JP3023577B2 - Flame retardant polycarbonate resin composition with excellent weld strength and heat resistance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant polycarbonate resin composition having excellent weld strength and heat resistance.

[0002]

2. Description of the Related Art Polycarbonate resin and ABS resin and A
Several methods have heretofore been proposed for flame retarding a mixture of an AS resin or the like, and these methods use various halogen compounds or an antimony compound in combination. For example, in Japanese Patent Application Laid-Open No. 22958/1990, flame retardation of a blend of a polycarbonate resin and a rubber-reinforced vinyl copolymer is carried out by adding a high molecular weight brominated epoxy compound and antimony trioxide. Has been proposed.

[0003]

However, the resin composition obtained by the above method has excellent impact resistance, but has insufficient weld strength. SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin which maintains impact resistance and has excellent weld strength and flame retardancy.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for improving the weld strength of a polycarbonate-based flame-retardant resin composition containing a rubbery polymer.
The present inventors have found that a resin composition having high weld strength and excellent heat resistance can be obtained by blending two kinds of halogen compounds having a specific chemical structure having different specific molecular weights in a specific ratio, and reached the present invention.

That is, the present invention relates to (A) a polycarbonate resin. (B) 10 to 45% by weight of a vinyl cyanide monomer and 25 to 8% of an aromatic vinyl monomer in the presence of the rubbery polymer (a).
Graft weight obtained by graft polymerization of a vinyl monomer (b) consisting of 5% by weight and 0 to 35% by weight of another vinyl monomer (the total amount of these monomer components is 100% by weight). Coalescing. (C) 15 to 40% by weight of vinyl cyanide monomer, 60 to 85% by weight of aromatic vinyl monomer and 0 of other vinyl monomer
A polymer obtained by polymerizing about 35% by weight. (D) The following general formula (I)

[0006]

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Wherein n is an average degree of polymerization of 35 to 100
It is. x independently represents hydrogen, chlorine or bromine; i,
j, k and l are each an integer of 1 to 4, and R and R ′ are each independently hydrogen, methyl, epoxypropyl, phenyl or

[0008]

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(Where m is 0, 1, 2, or 3). ]
And a high molecular weight halogen compound having a halogenation ratio of 10% by weight or more. (E) The above general formula (I) wherein n is an average degree of polymerization and is 0 to 10. x, i, j, k, l, R and R '
Is the same as above. And a halogenation rate of 10
Low molecular weight halogen compounds of at least% by weight. (F) Antimony compounds. (A) 50 to 90 parts by weight, (B) 10 to 50 parts by weight, and (C) 0 to 30 parts by weight. Quantity 1
(D) and (E) in a total amount of 5 to 40 parts by weight with respect to 00 parts by weight.
Parts by weight [however, the ratio of (D) / (E) is 2/1 by weight]
Ｆ) and (F) in an amount of 2 to 30 parts by weight, and is a flame-retardant polycarbonate resin composition having excellent weld strength and heat resistance.

The present invention will be described in detail. First, each component of the present invention will be described. (A) Polycarbonate resin. The polycarbonate resin (A) used in the present invention is a 4,4′-dioxydiarylalkane-based polycarbonate,
Especially 2,2 '-(4,4'-dihydroxydiphenyl)
Propane carbonate is preferred, but those containing a small amount of polyterephthalate carbonate copolymer are also used.

Resin components (A), (B) and (C) 100
The proportion of the polycarbonate resin (A) is 50 to 100 parts by weight.
When the amount is 90 parts by weight and the amount of the polycarbonate resin is less than 50 parts by weight, the impact strength tends to decrease and the weld reinforcement tends to decrease. On the other hand, when the content of the polycarbonate resin exceeds 90 parts by weight, there is a tendency that fluidity during molding and chemical resistance decrease.

(B) Graft polymer. The graft polymer (B) used in the present invention is obtained by graft-polymerizing a monomer (b) comprising a vinyl cyanide monomer and an aromatic vinyl monomer to a rubbery polymer (a). It is. (A)
The proportions of (a) and (b) in the graft polymer are 30 to 70% by weight, and (b) is 70 to 30% by weight.
Examples of the rubbery polymer (a) include at least one selected from a butadiene rubber, an acrylic rubber, an ethylene-propylene rubber, and a silicone rubber component.

The butadiene rubber component includes polybutadiene, butadiene-styrene copolymer, butadiene-
Acrylonitrile copolymer and the like can be mentioned. The acrylic rubber component is a rubber-like polymer obtained by polymerizing an acrylic acid ester monomer such as ethyl acrylate, butyl acrylate, or 2-ethylhexyl acrylate alone, or using the monomer as a main component. As the ethylene-propylene rubber component, ethylene and propylene are mixed in a ratio of 80:20 to
It is preferable to polymerize at a ratio of about 60:40, and may further contain butadiene. The silicone rubber component is preferably a polyorganosiloxane rubber component, and preferably has a repeating unit of mainly dimethylsiloxane. Further, for example, a composite rubber composed of a silicone rubber component and an acrylic rubber component and a composite rubber composed of a butadiene rubber component and an acrylic rubber component are also preferably used.

Examples of the vinyl cyanide monomer (b) used in the graft polymerization include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile and the like, and these can be used alone or in combination. . The proportion of the vinyl cyanide monomer in the graft monomer is preferably 15 to 40% by weight. If the amount is less than 15% by weight, the resulting resin composition tends to have poor impact resistance and chemical resistance. If the amount exceeds 40% by weight, coloring when forming the obtained resin composition becomes large.

The aromatic vinyl monomer used for the graft polymerization includes styrene, α-methylstyrene, o-methylstyrene, 1,3-dimethylstyrene, p-methylstyrene, t-butylstyrene, halogenated styrene,
Examples thereof include p-ethylstyrene and the like, and these may be used alone or in combination of two or more. The ratio of the aromatic vinyl monomer to the graft monomer is preferably 25 to 85.
If it is out of these ranges, at least one of impact resistance and moldability is inferior.

Further, a lower amount of another copolymerizable vinyl monomer can be copolymerized during the graft polymerization. Other copolymerizable vinyl monomers include methyl methacrylate, maleimide monomers such as methacrylates such as ethyl methacrylate and N-phenylmaleimide,
It is not particularly limited to these. These other copolymerizable vinyl monomers account for 35% by weight of the graft monomers.
Used as necessary in the range up to.

Resin components (A), (B) and (C) 100
The proportion of the graft polymer (B) is 10 to 50 parts by weight, and if less than 10 parts by weight, the impact strength or the weld strength tends to decrease. Also 5
Exceeding 0 parts by weight is likely to cause a decrease in fluidity, a decrease in weld strength, a decrease in heat resistance, and the like, which is not preferable.

(C) Copolymer. The copolymer (C) used in the present invention comprises a vinyl cyanide monomer of 15 to 40.
%, And 60 to 85% by weight of an aromatic vinyl monomer. As the vinyl cyanide monomer and the aromatic vinyl monomer, the same ones as those used in the graft polymer (B) can be used. The content of the vinyl cyanide monomer is 15 to 40% by weight, preferably 15 to 25% by weight, based on the total amount of the monomers used for the copolymer (C). If it is out of this range, at least one of impact resistance, chemical resistance and coloring property of the molded product is inferior.
The content of the aromatic vinyl monomer is from 60 to 85% by weight based on the total amount of the monomers used for the copolymer (C). The flow processability of the steel is reduced.

In the copolymer (C), in addition to the above-mentioned monomers, inferior amounts of other copolymerizable vinyl monomers can be used. Examples of these monomers include methacrylates such as methyl methacrylate, vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine, and maleimide monomers such as N-phenylmaleimide. It is not something to be done. These other copolymerizable monomers are used as needed in the range of up to 35% by weight in the copolymer (C).

Resin components (A), (B) and (C) 100
The amount of the copolymer (C) used is from 0 to 30 parts by weight, and if it exceeds 30 parts by weight, the weld strength decreases,
The impact strength tends to decrease. The copolymer (C)
Is preferably used together when the proportion of the rubbery polymer in the graft polymer (B) is large from the viewpoint of moldability and heat resistance.

(D) a high molecular weight halogen compound and (E)
Low molecular weight halogen compounds. The high molecular weight halogen compound (D) used in the present invention has a halogenation ratio of 10% by weight or more, is represented by the general formula (I), and has an average degree of polymerization n of 35 to 100. is there. The low molecular weight halogen compound (E) is represented by the general formula (I) having the same molecular structure as the high molecular weight halogen compound (D), and has an average degree of polymerization n of 0 to 10.

If the average degree of polymerization n of the high molecular weight halogen compound (D) exceeds 100, the dispersibility in the resin becomes poor, and the physical properties tend to be reduced, and the fluidity during molding tends to be reduced. On the other hand, when n is less than 35, the impact resistance and the heat resistance are reduced. On the other hand, if the average degree of polymerization n of the low molecular weight halogen compound (E) exceeds 10, the effect of improving the weld strength is undesirably reduced. These high-molecular-weight halogen compound (D) and low-molecular-weight halogen compound (E) do not necessarily have to be epoxy groups at both ends, as is apparent from the above-mentioned general formula (I), and the terminal is modified. Things are also used.

The proportion of the high molecular weight halogen compound (D) and the low molecular weight halogen compound (E) used is (D)
/ (E) is preferably a ratio of 2/1 to 1/4 by weight,
When there are more high molecular weight halogen compounds (D) than 2/1,
When the effect of improving the weld strength is small and the amount of the low molecular weight halogen compound (E) is larger than 1/4, the heat resistance and the impact strength are largely unfavorably reduced. Further, the total amount of the high molecular weight halide (D) and the low molecular weight halide (E) is the total amount of the resin components (A), (B) and (C).
It is 5 to 40 parts by weight with respect to 00 parts by weight. When the amount is 5 parts by weight, the flame retardancy is reduced. When the amount exceeds 40 parts by weight, the mechanical properties are undesirably reduced.

(F) Antimony compounds. Further, the antimony compound (F) used in the present invention includes antimony trioxide, antimony pentoxide, and sodium antimonate.
And surface-treated ones are commercially available. However, surface-treated ones may be used. The mixing ratio of the antimony compound is 2 to 30 parts by weight based on 100 parts by weight of the total amount of the resin components (A), (B) and (C). If the amount is less than 2 parts by weight, the flame-retardant effect is insufficient, and if it exceeds 30 parts by weight, the mechanical properties tend to decrease, which is not preferable.

The resin composition of the present invention may optionally contain additives such as a modifier, a release agent, a stabilizer against light and heat, and dyes and pigments. As a method for preparing the thermoplastic resin composition of the present invention, an apparatus such as a Henschel mixer and a tumbler used for blending of ordinary resins can be used. As for the shaping, a device used for normal shaping, such as a single-screw extruder, a twin-screw extruder, or an injection molding machine, can be used.

[0026]

The present invention will be described in more detail with reference to the following examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. In addition, each physical property evaluation in an Example was based on the following method. (1) Izod Impact Strength A 6.3 mm thick notched specimen was measured according to ASTM D-256. (2) Heat deformation temperature Measured according to ASTM D-648 (bending stress 4.
6 kgf / cm ² ). (3) Weld strength A 3.2 mm thick x 12.7 mm wide x 127 mm long sample with gates provided on both sides in the length direction to create a weld at the center. A 3.2 mm × 12.7 mm × 15 mm size sample was cut out and measured for Dinstadt impact strength.

(4) Short shot pressure (SS pressure) The SS pressure is set to 1 using an M-100 [Meiki Co., Ltd.].
The minimum moldable pressure when molding a 00 mm square plate and a thickness of 3 mm at a cylinder temperature of 240 ° C. was expressed as a percentage of the maximum pressure (2000 kg · f / cm ² ) of the molding machine. (5) Flammability A vertical burning test of UL-94 was performed using a 1.6 mm thick × 12.7 mm wide × 127 mm long specimen.

The components used in the comparative examples are as follows. (A) Polycarbonate resin A bisphenol A-type polycarbonate resin having an average molecular weight of 22,000 was used. (B) Graft polymer Graft polymer (B-1) Acrylonitrile and styrene in a weight ratio of 28/72 to butadiene rubber latex having a particle diameter of 0.3 μm,
For a solid content of 60 parts by weight of butadiene rubber latex,
It was produced by graft polymerization of 40 parts by weight. Graft polymer (B-2) Acrylonitrile and styrene in a weight ratio of 28/72 to butadiene rubber latex having a particle diameter of 0.3 μm,
For a solid content of 40 parts by weight of butadiene rubber latex,
It was produced by graft polymerization of 60 parts by weight.

Graft polymer (B-3) 36 parts (solid content) of butyl acrylate in the presence of 9 parts (solid content) of polybutadiene latex having a particle size of 0.3 μm
A mixture of 14 parts of acrylonitrile and 41 parts of styrene was graft-polymerized to a rubber component obtained by polymerizing the above. Graft polymer (B-4) A rubber component having a particle diameter of 0.25 μm obtained by polymerizing 40 parts of butyl acrylate in the presence of 30 parts (solid content) of polydimethylsiloxane rubber latex, and adding acrylonitrile 9
And 21 parts of styrene by graft polymerization.

(C) Polymer Acrylonitrile and methstyrene were charged at a weight ratio of 28/72 and polymerized. Dimethylformamide solution 2
Η _{sp / c at} 5 ° C. was 0.6. (D) High molecular weight halogen compound and (E) low molecular weight halogen compound Tetrabromobisphenol A, epichlorohydrin and tetrabromobisphenol A diglycidyl ether are represented by the following formula using lithium hydroxide as a catalyst. ,
The average degree of polymerization n is 1, 6, 20, 40, 70 and 90
A type of flame retardant was prepared.

[0031]

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(Wherein R and R 'represent H or an epoxypropyl group) Examples 1 to 8, Comparative Examples 1 to 10 The above components (A) to (E) and antimony trioxide are shown in Tables 1 and 2. Weigh at the ratio shown in 2, and use a Henschel mixer to weigh 3
After mixing for 2 minutes, the mixture was melt-kneaded at a cylinder temperature of 220 ° C. to 250 ° C. using a 30 mmφ twin screw extruder, and shaped into pellets to obtain various resin compositions. The pellets were subjected to a cylinder temperature of 240 using an M-100 injection molding machine manufactured by Meiki Seisakusho.
Various evaluation test pieces were molded at a temperature of 60 ° C. and a mold temperature of 60 ° C. and evaluated. The results are shown in Tables 1 and 2.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

The polycarbonate resin composition of the present invention containing the above-mentioned components (A) to (F) has an unprecedented weld strength, is excellent in heat resistance, and is suitable for molding. It is a flame-retardant synthetic resin material with a good balance of fluidity and the like, and is therefore extremely useful for electric appliances and OA equipment.

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

Claims (1)

(57) [Claims] 1. A polycarbonate resin composition comprising the following components (A) to (F), wherein (A) 50 to 90:
Parts by weight, 100 parts by weight of the total amount of resin components consisting of 10 to 50 parts by weight of (B) and 0 to 30 parts by weight of (C),
(D) and (E) in a total amount of 5 to 40 parts by weight [however,
The ratio of (D) / (E) is from 2/1 to 1/4 by weight] and 2 to 30 parts by weight of (F). Flame retardant polycarbonate having excellent weld strength and heat resistance. Bonnet resin composition. (A) Polycarbonate resin. (B) 10 to 45% by weight of a vinyl cyanide monomer and 25 to 8% of an aromatic vinyl monomer in the presence of the rubbery polymer (a).
Graft weight obtained by graft polymerization of a vinyl monomer (b) consisting of 5% by weight and 0 to 35% by weight of another vinyl monomer (the total amount of these monomer components is 100% by weight). Coalescing. (C) 15 to 40% by weight of vinyl cyanide monomer, 60 to 85% by weight of aromatic vinyl monomer and 0 of other vinyl monomer
A polymer obtained by polymerizing about 35% by weight. (D) General formula (I) of the following formula [In the formula, n is an average degree of polymerization and is 35 to 100. x independently represents hydrogen, chlorine or bromine; i, j, k and l are each an integer of 1 to 4; R and R ′ are each independently hydrogen, methyl, epoxypropyl, phenyl or Formula 2 (Where m is 0, 1, 2, or 3). And a high molecular weight halogen compound having a halogenation ratio of 10% by weight or more. (E) The above general formula (I) wherein n is an average degree of polymerization and is 0 to 10. x, i, j, k, l, R and R '
Is the same as above. And a halogenation rate of 10
Low molecular weight halogen compounds of at least% by weight. (F) Antimony compounds.