JP6488336B2 - Polybutylene terephthalate resin composition and molded article - Google Patents

Description

  The present invention relates to a polybutylene terephthalate resin composition and a molded article, and more specifically, a polybutylene terephthalate resin composition excellent in flame retardancy, impact resistance, hydrolysis resistance, heat discoloration, and releasability, and It relates to the molded product.

  In recent years, automobiles that include an electric motor as a power source, such as electric vehicles and plug-in hybrid vehicles, have become widespread, and it has been promoted to install a charging stand for battery charging for such vehicles, In addition, charger connectors for electric vehicles for battery charging and / or battery capacitor holders have been used.

Highly flame-retardant is required for a battery connector for an electric vehicle, a battery capacitor holder, a casing for constituting a charging stand for an electric vehicle, and many metal ones are used. In addition, there is a movement to convert this into a resin, and various resins are being studied.
Among these, polybutylene terephthalate resin has excellent properties as engineering plastics such as excellent heat resistance, moldability, chemical resistance, and electrical insulation, so electrical and electronic parts, automobile parts and other electrical parts, It is used for machine parts, etc., and it has been studied to make it flame-retardant.

  As a method for imparting flame retardancy to polybutylene terephthalate resin, generally, a flame retardant using antimony trioxide (see Patent Document 1) as a halogen compound or a flame retardant aid is added to polybutylene terephthalate resin. By doing so, a method of making it flame retardant is well known. Similarly to other electric and electronic parts, charger connectors for electric vehicles, battery capacitor holders, battery capacitor housings, or charging stand housings for electric vehicles are thin due to the trend toward smaller and lighter devices. Miniaturized and molded products used for it are becoming smaller and thinner, and high-level flame retardancy is required for thin molded products. Becomes difficult.

  In the field of electrical and electronic equipment, in addition to flame retardancy, it is necessary to have excellent tracking resistance, which is one of the electrical characteristics, in order to ensure safety against ignition against an electrical load.

Furthermore, polybutylene terephthalate resin has a problem that the toughness typified by impact strength is insufficient due to its excellent crystal characteristics, and research on polymer alloys has been conducted to solve this problem. Various proposals have been made for the flame retardant formulation.
For example, Patent Document 2 discloses a flame retardant polyester resin composition comprising a polybutylene terephthalate resin, a polycarbonate resin, a halogen flame retardant, a flame retardant assistant, and a transesterification inhibitor as constituents. 3 discloses a flame-retardant polyester resin composition comprising a polybutylene terephthalate resin, a polycarbonate resin, an elastomer, a flame retardant, and a flame retardant aid. Furthermore, Patent Document 4 discloses a polyester resin composition comprising a polyester resin, a polystyrene rubber and a flame retardant.

However, the required physical properties in the field of electrical and electronic equipment are becoming increasingly sophisticated, and it has become difficult to cope with conventional prescriptions.
Furthermore, excellent mold releasability that does not increase the mold release resistance is also required in injection molding, for example, there is no occurrence of ejector pin marks when taking out from the mold, the surface appearance is good, and warpage is not caused. There is a strong demand for something that does not exist.

JP-A-61-66746 JP 2007-314664 A JP-A-6-100713 JP 2005-112994 A

  An object of the present invention is to provide a polybutylene terephthalate resin composition excellent in flame retardancy, impact resistance, hydrolysis resistance, heat discoloration resistance and releasability, and a molded product thereof.

As a result of intensive studies to solve the above problems, the present inventor has contained a specific amount of a polycarbonate resin, a brominated polycarbonate flame retardant, and an antimony compound in a polybutylene terephthalate resin, and a polyolefin-based release agent. It has been found that by containing a mold agent, a polybutylene terephthalate resin composition excellent in flame retardancy, impact resistance, hydrolysis resistance, heat discoloration resistance and releasability and a molded product thereof can be provided. Was completed.
That is, according to the present invention, the following polybutylene terephthalate resin compositions and molded articles are provided.

[1] The (A) polybutylene terephthalate resin and the (B) polycarbonate resin are based on a total of 100 parts by mass of (A) and (B), (A) is 50 to 80 parts by mass, and (B) is 20 to 20 parts. 50 parts by mass, and (C) 5 to 40 parts by mass of brominated polycarbonate flame retardant, (D) 1 to 15 parts by mass of antimony compound, and (A) and 100 parts by mass of (B). E) containing 0.01 to 3 parts by mass of a polyolefin-based mold release agent , and (D) the antimony compound is a masterbatch with (A) polybutylene terephthalate resin having an antimony compound concentration of 30 to 90% by mass polybutylene terephthalate-based resin composition characterized in that there.
[2] The polybutylene terephthalate resin composition according to the above [1], wherein the (B) polycarbonate resin has a viscosity average molecular weight exceeding 28000.
[3] The polybutylene terephthalate resin composition according to [1] or [2] above, wherein the intrinsic viscosity of the (A) polybutylene terephthalate resin is 0.9 dl / g or more.
[4] The polybutylene according to any one of [1] to [3], further comprising (F) an elastomer in an amount of 5 to 20 parts by mass with respect to a total of 100 parts by mass of (A) and (B). A terephthalate resin composition.
[5] The polybutylene terephthalate resin composition as described in [4] above, wherein the (F) elastomer is an acrylic core / shell type graft copolymer.
[6] The polybutylene terephthalate resin composition according to the above [4] or [5], wherein the average particle diameter of the elastomer (F) is 300 nm or more .
[7 ] Furthermore, (G) the anti-dripping agent is contained in any one of the above [1] to [ 6 ] containing 0.05 to 1 part by mass with respect to 100 parts by mass in total of (A) and (B). The polybutylene terephthalate resin composition described.
[ 8 ] The polybutylene terephthalate resin composition according to any one of [1] to [ 7 ], wherein the dropping point of the (E) polyolefin release agent is 100 ° C. or lower.

[ 9 ] Furthermore, (H) the metal salt of the organic phosphate compound represented by any one of the following general formulas (1) to (4) is added to 100 parts by mass of the total of (A) and (B). 0.001 to 1 part by mass of the polybutylene terephthalate resin composition according to any one of [1] to [ 8 ] above.
(In General Formula (1), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and M represents an alkaline earth metal or zinc. .)
(In General Formula (2), R ⁵ represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and M represents an alkaline earth metal or zinc.)
(In General Formula (3), R ^{6 to} R ¹¹ each independently represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and M ′ represents a trivalent metal ion. Represents a metal atom.)
(In General Formula (4), R ^{12 to} R ¹⁴ each independently represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and M ′ represents a trivalent metal ion. Represents a metal atom, and two M's may be the same or different.)

[ 10 ] A molded product obtained by molding the polybutylene terephthalate resin composition according to any one of [1] to [ 9 ].
[ 11 ] A molded article obtained by molding the polybutylene terephthalate resin composition according to any one of [4] to [ 9 ] above, wherein the (A) polybutylene terephthalate series is formed at the core of the molded article. A molded article characterized in that the resin and the (B) polycarbonate resin form a co-continuous phase, and the (F) elastomer has a morphology existing in the (B) polycarbonate resin phase.
[ 12 ] The molded product according to [ 11 ] above, wherein 80% or more of the (D) antimony compound is present in the (A) polybutylene terephthalate resin phase in the core of the molded product.
[ 13 ] In the surface layer portion of the molded product, (F) the elastomer phase extends in the resin flow direction, and the ratio of the major axis to the minor axis (major axis / minor axis) is 3 to 20 above [ 11 ] or [ 12 ].
[ 14 ] The molded article according to any one of [ 11 ] to [ 13 ], wherein the (C) brominated polycarbonate-based flame retardant is present in the (B) polycarbonate resin phase.
[ 15 ] The molded product according to any one of [ 10 ] to [ 14 ], which is any one of a charger connector for an electric vehicle, a battery capacitor holder, a battery capacitor casing, or a casing for a charging stand for an electric vehicle.

  The polybutylene terephthalate resin composition of the present invention is a resin material excellent in flame retardancy, impact resistance, hydrolysis resistance, heat discoloration and releasability. Automotive charger connector, battery capacitor holder, battery capacitor housing or housing for electric vehicle charging station, electronic and electrical equipment parts housing, connector, relay, switch, sensor, actuator, terminal switch, rice cooker related parts It can be suitably used for grill cooking equipment parts and the like.

6 is a STEM photograph of a core part of a molded product obtained in Example 7. 6 is a STEM photograph of a core part of a molded product obtained in Example 7. 4 is a SEM photograph of a surface layer portion of a molded product obtained in Example 7.

[Summary of Invention]
The polybutylene terephthalate resin composition of the present invention comprises (A) 50 to 80 masses of A) polybutylene terephthalate resin and (B) polycarbonate resin based on a total of 100 parts by mass of (A) and (B). Parts, (B) is contained in an amount of 20 to 50 parts by mass, and (C) 5 to 40 parts by mass of a brominated polycarbonate flame retardant, and (D) antimony with respect to a total of 100 parts by mass of (A) and (B). (A) Polybutylene terephthalate containing 1 to 15 parts by mass of compound and 0.01 to 3 parts by mass of (E) polyolefin-based mold release agent , and (D) antimony compound having an antimony compound concentration of 30 to 90% by mass It is a master batch with a resin .

Hereinafter, the contents of the present invention will be described in detail.
The description of each constituent element described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is interpreted to be limited to such embodiments and specific examples. It is not a thing. In the specification of the present application, “to” is used in the sense of including the numerical values described before and after it as the lower limit value and the upper limit value.

[(A) Polybutylene terephthalate resin]
As the main component constituting the polybutylene terephthalate resin composition of the present invention, (A) polybutylene terephthalate resin (hereinafter sometimes abbreviated as “PBT resin”) includes terephthalic acid units and 1,4. -A polymer having a structure in which 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.

  The PBT 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, and 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) methane , Aromatic dicarboxylic acids such as anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 4,4′-dicyclohexyldicarboxylic acid, and adipic acid , Aliphatic dicarboxylic acids such as sebacic acid, azelaic acid, dimer acid, etc. .

  The diol unit may contain other diol units in addition to 1,4-butanediol, but specific examples of 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.

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

The PBT resin is produced by melt-polymerizing a dicarboxylic acid component containing terephthalic acid as a main component or an ester derivative thereof and a diol component containing 1,4-butanediol as a main component in a batch or continuous manner. Can do. In addition, after producing a low molecular weight polybutylene terephthalate resin by melt polymerization, the degree of polymerization (or molecular weight) can be increased to a desired value by further solid-phase polymerization under a nitrogen stream or under reduced pressure.
The PBT resin is preferably obtained by a production method in which a dicarboxylic acid component containing terephthalic acid as a main component and a diol component containing 1,4-butanediol as a main component are continuously melt polycondensed.

  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.

The PBT resin may be a polybutylene terephthalate resin modified by copolymerization. As a specific preferred copolymer thereof, a polyalkylene glycol (particularly, polytetramethylene glycol (PTMG)) is copolymerized. Examples include polyester ether resins, dimer acid copolymerized polybutylene terephthalate resins, and particularly isophthalic acid copolymerized polybutylene terephthalate resins. These copolymers are those having a copolymerization amount of 1 mol% or more and less than 50 mol% in all segments of the PBT 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 the preferable content of these copolymers is 10-100 mass% in the total amount of 100 mass% of (A) polybutylene terephthalate resin, Furthermore, 30-100 mass%, Especially it is 50-100 mass%. is there.

  The intrinsic viscosity ([η]) of the PBT resin is preferably 0.9 dl / g or more. If the intrinsic viscosity is lower than 0.9 dl / g, the resulting resin composition tends to have a low mechanical strength such as impact resistance. The intrinsic viscosity is preferably 1.8 dl / g or less, more preferably 1.6 dl / g or less, and further preferably 1.3 dl / g or less. If it is higher than 1.8 dl / g, the fluidity of the resin composition may deteriorate and the moldability may deteriorate. The intrinsic viscosity is measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

[(B) Polycarbonate resin]
The polybutylene terephthalate resin composition of the present invention contains (B) a polycarbonate resin.
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. The production method of the polycarbonate resin is not particularly limited, and a polycarbonate resin produced by a conventionally known phosgene method (interfacial polymerization method) or a melting method (transesterification method) can be used.

  As the raw material dihydroxy compound, an aromatic dihydroxy compound is preferable, 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. A compound in which one or more tetraalkylphosphonium sulfonates are bonded to the aromatic dihydroxy compound can also be used.

  As the 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 aromatic dihydroxy Aromatic polycarbonate copolymers derived from the compounds are 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.

  The viscosity average molecular weight (Mv) of the polycarbonate resin is preferably 20000 or more, more preferably 23000 or more, further preferably 25000 or more, and particularly preferably more than 28000. When a resin having a viscosity average molecular weight lower than 20000 is used, the resulting resin composition tends to have a low mechanical strength such as impact resistance. Moreover, it is preferable that it is 60000 or less, It is more preferable that it is 40000 or less, It is further more preferable that it is 35000 or less. If it is higher than 60000, the fluidity of the resin composition may deteriorate and the moldability may deteriorate.

In the present invention, the viscosity average molecular weight (Mv) of the polycarbonate resin is determined by measuring the viscosity of the methylene chloride solution of the polycarbonate resin at 20 ° C. using an Ubbelohde viscometer, and determining the intrinsic viscosity ([η]). The value calculated from the following Schnell viscosity equation is shown.
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83

  The method for producing the polycarbonate resin is not particularly limited, and a polycarbonate resin produced by any of the phosgene method (interfacial polymerization method) and the melting method (transesterification method) can also be used. Moreover, the polycarbonate resin which performed the post-process which adjusts the amount of terminal OH groups to the polycarbonate resin manufactured by the melting method is also preferable.

  The content of (B) polycarbonate resin is based on a total of 100 parts by mass of (A) polybutylene terephthalate resin and (B) polycarbonate resin, and (B) polycarbonate resin is 20 to 50 parts by mass, preferably 25 parts by mass. Part or more, more preferably 30 parts by weight or more, preferably 45 parts by weight or less, more preferably 43 parts by weight or less, and still more preferably 40 parts by weight or less. Below the lower limit, the effect of improving the impact resistance and toughness of the polybutylene terephthalate resin composition of the present invention is small, and the dimensional stability is lowered. Moreover, when it exceeds the said upper limit, fluidity | liquidity will worsen and a moldability will deteriorate.

[(C) Brominated polycarbonate flame retardant]
The polybutylene terephthalate resin composition of the present invention contains (C) a brominated polycarbonate flame retardant. Examples of flame retardants include halogen flame retardants, phosphorus flame retardants (such as melamine polyphosphate), nitrogen flame retardants (such as melamine cyanurate), metal hydroxides (such as magnesium hydroxide), The present invention is characterized by containing a bromine-based and brominated polycarbonate-based flame retardant as the halogen-based flame retardant. (C) Brominated polycarbonate flame retardant has good compatibility with (B) polycarbonate resin, and (C) Brominated polycarbonate flame retardant is easily present in (B) polycarbonate resin phase, improving impact resistance. To do.

  (C) As a brominated polycarbonate flame retardant, specifically, for example, a brominated polycarbonate obtained from brominated bisphenol A, particularly tetrabromobisphenol A is preferable. Examples of the terminal structure include a phenyl group, 4-t-butylphenyl group, 2,4,6-tribromophenyl group, etc., and particularly those having a 2,4,6-tribromophenyl group in the terminal group structure. Is preferred.

  The average number of carbonate repeating units in the brominated polycarbonate flame retardant may be appropriately selected and determined, but is usually 2 to 30. If the average number of carbonate repeating units is small, the molecular weight of the (A) polybutylene terephthalate resin may be lowered during melting. On the other hand, if it is too large, the melt viscosity of the polycarbonate resin (B) becomes high, causing a dispersion failure in the molded product, and the appearance of the molded product, particularly the glossiness may be lowered. Therefore, the average number of repeating units is preferably 3 to 15, particularly 3 to 10.

  The molecular weight of the brominated polycarbonate-based flame retardant is arbitrary and may be appropriately selected and determined. Preferably, the viscosity average molecular weight is 1000 to 20000, and preferably 2000 to 10,000. In addition, the viscosity average molecular weight of a brominated polycarbonate flame retardant can be calculated | required by the method similar to the measurement of the viscosity average molecular weight of (B) polycarbonate resin.

  The brominated polycarbonate flame retardant obtained from the brominated bisphenol A can be obtained by, for example, a usual method of reacting brominated bisphenol and phosgene. Examples of the end-capping agent include aromatic monohydroxy compounds, which may be substituted with a halogen or an organic group.

  The content of (C) brominated polycarbonate flame retardant is 5 to 40 parts by mass, preferably 7 parts by mass or more, based on 100 parts by mass of (A) polybutylene terephthalate resin and (B) polycarbonate resin. More preferably, it is 10 parts by mass or more, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and further preferably 20 parts by mass or less. (C) If the content of the flame retardant is too small, the flame retardancy of the resin composition becomes insufficient. On the other hand, if the content is too large, problems such as deterioration of mechanical properties and releasability and bleeding out of the flame retardant occur.

[(D) Antimony compound]
The polybutylene terephthalate resin composition of the present invention contains (D) an antimony compound.
Preferred examples of the antimony compound include antimony trioxide (Sb ₂ O ₃ ), antimony pentoxide (Sb ₂ O ₅ ), and sodium antimonate. Among these, antimony trioxide is preferable from the viewpoint of impact resistance.

  (D) As for an antimony compound, the mass concentration of the bromine atom derived from (C) brominated polycarbonate flame retardant and the antimony atom derived from an antimony compound in the resin composition is 3 to 25% by mass in total. Is preferably 4 to 22% by mass, and more preferably 10 to 20% by mass. If it is less than 3% by mass, the flame retardancy tends to decrease, and if it exceeds 20% by mass, the mechanical strength tends to decrease. The mass ratio (Br / Sb) of bromine atoms and antimony atoms is preferably 0.3 to 5, and more preferably 0.3 to 4. By setting it as such a range, it exists in the tendency for a flame retardance to express easily, and it is preferable.

In the present invention, the antimony compound (D) is preferably blended as a master batch with the (A) polybutylene terephthalate tree. Thereby, (D) the antimony compound is likely to be present in the (A) polybutylene terephthalate-based resin phase, (B) the adverse effect on the polycarbonate resin can be suppressed, and the thermal stability at the time of melt kneading and molding becomes good, A decrease in impact resistance is suppressed, and further, variations in flame retardancy and impact resistance tend to be reduced.
The content of the (D) antimony compound in the master batch is preferably 20 to 90% by mass. (D) When an antimony compound is less than 20 mass%, the ratio of the antimony compound in a flame retardant masterbatch is small, and the flame-retardant improvement effect to the polybutylene terephthalate resin which mix | blends this is small. On the other hand, when the antimony compound exceeds 90% by mass, the dispersibility of the antimony compound is liable to decrease, and when blended with a polybutylene terephthalate resin, the flame retardancy of the thermoplastic resin composition becomes unstable and difficult. The workability at the time of manufacturing the fuel master batch is also remarkably lowered. For example, when manufacturing using an extruder, the strand is not stable, and problems such as easy breakage are likely to occur.
The content of the antimony compound in the master batch is preferably 30 to 85% by mass, more preferably 40 to 80% by mass, and still more preferably 50 to 75% by mass.

  The content of the (D) antimony compound is 1 to 15 parts by mass, preferably 2 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 3 parts by mass or more, preferably 10 parts by mass or less, more preferably 7 parts by mass or less, further preferably 6 parts by mass or less, and particularly preferably 5 parts by mass or less. If it falls below the lower limit, the flame retardancy is lowered. On the other hand, when the above upper limit is exceeded, the crystallization temperature is lowered and the releasability is deteriorated, and mechanical properties such as impact resistance are lowered.

[(E) Polyolefin release agent]
The polybutylene terephthalate resin composition of the present invention contains (E) a polyolefin mold release agent. As the release agent, known release agents that are usually used for polybutylene terephthalate resins can be used. In the present invention, however, polyolefin compounds are used in terms of impact resistance, hydrolysis resistance, and release properties. Contains a mold release agent.

  Preferred examples of the polyolefin compound include compounds selected from paraffin wax and polyethylene wax. Among them, the weight average molecular weight is 700 to 10,000, more preferably 900 to 8,000, from the viewpoint of good dispersion of the polyolefin compound. Polyethylene wax is preferred.

In the present invention, the polyolefin compound is preferably not provided with a functional group having an affinity for the polybutylene terephthalate resin, but a carboxyl group (carboxylic acid (anhydride) group, that is, a carboxylic acid group and / Represents a carboxylic acid anhydride group, the same shall apply hereinafter), affinity with polybutylene terephthalate resin such as haloformyl group, ester group, carboxylate metal base, hydroxyl group, alcoholyl group, epoxy group, amino group, amide group, etc. Those having a functional group can be used. This concentration is preferably more than 5 mgKOH / g and less than 50 mgKOH / g, more preferably 10 to 40 mgKOH / g, more preferably 15 to 30 mgKOH / g, and particularly preferably 20 to 28 mgKOH / g as the acid value of the polyolefin compound. preferable.
In addition, an oxidized polyethylene wax can also be used as the polyolefin-based compound since it has a small amount of volatile matter and at the same time has a remarkable effect of improving the releasability.
The acid value can be measured according to a potentiometric titration method (ASTM D1386) using a 0.5 mol KOH ethanol solution.

The (E) polyolefin mold release agent preferably has a dropping point of 100 ° C. or lower, more preferably 90 ° C. or lower. The lower limit is usually 50 ° C., preferably 60 ° C. If the dropping point is less than 50 ° C., the release agent tends to bleed during preliminary drying before injection molding of the molded product, and the pellets may be fused together, which is not preferable. Moreover, since a mold release effect will fall easily when a dropping point exceeds 100 degreeC, it is unpreferable.
The dropping point can be measured by a method based on ASTM D127. Specifically, using a metal nipple, it is measured as the temperature at which molten wax first drops from the metal nipple. When the polyolefin mold release agent is difficult to measure the dropping point, the melting point by differential scanning calorimetry (DSC) can be set as the dropping point in the present invention.

  (E) Content of polyolefin mold release agent is 0.01-3 mass parts with respect to a total of 100 mass parts of (A) polybutylene terephthalate resin and (B) polycarbonate resin. If it is less than 0.01 parts by mass, the surface appearance tends to be reduced due to defective release during melt molding, while if it exceeds 3 parts by mass, the kneading workability of the resin composition is reduced, Gas is likely to be generated during molding, and gas burning at the resin flow end and fogging may be seen on the surface of the molded product. The content of the release agent is preferably 0.07 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 1.2 parts by mass or less, more preferably 1.0 parts by mass or less.

[(F) Elastomer]
The polybutylene terephthalate resin composition of the present invention preferably contains (F) an elastomer. (F) As the elastomer, a thermoplastic elastomer used for improving impact resistance by blending with a polyester resin or a polycarbonate resin may be used. For example, a rubber polymer or a rubber polymer may be used. A product obtained by copolymerizing a reacting compound is used.

Specific examples of (F) elastomers include, for example, polybutadiene, polyisoprene, diene copolymers (styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, acrylic / butadiene rubber, etc.), ethylene and carbon atoms of 3 or more. Copolymers with α-olefins (ethylene / propylene copolymers, ethylene / butene copolymers, ethylene / octene copolymers, etc.), copolymers of ethylene and unsaturated carboxylic acid esters (ethylene / methacrylate copolymer) Copolymers, ethylene / butyl acrylate copolymers, etc.), copolymers of ethylene and aliphatic vinyl compounds, terpolymers of ethylene, propylene and non-conjugated dienes, acrylic rubber (polybutyl acrylate, poly (2-ethylhexyl acrylate)) , Butyl acrylate, 2-ethylhexyl urea Relate copolymers), silicone rubber (a polyorganosiloxane rubber, a polyorganosiloxane rubber and a polyalkyl (meth) IPN type composite rubber consisting of acrylate rubber), and the like. These may be used alone or in combination of two or more.
In the present invention, (meth) acrylate means acrylate and methacrylate, and (meth) acrylic acid means acrylic acid and methacrylic acid.

  Another example of the elastomer (F) is a copolymer obtained by polymerizing a monomer compound with a rubber polymer. Examples of the monomer compound include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and the like. In addition, epoxy group-containing (meth) acrylic acid ester compounds such as glycidyl (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β- such as maleic acid, phthalic acid and itaconic acid Examples thereof also include unsaturated carboxylic acid compounds and anhydrides thereof (for example, maleic anhydride). These monomer compounds can be used alone or in combination of two or more.

(F) The elastomer is preferably an elastomer containing an acrylic and / or butadiene component, and is preferably a copolymer obtained by copolymerizing a butadiene-based and / or acrylic rubber-like polymer with a monomer compound that reacts therewith.
Specific examples of the impact modifier containing an acrylic and / or butadiene component include, for example, acrylonitrile-butadiene copolymer, acrylic-butadiene rubber, and a copolymer obtained by polymerizing a monomer compound with these rubbery polymers. Coalescence is mentioned. Examples of the monomer compound include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and the like. In addition, epoxy group-containing (meth) acrylic acid ester compounds such as glycidyl (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β- such as maleic acid, phthalic acid and itaconic acid Examples thereof also include unsaturated carboxylic acid compounds and anhydrides thereof (for example, maleic anhydride). These monomer compounds can be used alone or in combination of two or more.

  The elastomer containing the acrylic and / or butadiene component is preferably of the core / shell type graft copolymer type from the viewpoint of improving impact resistance, and the butadiene component-containing rubber and / or the acrylic component-containing rubber polymer is used as the core. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing a monomer selected from an acrylic ester, a methacrylic ester and an aromatic vinyl compound around the layer is particularly preferred.

  Examples of the core / shell type graft copolymer include butyl acrylate-methyl methacrylate copolymer, butadiene-methyl methacrylate / styrene copolymer, silicone / acryl-methyl methacrylate copolymer, methyl methacrylate-butadiene-styrene polymer. (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene polymer (MABS), methyl methacrylate-butadiene polymer (MB), methyl methacrylate-acryl-butadiene rubber copolymer, methyl methacrylate-acryl-butadiene rubber-styrene copolymer Examples include coalescence. These rubbery polymers may be used alone or in combination of two or more. Among these, an acrylic core / shell type elastomer in which both the core and the shell are acrylic acid esters is preferable from the viewpoint of impact resistance, heat aging resistance, and light resistance.

  The content of the acrylic and / or butadiene component in the elastomer containing the acrylic and / or butadiene component is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and even more preferably 70 to 85% by mass. If the content of the acrylic and / or butadiene component is less than 50% by mass, the impact resistance tends to be inferior, and if it exceeds 90% by mass, the flame retardancy and weather resistance tend to deteriorate, such being undesirable.

  (F) The average particle size of the elastomer is preferably 5 μm or less, more preferably 3 μm or less, further preferably 2 μm or less, particularly preferably 1 μm or less, and most preferably 800 nm or less. The lower limit is usually 50 nm, preferably 100 nm, more preferably 150 nm, still more preferably 200 nm, particularly preferably 300 nm or more, most preferably 400 nm or more, particularly 500 nm or more. It is preferable to use an elastomer having such a particle diameter because the moldability such as impact resistance such as surface impact, moisture and heat resistance, and releasability tends to be improved.

In addition, the average particle diameter of the elastomer (F) is obtained by observing the morphology of the cross-section of the molded product of the polybutylene terephthalate resin composition with an optical microscope, SEM (scanning electron microscope), TEM (transmission electron microscope), or the like. It can be measured.
Specifically, using a SEM, STEM, or TEM analyzer, the core part of the cross section of the molded product (the cross section parallel to the resin composition flow direction, the central part of the cross section, excluding the surface layer part having a depth of less than 20 μm). Is observed at a magnification of 3,000 to 100,000 times under an acceleration voltage of 20 kV.

The glass transition temperature of the (F) elastomer is preferably −30 ° C. or lower, more preferably −35 ° C. or lower, further preferably −40 ° C. or lower, and −50 ° C. or lower. It is particularly preferred. By using the (F) elastomer raw material having such a glass transition temperature, the flatness of the elastomer (ratio of the major axis to the minor axis of the elastomer) is easily improved by the orientation of the elastomer in the surface layer portion of the molded product, This is preferable because the impact characteristics tend to be significantly improved.
In addition, the glass transition temperature of (F) elastomer can be measured by calculating | requiring the peak temperature of the loss tangent (tan-delta) obtained by a dynamic viscoelasticity measurement. Specifically, using a hot press heated at 200 ° C., (F) elastomer raw material was press-molded for 3 minutes in a 0.7 mm thick × 10 cm × 10 cm mold, and after water cooling, 0.7 mm thick × A 5.5 mm × 25 mm test piece was cut out and subjected to dynamic viscoelasticity measurement at a temperature rise rate of 3 ° C./min and a frequency of 110 Hz in a temperature range of 50 to −100 ° C., and the tan δ peak temperature obtained. To obtain the glass transition temperature.

  The method for producing an acrylic core / shell type elastomer preferably used as the (F) elastomer of the present invention includes an emulsion polymerization method, which includes a core polymerization and a shell polymerization.

  The core polymerization is performed by polymerizing an acrylate monomer, and at this time, since there is one double bond in the molecular structure of the acrylate ester, there is no double bond after the completion of polymerization, Excellent weather resistance and good impact resistance due to low glass transition temperature. In addition to the acrylate monomer, a certain range of cross-linking agent is used to form a rubber structure as an elastomer, impart impact resistance, and control the glass transition temperature. The cross-linking agent formulated in a certain range not only maintains the stability of the latex during polymerization, but also acts to easily deform the core structure from a spherical shape to a flat shape during processing and also in the resin composition. To do.

  The shell polymerization is usually performed by using a methacrylic acid ester excellent in compatibility with a vinyl chloride resin as a monomer and allowing graft polymerization to proceed on the core surface. In order to increase the dispersibility of the elastomer, the shell may contain a small amount of acrylonitrile monomer.

  There are roughly two known methods for producing acrylic core / shell type elastomers by emulsion polymerization. The first method is disclosed in US Pat. No. 5,612,413, in which a seed having a small particle size is polymerized and the monomer is charged in 2 to 4 steps. This is a multi-stage emulsion polymerization method in which after the seed is grown, the core / shell structure is completed by introducing the shell component monomer and surrounding the core surface. The second method is disclosed in European Patent 0527605 (A1), in which a latex having a core / shell structure with a size of 100 nm or less is polymerized and converted into particles of a desired size through an aggregation process (Agglomeration). It is a microagglomeration method in which a core / shell structure is formed by forming an encapsulated shell on the agglomerated particles after growth.

  (F) The glass transition temperature of the elastomer increases as the crosslink density of the elastomer increases, and decreases as the crosslink density of the rubber decreases. Accordingly, the degree of crosslinking density can be adjusted by the amount of crosslinking agent used in producing the elastomer, and an elastomer having a low glass transition temperature can be produced by using a very small amount of the crosslinking agent. However, when the amount of the crosslinking agent used is too small, the stability of the latex is lowered during the polymerization, and it may be difficult to control the glass transition temperature.

  The preferred acrylic core / shell type elastomer of the present invention comprises, for example, polymerizing a seed, polymerizing the core component monomer in 2 to 4 times to grow core rubber particles, It is a large particle size elastomer having a particle size of 400 to 900 nm, which is produced by charging a polymer and surrounding the core surface with a shell.

  To this end, the large particle size elastomers have their respective cores i) 95 to 99.999 parts by weight of an acrylate ester having 2 to 8 carbon atoms in the alkyl group; and ii) a crosslinker 0.001 to 0.001. It is preferable that 5.0 mass parts is included.

The acrylic ester is one or more monomers selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate, It is preferable to include a homopolymer or copolymer of a polymer, and it is more preferable to use an acrylate ester including butyl acrylate, 2-ethylhexyl acrylate, or a mixture thereof.
The cross-linking agent includes 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, allyl methacrylate, Use one or more monomers selected from the group consisting of methylolpropane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate and divinylbenzene, and homopolymers or copolymers of these monomers. Is preferred. More preferably, it comprises 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, allyl acrylate, allyl methacrylate or mixtures thereof. It is preferable that 0.001-5 mass parts is used for the said crosslinking agent with respect to all the monomers with each elastomer of this invention. When the content of the crosslinking agent is less than 0.001 part by mass with respect to the total monomer, handling during processing is poor, and when it exceeds 5 parts by mass, the elastomer core becomes brittle and the impact reinforcement effect is reduced. There is a case.

  In the large particle size elastomer, the shell includes i) 80 to 100 parts by mass of a methacrylic acid ester having 1 to 4 carbon atoms in the alkyl group, and ii) to adjust the glass transition temperature of the shell component. Furthermore, ethyl acrylate, methyl acrylate and butyl acrylate can be added in a proportion of 10 parts by mass or less, and iii) in order to increase the compatibility between the matrix and the shell, nitrile compounds such as acrylonitrile and methacrylonitrile are further added. It can also be added at a ratio of 10 parts by mass or less.

  Moreover, it is preferable that the core of the preferable acrylic core / shell type elastomer (large particle size elastomer) of the present invention contains 70 to 95% by mass of a rubber component monomer with respect to the total monomers. If the amount is less than 70% by mass, the rubber content tends to be small and impact resistance is likely to deteriorate. If the amount exceeds 95% by mass, the shell component cannot completely surround the core. May not be performed well and impact resistance may be reduced.

  The polymerized elastomer can be obtained by coagulation with an electrolyte and then filtered, and the electrolyte is preferably calcium chloride or the like.

  The process for producing an acrylic core / shell type elastomer having a low glass transition temperature and a large average particle diameter, preferably 400 nm or more, preferably used in the present invention will be described in more detail. The manufacturing method mainly includes the following steps.

The large particle size elastomer having the low glass transition temperature is
i) 95 to 99.999 parts by mass of an acrylic ester having 2 to 8 carbon atoms in the alkyl group; 0.001 to 5 parts by mass of a crosslinking agent; 0.001 to 5 parts by mass of a polymerization initiator; 0.001 to emulsifier A primary polymerization step of producing a seed by subjecting a mixture containing 10 parts by mass; and 1000 parts by mass of ion-exchanged water to a crosslinking reaction at a temperature of 60 to 80 ° C .;
ii) 95 to 99.999 parts by mass of an acrylic ester having 2 to 8 carbon atoms in the alkyl group; 0.001 to 5 parts by mass of a crosslinking agent; 0.001 to 6 parts by mass of an emulsifier; and 80 parts by mass of ion-exchanged water A secondary polymerization step in which 0.001 to 5 parts by mass of a polymerization initiator is added and polymerized to produce a core rubber at the same time as the emulsion mixture containing;
iii) 95 to 99.999 parts by mass of acrylic acid ester having 2 to 8 carbon atoms of alkyl group; 0.001 to 5 parts by mass of cross-linking agent; 0.001 to 6 parts by mass of emulsifier; and 80 parts by mass of ion-exchanged water A third polymerization step in which 0.001 to 5 parts by mass of a polymerization initiator is added and polymerized to produce a core rubber at the same time as the emulsion mixture containing;
iv) 80-100 parts by mass of an acrylate ester having 1 to 4 carbon atoms in the alkyl group; 10 parts by mass or less of an acrylate selected from the group consisting of ethyl acrylate, methyl acrylate and butyl acrylate; acrylonitrile and methacrylonitrile Simultaneously adding an emulsion mixture containing 10 parts by mass or less of a nitrile component selected from the group consisting of: 0.001 to 4 parts by mass of an emulsifier; and 150 parts by mass of ion-exchanged water to the core produced in step iii), It is produced by a method including a quaternary polymerization step in which 0.001 to 5 parts by mass of a polymerization initiator is added and polymerized to form a shell.

  As the polymerization initiator used in the production of the large particle size elastomer, any compound capable of causing a crosslinking reaction can be used. Specifically, ammonium persulfate, potassium persulfate, benzoyl peroxide, azobisbutyro Nitrile, butyl hydroperoxide, cumene hydroperoxide and the like can be used.

  The emulsifiers used in the production of the large particle size elastomer include ionic emulsifiers such as unsaturated fatty acid potassium salt, potassium oleate, sodium lauryl sulfate, and sodium dodecylbenzene sulfate, and nonionic emulsifiers. Can be used.

  The large particle size elastomer thus produced is charged with ion exchange water to reduce the solid content to 10% by mass, and then 10% by mass calcium chloride solution is charged into the mixture to coagulate the polymer particles. Analyze. The coagulated slurry is heated to 90 ° C., aged and cooled. Thereafter, the cooled slurry is washed with ion-exchanged water and filtered to obtain an acrylic core / shell type elastomer preferably used in the present invention.

  (F) The preferable content of an elastomer is 5-20 mass parts with respect to a total of 100 mass parts of (A) polybutylene terephthalate resin and (B) polycarbonate resin. When the content of the elastomer (F) is less than 5 parts by mass, the effect of improving the impact resistance is small, and when it exceeds 20 parts by mass, the heat aging resistance and rigidity, as well as the fluidity and flame retardancy are liable to decrease. (F) The more preferable content of the elastomer is 7 parts by mass or more, 16 parts by mass or less, and further 13 parts by mass or less.

[(G) Anti-dripping agent]
The polybutylene terephthalate resin composition of the present invention preferably contains (G) an anti-dripping agent.
(G) As a dripping prevention agent, a fluoropolymer is preferable.
As the fluoropolymer, a known polymer having fluorine can be arbitrarily selected and used, and among these, a fluoroolefin resin is preferable.
As fluoroolefin resin, the polymer and copolymer containing a fluoroethylene structure are mentioned, for example. Specific examples thereof include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. As this fluoroethylene resin, a fluoroethylene resin having a fibril forming ability is preferable.
Examples of the fluoroethylene resin having a fibril-forming ability include Mitsui DuPont Fluorochemical Co., Ltd., Teflon (registered trademark) 6J, Daikin Industries, Ltd., Polyflon (registered trademark) F201L, Polyflon F103, and the like.

  Examples of the aqueous dispersion of fluoroethylene resin include Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Fullon D-1 manufactured by Daikin Industries, Ltd., and TF1750 manufactured by Sumitomo 3M Limited. Furthermore, a fluoroethylene polymer having a multilayer structure formed by polymerizing vinyl monomers can also be used as the fluoropolymer. Specific examples thereof include METABRENE (registered trademark) A-3800 manufactured by Mitsubishi Rayon Co., Ltd.

  The content of the (G) anti-dripping agent is preferably 0.05 to 1 part by mass, more preferably 0 with respect to a total of 100 parts by mass of (A) polybutylene terephthalate resin and (B) polycarbonate resin. 0.1 part by mass or more, more preferably 0.12 part by mass or more, particularly preferably 0.15 part by mass or more, more preferably 0.6 part by mass or less, still more preferably 0.45 part by mass or less, particularly preferably Is 0.35 parts by mass or less. (G) If the content of the anti-dripping agent is too small, the flame retardancy of the resin composition may be insufficient. Conversely, if it is too large, the appearance defect or mechanical strength of the molded product of the resin composition may be insufficient. Reduction may occur.

[Other ingredients]
The polybutylene terephthalate resin composition of the present invention may contain various additives as long as the effects of the present invention are not impaired. Examples of such additives include stabilizers, reinforcing fillers, pigments, ultraviolet absorbers, nucleating agents, antistatic agents, antifogging agents, antiblocking agents, plasticizers, dispersing agents, antibacterial agents, and the like.

<Stabilizer>
It is preferable that the polybutylene terephthalate-based resin composition of the present invention further contains a stabilizer because it has effects of improving thermal stability and preventing deterioration of mechanical strength, transparency, and hue. As the stabilizer, a phosphorus stabilizer, a sulfur stabilizer and a phenol stabilizer are preferable. In particular, when a phosphorus stabilizer is contained, the transesterification reaction between (A) polybutylene terephthalate resin and (B) polycarbonate resin can be effectively suppressed, and mechanical properties such as impact resistance are improved. It tends to be preferable. Moreover, the compatibility of (A) polybutylene terephthalate resin, (B) polycarbonate resin, and (C) brominated polycarbonate flame retardant can be remarkably improved, and a molded product having a morphological structure to be described later. It becomes easy to form stably.

  Examples of the phosphorus stabilizer include phosphorous acid, phosphoric acid, phosphite ester, phosphate ester, and the like, and among them, an organic phosphate compound is preferable.

  The organic phosphate ester compound has a partial structure in which 1 to 3 alkoxy groups or aryloxy groups are bonded to a phosphorus atom. In addition, a substituent may further be bonded to these alkoxy groups and aryloxy groups. Preferably, it is a metal salt of an organophosphate compound, and as the metal, at least one metal selected from Periodic Tables Ia, IIa, IIb and IIIa is more preferable, among which magnesium, barium, calcium, zinc Aluminum is further preferred, and magnesium, calcium or zinc is particularly preferred.

  In the present invention, it is preferable to use an organic phosphate compound represented by any one of the following general formulas (1) to (5), which is represented by any one of the following general formulas (1) to (4). It is more preferable to use an organic phosphate ester compound, and it is more preferable to use an organic phosphate ester compound represented by the following general formula (1) or (2). Two or more organic phosphate compounds may be used in combination.

In General Formula (1), R ^{1 to} R ⁴ each independently represents an alkyl group or an aryl group. M represents an alkaline earth metal or zinc.

In the general formula (2), R ⁵ represents an alkyl group or an aryl group, and M represents an alkaline earth metal or zinc.

In general formula (3), R < ⁶ > -R < ¹¹ > represents an alkyl group or an aryl group each independently. M ′ represents a metal atom that becomes a trivalent metal ion.

In general formula (4), R < ¹² > -R < ¹⁴ > represents an alkyl group or an aryl group each independently. M ′ represents a metal atom to be a trivalent metal ion, and two M ′ may be the same or different.

In the general formula (5), R ¹⁵ represents an alkyl group or an aryl group. n represents an integer of 0 to 2. When n is 0 or 1, two R ¹⁵ may be the same or different.

In general formulas (1) to (5), R ^{1 to} R ¹⁵ are usually an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. From the standpoints of residence heat stability, chemical resistance, wet heat resistance, etc., it is preferably an alkyl group having 2 to 25 carbon atoms, and most preferably an alkyl group having 6 to 23 carbon atoms. Examples of the alkyl group include octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, hexadecyl group, octadecyl group and the like. Further, M in the general formulas (1) and (2) is preferably zinc, and M ′ in the general formulas (3) and (4) is preferably aluminum.

  Preferable specific examples of the organic phosphate ester compound include a bis (distearyl acid phosphate) zinc salt as a compound of the general formula (1), a monostearyl acid phosphate zinc salt as a compound of the general formula (2), and a general formula (3 ) As a compound of tris (distearyl acid phosphate), a compound of general formula (4) as a salt of one monostearyl acid phosphate and two monostearyl acid phosphate aluminum salts, general formula Examples of the compound (5) include monostearyl acid phosphate and distearyl acid phosphate. Of these, bis (distearyl acid phosphate) zinc salt and monostearyl acid phosphate zinc salt are more preferable. These may be used alone or as a mixture.

  As an organic phosphate ester compound, the effect of inhibiting transesterification is very high, the thermal stability during molding is good, the moldability is excellent, and the setting temperature of the measuring section in the injection molding machine can be set higher. Bis (distearyl acid phosphate) zinc which is a zinc salt of an organic phosphate compound represented by the general formula (1) from the viewpoint of stable molding and excellent hydrolysis resistance and impact resistance. It is preferable to use a zinc salt of stearyl acid phosphate, such as a salt, a monostearyl acid phosphate zinc salt which is a zinc salt of an organic phosphate compound represented by the general formula (2). Examples of these commercially available products include “JP-518Zn” manufactured by Johoku Chemical Industry.

Moreover, an organic phosphite compound and an organic phosphonite compound can also be used.
As the organic phosphite compound, preferably, the following general formula:
^{R 2 O-P (OR 3} ) (OR 4)
Wherein R ² , R ³ and R ⁴ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and among R ² , R ³ and R ⁴ At least one of them is an aryl group having 6 to 30 carbon atoms.)
The compound represented by these is mentioned.

  Examples of the organic phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, and tris (tridecyl). ) Phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite Hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-t rt-butylphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4′-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, di Lauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite Phytopolymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Phosphite, 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like. Among these, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferable.

The organic phosphonite compound is preferably the following general formula:
R ⁵ -P (OR ⁶ ) (OR ⁷ )
(In the formula, R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and among R ⁵ , R ⁶ and R ⁷ , At least one of them is an aryl group having 6 to 30 carbon atoms.)
The compound represented by these is mentioned.

  Examples of the organic phosphonite compound include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2, -Di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, and tetrakis (2,6- And di-tert-butylphenyl) -3,3′-biphenylenediphosphonite.

  As the sulfur stabilizer, any conventionally known sulfur atom-containing compound can be used, and among these, thioethers are preferred. Specifically, for example, didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate), thiobis (N-phenyl-β-naphthylamine) ), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, trilauryltrithiophosphite. Among these, pentaerythritol tetrakis (3-dodecylthiopropionate) is preferable.

  Examples of the phenol-based stabilizer 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), pentaerythritol tetrakis (3- (3,5-di-neopentyl-4-hydroxyphenyl) ) Propionate) and the like. Among these, pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferred.

  One type of stabilizer may be contained, or two or more types may be contained in any combination and ratio.

  The content of the stabilizer is preferably 0.001 to 1 part by mass with respect to a total of 100 parts by mass of (A) polybutylene terephthalate resin and (B) polycarbonate resin. When the content of the stabilizer is less than 0.001 part by mass, it is difficult to expect an improvement in the thermal stability and compatibility of the resin composition, and a decrease in molecular weight and a deterioration in hue during molding are likely to occur. When it exceeds, it will become excess amount and there exists a tendency for generation | occurrence | production of silver and a hue deterioration to occur further easily. The content of the stabilizer is more preferably 0.01 to 0.8 parts by mass, still more preferably 0.05 to 0.7 parts by mass, and particularly preferably 0.1 to 0.5 parts by mass. .

<Ultraviolet absorber>
The polybutylene terephthalate resin composition of the present invention preferably further contains an ultraviolet absorber from the viewpoint of having an effect of improving light resistance. In particular, when used in combination with the above-described phosphorus stabilizer and / or phenol stabilizer, the light resistance tends to be more improved.
Examples of the ultraviolet absorber include organic ultraviolet absorbers such as a benzotriazole compound, a benzophenone compound, a salicylate compound, a cyanoacrylate compound, a triazine compound, an oxanilide compound, a malonic ester compound, and a hindered amine compound. Of these, benzotriazole-based UV absorbers, triazine-based UV absorbers or malonic ester-based UV absorbers are more preferable, and benzotriazole-based UV absorbers are particularly preferable.

  Specific examples of the benzotriazole ultraviolet absorber include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α -Dimethylbenzyl) phenyl] -benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -benzotriazole, 2- (2'-hydroxy-3'-tert-butyl) -5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'- Hydroxy-3 ′, 5′-di-tert-amyl) -benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotria Sol, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], among others, 2- (2 '-Hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) Phenol] is preferred, and 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferred.

  Specific examples of the triazine-based UV absorber include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy -4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6 (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4 -Diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) 1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4) -Butoxyethoxyphenyl) -1,3,5-triazine and the like.

  Specific examples of the malonic acid ester ultraviolet absorber include 2- (alkylidene) malonic acid esters, particularly 2- (1-arylalkylidene) malonic acid esters, and such malonic acid ester ultraviolet absorbers. Specific examples include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by BASF, and the like.

  The content of the ultraviolet absorber is preferably 0.05 parts by mass or more, 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. In addition, it is preferably 1 part by mass or less, more preferably 0.8 part by mass or less, and further preferably 0.6 part by mass or less. If the content of the ultraviolet absorber is less than the lower limit of the range, the light resistance improvement effect may be insufficient, and if the content of the ultraviolet absorber exceeds the upper limit of the range, the mold Debogit etc. may occur and cause mold contamination.

<Pigment>
The polybutylene terephthalate-based resin composition of the present invention preferably further contains a pigment from the viewpoint of improving light resistance, flame retardancy, impact resistance, and hydrolysis resistance. Examples of the pigment include inorganic pigments (black pigments such as carbon black (for example, acetylene black, lamp black, thermal black, furnace black, channel black, ketjen black), red pigments such as iron oxide red, molybdate orange, etc. Orange pigments such as titanium oxide, white pigments such as titanium oxide, organic pigments (yellow pigment, orange pigment, red pigment, blue pigment, green pigment, etc.) Carbon black from the viewpoint of colorability and weather resistance It is preferable to mix titanium oxide from the viewpoint of impact resistance, flame retardancy, and hydrolysis resistance.

  The polybutylene terephthalate resin composition of the present invention preferably contains titanium oxide. Contains titanium oxide in a predetermined amount together with (A) polybutylene terephthalate resin, (B) polycarbonate resin, (C) brominated polycarbonate flame retardant, (D) antimony compound and (E) polyolefin release agent By doing so, the crystallization of the (A) polybutylene terephthalate resin is appropriately delayed, higher impact resistance can be achieved, and flame retardancy is further improved. Furthermore, when carbon black is blended for the purpose of coloring the resin composition, appearance defects may occur in the welded part of the molded product or the stepped part of the molded product due to aggregation of the carbon black. It became clear that the external appearance defect is easily improved by blending. This specifically contains (C) a brominated polycarbonate flame retardant, (D) an antimony compound and (E) a polyolefin release agent in a mixed resin of (A) polybutylene terephthalate resin and (B) polycarbonate resin. This is an effect that is uniquely confirmed in the resin composition.

  The titanium oxide used is not particularly limited in terms of production method, crystal form, average particle size, and the like. There are sulfuric acid method and chlorine method in the production method of titanium oxide, but titanium oxide produced by sulfuric acid method tends to be inferior in whiteness of the composition to which this is added, so the object of the present invention can be effectively achieved. To achieve this, those produced by the chlorine method are preferred.

  Further, the crystal form of titanium oxide includes a rutile type and an anatase type, but a rutile type crystal form is preferable from the viewpoint of light resistance. The average particle diameter of titanium oxide is preferably 0.01 to 3 μm, more preferably 0.05 to 1 μm, still more preferably 0.1 to 0.7 μm, and particularly preferably 0.00. 1 to 0.4 μm. When the average particle size is less than 0.01 μm, the workability during the production of the resin composition is poor, and when it exceeds 3 μm, the surface of the molded product is easily roughened, and the mechanical strength of the molded product is likely to be lowered. Two or more types of titanium oxide having different average particle diameters may be mixed and used.

  The titanium oxide is preferably surface-treated with an organosiloxane-based surface treatment agent, but before that, it is preferably pretreated with an alumina-based surface treatment agent. Alumina hydrate is preferably used as the alumina-based surface treatment agent. Furthermore, it may be pretreated with silicic acid hydrate together with alumina hydrate. The pretreatment method is not particularly limited, and any method can be used. Pretreatment with alumina hydrate and, if necessary, silicic acid hydrate is preferably carried out in the range of 1 to 15% by mass with respect to titanium oxide.

  Titanium oxide with alumina hydrate, pretreated with silicic acid hydrate if necessary, further improves the thermal stability by surface-treating the surface with an organosiloxane surface treatment agent. In addition, by moderately suppressing the activity of titanium oxide, (B) it is preferable because it tends to easily suppress a decrease in mechanical properties such as impact resistance due to a decrease in the molecular weight of the polycarbonate resin and a decrease in hydrolysis resistance. .

As the organosiloxane surface treating agent, a reactive functional group-containing organosilicon compound having a reactive functional group that reacts with the surface of the inorganic compound particles is preferable. Examples of the reactive functional group include Si—H group, Si—CH ₃ group, Si—OH group, Si—NH group, and Si—OR group, but Si—H group, Si—OH group, Si— Those having an OR group are more preferred, and organosilicon compounds having a Si—H group and a Si—CH ₃ group are particularly preferred.

The Si—H, Si—CH ₃ group-containing organosilicon compound is not particularly limited as long as it is a compound having a Si—H group or a Si—CH ₃ group in the molecule, and may be appropriately selected and used. But, poly (methyl hydrogen siloxane), poly (dimethyl siloxane), polycyclo (methyl hydrogen siloxane), poly (ethyl hydrogen siloxane), poly (phenyl hydrogen siloxane), poly [(methyl hydrogen siloxane) (dimethyl Siloxane)] copolymer, poly [(methylhydrogensiloxane) (ethylmethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (diethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (hexylmethylsiloxane)] Copo Mer, poly [(methylhydrogensiloxane) (octylmethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (phenylmethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (diethoxysiloxane)] copolymer, Poly [(methylhydrogensiloxane) (dimethoxysiloxane)] copolymer, poly [(methylhydrogensiloxane) (3,3,3-trifluoropropylmethylsiloxane)] copolymer, poly [(dihydrogensiloxane) ((2 -Methoxyethoxy) methylsiloxane)] copolymers, poly [(dihydrogensiloxane) (phenoxymethylsiloxane)] copolymers and the like are preferred.

  Surface treatment methods using an organosiloxane surface treatment agent for titanium oxide include (1) a wet method and (2) a dry method. In the wet method, a mixture of an organosiloxane-based surface treatment agent and a solvent is added with alumina hydrate, and if necessary, titanium oxide pretreated with silicic acid hydrate. Furthermore, it is a method of heat-processing at 100-300 degreeC after that. In the dry method, pretreated titanium oxide and polyorganohydrogensiloxane are mixed with a Henschel mixer in the same manner as described above, and an organic solution of polyorganohydrogensiloxane is sprayed on the pretreated titanium oxide. And a method of heat-treating at 100 to 300 ° C.

The treatment amount of the siloxane compound is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of titanium oxide. When the amount of treatment is less than the above lower limit, the surface treatment effect is low, and the impact resistance, flame retardancy, and hydrolysis resistance of the polybutylene terephthalate resin composition of the present invention are likely to be lowered. Moreover, when the amount of treatment exceeds the above upper limit value, the fluidity of the polybutylene terephthalate resin composition tends to decrease, such being undesirable.
From such a viewpoint, the processing amount is more preferably 0.1 to 6 parts by mass, further preferably 0.5 to 5 parts by mass, and particularly preferably 1 to 4 parts by mass with respect to 100 parts by mass of titanium oxide.

  The content of the pigment is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass in total of (A) the polybutylene terephthalate resin and (B) the polycarbonate resin. When the amount is less than 0.05 parts by weight, the light resistance, impact resistance, flame retardancy, and hydrolysis resistance may not be sufficiently improved. When the amount exceeds 10 parts by weight, mechanical properties and moldability deteriorate. There is. The content of the pigment is more preferably 0.05 to 8 parts by mass, further preferably 0.1 to 6 parts by mass, and particularly preferably 0.5 to 5 parts by mass.

  In particular, when the pigment is titanium oxide, the content of titanium oxide is 0.5 to 10 parts by mass with respect to a total of 100 parts by mass of (A) polybutylene terephthalate resin and (B) polycarbonate resin. More preferably, it is 0.7 parts by mass or more, more preferably 1 part by mass or more, more preferably 8 parts by mass or less, further preferably 6 parts by mass or less, particularly preferably 5 parts by mass or less. . When the content of titanium oxide is less than 0.5 parts by mass, the impact resistance, flame retardancy, and hydrolysis resistance may not be sufficiently improved. When the content exceeds 10 parts by mass, mechanical properties and moldability are obtained. May decrease.

  Moreover, when a pigment is carbon black, Preferably it is 0.05-5 mass parts with respect to a total of 100 mass parts of (A) polybutylene terephthalate type-resin and (B) polycarbonate resin. If it is less than 0.05 parts by mass, the light resistance improving effect may not be sufficient, and if it exceeds 5 parts by mass, the mechanical properties may deteriorate. The content of the pigment is preferably 0.07 to 4 parts by mass, more preferably 0.1 to 3 parts by mass.

  In particular, in the present invention, the appearance defects in the welded part of the molded product and the stepped part of the molded product due to the aggregation of carbon black, etc., which are likely to occur when carbon black is blended, are further improved by blending titanium oxide. It became clear that it was easy. This is a mixed resin of (A) polybutylene terephthalate resin and (B) polycarbonate resin, containing a specific amount of (C) brominated polycarbonate flame retardant, (D) antimony compound and (E) polyolefin release agent This is an effect that is confirmed specifically for the resin composition to be performed, and is a remarkable effect.

<Reinforcing filler>
The polybutylene terephthalate-based resin composition of the present invention may contain a reinforcing filler as long as the effects of the present invention are not impaired. However, if high impact resistance is required, it should not contain a reinforcing filler. Is preferred. When the reinforcing filler is contained, a reinforcing filler having an effect of improving the mechanical properties of the resin composition obtained by blending with the resin is preferable, and a conventional inorganic filler for plastics can be used. Preferably, fibrous fillers such as glass fiber, carbon fiber, basalt fiber, wollastonite and potassium titanate fiber can be used. In addition, granular or amorphous fillers such as calcium carbonate, titanium oxide, feldspar minerals, clays, organic clays, glass beads, etc .; plate-like fillers such as talc; scale-like fillings such as glass flakes, mica and graphite A material can also be used. Among these, glass fibers are preferably used from the viewpoint of mechanical strength, rigidity, and heat resistance.
In addition, when using a filler such as talc as a nucleating agent for the purpose of improving the crystallization speed, 1% by mass or less based on a total of 100 parts by mass of (A) polybutylene terephthalate resin and (B) polycarbonate resin, Preferably, you may mix | blend in the quantity of 0.6 mass part or less.

  More preferably, the reinforcing filler is surface-treated with a surface treatment agent such as a coupling agent. The glass fiber to which the surface treatment agent is attached is preferable because it is excellent in durability, heat and humidity resistance, hydrolysis resistance, and heat shock resistance.

As the surface treatment agent, any conventionally known one can be used. Specifically, for example, silane coupling agents such as amino silane, epoxy silane, allyl silane, and vinyl silane are preferable.
Among these, aminosilane-based surface treatment agents are preferable, and specifically, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropyltrimethoxysilane are preferable. Take as an example.

Moreover, as a surface treating agent, epoxy resins, such as a novolac type, a bisphenol A type epoxy resin, etc. are mentioned preferably. Among these, novolac type epoxy resins are preferable.
The silane-based surface treatment agent and the epoxy resin may be used alone or in combination, and it is also preferable to use both in combination.

  The content of the reinforcing filler is preferably 0 to 100 parts by mass with respect to 100 parts by mass in total of (A) polybutylene terephthalate resin and (B) polycarbonate resin. When the content of the reinforcing filler exceeds 100 parts by mass, the fluidity is lowered, which is not preferable. The more preferable content of the reinforcing filler is 5 to 90 parts by mass, of which 15 to 80 parts by mass, more preferably 30 to 80 parts by mass, and particularly 40 to 70 parts by mass.

  Moreover, the polybutylene terephthalate resin composition of the present invention contains (A) a polybutylene terephthalate resin and (B) a thermoplastic resin other than the polycarbonate resin within a range not impairing the effects of the present invention. Can do. Specific examples of the other thermoplastic resins include polyethylene terephthalate, polyamide, polyphenylene oxide, polystyrene resin, polyphenylene sulfide, polysulfone, polyethersulfone, polyetherimide, and polyetherketone.

[Method for Producing Resin Composition]
As a manufacturing method of the polybutylene terephthalate-type resin composition of this invention, it can carry out in accordance with the conventional method of resin composition preparation. Usually, the components and various additives added as desired are mixed together and then melt-kneaded in a single-screw or twin-screw extruder. Moreover, it is also possible to prepare the resin composition of the present invention by mixing each component in advance or by mixing only a part of the components in advance and supplying them to an extruder using a feeder and melt-kneading them. Furthermore, (A) a polybutylene terephthalate-based resin or (B) a polycarbonate resin partly blended with a part of other components is melt-kneaded to prepare a masterbatch, and then the remaining other ingredients May be blended and melt-kneaded.
In addition, when using fibrous reinforcement fillers, such as glass fiber, it is also preferable to supply from the side feeder in the middle of the cylinder of an extruder.

As described above, in the present invention, (D) the antimony compound is blended as a master batch with a thermoplastic resin, in particular, (A) a polybutylene terephthalate-based resin, so that heat stability during melt-kneading and molding processing is achieved. In addition, it is preferable from the viewpoint that it has few variations in flame retardancy and impact resistance. The method of masterbatching is not particularly limited, and examples thereof include a method of melt-kneading a thermoplastic resin and an antimony compound.
Examples of the melt-kneading method include a single- or twin-screw extruder type kneader, a continuous kneader such as a kneading roll or a calender roll, or a method using a known kneader such as a pressure kneader or a Banbury mixer. It is done. Among these, it is preferable to use a twin screw extruder.
In addition, it is also preferable to dry a thermoplastic resin (preferably a polybutylene terephthalate resin) in advance during melt-kneading. As drying, hot air drying is preferable, the temperature is preferably 100 to 140 ° C., more preferably 110 to 130 ° C., and the drying time is preferably 1 to 5 hours, more preferably 2 to 4 hours.

When using an extruder, a thermoplastic resin (preferably a polybutylene terephthalate resin) and an antimony compound are supplied to the extruder, melt-kneaded, the resin composition is extruded from a die nozzle to form a strand, and then cooled. Then, a master batch pellet is produced by cutting.
At this time, it is preferable to use a twin screw extruder as the melt kneader. Especially, it is preferable that L / D which is the ratio of the screw length L (mm) to the diameter D (mm) of the screw satisfies the relationship of 10 <(L / D) <100, and 15 <(L / D) It is more preferable to satisfy <70. When the ratio is 10 or less, the thermoplastic resin and the antimony compound are not easily dispersed finely, and conversely exceeding 100 is not preferable because the thermoplastic resin is easily decomposed.

  As conditions for melt-kneading, the temperature is preferably 140 to 320 ° C., more preferably 160 to 310 ° C. at the barrel temperature. When the melting temperature is less than 140 ° C., the melting becomes insufficient, and aggregation of unmelted gel and antimony compound tends to occur frequently. Conversely, when the melting temperature exceeds 320 ° C., the resin composition is thermally deteriorated and easily colored.

  The screw rotation speed during melt kneading is preferably 100 to 1,000 rpm, and more preferably 120 to 800 rpm. If the screw rotation speed is less than 100 rpm, the antimony compound tends to hardly disperse, and conversely if it exceeds 1,000 rpm, the thermoplastic resin tends to be decomposed, which is not preferable. The discharge rate is preferably 5 to 2,000 kg / hr, more preferably 10 to 1,500 kg / hr. If the discharge amount is less than 5 kg / hr, the strands are not stable and the yield tends to decrease. Even if it exceeds 2,000 kg / hr, the antimony compound tends to aggregate and the dispersibility tends to decrease. Absent.

The ratio of the raw material thermoplastic resin (preferably polybutylene terephthalate resin) and antimony compound used for melt-kneading is 20 to 90% by mass of the antimony compound based on the total of 100% by mass of the thermoplastic resin and the antimony compound. Is preferred. When the antimony compound is less than 20% by mass, the ratio of the antimony compound in the flame retardant master batch is small, and the effect of improving the flame retardancy to the thermoplastic resin containing the antimony compound is small. On the other hand, when the antimony compound exceeds 90% by mass, the dispersibility of the antimony compound is liable to decrease, and when this master batch is blended with the (A) polybutylene terephthalate resin, the difficulty of the polybutylene terephthalate resin composition of the present invention is reached. The flammability becomes unstable, and the workability during the production of the flame retardant masterbatch is remarkably reduced. For example, when manufacturing using an extruder, the strands are not stable, and problems such as easy breakage occur. It is not preferable because it is easy.
The content of the antimony compound in the masterbatch is preferably 30 to 85% by mass, more preferably 40 to 80% by mass, and still more preferably 50 to 75%, based on a total of 100% by mass of the thermoplastic resin and the antimony compound. % By mass.

  When a thermoplastic resin (preferably a polybutylene terephthalate resin) and an antimony compound are melt-kneaded to form a masterbatch, various additives such as a stabilizer can be blended as necessary.

  The composition of the antimony compound master batch is such that the content of the antimony compound in the obtained polybutylene terephthalate resin composition is 0.5 to 10% by mass in 100% by mass of the whole polybutylene terephthalate resin composition. It is preferable to mix | blend, More preferably, it is 0.7-9 mass%, More preferably, it is 1-8 mass%, Especially 1.5-7 mass%, Most preferably, it is 2-6 mass%.

(D) When blending an antimony compound in a masterbatch, (A) polybutylene terephthalate resin, (B) polycarbonate resin, (C) brominated polycarbonate flame retardant, (E) polyolefin release agent and other The desired components are fed to a kneader such as an extruder at a desired ratio. At this time, the antimony compound master batch is preferably supplied to the extruder from a dedicated feeder provided separately from other raw materials. . The antimony compound masterbatch is not mixed with the components (A) to (C) and (E) and other desired additives and supplied from the same feeder, but from an independent dedicated feeder. Is preferable, because flame retardancy and impact resistance are improved, and variation is small.
When supplying an antimony buster batch from a dedicated feeder, it may be fed simultaneously to other raw materials from the dedicated feeder to the hopper of the extruder, or may be fed in the middle of the extruder. When feeding in the middle of an extruder, it is preferable to feed to the hopper side rather than a kneading zone.

  The heating temperature at the time of melt-kneading these components can be appropriately selected from the range of usually 220 to 300 ° C. If the temperature is too high, decomposition gas is likely to be generated, which may cause opacity. Therefore, it is desirable to select a screw configuration in consideration of shear heat generation. In order to suppress decomposition during kneading or molding in the subsequent process, it is desirable to use an antioxidant or a heat stabilizer.

[Morphology of molded resin composition]
As described above, the polybutylene terephthalate resin composition of the present invention preferably contains (F) an elastomer from the viewpoint of impact resistance. The molded product comprising the polybutylene terephthalate resin composition of the present invention preferably containing (F) an elastomer is preferably (A) a polybutylene terephthalate resin and (B) a polycarbonate resin at the core of the molded product. Form a co-continuous phase and (F) the elastomer has the morphology present in the (B) polycarbonate resin phase. Preferably, the (D) antimony compound is also present in the (A) polybutylene terephthalate resin phase.
Here, the core portion is a portion excluding the surface layer portion having a depth of less than 20 μm of the molded product, and means a central portion of a cross section parallel to the resin composition flow direction of the molded product, and the surface layer portion is the surface of the molded product. It is a surface layer part from the inside to a depth of 20 μm, and refers to a cross section parallel to the flow direction of the resin composition.

  The co-continuous phase means that (A) a phase made of polybutylene terephthalate resin and (B) a phase in which polycarbonate resins are in contact with each other form a continuous phase. By having such a co-continuous structure, and (F) the elastomer has the morphology present in the (B) polycarbonate resin phase, the molded article of the present invention has both flame retardancy and impact resistance. It becomes easy to express the characteristic that it is excellent in. The structure, shape and size of the co-continuous phase are not limited

The morphology of the polybutylene terephthalate resin composition molded product can be measured by observing the cross section of the molded product with an optical microscope, SEM (scanning electron microscope), TEM (transmission electron microscope), or the like.
Specifically, using a SEM, STEM, or TEM analyzer, the core part of the cross section of the molded product (the cross section parallel to the resin composition flow direction, the central part of the cross section, excluding the surface layer part having a depth of less than 20 μm). Is observed at a magnification of 3,000 to 100,000 times under an acceleration voltage of 20 kV.

1 and 2 show an example of the morphology of a molded product, and are STEM photographs of the core portion of the molded product obtained in Example 7 of the present invention.
In FIG. 1, the flow direction is from left to right in FIG. The light gray part is the (A) polybutylene terephthalate resin phase, and the darker gray is the (B) polycarbonate resin phase, and it can be seen that both form a co-continuous structure. It can be seen that the (F) elastomer phase is present in the (B) polycarbonate resin phase in the form of white circles, and the (F) elastomer is present in the (B) polycarbonate resin phase.
In the light gray portion (A) polybutylene terephthalate resin phase, the black portion having a large particle size is (D) antimony compound (antimony trioxide in FIG. 1), and (D) 80% or more of the antimony compound. It was also confirmed that (A) was dispersed in the phase of polybutylene terephthalate resin. A black part with a small particle diameter is considered to be titanium dioxide. Moreover, it is thought that (C) brominated polycarbonate flame retardant exists in (B) polycarbonate resin phase.

The average diameter of the (F) elastomer in the core part of the molded article in the (B) polycarbonate resin phase is preferably 200 nm or more, more preferably 300 nm or more, further preferably 400 nm or more. Is 2 μm or less, more preferably 1.5 μm or less, still more preferably 1.2 μm or less, and particularly preferably 1 μm or less.
The average diameter of the (D) antimony compound is preferably 4 μm or less, more preferably 3 μm or less, and further preferably 2 μm or less.

(F) Elastomer phase and (D) Antimony compound domain (or particle) particle diameter (dispersion diameter), etc., the image obtained by morphological observation is used as it is or the contrast is enhanced in these images, or the brightness is adjusted or both Can be read by applying the following adjustment to the image.
The particle diameter and the like of (F) elastomer phase and (D) antimony compound are calculated by measuring 200 or more particle diameters and arithmetically averaging the maximum diameters.

  In addition, in the surface layer part of the molded product of the polybutylene terephthalate resin composition, the (F) elastomer phase extends in the resin flow direction, and the ratio of the major axis to the minor axis (major axis / minor axis) is It is preferably 3-20, more preferably 4-19, and even more preferably 6-18. The major axis refers to the maximum diameter of the elastomer particles, and the minor axis refers to the maximum diameter in the direction perpendicular to the major axis. Further, the surface layer portion refers to a region from the surface of the molded product to a depth of 20 μm.

Such a preferable morphology of the surface layer part of the molded product can be confirmed by observing FIG. 3, for example. FIG. 3 is an SEM photograph of the surface layer portion of the molded product obtained in Example 7 of the present invention.
In FIG. 3, the flow direction of the resin during molding is from left to right in the figure. It is light gray and elongated in the horizontal direction in the (F) elastomer phase, and it can be confirmed that the resin phase extends in the flow direction. (A) Polybutylene terephthalate resin and (B) polycarbonate resin are considered to form a layered structure. A white portion having a large particle size is considered to be (D) an antimony compound, and a particle having a small particle size is considered to be titanium dioxide.
Thus, the molded article of the present invention preferably has such a unique morphological structure.

[Preferable control method of molded product morphology]
By having such a morphological structure, the molded product becomes a flame retardant molded product that is superior in both flame retardancy and impact resistance.
The polybutylene terephthalate resin composition used for the production of the molded article is preferably produced by a melt kneading method using a melt kneader such as an extruder, but the raw materials of the polybutylene terephthalate resin composition are mixed. Thus, it is difficult to stably form the morphological structure defined above by simply kneading, and it is recommended to knead by a special method.
Below, the preferable manufacturing method for forming stably the morphology structure prescribed | regulated above is demonstrated.

(A) Polybutylene terephthalate resin, (B) polycarbonate resin, (C) brominated polycarbonate flame retardant, (D) antimony compound, (E) polyolefin release agent and (F) elastomer, respectively After mixing, the mixture is supplied to a single-screw or twin-screw extruder provided with a die nozzle, melted and kneaded, and the resin composition is extruded from the die nozzle to form a strand, and then cut to produce pellets.
At this time, it is preferable to use a twin screw extruder as the melt kneader. Especially, it is preferable that L / D which is a ratio of the screw length L (mm) to the diameter D (mm) of the screw satisfies the relationship of 10 <(L / D) <150, and 15 <(L / D) <120 is more preferable, 20 <(L / D) <100 is more preferable, and 30 <(L / D) <70 is particularly preferable. . When this ratio is 10 or less, (B) polycarbonate resin and (C) brominated polycarbonate flame retardant, (D) antimony compound and (F) elastomer are difficult to finely disperse. The brominated polycarbonate flame retardant is undesirably deteriorated by heat and is liable to be finely dispersed.
The shape of the die nozzle is not particularly limited, but a circular nozzle having a diameter of 1 to 10 mm is preferable, and a circular nozzle having a diameter of 2 to 7 mm is more preferable in terms of pellet shape.

  Moreover, it is preferable that it is 200-300 degreeC, and, as for the melting temperature of the resin composition at the time of melt-kneading, it is more preferable that it is 210-295 degreeC. When the melting temperature is less than 200 ° C., melting is insufficient and unmelted gel is likely to occur frequently. On the other hand, when it exceeds 300 ° C., the resin composition is thermally deteriorated and easily colored.

  The screw rotation speed at the time of melt kneading is preferably 100 to 1,000 rpm, and more preferably 150 to 800 rpm. When the screw rotation speed is less than 100 rpm, (C) brominated polycarbonate flame retardant, (D) antimony compound and (F) elastomer tend to be difficult to finely disperse. D) The antimony compound is not preferred because it tends to aggregate and not finely disperse. The discharge rate is preferably 5 to 1,000 kg / hr, and more preferably 10 to 900 kg / hr. If the discharge rate is less than 5 kg / hr, the dispersibility of the antimony compound (D) tends to be reduced. Even if it exceeds 1,000 kg / hr, the dispersibility tends to decrease due to reaggregation of the antimony compound. It is not preferable.

Shear rate of polybutylene terephthalate resin composition in the die nozzle is preferably 10～10,000Sec ^-1, more preferably 50～5,000Sec ^-1, is 70～1,000Sec ^-1 More preferably. By making the shear rate in the above range, (C) brominated polycarbonate flame retardant, (D) antimony compound and (F) re-aggregation of elastomer are suppressed, and the morphology defined in the present invention is stably formed. It tends to be easy and preferable. Such shear rate is generally determined from the discharge amount of the resin composition and the shape of the cross section of the die nozzle. For example, when the cross section of the die nozzle is circular,
γ = 4Q / πr ³
Can be calculated. Here, γ represents the shear rate (sec ⁻¹ ), Q represents the discharge amount (cc / sec) of the resin composition per die nozzle, and r represents the radius (cm) of the die nozzle cross section.

  The resin composition extruded from the die nozzle in the form of a strand is cut into pellets by a pelletizer or the like, and the strand is cooled so that the surface temperature of the strand at the time of cutting is 60 to 150 ° C., particularly 70 to 150 ° C. It is preferable. Usually, it is cooled by a method such as air cooling or water cooling, but water cooling is preferable in terms of cooling efficiency. In such water cooling, the strand may be cooled in a water tank containing water, and a desired strand surface temperature can be obtained by adjusting the water temperature and the cooling time. In the case of a columnar shape, the pellets thus produced preferably have a diameter of 1 to 8 mm, more preferably 2 to 6 mm, still more preferably 3 to 5 mm, and a length of preferably 1 to 10 mm. Preferably it is 2-6 mm, More preferably, it is 3-5 mm.

The relationship between the shear rate γ (sec ⁻¹ ) in the die nozzle and the surface temperature T (° C.) of the strand at the time of strand cutting is as follows:
1 × 10 ³ <(γ · T) <9.9 × 10 ⁵
Satisfying the above relationship tends to improve electrical insulation, toughness, and flame retardancy, which is preferable. By setting the value of (γ · T) within the above range, the morphological structure defined above tends to be formed stably. In addition, the surface roughness of the molded product due to poor dispersion of each component of the resin composition and (C) brominated polycarbonate flame retardant, (D) antimony compound and (F) decrease in toughness due to reagglomeration of elastomer are suppressed. In addition, it is easy to maintain good mechanical properties, flame retardancy, insulation properties, and the like. The lower limit of (γ · T) is more preferably 1 × 10 ⁴ , and the upper limit is more preferably 8.5 × 10 ⁵ .
In order to adjust the value of (γ · T) within the above range, the shear rate and the surface temperature of the strand may be adjusted.

  A polybutylene terephthalate-based resin composition having a morphological structure as defined above can be produced by applying the above preferable conditions alone or in combination of a plurality of them, but among them, the value of (γ · T) It is effective to adopt production conditions that satisfy the above formula.

  By adopting such a method for producing a polybutylene terephthalate resin composition, a molded product of a polybutylene terephthalate resin composition having a morphological structure as defined above can be stably produced. However, the production is not limited to such a method, and other methods may be used as long as the morphological structure defined above is obtained.

In addition, in order to easily form a molded article having the above-described morphological structure, a molded article is produced using a polybutylene terephthalate resin composition to which the following methods and conditions 1) to 8) are applied. It is also preferable.
1) (C) The content of the chlorine compound as an impurity in the brominated polycarbonate flame retardant is usually 0.2% by mass or less, preferably 0.1% by mass or less, more preferably 0.08% by mass or less, Furthermore, it is preferable to set it as 0.05 mass% or less, especially 0.03 mass% or less. By controlling in this way, it becomes easy to stably form the morphological structure defined above.
The impurity chlorine compound is a chlorinated bisphenol compound or the like. When such a chlorine compound is present in the above amount or more, it becomes difficult to stably form the above morphological structure. The chlorine compound content can be quantified as a value in terms of decane by analyzing a gas generated by heating at 270 ° C. for 10 minutes by a gas chromatography method.

2) Setting the amount of free bromine, chlorine and sulfur in the polybutylene terephthalate resin composition to a specific amount or less is also effective in stably forming the above morphological structure. The amount of free bromine is preferably 800 ppm or less, more preferably 700 ppm or less, further preferably 650 ppm or less, and particularly preferably 480 ppm or less. Moreover, since removing the content up to 0 ppm requires purification so as not to be economical, the lower limit is usually 1 ppm, preferably 5 ppm, more preferably 10 ppm.
The amount of free chlorine is preferably 500 ppm or less, more preferably 350 ppm or less, further preferably 200 ppm or less, and particularly preferably 150 ppm or less. In addition, the chlorine content in the resin composition is not limited in what state / form the chlorine was present in the resin composition. Chlorine is mixed in from various environments such as raw materials, additives, catalysts, polymerization atmosphere, resin cooling water, and the like, and therefore the total amount of these is preferably controlled to 500 ppm or less.
The amount of free sulfur is preferably 250 ppm or less, more preferably 200 ppm or less, further preferably 150 ppm or less, and particularly preferably 100 ppm or less. In addition, the sulfur content in the resin composition is not limited in what state and form sulfur is present in the resin composition. Since sulfur is mixed in from various environments such as raw materials, additives, catalysts, polymerization atmospheres, etc., it is preferable to control the total amount of those mixed to 250 ppm or less.

  The content of free bromine, chlorine and sulfur in the polybutylene terephthalate resin composition can be measured by a combustion ion chromatography method. Specifically, using an automatic sample combustion apparatus of “AQF-100 type” manufactured by Mitsubishi Chemical Analytech Co., Ltd., the resin composition is heated under an argon atmosphere at 270 ° C. for 10 minutes, and the generated bromine, chlorine, The amount of sulfur can be determined by quantifying using “ICS-90” manufactured by Nippon Dionex.

3) Also, antimony trioxide is used as the (D) antimony compound.

4) A brominated polycarbonate flame retardant is used as the flame retardant. Since brominated polycarbonate flame retardants are more easily incorporated into (B) polycarbonate resin phase than other flame retardants, this increases (B) polycarbonate resin phase, and (A) polybutylene terephthalate resin and (B ) It becomes easy for polycarbonate resin to form a co-continuous structure.

5) (F) An elastomer having an average particle size of 300 to 1,500 nm and a relatively large particle size is used. As a result, the (B) polycarbonate resin phase incorporating the (F) elastomer is increased, and the (B) polycarbonate resin phase is easily brought into contact with each other, thereby making it easier to form a co-continuous structure in the core portion. (F) The elastomer phase is easily oriented in the resin flow direction.

6) The (D) antimony compound is blended as a master batch with the (A) polybutylene terephthalate resin. Thereby, the (D) antimony compound is likely to be present in the (A) polybutylene terephthalate resin phase.

7) As a stabilizer, (H) a metal salt of an organophosphate compound represented by any one of the following general formulas (1) to (4), preferably a zinc salt of stearyl acid phosphate is blended. As a result, the transesterification between (A) the polybutylene terephthalate resin and (B) the polycarbonate resin is more easily suppressed, and the molded article having the morphological structure of the present invention has excellent thermal stability during melt-kneading and molding. Can be formed stably.

8) When manufacturing a molded product by injection molding, for example, the screw configuration of the injection molding machine, the processing of the inner wall of the screw or cylinder, the selection of the molding machine conditions such as the nozzle diameter, the mold structure, plasticization, measurement, Various methods such as adjustment of molding conditions at the time of injection, addition of other components to the molding material, and the like can be mentioned. In particular, it is preferable to adjust, for example, cylinder temperature, back pressure, screw rotation speed, injection speed, and the like as conditions during plasticization, measurement, and injection. For example, when adjusting the cylinder temperature, it is preferably set to 230 to 280 ° C, more preferably 240 to 270 ° C. When adjusting the back pressure, it is preferably set to 2 to 15 MPa, more preferably 4 to 10 MPa. When adjusting a screw rotation speed, Preferably it sets to 20-300 rpm, More preferably, it sets to 20-250 rpm. When adjusting the injection speed, the injection speed is 5 to 1,000 mm / sec, further 10 to 900 mm / sec, especially 20 to 800 mm / sec, 30 to 700 mm / sec, 40 to 500 mm / sec. It is preferable to do. Thereby, in the surface layer part, the (F) elastomer phase is easily oriented in the resin flow direction. Among these, it is particularly preferable to employ a method of adjusting the injection speed in order to facilitate the orientation of the (F) elastomer phase in the surface layer portion of the molded product.

In particular, according to the above 4) to 8), in the core part, a co-continuous structure of (A) polybutylene terephthalate resin and (B) polycarbonate resin is formed, and the impact resistance is improved. ) When the elastomer phase is oriented, the expansion of craze by impact stops at the elastomer oriented phase, which is considered to lead to an improvement in impact resistance.
In addition, (B) the polycarbonate resin is likely to deteriorate (D) the antimony compound is likely to be present in the (A) polybutylene terephthalate resin phase, so that the adverse effect on the (B) polycarbonate resin can be suppressed, and the impact resistance is reduced. It tends to be suppressed.

  These methods and conditions of 1) to 8) may be used alone or in combination with a plurality of methods and conditions, and may be applied in combination with the above-described resin composition production conditions.

The polybutylene terephthalate resin composition of the present invention obtained by the above method preferably has a crystallization temperature of 100 ° C or higher, more preferably 130 ° C or higher, and further preferably 140 ° C or higher. . Moreover, it is preferable that the flame retardance of thickness 1.5mm based on UL94 is V-0, and the flame retardance of thickness 3.0mm based on UL94 5V test is 5VA determination. It is preferable that the Charpy notched impact strength is 30 kJ / ^{m 2} or more, more preferably 40 kJ / ^{m 2} or more, further preferably 45 kJ / ^{m 2} or more. The surface impact strength is preferably 80 cm or more, more preferably 100 cm or more, and even more preferably 150 cm or more, when the molded product is completely destroyed. In addition, the evaluation method of crystallization temperature, a flame retardance, and impact resistance is as the description in the below-mentioned Example.

[Molding]
A molded product obtained by molding the polybutylene terephthalate resin composition of the present invention can be suitably used as an electric / electronic part, an automobile part, other electrical parts, a machine part, a part of a household appliance such as a cooking utensil, and particularly, an electric car. Charger connector, battery capacitor holder, battery capacitor housing or housing for electric vehicle charging station, electronic and electrical equipment housing, connector, relay, switch, sensor, actuator, terminal switch, rice cooker related parts, It is suitable for grill cooking equipment parts and the like, and in particular, can be suitably used as a charger connector for an electric vehicle, a battery capacitor holder, a battery capacitor casing, or a casing for a charging stand for an electric vehicle.
The electric vehicle charger connector is a contact type connector for an electric vehicle charger used in the facility, which is charged in the facility provided with the charger when the amount of stored electricity is reduced. The battery capacitor holder is a holder for holding a large-capacity capacitor as an emergency auxiliary power source separately from the charger (battery). The battery capacitor casing is a casing constituting the capacitor. The electric vehicle charging stand housing is a housing constituting a stand for charging the battery of the electric vehicle from a 100V or 200V AC power supply.
The shape, size, thickness and the like of these molded products are arbitrary.

  The method for producing the molded article using the polybutylene terephthalate resin composition of the present invention is not particularly limited, and any molding method generally employed for the polyester 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. Of these, injection molding is preferred.

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.
In the following Examples and Comparative Examples, the components used are as shown in Table 1 below.

  The content of free bromine, chlorine and sulfur in the brominated polycarbonate flame retardant was quantified by a combustion ion chromatography method. Using an automatic sample combustion device of “AQF-100 type” manufactured by Mitsubishi Chemical Analytech Co., Ltd., heating a brominated polycarbonate flame retardant under an atmosphere of 270 ° C. for 10 minutes under an argon atmosphere, and the generated bromine, chlorine and sulfur The amount was measured using “ICS-90” manufactured by Nippon Dionex.

(Examples 1-7, Comparative Examples 1-2)
Each component shown in Table 1 was uniformly mixed with a tumbler mixer in the proportions shown in Table 2 (all parts by mass), and then meshed type co-directional twin-screw extruder (“TEX-30α” manufactured by Nippon Steel Works, Ltd., screw) A diameter of 32 mm, L / D = 52) was supplied at 40 kg / hr. Melting and kneading were carried out under the conditions that the barrel set temperatures C1 to C15 of the extruder were 260 ° C., the die was 250 ° C. and the screw rotation speed was 200 rpm, the number of nozzles was 4 (round (φ4 mm), length 1.5 cm), and the shear rate (γ ) Extruded as a strand under the condition of 211 sec ⁻¹ . The strand temperature immediately after extrusion was 270 ° C.
The extruded strand was introduced into a water tank adjusted to a temperature of 30 to 50 ° C. and quenched. The strand surface temperature (T) is cooled to 65 ° C. at a temperature measured with an infrared thermometer (γ · T = 1.4 × 10 ⁴ ), inserted into a pelletizer and cut, and a polybutylene terephthalate resin composition A product pellet was obtained.
In addition, (D) antimony compounds are 50% by mass of polybutylene terephthalate resin “Novaduran (registered trademark) 5020” manufactured by Mitsubishi Engineering Plastics, and polybutylene terephthalate resin “Novaduran (registered trademark) 5008” manufactured by Mitsubishi Engineering Plastics. 50% by mass of the mixture was used as a masterbatch of antimony compound based on the base resin (the content of (D) antimony compound in the masterbatch was 70% by mass), and the antimony compound masterbatch was blended from an independent dedicated feeder. The other ingredients were fed from the root feeder to the extruder.

Test specimens for evaluation of the following (1) to (5) are the cylinder temperature 250 ° C., the mold temperature 80 ° C., and the following (5) using an injection molding machine (NEX80-9E, manufactured by Nissei Plastic Industry Co., Ltd.). Except for the evaluation of releasability, the cooling time was 15 seconds, and the following (5) releasability evaluation was performed on a test piece injection-molded under a cooling time of 10 seconds. In molding, the resin composition was dried at 120 ° C. for 6 to 8 hours until immediately before the molding.
In addition, using an injection molding machine (“J85AD” manufactured by Nippon Steel Works), cylinder temperature 250 ° C., mold temperature 80 ° C., injection pressure 150 MPa, injection holding time 15 sec, cooling time 15 sec, injection speed 120 mm / sec. Under the conditions of a back pressure of 5 MPa and a screw rotation speed of 100 rpm, (6) an ISO tensile test piece (4 mm thickness) for morphological observation was injection molded.

(1) Flame retardance A test piece for UL94 test (125 mm × 12.5 mm × 1.5 mmt) was molded, and V-0, V-1, and V-2 were determined based on the UL94 standard.
Also, a test piece for UL94 5V Bar test (125 mm × 12.5 mm × 3.0 mmt) and a test piece for 5V Plate test (150 mm × 150 mm × 3.0 mmt) were formed, and 5 VA, according to UL94 5V test, A determination of 5 VB was made.

(2) Impact resistance characteristics Notched Charpy impact strength:
An ISO multi-purpose test piece (thickness: 4.0 mm) is injection-molded, and a 4.0 mm-thick notched test piece is produced from the test piece in accordance with ISO 179 standard. A notched Charpy impact strength (unit: kJ / m) ² ) was measured.
Surface impact strength:
A box-shaped molded product with a size of 150 x 80 x 40 mm (thickness 1.5 mmt) is formed, a 2.975 kg steel ball is dropped from a predetermined height, and the height at which the molded product is completely destroyed (unit) : Cm). It can be said that the higher the height at the time of complete destruction, the better the surface impact. The test was conducted up to a height of 205 cm, and those that did not break at 205 cm were listed in the table as “> 200”.

(3) Hydrolysis resistance properties Using an ISO multipurpose test piece (thickness: 4.0 mm), the tensile strength (before treatment) was measured in accordance with ISO 527 under conditions of a tensile speed of 50 mm / min (unit: MPa).
In addition, an ISO multipurpose test piece (thickness: 4.0 mm) was treated for 75 hours under the conditions of a temperature of 121 ° C., a relative humidity of 100% and a pressure of 2 atm using a pressure cooker tester (manufactured by Hirayama Seisakusho). The tensile strength (after 75 hr treatment) was measured (unit: MPa).

(4) Heat-resistant discoloration characteristics A plate trial molded product having a size of 100 × 100 × 3 mmt was injection-molded and left in a hot air oven at a temperature of 160 ° C. for 100 hours. The molded product before and after the test of the test piece was subjected to color difference measurement using “CE-7000A” (light source: D65, field of view: 10 °, method: SCI) manufactured by GretagMacbeth, and ΔE ^* was obtained.

(5) Releasability A box-shaped product (wall thickness 1.5mm) with a size of 150mm x 80mm x 40mm is injection-molded, and the molded product is released from the mold by a pressure sensor attached to the central ejector pin. The pressure (release resistance value, unit: MPa) applied during the measurement was measured and evaluated.

(6) Morphological observation:
From the core of the obtained ISO tensile test piece (thickness 4 mm) (the cross section parallel to the resin composition flow direction at the center of the cross section of the test piece at a portion other than the surface layer portion having a depth of less than 20 μm), Leica Using “UC7” manufactured by the manufacturer, an ultrathin section having a thickness of 100 nm was cut out with a diamond knife. The obtained ultrathin sections were stained with ruthenium tetroxide for 40 minutes, and then subjected to STEM observation using “S-4800” manufactured by Hitachi High-Tech Co. under the condition of an acceleration voltage of 25 kV.

Based on the obtained STEM photograph, the following evaluation was performed.
i) Whether (A) the polybutylene terephthalate resin phase and (B) the polycarbonate resin phase form a co-continuous phase. Table 2 below shows “○” when the co-continuous phase is formed, and “X” when the co-continuous phase is not formed.
ii) Whether (F) elastomer is present in (B) the polycarbonate resin phase. (B) The case where it is present in the polycarbonate resin phase is indicated as “PC phase”, and the case where it is not present in the (B) polycarbonate resin phase is indicated as “x”.
iii) Measurement of particle diameter of (F) elastomer phase 200 maximum particle diameters were measured and calculated by arithmetic averaging.
iv) Whether (D) the antimony compound is present in the (A) polybutylene terephthalate resin phase. The case where (D) 80% or more of the antimony compound is present in the (A) polybutylene terephthalate resin phase is “PBT phase”, and (D) 80% or more of the antimony compound is (A) the polybutylene terephthalate resin. The case where it was not present in the phase was defined as “x”.

  In addition, as a sample for observing the surface layer portion, the surface layer portion (surface layer portion having a depth of less than 20 μm) of the obtained ISO tensile test piece was used with “UC7” manufactured by Leica, and a diamond knife with a thickness of 100 nm or more. The cut cross section after cutting out the thin slice was used. The obtained cut section was stained with ruthenium tetroxide for 40 minutes, and then subjected to SEM observation under the condition of an acceleration voltage of 3 kV using “SU8020” manufactured by Hitachi High-Tech.

The following evaluation was performed based on the obtained SEM photograph.
v) (F) Whether or not the elastomer phase is stretched in the resin flow direction (“◯” for stretched material, “x” for unstretched material).
vi) (F) Measurement of ratio of major axis to minor axis of elastomer phase (F) For 200 elastomer phases, the major axis and minor axis were measured, and the major axis / minor axis ratio was arithmetically averaged. The major axis is the maximum diameter of the elastomer particles, and the minor axis is the maximum diameter in the direction perpendicular to the major axis.

  The core part of the molded product of Example 7 is as shown in FIGS. 1 and 2, respectively. (A) The polybutylene terephthalate resin phase and (B) the polycarbonate resin phase form a co-continuous phase, (F ) Elastomer is present in (B) polycarbonate resin phase, (D) 80% or more of antimony compound is present in (A) polybutylene terephthalate resin phase is uniformly dispersed. It could be confirmed. In Example 7, since (C) brominated polycarbonate is used as a flame retardant, it is considered that the flame retardant is present in the (B) polycarbonate resin phase. Moreover, from FIG. 3 which shows the surface layer part of Example 7, it has also confirmed that the (F) elastomer phase was extended in the flow direction of resin in the surface layer part. In addition, it was confirmed that the molded products of Examples 1 to 6 showed the same morphology.

Furthermore, also about the test piece for each of the above-mentioned characteristic evaluations (1) to (5), as a result of carrying out the morphological observation in the same manner, examples carried out on the above ISO tensile test piece for morphological observation (thickness 4 mm), It was confirmed that the morphology observation result was the same as that of the comparative example.
The above evaluation results are shown in Table 2 below.

  The polybutylene terephthalate resin composition of the present invention is a resin composition excellent in flame retardancy, impact resistance, hydrolysis resistance, heat discoloration and releasability. As parts of household electrical appliances such as electrical parts, machine parts, cooking utensils, etc., for example, charger connectors for electric vehicles, battery capacitor holders, casings for battery capacitors or casings for charging stands for electric vehicles, casings for electronic and electrical equipment parts Suitable for bodies, connectors, relays, switches, sensors, actuators, terminal switches, rice cooker-related parts, grill cooking equipment parts, etc., and has very high industrial applicability.

Claims (16)

(A) Polybutylene terephthalate-based resin and (B) polycarbonate resin based on a total of 100 parts by mass of (A) and (B), (A) being 50 to 80 parts by mass, and (B) being 20 to 50 parts by mass And (C) 5 to 40 parts by mass of a brominated polycarbonate flame retardant, (D) 1 to 15 parts by mass of an antimony compound, and (E) polyolefin with respect to 100 parts by mass in total of (A) and (B) 0.01 to 3 parts by mass of a mold release agent, and (D) the antimony compound is blended as a master batch with (A) polybutylene terephthalate resin having an antimony compound concentration of 50 to 90% by mass. A process for producing a polybutylene terephthalate-based resin composition . (B) The manufacturing method of the polybutylene terephthalate type-resin composition of Claim 1 whose polycarbonate resin has a viscosity average molecular weight exceeding 28000 . (A) The process for producing a polybutylene terephthalate resin composition according to claim 1 or 2, wherein the intrinsic viscosity of the polybutylene terephthalate resin is 0.9 dl / g or more . Furthermore, the polybutylene terephthalate-type resin composition of any one of Claims 1-3 which contain 5-20 mass parts of (F) elastomer with respect to a total of 100 mass parts of said (A) and (B). Manufacturing method. (F) The method for producing a polybutylene terephthalate resin composition according to claim 4, wherein the elastomer is an acrylic core / shell type graft copolymer . (F) The method for producing a polybutylene terephthalate resin composition according to claim 4 or 5, wherein an average particle size of the elastomer is 300 nm or more . The polybutylene according to any one of claims 1 to 6, further comprising 0.05 to 1 part by mass of (G) an anti-dripping agent with respect to a total of 100 parts by mass of the (A) and (B). A method for producing a terephthalate resin composition . (E) The dropping point of a polyolefin-type mold release agent is 100 degrees C or less, The manufacturing method of the polybutylene terephthalate-type resin composition of any one of Claims 1-7 . Furthermore, (H) a metal salt of an organophosphate ester compound represented by any one of the following general formulas (1) to (4) is added to a total of 100 parts by mass of the above (A) and (B) in an amount of 0. The manufacturing method of the polybutylene terephthalate-type resin composition of any one of Claims 1-8 which contain 001-1 mass part .
(In General Formula (1), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and M represents an alkaline earth metal or zinc. .)
(In General Formula (2), R ⁵ represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and M represents an alkaline earth metal or zinc.)
(In General Formula (3), R ^{6 to} R ¹¹ each independently represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and M ′ represents a trivalent metal ion. Represents a metal atom.)
(In General Formula (4), R ^{12 to} R ¹⁴ each independently represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and M ′ represents a trivalent metal ion. Represents a metal atom, and two M's may be the same or different.) Furthermore, 0.5-10 mass parts of titanium oxide surface-treated with the organosiloxane type surface treating agent is contained with respect to a total of 100 mass parts of (A) and (B). A process for producing a polybutylene terephthalate-based resin composition according to claim 1 . The manufacturing method of the molded article which shape | molds the polybutylene terephthalate-type resin composition obtained by the manufacturing method of the polybutylene terephthalate-type resin composition of any one of Claims 1-10 . A method of manufacturing a molded article for molding a polybutylene terephthalate resin composition obtained by the production method of the polybutylene terephthalate resin composition according to any one of claims 4-10, molded products of the core The (A) polybutylene terephthalate resin and (B) polycarbonate resin form a co-continuous phase, and the (F) elastomer has a morphology existing in the (B) polycarbonate resin phase. Product manufacturing method. The method for producing a molded article according to claim 12, wherein 80% or more of the (D) antimony compound is present in the (A) polybutylene terephthalate resin phase in the core of the molded article . The molding according to claim 12 or 13, wherein (F) the elastomer phase extends in the resin flow direction in the surface layer portion of the molded product, and the ratio of the major axis to the minor axis (major axis / minor axis) is 3 to 20. Product manufacturing method. The method for producing a molded article according to any one of claims 12 to 14, wherein (C) the brominated polycarbonate flame retardant is present in the (B) polycarbonate resin phase . The method for manufacturing a molded product according to any one of claims 11 to 15, which is any one of a charger connector for an electric vehicle, a holder for a battery capacitor, a casing for a battery capacitor, or a casing for a charging stand for an electric vehicle .