JP2002187957A - Hose, tube, gasket, packing or vessel manufactured from thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hose, tube, gasket, packing or a vessel all light in weight, showing an excellent strength, flexibility and product appearance which does not contaminate the matters brought into contact with it with endocrine distractors. SOLUTION: The hose, tube, gasket, packing or vessel is manufactured from a thermoplastic elastomer composition having a fluidity index I, determined through capillary flow test, of >=1.35 and which contains (A) from 5 to 95 wt.% ethylene/α-olefin copolymer with a tensile stress M100 according to JIS-K-6251 of <=2.5 MPa and (B) from 5 to 95 wt.% polyolefin resin with a tensile stress M100 according to JIS-K-6251 of >=2.5 MPa.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a hose, tube, gasket, packing or container made of a thermoplastic elastomer composition. More specifically,
The present invention relates to a hose, a tube, a gasket, a packing or a container which is excellent in strength, flexibility and product appearance, is lightweight, and does not contaminate a substance in contact with the product with an endocrine disrupting substance.

[0002]

2. Description of the Related Art A soft vinyl chloride material has a good balance between mechanical strength and flexibility, and is excellent in processability and cost performance. On the other hand, since the vinyl chloride resin has a high density and a heavy weight of the product, a large handling amount may impose a heavy burden on manual handling. Furthermore, among the plasticizers contained in the soft vinyl chloride resin, chemical substances that may cause endocrine disruption are used, and foods and beverages and resin pellets can be used with hoses, tubes or containers using this. When transported and stored, there is a concern that it may be contaminated by chemicals.

[0003]

Under these circumstances, the problem to be solved by the present invention is to have excellent strength, flexibility, product appearance, light weight, and to contaminate a substance in contact with the product with an endocrine disrupting substance. It is an object of the present invention to provide a hose, tube, gasket, packing or container made of a thermoplastic elastomer composition which does not need to be used.

[0004]

That is, the present invention contains the following (A) 5 to 95% by weight and (B) 5 to 95% by weight, and has a fluidity index I of 1.35 in a capillary fluidity test. The present invention relates to a hose, a tube, a gasket, a packing or a container made of the thermoplastic elastomer composition described above. (B): JIS-K-6251 ethylene -α- olefin copolymer tensile stress M ₁₀₀ measured in conformity is less than 2.5MPa to (b): Tensile was measured according to JIS-K-6251 polyolefin resin stress M ₁₀₀ is greater than or equal to 2.5MPa

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The component (a) of the present invention is a JIS-
Tensile stress M ₁₀₀ that was measured in accordance with K-6251 is 2.
It is an ethylene-α-olefin copolymer having a pressure of 5 MPa or less. Component (b) must tensile stress M ₁₀₀ measured according to JIS-K-6251 is less than 2.5 MPa, preferably 2.0MPa or less. If the value is excessive, the flexibility of the hose, tube, gasket, packing or container made of the obtained thermoplastic elastomer composition is inferior.

[0006] (A) is preferably an ethylene-α-olefin copolymer satisfying the following conditions (a) to (d). (A) α-olefin content is 5 to 95% by weight (b) Mooney viscosity: ML _{1 + 4} 100 ° C. is 5 to 70 (c) Q value in GPC measurement (weight average molecular chain length / (Number average molecular chain length) is 4 or more (d) Show bimodal molecular weight distribution curve

Specific examples of the α-olefin of component (a) include propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene , 1-dodecene, 1-hexadecene, 1-eicosene and the like. These α-olefins may be used alone,
Alternatively, two or more thereof may be used in combination. The α-olefin content in the copolymer of the present invention is preferably from 5 to 95% by weight, more preferably from 20 to 90% by weight, even more preferably from 25 to 40% by weight. If the α-olefin content is too low, bleeding may occur on the surface of a molded article molded using the obtained thermoplastic elastomer composition. On the other hand, if the α-olefin content is excessive, the strength of the resulting hose, tube, gasket, packing or container made of the thermoplastic elastomer composition may be poor.

[0008] Mooney viscosity of component (a): ML _{1 + 4} 10
0 ° C. is preferably from 5 to 70, and more preferably from 20 to 60. If the Mooney viscosity is too low, the strength of the resulting hose, tube, gasket, packing or container made of the thermoplastic elastomer composition may be poor. On the other hand, if the Mooney viscosity is excessive, the resulting thermoplastic elastomer composition obtained hose,
The product appearance of the tube, gasket, packing or container may be impaired.

The Q value (weight average molecular chain length / number average molecular chain length) of the component (a) in GPC measurement is preferably 4 or more, more preferably 6 or more. If the Q value is too small, the product appearance of a hose, tube, gasket, packing or container made of the obtained thermoplastic elastomer composition may be deteriorated. Further, as long as the constitutional requirements of the present invention are met, it is preferable that the Q value is large in terms of extrusion workability and calenderability. The Q value is measured by gel permeation chromatography (GPC) (for example,
Waters, 150C / GPC device). The elution temperature is 140 ° C., and the column used is, for example, Shodex Packed Column A manufactured by Showa Denko KK
-80M, the molecular weight standard is polystyrene (eg,
The molecular weight is 68-8,400,000 manufactured by Tosoh Corporation. The obtained polystyrene equivalent weight average molecular weight (M
w), the number average molecular weight (Mn), and this ratio (Q value) are defined as the molecular weight distribution. The measurement sample contains about 5 mg of polymer 5
dissolved in o-dichlorobenzene of about 1 mg / ml
Concentration. 400 μl of the obtained sample solution was injected, and the elution solvent flow rate was 1.0 ml / min.
And it is detected by the refractive index detector.

The component (a) preferably exhibits a bimodal molecular weight distribution curve. When the molecular weight distribution is a single peak, the expansion of the molecular weight distribution is insufficient, and a hose, a tube, and a thermoplastic elastomer composition are obtained.
The product appearance of the gasket, packing or container may deteriorate.

Component (a) is used in the presence of a catalyst system obtained by combining the following components (A) to (C) as described below.
It can be produced by subjecting ethylene and α-olefin to polymerization using a tank or two polymerization tanks. In addition, it is also possible to use three or more polymerization tanks as long as they meet the constitutional requirements of the present invention.

As the component (A), the general formula VO (OR)
_n X _3-n (where R is a hydrocarbon group, X is a halogen, 0 ≦ n
≦ 3) can be used, and VOCl ₃ , VO (OCH ₃ ) Cl ₂ , VO (OC
H ₃ ) ₂ Cl, VO (OCH ₃ ) ₃ , VO (OC ₂ H ₅ ) Cl
₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO (OC ₂ H ₅ ) ₃ , VO
(OC ₃ H ₇ ) Cl ₂ , VO (OC ₃ H ₇ ) ₂ Cl, VO (O
_{C 3 H 7) 3, VO} (Oiso-C 3 H 7) Cl 2, VO (O
_{iso-C 3 H 7) 2} Cl, VO (Oiso-C 3 H 7) 3,
_{VO (On-C 4 H 9} ) Cl 2, VO (On-C 4 H 9) 2 C
_{l, VO (On-C 4} H 9) 3, or it can be exemplified mixtures thereof. Among these, those other than VOCl ₃ can be easily obtained by reacting VOCl ₃ with alcohol or reacting VOCl ₃ with VO (OR) ₃ .

The component (B) is represented by the general formula R '_mAlX
_3-m(Where R ′ is a hydrocarbon group, X is a halogen, 0 ≦ m
≦ 3)
And (C_TwoH_Five)_TwoAlCl, (C_FourH₉)_TwoAlC
l, (C₆H₁₃)_TwoAlCl, (C _TwoH_Five)_1.5AlC
l_1.5, (C_FourH₉)_1.5AlCl_1.5, (C₆H₁₃)_1.5A
lCl_{1. Five}, C_TwoH_FiveAlCl_Two, C_FourH₉AlCl_Two, C₆H
₁₃AlCl_TwoEtc. can be exemplified.

Although it is possible to obtain the copolymer of the present invention by using a catalyst system consisting of only the components (A) and (B), the following will be described in order to further reduce the low molecular weight components that bleed. The component (C) may be used in combination.

As the component (C), a halogenated ester compound represented by the following general formula can be used. (However, R ″ is an organic group having 1 to 20 carbon atoms and is partially or completely halogen-substituted, and R ′ ″ is a hydrocarbon group having 1 to 20 carbon atoms). Compounds, more preferably perchlorcrotonates, are very effective. Specifically, ethyl dichloroacetate, methyltrichloroacetate, ethyltrichloroacetate, methyldichlorophenylacetate, ethyldichlorophenylacetate, methylperchlorocrotonate, ethyl perchlorcrotonate,
Examples thereof include propyl perchlor crotonate, isopropyl perchlor crotonate, butyl perchlor crotonate, cyclopropyl perchlor crotonate, and phenyl perchlor crotonate.

The molar ratio of the organoaluminum compound (B) to the vanadium compound (A) in the polymerization reaction is 2.5 or more, and the molar ratio of the halogenated ester compound (C) to the vanadium compound (A) is Must be at least 1.5.

The component (a) of the present invention may comprise the above catalyst system
In addition, a known Ziegler-Natta type catalyst or a known synth
Glucite catalyst (metallocene type, etc.) used alone or in combination
Production using one or more polymerization tanks.
The uniformity of the composition distribution of the resulting polymer
From the viewpoint of the conventional single-site catalyst (metallocene
System) is preferable, and as an example of such a single-site catalyst,
For example, Japanese Patent Application Laid-Open No. 58-19309,
JP-A-60-35005, JP-A-60-35006
, JP-A-60-35007, JP-A-60-35
008, JP-A-61-130314,
Japanese Unexamined Patent Publication No. Hei 3-163088, Japanese Unexamined Patent Publication No. Hei 4-268307
Gazette, JP-A-9-12790, JP-A-9-873
No. 13, JP-A-10-508055, JP-A-10-50805
No. 11-80233, Tokuyohei 10-508055
Patent Application Publication No. JP-A-10-31
No. 6710, JP-A-11-100394,
JP-A-11-80228, JP-A-11-80227
JP-A-10-513489, JP-A-10-513489
-338706, JP-A-11-71420
Non-metallocene complex catalysts described can be exemplified.
However, among these, metallocene catalysts are generally used.
As an example of a suitable metallocene catalyst
Has at least one cyclopentadiene-type anion skeleton
From the viewpoint of the flexibility of the resulting polymer
Is C₁Transition of Periodic Table Groups 3 to 12 with Symmetric Structure
Transfer metal complexes are preferred. Furthermore, obtain a high molecular weight polymer
Of a suitable production method using a metallocene catalyst for the production
The following (α) and the following (β) and / or
(Γ) in the presence of an olefin polymerization catalyst comprising
Example of a method obtained by copolymerizing ethylene and α-olefin
Can be shown. (Α): transition gold represented by the following general formulas [I] to [III]
At least one of the genus complexes(In the above general formulas [I] to [III], M¹Is
Represents a transition metal atom of Group 4 of the Periodic Table of the Elements, where A is an element
Indicates an atom belonging to Group 16 of the Periodic Table of the Elements, and J is the period of the element
Shows the atoms of Group 14 of the Rule. Cp¹Is cyclopentadi
A group having an ene-type anion skeleton is shown. X¹, X^Two,
R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are each independently water
Element atom, halogen atom, alkyl group, aralkyl group,
Reel group, substituted silyl group, alkoxy group, aralkyl group
It represents a xy group, an aryloxy group or a disubstituted amino group.
X^ThreeRepresents an atom belonging to Group 16 of the periodic table of the elements. R¹, R
^Two, R^Three, R^Four, R^FiveAnd R⁶Are optionally linked to form a ring
You may. Two M¹, A, J, Cp¹, X¹, X^Two,
X^Three, R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are the same for each
Or different. (Β): one or more selected from the following (β1) to (β3)
(Β1) General formula E¹ _aAlZ_3-aOrganic aluminum indicated by
Compound (β2) General formula ｛-Al (E^Two) -O-｝_bIndicated by
Cyclic aluminoxane having structure (β3) General formula E^Three｛-Al (E^Three) -O-｝_cAlE^Three
_TwoLinear aluminoxane having a structure represented by the following formula (provided that E¹, E^TwoAnd E^ThreeIs a hydrocarbon group
All E¹, All E ^TwoAnd all E^ThreeIs the same
Or different. Z is a hydrogen atom or a halogen atom
Represents a child, and all Z may be the same or different
No. a is a number satisfying 0 <a ≦ 3, b is an integer of 2 or more
And c represents an integer of 1 or more. (Γ): Boration of any of the following (γ1) to (γ3)
Compound (γ1) General formula BQ¹Q^TwoQ^ThreeBoron compound represented by
Object, (γ2) general formula G⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-E represented by
Iodine compound, (γ3) general formula (LH)⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-In table
(Where B is a boron atom in a trivalent state, Q
¹~ Q^FourIs a halogen atom, hydrocarbon group, halogenated hydrocarbon
Group, substituted silyl group, alkoxy group or disubstituted amino group
And they may be the same or different.
G⁺Is an inorganic or organic cation, and L is a neutral Lewis
A base, (LH)⁺Is a Bronsted acid
You. )

As the inert hydrocarbon medium used for preparing the catalyst, specifically, propane, butane, pentane,
Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; ethylene chloride and chlorin Examples thereof include halogenated hydrocarbons such as benzene and dichloromethane, and mixtures thereof. The preparation temperature is usually -100 to
The temperature is preferably in the range of 250 ° C., and the pressure and time can be arbitrarily set.

The polymerization in component (a) is carried out in a hydrocarbon solvent. As the hydrocarbon solvent, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cyclohexane, methylcyclopentane, cycloaliphatic hydrocarbons such as methylcyclohexane, benzene, toluene, Examples include aromatic hydrocarbons such as xylene. Further, α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene and the like can be used as a part or all of the solvent. The polymerization temperature is preferably from 40 to 160 ° C, more preferably from 40 to 80 ° C from the viewpoint of productivity and molecular weight control.

The polymerization is carried out under atmospheric pressure or under pressure using one polymerization tank or two polymerization tanks in series.
It is preferably carried out at 1 to 5 MPa, particularly 0.1 to 2 MPa.
Preferably between MPa. The average residence time of the reaction liquid per polymerization tank is preferably 2 to 180 minutes, more preferably 20 to 120 minutes. The polymer concentration is preferably 15% by weight or less, more preferably 12% by weight or less, from the viewpoint of reducing the viscosity of the reaction solution.

In order to control the molecular weight of the component (a), hydrogen, diethylamine, aryl chloride pyridine-N-oxide and the like are exemplified, and hydrogen is particularly preferable.

When two polymerization tanks are used, the temperature and molecular weight regulator of the first and second polymerization tanks can be arbitrarily set so as to satisfy the constitutional requirements of the present invention. It is preferable to synthesize the polymer and polymerize the low molecular weight polymer in the second tank, and the polymerization temperature in the first tank is preferably 40 to 60 ° C, and the polymerization temperature in the second tank is preferably 50 to 80 ° C. If the polymerization temperature in the first tank is too high, the molecular weight of the high molecular weight polymer may be insufficient, and if the polymerization temperature in the second tank is too low, it becomes necessary to use a large amount of the molecular weight regulator, which is not preferable. .

On the other hand, the molecular weight regulator can be added to either or both of the first and second tanks. However, by reducing the amount used in the first tank and increasing the amount used in the second tank, a sufficient amount can be obtained. It is preferable because a high molecular weight polymer and a low molecular weight polymer can be polymerized.

The ratio of the amount of copolymer produced in the first and second tanks is preferably in the range of 2.0 / 0.05 to 1 / 2.5. Furthermore, more preferable results can be obtained by performing the process in the range of 2.0 / 0.1 to 2 / 1.5.

A method is also conceivable in which a copolymer satisfying the same structural requirements as the copolymer obtained by the above-described method is synthesized by blending separately synthesized polymers.

However, it is possible to simultaneously polymerize and blend a high molecular weight polymer and a low molecular weight polymer by using (hybrid) a catalyst system comprising a known Ziegler-Natta type catalyst or a known single-site catalyst. It is a method suitable for mass production. In this case, a plurality of polymerization tanks are not necessarily required, and there is no problem even if one polymerization tank is used.

The component (b) of the present invention is JIS-K-62
The tensile stress M ₁₀₀ measured in accordance with No. 51 is 2.5 MPa
The above is a polyolefin-based resin. Ingredients (b)
, It is necessary tensile stress M ₁₀₀ measured according to JIS-K-6251 is not less than 2.5 MPa, preferably 3.0MPa or more. If the value is too small, the strength of the hose, tube, gasket, packing or container made of the thermoplastic elastomer composition obtained is inferior.

As the component (b), high density polyethylene,
Medium density polyethylene, low density polyethylene, LLDPE
(Linear low-density polyethylene) and other polyethylene-based resins, polypropylene-based resins, polybutene-based resins, poly-
4-methyl-pentene-1, ethylene-vinyl acetate copolymer resin, ethylene-methyl methacrylate copolymer resin, ethylene-methacrylate copolymer resin, ethylene-acrylate copolymer resin, ethylene-
Examples thereof include methacrylic acid copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-styrene copolymer resin, and the like. Also, two or more components (b) may be used in combination.

From the viewpoint of improving the product appearance of hoses, tubes, gaskets, packings or containers made of the thermoplastic elastomer composition obtained, the component (B) G
The Q value (weight average molecular chain length / number average molecular chain length) in the PC measurement is preferably 3 or more, and more preferably 3.5 or more. The method of measuring the Q value may be the method described in the section of the component (a).

The thermoplastic elastomer composition of the present invention comprises:
Essentially contains (A) 5 to 95% by weight and (B) 5 to 95% by weight, preferably (A) 10 to 90% by weight and (B) 10 to 90% by weight, more preferably (A) 20
-80% by weight and (b) 20-80% by weight.
If the amount of (a) is too small, the product appearance of the hose, tube, gasket, packing or container made of the thermoplastic elastomer composition obtained is inferior, while if the amount of (a) is too large, it is made of the obtained thermoplastic elastomer composition. Poor strength of hose, tube, gasket, packing or container. (B) a hose, a tube, a gasket comprising a thermoplastic elastomer composition obtained when the amount is too small;
If the packing or container is inferior in strength, while if (a) is excessive, the appearance of the resulting hose, tube, gasket, packing or container made of the thermoplastic elastomer composition is inferior.

The thermoplastic elastomer composition of the present invention comprises:
The fluidity index I in the capillary fluidity test is 1.3.
It is necessary to be 5 or more, preferably 1.40 or more, more preferably 1.50 or more. When the index is too small, the appearance of the hose, tube, gasket, packing or container made of the thermoplastic elastomer composition obtained is inferior. In addition, as long as the index conforms to the constitutional requirements of the present invention, it is preferable that the index is large from the viewpoint of product appearance.

The capillary flow test and the calculation of the flow index are performed by the following methods. Measurement device: Capillograph 1C manufactured by Toyo Seiki Seisakusho Orifice: Capillary diameter 1 mm, capillary length 10 mm Temperature: 190 ° C. Shear rate: 12, 37, 61, 122, 365, 60
8 (sec ^-1 ) The shear viscosity is measured at each shear rate.

The fluidity index is expressed by a shear viscosity ratio (shear viscosity at a shear rate of 12 (sec ^-1 ) / shear rate of 365).
(Shear viscosity at (sec ^-1 )) and a shear rate of 12 (s
From the plot of shear viscosity at ec ^-1 ) (see FIG. 1),
The fluidity index was calculated as I = A / B. The solid line in the figure is a master curve of an EPM having a Q value of 1.8 in GPC measurement and having no long-chain branch.
0.5917 × 10 ⁻³ X + 1.2640. The more the plot of the thermoplastic elastomer composition shifts in the positive direction of the Y-axis (shear viscosity ratio), the higher the non-Newtonian property of the composition, and the relation with the extrusion processability, for example, the melt flow behavior of the extruded surface skin etc. deep.

In the present invention, in addition to the above components, additional components such as antioxidants, antistatic agents, weathering agents, ultraviolet absorbers, slip agents, coloring agents, dispersants, lubricants, processing aids, etc. Additives, colorants such as carbon black, glass fibers, carbon fibers, metal fibers, aramid fibers, glass beads, asbestos, mica, calcium carbonate, potassium titanate whiskers, talc, barium sulfate, glass flakes and other fillers, Alternatively, another rubbery polymer, a thermoplastic resin, or the like can be appropriately compounded.

The thermoplastic elastomer composition of the present invention comprises:
If necessary, crosslinking such as sulfur crosslinking, peroxide crosslinking, metal ion crosslinking, silane crosslinking, or water crosslinking can be performed by a conventionally known method.

The thermoplastic elastomer composition of the present invention comprises:
(A), (B) and the additional components used as appropriate may be kneaded using a usual kneading apparatus, for example, a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader, a twin-screw extruder, or the like. The kneading device may be any of a closed type and an open type, but a closed type device which can be replaced with an inert gas is preferable.
The kneading temperature is a temperature at which all of the mixed components are melted, and is usually from 160 to 250 ° C, preferably from 180 to 240 ° C. The kneading time depends on the type and amount of the mixed components and the type of the kneading device, and is not generally discussed.However, when using a kneading device such as a pressure kneader or a Banbury mixer, the mixing time is usually ,
It is about 3 to 10 minutes. In the kneading step, each component may be kneaded at a time. Alternatively, after kneading some components, the remaining components are added to continue the kneading. A kneading method can also be adopted.

The thermoplastic elastomer composition obtained by the above-mentioned method is subjected to extrusion, calendering, injection molding, blow molding, press molding, inflation molding, foam molding and the like to obtain the hose of the present invention. A tube, gasket, packing or container can be obtained.

The hose, tube, gasket, packing or container made of the thermoplastic elastomer composition obtained by the present invention can be used for vehicle parts, light electric parts, household electric parts, industrial parts using conventional soft vinyl chloride resin products. It can be used for parts, tarpaulin parts and the like. Above all, in addition to excellent strength, flexibility, product appearance, light weight, and characteristics that do not contaminate substances that come into contact with products with endocrine disrupting substances, food and beverage handling members, vehicle members, or resin or rubber transportation It can be suitably used as an application member.

Examples of the food and beverage handling member include hoses, tubes, gaskets, and packings used for transporting beverages in cup-type beverage vending machines, and for transporting raw materials, intermediates and products in the food and beverage industry. Or a water bottle. In order to improve the smoothness inside the member, a thermoplastic resin such as polyethylene
It is preferable to laminate with a thickness of 500 μm. As a method of further improving the strength of the tube or blocking external odor, a means for laminating a tape-shaped metal foil or a synthetic resin around the tube according to the present invention may be used.

Examples of the vehicle member include a weather strip, various seal sponges, a washer liquid drain tube, a cushion material for a fuel tank, and members for railways, aircrafts, ships, and bicycles.

Examples of the resin or rubber conveying member include a resin or rubber pellet emptying hose. In order to improve the strength and flexibility of the member, it is preferable to use a composition according to the present invention in a hose body, and a composite hose using a thermoplastic resin composition such as polyethylene or polypropylene as a reinforcing material, to form an uneven hose. Among them, it is preferable to use a polyethylene composition or a polypropylene composition to which a filler such as talc is added as a reinforcing material. As a method for manufacturing a hose with irregularities, Japanese Patent Publication No. 59-3053
4, JP-A-3-75111, JP-A-5-5
0525 can be mentioned.

[0042]

The following examples further illustrate the present invention, but are by way of illustration and should not be construed as limiting the invention. [I] Production and evaluation of component (a) The measurement was performed as follows. (1) GPC measurement The GPC apparatus was 150C manufactured by Waters, the elution temperature was 140 ° C, and the column used was Shodex manufactured by Showa Denko KK
Packed Column A-80M, molecular weight standard substance is polystyrene (for example, Tosoh Corporation, molecular weight 68
-8,400,000). The obtained polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (M
n), and this ratio (Q value = Mw / Mn) was taken as the molecular weight distribution. The measurement sample was prepared by adding about 5 mg of polymer to 5 ml of o-
Dissolve in dichlorobenzene to a concentration of about 1 mg / ml. 400 μl of the obtained sample solution was injected, and the elution solvent flow rate was set to 1.0 ml / min, and detected by a refractive index detector. (2) Tensile stress samples were press-molded at 0.99 ° C., after obtaining a 2mm thick sheet, conforming to JIS-K-6251, were measured tensile stress M ₁₀₀ of the copolymer. A dumbbell-shaped No. 3 test piece was used. (3) Mooney viscosity The Mooney viscosity of the copolymer: ML _{1 + 4} 100 ° C. was measured in accordance with JIS-K-6300.

Reference Example 1 (Synthesis of Component (a) -1) Hexane was used as a polymerization solvent from a lower part of a 100-L stainless steel polymerization tank equipped with a stirrer at 62.8 K / h.
g, ethylene and propylene each at 5.90 kg / h, 2
Feed continuously at a rate of 2.44 Kg. V as catalyst
O (Oiso-C ₃ H ₇ ) ₃ , ethyl aluminum sesquichloride (EASC) 2.22 g / hr, 7.7
The mixture was continuously supplied at a rate of 9 g, and the temperature of the polymerization tank was maintained at 50 ° C. A part of the polymerization solution in the first tank was withdrawn, and the polymer was precipitated by steam stripping. After drying, 600 ppm of Irganox 1076 (an antioxidant manufactured by Ciba Specialty Chemicals) was added, and the mixture was granulated by an underwater cut method. Thus, an ethylene-propylene copolymer pellet was obtained. In this way, 4.6 kg of an hourly copolymer was obtained.
The molecular weight was adjusted with hydrogen. As a result, the propylene content was 27.8% by weight, and the Mooney viscosity: ML _{1 + 4} 1
00 ° C. = 49.5, Q value in GPC measurement = 7.8,
An ethylene-propylene copolymer pellet having a tensile stress M ₁₀₀ = 1.1 MPa and exhibiting a bimodal molecular weight distribution curve was obtained.

Reference Example 2 (Synthesis of Component (a) -2) Polymerization, precipitation, drying and granulation were carried out in the same manner as in Reference Example 1, except that the molecular weight was adjusted with hydrogen. As a result, the propylene content was 27.6% by weight, and the Mooney viscosity: M
L _{1 + 4} 100 ° C. = 40.9, Q value in GPC measurement =
6.6, a tensile stress M ₁₀₀ = 1.1 MPa, bimodal ethylene showing a molecular weight distribution curve - propylene copolymer pellets was obtained.

Reference Example 3 (Synthesis of Component (A) -3) Polymerization, precipitation, drying and granulation were carried out in the same manner as in Reference Example 1, except that the molecular weight was adjusted with hydrogen. As a result, the propylene content was 28.0% by weight, and the Mooney viscosity: M
L _{1 + 4} 100 ° C. = 30.7, Q value in GPC measurement =
6.8, a tensile stress M ₁₀₀ = 1.1 MPa, bimodal ethylene showing a molecular weight distribution curve - propylene copolymer pellets was obtained.

[II] Production and evaluation of beverage tube Using two 65 mmφ extruders and a crosshead die,
The thermoplastic elastomer compound shown in Examples 1 and 2 was used as the outer layer from one extruder, and the low density polyethylene was used as the inner layer from the other extruder to form an outer diameter of 7.4 mm and an inner diameter of 4. A 6 mm two-layer cylindrical tube was obtained. The extrusion conditions of the thermoplastic elastomer compound are as follows:
5 rpm, die temperature 185 ° C, cylinder temperature 145
１６165 ° C. The outer layer thickness of the thermoplastic elastomer was 1.3 mm, and the inner layer thickness of the low-density polyethylene was 0.1 mm.

[III] Production of a cushion material for a fuel tank for an automobile A cushion die for a fuel tank was obtained by attaching a profile die to a 50 mmφ extruder and extruding the thermoplastic elastomer compound shown in Example 3. The cross-sectional shape of the obtained cushion material is shown in FIG.

[IV] Production of Hose with Concavo-convex Two extruders and a crosshead die were used. From one extruder, the thermoplastic elastomer compound shown in Examples 4 and 5 was taped, and the other extruder was used. Then, a high-density polyethylene was extruded into a prismatic shape, integrally molded, and a tape-shaped thermoplastic elastomer was continuously wound around a mandrel to obtain an uneven hose.

[V] Evaluation of Thermoplastic Elastomer Composition and Molded Product The compound shown in Table 1 was heated at a temperature of 150 ° C. and a screw rotation speed of 100 rpm using a biaxial batch-type kneader Plasticoder (manufactured by Brabender). For 5 minutes. The composition was press-molded at 150 ° C., and the following tests were performed. Tensile test: Tensile strength at break (TB) and tensile elongation at break (EB) were measured according to JIS-K-6251. Hardness: Hardness was measured by a durometer A type hardness meter based on JIS-K-6253. Fluidity: The melt flow rate at 190 ° C. was measured according to JIS-K-7210. (Load 2.16 kg) Capillary fluidity test and calculation of fluidity index: using a Capillograph 1C (manufactured by Toyo Seiki Seisaku-sho, Ltd.), furnace temperature 190 ° C., capillary diameter 1 mm, capillary length 1
0 mm, shear rate 12, 37, 61, 122, 36
At 5,608 (sec ^-1 ), each shear viscosity was measured. The fluidity index is determined by the shear viscosity ratio (shear rate 12
Shear viscosity at (sec ^-1 ) / shear rate 365 (sec
c ^-1 ) and a shear rate of 12 (se
From the plot of the shear viscosity at the time of c ^-1 ) (see FIG. 1), the flowability index was calculated as I = A / B. Specific gravity: The specific gravity at 23 ° C. was measured according to JIS-K-7112. Molded product appearance: The extruded skin of the obtained molded product was observed. Judgment of appearance of molded article ：: Extruded skin is smooth. La: Extruded skin is not smooth and shark skin.

Examples 1 to 5 A beverage tube, a fuel tank cushion material and an uneven hose member satisfying the conditions of the present invention are lighter in weight than soft PVC, and endocrine disrupting a substance which comes into contact with the product. No contamination with substances.

[0051]

[Table 1] (B) -1: Ethylene-vinyl acetate copolymer resin (vinyl acetate content 26% by weight, MF at 2.16 kg load)
(R190 ° C = 2.3) (b) -2: Ethylene-hexene-1 copolymer (hexene-1 content 17% by weight, density 0.885 g / cm ³ ,
(MFR 190 ° C. under a load of 2.16 kg = 5.1) (b) -3: Ethylene-vinyl acetate copolymer resin (vinyl acetate content 10% by weight, MF under a load of 2.16 kg)
R190 ° C = 6.0)

[0052]

As described above, according to the present invention, hoses, tubes, gaskets, and the like, which are excellent in strength, flexibility and product appearance, light in weight and do not contaminate substances in contact with products with endocrine disrupting substances, Packing or container could be provided.

[Brief description of the drawings]

FIG. 1 is a plot diagram of a shear viscosity to a shear viscosity ratio when a fluidity index is obtained.

FIG. 2 is a cross-sectional shape of a cushion material for a fuel tank.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 3H111 AA02 BA15 BA34 CA53 CB03 DA26 DB02 EA04 3J040 FA20 4F071 AA15 AA15X AA20 AA20X AA21 AA21X AA81 AH05 AH17 BA01 BB05 BB06 BB05 BB06 BB03XBB BB03XBB BB03XBB BB03XBB BB03XBB BB03XBB FD090 GJ02 GM00 GN00

Claims (5)

[Claims] 1. The following (A) 5-95% by weight and (B) 5
A hose, a tube, a gasket, a packing or a container comprising a thermoplastic elastomer composition containing about 95% by weight and having a fluidity index I of 1.35 or more in a capillary fluidity test. (B): JIS-K-6251 ethylene -α- olefin copolymer tensile stress M ₁₀₀ measured in conformity is less than 2.5MPa to (b): Tensile was measured according to JIS-K-6251 polyolefin resin stress M ₁₀₀ is greater than or equal to 2.5MPa 2. A hose, tube, gasket or packing comprising the thermoplastic elastomer composition according to claim 1, wherein (a) satisfies the following conditions (a) to (d). (A) α-olefin content is 5 to 95% by weight (b) Mooney viscosity: ML _{1 + 4} 100 ° C. is 5 to 70 (c) Q value in GPC measurement (weight average molecular chain length / (Number average molecular chain length) is 4 or more (d) Show bimodal molecular weight distribution curve 3. A food and beverage handling member comprising the thermoplastic elastomer composition according to claim 1. 4. A vehicle member comprising the thermoplastic elastomer composition according to claim 1 or 2. 5. A resin or rubber conveying member comprising the thermoplastic elastomer composition according to claim 1 or 2.