JP2002069287A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which excels in rigidity, flame retardance, melt-flowability, impact resistance (surface impact), and in an appearance at the welded portion. SOLUTION: The thermoplastic resin composition comprises 100 pts.wt. thermoplastic resin composed of (A) 5-60 pts.wt. rubber reinforced resin and (B) 40-95 pts.wt. aromatic poly-carbonate resin, (C) 1-30 pts.wt. flame-retardant, (D) 0.1-20 pts.wt. flame-retardant auxiliary, and (E) 1-30 pts.wt. PAN based carbon fibers. Furthermore, the composition may comprise (F) 1-30 pts.wt. pitch based carbon fibers. The carbon fibers in this composition have a residual average fiber length of 0.05-0.7 mm, and the thermoplastic resin composition has a value of flowability (MFR) of 20-70 g/10 min (measured at 240 deg.C under a load of 10 kg).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition containing a rubber reinforced resin, an aromatic polycarbonate, a flame retardant, a flame retardant aid, and a PAN-based carbon fiber. The present invention relates to a thermoplastic resin composition having excellent flammability, fluidity, impact resistance (surface impact) and molded appearance.

[0002]

2. Description of the Related Art Resin materials obtained by making ABS resin / polycarbonate alloy materials flame-retardant are widely used for personal computer housings, PPC parts and the like. In particular, notebook personal computers are becoming thinner as products, and materials used for the housing of the products are required to be thinner and have higher rigidity. In order to obtain thin and high rigidity, carbon fiber etc. is blended, but if carbon fiber is used, the appearance at the weld line will be poor (particularly the weld part will be concave), and the molded product surface must be polished. The problem that it does not occur.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin composition which is excellent in rigidity, flame retardancy, fluidity, impact resistance (surface impact) and molded appearance (particularly, weld portion). It is.

[0004]

The thermoplastic resin composition of the present invention comprises, in the presence of (A) a rubbery polymer (a), an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylate ester. A graft copolymer obtained by polymerizing at least one monomer component (b) selected from the group consisting of a compound, an acid anhydride monomer compound and a maleimide-based compound, or a graft copolymer and a monomer It is composed of a mixture of the component (b) with the (co) polymer, and the proportion of the component (a) is 5-6.
5 to 60 parts by weight of a rubber reinforced resin having 0% by weight, a component (b) ratio of 40 to 95% by weight [however, (a) + (b) = 100% by weight], and an aromatic polycarbonate (B) 4
With respect to 100 parts by weight of the thermoplastic resin consisting of 0 to 95 parts by weight (provided that (A) + (B) = 100 parts by weight), (C)
It is characterized by containing 1 to 30 parts by weight of a flame retardant, 0.1 to 20 parts by weight of (D) a flame retardant aid, and 1 to 30 parts by weight of (E) PAN-based carbon fiber.

First, the rubber reinforced resin (A) will be described. The “rubber polymer (a)” that forms the rubber-reinforced resin (A) is not particularly limited as long as it is a polymer showing rubbery properties, but polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer Styrene-butadiene-styrene block copolymer, styrene-
Diene-based polymers such as isoprene-styrene block copolymer, ethylene-propylene- (non-conjugated diene) copolymer, ethylene-butene-1- (non-conjugated diene) copolymer, isobutylene-isoprene copolymer, and acrylic rubber Copolymer), hydrogenated products of these diene-based (co) polymers, polyurethane rubber, silicone rubber, and the like. Among these, polybutadiene, butadiene-styrene copolymer, and diene-based (co) polymer Hydrogenated product, ethylene-propylene- (non-conjugated diene) copolymer, acrylic rubber,
Silicone rubber is preferred. When a silicone rubber is used, a vinyl group-containing grafting agent (for example, p-vinylphenylmethyldimethoxysilane, 2-
(P-vinylphenyl) ethylmethyldimethoxysilane, 2- (p-vinylphenyl) ethylenemethyldimethoxysilane, etc.) is preferably co-condensed with polyorganosiloxane.

The particle size of the rubbery polymer (a) when it is a rubbery polymer latex is not particularly limited.
When a graft copolymer using two or more rubbery polymers having different particle diameters is used, a thermoplastic resin composition having more excellent impact resistance and physical property balance of a molded article can be obtained. As an example of a preferable particle diameter, the average particle diameter is (a
1) A combination of at least two of 80 to 180 nm and (a2) 180 to 480 nm. In this case, an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylate compound, an acid anhydride monomer compound and a maleimide compound are present in the presence of a rubbery polymer having at least two types of particle size distributions. Or a graft copolymer obtained by polymerizing at least one monomer component (b) selected from the group consisting of: a rubbery polymer (a1) and a component (b). The graft copolymer obtained by polymerizing the rubbery polymer (a2) and the component (b) may be used as a mixture.

In the present invention, the rubbery polymer (a)
Among the monomer components (b) that polymerize with styrene, “aromatic vinyl compound” includes styrene, α-methylstyrene, o-
Examples include methylstyrene, p-methylstyrene, vinyltoluene, methyl-α-methylstyrene, brominated styrene, and the like. Of these, styrene, α-methylstyrene and p-methylstyrene are preferably used.

The above “vinyl cyanide compound” includes:
Acrylonitrile, methacrylonitrile and the like can be mentioned, and acrylonitrile is preferably used. Examples of the “(meth) acrylate compound” include methyl acrylate, ethyl acrylate, butyl acrylate,
Examples thereof include methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Of these, methyl methacrylate and butyl acrylate are preferably used.

The above "acid anhydride monomer compound" includes:
Maleic anhydride is preferably used. Examples of the "maleimide-based compound" include maleimide, N-methylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide, and the like. And N-phenylmaleimide is preferably used.

In the preparation of the graft copolymer of the present invention, the charge composition for graft polymerization of the monomer component (b) to the rubbery polymer (a) is preferably the component (a).
0 to 70% by weight (more preferably 25 to 65% by weight, particularly preferably 30 to 60% by weight), and component (b) is preferably 30 to 80% by weight (more preferably 35 to 75% by weight, particularly preferably). 40 to 70% by weight) [However, (a)
+ (B) = 100% by weight]. The graft copolymer obtained as described above contains the monomer component (b)
Contains a non-grafted component (a (co) polymer of the monomer component (b)) not grafted to the rubbery polymer (a).
In addition, the rubber-reinforced resin (A) of the present invention means, in addition to the above graft copolymer, a monomer component (b) (co)
It may be a blend of (co) polymers obtained by polymerization. Therefore, the final ratio of the component (a) to the component (b) in the rubber-reinforced resin (A) of the present invention is such that the component (a) is 5 to 5.
60% by weight, preferably 8 to 60% by weight, more preferably 10 to 50% by weight, the component (b) is 40 to 95% by weight,
Preferably 40 to 92% by weight, more preferably 50 to 9% by weight.
0% by weight [however, (a) + (b) = 100% by weight]. If the content of the component (a) in the rubber-reinforced resin (A) is less than 5% by weight, the molded article will not have sufficient impact resistance, while if it exceeds 60% by weight, poor appearance and molding processability will result. A drop occurs.

The graft ratio of the rubber-reinforced resin (A) is usually from 10 to 200%, preferably from 50 to 150%, more preferably from 60 to 130%, and particularly preferably from 6 to 130%.
5 to 120%. (A) The graft ratio of the component is 10%.
If it is less than 3, the appearance of the molded article of the thermoplastic resin composition of the present invention is poor, and the impact strength is reduced. On the other hand, if it exceeds 200%, the moldability is poor.

The above graft ratio is a value determined by the following formula. Graft ratio (%) = 100 × (y−x) / x (where “x” represents the weight of the rubbery polymer in 1 g of the rubber reinforced resin and is a value calculated from the charged amount.
"Y" is a methyl ethyl ketone insoluble matter, 1 g of a rubber reinforced resin is put into 50 ml of methyl ethyl ketone, shaken at room temperature for 2 hours with a shaker to dissolve a free (co) polymer, and then centrifuged. The solution is brought to 15.0 with
Centrifuged at 00 rpm for 30 minutes, and the obtained insoluble matter was dried at 120 ° C. for 1 hour by vacuum drying to obtain the weight. )

In the present invention, the method of polymerizing the graft copolymer or the method of polymerizing the (co) polymer of the monomer component (b) when producing the rubber reinforced resin (A) includes emulsion polymerization, solution polymerization, Examples include bulk polymerization and suspension polymerization. When the above graft copolymer is produced by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier, water and the like are used. still,
Rubbery polymer (a) and monomer component (b) used for production
In the presence of the rubbery polymer (a), the monomer component (b) may be added and polymerized all at once, or may be polymerized by split or continuous addition. Moreover, you may superpose | polymerize by the method which combined these. Further, the whole or a part of the rubbery polymer (a) may be added during the polymerization to carry out the polymerization.

Examples of the "polymerization initiator" include cumene hydroperoxide, diisopropylbenzene hydroperoxide, potassium persulfate, azobisisobutyronitrile (AIBN), benzoyl peroxide, lauroyl peroxide, and t-butyl peroxide. Oxylaurate, t-butyl peroxy monocarbonate and the like can be mentioned.

Examples of the "chain transfer agent" include octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, tetraethylthiuram sulfide, acrolein, methacrolein, allyl alcohol and 2-ethylhexyl thioglycol. No.

The "emulsifier" used in the emulsion polymerization includes, for example, sulfates of higher alcohols, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, aliphatic sulfonates such as sodium lauryl sulfate, and higher aliphatic acids. Examples thereof include carboxylate, rosinate and phosphate-based anionic surfactants.

In the emulsion polymerization, the powder obtained by coagulation with a coagulant is usually washed with water and dried to obtain a rubber-reinforced resin powder. As this coagulant,
Inorganic salts such as calcium chloride, magnesium sulfate and magnesium chloride, or acids such as sulfuric acid can be used. Of these coagulants, sulfuric acid is preferred.

The rubber reinforced resin (A) may be a single graft copolymer or a blend of two or more graft copolymers. Alternatively, a method of separately mixing the (co) polymer of the monomer component (b) with the graft copolymer may be used. The amount of the (co) polymer obtained by separately polymerizing only the component (b) is preferably 10 to 80% by weight, more preferably 15 to 60% by weight in the rubber-reinforced resin (A). It is.

The ungrafted (co) polymer of the rubber-reinforced resin (A) or the (co) polymer and the monomer component (b)
The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the mixture with the (co) polymer is preferably from 0.1 to
It is 1 dl / g, more preferably 0.3 to 0.8 dl / g. When the content is within this range, a thermoplastic resin composition having excellent balance between impact resistance excellent in dispersibility of carbon fibers and moldability (fluidity) can be obtained.

The rubber-reinforced resin (A) may be copolymerized with a functional group-containing vinyl monomer. Examples of the functional group include an epoxy group, a hydroxyl group, a carboxylic acid group, an amino group, an amide group, and an oxazoline group. Specific examples of the functional group-containing vinyl monomer include glycidyl methacrylate, glycidyl acrylate, and 2-hydroxyethyl. Examples include methacrylate, 2-hydroxyethyl acrylate, acrylamide, acrylic acid, methacrylic acid, and vinyl oxazoline. Copolymerization of these functional group-containing vinyl monomers can enhance interfacial adhesion (compatibility) when the aromatic polycarbonate (B) or another thermoplastic resin is blended. In consideration of the compatibility with the component (B), the functional group is preferably an epoxy group or a hydroxyl group, and more preferably an epoxy group because the epoxy group can react with the hydroxyl group at the terminal of the polycarbonate.

Next, the aromatic polycarbonate (B) will be described. The above "aromatic polycarbonate (B)"
Various types can be used. For example,
(1) A compound obtained by a reaction between a dihydroxyaryl compound and phosgene (phosgene method), and (2) a compound obtained by a transesterification reaction between a dihydroxyaryl compound and diphenyl carbonate (ester exchange method).

Here, the dihydroxyaryl compound as a raw material of the polycarbonate includes bis (4-hydroxyphenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane, and 2,2'-bis (4-hydroxyphenyl) methane. Phenyl) propane, 2,2′-bis (4-hydroxyphenyl) butane, 4,4′-dihydroxy-3,3 ′
-Dimethyldiphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 '
-Dimethyldiphenyl sulfone, hydroquinone, resorcin and the like. These can be used alone or in combination of two or more. As a representative aromatic polycarbonate,
A polycarbonate obtained by reacting 2,2'-bis (4-hydroxyphenyl) propane with phosgene. Aromatic polycarbonate has an advantage of being superior in heat stability as compared with aliphatic polycarbonate.

The preferred viscosity average molecular weight of the aromatic polycarbonate (B) is 15,000 to 35,000, more preferably 17,000 to 28,000, and still more preferably 18,000 to 26,000. Within this range, a thermoplastic resin composition having more excellent moldability can be obtained. When it is desired to impart high fluidity, the aromatic polycarbonate preferably has a viscosity average molecular weight of 1
7,000-22,000. Further, polycarbonates having different molecular weights can be used. in this case,
Preferred two types of combinations have a viscosity average molecular weight of 1
8,000-22,000 and 26,000-30,00
This is a combination with 0.

The thermoplastic resin in the present invention comprises 5 to 60 parts by weight of the rubber reinforced resin (A) and 40 to 95 parts by weight of the aromatic polycarbonate (B), and (A) + (B) =
It satisfies 100 parts by weight. Preferred amounts are 10 to 40 parts by weight of component (A) and 60 to 90 parts by weight of component (B), and more preferred amounts are 15 to 30 parts by weight of component (A).
Parts by weight, 70 to 85 parts by weight of the component (B). When the amount of the component (A) is less than 5 parts by weight, the fluidity of the resin composition is poor, and when it exceeds 60 parts by weight, the flame retardancy and impact strength of the molded product are poor.

As the "flame retardant (C)", a bromine flame retardant and a phosphorus flame retardant can be used. The use of a phosphorus-based flame retardant is preferred in terms of environmental issues. On the other hand, when a bromine-based flame retardant is used, the heat resistance of a molded article of the thermoplastic resin composition containing the brominated flame retardant is increased. In the thermoplastic resin composition of the present invention, a brominated flame retardant and a phosphorus-based flame retardant may be used in combination.

As the "brominated flame retardant", an oligomer of tetrabromobisphenol-A (that is, a brominated epoxy resin; the terminal remains an epoxy group, or the epoxy group is sealed with tribromophenol, methyl alcohol, ethyl alcohol or the like) May be stopped), brominated styrene, post-brominated polystyrene, oligomers of brominated polycarbonate, tetrabromobisphenol-A, brominated triazine, and the like. Of these, oligomers of tetrabromobisphenol-A (brominated epoxy resins) are preferred (preferable molecular weights are from 1,000 to 6.0,
00, more preferably 1,500 to 4,500), and those whose ends are capped with tribromophenol are preferred. The bromine flame retardant preferably has a bromine concentration of 30 to 65% by weight, more preferably 45 to 60% by weight. Further, a preferable softening point (melting point) is 100 to 180.
° C, more preferably 110-140 ° C.

Examples of the “phosphorous flame retardant” include triphenyl phosphate, trixylenyl phosphate, tricresyl phosphate, trixylenyl thiophosphate, condensates of hydroquinone and diphenyl phosphate, and resorcinol and diphenyl phosphate. Condensates, condensates of resorcinol and dixylenyl phosphate, oligomers of triphenyl phosphate,
Examples include bisphenol A-bis (diphenyl phosphate), and condensates of bisphenol-A and dixylenyl phosphate. Among these, triphenyl phosphate, a condensate of resorcinol and dixylenyl phosphate (average degree of condensation: 1-2), an oligomer of triphenyl phosphate, bisphenol A
With diphenyl phosphate (average degree of condensation: 1
To 2) are preferred. The preferred phosphorus concentration of the phosphorus-based flame retardant is 4 to 30% by weight, more preferably 6 to 25% by weight. When an oligomer-type or condensation-type phosphorus-based flame retardant (two or more phosphorus elements in one molecule) is used, a thermoplastic resin composition capable of suppressing mold contamination can be obtained. Among the phosphorus-based flame retardants, those that are liquid at room temperature can also be used. When the phosphorus-based flame retardant is a liquid, it is preferable that the phosphorus-based flame retardant is fed during melt-kneading with an extruder.

In the present invention, the compounding amount of the flame retardant (C) depends on the amount of the thermoplastic resin 1 comprising the component (A) and the component (B).
The amount is 1 to 30 parts by weight, preferably 5 to 25 parts by weight, more preferably 10 to 20 parts by weight based on 00 parts by weight. If the amount of component (C) is less than 1 part by weight, the effect of imparting flame retardancy is small, and if it exceeds 30 parts by weight, the impact strength of the thermoplastic resin composition molded article is impaired.

Examples of the above-mentioned "flame retardant aid (D)" include an antimony compound, polytetrafluoroethylene (PTFE) and the like. When using a brominated flame retardant, it is preferable to use an antimony compound as a flame retardant auxiliary, and when using a phosphorus-based flame retardant, it is preferable to use polytetrafluoroethylene.

Examples of the "antimony compound" include antimony trioxide and antimony pentoxide. Further, “polytetrafluoroethylene” has an effect of preventing dripping (dripping of a melt) during combustion. The preferred weight average molecular weight is 500,000 or more, more preferably 1,000,000 or more. The preferred average particle size when mixing and kneading polytetrafluoroethylene with other components is 90 to 60.
0 μm, more preferably 100 to 500 μm, and still more preferably 120 to 400 μm. The polyfluoroethylene after being kneaded with other components is dispersed as a granular material having an average particle diameter of 0.1 to 100 μm or a fibrous material finer than that. The preferred specific gravity when mixing polytetrafluoroethylene with other components is 1.5 to
2.5, more preferably 2.1 to 2.3, and the preferred bulk density is 0.5 to 1 g / ml, more preferably 0.1 to 1.0 g / ml.
6-0.9 g / ml. When polytetrafluoroethylene is blended, dripping during combustion can be prevented, so that a higher flame retardant level can be achieved.
A dispersion-type polytetrafluoroethylene in which polytetrafluoroethylene or the like is dispersed in a solvent such as water or a lubricant (polyethylene len wax, an organic acid, or an organic metal salt such as magnesium stearylate) can also be used.

In the present invention, the compounding amount of the flame retardant auxiliary (D) is determined based on the amount of the thermoplastic resin 1 comprising the component (A) and the component (B).
The amount is 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, more preferably 0.3 to 8 parts by weight with respect to 00 parts by weight. If the amount of component (D) is less than 0.1 part by weight, the effect of imparting flame retardancy is small, and if it exceeds 20 parts by weight, the impact strength and moldability of the molded article of the thermoplastic resin composition are impaired.

In order to provide the molded article of the thermoplastic resin composition of the present invention with high rigidity, PAN-based carbon fibers are blended. When PAN-based carbon fiber is used, although the rigidity can be obtained by blending the carbon fiber, the welded part of the molded article may be conspicuous. It may be necessary to level it. In order to provide the thermoplastic resin composition molded article of the present invention with higher rigidity, two types of PAN-based and pitch-based carbon fibers can be used in combination. By using a combination of PAN-based and pitch-based carbon fibers, the weld portion does not become convex and high rigidity is obtained.

The above-mentioned "PAN-based carbon fiber (E)" is obtained by calcining polyacrylonitrile as a raw material, and preferably has a carbon fiber diameter of 5 to 15 μm, more preferably 6 to 10 μm. The smaller the fiber diameter, the more preferable in terms of imparting rigidity and forming appearance. The preferred tensile modulus is 100 to 700 GPa, more preferably 200 GPa.
５００500 GPa.

In the present invention, the compounding amount of the PAN-based carbon fiber (E) is 1 to 30 parts by weight, preferably 100 parts by weight of the thermoplastic resin comprising the components (A) and (B). 5 to 25 parts by weight, more preferably 10 to
20 parts by weight. If the amount of component (E) is less than 1 part by weight, the effect of imparting rigidity is small, and if it exceeds 30 parts by weight, the impact strength and appearance of the molded article of the thermoplastic resin composition are impaired.

In the present invention, the effect of the present invention can be improved by using “pitch-based carbon fiber (F)” together with the PAN-based carbon fiber. The "pitch-based carbon fiber (F)" is spun from pitch as a raw material,
It is obtained by heat treatment. The preferred carbon fiber diameter is 5 to 15 μm, more preferably 8 to 12 μm. The smaller the fiber diameter, the more preferable in terms of imparting rigidity and forming appearance.
Further, the preferred tensile modulus is 10 to 900 GPa,
More preferably, it is 30 to 600 GPa. Usually, a sizing agent such as an epoxy resin, an acrylic resin, or a urethane resin is used for the carbon fiber. The amount of the sizing agent used is about 3 to 9 parts by weight based on 100 parts by weight of the carbon fiber.

In the present invention, the compounding amount of the pitch-based carbon fiber (F) is preferably 1 to 30 parts by weight based on 100 parts by weight of the thermoplastic resin comprising the components (A) and (B).
Parts by weight, more preferably 5 to 25 parts by weight, particularly preferably 10 to 20 parts by weight. If the component (F) is less than 1 part by weight, the effect of imparting rigidity is small, and if it exceeds 30 parts by weight, the impact strength and the appearance of the molded article of the thermoplastic resin composition are impaired.

In the method of blending the two types of carbon fibers, the two types of carbon fibers are preliminarily blended with a tumbler even when the resin components are fed in the course of kneading with a twin screw extruder. You may feed it. When blending with a tumbler or the like, the speed is 5 to 20 revolutions / minute, which is about 1 to 3 minutes. If the number of revolutions is too high or the blending time is too long, the carbon fibers are defibrated, which is not preferable. Furthermore,
When blending about 100 to 10,000 ppm of a lubricant such as polyethylene wax and hardened castor oil to carbon fiber when tumbling and blending only carbon fiber, defibration of carbon fiber at the time of blending and feeding by a twin screw extruder. Can be prevented.

In the present invention, the average fiber length of carbon fibers remaining in the thermoplastic resin composition after kneading is preferably 0.05 to 0.7 mm, more preferably 0.10 mm.
To 0.5 mm, particularly preferably 0.15 to 0.4 mm. When the residual average fiber length is less than 0.05 mm, the effect of imparting rigidity is small, and when it exceeds 0.7 mm, the fluidity and the molded appearance are inferior. In addition, as a method of measuring the residual average fiber length, a pellet or a molded product is dissolved in dichloromethane (or methyl ethyl ketone, strong acid) to separate only carbon fibers. Thereafter, only the carbon fiber is photographed with an electron microscope, and the photograph is analyzed by image processing.

In order to increase the residual average fiber length of the carbon fibers, it is most effective to increase the processing temperature in a twin screw extruder. Preferred processing temperatures are 230-270
° C, more preferably 240-260 ° C. Also,
The screw dimension of the twin-screw extruder is preferably one having few kneaded parts. Furthermore, the position where the carbon fiber is fed is preferably closer to the tip (die side) of the biaxial extruder.

The preferred fluidity (MFR) value of the thermoplastic resin composition of the present invention is 20 to 70 at a measuring temperature of 240 ° C. and a load of 10 kg by a method according to ASTM D1238.
g / 10 min. , More preferably 25 to 65 g / 10
min. , More preferably 30 to 60 g / 10 min.
It is. If the thickness is within the above range, the case of an A4 size notebook personal computer having a thickness of 1.5 mm can be formed with pin gates having about 1 to 5 points. However, even if the MFR value is low, it can sufficiently withstand practical use as long as it is used for thick applications or if the number of gates of a molded product can be increased.

A known filler can be added to the thermoplastic resin composition of the present invention for the purpose of imparting rigidity.
Examples of the filler include wollastonite, talc, mica, zinc oxide whiskers, calcium titanate whiskers, glass fibers, glass beads and the like. Among these inorganic fillers, talc, mica and glass fiber are preferred, and talc is particularly preferred.

The preferred average particle diameter of the talc is 0.5
２０20 μm, more preferably 1-15 μm, even more preferably 1.3-13 μm. Average particle size 0.5μm
If the amount is less than the above, agglomeration occurs at the time of kneading, and the appearance of the molded article is inferior.

The inorganic filler whose surface is treated with a silane coupling agent can also be used. The amount of the silane coupling agent used is 0.1 to 5 with respect to the inorganic filler.
%, Preferably 0.5 to 3% by weight. As the silane coupling agent, those having a functional group such as an epoxy group, an amino group, a vinyl group, and a hydroxyl group can be used. Particularly, those having an epoxy group or an amino group are preferred.

Further, the thermoplastic resin composition of the present invention comprises
The decomposition reaction of the aromatic polycarbonate of the component (B) occurs at high temperatures (such as during molding) due to the residual emulsifier, coagulant, etc. in the rubber reinforced resin as the component (A), and the physical properties of the composition deteriorate. There is. However, the decomposition reaction of the aromatic polycarbonate at a high temperature can be suppressed by blending the inorganic phosphorus compound. (G) Inorganic phosphorus compounds include sodium dihydrogen phosphate, disodium hydrogen phosphate and hydrates thereof. The amount is usually 0.1 to 3 parts by weight based on 100 parts by weight of the present thermoplastic resin (total amount of the components (A) and (B)).
Preferably it is 0.2 to 2 parts by weight.

Further, the thermoplastic resin composition of the present invention includes:
Known additives such as a weathering agent, an antioxidant, a plasticizer, a lubricant, a coloring agent, an antistatic agent, and silicone oil can be blended. As the weathering agent, a phosphorus-based or sulfur-based organic compound, an organic compound having a hydroxyl group or a vinyl group (Sumitomo Chemical Co., Ltd .: Sumilizer GS, etc.) is preferable. Examples of the antistatic agent include a sulfonate having an alkyl group. The preferred amount of these additives is 0.1 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the present thermoplastic resin (the total amount of the components (A) and (B)).
5 to 5 parts by weight.

Further, other thermoplastic resins and thermosetting resins can be blended in the thermoplastic resin composition of the present invention according to the required use. For example, polypropylene,
Polyester, polysulfone, polyethersulfone,
Polyphenylene sulfide, liquid crystal polymer, styrene-
Vinylidene acetate copolymer, polyamide elastomer, polyester elastomer, polyetheresteramide, phenolic resin, epoxy resin, novolak resin,
Resol resin and the like. These blending amounts are preferably from 1 to 150 parts by weight per 100 parts by weight of the thermoplastic resin composition.
Parts by weight, more preferably 5 to 100 parts by weight.

The thermoplastic resin composition of the present invention can be formed into various molded products by injection molding, sheet extrusion, vacuum molding, profile extrusion, foam molding and the like. Various molded products obtained by the molding method described above can be used for housing materials of OA products and home electric appliances, especially for personal computers, DVDs, CD-ROM housing materials, various tray materials, etc. by utilizing their excellent properties. it can. In particular, it is suitable for personal computer housing materials. Further, the thermoplastic resin composition of the present invention can be printed and marked by using a laser marking method.

[0048]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples,
Parts and percentages are by weight unless otherwise indicated.

1. Evaluation method The evaluation method used in this example is as follows. (1) Average particle size of rubbery polymer The average particle size of the rubbery polymer dispersed particles is measured with an electron microscope to confirm that the particle size of the latex synthesized in advance in an emulsified state directly indicates the particle size of the dispersed particles in the resin. It has been confirmed that the particle diameter of the dispersed particles in the latex was measured by a light scattering method.
The measurement device used was LPA-3100 manufactured by Otsuka Electronics Co., Ltd., and the particle diameter was measured using the cumulant method at an accumulation of 70 times.

(2) Graft ratio Details are described in the text. (3) Intrinsic Viscosity The sample was dissolved in methyl ethyl ketone and measured with an Ubbelohde viscometer at a temperature of 30 ° C. (4) Viscosity average molecular weight The aromatic polycarbonate was dissolved in methylene chloride, and five samples having different concentrations were prepared. The limiting viscosity value was obtained from the result of measuring the reduced viscosities of the samples having different concentrations at 20 ° C. using an Ubbelohde type viscosity tube. From the obtained intrinsic viscosity value, using the Mark-Houwink equation,
The viscosity average molecular weight was calculated. Mark-Hou used
The win constant is K = 1.23 × 10 ⁻⁴ , α = 0.83
It is.

(5) Izod impact strength Measured according to ASTM D256. Measured with notch. (6) Fluidity (melt flow rate) Measured according to ASTM D1238. Measurement temperature is 2
At 40 ° C., the load is 10 kg. (7) Combustion test The test conformed to the UL-94 V test. The thickness is 1.0 mm.

(8) Evaluation of Weld Appearance A molded article of 150 × 150 × 2 mm was molded with gates at both ends, and the convexity of the weld was examined. Finally, the paint was applied, and it was judged whether or not the weld was noticeable. A: After coating, the weld portion is not noticeable at all. B: After painting, most of the weld is inconspicuous,
Some parts are noticeable. C: After coating, the weld portion is conspicuous. D: It can be seen that the weld portion is convex by touching the weld with the belly of the finger before painting.

(9) Evaluation of surface impact strength Using a Dupont impact measuring device, load 200 gr
Was dropped every 10 cm at a height of 10 to 50 cm, and the height at the time when the test piece was cracked was evaluated. Cracked height is 30cm
The above can be put to practical use. The sample thickness is 2.4 mm. (10) Thermal stability 150 × 1 at a cylinder temperature of 270 ° C.
A molded product of 50 × 2 mm was molded, and it was confirmed whether there was no silver streak near the gate and in the welded portion. ：: There is no silver streak. ×: There is a silver streak.

2. Rubbery Polymer As the rubbery polymer (a), a polybutadiene latex having an average particle size of 280 nm was used.

3. Preparation of Rubber Reinforced Resin In a 7-liter glass flask equipped with a stirrer, 100 parts of ion-exchanged water, 1.5 parts of sodium dodecylbenzenesulfonate, 0.1 part of t-dodecylmercaptan.
1 part, 40 parts of polybutadiene (a) (in terms of solid content), 15 parts of styrene and 5 parts of acrylonitrile were added, and the mixture was heated while stirring. When the temperature reaches 45 ° C., 0.1 part of sodium ethylenediaminetetraacetate and 0.1 part of ferrous sulfate are added.
003 parts, 0.2 parts of formaldehyde sodium sulfoxylate dihydrate and 15 parts of ion-exchanged water, and 0.1 part of diisopropylbenzene hydroperoxide were added, and the reaction was continued for 1 hour.
Thereafter, 50 parts of ion-exchanged water, 1 part of sodium dodecylbenzenesulfonate, 0.1 part of t-dodecyl mercaptan 0.1
, 30 parts of styrene and 10 parts of acrylonitrile were added continuously over 3 hours to continue the polymerization reaction. After the addition was completed, stirring was further continued for 1 hour, and then 2,2-methylene-bis- (4-ethylene-6-
0.2 parts of (t-butylphenol) was added, and the reaction product was taken out of the flask. The reaction product latex was coagulated with dilute sulfuric acid, the reaction product was thoroughly washed with water, and then dried at 75 ° C. for 24 hours to obtain a white powder rubber reinforced resin (A-1). The polymerization addition rate is 97.2%, the graft rate is 75%,
The intrinsic viscosity of the ungrafted (co) polymer is 0.44 dl / g
Met. Similarly, a rubber reinforced resin (A-2) and an acrylonitrile-styrene resin (A-3) to be contained in the rubber reinforced resin were obtained (see Table 1).

[0056]

[Table 1]

4. Examples 1 to 8 and Comparative Examples 1 to 5 The above-mentioned (A) and the following (B) to (G) were blended in the proportions shown in Tables 2 and 3 under a temperature condition of 230 to 250 ° C. and a twin-screw extruder. (Equipment name: TEM50, company name; manufactured by Toshiba Machine Co., Ltd.), and pelletized. When two types of carbon fibers were used, they were previously blended using a tumbler, and were fed halfway by a twin screw extruder. An evaluation sample was obtained from the obtained pellet by injection molding (molding temperature: 230 ° C.). In addition, the residual average fiber length of the carbon fibers in Tables 2 and 3 was evaluated using pellets.

(B) Aromatic polycarbonate B-1; "TAFLON FN220" manufactured by Idemitsu Petrochemical Co., Ltd.
0 "(viscosity average molecular weight: 22,000) B-2;" Teflon FN300 "manufactured by Idemitsu Petrochemical Co., Ltd.
0 "(viscosity average molecular weight: 29,500) (C) Flame retardant C-1;" Platherm EC-2 "manufactured by Dainippon Ink Co., Ltd.
0 "Brominated epoxy flame retardant (terminal is sealed with tribromophenol) C-2; Condensate of" PX200 "resorcinol and dixylenyl phosphate manufactured by Daihachi Chemical Co., Ltd. (average degree of condensation: 1. 0) C-3: "FP700" manufactured by Asahi Denka Kogyo Co., Ltd. Condensate of bisphenol A and diphenyl phosphate (average degree of condensation: 1.1) (D) Flame retardant aid D-1; antimony trioxide D- 2; “TF1620” manufactured by Hoechst Co., Ltd. (average particle diameter: 220 μm, bulk density: 0.85 g / dl) (E) PAN-based carbon fiber: “HT manufactured by Toho Rayon Co., Ltd.
A-C6 "(fiber diameter: 7 µm, fiber length: 6 mm chopped strand) (F) pitch-based carbon fiber;" K223 "manufactured by Mitsubishi Chemical Corporation
Y1 ”(fiber diameter: 10 μm, fiber length: 6 mm chopped strand) (G) Other additives: sodium dihydrogen phosphate dihydrate

[0059]

[Table 2]

[0060]

[Table 3]

From the results shown in Table 2, all of the thermoplastic resin compositions have excellent rigidity, fluidity, impact resistance (surface impact strength),
It showed flame retardancy.

[0062]

The thermoplastic resin composition of the present invention has good moldability due to its excellent fluidity, and the molded product has rigidity, flame retardancy, impact resistance (plane impact) and weld portion. Excellent in molding appearance. Therefore, the molded product is OA
Products, housing materials for home appliances, personal computers, DVDs,
It can be suitably used as a housing material of a CD-ROM, various tray materials, and the like. Above all, it is the best material for thin-walled molded products aimed at weight reduction.

Continued on the front page (72) Inventor Keigo Higaki 1-18-1 Kyobashi, Chuo-ku, Tokyo Inside Techno Polymer Co., Ltd. (72) Inventor Masahiko Noro 1-16-1 Kyobashi, Chuo-ku, Tokyo Inside Techno Polymer Co., Ltd. F term (reference) 4J002 BC113 BD154 BN06X BN12X BN14X BN17X CD123 CG00W CG01W CG02W CG033 DA018 DE127 EW046 EW166 FA048 FB268 FD01 FD136 FD137 GG00

Claims (2)

[Claims] (1) In the presence of (A) a rubbery polymer (a),
Aromatic vinyl compound, vinyl cyanide compound, (meth)
A graft copolymer obtained by polymerizing at least one monomer component (b) selected from the group consisting of an acrylate compound, an acid anhydride monomer compound and a maleimide compound; It consists of a mixture of the monomer component (b) with the (co) polymer, and the proportion of the component (a) is 5 to 60% by weight, and the proportion of the component (b) is 40 to 95% by weight [provided that (a) ) + (B) = 100% by weight] and 100 to 100 parts by weight of a thermoplastic resin comprising (B) 40 to 95 parts by weight of an aromatic polycarbonate (provided that (A) + (B) = 100 parts by weight], (C) 1 to 30 parts by weight of a flame retardant, and (D) a flame retardant auxiliary agent of 0.1 part by weight.
A thermoplastic resin composition comprising 1 to 20 parts by weight and (E) 1 to 30 parts by weight of a PAN-based carbon fiber. 2. The thermoplastic resin composition according to claim 1, further comprising (F) 1 to 30 parts by weight of pitch-based carbon fiber.