JP5265979B2 - Resin composition for high-voltage insulating material parts and molded product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for a high voltage insulating part suppressing breed-out of a flame retardant, having good balance of mechanical strength, moist heat resistance, shrinkage anisotropy and the like, and comprising reinforcing filler. <P>SOLUTION: The resin composition for high voltage insulating part comprises, based on (A) 100 pts.wt of a resin component of the following composition: (A-1) 100-40 wt.% of a rein containing, as a main ingredient, a thermoplastic resin selected from a thermoplastic polyester resin and a polyamide resin, (A-2) 0-50 wt.% of a polystyrene resin, and (A-3) 0-10 wt.% of a compatibilizing agent; (B) a flame retardant combination of the following ingredients in a total amount of 25-125 pts.wt: (B-1) 10-60 pts.wt of at least one phosphorous-based flame retardant selected from a group consisting of a phosphazene compound, a phosphate ester compound and a phosphinic acid salt, (B-2) 10-80 pts.wt of a nitrogen-based flame retardant consisting of a salt of an amino group-containing triazine, and (B-3) 0-45 pts.wt of a metal salt of boric acid; and (C) 5-200 pts.wt of a fibrous reinforcing material having a flat cross-sectional geometry, in which a ratio of the longer diameter to the shorter one (aspect ratio) of a cross-section perpendicular to a fiber length is 1.5-10, wherein none of polyphenylene ether resin content, polyphenylene sulfide resin content and phenol resin content exceed 1 wt.%. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

The present invention relates to a resin composition for high-voltage insulating material parts. Resin composition for fiber-reinforced high-voltage insulation material parts that are particularly excellent in flame retardancy, voltage resistance, tracking properties, glow wire properties, suppresses bleed-out of flame retardant, and at the same time has excellent mechanical properties and dimensional stability About. Furthermore, it is related with the high voltage insulation material components shape | molded from this resin composition.

Thermoplastic resins, in particular thermoplastic polyester resins and polyamide resins, are used in automotive electrical parts and electrical / electronic parts by taking advantage of moldability, recyclability, insulation, etc., instead of thermosetting resins.

In recent years, demands for electrical safety in electrical and electronic parts are becoming higher than before. These parts must simultaneously meet the requirements of the Underwriter's Laboratories Inc. UL-94 flame resistance and tracking index (CTI). Furthermore, in recent International Electrotechnical Commission (abbreviation IEC) standards, the Glow-wire Flammability Index (GWFI) and the Glow-wire Ignition Temperature (abbreviation: GWIT). ) Was also added to the required properties.

Some high-voltage components to which a high voltage of 100 V or higher is applied have strict regulations regarding resistance to ignition and flame propagation in addition to high voltage resistance, high flame resistance and tracking resistance. There is a need for parts that satisfy all requirements. However, recently, the thickness of resin molded products has been reduced from the viewpoint of miniaturization and weight reduction also in high voltage components. In addition to satisfying the required properties at a high level for flame retardancy, voltage resistance, tracking properties, and glow wire properties for thin molded products, mechanical strength, heat and humidity resistance, and shrinkage stability are stable. Materials with good balance such as properties have been demanded.

It is well known that when a halogen-based flame retardant is added to a thermoplastic resin, it can reach V-0, which is the highest evaluation in the UL-94 standard. However, the glow wire property against ignition and flame propagation is an index that is evaluated by a completely different method from the flame retardancy of the UL-94 standard, which is known as the evaluation of flame retardancy. While the flame retardancy of UL-94 indicates the “incombustibility” when a burner flame is brought into contact, the GWFI and GWIT values are indicators for evaluating the ignitability at high temperatures by glow wires. Show completely different properties. Moreover, even if it is V-0, which is the highest evaluation in the UL-94 standard, the glow wire property may be insufficient, and conversely, even if V-2 is less flame retardant than V-0, In some cases, high glow wire properties are exhibited. That is, the glow wire property and the tracking property cannot be predicted from the existing technical contents in which only the evaluation of flame retardancy of UL-94 is shown.

Patent Document 1 and Patent Document 2 disclose a polyester resin composition excellent in electrical safety using a halogen-based flame retardant. These documents indicate that the GWFI value and the GWIT value have a high level at a thickness of 3 mm. In addition, in recent years, there is a need for insulating material parts that do not use halogenated flame retardants due to concerns about adverse environmental impacts, such as incineration, for disposal after use of molded products using such halogenated flame retardants. It has been.

As non-halogen flame retardants for resins, phosphazene compounds (also referred to as phosphonitrile compounds) and phosphate esters have already been known, and in particular, phosphazene compounds have been known for a long time (see, for example, Patent Document 3). Although the said patent document 3 is application to a fiber, the application example to the field of injection molding is disclosed by patent document 4 and patent document 5. FIG. In Patent Document 4, (A) 0.5 to 100 parts by weight of a phosphonitrile linear polymer and / or a cyclic polymer, and (C) a triazine ring compound and cyanuric acid or 100 parts by weight of a thermoplastic resin. A flame retardant resin composition comprising 0.5 to 100 parts by weight of a salt made of isocyanuric acid is disclosed. In Examples of Patent Document 4 and Patent Document 5, a polybutylene terephthalate resin (PBT resin) composition that can reach excellent flame retardancy of V-0 and has high hydrolysis resistance is shown. ing. However, these documents do not disclose electrical safety such as tracking property and glow wire property at all. The phosphazene compound and melamine cyanurate are blended in the range of 11.0 to 17.4% by weight and 8 to 12% by weight, respectively, and the blending ratio is phosphazene / melamine cyanurate = 1.17 to 1.96. It is a range. That is, the phosphazene compound is excessive.

Further, claim 1 of Patent Document 5 is a composition composed of a flame retardant and a polyalkylene arylate resin, wherein the flame retardant is composed of a phosphazene compound and a polyphenylene oxide resin, A flame retardant resin composition containing at least a crosslinked phenoxyphosphazene compound is described. Further, in claim 5 of the same document, the composition according to claim 1, wherein the flame retardant further comprises at least one component selected from a styrene resin and a nitrogen-containing compound. Things are disclosed. According to Patent Document 5, when a flame retardant is constituted by combining a phosphazene compound and a polyphenylene oxide resin, the polyalkylene arylate resin can be made highly flame retardant and the flame retardant exudes from a molded product (bleed out). We are focusing on the fact that metal corrosivity and moldability during injection molding (mold deposit) can be greatly improved. On the other hand, there is no suggestion about improvement of electrical safety. Moreover, although patent document 5 does not necessarily need to use a phosphazene compound and a nitrogen-containing compound together, the combined use system is shown in the Example. In Patent Document 5, the blending ratio of the phosphazene compound and the nitrogen-containing compound (melamine cyanurate, etc.) is 1.47 to 10: 1, and the phosphazene compound is excessive.

Patent Document 6 discloses a composition composed of a resin component and a flame retardant, wherein the resin component is composed of a polyalkylene arylate resin and a styrene resin, and the flame retardant includes a phosphazene compound and a phenol resin. A flame retardant resin composition comprising: Patent Document 6 only shows the evaluation results of flame retardancy, flame retardant bleeding (bleed out), and mechanical strength, and no description of electrical safety is allowed. Moreover, although this patent document 6 does not necessarily need to be the combined use of a phosphazene compound and a nitrogen-containing compound, the combined use system is also shown in the Example. In Patent Document 6, the blending ratio of the phosphazene compound and the nitrogen-containing compound (such as melamine cyanurate) is about 2: 1, and the phosphazene compound is excessive. Moreover, although the example with many compounding quantities of a nitrogen-containing compound is also seen, in this example, the total amount of a phosphorus flame retardant and a nitrogen-containing compound is very much as 100 weight part.

There exist patent document 7 and patent document 8 as an example which mix | blended the phosphate ester. Patent Document 7 is an application technique of Patent Document 8, in which (A) the amount of terminal carboxyl groups is 30 eq / t or less and the temperature-falling crystallization temperature is 175 ° C. or higher, or the temperature-falling crystallization temperature is 175 ° C. (C) Compatibilizer with respect to 100 parts by weight of mixed resin comprising 95 to 50 parts by weight of polybutylene terephthalate having a residual tetrahydrofuran amount of 300 ppm or less and (B) 5 to 50 parts by weight of polyphenylene ether resin. 0.05 to 10 parts by weight, (D) 2 to 45 parts by weight of at least one compound selected from phosphate ester or phosphonitrile, (E) 0 to 150 parts by weight of reinforcing filler, (F) anti-drip agent 0 Flame retardant polybutylene containing 0.001 to 15 parts by weight, (G) 0 to 45 parts by weight of melamine cyanurate, and (H) 0 to 50 parts by weight of metal borate Phthalate resin compositions are disclosed. In Patent Document 7 and Patent Document 8, only the evaluation results of flame retardancy, hydrolysis resistance, and amount of generated gas are shown, and no description of electrical safety is recognized. Moreover, although this patent document 7 and patent document 8 do not necessarily need to use together a phosphazene compound and a nitrogen-containing compound, in the Example, the combined use system is also shown. In this example, phosphoric acid ester and melamine cyanurate are blended in equal amounts, and these are blended in a total amount of 21 to 29 parts by weight with respect to 100 parts by weight of PBT resin. In the specification, the ratio of the phosphate ester compound to melamine cyanurate is not particularly limited, but is usually 1 to 9 to 9 to 1, particularly 2 to 8 to 8 to 2, particularly preferably 2. Although there is a description that it is 5 to 7.5 to 7.5 to 2.5, it is wide-ranging and there is no suggestion for improving the electrical safety.

Thus, in order to improve the flame retardancy of the phosphorus-based flame retardant, there are many examples in which a polyphenylene ether resin or a phenol resin is blended.
The improvement of the withstand voltage has been performed by replacing all or part of glass fiber or the like with mica which is a plate-like filler. However, the mechanical strength of the resin composition substituted with mica is lower than that of the resin composition containing glass fiber, and the difference is particularly remarkable in the thin molded product. In addition, when mica is blended with a thermoplastic polyester resin, the heat and moisture resistance is remarkably lowered, so that it is difficult to use it especially in an automobile electrical component.

By the way, it is known that mechanical strength and warpage are improved by changing the cross-sectional shape of the glass fiber from a round shape to a flat shape (for example, Patent Documents 9 and 10).
Patent Document 10 describes (A) a thermoplastic resin, (B) a fibrous reinforcing material having a flat cross-sectional shape having a ratio of a major axis to a minor axis of 1.3 to 10, and 1 to all compositions. A fibrous reinforced thermoplastic resin composition comprising 65% by weight is disclosed. This document only shows that the deformation amount (warpage) and mechanical strength of the molded product are improved, and there is no description about the electrical characteristics. Further, in electrical component applications, some consideration is necessary for the flame retardancy of the material. In claim 6, the thermoplastic resin is made of a crystalline resin, and in claim 7, the crystalline resin and In particular, since a mixture with an amorphous resin, and in claim 8, the crystalline resin is defined as polyacetal, polyester, polyamide, polyphenylene sulfide, and flammable polyacetal is selected as the target resin, It cannot be assumed that an electric / electronic component to which a voltage is directly applied is assumed. However, in the effects of the invention, parts such as connectors, switches, and relays are used in electrical equipment. However, they are listed as examples of wide applications such as exterior parts for automobiles, structural parts for AV, and mechanical parts such as gears. It is difficult to estimate whether a high level of electrical characteristics can be obtained.

Furthermore, Patent Document 11 and Patent Document 12 disclose polybutylene terephthalate resin compositions containing flat glass fibers and an elastomer. The technique is intended to improve the heat shock resistance of insert molded products such as an ignition system and a distributor, which are automobile electrical components, disclosed in Patent Document 13 and Patent Document 14, and the like. This corresponds to a combination technique of Patent Document 14 and the warpage reduction technique of Patent Document 10. Moreover, although the electrical components, such as an ignition system and a distributor, are mentioned in the application examples of Patent Document 11 and Patent Document 12, there is no description about electrical characteristics, and there is a known problem in automotive electrical components (heat shock resistance). It is only an example of application from the viewpoint of improvement of (and low warpage), and whether sufficient characteristics can be obtained for the high voltage resistance required for high voltage components in recent years. It was unknown.

JP 2005-232410 A JP 2006-45544 A Japanese Patent Laid-Open No. 51-36266 JP 7-216235 A JP 2003-82211 A JP 2003-82210 A JP 2004-91584 A JP-A-10-77396 Japanese Patent Laid-Open No. 62-268612 Japanese Patent Laid-Open No. 02-173047 JP 2000-265001 A JP 2000-265046 A JP-A 63-3055 JP-A-6-304963

When the inventor examined Patent Documents 1 and 2, the resin composition in the document has a high level of GWFI value and GWIT value at a thickness of 3 mm, but the GWIT value is 1.5 mm or less. It turned out to be significantly reduced.
Further, as described above, the present inventors have found that CTI characteristics are drastically lowered when a polyphenylene ether resin or a phenol resin is blended in order to improve the flame retardancy of a phosphorus-based flame retardant. Such a rapid decrease in CTI characteristics is not suitable as an insulating material part. That is, there is a demand for the development of insulating material parts that do not substantially contain polyphenylene ether resin or phenol resin.
The present invention has been studied from such a viewpoint, and in addition to satisfying the required characteristics at a high level of flame retardancy, withstand voltage, tracking property, and glow wire property even in a thin wall, it is further difficult. The present invention provides a resin composition for a high-voltage insulating material part reinforced with a filler that has a good balance of mechanical strength, heat-and-moisture resistance, shrinkage rate anisotropy, etc., with suppressed bleed out of the fuel. Moreover, it is providing the molded article manufactured from this resin composition.

As a result of intensive studies to achieve the above object, the present inventors have combined a specific resin component and a flame retardant combination, and further replaced a glass having a flat cross-sectional shape instead of a conventional glass fiber having a circular cross-sectional shape. It has been found that by using a flat fibrous reinforcing material represented by fibers, flame retardancy, voltage resistance, tracking properties, and glow wire properties are improved in a balanced manner, and the present invention has been achieved.

Specifically, it was achieved by the following means.
(1) (A) For 100 parts by weight of a resin component having the following composition ratio,
(A-1) 100 to 40% by weight of a resin mainly composed of a thermoplastic resin selected from thermoplastic polyester resins and polyamide resins
(A-2) Polystyrene-based resin 0 to 50% by weight
(A-3) Compatibilizer 0-10% by weight
(B) Flame retardant combination Total amount of the following components 25-125 parts by weight,
(B-1) 10-60 parts by weight of a phosphorus-based flame retardant selected from the group of phosphazene compounds, phosphate compounds, and phosphinates (B-2) a nitrogen-based compound comprising a salt of an amino group-containing triazine Flame retardant 10 to 80 parts by weight (B-3) Boric acid metal salt 0 to 45 parts by weight (C) Flatness in which the ratio of the major axis to the minor axis (flatness) of the cross section perpendicular to the fiber length is 1.5 to 10 5 to 200 parts by weight of a fibrous reinforcing material having a cross-sectional shape,
A resin composition for high-voltage insulating material parts, wherein the content of any of polyphenylene ether resin, polyphenylene sulfide resin and phenolic resin is 1% by weight or less.
(2) In the (B) flame retardant combination, the composition ratio (weight ratio) of (B-1) phosphorus flame retardant and (B-2) nitrogen flame retardant is (B-1) / (B-2) = It is the range of 0.14-1.1, The resin composition as described in (1) characterized by the above-mentioned.
(3) The resin composition further comprises (D) an anti-dripping agent in an amount of 0.01 to 15 parts by weight with respect to 100 parts by weight of the resin component (A), (1) or (2) ).
(4) The resin composition as described in any one of (1) to (3), wherein the (A-2) polystyrene resin is an epoxy-modified polystyrene resin.
(5) The resin composition according to any one of (1) to (4), wherein the thermoplastic resin of component (A-1) is a thermoplastic polyester resin.
(6) The cross-sectional shape when cut perpendicularly to the length direction of the fiber of the (C) fibrous reinforcing material is a rectangle or an oval, and the flatness is 2.5 to 10, The resin composition according to any one of (1) to (5).
(7) A high-voltage insulating material part formed by molding the resin composition according to any one of (1) to (6).

The present invention has the following effects.
1) The resin composition of the present invention is generally excellent in flame retardancy, voltage resistance, tracking properties and glow wire properties. As a result, the molded product has a stable quality in which the bleed-out of the flame retardant is suppressed.
2) It can also be set as the structure which does not contain a halogenated flame retardant, and can consider environmental pollution.
3) A molded product excellent in mechanical strength, shrinkage anisotropy and appearance can be obtained.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, a “group” such as an alkyl group may or may not have a substituent unless otherwise specified. Further, in the case of a group having a limited number of carbons, the number of carbons means a number including the number of carbons that the substituent has.

The high-voltage insulating material component in the present invention is assumed to be an electric / electronic component intentionally designed to apply a high voltage constantly or at least instantaneously or temporarily, as well as an accidental application of a high voltage. It is an insulating material part that plays an insulating role against the high voltage. Examples of accidental events include lightning strikes and high voltage line shorts.

High voltage refers to AC and / or DC voltage exceeding the commonly used voltage (100V). More strictly, it means a voltage of 1 kV or more.

The shape of the resin molded product in the high-voltage component is not particularly limited, but the effect of the present invention is conspicuous when the wall thickness is 3 mm or less at least in part. A more preferable effect can be obtained when the thickness is 2.5 mm or less, and a case where the thickness is 2 mm or less is more preferable.

High-voltage components include discharge components in motors such as automobiles, transformer components used in lighting, etc. Specifically, engine ignition system parts such as automobile ignition and distributor parts, discharge lamps, etc. There are lighting parts. Also, accidental high voltage application is assumed to include leakage protection components such as electric breakers and leakage breakers, wiring components such as outlets, plugs, and terminals, and convert 100V voltage to high voltage or low voltage. There are transformer parts and coil bobbins for generating a magnetic field.

(A) Resin Component The resin component of the present invention comprises (A-1) a thermoplastic resin, (A-2) a polystyrene resin, and (A-3) a compatibilizer. Here, (A-2) polystyrene-based resin is not an essential component, but exhibits a remarkable suppression effect on the bleed-out of flame retardants, particularly phosphorus-based flame retardants, without lowering CTI characteristics and flame retardancy. Depending on the type and blending amount of the phosphorus flame retardant, blending is preferable. On the other hand, the (A-3) compatibilizing agent is blended as necessary in order to enhance the compatibility with the polystyrene-based resin that is not compatible with the thermoplastic resin component.

(A-1) Thermoplastic resin The resin composition of the present invention contains a thermoplastic resin. The thermoplastic resin in the present invention refers to a synthetic resin that exhibits fluidity when heated and can be molded using this. In the present invention, the main component is at least one resin selected from thermoplastic polyester resins and polyamide resins. Here, the main component means that the thermoplastic resin is a component having the largest content among the resin components of the resin composition of the present invention, and usually refers to a component occupying 80% by weight. Thermoplastic polyester resins and polyamide resins are preferred because of their high oxygen index and heat resistance. In the present invention, a thermoplastic polyester resin is more preferable. The thermoplastic resin used in the present invention is an ISO 4589 (JIS K7201), using a UL combustion test piece having a thickness of 0.8 mm molded using a resin composition having a stabilizer content of 1% by weight or less. In accordance with this, those having an oxygen index of 19 or more measured by using Toyo Seiki manufactured by OXIGEN INDEXERISO are preferable. Specifically, polyamide resins such as polyamide 6 (23) and polyamide 66 (28), polybutylene terephthalate (21), thermoplastic polyester resins such as polyethylene terephthalate (24), etc. [in parentheses are oxygen index]. In addition, as a guideline for heat resistance, a resin having a deflection temperature under a load of 0.45 MPa in ISO75 standard is preferably 150 ° C. or higher, more preferably 180 ° C. or higher. Moreover, although heat resistance improves with the content of (C) fibrous reinforcement, for example, (C) Resin with a deflection temperature under load of 15% by weight of fibrous reinforcement is employed is 200 ° C. or more. It is preferable. Examples of the resin that satisfies such requirements include polybutylene terephthalate and polyamide 6.

The thermoplastic resin in the resin composition of the present invention is more preferably a thermoplastic polyester resin.
In the (A) resin component, the ratio of the (A-1) thermoplastic resin is 100 to 40% by weight, preferably 100 to 50% by weight, more preferably 100 to 55% by weight in the (A) resin component. %, More preferably 100 to 60% by weight.

(A-1-1) Thermoplastic polyester resin As the (A-1-1) polyester resin as the component (A-1) used in the present invention, known polyester resins can be widely used. The polyester resin may be used alone or in combination of two or more. The polyester resin is preferably a polyester resin composed of a dicarboxylic acid or a derivative thereof and a diol.

As the dicarboxylic acid or derivative thereof, aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and aliphatic dicarboxylic acid, and esters of these lower alkyls or glycols are preferred, and aromatic dicarboxylic acids or their lower alkyls (for example, C1-C4) or an ester of glycol is more preferable, and terephthalic acid or a lower alkyl ester thereof is more preferable.

Aromatic dicarboxylic acids include terephthalic acid, phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 4,4′-diphenoxy. Preferred examples include ethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid and 2,6-naphthalenedicarboxylic acid. Preferred examples of the alicyclic dicarboxylic acid include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Preferred examples of the aliphatic dicarboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. These dicarboxylic acids or derivatives thereof may be used alone or in combination of two or more.

As the diol, an aliphatic diol, an alicyclic diol, and an aromatic diol are preferable. The aliphatic diol is preferably an aliphatic diol having 2 to 20 carbon atoms, such as ethylene glycol, 1,4-butanediol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, Preferable examples include polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol and 1,8-octanediol. The alicyclic diol is preferably an alicyclic diol having 2 to 20 carbon atoms, such as 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol and 1,4-cyclohexane. A preferred example is dimethylol. The aromatic diol is preferably an aromatic diol having 6 to 14 carbon atoms, such as xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane and bis (4- Hydroxyphenyl) sulfone can be mentioned as a preferred example. These diols may be used alone or in combination of two or more.

The polyester resin used in the present invention may have a hydroxycarboxylic acid, a monofunctional component, and / or a trifunctional or higher polyfunctional component. Preferable examples of the hydroxycarboxylic acid include lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid and p-β-hydroxyethoxybenzoic acid. Preferred monofunctional components include alkoxycarboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, tert-butylbenzoic acid and benzoylbenzoic acid. Preferred examples of the trifunctional or higher functional component include tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, and pentaerythritol.

As the (A-1-1) polyester resin, polybutylene terephthalate resin (PBT resin) or polyethylene terephthalate resin (PET resin) is preferable, and PBT resin is more preferable. The PBT resin is preferably a polybutylene terephthalate homopolymer having terephthalic acid as the only dicarboxylic acid unit and 1,4-butanediol as the only diol unit, from the viewpoint of moldability and heat resistance, but from the viewpoint of low warpage Is preferably a copolymer obtained by copolymerizing another monomer component such as isophthalic acid. In the present invention, the PBT resin means that terephthalic acid accounts for 50 mol% or more of all dicarboxylic acid components, and 1,4-butanediol accounts for 50 mol% or more of all diols. The PBT resin further preferably has a terephthalic acid ratio in the dicarboxylic acid unit of 70 mol% or more, more preferably 90 mol% or more. Moreover, 70 mol% or more is preferable and the ratio of 1, 4- butanediol in a diol unit has more preferable 90 mol% or more. Use of such a PBT resin is preferred because mechanical properties and heat resistance tend to be further improved.

In addition, when a polybutylene terephthalate resin is used as the (A-1-1) thermoplastic resin, a withstand voltage can be obtained by blending a small amount of a vinyl aromatic resin such as a later-described (A-2) polystyrene resin. However, it is necessary to consider the balance of withstand voltage, heat resistance, and mechanical strength because the heat resistance is reduced. .

The intrinsic viscosity of the PBT resin in the present invention is preferably 0.5 to 3.0 dl / g as measured at 30 ° C. in a mixed solvent of tetrachloroethane and phenol of 1: 1 (weight ratio), and 0.5 to 1. 5 dl / g is more preferable, and 0.6 to 1.3 dl / g is still more preferable. By setting the intrinsic viscosity to 0.5 or more, the mechanical properties are more effectively exhibited, and by setting the intrinsic viscosity to 3.0 or less, the molding process becomes easier. Further, two or more intrinsic viscosity PBT resins may be used in combination.
The melting point of the PBT resin in the present invention is preferably 225 to 190 ° C.

(A-1-2) Polyamide resin Next, the (A-1-2) polyamide resin as the component (A-1) used in the present invention is not particularly limited as long as it is a known polyamide resin, That is, the polymer contains an amide bond (—NHCO—) in the main chain and can be heated and melted. Specifically, various types of polyamide resins such as lactam polycondensates, polycondensates of diamine compounds and dicarboxylic acid compounds and salts, and polycondensates of ω-aminocarboxylic acids, or copolymer polyamide resins thereof, Such as blends.

Examples of the lactam include ε-caprolactam and ω-laurolactam. Examples of the diamine compound include tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, (2,2,4- or 2,4,4-) trimethylhexamethylenediamine. , 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3 , 5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, Aminoethyl piperazine etc. Aliphatic, alicyclic, include diamines aromatic.

Examples of the dicarboxylic acid compound include adipic acid, peric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5- Aliphatic, alicyclic and aromatic dicarboxylic acids such as sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and the like can be mentioned. Examples of the ω-aminocarboxylic acid include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid. In the present invention, polyamide homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture. A compound having 4 to 15 carbon atoms of dicarboxylic acid, diamine and lactam which are polyamide resin polymerization monomers is preferable. By setting the number of carbon atoms to 15 or less, the rigidity tends to increase, and by setting the number to 4 or more, the hygroscopicity tends to decrease and the voltage resistance is improved. Among these, polyamide 6, polyamide 66, and polyamide MXD6 are preferable because of their availability.

The polyamide resin suitable for the present invention preferably has a melt viscosity within a certain range. A preferred melt viscosity is 750 to 10000 poise, more preferably 800 to 8000 poise, measured using a capillary rheometer (Capillograph 1C manufactured by Toyo Seiki Co., Ltd.) at 280 ° C. and a shear rate of 100 sec ⁻¹ . Particularly preferred is 850 to 7000 poise. By setting the melt viscosity to 750 poise or more, the mechanical strength of the resin composition is further improved, and by setting it to 10,000 poise or less, fluidity is improved and productivity is improved, which is preferable.
The melting point of the polyamide resin in the present invention is preferably 280 to 160 ° C.

(A-2) Polystyrene resin As the (A-2) polystyrene resin of the present invention, an aromatic vinyl monomer alone or a copolymer, an aromatic vinyl monomer, a vinyl cyanide monomer, and Copolymer composed of at least one selected from rubber components (for example, copolymer of aromatic vinyl monomer and vinyl cyanide monomer, and aromatic vinyl monomer grafted to rubber component) A copolymerized polymer, an amorphous rubber-like polymer in which an aromatic vinyl monomer and a vinyl cyanide monomer are graft-copolymerized on a rubber component, etc.) are used.

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

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

Examples of the rubber component include conjugated diene rubber (polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, etc.), olefin rubber ( Examples include ethylene-propylene rubber (EPDM rubber), ethylene-vinyl acetate copolymer, halogenated polyolefin (such as chlorinated polyethylene), and acrylic rubber. These rubber components may be hydrogenated products. These rubber components can be used alone or in combination of two or more. Of these rubber components, conjugated diene rubbers are preferred. In the rubber component such as conjugated diene rubber, the gel content is not limited at all. The rubber component can be produced by a method such as emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, solution-bulk polymerization, bulk-suspension polymerization.

The aromatic vinyl monomer may be used in combination with another copolymerizable monomer. Examples of the copolymerizable monomer include (meth) acrylic acid esters (for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, (Meth) acrylic acid hexyl, (meth) acrylic acid octyl, (meth) acrylic acid 2-ethylhexyl (meth) acrylic acid C _1-18 alkyl ester, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic Hydroxyl group-containing (meth) acrylates such as 2-hydroxypropyl, glycidyl (meth) acrylate, etc.), carboxyl group-containing monomers (for example, (meth) acrylic acid, crotonic acid and other unsaturated monocarboxylic acids, maleic anhydride Aliphatic unsaturated dicarboxylic acids such as acid, maleic acid, fumaric acid and itaconic acid, maleic acid monoester (Monoalkyl maleate, monoethyl maleate, monobutyl maleate, etc., monoesters having 1 to 10 carbon atoms, such as unsaturated dicarboxylic acid monoesters such as fumaric acid monoester, etc.), maleimide series Examples thereof include N-alkylmaleimide such as maleimide and N-methylmaleimide, N-phenylmaleimide and the like. These copolymerizable monomers can be used alone or in combination of two or more. Preferred copolymerizable monomers include (meth) acrylic acid esters (particularly methyl methacrylate), (meth) acrylic acid, maleic anhydride, maleimide monomers and the like.

When other copolymerizable monomer is used, the ratio (weight ratio) between the aromatic vinyl monomer and the other polymerizable monomer is: aromatic vinyl monomer / other copolymerizable monomer And usually 100/0 to 10/90, preferably 95/5 to 10/90, and more preferably 80/20 to 20/80. A larger amount of aromatic vinyl monomer is preferred because the effect of suppressing the bleed-out of the flame retardant tends to be greater. On the other hand, although it is related to the degree of dispersion of the polystyrene resin, if there is a large amount of aromatic vinyl monomer, it tends to carbonize and tends to deteriorate tracking properties and glow wire characteristics. The vinyl monomer content is preferably 95% by weight or less, more preferably 80% by weight or less.

More specifically, when a vinyl cyanide monomer is used as a copolymerization component, the aromatic vinyl monomer and the vinyl cyanide monomer (weight ratio) are, for example, an aromatic vinyl monomer Body / vinyl cyanide monomer, usually 10/90 to 90/10, preferably 20/80 to 80/20.

When the rubber component is used, the ratio (weight ratio) between the rubber component and the aromatic vinyl monomer is, for example, rubber component / aromatic vinyl monomer = 5/95 to 80/20, preferably rubber component / aromatic. Group vinyl monomer = 10/90 to 70/30. By setting the ratio of the rubber component to the above lower limit value or more, the impact resistance of the resin composition is improved, and by setting the ratio to the upper limit value or less, the dispersion becomes good and the appearance tends to be improved.

Preferred styrene resins include polystyrene (GPPS), acrylonitrile-styrene copolymer (AS resin), impact-resistant polystyrene (HIPS), graft polymer [acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile- Acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS resin), acrylonitrile-ethylene-propylene rubber-styrene copolymer (AES resin), acrylonitrile-butadiene rubber-methacrylic acid Methyl-styrene copolymer (ABSM resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), etc.], block copolymer [for example, styrene-butadiene-styrene (SBS) copolymer, styrene -Isoprene-styrene (SIS) copolymer, styrene-ethylene-butylene-styrene (SEBS) copolymer, etc.), styrene-acrylonitrile-ethylene-propylene-ethylidene norbornene copolymer (AES), etc.], or water thereof Additives and the like. Particularly preferable styrene resins include polystyrene (GPPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and styrene-ethylene-butylene-styrene (SEBS) copolymer. More preferred are polystyrene (GPPS) and acrylonitrile-styrene copolymer (AS resin). These styrenic resins can be used alone or in combination of two or more.

In the (A) resin component, the proportion of the styrene resin is 0 to 50% by weight in the (A) resin component, and when blended, it is preferably 2.5 to 50% by weight, more preferably 5 to 5% by weight. 45% by weight, more preferably 10 to 40% by weight.

Among the (A-2) polystyrene resins in the present invention, an epoxy-modified polystyrene resin is preferably used as a polystyrene resin having good dispersibility and simultaneously improving hydrolysis resistance. Epoxy-modified polystyrene resins are those in which an epoxy group is introduced into a styrene resin. As a method for introducing the epoxy group, any conventionally known method can be used. Specifically, a styrene resin obtained by graft polymerization or copolymerization of an epoxy group-containing vinyl monomer is preferably used. Epoxy group-containing vinyl monomers are compounds that share both radically polymerizable vinyl groups and epoxy groups in one molecule. Specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and itaconic acid. Examples thereof include glycidyl esters of unsaturated organic acids such as glycidyl, glycidyl ethers such as allyl glycidyl ether, and the aforementioned derivatives such as 2-methylglycidyl methacrylate. Among them, glycidyl acrylate and glycidyl methacrylate are preferably used. Moreover, these can be used individually or in combination of 2 or more types.

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

Examples of the other monomer copolymerizable with styrene include aromatic vinyl compounds other than styrene, vinyl cyanide compounds, (meth) acrylic acid alkyl esters, maleimide monomers, and the like. Examples of the aromatic vinyl compound other than styrene include α-methylstyrene, vinyltoluene, and divinylbenzene. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and (meth) acrylic acid. Examples of the alkyl ester include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and stearyl acrylate. Examples of the maleimide monomer include N-substituted maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and derivatives thereof. Other examples include diene compounds, maleic acid dialkyl esters, allyl alkyl ethers, unsaturated amino compounds, and vinyl alkyl ethers. These can be used alone or in combination of two or more.

Preferable specific examples of the styrene resin used as a base when the epoxy group-containing vinyl monomer is graft-polymerized or copolymerized with the polystyrene resin by a radical generator or the like include polystyrene resin, high impact polystyrene resin, etc. Resin consisting mainly of polystyrene, acrylonitrile / styrene copolymer (AS resin), styrene / (meth) acrylic acid ester, styrene copolymer such as styrene / butadiene resin, styrene / butadiene / styrene resin, styrene / isoprene / Styrene resin, block copolymer containing styrene such as styrene / ethylene / butadiene / styrene resin, ABS resin such as acrylonitrile / butadiene / styrene resin, acrylonitrile / butadiene / methyl methacrylate / styrene resin And the like. Among these, a resin mainly composed of polystyrene and a styrene copolymer are preferable, and an acrylonitrile / styrene copolymer is most preferable.

The copolymer structure of the polymer having an epoxy group and the polystyrene polymer is not particularly limited. For example, it is a polymer composed of a copolymerizable unsaturated monomer having an epoxy group in the main chain. Comb-shaped polymer compound whose side chain is polystyrene, polymer compound composed of a copolymerizable unsaturated monomer containing an epoxy group and a block-copolymerized linear polymer compound, the main chain is polystyrene A polymer compound having a comb structure, which is a polymer composed of a copolymerizable unsaturated monomer having an epoxy group in the side chain, and a comb having an polystyrene group containing an epoxy group in the main chain and having a side chain made of polystyrene Examples thereof include a polymer compound having a mold structure, polystyrene having a small amount of an epoxy group added thereto, and the like. Among them, a polymer composed of a copolymerizable unsaturated monomer containing an epoxy group in the main chain and having a comb-shaped structure in which the side chain is polystyrene, a polystyrene containing an epoxy group in the main chain and the side A polymer compound having a comb structure in which the chain is polystyrene and a modified polystyrene having a small amount of an epoxy group added are preferred, and in particular, a polymer comprising a copolymerizable unsaturated monomer containing an epoxy group in the main chain and having a side chain A polymer compound having a comb structure in which is a polystyrene is preferable. These polystyrene-based resins containing epoxy groups may be a blend of a plurality of types.

The epoxy group content in the epoxy-modified polystyrene resin is particularly limited as long as it is effective to improve the compatibility of (A-1) thermoplastic polyester resin, polyalkylene terephthalate resin and epoxy-modified styrene resin. However, the epoxy group-containing monomer is preferably 0.05% by weight or more based on the epoxy-modified polystyrene resin. When copolymerized in a large amount, there is a tendency for fluidity reduction and gelation, and depending on the content of the epoxy group-containing monomer, (A) in the resin component, preferably 50% by weight or less, more preferably 45% by weight or less, More preferably, it is 40 weight% or less.

One or more of these epoxy-modified polystyrene resins can be used. Mixing an epoxy-modified polystyrene resin with a polystyrene resin not containing an epoxy group is also an effective means for adjusting the epoxy group content, molecular weight, and the like.

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

Examples of the epoxy-modified polystyrene resin obtained by graft polymerization or copolymerization of the epoxy group-containing vinyl monomer include styrene, styrene and other monomers copolymerizable therewith, and epoxy group-containing vinyl monomers. A copolymerized polymer is preferably used.

Among these, an epoxy-modified AS resin obtained by copolymerizing styrene, acrylonitrile and glycidyl methacrylate is particularly preferably used. The amount of copolymerization of glycidyl methacrylate in the epoxy-modified AS resin is not particularly limited as long as it is effective for improving the compatibility with the component (A), but 0.05 wt% in the epoxy-modified AS resin. % Or more is preferable. The upper limit is preferably 20% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less from the viewpoint of improving fluidity and suppressing gelation. The copolymerization amount of styrene and acrylonitrile is not particularly limited, but is preferably 50 to 99.9% by weight of styrene, 0.05 to 49.95% by weight of acrylonitrile, 70 to 99.9% by weight of styrene, The acrylonitrile is more preferably 0.05 to 29.95% by weight.

Moreover, the addition amount of said epoxy-modified polystyrene-type resin is 2.5-50 weight in (A) resin component from a viewpoint of the improvement of the molded article external appearance of a flame-retardant resin composition obtained, and a flame-resistant improvement. Part is preferable, and 5-45 parts by weight is more preferable.

(A-3) Compatibilizing agent In the present invention, a compatibilizing agent may be added. In the resin component of the present invention, polystyrene-based polyalkylene terephthalate resin and the like have a subtle effect on flame retardancy and tracking characteristics, so it is preferable to disperse in fine particles. In the case of a polyester resin having no reactive group, it may be difficult to perform good dispersion. When manufacturing the resin composition, troubles such as decomposition of the flame retardant may occur due to heat generation when mechanically dispersed by strong shearing. Therefore, the compatibilizing agent is blended at a ratio of 10% by weight or less. It is more preferable to add 5 to 0.01% by weight.

A preferable compatibilizer is an epoxy compound. Examples of the epoxy compound used in the present invention include bisphenol-type epoxy compounds, resorcin-type epoxy compounds, novolac-type epoxy compounds, alicyclic compound-type diepoxy compounds, glycidyl ethers, epoxidized polybutadiene, epoxy-modified thermoplastic resins, and epoxy flame retardants. Etc. More specifically, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, resorcinol type epoxy compounds, novolac type epoxy compounds, alicyclic compound type epoxy compounds such as vinylcyclohexene dioxide and dicyclopentadiene oxide, ethylene-glycidyl methacrylate A copolymer and an epoxy oligomer of tetrabromobisphenol A are preferably used. As an epoxy compound used in the present invention, a novolak type epoxy resin having an epoxy equivalent of 150 to 280 g / eq or a bisphenol A type epoxy resin having an epoxy equivalent of 600 to 3000 g / eq is used from the viewpoint of hydrolysis resistance and dispersion in the resin. Preferably used. More preferred is a novolak type epoxy resin having an epoxy equivalent of 180 to 250 g / eq and a molecular weight of 1000 to 6000, or a bisphenol A type epoxy resin having an epoxy equivalent of 600 to 3000 g / eq and a molecular weight of 1200 to 6000.

The compounding amount of the epoxy compound is preferably 0 to 10% by weight, more preferably 0.2 to 8% by weight in the resin component (A). Addition of an epoxy compound is preferred because the dispersibility tends to be improved. By setting it as 10 weight% or less, fluidity | liquidity improves and a flame retardance improves.

(B) Flame retardant combination The flame retardant combination in the resin composition of the present invention is a combination of (B-1) a phosphorus-based flame retardant, (B-2) a nitrogen-based flame retardant, and (B-3) a boric acid metal salt described later. Consists of. Here, with respect to 100 parts by weight of the resin component (A), the phosphorus flame retardant is 10 to 60 parts by weight, the nitrogen flame retardant is 10 to 80 parts by weight, and the boric acid metal salt is 0 to 45 parts by weight. The total amount needs to be 25 to 125 parts by weight. The total amount of the flame retardant combination is preferably 25 to 90 parts by weight. If it exceeds 125 parts by weight, the CTI and glow wire characteristics are degraded, and the generation of gas increases. If it is less than 25 parts by weight, flame retardancy, tracking characteristics and glow wire properties cannot be satisfied.

(B-1) Phosphorus Flame Retardant In the present invention, it is necessary to use a phosphazene compound, a phosphate ester compound or a phosphinate as the phosphorus flame retardant, and a phosphazene compound is preferred. These can be used alone or as a mixture of two or more.

(B-1a) Phosphazene Compound As the phosphazene compound that can be used in the present invention, conventionally known compounds can be widely used. For example, in Japanese Patent Application Laid-Open No. 2002-114981, phosphazene flame retardants are classified into the following three types. That is, crosslinked phenoxyphosphazene is named and classified as flame retardant A, cyclic phosphazene and / or linear phosphazene as flame retardant B, cyano-substituted phenoxy group-containing cyclic phosphazene and / or linear phosphazene as flame retardant C, Either can be used. Flame retardant A or flame retardant C is preferable from the viewpoint of thermal stability, and cyano-substituted phenoxy group-containing phosphazene of flame retardant C is preferable from the viewpoint of bleeding out of the flame retardant.

First, cyclic phosphazene and / or linear phosphazene (the flame retardant B) will be described. The cyclic phosphazene compound is represented by the following formula (1), and the chain phosphazene compound is represented by the following formula (2).

(In the formula, n is an integer of 3 to 25, m is an integer of 3 to 10000, and the substituents X are each an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 11 carbon atoms, and fluorine. A substituent selected from an atom, an aryloxy group having a substituent represented by the following formula (3), a naphthyloxy group, an alkoxy group having 1 to 6 carbon atoms and an alkoxy-substituted alkoxy group; The hydrogen on the substituent may be partially or entirely substituted with a fluorine atom, a hydroxyl group, or an organic group, and Y in the formula is —N═P (O ) (X) or -N = P (X) ₃ , Z represents -P (X) ₄ or -P (O) (X) ₂
All of the repeating units in formula (2) may be the same repeating unit or may be different.

(Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ in the formula are each a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group, a phenyl group, and a hetero element-containing group. Represents a substituent selected from the group consisting of
These compounds may be used alone or as a mixture of two or more. One factor that determines flame retardancy is the concentration of phosphorus atoms contained in the molecule. In the phosphazene compound, the chain phosphazene having a chain structure has a substituent at the molecular end, so that the phosphorus content is lower than that of the cyclic phosphazene compound, and when the same amount is added, the cyclic phosphazene than the chain phosphazene compound. Since the compound is considered to have a higher flame retardancy-imparting effect, the use of a phosphazene compound having a cyclic structure is preferred in the present invention, and a compound containing 95% by weight or more of a cyclic phosphazene compound is preferred.

The substituent X in the phosphazene compound is not particularly limited, and examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, tert-butyl group, n-amyl group, Alkyl group such as isoamyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,5-dimethylphenyl Group, aryl group such as 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, 4-tertiarybutylphenyl group, 2-methyl-4-tertiarybutylphenyl group, methoxy group, ethoxy group, n- Propyloxy group, isopropyloxy group, n-butyloxy group, tert-butyloxy group, s-butyloxy group, n-amyloxy group Alkoxy groups such as isoamyloxy group, tert-amyloxy group, n-hexyloxy group, alkoxy substituted alkoxy groups such as methoxymethoxy group, methoxyethoxy group, methoxyethoxymethoxy group, methoxyethoxyethoxy group, methoxypropyloxy group, phenoxy group 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,6-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,4-dimethylphenoxy group, 3,5-dimethylphenoxy group 3,4-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2 , 4,5-trimethylphenoxy group, 3,4,5- Limethylphenoxy group, 2-ethylphenoxy group, 3-ethylphenoxy group, 4-ethylphenoxy group, 2,6-diethylphenoxy group, 2,5-diethylphenoxy group, 2,4-diethylphenoxy group, 3,5 -Diethylphenoxy group, 3,4-diethylphenoxy group, 4-n-propylphenoxy group, 4-isopropylphenoxy group, 4-tertiarybutylphenoxy group, 2-methyl-4-tertiarybutylphenoxy group, 2-phenyl Examples thereof include alkyl-substituted phenoxy groups such as phenoxy group, 3-phenylphenoxy group, 4-phenylphenoxy group, aryl-substituted phenoxy groups, naphthyl groups, naphthyloxy groups, and the like. May be replaced by a group containing a hetero element Yes. Here, the group containing a hetero element is a group containing B, N, O, Si, P, and S atoms. For example, an amino group, an amide group, an aldehyde group, a glycidyl group, a carboxyl group , Groups containing a hydroxyl group, a cyano group, a mercapto group, a silyl group, and the like.

Next, a cyano-substituted phenoxy group-containing cyclic phosphazene and / or linear phosphazene (flame retardant C) will be described. In the present invention, a phosphazene compound in which a part of Y ¹ , Y ² , Y ³ , Y ⁴ and Y ^{5 in} the formula (3) is substituted with a cyano group (hereinafter abbreviated as a cyano group-containing phosphazene compound). In other words, it preferably has a structure of formula (4) or formula (5).

In the above formulas (4) and (5), m, n, Y, and Z are the same as those in formulas (1) and (2), and R ¹ and R ² are each a cyano group, a hydrogen atom, and a carbon number of 1 -10 alkyl groups, allyl groups or phenyl groups. However, the ratio in which R ¹ or R ² in the above compound is a cyano group is ² to 98% of the total number of R ¹ and R ² .

More specifically, examples of the phosphazene compound represented by the formula (4) or the formula (5) include cyclic phosphazenes such as cyclotriphosphazene, cyclotetraphosphazene, cyclopentaphosphazene and the like in which a cyanophenoxy group and a phenoxy group are mixed and substituted. A compound, or a linear phosphazene compound.

Specific examples of the cyclic phosphazene compound in which the cyanophenoxy group and the phenoxy group are mixed and substituted include, for example, monocyanophenoxypentaphenoxycyclotriphosphazene, dicyanophenoxytetraphenoxycyclotriphosphazene, tricyanophenoxytriphenoxycyclotriphosphazene, tetracyanophenoxy Cyclotriphosphazene compounds such as diphenoxycyclotriphosphazene and pentacyanophenoxymonophenoxycyclotriphosphazene, monocyanophenoxypeptaphenoxycyclotetraphosphazene, dicyanophenoxyhexaphenoxycyclotetraphosphazene, tricyanophenoxypentaphenoxycyclotetraphosphazene, tetra Cyanophenoxytetraphenoxycyclotetraphos Cyclotetraphosphazenes such as benzene, pentacyanophenoxytriphenoxycyclotetraphosphazene, hexacyanophenoxydiphenoxycyclotetraphosphazene, and heptacyanophenoxymonophenoxycyclotetraphosphazene, and cyclopentaphosphazene compounds in which cyanophenoxy group and phenoxy group are mixed and substituted And cyclic phosphazene compounds such as

Furthermore, the said classification | category bridge | crosslinking phenoxyphosphazene (flame retardant A) is demonstrated. These compounds are obtained by the technique disclosed in International Publication No. WO 00/09518, wherein the cyclic phosphazene and / or the linear phosphazene is a group consisting of a phenylene group, a biphenylene group and a group shown below (formula (6)). It may be crosslinked by a more selected crosslinking group.

(Wherein X represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—, and y represents 0 or 1).
The phosphazene compound having such a crosslinked structure is specifically produced by reacting a dichlorophosphazene oligomer with an alkali metal salt of phenol and an alkali metal salt of an aromatic dihydroxy compound. These alkali metal salts are added to the dichlorophosphazene oligomer slightly in excess of the theoretical amount. These phosphazene compounds may be used alone or as a mixture of two or more.

The phosphazene compound is a mixture of different structures such as cyclic trimers and cyclic tetramers, and chain phosphazenes and cross-linked products, but the processability when added to a resin is cyclic trimer, tetramer. In the case of using a phosphazene compound containing 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 85% by weight or more of a trimer or a crosslinked product. (B-2) A synergistic effect is effectively expressed with the component, an excellent flame retardancy imparting effect is obtained, and an excellent mechanical property improving effect is obtained.

The alkali metal components such as sodium and potassium contained in the phosphazene compound are each preferably 200 ppm or less, more preferably 50 ppm or less, and further preferably 50 ppm or less.

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

The phosphazene compound in which at least one of the substituents X is a hydroxyl group may have an oxo-form structure represented by the following formula (7), and such an oxo-form compound is also 1 weight in the same manner as the hydroxyl group-containing phosphazene compound. It is preferable that it is less than%. The same applies to phosphazene compounds having a chain structure represented by the above formula (2).

(In the formula, a + b = n, and n is an integer of 3 or more, and X in the formula represents an aryloxy group and / or an alkoxy group, respectively.)
The water content contained in the phosphazene compound suitably used in the present invention is preferably 1000 ppm or less, more preferably 800 ppm or less, still more preferably 650 ppm or less, particularly preferably, in consideration of electrical characteristics, hydrolysis resistance and the like. It is 500 ppm or less, most preferably 300 ppm or less, and the acid value measured based on JIS K6751 is preferably 1.0 or less, more preferably 0.5 or less.

In addition, in the phosphazene compound suitably used in the present invention, from the viewpoint of hydrolysis resistance and moisture absorption resistance, solubility in water (mixing a sample with distilled water at a concentration of 0.1 g / mL at room temperature) The amount of the sample dissolved in water after stirring for 1 hour) is preferably 100 ppm or less, more preferably 50 ppm, and still more preferably 25 ppm or less.

The phosphazene compound suitably used in the present invention can take various forms such as liquid, waxy, solid, etc., depending on the type and structure of the substituents contained, and the effects of the present invention can be achieved. Any shape can be used as long as it is not damaged. When it is necessary to consider handleability, workability, etc., a solid state is preferable. If the solid state, the bulk density is preferably 0.45 g / cm ³ or more, more preferably 0.45 g / cm ³ or more, the upper limit is preferably 0.75 g / cm ³ or less.

(B-1b) Phosphate ester compound The component (B-1b) phosphate ester compound used in the present invention includes a wide range of phosphate esters. Specific examples include, for example, trimethyl phosphate, triethyl phosphate, tributyl. Examples include phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, and the like. Among these, a compound represented by the following formula (8) is preferable.

（式中、Ｒ¹〜Ｒ⁸は、それぞれ、水素原子または炭素数１〜６のアルキル基を示し、ｍは０または１〜４の整数である。Ｒ⁹は、ｐ−フェニレン基、ｍ−フェニレン基、４，４'−ビフェニレン基または以下から選ばれる２価の基である。）。

(In the formula, R ^{1 to} R ⁸ each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is 0 or an integer of 1 to 4. R ⁹ is a p-phenylene group, m- A phenylene group, a 4,4′-biphenylene group or a divalent group selected from the following:

In the formula (8), R ^{1 to} R ⁸ are preferably an alkyl group having 6 or less carbon atoms, particularly an alkyl group having 2 or less carbon atoms, particularly methyl, in order to improve the hydrolysis resistance of the composition of the present invention. Groups are preferred. m is preferably an integer of 1 to 3, and 1 is more preferable. R ⁹ is preferably a p-phenylene group or an m-phenylene group, particularly preferably an m-phenylene group.

Among such phosphate ester compounds, compounds represented by the following formula (10) or formula (11) are preferable, and compounds represented by formula (10) are more preferable.

（式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵は、それぞれ、水素原子または炭素数１〜３０のアルキル基、アルケニル基、アリール基、アルキルアリール基若しくはアリールアルキル基を表し、Ｒ³は、２官能基を有するナフタレン環を表し、ｎは、１〜５の整数を表す。）
ｎが２以上のとき、それぞれの繰り返し単位は同じであってもよいし、異なっていてもよい。
上記式（１２）で表される芳香族ホスフェート化合物の中でも１, ５−ナフタレンビスジフェニルリン酸エステルが好ましい。 As a commercial item of such a phosphoric ester compound, it is selected from Daihachi Chemical Co., Ltd. PX-200, PX-201, PX-130, CR-733S, TPP, CR-741, CR747, TCP, TXP, CDP. 1 type or 2 or more types can be used, Preferably it is 1 type or 2 or more types chosen from PX-200, TPP, CR-733S, CR-741, CR747, More preferably, PX-200, CR It is 1 type, or 2 or more types chosen from -733S and CR-741, More preferably, it is PX-200.
Moreover, the aromatic phosphate compound represented by following formula (12) can also be used preferably.

(Wherein R ¹ , R ² , R ⁴ and R ⁵ each represents a hydrogen atom or an alkyl group, alkenyl group, aryl group, alkylaryl group or arylalkyl group having 1 to 30 carbon atoms, and R ³ represents A naphthalene ring having a bifunctional group is represented, and n represents an integer of 1 to 5.)
When n is 2 or more, the respective repeating units may be the same or different.
Among the aromatic phosphate compounds represented by the above formula (12), 1,5-naphthalene bisdiphenyl phosphate is preferable.

(B-1c) Phosphinic acid salt The phosphinic acid salt (B-1c) used in the present invention is a phosphinic acid salt represented by the following formula (13) and / or a diphosphinic acid represented by the following formula (14). It is a salt, manufactured in an aqueous solution using phosphinic acid and metal carbonate, metal hydroxide or metal oxide, and is essentially a monomeric compound, but depending on the reaction conditions, the degree of condensation depends on the environment. 1 to 3 are also included.

In the formula, R ¹ and R ² are each a linear or branched alkyl group having 1 to 6 carbon atoms and / or an aryl group, and R ³ is a linear or branched alkylene group having 1 to 10 carbon atoms. Group, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 6 to 10 carbon atoms, or an arylalkylene group having 6 to 10 carbon atoms, M is any one of Ca, Mg, Al, and Zn, and m is 2 or 3, n is 1 or 3, and x is 1 or 2.

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

Benzene-1,4- (dimethylphosphinic acid) aluminum, benzene-1,4- (dimethylphosphinic acid) zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, methylphenylphosphinic acid Examples include zinc, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate. In particular, aluminum diethylphosphinate and zinc diethylphosphinate are preferable from the viewpoint of flame retardancy and electrical characteristics.

In view of the mechanical strength of the molded product obtained by molding the composition of the present invention and the appearance of the molded product, the particle size of the phosphinate is preferably 100 μm or less, more preferably 50 μm or less. good. Use of a powder of 0.5 to 20 μm is particularly preferable because it not only exhibits high flame retardancy but also significantly increases the strength of the molded product. The phosphinate acts as a flame retardant, but when used in combination with a nitrogen-based flame retardant, it exhibits excellent flame retardancy and excellent electrical properties with a small amount of flame retardant. However, when these compounding amounts are large, mold release defects and mold deposits are likely to occur, and moldability deteriorates.

The amount of the phosphorus-based flame retardant is 10 to 60 parts by weight, preferably 15 to 50 parts by weight, and more preferably 20 to 40 parts by weight with respect to 100 parts by weight of the (A) resin component. When the blending amount of the phosphorus-based flame retardant exceeds 60 parts by weight, tracking characteristics and mechanical properties are liable to deteriorate, blooming is likely to occur, and the amount of generated gas increases.

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

Examples of the salt include salts of the triazines with inorganic acids and organic acids. Inorganic acids include nitric acid, chloric acid (such as chloric acid and hypochlorous acid), phosphoric acid (such as phosphoric acid exemplified in the above-mentioned metal hydrogen phosphate section), sulfuric acid (non-condensed sulfuric acid such as sulfuric acid and sulfurous acid, And condensed sulfuric acid such as peroxodisulfuric acid and pyrosulfuric acid), boric acid, chromic acid, antimonic acid, molybdic acid, tungstic acid and the like. Of these, phosphoric acid and sulfuric acid are preferred. Organic acids include organic sulfonic acids (aliphatic sulfonic acids such as methanesulfonic acid, aromatic sulfonic acids such as toluenesulfonic acid and benzenesulfonic acid), cyclic ureas (uric acid, barbituric acid, cyanuric acid, acetylene urea, etc.) ) And the like. Of these, alkane sulfonic acids having 1 to 4 carbon atoms such as methanesulfonic acid, arenesulfonic acids having 6 to 12 carbon atoms such as toluenesulfonic acid, and cyanuric acid are preferable.

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

Among such nitrogen-based flame retardants, those preferably used in the present invention are cyanuric acid or an adduct of isocyanuric acid and a triazine-based compound, usually 1 to 1 (molar ratio), sometimes 1 to 1 pair. It is an adduct having a composition of 2 (molar ratio). More specifically, they are melamine cyanurate, benzoguanamine cyanurate, acetoguanamine cyanurate, and further melamine cyanurate. These salts are produced by a known method. For example, a mixture of a triazine compound and cyanuric acid or isocyanuric acid is made into a water slurry and mixed well to form both salts in the form of fine particles. Is generally obtained in the form of a powder after filtration and drying. The salt does not need to be completely pure, and some unreacted triazine compound, cyanuric acid, or isocyanuric acid may remain. In addition, the average particle size of the salt before blending with the resin is preferably 100 to 0.01 μm, more preferably in terms of flame retardancy, mechanical strength, heat and humidity resistance, residence stability, and surface properties of the molded product. Is 80-1 μm. In addition, when the dispersibility of the salt is poor, 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 nitrogen-based flame retardant is 10 to 80 parts by weight, preferably 20 to 70 parts by weight with respect to 100 parts by weight of the resin component (A).
In the (B) flame retardant combination, the composition ratio (weight ratio) of the (B-1) phosphorus flame retardant and (B-2) nitrogen flame retardant is preferably (B-1) / (B-2). ) = 0.14 to 1.1, more preferably 0.2 to 1.0, and still more preferably 0.3 to 0.95. When the component ratio is 0.14 or more, flame retardancy tends to be further improved, and when it is 1.1 or less, the GWIT value can be further improved.

(B-3) Metal borate The polyester resin composition of the present invention preferably contains (B-3) a metal borate. The component (B-3) boric acid metal salt 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.

The amount of the boric acid metal salt is 0 to 45 parts by weight, preferably 1 to 20 parts by weight, and more preferably 2 to 15 parts by weight with respect to 100 parts by weight of the resin component (A). When the compounding amount of the boric acid metal salt exceeds 45 parts by weight, the mechanical properties tend to be lowered.

(C) Fibrous reinforcement having a flat cross-sectional shape (C) Fibrous reinforcement in the present invention improves the mechanical properties (tensile strength, bending strength, impact strength, etc.) of the reinforced resin composition, Improve heat shock resistance of molded products. The (C) fibrous reinforcing material in the present invention refers to a fibrous reinforcing material having an irregular cross section. Examples of the fibrous reinforcing material include glass fiber, carbon fiber, and basalt fiber.

The fibrous reinforcing material having an irregular cross-sectional shape according to the present invention has a D2 / D1 ratio (flatness) of 1.5 to 10 when the major axis of the cross section perpendicular to the fiber length direction is D2 and the minor axis is D1. It is preferably 2.5 to 10 and more preferably 2.5 to 8. By setting it to 2.5 or more, there is an effect of improving flame retardancy, heat shock resistance, and withstand voltage. Furthermore, when it is set as the average fiber length L of the fibrous reinforcing material, the (L × 2) / (D2 + D1) ratio (aspect ratio) is preferably 10 or more, and more preferably 50 to 10.

The flatness ratio (the ratio between the major axis and the minor axis) of the fibrous reinforcing material 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 fibrous reinforcing material. Commercially available fibrous reinforcing materials can utilize this value if the flatness is described in the catalog. In order to measure the reinforcing fiber length, a sample of about 5 g was cut out from a reinforcing resin composition containing a fibrous reinforcing material, and left in an electric furnace at a temperature of 600 ° C. for 2 hours to be ashed, and then the remaining fibrous state Measure for reinforcement. The fibrous reinforcing material 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. With respect to this photographic image, 1000 to 2000 reinforcing fibers are measured using image analysis software, and the average fiber length can be calculated.

The cross-sectional shape of the fibrous reinforcing material is, for example, a rectangular shape, an oval shape, an oval shape, or a saddle shape with a narrowed central portion in the longitudinal direction when cut at right angles to the length direction of the fiber. It is done. Examples of the cross-sectional shape of these fibrous reinforcing materials are described in Japanese Patent Application Laid-Open 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. The numerical value calculated by the weight average may be within the range of the flatness ratio and aspect ratio.

The glass fiber used in the present invention is surface-treated with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-aminopropyltriethoxysilane. It is desirable that the adhesion amount is 0.01% by weight or more of the glass fiber weight. Furthermore, if necessary, a lubricant such as a fatty acid amide compound, silicone oil, an antistatic agent such as a quaternary ammonium salt, a resin having a film forming ability such as an epoxy resin or a urethane resin, a resin having a film forming ability and a heat. What was surface-treated with what used a stabilizer, a flame retardant, etc. together can also be used.

In the present invention, the glass fiber is preferably composed of A glass, C glass, E glass or the like, and in particular, E glass (non-alkali glass) is preferable in that it does not adversely affect the thermal stability of the thermoplastic resin. . In addition, when using glass fiber, it is generally preferable to use a short fiber type (chopped strand) from the viewpoint of ease of handling, etc., especially in the case of a molded product that requires impact resistance characteristics. It is more preferable to use a long fiber type in order to keep the fiber length of the glass fiber in the molded product longer.

The resin composition of the present invention contains (C) a fibrous reinforcing material in an amount of 5 to 200 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of the resin component (A).

(D) Anti-dripping agent The resin composition of this invention may contain the (D) anti-dripping agent as needed. (D) An anti-dripping agent refers to a compound having the property of preventing dripping of a resin during combustion, and specific examples include layered silicates such as silicon oil, silica, asbestos, fluororesin, talc, and mica. Etc. Among these, fluororesins, layered silicates and the like are preferable as the anti-drip agent from the viewpoint of flame retardancy of the composition. More preferably, a fluororesin having an effect with a small amount is preferable.

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

(D) The fluororesin used as an anti-dripping agent includes polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer Polymers, fluorinated polyolefins such as vinylidene fluoride and polychlorotrifluoroethylene are preferred. Among them, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoro Ethylene / ethylene copolymers are more preferred, and polytetrafluoroethylene and tetrafluoroethylene / hexafluoropropylene copolymers are particularly preferably used.

(D) The fluororesin used as an anti-drip agent preferably has a melt viscosity at 350 ° C. of 1.0 × 10 ^{2 to} 1.0 × 10 ¹⁵ (Pa · s), and in particular, 1.0 × 10 10. ^{3 to} 1.0 × 10 ¹⁴ (Pa · s), particularly 1.0 × 10 ^{10 to} 1.0 × 10 ¹² (Pa · s) is preferably used. By setting the melt viscosity to 1.0 × 10 ² (Pa · s) or more, the anti-dripping ability during combustion tends to be improved, and by setting the melt viscosity to 1.0 × 10 ¹⁵ (Pa · s) or less, This is preferable because the fluidity of the composition tends to be improved.

The amount of the fluororesin is usually 0.01 to 15 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 0.7 to 12 parts per 100 parts by weight of the resin component (A). Parts by weight, more preferably 1 to 10 parts by weight. By making the addition amount of the fluororesin 0.01 parts by weight or more, the dripping prevention effect during combustion becomes better, and by making it 15 parts by weight or less, fluidity and mechanical properties are further improved.

(D) The use of a layered silicate as an anti-drip agent is preferable from the viewpoint of fluidity during melting of the resin composition of the present invention. Examples of layered silicates include layered silicates, modified layered silicates (layered silicates with a quaternary organic onium cation inserted between the layers), layered silicates having a reactive functional group, or modified layered silicates. From the viewpoint of the dispersibility of the layered silicate in the resin composition of the present invention and the ability to prevent dripping, a modified layered silicate, a layered silicate added with a reactive functional group or a modified layered silicate is preferred, particularly an epoxy group, A layered silicate or a modified layered silicate to which a reactive functional group such as an amino group, an oxazoline group, a carboxyl group, or an acid anhydride is added is more preferable. Although there is no restriction | limiting in particular as a functional group provision method, The method of processing with a functionalizing reagent (silane coupling agent) is simple and preferable.

Specific examples of functionalizing reagents include chlorosilanes having an epoxy group, chlorosilanes having a carboxyl group, chlorosilanes having a mercapto group, alkoxysilanes having an amino group, alkoxysilanes having an epoxy group, and the like. Among them, chlorosilanes having an epoxy group such as 3-glycidyloxypropyldimethylchlorosilane, β- (3,4-epoxycyclohexyl) ethyldimethylchlorosilane, 3-glycidyloxypropyltrichlorosilane, 3-aminopropyltriethoxysilane Alkoxysilanes having an amino group such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-glycidyloxy B pills methyl diethoxy silane, 3-glycidyloxypropyltrimethoxysilane, alkoxysilanes having a beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane and epoxy groups are preferred. The method for contacting these functionalizing reagents with the layered silicate is not particularly limited, but usually it is preferably carried out by mixing in a solvent-free or polar solvent.

Specific examples of the layered silicate used in the present invention include smectite clay minerals such as montmorillonite, hectorite, fluorine hectorite, saponite, beidellite, and subtinsite, Li-type fluorine teniolite, Na-type fluorine teniolite, and Na-type four. Swelling synthetic mica such as silicon fluorine mica and Li-type tetrasilicon fluorine mica, vermiculite, fluorine vermiculite, halloysite, and the like may be mentioned, which may be natural or synthesized. Of these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, and Na-type tetrasilicon fluorine mica are preferable.

There are no particular restrictions on the quaternary onium cation inserted between the layers of the modified layered silicate used in the present invention, but specific examples that can be suitably used include trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, and trimethyltetra Trimethylalkylammonium such as decylammonium, trimethylhexadecylammonium and trimethyloctadecylammonium, dimethyldialkyl such as dimethyldioctylammonium, dimethyldidecylammonium, dimethyldidodecylammonium, dimethylditetraammonium, dimethyldihexadecylammonium and dimethyldioctadecylammonium Ammonium etc. are mentioned.

When layered silicate is used as the (D) anti-dripping agent in the resin composition of the present invention, the addition amount is preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the (A) resin component. Preferably it is 0.3-12 weight part, More preferably, it is 0.5-10 weight part. (D) The addition of 0.1 parts by weight or more of the layered silicate as an anti-drip agent tends to improve the anti-drip effect during combustion, and the flowability and mechanical properties are remarkable when the amount is 15 parts by weight or less. To improve. In addition, a layered silicate may use 1 type, or may use 2 or more types together.

(D) It is also preferable to use silicone oil as the anti-dripping agent, and the silicone oil is a compound having a dimethylpolysiloxane skeleton represented by the following formula (15) (t is usually an integer of 10 to 20000). ), Part or all of the terminal or side chain is amino-modified, epoxy-modified, carboxyl-modified, carbinol-modified, methacryl-modified, mercapto-modified, phenol-modified, polyether-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester It may be functionalized by modification, higher alkoxy modification, or fluorine modification.

(D) The viscosity of the silicone oil used as the anti-dripping agent is preferably 1000 to 30000 (cs.) At 25 ° C., more preferably 2000 to 25000 (cs.), Particularly 3000 to 20000 (cs.). By setting it to 1000 (cs.) Or more, the drip-preventing action during combustion works well and the flame retardancy tends to improve. By setting it to 30000 (cs.) Or less, thickening is suppressed, and flow Tend to improve. (D) The amount of silicone oil used as an anti-drip agent is usually 0.01 to 10 parts by weight, preferably 0.02 to 8 parts by weight, based on 100 parts by weight of the resin component (A). Parts, more preferably 0.03 to 5.0 parts by weight. (D) By making silicon oil as an anti-dripping agent 0.01 parts by weight or more, the anti-dripping effect tends to be improved, and by making it 10 parts by weight or less, fluidity and mechanical properties are improved. There is a tendency.

Resin composition The resin composition of the present invention has an oxygen index of 19 or more measured using an OXIGEN INDEXERISO manufactured by Toyo Seiki in accordance with ISO 4589 (JIS K7201) using a UL combustion test piece having a thickness of 0.8 mm. It is preferable that it is 25 or more.
Further, the resin composition of the present invention has a deflection temperature under a load of 0.45 MPa in ISO 75 standard, preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher.
In addition to the components (A) to (D) described above, conventional additives and the like can be blended in the resin composition of the present invention as necessary. There are no particular restrictions on the additive to be added, for example, stabilizers such as antioxidants and heat stabilizers, additives such as lubricants, mold release agents, catalyst deactivators, crystal nucleating agents, and crystallization accelerators are resins. It can be added during or after the polymerization. Furthermore, in order to impart desired performance to the resin composition, stabilizers such as UV absorbers and weathering stabilizers, colorants such as dyes and pigments, antistatic agents, foaming agents, plasticizers, impact modifiers. Etc. can be blended. An epoxy compound, carbodiimide, oxazoline, or the like can be added to further improve the hydrolysis resistance of the polyester resin. In addition, elastic resins (for example, known elastic resins such as polyolefin-based elastomers, polyester-based elastomers, polyamide-based elastomers, urethane-based elastomers, acrylic-based elastomers, silicon-based elastomers, core-shell type elastomers) can be used to improve heat shock resistance. However, since it is considered that the flame retardancy is particularly disturbed, it is necessary to thoroughly examine the blending amount.
A flame retardant other than the above-mentioned flame retardant combination (B) may be added to the resin composition of the present invention within a range not departing from the gist of the present invention. Moreover, it is preferable that a halogenated flame retardant is 5 weight% or less in a resin composition.

Furthermore, in the resin composition of the present invention, a resin other than the thermoplastic polyester resin, the polyamide resin, and the polystyrene resin can be blended as necessary within a range not impairing the object of the present invention. However, as described above, the blending of the polyphenylene ether resin, polyphenylene sulfide resin, and phenol resin is not preferable because it decreases the tracking characteristics, and it is necessary to suppress the content to 1% by weight or less in the total resin composition. More preferably, it is 5% by weight or less. Here, the polyphenylene ether resin and the polyphenylene sulfide resin disclosed in Patent Document 8 and the phenol resin disclosed in Patent Document 6 are preferably applied in the present invention.
Polyolefin resins such as polyethylene and polypropylene have the effect of improving tracking characteristics, but tend to reduce flame retardancy. These thermoplastic resins and thermosetting resins can be used alone or in combination of two or more.

The method for producing the flame retardant resin composition of the present invention is not particularly limited, and can be easily achieved by mixing each component 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. Specific examples include a method of melt-kneading each component at once, a method of first melt-mixing a specific component, and the like. Among these, from the viewpoint of mechanical properties, (A) a resin component and (B) a flame retardant A production method is preferred in which the combination is first melt mixed and then the remaining components are mixed.

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.

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.

The flame-retardant resin composition of the present invention is excellent in electrical safety such as flame retardancy and electric resistance, mechanical physical properties, etc., and further excellent in low specific gravity and fluidity, and thus suitable for use in molded products having thin or complicated shapes. Can be used for Furthermore, since the bleed-out of the flame retardant from the obtained molded product is suppressed, the quality safety of the product is improved. Therefore, the resin molded part formed using the above-mentioned flame retardant resin composition achieves a high GWFI value and a high GWIT value, and has been conventionally required and has flame retardancy (V −0), tracking characteristics, withstand voltage, and other requirements, it is suitable as a material for manufacturing electric devices, electronic devices or general parts thereof.

A molded product that can particularly effectively utilize the characteristics of the resin composition of the present invention is a high-voltage insulating material part. High voltage insulation material components include leakage protection components such as electric breakers and leakage breakers, wiring components such as outlets, plugs and terminals, transformer components that convert 100V voltage to high or low voltage, and magnetic field generation An electric / electronic device such as a coil bobbin to be used. Also in the vehicle field, there are discharge parts for motors and other prime movers, transformer parts used for lighting, etc., engine ignition system parts such as automobile ignition and distributor parts, and lighting parts such as discharge lamps. It is done.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to the example described below.

[Ingredients used in Examples]
(A-1-1-a) PBT resin: manufactured by Mitsubishi Engineering Plastics, Novaduran 5008, melting point 224 ° C.
(A-1-1-b) PET resin: Mitsubishi Chemical Corporation, Novapex GS385, melting point 255 ° C.
(A-1-2) Polyamide-6 resin (PA-6 resin): Mitsubishi Engineering Plastics, Novamid 1010J, melting point 224 ° C.

(A-2a) Epoxy-modified AS resin: AS resin (manufactured by Technopolymer Co., Ltd., Sanrex SAN-C, melt mass flow rate 25 g / 10 min, PS / AN = 75/25) with respect to 100 parts by weight, methacrylic acid 3 parts by weight of glycidyl and 0.015 part by weight of 2.5-dimethyl-2.5-di- (tert-butylperoxy) hexyne were blended and kneaded at 210 ° C. using a 30 mm twin screw extruder. And then pelletized. When unreacted glycidyl methacrylate was extracted with acetone and then quantified for glycidyl methacrylate from ultraviolet absorption spectrum measurement, the reaction was 1.7% by weight.

(A-2b) EGMA-g-PS: Epoxy-modified polystyrene resin, manufactured by NOF Corporation, trade name Modiper A4100. This is a comb structure polymer obtained by grafting polystyrene (PS) to an ethylene-glycidyl methacrylate copolymer (EGMA), and EGMA / PS = 70/30 (weight ratio).
(A-2c) AS resin: Styrene-acrylonitrile copolymer resin, manufactured by Technopolymer Co., Ltd., Sanrex SAN-C, melt mass flow rate 25 g / 10 min, PS / AN = 75/25 (weight ratio)
(A-2d) PS resin: GPPS resin, manufactured by PS Japan, trade name HF77, melt flow rate 7.5 g / 10 min

(A-3) Epoxy compound: bisphenol A type epoxy resin as a compatibilizer, manufactured by Asahi Denka Kogyo Co., Ltd., trade name Adeka Sizer EP17
(A-4) Polyolefin elastomer: ethylene-glycidyl methacrylate copolymer (trade name Bond First 2C, manufactured by Sumitomo Chemical Co., Ltd.)

(B-1a) 4-Cyano Phenoxy-Containing Phosphazene Compound The compound was synthesized as follows with reference to Synthesis Example 15 of Patent Document 8 (Japanese Patent Laid-Open No. 10-77396).
To a 2-liter four-necked flask equipped with a stirrer, a heating device, a thermometer and a dehydrator, 1.76 mol of 4-cyanophenol, 0.88 mol of phenol, 2.64 mol of sodium hydroxide and 1000 ml of toluene were added. Added. Next, this mixture was heated to reflux, water was removed from the system, and a toluene solution of cyanophenol and a sodium salt of phenol was prepared. A 20% chlorobenzene solution containing 1 mol of dichlorophosphazene oligomer (85% or more of cyclic 3- to 8-mer and linear chain of less than 15%) in a toluene solution of sodium salt of cyanophenol and phenol. While stirring, 580 g was added dropwise at an internal temperature of 30 ° C. or lower. After the mixed solution was refluxed for 12 hours, a 5% aqueous sodium hydroxide solution was added to the reaction mixture and washed twice. Next, the organic layer was neutralized with dilute sulfuric acid, washed twice with water, filtered, concentrated and vacuum dried (vacuum drying conditions: 80 ° C., 5 mmHg, 12 hours) to contain a cyanophenoxy group. A phosphazene was obtained. This was found to be approximately N = P (OC ₆ H ₄ CN) _1.34 (OC ₆ H ₅ ) _0.66 by elemental analysis, and the ratio of cyanophenol group was 67%. The melting point of this product was unclear.

（Ｂ−１ｅ）ホスフィン酸塩：ジエチルホスフィン酸アルミ、クラリアントジャパン（株）製、商品名ＯＰ１２４０。 (B-1b) Phenoxyphosphazene compound having a cross-linked structure with 2,2-bis (p-oxyphenyl) propane group The synthesis was performed in addition to Synthesis Example 2 of Patent Document 8 (Japanese Patent Laid-Open No. 10-77396). The resulting crosslinked phosphazene has a final composition of N = P (—O—Ph—C (CH ₃ ) ₂ —Ph—O—) _0.25 (—O—Ph) based on the phosphorus content and the CHN elemental analysis value. _1.50 . The melting point of this product was unclear.
(B-1c) Phosphazene compound: Phosphazene compound mainly composed of a cyclic product (Fushimi Pharmaceutical Co., Ltd., trade name: FP-100)
(B-1d) Phosphate ester compound: Phosphate ester represented by the following formula (16).

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

(B-2) Triazine ring-containing compound: melamine cyanurate, manufactured by Mitsubishi Chemical Corporation, trade name MX44.

(B-3) Zinc borate: Borax Japan Co., Ltd., trade name Firebreak 500.

(C-1) Glass fiber (oval cross section flatness ratio 4): Nittobo Co., Ltd., CSH3PA830, for polyester (C-2) Glass fiber (oval cross section flatness ratio 4): Nittobo Co., Ltd., CSH3PA820, for polyamide (C-3) Glass fiber (eyebrows-shaped cross section flatness ratio 2): Nittobo Co., Ltd., CSH3PA860, for polyester (C-4) Glass fiber (circular cross section): Nippon Electric Glass Co., Ltd., ECS03T187, for polyester (C- 5) Glass fiber (circular cross section): manufactured by Nippon Electric Glass Co., Ltd., ECS03T289, for polyamide

(D) PTFE: polytetrafluoroethylene, manufactured by Daikin Industries, Ltd., tetrafluoroethylene resin, polyflon F201.

(E) Brominated flame retardant: Brominated polystyrene, Albemarle Japan Co., Ltd., trade name Saytex HP-7010.
(F) Antimony compound: antimony trioxide, manufactured by Moriroku Co., Ltd., trade name MIC-3.

(G) Stabilizer: Hindered phenolic compound, manufactured by Ciba Specialty Japan Co., Ltd., trade name Irganox 1010
(H) Mold release agent: calcium montanate, manufactured by Clariant Japan KK, trade name CaV102

(I-1) PPE resin: polyphenylene ether resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name Iupiace, intrinsic viscosity 0.36.
(I-2) Phenol resin: Novolac phenol resin, manufactured by Sumitomo Durez Co., Ltd., trade name Sumilite Resin PR-53195

[Performance evaluation method]
(1) Flame Retardancy Test UL test pieces (thickness 1/32 inch) were conducted by UL-94 standard vertical combustion test of Underwriter's Laboratories Inc. The flame retardancy level is evaluated in the order of V-0>V-1>V-2> HB in accordance with the standard, and flame retardancy of V-2 or higher is required, preferably V-0.

(2) Withstand voltage (Dielectric strength: KV)
For sheet molded products of 1 mm and 2 mm thickness of 100 mm × 100 mm in a dry state, in a breakdown test apparatus YST-243-100RHO manufactured by Yamayo Tester Co., Ltd., in a 23 ° C. oil in a short time method (2 kV / sec), the electrode is The dielectric breakdown voltage was measured with a combination of a 6 mm diameter cylinder and a 25 mm diameter cylinder.

(3) Comparative tracking index test (abbreviation: CTI 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. CTI 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.

(4) Glow-wire Flammability Index test (abbreviation: GWFI test)
The test method (flat plate with a thickness of 3 mm) was subjected to the test method defined in IEC60695-2-12. That is, a red hot rod having a predetermined shape (a nickel / chromium (80/20) wire having an outer diameter of 4 mm in a loop shape) is brought into contact for 30 seconds and then pulled apart. It is defined as the highest temperature at the tip that does not ignite during this time, or extinguishes within 30 seconds after being ignited, and tests to a maximum of 960 ° C. 850 ° C. or higher is required for flame retardant applications. In this invention, it was determined whether it passed at 960 degreeC.

(5) Glow-wire Ignition Temperature test (abbreviation: GWIT test)
Three types of flat plate test pieces having thicknesses of 0.75 mm, 1.5 mm, and 3 mm were subjected to the test method defined in IEC 60695-2-13. That is, it is defined as a temperature that is 25 ° C. higher than the highest temperature at the tip that does not ignite when a red hot rod having a predetermined shape (a nickel / chromium (80/20) wire having an outer diameter of 4 mm in a loop shape) is contacted for 30 seconds. For flame-retardant applications, a GWIT value of 0.8 to 3 mm thickness is required to be 775 ° C. or higher. More preferably, 800 ° C. or higher is required.

(6) Surface appearance evaluation test The surface of the flat test piece having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm was visually observed, and the appearance was evaluated with the glass fiber floating up. Those within the allowable appearance range of general molded products were marked with ◎ or ○. Glass fiber lift is good, ◎ good glass fiber lift is slightly recognized, glass fiber lift is partially observed △ glass fiber lift over a fairly wide range Is recognized and marked as x.

(7) Flame retardant bleed out test Using a 10 cm square flat plate with a thickness of 3 mm as a sample, heat treatment was performed for 48 hours in a hot air dryer controlled at 150 ° C., and then the surface of the test piece was difficult to observe by visual observation. The exudation of the fuel was classified into the following four stages, and ◎ and ○ were judged to be practically usable.
◎: No oozing ○: Slight oozing is observed slightly △: There is oozing out ×: Many oozing out

(8) Tensile test An ISO tensile test piece (ISO 3167) was used, and measurement was performed in accordance with ISO 527.

(9) Wet heat treatment test The ISO test piece was treated with a pressure cooker (PC-422R5F) manufactured by Hirayama Seisakusho Co., Ltd. under an environment of a temperature of 85 ° C. and a humidity of 95% for 2000 hours. After the treatment, the test piece was dried by vacuum drying. About the ISO test piece before and behind a process, the tensile test was done based on ISO527 and the tensile strength retention was measured.

(10) Warpage amount measurement test Evaluation of shrinkage anisotropy using a disc of 100 mm in diameter and 1.6 mm in thickness molded under the above molding conditions (the gate is a one-point gate on the circumference). As a result, the warpage was measured. One end of the disc was fixed to a flat plate, and the distance by which the opposite side was lifted from the flat plate was measured and used as the amount of warpage. The smaller this value, the less the anisotropy and the less the molded product is preferable.

[Examples 1 to 13 and Comparative Examples 1 to 14]
Ingredients other than the glass fibers listed in Table 1 are mixed together with a super mixer (SK-350 type, manufactured by Shinei Machinery Co., Ltd.), and L / D = 42 twin screw extruder (manufactured by Nippon Steel Works, TEX30HSST). It was put into a hopper, and (C) glass fiber was side-fed and extruded under conditions of a discharge rate of 20 kg / hour, a screw rotation speed of 150 rpm, and a barrel temperature of 260 ° C. to obtain pellets of a polyalkylene terephthalate resin composition.
For the resin composition pellets, using the injection molding machine (manufactured by Sumitomo Heavy Industries, Model SH-100), the tests of (1) to (7) above under the conditions of a cylinder temperature of 270 ° C. and a mold temperature of 100 ° C. Pieces (5 types of flat plate test pieces of 10 cm in length and width, thickness of 0.75 mm, 1 mm, 1.5 mm, 2 mm and 3 mm, and a test piece of UL-94 standard having a thickness of 1/32 inch) were manufactured. In addition, as a test piece of (8) and (9), an ISO tensile test piece (ISO 3167) was molded at 265 ° C. using an injection molding machine (model S-75 MIII, manufactured by Sumitomo Heavy Industries, Ltd.). did. The test piece of (10) was also molded at 265 ° C. and a mold temperature of 90 ° C. using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., model S-75 MIII). Said evaluation was implemented using the above test piece. The evaluation results are shown in Table 1.

The above Example 13 is a reference example.

The following was found from the above table.
(1) Examples 1 to 13 in which the modified cross section GF was blended had higher withstand voltage characteristics than Comparative Examples 1 and 3 to 6 in which the round section GF was blended.
(2) Comparative Examples 7 to 10 in which PPE resin or phenol resin is further added to the composition of Example 1 and the like have good flame retardancy and bleed-out property, but the tracking property is remarkably lowered. It turned out to be unfit for the purpose.
(3) In comparison between Examples 9 to 12 in which various polystyrene resins are blended and Example 1 in which no polystyrene resin is blended, the flame retardancy, tracking property, and glow wire property are substantially maintained, and warpage is maintained. And the withstand voltage characteristics were improved. On the other hand, the comparative example 12 which mix | blended the polyolefin-type elastomer deteriorated the flame retardance.

In the present invention, by adding a fibrous filler having an irregular cross section to a thermoplastic resin and, if necessary, an elastomer, an epoxy compound, and a vinyl aromatic resin, without impairing mechanical strength, molding fluidity, etc. In addition, electrical properties such as voltage resistance are greatly improved, and a resin composition suitable for the production of high-voltage parts can be provided. The high voltage component produced using this resin composition has a small decrease in withstand voltage characteristics even when used under severe environments such as high temperature and high humidity and thermal shock, and can be suitably used for high voltage components in automobiles and the like.

Claims (6)

(A) For 100 parts by weight of a resin component having the following composition ratio,
(A-1) 100 to 40% by weight of a resin mainly composed of a thermoplastic resin selected from thermoplastic polyester resins and polyamide resins
(A-2) Polystyrene-based resin 0 to 50% by weight
(A-3) Compatibilizer 0-10% by weight
(B) Flame retardant combination Total amount of the following components 25-125 parts by weight,
(B-1) 10-60 parts by weight of a phosphorus-based flame retardant selected from the group of phosphazene compounds, phosphate ester compounds and phosphinates (B-2) a nitrogen-based compound comprising a salt of an amino group-containing triazine Flame retardant 10 to 80 parts by weight (B-3) Boric acid metal salt 0 to 45 parts by weight (C) Flatness in which the ratio of the major axis to the minor axis (flatness) of the cross section perpendicular to the fiber length is 1.5 to 10 5 to 200 parts by weight of a fibrous reinforcing material having a cross-sectional shape,
The result was at least blended polyphenylene ether resin, any of the content of the polyphenylene sulfide resin and phenolic resin also Ri der than 1 wt%, in (B) a flame retardant combination, and (B-1) phosphorus-based flame retardant (B-2) The composition ratio (weight ratio) of the nitrogen-based flame retardant is in the range of (B-1) / (B-2) = 0.14 to 1.1. Resin composition. The resin composition according to claim 1, wherein the resin composition further comprises (D) an anti-dripping agent in an amount of 0.01 to 15 parts by weight with respect to 100 parts by weight of the resin component (A). . (A-2) The resin composition according to claim 1 or 2 , wherein the polystyrene resin is an epoxy-modified polystyrene resin. The resin composition according to any one of claims 1 to 3 , wherein the thermoplastic resin of the component (A-1) is a thermoplastic polyester resin. The cross-sectional shape when the (C) fibrous reinforcing material is cut at right angles to the fiber length direction is rectangular or oval, and the flatness is 2.5 to 10. the resin composition according to any one of 1-4. A high-voltage insulating material part formed by molding the resin composition according to any one of claims 1 to 5 .