JP2005232410A - Insulation material part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulation material electric/electronic part consisting of a flame retardant polyester resin material satisfying the revised IEC60335-1 standard. <P>SOLUTION: This insulation material part has a resin formed part formed by using a polyester resin composition containing (A) 100 pts. wt. polybutylene terephthalate resin, (B) 3-50 pts. wt. polyhalogenated benzyl (meth)acrylate, (C) 1-30 pts. wt. antimony pentoxide and (D) 0-200 pts. wt. inorganic filler, and is characterized in that the resin formed part directly supports a connected part through which a rated current of >0.2 A flows or is positioned within 3 mm distance from the connected part. The insulation material part of the electric/electronic instrument is aimed at the improvement of a resistance against ignition in operation and the spread of flame, therefore the safety of the insulation material part supporting the connected part having >0.2 A rated current and the electric insulation material in a distance within 3 mm from the connected part as the part of the instrument operated without having an operator is improved, and the part can be used widely. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an insulating material part made of polyester resin having flame retardancy and excellent electrical insulation. More specifically, the present invention relates to an insulating material part molded using a polybutylene terephthalate resin composition containing polyhalogenated benzyl (meth) acrylate and antimony pentoxide.

  In recent years, demands for electrical safety in electrical and electronic parts are becoming higher than before. For example, according to the recently revised IEC 60335-1 standard of the International Electrotechnical Commission (IEC), in household electrical products such as refrigerators and fully automatic washing machines, Among the parts, insulating material parts that support connection parts through which a current exceeding 0.2 A flows during normal operation, and electrically insulating material parts (printed circuit boards, terminals) within a distance of 3 mm from these connection parts The material of the base, plug, etc.) has a red-hot rod combustion index (abbreviation: GWFI) of 850 ° C. or higher and a red-hot rod ignition temperature (abbreviation: GWIT) of 775. I had to be satisfied that it was above ℃.

  Of course, these parts are already necessary for similar electrical and electronic parts, and underwriters laboratories (Underwriter's Laboratories Inc.) UL-94 flame retardancy and comparative tracking index (Comparative Tracking Index) In addition, requirements such as CTI) must be satisfied at the same time.

  In this way, in addition to flame retardancy and tracking resistance, strict regulations are provided for resistance to ignition and flame propagation, that is, electrical safety, and parts that satisfy all requirements in a well-balanced manner are required.

  By the way, polyester resins, especially polybutylene terephthalate resins (hereinafter sometimes abbreviated as “PBT resins”) are excellent in mechanical properties, electrical properties, heat resistance, and the like. It is used for many applications such as parts. In particular, since excellent flame retardancy can be easily obtained and at the same time excellent mechanical properties, it has been widely used as an insulating material for parts of electrical and electronic equipment that operate without an operator.

  Methods for imparting flame retardancy to polyester resins such as PBT resins include halogen-containing organic flame retardants such as halogenated aromatic bisimide compounds, halogenated polycarbonates, halogenated aromatic epoxy compounds, and halogenated benzyl acrylate, and trioxide A resin composition in which an inorganic flame retardant aid such as antimony, antimony pentoxide, aluminum hydroxide, magnesium hydroxide or the like is used in combination with a specific graft copolymer is known (for example, Patent Document 1). reference).

  In addition, a polyester resin, a halogen-containing compound selected from a halogenated aromatic epoxy compound, a halogenated aromatic bisimide compound, a halogenated benzyl acrylate, an antimony trioxide, an antimony pentoxide, an antimony halide, and the like having an average particle size of 1 μm or less In addition, a resin composition is known in which an antimony-based flame retardant aid is combined with a core-shell type compound having a multilayer structure (see, for example, Patent Document 2).

  In addition, a polyester resin is combined with a halogenated aromatic compound such as a brominated bisphenol epoxy resin and an alkali (earth) metal double salt of antimony pentoxide, and a polyhydric alcohol such as polyalkylene glycol is further added. A resin composition used in combination is known (see, for example, Patent Document 3).

  In addition, a resin composition in which a polyhalogenated (meth) acrylic resin, an antimony compound such as antimony trioxide and antimony pentoxide, and a hydrotalcite compound are used in combination with a polyester resin is known. (For example, refer to Patent Document 4).

  However, the flame retardancy test in the specific examples of these prior arts is mainly based on the above-mentioned UL standard, and as far as the present inventors know, in order to satisfy standard tests such as GWIT, GWFI, CTI, etc. Not reached.

Also known is polybutylene naphthalate in which a polyhalogenated benzyl (meth) acrylate and an antimony flame retardant aid are combined in order to improve the heat and moisture resistance of the flame retardant PBT resin (see, for example, Patent Document 5). ). However, polybutylene naphthalate has poor flowability compared to PBT resin and has a problem in moldability, and also has a problem in insulation due to aromaticity, so that it spreads to a wide range of uses like PBT resin. It has not reached.
JP-A-8-109320 JP-A-8-183896 JP-A-8-183877 JP-A-9-59475 JP-A-6-41406

  An object of the present invention is to provide an insulating material electrical and electronic component made of a flame-retardant polyester resin material that satisfies the revised IEC 60335-1 standard.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors combined a halogenated organic flame retardant polyhalogenated benzyl (meth) acrylate with a flame retardant auxiliary agent as an antimony pentoxide compound. In some cases, it has been found that a molded article having excellent flame retardancy and required characteristics such as GWFI and CTI can be obtained. This is a phenomenon peculiar to antimony pentoxide compounds. When antimony trioxide, which is most well known as a homologous compound, is used as a flame retardant aid, the above characteristics cannot be satisfied.

  Furthermore, even when antimony pentoxide compounds are used, when halogenated organic flame retardants are combined with brominated bisphenol epoxy resins (halogenated aromatic epoxy compounds), halogenated aromatic bisimide compounds, halogenated polycarbonates, etc. Similarly, it was found that the above characteristics could not be satisfied, and that the CTI characteristics were particularly inferior.

  Furthermore, it has also been found that when the low molecular weight fluororesin is contained in the PBT resin composition, the GWIT characteristics can be remarkably improved.

  Furthermore, in order to further improve GWIT of a thin insulating material part having a thickness of 2 mm or less, it has been found that the heat-resistant material is preferably disposed inscribed.

The present invention has been achieved based on the above findings, and the gist thereof is as follows.
(A) 3 to 50 parts by weight of (B) polyhalogenated benzyl (meth) acrylate with respect to 100 parts by weight of polybutylene terephthalate resin (C) 1 to 30 parts by weight of antimony pentoxide (D) 0 to 200 parts by weight of inorganic filler A resin molded part formed using a polyester resin composition containing parts, and the resin molded part directly supports a connection part through which a rated current exceeding 0.2 A flows, or from these connection parts Insulating material parts characterized by being within a distance of 3 mm.

  The present invention also resides in the above insulating material component in which a heat-resistant material is disposed in contact with a thin portion having a thickness of 2 mm or less in the resin molded portion.

  The present invention also resides in a contact electrical / electronic component selected from the group consisting of a relay, a switch, a connector, a sensor, an actuator, a microsensor, and a microactuator using the insulating material component.

  Insulating material parts for electrical and electronic equipment according to the present invention have improved resistance to ignition during operation and propagation of flames, and are parts of equipment that operate without an operator. Safety in parts with insulating materials supporting connections where rated current exceeds 0.2 A, that is, currents exceeding 0.2 A, and electrical insulating materials parts within a distance of 3 mm from these connections It can be used widely.

  In the present invention, (A) polybutylene terephthalate resin (PBT resin) means that terephthalic acid accounts for 50 mol% or more of all dicarboxylic acid components, and 1,4-butanediol accounts for 50 wt% or more of all diols. Say. The terephthalic acid preferably accounts for 80 mol% or more of the total dicarboxylic acid component, and more preferably 95 mol% or more. It is more preferable that 1,4-butanediol occupies 80 mol% or more of the total diol component, and it is even more preferable that 95 mol% or more. The intrinsic viscosity of the PBT resin is 0.50 or more, preferably 0 when measured at a temperature of 30 ° C. using a mixed solvent of 1,1,2,2-tetrachloroethane / phenol = 1/1 (weight ratio). 0.7 or more, while the upper limit is 3.0 or less, preferably 1.5 or less. If the intrinsic viscosity is less than 0.50, the mechanical strength is low, and if it is more than 3.0, molding becomes difficult. As the PBT resin of the present invention, two or more kinds of PBT resins having different intrinsic viscosities may be used in combination.

  Examples of dicarboxylic acid components other than terephthalic acid include phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, and 4,4′-diphenoxy. Aromatic dicarboxylic acids such as ethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid 1 Aliphatic dicarboxylic acids such as acids, aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, lower alkyl or glycol esters, etc. You may use a seed | species or 2 or more types together.

  Examples of diol components other than 1,4-butanediol include ethylene glycol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5 -Aliphatic diols such as pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1 , Cycloaliphatic diols such as 4-cyclohexanedimethylol, xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, etc. You may use together 1 type, or 2 or more types, such as aromatic diol.

  In the present invention, hydroxycarboxylic acids such as lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid, and alkoxycarboxylic acids. Monofunctional components such as acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid, tricarbaric acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane Trifunctional or polyfunctional components such as trimethylolpropane, glycerol and pentaerythritol can be used as the copolymerization component.

  In order to produce a polyester comprising the dicarboxylic acid or derivative thereof and a diol, any method is employed. For example, it is roughly classified into a direct polymerization method in which terephthalic acid and 1,4-butanediol are directly esterified and a transesterification method in which dimethyl terephthalate is used as a main raw material. The former is different in that water is produced in the initial esterification reaction, and the latter is produced in the initial transesterification reaction. The direct esterification reaction is advantageous from the viewpoint of raw material costs.

  Polyester production methods are broadly classified into batch methods and continuous methods, depending on the raw material supply or the polymer dispensing form. The initial esterification reaction or transesterification reaction is carried out in a continuous operation, and the subsequent polycondensation is carried out in a batch operation. Conversely, the initial esterification reaction or transesterification reaction is carried out in a batch operation, followed by polycondensation. There is also a method of performing the above by continuous operation.

  The (B) polyhalogenated benzyl (meth) acrylate used in the present invention is obtained by polymerizing a halogen-containing benzyl (meth) acrylate alone, copolymerizing two or more kinds, or copolymerizing with other vinyl monomers. The halogen atom is added to the benzene ring, and the addition number is in the range of 1 to 5, preferably 4 to 5, per benzene ring.

  Examples of the benzyl acrylate containing halogen include pentabromobenzyl acrylate, tetrabromobenzyl acrylate, tribromobenzyl acrylate, pentachlorobenzyl acrylate, tetrachlorobenzyl acrylate, trichlorobenzyl acrylate, and mixtures thereof. Examples of the benzyl methacrylate containing halogen include methacrylates corresponding to the above acrylates.

  Examples of vinyl monomers used for copolymerization with halogen-containing benzyl (meth) acrylates include acrylic acid esters such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and benzyl acrylate, methacrylic acid, and methyl. Methacrylic acid esters such as methacrylate, ethyl methacrylate, butyl methacrylate and benzyl methacrylate, unsaturated carboxylic acids such as styrene, acrylonitrile, fumaric acid and maleic acid or anhydrides thereof, vinyl acetate, vinyl chloride, etc. . These can usually be used in an equimolar amount or less, preferably 0.5 times the molar amount or less with respect to the benzyl (meth) acrylate containing halogen.

  Further, as the crosslinkable vinyl monomer, xylene diacrylate, xylene dimethacrylate, tetrabromoxylene diacrylate, tetrabromoxylene dimethacrylate, butadiene, isobrene, divinylbenzene, and the like can be used. 0.5 mol or less can be used with respect to benzyl acrylate or benzyl methacrylate containing.

  As the halogen, chlorine, bromine, iodine and the like can be used, but bromine is preferable in consideration of thermal stability, safety and flame retardancy. As a preferred polyhalogenated benzyl (meth) acrylate, polypentabromobenzyl acrylate is preferred because of its high bromine content. A compounding quantity is 3-50 weight part with respect to 100 weight part of PBT resin, Preferably it is 5-22.5 weight part, More preferably, it is 10-22 weight part. If the blending amount is less than 3 parts by weight, the effect of improving flame retardancy cannot be obtained, and if it exceeds 50 parts by weight, the mechanical properties of the polyester resin tend to be impaired, which is not preferable.

In the present invention, (C) antimony pentoxide is used as a flame retardant aid. (C) Sb ₂ O ₅ may be used alone as the antimony pentoxide, but an embodiment in which it is used as a double salt with other metal oxides is preferable because it is easy to obtain and blend. For example, it is preferable to use a double salt represented by the following general formula (1) or (2).

  More preferably, a double salt represented by the following general formula (3) can be used.

In the above formulas (1), (2), and (3), examples of X include lithium, sodium, potassium, and cesium, and examples of Y include calcium, magnesium, and barium. n is larger than 0, preferably 0.3 or more, particularly preferably in the range of 0.65 to 1.5. When n is less than 0.65, the desorption rate of adsorbed water is small, and thus the melt viscosity is likely to change. When n is larger than 1.5, the effect as a flame retardant aid is not exhibited due to the relative decrease in the amount of antimony. m is a number of 0 to 4, preferably 0 to 2, and exceeding 4 is not preferable because PBT is hydrolyzed. In particular, a one-to-one double salt of sodium oxide and antimony pentoxide represented by (Na ₂ O) _1.0 · Sb ₂ O ₅ is preferable from the viewpoint of hydrolysis resistance, such as NA-1070L manufactured by Nissan Chemical Co., Ltd. What is marketed with a brand name is mentioned.

In addition, as (C) antimony pentoxide of this invention, 2 or more types of compounds shown by Formula (1) and Formula (2) can also be mixed and used. In this case, in the above formula, n and m are determined independently. Further, antimony trioxide Sb ₂ O ₃ is known as a similar compound of antimony pentoxide. However, if this is used in combination with the present invention, the GWIT performance decreases, which is not preferable.

 (C) The compounding quantity of antimony pentoxide is 1-30 weight part with respect to 100 weight part of PBT resin, Preferably it is 5-10 weight part. When the amount is less than 1 part by weight, the flame retardant aid effect is not exhibited. If it exceeds 30 parts by weight, the blending effect is saturated and the mechanical strength of the resin molded member is lowered.

  The PBT resin composition of the present invention comprises (B) 3 to 50 parts by weight of polybenzyl halide (meth) acrylate and (C) 1 to 30 parts by weight of antimony pentoxide with respect to 100 parts by weight of (A) PBT resin. Although it contains as an essential component, (D) inorganic filler may be mix | blended as an arbitrary component especially when rigidity or dimensional stability is required. Moreover, when it is desired to further prevent dripping of the resin during combustion, (E) a dripping inhibitor may be blended.

  Examples of the inorganic filler (D) used in the present invention include fibrous materials, plate-like materials, granular materials, and mixtures thereof. Specifically, fibrous materials such as glass fibers, carbon fibers, mineral fibers, metal fibers, ceramic whiskers, wollastonite; plate-like materials such as glass flakes, mica, talc and / or layered silicates; silica, alumina, Well-known materials such as granular materials such as glass beads, carbon black and calcium carbonate can be mentioned. The criteria for these selections depend on the required properties of the product, but for mechanical strength and rigidity, fibrous materials, especially glass fibers, are selected, and when it is important to reduce the anisotropy and warpage of molded products, A material, especially mica, is selected. In addition, an optimum granular material is selected based on an overall balance in consideration of fluidity during molding.

  Examples of layered silicates include layered silicates, modified layered silicates (layered silicates with a quaternary organic onium cation inserted between the layers), layered silicates having a reactive functional group, or modified layered silicates. From the viewpoint of the dispersibility of the layered silicate in the resin composition of the present invention and the ability to prevent dripping, a modified layered silicate, a layered silicate added with a reactive functional group, or a modified layered silicate is preferable. A layered silicate or a modified layered silicate added with a reactive functional group such as a group, an oxazoline group, a carboxyl group, or an acid anhydride is preferably used. As a functional group imparting method, a method of treating with a functionalizing reagent (silane coupling agent) is simple and preferable.

  Examples of the functionalizing reagent include chlorosilanes having an epoxy group, chlorosilanes having a carboxyl group, chlorosilanes having a mercapto group, alkoxysilanes having an amino group, alkoxysilanes having an epoxy group, and the like. In particular, chlorosilanes having an epoxy group such as 3-glycidyloxypropyldimethylchlorosilane, β- (3,4-epoxycyclohexyl) ethyldimethylchlorosilane, 3-glycidyloxypropyltrichlorosilane, 3-aminopropyltriethoxysilane, N- Alkoxysilanes having amino groups such as (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane Alkoxysilanes having an epoxy group such as 3-glycidyloxypropyltrimethoxysilane and γ- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are preferred. The contact of the functionalizing reagent with the layered silicate is preferably carried out by mixing without solvent or in a polar solvent.

  Specific examples of the layered silicate used in the present invention include smectite clay minerals such as montmorillonite, hectorite, fluorine hectorite, saponite, beidellite, and subtinsite, Li type fluorine teniolite, Na type fluorine teniolite, and Na type four. Examples thereof include swelling synthetic mica such as silicon fluorine mica and Li-type tetrasilicon fluorine mica, vermiculite, fluorine vermiculite, halloysite, and the like, and any of natural products and synthetic products may be used. In particular, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, and Na-type tetrasilicon fluorine mica are preferable.

  Examples of the quaternary onium cation inserted between the layers of the modified layered silicate used in the present invention include trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethyltetradecylammonium, trimethylhexadecylammonium, trimethyloctadecylammonium and the like. Dimethyldialkylammonium such as trimethylalkylammonium, dimethyldioctylammonium, dimethyldidecylammonium, dimethyldidodecylammonium, dimethylditetraammonium, dimethyldihexadecylammonium, and dimethyldioctadecylammonium.

  When the layered silicate as described above is used, the silicate not only functions as an inorganic filler (D), but also serves as a secondary (E) function as an anti-dripping agent.

  (D) The compounding quantity of an inorganic filler is 0-200 weight part with respect to 100 weight part of PBT resin, What is necessary is just to determine a compounding quantity according to the level of required rigidity or dimensional stability. In some cases, for example, for the purpose of flexibility, an inorganic filler is not blended, but when blended, it is usually 5 to 120 parts by weight, more preferably 10 to 100 parts by weight. When it exceeds 200 parts by weight, the mechanical strength is lowered.

  In addition, the (E) anti-drip agent used in the present invention refers to a compound having the property of preventing the resin from dripping during combustion, and excludes those corresponding to the (D) inorganic filler. Specific examples thereof include silicon oil, fluorine (containing) resin, and the like. In particular, from the viewpoint of flame retardancy of the composition, a preferred anti-dripping agent is a fluorine-containing resin.

  (E) Examples of fluororesins used as anti-dripping agents include, for example, the specific gravity (SSG) of samples molded under the heat treatment conditions shown in ASTM D-1457-56T, the radioactive end group method and melting Examples include fluororesins having a number average molecular weight of 1 million or more, preferably 2 million or more, as determined from viscosity and a solution viscosity method at high temperature, and specific examples include polytetrafluoroethylene, tetrafluoroethylene / perfluoro. Examples thereof include fluorinated polyolefins such as alkyl vinyl ether copolymers, tetrafluoroethylene / hexafluoropropylene copolymers, tetrafluoroethylene / ethylene copolymers, vinylidene fluoride, and polychlorotrifluoroethylene. Polytetrafluoroethylene, tetrafluoroethylene / Perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, preferably tetrafluoroethylene / ethylene copolymer, polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer is more preferable.

  Moreover, (E) As a fluororesin used as a dripping prevention agent, what has a fibril formation ability is preferable. That is, it shows a tendency to easily disperse in the resin and to bond the polymers to form a fibrous material, and functions suitably as an anti-drip agent.

  These are commercially available, for example, as fine powders or molding powders. Specifically, “Polyflon FA-500”, “Polyflon F-201L” and “Polyflon M-18” from Daikin Chemical Industries, Ltd. “Freon CD-123” and “Freon G-190” by Asahi Glass Co., “Teflon (R) 6-J” and “Teflon (R) 7A-J” (Teflon is a registered trademark) by Mitsui and DuPont Fluorochemical, Dion “TF-2071”, “TF-1750”, etc.

(E) The melt viscosity at 350 ° C. of the fluororesin used as an anti-dripping agent is usually 1.0 × 10 ^{2 to} 1.0 × 10 ¹⁵ (Pa · s), preferably 1.0 × 10 ³ to 1. 0.0 × 10 ¹⁴ (Pa · s), more preferably 1.0 × 10 ^{10 to} 1.0 × 10 ¹² (Pa · s). When the melt viscosity is less than 1.0 × 10 ² (Pa · s), the drip prevention ability during combustion is insufficient, and when it is greater than 1.0 × 10 ¹⁵ (Pa · s), the fluidity of the composition Is significantly reduced.

  (E) Silicone oil is also preferable as the anti-dripping agent. Silicon oil is a compound having a dimethylpolysiloxane skeleton, and a part or all of the terminal or side chain is amino-modified, epoxy-modified, carboxyl-modified, carbinol-modified, methacryl-modified, mercapto-modified, phenol-modified, polyether-modified. It may be functionalized by methyl styryl modification, alkyl modification, higher fatty acid ester modification, higher alkoxy modification, and fluorine modification.

  (E) The viscosity of the silicone oil used as the anti-dripping agent is usually 1000 to 30000 (cs.), Preferably 2000 to 25000 (cs.), More preferably 3000 to 20000 (cs.) At 25 ° C. . When the viscosity is less than 1000 (cs.), The drip-preventing action during combustion is not sufficient, and the flame retardancy is lowered. When it is greater than 30000 (cs.), The fluidity of the composition is lowered due to the thickening effect. To do.

  In the flame-retardant PBT resin composition of the present invention, the content of the (E) anti-dripping agent is usually 0 to 15 parts by weight, preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the PBT resin. . (E) When content of a dripping inhibitor exceeds 15 weight part, there exists a possibility of causing the fall of fluidity | liquidity and a mechanical physical property.

  In the flame-retardant PBT resin composition of the present invention, it is preferable to contain a fluororesin having a molecular weight of less than 1 million as the component (F) because GWIT can be further improved. Examples of the fluororesin having a molecular weight of less than 1 million include the same resins as those mentioned in the section (E) Anti-dripping agent. Although the kind of preferable resin is the same, the most preferable is polytetrafluoroethylene. As a fluororesin having a molecular weight of less than 1 million, for example, “Lublon L-5” and “Lublon L-2” manufactured by Daikin Chemical Industries, Ltd. are commercially available. The content of the component (F) is usually 0 to 20 parts by weight, preferably 1 to 20 parts by weight with respect to 100 parts by weight of the PBT resin, and if it is less than 1 part by weight, the effect of improving GWIT is low, and 20 parts by weight. If it exceeds, the mechanical properties will decrease.

  The resin composition of the present invention is not limited to the components (A), (B), (C), (D), (E), and (F). Additives can be blended. For example, mold release agents such as paraffin wax, polyethylene wax, fatty acid (for example, stearic acid) and salts or esters thereof, silicone oil, etc .; and heat such as hindered phenols, phosphites, sulfur-containing ester compounds, etc. Stabilizers; crystallization accelerators; ultraviolet absorbers or weather resistance-imparting agents; dyes, pigments, foaming agents, etc.

  Various nylons such as nylon 6, nylon 66, nylon 12, nylon MXD6, various nylon elastomers, liquid crystal polymers, polycarbonate resins, polyester resins other than PBT resins (for example, polyethylene terephthalate, polybutylene naphthalate, etc.), polystyrene, ABS AS, MS and other styrene resins, various acrylic resins, polyethylene, polypropylene, olefin resins such as ethylene-propylene copolymers, fluorine resins such as polytetrafluoroethylene, and elastomers such as isobutylene-isoprene rubber, Styrene-butadiene rubber, styrene-butadiene rubber-styrene, ethylene-propylene rubber, acrylic elastomer, ionomer resin, phenoxy resin, polycaprolactam, etc. Lumpur resins, melamine resins, silicone resins may contain a thermosetting resin such as epoxy resin. Furthermore, a small amount of polyhydric alcohol or a derivative thereof, a hydrotalcite compound, an epoxy compound, or the like may be added to prevent contact corrosion.

  The polyester resin composition which is the raw material of the insulating material part of the present invention is composed of the components (A), (B), (C), (D), (E) and (F), and various additive components used as necessary. Can be obtained by blending and kneading. The blending is performed by a commonly used method, for example, a ribbon blender, a Hensell mixer, a drum blender, or the like. Various extruders, Brabender plastographs, lab plast mills, kneaders, Banbury mixers, etc. are used for melt-kneading. The heating temperature at the time of melt kneading is usually 230 to 290 ° C. In order to suppress decomposition during kneading, it is preferable to use the heat stabilizer. Each component including an additional component can be supplied to the kneader in a lump or can be supplied sequentially. In addition, two or more kinds of components selected from each component including an additional component can be mixed in advance. By adding a fibrous inorganic filler such as glass fiber after the resin is melted from the middle of the extruder, it can avoid crushing and exhibit high characteristics.

  The insulating material part of the present invention has a resin molded part formed using the above-mentioned flame retardant PBT resin composition, and the resin molded part has a current exceeding 0.2 A during normal operation, that is, 0. .Insulating material parts that directly support connections through which a rated current exceeding 2 A flows, or are within a distance of 3 mm from these connections. Thus, in the case of parts that require high electrical safety, the resin molded part formed using the above-mentioned flame-retardant PBT resin composition achieves a high GWFI value and a high GWIT, and is conventionally required It is preferable because requirements such as flame retardancy of UL standards and CTI can be satisfied.

  Here, “the resin molded part is at a distance of 3 mm or less from a connection part through which a current exceeding 0.2 A flows during normal operation” means that, for example, in the case of a relay part, the connection part is inside the resin molded part. This represents a case where a space of several millimeters is provided between the contact point and the resin molding part, instead of being in direct contact with the (contact point). Even in such a case, high electrical safety is still necessary, and the present invention is effective.

  In general, GWIT decreases as it becomes thinner. For example, when it has a thin resin molded part having a thickness of 2 mm or less, the GWIT is locally reduced in that part. In the insulating material part of the present invention, since the resin molded part is formed using the above-mentioned specific flame-retardant PBT resin composition, the GWIT of the thin part also has a high value, but means for further improving GWIT It is also effective to dispose a heat-resistant material plate or contact inside the resin molded portion. The heat-resistant material is preferably a metal or ceramic, and more preferably a metal having a melting point of 900 ° C. or higher, or a metal such as Cu, Au, Pt, Fe, Co, Ni, or Ti.

  The insulating material part of the present invention can be obtained by various known molding methods such as injection molding, hollow molding, extrusion molding, compression molding, calender molding, rotational molding, and the like, from the raw material obtained by the above-described method. A particularly preferable molding method is injection molding because of its good fluidity. In the injection molding, the resin temperature is preferably controlled to 240 to 280 ° C.

  The insulating material parts of the present invention molded by the above method are processed into electrical / electronic parts such as relays, switches, connectors, sensors, actuators, microsensors and microactuators by combining with metal contacts and copper plates. The

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded.

1. [Create specimen]
Various resin compositions were molded under the conditions of a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., model SH-100). The dimensions of the test piece are 10 cm in length and width, 3 mm in thickness; 10 cm in length and width, 0.5 mm in thickness, or any one of UL-94 standard stipulated in the thickness of 1/32 inch.

2. [Procurement of raw materials]
* Polyester resin (A) Polybutylene terephthalate resin (Mitsubishi Engineering Plastics, Nova Duran, [η] = 0.70)
* Halogen-based organic flame retardant (B-1) Polypentabromobenzyl acrylate (Bromochem Far East, PBBPA-FR1025)
(B-2) Tetrabromobisphenol A-tetrabromobisphenol A diglycidyl ether copolymer (manufactured by Sakamoto Pharmaceutical Co., Ltd., SR-T5000)
(B-3) Brominated polycarbonate oligomer (manufactured by Mitsubishi Gas Chemical Company, FR-53)
* Antimony compound (C-1) Sodium oxide and antimony pentoxide double salt (n = 1)
(Nissan Chemical Co., Ltd., Sun Epoch NA1070L)
(C-2) Double salt of sodium oxide and antimony pentoxide (n = 0.7)
(Nissan Chemical Co., Ltd., Sun Epoch NA1030)
(C-3) Antimony trioxide (Moroku 6)
* Inorganic filler (D) glass fiber (T187, manufactured by Nippon Electric Glass Co., Ltd.)
* Anti-dripping agent (E) Polytetrafluoroethylene (PTFE)
(Daikin Industries, Polyflon M-18, molecular weight 8 million)
(F) Polytetrafluoroethylene (PTFE)
(Daikin Industries, Lubron LA-5, molecular weight 300,000)

3. [Performance evaluation method]
(1) Flame Retardancy Test A test piece (thickness 1/32 inch) was subjected to a UL-94 standard vertical combustion test of Underwriter's Laboratories Inc. The flame retardancy level decreases in the order of V-0>V-1>V-2> HB.

(2) Comparative Tracking Index test (abbreviation: CTI rank test)
For the test piece (thickness 3 mm), the CTI rank was determined by the test method defined in UL-746A. This rank indicates the resistance to tracking at 600 V or lower when wet-contaminated with an electric field applied to the surface of the solid electrically insulating material. Rank 2 shows a resistance of 250 to 400V, and rank 3 shows a resistance of 175 to 250V. Therefore, the CTI rank has better characteristics as the number is smaller.

(3) Glow-wire Flamability Index test (abbreviation: GWFI test)
For the test piece (thickness 3 mm), the test method defined in IEC60695-2-12 was followed. That is, a red hot rod having a predetermined shape (a nickel / chromium (80/20) wire having an outer diameter of 4 mm in a loop shape) is brought into contact for 30 seconds and then pulled apart. It is defined as the maximum temperature at the tip that does not ignite during this time, or that extinguishes within 30 seconds after it is ignited. 850 ° C. or higher is required for flame retardant applications.

(4) Glow-wire Ignition Temperature test (abbreviation: GWIT test)
For various test pieces (3 mm thick flat plate and 0.5 mm thick flat plate with a 0.5 mm copper plate fixed to the back of the flat plate with a clip) according to the test method specified in IEC 60695-2-13 It was. That is, it is defined as a temperature that is 25 ° C. higher than the highest temperature at the tip that does not ignite when a red hot rod having a predetermined shape (a nickel / chromium (80/20) wire having an outer diameter of 4 mm in a loop shape) is contacted for 30 seconds. For flame retardant applications, 775 ° C. or higher is required as GWIT.

(5) Tensile test: Measured according to ISO527.
(6) Bending test: Measured according to ISO178.

[Example 1]
As shown in Table 1, (A) 100 parts by weight of PBT resin, (B-1) 13.5 parts by weight of halogenated flame retardant, (C-1) 8.5 parts by weight of antimony compound, (D) glass fiber 56. 7 parts by weight are mixed together with a super mixer (SK-350 type, manufactured by Shinei Machinery Co., Ltd.) and discharged using a twin screw extruder (TEX30HSST, manufactured by Nippon Steel Works, Ltd.) with L / D = 42. Extrusion was performed under the conditions of / h, screw rotation speed 150 rpm, barrel temperature 260 ° C. to obtain PBT resin composition pellets.

[Examples 2 to 4 and Comparative Examples 1 to 3]
A PBT resin composition was prepared in the same manner as in Example 1 except that the types and blending ratios of the components in Example 1 were changed as shown in Table 1, and various tests were conducted in the same manner.

  As shown in Table 1, flame retardancy, CTI rank, GWFI, GWIT and mechanical properties are good in a specific combination of (B-1) halogen flame retardant and (C-1) antimony compound. IEC 60335-1 conforms to insulating material parts that support connections through which current exceeding 0.2 A flows during normal operation and insulating material parts within 3 mm from these connections I understand that.

  Moreover, although GWIT fell by making a flat plate thin, GWIT of the flat plate made from the resin composition of this invention rose remarkably by arrange | positioning a metal plate behind a flat plate. Insulating material parts such as relays and connectors also have thin parts with a thickness of 2 mm or less, but the resin composition of the present invention can significantly improve the flame resistance of glow wires by placing a heat-resistant material inside. Can do.

  The molded article of the present invention is a part of a device that operates in a state where an operator is not attached to a household electric product such as a refrigerator or a fully automatic washing machine, and supports a connection portion through which a current exceeding 0.2 A flows during operation. Insulating material parts and electrical insulating material parts (printed circuit boards, terminal blocks, plugs, etc.) located within a distance of 3 mm from these connecting parts are adapted to improve electrical safety.

The molded article of the present invention is excellent in flame retardancy and has improved electrical safety, and can be used in the electrical / electronic equipment field, the automobile field, the machine field, and the like.

Claims (13)

(A) 3 to 50 parts by weight of (B) polyhalogenated benzyl (meth) acrylate with respect to 100 parts by weight of polybutylene terephthalate resin (C) 1 to 30 parts by weight of antimony pentoxide (D) 0 to 200 parts by weight of inorganic filler A resin molded part formed using a polyester resin composition containing parts, and the resin molded part directly supports a connection part through which a rated current exceeding 0.2 A flows, or from these connection parts Insulating material parts characterized by being within a distance of 3 mm.  The insulating material component according to claim 1, wherein (B) the polyhalogenated benzyl (meth) acrylate is polypentabromobenzyl acrylate.   The insulating material component according to claim 1 or 2, wherein (C) antimony pentoxide is blended as a double salt of antimony pentoxide and another metal oxide. (C) A double salt of antimony pentoxide and another metal oxide is represented by the following general formula (1) or (2).

(C) The insulating material component according to claim 4, wherein a double salt of antimony pentoxide and another metal oxide is represented by the following general formula (3).

 (D) An inorganic filler is glass fiber, The insulating material component as described in any one of Claims 1-5.   The polyester resin composition further comprises 0.01 to 15 parts by weight of (E) an anti-drip agent [excluding (D) inorganic filler] with respect to 100 parts by weight of (A) polybutylene terephthalate resin. The insulating material component according to any one of -6.   The polyester resin composition further comprises (F) 1 to 20 parts by weight of a low molecular weight fluororesin having a molecular weight of 1 million or less with respect to 100 parts by weight of (A) polybutylene terephthalate resin. The insulating material part according to one item.   The insulating material part according to any one of claims 1 to 8, wherein the resin molded portion has a thin portion having a thickness of 2 mm or less.   The insulating material component according to any one of claims 1 to 9, wherein a heat-resistant material is disposed in contact with a thin portion having a thickness of 2 mm or less in the resin molded portion.   The insulating material component according to claim 10, wherein the heat resistant material is plate-shaped.   The insulating material component according to claim 10 or 11, wherein the heat resistant material is a contact. A contact electrical / electronic component selected from the group consisting of a relay, a switch, a connector, a sensor, an actuator, a microsensor, and a microactuator using the insulating material component according to claim 1.