JP5264790B2 - Thermoplastic resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition that exhibits excellent flame retardancy, surely prevents adhesion of a flame-retardant and the like in a molding process, retains rigidity and toughness without deteriorating surface appearances and has high heat resistance. <P>SOLUTION: The thermoplastic resin composition comprises 100 pts.mass of a synthetic resin (A) composed of a thermoplastic resin having a true specific gravity of at most 1.2 g/mL and 1-40 pts.mass of a chlorite group mineral (B). <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a thermoplastic resin composition and a molded article.

  As a method of making flame-retardant synthetic resin flame retardant, a method such as adding a halogen compound or antimony trioxide has been generally used, but it is not preferable from the viewpoint of environmental hygiene. Therefore, improvement of flame retardant technique is desired.

Flame retardant methods other than the addition of halogen compounds or antimony trioxide include, for example, triphenyl phosphate, cresyl diphenyl phosphate, tricresin in flame retardant of polyphenylene ether or a mixed resin of styrene resin with this. There are methods using organic phosphate ester flame retardants such as monophosphate esters such as zilpphosphate, and condensed phosphate esters of resorcinol or bisphenol A and phenol compounds.
However, according to the above method, there are problems such as heat resistance, deterioration of physical properties, water absorption under high temperature and high humidity, smoke generation at the time of injection molding, and adhesion of flame retardant to the mold.
Among them, it is disclosed that the condensed phosphate ester obtained from bisphenol A and a phenol compound has relatively few problems as described above (for example, see Patent Documents 1 and 2).

Further, regarding the flame retardancy of polyphenylene ether or a mixed resin of this and a styrene resin, a resin composition containing a phosphazene compound such as phenoxyphosphazene as a flame retardant is disclosed (for example, see Patent Documents 3 and 4). .)
Furthermore, a resin composition in which a phosphinate or diphosphinate and / or a polymer thereof and a specific nitrogen compound are blended as a flame retardant is disclosed in a thermoplastic resin (see, for example, Patent Document 5).

On the other hand, as a technology to improve rigidity, toughness, etc., by blending a layered silicate mineral intercalated with an organic agent into a polyphenylene ether resin, there is little increase in specific gravity, and without reducing the appearance of the molded product surface. A method of adding a small amount of a layered silicate mineral that has been subjected to an interlayer treatment with an organic agent such as a quaternary ammonium compound substituted with an alkyl group is disclosed (see, for example, Patent Documents 6 and 7).
In these patent documents, when a layered silicate mineral is added to a polyphenylene ether resin or a thermoplastic resin containing the same, the layered silicate mineral is uniformly finely dispersed in the resin in order to maintain ductility. It is preferable that, for that purpose, melt kneading with a strong shearing force as in a twin-screw extruder is necessary, and that a resin component and a layered silicate mineral are preliminarily kneaded in advance.
Patent Document 7 discloses that a thermoplastic resin in any form such as addition of the layered silicate mineral under mechanical shearing in a molten state of the resin, powder, flakes, chips, etc. after polymerization is completed. A method is also described in which the layered silicate mineral is added to the mixture and melt mixed in a kneader such as an extruder (see, for example, Patent Document 7).

In addition, the polyphenylene ether resin is mixed with a layered silicate mineral that has been treated with an organic agent and a polar compound such as phosphite to improve the dispersibility of the layered silicate mineral in the resin. Also disclosed is a technique for improving the rigidity, tensile elongation, and durability of a molded product (see, for example, Patent Document 8).
Furthermore, a technique relating to a resin composition having excellent flame retardancy, in which a polyphenylene ether resin is blended with a layered silicate and a non-halogen flame retardant such as a phosphate ester flame retardant or magnesium hydroxide is also disclosed. (For example, refer to Patent Document 9).

JP-A-5-186681 JP 7-038776 A Japanese Patent Publication No. 3-73590 Japanese Patent Laid-Open No. 9-71708 JP 2000-508365 gazette Japanese Patent No. 3261784 Japanese Patent No. 3269277 JP 2002-256144 A JP 2003-26915 A

  However, in the techniques described in Patent Documents 1 to 4, sufficient flame retardancy is obtained by blending a polyphenylene ether with a flame retardant such as the above-described organic phosphate ester, condensed phosphate ester, or phosphazene compound. When doing, there exists a problem that the heat resistance and rigidity of polyphenylene ether will be impaired.

  Moreover, in the resin composition which mix | blended the thermoplastic resin described in the said patent document 5 with the phosphinate or diphosphinate and / or these polymers, and the specific nitrogen compound as a flame retardant, sufficient flame retardant There are problems in practical use such as adhesion of a flame retardant (mold deposit) to the mold during injection molding.

  Furthermore, in the techniques described in Patent Documents 6 and 7, when a layered silicate mineral that has been subjected to an interlayer treatment with an organic agent is blended with a polyphenylene ether resin, the rigidity and the surface appearance of the molded product are not deteriorated. Although the toughness is improved, the flame retardancy of the polyphenylene ether-based resin is remarkably lowered, and there is a problem that a sufficient flame retarding effect cannot be obtained even if a flame retardant is used.

  Moreover, in the technique described in the above-mentioned Patent Document 8, when a layered silicate mineral subjected to an interlayer treatment with an organic agent and a polar compound such as phosphite are blended, an effect of improving flame retardancy is obtained. There is a problem that can not be.

  Furthermore, it is described in the above-mentioned Patent Document 9, and in the technique of adding a layered silicate and a non-halogen flame retardant such as a phosphate ester flame retardant or magnesium hydroxide to a polyphenylene ether resin, molding is performed. It is still effective to obtain a polyphenylene ether resin composition that retains good surface gloss, imparts excellent surface impact resistance, tensile elongation and rigidity balance, and has excellent flame retardancy. It is insufficient.

  Therefore, in view of the above-mentioned problems of the prior art, the present invention is excellent in flame retardancy, can reliably prevent adhesion of flame retardant (mold deposit) to the mold during injection molding, and has a good surface appearance. It is an object of the present invention to provide a thermoplastic resin composition having practically good rigidity and toughness and high heat resistance.

The inventors of the present invention have intensively studied to solve the above problems.
As a result, a thermoplastic resin composition using a thermoplastic resin and a chlorite group mineral as a specific inorganic filler in a predetermined ratio is excellent in flame retardancy, suppresses adhesion of flame retardant, etc., and has a surface appearance. The present inventors have found that a thermoplastic resin having high heat resistance can be obtained while maintaining rigidity and toughness without deteriorating, and the present invention has been completed.
That is, the present invention is as follows.

[1]
A synthetic resin (A) made of a thermoplastic resin having a true specific gravity of 1.2 g / mL or less , comprising a polyphenylene ether resin (a) and a styrene resin (b) (A) : 100 parts by mass ,
A thermoplastic resin composition containing chlorite group mineral (B): 1 to 40 parts by mass.

[2]
The thermoplastic resin composition according to [1] , wherein the chlorite group mineral (B) is chlorite.

[3]
The synthetic resin (A) made of the thermoplastic resin is a polyphenylene ether resin (a) 5 to 5.
100 parts by weight of a styrene resin (b) consists of 95 to 1 part by weight,
The chlorite (B) is added to 1 to 100 parts by mass of the total amount of (a) and (b).
The thermoplastic resin composition according to [1] or [2] , containing 40 parts by mass.

[4]
A molded article molded using the thermoplastic resin composition according to any one of [1] to [3] .

[5]
The molded product according to [4] , which is an electrical / electronic component.

[6]
The molded product according to [4] or [5] , which is an electric / electronic part for automobiles.

  According to the present invention, it is possible to provide a thermoplastic resin composition that is excellent in flame retardancy, can prevent adhesion of a flame retardant, maintains rigidity and toughness without deteriorating the surface appearance, and has high heat resistance. can do.

Hereinafter, modes for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail.
In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present embodiment has a synthetic resin (A) containing a thermoplastic resin having a true specific gravity of 1.2 g / mL or less: 100 parts by mass and a chlorite group mineral (B): 1 to 40 masses. Part.

<Synthetic resin (A)>
The synthetic resin (A) constituting the thermoplastic resin composition of the present embodiment is made of a thermoplastic resin having a true specific gravity of 1.2 g / mL or less, and may be a mixture or polymer alloy composed of two or more kinds.
When the true specific gravity is 1.2 g / mL or less, weight reduction as a thermoplastic resin can be achieved, and dripping can be effectively suppressed due to low specific gravity during combustion.
Moreover, by using a lightweight thing as a thermoplastic resin, the weight of a thermoplastic resin composition becomes light and reduction of the cost at the time of transport is achieved.
The true specific gravity means “weight per unit volume without voids”. For example, an immersion method (Archimedes) using isopropyl alcohol or butanol in an atmosphere at an ambient temperature of 25 ° C. and a relative humidity of 50%. Method).

  As the thermoplastic resin having a true specific gravity of 1.2 g / mL or less, from the viewpoint of easy availability, polyphenylene ether resin, styrene resin, polyolefin resin, acrylonitrile / butadiene / styrene resin, methacryl resin, acrylonitrile / styrene resin And thermoplastic elastomers.

  The thermoplastic resin constituting the thermoplastic resin composition of the present embodiment preferably contains a polyphenylene ether resin (a) and a styrene resin (b).

(Polyphenylene ether (a))
The polyphenylene ether resin as component (a) is a homopolymer or copolymer having a repeating unit represented by the following general formula (1) and / or (2).

In the above formulas (1) and (2), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, and hydrogen.
However, R ₅ and R ₆ are not hydrogen at the same time.

Examples of the homopolymer of the polyphenylene ether resin (a) include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, and poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether poly (2,6-di-n-propyl-1,4- Phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6- Chloro-1,4-phenylene) ether, poly (2,6-dibromo-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether , Poly (2-methyl-6-chloroethyl-1,4-phenylene) homopolymer such as ether.
Among the above polymers, poly (2,6-dimethyl-1,4-phenylene) ether is preferable, and 2- (dialkylaminomethyl) -6-methyl described in JP-A-63-301222 and the like is preferable. A polyphenylene ether containing a phenylene ether unit, a 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit or the like as a partial structure is more preferable.
As a copolymer of the polyphenylene ether resin (a), a copolymer having a phenylene ether structure as a main monomer unit can be used. For example, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is used. Examples thereof include a polymer, a copolymer of 2,6-dimethylphenol and o-cresol, and a copolymer of 2,6-dimethylphenol, 2,3,6-trimethylphenol and o-cresol.

  When a polyphenylene ether resin is used as the thermoplastic resin constituting the thermoplastic resin composition of the present embodiment, as part or all of the polyphenylene ether resin, JP-A-2-276823, JP-A-63-108059, Polyphenylene ether modified with a compound having a carbon-carbon double bond described in JP-A-59-59724 and the like can be used.

The intrinsic viscosity of the polyphenylene ether resin (a): ηsp / c (measured with a chloroform solvent at 30 ° C.) is preferably in the range of 0.3 to 0.9 dl / g, and in the range of 0.4 to 0.6 dl / g. More preferably.
In order to sufficiently finely disperse the chlorite group mineral described later and other inorganic fillers, 0.3 dl / g or more is preferable, and 0.9 dl / g or less is preferable from the viewpoint of moldability.
The blending amount of the polyphenylene ether resin (a), which is the component (a) of the present invention, is selected from the range of 5 to 100 parts by mass when the total amount of the synthetic resin (A) is 100 parts by mass, and the preferred range is 10 -99 mass parts, a more preferable range is 30-97 mass parts, and a still more preferable range is 40-95 mass parts. A blending amount of 5 parts by mass or more is desirable from the viewpoint of heat resistance and workability, and a blending of 100 parts by mass or less is desirable from the viewpoint of mechanical properties such as rigidity.

(Styrene resin (b))
The styrene resin as the component (b) of the present invention is a styrene compound or a styrene compound and a compound copolymerizable with the styrene compound, which is polymerized in the presence or absence of a rubbery polymer. The resulting copolymer.
A styrene-type compound means the compound represented by following General formula (3).

In the general formula (3), R ₇ represents hydrogen, lower alkyl or halogen, Z is any selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl, and p is an integer of 0 to 5. is there.

As the styrene resin (b), polystyrene, rubber-reinforced polystyrene, styrene-acrylonitrile copolymer (AS resin), rubber-reinforced styrene-acrylonitrile copolymer (ABS resin), other styrene copolymers, and the like can be used. .
Specific examples include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene.
Examples of the compound copolymerizable with the styrene compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. And used with styrenic compounds.
The amount of the compound copolymerizable with the styrene compound is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total amount with the styrene compound.
Examples of the rubbery polymer include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, hydrogenated products thereof, and ethylene-propylene copolymer rubbers.
As the styrene resin (b), polystyrene and rubber-reinforced polystyrene are particularly preferable.
The blending amount of the styrene resin (b) is selected from the range of 95 to 0 parts by mass, preferably 90 to 1 when the synthetic resin (A) containing the component (b) is 100 parts by mass. It is mass parts, More preferably, it is 70-3 mass parts, More preferably, it is 60-5 mass parts. A blending amount of 95 parts by mass or less is desirable from the viewpoint of providing sufficient heat resistance.

(Polyolefin resin)
As the thermoplastic resin having a true specific gravity of 1.2 g / mL or less, a polyolefin resin can be used as described above.
For example, low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, ethylene-propylene random copolymer, ethylene-propylene block copolymer, polybutene-1, ethylene-polybutene-1 copolymer, propylene- Butene-1 copolymer, poly-4-methylpentene-1, ethylene-4-methylpentene-1 copolymer, ethylene-propylene-butene-1 terpolymer, ethylene-vinyl acetate copolymer, ethylene -(Meth) acrylic acid copolymer, ethylene-methyl (meth) acrylate copolymer, ethylene- (meth) butyl acrylate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl alcohol-vinyl acetate copolymer Polymer, ethylene-acrylonitrile copolymer, ethylene- (meth) acrylic Acid - acrylonitrile copolymer, an ethylene - styrene copolymer.
Examples of the thermoplastic resin having a true specific gravity of 1.2 g / mL or less include N-vinylalkylamide, which is an acid amide compound having a vinyl group, specifically, N-vinylformamide, N-vinylacetamide etc. are mentioned.

(Acrylonitrile / butadiene / styrene resin)
As the thermoplastic resin having a true specific gravity of 1.2 g / mL or less, acrylonitrile / butadiene / styrene resin (ABS resin) is used as described above.
For example, a so-called graft type ABS resin obtained by polymerizing a mixed monomer of styrene and acrylonitrile in the presence of a rubber-like substance such as polybutadiene rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, The rubber-like substance and the styrene-acrylonitrile copolymer are represented by a so-called blend type ABS resin obtained by mechanical mixing, or a mixed type of the graft type ABS resin and the blend type ABS resin. Resin composition similar to ABS resin in which all or part of the resin is replaced with α-methylstyrene to improve the heat resistance of the resin, and all or part of the acrylonitrile is replaced with methyl methacrylate to improve transparency. The thing containing a thing is mentioned.
These ABS resins can be produced by a known method.
Although there is no particular limitation on the use, a graft type ABS resin is more desirable in view of the physical properties of the final product.
The content of the rubber-like substance in the acrylonitrile / butadiene / styrene resin is usually preferably 10 to 60%, and the contents of styrene and acrylonitrile are preferably 30 to 70% and 10 to 40%, respectively.

As the thermoplastic resin having a true specific gravity of 1.2 g / mL or less, a methacrylic resin is used as described above.
Examples of the methacrylic resin include methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-propyl methacrylate, n-propyl acrylate, n-butyl methacrylate, n-butyl acrylate, t-butyl methacrylate, t-butyl acrylate, n -Hexyl methacrylate, n-hexyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, chloromethyl methacrylate, chloromethyl acrylate, 2-chloroethyl methacrylate, 2-chloroethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxy Propyl methacrylate, 3-hydroxypropyl acrylate, 2,3,4,5,6-pen Polymers of monomers such as hydroxyhexyl methacrylate, 2,3,4,5,6-pentahydroxyhexyl acrylate, 2,3,4,5-tetrahydroxypentyl methacrylate, 2,3,4,5-tetrahydroxypentyl acrylate Or a copolymer (copolymer) of the above monomer.

Further, as described above, acrylonitrile / styrene resin is used as the thermoplastic resin having a true specific gravity of 1.2 g / mL or less.
Acrylonitrile / styrene resin refers to a copolymer of acrylonitrile and a styrene monomer. The method for producing the copolymer is not particularly limited, and a known method can be employed. For example, bulk polymerization, solution polymerization, suspension polymerization, bulk suspension polymerization, emulsion polymerization and the like are used. It can also be obtained by blending separately copolymerized resins. As the styrene monomer, styrene, α-methylstyrene, p-methylstyrene, bromostyrene and the like are preferable, and styrene and / or α-methylstyrene is more preferable.
As the acrylonitrile / styrene resin, those commercially available as acrylonitrile styrene copolymer (AS) or acrylonitrile styrene copolymer (SAN) can be widely used.

(Thermoplastic elastomer)
As the thermoplastic resin having a true specific gravity of 1.2 g / mL or less, a thermoplastic elastomer is used as described above.
Examples of the thermoplastic elastomer include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, and ethylene-propylene copolymer rubbers.
For example, polybutadiene and styrene-butadiene copolymer are preferable.
In addition, when an unsaturated rubber polymer is used as the thermoplastic elastomer, it is preferable to use a partially hydrogenated rubber.

As the synthetic resin (A) component constituting the thermoplastic resin composition of this embodiment described above, polyphenylene ether alone or a mixture of polyphenylene ether and styrene resin is particularly preferable.
The mixing ratio of the polyphenylene ether and the styrenic resin is 100/0 to 5/95, preferably 90/10 to 30/70, by weight.

<Chlorite Group Ore (B)>
The thermoplastic resin composition of the present embodiment contains 1 to 40 parts by mass of chlorite group ore (B) with respect to 100 parts by mass of the synthetic resin (A) described above.
Chlorite group ore (B) is selected from each group of oxides composed of Mg, Fe, Mn, Ni, etc., oxides composed of Al, Fe, Cr, Ti, etc., oxides composed of Si, Al, etc. The ore containing a predetermined one, and the crystal structure includes a monoclinic system and an orthorhombic system.
By setting it as the structure containing the chlorite group ore (B) in the synthetic resin (A), it becomes possible to maintain a mechanical physical property, exhibiting a flame retardance effectively.
The chlorite group ore (B) is preferably contained in an amount of 3 to 30 parts by mass, and more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the synthetic resin (A) described above. Thereby, it is economically advantageous and can provide the thermoplastic resin composition excellent in the safety environment which does not generate | occur | produce halogen gas and phosphine gas.

Examples of the chlorite group mineral (B) include chlorite, cookite, and nanthite. These may be used alone or in combination of two or more. In particular, chlorite is preferable from the viewpoint of availability.
The addition amount of the chlorite group mineral (B) is preferably in the range of 1 to 40 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b), and 3 to 30 parts by mass. The range is more preferable, and 5 to 25 parts by mass is even more preferable. The addition of 40 parts by mass or less is desirable from the viewpoint of sufficient impact resistance and improvement of the surface gloss of the molded article, and the addition of 1 part by mass or more is desirable from the viewpoint of maintaining sufficient heat resistance.

<Other materials>
In addition to the chlorite group mineral (B), other inorganic fillers, organic fillers, and inorganic filler powders treated with an organic agent may be used for the thermoplastic resin composition of the present embodiment.
Examples thereof include silica, wollastonite, alumina, talc, mica, clays, magnesium hydroxide, titanium oxide, zinc white, iron oxide, calcium carbonate, barium sulfate and the like.
The particle shape of the inorganic filler powder is not particularly limited, and may be any of a scaly shape, a needle shape, a spherical shape, and an amorphous granular shape, and two or more kinds may be used in combination.
The primary particle size of the inorganic filler is preferably as fine as possible from the viewpoint of maintaining the gloss of the molded product, but is generally selected from the range of 0.05 to 5 μm, and preferably in the range of 0.1 to 1 μm. . From the viewpoint of handleability and resin dispersibility, it is preferably 0.05 μm or more, and more preferably 5 μm or less from the viewpoint of deterioration of the surface gloss of the molded product and reduction of surface impact resistance.

In order to impart other characteristics to the thermoplastic resin composition of the present embodiment, other additives such as antioxidants, ultraviolet absorbers, heat stabilizers and the like are included within the range not impairing the effects of the present invention. A stabilizer, antistatic agent, release agent, dye / pigment, colorant, or other resin may be added.
In addition, various flame retardants and flame retardant aids may be added, for example, cyclic nitrogen compounds, and specific examples thereof include melamine, ammelide, ammelin, benzoguanamine, succinoguanamine, melamine cyanurate, melam, melem, and methone. , Compounds having a triazine skeleton such as melon and their sulfates, or alkali metal hydroxides or alkaline earth metal hydroxides such as magnesium hydroxide and aluminum hydroxide containing crystal water, zinc borate compounds, tin By adding the zinc acid compound, a further effect of improving flame retardancy can be obtained.
Further, the thermoplastic resin composition of the present embodiment exhibits particularly excellent flame retardancy by blending an aromatic phosphate ester flame retardant.
For example, triphenyl substitution such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, dixylenyl phenyl phosphate, hydroxynon bisphenol, resorcinol bisphosphate, bisphenol A bisphosphate, etc. The type of aromatic phosphates is particularly preferably used. These may be used alone or in combination of two or more.

[Method for producing thermoplastic resin composition]
The thermoplastic resin composition of the present embodiment is obtained by mixing the above-described components and kneading using a kneader such as an extruder, a heating roll, a kneader, or a Banbury mixer.
In particular, kneading with an extruder is preferable from the viewpoint of productivity.
The kneading temperature may be in accordance with the preferred processing temperature of the base resin, and as a guideline it is in the range of 200 to 360 ° C, preferably in the range of 240 to 320 ° C.

In order to stably produce the thermoplastic resin composition of the present embodiment in a large amount, a single-screw or twin-screw extruder is preferably used.
In particular, in order to finely disperse the chlorite group mineral (B) component described above, it is preferable to use a twin screw extruder. For example, the component (A), or the component (a) and the component (b) It is more preferable to use a twin screw extruder equipped with a raw material feed port in the middle of the cylinder of the extruder so that the remaining component (B), the flame retardant, etc. can be fed after the mixture is sufficiently melt-kneaded. . Using a twin-screw extruder equipped with such a raw material feed port, it is possible to obtain the desired resin composition by single-stage extrusion. After extruding the mixture of component (B) or the mixture of component (b) and component (B), the remaining raw materials are blended into the extruded pellets, melt-kneaded, and finally the desired thermoplastic resin composition is obtained. May be obtained.

〔Molding〕
The thermoplastic resin composition of the present embodiment can be formed into a desired molded product by a conventionally known molding method.
Although there is no particular limitation on the molding method, for example, injection molding, extrusion molding, vacuum molding, pressure molding and the like are suitable.
In addition, molding waste such as runner parts generated by injection molding or the like of the thermoplastic resin composition of the present embodiment, or a molded product collected after being marketed, is crushed into unused resin pellets at an arbitrary ratio It is also possible to mix and create a new molded article from the viewpoint of maintaining and improving the physical properties of the material, which is preferable from the viewpoint of effective use of resources and environmental protection.
As a molded article using the thermoplastic resin composition of the present embodiment, various electric / electronic parts, specifically, electric / electronic parts for automobiles are preferable examples.

Hereinafter, the present invention will be specifically described with reference to specific examples and comparative examples.
First, methods for measuring physical properties in Examples and Comparative Examples are shown below.

[(1) Flame retardancy]
Based on UL-94 vertical combustion test, measured using 3.2 mm-thick injection-molded test pieces molded using the thermoplastic resin compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 7 described later. Then, the total combustion time (seconds) of 10 times flame contact and the presence or absence of dripping substances during combustion were evaluated.
The level of flame retardancy was best at V-0 and was inferior as the ranks of V-1 and V-2 were exceeded, and when the total combustion time exceeded 250 seconds, it was out of rank.
About the presence or absence of dripping, when not dripping, it showed as (circle) and when dripped, it was described as x.
If the burning time is 25 seconds or less, it corresponds to V-1 rank or higher, and is considered to be extremely good in practical use.

[(2) Heat-resistant temperature]
Based on ISO75-2, the deflection temperature under load was measured at a load of 1.83 MPa, and was used as a measure of the heat resistance temperature.

[(3) True specific gravity]
The true specific gravity of the thermoplastic resin was measured by an immersion method (Archimedes method) using butanol in an atmosphere having an environmental temperature of 25 ° C. and a relative humidity of 50%.
As a measurement sample, a pellet-shaped thermoplastic resin produced as described below was freeze-ground using liquid nitrogen, and a powder that passed through a 106 μm mesh was used.

[(4) Tensile strength]
Measurement was based on ISO527.

[(5) Bending strength and flexural modulus]
Based on the ISO178 standard, the flexural modulus and flexural strength were measured.
A bending elastic modulus of 2700 MPa or more and a bending strength of 103 MPa or more were judged to be practically excellent.

[(6) Appearance inspection]
Ten plates were visually evaluated using 50 mm × 90 mm × 2.5 mm (thickness) flat plates molded using the thermoplastic resins prepared in Examples 1 to 9 and Comparative Examples 1 to 8 described later.
A case where the sample was better than the sample of Comparative Example 8 was indicated as ◯, and a case where unevenness or whitening was observed was indicated as ×.

[Examples 1-9], [Comparative Examples 1-8]
The following components are mixed in the proportions shown in Table 1 below, supplied to a twin-screw extruder with a screw diameter of 25 mm with the maximum temperature of the heating cylinder set to 300 ° C., melt-kneaded at a screw rotation speed of 300 rpm, and strands Was cut by cooling to obtain thermoplastic resin composition pellets.
Next, the obtained thermoplastic resin composition pellets were molded into predetermined physical property test pieces by injection molding, and subjected to physical property tests by the above test methods, and the results shown in Table 1 below were obtained.

The components used in [Examples 1-9] and [Comparative Examples 1-8] are shown below.
[(1) Polyphenylene ether (PPE)]
Poly-2,6-dimethyl-1,4-phenylene ether having a reduced viscosity (ηsp / c) measured with a chloroform solution at 30 ° C. of 0.52 dl / g was used.

[(2) Rubber reinforced polystyrene (HIPS)]
PS Japan Co., Ltd. rubber reinforced polystyrene H9405 was used.

[(3) Polystyrene (GPPS)]
Polystyrene 685 manufactured by PS Japan Co., Ltd. was used.

[(4) Inorganic filler]
M-1: Chlolite whose structural formula is represented by 5MgO.Al ₂ O ₃ .3SiO ₂ .4H ₂ O and whose volume average particle diameter is 13.2 μm (trade name “WL-13L, manufactured by Fuji Talc Kogyo Co., Ltd.) ")
M-2: Chlolite whose structural formula is represented by 5MgO.Al ₂ O ₃ .3SiO ₂ .4H ₂ O and whose volume average particle diameter is 9.2 μm (trade name “WL-13M” manufactured by Fuji Talc Industrial Co., Ltd.) )
M-3: structural formula is represented in _{5MgO · Al 2 O 3 · 3SiO} · 4H 2 O, the volume average particle diameter of 5.6μm chlorite (Fuji Talc Kogyo Co., trade name "WL-13J")
M-4: Talc (manufactured by Takehara Chemical Industry Co., Ltd .: trade name “Hytron A”)
M-5: Kaolin (trade name “TRANSLINK445” manufactured by Hayashi Kasei Co., Ltd.)
M-6: Mica (manufactured by Kuraray Co., Ltd .: Product name “Szolite Mica 200-HK”
M-7: Magnesium hydroxide (manufactured by Kyowa Chemical Industry Co., Ltd .: trade name “Kisuma 5E”)
M-8: Silica (manufactured by Nippon Silica Industry Co., Ltd .: trade name “Nip Seal AQ”)
M-9: Calcium carbonate (manufactured by Takehara Chemical Industry Co., Ltd .: trade name “SL-2200”)
In addition, the said volume average particle diameter can be measured using Nikkiso Co., Ltd. laser diffraction type particle size distribution measuring apparatus MT3300.

As shown in Table 1, in Examples 1 to 9, the appearance is good, it has high bending elastic modulus, bending strength and tensile strength, has high toughness and rigidity, and exhibits practically good flame retardancy. A thermoplastic resin could be obtained.
Moreover, since the flame retarding effect excellent in practical use was acquired without containing a flame retardant, adhesion to the mold in the molding process could be prevented.

  The flame-retardant resin composition of the present invention has industrial applicability as various electric and electronic parts, for example, electric and electronic parts for automobiles, home appliances, parts for OA equipment, parts for electromagnetic shielding, parts for solar cells, etc. Have.

Claims (6)

A synthetic resin (A) made of a thermoplastic resin having a true specific gravity of 1.2 g / mL or less , comprising a polyphenylene ether resin (a) and a styrene resin (b) (A) : 100 parts by mass ,
Chlorite group mineral (B): 1 to 40 parts by mass;
A thermoplastic resin composition. The thermoplastic resin composition according to claim 1 , wherein the chlorite group mineral (B) is chlorite. The synthetic resin (A) made of the thermoplastic resin comprises 5 to 100 parts by mass of a polyphenylene ether resin (a) and 95 to 1 part by mass of a styrene resin (b).
For a total amount of 100 parts by mass of (a) and (b),
1 to 40 parts by mass of the chlorite (B),
The thermoplastic resin composition of Claim 1 or 2 to contain. A molded product molded using the thermoplastic resin composition according to any one of claims 1 to 3 . The molded article according to claim 4 , which is an electric / electronic component. The molded article according to claim 4 or 5 , which is an electric / electronic part for automobiles.