JP3290814B2 - Thermoplastic elastomer - 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, and more particularly, to a rubber composition having high flexibility, 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 has excellent oil resistance, light discoloration resistance, and extremely excellent toning while being a thermoplastic elastomer, and 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 vulcanizing step and have the same moldability as thermoplastic resins, have been used in automobile parts, home appliance parts, wire covering materials, medical parts. , Miscellaneous goods and footwear. A typical example of the structure of a thermoplastic elastomer is a type in which a hard segment and a soft segment are alternately contained in a copolymer chain as disclosed in JP-A-61-34050. is there. And
Various grades are manufactured 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, as disclosed in Japanese Patent Publication No. 53-21021 or the like, a thermoplastic blend of a monoolefin copolymer rubber and a polyolefin resin partially crosslinked using an organic peroxide, or a monoolefin copolymer rubber and a polyolefin A composition obtained by melt-kneading a resin with an organic peroxide as a crosslinking aid and partially crosslinking the resin 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 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 extremely complicated and the properties and ratio of each segment in the polymerization stage are increased. Is very difficult to control, and defective products may occur when switching grades. Furthermore, it is very difficult to recover the produced polymer because it contains a large amount of rubbery substances. Because the technology disclosed as a conventional styrenic elastomer belongs to this category,
The moldability and weather resistance are very good, and the scratch resistance is relatively good compared to olefin-based elastomers, but it also has the above-mentioned drawbacks, so it can be used in a wide range of applications such as industrial mechanical parts. Cannot be used.

A thermoplastic elastomer having a structure in which a monoolefin copolymer rubber in a component is partially crosslinked is insufficient in oil resistance and shape recovery at high temperatures because of partial crosslinking. Therefore, it cannot be used for various applications 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, 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 completely crosslinked 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 a high degree of freedom in toning. It cannot be used for applications such as automobile parts, home appliance parts, electric wire coating, etc.

Further, US Pat. No. 4,803,244 proposes a method of 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, low-temperature impact resistance is not satisfactory because the adhesion between rubber and resin is not sufficient because a compatibilizer is not added, and applications requiring low-temperature impact resistance-for example, automotive air It cannot be used for bag materials. 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, USP45
As disclosed in U.S. Pat. No. 94390, a method of dynamically heat-treating under a high shear of 2000 / sec or more has been proposed to solve the above-mentioned problem. Because the material is exposed under shear, not only the material itself tends to decompose and deteriorate, but also to achieve high shear, not only the rotational speed during melt-kneading but also the clearance of the kneading machine is reduced to about 1 / 3 to 1/5 or less, the productivity of the thermoplastic elastomer composition,
It is not practical in terms of the 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 a problem which has been difficult with a conventional thermoplastic elastomer composition, and has been made while taking advantage of the excellent characteristics of a styrene elastomer material. While maintaining good rubber properties over a wide temperature range, it has the characteristics of low-temperature impact resistance, wide degree of freedom in coloring, low residual heavy metals, etc., so it is used in applications where toning is required, hygiene, long-term reliability To provide a thermoplastic elastomer that can be used for a wide variety of applications, including applications that require the following.

[0007]

SUMMARY OF THE INVENTION As a cross-linking agent, an organic organo-organic compound having two or more SiH groups in a molecule having excellent light discoloration resistance and biocompatibility and having the property of selectively cross-linking an unsaturated double bond-containing rubber. The siloxane compounds are also crosslinked while being melt-kneaded using a hydrosilylation catalyst to selectively crosslink the rubber, and further enhance the interfacial adhesive strength with a compatibilizer to reduce only the mechanical shear force. Research has been developed based on the technical idea of highly dispersing crosslinked rubber particles without dependence, and as a result, while having good rubber properties over a wide temperature range, low-temperature impact resistance, toning, good It can be applied to various applications over a wide range including applications where a molded appearance is required. In addition, with a usual kneader, the shear rate is extremely common sense of 100 to 1000 / sec. 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, since the thermoplastic elastomer composition produced according to the present invention has been subjected to a compatibilizing method, it has been found that morphological changes hardly occur even if annealing treatment is performed, and as a result, the long-term reliability is extremely excellent. . The present invention provides an unsaturated double bond-containing rubber (a-1), partially or
Is a completely hydrogenated styrenic elastomer (a-
Rubber composition (a) comprising the mixture of 2), thermoplastic resin (b), organic organosiloxane crosslinking agent having two or more SiH groups in the molecule (c), hydrosilylation catalyst (d), phase A thermoplastic elastomer obtained by mixing a solubilizer (e) and dynamically heat-treating the thermoplastic elastomer. Preferably, the thermoplastic resin (b) 5 is added to 100 parts by weight of the rubber-like composition (a). To 300 parts by weight, an organic organosiloxane crosslinking agent having two or more SiH groups in the molecule (c)
0.5 to 30 parts by weight, hydrosilylation catalyst (d)
001 to 20 parts by weight and a compatibilizer (e) 0.5 to 20 parts by weight, and if necessary, a paraffinic oil (f)
Of a thermoplastic elastomer obtained by adding 30 to 300 parts by weight of a thermoplastic elastomer.

[0008] The unsaturated double bond-containing rubber of the rubbery composition (a) used in the present invention is not particularly limited, and is generally commercially available in the main chain and / or the side chain.
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 Acrylonitrile, the most frequently used nitrile-conjugated diene copolymer rubber
Butadiene copolymer rubber and the like. Then, the aliphatic double bonds contained in these rubbers are partially hydrogenated,
Partially hydrogenated rubber having a reduced 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, as the ethylene-α-olefin-nonconjugated diene copolymer rubber composed of ethylene, α-olefin and non-conjugated diene, α-olefin having 3 to 15 carbon atoms in the composition is suitable. 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 ethylene / α-olefin ratio of the copolymer rubber is 50 / weight ratio.
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. 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 has an iodine value of 5 to 30, especially 1
Those having 0 to 20 are preferred.

The styrenic elastomer used in the present invention is a copolymer which is a rubber elastic material at room temperature and is partially or completely hydrogenated. Specific examples thereof include hydrogenated 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, styrene-based elastomers which significantly improve low-temperature impact resistance and are preferably used are SEBS and SEPS, and the preferred styrene content is 10 to 80% by weight, more preferably 3% by weight.
The content is 0 to 70% by weight, and more preferably 40 to 70% by weight. The ratio of the unsaturated double bond-containing rubber to the styrene-based elastomer in the rubber-like 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
When the amount is out of the range of parts by weight, there is a tendency that physical properties exhibited when the rubber-like mixture is not blended are not so different.

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 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-based 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 include ethylene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, poly-4-methyl-1-pentene, polybutene-1, and the like. As a crystalline olefin resin,
When using isotactic polypropylene or its copolymer, the MFR (ASTM-D-1238L condition, 230 ° C.) is preferably from 0.1 to 50 g / 10 min, particularly preferably from 0.5 to 30 g / 10 min. Can be used. The amorphous olefin resin is a polymer having a cyclic olefin structure alone 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). If the amount exceeds 300 parts by weight, the hardness of the obtained elastomeric composition tends to be high and flexibility tends to be lost. If the amount is less than 5 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. As specific examples of the compounds, compounds having structures of cyclic polysiloxanes, linear polysiloxanes, and tetrahedral siloxanes as shown below are typical. Further, a compound and / or a polymer derived from the compound may be used. Here, m is an integer of 3 to 30, n is an integer of 0 to 200, and R is hydrogen, an alkyl group, an alkoxy group, an aryl group or an aryloxy group, and is bonded to a silicon atom. At least one silicon atom in which R is hydrogen is present two or more times in the molecule. The organoorganosiloxane having the above structure can selectively crosslink rubber.

The crosslinking reaction catalyst (d) used in the present invention refers to any catalyst that promotes a hydrosilylation reaction. Examples of the catalyst include transition metals such as palladium, rhodium, and platinum, or compounds and complexes thereof.
Also, peroxides, amines and phosphines are used. In addition, ultraviolet rays and γ rays can also be used. As the most common catalysts, dicyclobis (acetonitrile) palladium (II), chlorotris (triphenylphosphine) rhodium (I), chloroplatinic acid and the like are famous. 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 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.
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 compounds used in the present invention include N, N'-m-phenylenebismaleimide and toluylenebismaleimide. N, N'-m-phenylenebismaleimide is commercially available, for example, HVA-2 (manufactured by DuPont), Succinol B
M (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 used in which residual heavy metals pose a problem.
For example, it can be suitably used in the medical field. Also,
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, it is a method of dissolving in a solvent, supporting on an inorganic filler, or combining 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 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,
Examples thereof include magnesium hydroxide, mica, barium sulfate, natural silicic acid, rigid silicic acid (white carbon), and titanium oxide. A known method can be used for adjusting the supported catalyst.

Here, the thermoplastic elastomer composition dynamically vulcanized means that 1 g of the composition obtained in the present invention is refluxed for 10 hours with a Soxhlet extractor using boiling xylene, and the residue is treated with an 80 mesh wire mesh. The ratio of the dry weight of the insoluble matter remaining on the mesh (g) / the weight of the unsaturated double bond-containing rubber in the component a contained in 1 g of the composition is 1
A gel content of at least 30%, indicated by a value of 00,
Preferably, it is vulcanized so as to have a concentration of 50% or more (however, insoluble components such as inorganic fillers are not included), and the vulcanization is performed during melt-kneading of the thermoplastic elastomer composition. It is characterized by. In order to obtain such a dynamically vulcanized thermoplastic elastomer composition, the compounding amount of the organic organosiloxane-based crosslinking agent c is 0.5 to 100 parts by weight of the unsaturated double bond-containing rubber in the component a. 30
Parts by weight, preferably from 1 to 20 parts by weight, and the gel content thereof can be adjusted. Further, the amount of the catalyst d to be added is 0.1 to 100 parts by weight of the rubber component.
001 to 20 parts by weight of a catalyst can be optionally added. Addition amount of heavy metal catalyst is 0.005 to 5
Parts by weight are preferred, and more preferably 0.01 to 2 parts by weight. In the case of a peroxide-based catalyst, the addition amount is 0.1.
The amount is preferably from 01 to 15 parts by weight, more preferably from 0.1 to 10 parts by weight. Here, if the amount is less than 0.001 part by weight, the crosslinking does not proceed at a practical speed. Also, 20
If the amount is more than part by weight, not only does not have the effect of increasing the amount, but also the deactivated catalyst becomes blackish and becomes poor in appearance, and heat treatment tends to cause undesired side reactions (such as decomposition of unreacted SiH groups).

The compatibilizer e used in the present invention has a component having affinity for rubber and a thermoplastic resin in the same molecule and acts as a surfactant by acting as a surfactant. As a result, the usual kneading conditions (shear rate: 10
0-1000 / SEC) to finely disperse the rubber vulcanized to 30 microns or less, improve the adhesive strength at the interface between the vulcanized rubber and the thermoplastic resin, and significantly improve 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 rubbery composition a and the thermoplastic resin b each have a component having good affinity in the same molecule. Few monomer polymers 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 compatibilizers are listed below, and the unsaturated double bond-containing rubber and the thermoplastic resin in the rubbery composition (a) in which each compatibilizer suitably exerts its effect. The combination of resin (b) is shown. Compatibilizers (e-1) and (e-) wherein the compatibilizer (e) is modified with the following epoxy group:
2) When the compatibilizer is at least one 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 a compound-conjugated diene compound copolymer rubber, butadiene rubber, and butyl rubber, and the thermoplastic resin (b) is selected from a polyolefin-based resin, a polyester-based resin, a polyamide-based resin, and a polycarbonate-based resin. It is suitably used in one or more combinations. (E-1) Epoxy-modified water obtained by hydrogenating at least two terminal blocks A mainly composed of a vinyl aromatic compound and at least one intermediate polymer block copolymer mainly composed of a conjugated diene compound. (E-2) Epoxy-modified ethylene-α-olefin (-
(Non-conjugated diene) copolymer rubber (e-3) Epoxy-modified polyolefin-based resin In this combination, except for the polyolefin-based resin, the thermoplastic resin has a group that reacts with an epoxy group,
When this reacts with the 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 compatibilizer 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 anhydride and / or a carboxylic acid group. The one or more selected compatibilizers are such that the unsaturated double bond-containing rubber is ethylene-α-olefin-non-conjugated diene copolymer rubber, vinyl aromatic compound-conjugated diene compound copolymer rubber, butadiene rubber, butyl rubber One or more selected from
The thermoplastic resin (b) is suitably used in one or more combinations selected from polyolefin-based resins and polyamide-based resins. (E-4) Maleic anhydride obtained by hydrogenating at least two terminal blocks A mainly composed of a vinyl aromatic compound and at least one intermediate polymer block copolymer mainly composed of a 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 Except for the polyolefin resin, the thermoplastic resin has a group that reacts with a maleic anhydride group, and reacts with the maleic anhydride group to form an unsaturated double bond-containing rubber and a thermoplastic resin ( A graft copolymer having an affinity for any of 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 compatibilizing agent (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 may be an ethylene-containing rubber.
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 At least one thermoplastic resin (b) is a polyolefin resin,
It is suitably used in combination with at least one selected from a polyester resin, a polyamide resin, a polycarbonate resin, a vinyl chloride resin, and a methacrylate resin. 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 and the thermoplastic resin (b) has an improving effect. The compatibilizer (e-8) is selected from halogenated olefin resin, vinyl chloride-vinyl acetate copolymer, and vinyl aromatic compound-α, β-unsaturated nitrile-conjugated diene copolymer. Among the at least one compatibilizer, the unsaturated double bond-containing rubber is at least one selected from acrylic rubber and α, β-unsaturated nitrile-conjugated diene copolymer rubber, and the thermoplastic resin (b) is It is suitably used in combination with at least one selected from vinyl chloride resins, polyurethane resins, and methacrylate resins.

Examples of the method for adjusting the compatibilizer for the hydrocarbon rubber and the polyolefin resin among the thermoplastic resins are shown in (e-9) and (e-1) below.
0) and (e-11). (E-9) 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 And / or a melt reaction of at least one selected from a maleic anhydride group-modified resin such as a hydrogenated product thereof. (E-10) A maleic anhydride group is incorporated in the molecule. Having a polypropylene as an essential component, 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. A compatibilizer characterized by melting at least one selected from the group consisting of: (e-11) polypropylene as an essential component And a blend of at least one resin selected from polyethylene, an ethylene-based copolymer, a styrene block copolymer and / or a hydrogenated product thereof, a styrene random copolymer and / or a hydrogenated product thereof. Compatibilizers that are dynamically heat-treated in the presence of a peroxide. Modified resins having a maleic anhydride group and modified resins having an epoxy group, which are used as raw materials for the compatibilizers (e-9) and (e-10), Can be easily obtained by known techniques.
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 / terpolymer
Maleic anhydride 3 copolymer, maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene
Examples 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, and 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, grafted with glycidyl acrylate Styrene-ethylene
A butylene-styrene random copolymer is exemplified.

The modified resin having a maleic anhydride group and the epoxy-modified resin can be prepared by themselves.
The compatibilizers (e-9) and (e-10) of the present invention are obtained by mixing the above-mentioned composition comprising a modified resin having a maleic anhydride group in a molecule and a resin having an epoxy group with a batch-type kneader,
It is obtained by performing a melting 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 the maleic anhydride group contained in the raw material disappeared. It is probable that a reaction took place in between. The compatibilizer (e-11) 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 hydrogenated product thereof. A batch kneader 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 or an azo compound, and, if necessary, a cocatalyst such as a bismaleimide-based compound. At 150 ~
It is obtained by performing a melt reaction 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 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. If it exceeds 2 parts by weight, not only is there no effect of increasing the amount, but also there is a tendency to cause undesirable side reactions (such as decomposition of polypropylene and gelation reaction).

Here, for the compatibilizers (e-9) and (e-10), the ratio between the epoxy-modified resin and the maleic anhydride group-modified resin is used, and for (e-11), polypropylene and the specific group of the specific group are used. The ratio of at least one resin selected from the group is 1
0: 90-90: 10% by weight, preferably 70: 30-
30: 70% by weight, more preferably 60:40 to 40:
It is blended in the range of 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 of the present invention tends to be insufficient. The compatibilizers (e-9), (e-10), and (e-11) listed here are those in which the thermoplastic resin is an olefin resin or the rubber is EPD.
It is particularly effective for hydrocarbon materials such as M and butyl rubber. Further, the amount of the compatibilizer (e) added depends on the amount of the rubber component (a).
+ 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 of the total of the resin component (b). Is done.
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 the thermoplastic elastomer becomes insufficient, and the appearance of the molded article tends to deteriorate. On the other hand, if it exceeds 20 parts by weight, the thermoplastic elastomer of the present invention has a high hardness and low-temperature impact resistance, and tends 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. In general, a softening agent for mineral oil rubber called process oil or extender oil used for softening, increasing the volume of a rubber, and improving processability is a mixture of an aromatic ring, a naphthene ring, and a paraffin chain. Those having 50% or more of the total number of carbon atoms in the paraffin chain are called paraffinic, those having 30 to 45% naphthenic ring carbon are naphthenic, and those having more than 30% aromatic carbon are aromatic. System.
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 50.
0 cst, pour point -10 to -15 ° C and flash point 1
Indicates 70 to 300 ° C. The preferred amount of the paraffinic oil (f) is 3 parts per 100 parts by weight of the rubber component (a).
0 to 300 parts by weight, more preferably 30 to 25 parts by weight.
0 parts by weight. If the composition exceeds 300 parts by weight,
Softeners tend to bleed out, can cause tackiness in the final product, and tend to reduce mechanical properties. If it is less than 30 parts by weight, there is no point in adding.

The thermoplastic elastomer composition obtained by the production method of the present invention has remarkably improved heat resistance as compared with known styrene elastomers. In addition, the present invention provides a composition exhibiting excellent performance in mechanical strength and compression set at high temperatures as compared with a thermoplastic elastomer composition partially crosslinked using a known organic peroxide. 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. Furthermore, the adhesiveness at the interface is remarkably improved, as compared with a thermoplastic elastomer composition obtained only by crosslinking by hydrosilylation using a heavy metal catalyst such as chloroplatinic acid, as is known in the art. And 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 also has improved scratch resistance. In addition to the above-mentioned components, the composition of the present invention may further contain an inorganic filler, if necessary, particularly for applications where no toning is 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), titanium oxide, and the like. Furnace black and the like can be used. Of these inorganic fillers, talc and calcium carbonate are economically advantageous and preferred. Nucleating agent, outer lubricant, inner lubricant,
A hindered amine-based light stabilizer, a hindered phenol-based antioxidant, a coloring agent, silicone oil, and the like may be added. Further, other thermoplastic resins such as an ethylene-α-olefin copolymer and a thermoplastic urethane resin can 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, in which a single-screw extruder, a twin-screw extruder, a 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. Addition and dynamic vulcanization, or 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 can also be adopted. In this case, the temperature for melt-kneading can be suitably selected from 180 ° C to 300 ° C, and the shear rate can be suitably selected from 100 to 1000 / SEC. Further, first, (a), (c) and (d)
A thermoplastic elastomer of the present invention can be obtained by first preparing a cured product of rubber using the component (f), adding a crushed rubber cured product to the remaining components, and melt-kneading the mixture. 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, Brabender, rolls and the like are used. At this time, the temperature for melt-kneading is 180 ° C to 300 ° C, and the shear rate is 100 to 100.
0 / SEC.

The hardened rubber produced through the above steps can be roughly crushed 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 a batch-type kneader such as a kneader is used, the composition is thermosetting when the rubber is sufficiently cured, and is crushed in the kneader without providing a pulverizing 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 can be formed by injection molding, extrusion molding, calender molding, blow molding. And other various molding methods can be applied. 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. Further, in the extrusion / blow molding region at a medium shear rate, the viscosity becomes high to some extent, which leads to a low drawdown, so that extrusion / blow molding is easy.

[0026]

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 (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-1 (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-1 (3): SBR> Styrene-butadiene copolymer rubber JSR 1503 manufactured by Japan Synthetic Rubber Co., Ltd. [Styrene content: 23.5% by weight Mooney viscosity ML1 + 4
(100 ° C.): 75] <Component a-1 (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 a-2 (1): SEBS> Styrene-ethylene-butylene-styrene copolymer water additive Tuftec H1041 manufactured by Asahi Kasei Kogyo 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 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 ( Smirit 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): Medium> Chloroplatinic acid hexahydrate manufactured by Yasuda Pharmaceutical Co., Ltd. <Component d (2): catalyst> Dicumyl peroxide Parkmill D manufactured by NOF Corporation <Component d (3): catalyst> of component d (1) 1% by weight 2-
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: EP-SEBS> Epoxy group-modified styrene-ethylene-butylene-styrene copolymer (SEBS) Tuftec Z514 manufactured by Asahi Kasei Kogyo Co., Ltd. <Component e-5: MAH-EP> Maleic anhydride Group-modified ethylene-propylene copolymer EP T7741P manufactured by Nippon Synthetic Rubber Co., Ltd. <Component e-7: E-GMA-AM> Terpolymer of ethylene-glycidyl methacrylate-methyl acrylate manufactured by Sumitomo Chemical Co., Ltd. Bondfast 7M <Component e-8: VC-PVC> Vinyl acetate-vinyl chloride copolymer Sumigraf GE manufactured by Sumitomo Chemical Co., Ltd. <Component e-10: PP-MAH> An end of a polypropylene oligomer having an average molecular weight of 4000 is anhydrous. 100 parts by weight of maleic acid-modified (PP-MAH) were added to the epoxy-modified styrene block. United TAFTEC Z514
[Asahi Kasei Kogyo Co., Ltd.] 80 parts by weight were added and mixed thoroughly with a Henschel mixer.
After melt kneading for minutes, forming a roll sheet, cooling to room temperature,
Pellets were formed with a sheet pelletizer to obtain a compatibilizer e-2 (1) of the present invention. As a result of examining 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. It seems that the problem 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)
° C), average molecular weight 746, ring analysis: CA = 0%, CN =
27%, CP = 73%]

<< Examples 1 to 84 and Comparative Examples 1 to 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 various 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 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. × 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 ×. (9) Scratch resistance test: A pencil scratch test for paint film was conducted in accordance with JIS K5401, and a 9
When the pencil was scratched with the H pencil, it was evaluated as x, and when it was not, it was evaluated as o. )

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 performed using a heat-reactive alkylphenol resin [Schenectad
y Chemicals, Inc. SP1045] and 5 parts by weight of a crosslinking aid [stannous chloride] except that 2 parts by weight were used. In Comparative Examples 13 to 42, an organoorganosiloxane was used as a cross-linking agent, and the same chloroplatinic acid hexahydrate as the component d in Example was used as a catalyst. Comparative Examples 43-4
8 shows the evaluation result of the styrene-based elastomer material. From these results, the thermoplastic elastomer composition dynamically vulcanized using the organic organosiloxane compound of the present invention and the compatibilizing agent was added, and the thermoplastic elastomer composition dynamically vulcanized by blending a known organic peroxide system was used. It was found that a composition having more excellent mechanical strength, compression set at 70 ° C., and oil resistance was obtained. And furthermore,
It has been found that the composition of the present invention has a high degree of freedom in toning since it has 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. Furthermore, it was also found that it had scratch resistance comparable to that of a 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 property hardness 81 88 78 89 84 85 TS (MPa) 19 18 14 13 19 19 Eb (%) 625 590 625 510 605 615 615 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 Moldability 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 (%) 620 540 620 580 610 610 540 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 Moldability 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 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 (%) 580 570 570 570 540 580 540 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 ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 4 Example 19 20 21 22 23 24 Composition (parts by weight) EPDM 70 70 70 70 70 70 SEPS 30 30 30 30 30 30 PP 100 100 100 Ny66 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 SEBS 30 30 30 30 30 30 PP 100 200 95 195 100 PET 100 SiH 3 3 3 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 hardness 81 88 78 89 84 85 TS (MPa) 19 18 14 13 19 19 Eb (%) 625 590 625 510 605 605 615 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 Moldability 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 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 Moldability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 8 Example 43 43 45 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 Properties 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 Properties 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 Moldability test ○ ○ ○ ○ ○ ○ Long term Reliability ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 10 Examples 55 56 57 58 59 60 Composition (parts by weight) EPDM 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 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 hardness 81 88 78 89 84 85 TS (MPa) 19 18 16 13 19 19 Eb (%) 635 595 630 510 605 605 615 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 Moldability 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 Moldability 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 Properties Hardness 82 87 79 82 84 81 TS (MPa) 19 13 20 21 22 18 Eb (%) 640 540 620 580 590 590 640 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 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 Moldability test ○ ○ ○ ○ ○ ○ Long-term reliability ○ ○ ○ ○ ○ ○ Scratch resistance ○ ○ ○ ○ ○ ○

Table 14 Example 79 79 80 81 82 83 84 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 10 10 10 10 10 10 10 MAH-EP 10 10 10 10 E-GMA-AM 10 10 OIL 100 280 100 100 100 100 Properties Hardness 83 86 78 81 85 82 TS (MPa) 19 13 20 21 22 18 Eb (%) 640 540 630 570 570 590 640 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 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 2 OIL 100 200 190 280 100 100 280 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 Moldability 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 SP1045 5 5 5 5 5 5 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 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 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 100 100 100 100 100 100 100 Properties 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 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 × × × × × × 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 Property 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 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 100 100 100 100 100 100 100 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 Properties 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 Moldability 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 has excellent flexibility, heat creep performance, low temperature impact resistance, mechanical strength, scratch resistance, excellent rubber elasticity over a wide temperature range, good oil resistance, and free 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 parts, various electric wire coatings (insulation, sheath), and various industrial parts for which improvement in the degree of freedom of toning is desired.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 51/06 C08L 83/05 83/05 101/00 101/00 C08K 5/54 (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 21/00 C08K 3/18 C08K 5/14 C08K 5/54 C08L 23/00 C08L 51/06 C08L 83/05 C08L 101/00

Claims (14)

(57) [Claims] 1. A unsaturated double bond-containing rubber (a-1), part
Rubbery composition (a) consisting of a mixture of partially or completely hydrogenated styrene elastomers (a-2), thermoplastic resin (b), organic organosiloxane having two or more SiH groups in the molecule A thermoplastic elastomer obtained by mixing a system crosslinking agent (c), a hydrosilylation catalyst (d), and a compatibilizer (e) and dynamically subjecting the mixture to heat treatment. 2. 5-100 parts by weight of a thermoplastic resin (b) based on 100 parts by weight of a rubber-like composition (a), and S in a molecule.
0.5 to 30 parts by weight of an organoorganosiloxane-based crosslinking 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 0.1 to 20 parts by weight.
2. The thermoplastic elastomer according to claim 1, comprising 5 to 20 parts by weight. 3. The thermoplastic elastomer according to claim 2, wherein 30 to 300 parts by weight of a paraffinic oil (f) is further mixed with 100 parts by weight of the rubbery composition (a). 4. A block copolymer obtained by polymerizing a compatibilizer from a monomer comprising two or more components having at least an affinity for the rubbery composition (a) and a component having an affinity for the thermoplastic resin (b). 4. The thermoplastic elastomer according to claim 1, which is a polymer, a random copolymer, or a graft copolymer. 5. The thermoplastic elastomer according to 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 supported on at least one selected from a liquid component or a solid component. 7. The method 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. Thermoplastic elastomer. Or Here, m is an integer of 3 to 30, n is an integer of 0 to 200, and R is hydrogen, an alkyl group, an alkoxy group, an aryl group or an aryloxy group, and is bonded to a silicon atom. At least one silicon atom in which R is hydrogen is present two or more times in the molecule. 8. The ratio of the unsaturated double bond-containing rubber (a-1) and the partially or completely hydrogenated styrene-based elastomer (a-2) in the rubber-like composition (a). Is 10:90
1, 2, 3, 4, 5, 5 to 90: 10% by weight.
8. The thermoplastic elastomer according to 6 or 7. 9. The rubbery composition (a) wherein the unsaturated double bond-containing rubber is ethylene-α-olefin-nonconjugated diene copolymer rubber, vinyl aromatic compound-conjugated diene compound copolymer rubber, butadiene Rubber or 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 compatibilizer modified with the following epoxy group (e
The thermoplastic elastomer according to claim 1, 2, 3, 4, 5, 6, 7, or 8, which is selected from at least one of -1), (e-2) and (e-3). (E-1) Epoxy-modified water obtained by hydrogenating at least two terminal blocks A mainly composed of a vinyl aromatic compound and at least one intermediate polymer block copolymer mainly composed of a conjugated diene compound. (E-2) Epoxy-modified ethylene-α-olefin (-
(Non-conjugated diene) copolymer rubber (e-3) Epoxy-modified polyolefin resin 10. The rubber-like composition (a) wherein the rubber having an unsaturated double bond is ethylene-α-olefin-nonconjugated diene copolymer rubber, vinyl aromatic compound-conjugated diene compound copolymer rubber, butadiene. At least one selected from rubber and butyl rubber; the thermoplastic resin (b) is at least one selected from a polyolefin-based resin and a polyamide-based resin; An acid-modified compatibilizer (e-4), (e-5), or (e-6), at least one selected from the group consisting of:
9. The thermoplastic elastomer according to 7 or 8. (E-4) Maleic anhydride obtained by hydrogenating at least two terminal blocks A mainly composed of a vinyl aromatic compound and at least one intermediate polymer block copolymer mainly composed of a 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 rubber-like composition (a) wherein the rubber containing an unsaturated double bond is ethylene-α-olefin-non-conjugated diene copolymer rubber, vinyl aromatic compound-conjugated diene compound copolymer rubber, butadiene Rubber, butyl rubber, α, β-
At least one selected from unsaturated nitrile-conjugated diene copolymer rubbers and acrylic rubbers, and a thermoplastic resin (b)
Is one or more selected from polyolefin-based resins, polyester-based resins, polyamide-based resins, polycarbonate-based resins, vinyl chloride-based resins, and methacrylate-based resins, and the compatibilizer (e-7) is contained in the same molecule. The thermoplastic elastomer according to claim 1, 2, 3, 4, 5, 6, 7, or 8, which is a modified polyolefin resin having an epoxy group and an ester group. 12. The rubbery composition (a), wherein the unsaturated double bond-containing rubber is an acrylic rubber, α, β-unsaturated nitrile-
At least one selected from conjugated diene copolymer rubbers,
The thermoplastic resin (b) is at least one selected from a vinyl chloride resin, a polyurethane resin, and a methacrylate resin, and the compatibilizer (e-8) is a halogenated olefin resin, a vinyl chloride-vinyl acetate copolymer. The polymer is at least one member selected from the group consisting of a polymer and a vinyl aromatic compound-α, β-unsaturated nitrile-conjugated diene copolymer.
The thermoplastic elastomer according to 5, 6, 7 or 8. 13. An unsaturated double bond-containing rubber of the rubber composition (a) is an ethylene-α-olefin-nonconjugated diene copolymer rubber, and the thermoplastic resin (b) is a crystalline olefin resin. Yes, the compatibilizer (e) is the following (e-9)
(E-10) Claim 1, 2, 3, selected from (e-11).
The thermoplastic elastomer according to 4, 5, 6, 7 or 8. (E-9) 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 And / or a melt reaction of at least one selected from carboxylic acid-modified resins such as hydrogenated products thereof. (E-10) Polypropylene having a 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-11) a compatibilizer characterized in that at least one of the components is subjected to a melt reaction. Peroxide blends with at least one resin selected from the group consisting of ethylene, ethylene-based copolymer, styrene block copolymer and / or hydrogenated product thereof, styrene random copolymer and / or hydrogenated product thereof Compatibilizer dynamically heat-treated in the presence of substances 14. The compatibilizers (e-9) and (e-10) have a ratio of an epoxy-modified resin to a maleic anhydride group-modified resin, and the compatibilizer (e-11) has a ratio selected from polypropylene and a specific group. The ratio of the obtained one or more resin components is 10: 9.
0.5 to 20 parts by weight of a compatibilizer (e) in an amount of 0 to 90: 10% by weight based on 100 parts by weight of the total of the rubber component (a) and the resin component (b). 14. The thermoplastic elastomer according to claim 13, wherein