JPH07268138A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic polymer composition especially suitable as a molding material for medical tools.containers, having excellent balance of physical properties of heat resistance, mechanical strength, transparency and flexibility and improved gas permeability. CONSTITUTION:This thermoplastic elastomer composition comprises (A) 10-50-wt.% of a polyolefinic resin, (B) l-89wt.% of a hydrogenated diene copolymer obtained by hydrogenating >=80% of a double bond of a conjugated diene part of a specific vinyl aromatic-conjugated diene block copolymer and (C) 1-89wt.% of a hydrogenated diene copolymer obtained by hydrogenating >=80% of a double bond of a conjugated diene part of a specific vinyl aromatic- conjugated diene block copolymer.

Description

Detailed Description of the Invention

[0001]

The present invention relates to heat resistance, mechanical strength,
The present invention relates to a thermoplastic polymer composition which is excellent in transparency and flexibility and has extremely good gas permeability, and more specifically, mainly composed of a thermoplastic elastomer exhibiting excellent rubber properties and a crystalline thermoplastic polymer. It relates to a thermoplastic elastomer composition.

[0002]

2. Description of the Related Art Conventionally, a hydrogenated block copolymer obtained by hydrogenating a butadiene portion of a block copolymer composed of a polybutadiene segment having a small 1,2-vinyl structure and a polybutadiene segment having a large 1,2-vinyl structure. Is known [John Carl Falk and RJ Schlot
t, Macromolecules, 4, 152 (1971), M. Morton et a
l., ACS Symp. Ser., 193, 101-18 (1982)], and is known to be a thermoplastic elastomer exhibiting excellent elastomer elasticity at room temperature. Further, the hydrogenated block copolymer is structurally considered to be composed of a polyethylene (PE) segment and an ethylene-butene copolymer rubber (EB) segment.

However, a thermoplastic elastomer made of this block copolymer (hereinafter referred to as "E-EB type TPE")
The drawback is that, for example, the mechanical strength at a high temperature is drastically reduced, so that it has not been put to practical use industrially. Further, conventionally, a block copolymer obtained by hydrogenating the polybutadiene portion of a polystyrene-polybutadiene-polystyrene block copolymer (hereinafter referred to as "SE
It is known that "BS") is a thermoplastic elastomer that exhibits excellent elastomer elasticity at room temperature, like the E-EB type TPE. As a composition utilizing SEBS's original excellent rubber properties, polypropylene and SE
A composition comprising BS is industrially used as a composition having excellent performance as an elastomer, but lacks transparency and flexibility. A composition composed of polypropylene and SEBS is used as a molding material for medical devices and containers, but the physical properties of heat resistance, mechanical strength, transparency, and flexibility are not sufficiently balanced, and gas permeability is also insufficient. .

[0004]

DISCLOSURE OF THE INVENTION The present invention is suitable for use as a molding material for medical instruments and containers, having heat resistance, mechanical strength,
It is an object of the present invention to provide a thermoplastic elastomer composition having an excellent balance of physical properties of transparency and flexibility and an excellent gas permeability.

[0005]

[Means for Solving the Problems] That is, the present invention provides (a) 10 to 50% by weight of a polyolefin resin, (b) a vinyl aromatic compound polymer block (A) [hereinafter also referred to as "(A) block". ] And a random copolymer block (B) of a conjugated diene polymer or a vinyl aromatic compound and a conjugated diene (hereinafter also referred to as "(B) block") (A)-(B) or (A)- (B)
-(A) a block copolymer or a tapered block (C) [hereinafter also referred to as "(C) block"] consisting of a vinyl aromatic compound and a conjugated diene and gradually increasing the vinyl aromatic compound (A)-(B )-(C) block copolymer, wherein the ratio of vinyl aromatic compound / conjugated diene in all monomers constituting (b) component is 5 / 95-60 by weight.
/ 40, (A) block and optionally configured (C)
The binding amount of the vinyl aromatic compound in the block is 3 to 50% by weight of all monomers constituting the component (b), and the binding amount of the vinyl aromatic compound in the block (A) constitutes at least the component (b). 3% by weight or more of all the monomers, (B) the block copolymer or the block copolymer unit in which the vinyl bond amount of the conjugated diene portion in the block exceeds 20%, is added via the coupling agent residue. A hydrogenated block copolymer in which a united molecular chain is extended or branched, and the double bond of the conjugated diene portion is saturated by 80% or more, and the hydrogenated diene-based copolymer having a number average molecular weight of 50,000 to 700,000 1 to 89% by weight of a polymer, and (c) a polymer block (D) mainly composed of a vinyl aromatic compound (hereinafter also referred to as "(D) block"), 1, 2
-A polymer block (E) mainly composed of a conjugated diene having a vinyl bond content of more than 25% and 95% or less [hereinafter also referred to as "(E) block"] and a 1,2-vinyl bond content of 25% or less. Certain polybutadiene polymer block (F)
(Hereinafter also referred to as “(F) block”) (D)
-(E)-(F) block copolymer, wherein the content of the (D) block is 5 to 60% by weight, the content of the (E) block is 30 to 90% by weight, and the content of the (F) block is 5 To 60% by weight, [(however, (D) + (E) + (F) = 100], or the block copolymer unit is a polymer molecular chain via a coupling agent residue. Is extended or branched to obtain a block copolymer, and the double bond of the conjugated diene moiety is saturated by 80% or more, and the number average molecular weight is 50,000 to 7
It is intended to provide a thermoplastic elastomer composition comprising 1 to 89% by weight of a hydrogenated diene-based copolymer of 100,000 (however, (A) + (B) + (C) = 100% by weight).

The present invention will be described in detail below. In the present invention, the polyolefin resin constituting the component (a) is a polymer having a C 2-8 α-monoolefin as a main monomer component. Specific examples of the olefin polymer include low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene random copolymer, ethylene-propylene block copolymer, polymethylpentene,
Examples thereof include polybutene-1, copolymers of olefins with monomers other than ethylene and propylene, and these may be used alone or in admixture of two or more. A particularly preferred olefin polymer is a polymer containing ethylene or propylene as a main monomer component, and specifically, various polyethylene, polypropylene, ethylene-
A vinyl acetate random copolymer, an ethylene- (meth) acrylic acid random copolymer, an ethylene-based random copolymer such as an ethylene-glycidyl methacrylate random copolymer, a propylene block copolymer, and a mixture thereof. .

In the components (b) and (c) of the present invention, the hydrogenation rate of the double bond in the conjugated diene portion of the conjugated diene polymer is 80% or more, preferably 90% or more, more preferably 95% or more. And a number average molecular weight of 50,000 to 700,000, preferably 100,000 to 600,000. When the hydrogenation rate is less than 80%, the transparency, mechanical strength and heat resistance are poor. If the number average molecular weight is less than 50,000, the obtained hydrogenated diene copolymer will be easily blocked when pelletized, and the mechanical strength and molding appearance will be poor, and if it exceeds 700,000, the processability will be poor.

Examples of the components (b) and (c) include a random copolymer of a conjugated diene and a vinyl aromatic compound, a block copolymer composed of a polymer block of a vinyl aromatic compound and a polymer block of a conjugated diene. And a hydrogenated product of a diene polymer such as a block copolymer composed of a vinyl aromatic compound polymer block and a vinyl aromatic compound / conjugated diene copolymer block. The components (b) and (c) of the present invention will be described in detail below.

Component (b): Preferred vinyl aromatic compounds constituting component (b) are styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene,
Divinylbenzene, 1,1-diphenylstyrene, N,
N-dimethyl-p-aminoethyl styrene, N, N-diethyl-p-aminoethyl styrene, vinyl pyridine and the like can be mentioned, more preferably styrene and α-methyl styrene, which are used alone or in combination. As preferred conjugated dienes, 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 and chloroprene are mentioned, and more preferably 1,3
-Butadiene, isoprene, 1,3-pentadiene, most preferably 1,3-butadiene.

The block (A) in the component (B) is a polymer block containing a vinyl aromatic compound as a main component, and preferably contains 10% by weight or less, more preferably 5% by weight or less of a copolymerizable vinyl compound. You may copolymerize.

The preferred weight ratio of vinyl aromatic compound / conjugated diene in all monomers in component (b) is 5/9.
5 to 60/40, more preferably 7/93 to 5
It is 0/50. When the vinyl aromatic compound content is less than 5% by weight (the conjugated diene content exceeds 95% by weight), the mechanical strength, processability and heat resistance are poor, and when the obtained hydrogenated diene copolymer is pelletized, blocking occurs. Easier to do. When the vinyl aromatic content exceeds 60% by weight (the conjugated diene content is less than 40% by weight), it becomes resin-like and the impact resistance, flexibility, low temperature characteristics and transparency are poor.

The preferred amount of vinyl aromatic compound in the (A) block or (C) block is 3 based on the total amount of the 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 amount of the monomers constituting the component (B). 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.

The preferred vinyl bond content of the conjugated diene moiety before hydrogenation in the block (B) is more than 20%, more preferably 40% or more, most preferably 60% or more. When it is 20% or less, the effect of improving flexibility when blended with an ionomer resin is lowered. The hydrogenation rate of the double bond of the conjugated diene moiety is 80% or more, preferably 90% or more, more preferably 95% or more.
If it is less than 80%, the transparency, heat resistance, weather resistance and mechanical strength are poor, which is not preferable.

The preferred content of the (A), (B) and (C) blocks in the (B) block copolymer is
(A) Block 3 to 50% by weight, more preferably 4 to 4
0% by weight, (B) block 30 to 97% by weight, more preferably 35 to 94% by weight, (C) block 0 to 50% by weight, more preferably 2 to 40% by weight (A) +
(B) + (C) = 100% by weight. Also (A),
The preferred number average molecular weights of the blocks (B) and (C) are
(A) Block 1,500 to 350,000, more preferably 4,000 to 240,000, (B) Block 1
5,000-679 million, more preferably 35,
000 to 564,000, (C) block 0 to 350,
000, more preferably 2,000 to 240,000.

The number average molecular weight of the hydrogenated diene copolymer is 5
It is 10,000 to 700,000, preferably 100,000 to 600,000.
If it is less than 50,000, the obtained hydrogenated diene-based copolymer will be easily blocked when pelletized, and the mechanical strength will decrease, and if it exceeds 700,000, the fluidity and processability will be poor, such being undesirable. The (b) hydrogenated diene-based copolymer of the present invention can be obtained, for example, by the method disclosed in JP-A-3-72512.

In the hydrogenated diene copolymer used as the component (b) in the present invention, the polymer molecular chain represented by the following general formula is extended or branched by adding a coupling agent. It may be a block copolymer. [(A)-(B)] n-X, [(A)-(B)-(C)] n-X, or [(A)-(B)-(A)] n-X [wherein , (A), (B) and (C) are the same as above. n is 2
It is the above integer, preferably 2 to 6, and more preferably 2 to 4. X represents a coupling agent residue. As the coupling agent at this time, for example, diethyl adipate, divinylbenzene, tetrachlorosilane, butyltrichlorosilane, methyldichlorosilane, tetrachlorotin, butyltrichlorotin, dimethylchlorosilane,
Tetrachlorogermanium, 1,2-dibromoethane,
1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzenetriisocyanate and the like can be mentioned.

Component (c): Component (c) is (D)-
It is a block copolymer having a structure of (E)-(F). The aromatic vinyl compound and the conjugated diene used in the component (c) are the same as those used in the component (b). Here, the preferable (D) block constituting the hydrogenated diene-based copolymer of the component (c) is a polymer block mainly containing an aromatic vinyl compound, and specifically, a homopolymer of an aromatic vinyl compound. Alternatively, a polymer block in which 80% or more of the conjugated diene moiety 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) is preferably 5 to 60% by weight, more preferably 10 to 55.
% By weight. The preferred number average molecular weight of the (D) block is 2,000 to 420,000. 5% by weight
If it is less than 1, the heat resistance and mechanical strength are poor. On the other hand, when it exceeds 60% by weight, workability and flexibility are deteriorated.

The content of the block (E) which constitutes the (c) hydrogenated diene copolymer is preferably 30 to 90% by weight, more preferably 35 to 80% by weight. If the content of the (E) block is less than 30% by weight, the flexibility is lowered,
On the other hand, when it exceeds 90% by weight, workability and mechanical strength are deteriorated. The vinyl bond content of the conjugated diene portion before hydrogenation contained in the (E) block is preferably 25 to 95%, 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 3
The conjugated diene polymer block has a molecular weight of 5,000 to 420,000 and 80% or more of the double bonds in the conjugated diene moiety are hydrogenated.

Further, the preferable content of the (F) block constituting the hydrogenated diene-based copolymer of the component (C) is 5 to 6
It is 0% by weight, more preferably 5 to 50% by weight.
If the content of the (F) block is less than 5% by weight, the mechanical strength will be reduced, while if it exceeds 60% by weight, the flexibility will be poor.
The preferred vinyl bond content of the polybutadiene before hydrogenation in the (F) block is less than 25%, more preferably 20.
It is less than%. When the vinyl bond content is 25% or more, the resinous property is lost after hydrogenation and the property of the thermoplastic elastomer as the block copolymer is lost.
The preferred number average molecular weight of the (F) block is 2,500.
Is a polymer block having a hydrogen content of 40% or more and having a double bond of 80% or more of the butadiene portion of the polybutadiene block.

The number average molecular weight of the hydrogenated diene-based copolymer (c) of the present invention is preferably 5 to 700,000, more preferably 10.
If it is less than 50,000, the mechanical strength and heat resistance of the resulting composition will decrease, while if it exceeds 700,000, the fluidity will be
Workability is reduced. The hydrogenated diene-based copolymer (c) used in the present invention can be obtained, for example, by the method disclosed in JP-A-2-133406.

In the hydrogenated diene-based copolymer used as the component (c) in the present invention, the polymer molecular chain represented by the following general formula is extended or branched by adding a coupling agent. It may be a block copolymer. [(D)-(E)-(F)] m-Y, or [(D)-(E)-(F)] Y [(D)-(E)] [(wherein (D), (E) and (F) are the same as above, m is an integer of 2 to 4, and Y is a coupling agent residue.] As the coupling agent in this case, those used in the above-mentioned component (b) Is the same as.

In the composition of the present invention, the ratio of each component is such that the component (a) is 10 to 50% by weight, preferably 15 to.
50% by weight, the component (B) is 1 to 89% by weight, preferably 3 to 75% by weight, and the component (C) is 1 to 89% by weight, preferably 3 to 75% by weight. If the component (a) is less than 10% by weight, heat resistance is poor, and if it exceeds 50% by weight, flexibility,
Poor gas permeability. If the content of the component (b) is less than 1% by weight, the transparency, flexibility and workability are poor, while if it exceeds 89% by weight, the heat resistance and mechanical strength are poor. Further, if the content of the component (C) is less than 1% by weight, gas permeability and heat resistance are poor, while 89
If it exceeds 5% by weight, heat resistance and transparency are poor. (B)
If the total amount of the component and the component (c) exceeds 90% by weight, the heat resistance may be poor, and a sticky feeling may occur on the surface of the molded product.
Incidentally, the composition of the present invention, if necessary, by a conventionally known method, modification such as maleation, carboxylation, hydroxylation, epoxidation, halogenation, sulfonation, and sulfur crosslinking, peroxide crosslinking, metal Ionic crosslinking, electron beam crosslinking,
Crosslinking such as silane crosslinking can also be performed.

If desired, the thermoplastic elastomer composition of the present invention may contain additives used in conventional thermoplastic resins. Examples of the additive include a plasticizer such as phthalate ester, a softening agent for rubber, a filler or a reinforcing agent such as silica, talc, and glass fiber, as well as an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, Lubricants, foaming agents, colorants, pigments, nucleating agents, cross-linking agents, cross-linking aids, dispersants, metal deactivators, bleed bloom inhibitors, antibacterial and antifungal agents, or the like. A mixture may be mentioned. In addition, if necessary, a rubber-like polymer,
For example, SBR, NBR, BR, EPT, EPR, EPD
M, NR, IR, 1,2-polybutadiene, AR, C
R, IIR, HSR, a hydrogenated product of a conjugated diene polymer and the like can be added. In addition, if necessary, a thermoplastic resin other than the components (a) to (c), such as a diene resin, a polyvinyl chloride resin, a polycarbonate resin, a polyacetal resin, a polyamide resin,
A polyester resin, a polyether resin, polysulfone, polyphenylene sulfide, etc. can also be blended.

The thermoplastic elastomer composition containing the components (a) to (c) described above can be prepared by a conventional kneading machine such as a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader, a ruder or a twin-screw extruder. Although a closed type or an open type can be used, a type that can be replaced by an inert gas is preferable. The kneading temperature is the temperature at which all the components to be mixed melt.
Usually, 170 to 250 ° C, preferably 180 to 240 ° C
It is desirable that the range is. Further, the kneading time depends on the type and amount of the constituents and the kneading device, and therefore cannot be generally discussed. However, when a pressure kneader, Banbury mixer or the like is used as the kneading device, the kneading time is usually about 3
It takes about 10 minutes. Further, when kneading, each component may be kneaded together, or a multi-stage divided kneading method in which after kneading arbitrary components and then adding the remaining components and kneading can be performed. Further, the molding of the composition of the present invention, by a conventionally known method, for example, extrusion molding, injection molding, blow molding, compression molding, calendering,
It can be processed into a practically useful molded product. If necessary, processing such as painting and plating can be applied.

The thermoplastic elastomer composition of the present invention comprises:
Excellent heat resistance, gas permeability, impact resistance, processability, suppleness, low temperature characteristics, temperature dependence, compatibility, paintability, printability, hot stampability, deep drawability, hot water resistance, rubber elasticity, rubber It can be used for various purposes by taking advantage of the feel, flexibility, slip resistance, stress crack resistance and the like. For example, for meat and fresh fish trays, fruit and vegetable packs, frozen dessert foods, sheets such as containers, food packaging, daily sundries packaging, industrial material packaging, various rubber products, resin products, laminating products such as fabrics and leather products, and paper diapers. Film applications such as stretch tapes used, hoses, tubes, belts, sports shoes, leisure shoes, fashion sandals, footwear such as leather shoes, TVs,
Home appliances such as stereos and vacuum cleaners, bumper parts, body panels, side shields, interior and exterior parts for automobiles such as instrument panels, medical applications such as blood bags, blood tubes, catheters, infusion tubes, syringe gaskets, and roads. It can be used for asphalt blending materials such as paving materials, tarpaulins, and piping coatings, as well as a wide range of applications such as daily necessities, leisure goods, toys, stationery, and industrial goods.

[0026]

EXAMPLES The present invention will be described in more detail below with reference to Examples. However, the present invention is not limited to the above unless it exceeds the gist of the present invention.
The present invention is not limited to the following examples. In the examples, parts and% are based on weight unless otherwise specified.
In addition, in the examples, various physical properties were evaluated by the following methods.

It was measured by infrared analysis based on the absorption of a phenyl group having a bound vinyl aromatic compound content of 679 cm ^-1 . Vinyl bond content of conjugated diene Calculated by Hampton method using infrared analysis. Hydrogenation rate Using tetrachloroethylene as a solvent, 100 MHz, ¹ H-N
It was calculated from the MR spectrum. The number average molecular weight of hydrogenated diene copolymer trichlorobenzene was used as a solvent, and it was determined in terms of polystyrene using gel permeation chromatography (GPC) at 135 ° C. Tensile properties Measured according to JIS K6301. The unit of 100% modulus is kgf / cm ² , the unit of tensile breaking strength is kgf
/ Cm ² , and the unit of tensile elongation at break is%. Gas Permeability (Oxygen Permeability ) Based on ASTM D1434, it was measured under the conditions of 23 ° C. and 50% RH. The unit of oxygen permeability coefficient is mm.cc
/ M ² · day · atm. Heat resistance 2mm square sample with 2mm thickness at 120 ℃ for 30 minutes
After aging in a gear oven, the presence or absence of shrinkage of the sample after aging was judged. ○ indicates a shrinkage rate of less than 3%,
Δ indicates that the shrinkage is 3 to 6%, and x indicates that the shrinkage is greater than 6%. Vicat softening point was measured under a load of 1 kg according to ASTM D1525. The unit is ° C. Using transparent Suga Test Instruments Co., Ltd. Multi light source spectrophotometer, by measuring the haze of a sheet of about 0.4 mm, it was determined. The lower the number, the more transparent. Flexibility JIS A hardness was measured according to JIS K6301.

Reference Example Various polymers used in the compounding recipes of Examples and Comparative Examples are as follows. PP polypropylene [Polypropylene M manufactured by Mitsubishi Petrochemical Co., Ltd.]
A-8] PE polyethylene [Polyethylene YK-, manufactured by Mitsubishi Petrochemical Co., Ltd.]
30] was prepared hydrogenated diene copolymer hydrogenated diene copolymer (T-1~6). The microstructures, number average molecular weights, and hydrogenation rates of T-1 to T-6 are as shown in Tables 1 and 2.

Examples 1 to 10 and Comparative Examples 1 to 5 Using the formulation shown in Tables 3 and 4, each component was added to a Labo Plastomill whose temperature was adjusted to 190 ° C.
The mixture was kneaded at pm for 5 minutes. This mixture was discharged, formed into a sheet with a hot roll, press-formed into a square plate with a side of 10 cm, cut out with a damppel cutter to obtain a test piece for measurement, and various physical properties were evaluated. The results are shown in Tables 3 and 4. As is clear from Tables 3 and 4, Examples 1 to 10 are the compositions of the present invention, which are excellent in oxygen permeability, and also excellent in heat resistance, tensile properties, transparency, and flexibility, The composition intended for the present invention has been obtained.
On the other hand, Comparative Example 1 is an example in which (a) the polyolefin resin is less than the range of the present invention, and although it has excellent oxygen permeability, it has poor heat resistance. Comparative Example 2 is a case where (a) the polyolefin resin exceeds the range of the present invention,
Poor oxygen permeability and flexibility. Comparative Example 3 is an example in which the component (b) is not used, and although it has excellent heat resistance, it has poor transparency and flexibility. Comparative Example 4 is an example in which the hydrogenation rate of the component (B) is less than 80%, and the transparency and heat resistance are poor. Comparative Example 5 is an example in which the number average molecular weight of the component (C) exceeds 700,000, and the transparency and mechanical strength are poor.

[0030]

INDUSTRIAL APPLICABILITY The thermoplastic elastomer composition of the present invention has essentially excellent physical properties of a thermoplastic polymer, but uses a hydrogenated diene-based copolymer which has not been practically used so far. It is a novel composition having excellent gas permeability (particularly for oxygen and carbon dioxide), high heat resistance, no tackiness, and excellent tensile properties and flexibility. The thermoplastic polymer composition of the present invention is a material having excellent properties as described above, industrial parts,
It can be suitably used for automobile interior / exterior parts, toys, medical supplies, etc., and is a material of high industrial value.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihisa Fujinaga 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. (a) Polyolefin resin 10 to 50
% By weight, (b) vinyl aromatic compound polymer block (A) [also referred to as "(A) block" below) and conjugated diene polymer or random copolymer block of vinyl aromatic compound and conjugated diene (B) (Hereinafter also referred to as “(B) block”) (A)-(B) or (A)-(B)
-(A) a block copolymer or a tapered block (C) [hereinafter also referred to as "(C) block"] consisting of a vinyl aromatic compound and a conjugated diene and gradually increasing the vinyl aromatic compound (A)-(B )-(C) block copolymer, wherein the ratio of vinyl aromatic compound / conjugated diene in all monomers constituting (b) component is 5 / 95-60 by weight.
/ 40, (A) block and optionally configured (C)
The binding amount of the vinyl aromatic compound in the block is 3 to 50% by weight of all monomers constituting the component (b), and the binding amount of the vinyl aromatic compound in the block (A) constitutes at least the component (b). 3% by weight or more of all the monomers, (B) the block copolymer or the block copolymer unit in which the vinyl bond amount of the conjugated diene portion in the block exceeds 20%, is added via the coupling agent residue. A hydrogenated block copolymer in which a united molecular chain is extended or branched, and the double bond of the conjugated diene portion is saturated by 80% or more, and the hydrogenated diene-based copolymer having a number average molecular weight of 50,000 to 700,000 1 to 89% by weight of a polymer, and (c) a polymer block (D) mainly composed of a vinyl aromatic compound (hereinafter also referred to as "(D) block"), 1, 2
-A polymer block (E) mainly composed of a conjugated diene having a vinyl bond content of more than 25% and 95% or less [hereinafter also referred to as "(E) block"] and a 1,2-vinyl bond content of 25% or less. Certain polybutadiene polymer block (F)
(Hereinafter also referred to as “(F) block”) (D)
-(E)-(F) block copolymer, wherein the content of the (D) block is 5 to 60% by weight, the content of the (E) block is 30 to 90% by weight, and the content of the (F) block is 5 To 60% by weight, [(however, (D) + (E) + (F) = 100], or the block copolymer unit is a polymer molecular chain via a coupling agent residue. Is extended or branched to obtain a block copolymer, and the double bond of the conjugated diene moiety is saturated by 80% or more, and the number average molecular weight is 50,000 to 7
A thermoplastic elastomer composition comprising 1 to 89% by weight of a hydrogenated diene-based copolymer (where (A) + (B) + (C) = 100% by weight).