JPH1030046A - Production of flame-retardant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily obtain the subject composition having excellent physical properties and flame retardancy and simultaneously excellent in appearance and drip-preventing effect by using a perfluoropolymer powder-dispersing agent mixture produced at a low temperature as a drip-preventing agent. SOLUTION: The flame-retardant thermoplastic resin composition comprises (A) 100 pts.wt. of a thermoplastic resin mixture comprising (i) a graft copolymer produced by graft-copolymerizing a mixture comprising (a) 60-100wt.% of an aromatic vinyl monomer and (b) 0-40wt.% of a monomer capable of being copolymerized with the component (a) in the presence of a rubbery polymer and/or (ii) the copolymer of 60-100wt.% of the component (a) with 0-40wt.% of the component (b) or a thermoplastic resin mixture comprising the component (i) and/or the component (ii) and (iii) either one of a polycarbonate, a polyphenylene ether and a saturated polyester, (B) 1-35 pts.wt. of a flame retardant comprising an organic halogenated compound and/or an organic phosphorus compound, and (C) 0.01-1 pt.wt. of a drip-preventing agent comprising perfluoropolymer polymer. Therein, the component C comprising a mixture produced by preliminarily mixing and treating the perfluoropolymer with either one of higher fatty acids (metal salts) and higher fatty acid amides at a temperature of <=25 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a flame-retardant thermoplastic resin composition capable of obtaining a resin molded article having excellent drip resistance and appearance.

[0002]

2. Description of the Related Art Styrene resins typified by ABS, HIPS, etc. are widely used in electrical appliances, office automation equipment, office equipment, etc. due to their excellent moldability, mechanical properties, appearance, and the like. . In these applications, it is often necessary to make the resin flame-retardant due to problems such as heat generation of the internal components, and organic halogen compounds and organic phosphorus compounds are added as flame retardants,
Techniques for making resins flame-retardant are widely used.

On the other hand, the flame retardancy standard (UL94) of the United States Underwriters Laboratories (UL), which is generally used as an index of the flame retardancy of a resin, has a rule on dripping of a fire during combustion. , V-0 class, 5V, which is the flame retardancy level normally required for the application
The class requires that it not drip during combustion.
In order to satisfy this requirement, a technique has recently been proposed in which a powder of a perfluoropolymer (PFP) such as polytetrafluoroethylene (PTFE) is added to a resin as an anti-drip agent in addition to the above-mentioned flame retardant. For example, JP-A-50-44241, JP-A-59-98158, JP-A-61-89241, and JP-A-63-89241.
No. 135442 discloses a technique of blending a flame retardant and PFP powder with ABS. However, PFP powder which has been conventionally used as an anti-drip agent for thermoplastic resins has a drawback that powder flowability is poor due to non-uniform particle shape. Also, PFP has a property that under high-temperature and high-shear conditions, molecules are fiberized to form a spider web.

[0004] In the process of producing a resin composition, there is a premixing step of mixing a resin and additives using a Heschel mixer or a tumbler, prior to a kneading step using an extruder or the like. When conventional PFP powder is used as an anti-drip agent, due to the above-mentioned drawbacks, shear is likely to occur in the kneading tank, and PFP particles easily change into spider webs, and are difficult to disperse by being entangled with other resins and additives. There is a problem that a drug mass is formed. as a result,
The raw material feed feeder of the extruder is closed or the additive mass is not dispersed at the time of kneading in the extruder, and the unmixed additive mass is mixed in the produced resin composition, and the obtained resin molded product There were problems such as poor appearance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a flame-retardant thermoplastic resin composition capable of obtaining a resin molded article having excellent drip resistance and appearance. .

[0006]

Means for Solving the Problems As a result of diligent research for solving the above-mentioned problems, the present inventor has previously mixed PFP powder and a specific dispersant at a temperature of 25 ° C. or less prior to the premixing step. In addition, by using this mixture as an anti-drip agent, unlike the case of using untreated PFP powder, no additive lumps are generated at the time of premixing, and poor dispersion of PFP in the produced resin composition. The present inventors have found that the appearance defect of the obtained resin molded product can be eliminated, and have completed the present invention.

That is, the gist of the present invention is to provide (A) a thermoplastic resin mixture 100 comprising the following (A1) and / or (A2) or comprising (A1) and / or (A2) and (A3). When (B) 1 to 35 parts by weight of a flame retardant comprising an organic halogen compound and / or an organic phosphorus compound and (C) an anti-drip agent comprising a perfluoropolymer powder are added to , PFP) at a temperature of 25 ° C. or lower and at least one dispersant selected from higher fatty acids, higher fatty acid metal salts, and higher fatty acid amides. The present invention relates to a method for producing a thermoplastic resin composition. (A1) 60 to 100% by weight of an aromatic vinyl monomer and 0 to 40% by weight of a monomer copolymerizable with an aromatic vinyl monomer
(A2) 60 to 100% by weight of an aromatic vinyl monomer and a monomer copolymerizable with an aromatic vinyl monomer 0-40% by weight
(A3) Polycarbonate, polyphenylene ether,
At least one selected from the group consisting of saturated polyesters
Seed polymer

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The (A) resin mixture used in the present invention is a thermoplastic resin mixture comprising (A1) a graft copolymer and / or (A2) copolymer, or further (A3) a polymer. The graft copolymer (A1) used in the present invention is a mixture of 60 to 100% by weight of an aromatic vinyl monomer and 0 to 40% by weight of a monomer copolymerizable with an aromatic vinyl monomer. A graft copolymer obtained by graft copolymerization in the presence of a rubbery polymer.

In order for the resin composition produced according to the present invention to have excellent physical properties, flame retardancy and processability, it is necessary that (A1)
The weight average particle diameter of the rubbery polymer contained in the graft copolymer is 0.1 to 5 μm, more preferably 0.2 to 3 μm.
The rubber content is preferably 1 to 80% by weight, more preferably 5 to 70% by weight. When these values are less than the above ranges, the impact resistance of the finally obtained resin molded product is reduced, and when it exceeds the above range, the flame retardancy of the finally obtained resin molded product tends to be reduced. (A1) The rubbery polymer used in the graft copolymer has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, for example, polybutadiene, or butadiene and another copolymerizable monomer. And a rubbery polymer composed of a copolymer of the above.

(A1) Specific examples of the aromatic vinyl monomer which is a component of the graft copolymer include styrene, α
Α-alkylstyrene such as -methylstyrene, nuclear-substituted alkylstyrene such as p-methylstyrene, and vinylnaphthalene. These may be one kind or a mixture of two or more kinds. Specific examples of the monomer copolymerizable with the aromatic vinyl monomer include acrylonitrile, vinyl cyanide monomers such as methacrylonitrile, acrylic acid, methacrylic acid, and acrylic resins such as alkyl esters thereof. Examples include monomers, maleic anhydride, and unsaturated acid derivative-based monomers such as imidized products thereof.
These may be one kind or a mixture of two or more kinds.

(A1) The ratio of the aromatic vinyl monomer component in the monomer mixture used in the graft copolymer is from 60 to 60%.
The range is 100% by weight. If less than 60% by weight,
The heat resistance, impact resistance, color tone, and the like of the resin molded product obtained from the resin composition to be produced are deteriorated. (A1) The graft copolymer can be prepared from the above-mentioned monomer or a mixture thereof by a known method, for example, an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, or the like, in a batch system or a continuous system. It can be manufactured by the method.

(A1) Specific examples of the graft copolymer include impact-resistant polystyrene (HIPS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), and methyl methacrylate / butadiene / styrene copolymer (MBS resin). ), Methyl methacrylate / acrylonitrile / butadiene / styrene copolymer (MABS)
Resins), acrylonitrile / acrylic rubber / styrene copolymer (AAS resin), acrylonitrile / ethylene propylene rubber / styrene copolymer (AES resin), and resins such as acrylonitrile / chlorinated polyethylene / styrene copolymer (ACS resin) Or a mixture thereof.

The (A2) copolymer used in the present invention comprises 60 to 100% by weight of an aromatic vinyl monomer and 0 to 40% by weight of a monomer copolymerizable with an aromatic vinyl monomer. It means a copolymer obtained by copolymerization. Specific examples of the aromatic vinyl monomer which is a constituent component of the (A2) copolymer include the same monomers as in the (A1) graft copolymer. Specific examples of the monomer copolymerizable with the aromatic vinyl monomer, which is a component of the (A2) copolymer, include the same monomers as in the (A1) graft copolymer. it can.

(A2) The ratio of the aromatic vinyl monomer component used in the copolymer is in the range of 60 to 100% by weight. If the content is less than 60% by weight, the heat resistance, impact resistance, color tone, etc. of the resin molded product obtained from the resin composition to be produced are reduced. This (A2) copolymer is prepared, for example, according to a known acrylonitrile-styrene copolymer production technique.
It can be manufactured by a batch system or a continuous system using a method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, or a bulk polymerization method. The copolymer (A2) can be produced simultaneously in the same polymerization system in the polymerization operation of the graft copolymer (A1), or can be produced by separately setting a polymerization method and polymerization conditions.

The (A3) polymer used in the present invention is:
At least one polymer selected from the group consisting of polycarbonate, polyphenylene ether, and saturated polyester, optionally blended with the (A1) graft copolymer and / or (A2) copolymer as required. Is done.
Here, the polycarbonate is a homopolycarbonate or copolycarbonate based on an aromatic dihydroxy compound, and is particularly synthesized from bisphenol A and phosgene, and has a weight average molecular weight of 1700 to 30000.
The bisphenol A type polycarbonate is preferably used.

The polyphenylene ether is a polymer obtained by oxidative polymerization of phenols. In the present invention, poly (2,6-dimethyl-1,4-phenylene) is a polymer of 2,6-xylenol. ether)
Is preferably used. The saturated polyester is a polymer obtained by condensation polymerization of a dicarboxylic acid and a dihydroxy compound. In the present invention, polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) are particularly preferably used. In the resin mixture (A) according to the present invention, (A1) a graft copolymer, (A2) a copolymer, and (A3) a polymer can be blended in any ratio. (A1) graft copolymer and / or (A2) as an essential component
The copolymer must be contained, the amount of which is (A)
It is preferably at least 10% by weight based on the total amount of the resin mixture. When the resin mixture (A) does not contain any of the (A1) graft copolymer and the (A2) copolymer, the moldability of the resin composition produced by the present invention is reduced.

When the resin mixture (A) comprises only the (A1) graft copolymer and the (A2) copolymer, the (A1)
If the blending amount of the graft copolymer is less than 10% by weight, the impact resistance of the obtained resin molded product is reduced. Even in such a case, the drip preventing effect and the dispersing effect of the (D) anti-drip agent described later. Is valid. In the present invention, any other resin can be further added as necessary. Examples of other resins that can be added include polyamide resins.

The flame retardant (B) used in the present invention is an organic halogen compound and / or an organic phosphorus compound, and a conventional flame retardant which can impart sufficient flame retardancy when added to a resin is used. However, as the organic halogen compound, a compound containing bromine and / or chlorine, and as the organic phosphorus compound, a phosphate compound and / or a phosphazene compound are used. preferable. (B) When an organic halogen compound is used as the flame retardant, at least one compound selected from the group consisting of a halogenated bisphenol compound, a halogenated epoxy compound, and a halogenated triazine compound is used (B). The flame retardant of the flame retardant is high,
This is most preferable because the effects of the present invention are maximized.

The halogenated bisphenol compound used in the present invention is a bisphenol halide, for example, tetrabromobisphenol A, dibromobisphenol A, tetrachlorobisphenol A, dichlorobisphenol A, tetrabromobisphenol F, dibromobisphenol. F, tetrachlorobisphenol F, dichlorobisphenol F, tetrabromobisphenol S, dibromobisphenol S, tetrachlorobisphenol S, dichlorobisphenol S, and the like. These may be one kind or a mixture of two or more kinds. The halogenated epoxy compound used in the present invention is a reaction product of a halogenated bisphenol compound and epihalohydrin or halogenated bisphenol diglycidyl ether, and is represented by the following general formula.

[0020]

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(Wherein, n is an integer of 0 or 1 or more, X is a bromine atom or a chlorine atom, a, b, c, and d are integers of 1 to 4,
R ₁ is an isopropylidene group, a methylene group or a sulfone group; R ₂ and R ₃ are each a 2,3-epoxypropyl group or a —CH ₂ CH (OH) CH ₂ OR ₄ group [R ₄ is a bromine atom or a chlorine atom; An alkyl group or an allyl group which may be substituted]. Specific examples of the halogenated bisphenol compound used as a raw material of the halogenated epoxy compound include those exemplified in the preceding paragraph. The degree of polymerization n of the halogenated epoxy compound is 0 or an integer of 1 or more, more preferably an integer of 0 to 15;
More than one type may be used in combination.

The terminal of the halogenated epoxy compound may be an epoxy group, or the epoxy group may be sealed with an allyl group or an alkyl group. It may be substituted with a halogen atom such as chlorine or bromine. Specific examples of the terminal blocking group include phenyl group, unsubstituted allyl group such as naphthyl group, tribromophenyl group, pentabromophenyl group, trichlorophenyl group, halogenated allyl group such as pentachlorophenyl group, and alkyl such as stearyl group. And the like.

The terminal of the halogenated epoxy compound used in the present invention is not limited as long as it is within the above range, and the structure of one terminal and the other terminal may be the same or different. The halogenated triazine compound used in the present invention is an organic halogen compound having a triazine skeleton and is represented by the following general formula.

[0024]

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(Wherein Y is a —O— group or a —NH— group,
R ₄ represents a brominated or chlorinated allyl group and / or an alkyl group. Such a compound is generally obtained by reacting a compound having a triazine skeleton such as cyanuric acid or melamine with a compound having a hydroxyl group such as brominated or chlorinated phenols or alcohols or an amine compound. When an organic phosphorus compound is used as the flame retardant (B), the use of a phosphate compound is most preferable because the flame retardant of the flame retardant (B) is high and the effect of the present invention is maximized. The phosphate compound used in the present invention is an ester of phosphoric acid and a phenol, and is represented by the following general formula.

[0026]

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(Wherein n is a number from 0 to 10, and R ₅ is an allyl group and / or an alkyl group which may be substituted with a halogen atom.) (B) It is not necessary to use only one type of flame retardant. No, 2
At least one kind of different compounds may be used, or an organic halogen compound and an organic phosphorus compound may be used in combination. (B)
The compounding amount of the flame retardant is 1 to 35 parts by weight, preferably 5 to 30 parts by weight based on 100 parts by weight of the resin mixture (A).
If the compounding amount exceeds 35 parts by weight, the physical properties and light resistance of the obtained resin molded product decrease, and if the compounding amount is less than 1 part by weight, sufficient flame retardancy cannot be imparted to the obtained resin molded product. . The (D) anti-drip agent in the present invention refers to a mixture of a PFP powder and a specific dispersant, which has been mixed at a temperature of 25 ° C. or less before the premixing step.

(C) The PFP powder used for the anti-drip agent usually has a primary particle size of 0.05 to 0.5 μm, a secondary particle size of 300 to 700 μm, and a number average molecular weight of 1 × 10 ⁶ to
A homopolymer of about 1 × 10 ⁷ tetrafluoroethylene, and a binary or ternary copolymer of tetrafluoroethylene with hexafluoropropylene, perfluoroalkoxyethylene, or the like. As such PFP powder, those commercially available as resin additives can be used. For example, Mitsui Dupont Fluoro Chemical Co., Ltd., trade names "Teflon 6CJ", "Teflon 6J" and Asahi ICI Fluoropolymers, Product name "Fluon C
D076 ”,“ Fluon CD1 ”, and“ Polyflon TFE Fine Powder F-2 ”manufactured by Daikin Industries, Ltd.
01 "," F-104 "," Polyflon MPA FA "
-500 "and the like.

In the present invention, it is important to previously treat the above PFP powder with a specific dispersant, and the dispersant used here may be a higher fatty acid, a higher fatty acid metal salt, or a higher fatty acid amide. It is at least one compound selected. By this pretreatment, the dispersibility of the PFP powder is improved, and finally a good product can be obtained. As higher fatty acids, for example, stearic acid, behenic acid, lauric acid, palmitic acid, myristic acid, capric acid, oleic acid, coconut oil-based fatty acids, palm oil-based fatty acids, tallow fatty acids and the like having 4 to 30 carbon atoms And higher fatty acids.

The higher fatty acid metal salt is a salt of the above higher fatty acid and a metal hydroxide, for example, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate and the like are preferably used. Examples of the higher fatty acid amide include monoamides and bisamides of the above-mentioned higher fatty acids, and, for example, stearic acid amide, oleic acid amide, ethylene bisstearic acid amide and the like are preferably used.

The mixing ratio of the PFP powder and the dispersing agent is not particularly limited, and the dispersing agent may be mixed in an amount capable of substantially dispersing the PFP powder.
The ratio of 70 to 10% by weight of the dispersant to 0% by weight is most preferable. When the proportion of the PFP powder exceeds 90% by weight, sufficient dispersibility cannot be imparted to the obtained (C) anti-drip agent, and when it is less than 30% by weight, (C) for obtaining a sufficient anti-drip effect. ) Since the added amount of the anti-drip agent increases, the thermal stability of the produced resin composition decreases. In the present invention, the mixing of the PFP and the dispersant needs to be performed at a temperature of 25 ° C. or lower, more preferably 20 ° C. or lower. If the temperature exceeds 25 ° C., the production of (C) the anti-drip agent becomes unfavorable because the PFP is fiberized and thus the PFP and the dispersant are not uniformly mixed, and the dispersibility of the (C) anti-drip agent is remarkably deteriorated.

(C) In the production of the anti-drip agent,
A conventional mixer such as a Henschel mixer or a tumbler can be used. However, when this type of mixer is used, the temperature inside the mixing tank becomes higher than 40 ° C. due to shear heat generation.
In the production of the (C) anti-drip agent according to the present invention, it is important that the temperature in the vessel at the time of production is 25 ° C. or less, and the mixing machine is provided with a mixing tank cooling device such as a blower cooler or a refrigerant cooler. Must be equipped. Further, it is desirable that the PFP powder and the dispersant are cooled to 10 ° C. or lower before mixing. However, these measures are not necessarily required when, for example, the amount of the (D) anti-drip agent to be produced is small and the temperature in the tank does not exceed 25 ° C. due to shear heat generation.

The amount of the anti-drip agent (C) is 0.01 to 1.1 parts by weight based on 100 parts by weight of the thermoplastic resin mixture (A).
0 parts by weight, preferably 0.05 to 0.8 parts by weight.
If the addition amount is less than 0.01 part by weight, it is not possible to impart sufficient anti-drip properties to the produced resin composition,
If the added amount exceeds 1.0 part by weight, not only is it economically disadvantageous, but also the moldability of the produced resin composition deteriorates.

The production of the resin composition according to the present invention comprises:
This is performed by weighing (A) the resin mixture, (B) the flame retardant, and (C) the anti-drip agent in the above ranges, and mixing and kneading them by a known method. For example, powder, beads, flakes or a mixture of the respective components in the form of pellets, using a single-screw extruder, an extruder such as a twin-screw extruder, or a kneader such as a Banbury mixer, a pressure kneader, a two-roller or the like. By melt-kneading the resin composition, a resin composition can be produced. When it is necessary to mix a liquid, it may be kneaded by a known liquid injection device by the above method. Also, in that case, the kind and amount of lubricant, release agent, coloring agent, antistatic agent, antioxidant, other flame retardant, antimony trioxide, which do not inhibit the properties of the resin composition to be manufactured as required. Flame retardant aids, such as
Various resin additives such as other anti-drip agents, ultraviolet absorbers and heat-resistant stabilizers, fillers such as talc, reinforcing materials such as glass fibers, carbon fibers, and whiskers can be appropriately combined and added.

[0035]

Next, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples unless it exceeds the gist. Examples 1-4 and Comparative Examples 1-5 (1) (A1) Graft copolymer (A1-1) Butadiene rubber content 5 by emulsion polymerization method
An acrylonitrile-butadiene-styrene copolymer in the form of a white powder having 0% by weight, a rubber weight average particle diameter of 0.3 μm, a graft ratio of 40%, an acrylonitrile content of 25% by weight, and a matrix weight average molecular weight of 80,000 was polymerized. It was used as (A1-1). (A1-2) Butadiene rubber content 1 by suspension polymerization
An acrylonitrile-butadiene-styrene copolymer in the form of a white bead having 5% by weight, a rubber weight average particle diameter of 1.4 μm, a graft ratio of 60%, an acrylonitrile content of 24% by weight, and a matrix weight average molecular weight of 130,000 was polymerized. It was used as (A1-2).

(2) (A2) Copolymer An acrylonitrile-styrene copolymer having an acrylonitrile content of 26% by weight and a weight average molecular weight of 160,000 was polymerized by a bulk polymerization method and used as the (A2) copolymer. (3) (A3) Polycarbonate Commercially available polycarbonate resin (manufactured by Mitsubishi Engineering-Plastics Corporation, trade name NOVAREX 7022A,
7030A).

(4) (B) Flame Retardant (B-1) Halogenated Bisphenol Compound Commercially available tetrabromobisphenol A (trade name: RB100PC, manufactured by Albemarle Corporation) was used. The structure is shown below.

[0038]

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(B-2) Halogenated Epoxy Compound A commercially available terminal-sealed tetrabromobisphenol A type epoxy oligomer (trade name: Epototo TB62, manufactured by Toto Kasei Co., Ltd.) was used. The structure is shown below.

[0040]

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(However, a mixture of n = 0 and 1) (B-3) Halogenated triazine compound Commercially available tris (tribromophenoxy) cyanurate (Pirogard SR, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
245) was used. The structure is shown below.

[0042]

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(B-4) Phosphate Compound A commercially available phosphate ester dimer having the following structure (trade name: PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.) was used as the phosphate compound.

[0044]

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(5) (C) Anti-drip agent (C-1) 500 k of commercially available PFP powder (trade name: Teflon 6CJ, manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.)
g and 500 kg of magnesium stearate were mixed at a rotation speed of the blades of 20 rpm for 5 minutes while maintaining the temperature at 20 ° C. using a rotary wing tumbler equipped with a blower cooler.
Used as (C-1). (C-2) As a comparative example, a commercially available PFP powder (trade name: Teflon 6C, manufactured by Mitsui Dupont Fluorochemicals, Inc.)
J) was used as (C-2) without any pretreatment. (C-3) As a comparative example, the production was performed in the same manner as (C-1) except that the inside of the tank was not cooled, and used as (C-3). The temperature in the tank during mixing was about 50 ° C.

(6) (D) Antimony trioxide As a flame retardant aid, commercially available antimony trioxide (trade name: Fireshield H, manufactured by Laurel Industries, Ltd.)
It was used. (7) (E) Magnesium stearate Commercially available magnesium stearate was used as a dispersant.

(8) Preparation and Evaluation of Resin Composition The above (A1) graft copolymer, (A2) copolymer,
(A3) a polymer, (B) a flame retardant, (C) an anti-drip agent, (D) antimony trioxide, and (E) magnesium stearate, the mixing ratio (parts by weight) described in Table 1.
, And the mixture was kneaded with a twin-screw extruder equipped with a screw feeder to produce pellets of the resin composition. The melt flow rate was measured from the pellets of the resin composition, and test pieces were prepared by an injection molding method. The Izod impact strength of each test piece was measured by the following method, and a UL combustion test was performed. 90 × 50 × 3 mm for dispersion state of additives
The test pieces were molded into 10 pieces, and the number of test pieces in which an unkneaded additive mass was confirmed on the surface of the molded product was determined. Table 1 shows the measurement results.

Melt flow rate 10 k at 220 ° C. by a method according to JIS-K7210
The measurement was performed with a load of g, which was used as an index of fluidity.・ Izod impact strength Measured at 23 ° C by a method based on JIS-K7110,
It was used as an index of impact resistance (test piece thickness: 1/8 inch, with V notch). -UL burning test A vertical burning test was performed by a method based on UL94 issued by Underwriter Laboratories of the United States, and it was used as an index of flame retardancy. V-0 class test piece thickness 1/12 inch, 5V class test piece thickness 1/10 inch

[0049]

[Table 1]

From Table 1, it can be seen that, in the method for producing the resin composition according to the present invention, the use of the (D) anti-drip agent in which the PFP powder and the dispersant are mixed at a temperature of 25 ° C. or less makes the composition excellent. While maintaining the fluidity and the excellent impact resistance and flame retardancy of the molded product, the dispersibility of the anti-drip agent is improved, and the feeder feeder of the extruder is clogged and the resulting resin composition has It is understood that problems such as mixing of the kneading additive mass are eliminated (Examples 1 to 4). When a commercially available PFP powder is used as an anti-drip agent (Comparative Examples 1, 3, 4, and 5) or when (C) an anti-drip agent prepared at a temperature exceeding 25 ° C. is used (Comparative Example 2) It can be seen that, in addition to the blockage of the raw material feeder, the dispersion of the additive becomes poor and the obtained resin composition contains a large amount of unkneaded additive mass.

[0051]

According to the present invention, by using a mixture of a PFP powder produced at a low temperature and a dispersant as an anti-drip agent, the appearance and anti-drip effect can be maintained while maintaining excellent physical properties and flame retardancy. A method for easily producing an excellent flame-retardant thermoplastic resin composition can be provided, and its industrial utility value is extremely high.

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Claims (1)

[Claims] (A) The following (A1) and / or (A)
2) or (A1) and / or (A2) and (A
To 100 parts by weight of the thermoplastic resin mixture of 3), (B) 1 to 35 parts by weight of a flame retardant comprising an organic halogen compound and / or an organic phosphorus compound and (C) an anti-drip agent comprising perfluoropolymer powder. In this case, a mixture prepared by mixing a perfluoropolymer powder in advance with at least one dispersant selected from higher fatty acids, higher fatty acid metal salts and higher fatty acid amides at a temperature of 25 ° C. or lower is used as an anti-drip agent. A method for producing a thermoplastic resin composition. (A1) 60 to 100% by weight of an aromatic vinyl monomer and 0 to 40% by weight of a monomer copolymerizable with an aromatic vinyl monomer
(A2) 60 to 100% by weight of an aromatic vinyl monomer and a monomer copolymerizable with an aromatic vinyl monomer 0-40% by weight
(A3) Polycarbonate, polyphenylene ether,
At least one selected from the group consisting of saturated polyesters
Seed polymer