic absorption of the epoxy group and maleic anhydride group contained in the raw material disappeared, and it is considered that a reaction occurred between the epoxy group and the acid anhydride group. Can be

The compatibilizer (e-13) of the present invention comprises polypropylene as an essential component, and comprises polyethylene, ethylene-propylene copolymer rubber, styrene block copolymer and / or hydrogenated product thereof, styrene random copolymer and / or A blend with at least one resin selected from the hydrogenated products, an organic peroxide such as an organic perester, and a co-catalyst such as a bismaleimide-based compound, if necessary, are added to a batch kneader. At 150 to 250 ° C. for 5 to 30 minutes and co-crosslinking. Here, the addition amount of the organic peroxide catalyst is preferably 0.0001 to 2 parts by weight based on 100 parts by weight of the blend. If the peroxide catalyst is less than 0.0001 parts by weight, the reaction does not proceed at a practical rate. Further, if the amount is 2 parts by weight, not only does not have the effect of increasing the amount, but also tends to cause undesirable side reactions (such as decomposition of polypropylene and gelation reaction). Here, as for the compatibilizers (e-11) and (e-12), the ratio between the epoxy-modified resin and the maleic anhydride-modified resin is the same as (e-
For 13), the ratio of polypropylene to one or more resins selected from a specific group is from 10:90 to 90:10.
%, Preferably 70:30 to 30: 70% by weight, more preferably 60:40 to 40: 60% by weight. If the ratio of either component is less than 10% by weight, the effect of improving the interface adhesive strength tends to be insufficient, and the effect of improving the low-temperature impact resistance of the thermoplastic elastomer composition of the present invention tends to be insufficient. The compatibilizer (e
-11) (e-12) and (e-13) are particularly effective when the thermoplastic resin is an olefin resin or the rubber is a hydrocarbon resin such as EPDM or butyl rubber.

The compatibilizer (e) is a rubber component (a)
It is blended in an amount of 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight based on 100 parts by weight. When the amount is less than 0.5 part by weight, the effect of lowering the interfacial tension tends to decrease, and therefore the effect of improving the adhesive strength at the interface decreases, and the dispersed particles of the vulcanized rubber tend to increase. The effect of improving the low-temperature impact resistance of a thermoplastic elastomer is insufficient, and the appearance of a molded article tends to deteriorate. On the other hand, when the amount exceeds 20 parts by weight, the thermoplastic elastomer composition of the present invention tends to have high hardness and low-temperature impact resistance, and not to exhibit rubber elasticity as an elastomer.

The paraffinic oil (f) used in the present invention
Has an effect of adjusting the hardness of the obtained composition and giving flexibility, and is added as necessary. A mineral oil-based rubber softener generally called process oil or extender oil used for softening, increasing the volume, and improving processability of rubber is a mixture of an aromatic ring, a naphthene ring, and a paraffin chain. There are those in which the number of carbon atoms in the paraffin chain occupies 50% or more of the total number of carbon atoms is called paraffinic.
Those having a naphthene ring carbon number of 30 to 45% are naphthenic, and those having an aromatic ring carbon number exceeding 30% are aromatic. The oil used in the present invention is preferably a paraffinic oil in the above category, and a naphthenic or aromatic oil is not preferred in terms of dispersibility and solubility. The paraffin rubber softener has a kinematic viscosity at 37.8 ° C. of 20 to
500 cst, a pour point of -10 to -15 ° C and a flash point of 170 to 300 ° C. Paraffinic oil (f)
Is preferably from 30 to 300 parts by weight, more preferably from 30 to 300 parts by weight, per 100 parts by weight of the rubber component (a).
250 parts by weight. If the amount exceeds 300 parts by weight, the softener tends to bleed out, which may cause tackiness in the final product, and tends to lower the mechanical properties. If the amount is less than 30 parts by weight, the purpose of addition cannot be achieved.

The thermoplastic elastomer composition obtained by the production method of the present invention is superior in mechanical strength and compression set at high temperature to a thermoplastic elastomer composition partially crosslinked using an organic peroxide of a known technique. To give a composition comprising: In addition, a composition excellent in light discoloration resistance is provided as compared with a thermoplastic elastomer composition which is completely cross-linked using a heat-reactive alkylphenol resin of a known technique. Also, the use of a compatibilizer has significantly improved the adhesiveness of the interface between the rubber and the thermoplastic resin.
The low-temperature impact resistance is remarkably improved, and the appearance of a molded product is remarkably improved, as compared with a thermoplastic elastomer composition which is simply obtained by crosslinking by hydrosilylation using a heavy metal catalyst such as chloroplatinic acid. In addition to the above ingredients,
The composition of the present invention may further contain an inorganic filler, if necessary, particularly for applications in which toning is not required. This inorganic filler not only has the advantage of reducing the product cost as a bulking agent, but also has the advantage of giving a positive effect on quality improvement (heat-resistant shape retention, flame retardancy, etc.). Examples of the inorganic filler include calcium carbonate, carbon black, talc, magnesium hydroxide, mica, barium sulfate, natural silicic acid, synthetic silicic acid (white carbon), and titanium oxide. Carbon black is channel black, furnace black Etc. can be used. Of these inorganic fillers, talc and calcium carbonate are economically advantageous and preferred. Further, if necessary, a nucleating agent, an outer lubricant, an inner lubricant, a hindered amine light stabilizer, a hindered phenol antioxidant, a coloring agent, a silicone oil, and the like may be added. In addition, styrene block copolymer (SBC), ethylene-α ·
Other thermoplastic resins such as olefin copolymers and thermoplastic urethane resins can also be blended.

The method for producing the composition of the present invention includes:
All general methods used for producing ordinary resin compositions and rubber compositions can be employed. Basically, it is a mechanical melt kneading method, which includes a single screw extruder, a twin screw extruder,
Banbury mixer, various kneaders, Brabender, rolls and the like are used. At this time, the order of addition of each component is not limited.For example, rubber, resin components are preliminarily mixed with a mixer such as a Henschel mixer or a blender, melt-kneaded with the above-described kneader, and then a crosslinking agent and a catalyst component are added. The mixture is added and dynamically vulcanized, and then a compatibilizer is added and kneaded. When the scorch time of the rubber to be used is sufficiently long, an addition method such as melt-kneading components other than the catalyst in advance, further adding a catalyst, and melt-kneading may be employed. At this time, the temperature for melt-kneading is 180 ° C to 300 ° C, and the shear rate is 100 to 1
000 / sec. Further, a cured product of rubber is first manufactured using the components (a), (c), (d), and (f), and a crushed product of the cured rubber is added to the remaining components. The thermoplastic elastomer composition of the invention can be obtained. The method for obtaining a cured product of rubber is not particularly limited, and all methods used in the production of ordinary thermosetting resin compositions and thermosetting rubber compositions can be employed. Basically, it is a mechanical melt kneading method, in which a single screw extruder, a twin screw extruder, a Banbury mixer, various kneaders, a Brabender, a roll and the like are used. At this time, the temperature for melt-kneading is 180 ° C.
At 300 ° C., the shear rate can be suitably selected from 100 to 1000 / sec. In order to roughly crush the cured rubber produced through the above steps, it can be achieved by a usual crushing method. That is, a freeze-pulverization method using a pulverizer, particularly dry ice or liquid nitrogen, is suitably used. Further, an inorganic filler or the like can be used as a powdering agent. At this time,
When the rubber is sufficiently cured using a batch kneader such as a kneader, the rubber is coarsely crushed in the kneader without providing a pulverizing step, so that it is particularly preferably used. The dynamically vulcanized elastomer composition thus obtained is thermoplastic, and can be molded using a commonly used thermoplastic resin molding machine, and can be formed by injection molding, extrusion molding, calender molding, blow molding, etc. Various molding methods are applicable. That is, the dependency of the melt viscosity on the shear rate is particularly large, and the injection molding region having a high shear rate has a low viscosity and a high flow rate, so that the injection molding can be easily performed similarly to a general-purpose resin. In addition, in the extrusion / blow molding region with a medium shear rate, the viscosity becomes somewhat high,
Since this leads to low drawdown, extrusion and blow molding are also easy.

[0024]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The components blended in the following Examples and Comparative Examples are as follows. <Component a (1): EPDM> Ethylene-propylene-ethylidene norbornene copolymer rubber EP57C manufactured by Nippon Synthetic Rubber Co., Ltd. [Propylene content: 28% by weight Mooney viscosity ML1 + 4
(100 ° C.): 90 Iodine value: 15 Tg: −40 ° C.] <Component a (2): ANR> Acrylonitrile-butadiene copolymer rubber N240S manufactured by Nippon Synthetic Rubber Co., Ltd. [Acrylonitrile content: 26% by weight Mooney viscosity ML1
+4 (100 ° C.): 56] <Component a (3): SBR> Styrene-butadiene copolymer rubber JSR 1503 manufactured by Nippon Synthetic Rubber Co., Ltd. [Styrene content: 23.5% by weight Mooney viscosity ML1 + 4
(100 ° C.): 75] <Component a (4): BuR> Butyl Rubber JSR Butyl268 manufactured by Nippon Synthetic Rubber Co., Ltd. [Unsaturation degree: 1.5 mol% Mooney viscosity ML1 + 4 (12
5 ° C): 51]

<Component b (1): PP> Polypropylene Sumitomo Chemical Co., Ltd. W501 [MFR (230 ° C.) = 8.0 g / 10 minutes Heat deformation temperature: 115 ° C.] <Component b (2): PET> polyethylene Terephthalate Diamond Ray PA500 manufactured by Mitsubishi Rayon Co., Ltd. <Component b (3): Ny66> Polyamide (PA) -66 Ube Nylon 2020B manufactured by Ube Industries, Ltd. <Component b (4): PVC> PVC resin Sumitomo Chemical ( Smilyt SX-17 [straight Average polymerization degree: 1700]

<Component c (1): SiH> 1,3,5
7-tetramethylcyclotetrasiloxane manufactured by Toray Dow Corning Silicone Co., Ltd. <Component c (2): SiH> 1,1,3,3-tetramethylditetrasiloxane manufactured by Toray Dow Corning Silicone Co., Ltd. < Component d (1): Catalyst> chloroplatinic acid hexahydrate manufactured by Yasuda Pharmaceutical Co., Ltd. <Component d (2): catalyst> Dicumyl peroxide Nippon Yushi Co., Ltd. Park Mill D <Component d (3): catalyst> 1% by weight of component d (1)
A propanol solution was prepared, and 1 g of this solution was supported on 100 g of silica [Nipsil VN3 manufactured by Nippon Silica Co., Ltd.] and adjusted.

<Component e-1: SEBS> Styrene-ethylene-butylene-styrene copolymer (SEBS) Tuftec H1041 manufactured by Asahi Kasei Kogyo Co., Ltd. <Component e-3: EP-SEBS> Epoxy-modified styrene-ethylene-butylene -Styrene copolymer (SEBS) Tuftec Z514 manufactured by Asahi Chemical Industry Co., Ltd. <Component e-7: MAH-EP> Maleic anhydride-modified ethylene-propylene copolymer EP T7741P manufactured by Nippon Synthetic Rubber Co., Ltd. <Component e-9 : E-GMA-AM> ethylene-glycidyl methacrylate-methyl acrylate terpolymer Co., Ltd. Bondfast 7M manufactured by Sumitomo Chemical Co., Ltd. <Component e-10: VA-PVC> vinyl acetate-vinyl chloride copolymer Sumitomo Sumigraft GE manufactured by Chemical Industry Co., Ltd. <Component e-12: PP-MAH> A polypropylene oligomer having an average molecular weight of 4000 Relative to 100 parts by weight of those ends were modified with maleic anhydride, epoxy-modified styrene block copolymer Tuftec z 514 [Asahi Chemical Industry Co.,
80 parts by weight], thoroughly mixed with a Henschel mixer, melt-kneaded in a kneader at about 200 ° C. for 20 minutes, formed into a roll sheet, cooled to room temperature, pelletized with a sheet pelletizer, and made compatible according to the present invention. Agent e-12 was obtained. As a result of examining the infrared absorption spectrum of the compatibilizer e-12, the characteristic absorption of the epoxy group and the acid anhydride group contained in the raw material disappeared, and a reaction occurred between the epoxy group and the acid anhydride group. It seems to be. <Component f: OIL> Diana Process Oil PW-380 manufactured by Idemitsu Kosan Co., Ltd. [paraffin-based process oil, kinematic viscosity: 381.6 cst (40 ° C.), 30.1 (100)
° C), average molecular weight 746, ring analysis: CA = 0%, CN =
27%, CP = 73%]

<< Examples 1 to 84 and Comparative Examples 1 to 42 >> c
After sufficiently dry-blending all the components except the component and the d component, the thermoplastic composition before being extruded and dynamically vulcanized is melt-kneaded using a twin-screw kneader under the condition that the resin temperature becomes 190 to 270 ° C. This was pelletized. A considerable amount of the component c and the component d were added to the pellets, and the mixture was kneaded again using a twin-screw kneader at a shearing speed of 800 / SEC so that the resin temperature reached 190 to 270 ° C., and heat-cured. A plastic elastomer composition was obtained. Injection molding was performed using this composition, and the following various physical properties were evaluated. Examples are shown in Tables 1 to 14 and Comparative Examples are shown in Tables 15 to 21.

The evaluation method is as follows. (1) Hardness: JIS K6301 A type (2) Tensile strength TS [MPa] and Elongation Eb [%]: JI
(SK6301, No. 3 dumbbell) (3) Compression set CS [%]: JIS K6301, 25
% Compression 70 ° C × 22hr (4) Low temperature impact resistance: A test piece of 75 × 75 × t1 is immersed in a dry ice-methanol solution at −60 ° C. for 10 minutes, and a DuPont dropping ball impact test is performed. When no cracks were formed, it was evaluated as ○, and when cracks were formed, it was evaluated as X. [Test conditions Weight: 500 g Tip ball R: 3/16 Drop height: 1 m] (5) Oil resistance [%]: Use JIS K6301, No. 3 test oil (lubricating oil) at 70 ° C for 2 hours. A test piece of 50 × 50 × t2 was immersed, and the weight change (%) before and after immersion was determined. (6) Light discoloration resistance test: A natural composition was treated at 88 ° C. for 1000 hours using a sunshine weatherometer. And measured the color difference. (7) Formability test: Screw with L / D = 20 using a φ50 mm extruder and C / R = 3 using a 100 mm × t0.5 die.
0, at a kneading temperature of 200 ° C. and a rotation speed of 100 rpm, a tape of 150 × 500 mm was prepared, the surface was visually observed, and when one or more spots having a diameter of 100 μm or more were observed, ×, not observed. In this case, it was marked as ○. (8) Long-term reliability: A low-temperature impact test was performed according to (4) after the treatment at 100 ° C. for 1000 hours. When no cracks were formed after the test, it was evaluated as ○, and when cracks were generated, as ×.

In Comparative Examples 1 to 6, dynamic vulcanization was performed in the same manner as in Example except that 2 parts by weight of an organic peroxide [dicumyl peroxide (DCP)] and 3 parts by weight of divinylbenzene (DVB) were used. Made by the way. Further, in Comparative Examples 7 to 12, dynamic vulcanization was carried out using a heat-reactive alkylphenol resin [Schenectad.
y Chemicals SP1045] and 5 parts by weight of a crosslinking assistant [stannic chloride] except that 2 parts by weight were used. In Comparative Examples 13 to 18, an organoorganosiloxane was used as a cross-linking agent, and chloroplatinic acid hexahydrate similar to the component d in Example was used as a catalyst. from this result,
The thermoplastic elastomer composition dynamically vulcanized using the organic organosiloxane compound of the present invention and added with a compatibilizer has a higher mechanical strength than the thermoplastic elastomer composition dynamically vulcanized by blending a known organic peroxide system. And a composition having excellent compression set at 70 ° C. and excellent oil resistance. Further, it has been found that the composition of the present invention has a high degree of freedom in toning because of its good light discoloration resistance. Further, it was found that the vulcanized rubber particles were highly dispersed, and the low-temperature impact resistance was significantly improved.

Table 1 Example 1 2 3 4 5 6 Composition (parts by weight) EPDM 100 100 100 100 100 100 100 PP 100 200 95 95 195 100 PET 100 SiH 33 33 63 SiH 3 0.50.5 0.5 0.5 0.5 SEBS 10 10 10 10 10 10 OIL 100 200 190 280 100 100 Physical property hardness 81 88 78 89 84 85 TS (MPa) 19 18 14 13 19 19 Eb (%) 625 590 625 510 510 605 CS (%) 37 39 929 44 3334 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 15 9 15 914 14 15 Light discoloration resistance 8 7 8 8 9 8 Moldability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○

Table 2 Example 7 8 9 10 11 12 Composition (parts by weight) EPDM 100 100 100 100 100 100 PP 100 100 PET 100 195 100 100 SiH 33 33 SiH 33 33 Catalyst 0.5 0.5 0.5 0.5 0.5 SEBS 10 10 5 20 5 20 OIL 100 280 100 100 100 100 Physical property hardness 83 87 79 82 82 85 TS (MPa) 19 13 18 21 17 20 Eb (%) 620 540 620 580 580 610 540 CS (%) 34 42 33 39 31 38 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 12 9 13 13 14 12 Light discoloration resistance 9 88 89 89 Formability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○

Table 3 Example 13 14 15 16 17 18 Composition (parts by weight) EPDM 100 100 100 100 100 100 PP 100 100 100 PET 100 100 100 SiH 33 33 SiH 33 33 Catalyst 0.5 0.5 0.5 0.5 0.5 EP-SEBS 10 10 10 10 5 20 OIL 100 100 100 100 100 100 100 Physical property hardness 82 84 83 87 84 85 TS (MPa) 18 18 19 19 18 20 Eb (%) 580 570 570 540 580 540 CS (%) 35 33 38 36 32 39 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 11 10 14 11 13 11 Light discoloration resistance 9 10 8 9 10 10 Moldability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○

Table 4 Example 19 20 21 22 23 24 Composition (parts by weight) EPDM 100 100 100 100 100 100 PP 100 100 100 Ny66 100 100 100 SiH 33 33 SiH 33 33 Catalyst 0.5 0.5 0.5 0.5 0.5 MAH-EP 10 10 10 10 5 20 OIL 100 100 100 100 100 100 100 Physical properties Hardness 81 83 82 84 81 87 TS (MPa) 15 16 17 18 14 19 Eb (%) 600 595 610 580 630 550 CS (%) 37 35 35 34 34 37 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 14 13 14 12 15 13 Light discoloration resistance 8989 109 9 9 Moldability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○

Table 5 Example 25 26 27 28 29 30 Composition (parts by weight) EPDM 100 100 100 100 100 100 PP 100 200 95 195 100 PET 100 SiH 3 3 3 3 3 3 SiH 3 Catalyst 0.5 0.5 0.5 0.5 0.5 E-GMA-AM 10 10 10 10 10 20 OIL 100 200 190 280 100 100 Physical Hardness 81 88 78 89 84 85 TS (MPa) 19 18 14 13 19 19 Eb (%) 625 590 625 510 605 615 CS (%) 37 39 29 44 33 34 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 159 15 914 14 15 Light discoloration resistance 8 7 8 8 9 8 Moldability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○

Table 6 Example 31 32 33 34 35 36 Composition (parts by weight) ANR 100 100 100 100 100 100 PP 100 100 100 PET 100 100 100 SiH 33 33 SiH 33 33 Catalyst 0.5 0.5 0.5 0.5 0.5 0.5 0.5 E-GMA-AM 10 10 10 10 10 10 OIL 100 100 100 100 100 100 100 Physical property hardness 81 83 82 84 83 82 TS (MPa) 17 18 18 19 20 20 Eb (%) 600 600 590 560 610 620 CS (%) 34 32 35 31 32 29 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 12 11 13 8 11 11 Light discoloration resistance 9 9 8 9 10 10 Moldability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○

Table 7 Example 37 38 39 40 41 42 Composition (parts by weight) SBR 100 100 100 100 100 100 PP 100 100 100 PET 100 100 100 SiH 33 33 SiH 33 33 Catalyst 0.5 0.5 0.5 0.5 0.5 E-GMA-AM 10 10 10 10 10 10 10 OIL 100 100 100 100 100 100 100 Physical properties Hardness 79 83 82 84 83 82 TS (MPa) 15 16 16 17 18 18 Eb (%) 630 630 610 580 630 650 CS (%) 38 34 36 33 33 33 33 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 14 13 14 11 12 13 Light discoloration resistance 8 8 8 9 9 9 Moldability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○

Table 8 Example 43 43 45 45 46 47 48 Composition (parts by weight) BuR 100 100 100 100 100 100 100 PP 100 100 100 PET 100 100 100 SiH 33 33 SiH 33 33 Catalyst 0.5 0.5 0.5 0.5 0.5 E-GMA-AM 10 10 10 10 10 10 10 OIL 100 100 100 100 100 100 100 Physical properties Hardness 79 83 82 84 83 82 TS (MPa) 15 16 16 17 18 18 Eb (%) 630 630 610 580 630 650 CS (%) 34 30 32 30 30 28 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 10 10 11 9 9 10 Light discoloration resistance 77 77 88 88 Moldability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○

Table 9 Example 49 50 51 52 53 54 Composition (parts by weight) ANR 100 100 100 100 50 50 PVC 100 100 50 50 100 100 100 SiH 3 1.5 SiH 3 3 1.5 Catalyst 0.5 0.5 0.5 0.5 0.5 0.5 E-GMA-AM 10 10 10 VA-PVC 10 10 10 OIL 100 100 100 100 100 100 100 Physical properties Hardness 79 83 62 64 83 82 TS (MPa) 15 16 14 15 20 21 Eb (%) 530 530 560 580 430 450 CS (%) 34 30 27 25 40 38 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 10 10 11 9 9 10 Light discoloration resistance 9 9 9 9 9 9 Molding ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○

Table 10 Example 55 55 57 57 58 59 60 Composition (parts by weight) EPDM 100 100 100 100 100 100 PP 100 200 95 195 100 PET 100 SiH 3 3 3 3 3 3 3 3 3 SiH 3 Catalyst 0.5 0.5 0.5 0.5 0.5 PP-MAH 10 10 10 10 10 10 OIL 100 200 190 280 100 100 Physical property hardness 81 88 78 89 84 85 TS (MPa) 19 18 16 13 19 19 Eb (%) 635 595 630 510 510 605 615 CS (%) 36 38 28 42 31 32 Low temperature impact resistance ○ ○ ○ ○ ○ Oil resistance (%) 148 149 913 14 14 Light discoloration resistance 877 88 89 8 Moldability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○

Table 11 Example 61 62 63 64 65 66 Composition (parts by weight) EPDM 100 100 100 100 100 100 PP 100 200 95 195 100 100 100 SiH 3 3 3 3 6 SiH 3 3 2 Catalyst 0.2 0.2 0.20 .2 0.2 SEBS 10 10 10 10 10 10 OIL 100 200 190 280 100 100 Physical Hardness 80 86 75 89 83 82 TS (MPa) 19 17 14 12 20 20 Eb (%) 630 600 650 510 600 620 CS ( %) 35 39 29 44 34 36 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 14 9 15 8 14 15 Light discoloration resistance 8 7 8 9 9 8 Moldability test ○ ○ ○ ○ ○ ○ Long term reliability ○ ○ ○ ○ ○ ○

Table 12 Example 67 68 69 70 71 72 Composition (parts by weight) ANR 100 100 100 100 100 100 PET 100 195 100 100 100 100 100 SiH 3 3 3 SiH 3 3 3 Catalyst 2 2 2 2 2 EP-SEBS 10 10 10 10 10 E-GMA-AM 10 10 OIL 100 280 100 100 100 100 Physical properties Hardness 82 87 79 82 84 81 TS (MPa) 19 13 20 21 22 18 Eb (%) 640 540 620 580 580 590 640 CS (%) 33 42 33 33 32 32 33 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 138 13 13 13 12 12 Light discoloration resistance 89 89 89 89 Moldability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○

Table 13 Example 73 73 75 75 77 77 78 Composition (parts by weight) EPDM 100 100 100 100 100 100 PP 100 200 95 195 100 100 SiH 3 33 36 SiH 3 3 Catalyst 10 10 10 10 10 10 10 SEBS 10 10 10 10 10 10 10 10 10 OIL 100 200 190 280 100 100 Physical Properties Hardness 81 86 78 89 85 85 TS (MPa) 20 18 14 12 20 20 Eb (%) 630 600 650 510 600 620 CS (%) 35 39 28 43 43 32 34 Low Temperature Impact Resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 13 9 14 8 14 15 Light discoloration resistance 8 7 8 9 9 8 Moldability test ○ ○ ○ ○ ○ ○ Long term reliability ○ ○ ○ ○ ○ ○

Table 14 Example 79 80 81 82 83 84 Composition (parts by weight) ANR 100 100 100 100 100 100 PET 100 195 100 100 100 100 100 SiH 3 3 6 SiH 3 3 3 Catalyst 10 10 10 10 10 10 10 EP-SEBS 10 10 10 10 10 E-GMA-AM 10 10 OIL 100 280 100 100 100 100 Physical Properties Hardness 82 86 80 82 84 81 TS (MPa) 19 13 21 21 22 18 Eb (%) 640 540 600 570 580 630 CS (%) 32 41 32 32 32 32 33 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 12 8 12 12 12 10 Light discoloration resistance 89 89 89 89 Moldability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○

Table 15 Comparative Example 1 2 3 4 5 6 Composition (parts by weight) EPDM 100 100 100 100 100 100 PP 100 200 95 195 PET 100 195 DVB 3 3 3 3 3 3 DCP 2 2 2 2 2 OIL 100 200 190 280 100 280 Physical Properties Hardness 80 86 77 88 79 86 TS (MPa) 11 12 9 10 12 8 Eb (%) 510 480 500 430 490 480 CS (%) 4550 50 52 52 44 51 Low Temperature Impact Resistance X X X X X X Oil Resistance 18 19 22 13 19 12 Light discoloration resistance 8 7 8 9 9 8 Moldability test ○ ○ ○ ○ ○ ○ Long-term reliability × × × × × ×

Table 16 Comparative Example 7 8 9 10 11 12 Composition (parts by weight) EPDM 100 100 100 100 100 100 100 PP 100 200 95 195 PET 100 195 SP1045 55 55 55 55 Stannous chloride 22 22 22 OIL 100 200 190 280 100 280 Physical properties Hardness 80 86 77 88 79 86 TS (MPa) 18 17 14 12 20 20 Eb (%) 620 600 630 510 600 620 CS (%) 37 40 31 45 34 34 43 Low temperature impact resistance × × × × × × Oil resistance (%) 14 10 16 9 14 9 Light discoloration resistance 28 27 30 29 29 28 Moldability test × × × × × × Long term reliability × × × × × ×

Table 17 Comparative Example 13 14 15 16 17 18 Composition (parts by weight) EPDM 100 100 100 100 100 100 PP 100 200 95 100 PET 100 100 SiH 33 33 33 SiH 3 Catalyst 0.5 0.5 0.5 0.5 0.5 OIL 100 200 190 100 100 100 Physical hardness 80 86 75 82 83 82 TS (MPa) 19 17 14 18 20 20 Eb (%) 630 600 650 630 600 620 CS (%) 35 39 29 32 32 34 36 Low temperature impact resistance × × × × × × Oil resistance (%) 149 15 13 14 15 15 Light discoloration resistance 8 7 8 9 9 8 Moldability test × × × × × × Long term reliability × × × × × × ×

Table 18 Comparative Example 19 20 21 22 23 24 Composition (parts by weight) ANR 100 100 100 100 100 100 PP 100 100 100 PET 100 100 100 SiH 33 33 SiH 33 33 Catalyst 0.5 0.5 0.5 0.5 0.5 OIL 100 100 100 100 100 100 100 Physical hardness 81 83 82 84 83 82 TS (MPa) 17 18 18 19 20 20 Eb (%) 600 600 590 560 610 620 CS (%) 34 32 35 31 32 29 Low temperature impact resistance × × × × × × Oil resistance (%) 12 11 13 8 11 11 Light discoloration resistance 9 9 8 9 10 10 Moldability test × × × × × × Long term reliability × × × × × × ×

Table 19 Comparative Example 25 26 27 28 29 30 Composition (parts by weight) SBR 100 100 100 100 100 100 PP 100 100 100 PET 100 100 100 SiH 33 33 SiH 33 33 Catalyst 0.5 0.5 0.5 0.5 0.5 OIL 100 100 100 100 100 100 100 Physical property hardness 79 83 82 84 83 82 TS (MPa) 15 16 16 17 18 18 Eb (%) 630 630 610 580 630 650 CS (%) 38 34 36 33 34 33 Low temperature impact resistance × × × × × × Oil resistance (%) 14 13 14 11 12 13 Light discoloration resistance 8 8 8 9 9 9 Moldability test × × × × × × Long term reliability × × × × × × ×

Table 20 Comparative Example 31 32 33 34 35 36 Composition (parts by weight) BuR 100 100 100 100 100 100 PP 100 100 100 PET 100 100 100 SiH 33 33 SiH 33 33 Catalyst 0.5 0.5 0.5 0.5 0.5 OIL 100 100 100 100 100 100 100 Physical hardness 79 83 82 84 83 82 TS (MPa) 15 16 16 17 18 18 Eb (%) 630 630 610 580 630 650 CS (%) 34 30 32 30 30 28 Low temperature impact resistance × × × × × × Oil resistance (%) 10 10 11 9 9 10 Light discoloration resistance 77 77 88 88 Formability test × × × × × × Long term reliability × × × × × × ×

Table 21 Comparative Example 37 38 39 40 41 42 Composition (parts by weight) ANR 100 100 100 100 50 50 PVC 100 100 50 50 100 100 100 SiH 3 1.5 SiH 3 3 1.5 Catalyst 0.5 0.5 0.5 0.5 0.5 OIL 100 100 100 100 100 100 100 Physical properties Hardness 79 83 62 64 83 82 TS (MPa) 15 16 14 15 20 21 Eb (%) 530 530 560 560 580 430 450 CS (%) 34 30 27 25 40 38 Low temperature impact resistance × × × × × × Oil resistance (%) 10 10 11 9 9 10 Light discoloration resistance 9 9 9 9 9 9 Moldability test × × × × × × Long term reliability × × × × × ×

[0052]

According to the present invention, a highly functional thermoplastic elastomer composition can be obtained under extremely common kneading conditions. That is, the elastomer composition is excellent in flexibility, heat creep performance, low-temperature impact resistance, and mechanical strength, exhibits excellent rubber elasticity over a wide temperature range, has good oil resistance, and is free from toning, and therefore has excellent oil resistance. Suitable for automobile parts, home appliance parts, various wire coatings (for insulation and sheath), and various industrial parts for which improvement in properties, rubber elasticity, mechanical strength and molding speed, molding yield, freedom of color matching, etc. is desired. It can be molded and used.

Claims (13)

(57) [Claims] 1 to 100 parts by weight of an unsaturated double bond-containing rubber (a), 5 to 300 parts by weight of a thermoplastic resin (b),
0.5 to 30 parts by weight of an organosiloxane crosslinking agent (c) having two or more SiH groups in a molecule, 0.001 to 20 parts by weight of a hydrosilylation catalyst (d), and a compatibilizer (e)
A thermoplastic elastomer composition obtained by mixing 0.5 to 20 parts by weight and subjecting it to a dynamic heat treatment. 2. A thermoplastic resin (b) in an amount of 5 to 300 parts by weight based on 100 parts by weight of the unsaturated double bond-containing rubber (a).
0.5 to 30 parts by weight of an organosiloxane-based crosslinking agent (c) having two or more SiH groups in a molecule, 0.001 to 20 parts by weight of a hydrosilylation catalyst (d), and 0.1% by weight of a compatibilizer (e).
5 to 20 parts by weight and 30 parts of paraffinic oil (f)
What is claimed is: 1. A thermoplastic elastomer composition which is obtained by mixing up to 300 parts by weight. 3. The compatibilizer polymerizes two or more monomers containing at least a component having an affinity for the unsaturated double bond-containing rubber (a) and a component having an affinity for the thermoplastic resin (b). 3. The thermoplastic elastomer composition according to claim 1, which is a block copolymer, a random copolymer or a graft copolymer obtained by the above method. 4. The method according to claim 1, wherein the hydrosilylation catalyst (d) is of the type VIII
A transition metal-based or organic peroxide catalyst system,
4. The thermoplastic elastomer composition according to 2 or 3. 5. The thermoplastic elastomer composition according to 1, 2, 3 or 4, wherein the hydrosilylation catalyst (d) is dissolved or supported on at least one selected from a liquid component or a solid component. 6. The thermoplastic according to claim 1, wherein the organic organosiloxane crosslinking agent (c) having two or more SiH groups in the molecule has the following structural formula. Elastomer composition. Wherein m is an integer of 3 to 30, n is an integer of 0 to 200, R is hydrogen, an alkyl group, an alkoxy group, an aryl group or an aryloxy group, and At least one silicon atom in which at least one R is hydrogen is present in the molecule.) 7. The unsaturated double bond-containing rubber (a) is selected from ethylene-α-olefin-non-conjugated diene copolymer rubber, vinyl aromatic compound-conjugated diene compound copolymer rubber, butadiene rubber, and butyl rubber. The thermoplastic resin (b) is at least one selected from polyolefin-based resins, polystyrene-based resins, and polyphenylene ether-based resins, and the compatibilizer (e) has the following compatibility 7. The thermoplastic elastomer composition according to claim 1, which is at least one member selected from the group consisting of agents (e-1) and (e-2). (E-1) Water obtained by hydrogenating a copolymer containing at least two terminal blocks A mainly composed of a vinyl aromatic compound and at least one intermediate polymer block mainly composed of a conjugated diene compound Addition block copolymer (e-2) Ethylene-α-olefin copolymer 8. The unsaturated double bond-containing rubber (a) is selected from ethylene-α-olefin-non-conjugated diene copolymer rubber, vinyl aromatic compound-conjugated diene compound copolymer rubber, butadiene rubber, and butyl rubber. The thermoplastic resin (b) is at least one selected from a polyolefin-based resin, a polyester-based resin, a polyamide-based resin, and a polycarbonate-based resin, and the compatibilizer (e)
Is a compatibilizer (e-3) modified with the following epoxy group,
The thermoplastic elastomer composition according to claim 1, 2, 3, 4, 5, or 6, which is at least one selected from (e-4) and (e-5). (E-3) Epoxy obtained by hydrogenating a copolymer containing at least two terminal blocks A mainly composed of a vinyl aromatic compound and at least one intermediate polymer block mainly composed of a conjugated diene compound Modified hydrogenated block copolymer (e-4) Epoxy-modified ethylene-α-olefin (-non-conjugated diene) copolymer rubber (e-5) Epoxy-modified polyolefin resin 9. The unsaturated double bond-containing rubber (a) is selected from ethylene-α-olefin-non-conjugated diene copolymer rubber, vinyl aromatic compound-conjugated diene compound copolymer rubber, butadiene rubber, and butyl rubber. The thermoplastic resin (b) is at least one selected from a polyolefin-based resin and a polyamide-based resin, and the compatibilizer (e) is modified with the following maleic anhydride. The thermoplastic elastomer composition according to claim 1, 2, 3, 4, 5, or 6, which is at least one selected from solubilizers (e-6), (e-7), and (e-8). . (E-6) An anhydride obtained by hydrogenating at least two terminal blocks A mainly composed of a vinyl aromatic compound and at least one copolymer containing an intermediate polymer mainly composed of a conjugated diene compound. Maleic acid-modified hydrogenated block copolymer (e-7) Maleic anhydride-modified ethylene-α-olefin (-non-conjugated diene) copolymer rubber (e-8) Maleic anhydride-modified polyolefin resin 10. An unsaturated double bond-containing rubber (a) comprising an ethylene-α-olefin-non-conjugated diene copolymer rubber,
Vinyl aromatic compound-conjugated diene compound copolymer rubber,
At least one selected from butadiene rubber, butyl rubber, α, β-unsaturated nitrile-conjugated diene copolymer rubber, and acrylic rubber, wherein the thermoplastic resin (b) is a polyolefin resin, a polyester resin, or a polyamide resin. At least one selected from the group consisting of resins, polycarbonate resins, vinyl chloride resins, and methacrylate resins;
-9) is a modified polyolefin resin having an epoxy group and an ester group in the same molecule.
7. The thermoplastic elastomer composition according to 4, 5, or 6. 11. The thermoplastic resin (b), wherein the unsaturated double bond-containing rubber (a) is at least one selected from acrylic rubber and α, β-unsaturated nitrile-conjugated diene copolymer rubber. Is one or more selected from a vinyl chloride resin, a polyurethane resin, and a methacrylate resin, and the compatibilizer (e-10) is a halogenated olefin resin, a vinyl chloride-vinyl acetate copolymer, a vinyl aromatic resin. Compound-α, β
7. The thermoplastic elastomer composition according to claim 1, which is at least one member selected from the group consisting of unsaturated nitrile-conjugated diene copolymer. 12. The unsaturated double bond-containing rubber (a) is an ethylene-α-olefin-non-conjugated diene copolymer rubber,
The thermoplastic resin (b) is a crystalline olefin-based resin, and the compatibilizer (e) has the following (e-11) (e-12)
The thermoplastic elastomer composition according to claim 1, 2, 3, 4, 5, or 6 selected from (e-13). (E-11) Polyethylene having an epoxy group-containing polypropylene resin as an essential component and having a maleic anhydride group in the molecule, ethylene-based copolymer, styrene block copolymer and / or hydrogenated product thereof, styrene random copolymer A compatibilizer obtained by melting and reacting at least one selected from maleic anhydride group-modified resins such as coalesced and / or hydrogenated products thereof. (E-12) A polypropylene having a maleic anhydride group in the molecule. As an essential component, at least one selected from polyethylene having an epoxy group, an ethylene-based copolymer, a styrene block copolymer and / or a hydrogenated product thereof, a styrene random copolymer and / or a hydrogenated product thereof (E-13) Compatibilizer made by melt-reacting epoxy-modified resin of (e-13). A blend of at least one resin selected from a polymer, a styrene block copolymer and / or a hydrogenated product thereof, a styrene random copolymer and / or a hydrogenated product thereof in the presence of a peroxide Compatibilizer dynamically heat-treated 13. The method according to claim 1, wherein the compatibilizers (e-11) and (e-12) have a ratio of the epoxy-modified resin to the maleic anhydride group-modified resin, and the compatibilizer (e-13) has a ratio of the polypropylene to the polypropylene.
2, a compatibilizer (e) having a ratio of one or more resin components selected from a specific group of 10:90 to 90: 10% by weight is added to the rubber component (a) + the resin component (b). Total 100
13. The thermoplastic elastomer according to claim 12, wherein 0.5 to 20 parts by weight is added to parts by weight.