JP3169190B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition, and more particularly, to a polycarbonate resin composition having excellent flame retardancy and excellent transparency.

[0002]

2. Description of the Related Art
As one of useful methods for imparting flame retardancy to polycarbonate resins, a method of adding an alkali metal salt or an alkaline earth metal salt of perfluoroalkanesulfonic acid to polycarbonate (Japanese Patent Publication Nos. 47-40445 and 54-54).
No. 32456) or a method of adding an alkali metal salt or an alkaline earth metal salt of an organic sulfonic acid (JP-A-3-263459). But,
When the addition amount is increased to improve the flame retardancy by these methods, the transparency, which is a characteristic of the polycarbonate resin, is reduced, and there are various restrictions on use (Japanese Patent Application Laid-Open No. 3-26345).
No. 9).

[0003]

Accordingly, the present inventors have made intensive studies on suppressing the decrease in the transparency of a polycarbonate resin due to the addition of an alkali metal salt or an alkaline earth metal salt of perfluoroalkanesulfonic acid. As a result, by adding an appropriate amount of an epoxy resin together with an alkali metal salt or an alkaline earth metal salt of perfluoroalkanesulfonic acid to polycarbonate, a highly transparent polycarbonate resin having high flame retardancy can be obtained. Was found. The present invention has been completed based on such findings. That is, the present invention relates to (A) 100 parts by weight of a polycarbonate and (B) an alkali metal salt or an alkaline earth metal salt of perfluoroalkanesulfonic acid 0.1.
0.5 parts by weight and 0.1 to 5 parts by weight of the epoxy resin (C), and the weight ratio of the component (B) to the component (C) is
It is intended to provide a polycarbonate resin composition, wherein component (B) / component (C) = 1/1 to 1/10.

In the composition of the present invention, as the polycarbonate used as the component (A), those conventionally used can be suitably used.

[0005]

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Wherein Z is a single bond, an ether bond or an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkyl group having 5 to 15 carbon atoms. Alkylidene group, sulfonyl group, sulfoxide group, carbonyl group, sulfide group or formula

[0007]

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The groups represented by R ¹ and R ² are a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, which may be the same or different,
a and b are integers of 1 to 4, and when a is 2 or more, R ¹ may be the same or different; and when b is 2 or more, R ² may be the same. And may be different]. This polycarbonate is prepared by the solvent method, i.e., reaction of a dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or a molecular weight regulator, or a dihydric phenol and a diphenyl carbonate. It can be produced by a transesterification reaction with a suitable carbonate precursor.

The dihydric phenol which can be suitably used includes bisphenols, and 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferable. Further, bisphenol A may be obtained by partially or entirely substituting another dihydric phenol. As dihydric phenols other than bisphenol A,
For example, bis (4-hydroxyphenyl) alkane other than bisphenol A, hydroquinone, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) Sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-
Compounds such as hydroxyphenyl) ether and bis (4-hydroxyphenyl) ketone or bis (3,5-dibromo-4-hydroxyphenyl) propane and bis (3,5-dichloro-4-hydroxyphenyl) propane Examples thereof include halogenated bisphenols.

The polycarbonate used in the present invention may be a homopolymer using one of these dihydric phenols or a copolymer using two or more of these dihydric phenols. May be a thermoplastic random branched polycarbonate obtained in combination with the dihydric phenol. The polycarbonate used in the present invention preferably has a viscosity-average molecular weight of 10,000 to 100,000, particularly preferably 20,000 to 40,000, in view of mechanical strength and moldability.

As the alkali metal salt or alkaline earth metal salt of perfluoroalkanesulfonic acid which is the component (B) of the composition of the present invention, various ones can be mentioned. formula _{(II) (C n F 2n} + 1 SO 3) m M ··· (II) wherein, n represents an integer of 1 to 10, M is Li, Na,
Alkali metals such as K and Cs, or Mg, Ca, Sr, B
a represents an alkaline earth metal such as a, and m represents a valency of M]. For example, Shoko Sho 4
Japanese Patent Application Laid-Open No. 7-40445 corresponds to this. Here, M is preferably K, and suitable perfluoroalkanesulfonic acids include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, and perfluoromethylbutanesulfonic acid. , Perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid and the like, and potassium salts thereof are particularly preferred.

As the epoxy resin which is the component (C) of the composition of the present invention, various ones can be used, and a commercially available one can be appropriately applied, but a bisphenol type is preferably used. Can be For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin,
Bisphenol S type epoxy resin, Bisphenol AD
Examples thereof include a type epoxy resin and a halogenated bisphenol type epoxy resin. Of these, a bisphenol A type epoxy resin is particularly preferable. The epoxy equivalent of these epoxy resins is preferably 180 to 3500, particularly preferably 180 to 400. These epoxy resins have the general formula (III)

[0013]

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Wherein Y is an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a single bond, -SO _2- , -SO-, -S-,-
O-, -CO- or formula

[0015]

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In the various groups represented by, a part or all of the hydrogen atoms of Y may be substituted with halogen atoms. R ³ and R ⁴ are each a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, which may be the same or different, and p and q are each an integer of 1 to 4 When p is 2 or more, R ³ may be different from each other, and when q is 2 or more, R ⁴ may be different from each other. k is 0 or an integer of 1 or more. ].

The polycarbonate resin composition of the present invention comprises:
It comprises the above components (A), (B) and (C), and the mixing ratio of these components is 100 parts by weight of the polycarbonate (A) and the perfluoroalkane sulfone (B). 0.1 to 0.5 parts by weight, preferably 0.15 to 0.3 parts by weight of an alkali metal salt or alkaline earth metal salt of an acid
The epoxy resin as the component (C) is 0.1 to 5 parts by weight, and the weight ratio of the component (B) to the component (C) is (B) / (C) = 1/1. １／1/10, preferably ２〜２〜１ ／. Here, when the alkali metal salt or alkaline earth metal salt of perfluoroalkanesulfonic acid as the component (B) is less than 0.1 part by weight, the target flame retardancy (UL94, V-0) can be achieved. On the other hand, if it exceeds 0.5 parts by weight, no further flame retardancy can be expected, and rather, physical properties such as impact strength are reduced. On the other hand, if the amount of the epoxy resin (C) is too small and the weight ratio of (B) / (C) exceeds 1/1, sufficient transparency cannot be obtained, while the amount of the epoxy resin is too large (B If () / (C) is less than 1/10, flame retardancy and physical properties such as impact strength are reduced.

The polycarbonate resin composition of the present invention may contain various inorganic fillers, additives, or other synthetic fillers other than the above components (A), (B) and (C) as long as the object of the present invention is not impaired. Resins, elastomers and the like can be blended as required. First, as the above-mentioned inorganic filler compounded for the purpose of increasing the mechanical strength, durability or weight of the polycarbonate resin composition, for example, glass fiber (G
F), glass beads, glass flakes, carbon black, calcium sulfate, calcium carbonate, calcium silicate, titanium oxide, alumina, silica, asbestos, talc, clay, mica, quartz powder and the like. Examples of the additive include antioxidants such as hindered phenol-based, phosphorus-based (phosphite-based, phosphate-based, etc.) and amine-based antioxidants, such as benzotriazole-based additives.
Benzophenone-based ultraviolet absorbers, for example, aliphatic carboxylic acid ester-based and paraffin-based external lubricants, release agents, antistatic agents, coloring agents, and the like.

As the above hindered phenolic antioxidant, BHT (2,6-di-tert-butyl-p-cresol), "Irganox 107" manufactured by Ciba-Geigy, Inc.
6 "(trade name) and" Ilganox 1010 "(trade name)," Ethyl 330 "(trade name) manufactured by Ethyl Corporation," Sumilyzer GM "(trade name) manufactured by Sumitomo Chemical Co., Ltd. and the like are preferably used. . Examples of other synthetic resins include resins such as polyethylene, polypropylene, polymethyl methacrylate, and polycarbonate other than the polycarbonate as the component (A). Examples of the elastomer include isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, and acrylic elastomer.

The polycarbonate resin composition of the present invention can be obtained by blending each of the above-mentioned components and, if necessary, by melt-kneading. The compounding and melt kneading can be carried out by a usual method, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a co-kneader, a multi-screw extruder. be able to. The heating temperature for melt-kneading is usually 250 to 300.
C is appropriate. Thus, without lowering the transparency of the polycarbonate resin, the alkali metal salt or alkaline earth metal salt of perfluoroalkanesulfonic acid can be blended, and the polycarbonate of the present invention having high flame retardancy and high transparency A resin composition is obtained. This polycarbonate resin composition is known various molding methods,
For example, by applying hollow molding, injection molding, extrusion molding, vacuum molding, air pressure molding, hot bending molding, compression molding, calendar molding, rotational molding, etc., various types of highly flame-retardant and highly transparent moldings are applied. Goods can be manufactured.

[0021]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. Example 1 100 parts by weight of polycarbonate (PC (A1)) (trade name: A2500, manufactured by Idemitsu Petrochemical Co., Ltd.), potassium perfluorobutanesulfonate (C ₄ F ₉ SO ₃ K)
(Product name: F114, manufactured by Dainippon Ink and Chemicals, Inc.)
5 parts by weight and a bisphenol A type epoxy resin (trade name: Epicron 850, epoxy equivalent: 185, manufactured by Dainippon Ink and Chemicals, Inc.) are dried, blended, supplied to an extruder, and kneaded at a temperature of 280 ° C. And pelletized. Further, the obtained pellet was dried at 120 ° C. for 12 hours, and then injection molded at 80 ° C. in a mold to obtain a test piece. The transparency and flame retardancy of this test piece were measured. Table 1 shows the obtained results.

Examples 2 to 3 and Comparative Examples 1 to 3 As shown in Table 1, the mixing ratio of potassium perfluorobutanesulfonate and bisphenol A type epoxy resin was changed.
C (A2)) (trade name: IB2, manufactured by Idemitsu Petrochemical Co., Ltd.)
The same operation as in Example 1 was performed except that the compounded compound No. 500) was used. Table 1 shows the obtained results.

[0023]

[Table 1]

* 1 The transparency test is based on JIS K-710.
5 (Thickness 3 mm) * 2 The flame retardancy test conformed to the UL94 combustion test 1/16 inch (thickness). (Underwriters Laboratory Subject 94
The vertical combustion test was performed according to the following. )

From Table 1, it can be seen that by setting the mixing ratio of potassium perfluorobutanesulfonate and bisphenol A type epoxy resin to 1/1 to 1/10, the haze is remarkably reduced while maintaining the flame retardancy (implementation). Examples 1 to 3) show that when the amount of the epoxy resin is small, the haze hardly decreases (Comparative Example 2), whereas when the amount of the epoxy resin is too large, the flame retardancy is impaired (Comparative Example 3).

[0026]

As described above, the polycarbonate resin composition of the present invention has high flame retardancy and high transparency. Therefore, the polycarbonate resin composition of the present invention is effectively used as a material for various molded articles (for example, various parts such as automobiles, home appliances, and OA equipment).

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 69/00 C08K 3/00-13/08

Claims (1)

(57) [Claims] (A) 100 parts by weight of a polycarbonate,
(B) 0.1 to 0.5 parts by weight of an alkali metal salt or alkaline earth metal salt of perfluoroalkanesulfonic acid and (C)
It is composed of 0.1 to 5 parts by weight of the epoxy resin, and the weight ratio of the component (B) to the component (C) is (B) / (C) =
A polycarbonate resin composition, wherein the ratio is 1/1 to 1/10.