JP5412057B2 - Resin composition and electrical insulation component using the same - Google Patents

Description

The present invention relates to a resin composition that gives a molded article excellent in flame retardancy and electrical safety. Specifically, a polyalkylene terephthalate resin and a polystyrene-based resin, and further, a resin composition obtained by blending a polystyrene-based resin compatibilizer with the polyalkylene terephthalate resin and two non-halogen-based flame retardants, phosphorus-based and nitrogen-based, are included. Thus, in addition to flame retardancy and tracking resistance, a resin composition imparted with characteristics that are excellent in glow wire characteristics, and a flame retardant bleed-out molded at a high temperature formed using the resin composition. There are no electrical insulation parts.

In recent years, demands for electrical safety in electrical and electronic parts are becoming stricter than ever before. For example, according to the recently revised IEC 60335-1 standard of the International Electrotechnical Commission (abbreviated as IEC), in household electrical products such as refrigerators and fully automatic washing machines, equipment that operates without an operator attached. Among the components, electrical insulation components that support connections where a rated current exceeding 0.2 A flows during normal operation, and electrical insulation components (printed circuit boards, terminals) within a distance of 3 mm from these connections The material of the base, plug, etc. is that the red-hot rod burning index (GWFI) is 1.5 mm thick and 850 ° C. or higher, and the red-hot rod ignition temperature (Glow-wire Ignition Temperature). , Abbreviation: GWIT) be satisfied is required to be at 775 ° C. or more 0.8~3mm thickness. More desirably, GWFI satisfies 960 ° C. or higher, and GWIT satisfies 0.8 to 3 mm thickness and 800 ° C. or higher.

Of course, these components are already required for similar electrical and electronic components, such as Underwriters Laboratories Inc., UL-94 flame retardancy and tracking index (Comparative Tracking Index), Requirements such as CTI) or Proof Tracking Index (PTI) must be satisfied at the same time. That is, it is necessary to satisfy flame retardancy of V-2 or more at a thickness of 0.8 mm and 550 V or more in PTI (or CTI). Preferably, the flame retardancy is V-0 and the PTI (or CTI) is required to be 600V or higher.

In this way, electrical and electronic parts have strict regulations regarding resistance to ignition and flame propagation, that is, electrical safety, in addition to flame resistance and tracking resistance. Well-filled parts are required.

By the way, polyalkylene terephthalate resins, especially polybutylene terephthalate resin (hereinafter sometimes abbreviated as PBT resin) and polyethylene terephthalate resin (hereinafter sometimes abbreviated as PET resin) are mechanical properties, electrical properties. In recent years, it has been used in many applications such as electrical equipment parts and machine parts. In particular, since excellent flame retardancy is easily obtained and at the same time excellent mechanical properties, it is also used as an insulating material for parts of electrical and electronic equipment that operate without the above-mentioned operator. I came.

It is well known that when a halogen-based flame retardant is blended with a polyalkylene terephthalate resin such as a PBT resin, V-0, which is the highest evaluation in the UL-94 standard, can be reached. However, characteristics such as tracking characteristics and glow wire characteristics (hereinafter sometimes referred to as “electric safety”) are based on UL-94 standard flame resistance (hereinafter simply referred to as “flame resistance”), which is known as an evaluation of flame resistance. Is an index that is evaluated in a completely different manner. While the flame retardancy of UL-94 indicates “incombustibility” when a burner flame is brought into contact, GWFI and GWIT are glow wires as defined in the revised IEC 60335-1 standard. It is an index for evaluating the ignitability at high temperature by, and it relates to a completely different property. Moreover, even in the case of V-0, which is the highest evaluation in the UL-94 standard, the electrical safety may be insufficient. Since safety may be shown, electrical safety cannot be predicted from the evaluation of flame retardancy of UL-94.

For example, Patent Documents 1 and 2 disclose a polyester resin composition excellent in electrical safety using a halogen-based flame retardant. Although it has been shown that GWFI and GWIT pass the above standard at a thickness of 3 mm, the experiments by the present inventors have revealed that the test does not pass the GWIT standard particularly at a thickness of 1.5 mm or less. In recent years, molded products using such halogen-based flame retardants have the potential to adversely affect the environment if they are incinerated after use. Is required.

As non-halogen flame retardants for polyester resins, phosphazene compounds (sometimes referred to as phosphonitrile compounds) have been known (see, for example, Patent Documents 3 to 7). It is also known to use a nitrogen-based flame retardant together with a phosphazene compound. For example, Patent Document 4 discloses that (B) a phosphonitrile linear polymer and / or a cyclic polymer having a repeating unit of the general formula (1) and / or a cyclic polymer of 0.5 to 100 parts by weight per 100 parts by weight of the thermoplastic resin (B). And (C) a flame retardant resin composition comprising a compound represented by formula (2) and 0.5 to 100 parts by weight of a salt comprising cyanuric acid or isocyanuric acid.

And in an Example, when the said 2 types of flame retardant is mix | blended with PBT resin, it is shown that the outstanding flame retardance called V-0 is reachable. However, as other physical properties, only mechanical properties and hydrolysis resistance are shown, and there is no disclosure about electrical safety. The blending amounts of the phosphazene compound and melamine cyanurate to the resin are 11.0 to 17.4% by weight and 8 to 12% by weight, respectively, and the blending ratio is phosphazene / melamine cyanurate = 1.17 to 1. 96, more phosphazene compounds.

Furthermore, Patent Document 5 describes blending a phosphazene compound and a polyphenylene oxide compound as a flame retardant into a polyalkylene terephthalate resin. Further, it is also described that a styrene resin or a nitrogen-based flame retardant is added as a further flame retardant. However, in Patent Document 5, when a phosphazene compound and a polyphenylene oxide resin are combined to form a flame retardant, the polyalkylene terephthalate resin can be made highly flame retardant and the flame retardant bleeds out of the molded product (bleed out). However, as with Patent Document 4, there is no description of electrical safety, only that the metal corrosivity and the moldability at the time of injection molding (mold deposit) can be greatly improved. Moreover, the compounding quantity ratio of the phosphazene compound and nitrogen-containing compound (such as melamine cyanurate) in the examples is 1.47 to 10, and the phosphazene compound is considerably more.

Patent Document 6 describes blending a phosphazene compound and a phenol resin as a flame retardant into a resin component composed of a polyalkylene terephthalate resin and a styrene resin. And that

Describes that the presence of a phenolic resin suppresses a decrease in the molecular weight and mechanical properties of the polyalkylene terephthalate resin and can make the polyalkylene terephthalate resin highly flame-retardant compared to the case where the phosphazene compound is used alone. Yes. Further, it is also described that a carbonized resin or a nitrogen-based flame retardant is added as a further flame retardant. However, Patent Document 6 only shows evaluation results of flame retardancy, bleed-out of flame retardant (bleed out) mechanical strength, and kneadability, and does not describe electrical safety.

Patent Document 7 describes a flame retardant resin composition comprising a resin component comprising a polyester resin, a polyphenylene ether resin and / or a polyphenylene sulfide resin and a phosphazene compound or melamine cyanurate. However, as the physical properties of this resin composition, only mechanical properties, hydrolysis resistance, melt viscosity and the like are shown, and there is no description about electrical safety.

As described above, a number of flame retardant resin compositions in which a phosphazene compound and another flame retardant are blended as a flame retardant with a polyalkylene terephthalate resin have been proposed, but the electrical properties of these flame retardant resin compositions have been proposed. There is no information regarding safety. Further, according to the knowledge of the present inventors, when a polyphenylene ether resin or a phenol resin is blended with a polyalkylene terephthalate resin as in Patent Documents 5 to 7, tracking characteristics are drastically lowered.

JP 2005-232410 A JP 2006-45544 A Japanese Patent Laid-Open No. 51-36266 JP 7-216235 A JP 2003-82211 A JP 2003-82210 A JP-A-10-77396

An object of the present invention is to provide a molded product that satisfies the electrical safety such as the glow wire property and tracking property of the revised IEC 60335-1 standard, and suppresses the bleed out of the flame retardant, without using a halogen-based flame retardant. It is in providing the resin composition to give. Another object of the present invention is to provide a resin composition that is substantially free of any of a polyphenylene ether resin, a polyphenylene sulfide resin, and a phenolic resin, which is used in combination when a phosphazene compound is used as a flame retardant in the above patent document. It is to provide. Still another object is to provide a contacted electrical / electronic component using the resin composition.

As a result of intensive studies to solve the above problems, the present inventors have found that a polyalkylene terephthalate resin and a polystyrene resin, and further, a resin component obtained by blending a compatibilizer for polystyrene resin with this, a flame retardant A resin composition obtained by blending a specific amount of a phosphorus compound such as a phosphazene compound or a phosphinate, a nitrogen compound such as a salt of a melamine, and zinc borate is surprisingly GWIT, GWFI, PTI. It has been found that an electrical insulation component that satisfies the required characteristics of strict standards related to electrical appliances and the like, and that suppresses the bleed-out of the flame retardant is provided.

The present invention has been achieved based on the above findings, the gist of which is as follows:
(A-1) Polyalkylene terephthalate resin 40-96.5 parts by weight
(A-2) Polystyrene resin 3.5-50 parts by weight and (A-3) Compatibilizer The following flame retardant (B) with respect to 100 parts by weight of resin component (A) consisting of 0-10 parts by weight
(B-1) Phosphorus flame retardant selected from the group consisting of phosphazene compounds and phosphinates 10 to 60 parts by weight (B-2) Nitrogen flame retardant 20 to 70 parts by weight consisting of a salt of an amino group-containing triazine
(B-3) Boric acid metal salt 0-20 parts by weight (however, the total of these flame retardants is 40-100 parts by weight) and
(C) Inorganic filler 0 to 200 parts by weight, and any of polyphenylene ether resin, polyphenylene sulfide resin, and phenolic resin (except for epoxy group-containing novolak epoxy resins that act as compatibilizers) Is contained in the resin composition, which is at most 1% by weight or less.

Another aspect of the present invention has a molded part formed using this resin composition, and the molded part directly supports a connection part through which a rated current exceeding 0.2 A flows, Or it exists in the electrical insulation component characterized by forming the part in the distance within 3 mm from these connection parts.

The resin composition of the present invention provides an electrically insulating component with improved resistance to ignition and flame propagation during operation. Therefore, in parts of equipment that operates in the absence of an operator, a current exceeding 0.2 A flows during normal operation, i.e. an electrically insulating part supporting a connection with a rated current exceeding 0.2 A, and It can be widely used as a material for an electrical insulating component having a portion within a distance of 3 mm from these connecting portions.

The present invention is described in detail below.
The (A) resin component of the present invention comprises (A-1) a polyalkylene terephthalate resin, (A-2) a polystyrene-based resin, and (A-3) a compatibilizing agent.

(A-1) Polyalkylene terephthalate resin With polyalkylene terephthalate resin, terephthalic acid accounts for 50 mol% or more of the total dicarboxylic acid component, and ethylene glycol or 1,4-butanediol is 50% by weight of the total diol. It refers to a resin that occupies at least%. Terephthalic acid preferably accounts for 80 mol% or more of the total dicarboxylic acid component, more preferably 95 mol% or more. Ethylene glycol or 1,4-butanediol preferably accounts for 80 mol% or more of the total diol component, and more preferably 95 mol% or more. In the present invention, as the polyalkylene terephthalate resin, terephthalic acid accounts for 95 mol%, particularly 98 mol% or more of the total dicarboxylic acid component, and ethylene glycol or 1,4-butanediol is 95 wt% of the total diol. It is preferable to use polyethylene terephthalate, polybutylene terephthalate or a mixture thereof occupying the above.

The intrinsic viscosity of the polyalkylene terephthalate resin is 0.50 or more when measured at a temperature of 30 ° C. using a mixed solvent of 1,1,2,2-tetrachloroethane / phenol = 1/1 (weight ratio), preferably Is 0.6 or more and 3.0 or less, preferably 1.5 or less. When the intrinsic viscosity is less than 0.50, the mechanical strength of the resulting resin composition is low. Conversely, when the intrinsic viscosity is more than 3.0, the moldability of the resin composition is significantly deteriorated. In addition, as polyalkylene terephthalate resin, you may use together 2 or more types of polyalkylene terephthalate resin from which intrinsic viscosity differs.

Examples of dicarboxylic acid components other than terephthalic acid constituting the polyalkylene terephthalate resin include phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4′-diphenoxyethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid Commonly used aliphatic dicarboxylic acids such as alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc. Can be used.

Examples of diol components other than ethylene glycol or 1,4-butanediol include 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 , 4-cyclohexane dimethylol and other alicyclic diols, xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, etc. And aromatic diols are used. Even if ethylene glycol or butylene glycol is used, diethylene glycol or dibutylene glycol may be by-produced during the reaction and incorporated into the polyalkylene terephthalate.

  Further, if desired, hydroxycarboxylic acids such as lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid, alkoxycarboxylic acids, Monofunctional components such as stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid, tricarbaric acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane, trimethyl Trifunctional or higher polyfunctional components such as methylolpropane, glycerol and pentaerythritol can also be used as a copolymerization component. These copolymer components are preferably used in an amount of 5% by weight, particularly 3% by weight or less of the polyalkylene terephthalate to be produced.

Production of polyalkylene terephthalate from dicarboxylic acid or its derivative and diol can be carried out by any conventional method. That is, any of a direct polymerization method in which terephthalic acid and glycol are directly esterified and a transesterification method in which dimethyl terephthalate is used as a main raw material can be used. 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 polymerization method is advantageous from the viewpoint of raw material costs.

Either a batch method or a continuous method can be used. The initial esterification reaction or transesterification reaction is performed in a continuous operation, and the subsequent polycondensation is performed in a batch operation. Conversely, the initial esterification reaction or The transesterification reaction can be carried out by a batch operation, and the subsequent polycondensation can be carried out by a continuous operation.

In the present invention, a polybutylene terephthalate resin having a terminal carboxyl group amount of 30 eq / t or less and a residual tetrahydrofuran amount of 300 ppm (weight ratio) or less, or a mixture of such a polybutylene terephthalate resin and a polyethylene terephthalate resin is used. It is preferable to use it.

When a polybutylene terephthalate resin having a terminal carboxyl group amount of 30 eq / t or less is used, the hydrolysis resistance of the resulting resin composition can be enhanced. That is, the carboxyl group acts as an autocatalyst for the hydrolysis of polybutylene terephthalate. Therefore, if a terminal carboxyl group exceeding 30 eq / t is present, the hydrolysis starts early, and the generated carboxyl group becomes an autocatalyst. As a result, hydrolysis proceeds in a chain and the degree of polymerization of polybutylene terephthalate rapidly decreases. However, if the amount of terminal carboxyl groups is 30 eq / t or less, early hydrolysis can be suppressed even under conditions of high temperature and high humidity. The amount of terminal carboxyl groups of polybutylene terephthalate can be determined by dissolving polybutylene terephthalate in an organic solvent and titrating with an alkali hydroxide solution.

The amount of residual tetrahydrofuran in polybutylene terephthalate is preferably 300 ppm (weight ratio), particularly 200 ppm (weight ratio) or less. A resin composition using a polybutylene terephthalate resin having a large amount of residual tetrahydrofuran generates a large amount of organic gas at a high temperature. However, a molded product obtained from a resin composition using polybutylene terephthalate having a residual tetrahydrofuran amount of 300 ppm (weight ratio) or less generates little organic gas even when used at a high temperature, and therefore may cause corrosion of electrical contacts. Therefore, it can be suitably used for contacted electrical / electronic parts such as relay parts.

The lower limit of the residual tetrahydrofuran amount is not particularly limited, but is usually about 50 ppm (weight ratio). A smaller amount of residual tetrahydrofuran tends to reduce the generation of organic gas, but the residual amount and the amount of gas generated are not necessarily proportional, and the presence of about 50 ppm of tetrahydrofuran does not pose a problem for normal use. Rather, the presence of a small amount of diol is known to suppress corrosion of electrical contacts (Japanese Patent Laid-Open No. 8-20900), and similar effects are expected for tetrahydrofuran. The amount of residual tetrahydrofuran can be determined by immersing pellets of polybutylene terephthalate in water and holding at 120 ° C. for 6 hours, and quantifying the amount of tetrahydrofuran eluted in water by gas chromatography.

Polystyrene resin As the polystyrene resin, any thermoplastic resin may be used, such as an aromatic vinyl monomer homo- or copolymer, aromatic vinyl monomer and vinyl cyanide monomer or rubber. (For example, a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer, a polymer obtained by graft copolymerization of an aromatic vinyl monomer and a rubber component, a rubber component) A non-crystalline rubber-like polymer obtained by graft copolymerization of an aromatic vinyl monomer and a vinyl cyanide monomer is used. Further, modified polystyrene obtained by modifying these with an epoxy compound, or those obtained by bonding other polymer chains and polystyrene chains in various manners can also be used.

Examples of aromatic vinyl monomers include styrene and alkylstyrene (for example, vinyl toluenes such as o-, m-, and p-methylstyrene, vinylxylenes such as 2,4-dimethylstyrene, ethylstyrene, p- Alkyl-substituted styrenes such as isopropyl styrene, butyl styrene, p-t-butyl styrene), α-alkyl-substituted styrene (for example, α-methyl styrene, α-ethyl styrene, α-methyl-p-methyl styrene, etc.) Used. These styrenic monomers can be used alone or in combination of two or more. Of these, styrene, vinyltoluene or α-methylstyrene is preferably used, and styrene is particularly preferably used.

As the vinyl cyanide monomer, for example, (meth) acrylonitrile is used. Vinyl cyanide monomers can also be used alone or in combination of two or more. A preferred vinyl cyanide monomer is acrylonitrile.

Examples of the rubber component include conjugated diene rubber (polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, etc.), olefin rubber [ Ethylene-propylene rubber (EPDM rubber), ethylene-vinyl acetate copolymer, acrylic rubber and the like can be used, and these rubber components may be hydrogenated products. These rubber components can be used in combination of two or more. Of these rubber components, conjugated diene rubbers are preferred. The rubber component can be used regardless of the gel content. The rubber component can be produced by a method such as emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, solution-bulk polymerization, bulk-suspension polymerization.

The polystyrene-based resin may be used in combination with other copolymerizable monomers in addition to vinyl cyanide or instead of vinyl cyanide. Examples of such copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, Esters of (meth) acrylic acid such as octyl (meth) acrylate and 2-ethylhexyl (meth) acrylate and alcohols having 1 to 18 carbon atoms, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 2 -Hydroxyl group-containing (meth) acrylates such as hydroxypropyl, and epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate.

Also, carboxyl group-containing monomers [for example, unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; aliphatic unsaturated dicarboxylic acids such as maleic anhydride, maleic acid, fumaric acid and itaconic acid, and anhydrides thereof Products; maleic acid monoesters (monoesters of maleic acid and monohydric alcohols such as monomethyl maleate, monoethyl maleate and monobutyl maleate) and unsaturated dicarboxylic acids such as fumaric acid monoesters corresponding thereto Monoesters, etc.], maleimide monomers [eg, N-alkylmaleimides such as maleimide and N-methylmaleimide, N-phenylmaleimides, etc.]. These copolymerizable monomers can be used alone or in combination of two or more. Preferred copolymerizable monomers include (meth) acrylic acid esters (particularly methyl methacrylate), (meth) acrylic acid, maleic anhydride, maleimide monomers, and the like.

When another copolymerizable monomer is used in combination with the aromatic vinyl monomer, the ratio (weight ratio) between the two is aromatic vinyl monomer / other copolymerizable monomer = 100 / 0-10. / 90, preferably 95/5 to 10/90, more preferably about 80/20 to 20/80. The more aromatic vinyl monomer is, the greater the bleed-out suppression effect of the flame retardant is. On the other hand, although related to the degree of dispersion of the polystyrene resin in the resin composition, if the aromatic vinyl component is large, the resin composition tends to be carbonized, and the tracking property and the glow wire characteristic tend to be lowered.

More specifically, when vinyl cyanide monomer is used as a copolymerization component, the ratio (weight ratio) of aromatic vinyl monomer to vinyl cyanide monomer is aromatic vinyl monomer / cyan. Vinyl chloride monomer = 10/90 to 90/10, preferably about 20/80 to 80/20.

When the rubber component is used, the ratio (weight ratio) between the rubber component and the aromatic vinyl monomer is as follows: rubber component / aromatic vinyl monomer = 5 / 95-80 / 20, preferably 10 / 90-70 / About 30. When the ratio of the rubber component is small, the impact resistance of the resin composition is lowered, and when it is too large, the polystyrene resin is poorly dispersed and the appearance is liable to be impaired.

Preferred polystyrene resins include polystyrene (GPPS), acrylonitrile-styrene copolymer (AS resin), high impact polystyrene (HIPS), graft polymer [acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile- Acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-ethylene-propylene rubber-styrene copolymer (AES resin), acrylonitrile-butadiene rubber-methyl methacrylate-styrene copolymer (ABSM resin), methyl methacrylate- Butadiene-styrene copolymer (MBS resin, etc.)], block copolymer [for example, styrene-butadiene-styrene (SBS) copolymer, styrene-isoprene-styrene (SIS) copolymer, styrene-ethylene-butyl copolymer) Len - styrene (SEBS) copolymer, etc.), styrene - acrylonitrile - ethylene - propylene - ethylidene norbornene copolymer (AES), etc.], or the like of these hydrogenated products thereof.

Particularly preferred polystyrene resins include polystyrene (GPPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and styrene-ethylene-butylene-styrene (SEBS) copolymer. More preferred are polystyrene (GPPS) and acrylonitrile-styrene copolymer (AS resin). These polystyrene resins can be used alone or in combination of two or more.

Of the polystyrene resins, epoxy-modified polystyrene resins are preferable because they have good dispersibility and simultaneously improve the hydrolysis resistance of the resulting resin composition. The epoxy-modified polystyrene resin is a resin in which an epoxy group is introduced into a polystyrene resin. As a method for introducing the epoxy group, any conventionally known method can be used. Specifically, a styrene resin obtained by graft polymerization or copolymerization of an epoxy group-containing vinyl monomer is preferably used. Epoxy group-containing vinyl monomers are compounds that share both radically polymerizable vinyl groups and epoxy groups in one molecule. Specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and itaconic acid. Examples thereof include glycidyl esters of unsaturated organic acids such as glycidyl, glycidyl ethers such as allyl glycidyl ether, and the aforementioned derivatives such as 2-methylglycidyl methacrylate. Among them, glycidyl acrylate and glycidyl methacrylate are preferably used. These may be used alone or in combination of two or more.

As a method for producing a styrene resin obtained by graft polymerization or copolymerization of an epoxy group-containing vinyl monomer, a known method can be adopted. In particular, styrene or styrene and other monomers copolymerizable therewith A method of copolymerizing an epoxy group-containing vinyl monomer, an epoxy group-containing vinyl monomer in a (co) polymer obtained by copolymerizing styrene or styrene and other monomers copolymerizable therewith The method of graft-polymerizing a body is mentioned. Furthermore, a polymer compound having a structure obtained by block copolymerization or graft copolymerization of a polymer composed of a copolymerizable unsaturated monomer containing an epoxy group with polystyrene, a comb-type polystyrene having an epoxy group added thereto, and an epoxy group added thereto. Examples thereof include polystyrene. Such copolymerization and graft polymerization can also be performed by known methods.

Preferable specific examples of the styrene resin used as a base when the epoxy group-containing vinyl monomer is graft-polymerized or copolymerized with the polystyrene resin by a radical generator or the like are polystyrene (GPPS), impact-resistant polystyrene. Resin mainly composed of styrene such as (HIPS), acrylonitrile / styrene copolymer (AS resin), styrene / (meth) acrylate copolymer, styrene copolymer such as styrene / butadiene resin, styrene / butadiene / Styrene resin, styrene / isoprene / styrene resin, block copolymer containing styrene such as styrene / ethylene / butadiene / styrene resin, acrylonitrile / butadiene / styrene resin, acrylonitrile / butadiene / methyl methacrylate / styrene resin, etc. ABS resin, and the like. Of these, resins mainly composed of styrene and styrene copolymers are preferred, and acrylonitrile / styrene copolymers are most preferred.

The copolymer structure of the polymer having an epoxy group and the polystyrene-based polymer is not particularly limited. For example, it is a polymer composed of a copolymerizable unsaturated monomer containing an epoxy group in the main chain. Comb-shaped polymer compound having a chain of polystyrene, polymer compound of a copolymerizable unsaturated monomer containing an epoxy group and a polymer compound having a linear structure obtained by block copolymerization of polystyrene, and the main chain is polystyrene. Comb-shaped polymer compound that is a polymer composed of a copolymerizable unsaturated monomer having an epoxy group in the side chain, and a comb-shaped structure in which the main chain is polystyrene containing an epoxy group and the side chain is polystyrene. And high molecular weight compounds, polystyrene with a small amount of epoxy group added, and the like.

Among them, a polymer composed of a copolymerizable unsaturated monomer containing an epoxy group in the main chain and a polymer compound having a comb structure in which the side chain is polystyrene, and a polystyrene containing an epoxy group in the main chain. In particular, a high molecular compound having a comb structure in which the side chain is polystyrene, and a modified polystyrene to which a small amount of epoxy group is added, particularly a polymer composed of a copolymerizable unsaturated monomer containing an epoxy group in the main chain, A comb-shaped polymer compound in which the side chain is polystyrene is preferable. These polystyrene-based resins containing epoxy groups may be a blend of a plurality of types.

The epoxy group in the epoxy-modified polystyrene resin has an effect of improving the compatibility between the polyalkylene terephthalate resin and the epoxy-modified styrene resin. The amount of the epoxy group in the epoxy-modified polystyrene resin is not particularly limited as long as it is an amount effective for exhibiting this action, but is not limited as an epoxy group-containing monomer component in the epoxy-modified polystyrene resin. It is preferably at least 05% by weight. When copolymerized in a large amount, there is a tendency for fluidity and gelation. Although it depends on the content of the epoxy group-containing monomer, the proportion of the epoxy-modified polystyrene resin in the resin component (A) is preferably 45% by weight or less, more preferably 40% by weight or less.

Two or more of these epoxy-modified polystyrene resins can be used in combination. Further, an epoxy-modified polystyrene resin and a polystyrene resin not containing an epoxy group can be used in combination, and according to this method, the content of the epoxy group of the polystyrene resin can be easily adjusted. .

In the present invention, the styrene component (styrene residue) content of the epoxy-modified polystyrene resin is preferably 50% by weight or more, more preferably 70% by weight in the case of the above-mentioned polystyrene resin mainly composed of styrene. In the case of a styrene copolymer, it is preferably 30% by weight or more, more preferably 50% by weight or more, and particularly preferably 60% by weight or more. In the case of an ABS resin, it is preferably 30% by weight or more, more preferably 40% by weight or more, and in the case of a block copolymer, it is 10% by weight or more, more preferably 20% by weight or more.

Compatibilizer <br/> polystyrene resin is required to disperse into fine particles during the polyalkylene terephthalate resin, the dispersion state gives a subtle effect on the flame retardancy and tracking characteristics of the resulting resin composition . However, polystyrene resins that do not have a reactive group with a polyalkylene terephthalate resin such as an epoxy group are often difficult to disperse well. However, when a mechanically strong shearing force is applied in order to promote dispersion when the resin composition is produced, there is a possibility that troubles such as decomposition of the flame retardant occur due to heat generation. Therefore, it is preferable to add a small amount of a compatibilizing agent to promote dispersion. A preferable compatibilizer includes an epoxy compound. Examples of the epoxy compound include a bisphenol type epoxy compound, a resorcinol type epoxy compound, a novolac type epoxy compound, an alicyclic compound type diepoxy compound, a glycidyl ether, an epoxidized polybutadiene, an epoxy-modified thermoplastic resin, and an epoxy flame retardant. In addition, the novolak-type epoxy compound used as a compatibilizing agent has a low molecular weight unlike the novolak-type phenol resin used as a molding material.

Specifically, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, resorcinol type epoxy compounds, novolac type epoxy compounds, alicyclic compound type epoxy compounds such as vinylcyclohexene dioxide and dicyclopentadiene oxide, and ethylene-glycidyl methacrylate Polymer, tetrabromobisphenol A epoxy oligomer, and the like. From the viewpoint of hydrolysis resistance and dispersion in the resin, a novolac type epoxy resin having an epoxy equivalent of 150 to 280 g / eq or a bisphenol A type epoxy resin having an epoxy equivalent of 600 to 3000 g / eq is preferably used. Among them, it is preferable to use a novolak type epoxy resin having an epoxy equivalent of 180 to 250 g / eq and a molecular weight of 1000 to 6000, or a bisphenol A type epoxy resin having an epoxy equivalent of 600 to 3000 g / eq and a molecular weight of 1200 to 6000.

The blending ratio of the polyalkylene terephthalate resin, the polystyrene resin and the compatibilizer constituting the resin component is generally 40 to 96.5% by weight for the polyalkylene terephthalate resin and 3.5 to 50% by weight for the polystyrene resin. The compatibilizer is 0 to 10% by weight. The polyalkylene terephthalate resin preferably accounts for 45 to 95.5% by weight, especially 55 to 90% by weight. The polystyrene resin preferably accounts for 4.5% by weight or more, and the upper limit is preferably 45% by weight or less. The compatibilizer preferably accounts for 0.2 to 8% by weight. If the amount of the compatibilizer is more than 10% by weight, the fluidity and flame retardancy are lowered. When the polystyrene resin contains an epoxy-modified polystyrene resin, the content is 10 to 50% by weight, particularly 15 to 45% by weight, in the resin component from the viewpoint of the appearance and flame retardancy of the molded product. Is preferred. Epoxy-containing polystyrene resins generally have good dispersibility, so that good dispersion can often be achieved without a compatibilizer. Including the case of using a polystyrene resin that does not contain an epoxy group, the most preferable blending ratio is 55 to 90% by weight of a polyalkylene terephthalate resin, 4.5 to 45% by weight of a polystyrene resin, and 0 to 8% of a compatibilizer. %, That is, a composition mainly composed of polyalkylene terephthalate resin.

(B) Flame retardant The resin composition of the present invention has three types of difficulty: a phosphorus flame retardant (B-1), a nitrogen flame retardant (B-2), and a boric acid metal salt (B-3). It contains a flame retardant, and its content is 10 to 60 parts by weight of the phosphorus flame retardant (B-1) and 20 to 20% of the nitrogen flame retardant (B-2) with respect to 100 parts by weight of the (A) resin component. 70 parts by weight and 0 to 20 parts by weight of the boric acid metal salt (B-3), and at the same time, the total amount needs to be 40 to 100 parts by weight, preferably 50 to 100 parts by weight. When the flame retardant (B) exceeds 100 parts by weight, CTI and glow wire characteristics are deteriorated, and more gas is generated. On the other hand, if it is less than 40 parts by weight, flame retardancy, tracking characteristics and glow wire properties cannot be satisfied. From the point of further improving the CTI and glow wire characteristics, the blend ratio (B-1) / (B-2) (weight ratio) of the phosphorus flame retardant (B-1) to the nitrogen flame retardant (B-2) Is preferably in the range of 0.14 to 1.1, more preferably 0.2 to 1.0, and most preferably in the range of 0.3 to 0.95. If it is less than 0.14, sufficient flame retardancy may not be obtained, and if it exceeds 1.1, GWIT tends to decrease.

(B-1) Phosphorus flame retardant In the present invention, it is necessary to use a phosphazene compound or a phosphinate as the phosphorus flame retardant, and these are used alone or as a mixture of two or more. be able to.

(B-1a) Phosphazene compound As the phosphazene compound, conventionally known compounds can be widely used. In the present invention, for example, James E.M. Mark, Harry R. Allcock, Robert West, “Inorganic Polymers” Pretice-Hall International, Inc. , 1992, p61-p140, can be suitably used. For example, a cyclic phosphazene compound represented by the following general formula (3) and a chain phosphazene compound represented by the following general formula (4) are exemplified, and among them, those containing 95% by weight or more of phosphazene compounds having these structures. preferable.

(In the formula, n represents an integer of 3 to 25, m represents an integer of 3 to 10000. X is independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 11 carbon atoms, Substitution selected from the group consisting of a fluorine atom, a phenyloxy group optionally having a substituent represented by the following general formula (5), a naphthyloxy group, an alkoxy group having 1 to 6 carbon atoms and an alkoxy-substituted alkoxy group In addition to the general formula (5), part or all of the hydrogen atoms on the substituent X may be substituted with a fluorine atom, a hydroxyl group, or a cyano group, and Y represents —N═P (O). (X) or -N = P (X) 3, Z represents -P (X) 4 or -P (O) (X) 2, where X is as defined above.

(In the formula, Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y ₅ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group, a phenyl group, or a hetero-element-containing group. Represents a substituent selected from the group consisting of

These compounds may be used alone or as a mixture of two or more.
One of the factors that determine the effect of imparting flame retardancy of phosphazene compounds is the concentration of phosphorus atoms contained in the molecule. Since a chain phosphazene having a chain structure has a substituent at the molecular end, the phosphorus content is lower than that of a cyclic phosphazene compound. However, it is considered that the flame retardancy imparting effect is higher. Therefore, in the present invention, it is preferable to use a phosphazene compound having a cyclic structure, and those containing a cyclic phosphazene compound of 95% by weight or more are preferable.

Examples of the substituent X in the phosphazene compound represented by the general formula (3) or (4) include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, tert -Alkyl groups such as butyl group, n-amyl group, isoamyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethyl Aryl groups such as phenyl group, 2,5-dimethylphenyl group, 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, 4-tertiarybutylphenyl group, 2-methyl-4-tertiarybutylphenyl group ,

Methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, tert-butyloxy group, s-butyloxy group, n-amyloxy group, isoamyloxy group, tert-amyloxy group, n-hexyloxy group Alkoxy groups such as methoxymethoxy group, methoxyethoxy group, methoxyethoxymethoxy group, methoxyethoxyethoxy group, methoxypropyloxy group, etc., phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4 -Methylphenoxy group, 2,6-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 3,4-dimethylphenoxy group

2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group 3,4,5-trimethylphenoxy group, 2-ethylphenoxy group, 3-ethylphenoxy group, 4-ethylphenoxy group, 2,6-diethylphenoxy group, 2,5-diethylphenoxy group, 2,4-diethyl Phenoxy group, 3,5-diethylphenoxy group, 3,4-diethylphenoxy group, 4-n-propylphenoxy group, 4-isopropylphenoxy group, 4-tertiarybutylphenoxy group, 2-methyl-4-tertiarybutyl Such as phenoxy group, 2-phenylphenoxy group, 3-phenylphenoxy group, 4-phenylphenoxy group, etc. Kill substituted phenoxy group, an aryl-substituted phenoxy group naphthyl group, naphthyloxy group and the like.

In these groups, some or all of the hydrogen atoms may be replaced by groups containing fluorine atoms or heteroelements. Here, the group containing a hetero element is a group containing any atom of B, N, O, Si, P, and S. Examples of some of them include an amino group, an amide group, and an aldehyde group. Glycidyl group, carboxyl group, hydroxyl group, cyano group, mercapto group, silyl group and the like.

Further, these compounds may be cross-linked by a cross-linking group selected from the group consisting of a phenylene group, a biphenylene group and a group (6) shown below by the technique disclosed in International Publication No. WO 00/09518. Good.

(In the formula, X represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—, and y represents 0 or 1).

The phosphazene compound having such a crosslinked structure is produced, for example, by reacting a dichlorophosphazene oligomer with an alkali metal salt of phenol and an alkali metal salt of an aromatic dihydroxy compound. These alkali metal salts are added to the dichlorophosphazene oligomer slightly in excess of the theoretical amount.
These phosphazene compounds may be used alone or as a mixture of two or more.

The phosphazene compound is generally a mixture of compounds having different structures such as cyclic trimers and cyclic tetramers, chain phosphazenes, and cross-linked compounds, but the processability when added to a resin is cyclic trimer. There is a tendency that the higher the content of the body, tetramer or crosslinked body, the better. When a phosphazene compound containing 70% by weight or more, preferably 80% by weight or more, particularly 85% by weight or more of a trimer or a crosslinked product is used, a synergistic effect with the nitrogen-based flame retardant as component (B-2) is effective. Expresses. As a result, not only an excellent flame retardancy imparting effect can be obtained, but also an excellent mechanical property improving effect can be obtained.

The alkali metal components such as sodium and potassium contained in the phosphazene compound are each preferably 200 ppm or less, particularly preferably 50 ppm or less. More preferably, the total alkali metal component is 50 ppm or less.

The content of the phosphazene compound in which at least one of the substituents X in the general formula (3) is a hydroxyl group, that is, the phosphazene compound containing a P—OH bond is preferably less than 1% by weight, and chlorine It is preferable that the content is 1000 ppm or less, particularly 500 ppm or less. Most preferably, the chlorine content is 300 ppm or less.

A phosphazene compound containing a PO bond may have an oxo-form structure represented by the following general formula (7). Such an oxo-form compound is less than 1% by weight in the same manner as the hydroxyl group-containing phosphazene compound. It is desirable to be. The same applies to a phosphazene compound having a chain structure represented by the general formula (4).

(In the formula, a + b = n, and n is an integer of 3 or more. In the formula, each X independently represents an aryloxy group or an alkoxy group.)

The phosphazene compound preferably has a water content of 1000 ppm or less, more preferably 800 ppm or less, in consideration of electrical characteristics, hydrolysis resistance and the like. Most preferably, the water content is 500 ppm or less, particularly 300 ppm or less. In addition to this, the acid value measured based on JIS K6751 is preferably 1.0 or less, particularly preferably 0.5 or less.

In addition, phosphazene compounds are soluble in water from the viewpoint of hydrolysis resistance and moisture absorption (samples mixed with distilled water at a concentration of 0.1 g / mL, dissolved in water after stirring for 1 hour at room temperature Is preferably 100 ppm or less. More preferably, this value is 50 ppm, especially 25 ppm or less.

The phosphazene compound varies depending on the types and structures of substituents contained, but can take various forms such as liquid, wax, solid, etc., as long as it does not impair the effects of the present invention. The thing of such a form can also be used. In view of handleability, workability, etc., a solid state is preferable. Its bulk density 0.45 g / cm ³ or more, and particularly preferably between 0.45g ^/ cm ³ 0.75g ^/ cm 3 or less.

(B-1b) Phosphinic acid salt The phosphinic acid salt (B-1b) is represented by the following formula (8) or formula (9), and includes phosphinic acid, metal carbonate, and metal water. It is produced by reacting an oxide or metal oxide in an aqueous solution. Although it is essentially a monomeric compound, a polymer phosphinic acid salt having a degree of condensation of 1 to 3 is also included depending on the reaction conditions.

[In these formulas, R ¹ and R ² are each independently a linear or branched alkyl group or aryl group having 1 to 6 carbon atoms, and R ³ is a linear or branched group having 1 to 10 carbon atoms, or A branched alkylene group, an arylene group having 6 to 10 carbon atoms, or an alkylene arylene group having 7 to 10 carbon atoms is represented. M represents Ca, Mg, Al, or Zn. , M is 2 or 3, n is 1 to 3, and x is 1 or 2.]

Specific examples of phosphinates include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, ethylmethylphosphine Zinc oxide, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, Zinc methyl-n-propylphosphinate, methandi (methylphosphinic acid) calcium, methandi (methylphosphite) Acid) magnesium methanedi (methylphosphinate) aluminum methanedi (methylphosphinate) zinc-1,4 (dimethyl phosphinic acid) calcium-1,4 (dimethyl phosphinic acid) magnesium.

Benzene-1,4- (dimethylphosphinic acid) aluminum, benzene-1,4- (dimethylphosphinic acid) zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, methylphenylphosphinic acid Also included are zinc, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate. From the viewpoint of flame retardancy and electrical characteristics, aluminum diethylphosphinate and zinc diethylphosphinate are preferred.

From the viewpoint of the mechanical strength and appearance of the molded article, it is preferable to use a powder of phosphinate that is pulverized to 100 μm or less, particularly 50 μm or less. Use of a powder having a particle size of 0.5 to 20 μm is particularly preferable because it not only exhibits high flame retardancy but also significantly increases the strength of the molded product. The phosphinate acts as a flame retardant, but when used in combination with a nitrogen-based flame retardant, it exhibits excellent flame retardancy and excellent electrical properties with a small amount of flame retardant. However, when these compounding amounts are large, mold release defects and mold deposits are likely to occur, and moldability deteriorates.

The compounding quantity of a phosphorus flame retardant is 10-60 weight part with respect to 100 weight part of resin components (A). It is preferably 15 to 45 parts by weight, particularly 20 to 40 parts by weight. When the blending amount of the phosphorus-based flame retardant exceeds 60 parts by weight, tracking characteristics and mechanical properties are liable to deteriorate, blooming is likely to occur, and the amount of generated gas increases.

(B-2) Salts of amino group-containing triazines The amino group-containing triazines constituting the salt of amino group-containing triazines which are nitrogen-based flame retardants are usually amino group-containing 1,3,5. -Triazines are used, for example, melamine, substituted melamine (2-methylmelamine, guanylmelamine etc.), melamine condensate (melam, melem, melon etc.), melamine co-condensation resin (melamine-formaldehyde resin resin etc.), Examples include cyanuric acid amides (ammeline, ammelide, etc.), guanamine or derivatives thereof (guanamine, methylguanamine, acetoguanamine, benzoguanamine, succinoguanamine, adipoguanamine, phthaloguanamine, CTU-guanamine, etc.).

Examples of inorganic acids that form salts with these triazines include nitric acid, chloric acids (chloric acid, hypochlorous acid, etc.), phosphoric acids (phosphoric acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid, etc.), sulfuric acids (sulfuric acid, Non-condensed sulfuric acid such as sulfurous acid, condensed sulfuric acid such as peroxodisulfuric acid and pyrosulfuric acid), boric acid, chromic acid, antimonic acid, molybdic acid, tungstic acid and the like. Of these, phosphoric acid and sulfuric acid are preferred. 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.). Among these, an aromatic group in which an alkyl group having 1 to 3 carbon atoms may be substituted on an aromatic ring having 6 to 12 carbon atoms such as alkanesulfonic acid having 1 to 4 carbon atoms such as methanesulfonic acid or toluenesulfonic acid. A group sulfonic acid and cyanuric acid are preferred.

Examples of salts of amino group-containing triazines include melamine phosphates (melamine polyphosphate, melamine polyphosphate, melam, melem double salt, etc.), melamine sulfates (melamine sulfate, dimelamine sulfate, dimelam pyrosulfate), sulfone, etc. Melamines (Melamine methanesulfonate, melam methanesulfonate, melem methanesulfonate, melamine methanesulfonate, melam melem, double salt, melamine toluenesulfonate, melam toluenesulfonate, melamine toluene, melam memel double salt) Etc.). These salts of amino group-containing triazines can be used alone or in combination of two or more.

Among such nitrogen-based flame retardants, cyanuric acid or a salt of isocyanuric acid and a triazine-based compound (adduct) is preferably used in the present invention, and usually 1: 1 (molar ratio). 1 to 2 (molar ratio). More specifically, they are melamine cyanurate, benzoguanamine cyanurate, acetoguanamine cyanurate, and further melamine cyanurate. These salts can be obtained by publicly known methods, for example, mixing triazine compounds and cyanuric acid or isocyanuric acid well in water to precipitate both salts in the form of fine particles, and then filtering and drying them. Is generally obtained in powder form.

Further, the above-mentioned salt does not have to be completely pure, and some unreacted triazine compound, cyanuric acid, and isocyanuric acid may remain. In addition, the average particle diameter of the salt before being blended with the resin component is preferably 100 to 0.01 μm from the viewpoint of flame retardancy, mechanical strength and heat-and-moisture resistance properties, residence stability, and surface properties of the molded product. More preferably, it is 80-1 micrometer. Further, when the dispersibility of the salt is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate or a known surface treatment agent may be used in combination.

The amount of the nitrogen-based flame retardant is 20 to 70 parts by weight, preferably 25 to 60 parts by weight, with respect to 100 parts by weight of the component (A). When the compounding amount of the nitrogen-based flame retardant exceeds 70 parts by weight, mechanical properties are likely to be lowered.

(B-3) Metal borate The resin composition of the present invention preferably contains a metal borate as a further flame retardant. As the boric acid metal salt, those which are stable under the processing conditions usually used and have no volatile components are preferable. Examples of the boric acid metal salt include alkali metal salts of boric acid (for example, sodium tetraborate, potassium metaborate), alkaline earth metal salts (for example, calcium borate, magnesium orthoborate, barium orthoborate), zinc salts and the like. Among these, zinc borate is preferable. Zinc borate is generally a hydrate represented by 2ZnO · 3B ₂ O ₃ · xH ₂ O (x = 3.3 to 3.7), but X is 3.5 and 260 ° C. or higher. Those that are stable up to high temperatures are preferred. Commercially available products include Alkanex FRF-30, FRC-500, and FRC-600 manufactured by Mizusawa Chemical Co., Ltd.

The compounding amount of the boric acid metal salt is 0 to 20 parts by weight, preferably 15 parts by weight or less, based on 100 parts by weight of the component (A). When the compounding amount of the boric acid metal salt exceeds 20 parts by weight, the mechanical properties tend to be lowered. In order to fully express the effect of the metal borate, it is preferable to add 2 parts by weight or more.

(C) Inorganic filler It is preferable that the resin composition of the present invention further contains an inorganic filler. As fillers, fibrous fillers (glass fiber, carbon fiber, basalt fiber, silica / alumina fiber, zirconia fiber, boron fiber, boron nitride fiber, silicon nitride potassium titanate fiber, etc.), granular filler (kaolin, Silicates such as talc and wollastonite; carbonates of metals such as calcium carbonate; metal oxides such as titanium oxide), plate-like fillers (mica, glass flakes, various metal foils, etc.) and the like. Of these fillers, fibrous fillers, particularly glass fibers (such as chopped strands) are preferred in that they give a molded product having high strength and rigidity. These fillers can be used alone or in combination of two or more.

These fillers may be used in combination with a sizing agent or a surface treatment agent. Examples of such a sizing agent or surface treatment agent include compounds having a functional group such as an epoxy compound, a silane compound, and a titanate compound. The amount of the inorganic filler is 0 to 200 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of the resin component (A), but 50 parts by weight to fully develop the effect of the inorganic filler. More than 50 parts by weight, particularly 50 to 130 parts by weight is preferred.

(D) Anti- drip agent It is preferable to add an anti-drip agent to the resin composition of the present invention. The dripping preventive agent may be a compound having a property of preventing dripping of the resin during combustion, but a fluorine-containing polymer is preferable from the viewpoint of flame retardancy of the resin composition.

The amount of the component (D) anti-dripping agent is selected from a range of 0.01 to 15 parts by weight with respect to 100 parts by weight of the component (A) resin component. If the amount of the dripping inhibitor is small, the dripping preventing effect during combustion is insufficient, and if it is too large, the fluidity and mechanical properties may be lowered.

(D) Fluorine-containing polymers used as anti-dripping agents include polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer. Polymers, fluorinated polyolefins such as vinylidene fluoride and polychlorotrifluoroethylene are preferred. Among them, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetra Fluoroethylene / ethylene copolymers are more preferred, and polytetrafluoroethylene and tetrafluoroethylene / hexafluoropropylene copolymers are particularly preferably used.

(D) The fluorine-containing polymer used as an anti-dripping agent preferably has a melt viscosity at 350 ° C. of 1.0 × 10 ^{2 to} 1.0 × 10 ¹⁵ (Pa · s), and in particular, 1.0 × Those of 10 ^{3 to} 1.0 × 10 ¹⁴ (Pa · s), particularly 1.0 × 10 ^{10 to} 1.0 × 10 ¹² (Pa · s) are preferably used. When the melt viscosity is less than 1.0 × 10 ² (Pa · s), the ability to prevent dripping at the time of combustion is insufficient, and when it exceeds 1.0 × 10 ¹⁵ (Pa · s), the fluidity of the composition is low. It drops significantly.

The amount of the fluorine-containing polymer is 0.5 to 15 parts by weight, preferably 0.7 to 12 parts by weight, and particularly preferably 1 to 10 parts by weight with respect to 100 parts by weight of the component (A) resin component. If the addition amount is less than 0.5 parts by weight, the dripping prevention effect during combustion is insufficient, and if it is more than 15 parts by weight, the fluidity and mechanical properties are lowered.

In addition to the above components (A) to (D), conventional additives and the like can be further blended into the resin composition of the present invention as necessary. There is no restriction | limiting in particular in the additive to mix | blend. Among additives, stabilizers such as antioxidants and heat stabilizers, lubricants, mold release agents, catalyst deactivators, crystal nucleating agents, and crystallization accelerators are added during or after the polymerization of polyalkylene terephthalate. be able to. An epoxy compound, carbodiimide, oxazoline, or the like can be added to further improve the hydrolysis resistance. Further, stabilizers such as ultraviolet absorbers and weathering stabilizers, colorants such as dyes and pigments, antistatic agents, foaming agents, plasticizers, impact resistance improvers and the like can be blended.

Furthermore, in the resin composition of the present invention, a resin other than the resin component (A) can be blended as necessary within a range not impairing the object of the present invention. However, as described above, the blending of polyphenylene ether resin, polyphenylene sulfide resin, and phenol resin is not preferable because it decreases the tracking characteristics, and these are not contained at all, or even if they are contained, each is 1% by weight or less in the resin composition. It is necessary to limit the content of. In this specification, the polyphenylene ether resin and the polyphenylene sulfide resin mean those disclosed in JP-A-8-20900, and the phenol resin means those disclosed in Patent Document 6.
Polyolefin resins such as polyethylene and polypropylene have the effect of improving tracking characteristics, but have the drawback of significantly reducing flame retardancy.

The manufacturing method of the resin composition of this invention is not specifically limited, It can manufacture easily by mixing each component by a well-known method. For example, dry blending using a blender or mixer, melt mixing using an extruder, etc., etc., but usually using a screw extruder, melt mixing and extruding into a strand, pelletizing The method to do is suitable. Each component may be melted and kneaded at once, or the specific component may be melted and mixed first, but from the viewpoint of mechanical properties, (A) the resin component and (B) the flame retardant are melted and mixed first. Then, the method of mixing the remaining components is preferred.

The method for producing a molded product from the resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, molding methods such as injection molding, hollow molding, extrusion molding, and press molding are used. A particularly preferable molding method that can be applied is injection molding because of its good fluidity. In the injection molding, the resin temperature is preferably controlled to 240 to 280 ° C.

The resin composition of the present invention is excellent in flame retardancy, mechanical properties, etc., has no mold corrosion due to generation of corrosive gas, and has low specific gravity and excellent fluidity. It can be used suitably. Therefore, it is suitable as a material for producing parts such as electric equipment and electronic equipment.

Furthermore, among the components of electrical equipment, electronic equipment, etc., the resin molded part formed using this resin assembly is usually the reason why the excellent properties of the resin composition of the present invention are fully exhibited. Electrically insulating parts that directly support connections that carry a current exceeding 0.2 A, i.e. a rated current exceeding 0.2 A, during operation, or within a distance of 3 mm from these connections, ie high electrical safety It is a component that requires high performance. The resin molded part formed using the resin composition of the present invention realizes a high GWFI value and a high GWIT, and has been required from the conventional flame retardancy (V-0), PTI, Etc. can also be satisfied.

Here, “the resin molded part is within a distance of 3 mm from the 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 resin molded part is connected to the resin molded part. ) Means that a space of several millimeters is provided between the contact point and the resin molded portion. Even in such a case, high electrical safety is still necessary, and the resin composition of the present invention is effective.

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

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.

In Examples and Comparative Examples, the physical properties of polyalkylene terephthalate resins were measured and the resin compositions of the present invention were evaluated by the following methods.

(1) Terminal carboxyl group amount;
Polybutylene terephthalate (0.1 g) was dissolved in 3 ml of benzyl alcohol, and titrated with a 0.1 mol / liter-benzyl alcohol solution of sodium hydroxide.

(2) Temperature drop crystallization temperature;
Using a differential scanning calorimeter [Perkin Elmer, Model 1B], polybutylene terephthalate was heated from room temperature to 300 ° C. at a temperature increase rate of 20 ° C./min, and then decreased to 80 ° C. at a temperature decrease rate of 20 ° C./min. In this case, the temperature of the exothermic peak was measured and used as the temperature lowering crystallization temperature.

(3) residual tetrahydrofuran amount;
5 g of polybutylene terephthalate pellets were immersed in 10 g of water, treated under pressure at 120 ° C. for 6 hours, and tetrahydrofuran eluted in water was quantified by gas chromatography.

(4) Intrinsic viscosity;
Using a mixed solvent of an Ubbelohde viscometer and phenol / 1,1,2,2-tetrachloroethane (weight ratio 1/1) at 30 ° C., concentrations of 1.0 g / dl, 0.6 g / dl and 0.3 g The viscosity of the / dl solution was measured and the viscosity was extrapolated to zero concentration.

Each component used in Examples and Comparative Examples is as follows.
[raw materials]
(A-1a) PBT-1 : Polybutylene terephthalate resin produced by the following continuous polymerization method. The amount of terminal carboxyl groups was 20 eq / t, the temperature drop crystallization temperature was 178 ° C., the amount of residual tetrahydrofuran was 180 ppm (weight ratio), and the intrinsic viscosity was 0.85 dl / g.

[PBT-1 production method]
Both raw materials were supplied to the slurry preparation tank at a ratio of 1.8 mol of 1,4-butanediol with respect to 1.0 mol of terephthalic acid, and mixed with a stirrer to prepare a slurry. The slurry was continuously transferred to a first esterification reaction vessel having a temperature of 230 ° C. and a pressure of 101 kPa by a gear pump, and tetrabutyl titanate was supplied (the supply amount was 3.14 parts by weight relative to 2972 parts by weight of slurry). Part by weight) and a residence time of 2 hours, and an esterification reaction was carried out with stirring to obtain an oligomer.

This oligomer was transferred to a second esterification reaction vessel adjusted to a temperature of 240 ° C. and a pressure of 101 kPa, and the esterification reaction was further advanced with stirring for 1 hour. Further, this oligomer was transferred to a first polycondensation reaction tank adjusted to a temperature of 250 ° C. and a pressure of 6.67 kPa, and subjected to a polycondensation reaction with stirring for 2 hours to obtain a prepolymer. The prepolymer was transferred to a second double condensation reaction tank adjusted to a temperature of 250 ° C. and a pressure of 133 Pa, and the polycondensation reaction was further advanced with stirring for 3 hours to obtain a polymer. The polymer was extracted from the second double condensation tank, transferred to a die, drawn into a strand, and cut with a pelletizer to obtain a beret-like polybutylene terephthalate.

(A-1b) PBT-2 : Polybutylene terephthalate resin produced by the following batch polymerization method, terminal carboxyl group amount is 41 eq / t, temperature-falling crystallization temperature is 170 ° C., residual tetrahydrofuran amount is 680 ppm (weight ratio) The intrinsic viscosity was 0.85 dl / g.

[PBT-2 production method]
A total of 3,226 parts by weight is supplied to the transesterification reactor at a ratio of 1.8 moles of 1,4-butanediol to 1.0 mole of dimethyl terephthalate, and 3.14 parts by weight of tetrabutyl titanate is added. Then, an ester exchange reaction was performed at a temperature of 210 ° C. and a pressure of 101 kPa for 3 hours to obtain an oligomer. Subsequently, this oligomer was transferred to a polycondensation reaction tank, and under agitation, a polycondensation reaction was carried out at a temperature of 250 ° C. and a pressure of 133 Pa for 3 hours to obtain a polymer. Next, nitrogen pressure was applied to extract the strands, and the pellets were cut with a pelletizer to obtain pellets of polybutylene terephthalate.

(A-1c) PET : Polyethylene terephthalate resin (trade name Novapet PBK1 manufactured by Mitsubishi Chemical Corporation)

(A-2a) Epoxy-modified AS resin : 3 parts by weight and 2 parts of glycidyl methacrylate with respect to 100 parts by weight of AS resin (manufactured by Technopolymer Co., Ltd., trade name Sanrex SAN-C, melt mass flow rate 25 g / 10 min) 0.015 part by weight of 5-dimethyl-2.5-di- (t-butylperoxy) hexyne was mixed, kneaded at 210 ° C. using a 30 mm twin screw extruder, and pelletized. After the unreacted glycidyl methacrylate was extracted with acetone, the reacted glycidyl methacrylate was quantified by measuring the ultraviolet absorption spectrum. As a result, the content was 1.7% by weight.

(A-2b) EGMA-g-PS : Epoxy-modified polystyrene resin, manufactured by Nippon Oil & Fats Co., Ltd., trade name Modiper A4100 (comb structure polymer obtained by grafting polystyrene onto an ethylene-glycidyl methacrylate copolymer. EGMA / PS = 70 / 30 (weight ratio)

(A-2c) AS resin : Styrene-acrylonitrile copolymer resin, manufactured by Technopolymer Co., Ltd., trade name Sanrex SAN-C, melt mass flow rate 25 g / 10 min

(A-2d) GPPS resin : manufactured by PS Japan, trade name HF77, melt flow rate 7.5 g / 10 min

(A-3) Epoxy compound ( Compatibilizer): Bisphenol A type epoxy resin, manufactured by Asahi Denka Kogyo Co., Ltd., trade name Adeka Sizer EP17

(B-1a) Phosphazene compound : Phosphazene compound mainly composed of a cyclic product (Fushimi Pharmaceutical Co., Ltd., trade name: FP-100)

(B-1b) Phosphinate : Aluminum diethylphosphinate (manufactured by Clariant Japan Ltd., trade name OP1240)

(B-2a) melamine cyanurate; manufactured by Mitsubishi Chemical Corporation, trade name MX44.

(B-2b) Melamine polyphosphate (melapur200 / 70 manufactured by Ciba Special)

(B-3) Zinc borate : Borax Japan K.K., trade name Firebreak ZB.

(C) GF (inorganic filler): glass fiber ( manufactured by Nippon Electric Glass Co., Ltd., epoxysilane-treated product, 3 mm chopped strand, brand name: T-187).

(D) PTEF (anti-dripping agent) : polytetrafluoroethylene (manufactured by Daikin Industries, Ltd., tetrafluoroethylene resin, trade name Polyflon F201).

(E) Brominated flame retardant : Brominated polystyrene (Albemarle Japan Co., Ltd., trade name Saytex HP-7010).

(F) Antimony compound : antimony trioxide (manufactured by Moriroku Co., Ltd., trade name MIC-3).

(G) Stabilizer : Hindered phenolic compound (Ciba Specialty Japan Co., Ltd., trade name: Irganox 1010)

(H) Mold release agent : calcium montanate (manufactured by Clariant Japan Co., Ltd., trade name CaV102)

(I-1) PPE resin ( polyphenylene ether resin); manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name Iupiace, intrinsic viscosity 0.36

.
(I-2) Phenolic resin : Novolac phenolic resin (manufactured by Sumitomo Durez, trade name Sumilite Resin PR-53195)

[Performance evaluation method]
(1) Flame Retardancy Test UL specimens (thickness 1/32 inch) were conducted by the UL-94 standard vertical combustion test method of Underwriters Laboratories Inc. The flame retardancy level was evaluated in the order of V-0>V-1>V-2> HB according to the standard.

(2) Proof Tracking Index test (abbreviation: PTI test)
For the test piece (a flat plate having a thickness of 3 mm), the PTI was determined by the test method defined in the international standard IEC60112. This PTI is a numerical value of the guaranteed voltage in increments of 25V. PTI exhibits resistance to tracking at a voltage between 600 V and 100 V when wet-contaminated with an electric field applied to the surface of the solid electrical insulating material, and requires 550 V or more, preferably 600 V or more. is there.

(3) Glow-wire Flammability Index test (abbreviation: GWFI test)
The test piece (3 mm thick flat plate) was tested according to the test method defined in IEC60695-2-12. 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 highest temperature at the tip that does not ignite during this time, or extinguishes within 30 seconds after being ignited, and tests up to a maximum of 960 ° C. 850 ° C. or higher is required for flame retardant applications. In this invention, it was determined whether it passed at 960 degreeC.

(4) Glow-wire Ignition Temperature test (abbreviation: GWIT test)
Three types of flat plate test pieces having thicknesses of 0.75 mm, 1.5 mm, and 3 mm were tested according to the test method defined in IEC 60695-2-13. 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 use, 775 ° C. or higher is required as GWIT having a thickness of 0.8 to 3 mm. More preferably, 800 degreeC or more is calculated | required.

(5) Flame retardant bleed-out test Using a 10 cm square flat plate with a thickness of 3 mm as a sample, after heat treatment for 48 hours in a hot air dryer adjusted to 150 ° C., the surface of the test piece was visually observed and difficult. The exudation of the flame retardant was classified into the following four stages, and ◎ to △ were judged to be practically usable, but ◎ or ○ is preferable.
A: No exudation, ○: Exudation is slightly observed, Δ: Exudation, ×: Exudation is large

(6) Tensile test: Measured according to ISO 527 using an ISO tensile test piece (ISO 3167).

(7) Hydrolysis resistance test The ISO tensile test piece was held in saturated steam at a temperature of 121 ° C for 40 hours. About the ISO test piece before and behind holding | maintenance, the tension test was done based on ISO527 and the tensile strength retention rate was measured.

(8) evolved gas;
After putting 5 g of the resin composition pellets into a glass vial with an internal volume of 26 ml and heating at 150 ° C. for 2 hours, a sample was taken from the gas phase using a microsyringe and analyzed by gas chromatography. The peak area of the chromatogram was obtained, and the weight of tetrahydrofuran corresponding to the area was expressed as a ratio (ppm) to the resin.

[Examples 1 to 11 and Comparative Examples 1 to 12]
Components other than the glass fibers shown in Table 1 are mixed together with a super mixer (SK-350 type, manufactured by Shinei Machinery Co., Ltd.), and a hopper of L / D = 42 twin screw extruder (manufactured by Nippon Steel Works, TEX30HSST). The glass fiber was further side-feeded and extruded under conditions of a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, and a barrel temperature of 260 ° C. to obtain resin composition pellets.
About this resin composition pellet, using the injection molding machine (manufactured by Sumitomo Heavy Industries Co., Ltd., model SH-100), the above tests (1) to (5) under the conditions of a cylinder temperature of 270 ° C. and a mold temperature of 80 ° C. Pieces (three types of flat plate test pieces of 10 cm in length and width, thickness of 0.75 mm, 1.5 mm and 3 mm, and a test piece of UL-94 standard having a thickness of 1/32 inch) were manufactured. Moreover, as a test piece of (6) and (7), an ISO tensile test piece (ISO3167) was molded at 265 ° C. using an injection molding machine (model S-75 MIII manufactured by Sumitomo Heavy Industries, Ltd.). . The above evaluation was performed using these test pieces. The pellets of the resin composition were dried with hot air at 120 ° C. for 8 hours, and the amount of gas generated in (8) was measured. The evaluation results are shown in Table 1.

Table 1 shows the following.
(1) The comparative example 1 which mix | blended the brominated flame retardant and antimony compound as a flame retardant has low PTI, and GWIT does not reach 775V in the thickness of 1.5 mm or less.
(2) Although the flame retardant was blended as usual, Comparative Examples 2 and 3 in which the polystyrene resin as the component (A-2) was not blended, and Comparative Example 4 in which the blending amount of the polystyrene resin was less than the scope of the present invention. The flame retardant bleed out is remarkable. Conversely, in Comparative Example 5 in which the blending amount of the polystyrene-based resin is excessive and Comparative Example 6 in which the blending amount of the flame retardant is small, flame retardancy and electrical safety are lowered.
(3) Comparative Example 7 in which the flame retardant blending amount is excessive and Comparative Example 8 in which the blending amount of the flame retardant is appropriate but the phosphorous flame retardant is excessive are high in flame retardancy, but the amount of generated gas is high. Big and low physical properties.

(4) In Examples 1 to 11 within the scope of the present invention, flame retardancy is also V-0, PTI is 550 V, 960 ° C. GWFI is acceptable, and GWIT is also in the range of 0.75 to 3.0 mm thickness. In all, 775V or more is extremely high in electrical safety. In addition, there is little bleed out of the flame retardant and the hydrolysis resistance is good.
(5) Example 1 based on PBT resin with a small amount of terminal carboxyl groups and residual tetrahydrofuran is less generated gas than Example 11 using PBT resin with a large amount of these. Suitable for contact parts such as relays.

(6) When Example 1 and Example 7 in which the blending ratios of the phosphorus-based flame retardant and the nitrogen-based flame retardant are different are compared, the ratio of the phosphorus-based flame retardant / nitrogen-based flame retardant is in the range of 0.14 to 1.1. In Example 1, the flame retardant bleed out and the amount of gas generated is smaller.
(7) In Comparative Examples 9 to 12, in which a PPE resin or a phenol resin is further blended with the composition of Example 1, the flame retardancy and bleed-out property are good, but the tracking property is remarkably lowered.

.
(8) In the comparison of Examples 1 to 6 in which various polystyrene resins were blended, the flame retardant bleed-out in Example 2 in which only the component A-2b having a low content of aromatic vinyl monomer was blended was Many compared to the examples. On the other hand, the tracking property of Example 4 in which the component A-2d containing only the aromatic vinyl monomer is blended is slightly lower than the others.
(9) Examples 3 and 4 containing only a polystyrene-based resin that does not contain an epoxy group have slightly worse glow wire properties and hydrolysis resistance than Examples 1, 2, 5 and 6. Yes. The flame retardancy maintained V-0, but the combustion time was slightly longer.

  As can be seen from the above examples 1 to 11 in Table 1, the electrical insulation parts formed of the resin composition according to the present invention generally have very little flame retardant bleed-out, flame retardancy, PTI, GWFI, Good GWIT and mechanical properties, as shown in IEC 60335-1, insulative parts supporting connections that carry currents of more than 0.2 A during normal operation, and within 3 mm of these connections It can be seen that it conforms to the rules for insulation parts. Furthermore, it can be seen that when a PBT resin having a small amount of terminal carboxyl groups and residual tetrahydrofuran is used as a base, the amount of generated gas is further reduced and it is useful for contacted parts such as relays.

Claims (15)

(A-1) Resin component comprising 40 to 96.5 parts by weight of a polyalkylene terephthalate resin (A-2) 3.5 to 50 parts by weight of a polystyrene resin and (A-3) 0 to 10 parts by weight of a compatibilizer ( A) For 100 parts by weight,
The following flame retardant (B)
(B-1) 10-60 parts by weight of a phosphorus-based flame retardant selected from the group consisting of phosphazene compounds and phosphinates (B-2) 20-70 parts by weight of a nitrogen-based flame retardant comprising a salt of an amino group-containing triazine (B-3) 0-20 parts by weight of a metal borate salt (provided that the total of these flame retardants is 40-100 parts by weight) and (C) 0-200 parts by weight of an inorganic filler,
The polyalkylene terephthalate resin (A-1) is a mixture of a polybutylene terephthalate resin and a polyethylene terephthalate resin,
Polyphenylene ether resin, polyphenylene sulfide resin and a phenolic resin (provided that the phenolic resin. Excluding novolac epoxy resin Rue epoxy group-containing act as a compatibilizer) one or not also contained in, or containing In any case, the resin composition has a maximum content of 1% by weight or less. (A-1) 45 to 96.3 parts by weight of polyalkylene terephthalate resin (A-2) 3.5 to 50 parts by weight of polystyrene resin (A-3) Resin component comprising 0.2 to 8 parts by weight of compatibilizer (A) The following flame retardant (B) with respect to 100 parts by weight
(B-1) 15 to 45 parts by weight of a phosphorus-based flame retardant selected from the group consisting of phosphazene compounds and phosphinates (B-2) 25 to 60 parts by weight of a nitrogen-based flame retardant comprising a salt of an amino group-containing triazine (B-3) 0-15 parts by weight of boric acid metal salt (however, the total of these flame retardants is 50-100 parts by weight) and (C) 5-150 parts by weight of inorganic filler,
The polyalkylene terephthalate resin (A-1) is a mixture of a polybutylene terephthalate resin and a polyethylene terephthalate resin,
Polyphenylene ether resin, polyphenylene sulfide resin and a phenolic resin (provided that the phenolic resin, except novolak epoxy resin Rue epoxy group-containing act as a compatibilizer,) either or not also contained in, Or even if it contains, the maximum is 1 weight% or less in any case, The resin composition characterized by the above-mentioned. (A-1) Polyalkylene terephthalate resin 55 to 95 parts by weight (A-2) Polystyrene-based resin 3.5 to 45 parts by weight (A-3) Resin component (A) 100 parts by weight of epoxy compound 0 to 8 parts by weight The following flame retardant (B)
(B-1) 20-40 parts by weight of a phosphorus-based flame retardant selected from the group consisting of phosphazene compounds and phosphinates (B-2) 25-60 parts by weight of a nitrogen-based flame retardant comprising a salt of an amino group-containing triazine (B-3) 2 to 15 parts by weight of zinc borate (however, the total of these flame retardants is 50 to 100 parts by weight) and (C) 50 to 130 parts by weight of an inorganic filler,
The polyalkylene terephthalate resin (A-1) is a mixture of a polybutylene terephthalate resin and a polyethylene terephthalate resin,
Does not contain or contain any of polyphenylene ether resin, polyphenylene sulfide resin, and phenolic resin (however, excluding epoxy group-containing novolak epoxy resin that acts as a compatibilizer from phenolic resin) In any case, the maximum is 1% by weight or less. The resin composition according to any one of claims 1 to 3, wherein the amount of the polystyrene resin (A-2) in 100 parts by weight of the resin component (A) is 4.5 parts by weight or more. The resin composition according to any one of claims 1 to 4, wherein a weight ratio of the phosphorus-based flame retardant (B-1) to the nitrogen-based flame retardant (B-2) is 0.14 to 1.1. object. The resin composition according to any one of claims 1 to 5, wherein the polystyrene resin (A-2) is an epoxy-modified polystyrene resin. 7. The resin composition according to claim 1, wherein the polybutylene terephthalate resin has a terminal carboxyl group content of 30 eq / t or less and a tetrahydrofuran content of 300 ppm or less. The resin composition according to any one of claims 1 to 7, wherein the inorganic filler is fibrous. The resin composition according to any one of claims 1 to 8, wherein the resin composition (A) contains 0.01 to 15 parts by weight of a fluorine-containing polymer as an anti-drip agent for 100 parts by weight of the resin component (A). . The resin composition according to claim 1, wherein the resin composition is used for molding an electric insulating member. It has a molded part formed using a resin composition, and the molded part directly supports a connection part through which a rated current exceeding 0.2 A flows or is within a distance of 3 mm from these connection parts. Forming part,
The resin composition comprises (A-1) 40-96.5 parts by weight of a polyalkylene terephthalate resin (A-2) 3.5-50 parts by weight of a polystyrene resin and (A-3) 0-10 parts by weight of a compatibilizer. For 100 parts by weight of the resin component (A) comprising
The following flame retardant (B)
(B-1) 10-60 parts by weight of a phosphorus-based flame retardant selected from the group consisting of phosphazene compounds and phosphinates (B-2) 20-70 parts by weight of a nitrogen-based flame retardant comprising a salt of an amino group-containing triazine (B-3) 0-20 parts by weight of a borate metal salt (provided that the total of these flame retardants is 40-100 parts by weight) and (C) 0-200 parts by weight of an inorganic filler, polyphenylene ether resin, polyphenylene sulfide resin and a phenolic resin (provided that the phenolic resin. excluding novolac epoxy resin Rue epoxy group-containing act as a compatibilizer) one or not also contained in, or contain In any case, the electrical insulation is characterized in that it is a resin composition having a maximum content of 1% by weight or less, or a resin composition according to any one of claims 1 to 10. parts. The molded part has a thin part with a thickness of 2 mm or less, and the thin part directly supports a connection part through which a rated current exceeding 0.2 A flows, or within a distance of 3 mm from these connection parts. The electrically insulating component according to claim 11, wherein a portion is formed. The electrically insulating component according to claim 11 or 12, wherein the connecting portion is a contact point. 14. The device according to claim 11, which is used as a part of a contacted electrical / electronic component selected from the group consisting of a relay, a switch, a connector, a sensor, an actuator, a microswitch, a microsensor, and a microactuator. Electrical insulation parts as described in Crab. The electrically insulating component according to claim 11, wherein the electrically insulating component is molded by injection molding.