JP2982325B2 - Thermoplastic polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to heat resistance, mechanical strength,
Transparency, excellent in flexibility, and a very good gas permeability thermoplastic polymer composition, more specifically, mainly composed of a thermoplastic elastomer and a crystalline thermoplastic polymer exhibiting excellent rubber-like properties It relates to a thermoplastic polymer composition.

[0002]

2. Description of the Related Art Conventionally, a hydrogenated block copolymer obtained by hydrogenating a butadiene portion of a block copolymer comprising a polybutadiene segment having a small 1,2-vinyl structure and a polybutadiene segment having a large 1,2-vinyl structure. Are 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. The hydrogenated block copolymer is considered to be structurally composed of a polyethylene (PE) segment and an ethylene-butene copolymer rubber (EB) segment.

However, thermoplastic elastomers comprising this block copolymer (hereinafter referred to as "E-EB-based TPE")
The disadvantage is that, for example, the mechanical strength at a high temperature drops sharply, and at present, it has not been industrially put to practical use. Further, conventionally, a block copolymer obtained by hydrogenating a polybutadiene portion of a polystyrene-polybutadiene-polystyrene block copolymer (hereinafter referred to as “SE
BS) is known to be a thermoplastic elastomer exhibiting excellent elastomer elasticity at room temperature, like the E-EB-based TPE.

[0004] As a composition utilizing SEBS's original excellent rubber-like properties, a composition comprising polypropylene and SEBS is industrially used as having excellent properties as an elastomer. Lack. The composition consisting of polypropylene and SEBS,
Used as a molding material for medical instruments and containers,
The balance of physical properties of heat resistance, mechanical strength, transparency, and flexibility is not sufficient, and gas permeability is also insufficient.

[0005]

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

[0006]

Means for Solving the Problems The present invention provides (a) a polyolefin resin (hereinafter sometimes referred to as "component (a)") in an amount of from 10 to 50% by weight, and (b) a 1,2-vinyl bond content. Is 20% or less, a polybutadiene block segment (C) (hereinafter referred to as "block C"), a polybutadiene or vinyl aromatic compound-butadiene copolymer, wherein the 1,2-vinyl bond content of the butadiene portion is 25 to 95. % Of the block segment (D) (hereinafter referred to as “block D”), and the block structure is C- (D-C) n or (C
-D) a hydrogenated diene system obtained by hydrogenating a butadiene portion of a linear or branched block copolymer represented by m (where n is 1 or more and m is an integer of 2 or more) by 90% or more; (Hereinafter referred to as "hydrogenated diene polymer" or "(b) component") 1 to 89% by weight; (c); (c-1) conjugated with a polymer block mainly composed of a vinyl aromatic compound A block copolymer comprising a polymer block mainly composed of a diene compound (hereinafter referred to as “(C-1) component”); (C-2) hydrogen of a random copolymer of a vinyl aromatic compound and a conjugated diene compound An additive (hereinafter referred to as "(c-2) component"); and (c-3) a block copolymer comprising a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound. Hydrogenated products (hereinafter "( 1 to 89% by weight (herein, (A) + (B) + (C) = 100% by weight) selected from the group consisting of (-3) a component). And a thermoplastic polymer composition containing the same.

The (a) polyolefin resin used in the present invention is a resin obtained by polymerizing one or more monoolefins by a high-pressure method or a low-pressure method. Here, as the monoolefin, 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 And ethylene, propylene, 4-methyl-1-pentene, and more preferably propylene. Preferred (a) polyolefin-based resins are polyethylene, polypropylene, and poly-4-methyl-1-pentene, and the copolymer-type (a) components include ethylene, 1-butene, 1-
Pentene, 1-hexene, 4-methyl-1-pentene,
Examples thereof include polypropylene in which at least one selected from the group consisting of 2-methyl-1-propene, 3-methyl-1-pentene, and 5-methyl-1-hexene is copolymerized. (A) Polyolefin-based resins are more preferably polypropylene and the copolymer type polypropylene.

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

The block C in the 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 the block C is usually at most 20%, preferably at most 18%, more preferably at most 15%. If the 1,2-vinyl structure of the block C exceeds 20%, the crystal melting point after hydrogenation drops significantly, and the mechanical properties of the component (b) are inferior.

The block D is a polybutadiene or vinyl aromatic compound-butadiene copolymer,
By hydrogenation, a block segment having a structure similar to that of a rubbery ethylene-butene copolymer or vinyl aromatic compound-ethylene-butene copolymer is obtained. here,
Examples of the vinyl aromatic compound used for the block D include:
Styrene, t-butylstyrene, α-methylstyrene,
Examples include p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like.
-Methylstyrene is preferred. The amount of the vinyl aromatic compound used was 35% by weight of the monomers constituting the 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
Is unfavorable because the glass transition temperature increases and the mechanical properties of the component (ii) are inferior. Further, the 1,2-vinyl structure of the butadiene portion of the block D is usually 25 to 95%,
Preferably 25-75%, more preferably 25-55
%, And if less than 25% or more than 95%, after hydrogenation, each shows a crystal structure derived from a polyethylene chain and a polybutene-1 chain, and becomes a resinous property,
It is not preferable because the mechanical properties of the component (ii) are inferior.

The proportion of the block C and the block D in the component (b) is usually 5 to 90% by weight of the block C,
Block D 95 to 10% by weight, preferably Block C1
0 to 85% by weight and block D 90 to 15% by weight.
If the content of the block C is less than 5% by weight and the content of the block D exceeds 95% by weight, the crystalline block segments are insufficient, and the mechanical properties of the component (b) are inferior. When the content of the block C exceeds 90% by weight,
If the content is less than 10% by weight, the hardness of the component (b) increases, which is not preferable because it becomes unsuitable as a thermoplastic elastomer.

Further, the (b) hydrogenated diene-based polymer used in the present invention has at least 90%, preferably 9%, of the double bonds of the butadiene portion of the blocks C and D.
It is necessary that 5 to 100% is hydrogenated and saturated, and if it is less than 90%, heat resistance, weather resistance and ozone resistance are inferior. The weight average molecular weight of the blocks C and D is usually 5,000 or more, preferably 1
Desirably, it is not less than 5,000, more preferably not less than 15,000, and if it is less than 5,000, the mechanical properties of the component (b) are inferior, which is not preferable.

The (b) hydrogenated diene-based polymer of the present invention is obtained by subjecting block C and block D to living anionic polymerization in an organic solvent to obtain a block copolymer, and further subjecting the block copolymer to hydrogenation. It is obtained by doing. As the organic solvent, pentane, hexane, heptane,
Hydrocarbon solvents such as octane, methylcyclopentane, cyclohexane, benzene, xylene and the like are used. As the organic alkali metal compound as a polymerization initiator, an organic lithium compound is preferable. As the organic lithium compound, an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound are used. Specific examples of these include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, se
Examples thereof include c-butyllithium, t-butyllithium, hexamethylenedilithium, butadienyllithium, and isoprenyldilithium, which are used in an amount of 0.02 to 0.2 parts by weight per 100 parts by weight of the monomer. .

At this time, Lewis bases such as ethers and amines, such as diethyl ether, tetrahydrofuran, propyl ether, butyl ether, higher ethers, and the like, are used as regulators of the microstructure, ie, the vinyl bond content of the conjugated diene moiety. 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 tetramethylethylene diamine, pyridine and tributylamine; Used. Further, the polymerization reaction is usually carried out at -30 ° C.
Performed at 150 ° C. Furthermore, the polymerization may be carried out at a controlled temperature or at an elevated temperature without heat removal. Although any method may be used for forming the block copolymer, generally, the block C is first polymerized in the organic solvent using the polymerization initiator such as the alkali metal compound, and then the block D is polymerized.

The block copolymer thus obtained is a block copolymer having a polymer molecular chain extended or branched as represented by the following general formula by adding a coupling agent. Is also good. C- (DC) n (CD) m (wherein, n represents an integer of 1 or more, preferably 2 to 4, and m represents 2 or more, preferably an integer of 2 to 4). Examples of the coupling agent include diethyl adipate, divinylbenzene, tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2-dibromoethane, 1,4- Chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate and the like can be mentioned.

The content of the vinyl aromatic compound in the block copolymer is adjusted by the amount of the monomer supplied during the polymerization in each step, and the content of the vinyl bond in the conjugated diene compound is determined by changing the components of the micro-adjusting agent. It is adjusted by doing. Further, the weight-average molecular weight is adjusted by the addition amount of a polymerization initiator, for example, n-butyllithium. The method for producing the block copolymer used in the present invention will be described more specifically. First, to obtain a block copolymer, for example, an organic lithium compound such as sec-butyllithium is used as an initiator under vacuum or high pressure. 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 serving as block C, and then tetrahydrofuran or diethyl ether. Add a micro-adjusting agent such as 1 and 1,3-butadiene for the second stage, and after the polymerization is completed, add a calculated amount of a coupling agent such as dimethyldichlorosilane to couple the CD diblock polymer. As a result, a triblock polymer composed of CDC is obtained.

By using a polyfunctional coupling agent, a branched multi-block polymer having a plurality of CD blocks in a branch shape can be obtained. Here, 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 second-stage molecular weight is obtained by subtracting the first-stage molecular weight 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 the DC triblock polymer, the molecular weight of the block D is 2 times the molecular weight of the second stage determined by GPC measurement.
Double. By hydrogenating the block copolymer polymerized as described above, the (ii) hydrogenated diene polymer used in the present invention is obtained. The (b) 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 0 to 150 ° C. under pressurized hydrogen of 1 to 100 kg / cm ² .

Next, the block copolymer as the component (C-1) in the component (C) contains the vinyl aromatic compound in an amount of preferably 5 to 95% by weight, more preferably 10 to 90% by weight, and particularly preferably. Contains 15 to 70% by weight, and its structure may be any of linear, branched or radial, and is not particularly limited. Specifically, the general formulas (AB) n, (AB) nA, and (AB) nX
(In the formula, A is a polymer block mainly composed of an aromatic vinyl compound, 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.) Block copolymers. Here, a polymer block A mainly composed of a vinyl aromatic compound
A vinyl aromatic compound block is a vinyl aromatic compound alone or a copolymer block structure of a vinyl aromatic compound and a conjugated diene compound containing the vinyl aromatic compound in an amount of 60% by weight or more, preferably 80% by weight or more. Have The polymer block B mainly composed of a conjugated diene compound means that the conjugated diene compound block is composed of a conjugated diene compound alone or a conjugated diene compound of 60%.
A copolymer block of a conjugated diene compound and a vinyl aromatic compound containing at least 80% by weight, preferably at least 80% by weight, of a structure having at least one so-called tapered block in which the vinyl aromatic compound is randomly bonded or gradually increased. Any of them may be used.

Examples of the vinyl aromatic compound include the same compounds as those used in the block D. Examples of the conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 2-neopentyl-1,3.
-Butadiene, 2-chloro-1,3-butadiene, 2-
Examples include cyano-1,3-butadiene, substituted linear conjugated pentadienes, linear and side chain conjugated hexadienes, and the like. Of these, 1,3-butadiene, 2-methyl-
The use of 1,3-butadiene is particularly preferred. The hydrogenated product of the random copolymer (C-2) and the hydrogenated product of the block copolymer of the vinyl aromatic compound and the conjugated diene compound (C-3) are vinyl aromatic compounds. Is not more than 50% by weight, preferably 5 to 40% by weight.

As the random copolymer or block copolymer before hydrogenation, which constitutes the components (c-2) to (c-3), specifically, the general formulas (1) AB and (2) a-B-a, (3 ) a-B-E, (4) a-B 1 -B 2 ( vinyl bond B ₁ represents preferably 20% or more, a vinyl bond of B ₂ is preferably less than 20%) (5) B, (6) A / B, (7) AA / B, (8) AA / BE, (9) AA / BA, (10) EB (11) EBE, (12) EA / BE, (13) EAB (where A / B is a random number of a vinyl aromatic compound and a conjugated diene compound) The copolymer, E, is a copolymer of a vinyl aromatic compound and a conjugated diene compound, and is a taper block in which the vinyl aromatic compound increases gradually.) ) As a skeleton, and a copolymer having these basic skeletons repeatedly.
Further, a diene polymer obtained by coupling them may be used.

With respect to AB ₁ -B _{2 in the} above (4),
Japanese Patent Application No. 63-285774, B of (5),
The A / B of (6) is disclosed in JP-A-63-127400. A-A / B of the above (7), (8)
About AA / BE of said, Preferably the ratio of a vinyl aromatic compound / conjugated diene compound is 5-40 / 60-9.
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, and the vinyl bond content of the conjugated diene portion in A / B is 15% or more, particularly preferably 30% or more. ~ 80% by weight. (C-2), (C-3)
The aromatic vinyl compound and the conjugated diene compound constituting
This is the same as that used for the component (c-1). The hydrogenated product which is the component (c-2) to (c-3) used in the present invention can be obtained by hydrogenating the diene-based polymer (random copolymer, block copolymer). The hydrogenation rate of the olefinically unsaturated bond of the diene polymer is at least 70%, preferably at least 90%. The polymerization method of the diene polymer used for the components (c-2) to (c-3) and the hydrogenation method thereof are described in, for example, Japanese Patent Application No. 63-104256.

The microstructure of the diene polymer is 1,2
The vinyl bond content of-, 3,4-, etc. is preferably 10%
As described above, the number average molecular weight of the diene polymer is preferably 5,000 to 1,000,000, and more preferably 30,000 to 300%. , 000. Among the above components (c), the most preferred one is styrene-
An ethylene-propylene block copolymer and a styrene-ethylene-butylene block copolymer.

In the composition of the present invention, the proportion of each component is as follows: (a) 10 to 50% by weight of a polyolefin resin;
Preferably 15 to 50% by weight, (b) 1 to 89% by weight of the hydrogenated diene polymer, 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 is poor, while if it exceeds 50% by weight, flexibility and
Poor gas permeability. If (b) the hydrogenated diene polymer is less than 1% by weight, flexibility, processability and gas permeability are poor,
On the other hand, heat resistance exceeding 80% by weight is poor. Furthermore, (c)
If the component is less than 1% by weight, gas permeability and heat resistance are poor, while if it exceeds 80% by weight, heat resistance and transparency are poor. In addition,
When the total amount of the component (b) and the component (c) exceeds 90% by weight, heat resistance is poor, and a sticky feeling may be generated on the surface of the molded product. Incidentally, the composition of the present invention, if necessary, by a conventionally known method, maleation, carboxylation, hydroxylation,
Modifications such as epoxidation, halogenation, and sulfonation, and crosslinking such as sulfur crosslinking, peroxide crosslinking, metal ion crosslinking, electron beam crosslinking, and silane crosslinking can also be performed.

To the thermoplastic polymer composition of the present invention, additives used for ordinary thermoplastic resins can be added as required. Examples of the additive include a plasticizer such as a phthalate ester, a softener for rubber, a filler or a reinforcing agent such as silica, talc, and glass fiber, and other 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, if necessary, a rubbery polymer such as SBR, NBR, B
R, EPT, EPR, NR, IR, 1,2-polybutadiene, AR, CR, IIR, HSR and the like can be added. In addition, if necessary, the above (a)-
(C) a thermoplastic resin other than the component, for example, a diene resin,
Polyvinyl chloride-based resins, polyvinyl acetate-based resins, polycarbonate-based resins, polyacetal-based resins, polyamide-based resins, polyester-based resins, polyether-based resins, polysulfone, polyphenylene sulfide, and the like can also be blended.

The thermoplastic polymer composition containing the above components (A) to (C) can be mixed with a usual kneading apparatus such as a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader, a ruder, a twin screw extruder. Although a closed type or an open type can be used, a type which can be replaced by an inert gas is preferable. The kneading temperature is a temperature at which all components to be mixed are melted.
It is desirably in the range of 170 to 250 ° C, preferably 180 to 240 ° C. Further, the kneading time depends on the type and amount of the constituent components and the kneading apparatus, and therefore cannot be generally discussed. -10
Minutes. Further, in kneading, each component may be kneaded all at once, or a multi-stage kneading method may be adopted in which after kneading arbitrary components, the remaining components are added and kneaded. The composition of the present invention can be formed into a practically useful molded product by a conventionally known method, for example, extrusion molding, injection molding, hollow molding, compression molding, calendering, or the like. In addition, processing such as painting and plating can be performed as necessary.

The thermoplastic polymer composition of the present invention has excellent heat resistance, gas permeability, impact resistance, processability, flexibility,
Utilizing low temperature characteristics, temperature dependence, compatibility, paintability, printability, hot stamping, deep drawability, hot water resistance, rubber elasticity, rubber touch, flexibility, slip resistance, stress crack resistance, etc. It can be used for various applications. For example, sheet applications such as fresh fish trays, fruit and vegetable packs, frozen dessert foods, containers, etc., food packaging, daily miscellaneous goods packaging, industrial material packaging, various rubber products, resin products, fabrics, lamination of leather products, disposable diapers, etc. Film applications such as stretch tape used, hoses, tubes, belts, etc.
Footwear applications such as sports shoes, leisure shoes, fashion sandals, leather shoes, home appliances such as TVs, stereos and vacuum cleaners, automotive interior and exterior parts applications such as bumper parts, body panels, side shields, etc.
Medical applications such as blood bags, blood tubes, catheters, infusion tubes, and gaskets for syringes; materials for asphalt blends such as road paving materials, waterproof sheets and pipe coatings; and a wide range of other uses such as daily necessities, leisure goods, toys, and industrial goods Can be used.

[0027]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples. However, unless the gist of the present invention is exceeded, the present invention
The present invention is not limited to the following embodiments. In the examples, parts and% are by weight unless otherwise specified.
In the examples, various physical properties were evaluated by the following methods. Tensile properties Measured according to JIS K6301. The unit of 100% modulus is kgf / cm ² , and the unit of tensile breaking strength is kgf / cm ²
/ Cm ² , and the unit of tensile elongation at break is%. Gas Permeability (Oxygen Permeability ) Measured under the conditions of 23 ° C. and 50% RH in accordance with ASTM D1434. The unit of oxygen permeability coefficient is mm · cc
/ M ² · day · atm. Heat resistant 2mm square sample 2mm thick, 120 ℃, 30 minutes,
The sample was aged in a gear oven, and the presence or absence of shrinkage of the sample after aging was determined. ○ indicates shrinkage of less than 3%,
Δ indicates that the contraction rate is 3 to 6%, and X indicates that the contraction rate is greater than 6%. It was measured under a load of 1 kg according to the Vicat softening point 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. Complies with the flexibility JIS K6301, was measured JIS A hardness.

Reference Examples Various polymers used in the compounding formulations of the examples and comparative examples are as follows. PP polypropylene [Mitsubishi Yuka Co., Ltd., polypropylene M
A-8] PE polyethylene [Mitsubishi Yuka Co., Ltd., polyethylene YK-
30] CDC1 to CDC3 hydrogenated diene-based polymers obtained by hydrogenating the butadiene portion of a block copolymer comprising a polybutadiene segment having a low 1,2-vinyl bond content and a polybutadiene segment having a high 1,2-vinyl bond content (E-EB-based TPE), all manufactured by Nippon Synthetic Rubber Co., Ltd. Table 1 shows the microstructure, number average molecular weight, and hydrogenation ratio of CDC1-3.

[0029]

[Table 1]

SBS polystyrene-polybutadiene-polystyrene block copolymer [JSR Shell Elastomer Co., Ltd., TR
2000] SIS polystyrene-polyisoprene-polystyrene block copolymer [JSR Shell Elastomer Co., Ltd., SI
S5000] SEBS polystyrene-polybutadiene-polystyrene block copolymer obtained by hydrogenating a polybutadiene part [Clayton G165 manufactured by Shell Chemical Co., Ltd.]
0; SEBS-1, Clayton G1657; SEBS-
2] Block copolymer obtained by hydrogenating a polyisoprene part of SEPS SIS [Septon 2002, manufactured by Kuraray Co., Ltd.] Softener Idemitsu Petrochemical Co., Ltd., paraffin oil

Examples 1 to 13 and Comparative Examples 1 to 6 Using a formulation shown in Table 2, each component was added to a Labo Plastomill temperature-controlled at 190 ° C.
Kneaded for a minute. The mixture was discharged, formed into a sheet with a hot roll, and then press-formed to form a square plate having a side of 10 cm, cut out with a damper cutter to obtain a test piece for measurement, and various physical properties were evaluated. Table 2 shows the results. Table 2
As is apparent from Examples 1 to 13, the compositions of the present invention are excellent in oxygen permeability, and heat resistance, tensile properties,
It has excellent transparency and flexibility characteristics, and the composition intended for the present invention has been obtained. In contrast, Comparative Example 1
(A) The polyolefin resin is an example which is less than the range of the present invention, and is excellent in oxygen permeability, but inferior in heat resistance.
Comparative Example 2 is a case where (a) the polyolefin-based resin exceeds the range of the present invention, and is inferior in oxygen permeability and flexibility. Comparative Example 3 is an example in which (ii) the hydrogenated diene polymer was not used, and was excellent in heat resistance and transparency, but inferior in flexibility. Comparative Example 4 is an example in which the component (c) was not used, and although the oxygen permeability and the flexibility were excellent, the heat resistance was slightly inferior. Comparative Example 5 is a case where the component (b) exceeds the range of the present invention, and is inferior in heat resistance. Comparative Example 6
(C) The case where the component exceeds the range of the present invention, and the heat resistance is inferior.

[0032]

[Table 2]

[0033]

Industrial Applicability The thermoplastic polymer composition of the present invention, which has essentially the properties of a thermoplastic polymer, uses a novel E-EB-based TPE which has not been put to practical use. Composition and extremely gas permeable (especially,
Good against oxygen and carbon dioxide), high heat resistance,
A product with no stickiness and excellent in tensile properties and flexibility can be obtained. The thermoplastic polymer composition of the present invention is a material having such excellent properties as described above, and can be suitably used for industrial parts, automobile interior / exterior parts, toys, medical supplies, etc. It is a valuable material.

Continuation of the front page (72) Inventor Takumi Miyachi 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-3-128957 (JP, A) (58) Fields investigated (Int.Cl. ⁶ , DB name) C08L 23/00-23/36 C08L 25/00-25/18 C08L 53/00-53/02

Claims (1)

(57) [Claims] 1. A polyolefin resin 10 to 5
(B) a polybutadiene block segment (C) having a 1,2-vinyl bond content of 20% or less, a polybutadiene or vinyl aromatic compound-butadiene copolymer, wherein 1,2-butadiene moiety is Vinyl bond content is 2
Consists of block segments (D) that are 5-95%,
And the block structure is C- (D-C) n or (C-D)
hydrogenated diene-based polymer 1 obtained by hydrogenating 90% or more of a butadiene portion of a linear or branched block copolymer represented by m (where n is 1 or more and m is an integer of 2 or more) (C-1): a block copolymer comprising 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 composed of a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound 1 to 89% by weight of at least one selected from the group of hydrogenated copolymers [provided that (a) +
(B) + (c) = 100% by weight].