JP2013253172A - Aromatic polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polyester resin composition having a particularly high tracking resistance, and being excellent in mechanical strength, metal mold releasability and molded article appearance, and therefore being useful for electric parts applications such as electric and electronic parts and automobile electric parts.SOLUTION: An aromatic polyester resin composition contains, based on 100 pts.wt. of an aromatic polyester resin (A): 1 to 50 pts.wt. of at least an ethylene-vinyl alcohol-based copolymer (B); 30 to 200 pts.wt. of at least one inorganic filler (C) selected from magnesium hydroxide (C1), a hydrate (C2) of calcium borate represented by 2CaO3BO5HO and hydrotalcite (C3); and 30 to 200 pts.wt. of a fibrous filler (D).

Description

  The present invention has a high degree of tracking resistance without impairing the inherent heat resistance, electrical insulation, etc. of the aromatic polyester resin, and has excellent mechanical strength, mold releasability, and molded product appearance. More specifically, it requires high tracking resistance and excellent mechanical strength at the same time, such as electrical / electronic parts and automotive electrical parts that require high voltage resistance. The present invention relates to an aromatic polyester resin composition suitable for the intended use.

  Aromatic polyester resins are widely used in electrical / electronic parts, automotive electrical parts, and the like because of their excellent heat resistance, mechanical strength, electrical insulation, and moldability. In particular, tracking resistance is required for electrical / electronic parts and automotive electrical parts that are subjected to high voltage when exposed to moisture and dust in a non-sealed state. In recent years, these parts have been made thinner and smaller due to the trend of miniaturization of various devices. As a result, the insulation distance is shortened, and further improvement in tracking resistance and mechanical strength of molded products is desired. ing. However, aromatic polyester resins have low tracking resistance and are difficult to use in areas where high tracking resistance is required.

  Several attempts have been made to improve the tracking resistance of aromatic polyester resins, and (a) polybutylene terephthalate or polyamide resin, (b) glass fiber, and (c) komalenite are blended. A resin composition (for example, a patent) containing a resin composition (for example, see Patent Document 1), (a) a thermoplastic polyester resin, (b) a polyolefin-based resin, (c) zinc borate, and (d) an inorganic filler. Reference 2), etc. have been proposed.

Japanese Patent Laid-Open No. 10-204269 (see, for example, the claims) Japanese Patent Laid-Open No. 09-272791 (see, for example, claims)

  However, the resin compositions proposed in Patent Documents 1 and 2 have a problem that the tracking resistance is not yet satisfactory. In addition, in these proposed resin compositions, in order to obtain sufficiently excellent tracking resistance, a high filler content is essential, so that the mechanical strength of the composition is significantly reduced, and further, mold release is further reduced. The moldability and appearance of the molded product deteriorated. That is, these resin compositions are difficult to obtain excellent tracking resistance, high mechanical strength, good mold releasability and molded article appearance at the same time.

  Therefore, the present invention aims to provide an aromatic polyester resin composition that has a particularly high tracking resistance and is excellent in mechanical strength, mold releasability, and appearance of a molded product. Another object of the present invention is to provide an aromatic polyester resin composition useful for electric parts such as electric / electronic parts or automobile electric parts.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors blended an aromatic polyester resin with an ethylene-vinyl alcohol copolymer, an inorganic filler, and a fibrous filler, and further, if necessary. The present inventors have found that an aromatic polyester resin composition containing a release agent can be a composition having high tracking resistance and excellent mechanical strength, mold releasability, and appearance of a molded product. It came to complete.

That is, the present invention provides at least an ethylene-fatty acid vinyl ester-vinyl alcohol copolymer and / or ethylene-vinyl alcohol copolymer represented by the following general formula (1) with respect to 100 parts by weight of the aromatic polyester resin (A). Calcium borate hydrate (C2) represented by 1 to 50 parts by weight of ethylene-vinyl alcohol copolymer (B), magnesium hydroxide (C1), 2CaO.3B ₂ O ₃ .5H ₂ O, which is a coalescence ), 30 to 200 parts by weight of one or more inorganic fillers (C) selected from hydrotalcite (C3) and 30 to 200 parts by weight of fibrous filler (D) It relates to a composition.

（ここで、ｘ、ｚはいずれもが０を超え、ｙが０以上、ｘ＋ｙ＋ｚ＝１であり、Ｒは炭素数１〜１０の炭化水素基である。）
以下、本発明に関し詳細に説明する。

(Here, x and z are both greater than 0, y is 0 or more, x + y + z = 1, and R is a hydrocarbon group having 1 to 10 carbon atoms.)
Hereinafter, the present invention will be described in detail.

The aromatic polyester resin composition of the present invention comprises 1 to 50 parts by weight of an ethylene-vinyl alcohol copolymer (B), magnesium hydroxide (C1), 2CaO · 100 parts by weight of the aromatic polyester resin (A). Calcium borate hydrate represented by 3B ₂ O 3.5H ₂ O (C2), _{30 to 200} parts by weight of one or more inorganic fillers (C) selected from hydrotalcite (C3) and fibrous The filler (D) consists of 30 to 200 parts by weight.

  A publicly known aromatic polyester resin can be used as the aromatic polyester resin (A) constituting the aromatic polyester resin composition of the present invention. The aromatic polyester resin is a polyester having an aromatic ring in the polymer chain unit, and is a polymer obtained by a polycondensation reaction containing aromatic dicarboxylic acids and diols (and their ester-formation derivatives) as main components, or A copolymer is mentioned.

  Examples of the aromatic dicarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2 '-Dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4, 4'-dicarboxylic acid, diphenylisopropylidene-4,4'-dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, anthracene-2,6 -Dicarboxylic acid, p-terphenylene-4,4'-dicarboxylic acid, pyridine-2, - such as dicarboxylic acid and the like, preferably terephthalic acid.

  Examples of the diol component include aliphatic glycols, polyoxyalkylene glycols, alicyclic diols, and aromatic diols. Examples of the aliphatic glycol include 2 to 12 carbon atoms such as ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, octanediol, and decanediol. An aliphatic glycol of about 2 to 10 carbon atoms is preferable, and an aliphatic glycol having about 2 to 10 carbon atoms is preferable. Examples of the polyoxyalkylene glycol include glycols having an alkylene group having about 2 to 4 carbon atoms and having a plurality of oxyalkylene units, such as diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, Examples include tripropylene glycol and tritetramethylene glycol. Examples of the alicyclic diol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethylol, hydrogenated bisphenol A, and the like. Examples of the aromatic diol include 2,2-bis- (4- (2-hydroxyethoxy) phenyl) propane and xylene glycol. Further, as the diol component, halides such as halogenated diols such as tetrabromobisphenol A and alkylene oxide (ethylene oxide, propylene oxide, etc.) adducts of tetrabromobisphenol A can also be used. These diol components may be used alone or in combination of two or more. If the amount is small, one or more long-chain diols having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and the like may be copolymerized.

  Examples of the aromatic polyester resin (A) include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4′-dicarboxyl. Rate, polycyclohexylenedimethylene terephthalate, and the like.

  The ethylene-vinyl alcohol copolymer (B) represented by the general formula (1) constituting the aromatic polyester resin composition of the present invention is for improving the tracking resistance of the aromatic polyester resin composition. It is used. In the ethylene-vinyl alcohol copolymer (B), in the general formula (1), each of x and z exceeds 0, y is 0 or more, x + y + z = 1, and R is An ethylene-fatty acid vinyl ester-vinyl alcohol copolymer and / or an ethylene-vinyl alcohol copolymer comprising a hydrocarbon group having 1 to 10 carbon atoms.

  Here, when x is 0, the resulting composition is inferior in heat resistance. When z is 0, the resulting composition is inferior in tracking resistance. And since it becomes an aromatic polyester resin composition which has especially high tracking resistance and favorable mechanical strength, x = 0.25-0.94, y = 0-0.15, z = 0.02. It is preferably an ethylene-fatty acid vinyl ester-vinyl alcohol copolymer and / or an ethylene-vinyl alcohol copolymer in the range of 0.75, and each of x, y, z is more than 0. Fatty acid vinyl ester-vinyl alcohol copolymer, especially ethylene-fatty acid vinyl ester in the range of x = 0.69-0.94, y = 0.01-0.15, z = 0.02-0.30. -It is preferably a vinyl alcohol copolymer.

  R is a hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group. Here, in the case of an ethylene-fatty acid vinyl ester-vinyl alcohol copolymer having more than 10 carbon atoms, the resulting composition is inferior in mechanical strength.

  The method for producing the ethylene-vinyl alcohol copolymer (B) is not particularly limited. For example, a method of copolymerizing an ethylene monomer, a fatty acid vinyl ester monomer and a vinyl alcohol monomer; It can be obtained by a method of partially saponifying a polymer, among others, an ethylene-fatty acid vinyl ester-vinyl alcohol copolymer, an ethylene-vinyl alcohol copolymer obtained by partially saponifying an ethylene-fatty acid vinyl ester copolymer, among others. The coalescence is preferable because it is easily available industrially. Among them, ethylene-vinyl acetate-vinyl alcohol copolymer and ethylene-vinyl alcohol copolymer are industrially easily available, particularly tracking resistance. It is most preferable because it becomes an aromatic polyester resin composition having excellent resistance.

  The compounding quantity of this ethylene-vinyl alcohol-type copolymer (B) which comprises the aromatic polyester resin composition of this invention is 1-50 weight part with respect to 100 weight part of aromatic polyester resin (A). When the blending amount of the ethylene-vinyl alcohol copolymer (B) is less than 1 part by weight, the resulting composition is inferior in tracking resistance. On the other hand, when the blending amount of the ethylene-vinyl alcohol copolymer (B) exceeds 50 parts by weight, the resulting composition is inferior in mechanical strength and molded article appearance.

As the inorganic filler (C) constituting the aromatic polyester resin composition of the present invention, calcium borate hydrate (C2) represented by magnesium hydroxide (C1), 2CaO · 3B ₂ O ₃ · 5H ₂ O ), One or more inorganic fillers selected from hydrotalcite (C3).

Any magnesium hydroxide (C1) may be used as long as it belongs to the category called magnesium hydroxide. Among them, the obtained aromatic polyester resin composition has excellent tracking resistance, and since it comes to have a high mechanical strength, relatively pure magnesium hydroxide containing hydroxide 80 wt% or more of the chemical formula Mg (OH) ₂ is shown preferably, the chemical formula Mg (OH) ₂ More preferred is magnesium hydroxide having a hydroxide content of 80% by weight or more, a CaO content of 5% by weight or less, and a chlorine content of 1% by weight or less, Mg (OH) _{2 of} 95% by weight or more, and a CaO content of 1% by weight. hereinafter, magnesium hydroxide is more preferably 0.5 wt% or less chlorine content, Mg _(OH) 2 98% by weight or more, CaO content 0.1 wt% or less High purity magnesium hydroxide chlorine content 0.1 wt% or less is most preferred.

Since the magnesium hydroxide (C1) is an aromatic polyester resin composition that is particularly excellent in tracking resistance, mechanical strength, and appearance of a molded product, the average particle diameter (D ₅₀ ) measured by the laser diffraction scattering method is 0. It is preferable to have a range of 3 to 10 μm, and it is particularly preferable to have a range of 0.5 to 3 μm. Moreover, since the specific surface area of this magnesium hydroxide (C1) becomes an aromatic polyester resin composition excellent in tracking resistance and mechanical strength, the specific surface area is preferably 10 m ² / g or less.

  Examples of the magnesium hydroxide (C1) include magnesium hydroxide not subjected to surface treatment (hereinafter referred to as surface untreated magnesium hydroxide (C1-1)), higher fatty acid and / or metal salt of higher fatty acid. , Magnesium hydroxide surface-treated with a silane coupling agent, titanate coupling agent, aluminate coupling agent or the like (hereinafter referred to as surface treated magnesium hydroxide (C1-2)), and the like. Can be mentioned. And there is no restriction | limiting in particular about the surface coating processing agent of surface treatment magnesium hydroxide, As a higher fatty acid and its metal salt, for example, stearic acid, oleic acid, etc., and its alkali metal salt etc .; As an anionic surfactant, For example, sulfates of higher alcohols; phosphate esters such as esters of orthophosphoric acid and higher alcohols; silane coupling agents such as vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc .; titanate coupling agents such as isopropyltriisostearoyl titanate; aluminum coupling agents , For example, acetoalkoxyaluminum diisopropylate; the esters of polyhydric alcohols and fatty acids such as glycerin monostearate, and the like. And since it becomes an aromatic polyester resin composition which is especially excellent in mechanical strength among these magnesium hydroxide (C1), surface treatment is carried out with surface treatment unreasonable magnesium hydroxide (C1-1) and a silane coupling agent. Preferred is surface treated magnesium hydroxide (C1-2) and mixtures thereof.

The calcium borate hydrate (C2) used as the inorganic filler (C) constituting the aromatic polyester resin composition of the present invention is represented by the structural formula of 2CaO · 3B ₂ O ₃ · 5H ₂ O. In general, it may be referred to as komalenite, which is a natural mineral, and the calcium borate hydrate (C2) has a structure of 2CaO · 3B ₂ O ₃ · 5H ₂ O If it is a thing, it is not limited to a natural mineral.

And since the calcium borate hydrate (C2) is an aromatic polyester resin composition excellent in tracking resistance, mechanical strength, and molded article appearance, the average particle diameter measured by laser diffraction scattering method. (D ₅₀ ) is preferably in the range of 1 to 30 μm, particularly preferably in the range of 1 to 20 μm.

  As the calcium borate hydrate (C2), any of those whose surfaces are coated or not can be used. When the surface is coated, the surface coating treatment agent is not particularly limited, and higher fatty acid and / or metal salt of higher fatty acid, anionic surfactant, phosphate ester, silane coupling agent, titanate coupling Agents, aluminate coupling agents, polyhydric alcohols and fatty acid esters. Examples of higher fatty acids and metal salts thereof include stearic acid, oleic acid, and alkali metal salts thereof; examples of anionic surfactants include sulfates of higher alcohols; examples of phosphate esters include orthophosphoric acid Higher alcohol esters, etc .; Examples of silane coupling agents include vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Mercaptopropyltrimethoxysilane and the like; titanate coupling agents such as isopropyl triisostearoyl titanate and the like; aluminate coupling agents such as acetoalkoxyaluminum diisopropylate and the like; polyhydric alcohol Examples of the esters of fatty acids such as glycerin monostearate, and the like.

Any hydrotalcite (C3) used as the inorganic filler (C) constituting the aromatic polyester resin composition of the present invention can be used as long as it belongs to a category called hydrotalcite. Examples thereof include those represented by the following general formula (2).
(M _1-a N _a (OH) ₂ ) (C ⁿ⁻ ) _{a / n} · mH ₂ O (2)
(Where M is a divalent metal, N is a trivalent metal, C ⁿ⁻ represents an anion, a is 0 <a <1, m is m ≧ 0, and n is 1, 2 or 3. .)
The hydrotalcite represented by the above general formula (2) is composed of a composite metal hydroxide layer represented by (M _1-a N _a (OH) ₂ ) and C ⁿ⁻ inserted between the layers. It consists of a structure consisting of the anions and water shown. The water inserted between the layers (hereinafter referred to as interlayer water) can be desorbed from the layers by heating to about 200 ° C.

  When the aromatic polyester resin composition of the present invention is prepared, it is generally prepared by a hot melt kneading method, and the kneading temperature at that time often reaches 250 ° C. or higher. As the site (C3), it is possible to suppress the desorption of interlayer water at the time of heat-melting and kneading, and therefore, it is preferable that the site is desorbed in advance. As a method for desorbing interlayer water, for example, a method of heating and drying can be mentioned. Examples of such a heat drying apparatus include a stationary dryer, a rotary / stirring dryer, a transport dryer, and the like. The heating conditions vary depending on the amount of hydrotalcite to be treated and the type and size of the heating / drying apparatus. For example, the heating temperature is 200 to 280 ° C., and the heating time is about 2 hours to half a day. Preferably there is.

And as a bivalent metal which is M of the hydrotalcite shown by said general formula (2), Mg, Zn, Ca, Ni, Co etc. can be mentioned, for example, Trivalent metal which is N Examples thereof include Al, Fe, Mn, and Cr. Examples of the anion that is C ^n- include CO ₃ ²⁻ , SO ₄ ²⁻ , and Cl ⁻ . In addition, a is 0 <a <1, and m representing the amount of interlayer water is m ≧ 0, and less water is released when preparing the aromatic polyester resin composition of the present invention. To 0 ≦ m ≦ 5.

As the hydrotalcite (C3), specifically, (Mg _0.75 Al _0.25 (OH) ₂ ) (CO ₃ ²⁻ ) _0.125 · 4H ₂ O, (Mg _0.75 Al _{0. 25} (OH) ₂ ) (CO ₃ ²⁻ ) _0.125 , (Mg _0.67 Al _0.33 (OH) ₂ ) (CO ₃ ²⁻ ) _0.167 · 3H ₂ O, (Mg _0.67 Al _0.33 (OH) ₂ ) (CO ₃ ²⁻ ) _0.167 , (Mg _0.7 Al _0.3 (OH) ₂ ) (CO ₃ ²⁻ ) _0.15 · 3.5H ₂ O or (Mg _0.7 Al _0.3 (OH) ₂ ) (CO ₃ ²⁻ ) _{0.15 and the} like.

Since the hydrotalcite (C3) is an aromatic polyester resin composition particularly excellent in tracking resistance, mechanical strength, and molded product appearance, the average particle size (D ₅₀ ) measured by a laser diffraction scattering method is It is preferable to have a range of 0.3 to 10 μm, and it is particularly preferable to have a range of 0.4 to 2 μm. Further, the specific surface area of the hydrotalcite (C3) is preferably 20 m ² / g or less because it becomes an aromatic polyester resin composition excellent in tracking resistance and mechanical strength.

  As the hydrotalcite (C3), any of those whose surfaces are coated or not can be used. When the surface is coated, the surface coating agent is not particularly limited, and higher fatty acids and / or metal salts of higher fatty acids; anionic surfactants, phosphate esters, silane coupling agents, titanate couplings Agents, aluminate coupling agents, polyhydric alcohols and fatty acid esters. Examples of higher fatty acids and metal salts thereof include stearic acid, oleic acid, and alkali metal salts thereof; examples of anionic surfactants include sulfates of higher alcohols; examples of phosphate esters include orthophosphoric acid Higher alcohol esters, etc .; Examples of silane coupling agents include vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Mercaptopropyltrimethoxysilane and the like; titanate coupling agents such as isopropyl triisostearoyl titanate and the like; aluminate coupling agents such as acetoalkoxyaluminum diisopropylate and the like; polyhydric alcohol Examples of the esters of fatty acids such as glycerin monostearate, and the like.

  In the aromatic polyester resin composition of the present invention, magnesium hydroxide (C1), calcium borate hydrate (C2), and hydrotalcite (C3) may be used alone as the inorganic filler (C). It is also possible to use it as a mixture of two or more.

  The compounding quantity of the inorganic filler (C) which comprises the aromatic polyester resin composition of this invention is 30-200 weight part with respect to 100 weight part of aromatic polyester resin (A). When the compounding quantity of this inorganic filler (C) is less than 30 weight part, the composition obtained will be inferior to tracking resistance. On the other hand, when the blending amount of the inorganic filler (C) exceeds 200 parts by weight, the resulting composition is inferior in mechanical strength, mold releasability, and molded product appearance.

  The fibrous filler (D) constituting the aromatic polyester resin composition of the present invention is blended in order to improve the mechanical strength and dimensional stability of the aromatic polyester resin composition. Any fibrous filler can be used as long as it can achieve the above. Examples of the fibrous filler (D) include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, asbestos fiber, stone koji fiber, and metal fiber. Among them, glass fiber is preferable. Since the fibrous filler (D) has high mechanical strength of the aromatic polyester resin composition, the surface is covered with an isocyanate compound, a silane coupling agent, a titanate coupling agent, an epoxy compound, or the like. It is preferable that it has been processed.

  The compounding quantity of the fibrous filler (D) which comprises the aromatic polyester resin composition of this invention is 30-200 weight part with respect to 100 weight part of aromatic polyester resin (A). When the compounding quantity of this fibrous filler (D) is less than 30 weight part, the composition obtained will be inferior to mechanical strength. On the other hand, when the compounding quantity of this fibrous filler (D) exceeds 200 weight part, the composition obtained will be inferior to melt fluidity | liquidity and a molded article external appearance.

  The aromatic polyester resin composition of the present invention is preferably formed by blending a release agent (E) in order to further improve the mold releasability and appearance of the obtained molded product. The release agent (E) can be used as long as it belongs to a category known as a release agent. For example, carnauba wax (E1), polyethylene wax (E2), polypropylene wax (E3), Metal stearates (E4), acid amide waxes (E5) and the like can be mentioned, and among them, an aromatic polyester resin composition excellent in mold releasability and molded product appearance of a molded product obtained in particular can be used. To carnauba wax (E1).

  As the carnauba wax (E1), a general commercially available product can be used, and examples thereof include (trade name) purified carnauba No. 1 powder (manufactured by Nikko Fine Products).

  The compounding amount of the mold release agent (E) is 0.01% with respect to 100 parts by weight of the aromatic polyester resin (A) because it becomes an aromatic polyester resin composition excellent in mold releasability and molded article appearance. It is preferably ˜5 parts by weight.

  The aromatic polyester resin composition of the present invention may contain a non-fibrous filler within a range not departing from the object of the present invention. Examples of the non-fibrous filler include wollastonite, zeolite, and sericite. Silicates such as sight, kaolin, mica, clay, pyrophyllite, bentonite, talc, alumina silicate; oxides such as aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, zinc oxide, iron oxide; calcium carbonate And carbonates such as magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; nitrides such as silicon nitride, boron nitride and aluminum nitride; and glass flakes and glass beads, among which mica, clay, Talc, calcium carbonate, glass flakes and glass beads are preferred. The non-fibrous filler may be a surface treated with an isocyanate compound, a silane coupling agent, a titanate coupling agent, an epoxy compound, or the like.

  Furthermore, the aromatic polyester resin composition of the present invention is within a range not departing from the object of the present invention, various thermosetting resins, thermoplastic resins such as epoxy resins, cyanate ester resins, phenol resins, polyimides, silicone resins, One or more of polyolefin, polyphenylene oxide, polysulfone, polyarylene sulfide, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone, polyamide resin, polycarbonate resin and the like can be mixed and used.

  As a method for producing the aromatic polyester resin composition of the present invention, a conventionally used hot melt kneading method can be used. For example, a heat melt kneading method using a single screw or twin screw extruder, a kneader, a mill, a Brabender or the like can be mentioned, and a melt kneading method using a twin screw extruder excellent in kneading ability is particularly preferable. Moreover, the kneading | mixing temperature in this case is not specifically limited, Usually, it can select arbitrarily from 250-350 degreeC. The aromatic polyester resin composition of the present invention can be molded into an arbitrary shape using an injection molding machine, an extrusion molding machine, a transfer molding machine, a compression molding machine, or the like.

  Further, the aromatic polyester resin composition of the present invention is a conventionally known heat stabilizer, antioxidant, ultraviolet absorber, crystal nucleating agent, foaming agent, mold corrosion inhibitor within the range not departing from the object of the present invention. In addition, one or more additives such as flame retardants, flame retardant aids, colorants such as dyes and pigments, and antistatic agents may be used in combination.

  The aromatic polyester resin composition of the present invention includes a power module, various terminal boards, a generator, an electric motor, a transformer, a current transformer, a voltage regulator, a rectifier, an inverter, a multipolar rod, an electrical component cabinet, a light socket, and a plug. In particular, it can be suitably used for applications such as a capacitor sealing plate.

  The present invention provides an aromatic polyester resin composition having high tracking resistance and excellent in mechanical strength, mold releasability and appearance of a molded product, and the aromatic polyester resin composition Is particularly useful for electrical component applications such as electrical / electronic components or automotive electrical components.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention, this invention is not restrict | limited to these examples at all.

  Details of the aromatic polyester resin, ethylene-vinyl alcohol copolymer, inorganic filler, fibrous filler, and carnauba wax used in Examples and Comparative Examples are shown below.

<Aromatic polyester resin>
Aromatic polyester resin (A-1) (hereinafter simply referred to as PBT (A-1))
: BASF JAPAN, (trade name) Ultradur B4500, polybutylene terephthalate.

<Ethylene-vinyl alcohol copolymer>
Ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B-1) (hereinafter simply referred to as copolymer (B-1)): manufactured by Tosoh Corporation, (trade name) Mersen H6820, x = 0. 817, y = 0.021, z = 0.162, R is a methyl group.
Ethylene-vinyl alcohol copolymer (B-2) (hereinafter simply referred to as copolymer (B-2)): manufactured by Tosoh Corporation, (trade name) Mersen H6051, x = 0.802, y = 0, z = 0.198.
Ethylene-vinyl alcohol copolymer (B-3) (hereinafter simply referred to as copolymer (B-3)): Kuraray Co., Ltd., (registered trademark) EVAL F171B, x = 0.32, y = 0, z = 0.68.

<Magnesium hydroxide>
Surface untreated magnesium hydroxide (C1-1) (hereinafter simply referred to as magnesium hydroxide (C1-1)); manufactured by Martinsberg, (trade name) Magnifine H5; Mg (OH) ₂ content 99. 8% by weight, average particle size 0.8 μm, specific surface area 5.5 m ² / g.
Surface-treated magnesium hydroxide (C1-2) (hereinafter simply referred to as magnesium hydroxide (C1-2)); manufactured by Kyowa Chemical Industry Co., Ltd., (trade name) Kisuma 5P; Mg (OH) ₂ content 99 0.5% by weight, average particle size 0.7 μm, specific surface area 6.5 m ² / g, surface treatment: methacryloxysilane.
Calcium borate hydrate (C2-1) (hereinafter simply referred to as calcium borate (C2-1)); Kinsei Matec Co., Ltd. (trade name) UBP 3 micron product, average particle size 3 μm.
Hydrotalcite (C3-1) (hereinafter simply referred to as hydrotalcite (C3-1)); manufactured by Sakai Chemical Industry Co., Ltd., (trade name) STABIACE HT-1; (Mg _0.67 Al _{0. 33} (OH) ₂ ) (CO ₃ ²⁻ ) _0.167 · 3H ₂ O, average particle diameter 0.58 μm, BET specific surface area 10 m ² / g.
Hydrotalcite (C3-2) (hereinafter, simply referred to as hydrotalcite (C3-2)); Hydrotalcite (C3-1) is heat-treated to desorb and remove interlayer water (Mg _{0. 67} Al _0.33 (OH) ₂ ) (CO ₃ ²⁻ ) _0.167 .

<Fibrous filler>
Glass fiber (D-1); manufactured by NSG Vetrotex Co., Ltd. (trade name) RES03-TP91; fiber diameter 9 μm, fiber length 3 mm.

<Carnauba wax>
Carnauba wax (E1-1); Nikko Fine Products, (trade name) purified carnauba No. 1 powder.

Heat treatment of hydrotalcite Hydrotalcite (C3-1) is put into a blower constant temperature dryer (trade name: FC-610, manufactured by Advantech Co., Ltd.), heat treated at 220 ° C. for 5 hours, and interlayer water of hydrotalcite Was removed and hydrotalcite (C3-2) was obtained. By this heat treatment, the hydrotalcite (C3-1) was reduced by 11% by weight, and the interlayer water was removed.

  Evaluation and measurement methods used in Examples and Comparative Examples are shown below.

~ Measurement of tracking resistance ~
A disk-shaped test piece having a diameter of 50 mm and a thickness of 3 mm was produced by injection molding, and a comparative tracking index (hereinafter referred to as CTI) was measured using the test piece according to ICE112. A CTI exceeding 500 (V) was judged to be excellent in tracking resistance.

~ Measurement of bending strength ~
A test piece having a length of 127 mm, a width of 12.7 mm, and a thickness of 3.2 mm was prepared by injection molding, and the bending strength was measured using the test piece according to ASTM D-790 Method-1 (three-point bending method). did. The measuring device (trade name) AG-5000B (manufactured by Shimadzu Corporation) was used, and the test was performed under the test conditions of a distance between fulcrums of 50 mm and a measurement speed of 1.5 mm / min. A bending strength of 120 MPa or more was judged to be excellent in mechanical strength.

~ Mold releasability ~
The injection molding machine is mounted with a mold of a box-shaped product having a length of 120 mm, a width of 60 mm, a depth of 20 mm, and a thickness of 2 mm. Under the conditions, the engineering plastic composition was injected, and after cooling, the releasability of the box-shaped molded product from the mold core was evaluated. The state where it was possible to release from the mold core without any resistance was judged as ◯, the state where there was resistance but the time taken to release the mold was Δ, and the state where the resistance was large and time taken for release was judged as x. The state where the releasability was ○ was judged to be excellent.

~ Appearance of molded product ~
The same disk-shaped test piece as the measurement of tracking resistance was prepared, and the surface state of the test piece was visually observed. A case where the entire surface was glossy was evaluated as ◯, a portion where the surface was glossy was determined as Δ, and a case where the surface was not glossy was determined as ×. Those having a molded product appearance of ◯ were judged to be excellent in the molded product appearance.

Example 1
Blended in a ratio of 45.5% by weight of PBT (A-1), 9.0% by weight of copolymer (B-1) and 45.5% by weight of magnesium hydroxide (C1-1), and the cylinder temperature was 280 ° C. To a hopper of a twin screw extruder (manufactured by Toshiba Machine, (trade name) TEM-35-102B). On the other hand, the glass fiber (D-1) is put into the hopper of the side feeder of the twin-screw extruder, melted and kneaded at a screw rotational speed of 200 rpm, and the molten composition flowing out from the die is cooled and then cut. An aromatic polyester resin composition was prepared. The composition ratio of the aromatic polyester resin composition in that case is 20 parts by weight of copolymer (B-1), 100 parts by weight of magnesium hydroxide (C1-1), with respect to 100 parts by weight of PBT (A-1), It was 100 weight part of glass fiber (D-1).

  The aromatic polyester resin composition is put into a hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE75) heated to a cylinder temperature of 280 ° C., and CTI is measured to evaluate the appearance of the molded product. A disc-shaped test piece and a test piece for measuring the bending strength were respectively formed. Furthermore, mold releasability was evaluated. These results are shown in Table 1.

  The obtained aromatic polyester resin composition was excellent in CTI, bending strength, mold releasability, and molded product appearance.

Examples 2-6
PBT (A-1), copolymer (B-1,2,3), magnesium hydroxide (C1-1), magnesium hydroxide (C1-2), calcium borate (C2-1), hydrotalcite (C3-1), hydrotalcite (C3-2), glass fiber (D-1) and carnauba wax (E1-1), except that the blending ratios shown in Table 1 were used. An aromatic polyester resin composition was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  All the obtained aromatic polyester resin compositions were excellent in CTI, bending strength, mold releasability, and molded product appearance.

比較例１〜６
ＰＢＴ（Ａ−１）、共重合体（Ｂ−１）、水酸化マグネシウム（Ｃ１−１）、水酸化マグネシウム（Ｃ１−２）、ホウ酸カルシウム（Ｃ２−１）、及びガラス繊維（Ｄ−１）を表２に示す配合割合とした以外は、実施例１と同様の方法により組成物を作製し、実施例１と同様の方法により評価した。評価結果を表２に示した。
比較例１，２，３，５より得られた組成物はＣＴＩで劣り、比較例４，６より得られた組成物は曲げ強度で劣っていた。また、比較例３，４より得られた組成物は金型離型性で劣り、比較例４より得られた組成物は成形品外観でも劣っていた。

Comparative Examples 1-6
PBT (A-1), copolymer (B-1), magnesium hydroxide (C1-1), magnesium hydroxide (C1-2), calcium borate (C2-1), and glass fiber (D-1 ) Was prepared in the same manner as in Example 1 except that the blending ratio shown in Table 2 was used, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
The compositions obtained from Comparative Examples 1, 2, 3 and 5 were inferior in CTI, and the compositions obtained from Comparative Examples 4 and 6 were inferior in bending strength. Moreover, the composition obtained from Comparative Examples 3 and 4 was inferior in mold releasability, and the composition obtained from Comparative Example 4 was also inferior in molded product appearance.

  The aromatic polyester resin composition of the present invention has high tracking resistance, and is excellent in mechanical strength, mold releasability, and molded product appearance, and particularly in electrical / electronic parts or automotive electrical parts. It is expected to be used for electrical parts.

Claims (6)

Ethylene-vinyl which is an ethylene-fatty acid vinyl ester-vinyl alcohol copolymer and / or an ethylene-vinyl alcohol copolymer represented by the following general formula (1) with respect to 100 parts by weight of the aromatic polyester resin (A). alcohol copolymer (B) 1 to 50 parts by weight of magnesium hydroxide _{(C1), 2CaO · 3B 2} O 3 · 5H 2 hydrate of calcium borate represented by O (C2), hydrotalcite ( An aromatic polyester resin composition comprising 30 to 200 parts by weight of one or more inorganic fillers (C) selected from C3) and 30 to 200 parts by weight of a fibrous filler (D).

(Here, x and z both exceed 0, y is 0 or more, x + y + z = 1, and R is a hydrocarbon group having 1 to 10 carbon atoms.) Aromatic polyester resin (A) is polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4′-dicarboxylate, poly The aromatic polyester resin composition according to claim 1, wherein the aromatic polyester resin composition is one or more aromatic polyesters selected from cyclohexylenedimethylene terephthalate. Ethylene-fatty acid vinyl ester-vinyl alcohol in which the ethylene-vinyl alcohol copolymer (B) is x = 0.25 to 0.94, y = 0 to 0.15, z = 0.02 to 0.75 The aromatic polyester resin composition according to claim 1, wherein the aromatic polyester resin composition is a copolymer and / or an ethylene-vinyl alcohol copolymer. An ethylene-fatty acid copolymer in which the ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B) is x = 0.69 to 0.94, y = 0.01 to 0.15, and z = 0.02 to 0.30. It is a vinyl ester-vinyl alcohol copolymer, The aromatic polyester resin composition in any one of Claims 1-3 characterized by the above-mentioned. The aromatic according to any one of claims 1 to 4, further comprising 0.01 to 5 parts by weight of a release agent (E) per 100 parts by weight of the aromatic polyester resin (A). Polyester resin composition. The release agent (E) is one selected from the group consisting of carnauba wax (E1), polyethylene wax (E2), polypropylene wax (E3), stearic acid metal salt (E4), and acid amide wax (E5). The aromatic polyester resin composition according to claim 5, wherein the aromatic polyester resin composition is the above releasing agent.