JP2016060860A - Polybutylene terephthalate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polybutylene terephthalate resin composition having a high level of flame retardancy, excellent flowability and mechanical strength, free from the problem of flame retardant bleeding, and having sufficient insulating performance.SOLUTION: A polybutylene terephthalate resin composition comprises (A) polybutylene terephthalate resin 80-99 mass% and (B) polycarbonate resin 1-20 mass% and also comprises (C) polyphosphonate polymer 10-90 pts.mass based on 100 pts.mass of the total content of (A) and (B).SELECTED DRAWING: None

Description

  The present invention relates to a polybutylene terephthalate-based resin composition, and more specifically, it has excellent fluidity and mechanical strength while having high flame retardancy, has no problem of flame retardant bleed out, and has sufficient insulation. The present invention relates to a polybutylene terephthalate resin composition.

  Since polybutylene terephthalate resin is excellent in mechanical strength, chemical resistance, electrical insulation and the like, it is widely used in electrical parts such as electric and electronic parts and automobile parts, and machine parts. When used for such applications, it is necessary to have flame retardancy.

  In addition, due to the trend of reducing the size and weight of various devices, various types of electrical and electronic parts and electrical components used therefor have been rapidly reduced in size and thickness. In order to obtain a thin molded product, further good fluidity is required for the resin composition forming the molded product. Such molded products are required to have high flame retardancy of rank V-0 as defined in the UL-94 standard, and the flame retardancy of rank V-0 is also required for the thinnest part of the molded product. The The flame retardancy of the resin composition is more difficult as the molded product becomes thinner.

  On the other hand, as another flame retardancy evaluation method other than the UL-94 standard, there is a glow wire test assuming an electric fire. This test evaluates whether or not to ignite with a hot red glow wire pressed against a test piece. In other words, this is an ignitability evaluation test in an electric fire that assumes ignition by heating of the current-carrying part. In this test, severe characteristics such as a red-hot ignition temperature (Glow-wire Ignition Temperature, abbreviation: GWIT value, IEC60695-2-13) are 775 ° C. or higher recently.

  Furthermore, in an electrical fire, dust or the like containing moisture adheres to the current-carrying part resin surface, a slight current flows, and a carbonized conductive path (track) is formed, leading to heat generation and ignition. As a resistance evaluation against such a tracking phenomenon, there is a comparative tracking index (Comparison tracking index, abbreviation: CTI, IEC60112) based on a tracking resistance test. In recent years, electrical and electronic parts and electrical parts are rapidly becoming smaller and lighter. As a result, the insulation distance is reduced, and the required specifications for the tracking resistance of these parts (molded products) are also reduced. It is becoming increasingly sophisticated.

  As a method for flame-retarding polybutylene terephthalate resin, generally, a method using an aromatic compound containing bromine or chlorine as a flame retardant and an antimony compound such as antimony trioxide as a flame retardant aid is widely adopted. It is expected that the fire extinguishes quickly when the flame is released and that the flame drops fall in contact with the flame. However, this method has problems such as a large amount of smoke generated during combustion and generation of dioxins when the used molded product is incinerated. Therefore, in recent years, it has been strongly desired to use a flame retardant containing no halogen at all in order to overcome the disadvantages of these halogen flame retardants.

Until now, as a method for making a thermoplastic resin flame-retardant without using a halogen-based flame retardant, a method of copolymerizing or compounding a phosphorus compound is known.
For example, as a method for flame-retarding a thermoplastic polyester resin by copolymerization, copolymerization of a phosphonic acid unit or a phosphinic acid unit to a polyester, a copolymerization of a monomer having a cyclic phosphinite skeleton in a pendant, or the like is known. .

  Furthermore, blending calcium salt or aluminum salt of phosphinic acid as a flame retardant (Patent Documents 1 and 2) is also performed. However, this method has a problem that fluidity is lowered by blending a flame retardant, and mechanical properties such as tensile strength and glow wire properties are not sufficient.

  In addition, it is known to blend polyphosphonate as a phosphorus compound (Patent Documents 2 to 8). However, the polybutylene terephthalate resin composition containing a polyphosphonate is excellent in flame retardancy, but the original mechanical properties (for example, tensile strength) of the polybutylene terephthalate resin are impaired, and the polyphosphonate is easily bleed out. Furthermore, it has the big subject that the fluidity | liquidity of a resin composition worsens.

JP-A-8-73720 Japanese Patent Laid-Open No. 11-60924 Japanese Patent Publication No. 47-32297 Japanese Patent Publication No. 47-32299 Japanese Patent Publication No. 52-24943 Japanese Patent Application Laid-Open No. 5-140432 JP-A-8-120180 Special table 2013-522425 gazette

  The present invention has been made in view of such problems, and in the flame-retardant polybutylene terephthalate-based resin composition, both the UL-94 standard and the IEC 60695-2 standard, which have been considered difficult so far, have been developed. To provide a polybutylene terephthalate-based resin composition having excellent fluidity and mechanical strength while having flame retardancy, no problem of flame retardant bleed, sufficient insulation, and excellent balance of physical properties. Objective.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a polybutylene terephthalate resin composition containing a polyphosphonate polymer together with a polycarbonate resin is both UL-94 standard and IEC 60695-2 standard. In order to complete the present invention, the present inventors have found that the present invention satisfies the high flame retardancy, has excellent fluidity and mechanical strength, has no problem of flame retardant bleed, has sufficient insulation, and has excellent balance of physical properties. It came.
The present invention is as follows.

[1] (C) Polyphosphonate system with respect to a total of 100 parts by mass of (A) and (B) containing 80 to 99% by mass of (A) polybutylene terephthalate resin and 1 to 20% by mass of (B) polycarbonate resin A polybutylene terephthalate-based resin composition containing 10 to 90 parts by mass of a polymer.
[2] The polybutylene terephthalate resin composition according to [1], further comprising (D) a nitrogen-based flame retardant in an amount of 10 to 60 parts by mass with respect to a total of 100 parts by mass of (A) and (B). object.
[3] The polybutylene terephthalate resin composition according to the above [1] or [2], wherein the phosphorus content of the (C) polyphosphonate polymer is 5% by mass or more.
[4] Furthermore, (E) The fluoropolymer described in any one of [1] to [3] above, containing 0.01 to 3 parts by mass with respect to 100 parts by mass in total of (A) and (B). Polybutylene terephthalate resin composition.
[5] Furthermore, (F) In any one of the above [1] to [4], containing 0.1 to 5 parts by mass of barium sulfate with respect to 100 parts by mass in total of (A) and (B). Polybutylene terephthalate resin composition.

  The polybutylene terephthalate resin composition of the present invention has high flame retardancy of both UL-94 standard and IEC 60695-2 standard, is excellent in mechanical strength such as fluidity and tensile strength, and has flame retardant bleeding. There is no problem, it is very significant in that it has sufficient insulation and excellent balance of physical properties.

Hereinafter, although an embodiment, an example thing, etc. are shown and explained in detail about the present invention, the present invention is limited to an embodiment, an example, etc. shown below and is not interpreted.
In the present specification, unless otherwise specified, “to” is used in a sense that includes numerical values described before and after it as a lower limit value and an upper limit value.

  The polybutylene terephthalate resin composition of the present invention comprises (A) 80 to 99% by mass of a polybutylene terephthalate resin and (B) 1 to 20% by mass of a polycarbonate resin. A total of 100 parts by mass of (A) and (B). On the other hand, (C) 10-90 mass parts of polyphosphonate type | system | group polymers are contained, It is characterized by the above-mentioned.

[(A) Polybutylene terephthalate resin]
The (A) polybutylene terephthalate resin that is the main component of the polybutylene terephthalate resin composition of the present invention is a polymer having a structure in which terephthalic acid units and 1,4-butanediol units are ester-bonded. That is, in addition to polybutylene terephthalate resin (homopolymer), polybutylene terephthalate copolymer containing other copolymer components other than terephthalic acid units and 1,4-butanediol units, and homopolymers and copolymers thereof Including the mixture.

  (A) The polybutylene terephthalate resin may contain dicarboxylic acid units other than terephthalic acid. Specific examples of other dicarboxylic acids include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2, 5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2′-dicarboxylic acid, biphenyl-3,3′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, bis (4,4 ′ -Carboxyphenyl) Aromatic dicarboxylic acids such as methane, anthracene dicarboxylic acid, aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-dicyclohexyldicarboxylic acid And adipic acid, sebacic acid, azelaic acid, dimer acid, etc. Such as aliphatic dicarboxylic acids, and the like.

  The diol unit may contain other diol units in addition to 1,4-butanediol. Specific examples of the other diol units include aliphatic or alicyclic diols having 2 to 20 carbon atoms. And bisphenol derivatives. Specific examples include ethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, cyclohexanedimethanol, 4,4'-dicyclohexylhydroxymethane. 4,4′-dicyclohexylhydroxypropane, bisphenol A ethylene oxide addition diol, and the like. Furthermore, triols such as glycerin and trimethylolpropane are also included.

  (A) The polybutylene terephthalate resin is preferably a polybutylene terephthalate homopolymer obtained by polycondensation of terephthalic acid and 1,4-butanediol, and the carboxylic acid unit is a kind of dicarboxylic acid other than the terephthalic acid. A polybutylene terephthalate copolymer containing one or more diols other than 1,4-butanediol as the diol unit may be used. In the polybutylene terephthalate resin, the proportion of terephthalic acid in the dicarboxylic acid unit is preferably 70 mol% or more, more preferably 90 mol% or more, from the viewpoint of mechanical properties and heat resistance. Similarly, the proportion of 1,4-butanediol in the diol unit is preferably 70 mol% or more, more preferably 90 mol% or more.

  In addition to the above-mentioned bifunctional monomers, trifunctional monomers such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane are introduced to introduce a branched structure, and fatty acids are used for molecular weight control. A small amount of a monofunctional compound can be used in combination.

  (A) Polybutylene terephthalate resin is a batch polymerization or continuous polymerization of a dicarboxylic acid component having terephthalic acid as a main component or an ester derivative thereof and a diol component having 1,4-butanediol as a main component. Can be manufactured. In addition, after a low molecular weight polybutylene terephthalate resin is produced by melt polymerization, solid state polymerization can be performed under a nitrogen stream or under reduced pressure to increase the degree of polymerization (or molecular weight) to a desired value.

  (A) The polybutylene terephthalate resin is preferably produced by a continuous melt polycondensation of a dicarboxylic acid component mainly composed of terephthalic acid and a diol component mainly composed of 1,4-butanediol.

  The catalyst used in performing the esterification reaction may be a conventionally known catalyst, and examples thereof include a titanium compound, a tin compound, a magnesium compound, and a calcium compound. Of these, titanium compounds are particularly preferred. Specific examples of the titanium compound as the esterification catalyst include titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate and tetrabutyl titanate, and titanium phenolates such as tetraphenyl titanate.

(A) The polybutylene terephthalate resin may be a polybutylene terephthalate resin modified by copolymerization, but as a specific preferred copolymer thereof, a polyalkylene glycol (especially polytetramethylene glycol) is co-polymerized. Polymerized polyester ether resin, dimer acid copolymerized polybutylene terephthalate resin, particularly isophthalic acid copolymerized polybutylene terephthalate resin. These copolymers are those having a copolymerization amount of 1 mol% or more and less than 50 mol% in the total segment of (A) polybutylene terephthalate resin. Among them, the copolymerization amount is preferably 2 to 50 mol%, more preferably 3 to 40 mol%, and particularly preferably 5 to 20 mol%.
And preferable content of these copolymers is 50 mass% or less in the total amount of 100 mass% of (A) polybutylene terephthalate resin, Furthermore, 40 mass% or less, Especially 30 mass% or less.

  (A) The intrinsic viscosity of the polybutylene terephthalate resin is preferably 0.5 to 2 dl / g. From the viewpoint of moldability and mechanical properties, those having an intrinsic viscosity in the range of 0.6 to 1.5 dl / g are preferred. If the intrinsic viscosity is lower than 0.5 dl / g, the resulting resin composition tends to have a low mechanical strength. On the other hand, if it is higher than 2 dl / g, the fluidity of the resin composition may be deteriorated and the moldability may be deteriorated or the laser weldability may be lowered. The intrinsic viscosity is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

  Further, the terminal carboxyl group amount of the (A) polybutylene terephthalate resin may be appropriately selected and determined, but is usually 60 eq / ton or less, preferably 50 eq / ton or less, and preferably 30 eq / ton or less. More preferably. If it exceeds 60 eq / ton, gas tends to be generated during melt molding of the resin composition. Although the lower limit of the amount of terminal carboxyl groups is not particularly defined, it is usually 10 eq / ton in consideration of the productivity of production of polybutylene terephthalate resin.

  The amount of terminal carboxyl groups of the polybutylene terephthalate resin was obtained by dissolving 0.5 g of the polyalkylene terephthalate resin in 25 mL of benzyl alcohol and titrating with a 0.01 mol / l benzyl alcohol solution of sodium hydroxide. Value. As a method for adjusting the amount of terminal carboxyl groups, a conventionally known arbitrary method such as a method for adjusting polymerization conditions such as a raw material charge ratio during polymerization, a polymerization temperature, a pressure reduction method, a method for reacting a terminal blocking agent, etc. Just do it.

[(B) Polycarbonate resin]
The polybutylene terephthalate resin composition of the present invention contains (B) a polycarbonate resin. By containing the (C) polyphosphonate polymer together with the (B) polycarbonate resin, the polybutylene terephthalate resin composition of the present invention is excellent in fluidity while having high flame retardancy for the first time, and (C ) The problem of bleeding of the polyphosphonate polymer can be solved.
The content of (B) polycarbonate resin is based on a total of 100% by mass of (A) polybutylene terephthalate resin and (B) polycarbonate resin, and (B) polycarbonate resin is 1 to 20% by mass, preferably 3% by mass. As mentioned above, More preferably, it is 5 mass% or more, Preferably it is 17 mass% or less, 15 mass% or less is more preferable. If the content is less than the above lower limit value, the problem of flame retardant bleeding will occur, and if it exceeds the above upper limit value, the fluidity will decrease.

  The polycarbonate resin is an optionally branched thermoplastic polymer or copolymer obtained by reacting a dihydroxy compound or a small amount thereof with phosgene or a carbonic acid diester.

  (B) The dihydroxy compound as a raw material of the polycarbonate resin is preferably an aromatic dihydroxy compound, and 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -P-diisopropylbenzene, hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, etc. are mentioned, Preferably bisphenol A is mentioned. In addition, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound can also be used.

  (B) As polycarbonate resin, among the above-mentioned, aromatic polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other An aromatic polycarbonate copolymer derived from an aromatic dihydroxy compound is preferred. Further, it may be a copolymer mainly composed of an aromatic polycarbonate resin, such as a copolymer with a polymer or oligomer having a siloxane structure. Furthermore, you may mix and use 2 or more types of the polycarbonate resin mentioned above.

  In order to adjust the molecular weight of the polycarbonate resin, a monovalent aromatic hydroxy compound may be used. For example, m- and p-methylphenol, m- and p-propylphenol, p-tert-butylphenol, p-long chain And alkyl-substituted phenols.

(B) The viscosity average molecular weight of the polycarbonate resin is preferably 5,000 to 30,000, more preferably 10,000 to 25,000, and further preferably 15,000 to 23,000. preferable. If the viscosity average molecular weight is lower than 5,000, the resin composition tends to have a low mechanical strength. Moreover, in the thing higher than 30,000, the fluidity | liquidity of a resin composition worsens and a moldability may deteriorate. The viscosity average molecular weight of the polycarbonate resin is a viscosity average molecular weight [Mv] converted from the specific viscosity (η _sp ) measured at a temperature of 20 ° C. using methylene chloride as a solvent, according to the following formula.
η _sp /C=[η](1+0.28η _sp)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83

  (B) The manufacturing method of polycarbonate resin is not specifically limited, The polycarbonate resin manufactured by any method of the phosgene method (interfacial polymerization method) and a melting method (transesterification method) can also be used.

[(C) polyphosphonate polymer]
The polybutylene terephthalate resin composition of the present invention contains (C) a polyphosphonate polymer, and 10 to 90 parts by mass with 100 parts by mass of the total of (A) polybutylene terephthalate resin and polycarbonate resin (B). To do.
(C) By containing the polyphosphonate polymer (B) in such an amount together with the polycarbonate resin (B), the problem of bleed out of the polyphosphonate polymer is solved, and high flame retardancy is achieved. It is possible to achieve a polybutylene terephthalate-based resin composition having excellent properties, fluidity and mechanical strength, no bleed problem, and sufficient insulation.

  The preferred content of (C) polyphosphonate polymer is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, with respect to 100 parts by mass in total of (A) polybutylene terephthalate resin and polycarbonate resin (B). More preferably, it is 25 mass parts or more, Preferably it is 85 mass parts or less, More preferably, it is 80 mass parts or less.

  The polyphosphonate polymer is a polymer containing a phosphate ester bond obtained by polycondensation of a bisphenol-based or biphenol-based aromatic diol component and phosphonic dichloride. The (C) polyphosphonate polymer used in the present invention is not particularly limited, and various polymers can be used. Preferably, the following polyphosphonate homopolymer or poly (phosphonate-carbonate) copolymer is used. Can be mentioned.

（式中、Ｙは、炭素数１〜１０のアルキリデン基、炭素数１〜１０のアルキレン基、炭素数５〜１２のシクロアルキレン基、炭素数５〜１２のシクロアルキリデン基、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−または−ＣＯ−を示し、Ｒは炭素数１〜１０のアルキル基を示す。） Examples of the polyphosphonate homopolymer include a polyphosphonate homopolymer composed of a repeating unit represented by the following formula (1).

(In the formula, Y represents an alkylidene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, a cycloalkylidene group having 5 to 12 carbon atoms, -O-,- S—, —SO—, —SO ₂ — or —CO— is represented, and R represents an alkyl group having 1 to 10 carbon atoms.)

(1) Y in the formula may be linear or branched as the C1-C10 alkylidene group of Y. For example, ethylidene group, isopropylidene group, butylidene, hexylidene and the like are preferable. Particularly preferred are those having 1 to 6 carbon atoms.
Preferred examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylylene group, and a hexylene group, and those having 1 to 6 carbon atoms are particularly preferable.
Preferred examples of the cycloalkylene group having 5 to 12 carbon atoms include a cyclopentylene group, cyclohexylene, 2-isopropyl-1,4-cyclohexylene group and the like, and those having 6 to 10 carbon atoms are particularly preferable.
Preferred examples of the cycloalkylidene group having 5 to 12 carbon atoms include a cyclopentylidene group and a cyclohexylidene group, and those having 6 to 10 carbon atoms are particularly preferable.

  In particular, Y is preferably a cyclohexylidene group or a 2,2-propylidene group, particularly preferably a 2,2-propylidene group. In the above formula (1), 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol) A) A polymer composed of a residue and a phosphonic acid residue is particularly preferred.

  R in the phosphonic acid residue in the formula (1) is an alkyl group having 1 to 10 carbon atoms as described above, and is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a heptyl group. A group, an octyl group, a nonyl group, and a decyl group, and these may be branched. Preferred alkyl groups are alkyl groups having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms, particularly methyl groups, ethyl groups, and propyl groups. Among them, a methyl group and an ethyl group are preferable, and a methyl group is most preferable.

Preferred examples of the poly (phosphonate-carbonate) copolymer include a copolymer having a polyphosphonate unit represented by the above formula (1) and a polycarbonate unit represented by the following formula (2).

  The polycarbonate unit of the above formula (2) is composed of a 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A) residue and a carbonate residue.

  The molar ratio of the polyphosphonate unit (1) to the polycarbonate unit (2) in such a poly (phosphonate-carbonate) copolymer is (1) :( 2), preferably 10:90 to 90:10. More preferably, it is 20: 80-80: 20, More preferably, it is 30: 70-70: 30.

  The (C) polyphosphonate polymer preferably has a phosphorus content of 5% by mass or more from the viewpoint of flame retardancy, and high flame retardancy is easily secured even with a small content. The phosphorus content is more preferably 5.5% by mass or more, especially 6% by mass or more, further preferably 6.5% by mass or more, more preferably 20% by mass or less, especially 15% by mass or less, still more preferably. It is 10 mass% or less.

  In addition, the polyphosphonate homopolymer and the poly (phosphonate-carbonate) copolymer may contain both together, each may be used alone or in combination of two or more in any combination and ratio. May be.

  (C) The molecular weight of the polyphosphonate polymer is preferably 10,000 or more in terms of mass average molecular weight, more preferably 15,000 or more, still more preferably 20,000 or more, and preferably 300, 000 or less, more preferably 200,000 or less. When the weight average molecular weight is less than 10,000, the heat resistance of the polybutylene terephthalate resin composition is lowered, and when it exceeds 300,000, problems such as poor compatibility and poor appearance tend to occur. The measurement of the weight average molecular weight is obtained by polystyrene-based gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

  (C) The polyphosphonate polymer can be produced by a known method described in, for example, JP-A-56-5823 and JP-A-56-104934. For example, diphenyl alkylphosphonate and Bisphenol can be obtained by melt transesterification in the presence of a known transesterification catalyst. Further, it is commercially available under the trade name “Nofia” series from the US FRX Polymer Co., Ltd., and is also available.

[(D) Nitrogen-based flame retardant]
The polybutylene terephthalate resin composition of the present invention preferably contains (D) a nitrogen-based flame retardant from the viewpoint of further improving flame retardancy.
Examples of (D) nitrogen flame retardants include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amides, aromatic amides, urea, thiourea and the like.
Examples of the aliphatic amine include ethylamine, butylamine, diethylamine, ethylenediamine, butylenediamine, triethylenetetramine, 1,2-diaminocyclohexane, 1,2-diaminocyclooctane and the like.
Examples of aromatic amines include aniline and phenylenediamine, and examples of nitrogen-containing heterocyclic compounds include uric acid, adenine, guanine, 2,6-diaminopurine, 2,4,6-triaminopyridine, and triazine compounds. Can do.
Examples of the cyan compound include dicyandiamide, examples of the aliphatic amide include N, N-dimethylacetamide, and examples of the aromatic amide include N, N-diphenylacetamide.

The triazine compounds exemplified above are nitrogen-containing heterocyclic compounds having a triazine skeleton, and are triazine, melamine, benzoguanamine, methylguanamine, cyanuric acid, melamine cyanurate, melamine isocyanurate, trimethyltriazine, triphenyltriazine, amelin, and amelide. , Thiocyanuric acid, diaminomercaptotriazine, diaminomethyltriazine, diaminophenyltriazine, diaminoisopropoxytriazine and the like.
As melamine cyanurate or melamine isocyanurate, an adduct of cyanuric acid or isocyanuric acid and a triazine compound is preferable, and usually an adduct having a composition of 1 to 1 (molar ratio), sometimes 1 to 2 (molar ratio). Can be mentioned.

  (D) Among nitrogen-based flame retardants, nitrogen-containing heterocyclic compounds are preferable, among which triazine compounds are preferable, and melamine cyanurate is more preferable.

  (D) Content in the case of containing a nitrogen-based flame retardant is preferably 10 to 60 parts by mass, more preferably 100 parts by mass in total of (A) polybutylene terephthalate resin and (B) polycarbonate resin. 15 parts by mass or more, especially 20 parts by mass or more, more preferably 30 parts by mass or more, more preferably 55 parts by mass or less, especially 50 parts by mass or less, and further preferably 45 parts by mass or less. By including (D) a nitrogen-based flame retardant in such a range, the flame retardancy is further improved, which is preferable.

[(E) Fluoropolymer]
The polybutylene terephthalate resin composition of the present invention preferably contains (E) a fluoropolymer. The preferable content is 0.01-3 mass parts with respect to a total of 100 mass parts of (A) polybutylene terephthalate resin and (B) polycarbonate resin.

(E) As a fluoropolymer, fluoroolefin resin is preferable. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure, and specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, Of these, tetrafluoroethylene resin is preferred.
Moreover, as (E) fluoropolymer, what has a fibril formation ability is preferable, and specifically, the fluoro olefin resin which has a fibril formation ability is mentioned. Thus, it has the tendency to improve dripping prevention property at the time of combustion by having fibril formation ability.

  In addition, as the (E) fluoropolymer, an organic polymer-coated fluoroolefin resin can also be suitably used. By using the organic polymer-coated fluoroolefin resin, the dispersibility is improved, the surface appearance of the molded product is improved, and the surface foreign matter can be suppressed. The organic polymer-coated fluoroolefin resin can be produced by various known methods. For example, (1) a polyfluoroethylene particle aqueous dispersion and an organic polymer particle aqueous dispersion are mixed and powdered by coagulation or spray drying. (2) A method of polymerizing a monomer constituting an organic polymer in the presence of an aqueous dispersion of polyfluoroethylene particles, and then pulverizing or producing the powder by solidification or spray drying. 3) After emulsion polymerization of a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing an aqueous dispersion of polyfluoroethylene particles and an aqueous dispersion of organic polymer particles, a powder is obtained by coagulation or spray drying. And the like, and the like.

  As a monomer for producing an organic polymer covering a fluoroolefin resin, (A) from the viewpoint of dispersibility when blended with a polybutylene terephthalate resin, a monomer having high affinity with the polybutylene terephthalate resin An aromatic vinyl monomer, a (meth) acrylic acid ester monomer, and a vinyl cyanide monomer are more preferable.

  (E) One type of fluoropolymer may be used, or two or more types may be used in any combination and in any ratio.

  (E) The apparent density of the fluoropolymer is preferably 0.4 g / ml or more, more preferably more than 0.45 g / ml, more preferably more than 0.47 g / ml, still more preferably more than 0.48 g / ml, Particularly preferably 0.485 g / ml or more, preferably 0.8 g / ml or less, more preferably 0.7 g / ml or less, still more preferably 0.65 g / ml or less, particularly preferably 0.6 g / ml or less. It is.

  The content of (E) fluoropolymer is preferably 0.01 to 3 parts by mass with respect to a total of 100 parts by mass of (A) polybutylene terephthalate resin and (B) polycarbonate resin. If the amount is less, the flame retardancy improving effect tends to be insufficient, and if the amount exceeds 3 parts by mass, the appearance of the molded product and the mechanical strength are likely to be reduced. The content of (E) fluoropolymer is more preferably 0.1 parts by mass or more, further preferably 0.5 parts by mass or more, particularly preferably 1 part by mass or more, and more preferably 2.5 parts by mass. Hereinafter, it is more preferably 2 parts by mass or less. By including (E) a fluoropolymer in such a range, the flame retardancy is further improved, which is preferable.

[(F) Barium sulfate]
The polybutylene terephthalate resin composition of the present invention preferably contains (F) barium sulfate. (F) By containing barium sulfate, the insulation property of the polybutylene terephthalate resin composition, for example, the tracking resistance performance by a comparative tracking index test (CTI test) can be improved.

  (F) The barium sulfate may be naturally produced or may be obtained by synthesis. For example, natural barite pulverized may be used as the naturally produced barium sulfate. . Moreover, as what is obtained by synthesis, barium sulfate synthesized by a known synthesis method can be used.

  The method for producing barium sulfate is not particularly limited and can be produced by a known method. For example, sodium sulfate aqueous solution and barium sulfide aqueous solution are reacted as a method for obtaining particulate barium sulfate. A method in which a specific metaphosphate is allowed to coexist in an aqueous solution, and the reaction is carried out in the presence of a stoichiometrically excessive molar ratio of sodium sulfate to barium sulfide (Japanese Patent Laid-Open No. 47-31898), barium sulfide aqueous solution and sulfuric acid A method in which the aqueous solution is continuously introduced into a reaction vessel such as a pump so that the barium sulfide concentration becomes excessive, and the reaction is carried out with stirring (Japanese Patent Laid-Open No. 57-51119), a sulfuric acid aqueous solution and a specific barium salt aqueous solution Are fed separately and simultaneously in the correct stoichiometric ratio to the spraying device and reacted, and the medium containing the precipitate formed is pre-concentrated How to spray drying (Japanese Patent Laid-Open No. 2-83211), and the like.

(F) The moisture content in barium sulfate is preferably 1.5% by mass or less, more preferably 1% by mass or less, further preferably 0.8% by mass or less, It is particularly preferable that the content is not more than mass%. When it exceeds 1.5 mass%, the hydrolysis resistance and mechanical properties of the resulting polybutylene terephthalate resin composition may be lowered. In addition, the moisture content in (F) barium sulfate is measured by JIS K-5101.
(F) Although there is no restriction | limiting in particular in the average particle diameter of barium sulfate, Usually, it is 0.05-3 micrometers, It is preferable that it is 0.1-2 micrometers, It is more preferable that it is 0.15-1.5 micrometers. . (F) By making the average particle diameter of the barium sulfate particles in the above range, the balance between mechanical properties and tracking resistance is easily improved.

(F) The barium sulfate may have been surface-treated by a known method. Examples of the surface treatment agent include known organic compounds and inorganic compounds, but inorganic compounds are preferable.
For example, inorganic compounds such as aluminum hydroxide, alumina, silica, zirconia, zirconium hydroxide, zirconia hydrate, cerium oxide, cerium oxide hydrate, cerium hydroxide and other aluminum, silicon, zirconium, cerium and other inorganic compounds Preferred examples include oxides and hydroxides. These inorganic compounds may be hydrates. Among these, aluminum hydroxide and silica are preferable, and when silica is used, a silica hydrate represented by SiO ₂ · nH ₂ 0 is particularly preferable.
Moreover, as an organic compound, an amine compound is preferable and amine compounds, such as a monoethanolamine, a diethanolamine, a triethanolamine, a dichlorohexylamine, can be illustrated as a more preferable compound.
(F) When surface-treating barium sulfate, it may be surface-treated with an inorganic compound and then surface-treated with an organic compound. In particular, after surface-treating with aluminum hydroxide and / or silica hydrate, the organic compound Those subjected to surface treatment with are also preferably used.

Although the thickness of a surface treatment layer is not specifically limited, It is preferable that it is 0.05-0.5 micrometer, More preferably, it is 0.1-0.2 micrometer.
(F) When surface-treating barium sulfate, the content of barium sulfate in the surface-treated barium sulfate is preferably 85 to 99.5% by mass, more preferably 88 to 99% by mass. Preferably, it is 90-98 mass%. Such a barium sulfate content is preferred because it tends to be finely dispersed in the polybutylene terephthalate resin composition and the tracking resistance tends to be improved. The barium sulfate content in the surface-treated barium sulfate is measured according to JIS K-5115.

  The content of (F) barium sulfate is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 4 parts by mass with respect to a total of 100 parts by mass of (A) polybutylene terephthalate resin and (B) polycarbonate resin. Preferably, 1 to 3 parts by mass is more preferable. When the content is less than 0.1 parts by mass, the effect of improving the tracking resistance is difficult to obtain, and when it exceeds 5 parts by mass, the mechanical properties tend to deteriorate.

[Reinforcing filler]
The polybutylene terephthalate resin composition of the present invention preferably contains a reinforcing filler. In the present invention, the reinforcing filler means a material that is contained in a resin component to improve strength and rigidity, and may be in any form such as fibrous, plate-like, granular, and amorphous.

  When the form of the reinforcing filler is fibrous, it may be inorganic or organic. For example, glass fiber, carbon fiber, silica / alumina fiber, zirconia fiber, boron fiber, boron nitride fiber, silicon nitride potassium titanate fiber, metal fiber, organic fiber such as wollastonite, fluorine resin fiber, aramid fiber, etc. Fiber is included. When the reinforcing filler is fibrous, inorganic fibers are preferable, and among them, glass fibers are particularly preferable. The reinforcing filler may be a single type or a mixture of two types.

  When the form of the reinforcing filler is fibrous, the average fiber diameter, average fiber length, and cross-sectional shape are not particularly limited, but the average fiber diameter is preferably selected in the range of, for example, 1 to 100 μm, and the average fiber length is, for example, It is preferable to select in the range of 0.1 to 20 mm. The average fiber diameter is more preferably about 1 to 50 μm, more preferably about 5 to 20 μm. The average fiber length is preferably about 0.12 to 10 mm. In addition, when the fiber cross section is a flat shape such as an oval, an ellipse, or a bowl, the flatness ratio (major axis / minor axis ratio) is preferably 1.4 to 10, more preferably 2 to 6. 5 to 5 is more preferable. It is preferable to use glass fibers having such an irregular cross section because dimensional stability such as warpage of the molded product and anisotropy of the shrinkage rate is easily improved.

In order to improve the adhesion at the interface between the reinforcing filler and the resin component, the surface of the reinforcing filler is preferably treated with a sizing agent or a surface treatment agent. Examples of the sizing agent include epoxy compounds and acrylic compounds, and examples of the surface treatment agent include functional compounds such as isocyanate compounds, silane compounds, and titanate compounds. In particular, in the present invention, the reinforcing filler is preferably treated with a bisphenol type epoxy compound and / or a novolak type epoxy compound. From the viewpoint of alkali resistance, hydrolysis resistance and mechanical properties, the novolak type is used. Those treated with an epoxy compound are more preferred.
The reinforcing filler may be surface-treated in advance with the sizing agent or surface treatment agent, and may be surface-treated by adding a sizing agent or surface treatment agent when preparing the resin composition of the present invention.

  In addition to the fibrous reinforcing filler described above, other reinforcing fillers in the form of plates, granules, or amorphous can also be contained. The plate-like inorganic filler exhibits a function of reducing anisotropy and warping, and examples thereof include glass flakes, talc, mica, mica, kaolin, and metal foil. Among the plate-like inorganic fillers, glass flakes are preferable.

  Other inorganic fillers that are granular or amorphous include ceramic beads, asbestos, clay, zeolite, potassium titanate, barium sulfate, titanium oxide, silicon oxide, aluminum oxide, magnesium hydroxide, and the like.

  The content in the case of containing a reinforcing filler is preferably in the range of 30 to 100 parts by mass, more preferably 40 parts by mass or more, with respect to 100 parts by mass in total of (A) polybutylene terephthalate resin and (B) polycarbonate resin. 50 parts by mass or more, more preferably 90 parts by mass or less, and more preferably 80 parts by mass or less.

[Stabilizer]
The polybutylene terephthalate resin composition of the present invention preferably contains a phosphorus stabilizer and / or a phenol stabilizer.

  Any known phosphorous stabilizer can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. Particularly preferred.

Organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di- tert-butylphenyl) octyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetrakis ( , 4-di -t- butyl-phenyl) -4,4'-biphenylene phosphonite, and the like. Specific examples of such organic phosphite compounds include, for example, “ADK STAB 1178”, “ADK STAB 2112”, “ADK STAB HP-10”, “ADK STAB PEP36” manufactured by ADEKA, and “JP” manufactured by Johoku Chemical Industry Co., Ltd. -351 "," JP-360 "," JP-3CP "," Irgaphos 168 "manufactured by BASF, and the like.
In addition, 1 type may contain phosphorus stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the phosphorus stabilizer is usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably, with respect to 100 parts by mass in total of (A) polybutylene terephthalate resin and (B) polycarbonate resin. It is 0.3 mass part or more, and is 2 mass parts or less normally, Preferably it is 1.5 mass parts or less, More preferably, it is 1 mass part or less. If the content of the phosphorus stabilizer is less than the lower limit of the range, the thermal stability effect may be insufficient, and if the content of the phosphorus stabilizer exceeds the upper limit of the range, it is excessive. There is a tendency that the amount of silver and the deterioration of hue are more likely to occur, and the effect reaches its peak and is not economical.

  As a phenol type stabilizer, a hindered phenol type stabilizer is mentioned, for example. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″ (Mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4 -Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert) -Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (Octylthio) -1,3,5-triazin-2-ylamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6- -tert- pentylphenyl acrylate.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such a phenol-based stabilizer include “Irganox 1010”, “Irganox 1076” manufactured by BASF, “Adekastab AO-50”, “Adekastab AO-60” manufactured by ADEKA, and the like. Can be mentioned.
In addition, 1 type may be contained for the phenol type stabilizer, and 2 or more types may be contained by arbitrary combinations and ratios.

  The content of the phenol-based stabilizer is usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more with respect to 100 parts by mass in total of (A) polybutylene terephthalate resin and (B) polycarbonate resin. Preferably it is 0.3 mass part or more, and is 2 mass parts or less normally, Preferably it is 1.5 mass parts or less, More preferably, it is 1 mass part or less. If the content of the phenol-based stabilizer is less than the lower limit of the range, the thermal stability effect may be insufficient, and if the content of the phenol-based stabilizer exceeds the upper limit of the range, it is excessive. There is a tendency that the amount of silver and the deterioration of hue are more likely to occur, and the effect reaches its peak and is not economical.

[Release agent]
Moreover, it is also preferable that the polybutylene terephthalate resin composition of the present invention contains a release agent. Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane silicone oils, and the like.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the term “aliphatic” is used as a term including alicyclic compounds.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine and comprise one ester may each be used 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized.

Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
The aliphatic hydrocarbon may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

  In addition, 1 type may contain the release agent mentioned above, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the release agent is usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and particularly preferably 0 with respect to 100 parts by mass in total of (A) polybutylene terephthalate resin and (B) polycarbonate resin. .3 parts by mass or more, and usually 2 parts by mass or less, preferably 1.5 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.8 parts by mass or less. When the content of the release agent is less than the lower limit of the above range, the effect of releasability may not be sufficient, and in this case, the surface appearance tends to deteriorate. When the content of the release agent exceeds the upper limit of the above range, degradation of hydrolysis resistance, mold contamination during injection molding, and the like are likely to occur.

[Other ingredients]
The polybutylene terephthalate-based resin composition of the present invention may contain other components in addition to those described above, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polybutylene terephthalate resin and polycarbonate resin, various resin additives, and the like. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

Other resins Examples of other resins include thermoplastic polyester resins other than polybutylene terephthalate resins such as polyethylene terephthalate resin and polytrimethylene terephthalate; polystyrene resins, high impact polystyrene resins (HIPS), and acrylonitrile-styrene copolymers. Styrenic resins such as (AS resin); Polyolefin resins such as polyethylene resins and polypropylene resins; Polyamide resins; Polyimide resins; Polyetherimide resins; Polyurethane resins; Polyphenylene ether resins; Polyphenylene sulfide resins; Polysulfone resins; Can be mentioned.
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and a ratio.

Resin additives Examples of resin additives include ultraviolet absorbers, dyes and pigments (including carbon black), antistatic agents, antifogging agents, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents Etc. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.

[Production method of polybutylene terephthalate resin composition]
There is no restriction | limiting in the manufacturing method of the resin composition of this invention, The manufacturing method of a well-known polybutylene terephthalate type-resin composition can be employ | adopted widely.
Specific examples include (A) polybutylene terephthalate resin, (B) polycarbonate resin and (C) polyphosphonate polymer, and other components blended as necessary, such as a tumbler or Henschel mixer. Examples thereof include a method of premixing using various mixers and then melt-kneading with a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, or kneader.

In addition, for example, the polybutylene terephthalate resin composition of the present invention may be used without mixing each component in advance, or by mixing only a part of the components in advance, supplying the mixture to an extruder using a feeder, and melt-kneading the mixture. Can also be manufactured.
Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, this master batch is again mixed with the remaining components and melt-kneaded. The polybutylene terephthalate resin composition of the present invention can also be produced.
In addition, for example, when mixing a component that is difficult to disperse, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance, and kneaded with the solution or the dispersion. It can also improve sex.

The polybutylene terephthalate resin composition of the present invention thus obtained preferably has a flame retardance of 0.75 mm in conformity with UL-94 as V-0 in terms of flame retardancy. Further, GWIT defined in IEC60695-2-13 is preferably 800 ° C. or higher, more preferably 825 ° C. or higher, and further preferably 850 ° C. or higher. Furthermore, in terms of electrical characteristics, the CTI defined in IEC60112 is preferably 300 ° C. or higher, and more preferably 325 ° C. or higher. In terms of fluidity, temperature 250 ° C., preferably conditions with a measured melt volume rate of the load 5 kgf (MVR) is 10 cm ³ / 10min or ^more, and more preferably 15cm 3 / 10min or more. In terms of mechanical properties, the tensile strength at break measured according to ISO 527 is preferably 105 MPa or more, and more preferably 110 MPa or more. In addition, the evaluation method of a flame retardance, GWIT, CTI, MVR, and tensile breaking strength is as describing in the below-mentioned Example.

  As a method for producing the molded article, a molding method generally employed for the polybutylene terephthalate resin composition can be arbitrarily adopted. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, Examples thereof include a blow molding method, and a molding method using a hot runner method can also be used. Of these, injection molding methods such as injection molding, ultra-high speed injection molding, and injection compression molding are preferred.

[Molding]
Examples of molded products include parts such as electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods / miscellaneous goods, and lighting equipment. Among these, it is suitable for use in components such as electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, and lighting equipment.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
Each component used in Examples and Comparative Examples is as shown in Table 1 below.

(Examples 1-3, Comparative Examples 1-3)
Each component described in Table 1 above is blended so as to have a blending ratio (parts by mass) described in Table 2 below, and a twin-screw extruder (“TEX-30α” manufactured by Nippon Steel Works, screw diameter 30 mm) is used. Then, pellets of the extruded resin composition were made at a barrel set temperature of 250 ° C. and a screw rotation speed of 200 rpm.

[Flowability (MVR)]
After the pellets obtained above were dried at 120 ° C. for 6 hours using a melt indexer manufactured by Takara Industries Co., Ltd., the melt flow volume MVR per unit time measured at a temperature of 250 ° C. and a load of 5 kgf (unit: : it was measured ^cm 3 / 10min).

  Test pieces for evaluation for each evaluation were injection-molded at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. using an injection molding machine (“NEX-80” manufactured by Nissei Plastic Industry Co., Ltd.). In molding, the resin composition pellets were dried at 120 ° C. for 6 to 8 hours until immediately before.

[Tensile breaking strength]
Using an ISO multipurpose test piece (4 mm thickness) obtained by injection molding, the tensile strength at break (unit: MPa) was measured according to ISO 527.

[Flammability (UL-94) test]
Using a test piece for flammability test for UL-94 having a thickness of 0.75 mm obtained by injection molding, flammability was evaluated according to the UL-94 standard.

[Bleed-out property]
The ISO multi-purpose test piece obtained by injection molding is taken out after being left in a pressure cooker test machine maintained at a temperature of 121 ° C., a humidity of 100% and a pressure of 2 atm for 50 hours, and the surface of the test piece is visually and palpated for bleeding out. The presence or absence was confirmed.

[GWIT test]
In accordance with a test method defined in IEC 60695-2-13, a plate test piece having a size of 60 mm × 60 mm and a thickness of 4 mm obtained by injection-molding a Glow-wire Ignition Temperature test (abbreviation: GWIT test). went. Specifically, 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 with a test piece for 30 seconds, and a temperature 25 ° C. higher than the maximum temperature at the tip that does not ignite. Is defined by the red hot rod ignition temperature and the test method concerned.

[CTI test]
CTI was determined by a test method defined in the international standard IEC60112 for a flat plate test piece having a size of 60 mm × 60 mm and a thickness of 3 mm. CTI shows the resistance to tracking at a voltage in increments of 25V between 100V and 600V when wet-contaminated with an electric field applied to the surface of a solid electrical insulating material. The higher the value, the better. Means.
The above evaluation results are shown in Table 2 below.

  The polybutylene terephthalate resin composition of the present invention has high flame retardancy of both UL-94 standard and IEC 60695-2 standard, but has excellent fluidity and mechanical strength, and has no problem of flame retardant bleeding. Since it has sufficient insulation properties and excellent balance of physical properties, it can be suitably applied as a part of electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, lighting equipment, etc., and its industrial utility is very high. .

Claims (5)

  (A) Polybutylene terephthalate resin 80 to 99% by mass and (B) Polycarbonate resin 1 to 20% by mass with respect to a total of 100 parts by mass of (A) and (B), (C) Polyphosphonate polymer A polybutylene terephthalate resin composition containing 10 to 90 parts by mass.   Furthermore, the polybutylene terephthalate-type resin composition of Claim 1 which contains 10-60 mass parts of (D) nitrogen-type flame retardant with respect to a total of 100 mass parts of said (A) and (B).   (C) The polybutylene terephthalate resin composition according to claim 1 or 2, wherein the polyphosphonate polymer has a phosphorus content of 5% by mass or more.   Furthermore, the polybutylene terephthalate of any one of Claims 1-3 which contain 0.01-3 mass parts of (E) fluoropolymer with respect to a total of 100 mass parts of said (A) and (B). -Based resin composition.   Furthermore, the polybutylene terephthalate of any one of Claims 1-4 which contains 0.1-5 mass parts of (F) barium sulfate with respect to a total of 100 mass parts of said (A) and (B). -Based resin composition.