JP2591538B2 - Flame retardant polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant polycarbonate resin composition. More specifically, the present invention relates to a flame-retardant polycarbonate resin composition obtained by mixing a metal salt of a specific organic phosphate with a polycarbonate resin.

[0002]

2. Description of the Related Art Conventionally, many methods for flame retarding polycarbonate resins have been proposed. In many cases, an organic halogen compound is added. For example, Shoko Sho 4
JP-A-7-44537 discloses a method of adding an oligomer of tetrabromobisphenol A. However, in this method, a considerable amount of a halogen compound needs to be added, so that the thermal stability at the time of molding is reduced, and furthermore, there is a disadvantage that corrosive and toxic gas and smoke are generated at the time of molding and burning. is there.

One of the improved methods is disclosed in Japanese Patent Application Laid-Open No. 52-5 / 1982.
No. 4741 to JP-A-52-54747 propose a method of adding an aromatic sulfonate. However, aromatic sulfonates have the disadvantage of impairing the transparency of the polycarbonate resin.

[0004] Also, Japanese Patent Application Laid-Open No. Sho 59-140255,
JP-A-60-149658 proposes a method of adding a metal salt of a biphenyl type aromatic phosphonic acid or a metal salt of a halogenated phosphonic acid thereof. However, when a metal salt of a biphenyl-type aromatic phosphonic acid or a metal salt of a halogenated aromatic phosphonic acid is added, the polycarbonate resin is decomposed, and there is a disadvantage that thermal stability is poor.

The present inventors have found that a polycarbonate resin to which a metal salt of an organic phosphoric acid ester is added has excellent flame retardancy and heat resistance, and have proposed this . Also ,
When the amount added is increased by this method, there is a problem that transparency is slightly impaired. To solve this problem, Japanese Patent Application Laid-Open No. 2-180 discloses a method of blending a specific metal salt of a halogenated organophosphate with a polycarbonate resin.
No.956 . However, when the addition amount is increased by this method, it has been found that the transparency can be maintained but the molded product slightly yellows.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a flame-retardant polycarbonate resin composition which does not generate corrosive gas during molding and burning without impairing the transparency of the polycarbonate resin and which has excellent heat stability during molding. The purpose is to provide things.

As a result of further intensive studies to solve this problem, the present inventor has found that the addition of a specific phosphoric acid metal salt of cumyl phenyl ester to a polycarbonate resin provides excellent transparency, The present inventors have found that a practical material having good thermal stability and sufficient flame retardancy can be obtained, and have reached the present invention.

[0008]

According to the present invention, the following general formula [1] is added to 100 parts by weight of a polycarbonate resin.

[0009]

Embedded image Wherein X is a hydrogen atom or a halogen atom, and M is an alkali metal. A flame-retardant polycarbonate resin composition comprising 0.001 to 5 parts by weight of at least one metal salt of an organic phosphate represented by the formula: It is related to.

The polycarbonate resin used in the present invention is produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. As the dihydric phenol, 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A] is mainly used, but a part or all of the dihydric phenol may be replaced with another dihydric phenol. Other dihydric phenols include, for example, bis (4-hydroxyphenyl) methane, 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)
Sulfone and the like. Further, carbonyl halides as carbonate precursor, haloformate is Agerare, specifically phosgene, diphenyl carbonate, dihaloformate and mixtures thereof dihydric phenol.

Although the degree of polymerization of the polycarbonate resin is not particularly limited, it is usually 10,000 as a viscosity average molecular weight.
~ 50,000, preferably 13,000 ~ 40,00
0. In producing such a polycarbonate resin, an appropriate molecular weight regulator, a branching agent for improving processability, a catalyst for accelerating the reaction, and the like can be used as necessary. It is also possible to use a mixture of two or more polycarbonate resins obtained by thus.

The metal salt of an organic phosphoric ester used as a flame retardant in the present invention is represented by the general formula [1], wherein X is hydrogen or a halogen atom, and the halogen atom is bromine or chlorine. Is preferred. Further, K or Na is particularly preferable as the alkali metal represented by M.
Such a metal salt of an organic phosphoric acid ester can be easily produced by, for example, reacting cumylphenol or a halogenated cumylphenol with phosphorus oxychloride.

The compounding ratio of the metal salt of the organic phosphoric acid ester of the general formula [1] is 0.001 to 5 parts by weight, preferably 0.03 parts by weight, per 100 parts by weight of the polycarbonate resin.
It is 0.5 to 2 parts by weight. If the amount is less than 0.001 part by weight, the flame retardant effect is insufficient. If the amount exceeds 5 parts by weight, not only the thermal stability is lowered but also the flammability is increased. Further, by using it together with a conventional organic halogen-based flame retardant, its flame retardant effect can be greatly improved, and the amount of both used can be significantly reduced.

For producing the resin composition of the present invention, any method is employed. For example, a powdery polycarbonate resin and a powdery metal salt of an organic phosphate of the general formula [1] may be dry-blended using a supermixer, a tumbler or the like, or the organic phosphate of the general formula [1] May be added to the polycarbonate resin powder and then dry-mixed.

The obtained composition can be used as it is or in the form of pellets by an extruder to obtain a molded article by a method such as ordinary injection molding, extrusion molding, compression molding and the like. The molded article thus obtained retains excellent transparency.

The composition of the present invention may optionally contain any additives such as a stabilizer, a releasing agent, a lubricant, an antistatic agent, an ultraviolet absorber, and an organic halogen compound flame retardant. it can. If transparency is sacrificed, a fluorine-based polymer, a silicon-based polymer, an inorganic filler, glass fiber, carbon fiber, or the like can be added.

[0017]

EXAMPLES The present invention will be specifically described below with reference to examples.

[0018]

Examples 1 to 3 and Comparative Examples 1 to 3 A bisphenol A polycarbonate resin having a viscosity average molecular weight of about 23,000 previously dried [Panlite L-125 manufactured by Teijin Chemicals Ltd.]
0] 100 parts by weight of the additives shown in Table 1 were added in the amounts shown in the table, and preliminarily mixed by a V-type blender. ) VSK-30]. After the obtained pellets were dried at 120 ° C. for 6 hours, the cylinder temperature was 290 using an injection molding machine [CYCAP S480 / 150 manufactured by Sumitomo Heavy Industries, Ltd.].
At 120 ° C. and a mold temperature of 90 ° C., a test piece of 120 mm × 6.5 mm × 3.0 mm was formed . The combustion test was performed using this test piece in AS
According to TM D-2863-70. I. Measure the value,
The appearance was evaluated visually, and the results are shown in Table 1. In addition, the symbol in the kind of additive in a table | surface is as follows.

A: Diarylphosphoric acid chloride is prepared by reacting 4-cumylphenol with phosphorus oxychloride in the presence of a dehydrochlorinating agent, and is synthesized by hydrolyzing the diarylphosphoric acid chloride.

[0020]

Embedded image B: Brominated 4-cumylphenol by a conventional method, reacted with phosphorus oxychloride in the presence of a dehydrochlorinating agent to obtain diarylphosphoric chloride, and synthesized by hydrolysis to have the following structure: It is.

[0021]

Embedded image C: 4-Cumylphenol is chlorinated by a conventional method, this is reacted with phosphorus oxychloride in the presence of a dehydrochlorinating agent to give diarylphosphoric acid chloride, which is synthesized by hydrolysis to have the following structure. It is.

[0022]

Embedded image D: having the following structure [NA-10 manufactured by Adeka Argus Co., Ltd.]

[0023]

Embedded image E: 4-bromophenol and phosphorus oxychloride are reacted in the presence of a dehydrochlorinating agent to obtain diarylphosphoric chloride, which is synthesized by hydrolysis to have the following structure.

[0024]

Embedded image

[0025]

[Table 1]

[0026]

The composition of the present invention is ASTM D-286.
O.3 based on 3-70. I. It shows excellent flame retardancy in a flammability test by value measurement, is transparent when no fluoropolymer or glass fiber is added, and generates little corrosive gas during molding and combustion. As described above, the composition of the present invention has excellent performance as compared with conventional flame-retardant polycarbonate compositions, and can be used for a wide range of applications.

Claims (1)

(57) [Claims] 1. 100 parts by weight of a polycarbonate resin,
The following general formula [1] Wherein X is a hydrogen atom or a halogen atom, and M is an alkali metal. A flame-retardant polycarbonate resin composition comprising 0.001 to 5 parts by weight of at least one metal salt of an organic phosphate represented by the formula: .