JP3505897B2 - Thermoplastic elastomer composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic elastomer composition which is excellent in oil resistance, rubber elasticity (compression set), heat resistance, and is excellent in flexibility, mechanical strength and impact resistance.

[0002]

2. Description of the Related Art Recently, due to problems of process rationalization and recycling, substitution of vulcanized rubber with a thermoplastic elastomer has been required more than ever before. However, styrene-based thermoplastic elastomers containing hydrogenated styrene / conjugated diene block copolymer as a main component are excellent in flexibility and rubber elasticity (compression set), but inferior in oil resistance and heat resistance. However, it was not possible to replace all the applications in which vulcanized rubber is used.

Therefore, as an attempt to improve the oil resistance and heat resistance of the styrene thermoplastic elastomer, a method of adding a polyolefin hydrocarbon resin and a polyphenylene ether resin is disclosed in JP-B-6-80124 and JP-A-7-100184. It is described in each publication of the issue. However, none of the methods satisfies all of the vulcanized rubber substitute applications in terms of oil resistance and heat resistance.

[0004]

DISCLOSURE OF THE INVENTION The present invention has oil resistance and heat resistance which cannot be reached by the prior art, and is also excellent in flexibility, rubber elasticity (compression set) and impact resistance. An object is to provide a thermoplastic elastomer composition which gives a molded article.

[0005]

[Means for Solving the Problems]

[Summary of the Invention] As a result of intensive studies to solve the above problems, the present inventors have found that by adding a polyester elastomer and a polyphenylene ether resin, excellent oil resistance and heat resistance are exhibited. They have found the present invention and completed the present invention. That is, the thermoplastic elastomer composition of the present invention is a styrene / conjugated diene block copolymer hydrogenated product (component (A)) 30 to 30.
In a mixture of 80% by weight and 70 to 20% by weight of a softener for hydrocarbon rubber (component (B)), the following component (C) is 5 to 300 per 100 parts by weight of the mixture.
It is a thermoplastic elastomer composition in which 1 part by weight and 50 parts by weight of the following component (D) are blended. Component (C): Polyester elastomer component (D): Bonding unit is the following formula (1);

[0006]

[Chemical 2]

(Wherein R1, R2, R3 and R4 are each selected from the group consisting of hydrogen, halogen, hydrocarbons and substituted hydrocarbon groups and may be the same or different from each other), and chloroform Measured in 30
A polyphenylene ether resin having an intrinsic viscosity of 0.1 to 0.80 dl / g.

[0008]

DETAILED DESCRIPTION OF THE INVENTION

[1] Composition The thermoplastic elastomer composition of the present invention comprises components (A) to (A).
J consisting of component (D) and conforming to JIS-K6301
The IS-A hardness is preferably 20 to 95, more preferably 30 to 90, and most preferably 35 to 85. JI
If the S-A hardness is less than the above range, the moldability (release property) will be poor, and if it exceeds the above range, the rubber elasticity will be poor.

(1) Compounding ingredient (A): Hydrogenated product of styrene / conjugated diene block copolymer As a hydrogenated product of styrene / conjugated diene block copolymer, the conjugated diene is butadiene alone, isoprene alone, Alternatively, it is a polymer block composed of a mixture of isoprene and butadiene, specifically, a hydrogenated product of a styrene / butadiene / styrene block copolymer (hereinafter, simply referred to as “hydrogenated SBS”). ), A hydrogenated product of a styrene / isoprene / styrene block copolymer (hereinafter sometimes simply referred to as "hydrogenated S-I-S"), or a styrene / isoprene / butadiene / styrene block copolymer. A combined hydrogenated product (hereinafter sometimes simply referred to as "hydrogenated S-BI-S") can be mentioned.

The hydrogenated products of these styrene / conjugated diene block copolymers have a weight average molecular weight of 50,000-
500,000, preferably 120,000-450,
000, particularly preferably 150,000 to 400,000
0, styrene content 5 to 50% by weight, preferably 8 to
45% by weight, particularly preferably 10-40% by weight, 1,2
-It is important to use block copolymers having a microstructure of less than 20%, preferably less than 15% and a hydrogenation rate of 95% or more, preferably 97% or more.

Here, the "weight average molecular weight" is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC) under the following conditions. (Conditions) Equipment: 150C ALC / GPC (MILL
Column: AD80M / S (manufactured by Showa Denko KK) 3 solvents: o-dichlorobenzene temperature: 140 ° C. Flow rate: 1 ml / min Injection amount: 200 μl Concentration: 2 mg / ml (antioxidant 2,6-di) 0.2% by weight of -t-butyl-p-phenol was added, and the concentration was detected as F.
Measured with an infrared spectrophotometer MIRAN 1A manufactured by OXBORO at a wavelength of 3.42 μm. )

If the weight average molecular weight of the hydrogenated styrene / conjugated diene block copolymer is less than 50,000, rubber elasticity and mechanical strength are poor, and if it exceeds 500,000, moldability tends to be poor. Become. As a method for producing a hydrogenated product of these styrene / conjugated diene block copolymers, for example, a method described in JP-B-40-23798 is used, and a styrene / conjugated diene block is used in an inert solvent using a lithium catalyst. Synthesize a copolymer,
Next, for example, Japanese Patent Publication No. 42-8704 and Japanese Patent Publication No. 43
-6636, JP-A-59-133203, JP-A-6
According to the method described in each publication of 0-79005, a method of hydrogenating in the presence of a hydrogenation catalyst in an inert solvent can be mentioned.

Further, hydrogenated S-IS and hydrogenated S-BI
-S is for JP-A-2-102212 and JP-A3-1.
88114, i.e., styrene and isoprene or isoprene-butadiene as total monomer 100.
0.01 to 0.2 part by weight of the alkyl lithium compound as an initiator and 0.04 to 0.8 part by weight of the coupling agent, and 0.1 to 100 parts by weight of the initiator.
Obtained by sequentially polymerizing in an inert solvent at -20 to 80 ° C for 1 to 50 hours in the presence of ˜400 parts by weight of Lewis base, and then hydrogenating isoprene or isoprene-butadiene block. Examples of commercially available products include "Clayton G1650, 1651" manufactured by Shell Japan, "Septon 2006, 4055""High Blur HVS-3" manufactured by Kuraray Co., Ltd., and "Tough Tech H107" manufactured by Asahi Kasei Corporation.
1 ”,“ Dyalon 1320P ”manufactured by Japan Synthetic Rubber Co., Ltd., and the like.

Component (B): Hydrocarbon-based rubber softening agent A hydrocarbon-based rubber softening agent has a weight average molecular weight of 3
Examples thereof include those of 00 to 2,000, preferably 500 to 1,500. Such a hydrocarbon-based rubber softening agent is a mixture of three aromatic ring, naphthene ring and paraffin ring, and the paraffin chain carbon number is 50% by weight or more of the total carbon. It is called a system oil and has a naphthene ring carbon number of 30 to 45% by weight.
It is called naphthenic oil and has 3 aromatic carbons.
Those with more than 0% by weight are called aromatic oils and are classified. Among these, it is preferable to use paraffinic oil from the viewpoint of weather resistance.

The paraffinic oil used in the present invention has a kinematic viscosity at 40 ° C. of 20 to 800 cSt (centistokes), preferably 50 to 600 cSt, and a pour point of 0.
-40 ° C, preferably 0 to -30 ° C, and flash point (C
OC) is 200 to 400 ° C., preferably 250 to 350
Oils of ° C are preferably used. The hydrocarbon-based rubber softening agent is important for adjusting hardness and melt fluidity during molding.

Component (C): Polyester Elastomer The polyester elastomer of the present invention is JIS-K7.
The flexural modulus according to 203 is 1000 MPa or less, preferably 0 to 600 MPa, particularly preferably 10 to 600 M.
Pa is preferable. For such polyester elastomer, an aromatic polyester is used as a hard component, a polyester polyether block copolymer using an aliphatic polyether as a soft component, an aromatic polyester is used as a hard component, and an aliphatic polyester is used as a soft component. Polyester A polyester block copolymer is mentioned.

(A) Polyester polyether block copolymer The polyester polyether block copolymer comprises an aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, an aromatic dicarboxylic acid or its alkyl ester, and a weight. Esterification reaction using polyalkylene ether glycol having an average molecular weight of 400 to 6,000 as a raw material,
Alternatively, it is obtained by polycondensing an oligomer obtained by a transesterification reaction.

As the aliphatic and / or alicyclic diol having 2 to 12 carbon atoms used in the present invention, those known as raw materials for polyester, particularly polyester elastomer can be used, and examples thereof include ethylene glycol and propylene. Glycol, trimethylene glycol,
1,4-butanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like can be mentioned, preferably 1,4-butanediol and ethylene glycol, particularly preferably 1,4-butanediol. It is used as a component, and one kind or two or more kinds can be used.

As the aromatic dicarboxylic acid, those known as raw materials for polyesters, particularly polyester elastomers can be used, and terephthalic acid, isophthalic acid,
Examples thereof include phthalic acid and 2,6-naphthalenedicarboxylic acid, preferably terephthalic acid and 2,6-naphthalenedicarboxylic acid, and particularly preferably terephthalic acid as a main component. You may use together the above. Examples of the alkyl ester of aromatic dicarboxylic acid include dimethyl esters such as dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate and 2,6-dimethyl naphthalate, and dimethyl terephthalate and 2,6-dimethyl naphthalate are preferable. Yes, and particularly preferably, dimethyl terephthalate, and two or more of these can be used in combination. Also,
In addition to the above, small amounts of trifunctional diols, other diols, other dicarboxylic acids and their esters may be copolymerized, and further, aliphatic dicarboxylic acids such as adipic acid or alicyclic dicarboxylic acids, or alkyl esters thereof. Etc. may also be used as a copolymerization component.

As the polyalkylene ether glycol, those having a weight average molecular weight of 400 to 6,000 are used, preferably 500 to 4,000, particularly preferably 600 to 3,000. Molecular weight is 400
If it is less than the above range, the block property of the copolymer is insufficient, and if the weight average molecular weight exceeds 6,000, the physical properties of the polymer deteriorate due to phase separation in the system. Here, as the polyalkylene ether glycol, polyethylene glycol, poly (1,2 and 1,3 propylene ether) glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, a block or random copolymer of ethylene oxide and propylene oxide. , A block or random copolymer of ethylene oxide and tetrahydrofuran. Particularly preferred is polytetramethylene ether glycol. The content of the polyalkylene ether glycol is preferably 5 to 95% by weight, preferably 10 to 85% by weight, particularly preferably, based on the resulting block copolymer.
It is preferably 20 to 80% by weight. Content 95
If it is more than weight%, it is difficult to obtain a polymer by polycondensation.

(B) Polyester Polyester Block Copolymer The polyester polyester block copolymer of the present invention comprises an aliphatic or alicyclic dicarboxylic acid instead of the polyalkylene ether glycol having a weight average molecular weight of 400 to 6,000. And a polyester oligomer condensed with an aliphatic diol, a polyester oligomer synthesized from an aliphatic lactone or an aliphatic monoolcarboxylic acid, the aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, and an aromatic dicarboxylic acid Alternatively, it is obtained by polycondensing an oligomer obtained by an esterification reaction or a transesterification reaction using the alkyl ester as a raw material.

Examples of 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid,
Alicyclic dicarboxylic acids such as dicyclohexyl-4,4'-dicarboxylic acid or succinic acid, oxalic acid, adipic acid,
Examples include polyester oligomers having a structure in which one or more of aliphatic dicarboxylic acids such as sebacic acid and one or more of diols such as ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol are condensed. Examples thereof include polycaprolactone-based polyester oligomers synthesized from ε-caprolactone, ω-oxycaproic acid and the like.

(C) Method for producing polyester-based elastomer The esterification, transesterification and polycondensation reaction in the present invention can be carried out by a conventional method. As catalysts in these reactions, one or two or more known catalysts such as alcoholates such as tin, titanium, zinc and manganese, chlorides and oxides can be used, respectively. Catalysts, especially tetrabutyl titanate, are desirable. Moreover, you may add phosphoric acid, phosphorous acid, hypophosphorous acid, or those metal salts etc. as an adjuvant. In particular, the addition of an alkali metal hypophosphite is preferable because the content of terminal carboxyl groups is reduced and the hydrolysis resistance is improved.

Examples of the alkali metal hypophosphite include sodium hypophosphite, potassium hypophosphite and lithium hypophosphite, and sodium hypophosphite is particularly desirable. The amount of the alkali metal hypophosphite added is 1 to 1,0 relative to the polyester elastomer produced.
It is 00 ppm, preferably 3 to 200 ppm, more preferably 5 to 80 ppm. If it is less than 1 ppm, the effect of addition is not sufficiently obtained, and if it is added more than 1,000 ppm, further effect cannot be expected, and the polycondensation reaction is rather inhibited, which is not preferable. As the addition method, the alkali metal hypophosphite may be added to the molten polyester elastomer in any state of solution, slurry and solid, and the addition timing is preferably at least before the completion of the polycondensation reaction, That is, it may be added at any time between before the esterification reaction or before the transesterification reaction and before the end of the polycondensation reaction. In particular, it is preferable to add it in the form of a slurry immediately before the start of the polycondensation under reduced pressure, since the polymerizability is not lowered.

Further, other additives may be present in the reaction step. For example, in addition to a hindered phenol-based oxidation stabilizer, a hindered amine-based oxidation stabilizer, a phosphorus-based oxidation stabilizer, a sulfur-based oxidation stabilizer, a triazole-based light resistance stabilizer, and other known additives are used. Particularly, in the present invention, it is more preferable to add the hindered phenol-based oxidation stabilizer in an amount of 0.01 to 1% by weight with respect to the polymer in terms of the effect. The esterification or transesterification reaction is usually performed at 120 to 250 ° C., preferably 150 to 230 ° C., and the melt polycondensation reaction is usually performed at 200 to 280 ° C. for 2 to 6 hours under reduced pressure of 10 torr or less.

Usually, the polymer obtained by melt polymerization is
It is maintained at a temperature equal to or higher than the melting point, and discharged from the reaction can and pelletized in sequence. The pellets obtained here are
If necessary, solid phase polymerization may be further performed. As such a polyester polyether block copolymer,
Commercially available polymer "Perprene P" (trade name of Toyobo Co., Ltd.), "Hytrel" (trade name of DuPont Toray Co., Ltd.), "Low Mod" (trade name of GE Plastics Co., Ltd.), "Nichigo Polyester" ( Product name of Nippon Synthetic Chemical Industry Co., Ltd., "Teijin Polyester Elastomer"
(Teijin Co., Ltd. product name) and the like, and polyester polyester block copolymers include commercially available polymer “Perprene S” (Toyobo Co., Ltd. product name). Component (D): polyphenylene ether resin The polyphenylene ether resin used in the present invention has a bonding unit represented by the following formula (1);

[0027]

[Chemical 3]

(Wherein R1, R2, R3 and R4 are each selected from the group consisting of hydrogen, halogen, hydrocarbons and substituted hydrocarbon groups and may be the same or different from each other). Measured in chloroform, 3
Those having an intrinsic viscosity at 0 ° C. of 0.1 to 0.8 dl / g are preferable. More preferably, the intrinsic viscosity is 0.2 to 0.7 d
1 / g, and particularly preferably 0.25-
It is of 0.6 dl / g. Intrinsic viscosity is 0.1 dl /
If it is less than g, the impact resistance of the composition is insufficient, and 0.8 dl / g
If it exceeds, the moldability is unsatisfactory.

As such a polyphenylene ether resin, known ones can be used. Specific examples include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2,6-diphenyl-1). , 4-
Phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and also 2,6-dimethylphenol. And other phenols (eg 2,3,6-trimethylphenol or 2
Also included are polyphenylene ether copolymers such as copolymers with (methyl-6-butylphenol). Among them, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6) is particularly preferable. -Dimethyl-1,4-phenylene ether).

(2) Additional compounding agent (optional component) In the thermoplastic elastomer composition of the present invention, in addition to the above components (A) to (D), optional compounding components are compounded according to various purposes. can do. Specifically, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, neutralizing agents, lubricants, antifogging agents, antiblocking agents, slip agents, crosslinkers, crosslinkers, colorants, flame retardants. Various additives such as a dispersant and an antistatic agent can be added. Of these, it is particularly important to add an antioxidant, and at least one of various antioxidants such as phenol-based, phosphite-based, and thioether-based antioxidants can be used.

For the purpose of polymerizing the polyester elastomer, bifunctional compounds such as bisoxazoline compounds and diepoxy compounds, other polyfunctional compounds, monophosphites such as triphenylphosphite and bis (2,6) -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and other phosphite esters exemplified by diphosphites are effective, and alkali metal salts such as anhydrous potassium carbonate are used as catalysts. It can also be added.

Further, additional compounding materials such as various thermoplastic resins, various elastomers, various plasticizers, etc. can be compounded within a range that does not significantly impair the effects of the present invention. Examples of various thermoplastic resins include propylene-based polymers such as propylene homopolymer, propylene / ethylene block copolymer, and propylene / ethylene random copolymer, low density polyethylene (branched ethylene polymer), medium density, and high density polyethylene. Ethylene polymers such as (linear ethylene polymers), ethylene and unsaturated compounds such as ethylene / unsaturated carboxylic acid copolymers or their anhydrides (acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itacone An olefin resin such as a copolymer of acid, citraconic acid, tetrahydrophthalic acid, norbornene-5,6-dicarboxylic acid, and their anhydrides;
Examples thereof include styrene homopolymers, styrene resins such as acrylonitrile / styrene resin, and acrylonitrile / butadiene / styrene resin.

Of these, propylene-based polymers such as propylene homopolymer, propylene / ethylene block copolymer, and propylene / ethylene random copolymer are particularly preferable from the viewpoint of molding appearance. The various elastomers have rubber elasticity other than the hydrogenated product of the styrene / conjugated diene block copolymer described in the component (A), and specifically, include polybutadiene, polyisoprene,
Homopolymers of olefins such as polyisobutylene; ethylene / propylene copolymer rubber (EPM), as non-conjugated dienes, 5-ethylidene-2-norbornene, 5-methylenenorbornene, 5-vinylnorbornene, dicyclopentadiene, 1 Ethylene / propylene / non-conjugated diene copolymer rubber using 1,4-hexadiene, etc. (EP
DM), ethylene / butene copolymer rubber (EBM), ethylene / octene copolymer rubber, ethylene / propylene / butene copolymer rubber, and other olefin copolymer rubbers;
Ethylene-diene copolymers such as ethylene-butadiene copolymer, ethylene-isoprene copolymer, ethylene-chloroprene copolymer; ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-
Copolymer of ethylene and organic acid ester such as methyl acrylate copolymer; Copolymer (ACM) of acrylic acid ester and a small amount of monomer for crosslinking, acrylic acid ester-acrylonitrile polymer rubber (ANM ) Etc. acrylic rubber, acrylic ester-butadiene copolymer rubber, ethylene-acrylic rubber (AEM) and other acrylic polymer rubber; natural rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene copolymer rubber, acrylonitrile -Diene rubber such as butadiene copolymer rubber; butyl rubber; nitrile rubber; chloroprene rubber;
Silicone rubber; Fluorine rubber; Urethane rubber; Chlorine-based soft resin such as soft vinyl chloride resin and chlorinated polyethylene; Olefin-based thermoplastic elastomer containing the above-mentioned olefin-based copolymer rubber, commercially available from Mitsubishi Chemical Corporation "Thermo run", "Milastomer" by Mitsui Petrochemical Co., Ltd., "Sumitomo TPE" by Sumitomo Chemical Co., "Santplane" by AES Co., etc. can be mentioned.

(2) Blending ratio The blending ratio of each component constituting the thermoplastic elastomer composition of the present invention is such that the component (A) is 30 to 80% by weight based on the total amount of the component (A) and the component (B). , Preferably 35-75
%, Particularly preferably 40 to 70% by weight. If it is less than the above range, the mechanical strength will be poor, and if it exceeds the above range, the flexibility and moldability will be poor. On the other hand, component (B)
The blending ratio is 70 to 20% by weight, preferably 65 to 25% by weight, and particularly preferably 60 to 30% by weight, based on the total amount of the components (A) and (B).

If the blending ratio of the above component (B) exceeds the above range, the flexibility and moldability of the thermoplastic elastomer composition will be poor, and if it is less than the above range, the mechanical strength will be poor. The mixing ratio of the component (C) is 5 to 300 parts by weight, preferably 7 to 200 parts by weight, and particularly preferably 1 based on 100 parts by weight of the total amount of the components (A) and (B).
It is 0 to 100 parts by weight.

When the compounding ratio of the above component (C) exceeds the above range, the thermoplastic elastomer composition is inferior in flexibility and rubber elasticity (compression set), and when less than the above range, mechanical strength, heat resistance, It becomes inferior in oil resistance. Further, the blending ratio of the component (D) is 1 to 50 parts by weight, preferably 3 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B).
-40 parts by weight, particularly preferably 5-30 parts by weight.
When the compounding ratio of the component (D) exceeds the above range, the thermoplastic elastomer composition is poor in flexibility and moldability, and when less than the above range, heat resistance and rubber elasticity (compression set).
Will be inferior to.

(3) Compounding method The method for obtaining the thermoplastic elastomer composition of the present invention is not particularly limited, and may be a melting method, a solution method, a suspension method, or the like.
Practically, the method of melt kneading is desirable. As a specific method for melt-kneading, the powdery or granular component (A) is used.
Or after uniformly mixing the component (D) with the additives described in the section of the additional compounding ingredients within the range of the above compounding ratio by a Henschel mixer, a ribbon blender, a V-type blender or the like, Examples of the method include kneading and blending with a normal kneader such as a Banbury mixer, a kneader, a roll, and a multi-screw kneading extruder such as a single-screw or twin-screw.

The temperature of the melt-kneading of each component is 100 ° C to 4 ° C.
In the range of 00 ° C, preferably in the range of 150 ° C to 300 ° C,
Particularly preferably, it is in the range of 180 ° C to 280 ° C. Furthermore, the kneading order and method of each component are not particularly limited, and the method of kneading the components (A) to (D) and the additional compounding material components at once, and the components (A) to (D). After kneading a part of them, the remaining components including the additional compounding material component may be kneaded.

[II] Molded article As a method for producing a molded article of the thermoplastic elastomer composition of the present invention, extrusion molding method, blow molding method, rotational molding, press molding, injection molding method (insert injection molding method,
Various molding methods such as two-color injection molding method, core back injection molding method, sandwich injection molding method, injection press molding method) can be used. Especially injection molding method, (co)
The extrusion method is preferred.

In molding, it is important to use a dried material, and the drying temperature is 20 to 150 ° C, preferably 50 to 130 ° C, more preferably 80 to 120 ° C.
It is necessary to carry out the drying at 1 ° C for 1 to 24 hours, preferably 1 to 10 hours, more preferably 1 to 5 hours. Furthermore, it is more effective to perform drying under reduced pressure, and by drying under reduced pressure, it is possible to lower the drying temperature and shorten the drying time. When molded with a material that does not dry, the surface of the molded product may be roughened or the physical properties may be deteriorated.

The conditions for injection molding are generally 1
Molding temperature of 00 to 300 ° C, preferably 150 to 280 ° C, particularly preferably 200 to 260 ° C, 50 to 1,000
0 kg / cm ² , preferably 100 to 800 kg / cm
Molded with injection pressure of ² . Further, it is also possible to recycle and use molded parts other than products such as runners and spools and defective molded products.

[III] Uses The molded product made of the thermoplastic composition of the present invention can be used as various industrial parts. Specifically, vehicle interior parts such as instrument panels, center panels, center console boxes, door trims, pillars, assist grips, handles, airbag covers, exterior vehicle parts such as bumpers and malls, rack and pinion boots, suspension boots. Automotive functional parts such as constant velocity joint boots, vacuum cleaner bumpers, remote control switches, home appliances parts such as various rolls of OA equipment and various key tops, underwater products such as underwater glasses, underwater camera covers, various cover parts, hermeticity It can be used for industrial parts with various packings for the purpose of waterproofing, soundproofing, vibrationproofing, etc., curl cord electric wire coatings, electric parts such as belts, hoses, tubes, and sound deadening gears, electronic parts, sports equipment, etc. it can.

[0043]

The present invention will be described in more detail with reference to the following examples. [I] Evaluation Method Various evaluations in these Examples and Comparative Examples were performed by the following test methods. However, the measurement samples (1) to (5) were measured with an in-line screw type injection molding machine (small injection molding machine manufactured by Toshiba Machine Co .; IS90B) at an injection pressure of 500 kg / cm ² , an injection temperature of 240 ° C., and a mold temperature of 40.
Obtained by lateral punching of 120 mm x 120 mm x 3 mm sheets molded at ° C.

(1) JIS-A hardness [−] conforms to JIS-K-6301 (2) Compression set [%] conforms to JIS-K-6301 Compression set (70 ° C. × 70 ° C.) 22 hours) was measured. (3) Tensile Strength [kg / cm ² ] Based on JIS-K-6301 A tensile test was conducted as a standard of mechanical strength, and the tensile strength at break was measured. (4) About 2 g cut out from oil-proof injection-molded test piece
It was immersed in a glass tube containing S3 oil at 120 ° C. for 72 hours, and the swelling ratio [%] before and after the immersion was measured. (5) MFR [g / 10 min] JIS-K-7210 conformity MFR [230 ° C x 2.16 kg] as a guide for moldability
Was measured.

[II] Raw material component (A): Hydrogenated product of styrene / conjugated diene block copolymer

[0046]

[Table 1]

Component (B): Hydrocarbon softening material for rubber

[0048]

[Table 2]

Component (C): Polyester elastomer C-1: 60 parts by weight of dimethyl terephthalate, 1,4-
To 31 parts by weight of butanediol and 35 parts by weight of polytetramethylene ether glycol (average weight molecular weight 1,000), 200 ppm of tetrabutyl titanate as a catalyst, in terms of metallic titanium, was added to the produced polymer at 150 ° C to 230 ° C. The transesterification reaction is performed at 3.5 ° C. for 3.5 hours, and then 0.18 parts by weight of a hindered phenol-based oxidation stabilizer [Ciba-Geigy product, trade name: Irganox 1010] is added to the resulting polymer.
Melt polycondensation was performed at 230 to 245 ° C. under a reduced pressure of 3 torr or less, and a polyester elastomer (polyester polyether block copolymer: density 1.19 g / cm 3
³ , Shore D hardness 52, MFR (245 ° C, 2.16
(kg load) 34 g / 10 min) was produced.

C-2: Dimethyl terephthalate 54.4
Parts by weight, 30 parts by weight of 1,4-butanediol, polytetramethylene ether glycol (average weight molecular weight 1,0
00) 42 parts by weight, polyester elastomer (polyester polyether block copolymer: density 1.17 g / cm ³ , Shore D hardness 46, MFR (245 ° C., 2.16 kg load) in the same manner as C-1. ) 30 g
/ 10 minutes).

C-3: 48 parts by weight of dimethyl terephthalate, 27 parts by weight of 1,4-butanediol, polytetramethylene ether glycol (average weight molecular weight of 1,00)
0) For 50 parts by weight, a polyester-based elastomer (polyester polyether block copolymer: density 1.15 g / cm ³ , Shore D hardness 44, MFR (245 ° C., 2.16 kg load) was used in the same manner as C-1. ) 35 g /
10 minutes).

Component (D): Polyphenylene ether resin D-1: Poly (2,6-dimethyl-1,4-phenylene ether) (Nippon Polyether Co., Ltd., 30 ° C., intrinsic viscosity in chloroform: 0.32 dl / g) . Other components: Propylene resin

[0053]

[Table 3]

[III] Experimental Examples and Comparative Examples Examples 1 to 11 and Comparative Examples 1 to 10 In the compounding compositions (parts by weight) shown in Tables 4 to 5, first, the components (A) to (B) were mixed with a Henschel mixer. Then, the phenol-based antioxidant (trade name "Irganox 1010" manufactured by Ciba-Gaiki) was added to the remaining components and 100 parts by weight of the total amount of the compounding compositions shown in Tables 4 to 5.
2 parts by weight and 0.2 parts by weight of a thioether antioxidant (trade name "Cynox 412S" manufactured by Shiraishi Calcium Co., Ltd.) are added and mixed. Next, pellets of the thermoplastic composition were obtained by melt-kneading at a temperature of 240 ° C. using a twin-screw extruder having a compression ratio L / D = 33 and a cylinder diameter of 45 mm. The pellets were dried at 100 ° C. for 4 hours, injection-molded as described above into a sheet, and subjected to the above evaluation. The results of these evaluations are shown in Table 4.
~ 5.

[0055]

[Table 4]

[0056]

[Table 5]

Claims (5)

(57) [Claims] 1. A hydrogenated product of styrene / conjugated diene block copolymer (component (A)) 30 to 80% by weight and a hydrocarbon-based softening agent for rubber (component (B)) 70 to 20% by weight.
A thermoplastic elastomer in which the following component (C) is blended in an amount of 5 to 300 parts by weight and the following component (D) in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the mixture. Composition. Component (C): Polyester elastomer component (D): Bonding unit is represented by the following formula (1); (Wherein R1, R2, R3, and R4 are each selected from the group consisting of hydrogen, halogen, hydrocarbon, and substituted hydrocarbon group, and may be the same or different from each other), and measured in chloroform. The polyphenylene ether resin having an intrinsic viscosity at 30 ° C. in the range of 0.1 to 0.80 dl / g. 2. The thermoplastic elastomer composition according to claim 1, wherein the component (C) is a polyester polyether block copolymer. 3. The weight average molecular weight of the hydrogenated product of the styrene / conjugated diene block copolymer of the component (A) is 120,
The thermoplastic elastomer composition according to claim 1 or 2, which has a viscosity of 000 to 450,000. 4. The heat according to claim 1, wherein the proportion of the component (A) in the total of the component (A) and the component (B) is 40 to 70% by weight. Plastic elastomer composition. 5. A mixture 10 of component (A) and component (B).
The thermoplastic elastomer composition according to any one of claims 1 to 4, wherein the component C is blended in an amount of 10 to 100 parts by weight and the component (D) is in an amount of 5 to 30 parts by weight relative to 0 parts by weight.