JPH0827319A - Thermoplastic elastomer - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic elastomer characterized by low-temp. impact resistance, wide colorability, and low residual heavy metal content by dynamically thermally-treating a rubber and a thermoplastic resin in the presence of a specific substance. CONSTITUTION:A thermoplastic elastomer is obtd. by mixing a rubbery compsn. (A) comprising an unsatd. rubber and a styrenic elastomer, a thermoplastic resin (B), an organosiloxane cross-linker (C) having at least two SiH groups in the molecule, a hydrosilylation catalyst (D), and a compatibilizer (E) and dynamically thermally-treating the resulting mixture. An example of the unsatd. rubber is a hydrogenated styrene-butadiene copolymer, Pref., the amts. of components (B), (C), (D), and (E) compounded based on 100 pts.wt. component (A) are 5-300, 0.5-30, 0.001-20, and 0.5-20 pts.wt., respectively. The wt. ratio of the rubber to the elastomer in component (A) is (10:90)-(90:10).

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In recent years, thermoplastic elastomers, which are rubber-like soft materials and do not require a vulcanization step and have the same moldability as thermoplastic resins, are used in automobile parts, home electric appliances parts, wire coating materials and medical parts. It is used in fields such as, sundries and footwear. As a typical example of the structure of the thermoplastic elastomer, there is a type in which hard segments and soft segments are alternately contained in the copolymer chain as disclosed in JP-A-61-34050. is there. And
These grades are manufactured in various grades from flexible ones to rigid ones by changing the proportion of each segment. In addition, there are other types of thermoplastic elastomers derived from cheap and readily available source materials. That is, as disclosed in Japanese Patent Publication No. 53-21021 and the like, a thermoplastic blend of a monoolefin copolymer rubber and a polyolefin resin partially crosslinked with an organic peroxide or a monoolefin copolymer rubber and a polyolefin. A partially crosslinked composition obtained by melt-kneading a resin with an organic peroxide as a crosslinking aid 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 synthesizing a flexible grade by a multi-step synthesis method, it is necessary to synthesize the hard segment and the soft segment separately, which makes the polymerization equipment very complicated and the characteristics and proportion of each segment at the polymerization stage. Is very difficult to control, and defective products may occur when switching grades. Furthermore, the recovery of the produced polymer is very difficult because it contains a large amount of rubber-like properties. Since the technology disclosed as a conventional styrene elastomer belongs to this category,
Moldability and weather resistance are very good, and scratch resistance is relatively good compared to olefin elastomers, but since it also has the above-mentioned drawbacks, it can be used in a wide range of applications such as industrial mechanical parts. Cannot be used.

In the latter case, in the case of the thermoplastic elastomer having a structure in which the monoolefin copolymer rubber in the component is partially crosslinked, the oil resistance and the shape recovery property at high temperature are insufficient due to the partial crosslinking. Therefore, it cannot be used for various purposes over a wide range. 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, it is a means of preferentially promoting only the crosslinking of the monoolefin copolymer rubber by using the heat-reactive alkylphenol resin as the crosslinking agent. Since the thermoplastic elastomer obtained by this means is completely crosslinked, it has sufficient oil resistance and shape recovery properties at high temperatures, but since it uses an alkylphenol resin, it is extremely poor in light discoloration resistance and has a high degree of freedom in toning. It cannot be used for automobile parts, home appliance parts, wire coating, etc.

A method of using an organic organosiloxane compound as a crosslinking agent instead of an alkylphenol resin has been proposed in US Pat. No. 4,803,244. This method can preferentially proceed only the crosslinking of the monoolefin copolymer rubber in the same manner as the alkylphenol resin crosslinking, and obtains a material excellent in oil resistance, shape recovery at high temperature, light discoloration resistance, etc. Therefore, it can be used for applications such as automobile parts, home appliance parts, wire coatings, etc., which require flexibility in toning. However, in this method, since no compatibilizer is added, the adhesion between the rubber and the resin is not sufficient, so it cannot be said that the low-temperature impact resistance can be satisfied, and applications requiring low-temperature impact resistance-for example, automotive air It cannot be used for bag materials, etc. In addition, since there is no compatibilizer, the rubber is insufficiently dispersed by the usual kneading method, and the extruded appearance of the molded product is remarkably poor. Therefore, USP45
As disclosed in Japanese Patent No. 94390, a method of dynamically heat-treating under high shear of 2000 / sec or more has been proposed to solve the above problem. However, in this method, although the residence time of the material is short, it is high. Since it is exposed to shearing, not only the material itself tends to decompose and deteriorate, but in order to achieve high shearing, not only the number of rotations at the time of melt kneading but also the clearance of the kneading machine is about 1 / 3 to 1/5 or less, the productivity of the thermoplastic elastomer composition,
It is not practical in terms of 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.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the problems that were difficult with the conventional thermoplastic elastomer compositions, and while making full use of the excellent characteristics of the styrene elastomer material, While maintaining good rubber properties over a wide temperature range, it has characteristics such as low-temperature impact resistance, wide freedom of coloring, low residual heavy metal materials, etc., so applications requiring toning, hygiene, long-term reliability It is an object of the present invention to provide a thermoplastic elastomer that can be used in various applications over a wide range, including applications in which is required.

[0007]

An organic organoorganic having two or more SiH groups in a molecule having excellent photochromic resistance and biocompatibility as a crosslinking agent and having a property of selectively crosslinking unsaturated double bond-containing rubber. The siloxane compounds are cross-linked while being melt-kneaded with a hydrosilylation catalyst to selectively cross-link the rubber, and the compatibilizer improves the adhesive strength at the interface, so that only mechanical shearing force is applied. The research was developed based on the technical idea of highly dispersing crosslinked rubber particles without dependence, and as a result, while maintaining good rubber properties over a wide temperature range, low temperature impact resistance, toning, good It can be applied to a wide variety of applications including those requiring a molded appearance, and it is extremely common sense that the shear rate is 100 to 1000 / sec with a normal kneader. We found finding that can be achieved by melt kneading conditions, based on the findings, and further leading to the completion of the present invention promote various studies. Further, it has been found that since the thermoplastic elastomer composition produced by the present invention is subjected to the compatibilization method, the morphology change is unlikely to occur even after the annealing treatment, and as a result, the long-term reliability is also very excellent. . That is, the present invention relates to a rubber-like composition (a) composed of a mixture of an unsaturated double bond-containing rubber (a-1) and a styrene elastomer (a-2), a thermoplastic resin (b), and a SiH group in the molecule. A thermoplastic elastomer characterized by being obtained by mixing an organic organosiloxane-based cross-linking agent (c) having two or more of the above, a hydrosilylation catalyst (d), and a compatibilizing agent (e) and dynamically heat-treating them. , Preferably 5 to 300 parts by weight of the thermoplastic resin (b) with respect to 100 parts by weight of the rubber composition (a),
0.5 to 30 parts by weight of an organoorganosiloxane cross-linking agent (c) having two or more SiH groups in the molecule, 0.001 to 20 parts by weight of a hydrosilylation catalyst (d), and a compatibilizer (e) of 0. It is a thermoplastic elastomer characterized by being mixed by 5 to 20 parts by weight, and optionally by adding 30 to 300 parts by weight of paraffinic oil (f) and dynamically heat-treated.

The unsaturated double bond-containing rubber of the rubber-like composition (a) used in the present invention is not particularly limited, and generally commercially available main chain and / or side chain contains unsaturated carbon 2
It refers to all rubbers including heavy bonds. 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 block copolymer rubber or α, β-unsaturated Nitrile-Acrylonitrile most commonly used as conjugated diene copolymer rubber-
Butadiene copolymer rubber and the like can be mentioned. Then, the aliphatic double bonds contained in these rubbers are partially hydrogenated,
Partially hydrogenated rubbers with reduced 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 ethylene-α-olefin-non-conjugated diene copolymer rubber consisting of ethylene, α-olefin and non-conjugated diene is suitable in that α-olefin having 3 to 15 carbon atoms in its composition. As the non-conjugated diene, dicyclopentadiene, 1,4-hexadiene, ethylidene norbornene, methylene norbornene and the like can be used. In the present invention, polypropylene is suitable as the α-olefin from the viewpoint of easy availability and improvement of impact resistance. Therefore, EPDM is preferred. The copolymer rubber has an ethylene / α / olefin ratio of 50 / by weight.
50-90 / 10, more preferably 60 / 40-80 /
20 is suitable. Here, the Mooney viscosity of the rubber used,
ML1 + 4 (100 ° C) is 10 to 120, preferably 40
It can be suitably selected from the range of 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. Further, if it exceeds 120, the moldability is remarkably deteriorated and the appearance of the molded product is deteriorated, which is not preferable. The iodine value of this rubber is 5 to 30, especially 1.
Those of 0 to 20 are preferable.

The styrenic elastomer used in the present invention is a copolymer which is a rubber elastic body at room temperature, and means a partially or completely hydrogenated copolymer. Specific examples thereof include hydrogenated products of styrene-butadiene copolymers (including all random copolymers, block copolymers, graft copolymers, etc.), and more specifically, hydrogenated styrene- Butadiene-styrene copolymer (SEB
S), hydrogenated isoprene-styrene copolymer (SEP),
Hydrogenated styrene-isoprene-styrene copolymer (SEP
S), hydrogenated styrene-butadiene random copolymer (H
SBR) and the like. Among them, SEBS and SEPS are preferable styrene elastomers which significantly improve impact resistance at low temperature, and among them, preferable styrene content is 10 to 80% by weight, more preferably 3%.
It is 0 to 70% by weight, and more preferably 40 to 70% by weight. Further, the ratio of the unsaturated double bond-containing rubber and the styrene-based elastomer in the rubber composition (a) is 10: 9.
0 to 90: 10% by weight, preferably 20:80 to 80: 2
0 parts by weight, and more preferably 30:70 to 70:30 parts by weight. Here, 10:90 to 90:10
If the amount is out of the range of parts by weight, the physical properties developed when the rubbery mixture is not blended tend to be the same.

Next, the thermoplastic resin (b) used in the present invention is effective in improving the processability and heat resistance of the resulting composition. Here, the thermoplastic resin needs to be relatively inert to the hydrosilation reaction of the rubber crosslinking reaction. Specific examples include polyolefin resins, polystyrene resins such as ABS and polystyrene, vinyl chloride resins, polyamide resins, polyester resins, polycarbonate resins, polyacetal resins, and polyphenylene ether resins. it can. Further, two or more kinds of thermoplastic resins may be used in combination. Here, the crystalline olefin resin is, for example, polyethylene, isotactic polypropylene or a random or block copolymer of propylene and a small amount of other α-olefin, specifically polypropylene-.
Examples thereof include ethylene copolymers, propylene-1-hexene copolymers, propylene-4-methyl-1-pentene copolymers, poly-4-methyl-1-pentene, and polybutene-1. As a crystalline olefin resin,
When isotactic polypropylene or its copolymer is used, the MFR (ASTM-D-1238L condition, 230 ° C) is preferably 0.1 to 50 g / 10 minutes, particularly 0.5 to 30 g / 10 minutes. Can be used. The amorphous olefin resin is a polymer having a cyclic olefin structure alone or a copolymer of cyclic olefin and 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). When the amount is more than 300 parts by weight, the hardness of the obtained elastomer composition tends to be high and the flexibility tends to be lost, and when less than 5 parts by weight, the processability tends to be deteriorated.

Next, 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 a rubber component. In order to be a cross-linking agent, addition to two or more molecules of rubber is a necessary condition, so it is necessary to have two or more SiH groups in the molecule. Typical examples of specific compounds are compounds having structures of cyclic polysiloxanes, linear polysiloxanes, and tetrahedral siloxanes as shown below. Moreover, you may use the compound and / or polymer derived from this compound. Here, 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 is bonded to a silicon atom. Two or more silicon atoms in which at least one R is hydrogen are present in the molecule. The organic organosiloxane having the above structure can selectively crosslink rubber.

The crosslinking reaction catalyst (d) used in the present invention refers to all catalysts that accelerate the hydrosilylation reaction. Examples of the catalyst include group transition metals such as palladium, rhodium and platinum, or compounds and complexes thereof.
Further, peroxides, amines and phosphines are also used. In addition, ultraviolet rays and γ rays can also be used. The most common catalysts are dicuclobis (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 are 2,5-dimethyl 2,5-di (t-butylperoxy) hexane and 2,5-dimethyl 2,5-di (t-butylperoxy) hexyne-3,1, 3-bis (t-butylperoxyisopropyl) benzene, 1,1-di (t
-Butylperoxy) 3,5,5 trimethylcyclohexane, 2,5 dimethyl 2,5 di (peroxybenzoyl) hexyne 3, and dicumyl peroxide.
Furthermore, a system in which an organic peroxide is used in combination with a co-catalyst bismaleimide compound may be used as a catalyst. The bismaleimide compound used in the present invention includes N, N'-m-phenylene bismaleimide and toluylene bismaleimide. N, N'-m-phenylene bismaleimide is commercially available, for example, HVA-2 (manufactured by DuPont), Succinol B.
M (Sumitomo Chemical Co., Ltd.) or the like can be used. By using a peroxide-based catalyst, the thermoplastic elastomer composition obtained in the present invention is used in applications where residual heavy metal is a problem-
For example, it can be suitably used in the medical field. Also,
In order to disperse the catalyst in a higher degree, the hydrosilylation catalyst (d) can be dissolved or supported in one or more kinds selected from a liquid component and a solid component. That is, it is a method of dissolving it in a solvent, supporting it on an inorganic filler, or a combination of both. The solvent used here is not particularly limited, but needs to be relatively inert to the hydrosilylation reaction. Examples of the solvent type include hydrocarbon type, alcohol type, ketone type, ester type and the like. The concentration of the solution to be adjusted is not particularly limited. In addition, the inorganic filler needs to have adsorption ability, and calcium carbonate, carbon black, talc,
Examples include magnesium hydroxide, mica, barium sulfate, natural silicic acid, rigid silicic acid (white carbon), titanium oxide and the like. As a method for adjusting the supported catalyst, a known method can be used.

The term "dynamically vulcanized thermoplastic elastomer composition" as used herein means that 1 g of the composition obtained in the present invention is refluxed with boiling xylene in a Soxhlet extractor for 10 hours, and the residue is a mesh of 80 mesh. The dry weight of the insoluble matter remaining on the mesh (g) / the weight ratio of the unsaturated double bond-containing rubber in the component a contained in 1 g of the composition was set to 1
A gel content of at least 30%, which is multiplied by 00,
It is preferably vulcanized so as to be 50% or more (however, insoluble components such as inorganic fillers are not included therein), and the vulcanization is performed during melt-kneading of the thermoplastic elastomer composition. Is characterized by. In order to obtain such a dynamically vulcanized thermoplastic elastomer composition, the amount of the organic organosiloxane cross-linking agent c is 0.5 to 100 parts by weight of the unsaturated double bond-containing rubber in the component a. Thirty
It can be suitably selected from the weight part, preferably 1 to 20 parts by weight, and its gel content can be adjusted. The addition amount of the catalyst d is 0.1 with respect to 100 parts by weight of the rubber component.
001 to 20 parts by weight of catalyst can be optionally added. Addition amount of heavy metal catalyst as a catalyst is 0.005-5
It is preferably part by weight, more preferably 0.01 to 2 parts by weight. In addition, the addition amount of peroxide type catalyst is 0.
The amount is preferably 01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight. When the amount is less than 0.001 part by weight, the crosslinking does not proceed at a practical speed. Also, 20
If it exceeds 5 parts by weight, not only there is no effect of increasing the amount, but also the deactivated catalyst becomes black-colored lumps and the appearance becomes poor, and heat treatment tends to cause undesired side reactions (decomposition of unreacted SiH groups, etc.).

The compatibilizing agent e used in the present invention has components having affinity for rubber and thermoplastic resin in the same molecule, and this acts as a surfactant, As a result, normal kneading conditions (shear rate: 10
(0-1000 / SEC) vulcanized rubber is finely dispersed up to 30 microns or less, and the adhesive strength at the interface between vulcanized rubber and thermoplastic resin is improved, and impact resistance at low temperature is remarkably improved. Is added for the purpose of 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 to have components having good affinity with the rubber composition a and the thermoplastic resin b in the same molecule. There are few polymerized products of monomers that 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.

Some typical structures of the compatibilizer are listed below, and the unsaturated double bond-containing rubber and the thermoplastic resin in the rubber-like composition (a) in which the respective compatibilizer suitably exhibits the effect The combination of resin (b) is shown. The compatibilizing agent (e) modified with the following epoxy group (e-1), (e-
2) and (e-3), when the compatibilizer is one or more selected from (e-3), the unsaturated double bond-containing rubber is ethylene-α / olefin-non-conjugated diene copolymer rubber, vinyl aromatic At least one selected from compound-conjugated diene compound copolymer rubber, butadiene rubber, and butyl rubber, and the thermoplastic resin (b) is selected from polyolefin resin, polyester resin, polyamide resin, and polycarbonate resin. It is preferably used in a combination of one or more kinds. (E-1) Epoxy-modified water obtained by hydrogenating an end block A mainly composed of at least two vinyl aromatic compounds and an intermediate polymer block copolymer mainly composed of at least one conjugated diene compound Addition block copolymer (e-2) Epoxy-modified ethylene-α-olefin (-
Non-Conjugated Diene) Copolymer Rubber (e-3) Epoxy Modified Polyolefin Resin In this combination, the thermoplastic resin has a group that reacts with an epoxy group, except for the polyolefin resin,
By reacting this with an epoxy group, a graft copolymer having an affinity for both the unsaturated double bond-containing rubber 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,
Since the compatibilizing agent itself has an affinity, the vulcanized rubber can be highly dispersed in the thermoplastic resin.

Further, the compatibilizing agent (e) is selected from the following compatibilizing agents (e-4), (e-5) and (e-6) modified with a carboxylic acid anhydride and / or a carboxylic acid group. The one or more selected compatibilizers are unsaturated double bond-containing rubbers such as ethylene-α-olefin-non-conjugated diene copolymer rubber, vinyl aromatic compound-conjugated diene compound copolymer rubber, butadiene rubber, butyl rubber. Is one or more selected from
The thermoplastic resin (b) is preferably used in a combination of one or more selected from polyolefin resins and polyamide resins. (E-4) Maleic anhydride obtained by hydrogenating an end block A mainly composed of at least two vinyl aromatic compounds and an intermediate polymer block copolymer mainly composed of at least one conjugated diene compound. Group-modified hydrogenated block copolymer (e-5) Maleic anhydride group-modified ethylene-α-olefin (-non-conjugated diene) copolymer rubber (e-6) Maleic anhydride group-modified polyolefin resin In this combination, The thermoplastic resin has a group that reacts with a maleic anhydride group except for a polyolefin resin, and by reacting this with a maleic anhydride group, the unsaturated double bond-containing rubber and the thermoplastic resin ( A graft copolymer is formed which has an affinity for both b).
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-7) is a modified polyolefin resin having an epoxy group and an ester group in the same molecule, the unsaturated double bond-containing rubber is ethylene-
Selected from 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, acrylic rubber 1 or more, and the thermoplastic resin (b) is a polyolefin resin,
It is preferably used in combination with at least one selected from polyester resins, polyamide resins, polycarbonate resins, vinyl chloride resins, and methacrylate resins. 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 can react with or are compatible with this compatibilizer, and the resulting graft copolymers are listed above. The combination of the unsaturated double bond-containing rubber and the thermoplastic resin (b) has an improving effect. Further, the compatibilizer (e-8) is selected from halogenated olefin resin, vinyl chloride-vinyl acetate copolymer, vinyl aromatic compound-α, β-unsaturated nitrile-conjugated diene copolymer 1 In the one or more compatibilizers, the unsaturated double bond-containing rubber is one or more selected from acrylic rubber, α, β-unsaturated nitrile-conjugated diene copolymer rubber, and the thermoplastic resin (b) is It is preferably used in combination with one or more selected from vinyl chloride resins, polyurethane resins and methacrylate resins.

Further, as an example of a method for adjusting a compatibilizing agent of a hydrocarbon type rubber and a polyolefin type resin among thermoplastic resins, the following (e-9) and (e-1) are shown.
0) and (e-11). (E-9) Polypropylene resin having an epoxy group as an essential component, having a maleic anhydride group in the molecule, polyethylene, ethylene copolymer, styrene block copolymer and / or hydrogenated product thereof, styrene random copolymer And / or a maleic anhydride group-modified resin such as a hydrogenated product thereof, which is obtained by melting and reacting at least one selected from maleic anhydride group-modified resins. Having polypropylene as an essential component, having an epoxy group polyethylene, an ethylene copolymer, a styrene block copolymer and / or a hydrogenated product thereof, and an epoxy-modified resin such as a styrene random copolymer and / or a hydrogenated product thereof. Compatibilizer (e-11) characterized by being melt-reacted with at least one selected from (e-11) polypropylene as an essential component And a blend with at least one resin selected from polyethylene, ethylene-based copolymers, styrene block copolymers and / or hydrogenated products thereof, styrene random copolymers and / or hydrogenated products thereof. Compatibilizer obtained by dynamically heat-treating in the presence of peroxide A modified resin having a maleic anhydride group and a modified resin having an epoxy group, which are used as a raw material for the compatibilizing agent (e-9) (e-10), , Can be easily obtained by a known technique.
That is, it can be obtained by a method of graft copolymerization using a peroxide or the like or by copolymerization with a resin monomer component.
These may be commercially available products.

As the modified resin having a maleic anhydride group used in the present invention, ethylene / acrylic acid / maleic anhydride terpolymer, ethylene / ethyl acrylate / maleic anhydride terpolymer, ethylene / methacrylic acid
Maleic anhydride 3-copolymer, polypropylene grafted with maleic anhydride, polyethylene grafted with maleic anhydride, ethylene grafted with maleic anhydride-
Examples thereof include a propylene copolymer, a styrene-ethylene / butylene-styrene block copolymer grafted with maleic anhydride, and a styrene-ethylene / butylene-styrene random copolymer grafted with maleic anhydride. Examples of the epoxy-modified resin used in the present invention include ethylene / glycidyl methacrylate copolymer, ethylene / acrylic acid / glycidyl acrylate terpolymer, ethylene / acrylate / allyl glycidyl 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, glycidyl acrylate Styrene-Ethylene
Examples thereof include butylene-styrene random copolymer.

Alternatively, a modified resin having a maleic anhydride group or an epoxy modified resin may be prepared by itself.
As the compatibilizer (e-9) (e-10) of the present invention, a composition comprising a modified resin having a maleic anhydride group in the molecule and a resin having an epoxy group in the molecule is used in a batch-type kneading machine at 150 to
It is obtained by performing a melt reaction at 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. When the infrared absorption spectra of the compatibilizers (e-9) and (e-10) were examined, the characteristic absorption of the epoxy group and maleic anhydride group contained in the raw material disappeared, and the epoxy group and maleic anhydride group It is thought that a reaction occurred in the meantime. The compatibilizer (e-11) of the present invention contains 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 hydrogenated product thereof. A batch-type kneading machine comprising a blend with at least one or more resins selected from the above, an organic peroxide such as an organic peroxide, an organic perester, and an azo compound, and if necessary, a cocatalyst such as a bismaleimide compound. At 150 ~
It is obtained by melt-reacting at 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 with respect to 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 it exceeds 2 parts by weight, not only the effect of increasing the amount but also unfavorable side reactions (decomposition of polypropylene, gelation reaction, etc.) tend to occur.

Here, for the compatibilizers (e-9) and (e-10), the ratio of the epoxy-modified resin and the maleic anhydride group-modified resin is used, and for the (e-11), polypropylene and a specific group are used. The ratio of one or more resins selected from among is 1
0:90 to 90: 10% by weight, preferably 70:30 to
30: 70% by weight, more preferably 60:40 to 40:
It is compounded in the range of 60% by weight. If the proportion of either component is less than 10% by weight, the effect of improving the adhesive strength at the interface becomes insufficient, and the effect of improving the low temperature impact resistance of the thermoplastic elastomer of the present invention tends to become insufficient. The compatibilizers (e-9), (e-10), (e-11) listed here are olefinic resins as the thermoplastic resin or EPD as the rubber.
It is particularly effective for hydrocarbon-based materials such as M and butyl rubber. Further, the addition amount of the compatibilizer (e) is the rubber component (a)
+ 0.5 parts by weight to 20 parts by weight, preferably 1 part by weight to 15 parts by weight, and more preferably 2 parts by weight to 10 parts by weight, based on 100 parts by weight of the total of the resin component (b). To be done.
If it is less than 0.5 parts by weight, the effect of lowering the interfacial tension tends to decrease, and therefore the effect of improving the adhesive strength at the interface tends to decrease, and the dispersed particles of the vulcanized rubber tend to increase. The effect of improving the low temperature impact resistance of the thermoplastic elastomer is insufficient, and the appearance of the molded article tends to be deteriorated. On the other hand, if it exceeds 20 parts by weight, the hardness of the thermoplastic elastomer of the present invention becomes so hard that the low temperature impact resistance is deteriorated and the rubber elasticity as an elastomer tends not to be exhibited.

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. Mineral oil type rubber softening agents called process oils or extender oils, which are generally used for softening, increasing volume and improving processability of rubber, are a mixture of aromatic ring, naphthene ring and paraffin chain. Paraffin chains have 50% or more of the total number of carbon atoms are called paraffins, and those with 30 to 45% naphthene ring carbons are naphthenes, and aromatics with more than 30% aromatic ring carbons. It is considered a system.
The oils used in the present invention are preferably paraffinic oils in the above categories, and naphthenic and aromatic oils are not preferable in terms of dispersibility and solubility. The paraffinic rubber softener has a kinematic viscosity of 20 to 50 at 37.8 ° C.
0 cst, pour point -10 to -15 ℃ and flash point 1
70-300 degreeC is shown. The preferable blending amount of the paraffinic oil (f) is 3 with respect to 100 parts by weight of the rubber component (a).
0 to 300 parts by weight, more preferably 30 to 25
0 parts by weight. If the composition exceeds 300 parts by weight,
It tends to cause bleeding out of the softening agent, may cause tackiness in the final product, and tends to deteriorate mechanical properties. Further, if it is less than 30 parts by weight, it is meaningless to add it.

The thermoplastic elastomer composition obtained by the production method of the present invention has remarkably improved heat resistance as compared with known styrene elastomers. Further, it provides a composition exhibiting excellent mechanical strength and compression set at high temperature, as compared with a thermoplastic elastomer composition partially cross-linked using an organic peroxide of the known art. Further, it provides a composition which is remarkably excellent in light discoloration resistance as compared with a thermoplastic elastomer composition which is completely crosslinked using a heat-reactive alkylphenol resin of the known art. Further, the adhesiveness at the interface is remarkably improved, and as compared with the thermoplastic elastomer composition obtained by crosslinking by hydrosilylation using a heavy metal catalyst such as chloroplatinic acid as in the known art, The low temperature impact resistance is remarkably improved, and the appearance of the molded product is remarkably improved. The composition obtained in the present invention contains a styrene-based elastomer, and the scratch resistance is also improved. In addition to the above-mentioned components, the composition of the present invention may further contain an inorganic filler, if necessary, especially for applications in which color matching is unnecessary. This inorganic filler has not only the advantage of reducing the product cost as an extender but also an advantage of imparting a positive effect to quality improvement (heat-resistant shape retention, flame retardancy impartation, 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), titanium oxide, etc., and carbon black includes channel black, Furnace black etc. can be used. Among these inorganic fillers, talc and calcium carbonate are economically advantageous and preferable. If necessary, a nucleating agent, an external lubricant, an internal lubricant,
A hindered amine-based light stabilizer, a hindered phenol-based antioxidant, a colorant, silicone oil and the like may be added. It is also possible to blend other thermoplastic resins such as ethylene-α-olefin copolymer and thermoplastic urethane resin.

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, and a single-screw extruder, a twin-screw extruder, a Banbury mixer, various kneaders, brabenders, rolls and the like are used for these. At this time, the addition order of each component is not limited, for example, rubber, resin components are premixed in advance with a mixer such as a Henschel mixer, a blender and melt-kneaded with the above kneader, and then a crosslinking agent and a catalyst component are added. Addition methods such as dynamic vulcanization by addition and melt kneading of components other than the catalyst in advance when the scorch time of the rubber to be used is sufficiently long, and further addition of the catalyst and melt kneading can also be adopted. At this time, the temperature for melt-kneading can be suitably selected from the range of 180 ° C to 300 ° C and the shear rate of 100 to 1000 / SEC. Furthermore, first, (a) (c) (d)
The thermoplastic elastomer of the present invention can be obtained by first producing a cured product of rubber using the component (f), adding the crushed product of the cured rubber product to the remaining components, and melt-kneading. 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, and a single-screw extruder, a twin-screw extruder, a Banbury mixer, various kneaders, brabenders, rolls and the like are used for these. Further, at this time, the melting and kneading temperature is 180 ° C to 300 ° C, and the shear rate is 100 to 100
It can be suitably selected from 0 / SEC.

The crushing of the cured rubber produced through the above steps can be accomplished by a conventional crushing method. That is, a crusher, particularly a freeze crushing method using dry ice or liquid nitrogen is preferably used. Further, an inorganic filler or the like can be used as a powdering agent. At this time, when a batch-type kneader such as a kneader is used, the composition is thermosetting when the rubber is sufficiently cured, and the composition is roughly crushed in the kneader without providing a crushing step. Particularly preferably used. Since the dynamically vulcanized elastomer composition obtained here is thermoplastic, it can be molded using a commonly used thermoplastic resin molding machine, and injection molding, extrusion molding, calender molding, blow molding Various molding methods such as the above can be applied. That is, the shear rate dependency of the melt viscosity is particularly large, the viscosity is low and the fluidity is high in the injection molding region of high shear rate, and the injection molding can be easily performed like a general-purpose resin. Further, in the extrusion / blow molding region of medium shear rate, the viscosity becomes high to some extent, which leads to low drawdown, and therefore extrusion / blow molding is also easy.

[0026]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The components blended in the examples and comparative examples shown below are as follows. <Component a-1 (1): EPDM> Ethylene-propylene-ethylidene norbornene copolymer rubber EP57C manufactured by Nippon Synthetic Rubber Co., Ltd. [Propylene content: 28 wt% Mooney viscosity ML1 + 4
(100 ° C): 90 Iodine value: 15 Tg: -40 ° C] <Component a-1 (2): ANR> Acrylonitrile-butadiene copolymer rubber N240S manufactured by Nippon Synthetic Rubber Co., Ltd. [Acrylonitrile content: 26% by weight Mooni Viscosity ML1
+4 (100 ° C): 56] <Component a-1 (3): SBR> Styrene-butadiene copolymer rubber JSR 1503 manufactured by Nippon Synthetic Rubber Co., Ltd. [Styrene content: 23.5 wt% Mooney viscosity ML1 + 4
(100 ° C.): 75] <Component a-1 (4): BuR> Butyl rubber JSR Butyl268 manufactured by Nippon Synthetic Rubber Co., Ltd. [Unsaturation: 1.5 mol% Mooney viscosity ML1 + 4 (12
5 ° C.): 51] <Component a-2 (1): SEBS> Styrene-ethylene-butylene-styrene copolymer water additive Tuftec H1041 manufactured by Asahi Kasei Co., Ltd. <Component a-2 (2): SEPS> Styrene -Ethylene-isoprene-styrene copolymer water additive Septon 2104 manufactured by Kuraray Co., Ltd.

<Component b (1): PP> Polypropylene Sumitomo Chemical Co., Ltd. W501 [MFR (230 ° C.) = 8.0 g / 10 min Heat distortion temperature: 115 ° C.] <Component b (2): PET> Polyethylene Terephthalate Mitsubishi Rayon Co., Ltd. Dianite PA500 <Component b (3): Ny66> Polyamide (PA) -66 Ube Industries Co., Ltd. Ube nylon 2020B <Component b (4): PVC> Vinyl chloride resin Sumitomo Chemical ( SMILIT SX-17 [Straight average degree of polymerization: 1700] <Component c (1): SiH> 1,3,5,7-tetramethylcyclotetrasiloxane 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): Medium> Chloroplatinic acid hexahydrate manufactured by Yasuda Yakuhin Co., Ltd. <Component d (2): Catalyst> Dicumyl Peroxide NIPPON FOOD CORPORATION's Park Mill D <Component d (3): Catalyst> Component d (1) 1% by weight 2-
A propanol solution was prepared, and 1 g of this solution was loaded on 100 g of silica [Nipsil VN3 manufactured by Nippon Silica Co., Ltd.] to be prepared.

<Component e-1: EP-SEBS> Epoxy group-modified styrene-ethylene-butylene-styrene copolymer (SEBS) manufactured by Asahi Kasei Kogyo Co., Ltd. Tuftec Z514 <Component e-5: MAH-EP> Maleic anhydride Group-modified ethylene-propylene copolymer manufactured by Nippon Synthetic Rubber Co., Ltd. EP T7741P <Component e-7: E-GMA-AM> Ethylene-glycidyl methacrylate-methyl acrylate terpolymer manufactured by Sumitomo Chemical Co., Ltd. Bondfast 7M <Component e-8: VC-PVC> Vinyl acetate-vinyl chloride copolymer Sumitomo Chemical Co., Ltd. Sumigraft GE <Component e-10: PP-MAH> Anhydrous ends of polypropylene oligomers having an average molecular weight of 4000 For 100 parts by weight of maleic acid-modified (PP-MAH), epoxy-modified styrene block United TAFTEC Z514
[Asahi Kasei Kogyo Co., Ltd.] 80 parts by weight was added and thoroughly mixed with a Henschel mixer.
After melting and kneading for minutes, forming a roll sheet and then cooling to room temperature,
The compatibilizer e-2 (1) of the present invention was obtained by pelletizing with a sheet pelletizer. As a result of investigating the infrared absorption spectrum of the compatibilizer e-2 (1), the characteristic absorption of the epoxy group and the acid anhydride group contained in the raw material disappeared, and the reaction between the epoxy group and the acid anhydride group occurred. Is likely to have occurred. <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)
℃), average molecular weight 746, ring analysis value: CA = 0%, CN =
27%, CP = 73%]

<< Examples 1-84 and Comparative Examples 1-48 >> 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 physical properties were evaluated. Examples are shown in Tables 1 to 14 and comparative examples are shown in Tables 15 to 22.

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 sphere R: 3/16 Drop height: 1 m] (5) Oil resistance [%]: JIS K6301, No3 test oil (lubricating oil) is used at 70 ° C for 2 hours. The test piece of 50 × 50 × t2 was dipped, and the weight change (%) before and after the dipping was obtained. (6) Light discoloration resistance test: The natural composition was treated at 88 ° C. for 1000 hours using a sunshine weather ometer. Then, the color difference was measured. (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, a kneading temperature of 200 ° C. and a rotation speed of 100 rpm were used to prepare a tape of 150 × 500 mm, and the surface was visually observed. When one or more spots having a diameter of 100 μm or more were observed, x was not observed. The case was marked as ○. (8) Long-term reliability: A low temperature impact test was performed according to (4) after treatment at 100 ° C for 1000 hours. After the test, when no crack was generated, it was evaluated as ○, and when cracked was evaluated as ×. (9) Scratch resistance test: A pencil scratch test for a coating film according to JIS K5401 was conducted, and 9 under a load of 50 g.
When it was scratched with a pencil of H, it was marked with X, and when it was not marked, it was marked with ◯. )

Comparative Examples 1 to 6 were the same as those in Examples except that 2 parts by weight of organic peroxide [dicumyl peroxide (DCP)] and 3 parts by weight of divinylbenzene (DVB) were used for dynamic vulcanization. Made by way. Furthermore, in Comparative Examples 7 to 12, dynamic vulcanization was performed by using a thermoreactive 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 42, organic organosiloxane was used as the cross-linking agent, and chloroplatinic acid hexahydrate similar to the component d of Example was used as the catalyst. Comparative Examples 43-4
No. 8 shows the evaluation result of the styrene elastomer material. From these results, the thermoplastic elastomer composition dynamically vulcanized using the organoorganosiloxane compound of the present invention and having the compatibilizer added was a thermoplastic elastomer composition dynamically vulcanized by blending an organic peroxide system of the known art. It was revealed that the composition has a mechanical strength and a compression set of 70 ° C. which are more excellent in oil resistance. And further,
It has been found that the composition of the present invention has a high degree of freedom in color matching because it has good resistance to light discoloration. Further, it was found that the vulcanized rubber particles were highly dispersed, and the low-temperature impact resistance was significantly improved. It was also found to have scratch resistance equivalent to that of styrene elastomer.

Table 1 Example 1 2 3 4 5 6 Composition (parts by weight) EPDM 70 70 70 70 70 70 SEBS 30 30 30 30 30 30 PP 100 200 95 195 100 PET 100 SiH 3 3 3 6 3 SiH 3 catalyst 0.5 0.5 0.5 0.5 0.5 0.5 EP-SEBS 10 10 10 10 10 10 OIL 100 200 190 280 100 100 Physical properties 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 (%) 15 9 15 9 14 15 Light discoloration resistance 8 7 8 8 9 8 Formability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 2 Example 7 8 9 10 11 12 Composition (parts by weight) EPDM 70 70 70 70 70 70 SEBS 30 30 30 30 30 30 PP 100 100 PET 100 195 100 100 SiH 3 3 3 SiH 3 3 3 catalyst 0.5 0.5 0.5 0.5 0.5 0.5 EP-SEBS 10 10 5 20 5 20 OIL 100 280 100 100 100 100 Physical properties Hardness 83 87 79 82 82 85 TS (MPa) 19 13 18 21 17 20 Eb (%) 620 540 620 580 610 540 CS (%) 34 42 33 39 31 38 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 12 9 13 13 14 12 Light discoloration resistance 9 8 8 9 8 9 Formability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 3 Example 13 14 15 16 17 18 Composition (parts by weight) EPDM 70 70 70 70 70 70 SEBS 30 30 30 30 30 30 PP 100 100 100 PET 100 100 100 SiH 3 3 3 SiH 3 3 3 catalyst 0.5 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 Physical properties Hardness 82 84 83 87 84 85 TS (MPa) 18 18 19 19 18 20 Eb (%) 580 570 570 540 580 540 540 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 ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 4 Example 19 20 21 22 23 24 Composition (parts by weight) EPDM 70 70 70 70 70 70 70 SEPS 30 30 30 30 30 30 PP 100 100 100 Ny 66 100 100 100 SiH 3 3 3 SiH 3 3 3 catalyst 0.5 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 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 8 9 8 10 9 9 Moldability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 5 Example 25 26 27 28 29 30 Composition (parts by weight) EPDM 70 70 70 70 70 70 70 SEBS 30 30 30 30 30 30 PP 100 200 95 195 100 PET 100 SiH 3 3 3 6 3 SiH 3 catalyst 0.5 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 properties 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 (%) 15 9 15 9 14 15 Light discoloration resistance 8 7 8 8 9 8 Formability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 6 Example 31 32 33 34 35 36 Composition (parts by weight) EPDM 70 70 70 70 70 70 SEPS 30 30 30 30 30 30 PP 100 100 100 PET 100 100 100 SiH 3 3 3 SiH 3 3 3 catalyst 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 Physical properties Hardness 81 80 81 80 81 79 TS (MPa) 17 17 19 18 20 17 Eb (%) 600 600 640 560 610 620 CS ( %) 34 35 35 36 32 34 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 ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 7 Example 37 38 39 40 41 42 Composition (parts by weight) SBR 70 30 70 30 70 30 SEBS 30 70 30 70 30 70 PP 100 100 100 PET 100 100 100 SiH 3 3 3 SiH 3 3 3 catalyst 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 Physical properties Hardness 79 83 82 84 83 82 TS (MPa) 15 14 16 17 18 18 Eb (%) 630 630 610 580 630 650 CS ( %) 36 38 37 38 35 37 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 14 13 14 11 12 13 Light discoloration resistance 8 8 8 9 9 9 Formability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 8 Example 43 44 45 46 47 48 Composition (parts by weight) BuR 70 30 70 30 70 30 SEPS 30 70 30 70 30 70 PP 100 100 100 PET 100 100 100 SiH 3 3 3 SiH 3 3 3 catalyst 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 Physical Property Hardness 79 83 82 84 83 82 TS (MPa) 15 14 16 16 17 17 Eb (%) 630 630 610 580 630 650 CS ( %) 34 35 32 32 29 30 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 10 10 11 9 9 10 Light discoloration resistance 7 7 7 8 8 8 Moldability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 9 Example 49 50 51 52 53 54 Composition (parts by weight) ANR 70 30 70 30 35 15 SEPS 30 70 30 70 15 35 PVC 100 100 50 50 100 100 SiH 3 3 1.5 SiH 3 3 1.5 catalyst 0.5 0.5 0.5 0.5 0.5 0.5 0.5 E-GMA-AM 10 10 10 VC-PVC 10 10 10 OIL 100 100 100 100 100 100 Physical property Hardness 79 83 62 64 83 82 TS (MPa) 15 14 14 13 21 20 Eb (%) 530 530 560 580 430 450 CS (%) 32 34 27 30 38 39 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 10 10 11 9 9 10 Light discoloration resistance 9 9 9 9 9 9 Formability test ○ ○ ○ ○ ○ ○ Long term Reliability ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 10 Example 55 56 57 58 59 60 Composition (parts by weight) EPDM 70 70 70 70 70 70 70 SEPS 30 30 30 30 30 30 PP 100 200 95 195 100 PET 100 SiH 3 3 3 6 3 SiH 3 catalyst 0.5 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 properties Hardness 81 88 78 89 84 85 TS (MPa) 19 18 16 13 19 19 Eb (%) 635 595 630 510 605 615 CS (%) 36 38 28 42 31 32 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 14 8 14 9 13 14 Light discoloration resistance 8 7 8 8 9 8 Formability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 11 Example 61 62 63 64 65 66 Composition (parts by weight) EPDM 70 70 70 70 70 70 SEBS 30 30 30 30 30 30 PP 100 200 95 195 100 100 SiH 3 3 3 6 SiH 3 3 catalyst 0.2 0.2 0.2 0.2 0.2 0.2 EP-SEBS 10 10 10 10 10 10 OIL 100 200 190 280 100 100 Physical properties 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 Formability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 12 Example 67 68 69 70 71 72 Composition (parts by weight) ANR 70 70 70 70 70 70 SEPS 30 30 30 30 30 30 PET 100 195 100 100 100 100 SiH 3 3 3 SiH 3 3 3 catalyst 2 2 2 2 2 2 MAH-EP 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 (%) 640 540 620 580 590 640 CS (%) 33 42 33 32 32 33 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 13 8 13 13 13 12 Light discoloration resistance 8 9 8 9 8 9 Moldability test ○ ○ ○ ○ ○ ○ Long term Reliability ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 13 Example 73 74 75 76 77 78 Composition (parts by weight) EPDM 70 70 70 70 70 70 SEBS 30 30 30 30 30 30 PP 100 200 95 195 100 100 SiH 3 3 3 6 SiH 3 3 catalyst 10 10 10 10 10 10 EP-SEBS 10 10 10 10 10 10 OIL 100 200 190 280 100 100 Physical properties Hardness 80 86 75 89 83 82 TS (MPa) 19 17 14 12 20 20 Eb (%) 620 610 640 520 610 630 CS (%) 33 37 27 40 32 34 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 12 9 14 8 13 14 Light discoloration resistance 8 7 8 9 9 8 Formability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 14 Example 79 80 81 82 83 84 Composition (parts by weight) ANR 70 70 70 70 70 70 70 SEPS 30 30 30 30 30 30 PET 100 195 100 100 100 100 SiH 3 3 3 SiH 3 3 3 catalyst 10 10 10 10 10 10 MAH-EP 10 10 10 10 E-GMA-AM 10 10 OIL 100 280 100 100 100 100 Physical properties Hardness 83 86 78 81 85 82 TS (MPa) 19 13 20 21 22 18 Eb (%) 640 540 630 570 590 640 CS (%) 31 40 31 30 31 34 Low temperature impact resistance ○ ○ ○ ○ ○ ○ Oil resistance (%) 12 8 12 13 13 13 Light discoloration resistance 8 9 8 9 8 9 Moldability test ○ ○ ○ ○ ○ ○ Long term Reliability ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 15  Comparative example1 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 2OIL 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 (%) 45 50 50 52 44 51 Low temperature impact resistance × × × × × × Oil resistance (%) 18 19 22 13 19 12 Light discoloration resistance 8 7 8 9 9 8 Formability test ○ ○ ○ ○ ○ ○ Long-term reliability × × × × × ×Scratch resistance × × × × × ×

Table 16 Comparative Example 7 8 9 10 11 12 Composition (parts by weight) EPDM 100 100 100 100 100 100 PP 100 200 95 195 PET 100 195 SP10 45 5 5 5 5 5 5 Stannous chloride 2 2 2 2 2 2 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 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 × × × × × × Scratch resistance × × × × × ×

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 3 3 3 3 3 SiH 3 catalyst 0.5 0.5 0.5 0.5 0.5 0.5 OIL 100 200 190 100 100 100 Physical property 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 34 36 Low temperature impact resistance × × × × × × Oil resistance (%) 14 9 15 13 14 15 Light discoloration resistance 8 7 8 9 9 8 Moldability test × × × × × × Long-term reliability × × × × × × Scratch resistance × × × × × ×

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 3 3 3 SiH 3 3 3 catalyst 0.5 0.5 0.5 0.5 0.5 0.5 OIL 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 × × × × × × Scratch resistance × × × × × ×

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 3 3 3 SiH 3 3 3 catalyst 0.5 0.5 0.5 0.5 0.5 0.5 OIL 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 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 × × × × × × Scratch resistance × × × × × ×

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 3 3 3 SiH 3 3 3 catalyst 0.5 0.5 0.5 0.5 0.5 0.5 OIL 100 100 100 100 100 100 Physical properties Hardness 79 83 82 84 83 82 TS (MPa) 15 16 16 17 18 18 Eb (%) 630 630 610 580 630 650 650 CS (%) 34 30 32 30 30 28 Low temperature impact resistance × × × × × × Oil resistance (%) 10 10 11 9 9 10 Light discoloration resistance 7 7 7 8 8 8 Moldability test × × × × × × Long-term reliability × × × × × × Scratch resistance × × × × × ×

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 SiH 3 3 1.5 SiH 3 3 1.5 catalyst 0.5 0.5 0.5 0.5 0.5 0.5 OIL 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 Moldability test × × × × × × Long-term reliability × × × × × × × Scratch resistance × × × × × ×

Table 22 Comparative Example 43 44 45 46 47 48 Composition (parts by weight) SEBS 100 50 100 100 SEPS 100 50 100 PP 100 100 195 95 195 OIL 100 100 100 280 190 280 Physical hardness 79 80 82 84 83 82 TS (MPa) 10 9 10 7 10 6 Eb (%) 630 630 660 680 630 650 CS (%) 34 30 32 37 40 38 Low temperature impact resistance × × × × × × Oil resistance (%) 12 12 11 10 11 10 Light discoloration resistance 9 9 9 9 9 9 Formability test ○ ○ ○ ○ ○ ○ Long-term reliability × × × × × × Scratch resistance ○ ○ ○ ○ ○ ○

[0054]

According to the production method of 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 and creep resistance, low temperature impact resistance, mechanical strength, and scratch resistance, exhibits excellent rubber elasticity over a wide temperature range, has good oil resistance, and is free of toning. Therefore, oil resistance, rubber elasticity, mechanical strength and molding speed, molding yield,
It can be suitably molded and used for automobile parts, home electric appliance parts, various electric wire coatings (insulations, sheaths) and various industrial parts for which improvement in the degree of freedom in toning is desired.

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Claims (14)

[Claims] 1. A rubber-like composition (a) comprising a mixture of an unsaturated double bond-containing rubber (a-1) and a styrene elastomer (a-2), a thermoplastic resin (b), and SiH in the molecule.
A thermoplastic elastomer characterized by being prepared by mixing an organic organosiloxane cross-linking agent (c) having two or more groups, a hydrosilylation catalyst (d) and a compatibilizing agent (e) and dynamically heat-treating them. 2. A thermoplastic resin (b) in an amount of 5 to 300 parts by weight, and S in the molecule, based on 100 parts by weight of the rubber composition (a).
0.5 to 30 parts by weight of an organoorganosiloxane-based cross-linking agent (c) having two or more iH groups, 0.001 to 20 parts by weight of a hydrosilylation catalyst (d), and a compatibilizer (e) of 0.
The thermoplastic elastomer according to claim 1, which comprises 5 to 20 parts by weight. 3. The thermoplastic elastomer according to claim 2, further comprising 30 to 300 parts by weight of paraffin oil (f) mixed with 100 parts by weight of the rubber composition (a). 4. A block copolymer obtained by polymerizing a compatibilizing agent from a monomer comprising at least two kinds of a component having an affinity with the rubber composition (a) and a component having an affinity with the thermoplastic resin (b). The thermoplastic elastomer according to claim 1, 2 or 3, which is a polymer, a random copolymer or a graft copolymer. 5. The thermoplastic elastomer according to claim 1, 2, 3 or 4, wherein the hydrosilylation catalyst (d) is a metal catalyst and / or a peroxide catalyst system. 6. The thermoplastic elastomer according to 1, 2, 3 or 4, wherein the hydrosilylation catalyst (d) is dissolved or carried in one or more kinds selected from a liquid component and a solid component. 7. The organic organosiloxane cross-linking agent (c) having two or more SiH groups in the molecule has the following structural formula: Thermoplastic elastomer. Or Here, 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 is bonded to a silicon atom. Two or more silicon atoms in which at least one R is hydrogen are present in the molecule. 8. An unsaturated double bond-containing rubber (a-1) and a styrenic elastomer (a-2) of the rubber composition (a).
The thermoplastic elastomer according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the ratio is 10:90 to 90: 10% by weight. 9. The unsaturated double bond-containing rubber of the rubber composition (a) is an ethylene-α-olefin-non-conjugated diene copolymer rubber, a vinyl aromatic compound-conjugated diene compound copolymer rubber, or butadiene. At least one selected from rubber and butyl rubber, and the thermoplastic resin (b) is at least one selected from polyolefin-based resins, polyester-based resins, polyamide-based resins, and polycarbonate-based resins, and the compatibilizer (e) ) Is a compatibilizing agent (e
The thermoplastic elastomer according to claim 1, 2, 3, 4, 5, 6, 7 or 8, which is selected from one or more of (-1), (e-2) and (e-3). (E-1) Epoxy-modified water obtained by hydrogenating an end block A mainly composed of at least two vinyl aromatic compounds and an intermediate polymer block copolymer mainly composed of at least one conjugated diene compound Addition block copolymer (e-2) Epoxy-modified ethylene-α-olefin (-
Non-conjugated diene) Copolymer rubber (e-3) Epoxy-modified polyolefin resin 10. The unsaturated double bond-containing rubber of the rubber composition (a) is an ethylene-α-olefin-non-conjugated diene copolymer rubber, a vinyl aromatic compound-conjugated diene compound copolymer rubber, or butadiene. At least one selected from rubber and butyl rubber, the thermoplastic resin (b) is at least one selected from polyolefin-based resins and polyamide-based resins, and the compatibilizing agent (e) is the following maleic anhydride. The one or more selected from the compatibilizers (e-4), (e-5), and (e-6) modified with an acid, 1, 2, 3, 4, 5, 6,
7. The thermoplastic elastomer according to 7 or 8. (E-4) Maleic anhydride obtained by hydrogenating an end block A mainly composed of at least two vinyl aromatic compounds and an intermediate polymer block copolymer mainly composed of at least one conjugated diene compound. Group-modified hydrogenated block copolymer (e-5) Maleic anhydride group-modified ethylene-α-olefin (-non-conjugated diene) copolymer rubber (e-6) Maleic anhydride group-modified polyolefin resin 11. The unsaturated double bond-containing rubber of the rubber composition (a) is an ethylene-α-olefin-non-conjugated diene copolymer rubber, a vinyl aromatic compound-conjugated diene compound copolymer rubber, or butadiene. Rubber, butyl rubber, α, β-
One or more selected from unsaturated nitrile-conjugated diene copolymer rubber and acrylic rubber, and a thermoplastic resin (b)
Is one or more selected from a polyolefin resin, a polyester resin, a polyamide resin, a polycarbonate resin, a vinyl chloride resin, and a methacrylate resin, and the compatibilizing agent (e-7) is in the same molecule. The thermoplastic elastomer according to claim 1, which is a modified polyolefin resin having an epoxy group and an ester group. 12. The unsaturated double bond-containing rubber of the rubber composition (a) is acrylic rubber, α, β-unsaturated nitrile-
One or more selected from conjugated diene copolymer rubbers,
The thermoplastic resin (b) is at least one selected from vinyl chloride resin, polyurethane resin, and methacrylate resin, and the compatibilizer (e-8) is halogenated olefin resin, vinyl chloride-vinyl acetate 5. One or more selected from polymers and vinyl aromatic compound-α, β-unsaturated nitrile-conjugated diene copolymers.
The thermoplastic elastomer according to 5, 6, 7 or 8. 13. The unsaturated double bond-containing rubber of the rubber composition (a) is an ethylene-α-olefin-non-conjugated diene copolymer rubber, and the thermoplastic resin (b) is a crystalline olefin resin. Yes, the compatibilizer (e) is the following (e-9)
Claims 1, 2, 3 selected from (e-10) and (e-11),
The thermoplastic elastomer according to 4, 5, 6, 7 or 8. (E-9) Polypropylene resin having an epoxy group as an essential component, having a maleic anhydride group in the molecule, polyethylene, ethylene copolymer, styrene block copolymer and / or hydrogenated product thereof, styrene random copolymer And / or a compatibilizing agent (e-10) comprising a maleic anhydride group in the molecule, which is obtained by melt-reacting at least one selected from carboxylic acid-modified resins such as hydrogenated products thereof. 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. And a compatibilizing agent (e-11) polypropylene, which is obtained by melting and reacting at least one of them, as an essential component, Peroxidation of a blend with at least one resin selected from ethylene, ethylene-based copolymers, styrene block copolymers and / or hydrogenated products thereof, styrene random copolymers and / or hydrogenated products thereof. Compatibilizer formed by dynamically heat treating in the presence of a substance 14. The compatibilizers (e-9) and (e-10) are selected from epoxy-modified resin and maleic anhydride group-modified resin in the ratio, and (e-11) is selected from polypropylene and a specific group. The ratio of one or more resin components is 10: 9
It is characterized by adding 0.5 to 20 parts by weight of the compatibilizer (e) of 0 to 90: 10% by weight to 100 parts by weight of the total of the rubber component (a) and the resin component (b). The thermoplastic elastomer according to claim 13.