JPH08199031A - Resin composition for extrusion molding - Google Patents

Abstract

PURPOSE: To obtain a resin composition for extrusion molding, which, in spite of being a compound for an easily stickable ABS/PVC/inorganic pigment-mixed system compound for extrusion molding, can give a molding not deteriorated in heat resistance and impact resistance and does not suffer from stickiness within a die and plate-out. CONSTITUTION: This composition is prepared by mixing 100 pts.wt., in total, comprising 30-70 pts.wt. vinyl chloride resin having an average degree of polymerization of 500-800 and 70-30 pts.wt. acrylonitrile/butadiene/styrene resin with 0.1 pt.wt. or above inorganic pigment and 0.3-1.5 pts.wt. polypropylene glycol/ polyethylene glycol polymer prepared by effecting an addition reaction of both terminals of a polypropylene glycol of a molecular weight of 1500 or above with a polyethylene glycol and replacing either terminal by an OH group and having a melting point of 43 deg.C or above.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an extrusion molding resin composition capable of obtaining an extrusion molded article excellent in heat resistance and impact resistance without causing sticking or plate out in a die during extrusion molding. Regarding things.

[0002]

2. Description of the Related Art Conventionally, an extrusion molding compound composed of a vinyl chloride resin (hereinafter referred to as PVC), an acrylonitrile-butadiene-styrene resin (hereinafter referred to as ABS) and an inorganic pigment is widely known. AB
When extrusion molding is performed using an extrusion molding compound in which S and S are mixed in substantially equal amounts, PVC, ABS and the inorganic pigment are uniformly melt mixed in the extrusion molding machine due to the large difference in melt viscosity between the two. It is difficult to do so, and there is a drawback that plate-out and sticking of the extruded molten resin in the die, which are considered to be caused by the metal in the inorganic pigment, are likely to occur. Also,
When a foaming agent was added to and mixed with the above extrusion molding compound and extrusion foaming was performed, plate-out and sticking of the extruded molten resin in the die became more severe, and the long-run property was remarkably reduced.

[0003]

Therefore, an object of the present invention is to provide an ABS / PVC / inorganic pigment mixed system compound for extrusion molding, that is, a compound which is generally easy to stick, but does not impair heat resistance and impact resistance. The present invention provides an extrusion-molding resin composition that does not cause sticking in a die or plate-out under extrusion conditions equivalent to those of PVC compounds.

[0004]

Means for Solving the Problems The inventors of the present invention have investigated the impact resistance and heat resistance of a molded article from which an extrusion molding compound can be obtained.
100 parts by weight of 800 to 30 parts by weight of PVC and 70 to 30 parts by weight of (B component) ABS, 100 parts by weight of (C component) inorganic pigment and 0.1 parts by weight and (D component) polypropylene glycol having a molecular weight of 1500 or more. Polyethylene glycol is added to both ends of the, and one end thereof is substituted with an OH group. 0.3 to 1.5 parts by weight of a polypropylene glycol / polyethylene glycol polymer having a melting point of 43 ° C or more is added for extrusion molding. The resin composition has the above properties,
The present invention has been completed by finding that it is an ABS / PVC / inorganic pigment mixture compound for extrusion molding, which is excellent in heat resistance and impact resistance with good workability in which plate-out hardly occurs.

The present invention will be described in detail below. When extrusion molding is performed using the resin composition for extrusion molding of the present invention, PV
ABS, which has a higher melt viscosity than C, is mixed in a large amount with PVC / ABS = 30/70 to 70/30 in a weight ratio to PVC. It is liable to occur, and this causes plate-out and sticking of the extruded molten resin in the die due to a synergistic action with the metal in the inorganic pigment. Therefore, the PVC having an average degree of polymerization of 500 to 800 is used. If the average degree of polymerization is less than 500, the heat resistance and impact resistance provided by ABS are impaired. Also, if it exceeds 800, high torque and high heat generation during extrusion are likely to occur and it becomes difficult to control,
The appearance of the obtained molded product becomes poor and the heat deterioration due to high temperature becomes remarkable, and the original physical properties of the resin are impaired.

Examples of PVC as the component (A) include polyvinyl chloride resins and copolymers containing 50% by weight or more of vinyl chloride and a vinyl monomer copolymerizable with vinyl chloride. Of these, polyvinyl chloride resin is preferred. Examples of vinyl monomers copolymerizable with vinyl chloride include ethylene, propylene, acrylic acid, methyl acrylate, methacrylic acid, ethyl methacrylate, vinyl acetate, vinyl propionate, and vinylidene chloride. Are used alone or in combination of two or more.

As the ABS of the (B component), it is preferable to use a heat resistant grade. For example,
Examples thereof include a type in which a part or all of styrene in ABS is replaced with α-methylstyrene, a copolymer type with cyclohexylmaleimide, and the like. The mixing ratio of PVC and ABS in the resin composition for extrusion molding of the present invention is PV
In 100 parts by weight of the total amount of C and ABS, PVC is 30 to 70 parts by weight, preferably 40 to 60 parts by weight, ABS is 70 to 30 parts by weight,
It is preferably 60 to 40 parts by weight. Here, if PVC is less than 30 parts by weight or ABS is more than 70 parts by weight, a sufficient improvement effect cannot be obtained due to plate-out or sticking of extruded molten resin in the die, and if ABS is less than 30 parts by weight, 70 PVC
When it exceeds the weight part, heat resistance and impact strength are deteriorated, which is not preferable.

As the inorganic pigment of (C component), titanium oxide, zinc oxide, yellow lead, red pigment, iron oxide yellow, red iron oxide, red lead, navy blue, ultramarine, chrome oxide green, iron black, lithobon, titanium Examples include yellow, zinc chromate, chrome vermilion, amber, mineral violet, cobalt violet, carbon black and the like. The inorganic pigment is added and mixed in an amount of 0.1 parts by weight or more, preferably 0.6 to 1.5 parts by weight, based on 100 parts by weight of the total amount of (A component) and (B component).

Polypropylene glycol / polyethylene glycol polymer in which polyethylene glycol is added to both ends of polypropylene glycol having a molecular weight of 1500 or more as the component (D) and one end thereof is substituted with an OH group is represented by the general formula: HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _p (CH ₂ CH ₂ O) _n H (m
> 0, p> 0, n> 0), and has a melting point of 43 ° C. or higher. This polypropylene glycol / polyethylene glycol polymer is added and mixed in the range of 0.3 to 1.5 parts by weight, preferably 0.8 to 1.2 parts by weight, based on 100 parts by weight of the total amount of (A component) and (B component). It If it is less than 0.3 parts by weight, the effect of suppressing plate-out and sticking of extruded molten resin in the die cannot be sufficiently obtained, and if it exceeds 1.5 parts by weight, heat resistance, impact strength, weather resistance, etc. are deteriorated. Like Examples of commercially available polypropylene glycol / polyethylene glycol polymers include Pronone 208 (trade name, manufactured by NOF CORPORATION).

The resin composition for extrusion molding of the present invention can be used as an extrusion foam molding resin composition by adding and mixing a foaming agent in addition to the above-mentioned respective components. It is possible to effectively suppress the occurrence of sticking of the extruded molten resin in the die. In this case, the amount of the foaming agent added is preferably 0.5 to 3 parts by weight, more preferably 1 to 2 parts by weight, based on 100 parts by weight of the total amount of the (A component) and the (B component). The type of foaming agent applied is not particularly limited, but inorganic foaming agents such as sodium hydrogen carbonate and ammonium carbonate are preferable, and sodium hydrogen carbonate is particularly preferable. In addition to the above components, a stabilizer, a stabilizing aid, a processing aid, a lubricant, a colorant and the like can be added to the resin composition for extrusion molding of the present invention, if necessary.

The stabilizers and auxiliary agents used here include lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, strontium stearate, barium stearate, zinc stearate, cadmium stearate, stearic acid. Lead, calcium laurate, barium laurate, zinc laurate, cadmium laurate, barium 2-ethylhexoate, zinc 2-ethylhexoate, cadmium 2-ethylhexoate, lead 2-ethylhexoate, zinc naphthenate, cadmium octylate, di Metallic soaps such as basic lead stearate and dibasic lead phthalate; dibutyltin dilaurate type, dibutyltin laurate type, dibutyltin dimalate type, dibutyltin malate type, sulfur-containing diamine Chill tin malate type, monobutyl tin mercaptide type, butyl tin mercaptan type, dibutyl tin type, di-n-octyl tin maleate polymer, dioctyl tin malate type, di-n-octyl tin-s, s'-bis (isooctyl Mercaptoacetate), dioctyltin mercapto-based, dioctyltin-based organotin compounds; lead-based inorganic salts such as tribasic lead sulfate, basic lead sulfite, and dibasic lead phosphite; epoxy such as epoxidized soybean oil Compound;
Calcium-zinc system, barium-zinc system, calcium-
Zinc-tin-based composite stabilizers; and the like.

Examples of processing aids include acrylonitrile / styrene copolymers and polymethacrylate polymers. Examples of the lubricant include monoglycerin ester, monocarbonic acid ester, higher fatty acid alcohol, metal soap, bisamide, paraffin wax, polyethylene wax and the like.

[0013]

EXAMPLES Hereinafter, specific embodiments of the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these descriptions. Examples 1 to 4 and Comparative Examples 1 to 5 (Component A) PVC TK-600 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, average degree of polymerization 600) TK-700 (〃, 〃, 〃 700) (Component B) ABSH -100N (product name, heat resistance grade, manufactured by Ube Sicon) 〃 H-101N (〃, 〃, 〃) (C component) Titanium oxide (Ishihara Sangyo Co., Ltd.) (D component) Polypropylene glycol / polyethylene glycol polymer ( In the table, PPG-PEG polymer) Pronone 208 (Nippon Yushi Kogyo KK, trade name) was used as the formulation shown in Table 1, and dioctyltin mercapto TS-310A (Akishima Chemical Co., Ltd.) was used as a stabilizer for each formulation. , Trade name) 1.5 parts by weight, polyethylene wax AC-316 as a lubricant (manufactured by Allied Signan, trade name) 0.5 parts by weight, monocarbonate ester WAX-E
(Hoechst Japan Co., Ltd., trade name) 0.5 parts by weight and paraffin wax Lub1266 (Nippon Seiko Co., Ltd., trade name)
0.5 parts by weight, and 2 parts by weight of polymethylmethacrylate polymer P-530 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.) as a processing aid were added to a Henschel mixer and mixed with stirring, and the temperature of the mixture reached 130 ° C. At that time, the mixture was cooled to 40 ° C. or lower to obtain a powder compound.

Each of the powder compounds was kneaded with a 6-inch roll at 180 ° C. for 5 minutes and cut into roll sheets having a thickness of 0.8 mm. Four roll sheets were stacked and preheated for 6 minutes, temperature was 190 ° C., and pressure was for 4 minutes. Was pressed into a sheet having a thickness of 3 mm and subjected to a Vicat softening temperature test (JIS K 7206) and an Izod impact resistance test (JIS K 7110). Also, for each powder compound, a flat die extrusion molding with a thickness of 5 mm was performed using a 50 mmφ single screw extruder. ・ Screw C / R = 2.5 ・ Cylinder temperature C ₁ = 145 ° C, C ₂ = 160 ° C, C ₃ =
175 ° C., C ₄ = 185 ° C. ・ Die temperature D ₁ = 170 ° C. It was carried out for 3 hours under extrusion conditions, and after the completion of extrusion, the presence or absence of playout on the inner surface of the die was observed and the extrusion obtained immediately before the completion of extrusion. The appearance of the molded product was observed, and those having a smooth surface and gloss were evaluated as "good", and those having a rough surface and no gloss were evaluated as "no". The results of the above tests are also shown in Table 1.

[0015]

[Table 1]

Example 5 PVC powder was added to the powder compound obtained in Example 1.
1.5 parts by weight of sodium hydrogencarbonate as a foaming agent was added to 100 parts by weight of the total amount of (A component) and ABS (B component), and the mixture was uniformly mixed at 40 ° C or lower. Using this powder compound, extrusion molding of a round bar was performed for 3 hours under the same conditions as in Example 1. Observation of the die inner surface after completion of extrusion and extrusion molding obtained immediately before completion of extrusion, as in Example 1. The appearance of the product was observed. The obtained results are shown in Table 2.

Comparative Example 6 The powder compound obtained in Comparative Example 3 was added to Example 5
Similarly to the above, sodium hydrogencarbonate as a foaming agent was added, extrusion molding of a round bar was performed, and the same observation was performed, and the obtained results are also shown in Table 2.

[0018]

[Table 2]

[0019]

The compound obtained from the resin composition for extrusion molding of the present invention does not impair the heat resistance and impact resistance of the obtained molded product, and the adhesion and plate in the die are extruded under the same extrusion conditions as the PVC compound. Since it prevents the occurrence of out,
Productivity can be improved.

Claims (1)

[Claims] 1. A total amount of 30 to 70 parts by weight of (A component) vinyl chloride resin having an average degree of polymerization of 500 to 800 and 70 to 30 parts by weight of (B component) acrylonitrile-butadiene-styrene resin.
With respect to 100 parts by weight, (C component) an inorganic pigment of 0.1 part by weight or more and (D component) of polypropylene glycol having a molecular weight of 1500 or more, polyethylene glycol is added to both ends, and one end thereof is substituted with an OH group. Has a melting point
A resin composition for extrusion molding, comprising 0.3 to 1.5 parts by weight of a polypropylene glycol / polyethylene glycol polymer at 43 ° C. or higher.