JPH04236249A - Thermoplastic polymer composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic polymer composition suitable as a molding material especially for tools and containers for medical application, having excellent balance of physical properties of heat resistance, mechanical strength, transparency and flexibility. CONSTITUTION:A thermoplastic polymer composition comprising (a) 10-50 wt.% polyolefinic resin, (b) 1-89wt.% hydrogenated diene-based polymer obtained by hydrogenating >=90% of butadiene part of a block copolymer composed of a polybutadiene segment (C) and a polybutadiene or vinyl aromatic compound- butadiene copolymer block segment (D) and c 1-89wt.% at least one (c-1) a block copolymer composed of a vinyl aromatic compound and a conjugated diene compound, (c-2) a hydrogenated material of a random coplymer of a vinyl aromatic compound and a conjugated diene compound and (c-3) a hydrogenated material of a block copolymer of a vinyl aromatic compound and a conjugated diene compound.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention provides heat resistance, mechanical strength,
A thermoplastic polymer composition that has excellent transparency, flexibility, and extremely good gas permeability, and more specifically, a thermoplastic elastomer that exhibits excellent rubber properties and a crystalline thermoplastic polymer as main components. Thermoplastic polymer compositions.

0002

[Prior Art] Conventionally, a hydrogenated block copolymer is obtained by hydrogenating the butadiene portion of a block copolymer consisting of a polybutadiene segment with less 1,2-vinyl structure and a polybutadiene segment with more 1,2-vinyl structure. is well known [John Carl Falk a
nd R. J. Schlott, Macromo
M. lecules, 4, 152 (1971).
Morton et al. , ACS Symp.
Ser. , 193, 101-18 (1982)
], is known to be a thermoplastic elastomer that exhibits excellent elastomer elasticity at room temperature. Further, the hydrogenated block copolymer is structurally polyethylene (PE
) segment and an ethylene-butene copolymer rubber (EB) segment.

However, thermoplastic elastomers (hereinafter referred to as "E-EB TPE") made of this block copolymer
The disadvantages of this method include, for example, a sudden drop in mechanical strength at high temperatures, and it has not yet been put to practical use industrially. In addition, conventional block copolymers (hereinafter referred to as SE
BS'') is known to be a thermoplastic elastomer that exhibits excellent elastomer elasticity at room temperature, similar to E-EB TPE.

[0004] Compositions made of polypropylene and SEBS are used industrially as compositions that take advantage of the excellent rubber properties inherent to SEBS, but they lack transparency and flexibility. It lacks. The composition consisting of polypropylene and SEBS is
It is used as a molding material for medical instruments and containers.
The physical property balance of heat resistance, mechanical strength, transparency, and flexibility is insufficient, and gas permeability is also insufficient.

[0005]

[Problems to be Solved by the Invention] The present invention provides a material that has high heat resistance, mechanical strength, and is suitable as a molding material for medical instruments and containers.
The object of the present invention is to provide a thermoplastic polymer composition that has an excellent balance of physical properties such as transparency and flexibility, and has excellent gas permeability.

[0006]

[Means for Solving the Problems] The present invention provides: (a); 10 to 50% by weight of polyolefin resin (hereinafter sometimes referred to as "component (a)");(b); 1,2-vinyl bond content; is 20% or less (hereinafter referred to as "block C"), polybutadiene or a vinyl aromatic compound-butadiene copolymer, in which the 1,2-vinyl bond content of the butadiene moiety is 25 to 95%. % (hereinafter referred to as "block D"), and the block structure is C-(D-C)n or (C
-D) Hydrogenated diene system obtained by hydrogenating 90% or more of the butadiene portion of a linear or branched block copolymer represented by m (where n is an integer of 1 or more, m is an integer of 2 or more) Polymer (hereinafter referred to as "hydrogenated diene polymer" or "component (b)") 1 to 89% by weight, (c); (c-1) Conjugated with a polymer block mainly composed of a vinyl aromatic compound A block copolymer consisting of a polymer block mainly composed of a diene compound (hereinafter referred to as "(3-1) component"), (3-2) Hydrogen of a random copolymer of a vinyl aromatic compound and a conjugated diene compound an additive (hereinafter referred to as "component (III-2)"), and (III-3) a block copolymer consisting of a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound hydrogen additives (hereinafter referred to as
3) At least one type selected from the group (referred to as "ingredients")
(hereinafter referred to as "component (c)") 1 to 89% by weight [however,
(a) + (b) + (c) = 100% by weight].

The polyolefin resin (a) used in the present invention is a resin obtained by polymerizing one or more monoolefins by either a high-pressure method or a low-pressure method. Here, the monoolefins include ethylene,
Propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 2-methyl-1-propene, 3-methyl-1-pentene, 5-methyl-1-hexene, and mixtures thereof , preferably ethylene, propylene, 4-methyl-1-pentene, more preferably propylene. Preferred polyolefin resins (a) are polyethylene, polypropylene, and poly4-methyl-1-pentene, and copolymer type components (a) include ethylene, 1-butene, 1-pentene, and 1-hexene. , 4-methyl-1-pentene, 2
-Methyl-1-propene, 3-methyl-1-pentene,
and polypropylene copolymerized with at least one member selected from the group consisting of 5-methyl-1-hexene and the like. (a) More preferred polyolefin resins are polypropylene and the above-mentioned copolymer type polypropylene.

(b) The hydrogenated diene polymer used in the present invention comprises a polybutadiene block segment (C) having a 1,2-vinyl bond content of 20% or less, and polybutadiene or a vinyl aromatic compound-butadiene copolymer. A polymer consisting of a block segment (D) in which the content of 1,2-vinyl bonds in the butadiene moiety is 25 to 95%, and whose block structure is C-(D-C)n or (C-D
) m (where n is 1 or more, m is 2 or more) and is obtained by hydrogenating 90% or more of the butadiene portion of a linear or branched block copolymer.

Block C in component (b) becomes a crystalline block segment having a structure similar to ordinary low density polyethylene (LDPE) by hydrogenation. The 1,2-vinyl structure in block C is usually 20% or less, preferably 18% or less, and more preferably 15% or less. If the 1,2-vinyl structure of block C exceeds 20%, the crystal melting point after hydrogenation will drop significantly and the mechanical properties of component (b) will deteriorate, which is not preferable.

Block D is polybutadiene or a vinyl aromatic compound-butadiene copolymer,
Hydrogenation results in a block segment having a structure similar to that of a rubber-like ethylene-butene copolymer or a vinyl aromatic compound-ethylene-butene copolymer. here,
As the vinyl aromatic compound used in block D,
Styrene, t-butylstyrene, α-methylstyrene,
Examples include p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N,N-diethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, vinylpyridine, etc. In particular, styrene, α
- Methylstyrene is preferred. The amount of this vinyl aromatic compound used is 35% by weight of the monomers constituting block D.
or less, preferably 30% by weight or less, more preferably 2% by weight or less
5% by weight or less, and if it exceeds 35% by weight, block D
This is not preferable because the glass transition temperature of component (b) increases and the mechanical properties of component (b) deteriorate. In addition, the 1,2-vinyl structure of the butadiene moiety of block D is usually 25 to 95%,
Preferably 25-75%, more preferably 25-55%
%, and when it is less than 25% or more than 95%, after hydrogenation, it shows a crystal structure derived from polyethylene chains and polybutene-1 chains, respectively, and becomes resin-like.
b) Unfavorable because the mechanical properties of the components are poor.

(b) The proportion of block C and block D in the component is usually 5 to 90% by weight of block C,
Block D 95-10% by weight, preferably block C1
0 to 85% by weight, and block D 90 to 15% by weight. If the amount of block C is less than 5% by weight and the amount of block D is more than 95% by weight, this is not preferable because crystalline block segments will be insufficient and the mechanical properties of component (b) will be poor. In addition, block C exceeds 90% by weight and block D exceeds 1% by weight.
If it is less than 0% by weight, the hardness of component (b) increases,
This is not preferred because it becomes unsuitable as a thermoplastic elastomer.

Furthermore, the (b) hydrogenated diene polymer used in the present invention has at least 90% of the double bonds in the butadiene moieties of block C and block D, preferably 9
It is necessary that 5 to 100% is hydrogenated and saturated; if it is less than 90%, the heat resistance, weather resistance, and ozone resistance will be poor. The weight average molecular weight of block C and block D is usually 5,000 or more, preferably 1
It is desirable that it is 0,000 or more, more preferably 15,000 or more, and less than 5,000 is not preferred because the mechanical properties of component (b) are poor.

(b) The hydrogenated diene polymer of the present invention is produced by subjecting block C and block D to living anionic polymerization in an organic solvent to obtain a block copolymer, and then hydrogenating this block copolymer. obtained by doing. Examples of the organic solvent include pentane, hexane, heptane,
Hydrocarbon solvents such as octane, methylcyclopentane, cyclohexane, benzene, and xylene are used. As the organic alkali metal compound which is a polymerization initiator, an organic lithium compound is preferable. As this organic lithium compound, an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound are used. Specific examples of these include ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec.
-Butyl lithium, t-butyl lithium, hexamethylene dilithium, butadienyl lithium, isoprenyl dilithium, etc., and 0 per 100 parts by weight of monomer.
．． It is used in an amount of 0.02 to 0.2 parts by weight.

[0014] In this case, Lewis bases such as ethers, amines, etc., specifically diethyl ether, tetrahydrofuran, propyl ether, butyl ether, higher ethers, etc. Ether derivatives of polyethylene glycol such as ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, and triethylene glycol dimethyl ether; examples of amines include tertiary amines such as tetramethylethylenediamine, pyridine, and tributylamine; used. Furthermore, the polymerization reaction is usually carried out at -30°C to 1°C.
Performed at 50°C. Furthermore, the polymerization may be carried out at a controlled constant temperature or may be carried out at an elevated temperature without heat removal. Any method may be used to form the block copolymer, but generally in the organic solvent,
First, block C is polymerized using a polymerization initiator such as the alkali metal compound, and then block D is polymerized.

The block copolymer thus obtained is a block copolymer in which the polymer molecular chain is extended or branched as represented by the following general formula by adding a coupling agent. Good too. C-(D-C)n (C-D)m (In the formula, n represents an integer of 1 or more, preferably 2 to 4, and m represents an integer of 2 or more, preferably 2 to 4.) Examples of coupling agents include diethyl adipate, divinylbenzene, tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2-dibromoethane, 1,4- Examples include chloromethylbenzene, bis(trichlorosilyl)ethane, epoxidized linseed oil, tolylene diisocyanate, and 1,2,4-benzene triisocyanate.

The bond content of the vinyl aromatic compound in this block copolymer is controlled by the amount of monomer supplied during polymerization in each stage, and the vinyl bond content of the conjugated diene compound is controlled by varying the components of the microcontroller. It is adjusted by Further, the weight number average molecular weight is controlled by the amount of a polymerization initiator, such as n-butyllithium. To explain more specifically the method for producing the block copolymer used in the present invention, first, in order to obtain the block copolymer, an organic lithium compound such as sec-butyllithium is used as an initiator and the process is carried out under vacuum or at high temperature. Under a stream of pure nitrogen, 1,3-butadiene is polymerized in the first stage using an organic solvent such as benzene or cyclohexane as a polymerization solvent to polymerize a low vinyl polybutadiene block, which will become block C, and then tetrahydrofuran or diethyl ether is polymerized. and 1,3-butadiene for the second stage are added, and after the polymerization is completed, a calculated amount of a coupling agent such as dimethyldichlorosilane is added,
By coupling the C-D diblock polymer, a triblock polymer consisting of C-D-C is obtained.

Furthermore, by using a polyfunctional coupling agent, a branched multiblock polymer having a plurality of CD blocks in the form of branches can be obtained. At the end of the first stage, an appropriate amount of the polymerization solution is sampled and measured by gel permeation chromatography (GPC) to determine the molecular weight of block C. Similarly, the molecular weight of the second stage is determined by subtracting the molecular weight of the first stage from the molecular weight value obtained by GPC measurement of the sample at the end of the second stage. Therefore, C-
In the case of a D-C triblock polymer, the molecular weight of block D is 2 times the molecular weight of the second stage determined from GPC measurement.
It will be doubled. By hydrogenating the block copolymer polymerized as described above, the (b) hydrogenated diene polymer used in the present invention can be obtained. (b) The hydrogenated diene copolymer used in the present invention is obtained by dissolving the block copolymer thus obtained in an inert solvent,
It is carried out in the presence of a hydrogenation catalyst at 150° C. and under pressurized hydrogen of 1 to 100 kg/cm 2 .

Next, the block copolymer which is component (III) in component (III) preferably contains a vinyl aromatic compound in an amount of 5 to 95% by weight, more preferably 10 to 90% by weight.
, particularly preferably 15 to 70% by weight,
Its structure is not particularly limited and may be linear, branched, or radial. Specifically, the general formula (A-
B) n, (A-B) n-A, (A-B) n-X (in the formula,
A is a polymer block mainly composed of aromatic vinyl compounds,
B is a polymer block mainly composed of a conjugated diene compound, n
is an integer of 1 or more, and X is a coupling residue). Here, the polymer block A mainly composed of a vinyl aromatic compound refers to a vinyl aromatic compound block containing a vinyl aromatic compound alone, or a vinyl aromatic compound containing a vinyl aromatic compound in an amount of 60% by weight or more, preferably 80% by weight or more. It has a copolymer block structure of an aromatic compound and a conjugated diene compound. Polymer block B mainly composed of a conjugated diene compound means that the conjugated diene compound block contains a conjugated diene compound alone, or a conjugated diene compound containing 60% by weight, preferably 80% by weight or more of a conjugated diene compound and a vinyl aromatic compound. It may be a copolymer block with a compound, and may have a structure in which the vinyl aromatic compound is randomly bonded or has one or more so-called tapered blocks in which the vinyl aromatic compound is gradually increased.

[0019] As the vinyl aromatic compound, the same compounds as those used in the block D can be mentioned. In addition, conjugated diene compounds include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-
Examples include butadiene, 2-chloro-1,3-butadiene, 2-cyano-1,3-butadiene, substituted linear conjugated pentadienes, linear and side chain conjugated hexadiene, and the like. Among these, 1,3-butadiene, 2-methyl-1
, 3-butadiene is particularly preferred. Also, (Har-
The hydrogenated product of random copolymer of component 2) and the hydrogenated product of block copolymer of vinyl aromatic compound and conjugated diene compound of component (iii-3) contain 50% by weight or less of vinyl aromatic compound. , preferably 5 to 40% by weight.

[0020] The random copolymers or block copolymers before hydrogenation constituting the components (C-2) to (C-3) are specifically those of the general formulas (1)A-B, (2) A-B-A, (3) A-B-E, (4) A-B1 -B2 (B1 vinyl bond is preferably 20% or more, B2 vinyl bond is preferably 2
(less than 0%), (5) B, (6) A/B, (7) A-A/B, (8) A-A/B-E, (9) A-A/B-A, (10 ) E-B, (11) E-B-E, (12) E-A/B-E, (13) E-A-B (in these formulas, A/B represents a vinyl aromatic compound and a conjugated diene) A random copolymer with a compound, E is a copolymer of a vinyl aromatic compound and a conjugated diene compound, and is a tapered block in which the vinyl aromatic compound gradually increases). ) as a skeleton, and copolymers having these basic skeletons repeatedly. Alternatively, a diene polymer obtained by coupling them may be used.

[0021] Regarding A-B1-B2 of (4) above, B of (5),
Regarding A/B (6), it is shown in Japanese Unexamined Patent Publication No. 127400/1983. A-A/B in (7) above, (8)
Regarding A-A/B-E, preferably the ratio of vinyl aromatic compound/conjugated diene compound is 5 to 40/60 to 9.
5% by weight, the total amount of vinyl aromatic compounds of A or A and E is 3 to 25% by weight of the total copolymer, the vinyl bond content of the conjugated diene moiety in A/B is 15% or more, particularly preferably 30%. ~80% by weight. Said (Ha-2), (Ha-3)
The aromatic vinyl compounds and conjugated diene compounds that make up the
It is the same as that used for the component (C-1) above. The hydrogenated substances (C-2) to (C-3) used in the present invention can be obtained by hydrogenating the diene polymer (random copolymer, block copolymer). The hydrogenation rate of olefinic unsaturated bonds in the diene polymer is 70% or more, preferably 90% or more. The polymerization method of the diene polymer used in the components (C-2) to (C-3) and the hydrogenation method thereof are described, for example, in Japanese Patent Application No. 104256/1983.

The microstructure of the diene polymer is 1,2-
, 3,4-, etc., is preferably 10% or more, more preferably 20 to 80%, particularly preferably 3
The number average molecular weight of the diene polymer is preferably 5,000 to 1,000,000, more preferably 30,000 to 300,000. Among the above components (c), the most preferred are styrene-ethylene-propylene block copolymer and styrene-ethylene-butylene block copolymer.

In the composition of the present invention, the proportions of each component are (a) polyolefin resin 10 to 50% by weight, preferably 15 to 50% by weight, and (b) hydrogenated diene polymer 1 to 89% by weight. % by weight, preferably 3 to 75% by weight, (c)
The component is 1 to 89% by weight, preferably 3 to 75% by weight. (a) If the polyolefin resin is less than 10% by weight, heat resistance will be poor, while if it exceeds 50% by weight, flexibility and gas permeability will be poor. (b) If the hydrogenated diene polymer is less than 1% by weight, flexibility, processability, and gas permeability are poor;
Heat resistance exceeding 0% by weight is poor. Furthermore, if the component (c) is less than 1% by weight, gas permeability and heat resistance will be poor;
If it exceeds % by weight, heat resistance and transparency will be poor. Furthermore, (b)
If the total amount of component (c) exceeds 90% by weight, the heat resistance will be poor and the surface of the molded product may feel sticky. In addition, the composition of the present invention can be modified by conventionally known methods as necessary, such as maleation, carboxylation, hydroxylation, epoxidation, halogenation, and sulfonation, as well as sulfur crosslinking, peroxide crosslinking, and metallization. Ionic crosslinking, electron beam crosslinking,
Crosslinking such as silane crosslinking can also be performed.

Additives commonly used in thermoplastic resins can be added to the thermoplastic polymer composition of the present invention, if necessary. These additives include, for example, plasticizers such as phthalate esters, rubber softeners, fillers or reinforcing agents such as silica, talc, and glass fibers, as well as antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, lubricant,
Foaming agents, colorants, pigments, nucleating agents, crosslinking agents, crosslinking aids, etc.
or a mixture thereof. In addition, rubber-like polymers such as SBR, NBR, B
R, EPT, EPR, NR, IR, 1,2-polybutadiene, AR, CR, IIR, HSR, etc. can be added. In addition, as necessary, the above (a) to (a)
Thermoplastic resins other than component c), such as diene resins, polyvinyl chloride resins, polyvinyl acetate resins, polycarbonate resins, polyacetal resins, polyamide resins, polyester resins, polyether resins, polysulfone, polyphenylene Sulfide and the like can also be added.

The thermoplastic polymer composition containing the above components (a) to (c) can be prepared using a conventional kneading device such as a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader, a ruder, or a twin-screw extruder. However, whether it is a closed type or an open type, a type that can be replaced with an inert gas is preferable. The kneading temperature is the temperature at which all the ingredients to be mixed melt, and is usually
It is desirable that the temperature be in the range of 170 to 250°C, preferably 180 to 240°C. Further, the kneading time cannot be discussed unconditionally because it depends on the type and amount of the constituent components and the kneading equipment, but when using a pressure kneader, Banbury mixer, etc. as the kneading equipment, it is usually about 3. ~10
It takes about a minute. Furthermore, when kneading, each component may be kneaded all at once, or a multistage split kneading method may be used in which any component is kneaded and then the remaining components are added and kneaded. Furthermore, the composition of the present invention can be processed into a practically useful molded article by conventionally known methods such as extrusion molding, injection molding, blow molding, compression molding, and calendering. Furthermore, processing such as painting and plating can be applied as necessary.

The thermoplastic polymer composition of the present invention has excellent heat resistance, gas permeability, impact resistance, processability, flexibility,
Taking advantage of its low temperature properties, temperature dependence, compatibility, paintability, printability, hot stampability, deep drawability, hot water resistance, rubber elasticity, rubber feel, flexibility, slip resistance, stress crack resistance, etc. Can be used for various purposes. For example, ■Sheet applications such as trays for meat and fresh fish, fruit and vegetable packs, frozen desserts, and containers; ■Food packaging, daily goods packaging, industrial material packaging, laminates for various rubber products, resin products, fabrics, leather products, etc., and disposable diapers. Applications for films such as elastic tapes, etc. Applications for hoses, tubes, belts, etc.
Footwear applications such as sports shoes, leisure shoes, fashion sandals, and leather shoes ■Home appliance applications such as televisions, stereos, and vacuum cleaners ■Interior and exterior automotive parts applications such as bumper parts, body panels, and side shields,
■Medical applications such as blood bags, blood tubes, catheters, infusion tubes, and syringe gaskets; ■Asphalt blend material applications such as road paving materials, waterproof sheets, and piping coatings; ■Other daily necessities, leisure goods, toys, industrial supplies, etc. It can be used for a wide range of purposes.

[0027]

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but unless it goes beyond the gist of the present invention, the present invention
The present invention is not limited to the following examples. In the examples, parts and percentages are based on weight unless otherwise specified. In addition, in the Examples, various physical properties were evaluated by the following methods. Tensile properties were measured in accordance with JIS K6301. The unit of 100% modulus is kgf/cm2, the unit of tensile strength at break is kgf/cm2, and the unit of tensile elongation at break is %. Gas permeability (oxygen permeability) Based on ASTM D1434, 23°C, 50%RH
Measured under the following conditions. The unit of oxygen permeability coefficient is mm・c
c/m2・day・atm. Heat Resistance A 2 cm square sample with a thickness of 2 mm was aged in a gear oven at 120° C. for 30 minutes, and the presence or absence of shrinkage of the sample after aging was determined. ◯ indicates a shrinkage rate of less than 3%, △ indicates a shrinkage rate of 3 to 6%, and × indicates a shrinkage rate of greater than 6%. Vicat Softening Point ASTM D1525
Measured under a load of 1 kg. The unit is °C. Transparency Using a multi-light source spectrophotometer manufactured by Suga Test Instruments Co., Ltd., approximately 0
．． The haze of a 4 mm sheet was measured and judged. The lower the number, the more transparent it is. Flexibility JIS A hardness was measured in accordance with JIS K6301.

Reference Examples The various polymers used in the formulations of Examples and Comparative Examples are as follows. PP Polypropylene [Mitsubishi Yuka Co., Ltd., Polypropylene M
A-8] PE polyethylene [manufactured by Mitsubishi Yuka Co., Ltd., polyethylene YK-
30] CDC1 to CDC3 Hydrogenated diene polymers obtained by hydrogenating the butadiene portion of a block copolymer consisting of a polybutadiene segment with a low 1,2-vinyl bond content and a polybutadiene segment with a high 1,2-vinyl bond content. (E-EB type TPE), and both are manufactured by Japan Synthetic Rubber Co., Ltd. The microstructures, number average molecular weights, and hydrogenation rates of CDCs 1 to 3 are shown in Table 1.

[0029]

[Table 1]

SBS polystyrene-polybutadiene-polystyrene block copolymer [manufactured by JSR Shell Elastomer Co., Ltd., TR
2000] SIS Polystyrene-polyisoprene-polystyrene block copolymer [manufactured by JSR Shell Elastomer Co., Ltd., SI
S5000] SEBS A block copolymer obtained by hydrogenating the polybutadiene portion of a polystyrene-polybutadiene-polystyrene block copolymer [manufactured by Shell Chemical Co., Ltd., Kraton G1650
; SEBS-1, Clayton G1657; SEBS-2
] Block copolymer obtained by hydrogenating the polyisoprene portion of SEPS SIS [manufactured by Kuraray Co., Ltd., SEPTON 2002] Softener manufactured by Idemitsu Petrochemical Co., Ltd., paraffin oil

0031
] Examples 1 to 13, Comparative Examples 1 to 6 Using the formulation shown in Table 2, the mixture was placed in a laboplasto mill whose temperature was adjusted to 190°C.
Each component was added and kneaded at 60 rpm for 5 minutes. This mixture was discharged and formed into a sheet with hot rolls, and then press-molded into a square plate of 10 cm on each side, which was cut out with a damper cutter to provide test pieces for measurement, and various physical properties were evaluated. The results are shown in Table 2. As is clear from Table 2, Examples 1 to 13 are compositions of the present invention, which have excellent oxygen permeability, heat resistance, tensile properties, transparency, and flexibility. The desired composition has been obtained. On the other hand, Comparative Example 1 is an example in which (a) the polyolefin resin is below the range of the present invention, and has excellent oxygen permeability but poor heat resistance. Comparative Example 2 is a case in which (a) the polyolefin resin exceeds the scope of the present invention, and is inferior in oxygen permeability and flexibility. Comparative Example 3 is an example in which (b) no hydrogenated diene polymer is used, and although it is excellent in heat resistance and transparency, it is inferior in flexibility. Comparative Example 4 is an example in which component (iii) is not used, and is excellent in oxygen permeability and flexibility, but slightly inferior in heat resistance. Comparative Example 5 is a case where the component (b) exceeds the range of the present invention, and the heat resistance is poor. Comparative example 6 is (c)
This is a case where the components exceed the scope of the present invention, and the heat resistance is poor.

[0032]

[Table 2]

[0033]

Effects of the Invention The thermoplastic polymer composition of the present invention is a novel composition using E-EB TPE, which has essentially excellent physical properties as a thermoplastic polymer, but which has not been put to practical use so far. composition with extremely high gas permeability (especially
(against oxygen and carbon dioxide) and has high heat resistance.
A product with no sticky feeling and excellent tensile properties and flexibility can be obtained. The thermoplastic polymer composition of the present invention is a material having excellent properties as described above, and can be suitably used for industrial parts, automobile interior/exterior parts, toys, medical supplies, etc., and is industrially useful. It is a valuable material.

Claims (1)

[Claims] Claim 1: (A); Polyolefin resin 10~
(B) Polybutadiene block segment (C) having a 1,2-vinyl bond content of 20% or less, polybutadiene or a vinyl aromatic compound-butadiene copolymer, in which the 1,2- Vinyl bond content is 2
consisting of block segments (D) that are 5-95%;
and the block structure is C-(D-C)n or (C-D)
Hydrogenated diene polymer 1 obtained by hydrogenating 90% or more of the butadiene portion of a linear or branched block copolymer represented by m (where n is an integer of 1 or more, m is an integer of 2 or more) ~89% by weight, (c); (c-1) Block copolymer consisting of a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound, (c-2) Vinyl A hydrogenated product of a random copolymer of an aromatic compound and a conjugated diene compound, and (c-3) a block consisting of a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound At least one selected from the group of hydrogenated copolymers
Seeds 1 to 89% by weight [However, (a) + (b) + (c) =
100% by weight].