JPH06184421A - Flame-retardant aromatic polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent flameretardancy and free from corroding action on molding machine, etc., by compounding an aromatic polycarbonate resin with specific amounts of a perfluoroalkanesulfonic acid alkali salt add an organic phosphoric acid diester or monoester, etc. CONSTITUTION:This resin composition is produced by compounding (A) 100 pts.wt. of an aromatic polycarbonate resin (e.g. a resin produced by reacting a dihydric phenol such as bisphenol A with a carbonate precursor such as phosgene) with (B) 0.01-2 pts.wt. of a perfluoroalkanesulfonic acid alkali salt (e.g. potassium perfluorobutanesulfonate) and (C) 0.001-5 pts.wt. of a mixture of (i) an organic phosphoric acid diester or monoester (preferably diphenyl phosphate, etc.) and (ii) an organic phosphoric acid diester alkali metal salt of formula (R3 and R4 are independently aromatic group; M is preferably Na or K) at a mixing ratio i/ii of preferably 4/6 to 1/9.

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, an aromatic polycarbonate resin having excellent flame retardancy without deteriorating the original excellent physical properties of the aromatic polycarbonate resin without using a bromine compound that causes corrosion of a molding machine or a processing machine. It relates to a composition.

[0002]

Aromatic polycarbonate resins are widely used in a wide variety of fields because they have many excellent properties. However, the aromatic polycarbonate resin is flammable, and severe flame retardancy is required for some applications. 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 or processed, a molding machine or a processing machine is easily corroded, and this corrosion becomes more severe as the brom concentration increases. Therefore, development of an aromatic polycarbonate resin having excellent flame retardance with less corrosion of a molding machine or a processing machine has been earnestly desired.

Also known is a method of blending a non-halogen flame retardant with an aromatic polycarbonate resin. Japanese Patent Publication No. 47-40445 proposes a method of blending potassium perfluoroalkanesulfonate. According to this method, the generation of toxic gas is reduced, but the thermal stability of the resulting composition is lowered when the composition is blended in an amount showing sufficient flame retardancy.

[0004]

It is an object of the present invention to use a bromine compound that causes corrosion of a molding machine or a processing machine, without deteriorating the excellent physical properties of the aromatic polycarbonate resin. Another object of the present invention is to provide an aromatic polycarbonate resin having flame retardancy.

As a result of earnest studies aimed at achieving the above object, the present inventor has found that when a small amount of a mixture of an organic phosphoric acid diester and its alkali metal salt is used together with potassium perfluoroalkanesulfonate, the amount of potassium perfluoroalkanesulfonate used is increased. It has been clarified that the aromatic polycarbonate resin can be provided with excellent flame retardancy even if it is reduced, and the above-mentioned object can be achieved. As a result of further studies, the present invention has been completed.

[0006]

The present invention relates to 100 parts by weight of an aromatic polycarbonate resin, 0.01 to 2 parts by weight of an alkali salt of perfluoroalkanesulfonic acid, and an alkali metal salt of an organic phosphoric acid diester and an organic phosphoric acid diester. The present invention relates to a flame-retardant aromatic polycarbonate resin composition obtained by blending 0.001 to 5 parts by weight of the mixture.

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 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. Although the molecular weight of the aromatic polycarbonate resin is not particularly limited, it is usually 10,000 to 50,000, preferably 1 in terms of viscosity average molecular weight.
It is 5,000 to 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 alkali salt of perfluoroalkane sulfonic acid used in the present invention has an alkyl group having fluorinated carbon atoms of 1 to 8 and is, for example, potassium perfluorobutane sulfonate or perfluorooctane sulfonic acid. Examples include sodium. If the amount used is too small, it becomes difficult to obtain a sufficient flame retardant effect even if a mixture of an organic phosphoric acid diester and its alkali metal salt described later is used together, and if it is too large, the thermal stability of the resulting composition decreases. Therefore, it should be 0.01 to 2 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin.

The organic phosphoric acid diester used in combination with the perfluoroalkanesulfonic acid alkali salt is represented by the following general formula [1]

[0011]

[Chemical 1]

[Wherein R ₁ is an aromatic group, R ₂ is an aromatic group or a hydrogen atom, and when R ₁ and R ₂ are aromatic groups, R ₁ and R ₂ are bonded directly or with an alkylene group. Or may form one fused ring, and R ₁ and R ₂ may have an alkyl group, an aryl group and / or a halogen atom introduced thereinto]. And preferred examples of such organic phosphoric acid di- or monoesters include diphenyl phosphate, di (p-tert-butylphenyl) phosphate, di (p-bromophenyl) phosphate, di (4-cumylphenyl) phosphate, Di (2,6-dibromo-4-cumylphenyl) phosphate,

[0013]

[Chemical 2]

[In the formula, B is a tertiary butyl group, X is a halogen atom, and n is 0 or an integer of 1 to 4] and the like.
The alkali metal salt of an organic phosphoric acid diester is represented by the following general formula [2].

[0015]

[Chemical 3]

[In the formula, R ₃ and R ₄ are each independently an aromatic group, and R ₃ and R ₄ may be bonded directly or by an alkylene group, or may form one condensed ring. Further, an alkyl group, an aryl group and / or a halogen atom may be introduced into R ₃ and R ₄ . M is an alkali metal, preferably sodium or potassium],
Preferred examples of the alkali metal salt of the organic phosphoric acid diester include the sodium salt and potassium salt of the organic phosphoric acid diester.

If the mixing ratio of the organic phosphoric acid di- and monoesters and the alkali metal salt of the organic phosphoric acid diester is too small, the thermal stability of the resulting composition decreases. , If it gets too large, the thermal stability will rather deteriorate, so
The range of (organic phosphoric acid di- or monoester) / (alkali metal salt of organic phosphoric acid diester) is preferably 4/6 to 1/9, and the amount of the organic phosphoric acid di- or monoester and organic phosphoric acid used is The total amount of the alkali metal salt of the diester is 0.001 to 5 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin. If it is less than 0.001 part by weight, it is difficult to obtain a sufficient flame retardant effect, and if it is more than 5 parts by weight, the flame retardancy increasing effect is no longer recognized and the hue of the resulting composition deteriorates. .

Any method may be employed to produce the composition of the present invention. For example, the above-mentioned perfluoroalkanesulfonic acid alkali salt, organic phosphoric acid di- or monoester and alkali metal salt of organic phosphoric acid diester are mixed in advance or added to the aromatic polycarbonate resin in any order. For example, dry blending may be performed with a super mixer, a tumbler, or the like.

The obtained composition can be used as it is or after it is once made into pellets by an extruder and then made into a molded product by a method such as ordinary injection molding, extrusion molding or compression molding. 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, for example, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, poly By blending 0.01 to 2% by weight of a fluorine-based resin such as chlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, vinylidene fluoride-hexafluoropropylene copolymer, drip at the time of combustion is prevented and flame retardancy is achieved. It is possible to further improve the sex.

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 release agent include pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, stearyl stearate,
Examples include behenyl behenate, stearyl mono-, di- or triglyceride, sorbitan monostearate, paraffin wax, honey stick, polydimethylsiloxane, phenyl group-containing dimethylsiloxane, and the like.
~ 5 wt% used.

Examples of the antistatic agent include glycerin monostearate, ammonium dodecylbenzene sulfonate, phosphonium dodecylbenzene sulfonate,
High Boron LB-120 (made by Boron International),
Examples thereof include maleic anhydride mono- or diglyceride, graphite, metal powder, etc., 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 its ester, phosphorous acid and its ester, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-. 3-stearyl thiopropionate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,2 4-di-tert-butylphenyl) -4,4'-biphenylenephosphonite and the like can be mentioned, and usually 0.001 to 10% by weight is used.

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 usually used in an amount of 1 to 60% by weight.

[0026]

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.

[0027]

Examples 1 and 2 and Comparative Examples 1 and 2 Bisphenol A,
100 parts of a granular aromatic polycarbonate resin having a viscosity average molecular weight of 22,000 obtained by a conventional method from p-tert-butylphenol and phosgene as a molecular weight regulator, potassium perfluorobutanesulfonate, the following formula

[0028]

[Chemical 4]

Organophosphoric acid diester of

[0030]

[Chemical 5]

A mixture of the potassium salt of the organic phosphoric acid diester of 2) previously mixed in a weight ratio of 2: 8 and fibrillated polytetrafluoroethylene [Fluon CD076 manufactured by Asahi Glass Co., Ltd.] was used in an amount of 10 as shown in Table 1.
Mix for 1 minute, dry with a hot air circulation dryer at 120 ° C for 6 hours, pelletize with a 30φ extruder at a cylinder temperature of 290 ° C, dry the pellets obtained at 120 ° C for 4 hours, and then with a 3 ounce injection molding machine [Japan Made by Steel Manufacturing Co., Ltd.] at 290 ° C (125mm × 13mm × 1.6mm)
No. 20 was prepared and the flame retardancy was evaluated, and the results are shown in Table 1.

[0032]

Examples 3 and 4 and Comparative Examples 3 and 4 Bisphenol A as an aromatic polycarbonate resin and a molecular weight modifier
Flame retardancy was evaluated in the same manner as in the above Examples and Comparative Examples, except that 100 parts of a powdery granular aromatic polycarbonate resin having a viscosity average molecular weight of 30,000 obtained by a conventional method from p-tert-butylphenol and phosgene was used. The results are shown in Table 1. In addition, in Table 1, the mixture of the organic phosphoric acid diester and the potassium salt of the organic phosphoric acid diester is indicated as "P mixture".

[0033]

[Table 1]

[0034]

EFFECTS OF THE INVENTION The composition of the present invention has excellent flame retardancy without using the bromine compound which causes corrosion of the molding machine or the processing machine, without deteriorating the excellent physical properties of the aromatic polycarbonate resin. And has an industrial effect that is exceptional.

Claims (1)

[Claims] 1. A perfluoroalkanesulfonic acid alkali salt of 0.1 part is added to 100 parts by weight of an aromatic polycarbonate resin.
0. 1-2 parts by weight and a mixture of organic phosphoric acid di- or monoesters and alkali metal salts of organic phosphoric acid diesters 0.00
A flame-retardant aromatic polycarbonate resin composition containing 1 to 5 parts by weight.