JPH0987480A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic elastomer composition excellent in flexibility and useful as a substitute for flexible vinyl chlorides by dynamically heat- treating a specific olefin copolymer and a crosslinkable rubber in the presence of a crosslinking agent for rubber. SOLUTION: (A) 1-99wt.% of an olefin block copolymer comprising the blocks of a crystalline olefin polymer of 2 or more carbon atoms and the blocks of an amorphous olefin copolymer of 2 or more carbon atoms and (B) 1-99wt.% of a crosslinkable rubber, preferably a (halogenated) isobutylene-isoprene copolymer rubber and/or an ethylene-α-olefin-(diene) copolymer rubber and/or an acrylonitrile-butadiene copolymer rubber (where the components A+B=100wt.%) are dynamically heat-treated in the presence of a crosslinking agent for rubber. In addition, 1-98wt.% of the component A, 1-98wt.% of the component B and (C) 1-98wt.% of a hydrogenated diene copolymer or its functional group modifier are heat-treated as stated above (where the total of components A, B and C is 100%).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic elastomer composition, wherein an α-olefin polymer having 2 or more carbon atoms and an amorphous olefin copolymer having 2 or more carbon atoms are copolymerized in a block form. Olefin copolymer is cross-linkable represented by isobutylene-isoprene copolymer rubber (IIR), ethylene-propylene- (diene) copolymer rubber (EP (D) M), and acrylonitrile-butadiene copolymer rubber (NBR). Dynamically heat-treated rubber, hydrogenated diene copolymer and its functional group modified product in the presence of a crosslinking agent for rubber, which is excellent in mechanical strength and elastic recovery and is particularly flexible. A thermoplastic elastomer composition is provided.

[0002]

2. Description of the Related Art A crosslinkable rubber-polyolefin resin-based dynamically crosslinkable thermoplastic elastomer composition has hitherto been obtained by dynamically curing a rubber portion by a known method. By this method, it is possible to obtain a thermoplastic elastomer composition having moldability without deteriorating the characteristics of the vulcanized rubber such as elastic recovery, weather resistance, gas shielding property and oil resistance, which are peculiar to rubber. However,
It is said that the thermoplastic elastomer using an olefin resin as a matrix has particularly poor flexibility and lacks "rubber-likeness". For this reason, it has been practiced to blend a mineral oil-based softening agent to impart flexibility, but the addition of a large amount of softening agent causes a problem such as deterioration of physical properties such as elastic recovery and elution of the softening agent. Therefore, imparting flexibility is generally regarded as a difficult problem.

[0003]

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 which is particularly flexible and is excellent in elastic recovery and mechanical strength. The purpose is to do.

[0004]

[Means for Solving the Problems]

(A) 1 to 99% by weight of an olefin copolymer obtained by block-wise copolymerizing a crystalline olefin polymer having 2 or more carbon atoms and an amorphous olefin copolymer having 2 or more carbon atoms,
(B) (Halogenated) isobutylene-isoprene copolymer rubber and / or ethylene-propylene- (diene)
1 to 99% by weight of a crosslinkable rubber such as a copolymer rubber and / or an acrylonitrile-butadiene copolymer rubber [where (a) + (b) = 100% by weight] moves in the presence of a crosslinking agent for rubber. The thermoplastic elastomer composition is characterized in that it has been thermally treated. Or (a) carbon number 2
1 to 98% by weight of an olefin copolymer obtained by copolymerizing the above crystalline olefin polymer and an amorphous olefin copolymer having 2 or more carbon atoms in a block form, (b) (halogenated) isobutylene- 1 to 98% by weight of a crosslinkable rubber such as isoprene copolymer rubber and / or ethylene-propylene- (diene) copolymer rubber and / or acrylonitrile-butadiene copolymer rubber, and (c) hydrogenated diene copolymer and The modified functional group is 1 to 98% by weight (however, (A) + (B) + (C) = 100% by weight), and the components (A) and (B) or (B), (B) and (B). The present invention provides a thermoplastic elastomer composition characterized in that the component (c) is dynamically heat-treated in the presence of a crosslinking agent for rubber.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION

(A) a crystalline olefin polymer having 2 or more carbon atoms,
Among the olefin copolymers obtained by copolymerizing the amorphous olefin copolymer having 2 or more carbon atoms in a block form, the crystalline olefin polymer having 2 or more carbon atoms is ethylene,
Examples thereof include polymers such as propylene, 1-butene, poly-4-methyl-1-pentene, poly-1-hexene, and poly-1-octene. Of these, preferably propylene, 1
A homopolymer of -butene or a copolymer of propylene and 1-butene is preferable. The amorphous olefin copolymer having 2 or more carbon atoms is, for example, ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated diene terpolymer rubber, ethylene / 1-butene copolymer rubber, ethylene / 1. An amorphous elastic copolymer containing olefin as a main component such as butene / non-conjugated diene terpolymer rubber, preferably ethylene / propylene copolymer rubber. Each of these components is copolymerized in a reaction vessel in the presence of a suitable catalyst in a block or random manner. Such a copolymer is disclosed, for example, in JP-A-57-610.
12, JP-A-3-97747, JP-A-4-26141
3, the method disclosed in JP-A-5-93024. The component (a) may have a functional group. Examples of such a functional group include a hydroxyl group, a carboxyl group, an acid anhydride group, an amino group, an isocyanate group, an epoxy group and an ester group. The functional group may be introduced, for example, by modifying a propylene-ethylene copolymer. The JIS-A hardness according to the preferred K6301 of component (a) is 50 to 97, preferably 65.
To 97, more preferably 65 to 75 are used.

The crosslinkable rubber which is the component (b) means sulfur, peroxide, phenol resin, quinoid compound,
A crosslinking reaction is caused by a crosslinking agent which is usually used for vulcanizing rubber such as metal oxide. For example, ethylene-
Propylene- (diene) rubber, isobutylene-isoprene rubber, acrylonitrile-butadiene rubber, ethylene-1-butene rubber, styrene-butadiene rubber, styrene-isoprene rubber, natural rubber, isoprene rubber, polybutadiene, acrylic rubber, chloroprene rubber, fluorine rubber, silicone Examples thereof include rubbers, halides of the above rubbers, and functional group-modified products. Among the above rubbers, (halogenated) isobutylene-isoprene rubber, ethylene-propylene- (diene) rubber and acrylonitrile-butadiene rubber are preferable. The isobutylene-isoprene copolymer rubber is 0.5 to 15 mol%, preferably 0.8.
Isobutylene containing ~ 5.0 mol% isoprene /
It is a rubbery amorphous copolymer of isoprene. Examples of halogen in the halogenated isobutylene-isoprene copolymer rubber include chlorine and bromine. The halogen content is usually 0.5 to 4.0% by weight. These may be used alone or in combination of two kinds. Ethylene-propylene-
In the (diene) copolymer rubber and these ethylene-propylene- (diene) copolymer rubbers, it is desirable that they are copolymerized at a molar ratio of ethylene / propylene of 50/50 to 90/10, and 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 preferably have a Mooney viscosity ML _{1 + 4} , ₁₀₀ ° C. of 10 to 500, and more preferably 30 to 400. Ethylene
In the propylene- (diene) copolymer rubber, when the content of ethylene component is less than 50 mol% and the content of propylene is more than 50 mol%, the mechanical strength of the olefin copolymer becomes insufficient. Undesirably, the content of ethylene component is more than 90 mol%,
When the content of the propylene component is less than 10 mol%, the flexibility of the copolymer rubber is insufficient, which is not preferable. Further, when the Mooney viscosity ML _{1 + 4} , ₁₀₀ ° C. is less than 10, the strength becomes low, and when it is more than 500, poor dispersion with the polyolefin-based resin occurs, which is not preferable. Ethylene-propylene-
(Diene) A halogenated copolymer rubber in which a part of hydrogen atoms of the copolymer rubber is replaced by a halogen atom such as a chlorine atom or a bromine atom: or ethylene-propylene copolymer rubber, or a halogenated copolymer rubber, Vinyl chloride, vinyl acetate, (meth) acrylic acid or a derivative thereof (for example, methyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, etc.), maleic acid or a derivative thereof (for example, maleic anhydride, maleimide,
It is also possible to use a graft copolymer obtained by graft-polymerizing an unsaturated monomer such as dimethyl maleate) or a conjugated diene (eg, butadiene, isoprene, chloroprene). The ethylene-propylene- (diene) copolymer rubber can be polymerized by a known polymerization method, for example, in the presence of a vanadium-based, titanium-based, or metallocene-based catalyst. Further, the ethylene-propylene- (diene) copolymer rubber can be used alone or in combination of two or more kinds.
The acrylonitrile-butadiene rubber of the present invention includes α, such as acrylonitrile and methacrylonitrile.
It is a copolymer rubber obtained by copolymerizing β-unsaturated nitrile and a conjugated diene such as butadiene, and the amount of bound α, β-unsaturated nitrile is 10 to 50% by weight, preferably 10 to 4%.
0% by weight. If the α, β-unsaturated nitrile content in the nitrile rubber is less than 10% by weight, the oil resistance characteristic of the acrylonitrile-butadiene rubber is insufficient, and if it exceeds 50% by weight, the composition has poor cold resistance. Polymerization to obtain acrylonitrile-butadiene rubber is carried out by ordinary emulsion polymerization. Even if the monomers, emulsifiers, initiators, molecular weight modifiers and other polymerization agents are all added before the reaction starts, the reaction starts. The reaction mixture may be optionally added afterwards, and operating conditions such as temperature and stirring may be arbitrarily changed during the reaction. The polymerization system may be either a continuous system or a palindrome system. The molecular weight of the obtained polymer is not particularly limited, but the Mooney viscosity (ML1 + 4, 100 ° C.) is 20 to 1
20 is preferable. When it is less than 20, rubber elasticity is poor, and when it exceeds 120, workability is poor. It is also possible to use acrylonitrile-butadiene rubber partially crosslinked by copolymerizing a bifunctional monomer in the polymerization stage, or a rubber to which a plasticizer is added. Furthermore, two or more types of acrylonitrile-butadiene type rubber can be used together. The above-mentioned (B) component crosslinkable rubber alone is 2
More than one type can be used in combination.

The hydrogenated conjugated diene copolymer as the component (c) is a polymer in which at least 80% of the double bonds of the conjugated diene units in the polymer are hydrogenated. Examples of such hydrogenated conjugated diene polymers include hydrogenated products of block copolymers of vinyl aromatic compounds such as styrene / butadiene block copolymers and styrene / isoprene block copolymers and conjugated dienes; polybutadiene. Hydrogenated products of homopolymers of conjugated dienes such as polyisoprene;
Examples thereof include hydrogenated products of random copolymers of vinyl aromatic compounds and conjugated dienes, and particularly hydrogenated conjugated dienes shown in the following (C-1), (C-2) or (C-3). Polymers are preferred.

Component (C-1) Component (C-1) is composed of (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-conjugated diene taper block in which vinyl aromatic compound is gradually increased. (Hereinafter also referred to as “(C) block”)
It is obtained by hydrogenating a block copolymer arranged as (A)-(B), (A)-(B)-(C), or (A)-(B)-(A). It is a thing.

The vinyl aromatic compound used to obtain the component (c-1) is styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, N, N-dimethyl. -P-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, vinyl pyridine and the like can be mentioned, and styrene and α-methylstyrene are particularly preferable. Also, (C-1)
The conjugated diene used to obtain the component is 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,
In order to obtain a hydrogenated diene copolymer which can be industrially used and has excellent physical properties, 1,3-butadiene, isoprene,
1,3-pentadiene is preferred, and more preferably 1,
3-butadiene. (A) in the component (C-1)
The block is a polymer block containing a vinyl aromatic compound as a main component and preferably contains 10 other vinyl aromatic compounds.
It may be copolymerized in an amount of not more than 10% by weight, more preferably not more than 10% by weight.

In the block copolymer to be hydrogenated, the weight ratio of vinyl aromatic compound / conjugated diene constituting the block copolymer is preferably 5 to 60/95 to 40, more preferably 7 to 50/93 to. 50. When the vinyl aromatic compound content is less than 5% by weight (the conjugated diene content exceeds 95% by weight), the strength, processability and heat resistance are poor, and when the hydrogenated diene copolymer obtained is pelletized, blocking is likely to occur. Become. When the vinyl aromatic content exceeds 60% by weight (the conjugated diene content is less than 40% by weight), it becomes resin-like,
Poor impact resistance and low temperature characteristics.

The preferred bonding amount of the vinyl aromatic compound in the (A) block or the (C) block is 3 of all monomers.
˜50% by weight, more preferably 5 to 40% by weight, most preferably 5 to 30% by weight. (A)
If the vinyl aromatic bond content of the block and the (C) block is less than 3% by weight of all monomers, heat resistance and mechanical strength are poor, and blocking occurs when the obtained hydrogenated diene copolymer is pelletized. In addition to being easy, when blended with other ingredients, the processability is poor, while 50% by weight
If it exceeds, the transparency, flexibility, processability, and low temperature properties will be poor.
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 (C-1). If the content of the vinyl aromatic bond in the block (A) is less than 3% by weight based on the total amount of the monomers, mechanical strength, processability and heat resistance will be poor when blended with other components.

Further, in the block copolymer to be hydrogenated, the vinyl bond content in the conjugated diene portion in the (B) block is preferably 20% or more, more preferably 40% or more, most preferably 60% or more. Is. When the vinyl bond content is less than 20%, the effect of improving flexibility is not sufficiently exhibited even when blended with the resin component.

The above (A)-(B) block copolymer, (A)-(B)-(C) block copolymer, or (A)-(B)-(A) block copolymer. Is represented by the following formulas through a coupling agent residue,
It may be a block copolymer in which the polymer molecular chain is extended or branched. [(A)-(B)] n-X, [(A)-(B)-(C)] n-X [(A)-(B)-(A)] n-X (where (( A), (B) and (C) are the same as above.
Is an integer of 2 to 4, and X is a coupling agent residue. ) As the coupling agent in this case, for example, diethyl adipate, divinylbenzene, tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2-dibromoethane, 1, 4-chloromethylbenzene, bis (tricrosssilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4
-Benzene triisocyanate and the like.

The content of the (A) block, (B) block and (C) block in the block copolymer is usually 3 to 50% by weight of the (A) block, preferably 4 to 4%.
0% by weight, (B) block 30 to 97% by weight, preferably 35 to 94% by weight, (C) block 0 to 50% by weight,
Preferably 2 to 40% by weight [(A) + (B) +
(C) = 100% by weight]. Also, (A) to (C)
The polystyrene equivalent number average molecular weight of the block (hereinafter, simply referred to as “number average molecular weight”) is 0.
150,000 to 350,000, more preferably 40,000 to 240,000,
The (B) block is 15,000 to 67,000, more preferably 35,000 to 564,000, and the (C) block is 0 to 35.
10,000, more preferably in the range of 20,000 to 240,000.

The hydrogenation of the above block copolymer saturates the double bond of the conjugated diene portion of the block copolymer, resulting in a hydrogenated diene copolymer (C-1). ) Component is obtained. Here, the double bond of the conjugated diene moiety is 80% or more, preferably 90% or more.
% Or more, and more preferably 95 to 100% is required to be saturated, and if less than 80%, the thermal stability and durability of the thermoplastic elastomer composition will be poor. (Her
The number average molecular weight of component 1) is 50,000 to 700,000, preferably 100,000 to 600,000. Heat resistance of less than 50,000,
Strength, fluidity and workability deteriorate, and if it exceeds 700,000, fluidity, workability and flexibility deteriorate. Used in the present invention (Her
The component 1) can be obtained, for example, by the method disclosed in JP-A-3-72512.

Component (C-2) In the component (C-2), D is a polymer block containing a vinyl aromatic compound as a main component, E is a homopolymer block of a conjugated diene, and F is a polybutadiene block. -E-
It is a hydrogenated product of a block copolymer containing a block sequence of F. Here, the vinyl aromatic compound and the conjugated diene used to obtain the component (C-2) are
1) The same as that used to obtain the component.
The preferred (D) block constituting the hydrogenated diene-based copolymer of the component (C-2) is a polymer block mainly composed of an aromatic vinyl compound, specifically, a homopolymer of an aromatic vinyl compound, Alternatively, a polymer block in which 80% by weight or more of the conjugated diene portion of the copolymer with the conjugated diene having 90% by weight or more of the aromatic vinyl compound in the block (D) is hydrogenated is preferable. When the content of the aromatic vinyl compound in the block (D) is less than 90% by weight, strength and weather resistance are deteriorated. The content of the block (D) in the component (C-2) is preferably 5 to 60% by weight, more preferably 10 to 55.
% By weight. The preferred number average molecular weight of the block (D) is 20,000 to 420,000. If it is less than 5% by weight, heat resistance and mechanical strength are poor. On the other hand, if it exceeds 60% by weight,
Poor workability and flexibility.

Further, the preferable content of the block (E) constituting the hydrogenated diene copolymer (C-2) is 30 to 90.
%, More preferably 35 to 80% by weight.
When the content of the (E) block is less than 30% by weight, the flexibility is lowered, while when it exceeds 90% by weight, the workability and mechanical strength are lowered. The vinyl bond content of the conjugated diene moiety before hydrogenation contained in the (E) block is preferably 25 to 9
It is 5%, more preferably 30 to 90%. In the conjugated diene block before hydrogenation to be the (E) block, for example, when the conjugated diene is butadiene, if the vinyl bond content is less than 25%, a polyethylene chain is formed when hydrogenated and the rubber property is lost. On the other hand, if it exceeds 95%, the glass transition temperature becomes high when hydrogenated, and the rubbery property is lost, which is not preferable. The number average molecular weight of the (E) block is preferably 15,000 to 630,000, more preferably 35,000 to 420,000, and the double bond of the conjugated diene portion is 80%.
The above is a hydrogenated conjugated diene polymer block.

Further, the block (F) constituting the block copolymer for obtaining the component (C-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, the resinous property is lost when hydrogenated and the property of the thermoplastic elastomer as the block copolymer is lost. The content of the (F) block in the block copolymer is 5 to 60% by weight, preferably 5 to 50% by weight. (F) When the block content is less than 5% by weight,
The mechanical properties of the component (C-2) are inferior. On the other hand, when it exceeds 60% by weight, rubber properties are lost, which is not preferable. The preferred number average molecular weight of the (F) block is from 0.25 to 42.
It is a polymer block in which 80% or more of the double bonds in the butadiene portion of the polybutadiene block are hydrogenated.

Further, the block copolymer constituting the component (C-2) is at least one of the polymer blocks (D), (E) or (F) via the coupling agent residue. It may be a block copolymer which is bound to a polymer simple substance composed of a block and has a polymer molecular chain extended or branched as represented by the following formulas (1) to (4). [(D)-(E)-(F)] n-X [(D)-(E)-(F)] X [(D)-(E)] [-in formula, n is 2-4. An integer, X represents a coupling agent residue, and the coupling agent used is also (C-1).
Similar to those used in the ingredients]

The hydrogenation of the above block copolymer saturates the double bond of the conjugated diene portion of the block copolymer, resulting in a hydrogenated diene copolymer (C-2). ) Component is obtained. Here, the double bond of the conjugated diene needs to be 80% or more saturated, preferably 90% or more, and more preferably 95 to 100%. If the double bond saturation of the conjugated diene moiety is less than 80%, the thermal stability and durability of the thermoplastic elastomer composition will be poor. The number average molecular weight of the component (C-2) is 50,000 to 700,000, preferably 100,000 to 600,000. When it is less than 50,000, heat resistance, strength, fluidity and workability are deteriorated, and when it exceeds 700,000, fluidity, workability and flexibility are poor. The component (C-2) is, for example, JP-A-2-133406.
It can be obtained by the method disclosed in the publication.

Component (C-3) The hydrogenated diene-based copolymer (C-3) (hereinafter also referred to as "C (C-3)") has (G) a vinyl bond content of 25% or less. Which is a polybutadiene polymer block (hereinafter also referred to as “(G) block”), and (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 Is 25 to 95% of the polymer block (hereinafter, also referred to as "(H) block") is (G)-(H).
It is obtained by hydrogenating 80% or more of the double bond portion of a linear or branched block copolymer arranged like-(G) or (G)-(H).

Here, as the vinyl aromatic compound and the conjugated diene used to obtain the component (C-3),
The compounds exemplified as those used to obtain the component (C-1) can be mentioned. The (G) block in the component (C-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% or less, but preferably 2
It is desirable to be 0% or less, and more preferably 15% or less. When the 1,2-vinyl bond content in the block (A) exceeds 25%, the crystal melting point after hydrogenation is remarkably lowered, resulting in poor mechanical strength.

The block (H) is a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene copolymer block, and is a rubber-like ethylene-butene-1 copolymer block or a vinyl aromatic compound obtained by hydrogenation. It becomes a polymer block showing a structure similar to that of the compound-ethylene-butene-1 copolymer.

The vinyl aromatic compound used in the (H) block is used in an amount of 35% by weight or less, preferably 30% by weight or less of the monomers constituting the (H) block.
More preferably, it is 25% by weight or less, and if it exceeds 35% by weight, the glass transition temperature of the (H) block rises, resulting in poor low temperature characteristics and flexibility. The vinyl bond content of the conjugated diene portion of the (H) block is 25 to 95%, preferably 2
5 to 75%, more preferably 25 to 55%, 25
If it is less than 95% or more than 95%, hydrogenation results in a crystal structure derived from a polyethylene chain and a polybutene-1 chain, for example, when the conjugated diene is butadiene, resulting in a resin-like property and poor flexibility.

In the block copolymer for obtaining the component (C-3), the proportion of the (G) block and the (H) block is usually 5 to 90% by weight, preferably 10 to 50% by weight. 80% by weight, (H) block 95 to 10% by weight, preferably 90 to 20% by weight (however, (G) +
(H) = 100% by weight]. When the (G) block content is less than 5% by weight and the (H) block content exceeds 95% by weight, the crystalline polymer block is insufficient and the mechanical properties of the (C-3) component are inferior, which is not preferable. Further, when the content of the (G) block exceeds 90% by weight and the content of the (H) block is less than 10% by weight, the hardness of the component (C-3) increases, which is not preferable. The weight average molecular weight of the (G) block is preferably 0.25 to 630,000, more preferably 10,000 to
It is 480,000. The weight average molecular weight of the (H) block is preferably from 5,000 to 66,000, more preferably from 20,000 to 540,000.

The block copolymer for obtaining the component (C-3) is a block copolymer composed of at least one polymer block of the (G) block and the (H) block via the coupling agent residue. It may be a block copolymer which is combined with a simple substance and has a polymer molecular chain extended or branched, for example, as represented by the following formulas. [(G)-(H)] n-X [(G)-(H)-(G)] n-X (In the formulas, n and X are the same as above) Further, the coupling agent is also the above ( (C) The same compounds as those used for the component (1) can be mentioned.

The hydrogenation of the above block copolymer saturates the double bond of the conjugated diene portion of the block copolymer to give a hydrogenated diene copolymer (C-3). ) Component is obtained. Here, the double bond of the conjugated diene needs to be 80% or more saturated, preferably 90% or more, and more preferably 95 to 100%. If the double bond saturation of the conjugated diene moiety is less than 80%, the thermal stability and durability of the thermoplastic elastomer will be poor. The component (C-3) has a number average molecular weight of 50,000 to 700,000, preferably 100,000 to 600,000. When it is less than 50,000, heat resistance, strength, fluidity and workability are deteriorated, and when it exceeds 700,000, fluidity, workability and flexibility are poor.
The component (C-3) can be obtained, for example, by the method disclosed in Japanese Patent Laid-Open No. 3-1289576.

Each hydrogenated diene polymer used as the component (c) in the present invention may be a modified hydrogenated block polymer modified with a functional group. The modified hydrogenated block polymer is a hydrogenated block polymer selected from the group consisting of carboxyl group, acid anhydride group, hydroxyl group, epoxy group, halogen atom, amino group, isocyanate group, sulfonyl group and sulfonate group. It can be made by containing at least one kind of functional group. As a method of containing this functional group,
Using a conjugated diene or vinyl aromatic compound containing a functional group to obtain a block copolymer by copolymerizing with the functional group of the monomer protected, and after completion of polymerization, deprotection is in progress To the hydrogenated block polymer by a known grafting reaction of a radically polymerizable monomer having a functional group, using a monomer having a functional group, an organic peroxide or an azo compound In the presence or absence of, a hydrogenated block polymer kneader,
Examples thereof include a method of adding a functional group by kneading with a mixer, an extruder or the like. By using any of these methods, the functional group can be efficiently contained, but industrially, the methods 1 to 3 above are simple and effective. The amount of the functional group in the modified hydrogenated block polymer is usually 0.01 to 10 mol%, preferably 0.1 to 8 mol% with respect to the molecules constituting the hydrogenated block polymer.
More preferably, it is 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. Methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, dimethylaminoethyl methacrylate and the like can be mentioned.

As the cross-linking agent used in the present invention, a cross-linking agent usually used for vulcanization of rubber can be used. For example, sulfur, organic peroxide, phenol resin, metal oxide, metal hydroxide, metal chloride, p-quinonedioxime or bismaleimide type crosslinking agent can be used. When the component (b) is isobutylene-isoprene rubber, preferred crosslinking agents are sulfur type crosslinking agents, phenolic resin type crosslinking agents, p-quinonedioxime type derivatives, and halogenated isobutylene-isoprene rubbers. Metal oxides or metal hydroxides are also preferred. When the component (b) is ethylene-propylene rubber or acrylonitrile-butadiene rubber, preferred crosslinking agents are organic peroxides and phenol resin crosslinking agents,
Examples thereof include sulfur-based crosslinking agents.

Examples of the phenol resin type crosslinking agent used for crosslinking include alkylphenol formaldehyde resin and brominated phenol formaldehyde resin. The above substances are commonly used as a crosslinking agent for rubber, as described in, for example, US Pat. Nos. 3,287,440 and 3,709,840. This vulcanizing agent is obtained by polycondensation of a substituted phenol and an aldehyde in an alkali catalyst. The amount of the crosslinking agent used is 0.5 to 1 with respect to 100 parts by weight of the rubber to be crosslinked.
It is in the range of 5 parts by weight. When the amount of the cross-linking agent used is less than 0.5 parts by weight, the degree of cross-linking in the dynamic cross-linking is low, the oil resistance and shape recovery of the resulting composition are insufficient, and when it is more than 15 parts by weight, The flexibility of the resulting composition is impaired. The amount of the crosslinking agent used is preferably 1 to 10 parts by weight, more preferably 2 parts by weight, based on 100 parts by weight of the copolymer rubber.
-8 parts by weight. The cross-linking agent can be used alone, but can also be used in combination with a cross-linking accelerator in order to control the cross-linking speed. As a crosslinking accelerator, stannous chloride, ferric chloride metal halide, chlorinated polypropylene,
Organic halides such as butyl bromide rubber and chloroprene rubber can be used. It is more preferable to use a metal oxide such as zinc oxide or a dispersant such as stearic acid.

The organic peroxide used for crosslinking is, for example, dicumyl peroxide, 2,5-dimethyl-2,5-di (tertiary butylperoxy) hexane, 2,5-dimethyl-di (tertiary butylperoxy). Hexin-3,1,3-
Bis (tertiary butylperoxyisopropyl) benzene,
1,1-bis (tertiary butylperoxy) -3,3,5-
Trimethylcyclohexane, n-butyl-4,4-bis (tertiary butyl peroxy) valerade, tertiary butyl peroxy benzoate, tertiary butyl peroxy isopropyl carbonate, di-tertiary butyl peroxide and the like are used. The amount of the crosslinking agent used is in the range of 0.05 to 10 parts by weight based on 100 parts by weight of the rubber to be crosslinked. When the amount of the cross-linking agent used is less than 0.1 part by weight, the degree of cross-linking in the dynamic cross-linking is low, the oil resistance and shape recovery of the resulting composition are insufficient, and when it is more than 10 parts by weight, The flexibility of the resulting composition is impaired. The preferable amount of the cross-linking agent used is 0.1-5 with respect to 100 parts by weight of the copolymer rubber.
Parts by weight, more preferably 0.5 to 3 parts by weight. The cross-linking agent may be used alone, but a co-cross-linking agent such as a bismaleimide compound, a p-quinone dioxime derivative, divinylbenzene or trimethylolpropane trimethacrylate described below may be used.

Examples of the bismaleimide compound used in the present invention include N, N-m-phenylene bismaleimide and toluylene bismaleimide. N, N-m-phenylene bismaleimide is commercially available, for example, HVA-2 (Dupont Company), Barnock PM (manufactured by Ouchi Shinko Co., Ltd.), Sokushinol BM (manufactured by Sumitomo Chemical Co., Ltd.) and the like can be used. The preferred blending amount of the bismaleimide compound is 0.5 to
5 parts by weight, more preferably 1.0 to 2.0 parts by weight.

As the derivative of p-quinonedioxime, p-benzoquinonedioxime, p, p'-dibenzoylquinonedioxime, p-dibenzoylquinonediamide and the like are used. The amount of the crosslinking agent used is in the range of 0.2 to 10 parts by weight with respect to 100 parts by weight of the rubber to be crosslinked. If the amount of cross-linking agent used is less than 0.2 parts by weight,
The degree of cross-linking in the dynamic cross-linking is low, the oil resistance and shape recovery of the resulting composition are not sufficient, and when it is more than 10 parts by weight, the flexibility of the resulting composition is impaired. The amount of the crosslinking agent used is preferably 0.5 to 7 parts by weight, more preferably 0.8 to 3 parts by weight, based on 100 parts by weight of the rubber to be crosslinked. The cross-linking agent can be used alone, but can also be used in combination with a cross-linking accelerator in order to control the cross-linking speed. As the cross-linking accelerator, oxidants such as red lead, dibenzothiazoyl sulfide and tetrachlorobenzoquinone can be used. It is more preferable to use a dispersant such as a metal oxide such as zinc oxide or stearic acid.

As the sulfur-based cross-linking agent, sulfur, 4,
4'-dithio-bis-dimorpholine, 2- (4-morpholinodithio) benzothiazole, diauryl thiurea and the like can be mentioned. Usually aldehyde ammonias, aldehyde amines, guanidines, thioureas, thiazoles, dithiocarbamic acids, xanthogenic acids,
Used in combination with vulcanization accelerators such as thiurams.

When the rubber to be crosslinked is a halide such as halogenated butyl rubber, a metal oxide, a metal hydroxide,
It is also possible to use an organic carboxylic acid salt of a metal oxide. Examples of the metal oxide / hydroxide used for crosslinking include zinc oxide, magnesium oxide, lead oxide, calcium oxide, zinc hydroxide, magnesium hydroxide, lead hydroxide, calcium hydroxide and the like. Also, commonly used accelerators are 2,6-di-t-butyl-p-cresol, N, N
-Diethylthiobromine, di-o-tolyl guanidine, dipentamethylene thiuram tetrasulfide, ethylene trithiocarbonate, 2-mercapto-benzothiazole, benzothiazole disulfide, N-phenyl-
β-naphthylamine, tetramethylthiuram disulfide, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, and zinc dimethyldithiocarbamate. Preferred is a crosslinking system containing zinc oxide, magnesium oxide, zinc hydroxide, magnesium hydroxide. The carboxylic acid used in the organic carboxylate of the metal of the metal oxide used for crosslinking is, for example, propionic acid, acrylic acid, butyric acid, methacrylic acid, valeric acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid. , Decanoic acid, palmitic acid, myristic acid, lauric acid, stearic acid, oleic acid, naphthenic acid and benzoic acid.

In the present invention, it is also possible to add a softening agent and a plasticizer which are usually used for rubber within the range where bleeding out does not occur. For example, aromatic type, naphthene type, paraffin type petroleum softener, dioctyl phthalate, dibutyl phthalate, dioctyl adipate, dioctyl sebagate, tricresyl phosphate, adipic acid polyester, polyether type plasticizer, etc. are used. To be

The blending amounts of the above-mentioned (a) and (b) two-component systems used in the composition used in the present invention are as follows: 1 to 99% by weight, preferably 10 to 9% by weight of an olefin copolymer obtained by copolymerizing a crystalline olefin copolymer in a block form.
0% by weight, more preferably 15 to 80% by weight,
(B) The crosslinkable rubber is 1 to 99% by weight, preferably 1
0 to 90% by weight, more preferably 20 to 85% by weight
[(A) + (B) = 100% by weight] In addition, the blending amount of the above-mentioned (a), (b), (c) three-component system is
(I) 1 to 98% by weight, preferably 10% by weight of an olefin copolymer obtained by block-wise copolymerizing a crystalline olefin polymer having 2 or more carbon atoms and an amorphous olefin copolymer having 2 or more carbon atoms. ~ 85 wt%, more preferably 15-80
%, (B) 1 to 99% by weight of the crosslinkable rubber, preferably 10 to 90% by weight, more preferably 20 to 85% by weight.
% By weight, (C) 1 to 98% by weight, preferably 5 to 90% by weight, more preferably 10 to 80% by weight of a hydrogenated diene-based copolymer having a specific structure, provided that (B) + (B) )
+ (C) = 100% by weight].

The thermoplastic elastomer composition used in the present invention may be produced by any method as long as good dispersion of each component can be obtained, and is not particularly limited. Usually, the target polymer is melt-kneaded by a roll mill, a Banbury mixer, a closed kneader such as a pressure kneader, or a single-screw extruder or a twin-screw extruder used in the rubber / resin industry. Alternatively, the polymer components may be pre-kneaded in advance and then the cross-linking system may be added to carry out the dynamic heat treatment, or the polymer and the cross-linking system may be added all at once to carry out the dynamic heat treatment. In the production of the composition of the present invention, the mixing temperature (kneading temperature) is a temperature at which at least the components (a), (b) and (c) are melted, and usually 160 to 2
80 ° C. range. The thermoplastic elastomer composition of the present invention can be molded by methods such as injection molding, extrusion molding, blow molding, T die sheet processing, inflation molding, and powder slush molding. In addition, other olefin materials, urethane materials, various thermoplastic resins and /
Alternatively, the foam can be used as a multilayer by a method such as vacuum molding, multilayer extrusion, insert molding, and simultaneous molding. In addition, foaming using freon and its substitutes, a foaming method using a gas such as nitrogen and carbon dioxide, or a chemical foaming agent such as azodicarbozamide, azobisisobutyronitrile, and paratoluenesulfonitrile hydrazide. You may use it as a body.

The thermoplastic elastomer composition used in the present invention has mechanical strength, flexibility and moldability in addition to the above-mentioned components (a), (b) and (c), depending on the application. Antioxidant, antistatic agent, weatherproofing agent, UV absorber, lubricant, antiblocking agent, sealability improving agent, crystal nucleating agent, flame retardant, antibacterial, antifungal agent, tackifier , Softeners, plasticizers, coloring agents such as titanium oxide, carbon black, glass fibers, carbon fibers, metal fibers, aramid fibers, glass beads, mica, calcium carbonate, potassium titanate whiskers, talc, barium sulfate, glass flakes, A filler such as a fluororesin, a rubbery polymer, a thermoplastic resin such as polypropylene or polyethylene, and the like can be appropriately mixed.

The thermoplastic elastomer composition of the present invention comprises
Taking advantage of flexibility and molding processability without impairing mechanical strength, conventional vulcanized rubber and soft vinyl chloride resin are used, interior and exterior parts of automobiles, light electric Parts such as packing and housing of parts,
It can be used for industrial parts, waterproof sheet parts, vibration damping materials, medical containers and their stoppers, infusion tubes and the like.

[0041]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the examples, parts and% are based on weight unless otherwise specified.
In addition, various measurements in the examples were performed by the following methods. JIS A hardness Based on JIS K6301, it was measured using an A type spring type hardness tester. Elastic recovery The following substitute properties, permanent elongation and compression set were good. Permanent elongation: Based on JIS K6301, it was maintained under 100% elongation for 10 minutes, then the elongation was released, and it was determined from the elongation rate after standing for 10 minutes. The smaller the permanent elongation, the better the elastic recovery. Compression set: Based on JIS K6301, the sample was left for 22 hours in a thermostatic chamber maintained at 70 ° C. under a 25% compression condition and then taken out to measure the residual strain rate. The smaller the permanent set, the better the elastic recovery. Tensile strength and maximum elongation Measured according to JIS K6301. The test piece was type 3 and the pulling speed was 500 mm / min. Fluidity MFR was measured for fluidity under the following conditions. Temperature: 230 ℃ Load: 10 kg

The polymers used in the examples and comparative examples are as follows. (A) Component P-1 1-butene-ethylene / propylene-propylene copolymer [manufactured by Tokuyama, P. E. FIG. R. 142E] P-2 propylene-ethylene / propylene copolymer [manufactured by Tokuyama, P. E. FIG. R. 552E] (ii) component IIR1 isoprene - isobutylene copolymer rubber [JSR made, Butyl268] IIR2 chlorinated isoprene - isobutylene copolymer rubber [Japan Synthetic Rubber Ltd., JSR Chlorobutyl 1068] EP1 ethylene - propylene - ethylidene norbornene copolymer rubber (Paraffin oil 70 phr oil) [Nippon synthetic rubber, EP98A] EP2 ethylene-propylene-ethylidene norbornene copolymer rubber [Nippon synthetic rubber, EP57P] NBR1 acrylonitrile-butadiene copolymer rubber [Nippon synthetic rubber, N230S] NBR2 Acrylonitrile-butadiene copolymer rubber [N250S manufactured by Japan Synthetic Rubber] (C) Component Hydrogenated diene copolymer A Hydrogenated block copolymer A is manufactured by Japan Synthetic Rubber Co., Ltd. -B structure (A is a polystyrene block, B is a copolymer block of styrene and butadiene in which the double bond of the butadiene part is hydrogenated), the total bound styrene is 10%, and the amount of styrene in the A part is 6%. A hydrogenated block copolymer having a vinyl content (1,2 bond amount) of the butadiene portion before hydrogenation of 80% and a number average molecular weight of all molecules of 300,000. Hydrogenated diene-based copolymer B Hydrogenated block copolymer B is manufactured by Nippon Synthetic Rubber Co., Ltd. and has a D-E-F structure (D is a polystyrene block, E
Is 1.2-polybutadiene with a high vinyl content, and F is 1.
2-polybutadiene having a low vinyl content, and E and F have a hydrogenated double bond in the butadiene part)
A hydrogenated block copolymer having a vinyl content of 39%, a vinyl content of 15% and a number average molecular weight of 150,000. Hydrogenated Diene Copolymer C Hydrogenated block copolymer C is manufactured by Nippon Synthetic Rubber Co., Ltd. and has a G-H-G structure (G is 1.2-polybutadiene having a low vinyl content, and H is 1. 2-polybutadiene with a high vinyl content in which the double bond of each butadiene part is hydrogenated), the vinyl content of G part is 15%, the vinyl content of H part is 35%, and the total number of molecules is Average molecular weight is 30
10,000 hydrogenated block copolymers. Hydrogenated diene-based copolymer D Hydrogenated block copolymer C is manufactured by Nippon Synthetic Rubber Co., Ltd. and has a GH-G structure (G is polybutadiene having a low content of 1.2-vinyl, and H is 1. 2-polyvinyl with a high vinyl content in which the double bond of each butadiene part is hydrogenated), the vinyl content of C part is 15%, the vinyl content of B part is 80%, and the total number of molecules is Average molecular weight is 30
10,000 hydrogenated block copolymers. SEBS styrene-butadiene-styrene copolymer hydrogenated product [Shell, Krayton G1657] SEPS styrene-isoprene-styrene copolymer hydrogenated product [Kuraray, SEPTON 2023]

Other components PP propylene-ethylene random polymer [manufactured by Mitsubishi Chemical,
FL25R] PE low density polyethylene [Mitsubishi Chemical, LJ800] Plasticizer 1 Paraffin softener [Idemitsu Kosan, PW-90] Plasticizer 2 Dioctyl phthalate [New Nippon Rika, DOP] Inorganic filler Calcium carbonate [Shiraishi Industry] , Silver W] Crosslinking agent / crosslinking agent PR Brominated phenol formaldehyde resin [manufactured by Taoka Chemical,
Takkyrol 250-1] PO 2,5-dimethyl-2,5-di (t-butylperoxy) hexine [Nippon Yushi-Se, Perhexin 25B] BM N, N′-m-phenylene bismaleimide [Ouchi Shinko, Barnock PM] Q p-benzoquinoid dioxime [Kawaguchi Chemical Co., Actor Q] CL tetrachlorobenzoquinone [Kawaguchi Chemical Co., Actor CL] Zinc white zinc oxide [Sakai Chemical Co.] EZ diethyldithiocarbamine zinc [Ouchi Shinko Noxera EZ ] ST Stearic Acid [Lunack S-30, manufactured by Kao]

Examples 1 to 88, Comparative Examples 1 to 12 Compositions were prepared according to the following procedures according to the formulations shown in Tables 1 to 10. A twin-screw extruder (PCM45, manufactured by Ikegai Iron Works Co., Ltd.) set to a predetermined temperature was blended at a predetermined mixing ratio with (a), (b) and (c) components, and optionally an inorganic filler. And pellets were prepared. In addition, bale-shaped EP (D) M, butyl rubber, or acrylonitrile-butadiene rubber was crushed with a rubber crusher (manufactured by Tomoki Iron Works) and used. The obtained pellets were subjected to a test by forming a sheet having a thickness of 2 mm with a high temperature press having a surface temperature of 180 ° C. For evaluation of hardness JIS A, permanent elongation, and tensile strength, predetermined test pieces were punched out from the sheet with a dumbbell cutter. Furthermore, regarding the evaluation of compression set, 2 was prepared using the electrothermal roll.
Using a test piece having a thickness of mm, after punching, it was adjusted by stacking so as to have a predetermined dimension, and then subjected to a test. The results are shown in Tables 1-10.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

[Table 5]

[0050]

[Table 6]

[0051]

[Table 7]

[0052]

[Table 8]

[0053]

[Table 9]

[0054]

[Table 10]

As is clear from the comparison between Examples 1 to 88 and Comparative Examples 1 to 12, the composition of the present invention is (b) irrespective of the type of crosslinkable rubber or the type of crosslinking agent. It is particularly flexible when it contains the ingredients. further,
(C) By blending the hydrogenated diene-based copolymer, the mechanical strength and elastic recovery are improved. Especially (H
When component (1) is blended, flexibility is obtained, and when component (C-3) is blended, mechanical strength or elastic recovery is excellent.
Comparative Examples 1 to 12 are not preferable because they do not contain the component (a) and thus are greatly inferior in flexibility. Therefore, the composition of the present invention is suitable for use as a soft vinyl chloride substitute material and a vulcanized rubber substitute material.

[0056]

EFFECT OF THE INVENTION The thermoplastic elastomer composition of the present invention is particularly excellent in flexibility and mechanical strength and elastic recovery. Further, since it is not necessary to add a large amount of softening agent, there is no problem of elution of those components. Therefore, it is useful as an alternative material in the fields where soft vinyl chloride and vulcanized rubber are used.

Claims (3)

[Claims] 1. An olefin copolymer obtained by copolymerizing (a) a crystalline olefin polymer having 2 or more carbon atoms and an amorphous olefin copolymer having 2 or more carbon atoms in a block form.
99% by weight, (B) 1 to 99% by weight of the crosslinkable rubber (however, (B) + (B) = 100% by weight) are dynamically heat-treated in the presence of a crosslinking agent for rubber. A thermoplastic elastomer composition comprising: 2. The (b) component of claim 1 is a (halogenated) isobutylene-isoprene copolymer rubber and / or an ethylene-α-olefin- (diene) copolymer rubber and / or
Alternatively, the thermoplastic elastomer composition according to claim 1, which is an acrylonitrile-butadiene copolymer rubber. (A) 1 to 9 olefin copolymers obtained by block-wise copolymerizing a crystalline olefin polymer having 2 or more carbon atoms and an amorphous olefin copolymer having 2 or more carbon atoms.
8% by weight, (B) 1 to 98% by weight of crosslinkable rubber,
(C) 1 to 98% by weight of the hydrogenated diene-based copolymer or a functional group-modified product thereof (however, (A) + (B) + (C) =
100% by weight] (a) and (b) components or (a),
A thermoplastic elastomer composition, wherein the components (b) and (c) are dynamically heat-treated in the presence of a crosslinking agent for rubber.