JP3129556B2 - Flame retardant aromatic polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant aromatic polycarbonate resin composition. More specifically, an aromatic polycarbonate resin having excellent flame retardancy without using a bromo compound that causes corrosion of a molding machine or a processing machine, without deteriorating the excellent physical properties of the aromatic polycarbonate resin. Composition.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are widely used in a wide variety of fields because of their many excellent properties. However, aromatic polycarbonate resins are 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 conventionally been known. For example, Japanese Patent Publication No. 47-44537 proposes a method of blending a polycarbonate oligomer of tetrabromobisphenol A in such an amount that the bromine concentration becomes 5 to 15% by weight, and Japanese Patent Publication No. 47-24660 discloses a method of mixing tetrabromobisphenol A. A method has been proposed in which a copolymerized polycarbonate of A and bisphenol A is blended in such an amount that the bromine concentration becomes 5 to 9% by weight. However,
When a flame-retardant aromatic polycarbonate resin composition obtained by blending such a bromo-based flame retardant is molded or processed, a molding machine or a processing machine is easily corroded, and this corrosion becomes more severe as the bromide concentration increases. Therefore, development of an aromatic polycarbonate resin having excellent flame retardancy with less corrosion of a molding machine and a processing machine has been desired.

[0003] A method of blending an inorganic salt with an aromatic polycarbonate resin is also known. JP-A-52-175
No. 57 and Japanese Patent Application Laid-Open No. 52-17558 propose a method of blending an inorganic sulfite, a thiosulfate, a nitrite, a pyrosulfite, or an organic halogen compound together with these salts. According to these methods, the generation of toxic gas is reduced, but the impact resistance is remarkably reduced, and the above-mentioned salts are not dissolved in the aromatic polycarbonate resin, so that the transparency is impaired.
Furthermore, Japanese Patent Publication No. 56-26767 proposes a method of blending a sulfate metal salt of an alcohol.
According to this method, the generation of toxic gas is reduced, but if the compound is blended in an amount that exhibits sufficient flame retardancy, burns are likely to occur when the resulting composition is molded.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a molding machine or a processing machine which does not use a bromo compound which causes corrosion, without deteriorating the excellent physical properties inherent in an aromatic polycarbonate resin. To provide an aromatic polycarbonate resin having excellent flame retardancy. The present inventors have conducted intensive studies to achieve the above object.As a result, when a small amount of a mixture of an organic phosphoric acid di- or monoester and an alkali metal salt of an organic phosphoric acid diester is used in combination with a sulfate metal salt of an alcohol, the sulfate metal salt of an alcohol is used. Even when the amount of the salt used is small, it has been found that excellent flame retardancy can be imparted to the aromatic polycarbonate resin and the above object can be achieved, and the present invention has been completed.

[0005]

SUMMARY OF THE INVENTION The present invention is, in 100 parts by weight of an aromatic polycarbonate resin, mono- and / or polyhydric alcohol sulfuric acid ester metal salt of 0.001 to 0.1 parts by weight and an organic phosphoric acid di or Monoester and organophosphate
The ratio of the alkali metal salt of stell is 4: 6 to 1: 1 by weight.
9 relates to a flame-retardant aromatic polycarbonate resin composition comprising 0.001 to 5 parts by weight of the mixture of No. 9 .

[0006] The aromatic polycarbonate resin targeted in 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 sulfones and their aromatic rings in which an alkyl group, an aryl group, or the like is substituted. These may be used alone or in combination of two or more. Of these, bisphenol A is preferred. 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, and preferably 1 to 10,000 in terms of viscosity average molecular weight.
5,000 to 40,000. In producing such an aromatic polycarbonate resin, a suitable molecular weight regulator, a catalyst for accelerating the reaction, and the like can be used as necessary.

The aromatic polycarbonate resin to be used in the present invention is a branched polycarbonate resin obtained by copolymerizing a polyfunctional compound or a polyester obtained by copolymerizing an aromatic or aliphatic bifunctional 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 may be used.
It may be a mixture of an ultra-high molecular weight aromatic polycarbonate resin having a molecular weight of 000 or more.

The metal constituting the metal salt of a sulfate of a monohydric alcohol or a polyhydric alcohol used in the present invention is an alkali metal or an alkaline earth metal, and sodium and potassium are particularly preferable. Examples of the sulfate metal salts of alcohols include sodium methyl sulfate (or potassium), sodium lauryl sulfate (potassium), sodium hexadecyl sulfate (potassium), sodium polyoxyethylene alkyl ether sulfate (potassium), sodium polyoxyethylene alkyl phenyl ether sulfate (Potassium), mono- or sodium disulfate (potassium) such as ethylene glycol, propylene glycol, butanediol, etc., mono-, di-, tri- or tetra-sodium sulfate (potassium) of pentaerythritol, sodium monoglyceride monosulfate (potassium) monosulfate ,
1,3-bis (2-ethylhexyl) glycerin ether sodium (potassium) monosulfate, metal salts of phenoxyresin sulfate and the like, and halogen-substituted products thereof, may be used alone or in combination of two or more. Is also good. The amount of the metal sulfate sulfate used is 0.001-2 parts by weight, preferably 0.01-1 part by weight, per 100 parts by weight of the aromatic polycarbonate resin. If the amount is less than 0.001 part by weight, it is difficult to obtain a sufficient flame-retardant effect even by using a mixture of an organic phosphoric acid diester described below and an alkali metal salt thereof. If the amount is more than 2 parts by weight, burning will occur when the resulting composition is molded.

The organophosphoric acid diester used in combination with the above-mentioned metal sulfate metal salt of alcohol is represented by the following general formula [1]:

[0010]

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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,
₁ and R ₂ may be bonded directly or by an alkylene group, or may form one condensed ring, and an alkyl group, an aryl group and / or a halogen atom are introduced into R ₁ and R _2. And the organic phosphoric diester is preferably, for example, diphenyl phosphate, monophenyl phosphate, diphosphate (pt)
ert-butylphenyl), di (p-bromophenyl) phosphate, di (4-cumylphenyl) phosphate, di (2,6-dibromo-4-cumylphenyl) phosphate,

[0012]

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

[0014]

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[Wherein 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 a single condensed ring. And 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 sodium salts and potassium salts of the above organic phosphoric acid diester.

When the mixing ratio of the organic diphosphate or monoester and the alkali metal salt of the organic diphosphate is too small, the thermal stability of the resulting composition is reduced if the ratio of the organic diphosphate or monoester is too small. If it is too large, the thermal stability will deteriorate, so that the range of (organic phosphate di- or monoester) / (alkali metal salt of organic phosphate diester) is preferably 4/6 to 1/9, The total amount of the organic phosphoric acid di- or monoester and the alkali metal salt of the organic phosphoric acid diester is 0.00.0 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin.
It is in an amount of from 1 to 5 parts by weight. If the amount is less than 0.001 part by weight, it is difficult to obtain a sufficient flame retarding effect, and if the amount is more than 5 parts by weight, the effect of increasing the flame retardancy is no longer recognized, and the hue deteriorates.

Any method can be employed to produce the composition of the present invention. For example, the above-mentioned alcohol sulfate metal salt, organic phosphoric acid di- or monoester and alkali metal salt of organic phosphoric acid diester are previously mixed, or added to the aromatic polycarbonate resin in an arbitrary order. Dry blending may be performed using a super mixer, a tumbler or the like.

The composition obtained can be formed into pellets as it is or once in the form of pellets by an extruder, and then formed into a molded product by a method such as ordinary injection molding, extrusion molding, or compression molding. While having excellent flame retardancy, aromatic polycarbonate resin retains the original excellent physical properties,
No burns are observed.

In the composition of the present invention, for example, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, Combination of 0.01 to 2% by weight of a fluororesin such as chlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, vinylidene fluoride-hexafluoropropylene copolymer prevents drip during combustion and flame resistance. Properties can be further improved.

The composition of the present invention may contain, if necessary, optional additives such as a releasing 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 tetraperargonate, stearyl stearate,
Behenyl behenate, stearyl-mono, di- or triglyceride, sorbitan monostearate, paraffin wax, beeswax, polydimethylsiloxane, phenyl group-containing dimethylsiloxane, and the like, usually 0.001.
~ 5% by weight is used.

Examples of the antistatic agent include glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate,
Hiboron LB-120 (Boron International)
Maleic anhydride mono- or diglyceride, 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 and the like, and usually 0.01 to 5
Used by weight.

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

As the reinforcing agent, for example, metal fiber, glass fiber, carbon fiber, graphite fiber, alumina fiber,
Examples thereof include silicon nitride fibers, potassium titanate whiskers, boron fibers, wholly aromatic polyamide fibers, wholly aromatic polyester fibers, and the like, and usually 1 to 60% by weight.

[0025]

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

[0026]

Examples 1-4 and Comparative Examples 1 and 2, bisphenol A,
As a molecular weight regulator, 100 parts of a powdery aromatic polycarbonate resin having a viscosity average molecular weight of 23,000 obtained from p-tert-butylphenol and phosgene by a conventional method was added to a sulfuric acid ester metal salt of an alcohol shown in Table 1;

[0027]

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An organic phosphoric diester of the following formula:

[0029]

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A mixture of the potassium salt of an organic phosphoric acid diester previously mixed in a weight ratio of 2: 8 and fibrillated polytetrafluoroethylene [Daikin Industries, Ltd.
Polyflon F-201L] was mixed for 30 minutes at 500 rpm using a supermixer shown in Table 1, and 120
After drying at 6 ° C. for 6 hours, the resulting pellets were pelletized at a cylinder temperature of 290 ° C. by a vented single-screw extruder. The obtained pellets were dried at 120 ° C. for 4 hours and then tested at 290 ° C. by a 3 oz. 13mm x 1.6mm)
Were prepared, and the flame retardancy was evaluated. The results are shown in Table 1. In Table 1, the mixture of the organic phosphoric acid diester and the potassium salt of the organic phosphoric acid diester was indicated as "P mixture".

[0031]

[Table 1]

[0032]

Industrial Applicability The composition of the present invention provides excellent flame retardancy without using a bromo compound which causes corrosion of a molding machine or a processing machine, without deteriorating the excellent physical properties inherent to an aromatic polycarbonate resin. , And the industrial effects it produces are exceptional.

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 69/00

Claims (1)

(57) [Claims] 1. To 100 parts by weight of an aromatic polycarbonate resin, 0.001 to 0.1 parts by weight of a metal salt of a sulfuric ester of a monohydric and / or polyhydric alcohol and an organic phosphoric acid di- or monoester and an organic phosphoric acid diester Of alkali metal salts
A mixture having a ratio of 4: 6 to 1: 9 by weight , 0.001 to 5
A flame-retardant aromatic polycarbonate resin composition containing parts by weight.