JP6354162B2 - Flame retardant thermoplastic resin composition - Google Patents

Description

  The present invention relates to a flame retardant thermoplastic resin composition containing polyamide and a styrene resin, and a molded article thereof.

  Alloy compositions of styrenic resin and polyamide represented by acrylonitrile-butadiene-styrene (ABS) resin are excellent in chemical resistance, mechanical strength, and moldability, so electrical appliances for home use, cooking equipment, etc. It is used in a wide range of fields including housing equipment. In particular, a composition used for cooking appliances is required to have high fluidity at the time of molding, in addition to being required to have flame retardancy, heat resistance, toughness, and the like.

  As a general method for flame-retarding a resin, a method of blending a flame retardant aid represented by a halogen-based flame retardant and antimony oxide can be mentioned. In addition, in order to impart higher heat resistance, a method of blending an inorganic filler is also known. However, a molded product obtained using such a resin composition has a problem that it has low toughness and breaks during bending deformation. Further, depending on the inorganic filler to be blended, there is a problem that the fluidity at the time of molding processing is lowered.

  Therefore, as a thermoplastic resin pellet composition excellent in rigidity, flame retardancy, impact resistance, and molding processability, for example, a fiber reinforced thermoplastic resin pellet made of a thermoplastic resin and a fibrous filler, a rubber reinforced resin, A thermoplastic resin pellet composition containing a flame retardant thermoplastic resin pellet composed of a flame retardant and a flame retardant aid has been proposed (see, for example, Patent Document 1). However, a molded product obtained using such a thermoplastic resin pellet composition has a problem that the toughness is insufficient.

  In addition, as a flame retardant thermoplastic resin composition excellent in molding processability, mechanical properties and appearance of a molded product, for example, a styrene resin, polyamide resin, ammonium polyphosphate, and melamine sulfate and / or ammonium sulfate are blended. A flame retardant thermoplastic resin composition is proposed (see, for example, Patent Document 2). However, such a resin composition has a problem that the fluidity at the time of molding is low and the flame retardancy of the molded product is insufficient.

  On the other hand, as a thermoplastic resin composition excellent in heat resistance, low-temperature impact properties, and paintability, for example, graft copolymers, vinyl copolymers, modified vinyl copolymers, polyamides, impact resistance improvers and fiber reinforcements Has been proposed (see, for example, Patent Document 3). However, such a thermoplastic resin composition has a problem that the fluidity at the time of molding is low and the flame retardancy of the molded product is insufficient.

Japanese Patent Laid-Open No. 2002-20606 JP 2000-44763 A JP 2011-208127 A

  The present invention provides a flame retardant thermoplastic resin composition that is excellent in fluidity during molding and can provide a molded product having high flame retardancy, heat resistance, and toughness in view of the above-described problems of the prior art. For the purpose.

As a result of intensive studies to solve the above problems, the present inventor has found that graft copolymers, vinyl copolymers, modified vinyl copolymers, polyamides, specific brominated polystyrenes, antimony trioxide and non-fibers It has been found that the above-mentioned problems can be solved by containing the fibrous inorganic filler in a specific ratio, and the present invention has been achieved. That is, this invention is comprised by the following (1)-(4).
(1) (A) Rubber polymer (a) In the presence of 40 to 80% by weight, aromatic vinyl monomer (a) 15 to 45% by weight and vinyl cyanide monomer (c) 5 Graft copolymer obtained by graft copolymerization of a monomer mixture containing ˜20% by weight,
(B) a vinyl copolymer obtained by copolymerizing a vinyl monomer mixture containing an aromatic vinyl monomer (ii) and a vinyl cyanide monomer (c);
(C) Unsaturated carboxylic acid and / or α, β-unsaturated carboxylic acid anhydride (d) 0.1 to 10% by weight, aromatic vinyl monomer (a) 50 to 85% by weight and vinyl cyanide A modified vinyl copolymer obtained by copolymerizing 10 to 40% by weight of a monomer (c),
(D) polyamide,
(E) brominated polystyrene having a number average molecular weight of 1,000 to 4,500,
(F) An antimony trioxide and (G) a flame-retardant thermoplastic resin composition containing a non-fibrous inorganic filler, wherein (A) to (D) in total 100 parts by weight, 10 to 25 parts by weight of A), 5 to 20 parts by weight of (B), 1 to 10 parts by weight of (C), 65 to 80 parts by weight of (D), 28 to 38 parts by weight of (E), A flame retardant thermoplastic resin composition containing 8 to 13 parts by weight of F) and 10 to 20 parts by weight of (G).
(2) The flame retardant thermoplastic resin composition according to (1), wherein the non-fibrous inorganic filler (G) includes talc.
(3) The flame-retardant thermoplastic resin composition according to (1) or (2), wherein the polyamide (D) includes polyamide 6.
(4) A molded product obtained by molding the flame retardant thermoplastic resin composition according to any one of (1) to (3).

  The flame-retardant thermoplastic resin composition of the present invention is excellent in fluidity during molding. With the flame-retardant thermoplastic resin composition of the present invention, a molded article excellent in flame retardancy, heat resistance and toughness can be obtained.

  Hereinafter, the form for implementing this invention is described concretely.

  The flame-retardant thermoplastic resin composition of the present invention (hereinafter sometimes referred to as “resin composition”) includes the above-mentioned (A) graft copolymer, (B) vinyl copolymer, (C) It contains a modified vinyl copolymer, (D) polyamide, (E) brominated polystyrene, (F) a flame retardant aid and (G) a non-fibrous inorganic filler. Each of these components will be described.

<(A) Graft copolymer>
The graft copolymer (A) in the present invention is a rubbery polymer (a) in the presence of 40 to 80% by weight, an aromatic vinyl monomer (a) 15 to 45% by weight and a vinyl cyanide It is obtained by graft copolymerization of a monomer mixture containing 5 to 20% by weight of monomer (c). By containing this (A) graft copolymer, the toughness of a molded article can be improved. In addition, the resin composition containing brominated polystyrene having a specific molecular weight described later tends to break the strands during extrusion, but by combining with the (A) graft copolymer, the strand composition is suppressed and the resin composition is suppressed. Productivity can be improved. In addition, the above-mentioned weight% is a value with respect to a total of 100 weight% of the rubber-like polymer (A) and the monomer mixture containing (A) to (U). The term “graft copolymer” as used herein includes not only those obtained by graft copolymerization of a monomer mixture with a rubbery polymer (a) but also copolymers of ungrafted vinyl monomer mixtures. Good. The copolymer of the ungrafted vinyl monomer mixture is dissolved in acetone.

In addition, the graft ratio of the graft copolymer (A) is not particularly limited, but is preferably 5% or more and more preferably 10% or more from the viewpoint of collision ductility. On the other hand, from the viewpoint of moldability, 60% or less is preferable, and 50% or less is preferable. The graft ratio (%) of the graft copolymer (A) is represented by the following formula.
Graft ratio (%) = {[Amount of copolymer graft-polymerized to rubbery polymer] / [Rubber content of graft copolymer]} × 100

  (A) Examples of the rubbery polymer (a) constituting the graft copolymer include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, and butyl acrylate. -Diene rubber-like polymers, such as a butadiene copolymer, are mentioned. Two or more of these may be used. The glass transition temperature of the rubbery polymer (a) is preferably 0 ° C. or lower. On the other hand, the glass transition temperature is practically −80 ° C. or higher. In the present invention, polybutadiene is preferably employed from the viewpoint of production operability.

  Examples of the aromatic vinyl monomer (A) constituting the graft copolymer (A) include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, p-methylstyrene, chlorostyrene and bromostyrene. Etc. Two or more of these may be used. Styrene is preferably employed from the viewpoint of further improving the fluidity during the molding process.

  Examples of the vinyl cyanide monomer (U) constituting the (A) graft copolymer include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like. Two or more of these may be used. Acrylonitrile is preferably employed.

  Moreover, you may use for the copolymer (A) in this invention the other copolymerizable monomer to such an extent that the effect of this invention is not lost. Examples of other copolymerizable monomers include N-phenylmaleimide, N-methylmaleimide, and methyl methacrylate, and can be selected according to the respective purposes. Two or more of these may be used. For example, N-phenylmaleimide is preferable in order to further improve heat resistance and flame retardancy. In order to improve the hardness, methyl methacrylate is preferably used.

  The weight average particle diameter of the rubber polymer (a) is not particularly limited, but is preferably 0.10 μm or more, and more preferably 0.15 μm or more from the viewpoint of further improving the toughness and impact resistance of the molded product. On the other hand, from the viewpoint of further improving the fluidity during molding, it is preferably 0.50 μm or less, and more preferably 0.40 μm or less. The weight average particle diameter of the rubber polymer (a) is determined by the sodium alginate method (concentration of sodium alginate) described in “Rubber Age Age Vol. 88 p.484-490 (1960) by E. Schmidt, PH Biddison”. The particle diameter of 50% cumulative weight fraction can be measured from the cumulative proportion by weight and the cumulative weight fraction of sodium alginate concentration.

  (A) The weight fraction of the rubber-like polymer (a) in the raw material which comprises a graft copolymer is 40 to 80 weight%. If the weight fraction of the rubber-like polymer (a) is less than 40% by weight, the toughness of the molded product is lowered. When a large amount of (A) graft copolymer is contained in order to improve toughness, the flame retardancy of the molded product is lowered. 45 weight% or more is preferable. On the other hand, when the weight fraction of the rubbery polymer (a) exceeds 80% by weight, the fluidity at the time of molding processing is lowered. In addition, the surface appearance of the molded product may deteriorate. 75 weight% or less is preferable and 70 weight% or less is more preferable.

  (A) The weight fraction of the aromatic vinyl monomer (A) in the raw material constituting the graft copolymer is 15 to 45% by weight. When the weight fraction of the aromatic vinyl monomer (A) is less than 15% by weight, the fluidity at the time of molding processing is lowered. 25 weight% or more is preferable. On the other hand, when the weight fraction of the aromatic vinyl monomer (A) exceeds 45% by weight, the toughness of the molded product is lowered.

  (A) The weight fraction of the vinyl cyanide monomer (c) in the raw material constituting the graft copolymer is 5 to 20% by weight. When the weight fraction of the vinyl cyanide monomer (c) is less than 5% by weight, the toughness of the molded product is lowered. On the other hand, when the weight fraction of the vinyl cyanide monomer (c) exceeds 20% by weight, the fluidity at the time of molding processing is lowered. It is preferably 15% by weight or less.

<(B) Vinyl-based copolymer>
The (B) vinyl copolymer in the present invention is obtained by copolymerizing a vinyl monomer mixture containing an aromatic vinyl monomer (ii) and a vinyl cyanide monomer (c). Copolymer. By containing the vinyl copolymer (B), the fluidity at the time of molding can be improved.

  (B) The aromatic vinyl monomer (A) constituting the vinyl copolymer is exemplified as the aromatic vinyl monomer (A) constituting the graft copolymer (A). In particular, styrene is preferably employed.

  (B) Examples of the vinyl cyanide monomer (c) constituting the vinyl copolymer include those exemplified as the vinyl cyanide monomer (c) constituting the graft copolymer (A). In particular, acrylonitrile is preferably employed.

  In addition to (B) the vinyl-based copolymer, other copolymerizable monomers may be used to the extent that the effects of the present invention are not lost. Examples of the other copolymerizable monomer include those exemplified as the other copolymerizable monomer constituting the graft copolymer (A). However, the copolymer obtained by copolymerizing an unsaturated carboxylic acid and / or an α, β-unsaturated carboxylic acid anhydride described later shall be classified as a (C) modified vinyl copolymer described later. .

  (B) The composition ratio of the monomer constituting the vinyl copolymer is 60 to 85% by weight of the aromatic vinyl monomer (ii) in the total 100% by weight of the vinyl monomer mixture, and vinyl cyanide. The monomer (c) is preferably 15 to 40% by weight.

  The (B) vinyl copolymer in the present invention preferably has an intrinsic viscosity [η] at 30 ° C. of the methyl ethyl ketone-soluble component in the range of 0.25 to 0.60 dl / g. When the intrinsic viscosity is 0.25 dl / g or more, the fluidity of the resin composition can be further improved, and a molded product having a complicated shape can be easily formed. 0.40 dl / g or more is preferable. On the other hand, if the intrinsic viscosity is 0.60 dl / g or less, the toughness of the molded product can be further improved. 0.55 dl / g or less is more preferable.

<(C) Modified vinyl copolymer>
The (C) modified vinyl copolymer in the present invention is an unsaturated carboxylic acid and / or an α, β-unsaturated carboxylic acid anhydride (d) 0.1 to 10% by weight, an aromatic vinyl monomer. (A) A copolymer obtained by copolymerizing 50 to 85% by weight and 10 to 40% by weight of a vinyl cyanide monomer (c). By containing the (C) modified vinyl copolymer, the compatibility of (A) graft copolymer and / or (B) vinyl copolymer and (D) polyamide is improved, and the toughness of the molded product is improved. Can be improved.

  (C) Unsaturated carboxylic acid or α, β-unsaturated carboxylic acid anhydride (d) constituting the modified vinyl copolymer includes, for example, methacrylic acid, maleic acid, fumaric acid, itaconic acid, methylmaleic acid And unsaturated carboxylic acids such as methyl fumaric acid and glutaconic acid, and α, β-unsaturated carboxylic acid anhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, methyl maleic anhydride and methyl fumaric anhydride. . Two or more of these may be used. Among these, methacrylic acid, maleic acid and maleic anhydride are preferable, and methacrylic acid is more preferable.

  (C) The aromatic vinyl monomer (A) constituting the modified vinyl copolymer is exemplified as the aromatic vinyl monomer (A) constituting the graft copolymer (A). In particular, styrene is preferably employed.

  (C) The vinyl cyanide monomer (c) constituting the modified vinyl copolymer is exemplified as the vinyl cyanide monomer (c) constituting the graft copolymer (A) described above. In particular, acrylonitrile is preferably employed.

  (C) The weight fraction of the unsaturated carboxylic acid and / or the α, β-unsaturated carboxylic acid anhydride (d) in the raw material constituting the modified vinyl copolymer is 0.1 to 10% by weight. is there. When the weight fraction of the unsaturated carboxylic acid and / or α, β-unsaturated carboxylic acid anhydride (d) is less than 0.1% by weight, the compatibility and reactivity with (D) polyamide is poor, and Toughness decreases. On the other hand, when the weight fraction of the unsaturated carboxylic acid and / or α, β-unsaturated carboxylic acid anhydride (d) exceeds 10% by weight, the fluidity at the time of molding processability decreases, and the surface of the molded product is reduced. A flow mark may occur.

  (C) The weight fraction of the aromatic vinyl monomer (b) and the vinyl cyanide monomer (c) constituting the modified vinyl copolymer is the sum of (a), (c) and (d). In 100% by weight, the aromatic vinyl monomer (i) is 50 to 85% by weight, and the vinyl cyanide monomer (c) is 10 to 40% by weight. When the weight fraction of the aromatic vinyl monomer (a) is less than 50% by weight, the fluidity at the time of molding processing is lowered. On the other hand, when the weight fraction of the aromatic vinyl monomer (A) exceeds 85% by weight, the toughness of the molded product is lowered. When the weight fraction of the vinyl cyanide monomer (c) is less than 10% by weight, the toughness of the molded product is lowered. On the other hand, when the weight fraction of the vinyl cyanide monomer (c) exceeds 40% by weight, the fluidity during the molding process is lowered.

  In the present invention, (A) the graft copolymer, (B) the vinyl copolymer and (C) the modified vinyl copolymer can be produced by, for example, bulk polymerization, suspension polymerization, bulk suspension polymerization, Examples of the polymerization method include solution polymerization, emulsion polymerization, and precipitation polymerization. Two or more of these may be combined. The method for charging the monomers constituting each copolymer is not particularly limited, and may be charged all at once in the initial stage. In order to adjust the composition distribution of the copolymer to a desired range, the number of monomers is not limited. You may charge in batches.

  In the present invention, an initiator may be used in the polymerization of (A) the graft copolymer, (B) the vinyl copolymer and (C) the modified vinyl copolymer. As the initiator, a peroxide or an azo compound is preferably used. These may be combined.

  Examples of the peroxide include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butyl cumyl peroxide, t-butyl peroxyacetate, t -Butylperoxybenzoate, t-butylperoxyisopropyl carbonate, di-t-butyl peroxide, t-butylperoctate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 1,1-bis (t-butylperoxy) cyclohexane, t-butylperoxy-2-ethylhexanoate, and the like. Two or more of these may be used. Of these, cumene hydroperoxide and 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane are preferably used.

  Examples of the azo compound include azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano-2-propylazo. Formamide, 1,1′-azobiscyclohexane-1-carbonitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 1-t-butylazo-1 -Cyanocyclohexane, 2-t-butylazo-2-cyanobutane, 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane, and the like. Two or more of these may be used. Of these, azobisisobutyronitrile is preferably used.

  In the production of (A) graft copolymer, (B) vinyl copolymer and (C) modified vinyl copolymer, chain transfer agents such as mercaptans and terpenes may be used. The desired range can be adjusted. Specific examples of the chain transfer agent include n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan and terpinolene. Two or more of these may be used. Of these, n-octyl mercaptan, t-dodecyl mercaptan and n-dodecyl mercaptan are preferably used.

<(D) Polyamide>
The resin composition of this invention can improve the flame retardance, toughness, and heat resistance of a molded article by containing (D) polyamide.

  The polyamide (D) in the present invention is a resin obtained by polycondensation of aminocarboxylic acid, lactam or diamine and dicarboxylic acid. Examples of the raw material for polyamide (D) include aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, lactams such as ε-caprolactam and ω-laurolactam, tetramethylenediamine, hexa Methylenediamine, ethylenediamine, trimethylenediamine, pentamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, nonamethylenediamine, 5-methylnonamethylenediamine and other aliphatic diamines, metaxylylenediamine, Aromatic diamines such as paraxylylenediamine, alicyclic diamines such as aminomethylcyclohexane, bis (4-aminocyclohexyl) propane, aminoethylpiperazine, adipic acid, suberic acid, aze Aliphatic dicarboxylic acids such as linear acid, sebacic acid, dodecanedioic acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid And aromatic dicarboxylic acids such as 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and 2,6-naphthalenedicarboxylic acid. Two or more of these may be used.

  Specific examples of the polyamide (D) in the present invention include polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polyhexamethylene terephthalamide (polyamide 6T), polytetramethylene adipamide (polyamide). 4, 6), polyundecanamide (polyamide 11), polynonamethylene terephthalamide (polyamide 9T) and the like. Polyamide 6 is preferred from the viewpoint of achieving both flowability during molding and heat resistance of the molded product at a higher level.

  In the present invention, the polyamide (D) has a viscosity number of 90 ml / g to 140 ml / g in a sulfuric acid solution prepared at a concentration of 0.005 g / ml using an Ubbelohde viscometer in an atmosphere at 25.0 ° C. It is preferable to be in the range of g. If the viscosity number is 90 ml / g or more, the toughness of the molded product can be further improved. 100 ml / g or more is more preferable. On the other hand, if the viscosity number is 140 ml / g or less, the fluidity of the resin composition can be further improved, and a molded product having a complicated shape can be easily formed. 120 ml / g or less is more preferable.

The viscosity number is given by (Equation 1) below.
Viscosity (ml / g) = (t / t ₀ −1) × 1 / 0.005 (Formula 1)
t: Flow time of sulfuric acid solution, t ₀ : Flow time of sulfuric acid.

<(E) Brominated polystyrene>
The brominated polystyrene in the present invention refers to one in which at least a part of hydrogen atoms of polystyrene is substituted with bromine. Examples thereof include those obtained by introducing a bromine group into the benzene ring of polystyrene and those obtained by polymerizing a brominated styrene monomer. By containing such brominated polystyrene, the radical species generated during combustion of the molded product reacts with bromine groups, so that the flame retardancy of the molded product can be improved.

  (E) The bromine content in brominated polystyrene is preferably 55 to 75% by weight. If the bromine content is 55% by weight or more, the flame retardancy can be improved with a smaller content, and the toughness and heat resistance of the molded product can be maintained at a higher level. On the other hand, if the bromine content is 75% by weight or less, the thermal stability of brominated polystyrene is excellent, and thermal decomposition during melt processing such as extrusion and molding, and gas generation resulting therefrom can be suppressed. (E) The bromine content of brominated polystyrene can be measured by an analyzer such as a fluorescent X-ray analyzer.

  In the present invention, it is important that the number average molecular weight (Mn) of (E) brominated polystyrene is in the range of 1000 to 4500. When the number average molecular weight is less than 1000, the heat resistance of the molded product is lowered. Further, since the thermal stability of brominated polystyrene is reduced, thermal decomposition is likely to occur during melt processing such as extrusion and molding, which causes gas generation leading to poor appearance of the molded product. 2000 or more is preferable. On the other hand, when the number average molecular weight is larger than 4500, the toughness of the molded product is lowered. 4000 or less is preferable. In addition, when the content of the above-mentioned (A) graft copolymer in the resin composition increases, flame retardancy tends to decrease, but by combining with (E) brominated polystyrene in which Mn is in the above range. Thus, a resin composition having an excellent balance between toughness and flame retardancy of a molded product can be obtained. The number average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

  (E) As a manufacturing method of brominated polystyrene, after polymerizing a styrene monomer and manufacturing polystyrene, the method of brominating the benzene ring of polystyrene, brominated styrene monomer (monobromostyrene, And a method of polymerizing such as dibromostyrene and tribromostyrene.

<(F) Flame retardant aid>
The resin composition of the present invention contains (F) a flame retardant aid together with the specific (E) brominated polystyrene, so that (E) the brominated polystyrene and (F) the flame retardant when the molded product is burned. Flame retardancy can be improved by the nonflammable gas resulting from the reaction with the auxiliary agent.

  Examples of the flame retardant aid (F) in the present invention include antimony oxides such as antimony trioxide, antimony tetroxide, antimony pentoxide and sodium antimonate, tin oxides such as tin monoxide and tin dioxide, Examples thereof include iron oxides such as ferric iron, zinc oxide, zinc borate, calcium oxide, copper oxide, titanium oxide, and aluminum oxide. Two or more of these may be used. Among these, antimony oxides such as antimony trioxide, antimony tetraoxide, antimony pentoxide, and sodium antimonate, and zinc borate are more preferable, and antimony trioxide is more preferable.

  The average particle size of the flame retardant aid is preferably 0.01 μm or more and 10 μm or less, and the flame retardant effect can be further improved.

<(G) Non-fibrous inorganic filler>
The resin composition of this invention can improve the heat resistance of a molded article by containing (G) non-fibrous inorganic filler. Moreover, the fluidity | liquidity at the time of a shaping | molding process can be improved by containing the (G) non-fibrous inorganic filler compared with the resin composition containing the fibrous inorganic filler.

  (G) Examples of non-fibrous inorganic fillers include, for example, granular inorganic fillers such as talc, kaolin, mica, calcium carbonate, magnesium carbonate, aluminum oxide, glass flakes (flaky glass), glass beads (spherical glass) and Examples thereof include powdery inorganic fillers such as glass balloons (spherical hollow glass). Two or more of these may be used. Among these, talc, kaolin and mica are more preferable, and talc is more preferable.

  The content of the graft copolymer (A) in the resin composition of the present invention is as follows: graft copolymer (A), vinyl copolymer (B), modified vinyl copolymer (C), and polyamide (D). 10 to 25 parts by weight with respect to a total of 100 parts by weight. When the content of the graft copolymer (A) is less than 10 parts by weight, the toughness of the molded product is lowered. 15 parts by weight or more is preferable. On the other hand, if the content of the graft copolymer (A) exceeds 25 parts by weight, the flame retardancy of the molded product and the fluidity during the molding process are lowered. 20 parts by weight or less is preferable.

  The content of the vinyl copolymer (B) in the resin composition of the present invention is such that the graft copolymer (A), the vinyl copolymer (B), the modified vinyl copolymer (C) and the polyamide (D ) To 5 to 20 parts by weight per 100 parts by weight in total. When the content of the vinyl copolymer (B) is less than 5 parts by weight, the fluidity at the time of molding processing is lowered. On the other hand, if the content of the vinyl copolymer (B) exceeds 20 parts by weight, the toughness of the molded product may be lowered.

  The content of the modified vinyl copolymer (C) in the resin composition of the present invention is such that the graft copolymer (A), the vinyl copolymer (B), the modified vinyl copolymer (C) and the polyamide ( It is 1-10 weight part with respect to the total 100 weight part of D). When the content of the modified vinyl copolymer (C) is less than 1 part by weight, the compatibility and reactivity with the polyamide (D) are poor, and the toughness of the molded product is lowered. Moreover, there exists a possibility that the external appearance of a molded article may fall. 2 parts by weight or more is preferable, and 4 parts by weight or more is more preferable. On the other hand, when the content of the modified vinyl copolymer (C) exceeds 10 parts by weight, the heat resistance of the molded product is lowered. In addition, gelation may occur during melt mixing, which may reduce the surging of the extruder and the appearance of the molded product. 8 parts by weight or less is preferable.

  The content of polyamide (D) in the resin composition of the present invention is 100 in total of graft copolymer (A), vinyl copolymer (B), modified vinyl copolymer (C) and polyamide (D). It is 65 to 80 parts by weight with respect to parts by weight. There exists a possibility that a flame retardance may fall that content of polyamide (D) is less than 65 weight part. 68 parts by weight or more is preferable. On the other hand, when the content of the polyamide (D) exceeds 80 parts by weight, the fluidity may be lowered. Moreover, strand breakage at the time of extrusion tends to occur, and productivity is lowered. 75 parts by weight or less is preferable, and 73 parts by weight or less is more preferable.

  The content of brominated polystyrene (E) in the resin composition of the present invention is such that the graft copolymer (A), the vinyl copolymer (B), the modified vinyl copolymer (C) and the polyamide (D). It is 28-38 weight part with respect to a total of 100 weight part. If content of brominated polystyrene (E) is less than 28 weight part, the flame retardance of a resin composition will fall. On the other hand, if the content of brominated polystyrene (E) exceeds 38 parts by weight, the toughness of the molded product may be lowered. 33 parts by weight or less is preferable.

  The content of the flame retardant aid (F) in the resin composition of the present invention is as follows: graft copolymer (A), vinyl copolymer (B), modified vinyl copolymer (C), and polyamide (D). Is 8 to 13 parts by weight with respect to a total of 100 parts by weight. If content of a flame retardant adjuvant (F) is less than 8 weight part, the flame retardance of a resin composition will fall. 9 parts by weight or more is preferable. On the other hand, if the content of the flame retardant aid (F) exceeds 13 parts by weight, the toughness of the molded product may be lowered. 11 parts by weight or less is preferable.

  The content of the non-fibrous inorganic filler (G) in the resin composition of the present invention is such that the graft copolymer (A), the vinyl copolymer (B), the modified vinyl copolymer (C) and the polyamide ( It is 10 to 20 parts by weight based on 100 parts by weight of D). If content of a non-fibrous inorganic filler (G) is less than 10 weight part, the heat resistance of a molded article will fall. 13 parts by weight or more is preferable. On the other hand, if the content of the non-fibrous inorganic filler (G) exceeds 20 parts by weight, the toughness and flame retardancy of the molded product may be reduced.

  If necessary, the resin composition of the present invention may further comprise a hindered phenol-based antioxidant, a sulfur-containing compound-based antioxidant, a heat-resistant agent such as copper iodide or potassium iodide, or a phosphorus-containing organic compound-based antioxidant. Agents, phenolic and acrylate thermal antioxidants, benzotriazole, benzophenone, succinate UV absorbers, silver antibacterial agents, antifungal agents, carbon black, titanium oxide, Release agents, lubricants, pigments and dyes can also be contained.

  The resin composition of this invention can be obtained by melt-kneading each component to comprise, for example. The melt kneading method is not particularly limited, and for example, a melt kneading method using a single screw or biaxial screw in a heating device or a cylinder having a vent can be employed. The heating temperature at the time of melt kneading is usually selected from the range of 210 to 320 ° C. It is also possible to freely set a temperature gradient or the like at the time of melt-kneading as long as the object of the present invention is not impaired. Further, when a biaxial screw is used, it may be the same rotational direction or a different rotational direction.

  A molded product can be obtained by molding the resin composition of the present invention. As a molding method, injection molding is preferable. The injection molding temperature is generally 220 to 300 ° C. More preferably, it is 240-280 degreeC, Most preferably, it is 240-270 degreeC. The mold temperature during injection molding is generally 30 to 80 ° C. 40-70 degreeC is preferable, Especially preferably, it is 50-70 degreeC.

  The resin composition of the present invention is excellent in fluidity at the time of molding, and can obtain a molded product excellent in flame retardancy, heat resistance and toughness. Therefore, electrical / electronic parts, automobile parts, mechanical mechanism parts, OA It can be used in various applications such as housings for appliances, home appliances, and parts thereof. For example, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards , Tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts TV parts such as VTR parts, TV frames, pedestals, back cavities, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio laser discs (registered trademark), compact discs Audio equipment parts such as lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, household electrical appliance parts, office computer related parts, telephone related parts, facsimile related parts, copying machine related parts , Cleaning jigs, oilless bearings, stern bearings, underwater bearings and other bearings, motor-related parts such as motor parts, lighters and typewriters, optical equipment such as microscopes, binoculars, cameras and watches , Precision machinery-related parts, alternator terminals, alternator connectors, IC regulators, various valves such as exhaust gas valves, fuel-related / exhaust / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, key Bretter main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, thermostat base for air conditioner, heating hot air flow control valve, Brush holder for radiator motor, water pump impeller, wiper motor related parts, dust distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, fuse connector, Horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp riff It is extremely useful for the application of automobile parts represented by a reflector, a lamp housing, a brake piston, a solenoid bobbin, an engine oil filter, an ignition device case, and the like.

  In order to describe the present invention more specifically, examples are given below, but these examples do not limit the present invention in any way. Unless otherwise specified, “%” represents wt%, and “part” represents part by weight.

  First, an evaluation method in each example and comparative example is described below.

(1) Weight average particle diameter of rubber polymer (a) The weight average particle diameter of rubber polymer (a) is "Rubber Age Vol. 88 p.484-490 (1960) by E. Schmidt, P. et al. It was determined by the sodium alginate method described in “H. Biddison”. That is, utilizing the fact that the diameter of the polybutadiene particles to be creamed differs depending on the concentration of sodium alginate, the particle size of 50% cumulative weight fraction was determined from the weight proportion of cream and the cumulative weight fraction of sodium alginate concentration.

(2) Graft ratio of graft copolymer (A) 200 ml of acetone was added to a predetermined amount (m; about 1 g) of the graft copolymer and refluxed in a hot water bath at a temperature of 70 ° C. for 3 hours. This solution was added to 8800 r. p. m. After centrifuging at (10000 G) for 40 minutes, the insoluble matter was filtered. This insoluble matter was dried under reduced pressure at a temperature of 60 ° C. for 5 hours, and its weight (n) was measured. The graft ratio was calculated from the following formula. Here, L is the rubber content of the graft copolymer.
Graft rate (%) = {[(n) − ((m) × L)] / [(m) × L]} × 100

(3) Flame retardance Flame retardancy was evaluated according to the following UL94 standard established by the Underwriters Laboratory in the United States. The upper end of the flame retardant evaluation test piece having a thickness of 1.5 mm obtained by each of the examples and the comparative examples is fixed with a clamp so that the test piece is vertical, and a predetermined flame is applied to the lower end for 10 seconds to release the test piece. The combustion time (first time) of was measured. Immediately after confirming extinction, the flame was again applied to the lower end for 10 seconds and released, and the burning time (second time) of the test piece was measured. This measurement was repeated for five test pieces, and a total of 10 data items were obtained, including 5 pieces of first combustion time data and 5 pieces of second combustion time data. The total of 10 data is 50 seconds or less, the maximum value of 10 data is 10 seconds or less, the test piece does not burn up to the clamp, and the flamed melt falls, 12 inches below If no gauze was ignited, it was evaluated as equivalent to V-0. As the evaluation results, those that passed the V-0 standard were determined as “V-0”, and those that did not pass were determined as “NG”.

(4) Deflection temperature under load (heat resistance)
With respect to the load deflection temperature measurement specimen having a thickness of 4.0 mm obtained in each example and comparative example, the deflection temperature under load was measured under the condition of a load of 0.45 MPa in accordance with the provisions of ISO-75 (2004). .

(5) Melt flow rate (fluidity)
After drying the flame-retardant thermoplastic resin composition pellets obtained in each of the examples and comparative examples for 5 hours or more in a vacuum at 80 ° C., in accordance with ISO-1133 (2005), 240 ° C., The melt flow rate was measured at 49N.

(6) Toughness Test specimens for toughness evaluation obtained in each example and comparative example were subjected to a bending property test in accordance with ISO-178 (2004). After the bending property test, the acceptability of toughness was determined according to the following criteria. The measurement was performed at n = 3, and those judged as ◯ passed and those judged as x rejected.
○: No crack occurs in any of the three test pieces when the amount of change in bending deflection of the test piece exceeds 12.0 mm.
X: One or more test pieces crack when the amount of change in bending deflection of the test pieces exceeds 12.0 mm.

(7) Productivity In each Example and Comparative Example, workability when the resin composition was pelletized for 2 hours was evaluated according to the following criteria.
○: Strand breakage does not occur in pelletizing for 2 hours.
Δ: Strand breakage occurs once or more and less than 5 times in 2 hours of pelletizing.
X: Strand breakage occurs 5 times or more in pelletizing for 2 hours.

  Next, the raw materials used in each example and comparative example are described below.

Reference Example 1 [Production of (A) Graft Copolymer]
A reactor purged with nitrogen was charged with 120 parts by weight of pure water, 0.5 parts by weight of glucose, 0.5 parts by weight of sodium pyrophosphate, 0.005 parts by weight of ferrous sulfate and polybutadiene latex (weight average particle size 0.3 μm, Gel content 85%) 45 parts by weight (in terms of solid content) was charged, and the temperature in the reactor was raised to 65 ° C. while stirring. The polymerization was started when the internal temperature reached 65 ° C., and a mixture of 40 parts by weight of styrene, 15 parts by weight of acrylonitrile and 0.3 parts by weight of t-dodecyl mercaptan was continuously added dropwise over 5 hours. At the same time, an aqueous solution consisting of 0.25 parts by weight of cumene hydroperoxide, 2.5 parts by weight of potassium oleate and 25 parts by weight of pure water was continuously dropped over 7 hours to complete the reaction. The obtained latex was coagulated with 0.3% dilute sulfuric acid at a temperature of 90 ° C., neutralized with an aqueous sodium hydroxide solution, and then subjected to washing, dehydration and drying steps to prepare (A) a graft copolymer. The graft ratio of this (A) graft copolymer was 24%.

(Reference Example 2) [(B) Production of vinyl copolymer]
While charging 80 parts by mass of acrylamide, 20 parts by mass of methyl methacrylate, 0.3 parts by mass of potassium persulfate and 1800 parts by mass of ion-exchanged water into the reactor, the gas phase in the reactor was replaced with nitrogen gas and mixed well. Maintained at 70 ° C. The reaction was continued until the monomer was completely added to the polymer to obtain an aqueous solution of acrylamide and methyl methacrylate binary copolymer. The obtained reaction liquid was an aqueous solution having a slightly cloudy viscosity. To this was added 35 parts by mass of sodium hydroxide and ion-exchanged water, and the mixture was kept alkaline as a binary copolymer aqueous solution of 0.6% acrylamide and methyl methacrylate and stirred at 70 ° C. for 2 hours. To obtain a transparent aqueous solution of methyl methacrylate-acrylamide copolymer for suspension polymerization.

  In a 20 L autoclave, 6 parts by mass of an aqueous solution of methyl methacrylate-acrylamide copolymer obtained by the above method was added and stirred at 400 rpm, and the system was replaced with nitrogen gas. Next, a monomer mixture of 24.0 parts by mass of acrylonitrile, 76 parts by mass of styrene, 0.35 parts by mass of azobisisobutyronitrile and 0.35 parts by mass of t-dodecyl mercaptan was added while stirring the reaction system. It was added over a period of time and the copolymerization reaction was started at 70 ° C. Thereafter, the temperature was raised to 100 ° C. over 180 minutes. After reaching 100 ° C., the mixture was kept at 100 ° C. for 30 minutes, and then cooled, separated, washed and dried, to obtain (B) a vinyl copolymer. The intrinsic viscosity of the (B) vinyl copolymer soluble in methyl ethyl ketone measured with a methyl ethyl ketone solvent (temperature 30 ° C.) was 0.42 dl / g.

(Reference Example 3) [Production of Modified Vinyl Copolymer (C)]
A slurry obtained by suspension polymerization of a monomer mixture composed of 70% by weight of styrene, 25% by weight of acrylonitrile and 5% by weight of methacrylic acid was subjected to washing, dehydration and drying steps, and (C) modified vinyl copolymer A coalescence was prepared.

Reference Example 4 [Polyamide (D)]
(D-1) Polyamide 6 “Amilan” (registered trademark) CM1001 (viscosity number: 108 ml / g) manufactured by Toray Industries, Inc. was used.
(D-2) Polyamide 6 “Amilan” (registered trademark) CM1010 (viscosity number: 135 ml / g) manufactured by Toray Industries, Inc. was used.

(Reference Example 5) [(E) Brominated polystyrene]
(E-1) (1) Albemarle Brominated polystyrene “SAYTEX” (registered trademark) HP-3010 (number average molecular weight (Mn) 2600 by GPC, bromine content 68.5% by weight) was used.
(E-2) (2) Albemarle Brominated polystyrene “SAYTEX” (registered trademark) HP-7010G (number average molecular weight (Mn) 11000 by GPC, bromine content 68.5 wt%) was used.

(Reference Example 6) [(F) Flame retardant aid]
Antimony trioxide “PATOX” (registered trademark) M (purity 99% or more, average particle size 0.5 μm) manufactured by Nippon Seiko Co., Ltd. was used.

Reference Example 7 [(G) Non-fibrous inorganic filler]
(G-1) Talc LMP-90 manufactured by Fuji Talc Industry Co., Ltd. was used.
(G-2) Sankyo Seiko Co., Ltd. calcium carbonate A was used.

(Reference Example 8) [Glass fiber]
Glass fiber T-351 manufactured by Nippon Electric Glass Co., Ltd. was used.

(Reference Example 9) [Impact resistance improving material]
An ethylene / butene-1 / maleic anhydride copolymer “Tuffmer” (registered trademark) MH7020 manufactured by Mitsui Chemicals, Inc. was used.

  Hereinafter, examples and comparative examples will be described.

(Examples 1-9, Comparative Examples 1-12)
(A) Graft copolymer, (B) vinyl copolymer, (C) modified vinyl copolymer, (D) polyamide, (E) brominated polystyrene, (F) flame retardant aid described in Reference Examples Agent, (G) non-fibrous inorganic filler, glass fiber, impact resistance improver, blended in parts by weight shown in Table 1 and Table 2, and screw-screw 30 mm in the same direction rotating twin screw extruder (PCM30 manufactured by Ikegai Co., Ltd.) was used for melt kneading under conditions of a cylinder set temperature of 250 ° C., a screw rotation speed of 250 rpm, and a discharge rate of 10 kg / hour to obtain resin composition pellets.

  After drying the pellet of the obtained resin composition in an 80 degreeC vacuum for 5 hours or more, using Sumitomo Heavy Industries, Ltd. electric injection molding machine SE50-DU, cylinder temperature 250 degreeC and mold temperature 60 degreeC Under the conditions described above, a test piece (full length 150 mm, test portion width 10 mm, thickness 4 mm) defined in ISO 527 (1993) was injection molded. The molded product was processed to prepare a test piece for evaluating the deflection temperature under load and toughness. Similarly, after preliminary drying, a length of 125 mm, a width of 12.5 mm, and a thickness were measured under the conditions of a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine PS60E-12A manufactured by Nissei Plastic Industry Co., Ltd. A test piece for flame retardancy evaluation of 1.5 mm was injection molded. The result of having evaluated each physical property using each test piece was shown to Tables 1-2.

  From the evaluation results of Table 1, the flame-retardant thermoplastic resin compositions (Examples 1 to 9) of the present invention are all excellent in balance of flame retardancy, heat resistance, fluidity and toughness during molding. I understand that.

  On the other hand, in Comparative Example 1, the content of (A) graft copolymer was small, and the toughness was inferior to Example 1. Conversely, in Comparative Example 2, the content of the (A) graft copolymer is large and the flame retardancy is poor. In Comparative Example 3, the content of (D) polyamide is small, and the flame retardancy is inferior to Example 1. On the contrary, in Comparative Example 4, the content of (D) polyamide was large, and the fluidity was remarkably inferior compared with Example 1. In Comparative Example 5, the content of (E) brominated polystyrene was small, and the flame retardancy was inferior to that of Example 1. On the contrary, in Comparative Example 6, the content of (E) brominated polystyrene was large, and the toughness was inferior to that of Example 1. In Comparative Example 7, the toughness was inferior to that of Example 1 due to the use of (E) brominated polystyrene having a large molecular weight. In Comparative Example 8, the content of (G) non-fibrous inorganic filler was small, and the heat resistance was significantly inferior to that of Example 1. In Comparative Example 9, since the content of (G) non-fibrous inorganic filler was large, the flame retardancy and toughness were inferior to those of Example 1. In Comparative Example 10, glass fibers were blended in place of the non-fibrous inorganic filler, and the fluidity and toughness were inferior to those of Example 1, and the extrudability was slightly inferior. In Comparative Example 11, (A) the graft copolymer was not contained, and the glass fiber was contained in a large amount. Since strand breakage occurred frequently during extrusion, the subsequent evaluation could not be performed. Comparative Example 12 contained (E) ammonium polyphosphate and melamine sulfate instead of brominated polystyrene, and was inferior in flame retardancy, heat resistance and toughness as compared to Example 1.

Claims (4)

(A) Rubber polymer (a) In the presence of 40 to 80% by weight, aromatic vinyl monomer (a) 15 to 45% by weight and vinyl cyanide monomer (c) 5 to 20% by weight %, A graft copolymer obtained by graft copolymerization of a monomer mixture containing
(B) a vinyl copolymer obtained by copolymerizing a vinyl monomer mixture containing an aromatic vinyl monomer (ii) and a vinyl cyanide monomer (c);
(C) Unsaturated carboxylic acid and / or α, β-unsaturated carboxylic acid anhydride (d) 0.1 to 10% by weight, aromatic vinyl monomer (a) 50 to 85% by weight and vinyl cyanide A modified vinyl copolymer obtained by copolymerizing 10 to 40% by weight of a monomer (c),
(D) polyamide,
(E) brominated polystyrene having a number average molecular weight of 1,000 to 4,500,
(F) An antimony trioxide and (G) a flame-retardant thermoplastic resin composition containing a non-fibrous inorganic filler, wherein (A) to (D) in total 100 parts by weight, 10 to 25 parts by weight of A), 5 to 20 parts by weight of (B), 1 to 10 parts by weight of (C), 65 to 80 parts by weight of (D), 28 to 38 parts by weight of (E), A flame retardant thermoplastic resin composition containing 8 to 13 parts by weight of F) and 10 to 20 parts by weight of (G). The flame-retardant thermoplastic resin composition according to claim 1, wherein the (G) non-fibrous inorganic filler contains talc. The flame-retardant thermoplastic resin composition according to claim 1, wherein the polyamide (D) includes polyamide 6. The molded article formed by shape | molding the flame-retardant thermoplastic resin composition in any one of Claims 1-3.