JP2000265035A - Thermoplastic elastomer composition and molded product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an elastomer composition excellent in flexibility, excellent in adhesive strength in coextrusion with an ABS resin and proof against blocking of pellets during storage by compounding a polyether ester with a block copolymer and/or its hydrogenation derivative and an inorganic filler in a specified ratio. SOLUTION: This composition comprises (A) 20-60 pts.wt. polyether ester, (B) 40-80 pts.wt. A-B-A block copolymer and/or its hydrogenation derivative thereof, and (C) 5-25 pts.wt., per 100 pts.wt. total of components A and B, inorganic filler. In the formula, A is a polymer block of an aromatic vinyl monomer; and B is an elastomeric polymer block of a conjugated diene. Component C is desirably calcium carbonate or a quartz powder and is more desirably calcium carbonate having a specific surface area of 7,000 cm2/g or above or a quartz powder having a mean particle diameter of 0.1-20 μm. It is desirable that a specified sample injection-molded from the composition has a durometer hardness (HDA) of at most 80.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition for extrusion molding which has excellent flexibility, extrudability and excellent melt adhesion at the time of coextrusion molding with a hard thermoplastic resin such as an ABS resin. Things.

[0002]

2. Description of the Related Art In a housing building material, as a composite building material application in which a soft material molding is bonded to a hard material molding or a hard material and a soft material are joined by co-extrusion molding, hard vinyl chloride, hard vinyl chloride and carbonic acid are used. Calcium-filled composites and soft vinyl chloride have mainly been used.
In recent years, the use of the vinyl chloride has been avoided due to environmental problems and the like, and alternative materials which are relatively inexpensive and have excellent extrudability as well as vinyl chloride have been studied. As an alternative to hard vinyl chloride, styrene resins such as ABS resin, whose extrusion conditions are relatively equivalent to vinyl chloride, are mentioned. However, in co-extrusion molding with soft materials, the adhesion strength between hard and soft materials is low. It was low, and there was a problem that a soft portion was peeled off from the co-extruded product, and the flexibility was not sufficient. Currently, there is a demand for a flexible material having excellent adhesion strength to a styrene resin such as an ABS resin and having a durometer hardness of HDA80 or less.

[0003]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that polyetherester, a block polymer of an aromatic vinyl polymer block and a conjugated diene polymer block, The present inventors have found a resin composition containing an inorganic filler, having excellent flexibility, excellent adhesion strength in co-extrusion molding with an ABS resin, and capable of preventing blocking of pellets during storage.

[0004]

That is, the present invention relates to a polyetherester (I) of 20 to 60 parts by weight,
BA (A is a polymer block of an aromatic vinyl monomer,
B is a block copolymer represented by a conjugated diene elastomeric polymer block) and / or a general formula ABA
Derivative (II) 4 of the block copolymer represented by
It is a thermoplastic elastomer composition comprising 0 to 80 parts by weight of (I) + (II) = 100 parts by weight and 5 to 25 parts by weight of an inorganic filler (III).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The polyether ester (I) used in the present invention is a copolymer having at least one segment consisting of polyether glycol or copolyether glycol, and is composed of aromatic dicarboxylic acid and alkyl dicarboxylic acid. It is prepared from at least one acid or cycloalkyldicarboxylic acid and at least one alkylene glycol or cycloalkylene glycol. For example, a block copolymer obtained by a reaction between a polytetramethylene terephthalate-forming component and polytetramethylene glycol or a reaction between a polytetramethylene terephthalate and isophthalate copolymer-forming component and polyethylene glycol can be used.
These polyetheresters have a durometer hardness of HD
Those having a D50 or less are preferred in terms of flexibility.

The general formula AB- used in the present invention
A block copolymer represented by A (A is a polymer block of an aromatic vinyl monomer, B is an elastomeric polymer block of a conjugated diene) and / or a block represented by the general formula ABA As the aromatic vinyl monomer used in the hydrogenated derivative (II) of the copolymer, styrene is mentioned as a particularly general one, and 1.3- as the conjugated diene is particularly common. Butadiene and 2-methyl-1,3-butadiene. The block copolymer (II) used in the present invention has a durometer hardness HD.
A70 or less is preferred in terms of flexibility.

The inorganic filler (II) used in the present invention
As I), inorganic fillers generally used for thermoplastic resins such as calcium carbonate, mica, talc, quartz powder and feldspar powder are used, and calcium carbonate and quartz powder are particularly preferably used.

Further, calcium carbonate having a specific surface area of 7000 cm ² / g or more is more preferable in terms of flexibility and product appearance, and quartz powder having an average particle diameter of 0.1 to 20 μm prevents blocking of the elastomer pellets and molded articles. Is more preferable.

In the thermoplastic elastomer composition of the present invention, the blending ratio of the polyetherester (I), the block copolymer (II) and the inorganic filler (III) is 20 to 60 parts by weight of the polyetherester (I). (I) + (I) comprising 40 to 80 parts by weight of a block copolymer (II)
I) = 100 parts by weight, inorganic filler (III) 5-2
5 parts by weight, preferably 30 to 50 parts by weight of polyetherester (I), 50 parts by weight of block copolymer (II)
To 70 parts by weight, and 10 to 20 parts by weight of the inorganic filler (III). If the amount of the polyetherester (I) is less than 20 parts by weight, the adhesion strength is reduced, and if it exceeds 60 parts by weight, the flexibility is impaired. If the amount of the block copolymer (II) is less than 40 parts by weight, the flexibility is impaired, and if it exceeds 80 parts by weight, the adhesion strength is reduced, and the pellets are blocked during storage of the thermoplastic elastomer composition. Inorganic filler (II
If I) is less than 5 parts by weight, blocking occurs in the pellets during storage of the thermoplastic elastomer composition, and if it exceeds 25 parts by weight, the flexibility is impaired and the product appearance is poor.

The durometer hardness of the thermoplastic elastomer composition is preferably HDA 80 or less from the viewpoint of flexibility.
More preferably, the HDA is 75 or less.

The thermoplastic elastomer composition of the present invention comprises:
It is excellent in flexibility and has excellent adhesion strength in co-extrusion molding with hard thermoplastic resin represented by styrene resin such as ABS resin, so it is a material suitable for extruded products formed by co-extrusion with these hard thermoplastic resins. is there.

In the present invention, 2,6-di-tert-butyl-4-methylphenol, 4,
Phenolic antioxidants such as 4'-butylidene-bis (3-methyl-6-t-butylphenol); phosphorus-based oxidations such as tris (mixed, mono- and dinonylphenyl) phosphites and diphenyl isodecyl phosphite Antioxidants, sulfur-based antioxidants such as dilauryl thiodipropionate, dimyristyl thiodipropionate diasterial thiodipropionate, 2-hydroxy-4
-Octoxybenzophenone, 2- (2-hydroxy-
UV absorbers such as 5-methylphenyl) benzotriazole, bis (2,2,6,6, -tetramethyl-4-
It is also possible to add a light stabilizer such as piperidinyl), an antistatic agent such as hydroxylalkylamine and sulfonate, a lubricant such as ethylenebisstearylamide, and a coloring agent such as titanium oxide and carbon black.

An example of a method for producing the thermoplastic elastomer composition of the present invention will be described below.

The blending and melt extrusion of the thermoplastic elastomer composition of the present invention are not particularly limited, and a generally known method can be employed. For example, kneading using a mixer such as a ribbon blender, a V-type blender, a Henschel mixer, an extruder such as a single screw extruder, a twin screw extruder, a Banbury mixer, a mixing roll, a pressure kneader, or the like can be employed. .

The thermoplastic elastomer composition obtained as described above can be used not only for extrusion molding and injection molding of a single composition, but also for co-extrusion with the hard thermoplastic resin represented by ABS resin. It can be used for various extrusion molding such as sheet extrusion molding, profile extrusion molding, and two-color injection molding with hard thermoplastic resin. Among them, it can be used for coextrusion molding with ABS resin and sheet extrusion molding. preferable.

[0016]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but these examples do not limit the present invention. Parts and% in Reference Examples, Examples and Comparative Examples represent parts by weight and% by weight, respectively. In addition, each physical property value was calculated | required by the following test method.

(1) Flexural modulus Measured according to ASTM D790.

(2) Durometer hardness Measured according to JIS K7215. 120mm × 6
A square plate of 0 mm × 3 mm was prepared by injection molding and measured with a type A durometer. When the value measured with a type A durometer exceeds HDA90, type D
It was measured with a durometer.

(3) Adhesion strength A square plate of 120 mm × 60 mm × 3 mm is prepared by injection molding, and a half, 60 mm × 60 mm portion of the square plate is formed on an ABS resin square plate at 200 ° C. using a press molding machine. Melt compression bonding was performed at a temperature. After cooling, the square plate was pulled perpendicularly to the pressure-bonded surface of the hard material square plate, and the load leading to peeling was measured. In addition, when 30% or more of elongation deformation occurs in the square plate without peeling, and when the load leading to peeling is 30 kgf
In the above cases, it was judged as "good" as having sufficient adhesion strength, and as "poor" when peeling occurred under a load of less than 30 kgf.

(4) Specific surface area 3 g of material was measured with a Shimadzu type powder specific surface area measuring instrument at 2 cm ² ×
The sample was filled in a 1 cm sample tube, and measured with a 500 mm water column from an air permeation time of 5 cc.

(5) Appearance of molded product The extruded product was visually judged. A sample having a smooth surface was rated as ○, and a sample having poor surface and poor smoothness was rated as ×.

(6) Blocking property 25 kg of pellets of the thermoplastic elastomer composition are packed in a paper bag and allowed to stand on the floor, and 300 mm × 6
A 100 mm × 5 mm iron plate was placed, and a load of 100 kgf was further applied to evaluate the blocking property after 168 hours. Those with blocking were evaluated as x, and those without blocking were evaluated as ○.

Hereinafter, Examples and Comparative Examples will be described. Reference Example 1 Polyetherester (I) A: "Hytrel" 3078 (Durometer hardness HDD30) manufactured by Dupont Toray B: "Hytrel" 4057 (Durometer hardness HDD40) manufactured by Dupont Toray Reference Example 2 Block copolymer (II) "VECTOR" 8 made by DEXCO POLYMERS
508-D (durometer hardness HDA65) Reference Example 3 Inorganic filler (III) A: Calcium carbonate (specific surface area 2700 cm ² /
g) B: calcium carbonate (specific surface area 5700 cm ² /
g) C: calcium carbonate (specific surface area 22000 cm ² /
g) D: Quartz powder (average particle diameter 30 μm) E: “SIKRON” M499 manufactured by SIBERCO
(Quartz powder: average particle diameter 7 μm) Examples 1 to 15 and Comparative Examples 1 to 8 Combinations shown in Table 1 with the polyetherester (I), block copolymer (II), and inorganic filler (III) described in Reference Examples. The resulting mixture was kneaded with a Henschel mixer at a ratio and then compounded with a 40 mmφ single screw extruder to obtain a thermoplastic elastomer composition. A test piece of the composition was prepared from the obtained composition by injection molding, and the flexural modulus, durometer hardness, and adhesion strength were measured. The measured values are shown in Table 2. In addition, extrusion molding was performed, and the appearance of the molding surface is also shown in Table 2. Further, the blocking properties of the thermoplastic elastomer composition pellets were also evaluated, and the results are shown in Table 2.

From the examples and comparative examples, it is understood that the thermoplastic elastomer composition of the present invention has excellent flexibility, excellent adhesion strength, and does not cause blocking during storage in the thermoplastic elastomer composition pellets. This is realized only by mixing a specific resin in a specific ratio.

In Comparative Examples 1, 2, 3, 4, 5, and 6, if the amount of the polyetherester (I) is less than 20 parts by weight, the adhesion strength is reduced, and if it exceeds 60 parts by weight, the flexibility is impaired. If the amount of the block copolymer (II) is less than 40 parts by weight, the flexibility is impaired, and if it exceeds 80 parts by weight, the adhesion strength decreases. Comparative Examples 7 and 8 Inorganic Filler (III)
If it is less than 5 parts by weight, blocking occurs in the thermoplastic elastomer composition pellets, and if it exceeds 25 parts by weight, adhesion strength is reduced, flexibility is impaired, and product appearance is further deteriorated.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

The thermoplastic elastomer composition of the present invention is obtained by blending a specific additive in a specific ratio.
A thermoplastic elastomer composition having excellent flexibility and excellent adhesion strength during co-extrusion molding with a hard thermoplastic resin composition such as an ABS resin can be obtained.

The thermoplastic elastomer composition of the present invention comprises:
These features are utilized in extrusion molding applications, and are particularly suitable as a resin material for coextrusion molding as a building material or furniture material or as a decorative material for a part thereof.

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Claims (5)

[Claims] 1. A polyetherester (I) of 20 to 60 parts by weight, a general formula ABA (A is a polymer block of an aromatic vinyl monomer, and B is an elastomeric polymer block of a conjugated diene) (I) + (I) comprising 40 to 80 parts by weight of a block copolymer represented by the formula (1) and / or a hydrogenated derivative (II) of the block copolymer represented by the general formula ABA:
I) = 100 parts by weight, inorganic filler (III) 5
A thermoplastic elastomer composition containing 25 parts by weight. 2. An inorganic filler (III) having a specific surface area of 7000
cm ² / g is more calcium carbonate claim 1 thermoplastic elastomer composition. 3. An inorganic filler (III) having an average particle size of 0.1
2. The thermoplastic elastomer composition according to claim 1, which is a quartz powder having a size of from 20 to 20 [mu] m. 4. The thermoplastic elastomer composition according to claim 1, wherein the durometer hardness of the thermoplastic elastomer composition is 80 or less. 5. A molded article obtained by extruding or injection molding the thermoplastic elastomer composition according to claim 1.