JP2001131368A - Thermoplastic resin composition for extrusion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition for extrusion excellent in extrusion properties and a mechanical strength and using a reinforced styrene- based resin as a base. SOLUTION: This thermoplastic resin composition for extrusion is obtained by adding (c) a polyorganosiloxane in an amount of 0.01-5 pts.wt. and (d) at least one kind selected from an ester-based wax and a low molecular weight olefin wax in an amount of 0.01-5 pts.wt. to 100 pts.wt. of a composition composed of (a) 5-95 pts.wt. of a graft polymer having 10-100% graft ratio obtained by copolymerizing an aromatic vinyl-based compound and other aromatic vinyl- based compound capable of copolymerizing therewith as necessary in the presence of a rubber-like polymer and (b) 5-95 pts.wt. of a copolymer having number- average molecular weight within the range of 70,000-90,000 and Q value within the range of 2.1-2.8 obtained by copolymerizing the aromatic vinyl-based compound and other aromatic vinyl-based compound capable of copolymerizing therewith as necessary.

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 having excellent extrudability and mechanical strength.

[0002]

2. Description of the Related Art Conventionally, HIPS resin, ABS resin, A
Rubber-reinforced styrene resins represented by ES resins, AAS resins, etc. are widely used in OA equipment, home electric appliances or vehicles because of their good workability and product appearance. The system resin generally has a drawback that rigidity and dimensional stability are inferior to metal. Therefore, in order to improve such a defect, it is usual to mix an inorganic or organic filler such as glass fiber, talc, mica or wood flour with the resin.
There is a problem that the appearance of the product, which is a characteristic of the rubber-reinforced styrene resin, is significantly impaired. In recent years, replacement of general-purpose vinyl chloride resin has been considered due to environmental issues or recycling issues.
There is a need for a material that is more suitable for extrusion molding including a variant than injection molding. However, conventional rubber-reinforced styrene-based resins are inferior to vinyl chloride resins in terms of productivity, product appearance or product dimensional stability during extrusion molding (unconventional), and therefore these rubber-reinforced styrene-based resins are inferior. In order to substitute this, it was necessary to change production conditions or significantly modify the mold.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic resin composition for extrusion molding based on a rubber-reinforced styrene resin having excellent extrusion moldability and mechanical strength.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, by combining specific additives, the processability and product appearance inherent in the rubber-reinforced styrene resin have been improved. The present inventors have found that practical properties can be improved without impairment, and have led to the present invention.

That is, the present invention relates to (1) (a) a graft ratio obtained by copolymerizing an aromatic vinyl compound and optionally another copolymerizable vinyl compound in the presence of a rubbery polymer. Is 10 to 100%
5 to 95 parts by weight of a graft polymer, (b) a number average molecular weight obtained by copolymerizing an aromatic vinyl compound and another vinyl compound which can be copolymerized if necessary, is 70,
000-90,000 and Q value is 2.1
(C) 0.01 to 5 parts by weight of a polyorganosiloxane, (d) an ester wax, and a low molecular weight olefin, based on 100 parts by weight of a composition comprising 5 to 95 parts by weight of a copolymer having a molecular weight of from 2.8 to 2.8 A thermoplastic resin composition for extrusion molding obtained by adding 0.01 to 5 parts by weight of at least one selected from waxes; and (2) an aromatic vinyl compound in the presence of (a) a rubbery polymer And the graft ratio obtained by copolymerizing other copolymerizable vinyl compounds as required is 10 to 100%.
5 to 95 parts by weight of a graft polymer, (b) a number average molecular weight obtained by copolymerizing an aromatic vinyl compound and another vinyl compound which can be copolymerized if necessary, is 70,
000-90,000 and Q value is 2.1
(C) 0.01 to 5 parts by weight of a polyorganosiloxane, (d) an ester wax, relative to 100 parts by weight of a composition comprising 5 to 95 parts by weight of a copolymer having a range of from 2.8 to 2.8.
Extrusion molding thermoplastic resin composition comprising 0.01 to 5 parts by weight of at least one selected from low molecular weight olefin waxes and (e) 1 to 100 parts by weight of an inorganic filler and / or an organic filler. It provides things.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The graft polymer used as the component (a) in the present invention is obtained by copolymerizing an aromatic vinyl compound and optionally another copolymerizable vinyl compound in the presence of a rubbery polymer. Things. The rubbery polymer used in the present invention includes polybutadiene and styrene-
Butadiene copolymer, acrylonitrile-styrene copolymer, styrene-butadiene block polymer, acrylic rubber containing butyl acrylate or ethyl acrylate as a main component, ethylene-propylene (diene) polymer, silicon rubber, chlorinated polyethylene, nitrile rubber , Urethane rubber, isoprene rubber and the like. In particular, polybutadiene, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, styrene-butadiene block polymer, acrylic rubber containing butyl acrylate or ethyl acrylate as a main component, and ethylene-propylene (diene) polymer have practical physical properties or It is preferable from the viewpoint of product appearance.

The aromatic vinyl compound used in the present invention includes styrene, α-methylstyrene and the like, and can be used alone or as a mixture. Other copolymerizable vinyl compounds include acrylonitrile,
Vinyl cyanide compounds such as methacrylonitrile and (meth) such as methyl methacrylate and methyl acrylate
Acrylic ester compounds, maleimide, maleimide compounds such as N-phenylmaleimide, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid, unsaturated carboxylic acids such as maleic anhydride and itaconic anhydride Products, unsaturated epoxy compounds such as glycidyl methacrylate and allyl glycidyl ether, and hydroxyl-containing unsaturated compounds such as hydroxyethyl acrylate and hydroxyethyl methacrylate.
They can be used alone or in combination of two or more. The composition ratio of each component constituting the graft polymer (a) is not particularly limited, but is 10 to 80% by weight of a rubbery polymer, 20 to 100% by weight of an aromatic vinyl compound, and another copolymerizable compound. Compound consisting of 0 to 80% by weight (total)
It is preferably 90 to 20% by weight, particularly 10 to 80% by weight of the rubbery polymer and the aromatic vinyl compound 2
0 to 90% by weight and 90 to 20% by weight of a compound (total) composed of 10 to 80% by weight of a vinyl cyanide compound and / or a (meth) acrylate compound as another copolymerizable compound. preferable.

The graft ratio of the above graft polymer is 10 to 10.
Must be 100%. If the graft ratio of the graft polymer is less than 10%, the mechanical strength is inferior, and 100%
Exceeding the range is not preferable because the moldability is significantly reduced.
The graft ratio of the above graft polymer was determined by the following formula, using acetone as a solvent and separating into soluble and insoluble components. Graft ratio (%) = [weight of acetone-insoluble component−weight of rubbery polymer in graft polymer] / [weight of rubbery polymer in graft polymer] × 100

The aromatic vinyl compound and other copolymerizable vinyl compounds used for the component (b) include:
The same one as exemplified in the section (a) can be used.
Although there is no particular limitation on the composition ratio of each component constituting the copolymer (b), the aromatic vinyl compound is 20 to 100% by weight.
And 0 to 80% by weight of another copolymerizable compound, and in particular, an aromatic vinyl compound of 20 to 90% by weight.
It is preferable that the compound is 10 to 80% by weight of the vinyl cyanide compound and / or the (meth) acrylate compound as another copolymerizable compound.

The number average molecular weight of the copolymer (b) is
70,000-90,000, and the Q value is 2.1-
It needs to be 2.8. The number average molecular weight is 7
If it is less than 000, the impact strength is reduced, and it is difficult to maintain the shape during molding. If it exceeds 90,000, the moldability deteriorates, which is not preferable. When the Q value is 2.
If it is less than 1, the thickness immediately after being extruded from the molding machine cannot be obtained, resulting in poor dimensional accuracy. If it exceeds 2.8, the die swell becomes extremely large, and consequently the sizing dies may be caught in the sizing die. Therefore, it is not preferable. The number average molecular weight and Q value (weight average molecular weight / number average molecular weight) of the copolymer (b) can be obtained by converting an elution curve obtained by gel permeation chromatography (GPC) into standard polystyrene. it can.

The above graft polymer (a) and copolymer (b) can be produced by known polymerization methods, for example, emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization and the like. The mixing ratio of the component (a) and the component (b) is 5 to 95 parts by weight of the component (a) and the component (b).
Component 95 to 5 parts by weight ((a) + (b) = 100 parts by weight)
Outside of this range, the balance between extrudability and mechanical strength is poor, which is not preferable.

The polyorganosiloxane (c) used in the present invention is exemplified by polydimethylsiloxane, polymethylethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane and the like. The viscosity of the polyorganosiloxane (c) is not particularly limited.
It is preferably in the range of 000 cps. The mixing ratio of the component (c) is as follows: the component (a) and the component (b)
It is 0.01 to 5 parts by weight based on 100 parts by weight of the total components. If the amount is less than 0.01 part by weight, sufficient slipperiness cannot be obtained, resulting in poor molded product appearance. If the amount exceeds 5 parts by weight, supply of raw materials to a molding machine becomes unstable, and formability is significantly impaired. .

The ester wax (d) used in the present invention includes alcohol fatty acid esters such as butyl stearate, stearyl stearate and pentaerythritol stearate, glycerin aliphatic esters such as monoglyceride and organic acid monoglyceride, and polyglycerin fatty acid. Esters, propylene glycol fatty acid esters, polyhydric alcohol fatty acid esters and the like.
Species or a mixture of two or more can be used. Examples of the low-molecular-weight olefin wax (d) include low-molecular-weight polyethylene having a molecular weight of about several thousands, polypropylene, and acid-modified polyethylene, and may be used alone or in combination of two or more. The mixing ratio of the component (d) is 0.01 to 5 parts by weight based on 100 parts by weight of the total of the components (a) and (b). If the amount is less than 0.01 part by weight, the appearance of the molded article is inferior, and if it exceeds 5 parts by weight, the molding stability is inferior.

The inorganic and / or organic filler (e) used in the present invention includes oxides such as silica and diatomaceous earth, hydroxides such as aluminum hydroxide, and carbonates such as calcium carbonate and magnesium carbonate. Salts, sulfates or sulfites such as barium sulfate, talc, clay, mica,
Silicates such as glass beads, carbons such as carbon black, graphite and carbon fibers, molybdenum sulfide, boron fibers, zinc borate, calcium borate and stainless steel fibers;
Inorganic fillers such as metal fibers such as potassium titanate fiber and ceramic fillers such as whiskers and silicon carbide, and plant substances such as wood flour, paper, pulp, rice husk, bagasse, or pulverized products thereof The exemplified organic fillers are exemplified, and one kind or a mixture of two or more kinds can be used. In particular, the shape of the organic filler includes all shapes such as powder and fiber, but it is preferable to use powder in consideration of dispersion in resin. There are no restrictions on the type of wood flour among them. Can be used, and delignified products of these cellulosic substances can also be used. The mixing ratio of the component (e) is 1 to 100 parts by weight with respect to the total of 100 parts by weight of the components (a) and (b). However, if it exceeds 100 parts by weight, the mechanical strength is significantly reduced, which is not preferable.

The thermoplastic resin composition for extrusion molding of the present invention contains other resins such as polycarbonate, polyester, polyphenylene ether, and polyamide, as well as stabilizers, antioxidants, and ultraviolet rays, as long as the purpose is not impaired. You may add an inhibitor, a coloring agent, etc.

For mixing the thermoplastic resin composition for extrusion molding of the present invention, a roll, a kneader, a Banbury mixer, a single-screw or twin-screw extruder or the like can be used. Further, a molded product can be obtained from the composition thus obtained by known extrusion such as profile extrusion, sheet extrusion, pipe extrusion, rod extrusion, and the like. Also, the obtained molded products are building materials, OA
It can be used as various parts in the field of equipment, home electric appliances, vehicles, sundries and so on.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited by these examples. Graft polymer (a) a-1: 35 parts by weight of styrene and 15 parts by weight of acrylonitrile were graft-polymerized to 50 parts by weight of polybutadiene by a known emulsion polymerization method to prepare a graft polymer having a graft ratio of 30%. a-2: 35 parts by weight of styrene and 15 parts by weight of acrylonitrile were graft-polymerized to 50 parts by weight of polybutadiene by a known emulsion polymerization method to prepare a graft polymer having a graft ratio of 90%. a-3: 15 parts by weight of acrylonitrile and 35 parts by weight of styrene were graft-polymerized to 50 parts by weight of ethylene-propylene-ethylidene norbornene rubber by a solution polymerization method to prepare a graft polymer having a graft ratio of 40%. a-4: Graft polymerization of 35 parts by weight of styrene and 15 parts by weight of acrylonitrile to 50 parts by weight of butyl acrylate rubber by a known emulsion polymerization method to obtain a graft ratio of 30%
Was prepared. ai: Graft polymerization of 50 parts by weight of polybutadiene and 35 parts by weight of styrene and 15 parts by weight of acrylonitrile was carried out by a known emulsion polymerization method to prepare a graft polymer having a graft ratio of 120%.

Copolymer (b) b-1: 75 parts by weight of styrene and acrylonitrile 2
Five parts by weight were copolymerized by a known bulk polymerization method to prepare a copolymer having a molecular weight of 70,000 and a Q value of 2.3. b-2: 75 parts by weight of styrene and acrylonitrile 2
Five parts by weight were copolymerized by a known suspension polymerization method to prepare a copolymer having a molecular weight of 85,000 and a Q value of 2.1. bi: 75 parts by weight of styrene and acrylonitrile 2
Five parts by weight were copolymerized by a known emulsion polymerization method to prepare a copolymer having a molecular weight of 72,000 and a Q value of 3.1.

Polyorganosiloxane (c) c-1: Polyorganosiloxane (Shin-Etsu Silicone K
F96-500, manufactured by Shin-Etsu Chemical Co., Ltd.)

Ester wax, low molecular weight olefin wax (d) d-1: Higher alcohol fatty acid ester wax (Rikemar SL-900, manufactured by Riken Vitamin Co., Ltd.) d-2: Polyhydric fatty acid ester wax (Rikemar)
SL-02, manufactured by Riken Vitamin Co., Ltd.) d-3: Higher fatty acid ester-based wax (Kawawax-L, manufactured by Kawaken Fine Chemical Co., Ltd.) d-4: Polypropylene wax (Mitsui High Wax)
D-5: Polyethylene wax (Mitsui High Wax 2)
20MP, manufactured by Mitsui Chemicals, Inc.)

Inorganic filler and / or organic filler (e) e-1: talc (micron white # 5000S, manufactured by Hayashi Kasei Co., Ltd.) e-2: calcium carbonate (Escalon # 800, manufactured by Mitsui Flour Milling Co., Ltd.) E-3: Wood flour (Wood Flour 4010, manufactured by American Wood Fibers) e-4: Bamboo flour (Moso bamboo flour manufactured by Okayama Castle Nandenki Co., Ltd.)

[Examples] The above components were mixed in a tumbler at the ratios shown in Tables 1 and 2, and then melt-kneaded using a 40 mm single screw extruder (L / D 28) manufactured by Tanabe Plastic Machinery Co., Ltd. (Temperature 180 ° C.) and pelletized. The following evaluation was performed using the obtained pellets.
In addition, about the test piece for impact strength, the press plate was produced by extrusion molding, cut into the shape based on JIS method, and used for the measurement. The results are shown in Tables 1 and 2.

Impact strength: Izod impact strength (with notch) was measured according to JIS K-7110.

Formability: Using a 40 mm single screw extruder (set temperature: 180 ° C.) manufactured by Tanabe Plastic Machinery Co., Ltd.
A concave shaped extrusion having a width of 50 mm and a thickness of 2 mm was extruded, and the stability of discharge was evaluated according to the following criteria. ；: Good moldability, ×: bulging edge or poor surface gloss

Dimensional stability: At the same time as evaluation of moldability, dimensional stability was evaluated according to the following criteria. ；: Good dimensional stability, ×: Product dimensions change significantly due to surging, etc.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

As described above, the present invention can provide a thermoplastic resin composition for extrusion molding based on a rubber-reinforced styrene resin having excellent extrudability and mechanical strength.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 83:04 C08L 83:04 91:06 91:06 97:02) 97:02) F-term (Reference) 4J002 AB014 AH004 BC02X BC09X BG01X BG04X BG05X BG07X BG10X BH02X BN03W BN06W BN10W BN12W BN14W BN17W CD19X CH11X CP033 DA017 DA027 DA037 DA067 DE147 DE237 DG027 DJ077 DJ077 DJ007 DJ077 DJ007 DJ077

Claims (2)

[Claims] The graft ratio obtained by copolymerizing (a) an aromatic vinyl compound and optionally another copolymerizable vinyl compound in the presence of a rubbery polymer is 10 to 1
5% to 95 parts by weight of a graft polymer having a number average molecular weight of 70,000 obtained by copolymerizing (b) an aromatic vinyl compound and another copolymerizable vinyl compound as required. 100 parts by weight of a composition consisting of 5 to 95 parts by weight of a copolymer having a Q value in the range of 2.1 to 2.8 in the range of 90,000 and (c) 0.01 parts of the polyorganosiloxane. A thermoplastic resin composition for extrusion molding, comprising at least 0.01 part by weight of at least one selected from ester waxes and low molecular weight olefin waxes. 2. The graft ratio obtained by copolymerizing (a) an aromatic vinyl compound and optionally another copolymerizable vinyl compound in the presence of a rubbery polymer is 10 to 1
5% to 95 parts by weight of a graft polymer having a number average molecular weight of 70,000 obtained by copolymerizing (b) an aromatic vinyl compound and another copolymerizable vinyl compound as required. 100 parts by weight of a composition consisting of 5 to 95 parts by weight of a copolymer having a Q value in the range of 2.1 to 2.8 in the range of 90,000 and (c) 0.01 parts of the polyorganosiloxane. To 5 parts by weight, (d) 0.01 to 5 parts by weight of at least one selected from ester wax and low molecular weight olefin wax, and (e) 1 to 100 parts by weight of an inorganic filler and / or an organic filler. And a thermoplastic resin composition for extrusion molding.