JP3250383B2 - Thermoplastic elastomer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer composition and relates to a olefin copolymer rubber and a crystalline α-olefin copolymer mainly composed of an α-olefin having 3 or more carbon atoms. An object of the present invention is to provide a thermoplastic elastomer composition having high strength, flexibility and fluidity by blending a hydrogenated diene copolymer having a united structure and a specific structure.

2. Description of the Related Art Soft PVC is a material that has a good balance between mechanical strength and flexibility and is excellent in cost performance, but its use is restricted from the viewpoint of the global environment.
Some of them are being replaced with olefin-based thermoplastic elastomers. Conventionally, an olefin-based thermoplastic elastomer composition has been obtained by dynamically curing a rubber portion by a known method. According to this method, it is possible to obtain a thermoplastic elastomer composition having excellent mechanical strength without impairing the cold resistance, weather resistance, and chemical resistance of EPM and / or EPDM. However, there is a problem of odor and discoloration due to a crosslinking agent or a crosslinking aid during dynamic curing. On the other hand, sufficient mechanical strength cannot be obtained unless dynamic hardening is performed. Further, olefin-based thermoplastic elastomers are generally said to have poor flexibility and lack "rubberiness". For this reason, mineral oil-based softeners are blended to give flexibility, but the addition of a large amount of softener causes deterioration of physical properties such as elastic recovery and the problem of elution of the softener. Therefore, the adoption is restricted.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and provides a thermoplastic elastomer composition having flexibility and fluidity and exhibiting sufficient mechanical strength. The purpose is to:

[0002]

The present invention relates to (a) an olefin copolymer rubber (ethylene content of less than 90 mol%)
(B) at least one hydrogenated diene (co) polymer selected from the group consisting of the following (b-1), (b-2) and (b-3): 1 to 80% by weight % (B-1); (A)-(B) block copolymer, (A)
-(B)-(C) block copolymer or (A)-
(B)-(A) block copolymer [where (A) is a vinyl aromatic compound polymer block, (B) is a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene random copolymer block, C) is a polymer showing a vinyl aromatic compound / conjugated diene taper block in which the vinyl aromatic compound gradually increases, and the ratio of vinyl aromatic compound / conjugated diene is 5 to 60/95 to 4 by weight.
0, the bond content of the vinyl aromatic compound in the block (A) is 3% by weight or more with respect to all the monomers constituting the block copolymer, and the total vinyl aromatic compound in the blocks (A) and (C) (B) a block copolymer or a block copolymer unit having a vinyl bond content of a conjugated diene portion of more than 60% in a conjugated diene portion in a block is a coupling agent residue. Block copolymer in which the polymer molecular chain is extended or branched through hydrogenation, at least 8 of the double bonds of the conjugated diene moiety
A hydrogenated diene-based copolymer or a modified hydrogenated diene-based copolymer having a number average molecular weight of 50,000 to 700,000 saturated at 0%. (B-2): a block copolymer having one or more polymer blocks (D), (E) and (F) in the molecule, respectively (provided that (D) is a polymer mainly composed of a vinyl aromatic compound) A block, (E) a polymer block mainly composed of a conjugated diene having a 1,2-vinyl bond content of 25 to 95%, and (F) a polybutadiene polymer block having a 1,2-vinyl bond content of less than 25%. In these block copolymers, the polymer molecular chain may be extended or branched via a coupling agent residue], and the content of the polymer block (D) in the block copolymer Is 5-60
% By weight, the content of the polymer block (E) is 30 to 90% by weight, and the content of the polymer block (F) is 5 to 60% by weight [however, (D) + (E) + (F) = 100% by weight] ] The hydrogenated diene-based copolymer or modified water having a number average molecular weight of 50,000 to 700,000, wherein the block copolymer is hydrogenated and at least 80% of the double bonds of the conjugated diene portion are saturated. Addition diene copolymer. (B-3); (G)-(H)-(G) or (G)-
(H) is a polybutadiene polymer block having a 1,2-vinyl bond content of 25% or less, and (H) is a conjugated diene polymer block or a vinyl aromatic compound. A conjugated diene copolymer block, wherein the conjugated diene moiety has a vinyl bond content of 2
Exhibit more than 5% polymer blocks, and these block copolymers may have polymer chains extended or branched via coupling agent residues]
A hydrogenated diene copolymer or functionally modified product having a number average molecular weight of 50,000 to 700,000, wherein at least 80% of the double bonds of the conjugated diene portion are saturated. (C) α- having 3 or more carbon atoms
5 to 80% by weight of a crystalline α-olefin-based polymer having an olefin as a main component, and (d) 5 to 80% by weight of an ethylene-based polymer (ethylene content of 90 mol% or more) [where (A) + (B) +
(C) + (D) = 100% by weight], (E) Mineral oil-based softener based on the component (A) is 0 to 200%.
It is intended to provide a thermoplastic elastomer composition consisting of parts by weight.

[0003] The olefin copolymer rubber of component (a) must have an ethylene content of less than 90 mol%. When the content of the ethylene component becomes 90 mol% or more, α
-When the content of the olefin component is 10 mol% or less, the flexibility of the olefin copolymer rubber becomes insufficient. Examples of the olefin copolymer rubber of the component (a) include ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene terpolymer rubber, and ethylene / 1-
An amorphous elastic copolymer containing an olefin as a main component, such as butene copolymer rubber and ethylene / 1-butene / non-conjugated diene terpolymer rubber, is used. These ethylene
In α-olefin / non-conjugated diene copolymer rubber,
50/50 as a molar ratio of ethylene / α-olefin
Preferably, the copolymer is 90/10 copolymerized. As the non-conjugated diene, ethylidene norbornene, dicyclopentadiene, and 1,4-hexadiene are preferably present in an amount such that the iodine value is 40 or less. These copolymer rubbers have Mooney viscosity ML.
_{1 + 4, 100 ° C.} is preferably 10 to 500, preferably 30 to 400. In the olefin copolymer rubber, when the content of the ethylene component is less than 50 mol% and the content of the α-olefin component is more than 50 mol%, the mechanical strength of the olefin copolymer becomes insufficient. Not preferred. In addition, Mooney viscosity ML _{1 + 4, 100 ° C} is 1
If it is less than 0, the strength will be low, and if it is more than 500, poor dispersion with the polyolefin resin will occur, which is not preferable.
The olefin copolymer rubbers may be used alone or in combination of two or more.

[0004] Next, the hydrogenated diene copolymer of the component (ii) will be described separately for the components (ii-1), (ii-2) and (ii-3). Component (B-1) The component (B-1) comprises (A) a vinyl aromatic compound polymer block (hereinafter also referred to as “(A) block”) and (B)
Conjugated diene copolymer block or vinyl aromatic compound-conjugated diene random copolymer block (hereinafter also referred to as "(B) block"), and (C) vinyl aromatic compound in which vinyl aromatic compound gradually increases-conjugated diene taper A block (hereinafter also referred to as a “(C) block”) is represented by (A)-(B), (A)-(B)-(C), or (A)-(B)-(A). It is obtained by hydrogenating the arranged block copolymer.
Here, styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-difinylstyrene are used as the vinyl aromatic compound used to obtain the component (b-1). , N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like, and styrene and α-methylstyrene are particularly preferred. The conjugated diene used to obtain the component (b-1) includes 1,3-butadiene, isoprene,
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3
-Hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like, and are hydrogenated diene copolymers which can be used industrially and have excellent physical properties. In order to obtain, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, and 1,3-butadiene is more preferable. (B
The (A) block in the component (1) is a polymer block mainly composed of a vinyl aromatic compound, and is preferably copolymerized with 10% by weight or less, more preferably 10% by weight or less of other possible vinyl aromatics. Good. In the block copolymer to be hydrogenated, a preferable weight ratio of the vinyl aromatic compound / conjugated diene constituting the block copolymer is 5 to 60/9.
5 to 40, more preferably 7 to 50/93 to 5
0. When the amount of the vinyl aromatic compound is less than 5% by weight (the amount of the conjugated diene exceeds 95% by weight), the strength, processability, and heat resistance are poor, and when the obtained hydrogenated diene-based copolymer is pelletized, it is easily blocked. Become. If the vinyl aromatic content exceeds 60% by weight (the conjugated diene is less than 40% by weight), the composition becomes resinous, and the impact resistance and low-temperature properties are poor.
The preferred amount of the vinyl aromatic compound in the (A) block or (C) block is 3 to 50% by weight of the total monomers.
And more preferably 5 to 40% by weight, and most preferably 5 to 30% by weight. When the vinyl aromatic bond content of the (A) block and the (C) block is less than 3% by weight of all monomers, heat resistance and mechanical strength are poor, and when the obtained hydrogenated diene copolymer is pelletized. ,
In addition to easy blocking, when blended with other components, processability is poor, while when it exceeds 50% by weight, transparency, flexibility, processability, and low temperature properties are poor. Further, the preferred content of the vinyl aromatic compound in the block (A) is at least 3% by weight, more preferably 5 to 30% by weight, based on the total monomers constituting the component (II-1).
(A) When the content of vinyl aromatic bonds in the block is less than 3% by weight of the total monomers, when blended with other components,
Poor mechanical strength, workability and heat resistance. Further, in the block copolymer to be hydrogenated, the vinyl bond content of the conjugated diene portion in the block (B) is preferably 60 or less.
% Or more . When the vinyl bond content is less than 60% , the effect of improving flexibility is not sufficiently exhibited even when blended with a resin component.

The above (A)-(B) block copolymer, (A)-(B)-(C) block copolymer, or (A)-(B)-(A) block copolymer Is represented by the following formula through a coupling agent residue,
The polymer molecular chain may be an extended or branched block copolymer. [(A)-(B)] nx [(A)-(B)-(C)] nx [(A)-(B)-(A)] nx [wherein (A ), (B) and (C) are the same as above. n
Represents an integer of 2 to 4, and X represents a coupling agent residue. As the coupling agent at this time, for example, diethyl adipate, divinylbenzene, tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2-dibromoethane, 1,1 4-chloromethylbenzene, bis (triclossilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4
-Benzene triisocyanate. The content of the (A) block, (B) block and (C) block in the block copolymer is usually (A) 3 to 50% by weight, preferably 4 to 40% by weight, and (B)
30 to 97% by weight, preferably 35 to 94% by weight, (C) 0 to 50% by weight, preferably 2 to 4% by weight of the block.
0% by weight [however, (A) + (B) + (C) = 100% by weight]. The number average molecular weight of the blocks (A) to (C) is 0.150,000 to 350,000, more preferably 0.4000 to 240,000 for the block (A), and 1.5 for the block (B).
10,000 to 67,000, more preferably 35,000 to 56.4
10,000, (C) block is 0-350,000, more preferably 0.
The range is from 20,000 to 240,000. By hydrogenating the above block copolymer, the double bond of the conjugated diene portion of the block copolymer is saturated, so that the component (b-1), which is a hydrogenated diene copolymer, can get. Here, the double bond of the conjugated diene portion is 80% or more thereof,
Preferably 90% or more, more preferably 95-100
% Is required to be saturated, and if it is less than 80%, the thermal stability and durability of the thermoplastic elastomer composition become poor. The component (b-1) has a number average molecular weight of 50,000 to 700,000, preferably 100,000 to 600,000. If it is less than 50,000, heat resistance, strength, fluidity and workability will be reduced, and if it exceeds 700,000, fluidity, workability and flexibility will be poor. The component (b-1) used in the present invention is described in, for example, JP-A-3-72512.
Can be obtained by the method disclosed in Japanese Patent Application Laid-Open No. H10-260, 1988.

Component (b-2) Here, the vinyl aromatic compound and conjugated diene used to obtain the component (b-2) are the same as those used to obtain the component (b-1). is there. The preferred (D) block that constitutes the hydrogenated diene copolymer of the component (b-2) is a polymer block mainly composed of an aromatic vinyl compound, and specifically, a homopolymer of an aromatic vinyl compound,
Alternatively, an aromatic vinyl compound is added to the (D) block in an amount of 90.
Preferred is a polymer block in which 80% by weight or more of the conjugated diene portion of the copolymer with a conjugated diene having not less than 80% by weight is hydrogenated. When the content of the aromatic vinyl compound in the block (D) is less than 90% by weight, the strength and the weather resistance are reduced. The preferred content of the (D) block in the component (b-2) is 5-6.
0% by weight, more preferably 10 to 55% by weight.
The preferred number average molecular weight of (D) block is 0.2
10,000 to 420,000. If it is less than 5% by weight, heat resistance and mechanical strength are inferior. On the other hand, if it exceeds 60% by weight, processability and flexibility are inferior. The content of the block (E) constituting the hydrogenated diene copolymer (b-2) is preferably 30 to 90% by weight, more preferably 35 to 80% by weight. When the content of the block (E) is less than 30% by weight, the flexibility is reduced. On the other hand, when the content is more than 90% by weight, the workability and the mechanical strength are reduced. (E) The vinyl bond content of the conjugated diene moiety contained in the block before hydrogenation is preferably 25 to 95%, more preferably 30 to 90% by weight. (E) In the conjugated diene block before hydrogenation to form a block, for example, when the conjugated diene is butadiene, the vinyl bond content is 25%.
If it is less than 95%, hydrogenation causes the formation of polyethylene chains and loses its rubber-like properties, while if it exceeds 95%, if it is hydrogenated, its glass transition temperature becomes high, and its rubber-like properties are lost. . (E) The block preferably has a number average molecular weight of 15,000 to 630,000, more preferably 35,000 to
420,000, which is a conjugated diene polymer block in which the double bond of the conjugated diene portion is hydrogenated by 80% or more. Further, the block (F) constituting the block copolymer for obtaining the component (b-2) is a polybutadiene polymer block having a vinyl bond content of less than 25%, preferably less than 20%. When the vinyl bond content is 25% or more, resinous properties are lost when hydrogenated, and properties of the thermoplastic elastomer as a block copolymer are lost. The content of the (F) block in the block copolymer is 5
-60% by weight, preferably 5-50% by weight.
(F) When the content of the block is less than 5% by weight, (B-2)
If the mechanical properties of the components are poor, on the other hand, if it exceeds 60% by weight,
Rubbery properties are lost and are not preferred. The preferred number average molecular weight of the (F) block is a polymer block in which the double bond of the butadiene portion of the polybutadiene block is hydrogenated by 80% or more by 0.25 to 420,000. Further, the block copolymer constituting the component (b-2) is a polymer block (D) via a coupling agent residue,
(E) or (F), which binds to a single polymer composed of at least one polymer block, for example,
May be a block copolymer in which the polymer molecular chain is extended or branched. [(D)-(E)-(F)] nx [(D)-(E)-(F)] X [(D)-(E)] [where n is 2-4 The integer X represents a coupling agent residue, and the coupling agent used is also (II)
It is the same as that used for the component.) By hydrogenation of the above block copolymer,
When the double bond of the conjugated diene portion of the block copolymer is saturated, the component (b-1), which is a hydrogenated diene copolymer, is obtained. Here, it is necessary that the double bond of the conjugated diene is saturated by 80% or more.
Preferably 90% or more, more preferably 95-100
%. 80% saturation of double bond in conjugated diene moiety
If it is less than 1, the thermal stability and durability of the thermoplastic elastomer composition are inferior. The component (b-2) has a number average molecular weight of 50,000 to 7
It is 100,000, preferably 100,000 to 600,000. If it is less than 50,000, heat resistance, strength, fluidity and workability will be reduced, and if it exceeds 700,000, fluidity, workability and flexibility will be poor. (B-2)
The components can be obtained, for example, by the method disclosed in JP-A-2-133406.

(B-3) Component (b-3) A hydrogenated diene-based copolymer (hereinafter also referred to as a "(b-3) component") comprises (G) a polybutadiene polymer having a vinyl bond content of 25% or less. (H) a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene copolymer block, wherein the vinyl bond content of the conjugated diene portion is 2
A polymer block of 5 to 95% (hereinafter also referred to as "(H) block") is a polymer block directly arranged like (G)-(H)-(G) or (G)-(H). It is obtained by hydrogenating 80% or more of the double bond portion of the chain or branched block copolymer. Here, examples of the vinyl aromatic compound and the conjugated diene used to obtain the component (II-3) include the compounds exemplified as those used to obtain the above component (II-1). The (G) block in the component (b-3) becomes a crystalline polymer block having a structure similar to that of ordinary low density polyethylene (LDPE) by hydrogenation. The 1,2-vinyl bond content in the block (G) is usually 25%
It is preferably at most 20%, more preferably at most 15%. When the 1,2-vinyl bond content in the block (A) exceeds 25%,
The crystal melting point after hydrogenation drops remarkably, resulting in poor mechanical strength. The (H) block is a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene copolymer block, and is a rubbery ethylene-butene-1 copolymer block or a vinyl aromatic compound-
A polymer block having a structure similar to that of the ethylene-butene-1 copolymer is obtained. The amount of the vinyl aromatic compound used in the (H) block is 35% by weight or less, preferably 30% by weight of the monomers constituting the (H) block.
The content is more preferably 25% by weight or less, and if it exceeds 35% by weight, the glass transition temperature of the (H) block increases, and the low-temperature properties and flexibility are poor. Further, the vinyl bond amount of the conjugated diene portion of the (H) block is 25 to 95%, preferably 25 to 75%, and more preferably 25 to 55%. When the conjugated diene is butadiene, the conjugated diene exhibits a crystal structure derived from a polyethylene chain and a polybutene-1 chain, respectively, and has resin-like properties, resulting in poor flexibility. Also,
In the block copolymer for obtaining the component (b-3), the ratio of the (G) block to the (H) block is usually 5 to 90% by weight of the (G) block, preferably 10 to 80% by weight.
%, (H) block 95 to 10% by weight, preferably 90 to 20% by weight [however, (G) + (H) = 100% by weight]. (G) less than 5% by weight of blocks, (H)
If the content of the block is more than 95% by weight, the crystalline polymer block is insufficient, and the mechanical properties of the component (b-3) are inferior. If the content of the block (G) exceeds 90% by weight and the content of the block (H) is less than 10% by weight, the hardness of the component (B-3) increases, which is not preferable. The preferred weight average molecular weight of the (G) block is 0.1.
It is 250,000-630,000, more preferably 10,000-480,000.
The preferred weight average molecular weight of the (H) block is 0.1.
It is 50,000-66,000, more preferably 20,000-540,000. In addition, the block copolymer for obtaining the component (b-3) is composed of a single polymer composed of at least one polymer block of the (G) block and the (H) block via a coupling agent residue. Bind, for example,
As shown in the above, a block copolymer having a polymer molecular chain extended or branched may be used. [(G)-(H)] nx [(G)-(H)-(G)] nx (wherein, n and X are the same as described above). B-1) The same ones as used in the component can be mentioned. By hydrogenating the above block copolymer, the double bond of the conjugated diene portion of the block copolymer is saturated, so that the component (b-3), which is a hydrogenated diene copolymer, can get. Here, the double bond of the conjugated diene must be saturated at least 80%, preferably 90%.
As described above, the content is more preferably 95 to 100%. If the saturation of the double bond in the conjugated diene portion is less than 80%, the thermal stability and durability of the thermoplastic elastomer will be poor. (B-3)
The number average molecular weight of the components is from 50,000 to 700,000, preferably from 100,000 to 600,000. If less than 50,000, heat resistance, strength,
Fluidity and processability are reduced, and if it exceeds 700,000, fluidity, processability and flexibility are inferior. The component (b-3) can be obtained, for example, by the method disclosed in JP-A-3-129576.

Each hydrogenated diene polymer used as the component (b) in the present invention may be a modified hydrogenated block polymer modified with a functional group. Such a modified hydrogenated block polymer is selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group, an epoxy group, a halogen atom, an amino group, an isocyanate group, a sulfonyl group and a sulfonate group. It can contain at least one kind of functional group. As a method for containing this functional group,
Using a conjugated diene or vinyl aromatic compound containing a functional group, copolymerization is performed while protecting the functional group of the monomer to obtain a block copolymer. A method of adding a radical-polymerizable monomer having a functional group to a hydrogenated block polymer by a known grafting reaction, using a monomer having a functional group, an organic peroxide or an azo compound A method in which a hydrogenated block polymer is kneaded using a kneader, a mixer, an extruder, or the like in the presence or absence of a functional group to add a functional group. Although any of these methods can be used to efficiently contain a functional group, the above methods (1) to (5) are simple and effective industrially. The amount of the functional group in the modified hydrogenated block polymer is usually from 0.01 to 10 mol%, preferably from 0.1 to 8 mol%, more preferably from 0.1 to 8 mol%, based on the molecules constituting the hydrogenated block polymer. 0.15 to 5 mol%. Preferred examples of the monomer that adds a functional group to the hydrogenated block polymer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and hydroxyethylene. Examples include methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and dimethylaminoethyl methacrylate.

Next, (c) used in the composition of the present invention
Crystalline α mainly composed of α-olefin having 3 or more carbon atoms
-As the olefin copolymer, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, poly 1
-Hexene, a propylene-ethylene copolymer, a propylene-1-butene copolymer, and the like, and the content of the α-olefin component having 3 or more carbon atoms is preferably 50 mol% or more. Of these, polypropylene and random or block ethylene-propylene copolymers are preferred. The component (c) is crystalline, and specifically has an n-decane insoluble content of 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more. n
If the decane-insoluble content is less than 50% by weight, the mechanical strength and moldability of the resulting thermoplastic elastomer composition may be impaired. Next, as the (d) ethylene polymer used in the present invention, the ethylene content is 90 mol% or more, and the polyethylene produced by a known low-pressure method or high-pressure method, or the ethylene content is 90 mol%. % Or more of a copolymer of ethylene and an α-olefin such as propylene, butene-1, 4-methyl, pentene-1 or hexene-1 having 3 to 6 carbon atoms, or a copolymer of ethylene and vinyl acetate It may be. The compounding amount of the above components (A) to (C) used in the composition of the present invention is such that (A) the olefin-based copolymer rubber is 10% by weight or more and
0% by weight or less, preferably 30 to 80% by weight, more preferably 50 to 75% by weight (b) 1 to 80% by weight, preferably 20 to 80% by weight of a hydrogenated diene copolymer having a specific structure.
60% by weight, more preferably 30 to 60% by weight (c)
Crystalline α mainly composed of α-olefin having 3 or more carbon atoms
5 to 80% by weight, preferably 2% by weight, of the olefin polymer
0 to 40% by weight (d) Ethylene copolymer is 5 to 80% by weight, preferably 8 to 30% by weight [however, (a) +
(B) + (c) + (d) = 100% by weight]. Here, if the blending amount of the (a) olefin copolymer rubber is less than 10% by weight, the rubber elasticity and flexibility of the obtained composition will be deteriorated. On the other hand, the component (a) is 90% by weight.
If the ratio exceeds the above range, the moldability and mechanical strength of the obtained composition will deteriorate. Further, when the component (c) is less than 5% by weight, the heat resistance of the obtained composition deteriorates. When the component (d) is less than 5% by weight, the mechanical strength of the obtained composition is reduced. As the mineral oil-based plasticizer (component (e)) used in the present invention, naphthenic oil and paraffin-based mineral oil can be used. By such oil extension, processability and flexibility are further improved. In this case, the oil extension amount is 0 to 200 weight per olefin-based copolymer rubber, preferably 0 to 200.
100 parts by weight, more preferably 0 to 50 parts by weight.

[0010] The production of the thermoplastic elastomer composition of the present invention is not particularly limited, and any method may be adopted as long as a good dispersion of each component can be obtained. Usually, the target polymer is melt-kneaded by a closed kneader such as a roll mill, a Banbury mixer, or a pressure kneader used in the rubber and resin industries, or a single-screw extruder or a twin-screw extruder. In the production of the composition of the present invention, the mixing temperature (kneading temperature) is at least (b)
This is the temperature at which the components (c) and (d) melt, and is usually in the range of 120 to 280 ° C. Further, the thermoplastic elastomer composition of the present invention comprises the above component (A),
In addition to component (b), component (c) and component (d), antioxidants, antistatic agents, weathering agents, and ultraviolet absorbers in amounts that do not impair mechanical strength, flexibility, and moldability depending on the application. Agent, lubricant, antiblocking agent, sealant, crystal nucleating agent,
Flame retardant, antibacterial, fungicide, tackifier, softener, plasticizer, coloring agent such as titanium oxide, carbon black, glass fiber, carbon fiber, metal fiber, aramid fiber, glass beads, asbestos, mica, Fillers such as calcium carbonate, potassium titanate whiskers, talc, barium sulfate, glass flakes, and fluororesins; plasticizers such as naphthenic oil and paraffinic mineral oil; rubbery polymers such as isobutylene-isoprene copolymer; and thermoplastics Resins and the like can be appropriately compounded. The thermoplastic elastomer composition of the present invention can be used in automobiles in which a conventional soft vinyl chloride resin is used by utilizing flexibility and moldability without impairing mechanical strength. -Can be used for parts such as packing and housing of exterior parts and weak electric parts, industrial parts, waterproof sheet parts, etc.

[0011]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the examples, parts and% are by weight unless otherwise specified. Various measurements in the examples were performed by the following methods. JIS A hardness Measured according to JIS K6301. Elastic recovery properties The following substitute properties and those with good permanent elongation were evaluated as good. Permanent elongation: According to JIS K6301, permanent elongation was maintained at 100% elongation for 10 minutes, then elongation was released, and the elongation was determined from elongation after standing for 10 minutes. The smaller the permanent set, the better the elastic recovery. 100% modulus (M100) tensile strength and maximum elongation
And JIS K6301. The fluidity MFR was measured under the following conditions. Temperature: 230 ° C. Load: 5 kg n-decane-insoluble component 5.0 g of a crystalline α-olefin polymer was dissolved in 150 ml of n-decane at a temperature of 150 ° C., cooled to room temperature, and allowed to cool all day and night. (Insoluble matter) by centrifugation (2
(3,000 rpm, 30 minutes) twice to separate
Dissolved crystalline α- weight of the measured precipitate (insoluble matter) weight
The ratio to the total weight of the olefin-based polymer was expressed as a percentage.

The polymers used in Examples and Comparative Examples are as follows.
The one below.EP1 Ethylene-propylene-ethylidene norbornene copolymer
Rubber (Ethylene content 80 mol%, paraffinic oil
70 phr oil exhibition) [Nippon Synthetic Rubber EP98A]EP2 Ethylene-propylene-dicyclopentadiene copolymer
(Ethylene content 78 mol%)
 [Nippon Synthetic Rubber EP75F]EP3 Ethylene-propylene-ethylidene norbornene copolymer
Rubber (ethylene content 80 mol%)
 [Nippon Synthetic Rubber EP57C]EP4 Ethylene-propylene copolymer rubber (ethylene content 81
Mol%) [Made by Nippon Synthetic Rubber, EP02P]IIR Ethylene-isoprene copolymer rubber [Nippon Synthetic Rubber,
[Buty 1065]PP1 Propylene-ethylene block polymer (without n-decane
(Solution 93.5% by weight) [Mitsubishi Yuka, BC5C]PP2 Propylene-ethylene random polymer (without n-decane
(Solution 92.2% by weight) [Mitsubishi Yuka EX6]PP3 Polypropylene (n-decane insoluble content: 98.7% by weight) [Mitsubishi Yuka, FL6CK]PE1 Low density polyethylene [Mitsubishi Yuka, YK30]PE2  Linear low density polyethylene [Mitsubishi Yuka UJ370]PE3 High-density polyethylene [Mitsubishi Yuka, FY50D]Hydrogenated diene copolymer A The hydrogenated block copolymer A was manufactured by Nippon Synthetic Rubber Co., Ltd.
Therefore, the AB structure (A is a polystyrene block, B is
Butadiene part of copolymer block of Tylene and Butadiene
Is obtained by hydrogenating the double bond of
10%, styrene content in part A 6%, butadiene part before hydrogenation
Has a vinyl content (1,2 bond content) of 80% and a total molecular weight of 30
000 hydrogenated block copolymer.Hydrogenated diene copolymer B The hydrogenated block copolymer B was manufactured by Nippon Synthetic Rubber Co., Ltd.
Therefore, the DEF structure (D is a polystyrene block, E
Is 1.2-vinyl-rich polybutadiene, F is 1,
E and F in polybutadiene with low 2-vinyl content
The double bond of the butadiene moiety is hydrogenated);
Part vinyl content is 39%, part F vinyl content is 15%,
A hydrogenated block copolymer having a molecular weight of 150,000.Hydrogenated diene copolymer C The hydrogenated block copolymer C was manufactured by Nippon Synthetic Rubber Co., Ltd.
Therefore, a GHG structure (G has a small 1,2-vinyl content)
Polybutadiene, H is a poly-1,2-vinyl
Double bonds in each butadiene moiety are hydrogenated in butadiene
), The vinyl content in part G is 15%,
Water with a vinyl content of 35% and a total molecular weight of 300,000
Addition block copolymer.Mineral oil plasticizer Paraffin softener [PW-380 manufactured by Idemitsu Kosan Co., Ltd.] The following were prepared as other additives. Anti-aging; Irganox 1010, Nippon Ciba-Geigy Inorganic filler; Calcium carbonate, Fuji Talc

Examples 1 to 21 and Comparative Examples 1 to 7 Compositions were prepared according to the following procedures according to the formulations shown in Tables 1 and 2. First, a bale-shaped EPDM was heated to 120 ° C.
(IIR is 20 ° C.) into a sheet, and if necessary, oil-extended, and a 5 mm square pellet is prepared with a sheet cutter. Olefin copolymer rubber, hydrogenated diene copolymer having a specific structure, polypropylene resin, polyethylene resin blended into a single screw extruder (manufactured by Nippon Placon) at a predetermined temperature at a predetermined mixing ratio. Accordingly, pellets were prepared by continuously supplying an antiaging agent, an inorganic filler, butyl rubber and the like. A 2 mm-thick sheet was prepared from the obtained composition using a 0.5 _oz injection molding machine and subjected to a test. For the evaluation of hardness JIS A, permanent elongation and tensile strength, a predetermined test piece was punched out of a sheet with a dumbbell cutter. Further, for evaluation of compression set, a test piece having a thickness of 2 mm produced by the above-mentioned injection molding machine was used, punched out, adjusted to a prescribed size by stacking, and subjected to a test. The results are shown in Tables 1 and 2.

[0014]

[Table 1]

[0015]

[Table 2]

As is clear from the comparison between Examples 1 to 21 and Comparative Examples 1 to 7, the composition of the present invention is excellent in the following points. The thermoplastic elastomer composition of the present invention exhibits a flexible property without impairing mechanical strength, has excellent elastic recovery, and also has good fluidity required for molding. In addition, since a small amount of the softening agent is required, there is no problem of bleed-out of these components. Comparative Example 1 does not contain the components (b) and (d), and thus has a significantly poor mechanical strength. Comparative Examples 2 to 4 do not contain the component (d), so that although the flexibility is imparted, the mechanical strength is inferior to the examples. Comparative Examples 5 to 7
Does not contain component (b). Compared with Examples 1 to 21, the mechanical strength is sufficient but the flexibility is inferior.

[0017]

According to the thermoplastic elastomer composition of the present invention, flexibility and fluidity are excellent, and mechanical strength and elastic recovery are also good. Also, since no mineral oil-based softening agent is contained or only a small amount is required, there is no problem of contamination due to elution of the softening agent, and a decrease in mechanical strength and elastic recovery due to the addition of a large amount of the softening agent. No problem. Therefore, soft vinyl chloride resin is used,
It can be used for interior / exterior parts of automobiles, parts such as packing housing for light electrical parts, industrial parts, waterproof sheet parts, gasket seal parts, etc.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yoichi Kamoshida 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-61-34048 (JP, A) 3-72512 (JP, A) JP-A-2-133406 (JP, A) JP-A-3-128957 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/00 -57/12

Claims (1)

(57) [Claims] 1. (a) 10 to 90% by weight of an olefin-based copolymer rubber (ethylene content of less than 90 mol%), (b) the following (b-1), (b-2) and (b-3) 1 to 80% by weight of at least one hydrogenated diene (co) polymer selected from the group: (b-1); (A)-(B) block copolymer, (A)
-(B)-(C) block copolymer or (A)-
(B)-(A) block copolymer [where (A) is a vinyl aromatic compound polymer block, (B) is a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene random copolymer block, C) is a polymer showing a vinyl aromatic compound-conjugated diene taper block in which the vinyl aromatic compound gradually increases, wherein the ratio of vinyl aromatic compound / conjugated diene is 5 by weight.
-60 / 95-40, based on all monomers constituting the block copolymer, the bond content of the vinyl aromatic compound in the (A) block is 3% by weight or more, and the (A) block and the (C) block (B) the block copolymer or the block copolymer unit in which the vinyl bond content of the conjugated diene portion in the block exceeds 60% by weight; A block copolymer in which the polymer molecular chain is extended or branched via a ring agent residue, wherein at least 80% of the double bonds of the conjugated diene portion are saturated, and the number average molecular weight is 50,000 to 70. Hydrogenated diene-based copolymer or modified hydrogenated diene-based copolymer. (B-2): a block copolymer having one or more polymer blocks (D), (E) and (F) in the molecule, respectively (provided that (D) is a polymer mainly composed of a vinyl aromatic compound) A block, (E) a polymer block mainly composed of a conjugated diene having a 1,2-vinyl bond content of 25 to 95%, and (F) a polybutadiene polymer block having a 1,2-vinyl bond content of less than 25%. In these block copolymers, the polymer molecular chain may be extended or branched via a coupling agent residue], and the content of the polymer block (D) in the block copolymer Is 5-60
% By weight, the content of the polymer block (E) is 30 to 90% by weight, and the content of the polymer block (F) is 5 to 60% by weight [however, (D) + (E) + (F) = 100% by weight] ] The hydrogenated diene-based copolymer or modified water having a number average molecular weight of 50,000 to 700,000, wherein the block copolymer is hydrogenated and at least 80% of the double bonds of the conjugated diene portion are saturated. Addition diene copolymer. (B-3); (G)-(H)-(G) or (G)-
(H) is a polybutadiene polymer block having a 1,2-vinyl bond content of 25% or less, and (H) is a conjugated diene polymer block or a vinyl aromatic compound. A conjugated diene copolymer block, wherein the conjugated diene moiety has a vinyl bond content of 2
Exhibit more than 5% polymer blocks, and these block copolymers may have polymer chains extended or branched via coupling agent residues]
A hydrogenated diene copolymer or a modified hydrogenated diene copolymer having a number average molecular weight of 50,000 to 700,000, wherein at least 80% of the double bonds of the conjugated diene portion are saturated. (C) 5 to 80% by weight of a crystalline α-olefin-based polymer having an α-olefin having 3 or more carbon atoms as a main component, and (d) 5 to 5% of an ethylene-based polymer (ethylene content of 90 mol% or more). 80% by weight [However, (A) + (B) +
(C) + (D) = 100% by weight], (E) Mineral oil-based softener based on the component (A) is 0 to 200%.
A thermoplastic elastomer composition comprising parts by weight.