JPH06271756A - Flame-retardant aromatic polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject compsn. which has excellent properties and does not corrode a molding or processing machine by compounding an arom. polycarbonate resin with a specific flame retardant, two specific compds., and a specific fluororesin each in a specified amt. CONSTITUTION:This resin compsn. is prepd. by compounding 100 pts.wt. arom. polycarbonate resin (e.g. one obtd. from bisphenol A, p-t-butylphenol, and COCl2 by the usual method) with 1-15 pts.wt. polycarbonate flame retardant derived from tetrabromobisphenol A, 0.01-2 pts.wt. alkali perfluoroalkanesulfonate (e.g. potassium perfluorobutanesulfonate), 0.001-2 pts.wt. metal salt of a sulfate of a mono- or polyhydric alcohol (e.g. sodium methyl sulfate), and 0.01-2 pts.wt. fibril-forming fluororesin (e.g. polytetrafluoroethylene).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant aromatic polycarbonate resin composition. More specifically, the present invention relates to an aromatic polycarbonate resin composition that has little corrosion in a molding machine or a processing machine, has excellent flame retardancy without deteriorating the original excellent physical properties of the aromatic polycarbonate resin.

[0002]

Aromatic polycarbonate resins are widely used in a wide variety of fields because they have many excellent physical properties. However, aromatic polycarbonate resins are flammable, and their use in applications requiring severe flame retardancy is limited. As a method of making an aromatic polycarbonate resin flame-retardant, a method of blending an organic halogen compound has been conventionally known. For example, Japanese Patent Publication No. 47-44537 proposes a method of blending a polycarbonate oligomer of tetrabromobisphenol A in an amount such that the bromine concentration becomes 5 to 15% by weight, and Japanese Patent Publication No. 47-24660 discloses tetrabromobisphenol. A method has been proposed in which a copolymerized polycarbonate of A and bisphenol A is blended in an amount such that the bromine concentration is 5 to 9% by weight. However, when a flame-retardant aromatic polycarbonate resin composition obtained by blending such a brominated flame retardant is molded and processed,
A molding machine or a processing machine is easily corroded, and this corrosion becomes more severe as the bromine concentration increases. Therefore, development of an aromatic polycarbonate resin having excellent flame retardancy with less corrosion of a molding machine or a processing machine has been earnestly desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aromatic polycarbonate having excellent flame retardancy without causing corrosion of a molding machine or a processing machine and deteriorating excellent physical properties of the aromatic polycarbonate resin. It is to provide a resin.

The inventors of the present invention have made extensive studies as a means to achieve the above object, and as a result, together with the above-mentioned polycarbonate type flame retardant, perfluoroalkanesulfonic acid alkali salt, sulfuric acid ester metal salt of monohydric and / or polyhydric alcohol and polytetrafluorocarbon. When ethylene is used in a small amount, it is possible to impart excellent flame retardancy to the aromatic polycarbonate resin even if the amount of the polycarbonate type flame retardant used is remarkably reduced. Completed the invention.

[0005]

According to the present invention, 100 parts by weight of an aromatic polycarbonate resin, 1 to 15 parts by weight of a tetrabromobisphenol A-based polycarbonate flame retardant, and 0.04 parts of a perfluoroalkanesulfonic acid alkali salt are used.
Flame-retardant aromatic polycarbonate resin prepared by blending 1 to 2 parts by weight, 0.001 to 2 parts by weight of a sulfuric acid ester metal salt of a monohydric alcohol or a polyhydric alcohol, and 0.01 to 2 parts by weight of a fibril-forming fluororesin. It relates to the composition.

The aromatic polycarbonate resin targeted by the present invention is obtained by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. Examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), bis (4-hydroxyphenyl) methane, and 1,1-bis (4
-Hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,
2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) Examples thereof include sulfone and its aromatic ring substituted with, for example, an alkyl group and an aryl group, and these may be used alone or in combination of two or more kinds. Of these, bisphenol A is preferable. Examples of the carbonate precursor include carbonyl halide, diaryl carbonate, haloformate and the like, and specific examples thereof include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and a mixture thereof. The molecular weight of the aromatic polycarbonate resin is not particularly limited, but is usually 10,000 to 50,000, preferably 15,
It is 000-40,000. When producing such an aromatic polycarbonate resin, an appropriate molecular weight modifier, a catalyst for accelerating the reaction and the like can be used, if necessary.

The aromatic polycarbonate resin targeted by the present invention is a branched polycarbonate resin obtained by copolymerizing a polyfunctional compound or a polyester obtained by copolymerizing an aromatic or aliphatic difunctional carboxylic acid having 8 or more carbon atoms. It may be a carbonate resin or a mixture of two or more aromatic polycarbonate resins, for example, an aromatic polycarbonate resin having a normal molecular weight and a viscosity average molecular weight of 5
It may be a mixture of aromatic polycarbonate resins having an ultra high molecular weight of 10,000 or more.

The tetrabromobisphenol A-based polycarbonate flame retardant used in the present invention is obtained by reacting tetrabromobisphenol A with a carbonate precursor by a solution method or a melting method using an appropriate molecular weight modifier. As the carbonate precursor, the carbonate precursor described in the above aromatic polycarbonate resin is used. Further, it may be a copolymerization type in which a part of tetrabromobisphenol A is replaced with another dihydric phenol, and the dihydric phenol described in the above aromatic polycarbonate resin is used as the other dihydric phenol. Of these, bisphenol A is preferable. in this case,
It is preferable to use tetrabromobisphenol A in an amount of 50 mol% or more. The degree of polymerization of such a polycarbonate type flame retardant is not particularly limited, but those having a degree of polymerization of 1 are likely to bleed out from a molded article obtained by blending with an aromatic polycarbonate resin, and as the degree of polymerization increases, bleed out becomes more difficult. The degree of polymerization is preferably in the range of 2 to 200 because the melt viscosity increases and it becomes difficult to react. The amount of the polycarbonate type flame retardant used is 1 to 15 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin. If it is less than 1 part by weight, it becomes difficult to obtain a sufficient flame retardant effect, and if it is more than 15 parts by weight, the bromine concentration becomes large and the molding machine and the processing machine are corroded, so that the object of the present invention cannot be achieved.

The perfluoroalkanesulfonic acid alkali salt used in combination with the above polycarbonate type flame retardant has 1 carbon atom.
To 8 each have a fluorinated alkyl group, and examples thereof include potassium perfluorobutane sulfonate and sodium perfluorooctane sulfonate. If the amount used is too small, it will be difficult to obtain a sufficient flame retardant effect, and if the amount is too large, burning will occur at the time of molding the obtained composition. .01
Should be ~ 2 parts by weight.

The metal constituting the sulfuric acid ester metal salt of a monohydric alcohol or a polyhydric alcohol is an alkali metal or an alkaline earth metal, and sodium and potassium are particularly preferable. Examples of sulfuric acid ester metal salts of monohydric or polyhydric alcohols include sodium methyl sulfate (or potassium), sodium lauryl sulfate (potassium), sodium hexadecyl sulfate (potassium), sodium polyoxyethylene monomethyl ether sulfate (potassium), polyoxyethylene. Monotolyl ether Sodium (potassium) sulfate, ethyleneglycol, propyleneglycol, butanediol and other mono- or disodium sulfate (potassium), pentaerythritol mono-, di-, tri- or tetrasulfate sodium (potassium) stearate monoglyceride mono Sodium sulfate (potassium),
1,3-bis (2-ethylhexyl) glycerin ether sodium monosulfate (potassium), phenoxy resin sulfate metal salt and the like or halogen substitution products thereof are mentioned. These may be used alone or in combination of two or more kinds. Good. The amount of the sulfuric acid ester metal salt of the alcohol used is 0.001 to 2 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the aromatic polycarbonate resin. When it is less than 0.001 part by weight, it is difficult to obtain a sufficient flame retardant effect, and when it is more than 2 parts by weight, burning occurs when molding the obtained composition.

Polytetrafluoroethylene is well known as a fibril-forming fluororesin, but any fluororesin that can be dispersed in a fibril form in a polycarbonate resin molded article will do. The amount of the fluorine-based resin used is 0.01 to 2 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin. If it is less than 0.01 parts by weight, it is difficult to prevent drip during combustion and it is difficult to obtain a sufficient flame retardant effect. If it is more than 2 parts by weight, the physical properties of the resulting composition may be deteriorated or the appearance may be deteriorated. Will be reduced.

Any method may be employed to make the compositions of the present invention. For example, the above components may be mixed in advance, or each of the above components may be added to the aromatic polycarbonate resin in any order and dry blended with, for example, a super mixer or a tumbler.

The obtained composition can be used as it is or after it is once pelletized by an extruder and then formed into a molded product by a method such as ordinary injection molding, extrusion molding, compression molding, and the like. It has excellent flame retardancy and at the same time retains the original excellent physical properties of aromatic polycarbonate resin.

In the composition of the present invention, if desired, any additive such as a release agent, an antistatic agent, a light stabilizer,
Antioxidants, reinforcing agents, foaming agents, dyes and pigments, inorganic fillers and the like can be added.

Examples of the releasing agent include pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, stearyl stearate, behenyl behenate, stearyl mono-, di- or triglycerides, sorbitan monostearate, paraffin wax, bees paste, Examples thereof include polydimethylsiloxane and phenyl group-containing dimethylsiloxane, which are usually used in an amount of 0.001 to 5% by weight.

Examples of the antistatic agent include glycerin monostearate, ammonium dodecylbenzene sulfonate, phosphonium dodecylbenzene sulfonate, Hyboron LB-120 (manufactured by Boron International), mono- or diglyceride maleic anhydride, graphite,
Metal powder and the like can be mentioned, and usually 0.1 to 10% by weight is used.

Examples of the light stabilizer include 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole and 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzo. Triazole, 2
-(5-Methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α,
α-Dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis (3,1-benzoxazine-4-) ON), polyalkylene naphthalate, etc., and usually 0.01 to 5
Used by weight percent.

Examples of the antioxidant include phosphoric acid and phosphoric acid esters such as trimethyl phosphate, phosphorous acid and phosphorous acid esters such as tris (2,4-di-tert-butylphenyl) phosphite. , Pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, octadecyl-3- (3,5-
Examples thereof include di-tert-butyl-4-hydroxyphenyl) propionate and tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenephosphonite, which are usually used in an amount of 0.001 to 10% by weight. It

Examples of the reinforcing agent include metal fibers, glass fibers, carbon fibers, graphite fibers, alumina fibers,
Examples thereof include silicon nitride fibers, potassium titanate whiskers, boron fibers, wholly aromatic polyamide fibers, wholly aromatic polyester fibers, etc., and they are usually used in an amount of 1 to 60% by weight.

[0020]

EXAMPLES The present invention will be further described below with reference to examples. Parts in the examples are parts by weight, and flame retardancy is
It was evaluated according to Subject 94 (UL-94) of Laboratories.

[0021]

Examples 1 to 9 and Comparative Examples 1 to 5 As the aromatic polycarbonate resin, (A) bisphenol A, p-tert-butylphenol (molecular weight modifier) and phosgene were used to obtain a viscosity average molecular weight of 21,000 by a conventional method. Granular aromatic polycarbonate resin, (B) granular aromatic polycarbonate resin having a viscosity average molecular weight of 25,000 obtained in the same manner, (C) tetrabromobisphenol A as a flame retardant,
A powdery polycarbonate oligomer having an average degree of polymerization of 7 obtained from phenol (molecular weight modifier) and phosgene by a conventional method, (D) potassium perfluorobutanesulfonate [Megafac F-114 manufactured by Dainippon Ink and Chemicals, Inc.],
(E) Sulfate metal salt of alcohol [Emar 10 manufactured by Kao Atlas Co., Ltd.], (F) Polytetrafluoroethylene capable of forming fibrils [Polyflon manufactured by Daikin Industries, Ltd.]
F-201 L] and [Fluon CD 07 manufactured by Asahi Glass Co., Ltd.]
6] was mixed for 10 minutes at 500 rpm with a supermixer in the amount shown in Table 1, dried at 120 ° C. for 6 hours, and then pelletized at a cylinder temperature of 280 ° C. with a vented single-screw extruder to obtain 120 pellets. After drying at 4 ° C. for 4 hours, 20 test pieces (125 mm × 13 mm × 1 mm) were prepared at 280 ° C. by a 5 ounce injection molding machine, flame retardancy was evaluated, and the results are shown in Table 1. The symbols in Table 1 are as follows. PC: Aromatic Polycarbonate Resin P-1: Granular Aromatic Polycarbonate Resin with Viscosity Average Molecular Weight 21,000 P-2: Granular Aromatic Polycarbonate Resin with Viscosity Average Molecular Weight 25,000 Flame Retardant A: From Tetrabromobisphenol A Polycarbonate oligomer Flame retardant B: Potassium perfluorobutane sulfonate Flame retardant C: Sulfate ester metal salt of alcohol F-1: Fibril-forming polytetrafluoroethylene [Polyflon F-201 L manufactured by Daikin Industries, Ltd.] F-2: Fibril-forming polytetrafluoroethylene [Fluon CD 076 manufactured by Asahi Glass Co., Ltd.]

[0022]

[Table 1]

[0023]

Since the composition of the present invention can significantly reduce the bromine concentration as compared with the conventional polycarbonate type flame retardant alone, it is possible to significantly reduce the corrosion of the molding machine and the processing machine. In addition, the flame retardancy is improved, and the physical properties inherent in the aromatic polycarbonate resin are hardly deteriorated, and the industrial effect produced by the aromatic polycarbonate resin is remarkable.

Claims (1)

[Claims] 1. 100 parts by weight of an aromatic polycarbonate resin, 1 to 15 parts by weight of a tetrabromobisphenol A-based polycarbonate flame retardant, 0.01 to 2 parts by weight of a perfluoroalkanesulfonic acid alkali salt, a monohydric alcohol or a polyhydric alcohol or a polyhydric alcohol. Sulfate ester metal salt of polyhydric alcohol 0.001
2 parts by weight and 0.01% fibril-forming fluororesin
A flame-retardant aromatic polycarbonate resin composition comprising 2 parts by weight.