JP5538198B2 - Flame retardant thermoplastic polyester resin composition - Google Patents

Description

  The present invention relates to a flame retardant thermoplastic polyester resin composition. In particular, the present invention relates to a thermoplastic polyester resin composition that does not contain a halogen-based flame retardant, and relates to a flame-retardant thermoplastic polyester resin composition that has excellent weldability in addition to flame retardancy.

  Thermoplastic polyester resins such as polybutylene terephthalate resins are widely used in electrical and electronic equipment, automobile parts and the like because of their excellent characteristics. When using a polyester resin for these uses, it is generally used as a flame retardant thermoplastic polyester resin composition containing a flame retardant.

  Conventionally, halogen-based flame retardants have been mainly used as flame retardants to be blended with thermoplastic polyester resins (for example, Patent Documents 1 and 2). However, since halogen-based flame retardants have various problems, it is required to use an alternative flame retardant. In addition, with the recent miniaturization and higher functionality of electronic and electrical equipment, the demand for flame retardance has become increasingly sophisticated, and it has become difficult to satisfy this requirement. Furthermore, demands such as strength and weldability are increasing.

JP 2006-117722 A JP 2010-174223 A

  The present invention has been made to solve the above-mentioned problems, and a flame-retardant thermoplastic polyester resin composition having excellent weldability in addition to flame retardancy without using a halogen-based flame retardant. The purpose is to provide.

  Based on the above-mentioned problems, the inventors of the present application have conducted a study. As a result, in the thermoplastic polyester resin composition that does not substantially use a halogen-based flame retardant, a graft polymer that does not contain a styrene-derived component in the rubbery polymer is obtained. By adding, it has been found that flame retardancy is improved and weldability is also improved, and the present invention has been completed. In general, it is known that when an elastomer component is added, the flame retardancy is lowered, but in the present invention, high flame retardancy is achieved by adopting an elastomer component having a specific composition. It is a thing. Specifically, the object of the present invention has been achieved by the following means.

（式中、Ｒ¹およびＲ²は、ぞれぞれ、直鎖または分岐鎖の炭素数１〜６のアルキル基、または、フェニル基を表し、Ｒ³は、直鎖または分岐鎖の炭素数１〜１０のアルキレン基、炭素数６〜１０のアリーレン基、炭素数７〜１０のアルキルアリーレン基、または、炭素数７〜１０のアリールアルキレン基を表し、Ｍは、カルシウムイオン、アルミニウムイオン、亜鉛イオンまたはマグネシウムイオンを表し、ｍは２または３であり、ｎは１または３であり、そしてＸは１または２である。）
（２）前記（Ｄ）グラフト重合体が、少なくともブタジエンを重合してなるゴム質重合体に、少なくともメチルメタクリレートをグラフト重合させたグラフト重合体である、（１）に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（３）前記（Ｄ）グラフト重合体が実質的にスチレン由来の成分を含まない、（１）または（２）に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（４）前記ゴム質重合体が実質的にブタジエンのみを重合してなるゴム質重合体である、（１）〜（３）のいずれか１項に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（５）（Ａ）熱可塑性ポリエステル樹脂が、ポリブチレンテレフタレート樹脂を含む、（１）〜（４）のいずれか１項に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（６）前記（Ｄ）グラフト重合体を、（Ａ）熱可塑性ポリエステル樹脂１００重量部に対し、０．５〜１０重量部の割合で含む、（１）〜（５）のいずれか１項に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（７）さらに、（Ｃ）難燃助剤として、（Ｃ−１）アミノ基含有化合物、（Ｃ−２）ケイ素含有化合物および（Ｃ−３）ホウ素含有化合物の少なくとも１種を、（Ａ）熱可塑性ポリエステル樹脂１００重量部に対し、３５重量部以下の割合で含む、（１）〜（６）のいずれか１項に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（８）さらに、（Ｃ）難燃助剤として、シアヌル酸メラミン、ポリ燐酸メラミン、燐酸メラミン、シリコーンレジン、ホウ酸亜鉛およびコレマナイト鉱物の少なくとも１種を、（Ａ）熱可塑性ポリエステル樹脂１００重量部に対し、３５重量部以下の割合で含む、（１）〜（６）のいずれか１項に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（９）さらに、（Ｅ）強化充填剤を含む、（１）〜（８）のいずれか１項に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（１０）ハロゲン系難燃剤を実質的に含まない、（１）〜（９）のいずれか１項に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（１１）（１）〜（１０）のいずれか１項に記載の難燃性熱可塑性ポリエステル樹脂組成物を成形してなる成形品。 (1) (A) 100 parts by weight of a thermoplastic polyester resin, (B) 5 to 60 parts by weight of a phosphinate represented by the following general formula (1) or (2), and (D) polymerizing at least butadiene And a graft polymer obtained by graft-polymerizing at least methyl methacrylate to a rubbery polymer that does not substantially contain a component derived from styrene, and the content of the component derived from styrene in the graft polymer is 5 A flame-retardant thermoplastic polyester resin composition obtained by blending 0.5 to 30 parts by weight of a graft polymer that is not more than wt%.

(Wherein R ¹ and R ² each represent a linear or branched alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ³ represents a linear or branched carbon number. Represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 10 carbon atoms, or an arylalkylene group having 7 to 10 carbon atoms, and M represents a calcium ion, an aluminum ion, zinc Represents an ion or magnesium ion, m is 2 or 3, n is 1 or 3, and X is 1 or 2.)
(2) The flame retardant thermoplastic according to (1), wherein the graft polymer (D) is a graft polymer obtained by graft polymerizing at least methyl methacrylate to a rubber polymer obtained by polymerizing at least butadiene. Polyester resin composition.
(3) The flame-retardant thermoplastic polyester resin composition according to (1) or (2), wherein the (D) graft polymer does not substantially contain a component derived from styrene.
(4) The flame-retardant thermoplastic polyester resin composition according to any one of (1) to (3), wherein the rubbery polymer is a rubbery polymer obtained by substantially polymerizing only butadiene. .
(5) The flame-retardant thermoplastic polyester resin composition according to any one of (1) to (4), wherein the (A) thermoplastic polyester resin contains a polybutylene terephthalate resin.
(6) In any one of (1) to (5), the (D) graft polymer is included at a ratio of 0.5 to 10 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. The flame-retardant thermoplastic polyester resin composition as described.
(7) Further, as (C) a flame retardant aid, at least one of (C-1) an amino group-containing compound, (C-2) a silicon-containing compound, and (C-3) a boron-containing compound, (A) The flame-retardant thermoplastic polyester resin composition according to any one of (1) to (6), which is contained at a ratio of 35 parts by weight or less with respect to 100 parts by weight of the thermoplastic polyester resin.
(8) Further, (C) at least one of melamine cyanurate, melamine polyphosphate, melamine phosphate, silicone resin, zinc borate and colemanite mineral as a flame retardant aid, (A) 100 parts by weight of thermoplastic polyester resin The flame-retardant thermoplastic polyester resin composition according to any one of (1) to (6), which is contained at a ratio of 35 parts by weight or less.
(9) The flame-retardant thermoplastic polyester resin composition according to any one of (1) to (8), further comprising (E) a reinforcing filler.
(10) The flame-retardant thermoplastic polyester resin composition according to any one of (1) to (9), which does not substantially contain a halogen-based flame retardant.
(11) A molded product obtained by molding the flame-retardant thermoplastic polyester resin composition according to any one of (1) to (10).

  According to the present invention, it is possible to provide a thermoplastic polyester resin composition excellent in flame retardancy and weldability. In particular, it has become possible to provide a thermoplastic polyester resin composition containing an elastomer and capable of maintaining high flame retardancy and exhibiting excellent weldability even without containing a halogen-based flame retardant.

FIG. 1 is a diagram for explaining the shape of a polybutylene terephthalate resin integrally molded product sample (test piece B) for measuring the welding strength between the primary molded product (test piece A) and the secondary molding material.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, a “group” such as an alkyl group may or may not have a substituent unless otherwise specified. Further, in the case of a group having a limited number of carbons, the number of carbons means a number including the number of carbons that the substituent has.

  The flame-retardant thermoplastic polyester resin composition of the present invention comprises (B) phosphinic acid salt 5-60 represented by the above general formula (1) or (2) with respect to 100 parts by weight of (A) thermoplastic polyester resin. And (D) a graft polymer obtained by polymerizing at least methyl methacrylate to a rubbery polymer obtained by polymerizing at least butadiene and substantially free of components derived from styrene. A graft polymer in which the content of the component derived from styrene in the coalescence is 5% by weight or less is blended in an amount of 0.5 to 30 parts by weight, at least. Details of these will be described below.

(A) Thermoplastic polyester resin The thermoplastic polyester resin which is the main component of the resin composition (A) of the present invention is a polycondensation of a dicarboxylic acid compound and a dihydroxy compound, a polycondensation of an oxycarboxylic acid compound, or these compounds. It is a polyester obtained by polycondensation of the above mixture, and may be either a homopolyester or a copolyester. Examples of the dicarboxylic acid compound constituting the thermoplastic polyester resin include alicyclic acids such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid, diphenylether dicarboxylic acid, diphenylethanedicarboxylic acid, and cyclohexanedicarboxylic acid. Aliphatic dicarboxylic acids such as dicarboxylic acid, adipic acid and sebacic acid can be mentioned.

  As is well known, these can be used in polycondensation reactions as ester-forming derivatives such as dimethyl esters in addition to free acids. Examples of the oxycarboxylic acid include paraoxybenzoic acid, oxynaphthoic acid, and diphenyleneoxycarboxylic acid. These can be polycondensed alone, but are often used in a small amount together with a dicarboxylic acid compound.

  As the dihydroxy compound, aliphatic diols such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, and polyoxyalkylene glycol are mainly used. Hydroquinone, resorcin, naphthalenediol, dihydroxydiphenyl ether, 2,2-bis (4 Aromatic diols such as -hydroxyphenyl) propane and cycloaliphatic diols such as cyclohexanediol can also be used.

  In addition to these bifunctional compounds, trifunctional or higher polyfunctional compounds such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane are introduced to introduce a branched structure. A small amount of a monofunctional compound such as a fatty acid can also be used.

  In the present invention, the thermoplastic polyester resin is usually a polycondensate composed mainly of a dicarboxylic acid compound and a dihydroxy compound, that is, a structural unit which is an ester of a dicarboxylic acid compound and a dihydroxy compound in calculation, Those which occupy 70% by weight or more, more preferably 90% by weight or more are used. The dicarboxylic acid compound is preferably an aromatic dicarboxylic acid, and the dihydroxy compound is preferably an aliphatic diol.

  Among them, a polyalkylene terephthalate resin in which 95 mol% or more of the acidic component is terephthalic acid and 95 mol% or more of the alcohol component is an aliphatic diol is preferable. Typical examples thereof are a polybutylene terephthalate resin and a polyethylene terephthalate resin. In the present invention, it is preferable that at least the polybutylene terephthalate resin is included.

  The intrinsic viscosity of the thermoplastic polyester resin may be appropriately selected and determined. However, it is usually preferably 0.5 to 2 dl / g, and in particular, from the viewpoint of moldability and mechanical properties of the resin composition, 0.6 to It is preferably 1.5 dl / g. If a material having an intrinsic viscosity of less than 0.5 dl / g is used, the mechanical strength of the molded product obtained from the resin composition tends to be low, and conversely if it is greater than 2 dl / g, the fluidity of the resin composition decreases. However, moldability may be reduced.

  In the present specification, the intrinsic viscosity of the polyester resin is a value measured at 30 ° C. in a 1: 1 (weight ratio) mixed solvent of tetrachloroethane and phenol.

（式中、Ｒ¹およびＲ²は、ぞれぞれ、直鎖または分岐鎖の炭素数１〜６のアルキル基、または、フェニル基を表し、Ｒ³は、直鎖または分岐鎖の炭素数１〜１０のアルキレン基、炭素数６〜１０のアリーレン基、炭素数７〜１０のアルキルアリーレン基、または、炭素数７〜１０のアリールアルキレン基を表し、Ｍは、カルシウムイオン、アルミニウムイオン、亜鉛イオンまたはマグネシウムイオンを表し、ｍは２または３であり、ｎは１または３であり、そしてＸは１または２である。） (B) Phosphinate represented by general formula (1) or (2)

(Wherein R ¹ and R ² each represent a linear or branched alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ³ represents a linear or branched carbon number. Represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 10 carbon atoms, or an arylalkylene group having 7 to 10 carbon atoms, and M represents a calcium ion, an aluminum ion, zinc Represents an ion or magnesium ion, m is 2 or 3, n is 1 or 3, and X is 1 or 2.)

In the above formulas (1) and (2), R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, a butyl group, or a pentyl group, or a phenyl group. Is preferred. The phenyl group may have a substituent. A methyl group is mentioned as a substituent. R ¹ and R ² are more preferably a methyl group or an ethyl group.

R ³ is preferably an alkylene group having 1 to 10 carbon atoms such as a methylene group, ethylene group, propylene group, butylene group or 2-ethylhexylene group, or a phenylene group, and is an alkylene group or phenylene group having 1 to 4 carbon atoms. It is preferable.

  Specific examples of phosphinates include calcium dimethylphosphinate, aluminum dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, calcium methyl-n-propylphosphinate, Aluminum methyl-n-propylphosphinate, calcium methylphenylphosphinate, aluminum methylphenylphosphinate, calcium diphenylphosphinate, aluminum diphenylphosphinate, calcium methanebis (dimethylphosphinate), aluminum methanebis (dimethylphosphinate), benzene-1 , 4-bis (dimethylphosphinic acid) calcium, benzene-1,4-bis (dimethylphosphine) Etc. phosphate) aluminum. Of these, aluminum diethylphosphinate is preferable from the viewpoint of flame retardancy and electrical characteristics.

  Furthermore, in the present invention, from the viewpoint of the appearance and mechanical strength of the resin molded product obtained from the resin composition of the present invention, the phosphinic acid salt has a particle diameter of 100 μm or less as measured by a laser diffraction method, particularly an average particle. It is preferable to use one having a diameter of 50 μm or less. The lower limit of the average particle size is not particularly limited, but usually it is not necessary to reduce the particle size by pulverization or the like until it falls below 0.5 μm, and the normal lower limit is sufficient if the average particle size is 1 μm by pulverization or the like. . Such a fine powder is particularly preferable because it not only exhibits high flame retardancy but also significantly increases the strength of the molded product.

  (A) The compounding quantity of (B) phosphinic acid salt with respect to 100 weight part of thermoplastic resin components is 5-60 weight part. If the blending amount is less than 5 parts by weight, the desired flame retardancy is not exhibited in the resin composition. On the contrary, if the amount exceeds 60 parts by weight, the moldability of the resin composition deteriorates and the mechanical strength also decreases. Among them, the preferred blending amount of the phosphinate is 5 to 50 parts by weight, particularly 5 to 40 parts by weight with respect to 100 parts by weight of the (A) thermoplastic resin component.

(C) Flame retardant aid The resin composition of the present invention may contain a flame retardant aid. Here, the flame retardant aid is intended to exclude (D) graft polymer described later.
Examples of flame retardant aids include (C-1) amino group-containing compounds, (C-2) silicon-containing compounds, and (C-3) boron-containing compounds. Among them, melamine cyanurate, melamine polyphosphate, melamine phosphate, Silicone resins, zinc borate and colemanite minerals are preferred.

(C-1) Amino Group-Containing Compound As the (C-1) amino group-containing compound used as the flame retardant aid (C) in the present invention, a salt of an amino group-containing triazine is particularly preferable. As amino group-containing triazines (triazines having an amino group), amino group-containing 1,3,5-triazines are usually used. Specifically, for example, melamine, substituted melamine (2-methylmelamine, guanylmelamine etc.), melamine condensate (melam, melem, melon etc.), melamine co-condensation resin (melamine-formaldehyde resin etc.), cyanuric amides (Ammelin, Ammelide, etc.), guanamine or derivatives thereof (Guanamine, methylguanamine, acetoguanamine, benzoguanamine, succinoguanamine, adipoguanamine, phthaloguanamine, CTU-guanamine, etc.).

  Examples of the salts of these triazines include salts of the triazines with inorganic acids and organic acids. Specific examples of inorganic acids include nitric acid, chloric acid (chloric acid, hypochlorous acid, etc.), phosphoric acid (phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, etc.), sulfuric acid (sulfuric acid and sulfurous acid). Non-condensed sulfuric acid, condensed sulfuric acid such as peroxodisulfuric acid and pyrosulfuric acid), boric acid, chromic acid, antimonic acid, molybdic acid, tungstic acid and the like. Among these, phosphoric acid, polyphosphoric acid, and sulfuric acid are preferable as the acid. Specific examples of these compounds include melamine polyphosphate (melaure 200/70, 200 manufactured by BASF).

On the other hand, organic acids include organic sulfonic acids (aliphatic sulfonic acids such as methanesulfonic acid, aromatic sulfonic acids such as toluenesulfonic acid and benzenesulfonic acid), and cyclic ureas (uric acid, barbituric acid, cyanuric acid, acetylene). Urea, etc.). C _1-4 alkanesulfonic acids such as methanesulfonic acid Of these, C _1-3 alkyl C _6-12 arene sulfonic acids such as toluene sulfonic acid, cyanuric acid are preferred.

  Examples of salts of amino group-containing triazines include, for example, melamine cyanurate, melam, melem double salt, melamine phosphate (melamine polyphosphate, melamine polyphosphate, melam, melem double salt, etc.), melamine sulfate (melamine sulfate, Dimelamine sulfate, dimram pyrosulfate), melamine sulfonates (melamine methanesulfonate, melam methanesulfonate, melem methanesulfonate, melamine methanesulfonate, melam, melem double salt, melamine toluene sulfonate, melam toluene sulfonate, And melamine toluenesulfonate, melam, melem double salt, etc.). These may be used alone or in combination of two or more at any ratio.

  As the (C-1) amino group-containing compound used in the present invention, an adduct of cyanuric acid or isocyanuric acid and a triazine-based compound is preferable, and usually an acid part and a base part are 1: 1 (molar ratio). In some cases, an adduct having a composition of 1: 2 (molar ratio) is preferred. Specific examples include melamine cyanurate, benzoguanamine cyanurate, acetoguanamine cyanurate, and melamine cyanurate is particularly preferable. Specific examples of these compounds include melamine cyanurate (MX44 manufactured by Nippon Synthetic Chemical Co., Ltd., MC-4000 manufactured by Nissan Chemical Co., Ltd.) and the like.

  The production method of these adducts of cyanuric acid or isocyanuric acid and triazine compounds (hereinafter sometimes simply referred to as adducts) is arbitrary, and any conventionally known one can be used. Specifically, for example, a mixture of a triazine compound and cyanuric acid or isocyanuric acid is made into an aqueous slurry and mixed well to form both salts in the form of fine particles, and then the slurry is filtered and dried. can get. The adduct need not be completely pure, and some unreacted triazine-based compound, or cyanuric acid or isocyanuric acid may remain.

  Further, the average particle size of the adduct is preferably 0.01 to 100 μm from the viewpoint of flame retardancy, mechanical strength, heat and humidity resistance, residence stability, and surface properties of the resin molded product, and more preferably 1 to 100 μm. It is preferable that it is 80 micrometers. In addition, when the dispersibility of the adduct is low, a dispersant such as tris (β-hydroxyethyl) isocyanurate or a known surface treatment agent may be used in combination.

  The amount of the (C-1) amino group-containing compound used in the present invention is 0 to 30 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin, among which 5 to 30 parts by weight, and more preferably 10 to 25 parts. Part by weight, particularly 15 to 25 parts by weight is preferred. If this amount is too large, the mechanical properties tend to be lowered.

(C-2) Silicon-containing compound As the silicon-containing compound used as the flame retardant aid (C) in the present invention, an organosiloxane polymer is particularly preferable. Here, the organosiloxane polymer is in a solid state at 25 ° C., and is a copolymer of an organosiloxane compound or an organosiloxane compound and a compound having this reactivity, specifically, for example, a copolymer of a vinyl compound, a carbonate compound and the like. It is a coalescence. In addition, being in a solid state at 25 ° C. means that it does not flow at 25 ° C. and can be handled as a solid.

  Specific examples of the organosiloxane polymer (C-2) used in the invention include the following (C-2-1) to (C-2-4).

(C-2-1) Organosiloxane polymer supported on inorganic fine particles In the present invention, an organosiloxane polymer is supported on inorganic fine particles (hereinafter sometimes referred to simply as a supported polymer). As the inorganic fine particles, any conventionally known fine particles can be appropriately selected, determined and used. Specific examples include silica powder, titanium oxide powder, mica powder, clay powder, kaolin powder, magnesium hydroxide powder, and aluminum hydroxide powder. Of these, silica powder is preferred. Examples of the silica powder include a dry process silica obtained by a vapor phase method and a wet process silica obtained by a wet process, and any of them can be used.

The particle size of the inorganic fine particles is arbitrary, and may be appropriately selected and determined. Usually, 90% by weight or more is preferably 0.01 to 100 μm, more preferably 0.1 to 30 μm, as measured by a laser diffraction method. Among these, those having a specific surface area of 50 m ² / g or more are preferable, and those having a specific surface area of 100 m ² / g or more are particularly preferable. The inorganic fine particles are preferably treated with a surface treatment agent such as a silane coupling agent because the bond with the organosiloxane polymer can be further strengthened. When the organosiloxane polymer has a functional group such as an epoxy group or a methacryl group, the bond is further strengthened, which is preferable.

  The organosiloxane polymer used here may be a polymer of an organosiloxane compound or a polymer chain having a carbon chain as a copolymerization component. As a copolymerization component, a C1-C20 chain | strand-like saturated or unsaturated hydrocarbon group, a halogenated hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group etc. are mentioned, for example.

  Furthermore, the organosiloxane polymer may have a functional group. As the functional group, a methacryl group or an epoxy group is preferable, and the polymer having these functional groups has good dispersibility because of good compatibility with the thermoplastic polyester resin, and has a high effect of improving toughness. Furthermore, since a crosslinking reaction with the polyester resin can be caused at the time of combustion, a reduction in flame retardancy is suppressed. The organosiloxane polymer may be linear or branched, but is preferably linear. The amount of the functional group in the organosiloxane polymer is usually about 0.01 to 1 mol%, more preferably 0.03 to 0.5 mol%, especially 0.05 to 0.3 mol%. preferable.

  The method for supporting the organosiloxane polymer on the inorganic fine particles is arbitrary, and any conventionally known method can be used. Specifically, for example, there is a method in which an organosiloxane polymer is dissolved in a solvent and impregnated with inorganic fine particles, and then dried. The supported amount is usually 0.1 to 10 g with respect to 1 g of inorganic fine particles, and preferably 0.4 to 4 g.

  In carrying, it is preferable to use an alkoxysilane having a functional group such as an epoxy group as an adhesion promoter because the bond between the inorganic fine particles and the polymer can be further strengthened. The bond between the inorganic fine particles and the polymer may be a simple physical bond such as adsorption or absorption, or may be caused by a chemical reaction. It is considered that the polymer supported on the inorganic fine particles forms a mild cross-linked structure with the thermoplastic polyester resin by synergistic action with the inorganic fine particles, thereby contributing to the improvement of flame retardancy as well as toughness.

  The supported polymer used in the present invention is preferably one in which an organosiloxane polymer is supported on silica. Specifically, for example, commercially available products such as “Si powder” and “Trefill F” manufactured by Toray Dow Corning Co., Ltd. Can be mentioned.

(C-2-2) Organosiloxane polymer having a softening point exceeding 25 ° C. The organosiloxane polymer having a softening point exceeding 25 ° C. used in the present invention is generally referred to as a silicone resin. It is shown by the following formula (3).
(R ^{1 ′} SiO _3/2 ) _a (R ^{2 ′} ₂ SiO _2/2 ) _b (R ^{3 ′} ₃ SiO _1/2 ) _c (SiO _4/2 ) _d (XO _1/2 ) _e (3)

In Formula (3), X is a hydrogen atom or an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a heptyl group. R ^{1 ′} , R ^{2 ′} and R ^{3 ′} may be different from each other, and are a hydrocarbon group or an epoxy group-containing organic group.

  Examples of the hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; an alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group; Aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group; aralkyl groups such as benzyl group, phenethyl group; chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, nonafluorobutyl Examples include halogenated alkyl groups such as an ethyl group.

Examples of the epoxy-containing organic group include 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group and the like; 2-glycidoxyethyl group, 3-glycid Glycidoxyalkyl groups such as xylpropyl group and 4-glycidoxybutyl group; Epoxycyclohexylalkyl groups such as 2- (3,4-epoxycyclohexyl) ethyl group and 3- (3,4-epoxycyclohexyl) propyl group Is mentioned. The epoxy group-containing organic group is not essential, but the ratio of the epoxy group-containing organic group in the total of R ^{1 ′ to} R ^{3 ′} in formula (3) is preferably 0.1 to 40 mol%.

  If the content is less than 0.1 mol%, bleeding tends to occur during molding of a resin composition obtained by blending the content. Moreover, when it exceeds 40 mol%, there exists a tendency for the mechanical characteristics of a molding to fall.

Also, since when there is a phenyl group excellent in affinity for the thermoplastic polyester resin is preferably R ^{1 'to} R ^3' total of 10 mol% or more of the is a phenyl group in the formula (3), among others R ^{1 'of} 10 mol% or more, preferably particularly more than 30 mol% are phenyl groups.

Furthermore, in order to reduce the steric hindrance of organopolysiloxane molecules containing bulky phenyl groups and improve the spatial freedom, to facilitate the overlapping of the phenyl groups and enhance the flame retardancy, the formula (2) ^'the so preferably has a methyl group or a vinyl group, R ^1' R ¹ in the proportion of the phenyl group to total is preferably 10 to 95 mol%, more preferably from 30 to 90 mol%.

  In Expression (3), a is a positive number, and b, c, d, and e are each 0 or a positive number. b / a is a number from 0 to 10, c / a is a number from 0 to 0.5, d / (a + b + c + d) is a number from 0 to 0.3, and e / (a + b + c + d) is from 0 to 0. It is a number of 0.4. A silicone resin having a b / a exceeding 10 has a softening point of 25 ° C. or lower and a low affinity with a resin. Moreover, the silicone resin in which d / (a + b + c + d) exceeds 0.3 tends to reduce the dispersibility of the resin.

  The weight average molecular weight of the organosiloxane polymer having a softening point exceeding 25 ° C. is usually 500 to 50,000, preferably 500 to 10,000. Although the softening point should just exceed 25 degreeC, it is preferable that it is 40-250 degreeC especially 40-150 degreeC. When the softening point is 25 ° C. or lower, bleeding occurs during molding of a resin composition obtained by blending the resin composition to contaminate the mold, lower the mechanical properties of the molded product, or lengthen the molded product. There is a tendency to ooze out on the surface of the molded product during the period of use.

  If the softening point is too high, it tends to be difficult to uniformly disperse the resin composition. The softening point was determined when the organosiloxane polymer was melted and changed into droplets when heated at a heating rate of 1 ° C./min using a melting point measuring machine (micro melting point apparatus manufactured by Yanagimoto Seisakusho Co., Ltd.). Is the softening point.

The silicone resin represented by the above formula (3) is, for example,
(I) a unit represented by the formula: R ⁴ SiO _3/2 (wherein R ⁴ is a monovalent hydrocarbon group),
(Ii) a unit represented by the formula: R ⁵ ₂ SiO _2/2 (wherein R ⁵ are the same or different monovalent hydrocarbon groups);
(Iii) a unit represented by the formula: R ⁶ ₃ SiO _1/2 (wherein R ⁶ are the same or different monovalent hydrocarbon groups), and (iv) a formula: SiO _4/2 One or a mixture of two or more silanes or siloxanes having at least one unit selected from the group consisting of the units shown, and a general formula: R ⁷ R ⁸ _f Si (OR ⁹ ) _(3-f) ( In the formula, R ⁷ is an epoxy group-containing organic group, R ⁸ is a monovalent hydrocarbon group, R ⁹ is an alkyl group, and f is 0, 1, or 2.) It can manufacture by making a containing alkoxysilane or its partial hydrolyzate react with a basic catalyst.

  In the above production method, the main component is one or a mixture of two or more silanes or siloxanes having at least one unit selected from the group consisting of units represented by the above (i) to (iv). These silanes or siloxanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane. Dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, methylphenyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, dimethoxydiethoxysilane, Examples include decomposition condensates.

In addition, an epoxy group-containing alkoxysilane represented by the general formula: R ⁷ R ⁸ _f Si (OR ⁹ ) _(3-f) to be copolymerized with these silanes and siloxanes or a partially hydrolyzed product thereof is added to the silicone resin with an epoxy group. It is a component to introduce. R ⁷ in the formula is an epoxy group-containing organic group, and examples thereof include the same epoxy group-containing organic group as R ^{1 ′} , R ^{2 ′} , or R ^{3 ′} .

R ⁸ in the formula is a monovalent hydrocarbon group, and examples thereof include the same monovalent hydrocarbon groups as R ^{1 ′} , R ^{2 ′} , or R ^{3 ′} . R ⁹ in the formula is an alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. F in the formula is 0, 1, or 2, preferably 0.

  As such an epoxy group-containing alkoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (methyl) dibutoxysilane, 2 -(3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2,3- Epoxypropyl (phenyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, 2- (3,4 Epoxycyclohexyl) ethyl triethoxysilane, 2,3-epoxypropyl trimethoxysilane, and 2,3-epoxypropyl triethoxysilane.

  Examples of the basic catalyst include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkali metal alkoxides such as sodium-tert-butoxide, potassium-tert-butoxide, and cesium-tert-butoxide. An alkali metal silanol compound such as a sodium silanolate compound, a potassium silanolate compound, or a cesium silanolate compound; Preferably, a potassium-based or cesium-based basic catalyst is used. In the reaction, water may be added as necessary.

  During the reaction, cleavage and recombination of siloxane bonds occur randomly by the equilibration reaction, and as a result, the resulting epoxy group-containing silicone resin is in an equilibrium state. The reaction temperature is preferably 80 ° C. to 200 ° C. because the equilibration reaction does not proceed sufficiently when the reaction temperature is low, and the silicon atom-bonded organic group is thermally decomposed when the reaction temperature is too high, In particular, the temperature is preferably 100 ° C to 150 ° C.

  Further, by selecting an organic solvent having a boiling point of 80 to 200 ° C., the equilibration reaction can be easily performed at the reflux temperature. The equilibration reaction can be stopped by neutralizing the basic catalyst. For this neutralization, it is preferable to add a weak acid such as carbon dioxide or carboxylic acid. The salt formed by neutralization can be removed by filtration or washing with water.

(C-2-3) Crosslinked Organosiloxane Polymer The cross-linked organosiloxane polymer used in the present invention is a so-called silicone elastomer, addition reaction curing, condensation reaction curing, radical reaction by organic peroxide. It is synthesized by curing and ultraviolet irradiation curing. Among these, as the silicone elastomer used in the present invention, those obtained by addition reaction curing or condensation reaction curing are preferable. Most preferred is an addition reaction curable silicone elastomer composition.

  The addition reaction curable silicone elastomer composition refers to a composition in which functional groups in two types of organopolysiloxane are bonded and crosslinked by an addition reaction to form an elastomer. Typical examples include silicone elastomer compositions comprising an organopolysiloxane containing an aliphatic unsaturated group such as a vinyl group or a hexenyl group, an organohydrogenpolysiloxane, and a platinum group compound catalyst.

  Aliphatic unsaturated group-containing organopolysiloxanes include vinyl dimethylsiloxy group-blocked dimethylpolysiloxane at both ends, vinyldimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer at both ends, and vinylmethylphenylsiloxy group-blocked dimethylsiloxane at both ends. -A methylphenylsiloxane copolymer is mentioned.

  Examples of the organohydrogenpolysiloxane include trimethylsiloxy group-capped methylhydrogen polysiloxane at both ends, trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydrol at both ends. Examples include a gen siloxane copolymer and methyl hydrogen cyclopolysiloxane.

  Examples of the platinum group compound catalyst include particulate platinum, chloroplatinic acid, platinum and olefin complexes, platinum and vinylsiloxane complexes, platinum and diketone complexes, palladium compound catalysts, and rhodium compound catalysts. Among these, a platinum compound catalyst is preferable from the viewpoint of catalytic activity. This addition reaction curable silicone elastomer composition is usually cured by heating from the viewpoint of curability and productivity. In addition, the addition reaction curable silicone elastomer composition comprises an organopolysiloxane containing an aliphatic unsaturated group such as a vinyl group and an organopolysiloxane containing a mercaptoalkyl group. The composition which hardens | cures is mentioned.

  Condensation reaction curable type silicone elastomer composition is an elastomer by functional groups in two types of organopolysiloxanes, or functional groups in organopolysiloxanes and silicon compounds such as silica and silane, which are linked by a condensation reaction and crosslinked. Refers to the composition. Specific examples of the condensation reaction curable silicone elastomer composition include, for example, dehydrogenation condensation type, dehydration condensation type, acetic acid condensation type, deoxime condensation type, dealcohol condensation type, deamidation condensation type, dehydroxylamine condensation type. Examples of the composition include a mold and a deacetone condensation type.

  Representative examples of the dehydrogenative condensation reaction curable silicone elastomer composition include a composition comprising a condensation reaction catalyst such as a silanol group-blocked diorganopolysiloxane, an organohydrogenpolysiloxane, and a heavy metal salt of an organic acid. As both-end silanol-blocked diorganopolysiloxane, both-end silanol-blocked dimethylpolysiloxane, both-end silanol-blocked dimethylsiloxane / methylphenylsiloxane copolymer, both-end silanol-blocked methyl (3,3,3-trimethyl) Fluoropropyl) polysiloxane and the like. Since this diorganopolysiloxane has an action of suppressing the condensation reaction, a part of the terminal silanol group may be alkoxylated.

  Examples of the organohydrogenpolysiloxane that is a crosslinking agent include a dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, a trimethylsiloxy group-capped methylhydrogenpolysiloxane, a methylhydrogencyclopolysiloxane, etc. Is mentioned. Examples of the condensation reaction catalyst include dibutyltin dilaurate, dibutyltin diacetate, tin octenoate, dibutyltin dioctate, tin laurate, ferric stanooctenoate, lead octenoate, lead laurate, and zinc octenoate.

  The dehydrogenative condensation curable silicone elastomer composition needs to be cured by heating from the viewpoint of curability and productivity, but is dehydrated condensation type, deacetic acid condensation type, deoxime condensation type, dealcohol condensation type, The deamidation-condensation type, dehydroxylamine condensation-type, and deacetone-condensation type silicone elastomer compositions can be cured at room temperature into an elastomer in the presence of moisture. Among moisture-curable silicone elastomer compositions, silicone water-based elastomers that can form elastomers by removing water are particularly useful.

  This silicone water-based elastomer usually has (a) a substantially linear organopolysiloxane having at least two silanol groups in one molecule, (b) colloidal silica, alkali metal silicate, hydrolysis An aqueous organopolysiloxane emulsion composition comprising a cross-linking agent selected from the group consisting of possible silanes and partial hydrolysis condensates thereof, (c) a curing catalyst, (d) an emulsifier and (e) water is used.

  Here, the organopolysiloxane of component (a) is crosslinked by the action of component (b) to form a rubbery elastic body, and is a polymer having at least two silanol groups in one molecule. The position of the silanol group is not particularly limited, but it is preferably present at both ends. As the organic group bonded to the silicon atom other than the silanol group, an unsubstituted or substituted monovalent hydrocarbon group is preferable, an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group; a vinyl group, an aryl group, or the like Examples include alkenyl groups; aryl groups such as phenyl groups; aralkyl groups such as benzyl groups; alkaryl groups such as styryl groups and tolyl groups; cycloalkyl groups such as cyclohexyl groups and cyclopentyl groups.

  In addition, a group in which some or all of the hydrogen atoms in these groups are substituted with halogen atoms such as fluorine, chlorine, bromine, for example, 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc. . Among these, a methyl group, a vinyl group, and a phenyl group are preferable, and a methyl group is more preferable. However, all of them are not necessarily the same and may be a combination of different monovalent hydrocarbon groups. Further, the term “substantially linear” means that a part of the main chain includes a branched chain.

  The molecular weight of the organopolysiloxane is not particularly limited, but is preferably 5000 or more. This is because a reasonable tensile strength and elongation can be obtained when the molecular weight is 3000 or more, but the most preferable tensile strength and elongation can be obtained only when the molecular weight is 5000 or more. However, from the viewpoint of the possibility of emulsification into an emulsion, it is preferably 1000000 or less.

  Specific examples of such organopolysiloxanes include dimethylpolysiloxane, methylphenylpolysiloxane, dimethylsiloxane-methylphenylsiloxane copolymer, methylvinylpolysiloxane, dimethylsiloxane-methyl, both ends of which are blocked with silanols. A vinyl siloxane copolymer is mentioned. Such an organopolysiloxane can be synthesized, for example, by a method of hydrolytic condensation of a cyclic or branched organopolysiloxane or a method of hydrolyzing one or more diorganodihalogenosilanes.

  The crosslinking agent of component (b) acts as a crosslinking component of component (a), and includes colloidal silica, alkali metal silicate, hydrolyzable silane, or a partial hydrolysis condensate thereof. Examples of colloidal silica include fumed colloidal silica, precipitated colloidal silica, or colloidal silica having a particle size of 0.0001 to 0.1 μm stabilized with sodium, ammonia or aluminum ions. The amount of colloidal silica blended is preferably 1 to 150 parts by weight, more preferably 1 to 70 parts by weight, based on 100 parts by weight of the organopolysiloxane of component (a).

  Examples of the alkali metal silicate include lithium silicate, sodium silicate, potassium silicate, and rubidium silicate. The blending amount of the alkali metal silicate is preferably 0.3 to 30 parts by weight, and more preferably 0.3 to 20 parts by weight with respect to 100 parts by weight of the organopolysiloxane of the component (a). As the hydrolyzable silane, a silane having at least three hydrolyzable groups bonded to a silicon atom in one molecule is used. This is because an elastomer cannot be obtained when the number is less than three.

  Examples of the hydrolyzable group include alkoxy groups such as methoxy group, ethoxy group and butoxy group; acyloxy groups such as acetoxy group; substituted or unsubstituted acetamide groups such as acetamide group and N-methylacetamide group; propenoxy An alkenyloxy group such as a group; a substituted amino group such as an N, N-diethylamino group; and a ketoxime group such as a methylethylketoxime group.

  Specific examples include methyltrimethoxysilane, vinyltrimethoxysilane, normal propyl orthosilicate, ethylpolysilicate, propylpolysilicate, methyltri (propanoxy) silane, and methyltri (methylethylketoxime) silane. Two or more kinds of such silanes can be mixed and used. The amount of the hydrolyzable silane or its partially hydrolyzed condensate is preferably 1 to 150 parts by weight with respect to 100 parts by weight of the component (a) organopolysiloxane.

  The component (c) curing catalyst is a component that accelerates the condensation reaction between the component (a) organopolysiloxane and the component (b) crosslinking agent, such as dibutyltin dilaurate, dibutyltin diacetate, and tin octenoate. Organic acid metal salts such as dibutyltin dioctate, tin laurate, ferric stanooctenoate, lead octenoate, lead laurate, zinc octenoate; tetrabutyl titanate, tetrapropyl titanate, dibutoxy titanium bis (ethyl acetoacetate), etc. And titanic acid esters; amine compounds such as n-hexylamine and guanidine or hydrochloric acids thereof.

  These curing catalysts are preferably preliminarily made into an emulsion form by using an emulsifier and water by an ordinary method. The addition amount of the curing catalyst is preferably 0.01 to 1.5 parts by weight, and more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the organopolysiloxane of component (a).

  The emulsifier of component (d) is a component that mainly emulsifies the organopolysiloxane of component (a), and examples thereof include an anionic emulsifier, a nonionic emulsifier, and a cationic emulsifier. Examples of the anionic emulsifier include higher fatty acid salts, higher alcohol sulfates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl phosphinates, and polyethylene glycol sulfates.

Examples of nonionic emulsifiers include polyoxyethylene alkylphenyl ethers,
Examples include sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyethylene polyoxypropylenes, and fatty acid monoglycerides.

Examples of the cationic emulsifier include aliphatic amine salts, quaternary ammonium salts, and alkylpyridinium salts. These emulsifiers may be used alone or in a mixture of two or more. The amount of the emulsifier is preferably 2 to 30 parts by weight with respect to 100 parts by weight of the organopolysiloxane of component (a).

  The amount of water in component (e) is determined by emulsifying the organopolysiloxane in component (a), the crosslinking agent in component (b), and the curing catalyst in component (c) by the action of the emulsifier in component (d). The amount is not particularly limited as long as it is sufficient to prepare an aqueous emulsion.

  This silicone water-based elastomer emulsion can be prepared by uniformly mixing the components (a) to (e). For example, dimethylpolysiloxane having silanol groups at both ends is emulsified in water using an emulsifier such as a homomixer, homogenizer, or colloid mill in the presence of an emulsifier, and then a crosslinking agent such as colloidal silica or a curing catalyst is added. Both ends are mixed with each other by emulsifying in water using a cyclic diorganopolysiloxane such as octamethylcyclotetrasiloxane as an emulsifier, and then polymerizing under heating by adding a ring-opening polymerization catalyst. There is a method in which an emulsion of dimethylpolysiloxane blocked with is prepared, and a cross-linking agent such as colloidal silica or a curing catalyst is added thereto and mixed.

  Moreover, after preparing the base emulsion which consists of (a)-(e) component, the emulsion which was extremely excellent in storage stability can be obtained by adjusting the pH to 9-12. Examples of the pH adjuster include amines such as dimethylamine and ethylenediamine; and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Among these, organic amines are preferable, and examples of organic amines other than the above include monoethanolamine, triethanolamine, morpholine, and 2-amino-2-methyl-1-propanol. After adjusting the pH in this way, it is preferable to age at a constant temperature for a fixed period.

  The aging temperature is preferably a temperature at which the emulsion is not broken, that is, a range of 10 to 60 ° C, and more preferably a range of 15 to 50 ° C. The aging period is set according to the aging temperature, and for example, it is preferably 1 week or more under the temperature condition of 25 ° C. and 4 days or more under the temperature condition of 40 ° C.

  The organopolysiloxane emulsion thus obtained is excellent in storage stability at room temperature, and can be easily cured at room temperature to form an elastomer by removing water. On the other hand, when storage stability at room temperature is not required, the pH of the base emulsion may be less than 9. In addition, components other than those described above, for example, fillers, thickeners, pigments, dyes, heat-resistant agents, preservatives, penetrating aids such as aqueous ammonia, and the like can be appropriately added to the organopolysiloxane emulsion.

  In particular, when colloidal silica is not used as the crosslinking agent for the component (b), the viscosity of the organopolysiloxane emulsion is poor and it is difficult to obtain a thick elastomer. Calcium carbonate, magnesium oxide, zinc dioxide, titanium dioxide powder, carbon black and the like are preferably added and blended.

  Furthermore, these fillers are preferably colloidal because when they are colloidal, the tensile strength and elongation of the elastomer produced by the removal of moisture increase. Moreover, as a thickener, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, polyvinyl alcohol, polyacrylic acid, etc. can be used.

  In addition to this, the moisture-curable silicone elastomer composition is mainly composed of the above-mentioned both-end silanol-blocked diorganopolysiloxane (preferably having a viscosity at 25 ° C. of 1000 to 60000 centistokes), and is crosslinked. Deacetic acid condensation type silicone elastomer composition obtained by blending, for example, vinyl triacetoxysilane as an agent, dibutyltin diacetate or dibutyltin dilaurate as a catalyst, and further adding reinforcing fillers such as aerosil and kneading uniformly. In this deacetic acid condensation type composition, a deoxime condensation type silicone elastomer composition in which vinyltriacetoxysilane is replaced with vinyltrioximesilane, and similarly, vinyltriacetoxysilane is replaced with tetraethoxysilane or the like. Alcohol condensation type silicone elastomer composition. The cross-linking agent used is not limited to the cross-linking system as described above as long as it can elastomerize the silanol-blocked diorganopolysiloxane.

  Examples of the radical reaction curable silicone elastomer composition include a composition comprising an organopolysiloxane, a reinforcing filler and an organic peroxide, and additional fillers, heat resistant agents, flame retardants, pigments, organic solvents as additional components. Etc. can be contained. As organopolysiloxane, both ends are blocked with trimethylsiloxy group, dimethylvinylsiloxy group, methylphenylvinylsiloxy group or silanol group, and the main chain is dimethylpolysiloxane, dimethylsiloxane / methylphenylsiloxane copolymer, dimethylsiloxane / Examples thereof include a raw rubber-like polymer which is a methyl vinyl siloxane copolymer, a dimethyl siloxane / methyl phenyl siloxane / methyl vinyl siloxane copolymer, or a methyl (3,3,3-trifluoropropyl) / methyl vinyl siloxane copolymer.

An example of the reinforcing filler is fumed silica. Examples of organic peroxides include benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl- Examples include 2,5-di (t-butylperoxy) hexene. This radical reaction curable silicone elastomer composition is usually cured by heating from the viewpoint of curability and productivity.

  In addition to this, the radical reaction curable silicone elastomer composition mainly comprises an organopolysiloxane raw rubber and a reinforcing filler, and contains additional fillers, heat-resistant agents, flame retardants, pigments, organic solvents and the like as additional components. And a composition that is cured by irradiation with β rays or γ rays, or a composition that is cured by irradiation with ultraviolet rays, which is composed of a silicon-bonded alkenyl group-containing organopolysiloxane, a sensitizer, and a reinforcing filler.

  The average primary particle size of the silicone elastomer is preferably 0.1 to 100 μm, more preferably 2 to 15 μm. Commercially available products include the Trefill E series manufactured by Toray Dow Corning Co., Ltd., specifically, Trefill E-500, E-505C, Trefill E-506S, Trefill E-507, Trefill E-508, E-600. , E-601, E-606 and the like.

(C-2-4) Polyorganosiloxane core graft copolymer A polyorganosiloxane core graft copolymer is a polyfunctional monomer and other copolymerizable monomers in the presence of polyorganosiloxane particles. A vinyl monomer composed of a polymer is polymerized to form a cross-linked structure in which the polyorganosiloxane component and the vinyl polymer component are intertwined with each other, and the vinyl monomer is further polymerized to form a shell. This is a composite rubber-based multilayer structure polymer in which (shell) is formed.

  The polyorganosiloxane particles may be modified polyorganosiloxanes containing other (co) polymers as well as particles composed only of polyorganosiloxanes. That is, the polyorganosiloxane particle may contain, for example, 5% by weight or less of polybutyl acrylate, butyl acrylate-styrene copolymer, etc. It is preferable from the viewpoint of flame retardancy.

  The polyorganosiloxane particles preferably have a number average particle diameter of 0.008 to 0.6 μm determined from observation with an electron microscope. The number average particle diameter is more preferably 0.01 to 0.2 μm, particularly preferably 0.01 to 0.15 μm. Those having an average particle diameter of less than 0.008 μm are difficult to obtain, and those having an average particle diameter exceeding 0.6 μm tend to deteriorate the flame retardancy of a resin composition using the same.

  The polyorganosiloxane particles have a toluene insoluble content (the amount of toluene insoluble when 0.5 g of the particles are immersed in 80 ml of toluene at room temperature for 24 hours) of 95% or less, more preferably 50% or less, especially 20% or less. Is preferable from the viewpoint of flame retardancy and impact resistance.

  Specific examples of the polyorganosiloxane particles include siloxanes selected from dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, etc., alone or in combination of two or more, bifunctional silane compounds, and vinyl polymerizable group-containing silane compounds. Can be obtained by copolymerization with a silane compound having three or more functional groups.

  A polyfunctional monomer which is one of vinyl monomers is a compound containing two or more polymerizable unsaturated bonds in the molecule. Specific examples thereof include allyl methacrylate, triallyl cyanurate, isocyanuric acid. Examples include triallyl, diallyl phthalate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and divinylbenzene. These may be used alone or in combination of two or more. Among these, use of allyl methacrylate is particularly preferable from the viewpoints of economy and effects.

  Examples of other copolymerizable monomers that are vinyl monomers include aromatic vinyl monomers such as styrene, α-methyl styrene, paramethyl styrene, parabutyl styrene, acrylonitrile, methacrylo Vinyl cyanide monomers such as nitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, methacrylic acid (Meth) acrylic acid ester monomers such as methyl, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate, itaconic acid, (meth) acrylic acid, fumaric acid, maleic acid, etc. Carboxyl group-containing vinyl Monomers, and the like. These may be used alone or in combination of two or more. From the viewpoint of reactivity and stability, it is preferable to use a (meth) acrylic acid ester monomer.

  The vinyl monomer forming the shell layer ensures compatibility between the graft copolymer and the resin when the graft copolymer is blended with the thermoplastic polyester resin, so that the graft copolymer is evenly mixed with the resin. It is also a component having an effect of dispersing. For this reason, it is preferable to mainly use the above (meth) acrylic acid ester monomer for the vinyl monomer forming the shell layer.

  As the polyorganosiloxane core graft copolymer, a polymer produced by continuous multi-stage seed polymerization in which the polymer in the previous stage is sequentially coated with the polymer in the subsequent stage is preferable. The basic polymer structure includes an inner core layer having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component, which are crosslinking components having a low glass transition temperature, are intertwined with each other, and a matrix component of the resin composition It is a multilayer structure polymer which has an outermost shell layer which consists of an alkyl (meth) acrylate type polymer substance which improves adhesiveness. Furthermore, the innermost core layer is formed of a polymer composed of an aromatic vinyl monomer, and the intermediate layer is formed of a polymer having a structure in which a polyorganosiloxane component and a polyalkyl (meth) acrylate component are intertwined with each other. A polymer having a three-layer structure in which the outermost shell layer is formed of an alkyl (meth) acrylate polymer can also be used.

  The alkyl group of the alkyl (meth) acrylate has about 1 to 8 carbon atoms. Examples of such an alkyl group include an ethyl group, a butyl group, and a 2-ethylhexyl group. The alkyl (meth) acrylate polymer may be crosslinked with a crosslinking agent such as an ethylenically unsaturated monomer. Examples of the crosslinking agent include alkylene diol di (meth) acrylate and polyester di (meth) acrylate. , Divinylbenzene, trivinylbenzene, triallyl cyanurate, allyl (meth) acrylate, and the like.

  The polyorganosiloxane core graft copolymer is used in the presence of 40 to 90 parts by weight of polyorganosiloxane particles, preferably 60 to 80 parts by weight, more preferably 60 to 75 parts by weight. 5 to 10 parts by weight, preferably 1 to 5 parts by weight, more preferably 2 to 4 parts by weight, and 5 to 50 parts by weight of vinyl monomer for shell layer, preferably 10 to 39 parts by weight, More preferably, it is obtained by polymerizing 15 to 38 parts by weight so that the total amount becomes 100 parts by weight.

  Whether the amount of polyorganosiloxane particles is too small or too large, the flame retarding effect of the resin composition obtained using these particles tends to be low. Moreover, when there are too few vinylic monomers for cores, there exists a tendency for a flame-retarding effect and a toughness improvement effect to become low, and when too large, there exists a tendency for the toughness improvement effect to become low. Further, if the vinyl monomer for the shell layer is too little or too much, the flame retarding effect tends to be low. As such a polyorganosiloxane core graft copolymer, commercially available products such as METABRENE S-2001, S-2200 or SRK-200 manufactured by Mitsubishi Rayon Co., Ltd. may be used.

  The compounding amount of the (C-2) silicon-containing compound used in the present invention is 0 to 30 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin, and particularly 0.01 to 10 parts by weight. preferable. If the amount is less than 0.01 part by weight, the effect of improving the toughness corresponding to the added amount is not exhibited. Conversely, if it exceeds 10 parts by weight, the flame retardancy may be lowered. Therefore, it is preferably 0.1 to 8 parts by weight, particularly 0.5 to 6 parts by weight.

  Specific examples of these (C-2) silicon-containing compounds include the following.

  Product name: 217 Flake (phenyl silicone resin softening point 86 ° C), manufactured by Toray Dow Corning Co., Ltd., showing a solid state at 25 ° C.

217 Flake (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., weight average molecular weight (Mw): 2000, hydroxyl group content: 7% by weight, content of phenyl group bonded to silicon atom directly or through oxygen atom : 100 mol%, average molecular formula: (PhSiO _3/2 ) _1.0 (HO _1/2 ) _0.57 . Solid state at 25 ° C

  TMS217 (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., Mw: 2000, hydroxyl group content: 2% by weight, phenyl group content: 100 mol%, silicone obtained by subjecting the above-mentioned 217 Flakes to end-capping treatment with a trimethylsilyl group Resin. Solid state at 25 ° C

SR-21 (trade name) manufactured by Konishi Chemical Industries, Mw: 3800, hydroxyl group content: 6% by weight, phenyl group content: 100 mol%, average molecular formula: (PhSiO _3/2 ) _1.0 (HO _1/2 ) _0.48 Shows a solid state at 25 ° C.

SR-20 (trade name) manufactured by Konishi Chemical Industry, Mw: 6700, hydroxyl group content: 3% by weight, phenyl group content: 100 mol%, average molecular formula: (PhSiO _3/2 ) _1.0 (HO _1/2 ) _0.24 Shows a solid state at 25 ° C.

SH6018 (trade name) manufactured by Toray Dow Corning Silicone Co., Mw: 2000, hydroxyl group content: 6% by weight, phenyl group content: 70 mol%, propyl group 30 mol%, average molecular formula: (PhSiO _3/2 ) _0.7 (ProSiO _3/2 ) _0.3 (HO _1/2 ) _0.48 shows a solid state at 25 ° C.

  X40-9805 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., methylphenyl-based organosiloxane, phenyl group content: 50 mol%, solid state at 25 ° C.

Z6800 (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., triphenylsilanol, phenyl group content: 100 mol%, average molecular formula: Ph ₃ SiOH, solid state at 25 ° C.

  Made by Shin-Etsu Chemical Co., Ltd., octaphenyltetracyclosiloxane, Mw: 793, hydroxyl group content: 0 wt%, phenyl group content 100 mol%, average molecular formula: General formula (5) below.

  DC4 7081 manufactured by Toray Dow Corning Silicone Co., Ltd. Silica-supported silicon powder: 60% by weight of polydimethylsiloxane having a methacryl group supported on 40% by weight of silica and powdered, hydroxyl group content: 0% by weight, phenyl group It shows a solid state at a content of 0 mol% and 25 ° C.

SH200 (trade name) manufactured by Toray Dow Corning Silicone Co., polydimethylsiloxane, Mw: 4 × 10 ⁴ , hydroxyl group content 0 wt%, phenyl group content weight 0 mol%, viscosity 60000 centistokes, solid at 25 ° C. Not in state.

(C-3) Boron-containing compound As the boron-containing compound used in the present invention, a borate metal salt is particularly preferable. Examples of boric acid forming a boric acid metal salt include non-condensed boric acid such as orthoboric acid and metaboric acid, condensed boric acid such as pyroboric acid, tetraboric acid, pentaboric acid and octaboric acid, and basic boric acid. Is preferred. The metal that forms a salt with these may be an alkali metal, but among them, polyvalent metals such as alkaline earth metals, transition metals, and Group 2B metals of the periodic table are preferred. The metal borate may be a hydrate.

  Examples of the boric acid metal salt include a non-condensed boric acid metal salt and a condensed boric acid metal salt. Non-condensed borate metal salts include alkaline earth metal borates such as calcium orthoborate and calcium metaborate; transition metal borates such as manganese orthoborate and copper metaborate; zinc metaborate and cadmium metaborate Examples thereof include borate salts of Group 2B metal of the periodic table, and among them, metaborate is preferable.

  Condensed borates include alkaline earth metal borates such as trimagnesium tetraborate and calcium pyroborate; transition metal borates such as manganese tetraborate and nickel diborate; zinc tetraborate and tetraborate Examples thereof include borate salts of group 2B metals of the periodic table such as cadmium acid. Examples of the basic borate include basic borates of Group 2B metals of the periodic table such as basic zinc borate and basic cadmium borate. In addition, hydrogen borates corresponding to these borates (such as manganese orthoborate) can also be used.

As the boric acid metal salt used in the present invention, it is preferable to use an alkaline earth metal or a Group 2B metal salt of the periodic table such as zinc borate or calcium borate. Zinc borates include zinc borate (2ZnO.3B ₂ O ₃ ), zinc borate.3.5 hydrate (2ZnO.3B ₂ O ₃ .3.5H ₂ O), etc. Calcium borate includes calcium borate (2CaO · 3B ₂ O ₃ ), calcium borate · pentahydrate (2CaO · 3B ₂ O ₃ · 5H ₂ O), and the like. Among these zinc borates and calcium borates, hydrates are particularly preferable.

  Specific examples of these boron-containing compounds include zinc borate (manufactured by Borax Japan, Firebreak 500, 415, ZB), calcium borate ore: UBP, UBP5M, manufactured by Kisei Matec.

  By adding the boric acid metal salt, the combustion inhibiting action of the resin composition is improved. Phenomenologically, it foams during combustion and blocks the unburned part from the flame. The compounding amount of the boric acid metal salt is 0 to 30 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin, but it is preferable to add 1 part by weight or more in order to express the compounding effect. However, even if it is excessively added, the improvement in the effect commensurate with the increase in the amount of mixture will reach its peak, so the amount of the metal borate salt is 1 to 20 parts by weight relative to 100 parts by weight of the (A) thermoplastic polyester resin. It is preferably 1 to 10 parts by weight, particularly 3 to 5 parts by weight.

  The content of the flame retardant aid used in the present invention is 35 parts by weight or less, preferably 1 to 30 parts by weight, and 1.5 to 25 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. More preferred.

(D) Graft polymer The resin composition of the present invention comprises a graft polymer obtained by polymerizing at least methyl methacrylate to a rubbery polymer obtained by polymerizing at least butadiene and substantially not containing a component derived from styrene. A graft polymer in which the content of a component derived from styrene in the graft polymer is 5% by weight or less.
The graft polymer used in the present invention is usually referred to as a core-shell structure, but does not necessarily have a core-shell structure.
The rubbery polymer in the graft polymer used in the present invention is characterized by substantially not containing a component derived from styrene. By setting it as such a structure, high flame retardance can be achieved. Here, “substantially free of components derived from styrene” means that it is not contained within a range that affects the effects of the present invention, and is usually 0.1% by weight or less of the rubbery polymer.
The rubbery polymer obtained by polymerizing at least butadiene may be composed only of butadiene, or may be a rubbery polymer obtained by copolymerizing butadiene and another monomer. It is preferable that it consists only of.
The graft polymer used in the present invention is a polymer obtained by graft-polymerizing at least methyl methacrylate to a rubbery polymer. In the present invention, only methyl methacrylate may be polymerized, or a monomer other than methyl methacrylate may be used in combination. Examples of the monomer other than methyl methacrylate include styrene.
The graft polymer used in the present invention contains a component derived from styrene in a proportion of 5% by weight or less, preferably 3% by mass or less, and more preferably substantially free of a component derived from styrene.

  The volume average particle diameter of the graft polymer used in the present invention is not particularly limited, but is preferably 30 to 1000 μm.

  The graft polymer used in the present invention can be produced according to a known method such as the method described in JP-A-2005-112907. Commercial products can also be used. As a commercial item, what is employ | adopted by the Example mentioned later is illustrated.

  The content of the graft polymer used in the present invention is 0.5 to 30 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the (A) thermoplastic polyester resin. 8 parts by weight is more preferable.

  In this invention, it is preferable that the elastomer component other than the said graft polymer (D) is not included substantially. “Substantially not contained” is usually 1% by mass or less based on the resin component.

(E) In order to obtain a resin molded article excellent in performance such as mechanical strength, heat resistance, dimensional stability (deformation resistance, warpage), and electrical properties in the reinforcing filler or the resin composition of the present invention, You may mix | blend various (E) reinforcement | strengthening fillers, such as fibrous form, a granular form, and plate shape.

  Examples of the fibrous reinforcing filler include glass fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, and further stainless steel, aluminum, titanium, Examples thereof include metallic fibrous materials such as copper and brass. Particularly typical fibrous reinforcing fillers are glass fiber and carbon fiber.

Examples of the granular reinforcing filler include silicates such as carbon black, silica, quartz powder, glass beads, glass powder, calcium oxalate, aluminum oxalate, kaolin, talc, clay, diatomaceous earth, and wollastonite. Metal oxides such as iron oxide, titanium oxide, zinc oxide and alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, other silicon carbide, silicon nitride and boron nitride And various metal powders.
Examples of the plate-like reinforcing filler include mica, glass flakes, various metal foils and the like.
These reinforcing fillers may be used alone or in combination of two or more at any ratio.

  In using these reinforcing fillers, a sizing agent or a surface treatment agent can be used if necessary. For example, functional compounds such as epoxy compounds, silane compounds, and titanate compounds are used. The reinforcing filler may be previously treated with these compounds, or may be added simultaneously or individually during the production of the resin composition.

  (E) The compounding quantity of a reinforcement filler is 90 weight part or less with respect to 100 weight part of component (A) thermoplastic polyester resins, Preferably it is 5 to 85 weight part, More preferably, it is 8 to 80 weight. Parts, particularly preferably 10 to 70 parts by weight. When it mix | blends exceeding 90 weight part, it will become difficult to ensure the toughness of a resin composition.

Furthermore, various additives commonly used in thermoplastic resin compositions can be added to the resin composition of the present invention within a range that does not impair the object of the present invention. Examples of such additives include stabilizers such as antioxidants, ultraviolet absorbers, light stabilizers, hydrolysis inhibitors (epoxy compounds, carbodiimide compounds, etc.), antistatic agents, lubricants, mold release agents, dyes, Colorants such as pigments, plasticizers and the like can be mentioned. In particular, the addition of a stabilizer and a release agent is effective. The addition amount of these additives is usually 10 parts by weight or less, preferably 5 parts by weight or less with respect to 100 parts by weight of the thermoplastic polyester resin.

It is preferable that the resin composition of the present invention does not substantially contain a halogen-based flame retardant flame retardant. “Substantially not contained” means that it is not added in an addition amount that functions as a flame retardant, and is usually 0.1% by mass or less based on the resin component.
In addition, the resin composition of the present invention can also be prevented from dripping during combustion by adding a dripping inhibitor such as polytetrafluoroethylene or fumed colloidal silica obtained by suspension polymerization. However, in the present invention, high flame retardancy can be achieved without substantially including such an anti-dripping agent. “Substantially not contained” means that it is not added in an addition amount that functions as an anti-dripping agent, and is usually 0.1% by mass or less based on the resin component.

  The flame-retardant thermoplastic polyester resin composition of the present invention may further use another thermoplastic resin, and can be used as long as the resin is stable at high temperatures. Specifically, for example, polycarbonate, polyamide , Polyphenylene oxide, polystyrene resin, polyphenylene sulfide ethylene, polysulfone, polyethersulfone, polyetherimide, polyetherketone, fluororesin and the like.

  The flame-retardant thermoplastic polyester resin composition of the present invention can be prepared according to a conventional method for preparing a resin composition. Usually, the components and various additives added as desired are mixed together and then melt-kneaded in a single-screw or twin-screw extruder. Also, the resin composition of the present invention can be prepared by mixing each component in advance or by mixing only a part of the components in advance and supplying them to an extruder using a feeder and melt-kneading them. Further, a master batch is prepared by melting and kneading a part of a polyester resin and a part of other components, and then the remaining polyester resin and other ingredients are blended and melt kneaded. Good.

  In the flame-retardant thermoplastic polyester resin composition of the present invention, the resin composition in a molten state as described above can be formed into a resin molded body by any conventionally known production method. Specifically, for example, it can be molded into a resin molded body by various thermoplastic resin molding methods such as injection molding, extrusion molding, press molding, blow molding, and the like. Among these, since the molding cycle is short and the productivity is stable, a molded body molded by an injection molding method is preferable because its features become remarkable.

  The resin molded body of the present invention is not only the above-described injection molding, but also in various forms such as a resin molded body such as a resin film and a resin sheet, an electronic material, a magnetic material, a catalyst material, a structural material, an optical material, It can be widely used for various applications such as medical materials, automobile materials, and building materials. Since the resin molded body of the present invention can be used in a general plastic molding machine that is widely used at present, it can be formed into a molded body having a complicated shape.

  Since the thermoplastic resin composition of the present invention has properties excellent in impact strength, appearance, and weldability in addition to flame retardancy, it can be suitably used as a member for various industrial products and parts. In particular, it can be suitably used as a resin molded body constituting electric / electronic parts in the automobile field, specifically, member parts such as connectors.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Evaluation method of resin composition>
In the weight ratio shown in Table 1, components other than glass fiber among the raw materials used in Examples and Comparative Examples shown in Table 3 to be described later are mixed together with a super mixer (SK-350 type manufactured by Shinei Machinery Co., Ltd.), The mixture was put into a hopper of a twin screw extruder (manufactured by Nippon Steel Co., Ltd., TEX30HSST) with L / D = 42, and glass fiber was side-fed to a discharge rate of 20 kg / h, screw rotation speed 250 rpm, barrel temperature 260 ° C. Extrusion was performed under the above conditions to obtain pellets of a polybutylene terephthalate resin composition. The obtained pellet was formed into a test piece according to the following evaluation method.

Flame retardant test:
According to the method of UL-94, a flame retardancy test is performed using five test pieces (thickness: 0.75 mm), and according to the evaluation method described in UL94, V-0, V-1, V-2, HB (V-0 indicates the highest flame retardancy). The total combustion time is the total combustion time of 5 tubes (including the combustion time at the time of the first flame contact and the second flame contact), and the unit is shown in seconds.

Charpy impact strength with notch Using a polybutylene terephthalate resin composition pellet, an ISO test piece was molded with an injection molding machine (NEX80-9E type manufactured by Nissei Plastic Industries Co., Ltd.). The notched Charpy impact strength was measured according to ISO 179-2.

  Using the obtained polybutylene terephthalate resin composition (the primary molding material and the secondary molding material are the same), the test piece A (primary molded product) shown in FIG. ), Held in a hot air oven (120 ° C.) for 30 minutes and then taken out, immediately mounted in a secondary molding die, and the obtained polybutylene terephthalate resin composition (secondary molding material) The test piece was injection-molded using the test piece, and the test piece A and the test piece made of the secondary molding material were welded in the mold to obtain an injection-welded integrally molded product B. The injection weld strength of the obtained injection welded integral molded product was measured.

Measurement of welding strength:
The integrally molded product (test piece B shown in FIG. 1) was pulled under the conditions of a bending speed of 2 mm / min and a span distance of 64 mm, the load at break was measured, and the size was represented by kgf, which was defined as the welding strength. .

The content ratio of each component in the above table is as follows.

  As apparent from the above table, it was found that a resin composition excellent in flame retardancy and weldability can be obtained by using a graft polymer having a low styrene content.

 The flame-retardant thermoplastic polyester resin composition of the present invention can be expected to be applied to a wide range of parts such as electric and electronic parts such as connectors and terminals. Furthermore, it can be applied to automobile parts and building material parts.

1 Part of Test Specimen A in Specimen B 2 Molded Product Part Consisting of Secondary Molding Material in Specimen B 3 218mm
4 12.82mm
5 25mm
6 121.5mm
7 28mm
8 3.0mm
9 3.0mm
10 45 degrees

Claims (10)

(A) For 100 parts by weight of the thermoplastic polyester resin,
(B) 5 to 60 parts by weight of a phosphinic acid salt represented by the following general formula (1) or (2), and (D) at least butadiene is polymerized and substantially does not contain a component derived from styrene. 0.5 to 30 parts by weight of a graft polymer obtained by graft-polymerizing at least methyl methacrylate to a rubber polymer, wherein the content of the styrene-derived component in the graft polymer is 5% by weight or less. Parts by weight,
A flame retardant thermoplastic polyester resin composition comprising:

(Wherein R ¹ and R ² each represent a linear or branched alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ³ represents a linear or branched carbon number. Represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 10 carbon atoms, or an arylalkylene group having 7 to 10 carbon atoms, and M represents a calcium ion, an aluminum ion, zinc Represents an ion or magnesium ion, m is 2 or 3, n is 1 or 3, and X is 1 or 2.) Wherein (D) does not contain a component derived from the graft polymer gas styrene, flame retardant thermoplastic polyester resin composition according to claim 1. Wherein a rubber polymer Gab Tajien rubbery polymer only the polymerisation comprising, according to claim 1 or flame retardant thermoplastic polyester resin composition according to 2. (A) The flame-retardant thermoplastic polyester resin composition according to any one of claims 1 to 3 , wherein the thermoplastic polyester resin comprises a polybutylene terephthalate resin. The flame retardant according to any one of claims 1 to 4 , comprising (D) the graft polymer in a proportion of 0.5 to 10 parts by weight with respect to 100 parts by weight of (A) the thermoplastic polyester resin. Thermoplastic polyester resin composition. Further, (C) at least one of (C-1) an amino group-containing compound, (C-2) a silicon-containing compound, and (C-3) a boron-containing compound is used as a flame retardant aid, and (A) a thermoplastic polyester. The flame-retardant thermoplastic polyester resin composition according to any one of claims 1 to 5 , which is contained at a ratio of 35 parts by weight or less with respect to 100 parts by weight of the resin. Further, (C) as a flame retardant aid, at least one of melamine cyanurate, melamine polyphosphate, melamine phosphate, silicone resin, zinc borate and colemanite mineral is used with respect to (A) 100 parts by weight of thermoplastic polyester resin, The flame-retardant thermoplastic polyester resin composition according to any one of claims 1 to 5 , which is contained at a ratio of 35 parts by weight or less. Additionally, (E) containing reinforcing fillers, flame retardant thermoplastic polyester resin composition according to any one of claims 1-7. The flame-retardant thermoplastic polyester resin composition according to any one of claims 1 to 8 , which is substantially free of a halogen-based flame retardant. A molded product obtained by molding the flame-retardant thermoplastic polyester resin composition according to any one of claims 1 to 9 .

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