JP2002220533A - Thermoplastic resin composition and additive for improving moldability and compatibility and master batch using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which inhibits deposits and plate-out developed, when molded, has excellent continuous moldability, and gives excellent appearance. SOLUTION: The thermoplastic resin composition comprises 100 pts.wt. of a thermoplastic resin, 0.1 to 20 pts.wt. of an acrylic copolymer, and 0.1 to 50 pts.wt. of polytetrafluoroethylene-containing mixture powder comprising polytetrafluoroethylene particles and an organic polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is capable of continuous molding without the occurrence of die build-up or plate-out during molding.
The present invention relates to a thermoplastic resin composition having improved compatibility, an additive for producing the thermoplastic resin composition, and a masterbatch using the same.

[0002]

2. Description of the Related Art Thermoplastic resins are widely used in various fields such as soft or hard films, sheets, flooring materials and irregularly shaped articles. In particular, polyolefin-based resins are widely used in various fields because of their excellent mechanical properties and chemical properties. These are formed by applying various methods such as extrusion, calendar, blow, injection molding, etc., depending on the target product. In addition, various additives, for example, fillers, flame retardants, pigments, etc., are used in order to develop various properties such as required strength according to the target product.

[0003]

However, during molding of a thermoplastic resin, particularly during extrusion molding, calendar molding, and blow molding, deteriorated resin and additives in the resin adhere to the lip of the die. Dust may occur. Further, at the time of molding, plate-out in which the additive in the resin composition migrates to the metal surface in contact with the resin may occur. If such eye frays or plate-outs occur, the appearance of the molded product may deteriorate or subsequent molding may not be possible.Therefore, the molding operation is interrupted at regular intervals and the die lip is cleaned. Must be performed, which greatly reduces productivity.

Japanese Patent Application Laid-Open No. H11-310668 discloses the effect of adding an acrylic polymer lubricant to the prevention of tarnish on a polyolefin-based thermoplastic resin. However, thermoplastic resins other than the polyolefin-based thermoplastic resin and alloys are disclosed. In the case of resin, this method has not always exerted a sufficient effect. In particular, polyolefin-based resins are desired to be imparted with functions by alloying with other thermoplastic resins, but have poor compatibility with other thermoplastic resins and have a drawback that they are difficult to mix, so that The actual condition is that the strength and appearance of the molded product are not obtained.

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic resin composition which suppresses eye frays and plate-out during molding, has excellent continuous moldability, and has a good appearance, an additive therefor, and a masterbatch using the same. Is to provide.

[0006]

The thermoplastic resin composition of the present invention comprises 0.1 to 20 parts by mass of an acrylic polymer copolymer, 100 parts by mass of a thermoplastic resin, and polytetrafluoroethylene particles. 0.1 to 50 parts by mass of a polytetrafluoroethylene-containing mixed powder composed of an organic polymer.

The additive of the present invention comprises an acrylic polymer copolymer and a polytetrafluoroethylene-containing mixed powder comprising polytetrafluoroethylene particles and an organic polymer.

Further, the masterbatch of the present invention comprises a mixture of an acrylic polymer copolymer, a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer, and a thermoplastic resin. It has been done.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the thermoplastic resin composition of the present invention, various commonly used olefin resins can be applied to the thermoplastic resin serving as a matrix resin, and specifically, PP, HDPE, LDPE , LLDPE, ethylene-propylene random or block copolymer, and the like. These are preferred in that they have high versatility and are inexpensive. These olefin resins may be used in combination of two or more kinds.
FR is not particularly limited.

[0010] The thermoplastic resin serving as the matrix resin includes:
Other thermoplastic resins besides olefin resins can also be used, for example, styrene resins such as polystyrene (PS) and styrene / acrylonitrile copolymer resin (SAN); and acrylic vinyl such as polymethyl methacrylate (PMMA). Polymer; polyvinyl chloride resin (PV
C), polyphenylene ether resin (PPE) and its modified products, aromatic polyester resin (PET, PBT),
Polyamide resins (PA) such as polycarbonate resin (PC), polycaproamide (nylon 6), and polyhexamethylene adipamide (nylon 66).
These can be used in combination of two or more, and can also be used in combination with one or more olefin-based resins. However, the above-mentioned number of types of thermoplastic resin does not include the thermoplastic resin constituting the mixed powder containing acrylic polymer and polytetrafluoroethylene described below.

As the thermoplastic resin used as the matrix in the present invention, it is preferable to use two or more different thermoplastic resins from the viewpoint that the effects of the present invention are more exhibited. It is preferably a mixture of other thermoplastic resins.

The acrylic polymer copolymer used in the present invention is a copolymer containing an acrylic monomer as a main component, and has an alkyl group of a (meth) acrylic acid alkyl ester unit having 1 to 18 carbon atoms. And a vinyl monomer unit copolymerizable therewith. When an alkyl group having 19 or more carbon atoms is used, the copolymerization reaction tends to be difficult. Such alkyl (meth) acrylates include, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, methyl acrylate, acrylic Ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, and the like. These may be used alone or in combination of two or more. Can be. Examples of the vinyl monomer copolymerizable therewith include, for example, styrene, α-methylstyrene, acrylonitrile, vinyl acetate and the like, and these can be used alone or in combination of two or more.

The acrylic polymer copolymer comprises 40 to 95% by weight of an alkyl methacrylate, 5 to 60% by weight of an alkyl acrylate, and 0 to 30% of another vinyl monomer copolymerizable therewith. It is preferable to use a polymer consisting of% by mass.

Further, the acrylic polymer copolymer is as follows:
Preferably, the polymer has a reduced viscosity (η sp / C) of 3 or less, more preferably 1 or less. The acrylic polymer copolymer has a reduced viscosity (η
When the polymer (sp / C) is larger than 3, the lubricating effect tends to be lost. It should be noted that the reduced viscosity (η
(sp / C) is defined as 0. 1 in 100 ml of chloroform.
It refers to the reduced viscosity measured at 25 ° C. of a solution in which 1 g of a polymer is dissolved.

In the production of the acrylic polymer copolymer, an emulsion polymerization method is the most suitable polymerization method, and the polymerization can be carried out in one step or in multiple steps. To achieve both lubricity and dispersibility, polymerization in two or three stages is preferred. When produced by an emulsion polymerization method, the acrylic polymer copolymer is obtained in a latex state. Therefore, various means are used to make it solid. Generally, it can be obtained as a powder by a rapid coagulation method using an acid or a salt.

The acrylic polymer copolymer can exert the effect of the present invention even when used in the form of a powder added to a thermoplastic resin, but the thermoplastic resin as a matrix resin is usually in the form of beads. In many cases, the powder is in the form of particles or pellets. If the powder is used as it is, the powder may be classified.

As a means for forming a granular powder, a solvent is added during the coagulation of the latex with an acid or a salt, and the resulting solution is subjected to acid precipitation to form a granule, or under a slow condition using an acid or a salt. A means by a slow coagulation method to coagulate and precipitate out by acidification to form granules, a means by a spray dry method of spraying latex in a high-temperature air stream and drying to form granulated powders, and the like can be used.

The polytetrafluoroethylene-containing mixed powder used in the present invention comprises polytetrafluoroethylene particles and an organic polymer. Polytetrafluoroethylene particles have a particle size of 10 μm or less,
10 μm polytetrafluoroethylene in powder
It is preferable that the above aggregates are not formed. Such a polytetrafluoroethylene-containing mixed powder can be produced by various methods, and 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 used. A method of mixing and powdering by dispersion or coagulation or spray drying to produce an organic polymer in the presence of an aqueous dispersion of polytetrafluoroethylene particles having a particle size of 0.05 to 1.0 μm. A method in which a monomer is polymerized and then produced by pulverization by coagulation or spray drying, or an aqueous dispersion of polytetrafluoroethylene particles having a particle diameter of 0.05 to 1.0 μm and an aqueous dispersion of organic polymer particles A method in which a monomer having an ethylenically unsaturated bond is emulsion-polymerized in a dispersion mixed with a liquid and then powdered by coagulation or spray drying to produce the same. It is preferable that more obtained.

The above-mentioned aqueous dispersion of polytetrafluoroethylene particles having a particle size of 0.05 to 1.0 μm can be obtained by polymerizing a tetrafluoroethylene monomer by an emulsion polymerization method using a fluorinated surfactant. In this emulsion polymerization, a fluorinated olefin such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, or perfluoroalkylvinyl ether, or a perfluoroalkyl ( Fluorine-containing alkyl (meth) such as (meth) acrylate
Acrylates can be used. The content of the copolymer component was 10% by mass based on the weight of tetrafluoroethylene.
The following is preferred.

Aqueous dispersions of polytetrafluoroethylene particles are commercially available, Fluon AD-1, AD-936 manufactured by Asahi ICI Fluoropolymer Co., Ltd., Polyflon D-1, D-2 manufactured by Daikin Industries, and DuPont Mitsui. A typical example is Teflon 30J manufactured by Fluorochemicals.

The organic polymer constituting the polytetrafluoroethylene-containing mixed powder is not particularly limited. However, from the viewpoint of dispersibility when added to a thermoplastic resin which is a matrix resin, the organic polymer may be mixed with the matrix resin. Is preferably high in affinity.

Specific examples of monomers for producing such an organic polymer include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, t-butylstyrene, and o-ethylstyrene. , P-chlorostyrene, o-chlorostyrene, 2,4-dichlorostyrene,
p-methoxystyrene, o-methoxystyrene, 2,4
-Aromatic vinyl monomers such as dimethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate,
Ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, (Meth) acrylate monomers such as cyclohexyl acrylate and cyclohexyl methacrylate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; α, β-unsaturated carboxylic acids such as maleic anhydride; Maleimide monomers such as phenylmaleimide, N-methylmaleimide and N-cyclohexylmaleimide; glycidyl group-containing monomers such as glycidyl methacrylate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether Vinyl monomers such as vinyl acetate and vinyl butyrate; olefin monomers such as ethylene, propylene and isobutylene; and diene monomers such as butadiene, isoprene and dimethylbutadiene. be able to. These monomers can be used alone or in combination of two or more.

Among these monomers, preferred are aromatic vinyl monomers, (meth) acrylates, from the viewpoints of imparting affinity, coloring properties and adhesion to thermoplastic resins, especially polyolefin resins. Acrylic ester monomers and vinyl cyanide monomers can be mentioned.

The content of polytetrafluoroethylene in the polytetrafluoroethylene-containing mixed powder used in the present invention is preferably 0.5 to 80% by mass.
If the content of polytetrafluoroethylene is less than 0.5% by mass, the compatibilizing effect is insufficient, and if it exceeds 80% by mass, the dispersibility tends to be poor and the surface appearance tends to be insufficient.

The mixed powder containing polytetrafluoroethylene used in the present invention is poured into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, salted out, solidified, and dried. Or powdered by spray drying. Although ordinary polytetrafluoroethylene fine powder becomes an aggregate of 100 μm or more in the process of recovering as a powder from the state of a particle dispersion, it is difficult to uniformly disperse it in an olefin resin. On the other hand, according to the above-mentioned production method, polytetrafluoroethylene alone has a particle diameter of 1
Since no domain exceeding 0 μm is formed, the dispersibility in the polyolefin resin is extremely excellent. As a result, polytetrafluoroethylene is efficiently fiberized in the matrix resin, imparts compatibility between the alloy resins (particularly, between the polyolefin resin and another thermoplastic resin), and has excellent surface properties. Provides a thermoplastic resin.

The addition ratio of the acrylic polymer copolymer to the thermoplastic resin is 0.1 to 20 parts by mass of the acrylic polymer copolymer per 100 parts by mass of the thermoplastic resin. If the amount of the acrylic polymer copolymer is less than 0.1 part by mass, the effect cannot be sufficiently obtained. If the amount exceeds 20 parts by mass, the surface of the molded article tends to have bumps and the appearance tends to deteriorate. is there.

The mixing ratio of the polytetrafluoroethylene-containing mixed powder is 0.1 to 5 parts per hundred parts by mass of the thermoplastic resin.
0 parts by mass. If the addition amount is less than 0.1 part by mass, the effect of improving compatibility is poor, and if it exceeds 50 parts by mass, the surface appearance tends to deteriorate.

The acrylic polymer copolymer and the polytetrafluoroethylene-containing mixed powder can be separately added to the thermoplastic resin, but the acrylic polymer copolymer and the polytetrafluoroethylene-containing mixed powder can be added separately. It is preferable to mix the powder with the powder in advance and prepare it as an additive, because the classification can be reduced. If such additives are used as pellet-like particles, the classification can be further reduced. Examples of the means for forming pellet-shaped particles include an extrusion granulation method using an extruder, a roll-pellet method for cutting a roll sheet to obtain cube-shaped pellets, and a means for pelletizing with a briquetting roll having a pellet-shaped dent. Etc. can be used. In this case, in order to improve the dispersibility in the matrix resin, it is preferable to compress as loosely as possible into pellet-like particles.

Further, a masterbatch is prepared by diluting an acrylic polymer copolymer and a mixed powder containing polypolytetrafluoroethylene with a thermoplastic resin, and this masterbatch is mixed with a thermoplastic resin serving as a matrix. This is preferable because the dispersibility of the acrylic polymer copolymer and polytetrafluoroethylene in the thermoplastic resin can be further improved. In this case, the content of the thermoplastic resin for dilution in the master batch is preferably set to 70% by mass or less. When the content of the thermoplastic resin for dilution exceeds 70% by mass, productivity tends to decrease.
The content of the thermoplastic resin for dilution in the master batch is 30.
More preferably, it is within the range of 60% by mass. The type of the thermoplastic resin for dilution used in the preparation of the masterbatch does not need to be the same as the matrix resin as long as it is dispersed in the matrix resin at the time of molding. preferable.

[0030] The masterbatch is preferably formed into pellet-like particles. An extrusion method and a roll pellet method can be used as a method for producing a masterbatch which is a pellet-like particle.

Various additives such as a filler, a flame retardant, a pigment or a dye can be added to the thermoplastic resin composition of the present invention. Examples of the filler include talc, mica, calcium carbonate, clay and the like, and examples of the flame retardant include hydrated metal compounds such as Al (OH) ₃ and Mg (OH) ₂ , red phosphorus, metal oxide, stannic acid A combination of zinc, metal sulfate, etc., silicone oil, silicone polymer, silicone flame retardant such as fumed silica, phosphoric acid compound such as red phosphorus, phosphate ester, ammonium polyphosphate, and halogen flame retardant are pigments Examples of the dye include titanium oxide and ultramarine blue. If necessary, lubricants,
Additives such as stabilizers, foaming agents and antistatic agents may be added. Further, another compatibilizer may be used in combination.

The thermoplastic resin composition of the present invention is obtained by mixing the above-mentioned mixed powder containing polytetrafluoroethylene, an acrylic polymer copolymer and a thermoplastic resin so that the dispersibility becomes good. It may be prepared. For the thermoplastic resin composition of the present invention, various well-known molding methods can be applied depending on a target molded product. For example, a film using a T-die, sheet extrusion molding, profile extrusion molding, calendar molding, Blow molding or the like can be applied.

[0033]

EXAMPLES The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention thereto. In the description of Examples, "parts" and "%" are based on mass, respectively, and various physical properties are measured by the following methods. [Solid content concentration] It was determined by drying the particle dispersion at 170 ° C for 30 minutes. [Particle size distribution, weight average particle size] A particle dispersion diluted with water was used as a sample solution and measured by a dynamic light scattering method (ELS800, manufactured by Otsuka Electronics Co., Ltd., temperature: 25 ° C, scattering angle: 90 °). . [Zeta potential] The particle dispersion was treated with 0.01 mol / L NaC.
The solution diluted with 1 aqueous solution was used as a sample solution and measured by electrophoresis (ELS800, manufactured by Otsuka Electronics Co., Ltd., temperature 25 ° C., scattering angle 10 °).

Reference Example 1 Production of Acrylic Polymer Copolymer (A) In a reactor equipped with a stirrer and a reflux condenser,
280 parts of ion-exchanged water, 1.5 parts of potassium alkenyl succinate, 2 parts of ammonium persulfate, 25 parts of methyl methacrylate and 0.05 part of n-octyl mercaptan were charged, and the inside of the vessel was replaced with nitrogen. The mixture was heated and stirred for 2 hours. Subsequently, a mixture of 25 parts of n-butyl methacrylate, 25 parts of n-butyl acrylate and 0.5 part of n-octyl mercaptan was added dropwise over 1 hour, and the mixture was further stirred for 2 hours after completion of the addition.

Thereafter, a mixture of 25 parts of methyl methacrylate and 0.03 parts of n-octyl mercaptan was added to the reaction system over 30 minutes, and the mixture was further stirred for 2 hours. A copolymer (LA) was obtained. The reduced viscosity (η sp / C) of this acrylic polymer copolymer was 0.8.

A reactor equipped with a stirrer was charged with 600 parts of ion-exchanged water and 3 parts of sulfuric acid, heated to 50 ° C., charged with the prepared latex LA over 5 minutes while stirring, and added 95% after the charging. After raising the temperature to 5 ° C. and holding for 5 minutes, filtration, washing and drying were performed to obtain an acrylic polymer copolymer (A) as an acid precipitate.

Reference Example 2: Production of polytetrafluoroethylene-containing mixed powder (B-1) As a dispersion of polytetrafluoroethylene-based particles, Fluon AD936 manufactured by Asahi ICI Fluoropolymers was used. AD936 has a solids concentration of 63.0% and contains 5 parts of polyoxyethylene alkylphenyl ether per 100 parts of polytetrafluoroethylene. The particle size distribution of AD936 shows a single peak, and the weight average particle size is 290.
nm and the surface potential was -20 mV.

In a separable flask equipped with a stirring blade, a condenser, a thermocouple, a nitrogen inlet, and a dropping funnel, 8
To 33 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%. (F-1) contained 25% of polytetrafluoroethylene particles and 1.2% of polyoxyethylene nonylphenyl ether.

(F-1) 160 parts (polytetrafluoroethylene 40 parts), dodecylbenzenesulfonic acid 1.0
And 70 parts of distilled water, and heated to 80 ° C. under a nitrogen stream. Next, a mixed solution of 0.001 part of iron (II) sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.24 part of Rongalite salt and 10 parts of distilled water was added, and 20 parts of n-butyl acrylate and styrene were added. A mixture of 40 parts and 0.3 part of tertiary butyl peroxide was dropped from the dropping funnel over 90 minutes to allow radical polymerization to proceed, and after the completion of dropping, the internal temperature was maintained at 80 ° C. 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 33.2%, the particle size distribution was relatively broad, and the weight average particle size was 248 nm.

301.5 parts of this particle dispersion was poured into 700 parts of 85 ° C. hot water containing 5 parts of calcium chloride to separate a solid, filtered and dried to obtain a mixed powder containing polytetrafluoroethylene. (B-1) 98 parts were obtained. (B-
After 1) was shaped into a strip by a press molding machine at 250 ° C., ultrathin sections were observed with a microtome without staining using a transmission electron microscope. Although polytetrafluoroethylene was observed as a dark part, no aggregate exceeding 10 μm was observed.

Reference Example 3: Production of mixed powder containing polytetrafluoroethylene (B-2) 0.1 part of azobisdimethylvaleronitrile was dissolved in a mixed solution of 75 parts of dodecyl methacrylate and 25 parts of methyl methacrylate. . A mixed solution of 2.0 parts of sodium dodecylbenzenesulfonate and 300 parts of distilled water was added thereto, and mixed with a homomixer.
After stirring at 0000 rpm for 4 minutes, the mixture was passed through a homogenizer twice at a pressure of 30 MPa to obtain a stable dodecyl methacrylate / methyl methacrylate preliminary dispersion. This was charged into a separable flask equipped with a stirring blade, a condenser, a thermocouple and a nitrogen inlet, the internal temperature was raised to 80 ° C. under a nitrogen stream, and the mixture was stirred for 3 hours to undergo radical polymerization.
A dodecyl methacrylate / methyl methacrylate copolymer particle dispersion (hereinafter referred to as LB-2) was obtained. LB-
The solid content concentration of No. 2 was 25.1%, the particle size distribution showed a single peak, the weight average particle size was 198 nm, and the surface potential was -39 mV.

160 parts of (F-1) used in Reference Example 2 (40 parts of polytetrafluoroethylene) and 159.4 parts of LB-2 (40 parts of dodecyl methacrylate / methyl methacrylate copolymer) were stirred with a stirring blade. , A condenser, a thermocouple, a nitrogen inlet and a dropping funnel, and stirred for 1 hour at room temperature under a nitrogen stream. Thereafter, the temperature in the system was raised to 80 ° C.
01 parts, disodium ethylenediaminetetraacetate 0.00
After adding a mixture of 3 parts, 0.24 part of Rongalite salt and 10 parts of distilled water, a mixture of 20 parts of methyl methacrylate and 0.1 part of tertiary butyl peroxide was added to 3 parts.
The solution was added dropwise over 0 minutes, and after completion of the addition, the internal temperature was maintained at 80 ° C. for 1 hour to complete the radical polymerization. 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 28.5%, the particle size distribution was relatively broad, and the weight average particle size was 248 nm.

349.7 parts of this particle dispersion was poured into 600 parts of 75 ° C. hot water containing 5 parts of calcium chloride to separate a solid, filtered and dried to obtain a mixed powder containing polytetrafluoroethylene. (B-2) 97 parts were obtained. The dried (B-2) was shaped into a strip shape at 220 ° C. by a press molding machine, and the ultrathin section was observed with a microtome without staining using a transmission electron microscope. Although polytetrafluoroethylene was observed as a dark part, no aggregate exceeding 10 μm was observed.

Reference Example 4: Production of mixed pellet (C-1) Acrylic polymer copolymer (A) and polytetrafluoroethylene-containing mixed powder (B-1) were extruded into a 30 mm bidirectional twin screw extruder. The mixture was extruded at a head temperature of 150 ° C. and a rotation speed of 50 rpm by using to obtain a mixed pellet (C-1).

Reference Example 5 Production of Mixed Pellets (C-2) Acrylic polymer copolymer (A) and polytetrafluoroethylene-containing mixed powder (B-2) were mixed with a 30 mmφ bidirectional twin screw extruder. The mixture was extruded at a head temperature of 150 ° C. and a rotation speed of 50 rpm using a mixed pellet (C-2).
I got

Reference Example 6 Production of Master Pellets (D) of Mixed Powder Containing Acrylic Polymer and Polytetrafluoroethylene] Linear homopolypropylene pellets (EA7: MFR1.2 / Nippon Polychem) 10 minutes)
5 parts of the acrylic polymer copolymer (A) obtained in Reference Example 1 and 20 parts of the tetrafluoroethylene-containing mixed powder (B-2) obtained in Reference Example 3 were blended into 75 parts, and hand After blending, the twin screw extruder (Werner & Pfleid)
erer ZSK30), barrel temperature 200
The mixture was melt-kneaded at 200 ° C. and a screw rotation speed of 200 rpm, and shaped into pellets to obtain master pellets (D) of a mixed powder containing polytetrafluoroethylene.

[Production of olefin-based thermoplastic resin composition] Examples 1-27 and Comparative Examples 1-17 As shown in Tables 1-3, each olefin-based thermoplastic resin and various additives were mixed using a mixer. And pelletized at a die temperature of 200 ° C. using a twin-screw extruder.
A blend of the above-mentioned acrylic polymer copolymer and polytetrafluoroethylene-containing mixed powder or a mixed pellet or a master pellet thereof was added thereto and mixed to produce each olefin-based thermoplastic resin composition.

With respect to each of the obtained olefin-based thermoplastic resin compositions, classification in an extruder hopper, occurrence of tanning, appearance in a molded product, moldability such as generation of plate-out, peeling surface impact strength, phase The physical properties of the molded product, such as solubility and appearance, were evaluated. In addition, in Tables 1-3, thermoplastic resin,
The following additives were used. PP: Novatec FY-4 HDPE manufactured by Nippon Polychem Co., Ltd. Novatec HY430 LDPE manufactured by Nippon Polychem Co., Ltd .: Novatec HE30 LLDPE manufactured by Nippon Polychem Co., Ltd. LLDPE: Novatec UR35 manufactured by Nippon Polychem Co., Ltd.
0 PET: Diamond Night KR-56 manufactured by Mitsubishi Rayon Co., Ltd.
0 Recycled PET: PET obtained by removing bottles of other materials using X-rays from a group of used bottles mainly composed of PET bottles for beverages, etc., which are used by general consumers and collected separately. After washing the bottle group with a weakly alkaline aqueous solution and water, wet grinding, and then using a difference in specific gravity to separate resin pieces and metal pieces other than polyethylene terephthalate, crushed PET bottles PBT: Mitsubishi Rayon Toughpet N1000 by Sumitomo Chemical Co., Ltd. PS: Sumibright M140 by Sumitomo Chemical Co., Ltd. Sumibright E580 by Sumitomo Chemical Co., Ltd. PMMA: Acrypet VH PVC by Mitsubishi Rayon Co., Ltd .: Polyvinyl chloride by Shin-Etsu Chemical Co., Ltd. Resin TK70
0 100 parts, dioctyltin mercaptide 3 parts as stabilizer and lubricant, METABLEN P-5 manufactured by Mitsubishi Rayon Co., Ltd.
50 2 parts and Metabrene P- manufactured by Mitsubishi Rayon Co., Ltd.
710 A mixture obtained by mixing 1 part with a Henschel mixer until the temperature reaches 110 ° C. for 10 minutes. PC: Novarex 7022A manufactured by Mitsubishi Engineering-Pla Corporation PPE: (2,6-dimethyl-1,4-phenylene) ether, reduced viscosity (ηsp / c) = 0.59 dl / g PA6: CM1017 PA66 manufactured by Toray Industries, Inc. : CM3001N ABS manufactured by Toray Industries, Inc.: Diapet 3001 manufactured by Mitsubishi Rayon Co., Ltd. The evaluation method was as follows. [Classification in Extruder Hopper] The classification in the hopper during extrusion with a 30 mmφ single screw extruder was visually observed. ○: No classification △: Somewhat classification ×: Direct classification Was measured. [Appearance of Molded Article] The number of bumps formed on the surface in 1 m ^{2 of the} molded article was measured. [Plate-out] Using a two-roll mill at a temperature of 230
At ℃, the roll surface during the molding was visually observed. ○: No plate-out △: Roll surface was slightly contaminated ×: Roll surface was very contaminated [Peel surface impact strength] Pelletized using 30 mm φ co-axial twin screw extruder, and sampled using 30 mm φ single screw extruder (Thickness: 1 mm) and molded with a DuPont impact tester (50
(0 g load) to measure the height at which delamination or destruction occurred. The measurement conditions were a temperature of 23 ° C. and a humidity of 50%.
Unit (cm) [Compatibility] 0.1 parts of Bengala is added to the mixture, and 30 mm
φPelletize using the same direction twin screw extruder, 30mmφ
A test piece (thickness: 1 mm) was molded using a single screw extruder, and coloring unevenness of the molded product was visually evaluated according to the following criteria. ：: A molded product having a uniform color tone without coloring unevenness can be obtained. △: Slightly uneven coloring can be seen. ×: The colored portion and the non-colored portion can be clearly distinguished. [Appearance] A specimen is inspected using a 75-ton injection molding machine. After molding, the surface appearance of the molded article was evaluated according to the following criteria. ：: Smooth and good appearance △: Slight surface roughness is observed ×: Surface roughness is severe and appearance is poor

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

From Tables 1 to 3, it can be seen that, in the case of the thermoplastic resin composition of the comparative example, the tanning occurs and the plate-out occurs in a short time. If there is, it can be seen that the eye stain does not occur for a long time, and the plate out can be reliably prevented. Further, the compatibility is good, and an excellent appearance can be obtained.

[0053]

Industrial Applicability The thermoplastic resin composition of the present invention can prevent eye fray and plate-out occurring during molding, is excellent in continuous moldability, and is particularly excellent in compatibility with a polyolefin resin having good compatibility. An alloy with a thermoplastic resin can be obtained, and a product having physical properties according to the purpose and excellent appearance can be obtained.

Continued on the front page (72) Inventor Masaaki Mohri 3816 Noboru Noto, Tama-ku, Kawasaki City, Kanagawa Prefecture F-term (reference) 4F070 AA11 AA13 AA18 AA22 AA24 AA32 AA41 AA47 AA54 AA71 FA03 FB03 4J002 AA011 AA014 BB001 BB031 BB051 BB151 BC004 BC031 BC061 BD041 BD153 BG004 BG042 BG052 BG061 BG062 CF061 CF071 CH071 CL011 CL031

Claims (10)

[Claims] 1. A polytetrafluoroethylene-containing mixed powder composed of 0.1 to 20 parts by mass of an acrylic polymer copolymer, polytetrafluoroethylene particles and an organic polymer with respect to 100 parts by mass of a thermoplastic resin. 0.1 to 50 parts by mass of a thermoplastic resin composition. 2. The thermoplastic resin composition according to claim 1, comprising two or more thermoplastic resins. 3. The polytetrafluoroethylene-containing mixed powder comprises polytetrafluoroethylene particles having a particle diameter of 10 μm or less and an organic polymer, and the polytetrafluoroethylene content in the mixed powder is 0.5 to 80. The thermoplastic resin composition according to claim 1, which is in mass%. 4. An acrylic polymer copolymer comprising a (meth) acrylic acid alkyl ester unit having an alkyl group of 1 to 18 carbon atoms and a vinyl monomer unit copolymerizable therewith. The thermoplastic resin composition according to any one of claims 1 to 3, which is a union. 5. The thermoplastic according to claim 1, wherein the acrylic polymer copolymer has a reduced viscosity (η sp / C) at 25 ° C. of 3 or less. Resin composition. 6. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 5. 7. An additive comprising an acrylic polymer copolymer and a polytetrafluoroethylene-containing mixed powder comprising polytetrafluoroethylene particles and an organic polymer. 8. The additive according to claim 7, which is in the form of pellet-like particles. 9. A masterbatch comprising a mixture of an acrylic polymer copolymer, a polytetrafluoroethylene-containing mixed powder comprising polytetrafluoroethylene particles and an organic polymer, and a thermoplastic resin. 10. The method according to claim 9, wherein the particles are in the form of pellets.
Master batch described.