JPH0649822B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a novel polycarbonate resin composition, and more specifically, it is excellent in mechanical properties such as impact resistance, heat resistance, dimensional stability, and moldability. The present invention relates to a polycarbonate resin composition having excellent flame retardancy and suitable as a material for frames and chassis in electric and electronic devices.

[Prior Art] In recent years, polycarbonate resins have been widely used in various fields as engineering plastics because of their excellent mechanical properties such as rigidity and impact resistance, heat resistance, and electrical properties. In particular, glass fiber reinforced materials are used for applications requiring excellent heat resistance, mechanical properties, dimensional stability, etc., such as chassis for electric / electronic devices. Moreover, the thing which added the flame retardant is used for the application in which flame retardancy is required.

By the way, this polycarbonate resin generally has a drawback that the melt viscosity is high and the moldability is poor. Therefore, in order to improve such a drawback, the polycarbonate resin has a rubber-reinforced vinyl-based copolymer copolymer. Attempts have been made to blend the coalesced products to improve the fluidity without impairing the heat resistance and mechanical properties inherent in the polycarbonate resin.

However, in order to obtain a polycarbonate resin composition having excellent flame resistance and mechanical properties such as excellent heat resistance and impact resistance, dimensional stability, and moldability, a polycarbonate resin / rubber reinforced with glass fiber When a conventional flame retardant is added to the reinforced vinyl copolymer, the resin composition obtained has a problem that the impact resistance and the heat resistance are unavoidably deteriorated.

[Problems to be Solved by the Invention] Under these circumstances, the present invention provides a polycarbonate resin having an excellent balance of mechanical properties such as heat resistance and impact resistance, dimensional stability, moldability and flame retardancy. It was made for the purpose of providing a composition.

[Means for Solving the Problems] As a result of intensive studies to develop a polycarbonate resin composition having the above-mentioned preferable properties, the present inventors have found that the resin component of the polycarbonate resin and the rubber-reinforced vinyl copolymer is a resin component. It has been found that the object can be achieved by a resin composition in which a specific flame retardant and glass fiber are mixed in predetermined proportions, respectively, and the present invention has been completed based on this finding.

That is, the present invention is based on 100 parts by weight of a resin component of (A) a polycarbonate resin and (B) a rubber-reinforced vinyl copolymer, and (C) a general formula. ^{[X 1, X 2, X} 3 and X ⁴ in the formula are the same or different hydrogen atom or a chlorine atom or a bromine atom, at least one of which is a chlorine atom or a bromine atom, R ¹ and R ² are the same or different hydrogen atom, methyl group, epoxypropyl group, phenyl group or (However, m is 0 or an integer of 1 to 3), i, j, k, and h are integers of 1 to 4, respectively, and n is a natural number]. The molecular weight is 10,000-40,000. 2 to 30 parts by weight of a halogen-containing flame retardant represented by and (D) a glass fiber 5 to 14 converged with a converging agent containing an epoxy resin as a main component
The present invention provides a polycarbonate resin composition containing 0 part by weight.

Hereinafter, the present invention will be described in detail.

In the composition of the present invention, the polycarbonate resin used as the component (A) has a general formula (Z in the formula is an alkylene group having 1 to 8 carbon atoms, 2 to 2 carbon atoms
8 alkylidene group, 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 R ³ and R ⁴ are each a hydrogen atom, a chlorine atom, a bromine atom or an alkyl group having 1 to 8 carbon atoms, which may be the same or different, and o and p are respectively Is an integer of 1 to 4, R ³ may be different from each other when o is 2 to 4, and R ⁴ may be different from each other when p is 2 to 4. A polymer having a structural unit represented by

The polycarbonate resin can be obtained by reacting 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 modifier, or by dihydric phenol and diphenyl carbonate. It can be produced by a transesterification reaction with a carbonate precursor such as.

Examples of the dihydric phenol include 2,2-bis (4
-Hydroxyphenyl) propane (bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4)
-Hydroxyphenyl) propane, 1,2-bis (4-
Hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1- (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4 -Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-
Hydroxyphenyl) ether, 4,4'-dihydroxybenzophenone, etc., or 2,2-bis (3,5
-Dibromo-4-hydroxyphenyl) propane, 2,
2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-)
Examples thereof include halogenated bisphenols such as 4-hydroxyphenyl) propane, and among these dihydric phenols, bisphenol A is particularly preferable. Further, these dihydric phenols may be used alone or in combination of two or more kinds. Furthermore, the polycarbonate resin used in the present invention is
It may be a thermoplastic random branched polycarbonate obtained by reacting a polyfunctional aromatic compound with a dihydric phenol and / or a carbonate precursor, or may be a blend of two or more polycarbonate resins.

The polycarbonate resin has a viscosity average molecular weight of 10,000 to 100,0 from the viewpoint of mechanical strength and moldability.
00 is preferable, and 20,000 to 40,0 is particularly preferable.
00 is preferable.

The rubber-reinforced vinyl-based copolymer used as the component (B) in the composition of the present invention may be a blend of a rubber component and a vinyl-based copolymer, or may be a vinyl-based copolymer in the presence of the rubber component. It may be one obtained by copolymerizing a monomer forming a copolymer, but it is particularly preferable that the rubber component and the vinyl copolymer form a graft structure.

Examples of the rubber component include butadiene rubber such as polybutadiene, butadiene-styrene copolymer, and butadiene-acrylonitrile copolymer, and acrylic ester monomers such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Acrylic rubber obtained by homopolymerization or copolymerization, ethylene-propylene copolymer, ethylene-propylene rubber such as ethylene-propylene-diene copolymer, further ethylene-vinyl acetate copolymer, silicone rubber and the like Can be mentioned.
These rubber components may be used alone or in combination of two or more.

On the other hand, examples of the vinyl-based copolymer include a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, a styrene-methyl methacrylate copolymer, a styrene-acrylic acid copolymer and the like.

The content ratio of the rubber component and the vinyl copolymer is not particularly limited, but is usually selected in the range of 5:95 to 80:20.

The blending ratio of the component (A) and the component (B) is not particularly limited, but is usually selected in the range of 80:20 to 20:80, preferably 70:30 to 40:60.

In the composition of the present invention, as the component (C), a compound represented by the general formula The halogen-containing flame retardant represented by is used. X ¹ , X ² , X ³ and X ⁴ in the general formula (I) are each a hydrogen atom,
A chlorine atom or a bromine atom, which may be the same or different from each other, at least one of which is a chlorine atom or a bromine atom. i, j,
k and h are each an integer of 1 to 4, but in the case of 2 to 4, X ¹ , X ² , X ³ and X ⁴ may be the same or different in each case. Good. Also, R ¹
And R ² are a hydrogen atom, a methyl group, and an epoxypropyl group, respectively. Phenyl group or (M is 0 or an integer of 1 to 3), and they may be the same or different from each other. That is, both ends are not necessarily epoxy groups and may be modified.

Such a halogen-containing flame retardant has a halogenation rate of 10% by weight or more and a molecular weight of 10,000 to 40,
Those in the range of 000 are preferable.

In the composition of the present invention, the content of the halogen-containing flame retardant as the component (C) is 2 to 30 parts by weight, preferably 100 parts by weight of the resin component of the components (A) and (B). It is necessary to select in the range of 5 to 20 parts by weight. If this amount is less than 2 parts by weight, sufficient flame retardancy cannot be obtained, and
If it exceeds the weight part, the mechanical strength tends to decrease, and the molded product tends to be discolored due to the bleeding of the flame retardant.

In the composition of the present invention, in order to improve flame retardancy,
If necessary, an antimony compound such as antimony trioxide, antimony pentoxide or sodium antimonate may be used together with the halogen-containing flame retardant as the component (C). In this case, the compounding amount of the antimony compound is usually selected in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the resin component. If this amount is less than 1 part by weight, the flame retardancy-improving effect is not sufficiently exhibited, and if it exceeds 10 parts by weight, the mechanical strength tends to decrease, which is not preferable.

In the composition of the present invention, the glass fiber used as the component (D) may be any of alkali-containing glass, low-alkali glass and non-alkali glass, and
The form is not particularly limited, and any of roving, chopped strand, milled fiber and the like can be used.

Further, in the present invention, it is necessary to use, as the glass fiber, glass fiber which has been previously treated with a surface treatment agent and which has been converged with a converging agent containing an epoxy resin as a main component, as necessary. In this case, it is preferable to use chopped strands obtained by treating glass fibers having an average fiber diameter of 3 to 15 μm with the sizing agent to converge them to about 100 to 1000 and cutting the obtained strands to an average length of about 1 to 6 mm. It is advantageous.

Examples of the surface treatment agent include silane-based, titanate-based, aluminum-based, chromium-based, zirconium-based, borane-based coupling agents and the like. Among these, silane-based coupling agents and titanate-based coupling agents are included. A silane coupling agent is particularly preferable.

Examples of the silane coupling agent include triethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)
-Γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-
Examples thereof include aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like. Among these, γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane are preferable.

The method of treating the glass fiber with the surface treatment agent is not particularly limited, and any conventionally used method such as an aqueous solution method, an organic solvent method, or a spray method can be used.

Examples of the sizing agent having an epoxy resin as a main component used in the present invention include bisphenol / epichlorohydrin type epoxy resin, glycidyl ether type epoxy resin, tetraepoxy, novolac type epoxy resin, glycidyl amine, epoxy alkyl ester, epoxidation non-adhesive. Examples thereof include those containing an epoxy resin such as a saturated compound as a main component.

There is no particular limitation on the method for converging glass fiber using these converging agents, a conventionally used method,
For example, any method such as dip coating, roller coating, spray coating, flow coating, and spray coating can be used.

The surface treatment agent and the sizing agent are usually used in a proportion such that the total amount thereof is 0.1 to 0.5% by weight with respect to the glass fiber.

In the composition of the present invention, the blending amount of the glass fiber of the component (D) is 5 to 140 parts by weight, preferably 1 part by weight with respect to 100 parts by weight of the resin component of the components (A) and (B).
It is necessary to select in the range of 0 to 100 parts by weight. If this amount is less than 5 parts by weight, the effect of improving the rigidity will not be sufficiently exhibited, and if it exceeds 140 parts by weight, the fluidity and the appearance of the molded article tend to deteriorate.

In the composition of the present invention, to the extent that the object of the present invention is not impaired, fibrous reinforcing agents other than the glass fibers, inorganic fillers, organic fillers, other thermoplastic resins, lubricants, colorants,
Stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, plasticizers and the like can be added.

The composition of the present invention comprises a predetermined amount of component (A), component (B),
It may be prepared by mixing the component (C), the component (D), and various optional components that are optionally used, and kneading with a kneader. Alternatively, components other than the fibrous filler may be quantitatively supplied to the kneader. Alternatively, the fibrous filler may be side-fed into the melted portion of the resin in a fixed amount and kneaded, but the latter method is advantageous.

There is no particular limitation on the kneader, for example, a single-screw extruder,
Screw extruder such as multi-screw extruder, elastic extruder, hydrodynamic extruder, ram type continuous extruder,
Non-screw extruders such as roll type extruders and gear type extruders can be mentioned. Among these, screw extruders, particularly twin screw extruders are preferable. The kneading is performed at a temperature equal to or higher than the melting temperature or softening point of the resin used.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Each physical property of the composition was determined as follows.

(1) Izod impact strength (with a notch) It was determined according to JIS K-7110.

(2) Heat distortion temperature (HDT) Based on JIS K-7207, it was determined under the condition of a load of 18.6 kg / cm ² .

(3) Flame retardance Based on UL94 VO, the thickness of the molded product was determined to be 1.6 mm.

(4) SFL (spiral flow length) molding temperature of 260 ° C, injection pressure of 80 kg / cm ² · G,
The length when injection-molded in an Archimedes-shaped mold having a thickness of 3 mm was determined.

The following materials were used as the materials used for the resin composition.

(1) Polycarbonate resin (PC) Idemitsu Taflon FN2200 [trade name, manufactured by Idemitsu Petrochemical Co., Ltd.] (2) Rubber reinforced vinyl copolymer-ABS Rubber component content 18% by weight, acrylonitrile unit content 20% by weight , Styrene unit content 62% by weight, MI
(220 ° C., 10 kg) 3.5 g / 10 minutes SMA (styrene-maleic anhydride copolymer) Rubber component content 22% by weight, maleic anhydride unit content 14 mol%, MI (230 ° C., 2.16 kg) ) 2g / 10
(3) Flame Retardant-Flame Retardant A Tetrabisphenol A diglycidyl ether and tetrabromobisphenol A were prepared by heating reaction, and the weight average molecular weight (GPC method, standard substance polystyrene, solvent THF) was 33,000. there were.

Flame retardant B Brominated PC oligomer BC-52 (manufactured by Great Lakes, trade name) Flame retardant C Brominated PPO oligomer PO-64P (manufactured by Great Lakes, trade name) (4) Antimony compound Antimony trioxide ANTIMONTBLOOM 50
0A [trade name, manufactured by Dowa Mining Co., Ltd.] (5) Glass fiber (GF) -GF-A coupling agent aminosilane, sizing agent: bisphenol epoxy resin, type: chopped strand (diameter 13 μm, length 3 mm)- GF-B coupling agent: aminosilane, sizing agent: urethane resin, type: chopped strand (diameter 13 μm, length 3 mm) GF-C coupling agent: aminosilane, sizing agent: acrylic resin, type: chopped strand (diameter 13 μm , Length 3 mm) Examples 1 to 4 and Comparative Examples 1 to 10 Kneading at 240 ° C. in a GF side-feed twin-screw extruder (TEH-35B) using each type and amount of the components shown in Table 1. , Pelletized.

Next, using the pellets, a molded product for physical property test was prepared by an injection molding machine, and physical properties were evaluated. The results are shown in Table 1.

[Effects of the Invention] The composition of the present invention comprises a resin component of a polycarbonate resin and a rubber-reinforced vinyl copolymer, and a specific flame retardant and glass fiber blended therein. It has an excellent balance of physical properties, dimensional stability, moldability, flame retardancy and the like, and is suitably used as a material for frames and chassis in electric and electronic devices.

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Claims (1)

[Claims] 1. A general formula (C) for 100 parts by weight of a resin component of (A) a polycarbonate resin and (B) a rubber-reinforced vinyl copolymer. [Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different hydrogen atoms, chlorine atoms or bromine atoms, at least one of which is a chlorine atom or a bromine atom, and R ¹
And R ² are the same or different hydrogen atom, methyl group, epoxypropyl group, phenyl group or (However, m is 0 or an integer of 1 to 3), i, j, k, and h are integers of 1 to 4, respectively, and n is a natural number. The molecular weight is 10,000-40,000. ] 2 to 30 parts by weight of a halogen-containing flame retardant represented by the formula (D), and (D) a glass fiber 5 to 14 bundled with a sizing agent containing an epoxy resin as a main component.
A polycarbonate resin composition comprising 0 parts by weight.