JP2006169356A - Flame-retardant thermoplastic resin composition and molded product therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a flame-retardant thermoplastic resin composition excellent in dimensional accuracy, heat resistance, rigidity, flame retardancy and sustainable antistaticity, and to provide a molded product therefrom. <P>SOLUTION: The flame-retardant thermoplastic resin composition is obtained by compounding 100 pts.wt. of (I) a resin composition comprising (A) 93-80 pts.wt. of a rubber-reinforced styrene-based resin and (B) 7-20 pts.wt. of a polyamide elastomer with (C) 5-30 pts.wt. of flat-plate-like glass flakes, (D) 8-45 pts.wt. of glass fiber, (E) 10-30 pts.wt. of a flame retardant and (F) 1-15 pts.wt. of antimony trioxide. The molded product made from the composition is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a flame retardant thermoplastic resin composition and a molded article comprising the same. More specifically, in the present invention, a flat glass flake, glass fiber, and a flame retardant are blended with an alloy resin of polyamide elastomer with a rubber-reinforced styrene resin. Molded products made of the flame retardant thermoplastic resin composition have excellent erasure of static electricity generated when banknotes and papers typified by banknote identifiers and copiers are passed, and have dimensional stability and self-extinguishing properties. The present invention relates to a flame retardant thermoplastic resin composition excellent in flame retardancy, high rigidity, heat resistance and molding processability, and a molded article comprising the same.

In recent years, in a wide range of fields such as home electrical equipment, OA equipment, automobiles, etc., replacement of some metal sheets with resin products has been promoted for the purpose of reducing the weight, reducing the price, and handling complex shapes. It has been. The characteristics of sheet metal include dimensional stability, high rigidity, flame retardancy, and heat distortion resistance. As a method for imparting these characteristics to resin products, an engineering resin reinforced with a reinforcing material has been proposed. For example, polybutylene terephthalate resin, which is a crystalline resin, polyamide resin, a resin composition in which a glass fiber is blended with a polyester resin, a polycarbonate resin that is an amorphous resin, and a resin composition in which a glass fiber is blended with an ABS resin have been proposed. Yes. However, when only a fibrous material such as glass fiber is added as a reinforcing material, the rigidity and heat resistance are improved, but the glass fiber is oriented in the flow direction at the time of injection molding. (The value obtained by dividing the rate by the shrinkage rate in the vertical direction), which causes problems in terms of warpage and dimensional stability. Therefore, as a method for improving warpage and dimensional stability of the reinforcing material-filled resin, for example, a resin composition (Patent Document 1) in which a flat glass flake is blended with an aromatic polyester resin, or an amorphous rubber-modified styrene-acrylonitrile copolymer. A resin composition in which flat glass flakes are blended with a resin (Patent Document 2) is cited. However, when flat glass flakes are blended alone with a crystalline resin such as an aromatic polyester resin, an improvement effect is recognized in the shrinkage ratio, but a considerable amount of blending is necessary to obtain an improvement effect in rigidity and heat resistance. Necessary, resulting in deterioration of moldability and toughness. In addition, when flat glass flakes and fibrous reinforcing materials such as glass fibers are used in combination, a significant effect of improving the rigidity and heat resistance is recognized due to the synergistic effect of the crystalline resin and glass fibers, but the glass fibers are a resin flow. Due to the orientation in the direction, a large difference in shrinkage rate appears in the direction perpendicular to the flow direction with the crystallization of the crystalline resin, causing warping of the molded product. When the flat glass flakes are blended alone with the amorphous rubber-modified styrene-acrylonitrile copolymer resin, an improvement effect is recognized in the shrinkage ratio, but the rigidity and heat resistance are poor. In addition, when flat glass flakes and fibrous reinforcing materials such as glass fibers are used in combination, an improvement effect on the shrinkage ratio as well as an improvement in rigidity is recognized, but a considerable amount of flat glass is required to improve heat resistance. Flakes or glass fibers need to be blended, and when glass flakes are frequently used, molding processability and toughness are reduced. Moreover, when glass fiber is used frequently, since the glass fiber is oriented in the flow direction, a shrinkage difference appears in the direction perpendicular to the flow direction, resulting in a large shrinkage ratio and lack in dimensional stability. Furthermore, since these resin compositions are not provided with antistatic technology, they are not suitable for use in medical applications such as banknote discriminators and paper-passing parts of copiers where parts that generate electrification and dust do not adhere. It was.
JP 60-17223 Japanese Patent Laid-Open No. 08231812

The present invention relates to a flame retardant thermoplastic resin composition having excellent dimensional accuracy, heat resistance, rigidity, flame retardancy, and sustained antistatic properties. More specifically, the present invention comprises a flat glass flake, glass fiber, and a flame retardant blended with an alloy resin of a rubber-reinforced styrene resin and a polyamide elastomer, so that the shrinkage ratio of the injection molded product and the Provides a flame-retardant thermoplastic resin composition having excellent heat resistance, high rigidity, self-extinguishing properties, sustained antistatic properties, and excellent moldability, and a molded product comprising the same There is.

  In the present invention, as a result of intensive studies to solve the above-mentioned problems, the maximum diameter of an alloy resin of a rubber-reinforced styrene resin and a polyamide elastomer is 1000 μm or less, and the aspect ratio (ratio of major axis to thickness) is 5 or more. It has been found that by adding flat glass flakes, glass fibers, and flame retardants, excellent dimensional stability, rigidity, and heat resistance can be obtained, as well as sustained antistatic properties and flame retardancy can be imparted. It is.

  That is, according to the present invention, (A) with respect to 100 parts by weight of resin composition (I) comprising 93 to 80 parts by weight of rubber-reinforced styrene resin and (B) 7 to 20 parts by weight of polyamide elastomer, (C) It is difficult to mix 5 to 30 parts by weight of flat glass flakes, (D) 5 to 45 parts by weight of glass fibers, (E) 10 to 30 parts by weight of a flame retardant, and (F) 1 to 15 parts by weight of antimony trioxide. A flammable thermoplastic resin composition is provided.

In the flame-retardant thermoplastic resin composition of the present invention, the polymer contains crystal units in order to significantly improve heat resistance with a small amount of reinforcing material and to provide sustained antistatic properties (B ) Polyamide elastomer is essential. In order to give dimensional stability and low warpage,
(C) The maximum diameter of the flat glass flakes is 1000 μm or less, and the aspect ratio (ratio of the major axis to the thickness) is 5 or more, and the mixing ratio of the (C) flat glass flakes and (D) glass fibers. Is preferably 1: 1 to 1: 1.5.

  According to the present invention, as described below, without damaging the mechanical properties, excellent dissipation of static electricity generated during the passage of banknotes and paper represented by banknote identification machines and copiers, and dimensional stability, Flame retardant thermoplastic resin composition and molding having excellent rigidity, heat resistance and molding processability, and at the same time V-0 flame resistance according to UL94 standard is any specimen thickness of 1.5 to 3.0 mmt Goods are obtained.

  Below, the flame-retardant thermoplastic resin composition and molded article of the present invention will be described in detail.

  The (A) rubber-reinforced styrenic resin used in the present invention is a graft polymer in which a rubber-like polymer is dispersed in the form of fine particles in a matrix made of a vinyl aromatic polymer. A monomer mixture in which an aromatic vinyl monomer and, if necessary, a vinyl monomer copolymerizable therewith are added in the presence of a polymer, known bulk polymerization, bulk suspension polymerization, solution polymerization, emulsion polymerization, etc. It is a polymer obtained by subjecting to.

  Specific examples of such (A) rubber-reinforced styrene resin include, for example, impact-resistant polystyrene, ABS resin, AAS resin (acrylonitrile-acrylic rubber-styrene copolymer) and AES resin (acrylonitrile-ethylenepropylene rubber- Styrene copolymer).

  Such (A) rubber-modified styrenic resins include those having a structure in which a (co) polymer containing a styrene monomer is grafted to a rubbery polymer, and those containing a styrene monomer (co-polymer). ) A polymer having a structure in which a rubbery polymer is not grafted is included.

  Specifically, it is obtained by graft polymerization of 95 to 20 parts by weight of a monomer or monomer mixture containing 20% by weight or more of an aromatic vinyl monomer to 5 to 80 parts by weight of a rubbery polymer. (A-1) It is obtained by polymerizing a monomer or a monomer mixture containing 5 to 100% by weight of a graft (co) polymer and 20% by weight or more of an aromatic vinyl monomer (A-2). ) A vinyl (co) polymer consisting of 0 to 95% by weight is preferred.

  As the rubber polymer, those having a glass transition temperature of 0 ° C. or lower are suitable, and diene rubber is preferably used. Specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, diene rubber such as butyl acrylate-butadiene copolymer, polybutyl acrylate, etc. Examples include acrylic rubber, polyisoprene, and ethylene-propylene-diene terpolymer. Of these, the use of polybutadiene or butadiene copolymer is preferred.

  The rubber particle diameter of the rubber polymer is not particularly limited, but the rubber particles having an average particle diameter of 0.15 to 0.60 μm, particularly 0.2 to 0.55 μm, have excellent impact resistance. To preferred. Among them, the weight ratio of rubber particles having an average particle diameter in the range of 0.20 to 0.25 μm and that in the range of 0.50 to 0.65 μm is 90:10 to 60:40. The coalescence is more preferable because the impact resistance and the falling weight impact of the thin molded product are remarkably excellent.

  Specific examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, pt-butylstyrene, and the like, and styrene is particularly preferably used.

  As monomers other than aromatic vinyl monomers, vinyl cyanide monomers are used for the purpose of further improving impact resistance. A (meth) acrylic acid ester monomer is preferably used.

  Specific examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferable. Specific examples of the (meth) acrylic acid ester monomer include esterified products of acrylic acid and methacrylic acid with methyl, ethyl, propyl, n-butyl, i-butyl, and the like. Is preferred.

  Further, if necessary, other vinyl monomers such as maleimide monomers such as maleimide, N-methylmaleimide and N-phenylmaleimide can also be used.

  (A-1) The monomer or monomer mixture used in the graft (co) polymer preferably has an aromatic vinyl monomer of 20% by weight or more, more preferably 50% by weight or more. is there. When the ratio of the aromatic vinyl monomer is less than 20% by weight, the impact resistance of the resin composition may be inferior. When a vinyl cyanide monomer is mixed, it is preferably 60% by weight or less, particularly 50% by weight or less from the viewpoint of moldability of the resin composition. When a (meth) acrylic acid ester monomer is mixed, it is preferably 80% by weight or less, particularly 75% by weight or less from the viewpoint of toughness and impact resistance. The total amount of the aromatic vinyl monomer, vinyl cyanide monomer and (meth) acrylate monomer in the monomer or monomer mixture is in the range of 95 to 20% by weight. The range of 90 to 30% by weight is more preferable.

  (A-1) The ratio of the rubber polymer and the monomer mixture in obtaining the graft (co) polymer is such that the rubber polymer is 5 parts by weight or more and 80 parts by weight in 100 parts by weight of the total graft copolymer. The range of less than or equal to parts is preferable, and the range of 10 to 70 parts by weight is more preferable. The ratio of the monomer or monomer mixture is preferably 95 parts by weight or less and 20 parts by weight or more, more preferably 90 parts by weight or less and 30 parts by weight or more. From the viewpoint of the impact resistance of the resin composition, the ratio of the rubbery polymer is preferably 5 parts by weight or more, and from the viewpoint of the impact resistance of the resin composition and the appearance of the molded product, it is 80 parts by weight or less. It is preferable that

  (A-1) The graft (co) polymer can be obtained by a known polymerization method. For example, it can be obtained by a method in which a mixture of a monomer and a chain transfer agent and a solution of a radical generator dissolved in an emulsifier are continuously supplied to a polymerization vessel in the presence of a rubbery polymer latex and subjected to emulsion polymerization.

  (A-1) The graft (co) polymer contains a non-grafted copolymer in addition to a material having a structure in which a monomer or a monomer mixture is grafted to a rubbery polymer. is there. (A-1) The graft ratio of the graft (co) polymer is not particularly limited, but in order to obtain a resin composition having excellent balance of impact resistance and gloss, the graft ratio is 20 to 80% by weight. In particular, it is preferably in the range of 25 to 50% by weight. The graft ratio here is a value calculated by the following formula.

Graft rate (%) = <Amount of vinyl copolymer graft-polymerized to rubbery polymer> / <Rubber content of graft copolymer> × 100
The properties of the uncografted (co) polymer are not particularly limited, but the intrinsic viscosity [η] (measured at 30 ° C.) of methyl ethyl ketone solubles is 0.25 to 0.60 dl / g, particularly 0.25. The range of ˜0.50 dl / g is preferable because a resin composition having excellent impact resistance can be obtained.

  (A-2) A vinyl (co) polymer is a copolymer essentially comprising an aromatic vinyl monomer. Specific examples of the aromatic vinyl monomer include styrene, α-methyl styrene, p-methyl styrene, t-butyl styrene, vinyl toluene and o-ethyl styrene, and styrene is particularly preferably used. . These can use 1 type (s) or 2 or more types.

  As the monomer other than the aromatic vinyl monomer, a vinyl cyanide monomer is preferably used for the purpose of further improving impact resistance. For the purpose of improving toughness and color tone, (meth) acrylic acid ester monomers are preferably used.

  Specific examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferably used. Specific examples of the (meth) acrylic acid ester monomer include esterified products of acrylic acid and methacrylic acid with methyl, ethyl, propyl, n-butyl, i-butyl, etc., and methyl methacrylate is particularly preferred. Used.

  Specific examples of other vinyl monomers copolymerizable with these used as needed include maleimide monomers such as maleimide, N-methylmaleimide and N-phenylmaleimide.

  (A-2) The proportion of the aromatic vinyl monomer that is a constituent component of the vinyl (co) polymer is preferably 20% by weight or more, more preferably 50% by weight or more based on the total monomers. . When the ratio of the aromatic vinyl monomer is less than 20% by weight, the impact resistance of the resin composition may be inferior. In the case of mixing a vinyl cyanide monomer, it is preferably 60% by weight or less, particularly preferably 50% by weight or less from the viewpoint of impact resistance and fluidity. Further, when the (meth) acrylic acid ester monomer is mixed, it is preferably 80% by weight or less, particularly preferably 75% by weight or less from the viewpoint of toughness and impact resistance. When other vinyl monomers copolymerizable with these are mixed, it is preferably 60% by weight or less, particularly preferably 50% by weight or less.

  (A-2) Although there is no restriction | limiting in the characteristic of a vinyl type | system | group (co) polymer, Intrinsic viscosity [(eta)] (methyl ethyl ketone solvent, 30 degreeC measurement) is 0.40-0.65dl / g, Especially 0.45. In the range of ~ 0.55 dl / g, also in N, N-dimethylformamide solvent, measured at 30 ° C, 0.35 to 0.85 dl / g, especially in the range of 0.45 to 0.70 dl / g Is preferable because a resin composition having excellent impact resistance and molding processability can be obtained.

  (A-2) There are no particular limitations on the method for producing the vinyl (co) polymer, and usual methods such as bulk polymerization, suspension polymerization, emulsion polymerization, bulk-suspension polymerization, and solution-bulk polymerization are used. The method can be used.

  In the present invention, a modified vinyl polymer containing at least one functional group selected from a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and an oxazoline group (hereinafter referred to as a modified vinyl polymer) is optionally used. Abbreviated as coalesced). The modified vinyl polymer has a structure obtained by polymerizing or copolymerizing one or two or more types of vinyl monomers, and has a carboxyl group, a hydroxyl group, an epoxy group, an amino group in the molecule, and It is a polymer containing at least one functional group selected from oxazoline groups. The content of the compound containing these functional groups is not limited, but is preferably in the range of 0.01 to 20% by weight per 100 parts by weight of the modified vinyl polymer.

  The method for introducing a carboxyl group into the modified vinyl polymer is not particularly limited, but carboxyl groups such as acrylic acid, methacrylic acid, maleic acid, maleic acid monoethyl ester, maleic anhydride, phthalic acid and itaconic acid, Alternatively, a method of copolymerizing a vinyl monomer having an anhydrous carboxyl group with a predetermined vinyl monomer, γ, γ′-azobis (γ-cyanovaleric acid), α, α′-azobis (α-cyanoethyl)- Polymerization generators and / or thioglycolic acid, α-mercaptopropionic acid, β-mercaptopropionic acid, α-mercapto-isobutyric acid and 2,3 or 4- having a carboxyl group such as p-benzoic acid and peroxysuccinic acid Using a polymerization degree regulator having a carboxyl group, such as mercaptobenzoic acid, the specified vinyl monomer (co) A polymerization method, and a copolymer of a (meth) acrylic acid ester monomer such as methyl methacrylate or methyl acrylate and an aromatic vinyl monomer, and, if necessary, a vinyl cyanide monomer. A method of saponifying with an alkali can be used.

  Here, the method for introducing a hydroxyl group is not particularly limited. For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, acrylic acid 2, 3,4,5,6-pentahydroxyhexyl, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5-tetrahydroxypentyl acrylate, 2,3,4, methacrylate 5-tetrahydroxypentyl, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl- 1-propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pe And the like can be used ten and 4-dihydroxy-2-butene method of copolymerizing a vinyl monomer with a predetermined vinyl monomer having a hydroxyl group such as.

  The method for introducing the epoxy group is not particularly limited. For example, epoxy groups such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether and p-glycidyl styrene For example, a method of copolymerizing a vinyl monomer having a predetermined vinyl monomer with a predetermined vinyl monomer can be used.

  The method for introducing the amino group is not particularly limited. For example, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl acrylate, propylaminoethyl acrylate, dimethylamino methacrylate Amino groups such as ethyl, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, and For example, a method of copolymerizing a vinyl monomer having the derivative with a predetermined vinyl monomer can be used.

  The method for introducing an oxazoline group is not particularly limited. For example, a vinyl-based unit having an oxazoline group such as 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline, and 2-styryl-oxazoline. A method of copolymerizing a monomer with a predetermined vinyl monomer can be used.

  The properties of the modified vinyl polymer are not limited, but the intrinsic viscosity [η] (methyl ethyl ketone solvent, measured at 30 ° C.) is 0.20 to 0.65 dl / g, particularly 0.35 to 0.60 dl / g. N, N-dimethylformamide solvent, measured at 30 ° C., 0.30-0.90 dl / g, especially 0.40-0.75 dl / g It is preferable because a resin composition having flammability, impact resistance and moldability can be obtained.

  As the (B) polyamide elastomer used in the present invention, known ones can be used, but an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt of a diamine and dicarboxylic acid having 6 or more carbon atoms (B- A graft or block copolymer containing 1) and a poly (alkylene oxide) glycol (B-2) having a number average molecular weight of 200 to 6000 as constituent components is preferred, and the poly (alkylene oxide) glycol (B-2) is polyethylene oxide. More preferred is glycol.

  Here, aminocarboxylic acids or lactams having 6 or more carbon atoms, or salts of diamines and dicarboxylic acids having 6 or more carbon atoms, specifically, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocapryl. Acids, aminocarboxylic acids such as ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, or lactams such as caprolactam, enantolactam, capryllactam, laurolactam, hexamethylenediamine-adipine Examples thereof include nylon salts such as acid salts, hexamethylenediamine-sebacate, and hexamethylenediamine-isophthalate.

  Examples of poly (alkylene oxide) glycols include polyethylene oxide glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) ) Glycol, ethylene oxide and propylene oxide block or random copolymer, ethylene oxide and tetrahydrofuran block or random copolymer, and the like. Further, bisphenol A or an alkylene oxide adduct of fatty acid may be copolymerized. The number average molecular weight of the poly (alkylene oxide) glycol is preferably 200 to 6000, particularly preferably 300 to 4000. Further, if necessary, both ends of the poly (alkylene oxide) glycol component may be aminated or carboxylated.

  In the present invention, an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a diamine having 6 or more carbon atoms and a dicarboxylic acid salt (C-1) and a poly (alkylene oxide) glycol are usually linked by an ester bond or an amide bond. However, the present invention is not limited to these. A third component such as dicarboxylic acid or diamine can also be used as a reaction component. In this case, the dicarboxylic acid component preferably has 4 to 20 carbon atoms, and examples thereof include terephthalic acid and isophthalic acid. , Phthalic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, diphenoxyethanedicarboxylic acid, aromatic dicarboxylic acid such as sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, Alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid, succinic acid, oxalic acid, adipic acid, sebacic acid, 1,10-decanedicarboxylic acid are polymerizable, color tone From the physical properties, it is preferable. On the other hand, as the diamine component, aromatic, alicyclic, and aliphatic diamines are used, and among them, aliphatic diamine hexamethylenediamine is preferable.

  It does not specifically limit about the manufacturing method of a polyamide elastomer (B), A well-known method can be utilized. For example, an aminocarboxylic acid or lactam or a diamine having 6 or more carbon atoms and a dicarboxylic acid salt (ii) and a dicarboxylic acid (b) are reacted to form a polyamide prepolymer having carboxylic acid groups at both ends. Oxide) glycol (c) reacts under vacuum, or (b), (b), (c) compounds are charged into a reaction vessel and heated at high temperature in the presence or absence of water A method is known in which a carboxylic acid-terminated polyamide elastomer is produced by the above-described method, and then polymerization is carried out under normal pressure or reduced pressure. There is also a method in which the compounds (a), (b), and (c) are charged into a reaction vessel at the same time, melt polymerization is performed, and then polymerization is advanced at a time under high vacuum.

  The amount of (A) rubber-reinforced styrene resin and (B) polyamide elastomer used is preferably in the range of (A) component: (B) component = 93-80: 7-20 parts by weight, more preferably 90-85: It is in the range of 10 to 15 parts by weight.

  When the amount of the polyamide elastomer used is 7 parts by weight or less, the antistatic property is low and the effect of improving the heat resistance is low. Further, when the amount of the polyamide elastomer used exceeds 20 parts by weight, the rigidity is lowered, which is not preferable.

  The flat glass flake (C) used in the present invention has a maximum diameter of 1000 μm or less and an aspect ratio (major axis to thickness ratio) of 5 or more. Preferably, the maximum diameter is in the range of 1 to 500 μm and the aspect ratio (ratio of major axis to thickness) is 10 or more, more preferably 20 or more. (C) When the flat glass flakes have a maximum diameter exceeding 1000 μm, uniform dispersion during blending becomes difficult, causing defects in the appearance of the molded product, and also causing non-uniform mechanical properties. Also, those having an aspect ratio of less than 5 are not preferred because the effect of improving the shrinkage ratio is low.

  The amount of the (C) flat glass flake used in the present invention is usually 5 to 100 parts by weight of the resin composition (I) composed of (A) rubber-reinforced styrene resin and (B) polyamide elastomer. It is in the range of 30 parts by weight, preferably 7 to 20 parts by weight, more preferably in the range of 8 to 15 parts by weight.

  When the amount of (C) flat glass flake used in the present invention is less than 5 parts by weight, the effect of improving the shrinkage ratio is low, and when it is 30 parts by weight or more, the toughness of the molded product is lowered and the moldability is also improved. Since it falls, it is not preferable.

  The glass fiber (D) used in the present invention preferably has a C glass composition when used in an acidic atmosphere, and preferably has an E glass composition when used in a neutral to weakly alkaline atmosphere. is there. (D) Although a commercially available glass fiber can be used, the average diameter of the glass fiber is preferably 0.3 to 20 μm, and the average length is preferably 0.1 to 10 mm, and more preferably 5 to 13 μm. An average length of 0.5 to 5 mm is more preferable. (D) The glass fiber is used in an amount of usually 5 to 45 parts by weight, preferably 7 to 100 parts by weight, based on 100 parts by weight of the resin composition (I) comprising (A) a rubber-reinforced styrene resin and (B) a polyamide elastomer. It is the range of 30 weight part, More preferably, it is the range of 8-20 weight part.

  When the amount of the (D) glass fiber used in the present invention is less than 5 parts by weight, the effect of improving the rigidity and heat resistance is low, and when it is 45 parts by weight or more, the shrinkage ratio of the molded product increases and the dimensional stability decreases. However, it is not preferable because molding processability is also lowered.

Examples of the flame retardant (E) that can be used in the present invention include brominated polycarbonate oligomers. The degree of polymerization of the brominated polycarbonate oligomer is preferably 2-10. If the degree of polymerization is less than 2, volatilization occurs during molding or bleeding out to the surface of the molded product occurs. On the other hand, if the degree of polymerization is greater than 10, the compatibility with the base resin is lowered, which is not preferable.
(E) The usage-amount of a flame retardant is 10-30 weight part, Preferably it is the range of 11-28 weight part, More preferably, it is 12-25 weight part. If the content is less than 10 parts by weight, the flammability is remarkably lowered. On the other hand, if it exceeds 30 parts by weight, impact resistance is lowered, which is not preferable.

  The antimony trioxide (F) in the present invention is obtained by melting bright ore and metal antimony and obtained by a sublimation method, but is not limited to this production method. The purity is preferably 99.5% by weight or more from the viewpoint of environment and safety. The lead oxide content in antimony trioxide (F) is preferably 0.03% by weight or less, and the arsenic trioxide content is preferably 0.1% by weight or less. The content of antimony trioxide (F) in the thermoplastic resin composition needs to be 1 to 15 parts by weight, preferably 1.5 to 12 parts by weight, and more preferably 2 to 10 parts by weight. Parts by weight. If the content is less than 1 part by weight, sufficient flammability cannot be obtained. On the other hand, if it exceeds 15 parts by weight, mechanical strength such as impact resistance is lowered, which is not preferable.

  There is no restriction | limiting in particular regarding the manufacturing method of the flame-retardant thermoplastic resin composition of this invention, (A) rubber-reinforced styrene resin, (B) polyamide elastomer, (C) flat glass flakes, (D) glass fiber, (E) Flame retardant thermoplastic resin and (F) Antimony trioxide can be produced by, for example, melt kneading with a Banbury mixer, roll, extruder, kneader or the like. It is preferable that the composition is in a melt-kneading condition in which the number average length of (D) glass fibers of the composition is 250 μm or more, and the number average length of (D) glass fibers is more preferably 1 mm or more, and further preferably 2 mm or more. (D) If the number average length of the glass fibers is less than 250 μm, the heat resistance and the flexural modulus are not preferred. Furthermore, it is preferable that (C) the maximum diameter of the flat glass flakes is 1000 μm or less and the aspect ratio (ratio of major axis to thickness) is 5 or more, and (C) the flat glass flakes and (D) the glass fibers The blending ratio is more preferably in the range of 1: 1 to 1: 1.5.

  The flame retardant thermoplastic resin composition of the present invention is further improved in performance as a molding resin composition by blending various thermoplastic resins and elastomers within a range not impairing the object of the present invention. Can do. Furthermore, antioxidants and heat stabilizers such as hindered phenol, phosphorus and sulfur antioxidants, UV absorbers (eg resorcinol, salicylate, benzotriazole, benzophenone), lubricants and mold release agents as necessary. (Montanic acid and its salt, its ester, its half ester and ethylene wax, etc.), 1 type of usual additives such as anti-coloring agent (phosphite, hypophosphite, etc.), nucleating agent and plasticizer More can be added.

  The flame retardant thermoplastic resin composition of the present invention obtained as described above is a known one that is currently used for molding thermoplastic resins such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding, and gas assist molding. It can shape | mold by a method and the shaping | molding method itself is not restrict | limited in particular.

  The molded product of the present invention thus obtained has a small warp of the molded product and is excellent in heat resistance and anti-static properties. It can be expected to be applied to applications that do not like dust adhesion.

  Specific examples of the molded product of the present invention include, for example, bill validators, copying machine paper passing parts, sensors, connectors, relay cases, switches, coil bobbins, condensers, optical pickup chassis, tuners, speakers, computers, VTRs, televisions. DVD chassis, disk drives, fax machines, transformer members, personal computer parts, notebook personal computers, pachinko parts and mobile phones.

  As described above, the flame retardant thermoplastic resin composition of the present invention and a molded article made thereof are not only dimensional stability, heat resistance and antistatic properties, but also have flame retardancy, high rigidity, self-extinguishing properties, Because it has the characteristics of excellent impact resistance and moldability, it can be used as a chassis and housing for bill discriminator parts, copier parts, electrical / electronic parts, OA equipment, home appliances, miscellaneous goods, etc. It can be suitably used as parts.

  In order to describe the present invention more specifically, examples and comparative examples will be described below, but the present invention is not limited thereby. In Examples and Comparative Examples, unless otherwise specified, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

First, the evaluation method of the characteristic of a flame-retardant thermoplastic resin composition is described below.
(1) Charpy impact strength The Charpy impact strength was measured under the conditions of 80 × 10 × 4 mm, type A notch, and 23 ° C. in accordance with the provisions of ISO 179.
(2) Flexural modulus The flexural modulus was evaluated in accordance with the provisions of ISO 178.
(3) Deflection temperature under load (heat resistance)
The heat resistance was evaluated according to the regulations of ISO 75 (load: 1.8 MPa).
(4) Surface resistivity value A square plate test piece having a thickness of 40 × 50 × 3 mm obtained by injection molding with a PS60E molding machine manufactured by Nissei Plastic Industry Co., Ltd. set to a cylinder setting temperature of 230 ° C. and a mold temperature of 40 ° C. After being allowed to stand for 24 hours in an environment of 23 ° C. and 50% Rh, the measurement was performed according to ASTM D257.

The applied voltage was 500 V, and the value after 1 minute was read.
(5) Melt flow rate The melt flow rate was evaluated according to ISO 1133 (temperature: 220 ° C., load: 98 N).
(6) Flame Retardancy Flame retardant evaluation of 1.5 mm thickness and 3.0 mm thickness obtained by injection molding with a PS60E molding machine manufactured by Nissei Plastic Industry Co., Ltd. set to a cylinder temperature of 230 ° C and a mold temperature of 40 ° C. The test piece was evaluated for flame retardancy according to the evaluation criteria defined in UL94. The flame retardancy level decreases in the order of V-0, V-1, V-2, and HB, and V-0 and V-1 are classified as self-extinguishing.
(7) Mold Shrinkage A flat plate of 150 mm (W) x 150 mm (L) x 3 mm (t) formed by injection molding with a PS60E molding machine manufactured by Nissei Plastic Industry Co., Ltd., set at a cylinder temperature of 230 ° C and a mold temperature of 40 ° C. A specimen was obtained. The obtained test piece was allowed to stand for 24 hours in an environment of 23 ° C. and 50% Rh, and then the shrinkage in the direction perpendicular to the flow direction of the molded product was measured with a caliper. The shrinkage rate is preferably 0.4% or less as the dimensional accuracy.
(8) Shrinkage ratio A value obtained by dividing the shrinkage in the horizontal direction by the shrinkage in the vertical direction. The closer the shrinkage ratio is to 1.0, the smaller the warp of the molded product.

[Reference Example 1] Preparation of rubber-reinforced styrene resin <A-1> Graft (co) polymer A method for preparing a graft copolymer is shown below. The graft ratio was determined by the following method. Acetone was added to a predetermined amount (m) of the graft copolymer and refluxed for 4 hours. This solution was centrifuged at 8000 rpm (centrifugal force 10,000 G (about 100 × 10 ³ m / s ² )) for 30 minutes, and then insoluble matter was filtered. This insoluble matter was dried under reduced pressure at 70 ° C. for 5 hours, and the weight (n) was measured.

Graft ratio = [(n) − (m) × L] / [(m) × L] × 100
Here, L means the rubber content of the graft copolymer.

  In the presence of 60 parts (in terms of solid content) of polybutadiene latex (average rubber particle size 0.3 μm, gel content 85%), 40 parts of a monomer mixture composed of 70% styrene and 30% acrylonitrile was added to carry out emulsion polymerization. . The obtained graft copolymer was coagulated with sulfuric acid, neutralized with sodium hydroxide, washed, filtered, and dried to prepare a powdery graft copolymer <A-1>.

  The graft ratio of the obtained graft copolymer <A-1> was 36%. This graft copolymer <A-1> contained 18.1% of a non-graft copolymer composed of 70% styrene structural units and 30% acrylonitrile structural units. The intrinsic viscosity of the N, N-dimethylformamide-soluble component was 0.48 dl / g.

<A-2> Preparation of vinyl-based (co) polymer A monomer mixture consisting of 70% styrene and 30% acrylonitrile was subjected to suspension polymerization to prepare a vinyl-based copolymer <A-2>. The intrinsic viscosity of the N, N-dimethylformamide-soluble component of the obtained vinyl copolymer <A-2> was 0.73.

[Reference Example 2] (B) Polyamide Elastomer 60 parts of nylon 6,6 salt, 30 parts of polyethylene glycol having a number average molecular weight of 800 and 10 parts of adipic acid were used at 250 ° C. for 4 hours in the presence of an antimony trioxide catalyst. Polymerized. The obtained polymer was discharged in a strand shape and cut to obtain a pellet-like polyamide elastomer.

[Reference Example 3] (C) Flat glass flake REFG-301 (manufactured by Nippon Sheet Glass Co., Ltd.) (average diameter 140 μm, aspect ratio 28) was used. It was used.

[Reference Example 4] (D) Glass fiber ECS03T-351 (manufactured by Nippon Sheet Glass Co., Ltd.) (number average length 3 ± 1 mm) was used.

[Reference Example 5] (E) Flame Retardant “Fireguard” FG-8500 manufactured by Teijin Chemicals Ltd. was used.

[Reference Example 6] Antimony trioxide “PATOX-C” (purity 99 wt% or more, lead content 0.03 wt% or less, arsenic content 0.1 wt% or less) manufactured by Nippon concentrate Co., Ltd. was used. .

[Examples 1 to 4]
Table 1 shows (A) rubber-reinforced styrene-based resin, (B) polyamide elastomer, (C) flat glass flakes, (D) glass fiber, (E) flame retardant, and (F) antimony trioxide shown in Reference Examples. Blended at the indicated blending ratio, and melt-kneaded and extruded using a vented 30 mmφ twin screw extruder (Ikegai PCM-30) to produce a flame-retardant thermoplastic resin composition in the form of pellets did. Then, using an injection molding machine, a test piece was molded at a cylinder temperature of 230 ° C. and a mold temperature of 40 ° C. The test pieces were measured for physical properties under the above conditions, and the results are shown in Table 1.

[Comparative Examples 1-7]
Table 2 shows (A) rubber-reinforced styrene-based resin, (B) polyamide elastomer, (C) flat glass flakes, (D) glass fiber, (E) flame retardant, and (F) antimony trioxide shown in Reference Examples. The physical properties of the test pieces obtained by mixing at the indicated blending ratios and molded by the same method as in the examples were measured, and the measurement results are also shown in Table 2.

  From the results of Tables 1 and 2, the following is clear. That is, the flame-retardant thermoplastic resin compositions (Examples 1 to 4) of the present invention all have molding shrinkage ratio, shrinkage ratio, heat resistance, antistatic property, flame retardancy, flexural modulus, and impact resistance. And it was excellent in moldability.

  On the other hand, (C) the amount of the flat glass flakes less than 5 parts by weight (Comparative Example 1) was inferior in bending elastic modulus, load deflection temperature and molding shrinkage. Further, (C) the amount of the flat glass flakes exceeding 30 parts by weight (Comparative Example 2) has low Charpy impact strength and melt flow rate, and also has a low bending elastic modulus and load deflection temperature, and the effect of the reinforcing material. Is insufficient. (D) The glass fiber used alone as the reinforcing material (Comparative Example 3) has a large shrinkage ratio and is insufficient in terms of warpage. (C) The ratio of flat glass flakes and (D) glass fibers exceeding 1: 1 to 1: 1.5 (Comparative Example 6) has a large shrinkage ratio and is insufficient in terms of warpage. A resin using polybutylene terephthalate, which is a crystalline resin, as the base resin (Comparative Example 7) has a large molding shrinkage ratio and shrinkage ratio and is insufficient in terms of dimensional stability and warpage.

  As described above, the flame retardant thermoplastic resin composition of the present invention and a molded article made thereof are not only dimensional stability, heat resistance and antistatic properties, but also have flame retardancy, high rigidity, self-extinguishing properties, Because it has the characteristics of excellent impact resistance and molding processability, it can be used as a chassis and housing for bill discriminator parts, copier parts, electrical / electronic parts, OA equipment, home appliances, miscellaneous goods, etc. It can be suitably used as parts.

  Specific examples of the molded article of the present invention include, for example, bill discriminators, copying machine paper passing parts, sensors, connectors, relay cases, switches, coil bobbins, capacitors, optical pickup chassis, tuners, speakers, computers, VTRs, televisions, DVDs. A chassis, a disk drive, a fax machine, a transformer member, a personal computer part, a notebook personal computer, a pachinko part, a mobile phone, and the like are listed, and they are effective for these various applications.

Claims (7)

(C) Flat glass flakes 5-30 with respect to 100 parts by weight of resin composition (I) comprising 93-80 parts by weight of rubber-reinforced styrene resin and 7-20 parts by weight of polyamide elastomer (B) A flame retardant thermoplastic resin composition comprising 5 parts by weight and (D) 5 to 45 parts by weight of glass fiber, (E) 10 to 30 parts by weight of a flame retardant, and (F) 1 to 15 parts by weight of antimony trioxide. A flame retardant thermoplastic resin composition having a deflection temperature under load (ISO75: maximum surface stress of 1.8 MPa) of 100 ° C. or higher. The flame retardant thermoplastic resin composition according to claim 1, wherein the flame retardant thermoplastic resin composition has a flexural modulus (ISO 178) of 3000 MPa or more. 3. The flame-retardant thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a surface specific resistance value (ASTMD257) of 9 × 10 ¹³ Ω or less. The flame retardant thermoplastic resin according to any one of claims 1 to 3, wherein the (C) flat glass flake has a maximum diameter of 1000 µm or less and an aspect ratio (ratio of major axis to thickness) of 5 or more. Composition. The flame retardant thermoplastic resin according to any one of claims 1 to 4, wherein a blending ratio of the (C) flat glass flakes and (D) glass fibers is in a range of 1: 1 to 1: 1.5. Composition. It is V-0 in a UL-94 vertical combustion test, The flame-retardant thermoplastic resin composition of any one of Claims 1-5. The molded article which consists of a flame-retardant thermoplastic resin composition of any one of Claims 1-6.