JP2001011314A - Thermoplastic resin composition, production method thereof and molded product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded article having excellent appearance and impact strength even when a filler and / or a recycled filler is added to a thermoplastic resin and / or a recycled thermoplastic resin, especially for extrusion molding. Suitable thermoplastic resin composition, method for producing the same, and molded article. SOLUTION: A polytetrafluoroethylene-containing mixed powder (B) containing a polytetrafluoroethylene particle having a particle diameter of 10 μm or less and an organic polymer is mixed with 100 parts by weight of a thermoplastic resin (A). The tetrafluoroethylene component is blended in an amount of 0.01 to 20 parts by weight, and the filler (C) is blended in an amount of 10 to 200 parts by weight.

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 containing a large amount of filler such as wood flour, paper, fiber and the like, which is suitable for extrusion molding having excellent surface appearance and impact strength. The present invention relates to a plastic resin composition and a molded article thereof.

[0002]

2. Description of the Related Art In a thermoplastic resin composition, a filler such as wood flour, paper, fiber or the like is added for the purpose of improving the mechanical strength, moldability and the like and increasing the amount. In particular, in recent years, various kinds of fillers are blended in order to enhance the performance when reusing a resin molded product. Further, as a use of reuse of waste paper or the like, reuse as a filler of a thermoplastic resin is being studied. However, if a large amount of filler is added in order to exert the effect of the filler greatly, the surface of the molded product becomes rough, and the filler is damaged (filler speck).
May occur and the impact strength may decrease. In particular,
When the amount of the filler is 50 parts by weight or more with respect to 100 parts by weight of the thermoplastic resin, these problems become remarkable. As a countermeasure, for the vinyl chloride resin, an acrylic processing aid is used in combination (JP-A-8-333469), and the mixture with the resin is plasticized in an extruder.
A method is used in which a molded product is formed into a predetermined shape by a die attached to the extruder tip, and then cooled and solidified in a cooling zone such as a sizing plate, a sizing die, and a water tank.

[0003]

However, various thermoplastic resins other than vinyl chloride resins, such as olefin resins, have a low melt tension, so that the above problems have not been solved yet. The present invention has been made in order to solve the above-mentioned problems, and even if a filler and / or a recycled filler is added to a thermoplastic resin and / or a recycled thermoplastic resin, the molded article has excellent appearance and impact strength. It is another object of the present invention to provide a thermoplastic resin composition particularly suitable for extrusion molding, a method for producing the same, and a molded article.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that the particle diameter is 10 μm.
By adding a small amount of a polytetrafluoroethylene-containing mixed powder containing the following polytetrafluoroethylene particles and an organic polymer to a thermoplastic resin, an extruded product having an excellent molded product appearance and excellent impact strength is obtained. The present inventors have found out that the present invention can be obtained. That is, the thermoplastic resin composition of the present invention comprises a polytetrafluoroethylene-containing mixture containing polytetrafluoroethylene particles having a particle diameter of 10 μm or less and an organic polymer with respect to 100 parts by weight of the thermoplastic resin (A). The powder (B) is blended so that the amount of the polytetrafluoroethylene component is 0.01 to 20 parts by weight, and the filler (C) is blended to 10 to 200 parts by weight. It is.

The method for producing a thermoplastic resin composition according to the present invention comprises a polytetrafluoroethylene-containing mixed powder (B) containing polytetrafluoroethylene particles having a particle diameter of 10 μm or less and an organic polymer, and a thermoplastic resin. The master pellet containing (A), the thermoplastic resin (A), and the filler (C) were mixed with each other so that the amount of the polytetrafluoroethylene component was 0 with respect to 100 parts by weight of the total amount of the thermoplastic resin (A). .
It is mixed so as to be 01 to 20 parts by weight. The molded article of the present invention comprises the above thermoplastic resin composition, and is particularly suitable as an extruded molded article.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin (A) used in the present invention can be almost any of various thermoplastic resin compositions, for example, polypropylene (PP), high-density polyethylene (HDPE), and low-density polyethylene. Polyethylene (LDPE),
Linear low density polyethylene (LLDPE), polyvinyl chloride resin (PVC), polystyrene (PS), high impact polystyrene (HIPS), copolymer of acrylonitrile and styrene (AS), copolymer of acrylonitrile and styrene rubber reinforced (ABS, ASA, SAS), methacrylic resin, polycarbonate (PC), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polybutylene naphthalate (PB)
N), polyethylene naphthalate (PEN), polycyclohexane terephthalate (PCT), poly-1-butene, polyisobutylene, random copolymer or block copolymer in any ratio of propylene to ethylene and / or 1-butene Cyclic polyolefins such as ethylene-propylene-diene terpolymers, polymethylpentenes, copolymers of cyclopentadiene with ethylene and / or propylene, wherein the diene component is 50% by weight or less in any ratio of ethylene and propylene ,
Random copolymers, block copolymers or graft copolymers of ethylene or propylene with not more than 50% by weight of vinyl compounds such as vinyl acetate, alkyl methacrylate, acrylate, aromatic alkyl ester and aromatic vinyl And the like. These can be used alone or in combination of two or more. Above all, PP, HDPE, LDPE, LLDP
E, PVC, PS, HIPS, AS, ABS, ASA,
SAS, methacrylic resin, PC, PBT, PET, PB
N, PEN, PCT, at least one selected from ethylene-propylene random or block copolymer,
This is preferable in that it has high versatility and is inexpensive.

The thermoplastic resin (A) having a melt flow rate (MFR) of 0.1 to 60 g / 10 minutes, preferably 0.3 to 50 g / 10 minutes, is a mixed powder containing polytetrafluoroethylene. When (B) is blended, the melt strength of the resin at the time of extrusion molding can be kept high, and as a result, an extruded body having an almost uniform thickness, excellent appearance and excellent impact strength can be obtained. It is desirable because it is easy. When the thermoplastic resin (A) is a high-density polyethylene, a low-density polyethylene, a linear low-density polyethylene, or a mixture of two or more thereof, the MFR is 0.3.
More preferably, it is about 45 g / 10 min. In the case where the thermoplastic resin (A) contains propylene and ethylene and / or a monomer copolymerizable therewith, a random copolymer composed of a crosslinkable monomer, or a block copolymer,
Those having an FR of 0.3 to 40 g / 10 minutes are more preferred. When the thermoplastic resin (A) is blended so as to be polystyrene, impact-resistant polystyrene, or a mixture of two or more of them, the MFR is 0.3 to 40 g.
/ 10 minutes is more preferable. MFR is ASTM
It was measured according to D1238. For example, it is a value at 230 ° C. for propylene-based polyolefin, and a value at 190 ° C. for ethylene-based polyolefin. When the thermoplastic resin (A) is a vinyl chloride resin, the average degree of polymerization is preferably from 400 to 2,000, more preferably from 700 to 2,000. If it is less than 400, the moldability may deteriorate.

The polytetrafluoroethylene-containing mixed powder (B) used in the present invention comprises polytetrafluoroethylene particles having a particle diameter of 10 μm or less and an organic polymer. Is not an aggregate larger than 10 μm. As such a polytetrafluoroethylene-containing mixed powder, an aqueous dispersion of polytetrafluoroethylene particles having a particle size of 0.05 to 1.0 μm and an aqueous dispersion of organic polymer particles are mixed, and coagulated or mixed. What is obtained by pulverization by spray drying, or having a particle size of 0.05 to 1.0
A polymer obtained by polymerizing a monomer constituting an organic polymer in the presence of an aqueous dispersion of polytetrafluoroethylene particles having a particle diameter of 0.05 μm, or a powder obtained by coagulation or spray-drying, or having a particle diameter of 0.05 to 5 μm. Emulsion polymerization of a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing an aqueous dispersion of 1.0 μm polytetrafluoroethylene particles and an aqueous dispersion of organic polymer particles, followed by coagulation or spraying Those obtained by pulverization by drying are preferred.

The aqueous dispersion of polytetrafluoroethylene particles having a particle diameter of 0.05 to 1.0 μm used for obtaining the polytetrafluoroethylene-containing mixed powder (B) used in the present invention contains a fluorine-containing surfactant. It is obtained by polymerizing a tetrafluoroethylene monomer by the emulsion polymerization used. At the time of emulsion polymerization of polytetrafluoroethylene particles, hexafluoropropylene as a copolymer component, as long as the properties of polytetrafluoroethylene are not impaired,
Fluorine-containing olefins such as chlorotrifluoroethylene, fluoroalkylethylene, and perfluoroalkylvinyl ether, and fluorine-containing alkyl (meth) acrylates such as perfluoroalkyl (meth) acrylate can be used. The content of the copolymer component is preferably 10% by weight or less based on tetrafluoroethylene.

Commercially available raw materials for the polytetrafluoroethylene particle dispersion include "Fluon AD-1, AD-936" manufactured by Asahi ICI Fluoropolymer Co., Ltd. and "Polyflon D-1, D-2" manufactured by Daikin Industries, Ltd. And "Teflon 30J" manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd. as a representative example. The organic polymer that constitutes the polytetrafluoroethylene-containing mixed powder (B) used in the present invention is not particularly limited, but in consideration of dispersibility when blended with the thermoplastic resin (A), It is preferable that the resin has high compatibility with the thermoplastic resin used.

Specific examples of the monomer for forming the organic polymer include styrene, p-methylstyrene, o-methylstyrene, p-chlorostyrene, o-chlorostyrene, p-methoxystyrene, and o-methoxystyrene. Styrene, α
-Styrene-based monomers such as methylstyrene: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid-
(Meth) acrylate-based monomers such as 2-ethylhexyl, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate: acrylonitrile, Vinyl cyanide monomers such as methacrylonitrile: vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether: vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate; ethylene, propylene, isobutylene, etc. Olefin-based monomers: Diene-based monomers such as butadiene and isoprene can be exemplified. These monomers can be used alone or in combination of two or more.

Among these monomers, styrene-based monomers, (meth) acrylate-based monomers, and olefin-based monomers are preferable in terms of compatibility with the thermoplastic resin (A). The body can be mentioned. Particularly preferred is one or more monomers selected from the group consisting of long-chain alkyl (meth) acrylate monomers having 12 or more carbon atoms, styrene and olefin monomers in an amount of 20% by weight. The monomers contained above can be mentioned.

The content of polytetrafluoroethylene in the polytetrafluoroethylene-containing mixed powder (B) used in the present invention is preferably 0.1 to 90% by weight. When the content is within this range, an extruded product having excellent appearance of the molded product and excellent impact strength can be obtained.
The content of polytetrafluoroethylene in the polytetrafluoroethylene particles is preferably from 0.5 to 80% by weight. When the content is within this range, an extruded product having excellent appearance of the molded product and excellent impact strength can be obtained.
The polytetrafluoroethylene-containing mixed powder (B) used in the present invention is obtained by charging an aqueous dispersion thereof into hot water in which metal salts such as calcium chloride and magnesium sulfate are dissolved,
Then, after salting out and coagulating, it can be dried or powdered by spray drying. While ordinary polytetrafluoroethylene fine powder becomes an aggregate of 100 μm or more in the step of recovering as a powder from the state of a particle dispersion, it is difficult to uniformly disperse it in a thermoplastic resin. Since the polytetrafluoroethylene-containing mixed powder (B) used in the present invention does not form a domain having a particle diameter of more than 10 μm by itself, the thermoplastic resin (A)
Is extremely excellent in dispersibility. As a result, in the resin composition of the present invention, polytetrafluoroethylene is efficiently fiberized in the thermoplastic resin (A), and the addition thereof improves the melt strength of the resin at the time of profile extrusion molding,
As a result, an extruded body having an almost uniform thickness and excellent appearance and impact strength can be obtained.

In the thermoplastic resin composition of the present invention, the polytetrafluoroethylene-containing mixed powder (B) has a polytetrafluoroethylene component content of 100 parts by weight based on 100 parts by weight of the thermoplastic resin (A). It is blended so as to be 01 to 20 parts by weight. If the amount of the polytetrafluoroethylene component is less than 0.01 part by weight, the effect of improving the melt strength is poor, and the effect of the present invention may not be effectively obtained. If the polytetrafluoroethylene component exceeds 20 parts by weight, the surface appearance may be rather deteriorated. The amount of the polytetrafluoroethylene-containing mixed powder (B) added to 100 parts by weight of the thermoplastic resin (A) is as follows:
0.5 to 50 parts by weight is preferred. If the amount of the polytetrafluoroethylene-containing mixed powder (B) is less than 0.5 part by weight, the appearance tends to be poor, the surface of the molded article becomes rough, and the impact strength is reduced. Also, if it exceeds 50 parts by weight,
In some cases, the rubber elasticity of the molten resin becomes too high and the surface appearance deteriorates.

The filler (C) includes metal powder, oxide, hydroxide, silicic acid or silicate, carbonate, silicon carbide, vegetable fiber,
Animal fibers, synthetic fibers, and the like, as typical examples, for example, natural wood, paper, calcium carbonate, talc,
Glass fiber, magnesium carbonate, mica, kaolin, calcium sulfate, aluminum hydroxide, magnesium hydroxide, silica, clay, zeolite, and waste wood materials, recycled filler materials such as waste paper, and the like, alone or Two or more kinds can be used as a mixture. Among them, the obtained effect is remarkable in the filler made of wood flour, paper, and fiber. The compounding amount of such a filler is preferably 10 to 200 parts by weight based on 100 parts by weight of the thermoplastic resin (A).

In the present invention, a foaming agent can be used, and typical examples thereof include an inorganic foaming agent, a volatile foaming agent,
A decomposition type foaming agent or the like can be used. As inorganic blowing agents, carbon dioxide, air, nitrogen, etc., and as volatile blowing agents, propane, n-butane, isobutane, pentane,
Aliphatic hydrocarbons such as hexane, halogenated hydrocarbons such as trichlorofluoromethane, dichlorofluoromethane, dichlorotetrafluoroethane, methyl chloride, ethyl chloride, and methylene chloride can be used. In addition, azodicarbonamide, dinitrosopentamethylenetetramine, azobisisobutyronitrilyl, sodium bicarbonate, and the like can be used as the decomposition-type foaming agent. These foaming agents can be appropriately mixed and used.

When a foaming agent is used, a foam regulator may be further added to the melt-kneaded material. Examples of the foam control agent include inorganic powders such as talc and silica, acidic salts of polycarboxylic acids, and reaction mixtures of polycarboxylic acids with sodium carbonate or sodium bicarbonate.

[0018] Additives such as stabilizers and lubricants can be added to the resin composition of the present invention, if necessary. As the stabilizer, pentaerythrityl-tetrakis 3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate}, triethylene glycol-bis {3- (3
-T-butyl-5-methyl-4-hydroxyphenyl)
Phenolic stabilizers such as propionate II, tris (monononylphenyl) phosphite, tris (2,
Examples thereof include phosphorus-based stabilizers such as 4-di-t-butylphenyl) phosphite and sulfur-based stabilizers such as dilauroyldipropionate. These may be used alone or in combination of two or more. it can.

Representative examples of the lubricant include sodium, calcium and magnesium salts of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid and the like.
A mixture of more than one species can be used.

The thermoplastic resin composition of the present invention is prepared by mixing a predetermined amount of each of the above-mentioned essential components and, if desired, optional components, and kneading the mixture with a roll, a Banbury mixer, a single-screw extruder, a twin-screw extruder or the like. It is prepared by kneading with a machine. In general, it is preferable to form a pellet. Alternatively, a master batch containing the polytetrafluoroethylene-containing mixed powder (B) at a high concentration may be diluted with the thermoplastic resin (A) and the filler (C) to form a resin composition. The thermoplastic resin composition of the present invention can be applied to various molding methods, and can include injection molding, calendar molding, blow molding, extrusion molding, thermoforming, foam molding, melt spinning, and the like. Examples include injection molded articles, sheets, films, hollow molded articles, pipes, square rods, irregularly shaped articles, thermoformed articles, foams, fibers, and the like. Notable. In extrusion molding, there is no particular limitation, and general extrusion production equipment can be used. The extruder can be a single screw extruder, a parallel twin screw extruder, a conical twin screw extruder, etc.
As the die provided at the tip of the extruder, a generally used die can be used without any limitation.

[0021]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, "part" in an example shows a weight part, and the measurement of the solid content density | concentration etc. was based on the following method. (1) Solid concentration: determined by drying the particle dispersion at 170 ° C. for 30 minutes. (2) Particle size distribution, weight-average particle size: A sample obtained by diluting a particle dispersion with water was subjected to a dynamic light scattering method (“ELS800” manufactured by Otsuka Electronics Co., Ltd., temperature 25 ° C., scattering angle 90).
Degree).

REFERENCE EXAMPLE 1: Polytetrafluoroethylene-containing mixed powder (B-1) In a separable flask equipped with a stirrer, a condenser, a thermocouple, and a nitrogen inlet, 190 parts of distilled water and dodecylbenzenesulfonic acid were added. Sodium 1.
5 parts, 100 parts of styrene and 0.5 part of cumene hydroperoxide were charged and heated to 40 ° C. under a nitrogen stream. Next, a mixed solution of 0.001 part of iron sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.24 part of Rongalit salt, and 10 parts of distilled water was added to carry out radical polymerization. After the end of the heat generation, the temperature in the system was maintained at 40 ° C. for 1 hour to complete the polymerization, and the styrene polymer particle dispersion (hereinafter referred to as P-1)
). Styrene polymer particle dispersion (P-
The solid concentration of 1) was 33.3% by weight, the particle size distribution showed a single peak, and the weight average particle size was 96 nm. On the other hand, as a polytetrafluoroethylene-based particle dispersion, “Fluon AD93” manufactured by Asahi ICI Fluoropolymer Co., Ltd.
6 "was used. The solid content of “Fluon AD936” is 63.0% by weight, and polytetrafluoroethylene 1
It contains 5 parts of polyoxyethylene alkylphenyl ether with respect to 00 parts. "Fluon AD93
The particle size distribution of "6" showed a single peak, and the weight average particle size was 290 nm.

To 833 parts of "Fluon AD936", 1167 parts of distilled water was added to obtain a polytetrafluoroethylene particle dispersion (F-1) having a solid content concentration of 26.2% by weight. Polytetrafluoroethylene particle dispersion (F-1)
Is 25% by weight of polytetrafluoroethylene particles and 1.
It contains 2% by weight of polyoxyethylene nonylphenyl ether. 160 parts of F-1 (40 parts of polytetrafluoroethylene) and 181.8 parts of P-1 (60 parts of polystyrene) were charged into a separable flask equipped with a stirrer, a condenser, a thermocouple, and a nitrogen inlet, The mixture was stirred at room temperature for 1 hour under a nitrogen stream. Thereafter, the inside of the system was heated to 80 ° C. and kept for 1 hour. No solid matter was separated through a series of operations, and a uniform particle dispersion was obtained. The solid content concentration of the particle dispersion was 29.3% by weight, the particle size distribution was relatively broad, and the weight average particle size was 168 nm. 341.8 parts of this particle dispersion was mixed with 85 parts of 5 parts of calcium chloride.
C. into 700 parts of hot water at 700 ° C. to separate solids,
Dried and mixed powder containing polytetrafluoroethylene (B
-1) 98 parts were obtained. After the polytetrafluoroethylene-containing mixed powder (B-1) was shaped into strips at 250 ° C. by a press molding machine, ultrathin sections were observed with a microtome without staining using a transmission electron microscope. Although polytetrafluoroethylene is observed as a dark area, 10 μm
No aggregates exceeding m were observed.

Reference Example 2: Mixed powder containing polytetrafluoroethylene (B-2) Dodecyl methacrylate 75
Azobisdimethylvaleronitrile (0.1 part) was dissolved in a mixed solution of 1 part and 25 parts of methyl methacrylate. Add 2.0 parts of sodium dosylbenzenesulfonate and 3 parts of distilled water
Add 00 parts of the mixed solution, and mix
After stirring for 4 minutes at rpm, the homogenizer was
Passing twice at a pressure of g / cm ² gave a stable dodecyl methacrylate / methyl methacrylate pre-dispersion. This was charged into a separable flask equipped with a stirrer, a condenser, a thermocouple, and a nitrogen inlet, and the internal temperature was raised to 80 under a nitrogen stream.
The mixture was stirred at a temperature of 3 ° C. for 3 hours for radical polymerization to obtain a dodecyl methacrylate / methyl methacrylate copolymer particle dispersion (hereinafter referred to as P-2). The solid concentration of P-2 was 25.1% by weight, the particle size distribution showed a single peak, and the weight average particle size was 198 nm. 160 parts of F-1 (40 parts of polytetrafluoroethylene) and 159.4 parts of P-2 (40 parts of dodecyl methacrylate / methyl methacrylate copolymer) used in Reference Example 1 were mixed with a stirrer, a condenser, and a thermoelectric device. The mixture was charged into a separable flask equipped with a nitrogen inlet and a dropping funnel, and stirred at room temperature for 1 hour under a nitrogen stream. Thereafter, the temperature of the system was raised to 80 ° C., and a mixed solution of 0.001 part of iron sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.24 part of Rongalite salt and 10 parts of distilled water was added, and then methyl methacrylate was added. 2
A mixed solution of 0 parts and 0.1 part of tertiary butyl peroxide was added dropwise over 30 minutes. After completion of the addition, the internal temperature was maintained at 80 ° C. for 1 hour to complete the radical polymerization. No solid content was separated through a series of operations, and a uniform particle dispersion was obtained. The solid content concentration of the particle dispersion is 28.5% by weight, the particle size distribution is relatively broad, and the weight average particle size is 248 n.
m. 349.7 parts of this particle dispersion liquid is poured into 600 parts of 75 ° C. hot water containing 5 parts of calcium chloride, the solid content is separated, filtered and dried to obtain a mixed powder containing polytetrafluoroethylene (B-2). 97 parts were obtained. The dried polytetrafluoroethylene-containing mixed powder (B-2) was mixed with 22
After shaping into a strip shape at 0 ° C. by a press molding machine, ultrathin sections were observed with a microtome without transmission using a transmission electron microscope. Although polytetrafluoroethylene was observed as a dark part, no aggregate exceeding 10 μm was observed.

Reference Example 3: Master batch (M-1) of polytetrafluoroethylene-containing mixed powder] Linear homopolypropylene pellets ("EA" manufactured by Nippon Polychem Co., Ltd.)
7 ", MFR: 1.2 g / 10 min.) 75 parts of the tetrafluoroethylene-containing mixed powder (B
After blending 25 parts of -2) and hand blending, using a twin-screw extruder (“ZSK30” manufactured by Werner & Pfleiderer), a barrel temperature of 200 ° C. and a screw rotation speed of 200 rpm
m, kneaded and shaped into pellets, and a master batch of polytetrafluoroethylene-containing mixed powder (hereinafter, referred to as
M-1).

Examples 1 to 20 and Comparative Examples 1 to 6 The following polypropylene pellets were mixed with the tetrafluoroethylene-containing mixed powder (B-1 to 2) or master pellet (M- Table 1 shows 1) and various fillers
The mixture was blended at the ratio shown in No. 2 and extruded under the following molding machine and conditions to produce a sheet-like molded body. The molded body was observed for strength (impact test) and appearance, and the results are shown in Tables 1 and 2. As a comparative example,
When using commercially available powdered polytetrafluoroethylene ("Fluon CD123" manufactured by Asahi ICI Fluoropolymers Co., Ltd., molecular weight: 12,000,000) not treated with an organic polymer (Comparative Example 1), or a mixed powder containing polytetrafluoroethylene When the amount of the body was out of the specified range and the like, it was molded and tested in the same manner.

Polypropylene: "Novatec PP" manufactured by Nippon Polychem Co., Ltd. "BC05B": MFR; 50 g / 10 min. "BC03B": MFR; 30 g / 10 min. "FY-4": MFR; 5 g / 10 min. Extrusion molding Machine: IKG company Screw diameter: φ50mm single screw extruder, rotation speed 30rpm
m Die shape: width 60 mm, thickness 5 mm Strength of molded body: JIS K-7
It carried out according to 211 and measured the 50% breaking height (cm). Appearance of molded article: The appearance of the sheet was visually judged according to the following criteria. ○: good ×: rough skin or scum

[0028]

[Table 1]

[0029]

[Table 2]

[Examples 21 to 40, Comparative examples 7 to 12] The following polyethylene-containing pellets were mixed with the following polyethylene-containing pellets (B-1 and 2).
Table 3 shows the master pellet (M-1) and various fillers.
To 4, the sheet was extruded using the above-mentioned molding machine and conditions in the same manner as in Examples 1 to 20, and the obtained molded body was evaluated for strength (impact test) and appearance. The results are shown in Tables 3 and 4. As a comparative example,
When using commercially available powdered polytetrafluoroethylene ("Fluon CD123" manufactured by Asahi ICI Fluoropolymers Co., Ltd., molecular weight: 12,000,000) not treated with an organic polymer (Comparative Example 7), or a mixed powder containing polytetrafluoroethylene The case where the amount of the body is out of specification is also shown. Polyethylene: "Novatec" manufactured by Nippon Polychem Co., Ltd. "HD HJ490" (HDPE): MFR; 20 g
/ 10 minutes ・ "LD LJ900N" (LDPE): MFR; 45
g / 10 minutes ・ "HD HJ360" (HDPE): MFR; 5g
/10 minutes

[0031]

[Table 3]

[0032]

[Table 4]

Examples 41 to 53 and Comparative Examples 13 to 18
The following thermoplastic resin-containing pellets were mixed with the tetrafluoroethylene-containing mixed powder (B-1 to
2) Alternatively, the master pellet (M-1) and various fillers were blended in the ratios shown in Tables 5 to 6, and a sheet was extruded using the molding machine and conditions described above in the same manner as in Examples 1 to 40 to obtain a sheet. The obtained molded body was evaluated for strength (impact test) and appearance, and the results are shown in Tables 5 to 6. As a comparative example, a case where a commercially available powdered polytetrafluoroethylene (“Fluon CD123” manufactured by Asahi ICI Fluoropolymers Co., Ltd., molecular weight: 12,000,000) not treated with an organic polymer was used (Comparative Example 13), The case where the amount of the tetrafluoroethylene-containing mixed powder is out of the specified range is also shown.

Linear low-density polyethylene: "Novatec" manufactured by Nippon Polychem Co., Ltd. "UE 320" (LLDPE): MFR; 0.7 g
/ 10 min Polyvinyl chloride: "Shin-Etsu PVC Compound" manufactured by Shin-Etsu Polymer Co., Ltd. "EX 282E" (PVC) Polystyrene: manufactured by A & M Styrene Co., Ltd. "SC001" (PS): MFR: 3.7 g / 10 min Impact Polystyrene : Manufactured by Nippon Polystyrene Co., Ltd. "H450K" (HIPS) poly-1-butene: "Buron" manufactured by Mitsui Petrochemical Co., Ltd. "P5040B": MFR: 0.4 g / 10 min Copolymer of acrylonitrile and styrene: Asahi Kasei Corporation "Styrac"-"AS783" (AS): MFR: 9.0 g / 10 min Copolymer of rubber-reinforced acrylonitrile and styrene (ABS, ASA, SAS): "Diapet ABS" manufactured by Mitsubishi Rayon Co., Ltd. SW-3 "(ABS): MFR; 0.4 g / 10 minutes Methacrylic resin:" Acripet "manufactured by Mitsubishi Rayon Co., Ltd. H "(MMA): MFR; 0.4 g / 10 min Polycarbonate:" NOVAREX "manufactured by Mitsubishi Engineering-Plastics Co., Ltd." 7030A "(PC): MFR; 3.5 g / 10 min Polybutylene terephthalate: manufactured by Mitsubishi Rayon "Dianite""PA-200" (PBT) Polyethylene terephthalate: "Dianight" manufactured by Mitsubishi Rayon Co., Ltd. "N-1000" (PET) Polymethylpentene, copolymer of cyclopentadiene with ethylene and / or propylene, etc. Cyclic polyolefin: manufactured by Mitsui Petrochemical Co., Ltd. "MX001" (PMP): MFR; 26 g / 10 min EVA: "Mitsubishi Polyethylene EVA" manufactured by Mitsubishi Chemical Corporation "LV260": MFR; 8.5 g / 10 min

[0035]

[Table 5]

[0036]

[Table 6]

As is clear from Tables 1 to 6, the molded article of this example has high impact strength and excellent surface appearance.

[0038]

According to the present invention, it is possible to solve the drawbacks of the conventional extruded product using a thermoplastic resin such as polyolefin to which a large amount of filler is added, and to provide a thermoplastic resin and / or a regenerated thermoplastic resin. On the other hand, even if a filler and / or a recycled filler is added, the melt strength during resin molding is excellent, and regardless of the amount of the filler and the presence or absence of a foaming agent, the appearance of the molded body is excellent,
A thermoplastic resin composition and a molded article, particularly an extruded article, having excellent impact strength and suitable for extrusion molding can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI theme coat (Reference) C08L 27:18) (72) Inventor Mamoru Mori 3816 Nototo, Tama-ku, Kawasaki-shi, Kanagawa Prefecture Mitsubishi Rayon Co., Ltd.・ Information center

Claims (3)

[Claims] 1. A polytetrafluoroethylene-containing mixed powder (B) containing a polytetrafluoroethylene particle having a particle diameter of 10 μm or less and an organic polymer with respect to 100 parts by weight of a thermoplastic resin (A), A thermoplastic resin composition characterized in that the amount of the polytetrafluoroethylene component is 0.01 to 20 parts by weight and the filler (C) is 10 to 200 parts by weight. 2. A master pellet containing a polytetrafluoroethylene-containing mixed powder (B) containing polytetrafluoroethylene particles having a particle diameter of 10 μm or less and an organic polymer, and a thermoplastic resin (A); The thermoplastic resin (A) and the filler (C) are mixed such that the amount of the polytetrafluoroethylene component is 0.01 to 20 parts by weight based on 100 parts by weight of the total amount of the thermoplastic resin (A). A method for producing a thermoplastic resin composition. 3. A molded article comprising the thermoplastic resin composition according to claim 1.