JP2002060597A - Flame-retardant polybutylene terephthalate resin composition and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a halogen-free flame-retardant polybutylene terephthalate(PBT) resin composition using a nonhalogen flame retardant and excellent in the flame retardance, mechanical characteristics and fluidity, and to provide a molded product having high reliability over a long period. SOLUTION: This flame-retardant PBT resin composition is obtained by compounding (A) 100 pts.wt. of a PBT resin with (B) 0.1-100 pts.wt. of a phosphonitrile linear polymer and/or cyclic polymer having a repeating unit represented by the general formula (1) and >=3 number-average degree of polymerization, (C) 0.1-100 pts.wt. of a carbonization accelerating substance and (D) a polycarbonate resin in an amount of 11 to <100 pts.wt. based on 100 pts.wt. of the sum of the components (A) and (C) and <100 pts.wt. based on 100 pts.wt. of the component (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant polybutylene terephthalate resin composition and a molded product using a non-halogen flame retardant. More specifically, a resin composition that maintains high flame retardancy, mechanical properties, fluidity during injection molding, and a high breakdown voltage and appearance of a molded product over a long period of time is obtained. The present invention relates to a flame-retardant polybutylene terephthalate resin composition and molded articles suitable for machine parts.

[0002]

2. Description of the Related Art Polybutylene terephthalate resin (PB)
T) is utilized in a wide range of fields such as mechanical mechanism parts, electric / electronic parts, and automobile parts by making use of its excellent properties such as excellent injection moldability and mechanical properties.

[0003] Further, by combining PBT with a fiber reinforcing material, it is widely used as a material having further excellent mechanical properties and heat resistance. Among the fiber reinforcements, glass fibers are particularly used.

[0004] Because PBT is inherently flammable, it cannot be used for industrial materials such as mechanical and mechanical parts, electric and electronic parts, and automobile parts in addition to the general balance of chemical and physical properties. In many cases, fire safety, that is, flame retardancy is required.

[0005] As a method for imparting flame retardancy to PBT,
In general, a method of compounding a resin with a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant aid is used. However, this method tends to generate a large amount of smoke during combustion.

Therefore, in recent years, it has been strongly desired to use a flame retardant containing no halogen at all.

Heretofore, as a method of making a thermoplastic resin flame-retardant without using a halogen-based flame retardant, it has been widely known to add a hydrated metal compound such as aluminum hydroxide or magnesium hydroxide. In order to obtain sufficient flame retardancy, it is necessary to add a large amount of the above-mentioned hydrated metal compound, which has a disadvantage that the inherent properties of the resin are lost.

On the other hand, as a method for making a thermoplastic resin flame-retardant without using such a hydrated metal compound, the addition of red phosphorus is disclosed in JP-A-51-150553 and JP-A-5-150553.
JP-A-8-108248, JP-A-59-81351, JP-A-5-78560, JP-A-5-2871
No. 19, JP-A-5-295164, JP-A-5-295164
It is disclosed in Japanese Patent Application Laid-Open No. 320486 and Japanese Patent Application Laid-Open No. 5-339417.

However, although it is a useful flame-retardant resin material that does not use a halogen-based flame retardant, it has a problem that the color tone is limited because it is colored in a specific color.

Also, a phosphonitrile linear polymer and / or
Alternatively, a method of adding a cyclic polymer is disclosed in JP-A-50-48.
No. 055, Japanese Patent Application Laid-Open No. 50-92950, Japanese Patent Application Laid-Open No. 51-36266, and the like, but are mainly intended for flame retardancy in fibers, and are not aimed at resin molded products. Was. On the other hand, JP-A-50-919
No. 57 discloses a method of adding a phosphonitrile linear polymer and / or a cyclic polymer to make a PBT resin molded article flame-retardant. However, a large amount of a metal compound such as antimony trioxide is used as a flame-retardant aid. Has been blended.

In addition, a method of adding only a phosphonitrile linear polymer and / or a cyclic polymer to the flame retardancy of a PBT resin molded article has a small flame retarding effect, and melamine cyanurate, polyphenylene ether resin, polyphenylene as a flame retardant auxiliary. Japanese Patent Application Laid-Open No. 7-216 discloses blending of a sulfide resin, a dripping inhibitor such as a fluororesin or a layered silicate.
235, JP-A-9-183864 and JP-A-10-77396, all of which are useful flame-retardant resin materials that do not use a halogen-based flame retardant, If the mechanical properties are reduced or the hydrolysis treatment is carried out, bleed-out and the dielectric breakdown voltage are greatly reduced, and there is a problem that the excellent appearance and electrical properties of the PBT molded product cannot be maintained for a long period of time.

[0012]

That is, the present invention uses a non-halogen flame retardant, is excellent in flame retardancy and mechanical properties and fluidity at the time of injection molding, and has a high dielectric breakdown voltage and a molded product over a long period of time. An object of the present invention is to obtain a highly reliable flame-retardant PBT resin composition and a molded product while maintaining the appearance.

[0013]

Means for Solving the Problems In view of the above situation, the present inventors have conducted intensive studies and as a result, have found that a specific amount of a phosphonitrile linear polymer and / or cyclic polymer, a carbonization promoting substance and By combining a polycarbonate resin, it has excellent mechanical properties and excellent fluidity during injection molding, while maintaining high flame retardancy, and maintains a high dielectric breakdown voltage and molded product appearance over a long period of time. The present inventors have found that a resin molded product capable of performing the above-mentioned process is obtained, and arrived at the present invention.

That is, the present invention relates to (B) a phosphonitrile linear polymer having a number average polymerization degree of 3 or more having (B) a repeating unit of the general formula (1) and / or 100 parts by weight of a polybutylene terephthalate resin and / or 0.1 to 100 parts by weight of a cyclic polymer, and (C) a carbonization promoting substance
1 to 100 parts by weight, and 100 parts by weight of the polycarbonate resin (D) is less than 11 to 100 parts by weight based on 100 parts by weight of the total of the components (A) and (C) and 100 parts by weight based on the component (A). Flame-retardant polybutylene terephthalate resin composition comprising less than parts by weight,

[0015]

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(In the above formula, A and B represent the same or different O, N and S. R1 and R2 represent the same or different aryl, alkyl, aralkyl or cycloalkyl having 1 to 15 carbon atoms) It represents an alkyl group and may have a cyclic structure in which R1 and R2 are linked, and x and y represent 0 or 1.) A molded article comprising the above flame-retardant polybutylene terephthalate resin composition, and the above-mentioned flame-retardant polybutylene An object of the present invention is to provide a mechanical mechanism part, an electric / electronic part, or a molded part for an automobile part comprising a terephthalate resin composition.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant polybutylene terephthalate resin composition and molded article of the present invention will be specifically described below.

The (A) polybutylene terephthalate resin in the present invention is a polymer obtained by a polycondensation reaction between terephthalic acid or its ester-forming derivative and 1,4-butanediol or its ester-forming derivative. , In addition to the acid component, isophthalic acid,
Naphthalenedicarboxylic acid, adipic acid, sebacic acid, dodecandic acid, oxalic acid, etc., as a glycol component,
Ethylene glycol, propylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-
Hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, or the like, or long-chain glycols having a molecular weight of 400 to 6000, ie, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc.
0 mol% or less can be copolymerized. Preferred examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate),
Examples thereof include polybutylene (terephthalate / decanedicarboxylate) and polybutylene (terephthalate / naphthalate), which may be used alone or as a mixture of two or more. Here, “/” means copolymerization.

The polymer or copolymer has an intrinsic viscosity of 0.36 to 1.60, particularly 0.42 to 1.25, measured at 25 ° C. using an O-chlorophenol solvent. Is suitable from the viewpoints of impact strength and moldability of the composition obtained. Further, (A) polybutylene terephthalate resins having different intrinsic viscosities may be used in combination, and the intrinsic viscosities of 0.36 to 1.60 may be used.
Is preferably within the range.

Further, those polybutylene terephthalate resins having a COOH terminal group amount determined by potentiometric titration of an m-cresol solution with an alkaline solution in the range of 1 to 50 eq / t (terminal group amount per ton of polymer) are used. durability,
It can be preferably used in view of the effect of suppressing anisotropy.

The (B) phosphonitrile linear polymer and / or cyclic polymer used in the present invention is an oligomer or polymer having a repeating unit represented by the above formula (1), and has a number average polymerization degree. Three or more. In addition, any of linear or cyclic or a mixture thereof may be used, but one containing linear phenoxyphosphazene as a main component is particularly preferably used. The upper limit of the number average polymerization degree is not particularly limited, but is preferably 500 or less.

The above-mentioned phosphonitrile linear polymer and / or cyclic polymer can be synthesized by a known method described in Kajiwara's "Synthesis and Application of Phosphazene Compounds". Alternatively, it is synthesized by reacting phosphorus trichloride, ammonium chloride or ammonia gas as a nitrogen source by a known method (a cyclic substance may be purified), and substituting the obtained substance with alcohol, phenol and amines. be able to.

Specific examples of the repeating unit represented by the above (I) in the (B) phosphonitrile linear polymer and / or cyclic polymer used in the present invention include the examples shown in the following (2). However, the present invention is not limited to this.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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The addition amount of the (B) phosphonitrile linear polymer and / or cyclic polymer used in the present invention is as follows:
(A) 0.1 to 100 parts by weight, preferably 1 to 70 parts by weight, based on 100 parts by weight of polybutylene terephthalate;
More preferably, the amount is 2 to 50 parts by weight. When the amount is too small, the effect of improving the flame retardancy is small, and when the amount is too large, the mechanical properties of the excellent polybutylene terephthalate resin are unfavorably deteriorated.

The (C) carbonization promoting substance used in the present invention has an oxygen index of 2 which indicates the amount of oxygen necessary for continuing combustion.
By blending 8 or more non-flammable thermoplastic resins, the thermoplastic resin which delays the start of combustion of the resin composition and promotes carbonization to improve flame retardancy, or suppresses the resin from melting and falling during combustion It is a substance that promotes carbonization and a substance that has the effect of a flame-retardant aid that moves to the surface layer during combustion to promote carbonization of the resin and improve flame retardancy. However, the above properties may be duplicated.

Examples of the non-flammable thermoplastic resin having an oxygen index of 28 or more required for combustion include polyetherimide resin, polyphenylene oxide resin, and polyphenylene sulfide resin. In addition, examples of the substance having a flame-retardant aid effect of suppressing the resin from melting and dropping during combustion and promoting carbonization to improve flame retardancy include a fluorine-based resin and a silicone-based compound described below. In addition, substances having a flame-retardant aid effect that moves to the surface layer during the above-mentioned combustion and promotes carbonization of the resin to improve the flame retardancy include:
Examples thereof include phenol resins, phenoxy resins, and epoxy resins described below. Note that the above properties may overlap. It is also possible to use two or more (C) carbonization promoting substances in combination.

Further, the compounding amount of the (C) carbonization promoting substance is
(A) It is preferably 0.1 to 100 parts by weight, particularly preferably 0.5 to 70 parts by weight, based on 100 parts by weight of the polybutylene terephthalate resin. If it is too much, crystallization will be slow and PBT
Impairs excellent injection moldability.

Examples of the polyetherimide resin (C) include a thermoplastic resin having a repeating unit represented by the following general formula, wherein n represents an integer of 1 or more;
For example, it is 10 to 10000. Or, JP
The polyetherimide resin described in JP-A-162547 may be used, and the melt viscosity measured at 370 ° C. is 1000 poise (100 Pa · s), although not limited thereto.
Those having a range of 100 to 100,000 poise (10000 Pa · s) are preferably used. An example of a method for producing a polyetherimide resin is described in US Pat. No. 3,847,867.
No. 3,847,869, U.S. Pat.
885, U.S. Patent No. 3,852,242, and U.S. Patent No. 3,855,178. The above polyetherimide resin has a specific viscosity measured at 25 ° C. using an m-cresol solvent of 0.30 to 1.60, particularly a composition having a range of 0.40 to 1.20. It is suitable in terms of impact strength.

[0035]

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The polyphenylene oxide resin (C) is an amorphous polymer in which a benzene ring and oxygen are bonded, and is not limited, but preferably has a glass transition temperature of about 200 ° C. And a molecular weight of 5,000 to 30,000 is preferably used. Specific examples include poly (2,6-dimethyl-1,4-phenylene) ether,
Poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,
4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-
6-propyl-1,4-phenylene) ether and the like. Further, an alkyl trisubstituted phenol may be copolymerized with the above polyphenylene oxide, a styrene compound may be graft-copolymerized, and an acid anhydride may be graft-copolymerized.

The polyphenylene sulfide resin (C) is a polymer in which a benzene ring and sulfur are bonded, and is not limited, but has a glass transition temperature of about 9%.
0 ° C., a crystalline material having a melting point of about 280 ° C. is preferred, and any of a crosslinked type or a linear type having a high molecular weight by heat treatment at a melting point or lower may be used,
A molecular weight of 10,000 to 40,000 is preferably used, and a glass fiber or a polyphenylene sulfide resin mixed with a plate-like, granular, or layered inorganic filler may be used.

The fluorine-containing resin (C) is a resin containing fluorine in the molecule, for example, polytetrafluoroethylene, polyhexafluoropropylene,
(Tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, (tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, poly Vinylidene fluoride, (vinylidene fluoride / ethylene) copolymer and the like can be mentioned. Among them, polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer Preferred are polymers, (tetrafluoroethylene / ethylene) copolymers, and polyvinylidene fluorides, and particularly preferred are polytetrafluoroethylene and (tetrafluoroethylene / ethylene) copolymers.

The silicone compound (C) includes silicone resin, silicone oil and silicone powder.

As the above silicone resin, a siloxane is chemically bonded to a group selected from a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryl group, a vinyl or allyl group. About 200 to 3 at room temperature.
Although a resin having a viscosity of 000000000 centipoise is preferable, as long as it is the above-mentioned silicone resin, it is not limited thereto, and the product shape may be oil-like, powder-like or gum-like, and an epoxy group as a functional group, A methacle group and an amino group may be introduced, or a mixture with two or more silicone resins may be used.

As the silicone oil, a polyisocyanate in which siloxane is chemically bonded to a group selected from a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryl group, a vinyl or allyl group, and the like. Organosiloxanes, at room temperature of about 0.65 to
A resin having a viscosity of 100,000 centistokes is preferred, but is not limited to the above silicone oil resin, and the product may be in the form of an oil, powder, or gum, and may have an epoxy group as a functional group. A group, a methacle group and an amino group may be introduced, or a mixture with two or more silicone oils or silicone resins may be used.

The silicone powder is obtained by blending the above-mentioned silicone resin and / or silicone oil with an inorganic filler. As the inorganic filler, silica or the like is preferably used.

As the phenolic resin (C),
Any polymer may be used as long as it has a plurality of phenolic hydroxyl groups, and examples thereof include novolak-type, resol-type and heat-reactive resins, and resins modified from these.
These may be an uncured resin, a semi-cured resin, or a cured resin without a curing agent added. Above all, a novolak type phenol resin which is non-thermally reactive without the addition of a curing agent is preferred in terms of flame retardancy, mechanical properties, and economy.

The shape is not particularly limited, and any of pulverized products, granules, flakes, powders, needles, liquids and the like can be used, and if necessary, one or more kinds can be used. The phenolic resin is not particularly limited, and a commercially available phenolic resin is used. For example,
In the case of a novolak-type phenol resin, the phenols and the aldehydes are charged into the reaction tank at a molar ratio of 1: 0.7 to 1: 0.9, and oxalic acid, hydrochloric acid, sulfuric acid, toluenesulfonic acid and the like are further charged. After adding the catalyst of the above, heating,
The reflux reaction is performed for a predetermined time. Vacuum dehydration or static dehydration to remove generated water, and further, a method of removing remaining water and unreacted phenols can be obtained. The co-condensed phenol resin obtained by using these resins or a plurality of raw material components can be used alone or in combination of two or more.

In the case of a resole type phenol resin,
The molar ratio of phenols to aldehydes is 1: 1 to 1: 2
After charging into a reaction tank at such a ratio as follows and adding a catalyst such as sodium hydroxide, aqueous ammonia, or another basic substance, the same reaction and treatment as for the novolak type phenol resin can be performed.

Here, the phenols include phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, te
rt-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4'-dihydroxyphenyl-2,2-propane, isoamyl salicylate,
Benzyl salicylate, methyl salicylate, 2,6-di-
tert-butyl-p-cresol and the like. One or more of these phenols can be used. On the other hand, examples of the aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, and trioxane. One or more of these aldehydes can be used as needed.

The molecular weight of the phenolic resin is not particularly limited, but is preferably 200 to 2,000 in number average molecular weight.
In particular, those having a range of 400 to 1,500 are preferable because of excellent mechanical properties, fluidity and economy. The molecular weight of the phenolic resin can be measured by gel permeation chromatography using a tetrahydrafuran solution and a polystyrene standard sample.

The phenoxy resin (C) can be obtained by reacting an aromatic dihydric phenol compound with epichlorohydrin at various mixing ratios. The molecular weight of the phenoxy resin phenoxy copolymer is not particularly limited, but the viscosity average molecular weight is 1,000 to 10,000.
It is in the range of 0. Here, examples of the aromatic dihydric phenol compound include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and bis (4 −
Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5 diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, -Phenyl-1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) methane and the like can be used, and these can be used alone or as a mixture. In addition, the shape is not particularly limited, pulverized products,
Any of granules, flakes, powders, and liquids can be used. One or more of these phenoxy resins can be used as necessary.

As the epoxy resin (C), one or more epoxy compounds selected from glycidyl ester compounds, glycidyl ether compounds and glycidyl ester ether compounds can be added. As the above epoxy compound, an epoxy compound having an epoxy equivalent of less than 1,000 is preferable. Here, the epoxy equivalent refers to the number of grams of an epoxy compound containing 1 gram equivalent of epoxy group. Here, as an example of measuring the epoxy equivalent, an epoxy compound is dissolved in pyridine, 0.05N hydrochloric acid is added, and the mixture is heated at 40 to 45 ° C. Then, a mixture of thymol blue and cresol red is used as an indicator. A method of back titration with 05N caustic soda is known.

Further, among the (C) carbonization promoting substances, substances preferably used are a pophenylene oxide resin, a fluorine-based resin and a phenol resin, and a particularly preferably used substance is a polyphenylene oxide resin.

The (D) polycarbonate resin used in the present invention includes an aromatic homo- or copolycarbonate obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. The aromatic homo- or copolycarbonate resin,
The viscosity average molecular weight is usually in the range of 10,000 to 1,000,000, and the viscosity average molecular weight is 10,000 to 10
Within the range of 00000, polycarbonate resins having different viscosity average molecular weights may be used in combination. Here, as the dihydric phenol compound, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane , 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-
3,5-diphenyl) butane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2
-Bis (4-hydroxy-3,5-diethylphenyl)
Propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane and the like can be used, and these can be used alone or as a mixture. (D)
The amount of the polycarbonate resin to be added is less than 11 to 100 parts by weight based on the total of 100 parts by weight of the components (A) and (C), in view of the effect of improving the flame retardancy and the crystallinity of the obtained composition. It is necessary that the amount is less than 100 parts by weight based on 100 parts by weight of the component (A). Further, the component (D) is preferably 15 to 90 parts by weight, more preferably 20 to 70 parts by weight, based on 100 parts by weight of the total of the components (A) and (C).

In the present invention, by further mixing (E) a polyester resin, it is possible to improve the strength and fluidity without lowering the flame retardancy.
Examples of the (E) polyester resin include polyester resins other than the above (A) polybutylene terephthalate resin, such as polyethylene terephthalate resin, polyester elastomer, polyarylate resin, wholly aromatic liquid crystal polyester, semi-aromatic liquid crystal polyester, and polycyclohexane. It is a dimethylene terephthalate resin, and a polyethylene terephthalate resin and a polyarylate resin are particularly preferable.

The amount of the polyester resin (E) is from 1 to 100 parts by weight of the polybutylene terephthalate resin (A) in view of the effect of improving the flame retardancy and the crystallinity of the obtained polybutylene terephthalate resin composition. 100 parts by weight, preferably 2 to 90 parts by weight, more preferably 5 to 7 parts by weight
5 parts by weight.

The polyethylene terephthalate resin (E) preferably used in the polyester resin is as follows:
Terephthalic acid as an acid component, polycondensed using ethylene glycol as a glycol component, refers to a high-molecular-weight thermoplastic polyester resin having an ester bond in the main chain, as well as other acid components, isophthalic acid, adipic acid, Oxalic acid or the like, as a glycol component, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, or the like, or Long-chain glycols having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol or the like can be copolymerized in an amount of 20 mol% or less. In addition, polyethylene terephthalate resin is prepared by using an O-chlorophenol solvent.
It is suitable from the viewpoints of impact strength and moldability of a composition that can be obtained having an intrinsic viscosity measured at 5 ° C. in the range of 0.36 to 1.60, particularly 0.45 to 1.15.

In the present invention, it is possible to improve the strength without lowering the flame retardancy by further adding (F) a fibrous reinforcing material. , Glass fiber, aramid fiber, carbon fiber and the like. The above-mentioned glass fiber is a chopped strand type or roving type glass fiber used for an ordinary PBT reinforcing material, and is a silane coupling agent such as an aminosilane compound or an epoxysilane compound and / or urethane, vinyl acetate, bisphenol A. Glass fibers treated with a sizing agent containing one or more epoxy compounds such as diglycidyl ether and novolak epoxy compounds are preferably used.
Further, the above silane coupling agent and / or sizing agent may be used in an emulsion liquid. The compounding amount of the (F) fibrous reinforcing material is preferably 5 to 200 parts by weight, particularly preferably 6 to 200 parts by weight, per 100 parts by weight of the (A) polybutylene terephthalate resin, in view of flame retardancy and fluidity during molding. 190 parts by weight. In addition, glass flakes, kaolin, silica, glass beads, milled fiber, potassium whisker,
Fillers such as wollastenite, barium carbonate, calcium carbonate and the like and metal fibers may be used, and the compounding amount is preferably not more than the compounding amount of the fiber reinforcing agent of the present invention.

In the present invention, the flame retardancy can be improved by further blending (G) a phosphate ester.
And at least one phosphoric acid ester selected from pentavalent phosphonite compounds and phosphinite compounds or pentavalent phosphate compounds, phosphite compounds, phosphinate compounds and phosphonate compounds. Esters can be used. Specific examples include tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tris isopropiphenyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl. Phosphate, orthophenylphenol phosphate, pentaerythritol phosphate, neopetyl glycol phosphate, substituted neopetyl glycol phosphonate, nitrogen-containing phosphate, resorcinol bis (diphenyl phosphate) of aromatic bisphosphates ,
Examples thereof include resorcinol bis (dixylenyl phosphate) and hydroquinone bis (dixylenyl phosphate), and aromatic bisphosphates are particularly preferably used.

The amount of the phosphate ester (G) is as follows:
(A) 0.1 to 75 parts by weight, preferably 1 to 60 parts by weight, more preferably 2 to 50 parts by weight, based on 100 parts by weight of polybutylene terephthalate. Further, it is preferable that the compounding amount is smaller than (B) the phosphonitrile linear polymer and / or the cyclic polymer. In some cases, problems such as bleed out (precipitation) may occur.

In the present invention, the flame retardancy can be improved by further blending the (H) triazine compound with a salt of cyanuric acid or isocyanuric acid. The acid or isocyanuric acid salt is preferably an adduct of cyanuric acid or isocyanuric acid with a triazine-based compound, usually 1 to 1 (molar ratio), and sometimes 1 to 2 in some cases.
(Molar ratio). Of the triazine compounds, those that do not form a salt with cyanuric acid or isocyanuric acid are excluded.

Among (H) salts of triazine compounds with cyanuric acid or isocyanuric acid, melamine, benzoguanamine, acetoguanamine, 2-amide-4,6-diamino-1,3,5-triazine, Mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine, and tri (hydroxymethyl) melamine salts are preferred, and melamine, benzoguanamine, and acetoguanamine salts are particularly preferred, and are produced by known methods. A mixture of the compound and cyanuric acid or isocyanuric acid is made into a water slurry, mixed well to form both salts into fine particles, and then the slurry is filtered and dried, and is generally obtained in powder form. Also,
The above-mentioned salt does not need to be completely pure, and a somewhat unreacted triazine-based compound or cyanuric acid or isocyanuric acid may remain.

The average particle size of the salt before being mixed with the resin is preferably 100 to 0.01 μm from the viewpoints of flame retardancy, mechanical strength, wet heat resistance, retention stability and surface properties of the molded product. And more preferably 80 to 10 μm. When the dispersibility of the salt is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination.

The amount of the above salt is usually 0.1 to 75 parts by weight, preferably 1 to 60 parts by weight, more preferably 2 to 60 parts by weight, based on 100 parts by weight of the polybutylene terephthalate resin.
50 parts by weight.

In the present invention, the lowering of the melting point can be improved by further mixing (I) phosphoric acid. Such (I) phosphoric acid includes phosphoric acid, phosphorous acid, phosphonic acid, Phosphoric acid such as phosphinic acid and phosphonium salt; examples thereof include, but are not limited to, phosphoric acid, triethyl phosphate, trimethyl phosphate, polyphosphoric acid and phosphate, and particularly phosphoric acid and triethyl phosphate; It is preferably used. The compounding amount of phosphoric acid is 0.1 to 5 parts by weight, preferably 0.1 to 3 parts by weight, more preferably 0.1 to 2 parts by weight based on 100 parts by weight of the polybutylene terephthalate resin (A). If it exceeds 5 parts by weight, the impact strength is impaired, which is not preferable.

In the present invention, ethylene (co)
It is possible to improve the toughness by adding one or more polymers. Examples of such an ethylene (co) polymer include ethylene polymers and / or ethylene copolymers such as high-density polyethylene, low-density polyethylene, and ultra-low-density polyethylene, and the above-mentioned ethylene copolymer includes ethylene and ethylene and It is obtained by copolymerizing a copolymerizable monomer. Examples of the copolymerizable monomer include propylene, butene-1, vinyl acetate, isoprene, butadiene and monocarboxylic acids such as acrylic acid and methacrylic acid, and ester acids thereof, maleic acid, dicarboxylic acids such as fumaric acid and itaconic acid, and the like. No. The ethylene copolymer can be usually produced by a known method. Specific examples of the ethylene copolymer include ethylene / propylene, ethylene / butene 1, ethylene / vinyl acetate, ethylene / ethyl acrylate, ethylene / methyl acrylate, and ethylene / propylene.
Ethyl methacrylate acrylate and the like. Further, a copolymer obtained by grafting or copolymerizing the above ethylene (co) polymer with an acid anhydride or glycidyl methacrylate is also preferably used. These may be used alone or in combination of two or more, and may be used by mixing with one or more of the above ethylene (co) polymers. In addition, ethylene (co)
Among the polymers, a copolymer obtained by grafting or polymerizing an acid anhydride or glycidyl methacrylate to polyethylene is preferably used because of its good compatibility with PBT.
Further, the addition amount of the ethylene (co) polymer is preferably 1 to 50 parts by weight, particularly preferably 100 parts by weight of the polybutylene terephthalate resin (A) from the viewpoint of mechanical properties and flame retardancy of the obtained composition. Is 1 to 40 parts by weight or less.

In the present invention, the toughness can be improved by further adding one or more styrene resins. Examples of such a styrene-based resin include resins containing 10% or more of styrene, and are not limited thereto. Specific examples thereof include polystyrene resin, acrylonitrile / styrene resin, and acrylonitrile / polybutadiene (acrylonitrile or styrene is contained. / Styrene resin, acrylonitrile / polybutadiene / methyl methacrylate / styrene resin, high impact polystyrene resin, styrene / polybutadiene / styrene resin, styrene / butadiene resin, styrene / polyisoprene / styrene resin, styrene / ethylene / polybutadiene / Styrene resins and the like, and monocarboxylic acids, dicarboxylic acids, acid anhydrides or copolymers obtained by grafting or copolymerizing glycidyl methacrylate may be used. Grafted anhydride or glycidyl methacrylate or a copolymer styrenic resin in compatibility with PBT well is preferably used. Further, the addition amount of the styrene resin is preferably from 0.1 to 30 parts by weight, particularly preferably 100 parts by weight of the polybutylene terephthalate resin (A), from the viewpoint of the mechanical properties and flame retardancy of the obtained composition. It is 0.5 to 20 parts by weight or less.

In the present invention, the strength can be improved by further adding one or more layered inorganic fillers. Such a layered inorganic filler is an inorganic compound having a layered crystal structure in which unit crystal layers are stacked on each other and having cleavage properties. Specific examples of the layered inorganic filler include kaolinite, talc, smectite-based clay minerals (montmorillonite, hectorite), silicates such as vermiculite, mica, and fluoroteniolite, and phosphates such as zirconium phosphate and titanium phosphate. These inorganic layered compounds may be subjected to a coupling agent treatment or an organic treatment for ion-exchanging the inorganic ions with organic ions for those having an inorganic ion between layers. The amount of the layered inorganic filler to be added is usually 0.1 to 100 parts by weight of (A) polybutylene terephthalate from the viewpoint of the impact strength of the obtained composition.
It is 1 to 30 parts by weight, preferably 0.1 to 25 parts by weight. Further, the average particle size of the layered inorganic filler is preferably from 0.1 to 20 μm, particularly preferably from 0.2 to 10 μm from the viewpoint of impact strength.

In the present invention, it is possible to improve fluidity and mold release during molding by further adding one or more lubricants. Examples of such a lubricant include metal soaps such as calcium stearate and barium stearate, fatty acid esters, salts of fatty acid esters (including partially salted forms), fatty acid amides such as ethylenebisstearamide, ethylenediamine and stearic acid. And fatty acid amides comprising polycondensates of sebacic acid or polycondensates of phenylenediamine with stearic acid and sebacic acid, polyalkylene waxes, acid anhydride-modified polyalkylene waxes and the above lubricants and fluororesins or fluorine compounds. Mixtures include, but are not limited to. The amount of the lubricant to be added is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of polybutylene terephthalate.

In the present invention, heat-expandable graphite is further used.
It is also possible to improve the color tone by blending one or more types of carbon black and titanium oxide. The blending amount is 0% based on 100 parts by weight of the polybutylene terephthalate resin (A) in view of the mechanical properties of the resulting composition. 0.1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight,
More preferably, it is 0.1 to 15 parts by weight.

In the present invention, by blending one or more hindered phenol-based stabilizers and / or phosphite-based stabilizers, extremely good heat aging resistance can be obtained even when exposed to a high temperature for a long time. An example of such a hindered phenol-based stabilizer is triethylene glycol-bis [3- (3-t-butyl-5-
Methyl-4-hydroxyphenyl) propionate],
1,6-hexanediol-bis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,
5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis or tris (3-t
-Butyl-6-methyl-4-hydroxyphenyl) propane, N, N'-hexamethylenebis (3,5-di-t
-Butyl-4-hydroxy-hydrocinnamamide),
N, N'-trimethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) and the like. Examples of the phosphite-based stabilizer include tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl osfite, Trisnonylphenyl phosphite, alkyl allyl phosphite, trialkyl phosphite, triallyl phosphite, pentaerythritol phosphite compound and the like can be mentioned. The amount of the hindered phenol-based stabilizer and / or the phosphite-based stabilizer may be adjusted depending on the mechanical properties of the resulting composition.
The amount is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 4 parts by weight, still more preferably 0.1 to 5 parts by weight with respect to 0 parts by weight.
1 to 3 parts by weight.

In the present invention, one or more known non-halogen flame retardants other than the present invention can be further added. Such known non-halogen flame retardants include, but are not limited to, for example, aluminum hydroxide, magnesium hydroxide, hydrotalcite, boric acid, calcium borate, calcium borate hydrate, zinc borate, zinc borate hydrate. , Zinc hydroxide, zinc hydroxide hydrate, zinc tin hydroxide, zinc tin hydroxide hydrate, red phosphorus, dawsonite, etc., all of which contain 50% or more of the main component of the flame retardant. If surface coating, surface treatment may be applied,
A mixture of these flame retardants and other components may be used. The compounding amount of the known non-halogen flame retardant is 0.1 to 100 parts by weight of the polybutylene terephthalate resin (A) in view of mechanical properties and coloring properties of the obtained composition.
It is preferably 20 parts by weight, more preferably 0.5 to 15 parts by weight, still more preferably 1 to 10 parts by weight.

Further, the flame-retardant polybutylene terephthalate resin composition and the molded article of the present invention may be sulfur-based antioxidants, ultraviolet absorbers, mold release agents, plasticizers, as long as the object of the present invention is not impaired. UV inhibitors and dyes,
A material in which one or more known additives such as a coloring agent including a pigment are blended can also be used.

The flame-retardant polybutylene terephthalate resin and molded article of the present invention are produced by a generally known method. For example, (A) polybutylene terephthalate resin, (B)
A phosphonitrile linear polymer and / or cyclic polymer, (C) a carbonization promoting substance, and (D) a polycarbonate resin, if necessary, (E) a polyester resin, (F)
Premixing fiber reinforcing material, (G) phosphate ester, (H) salt of triazine compound and cyanuric acid or isocyanuric acid, and (I) phosphoric acid, and if necessary, other necessary additives The resin composition is prepared by being supplied to an extruder or the like without or with sufficient melting and kneading.

As an example of the above premixing, the effect of the present invention can be exerted only by dry blending, but mixing using a mechanical mixing device such as a tumbler, a ribbon mixer, and a Henschel mixer can be mentioned. Further, (F) a method may be used in which the fiber reinforcing material is added by installing a side feeder in the middle of the base portion and the vent portion of a multi-screw extruder such as a twin-screw extruder. In the case of liquid,
It is a method of installing a liquid addition nozzle in the middle of the filling part and vent part of a multi-screw extruder such as a twin-screw extruder and adding a plunger pump, or a method of supplying with a metering pump from the filling part. Is also good.

In producing the flame-retardant polybutylene terephthalate resin composition, for example, but not limited to, a single-screw extruder or a twin-screw extruder equipped with a “Unimelt” or “Dalmage” type screw And a three-screw extruder and a kneader-type kneader.

The flame-retardant polybutylene terephthalate resin composition thus obtained can be usually molded by a known method. For example, injection molding, extrusion molding, compression molding, sheet molding, film molding, etc. In particular, injection molding is preferable, and a molded product obtained by an injection molding method by insert molding in which a part of a metal component is directly integrated with the molded product may be used.

Further, the molded article made of the flame-retardant polybutylene terephthalate resin composition of the present invention maintains safety against fire inside the equipment and excellent mechanical properties of polybutylene terephthalate. Products,
It is a molded product suitable for electrical parts such as housings for OA equipment, coil bobbins, connectors, relays, disk drive chassis and transformers, mechanical mechanism parts and automobile parts. The present invention is particularly useful for electric and electronic parts because it can maintain a high dielectric breakdown voltage and appearance of a molded product particularly over a long period of time.

[0076]

The effects of the present invention will be described in more detail with reference to the following examples. Here, all parts are parts by weight. The measuring method of each characteristic is as follows.

Reference Example 1 (A) Polybutylene terephthalate <A-1> Toray PBT1100S which is a polybutylene terephthalate (PBT) resin (manufactured by Toray Industries, Inc.)
It was used.

Reference Example 2 (B) Phosphonitrile Linear Polymer and / or Cyclic Phosphonitrile Linear Polymer <B-1> A dichlorophosphazene oligomer having a number average degree of polymerization n = 20 and phenol are added in the presence of triethylamine. And evaporate the resulting reaction solution.
-To dryness, the residue was washed with water to remove salts. Further purification was carried out by washing with acetone and then ethanol. The yield was 90%, n = 20.

Reference Example 3 (B) Phosphonitrile Linear Polymer and / or Phosphonitrile Cyclic Polymer of Cyclic Polymer <B-2> Hexachlorocyclotriphosphazene (cyclic trimer) is reacted with phenol in the presence of triethylamine. The obtained reaction solution was evaporated and dried, and the residue was washed with water to remove salts. Further, it was purified by washing with acetone and then with ethanol. The yield was 95%, n = 3.

Reference Example 4 (C) Polyetherimide resin (hereinafter abbreviated as PEI resin) as a carbonization promoting substance <C-1>"Ultem" 1000 (manufactured by General Electric) was used. The melt viscosity is about 500
It was 0 poise (Koka type flow tester, 370 ° C., shear rate 1000 sec ⁻¹ ).

Reference Example 5 (C) Polyphenylene oxide resin as a carbonization promoting substance (hereinafter abbreviated as PPO resin) <C-2> HPX100L (manufactured by Mitsubishi Chemical Corporation) Reference Example 6 (C) Polyphenylene sulfide resin as a carbonization promoting substance ( Hereinafter, abbreviated as PPS resin) <C-3> “TORELINA” A504 (manufactured by Toray Industries, Inc.) was used.

Reference Example 7 (C) Fluorinated resin of carbonization promoting substance <C-4> Polytetrafluoroethylene “Teflon 6J” (manufactured by Du Pont-Mitsui Fluorochemicals) was used.

Reference Example 8 (C) Silicone compound of carbonization promoting substance <C-5> Silicone powder “DC4-710”
5 "(manufactured by Dow Corning Toray Silicone Co., Ltd.).

Reference Example 9 (C) Phenolic resin of carbonization promoting substance <C-6> Novolak type phenol resin "Sumilite Resin" PR53195 (manufactured by Sumitomo Durez) was used.

Reference Example 10 (C) Phenoxy resin of carbonization promoting substance <C-7>"Phenototo" YP-50 (manufactured by Toto Kasei Co., Ltd.) was used.

Reference Example 11 (C) Epoxy resin of carbonization promoting substance <C-8> Bisphenol A diglycidyl ether “Epicoat” 1002 Epoxy equivalent 650 (manufactured by Yuka Shell Epoxy) was used.

Reference Example 12 (D) Polycarbonate resin (hereinafter abbreviated as PC resin) <D-1>"Iupilon" S3000 (manufactured by Mitsubishi Engineering-Plastics Corporation) was used.

Reference Example 13 (E) Polyester resin <E-1>"MitsuiPET" J005 (manufactured by Mitsui Pet Resin Co., Ltd.), having an intrinsic viscosity of 0.63 (25 ° C., 1: 1 phenol / tetrachloroethane mixed solvent) ) Polyethylene terephthalate resin (hereinafter abbreviated as PET resin).

Reference Example 14 (F) Glass Fiber <F-1> A chopped strand glass fiber “CS3 J948” (manufactured by Nitto Boseki) having a fiber diameter of about 10 μm was used.

Reference Example 15 (G) Phosphate Ester <G-1> Resorcinol bis (dixylenyl phosphate) "PX-200" (manufactured by Daihachi Chemical Co., Ltd.) was used.

Reference Example 16 (H) Salt of triazine compound and cyanuric acid or isocyanuric acid <H-1> Melamine cyanurate “MCA” (manufactured by Mitsubishi Chemical Corporation) was used (hereinafter abbreviated as MC salt). ).

Reference Example 17 (I) Phosphoric Acid <I-1> Triethyl phosphate of the first grade was used.

Examples 1 to 23 and Comparative Examples 1 to 14 (A) Polybutylene was prepared using a twin screw extruder (TEX-30α, manufactured by Nippon Steel Works) having a screw diameter of 30 mm and an L / D 35 co-rotating vent. Terephthalate resin (PB)
T), (B) a phosphonitrile linear polymer and / or
Or a cyclic polymer, (C) a carbonization promoting substance, (D) a polycarbonate resin, and other additives (E),
(G), (H), and (I) were mixed in the composition shown in Table 1 and added from the filling portion. Further, a compound having an addition amount shown in Table 3 was added from the main filling section in the same manner as described above, except that a glass fiber was added by placing a side feeder in the middle of the main filling section and the vent section. The kneading temperature 27
0 ° C (300 ° C for a compound using polyphenylsulfide resin as a carbonization promoting substance), screw rotation 150 rpm
The mixture was melt-mixed under extrusion conditions of m, discharged in a strand shape, passed through a cooling path, and pelletized by a strand cutter.

After drying the obtained pellets, each test piece was molded by an injection molding machine, and the physical properties were measured under the following conditions. Tables 2 and 4 show the results. (1) Flame retardancy Using a Toshiba Machine's IS55EPN injection molding machine, a test piece for flame retardancy evaluation was injection molded at a molding temperature of 270 ° C and a mold temperature of 80 ° C, and the evaluation specified in UL94. Flame retardancy was evaluated according to criteria. Flame retardancy level is V-0>
V-1>V-2> HB. The thickness of the test piece was 1/16 inch (about 1.59 mm) and 1/32
Inch (approximately 0.79 mm) thickness is used, and the smaller the thickness is, the more severe the flame retardancy is determined. (2) Tensile strength Using a Toshiba Machine's IS55EPN injection molding machine, a 3 mm thick AS was used at a molding temperature of 270 ° C and a mold temperature of 80 ° C.
Injection molding of TM1 dumbbell pieces and ASTM D6
The tensile strength was measured according to No. 38. (3) Fluidity Injection molding of a 1/16 inch (approximately 1.59 mm) thick flame-retardant evaluation test piece at a molding temperature of 270 ° C and a mold temperature of 80 ° C using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd. Was performed to determine a molding lower limit pressure of a minimum molding pressure at which the test piece was filled.

The lower the molding minimum pressure, the better the fluidity during injection molding. (4) Insulation Breakdown Voltage Injection molding was performed using a Toshiba Machine's IS55EPN injection molding machine at a molding temperature of 270 ° C. and a mold temperature of 80 ° C.
A square plate of 0 mm x 80 mm x 3 mm thickness was used as a sample, and AS
The dielectric breakdown voltage was determined according to the test method of the TM D149 standard. Furthermore, the above-mentioned square plate is heated at 121 ° C. and 100% RH.
Was charged for 200 hours into a pressure cooker tester made of TABAI ESPEC CORP set under the conditions described in (1), and the dielectric breakdown voltage was determined again. (5) Appearance of Molded Article The appearance of the square plate before and after the treatment in the pressure cooker tester of the above (4) was visually observed, and the appearance was judged according to the following criteria.

：: No problem in appearance of molded article surface △: Irregularities or bleed-out observed on part of molded article surface ×: Irregularities or bleed-out observed on 1/4 or more of total surface area of molded article

[0097]

[Table 1]

[0098]

[Table 2]

[0099]

[Table 3]

[0100]

[Table 4]

From the evaluation results of Examples 1 to 10 in Table 2, P
By blending a BT resin with a phosphonitrile linear polymer and / or cyclic polymer, a carbonization promoting substance and a PC resin, a resin composition having excellent mechanical properties and excellent fluidity during injection molding while maintaining high flame retardancy is obtained. It can be seen that the obtained high dielectric breakdown voltage and the appearance of the molded product are maintained for a long time.

On the other hand, from Comparative Examples 1 to 3 and Comparative Examples 6 to 8 in Tables 2 and 4, one component of a phosphonitrile linear polymer and / or cyclic polymer, a carbonization promoting substance and a PC resin was added to the PBT resin. It is clear that uncombined compositions do not provide materials with a high degree of flame retardancy. Further, the composition of Comparative Example 1 is inferior not only in flame retardancy but also in fluidity. In addition, the composition of Comparative Example 3 was inferior not only in flame retardancy but also in dielectric breakdown voltage and appearance of the molded product after the pleat cooker treatment, and a highly reliable molded product was not obtained over a long period of time. I understand.

Also, from Examples 11 to 23 in Tables 1 and 4, when two or more carbonization promoting substances of the present invention were used, the fibrous reinforcing material, phosphate ester, MC salt, and phosphoric acid were removed. Even when used, a resin composition having excellent mechanical properties and fluidity during injection molding can be obtained without lowering high flame retardancy, and it can be seen that a high dielectric breakdown voltage and a molded article appearance are maintained for a long time.

Also, by blending the fibrous reinforcing materials of Examples 16 to 23, the tensile strength is dramatically increased,
A high-strength flame-retardant PBT resin can be obtained. Example 1
From the comparison of 6 to 18, it is possible to obtain a material having higher flame retardancy by adding a phosphate ester or an MC salt. Further, by blending the phosphoric acid of Example 19, the heat distortion temperature (ASTM) was higher than that of the composition of Example 16 which was not shown in the table but did not contain phosphoric acid.
A composition having excellent heat resistance with a D256 load of 0.45 MPa) was obtained.

Also, from Comparative Examples 4 and 9 in Tables 2 and 4, when the blending amount of the PC resin of the present invention is less than 11 parts by weight with respect to the total of 100 parts by weight of the PBT resin and the carbonization promoting substance,
In particular, it is found that the appearance of the molded product, the breakdown voltage after the pressure cooker treatment, and the appearance of the molded product are inferior, and a highly reliable molded product cannot be obtained over a long period of time.

Further, Comparative Examples 5 and 10 of Tables 2 and 4
Therefore, when the amount of the PC resin of the present invention exceeds 100 parts by weight with respect to 100 parts by weight of the PBT resin, the dielectric breakdown voltage after the pressure cooker treatment and the appearance of the molded product are inferior, and the reliability is high over a long period of time. It can be seen that a molded article having a defect cannot be obtained.

As Comparative Example 11, nylon 66 having an oxygen index of 24.3 (dry product, “Amilan” CM30 manufactured by Toray Industries Inc.) was used in place of the carbonization promoting substance PPO resin of Example 23.
01-N) were blended in the same amount and evaluated in the same manner. As a result, the flame retardancy was HB, and the flame retardancy was poor. Therefore,
It is clear that a high degree of flame retardancy can be obtained by combining a specific carbonization promoting substance with a PC resin.

Further, as Comparative Examples 12 to 14, Example 4
Styrene / acrylonitrile copolymer (copolymerization ratio 78/28 (% by weight)) in place of PBT of No.
When the evaluation was performed in the same manner, a material showing the flame retardancy was not obtained because it did not apply to HB, which had the lowest flame retardancy. Therefore, it is apparent that a high degree of flame retardancy can be obtained by combining PBT with a specific phosphonitrile linear polymer and / or cyclic polymer, a carbonization promoter, and a PC resin.

[0109]

According to the present invention, a PBT resin is prepared by adding a phosphonitrile linear polymer and / or a cyclic polymer, a carbonization promoting substance and PC.
By blending resin, it is a non-halogen flame-retardant P which has high flame retardancy, excellent mechanical properties and fluidity during injection molding, and maintains high breakdown voltage and appearance of molded products for a long time.
It is possible to obtain a BT resin composition and a molded product, and it can be expected to greatly contribute to market expansion of automobile parts, electric / electronic parts and mechanical parts.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 7/02 C08K 7/02 C08L 69/00 C08L 69/00 85/02 85/02 101/00 101 / 00 F-term (reference) 4F071 AA27 AA41 AA42 AA45 AA46 AA50 AA51 AA60 AA63 AA67 AA68 AB28 AC12 AC15 AE07 AF47 AH07 AH12 AH17 BA01 BB05 BC03 4J002 BD12Y BD14Y BD15Y BD16Y CC03Y CC04U CF00Y CF04U CF00Y CF04U CP03Y CQ01X DA016 DH029 DL006 EU188 EU198 EW047 EW067 EW117 FA046 FB086 FB096 FB146 FD010 FD016 FD030 FD090 FD130 FD137 FD170 GM00 GN00 GQ00

Claims (9)

[Claims] 1. A polybutylene terephthalate resin (A)
(B) 0.1 to 100 parts by weight of a phosphonitrile linear polymer and / or cyclic polymer having a number average degree of polymerization of 3 or more having a repeating unit of the general formula (1), and 0.1 to 100 parts by weight of an accelerating substance,
And (D) 11 to 100 parts by weight of the polycarbonate resin based on 100 parts by weight of the total of the components (A) and (C).
Less than 10 parts by weight and 100 parts by weight of component (A)
A flame-retardant polybutylene terephthalate resin composition containing less than 0 parts by weight. Embedded image (In the above formula, A and B are the same or different O, N,
Represents S. R1 and R2 are the same or different and have 1 to 1 carbon atoms.
15 represents an aryl group, an alkyl group, an aralkyl group, or a cycloalkyl group, and may have a cyclic structure in which R1 and R2 are linked. x and y represent 0 or 1. ) (C) The carbonization promoting substance is a polyetherimide resin, a polyphenylene oxide resin, a polyphenylene sulfide resin, a fluorine resin, a silicone compound,
The flame-retardant polybutylene terephthalate resin composition according to claim 1, wherein at least one selected from a phenol resin, a phenoxy resin and an epoxy resin is blended. 3. A polybutylene terephthalate resin (A)
(E) 1 to 1 part by weight of polyester resin
3. The flame-retardant polybutylene terephthalate resin composition according to claim 1, further comprising 00 parts by weight. 4. A polybutylene terephthalate resin (A)
The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 3, further comprising (F) 5 to 200 parts by weight of a fibrous reinforcing material with respect to 00 parts by weight. 5. A polybutylene terephthalate resin (A)
(G) 0.1 to 7 parts by weight of phosphate ester
The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 4, further comprising 5 parts by weight. 6. A polybutylene terephthalate resin (A)
0.1 to 75 parts by weight of a salt of the (H) triazine compound and cyanuric acid or isocyanuric acid with respect to 00 parts by weight.
The flame-retardant polybutylene terephthalate resin composition according to claim 1, further comprising parts by weight. 7. A polybutylene terephthalate resin (A)
The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 6, further comprising 0.1 to 5 parts by weight of phosphoric acid (I) based on 00 parts by weight. 8. A molded article comprising the flame-retardant polybutylene terephthalate resin composition according to claim 1. 9. A molded article for a mechanical mechanism part, an electric / electronic part or an automobile part, comprising the flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 7.