JP2011148917A - Thermally conductive polyalkylene terephthalate resin composition and resin molded body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyalkylene terephthalate resin composition which is excellent in flame retardancy, thermal conductivity, electrical characteristics (tracking resistance), and insulating properties, and has good productivity, even if any halogen flame retardant is not contained; and to provide a resin molded body prepared by injection-molding it. <P>SOLUTION: The polyalkylene terephthalate resin composition comprises the following (A) to (D) components: (A) 100 pts.mass of polyalkylene terephthalate resin; (B) 10-100 pts.mass of one or more inorganic compounds selected from boron nitride and magnesium silicate salts; (C) 20-90 pts.mass of glass fiber; and (D) 10-60 pts.mass of a phosphinate salt of which the specific anion and cation moieties are aluminum or calcium ions. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a heat conductive resin composition that exhibits excellent flame retardancy without containing a halogen-based flame retardant and is excellent in thermal conductivity. More specifically, the polyalkylene terephthalate resin composition for fiber-reinforced thermal conductive material parts having excellent thermal conductivity, flame retardancy, and electrical properties (tracking resistance) and good productivity, and The present invention relates to a thermally conductive resin molded product formed from a resin composition.

Polyalkylene terephthalate resins, among them polybutylene terephthalate resin (hereinafter sometimes abbreviated as PBT resin) and polyethylene terephthalate resin (hereinafter sometimes abbreviated as PET resin) are mechanical properties and electrical properties. In recent years, it has been used in many applications such as electrical equipment parts and mechanical parts because of its excellent heat resistance.

In these fields, most devices are equipped with components that generate heat, but in recent years, power consumption has increased along with higher performance of devices and components, and the amount of heat generated from components tends to increase. There is a concern that local high temperatures may cause troubles such as malfunctions. At present, the heat generated by using metal materials is diffused in the chassis, chassis, heat sink, etc., but the demand for replacement of these metal parts has increased by increasing the thermal conductivity of inexpensive resin materials. ing. In OA and electrical / electronic parts, there are many uses that require insulation, and materials having both high thermal conductivity and insulation are desired.

Also, such electrical equipment components must meet the flame retardancy of the Underwriters Laboratories Inc. UL-94 standard and have a tracking index (CTI) or warranty There has been a demand for materials that simultaneously satisfy the requirements of the tracking index (Proof Tracking Index, abbreviated as PTI).

Specifically, for example, in a thin resin molded body having a thickness of 0.8 mm, a material having flame retardancy of V-2 or more and satisfying PTI (or CTI) of 550 V or more is preferably flame retardant. A material having the highest V-0 and PTI (or CTI) of 600 V or more has been demanded.

In order to cope with this, for example, a technique using carbon fiber in addition to boron nitride as an inorganic compound for improving thermal conduction has been proposed (for example, see Patent Document 1). However, this method has a problem in that it does not have the insulating properties required for resin materials used for OA and electric / electronic parts because there is a concern that electricity partially flows.

On the other hand, a polyester-based insulating heat conductive material (for example, see Patent Document 2) using a halogen-based flame retardant has been proposed, but there is no suggestion regarding the flame retardancy test, and the flame retardancy is not sufficiently examined. In addition, since a halogen-based flame retardant is used, there is a problem that there is a concern about the influence on the surrounding environment, such as generation of a halogen compound when incinerated at the time of disposal.

A polyester-based resin composition excellent in glow wire properties using boron nitride as a flame retardant aid has also been proposed (see, for example, Patent Document 3), but is not even suggested for thermal conductivity and can be applied as a heat dissipation member. The examination was insufficient.

JP 2005-298552 A JP 2008-207709 A Japanese translation of PCT publication No. 2004-510837

An object of the present invention is a heat conductive polyalkylene terephthalate system that has excellent heat conductivity, exhibits high flame resistance in the UL-94 standard without using a halogen-based flame retardant, and satisfies tracking resistance. It is providing a resin composition and a resin molding.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have selected a polyalkylene terephthalate resin component as a kind of inorganic compound for greatly improving thermal conductivity selected from boron nitride and magnesium silicate salt. Thermal conductivity with excellent productivity, thermal conductivity, flame retardancy, and tracking resistance by using the above inorganic compounds and phosphinates as flame retardants and blending specific amounts of glass fiber as reinforcing agents It has been found that a polyalkylene terephthalate resin composition is obtained.

And since the polybutylene terephthalate resin composition of the present invention is excellent in fluidity, it has also been found that precision shaped parts and micro parts having thin-walled parts can be produced efficiently and with high quality by injection molding. It was.

Furthermore, at least one non-halogen flame retardant of a specific group in this resin composition, specifically a phosphate ester, a salt of an amino group-containing triazine, an organosiloxane in a solid state at 25 ° C. The present invention has also been found by containing a specific amount of at least one flame retardant selected from the group consisting of a polymer and a metal borate salt, while maintaining the above-mentioned characteristics and improving laser marking properties. I let you.

That is, the gist of the present invention is (A) a polyalkylene terephthalate resin composition comprising the following components (B) to (D) with respect to 100 parts by mass of a polyalkylene terephthalate resin, and molding the same: It is related with the resin molding formed.
(B) 10 to 100 parts by mass of an inorganic compound comprising boron nitride and / or magnesium silicate salt,
(C) Glass fiber: 20 to 90 parts by mass,
(D) 10-60 parts by mass of a phosphinic acid salt in which the anion moiety is represented by the following formula (1) or (2) and the cation moiety is an aluminum ion or a calcium ion;

（式中、Ｒ^１およびＲ^２は、それぞれ独立して、炭素数１〜６のアルキル基又は置換されていてもよいアリール基を表し、Ｒ^１同士は同一でも異なっていてもよく、Ｒ^３は炭素数１〜１０のアルキレン基、置換されていてもよいアリーレン基、又はこれらの混合基を表し、ｎは０〜４の整数を表す。）

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, and R ¹ may be the same or different, and R ³ Represents an alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group, or a mixed group thereof, and n represents an integer of 0 to 4.)

The polybutylene terephthalate resin composition of the present invention is a resin excellent in thermal conductivity, showing excellent flame retardancy even without containing a halogen flame retardant, and also excellent in tracking resistance and thermal conductivity It has the characteristic that it can be set as the resin composition excellent also in laser marking property not only in a composition. By using the resin composition of the present invention, a resin molded product can be provided with high productivity regardless of the shape, and can be widely used as a material for OA and electric / electronic parts.

FIG. 1 is a schematic view of a spiral long resin molded product for spiral flow length measurement.

The present invention is described in detail below.
(A) Polyalkylene terephthalate resin (A) Polyalkylene terephthalate resin used in the present invention is (A-1) polyalkylene terephthalate resin (so-called homopolymer), (A-2) polytetramethylene ether glycol copolymer. It is comprised from a polyester resin, (A-3) dimer acid copolymerization polyester resin, and (A-4) isophthalic acid copolymerization polyester resin.

(A-1) Polyalkylene terephthalate resin (A-1) The polyalkylene terephthalate resin used in the present invention is a so-called homopolymer, and terephthalic acid accounts for 50 mol% or more of the total dicarboxylic acid component. , A resin in which ethylene glycol or 1,4-butanediol accounts for 50% by mass or more of the total diol. Terephthalic acid preferably accounts for 80 mol% or more of the total dicarboxylic acid component, more preferably 95 mol% or more. Ethylene glycol or 1,4-butanediol preferably accounts for 80 mol% or more of the total diol component, and more preferably 95 mol% or more.

In the present invention, as the (A-1) polyalkylene terephthalate resin, terephthalic acid accounts for 95 mol%, particularly 98 mol% or more of the total dicarboxylic acid component, and ethylene glycol or 1,4-butanediol is all It is preferable to use polyethylene terephthalate resin (PET resin), polybutylene terephthalate (PBT resin) or a mixture thereof occupying 95% by mass or more of the diol.

(A-1) The intrinsic viscosity of the polyalkylene terephthalate resin is arbitrary, but in general, using a mixed solvent of 1,1,2,2-tetrachloroethane / phenol = 1/1 (mass ratio), When measured at a temperature of 30 ° C., it is 0.50 or more, preferably 0.6 or more, and 3.0 or less, particularly preferably 1.5 or less. If the intrinsic viscosity is less than 0.50, the mechanical strength of the resulting resin composition is low, and conversely if it is greater than 3.0, the moldability of the resin composition may be significantly reduced. In addition, as (A-1) polyalkylene terephthalate resin, you may use what used two or more types of (A-1) polyalkylene terephthalate resin from which intrinsic viscosity differs to make desired intrinsic viscosity. .

(A-1) As dicarboxylic acid components other than terephthalic acid constituting the polyalkylene terephthalate resin, phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4 ′ -Aromatic dicarboxylic acids such as benzophenone dicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, Alicyclic dicarboxylic acids such as 3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid Commonly used ones can be used.

Examples of diol components other than ethylene glycol or 1,4-butanediol include diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5 -Aliphatic diols such as pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1 , 4-cyclohexane dimethylol and other alicyclic diols, xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, etc. And aromatic diols are used. Even if ethylene glycol or butylene glycol is used, diethylene glycol or dibutylene glycol may be by-produced during the reaction and incorporated into the polyalkylene terephthalate.

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

The production method of the (A-1) polyalkylene terephthalate resin from dicarboxylic acid or its derivative and diol is arbitrary. Specifically, for example, any of a direct polymerization method in which terephthalic acid and glycol are directly esterified and a transesterification method in which dimethyl terephthalate is used as a main raw material can be used. The former is different in that water is produced in the initial esterification reaction, and the latter is produced in the initial transesterification reaction. The direct polymerization method is advantageous from the viewpoint of raw material costs.

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

In the (A-1) polyalkylene terephthalate resin used in the present invention, the PBT resin alone having a terminal carboxyl group amount of 30 eq / t or less and a residual tetrahydrofuran amount of 300 ppm (mass ratio) or less, or the PBT resin and PET resin is used. A mixture with is preferred.

When a PBT resin having a terminal carboxyl group content of 30 eq / t or less is used, the hydrolysis resistance of the resulting resin composition can be improved. That is, since the carboxyl group acts as an autocatalyst for the hydrolysis of PBT, if a terminal carboxyl group exceeding 30 eq / t is present, the hydrolysis starts at an early stage, and the generated carboxyl group becomes the autocatalyst as a chain. Hydrolysis proceeds and the degree of polymerization of PBT may decrease rapidly.

However, if the amount of terminal carboxyl groups is 30 eq / t or less, early hydrolysis can be suppressed even under conditions of high temperature and high humidity. The amount of terminal carboxyl groups of the PBT resin can be determined by dissolving the PBT resin in an organic solvent and titrating with an alkali hydroxide solution.

The amount of residual tetrahydrofuran in the PBT resin is preferably 300 ppm (mass ratio), particularly 200 ppm (mass ratio) or less. A resin composition using a PBT resin having a large amount of residual tetrahydrofuran generates a large amount of organic gas at a high temperature. However, a molded product obtained from a resin composition using a PBT resin having a residual tetrahydrofuran amount of 300 ppm (mass ratio) or less generates little organic gas even when used at a high temperature, and therefore there is a risk of corrosion of electrical contacts. Since there are few, it can be used conveniently for contact electrical / electronic components, such as a relay component.

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

As the components other than terephthalic acid and 1,4-butanediol, in the (A) polyalkylene terephthalate resin, if it is 60% by mass or less, other monomer components other than the homopolymer described above May be a copolymer formed by copolymerizing, and among them, the following copolymer resins (A-2) to (A-4) are preferable.

(A-2) Polytetramethylene ether glycol copolymer polyester resin

(A-2) Polytetramethylene ether glycol copolymerized polyester resin (hereinafter sometimes referred to as polyester ether resin) used in the present invention is a dicarboxylic acid containing terephthalic acid as a main component and 1,4-butane. A polyester ether resin obtained by copolymerizing a diol having diol and polytetramethylene ether glycol (hereinafter sometimes referred to as PTMG) as main components, and the proportion of the component derived from PTMG is 2 to 30. % By mass. If the ratio of this component is less than 2% by mass, it is difficult to develop desired toughness. If it exceeds 30% by mass, the moldability is lowered, and the strength and heat resistance of the resin molded product are insufficient. Become. The proportion of the component derived from PTMG is preferably 3 to 25% by mass, particularly 5 to 20% by mass.

The number average molecular weight of PTMG used in the present invention is arbitrary and may be appropriately selected and determined, but is preferably 300 to 6000, more preferably 500 to 5000, and particularly preferably 500 to 3000. . If the number average molecular weight is too small, the effect of improving toughness is not sufficiently exhibited. On the contrary, if this number average molecular weight is too large, not only the strength and heat resistance are likely to be insufficient, but also compatibility with other polyalkylene terephthalate resins, specifically when used as a mixture with, for example, resin PBT. The toughness improving effect of the resulting resin composition may not be exhibited.

The number average molecular weight of PTMG can be determined by reacting this with excess acetic anhydride, decomposing the remaining acetic anhydride with water to give an acid, and quantifying this acid by alkali titration.

The solution viscosity [η] of the polyester ether resin used in the present invention is arbitrary, but usually a value measured at 30 ° C. using a mixed solvent having a mass ratio of 1/1 of tetrachloroethane and phenol is 0.7-2. It is preferable that it is 0.8-1.6 among them.

If the solution viscosity of the polyester ether resin is too low or too high, the moldability of the resin composition using the polyester ether resin and the toughness of the resin molded body are lowered. The melting point of the polyester ether resin is usually 200 to 225 ° C, and preferably 205 to 222 ° C.

(A-3) Dimer acid copolymer polyester resin

The (A-3) dimer acid copolyester resin used in the present invention is a copolyester obtained by copolymerizing glycol mainly composed of 1,4-butanediol, terephthalic acid, and dimer acid.

The ratio of the dimer acid component to the total carboxylic acid component is 0.5 to 30 mol% as the carboxylic acid group. If the proportion of the dimer acid is too large, the long-term heat resistance of the resin composition using the dimer acid is significantly reduced. On the other hand, if the amount is too small, the toughness is significantly reduced. Therefore, the ratio of the dimer acid component to the total carboxylic acid component is preferably 1 to 20 mol%, particularly preferably 3 to 15 mol%, as the carboxylic acid group.

The dimer acid used in the present invention is usually a dimerization reaction of an unsaturated fatty acid having 18 carbon atoms, specifically, for example, oleic acid, linoleic acid, linolenic acid, elaidic acid, etc. with a clay catalyst such as montmorillonite. The thing obtained by letting it be mentioned is mentioned.

The reaction product of the dimerization reaction is a mixture mainly containing a dimer acid having 36 carbon atoms, and further containing a trimer acid having 54 carbon atoms, a monomer acid having 18 carbon atoms, and the like. This mixture is purified by vacuum distillation, molecular distillation, hydrogenation reaction or the like to obtain dimer acid.

Dimer acid is not a single compound, but is generally a mixture of compounds having a chain, aromatic ring, alicyclic monocyclic and alicyclic polycyclic structures. For example, when a material having a large amount of linoleic acid is used as a dimer acid raw material, a compound having a chain structure is reduced and a compound having a cyclic structure is increased in the obtained dimer acid.

As the dimer acid used in the production of the copolyester used in the present invention, it is preferable to use one containing 10% by mass or more of a chain dimer acid represented by the following general formula (3).

（式中、Ｒはアルキル基を示し、Ｒ^ｍ、Ｒ^ｎ、Ｒ^ｐ及びＲ^ｑの炭素数の和は３１である）

(In the formula, R represents an alkyl group, and the sum of the carbon number of R ^m , R ⁿ , R ^p and R ^q is 31)

If the chain dimer acid is used in an amount of 10% by mass or more, the resulting copolymer polyester resin itself has a good tensile elongation. Therefore, the tensile elongation of the resin composition of the present invention using the same is also good. Therefore, it is preferable.

The proportion of the monomer acid contained in the dimer acid is preferably 1% by mass or less. The monomer acid inhibits the polymerization of the resin produced during the copolymerization, but if it is 1% by mass, the condensation polymerization proceeds sufficiently during the copolymerization, so that a copolymer having a high molecular weight can be obtained. The toughness of the composition is improved.

Preferred examples of the dimer acid include PRIIPOL 1008 and PRIPOL 1009 manufactured by Unikema, and further PRIPLAST 3008 and PRIPLAST 1899 manufactured by Unichema as ester-forming derivatives of PRIPOL 1008.

In addition, it does not restrict | limit especially as a manufacturing method of the copolyester resin using a dimer acid, It can carry out according to the conventionally well-known arbitrary methods, for example, the method disclosed by Unexamined-Japanese-Patent No. 2001-064576.

(A-4) Isophthalic acid copolymer polyester resin The isophthalic acid copolymer polyester resin is a copolymer of glycol mainly composed of 1,4-butanediol and dicarboxylic acid mainly composed of terephthalic acid and isophthalic acid. Copolyester.

The proportion of the isophthalic acid component in the total carboxylic acid component is 1 to 30 mol% as the carboxylic acid group. When the proportion of the isophthalic acid component is too large, the heat resistance of the resin composition using the isophthalic acid component is lowered, and the injection moldability is also lowered. On the other hand, if the amount is too small, the effect of improving toughness is insufficient. Therefore, the ratio of the isophthalic acid component to the total carboxylic acid component is preferably 1 to 20 mol%, particularly preferably 3 to 15 mol%, as the carboxylic acid group.

(B) Inorganic compound comprising boron nitride and / or magnesium silicate salt (B) An inorganic compound comprising boron nitride and / or magnesium silicate salt used in the present invention is (B-1) boron nitride, and / Or (B-2) An inorganic compound comprising a magnesium silicate salt, which is important for greatly improving the thermal conductivity in the resin composition of the present invention.

The shape of (B) component used for this invention is not specifically limited, What is necessary is just to select suitably and determine. Specifically, for example, it can be spherical, linear (fibrous), flat (scale-like), curved, needle-like, etc., and used as a single grain type or a granule type (single grain aggregate) May be. Of these, the use of a scaly product is preferable because a molded article having excellent thermal conductivity can be obtained and the mechanical properties can be improved.

The aspect ratio of the inorganic compound (B) used in the present invention is arbitrary, but is preferably 3 or more, more preferably 5 or more, and still more preferably 6 to 20. Further, the higher the purity and the bulk density, the better the thermal conductivity. Therefore, the purity is preferably 98% or more, particularly 99% or more, and the bulk density is 0.4 g / cm ³ or more, especially 0.6 g. / Cm ³ or more is preferable.

The content of the component (B) in the resin composition of the present invention is preferably 10 to 100 parts by mass, more preferably 20 to 90 parts by mass, with 100 parts by mass of the (A) polyalkylene terephthalate resin. Furthermore, it is preferable that it is 30-70 mass parts, especially 40-60 mass parts. In the present invention, if the content of the component (B) is too large, the moldability, impact resistance and bending strain characteristics tend to be inferior, and conversely if too small, the thermal conductivity becomes insufficient.

(B-1) Boron nitride (B-1) Boron nitride used in the present invention includes c-BN (zinc blende structure), w-BN (wurtzite structure), h-BN (hexagonal crystal). Structure) and boron nitride having a plurality of known stable structures such as r-BN (rhombohedral crystal structure) can be used. Among them, boron nitride having a hexagonal crystal structure is preferable because wear of a molding machine and a mold used for obtaining a molded product can be reduced.

Further, spherical boron nitride having an aspect ratio of less than 3 obtained by spraying and drying spherical irregular non-spherical BN particles with a binder is used alone or in combination with scaly particles having an aspect ratio of 3 or more. It may be used. Boron nitride preferably has a thermal conductivity at 25 ° C. of 30 W / (m · K) or more, and more preferably 50 W / (m · K) or more.

The boron nitride (B-1) used in the present invention preferably has an average particle size of 1 to 350 μm, more preferably 2 to 200 μm, and two or more types having an average particle size within this range, You may use together in arbitrary ratios. When the average particle size is in this range, a resin composition excellent in thermal conductivity and insulation can be obtained. In addition, the average particle diameter here is a value measured according to JIS Z8825-1, measured by a laser diffraction method, and determined according to JIS Z8819-2.

(B-2) Magnesium silicate salt As the (B-2) magnesium silicate salt used in the present invention, in addition to a synthetic material, a mineral mainly composed of magnesium silicate, specifically, for example, talc, sepiolite. Furthermore, an apatalite containing an aluminum component may be used. In the present invention, talc is preferably used from the viewpoint of thermal conductivity.

Talc as the component (B-2) used in the present invention is a kind of natural mineral, and its chemical formula is represented by 3MgO.4SiO ₂ .H ₂ O or Mg ₃ Si ₄ O ₁₀ (OH) ₂ . Talc usually contains impurities according to the production area, etc., but the talc used in the present invention is not particularly limited with respect to the production area, the type of impurities and the amount thereof.

Although there is no restriction | limiting in particular about the magnitude | size of talc, Usually, mass median particle diameter (D50) is 1-50 micrometers, More preferably, it is 3-40 micrometers. Here, the mass median particle diameter is a value measured by a laser diffraction method or the like. In addition, talc may use what gave the process of coating the surface with an organic compound, etc. for the purpose of improving affinity with a component (A) and improving the dispersibility in a resin composition. .

Moreover, although the bulk specific gravity of talc is arbitrary, it is preferable that it is 0.4 or more from the point of productivity. Here, the bulk specific gravity value is a method in which 10 g of a sample is weighed, and this is gently put into a test tube with a 50 ml scale and calculated from the numerical value of the volume. Bulk specific gravity (g / ml) = 10 g / ml Expressed in volume (ml).

In the present invention, it is preferable to use compressed fine powder talc because it has high uniform dispersibility, can improve kneading workability and mechanical characteristics, and can greatly improve electrical characteristics such as tracking resistance. In this case, the bulk specific gravity of talc is preferably 0.4 or more, and more preferably 0.6 or more. In addition, when using talc with such high bulk specific gravity, as long as it is more than this numerical value, you may use combining talc with different bulk specific gravity.

The component (B) used in the present invention includes, among others, the above-mentioned (B-1) boron nitride and (B-2) magnesium silicate salt, particularly bulky particles having a bulk density of 0.4 or more like granular talc. By using together with a high-density magnesium silicate salt, while maintaining various physical properties such as thermal conductivity, the meterability during the production of the resin composition is stable, and industrially superior, the thermal conductivity of the present invention Since a resin composition can be manufactured, it is preferable.

In addition, since the boron nitride and magnesium silicate, which are the components (B) used in the present invention, are excellent in insulation, they are difficult to be installed with a heat conductive member such as a metal, and are installed in a place close to or in contact with an electronic device. Is possible. The surface specific resistance of the resin molded body obtained by the present invention is usually 1 × 10 ¹³ Ω or more, preferably 1 × 10 ¹⁴ Ω or more.

In addition to these, additives having excellent insulating properties, specifically, for example, aluminum silicate, aluminum nitride, silicon nitride, zinc oxide, aluminum oxide, magnesium oxide, calcium titanate and the like may be used in combination. These may be combined and used as a composite filler having a core-shell structure.

(C) Glass fiber The (C) glass fiber used in the present invention is preferably composed of A glass, C glass, E glass or the like, and in particular, E glass (non-alkali glass) is polyalkylene terephthalate. It is preferable at the point which does not have a bad influence on the thermal stability of a resin. In general, it is preferable to use short fiber type (chopped strand) glass fibers because they are easy to handle and give a molded product having high strength, rigidity and heat resistance. In particular, in the case of a resin molded product that requires impact resistance, it is preferable to use a long fiber type in order to keep the fiber length of the glass fiber in the resin molded product longer. These fillers can be used alone or in combination of two or more.

These fillers may be used in combination with a sizing agent or a surface treatment agent. Examples of such a sizing agent or surface treatment agent include compounds having a functional group such as an epoxy compound, a silane compound, and a titanate compound.

Furthermore, as (C) glass fiber used for this invention, what has an irregular cross-sectional shape is preferable. This irregular cross-sectional shape means that the D2 / D1 ratio (flatness) when the major axis of the cross section perpendicular to the longitudinal direction of the fiber is D2 and the minor axis is D1 is 1.5 to 10, especially 2.5. Is preferably 10 to 10, more preferably 2.5 to 8, and particularly preferably 2.5 to 5. By setting it to 2.5 or more, flame retardancy, heat shock resistance, and withstand voltage are improved.

When glass fibers having such an irregular cross-sectional shape are used, heat conduction is surprisingly compared with the case of using so-called normal glass fibers having a normal cross-sectional shape (roundness is 1). The rate is also favorable, which is preferable. This is because the glass fiber having an irregular cross-sectional shape is in the resin molded body, particularly in the resin molded body obtained by injection molding, in a wide range from the surface to the inside of the resin molded body, the molten resin at the time of resin molding This is considered to be due to the orientation in the flow direction and the orientation of the plate-like inorganic compounds such as boron nitride and magnesium silicate along the orientation of the glass fibers.

Further, as the glass fiber having an irregular cross-sectional shape, when the average fiber length is L, the (L × 2) / (D2 + D1) ratio (aspect ratio) is preferably 10 or more, especially 50 to 10. Is preferred.

The flatness of the glass fiber can be easily calculated from the measured values of the major axis and the minor axis with a microscope of the cross section of the fiber. If the flatness is described in the catalog for a commercially available glass fiber, this value may be used. The fiber length of the glass fiber in the resin molded body is, for example, about 5 g of a sample cut out from the resin molded body and left to stand in an electric furnace at 600 ° C. for 2 hours to be ashed. Can be measured. Specifically, for example, the glass fiber is dispersed in a neutral surfactant aqueous solution so as not to break, and the dispersed aqueous solution is transferred onto a slide glass by a pipette and photographed with a microscope. For this photographic image, it is only necessary to measure 1000 to 2000 reinforcing fibers using image analysis software and calculate the average fiber length.

Specifically, as the cross-sectional shape of the glass fiber having an irregular cross-sectional shape used in the present invention, for example, the cross-sectional shape when cut at right angles to the length direction of the fiber is a rectangle, an oval, an ellipse, the center in the longitudinal direction One that has a constricted bowl shape. Examples of the cross-sectional shape of these glass fibers are described in JP-A No. 2000-265046.

The fiber-shaped reinforcing material having a saddle-shaped cross-section has a constricted central part, the strength of the part is low, and the central part may crack, and the constricted part may have poor adhesion to the base resin. Therefore, in order to improve mechanical properties, it is preferable to use a cross-sectional shape that is rectangular, oval, or elliptical, and it is more preferable that the cross-sectional shape is rectangular or oval. The term “oval” is intended to include a shape formed of a smooth curve having different lengths and widths and rounded as a whole, and a shape formed of two arcs and two straight lines connecting these arcs.

The glass fiber having an irregular cross section that can be suitably used as the glass fiber of the resin composition of the present invention is described in, for example, Japanese Patent Publication No. 3-59019, Japanese Patent Publication No. 4-13300, Japanese Patent Publication No. 4-32775, and the like. It can be manufactured using a method. In particular, in an orifice plate having a large number of orifices on the bottom surface, an outer periphery of an orifice plate surrounding a plurality of orifice outlets and having a convex edge extending downward from the bottom surface of the orifice plate, or a nozzle tip having one or more orifice holes A glass fiber having a flat cross section produced using a nozzle chip for deformed cross section glass fiber spinning provided with a plurality of convex edges extending downward from the tip of the section is preferred.

In the present invention, a general circular (or round) cross-section glass fiber (flatness 1) may be used in combination with the above-mentioned irregular cross-section glass fiber, but the flatness and aspect ratio at that time are mass average. It is sufficient that the numerical value calculated as described above falls within the range of the aspect ratio and aspect ratio.

(D) Phosphinic acid salt In the present invention, (D) phosphinic acid metal is used as a flame retardant. The (D) phosphinate used in the present invention has an anion moiety represented by the following formula (1) or (2), and the cation moiety is any of calcium ion, magnesium ion, aluminum ion or zinc ion. Of these, calcium ions or aluminum ions are preferable, and aluminum ions are particularly preferable.

(In the formula, R ¹ and R ² each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms, an aryl group, preferably a phenyl group, and R ¹ may be the same or different. R ³ represents a linking group having 1 to 10 carbon atoms, and is preferably a linear or branched alkylene group, an arylene group, or a mixed group thereof, n represents an integer of 0 to 2, among which 0 is preferable.)

Specific examples of phosphinates include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, ethylmethylphosphine Zinc oxide, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, Zinc methyl-n-propylphosphinate, methandi (methylphosphinic acid) calcium, methandi (methylphosphite) Acid) magnesium, methanebis (methylphosphinic acid) aluminum, methanebis (methylphosphinic acid) zinc, benzene-1,4-bis (methylphosphinic acid) calcium, benzene-1,4-bis (methylphosphinic acid) magnesium, benzene- 1,4-bis (methylphosphinic acid) aluminum, benzene-1,4-bis (methylphosphinic acid) zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, Examples include calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate.

In the present invention, these compounds may be used alone or in combination of two or more at any ratio. Among these, particularly from the viewpoint of flame retardancy and electrical properties, aluminum diethylphosphinate, calcium diethylphosphinate, and zinc diethylphosphinate are preferred, among which aluminum diethylphosphinate and calcium diethylphosphinate are preferred, particularly diethylphosphinic acid. Aluminum is preferred. . From the viewpoint of toughness, it is preferable that all melting peak temperatures (Tm) appear at 180 ° C. or higher in DSC measurement.

Since the particle size of the (D) phosphinate used in the present invention affects the appearance and mechanical strength of the resin molding obtained from the resin composition, particles of 95% by mass or more are measured by laser diffraction. The diameter is preferably 100 μm or less. Of these, particles having a particle size of 95% by mass or more and 50 μm or less, specifically, for example, powder obtained by pulverization are preferable. In general, however, the smaller the particle size, the higher the preparation cost, but the effect obtained is reduced for a while. Therefore, the particle size of 20 to 40 μm is preferably 90% by mass or more.

The (D) phosphinate used in the present invention is blended in an amount of 10 to 60 parts by mass with respect to 100 parts by mass of the (A) polyalkylene terephthalate resin. If it is less than 10 parts by mass, the intended flame retardancy is not sufficient, and if it exceeds 60 parts by mass, mechanical properties, moldability, mold release defects and mold deposits are likely to occur. From the viewpoint of both flame retardancy and mechanical properties, the preferred blending amount is 10 to 60 parts by mass with respect to 100 parts by mass of the (A) polyalkylene terephthalate resin, among which 20 to 50 parts by mass, and further 20 to 40 parts. It is preferable that it is a mass part, especially 25-40 mass parts.

(E) Flame retardant In the present invention, the (A) polyalkylene terephthalate resin described above may further contain (E) a flame retardant in addition to the components (B) to (D). (E-1) a phosphoric ester, (E-2) a nitrogen-based flame retardant comprising a salt of an amino group-containing triazine, (E-3) an organosiloxane polymer in a solid state at 25 ° C., and (E -4) A specific amount of at least one flame retardant selected from the group consisting of boric acid metal salts may be contained, and these may be used in combination.

(E-1) Phosphate ester Specific examples of the phosphate ester used in the present invention include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl Examples include diphenyl phosphate and octyl diphenyl phosphate.

Among these, the phosphoric acid ester compound represented by the following general formula (a) is preferable from the viewpoints of heat resistance and hydrolysis resistance.

（但し上記式中、Ｒ^１〜Ｒ^８は炭素数１〜６のアルキル基を示し、Ｒ^９はアリーレン基を示し、ｎは１〜５を示す。）

(However in the above ^formula, R 1 to R ⁸ represents an alkyl group having 1 to 6 carbon atoms, ^{R 9} represents an arylene radical, n denotes 1 to 5.)

The amount of the phosphoric acid ester (E-1) used in the polyester resin composition of the present invention may be appropriately selected and determined. However, if the amount is too large, the mechanical properties are liable to decrease, and conversely too small. However, since the addition effect is insufficient, it is usually 0.1 to 10 parts by weight, particularly 1 to 8 parts by weight, particularly 1 to 5 parts by weight with respect to 100 parts by weight of the polyalkylene terephthalate resin (A). Preferably there is.

(E-2) Salt of amino group-containing triazine In the present invention, a comparison is made by blending a salt of amino group-containing triazine (triazine having an amino group) which is a nitrogen-based flame retardant. It is preferable to add a small amount of phosphinic acid salt because a desired flame retardant effect can be expressed.

As the amino group-containing triazines, amino group-containing 1,3,5-triazines are usually used. Specifically, for example, melamine, substituted melamine (2-methylmelamine, guanylmelamine, etc.), melamine condensate ( Melam, melem, melon, etc.), melamine co-condensation resin (melamine-formaldehyde resin, etc.), cyanuric amides (ammelin, ammelide, etc.), guanamine or its derivatives (guanamine, methylguanamine, acetoguanamine, benzoguanamine, succinoguanamine , Adipoguanamine, phthalogamine, CTU-guanamine, etc.).

As an acid which forms a salt with this, either an inorganic acid or an organic acid may be used. Specific examples of inorganic acids include nitric acid, chloric acid (chloric acid, hypochlorous acid, etc.), phosphoric acid (phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, etc.), sulfuric acid (sulfuric acid and sulfurous acid). Non-condensed sulfuric acid, condensed sulfuric acid such as peroxodisulfuric acid and pyrosulfuric acid), boric acid, chromic acid, antimonic acid, molybdic acid, tungstic acid and the like. Of these, phosphoric acid and sulfuric acid are preferable.

Specific examples of organic acids include organic sulfonic acids (aliphatic sulfonic acids such as methanesulfonic acid, aromatic sulfonic acids such as toluenesulfonic acid and benzenesulfonic acid), cyclic ureas (uric acid, barbituric acid, And cyanuric acid and acetylene urea).

Among these, C1-C4 alkanesulfonic acid, such as methanesulfonic acid, Arylsulfonic acid which may have C1-C3 alkyl groups, such as toluenesulfonic acid, and cyanuric acid are preferable.

Specific examples of salts of amino group-containing triazines include, for example, melamine cyanurate, melam, melem double salt, melamine phosphate (melamine polyphosphate, melamine polyphosphate, melam, melem double salt, etc.), melamine sulfate (Melamine sulfate, dimelamine sulfate, dimelam pyrosulfate, etc.), melamine sulfonates (melamine methanesulfonate, melam methanesulfonate, melem methanesulfonate, melamine methanesulfonate, melam, melem double salt, melamine toluenesulfonate, toluene Melamine sulfonate, melamine toluenesulfonate, melam, melem double salt, etc.). These may be used alone or in combination of two or more at any ratio.

Among such nitrogen flame retardants, it is preferable to use an adduct of cyanuric acid or isocyanuric acid and a triazine compound. The composition of this adduct is usually 1 to 1 (molar ratio), optionally 1 to 2 (molar ratio).

More specifically, examples include melamine cyanurate, benzoguanamine cyanurate, acetoguanamine cyanurate, and melamine cyanurate is particularly preferable. These salts are obtained, for example, by mixing a mixture of amino group-containing triazines and cyanuric acid or isocyanuric acid into an aqueous slurry and mixing to form both salts into fine particles, and then filtering and drying the slurry to obtain a powder. .

These amino group-containing triazine salts need not be completely pure, and unreacted triazines, cyanuric acid, and isocyanuric acid may remain. In addition, the average particle diameter of the salt before blended with the resin is such as flame retardancy, mechanical strength and heat-and-moisture resistance properties, residence stability, and surface properties of the resin molded product obtained from the resin composition of the present invention. Therefore, it is preferable that 95% by mass or more of the particles have a particle size of 100 μm or less, particularly 80 μm or less as measured by a laser diffraction method.

When the above-described salt dispersibility is insufficient, a dispersant such as tris (β-hydroxyethyl) isocyanurate, a known surface treatment agent, or the like may be used in combination.

  The amount of the salt of the (E-2) amino group-containing triazines used in the polyester resin composition of the present invention may be appropriately selected and determined, but if it is too much, the mechanical properties tend to decrease, On the other hand, since the effect of addition is insufficient even if the amount is too small, the amount is usually 1 to 50 parts by weight, particularly 5 to 30 parts by weight, particularly 10 to 25 parts by weight, based on 100 parts by weight of the (A) polyalkylene terephthalate resin. Part.

The blending ratio of (D) phosphinic acid salt and (E-2) salt of amino group-containing triazine is usually (D) / (E-2) = 0-3 in terms of mass ratio. When the ratio is larger than 3, it becomes difficult to ensure the flame retardancy of the resin composition obtained. Therefore, it is preferably 0.1 to 2, and more preferably 0.3 to 1.5.

Further, in the present invention, in order to improve the dispersibility of the salt of (D) phosphinic acid salt and (E-2) amino group-containing triazine, these are previously treated with a dispersant and then mixed with other components. A resin composition may be produced, or a dispersant may be added during production of the resin composition. Examples of such a dispersant include liquid dispersants such as monomers and polymers disclosed in JP-A No. 2004-269885.

Specifically, examples of the monomer include glycols such as ethylene glycol and butanediol, and isocyanates such as TDI and MDI. Examples of the polymer include polyether polyols such as polyethylene glycol, polyester polyol, bisphenol A diglycidyl ester, phenol-formaldehyde resin, or epoxy resin such as cresol-formaldehyde resin polyglycidyl ester.

In order to improve the dispersibility, it is also preferable to blend the flame retardant after granulating it. Specifically, for example, a phosphinate-containing flame retardant granulated with a binder as disclosed in JP-A-2004-99893 is preferably used.

Specific examples of preferable binders include waxes such as carnauba wax, montan wax, and polyethylene wax, and polyethylene glycol. The melting point of the binder is preferably 50 to 200 ° C., and the amount of the binder is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the flame retardant.

(E-3) Organosiloxane polymer in a solid state at 25 ° C. (E-3) A typical organosiloxane polymer in a solid state at 25 ° C. used in the present invention is a so-called silicone resin. And the composition is represented by the following formula (4).
(R ¹ SiO _3/2 ) _a (R ² ₂ SiO _2/2 ) _b (R ³ ₃ SiO _1/2 ) _c (SiO _4/2 ) _d (XO _1/2 ) _e (4)

In the formula (4), X is a hydrogen atom or an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a heptyl group. R ¹ , R ² , and R ³ in Formula (4) may be different from each other and are a hydrocarbon group or an epoxy group-containing organic group.

Examples of the hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; an alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group; Aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group; aralkyl groups such as benzyl group, phenethyl group; chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, nonafluorobutyl Examples include halogenated alkyl groups such as an ethyl group.

Examples of the epoxy group-containing organic group include 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group and the like; 2-glycidoxyethyl group, 3-glycol Glycidoxyalkyl groups such as sidoxypropyl group and 4-glycidoxybutyl group; Epoxycyclohexylalkyls such as 2- (3,4-epoxycyclohexyl) ethyl group and 3- (3,4-epoxycyclohexyl) propyl group Groups.

The epoxy group-containing organic group is not essential, but the ratio of the epoxy group-containing organic group in the total of R ^{1 to} R ³ in Formula (4) is preferably 0.1 to 40 mol%. If the content is less than 0.1 mol%, bleeding tends to occur during molding of a resin composition obtained by blending the content. Moreover, when it exceeds 40 mol%, there exists a tendency for the mechanical characteristics of a molding to fall.

Further, when a phenyl group is present, it is excellent in affinity for (A) polyalkylene terephthalate resin, and therefore, it is preferable that 10 mol% or more of the total of R ^{1 to} R ³ in formula (4) is a phenyl group, Among them, those in which 10 mol% or more, particularly 30 mol% or more of R ¹ are phenyl groups are preferable.

Furthermore, in order to reduce the steric hindrance of the organopolysiloxane molecule containing a bulky phenyl group and improve the degree of spatial freedom, to facilitate the overlapping of the phenyl groups and enhance the flame retardancy, the formula (4) R ¹ in the formula preferably has a methyl group or a vinyl group, and therefore the proportion of the phenyl group in R ¹ is preferably 10 to 95 mol%, more preferably 30 to 90 mol%.

In Expression (4), a is a positive number, and b, c, d, and e are each 0 or a positive number. b / a is a number from 0 to 10, c / a is a number from 0 to 0.5, d / (a + b + c + d) is a number from 0 to 0.3, and e / (a + b + c + d) is from 0 to 0. It is a number of 0.4. A silicone resin having a b / a exceeding 10 has a softening point of 25 ° C. or lower and a low affinity with a resin. Moreover, the silicone resin in which d / (a + b + c + d) exceeds 0.3 tends to reduce the dispersibility of the resin.

The weight average molecular weight of the organosiloxane polymer (E-3) used in the present invention in a solid state at 25 ° C. is preferably 500 to 50,000, particularly preferably 500 to 10,000. Although the softening point should just be 25 degreeC or more, it is usually 40-250 degreeC, and it is preferable that it is especially 40-150 degreeC. In a resin composition containing a silicone resin having a softening point of less than 25 ° C., bleeding easily occurs during molding, mold contamination, deterioration of mechanical properties of the resin molding, and silicone during long-term use of the resin molding. The resin may ooze out on the surface.

In addition, a silicone resin having a too high softening point tends to be difficult to uniformly disperse during the preparation of the resin composition. The softening point is the temperature at which the silicone resin melts and turns into droplets when heated at a heating rate of 1 ° C./min using a melting point measuring machine (micro melting point apparatus manufactured by Yanagimoto Seisakusho Co., Ltd.). Is the softening point.

The silicone resin represented by the above formula (4) is, for example, a unit represented by (i) formula: R ⁴ SiO _3/2 (wherein R ⁴ is a monovalent hydrocarbon group), (ii) A unit represented by the formula: R ⁵ ₂ SiO _2/2 (wherein R ⁵ are the same or different monovalent hydrocarbon groups), (iii) Formula: R ⁶ ₃ SiO _1/2 (formula Wherein R ⁶ are the same or different monovalent hydrocarbon groups), and (iv) at least one selected from the group consisting of units represented by the formula: SiO _4/2 One or a mixture of silane or siloxane having a unit and a general formula: R ⁷ R ⁸ _f Si (OR ⁹ ) _(3-f) (wherein R ⁷ is an epoxy group-containing organic group, R ⁸ is a monovalent hydrocarbon group, ^{R 9} is an alkyl group, f is 0, 1, also 2. The term. The epoxy-containing alkoxysilane or its partial hydrolyzate represented by), can be prepared by reacting with a basic catalyst.

In the above production method, the main component is one or a mixture of two or more silanes or siloxanes having at least one unit selected from the group consisting of units represented by the above formulas (i) to (iv). . These silanes or siloxanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane. Dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, methylphenyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, dimethoxydiethoxysilane and their water Examples include decomposition condensates.

In addition, an epoxy group-containing alkoxysilane represented by the general formula: R ⁷ R ⁸ _f Si (OR ⁹ ) _(3-f) or a partially hydrolyzed product thereof, which is copolymerized with these silanes and siloxanes, is an epoxy group on a silicone resin. It is a component to introduce. R ⁷ in the formula is an epoxy group-containing organic group, and examples thereof include the same epoxy group-containing organic group as R ¹ , R ² , or R ³ .

R ⁸ in the above formulas (i) to (iv) is a monovalent hydrocarbon group, and the same monovalent hydrocarbon group as R ¹ , R ² , or R ^{3 in the} formulas (i) to (iv) Is exemplified. R ⁹ in the formulas (i) to (iv) is an alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. F in the formula is 0, 1, or 2, preferably 0.

As such an epoxy group-containing alkoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (methyl) dibutoxysilane, 2 -(3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2,3- Epoxypropyl (phenyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, 2- (3,4 Epoxycyclohexyl) ethyl triethoxysilane, 2,3-epoxypropyl trimethoxysilane, and 2,3-epoxypropyl triethoxysilane.

Examples of the basic catalyst include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkali metal alkoxides such as sodium-tert-butoxide, potassium-tert-butoxide, and cesium-tert-butoxide. An alkali metal silanol compound such as a sodium silanolate compound, a potassium silanolate compound, or a cesium silanolate compound; Preferably, a potassium-based or cesium-based basic catalyst is used. In the reaction, water may be added as necessary.

During the reaction, cleavage and recombination of siloxane bonds occur randomly by the equilibration reaction, and as a result, the resulting epoxy group-containing silicone resin is in an equilibrium state. The reaction temperature is preferably 80 ° C. to 200 ° C. because the equilibration reaction does not proceed sufficiently when the reaction temperature is low, and the silicon atom-bonded organic group is thermally decomposed when the reaction temperature is too high, In particular, the temperature is preferably 100 ° C to 150 ° C.

Further, by selecting an organic solvent having a boiling point of 80 to 200 ° C., the equilibration reaction can be easily performed at the reflux temperature. The equilibration reaction can be stopped by neutralizing the basic catalyst. For this neutralization, it is preferable to add a weak acid such as carbon dioxide or carboxylic acid. The salt produced by neutralization can be easily removed by filtration or washing with water.

  The amount of the (E-3) organosiloxane polymer in the solid state at 25 ° C. used in the polyester resin composition of the present invention may be selected and determined as appropriate. Since the addition effect is insufficient even if the amount is too small, the amount is usually 1 to 10 parts by weight, particularly 2 to 8 parts by weight, based on 100 parts by weight of the polyalkylene terephthalate resin (A). In particular, it is preferably 3 to 5 parts by mass.

(E-4) Metal borate The polyester resin composition of the present invention preferably contains (E-4) a metal borate. The component (B-4) metal borate used in the present invention is preferably stable under normal processing conditions and free from volatile components. Examples of the boric acid metal salt include alkali metal salts of boric acid (for example, sodium tetraborate, potassium metaborate, etc.) or alkaline earth metal salts (for example, calcium borate, magnesium orthoborate, barium orthoborate, zinc borate, etc.). . Among these, zinc borate is preferable. Zinc borate is generally represented by 2ZnO.3B ₂ O ₃ .xH ₂ O (x = 3.3 to 3.7). The hydrated zinc borate is preferably one having the formula 2ZnO · 3B ₂ O ₃ · 3.5H ₂ O and stable up to a temperature of 260 ° C. or higher.

Colemanite is an example of calcium borate. Colemanite is an inorganic compound mainly composed of calcium borate and is usually a hydrate represented by the chemical formula 2CaO · 3B ₂ O ₃ · 5H ₂ O. The colemanite used in the present invention may be any one of colemanite, colemanite or calcium borate or soluite, or a synthetic material. Among them, the colemanite produced as a mineral is thermally stable. Since it is excellent in property, it is preferable.

The amount of the (E-4) metal borate used in the polyester-based resin composition of the present invention may be appropriately selected and determined. However, if the amount is too large, the mechanical properties tend to decrease. Since the effect of addition is insufficient, it is usually 0.1 to 5 parts by weight, particularly 0.1 to 4 parts by weight, and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the (A) polyalkylene terephthalate resin. In particular, the amount is preferably 1.5 to 2 parts by mass.

The colemanite used in the present invention is a hydrous calcium borate mineral as a mineral, for example, which forms in evaporite deposits to form short columnar crystals and pseudorhombic crystals belonging to the monoclinic system. Either a dense lump or a round aggregate can be used. There are many colors such as colorless, white, milky white, yellowish white, and gray, but in the present invention, colors of other colors can also be used.

When using a mineral as a colemanite used for this invention, you may contain the impurity in the state produced. The composition of colemanite as such a mineral is generally B ₂ O ₃ (45.2 to 42.18%), Fe ₂ O ₃ (0.35 to 0.03%) in terms of mass% including impurities. _{), SiO 2 (3.50~4.08%)} , Al 2 O 3 (0.51~0.16%), CaO (26.01~27.06%), SrO (0.62~1. 19%), MgO (1.06 to 1.43%), Na ₂ O ₃ (0.03 to 0.10%), K ₂ O (0.16 to 0.03). A chemical composition may be included.

As the colemanite used in the present invention, for example, those sold under a trade name such as Koleman Material Colemanite, Kinsei Matec UBP or the like can be used. The colemanite used in the present invention may be a natural product as described above as it is or a partly treated product. Specifically, for example, when colemanite is baked at 400 ° C. or higher, a part thereof becomes CaO · 2B ₂ O ₃ . It has been reported that this fired product has an antibacterial effect, an antifungal effect, an algal control effect, and the like.

The average particle size of the colemanite is preferably 1 to 50 μm, more preferably 3 to 20 μm, and particularly preferably 3 to 10 μm. By setting it as such a range, it exists in the tendency for various physical properties, such as a softness | flexibility, and a flame retardance of the polyalkylene terephthalate-type resin composition of this invention to improve.

The average particle size of the above-described colemanite indicates a particle size at which the integrated mass distribution is 50% in the particle size distribution obtained by measurement with a cedy graph (X-ray transmission type particle size distribution measuring device). The Cedygraph is an apparatus that irradiates a suspension during sedimentation with X-rays and measures the particle size distribution from the amount of X-ray transmission.

For example, if the colemanite used in the present invention is a naturally occurring ore, it can be pulverized using any conventionally known method such as a dry pulverization method or a wet pulverization method, and adjusted to a predetermined particle size. Good. Examples of the pulverizing means include pulverizing means such as a ball mill, a roller mill, a jet mill, a vibration mill, a planetary mill, and a stirring frame mill.

Moreover, the colemanite used for this invention may use what was surface-treated with surface treatment agents, such as a silane coupling agent. As the surface treatment agent, any conventionally known one can be used. Specifically, examples of the silane coupling agent include surface treatment agents such as aminosilane, epoxysilane, allylsilane, and vinylsilane.

Of these, aminosilane-based surface treatment agents are preferred. Specific examples of the aminosilane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropyltrimethoxysilane. .

As the surface treatment agent for colemanite, as long as the effects of the present invention are not impaired, the surface treatment agent such as the silane coupling agent may include other components, specifically, for example, epoxy resin, urethane resin, acrylic resin. It may contain a resin, an antistatic agent, a lubricant, a water repellent and the like.

Specific examples of the surface treatment method using such a surface treatment agent include a surface treatment agent previously prepared by a surface treatment agent, such as the methods described in JP-A Nos. 2001-172555 and 53-106749. It may be treated, or when preparing the polyalkylene terephthalate resin composition of the present invention, a surface treatment agent may be added and surface treated separately from untreated colemanite. Conventionally, it has been known that when a fibrous reinforcement is added, the fluidity is lowered, but even if a fibrous reinforcement is added by adding colemanite to the resin composition of the present invention, the fluidity is reduced. Is beneficial in that it does not decrease.

You may mix | blend an anti-dripping agent with the polyalkylene terephthalate-type resin composition of this invention. The anti-dripping agent is preferably a fluororesin, and specifically, for example, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer. A polymer etc. are mentioned.

The method for producing the polyalkylene terephthalate resin composition of the present invention is not particularly limited, and can be easily achieved by mixing the components by a known method. For example, a dry blending method using a blender or a mixer, a melt mixing method using an extruder, and the like can be mentioned. Usually, a screw extruder is used to melt and extrude a strand to form a pellet. The method is suitable. Specifically, a method of melting and kneading each component at once, a method of melting and mixing a specific component first, and the like can be mentioned.

The mixing method of each component is not particularly limited, and a batch blending method in which components are melted and kneaded at once using a twin screw extruder, and split blending in which reinforcing fillers are added from other supply ports The method etc. are mentioned. Especially, since it can be satisfactorily produced by feeding the (B) inorganic compound separately from the pellets from the side feeder and the main feeder, it is preferable.

There is no particular limitation on the molding method for obtaining a molded product from the resin composition of the present invention, and molding methods generally used for thermoplastic resins, that is, molding such as injection molding, hollow molding, extrusion molding, press molding, etc. A particularly preferable molding method is injection molding because of its good fluidity. In the injection molding, the resin temperature is preferably controlled to 240 to 280 ° C.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to the example described below. The raw materials used in Examples and Comparative Examples are described below.

(A) Polyalkylene terephthalate resin (A-1) PBT resin: NOVADURAN (registered trademark) 5007 manufactured by Mitsubishi Engineering Plastics Co., Ltd., intrinsic viscosity 0.70 dl / g

(A-2) Polytetramethylene glycol (PTMG) copolymerized PBT resin:
Instead of 1,4-butanediol, a PBT resin (Novaduran (registered trademark) 5510 manufactured by Mitsubishi Engineering Plastics Co., Ltd.) having 20% by mass of PTMG unit (number average molecular weight = about 1016), intrinsic viscosity: 1.3 dl / g

(A-3) Dimer acid copolymer polyester resin:
PBT resin copolymerized with 10 mol% of dimer acid instead of terephthalic acid (Novaduran (registered trademark) P02120 manufactured by Mitsubishi Engineering Plastics Co., Ltd., intrinsic viscosity 0.96)

(A-4) Isophthalic acid copolymer polyester resin:
PBT resin copolymerized with 10 mol% of isophthalic acid instead of terephthalic acid (Novaduran (registered trademark) 5605 manufactured by Mitsubishi Engineering Plastics), intrinsic viscosity 1.0

(B) Inorganic compound (B-1) Boron nitride:
SGP (trade name) manufactured by Denki Kagaku Kogyo Co., Ltd., scaly, purity: 99%, average particle size: 18 μm

(B-2) Talc:
High filler # 12C (trade name) manufactured by Matsumura Sangyo Co., Ltd., compression talc, average particle size: 5-7 μm, bulk specific gravity: 0.75-0.9 g / ml

(C) Glass fiber (C-1) Chopped strand 03JA-FT592 (trade name) manufactured by Asahi Fiber Glass Co., Ltd. Circular section

(C-2) CSH3PA830 (trade name) manufactured by Nittobo Co., Ltd., oval cross section, flatness ratio 4, polyester

(D) Phosphinate Aluminum diethylphosphinate: OP1240 (trade name) manufactured by Clariant Japan

(E) Other flame retardant (E-1) Phosphate ester compound:
Resorcinol-type aromatic phosphate ester compound (1,3-phenylene bis-dioxyrenyl phosphate), PX200 (trade name) manufactured by Daihachi Chemical Co., Ltd.

(E-2) Nitrogen-based flame retardant:
Melamine cyanurate, MCA (trade name) manufactured by Sun Chemical Co., Ltd., average particle size 5 μm

(E-3) Organosiloxane polymer:
Phenyl silicone resin, 217 Flake (trade name) manufactured by Toray Dow Corning, solid state at 25 ° C, softening point 86 ° C

(E-4) Boric acid metal salt (E-4-1) Zinc borate: Firebreak ZB (trade name) manufactured by Borax Japan

(E-4-2) Calcium borate:
KINSEI MATEC Co. calcium borate ore (the main component is _{2CaO · 3B 2 O 3 · 5H} 2 O), the average particle diameter of 5μm

(Other ingredients)
Antioxidant: Hindered phenol-based compound Ciba Specialty Japan Irganox 1010 (trade name)

Mold release agent: Paraffin wax FT100 (trade name) manufactured by Nippon Seiwa Co., Ltd.

(Flame retardants)
Phosphazene compounds:
Phosphazene compound mainly composed of cyclic products FP-100 (trade name) manufactured by Fushimi Pharmaceutical Co., Ltd.

Brominated flame retardant:
Polypentabromobenzyl acrylate FR-1025 (trade name) manufactured by Bromochem Far East

(Flame retardant aid)
Antimony trioxide: Suzuhiro Chemical Co., Ltd. Fire Cut AT-3CN (trade name)

[productivity]:
Components other than glass fibers were mixed together with a supermixer (SK-350 type, manufactured by Shinei Machinery Co., Ltd.) at the blending ratio shown in Table 1 (numerical values indicate parts by mass), and L / D = 42 2 It is put into the hopper of a shaft extruder (manufactured by Nippon Steel Co., Ltd., TEX30HSST), and (C) glass fiber is side-feeded and extruded under the conditions of discharge rate 20 kg / hour, screw rotation speed 150 rpm, barrel temperature 260 ° C. A pellet of a polyalkylene terephthalate resin composition was obtained. According to the state of the strand at that time, it is classified into the following three stages.

A: Can be extruded without problems. A strand can be obtained stably.
○: Extrusion is possible with almost no strand breakage.
Δ: Many strand breaks. Extrusion difficulty.

[Performance evaluation method]
(1) Laser printability:
The test piece was subjected to laser marking with an Nd-YAG laser under the following conditions and evaluated. The apparatus uses a marker engine SL475H / HF manufactured by NEC Corporation, high output: 50 W or more, output current value of laser marking: 10 A or 15 A, oscillation wavelength: 1060 nm, ultrasonic Q switch: 2 KHz, scanning speed: 200 mm / sec It was. For the marking design, different markings were applied to the two plates. One plate was marked so as to fill a square of 20 × 20 mm, and another one was marked with 10 letters of alphabet (ABCDEFGHIJ) with a font of 5 mm.

The determination of the laser marking property was made by visually observing two plates subjected to the laser marking process, making a comprehensive judgment, and dividing into the following three ranks based on the following judgment criteria.

A: Very clear markings are made and good.
○: Clear marking is made and can be easily recognized.
×: Marking is not made at all, or printed but difficult to recognize

(2) Volume resistivity:
By injection molding machine (manufactured by Sumitomo Heavy Industries, SH100, mold clamping force 100T), resin temperature (measured temperature of purge resin): 260 ° C., mold temperature: 80 ° C., mold: vertical 100 mm, horizontal 100 mm, thickness 3 mm The molded product injection-molded under the above conditions was measured with a resistivity meter (manufactured by Advantest Co., Ltd .: R8340 digital ultrahigh resistance / microammeter and R12704 resiliency chamber). Volume resistivity is expressed in units of Ω · cm. This value is preferably 10 ¹⁴ Ω · cm or more.

(3) Thermal conductivity:
Using an injection molding machine (manufactured by Sumitomo Heavy Industries, SH100, mold clamping force 100T), resin temperature (measured temperature of purge resin): 260 ° C, mold temperature: 80 ° C, mold: length 100mm, width A molded product of 100 mm and a thickness of 3 mm is injection-molded, and the obtained three injection-molded products are stacked, and the heat of the injection-molded product is measured using a rapid thermal conductivity measuring device (Kemtherm QTM-D3, manufactured by Kyoto Electronics Industry). Conductivity was measured.

(4) Spiral flow length:
The spiral flow length of the resin composition was evaluated using SE50 manufactured by Sumitomo Heavy Industries, Ltd. as an injection molding machine. The injection pressure was 170 MPa, the injection speed was 100 mm / sec, the cylinder temperature was 270 ° C., the injection time was 2 sec, the cooling was 7 sec, the mold temperature was 80 ° C., and the suck back was 1 mm. Moreover, the shape of the evaluated resin molded product is a long resin molded product having a cross section of 1 mm in thickness and a width of 1.5 mm, and has a spiral shape. The size of the spiral long resin molded product is 90 mm × 105 mm as the distance between the centers of the long resin molded products. A schematic diagram of this spiral long resin molded product is shown in FIG.

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

(6) Flame retardancy test:
The UL test piece (thickness: 0.75 mm) was subjected to a UL-94 standard vertical combustion test by Underwriters Laboratories Inc. The flame retardancy level was evaluated in the order of V-0>V-1>V-2> HB according to the standard. The total combustion time is a total of five combustion times (including the time of the first flame contact and the time of the second flame contact).

[Examples 1 to 13 and Comparative Examples 1 to 6]
At a blending ratio shown in Table 1 (numerical values indicate parts by mass), components other than glass fibers are mixed together with a super mixer (SK-350 type, manufactured by Shinei Machinery Co., Ltd.), and L / D = 42. Put into a hopper of a twin screw extruder (manufactured by Nippon Steel Works, TEX30HSST), (C) side feed the glass fiber, and extrude under conditions of discharge rate 20kg / hour, screw rotation speed 150rpm, barrel temperature 260 ° C A pellet of a polyalkylene terephthalate resin composition was obtained.

About the resin composition pellet, the above-mentioned (1), (2) and (3) are performed under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. using an injection molding machine (model SH-100 manufactured by Sumitomo Heavy Industries). The test piece of (5) is a flat plate test piece of 10 cm in length and width, and 3 mm in thickness. Also, using SE50 manufactured by Sumitomo Heavy Industries, Ltd., injection pressure is 170 MPa, injection speed is 100 mm / sec, cylinder temperature is 270 ° C. The test piece of the above (4) was used under the conditions of injection time 2 sec, cooling 7 sec, mold temperature 80 ° C., suck back 1 mm, and cylinder temperature 250 ° C. using SE50 manufactured by Sumitomo Heavy Industries, Ltd. Under the condition of a mold temperature of 80 ° C., a UL-94 standard test piece (6) having a thickness of 0.75 mm was obtained. Said evaluation was implemented using the above test piece. The evaluation results are shown in Table 1.

The following is clear from the above table.
(1) Comparing Examples and Comparative Examples, it can be seen that the resin composition of the present invention is excellent in all of thermal conductivity, tracking resistance and flame retardancy.
(2) It can be seen that in the example in which the modified cross section GF is blended, the thermal conductivity is increased as compared with the examples in which the round section GF is blended (Examples 1 and 12). Furthermore, it can be seen that an unexpected effect of reducing the total combustion time is obtained.
(3) As in Examples 3 to 13, by using a copolymer polyester resin in combination with the component (A) (by comparison with Examples 1 and 2 that are not used in combination), the product is excellent in productivity. I understand.
(4) From Examples 10 to 13, it can be seen that when an organosiloxane copolymer and a metal borate are used in combination, the laser printability is excellent and the total combustion time is also reduced.

Claims (7)

(A) A polyalkylene terephthalate resin composition comprising the following components (B) to (D) with respect to 100 parts by mass of a polyalkylene terephthalate resin.
(B) Inorganic compound consisting of boron nitride and / or magnesium silicate 10 to 100 parts by mass (C) Glass fiber: 20 to 90 parts by mass (D) The anion moiety is represented by the following formula (1) or formula (2). 10 to 60 parts by mass of a phosphinic acid salt whose cation moiety is aluminum ion or calcium ion

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, and R ¹ may be the same or different, and R ³ Represents an alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group, or a mixed group thereof, and n represents an integer of 0 to 4.) The component (A) is such that 70 mol% or more of each of the carboxylic acid component and the alcohol component is derived from terephthalic acid and 1,4-butanediol, and polytetramethylene ether glycol, dimer acid and isophthalic acid as copolymerization components 2. The polyalkylene terephthalate resin composition according to claim 1, which contains a component derived from any of acids. The component (C) has a D2 / D1 ratio (flatness) in the range of 1.5 to 10 when the major axis D2 and the minor axis of the cross section perpendicular to the longitudinal direction of the fiber are D1. The polyalkylene terephthalate-based resin composition according to claim 1 or 2, characterized in that: The polyalkylene terephthalate resin composition according to any one of claims 1 to 3, wherein the magnesium silicate salt in the component (B) is talc. The polyalkylene terephthalate resin composition according to claim 4, wherein the bulk specific gravity of talc is 0.4 or more. The polyalkylene terephthalate according to any one of claims 1 to 5, further comprising at least one (E) flame retardant selected from the group consisting of the following (E-1) to (E-4): -Based resin composition.
(E-1) Phosphoric acid ester 0.1-20 parts by mass (E-2) Nitrogen-based flame retardant 1-50 parts by mass comprising a salt of amino group-containing triazines (E-3) Solid state at 25 ° C 1-10 parts by mass of organosiloxane polymer (E-4) 0.1-4 parts by mass of metal borate A resin molded product obtained by injection molding the polyalkylene terephthalate resin composition according to any one of claims 1 to 6.

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