JPH11323105A - Flare-retardant polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant polyester resin compsn. which gives a flame-retardant molded article excellent in weld strength by compounding a thermoplastic polyester resin with an organophosphorus flame retardant, stabilized red phosphorus, a melamine-cyanuric acid adduct, an ethylene-alkyl (meth) acrylate copolymer, and glass fibers. SOLUTION: This compsn. is prepd. by compounding (A) 30-70 wt.% thermoplastic polyester resin with (B) 0.5-20 wt.% organophosphorus flame retardant, (C) 0-5 wt.% red phosphorus flame retardant stabilized by coating, (D) 4-20 wt.% melamine-cyanuric acid adduct, (E) 0.5-15 wt.% copolymer having a melt index (according to JIS K 6730) of 2-500 g/10 min and comprising 30-90 wt.% ethylene units, 10-50 wt.% (1-10C)-alkyl (meth)acrylate units., etc., and (F) 5-50 wt.% glass fibers. Pref., ingredient B is a condensed phosphoric ester flame retardant of the formula (wherein R<1> to R<17> are each H or 1-4C alkyl; Y is a direct bond, a methylene group, or the like; n is 0 or 1; and m is 1-10).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant polyester resin composition containing no bromine, chlorine-based flame retardant and antimony compound.

[0002]

2. Description of the Related Art Thermoplastic polyester resins represented by polyalkylene terephthalate and the like are widely used for electric and electronic equipment parts, automobile parts, and the like because of their excellent properties. In recent years, especially in the field of electric and electronic equipment parts, UL-9
4 (US Underwriters Laboratory Standard) V-0 is required in many cases, and a high degree of flame retardancy is required. For this reason, various flame retardant compounds have been studied.

[0003] When imparting flame retardancy to a thermoplastic polyester resin, a halogen-based flame retardant is generally used as a flame retardant.
It is used in combination with a flame retardant aid such as antimony trioxide if necessary. However, although halogen-based flame retardants have a large flame-retardant effect, the halogen compounds generated by decomposition of the halogen-based flame retardants during resin processing corrode the surfaces of the compound extruder cylinders and molding dies. was there. For this reason, a method of flame retardation without using any halogen-based flame retardant has been studied.

As such a flame retardant, various uses of a nitrogenous flame retardant such as an organic phosphorus flame retardant or a triazine compound (for example, melamine / cyanuric acid adduct) have been studied.
As organophosphorus flame retardants, triphenyl phosphate,
In addition to cresyl diphenyl phosphate, tricresyl phosphate, and the like, organic phosphorus-based flame retardants having relatively large molecular weights such as phosphate ester condensates have recently been studied due to problems such as heat resistance and bleeding of flame retardants. . Examples of the flame-retardant resin composition using such a phosphorus-based flame retardant include JP-B-51-19858, JP-B-51-39271, and JP-A-52-102255. Further, in order to achieve a higher degree of flame retardancy, a method of further using a nitrogen-based flame retardant has been studied. For example, JP-A-3-281652 discloses a melamine / cyanuric acid adduct and a phosphorus-based flame retardant. A method using a flame retardant in combination is disclosed in
No. 70671 and JP-A-6-157880 disclose:
A method for improving flame retardancy, generation of toxic gas, and corrosiveness by using a melamine / cyanuric acid adduct and a specific phosphorus-based flame retardant is disclosed. The present inventors have also added mechanical phosphorus and organic phosphorus-based flame retardants to a thermoplastic polyester resin, and mechanical strength and impact resistance generated when a triazine compound such as melamine / cyanuric acid adduct is used as a nitrogen-based flame retardant. It has been found that the decrease in moisture resistance can be improved by using a compound having two or more functional groups in the same molecule such as a diepoxy compound in combination.
And Japanese Patent Laid-Open No. 7-233311.

[0005]

In recent years, in electric / electronic parts and housing parts, in order to make the products themselves more sophisticated and lower in cost, integration of parts as much as possible has been promoted. For this reason, it is no longer possible to use different materials for each part according to the required characteristics as in the past, for example, various characteristics such as higher flame retardancy, tracking resistance, heat resistance, mechanical strength, etc. It was to be required at the same time. In addition, the integration of parts requires that the shape of the molded product be made more complicated, so that the material must have higher fluidity and a smaller decrease in the strength of the weld portion in the molded product. It has become.
In response to these problems, the flame-retardant polyester resin composition obtained from the above-described technology has flame retardancy, tracking resistance, heat resistance, and mechanical strength that are satisfactory, but the fluidity of the resin and the weld portion of the resin are satisfactory. The strength is not sufficient, and in particular, the strength of the welded part is significantly lower than that of the normal part, so that improvement has been strongly demanded.

[0006]

The present inventors have conducted intensive studies to improve the above-mentioned problems, and as a result, surprisingly, an organic phosphorus-based flame retardant has been added to a thermoplastic polyester resin.
By using the coated stabilized red phosphorus-based flame retardant, melamine / cyanuric acid adduct, specific copolymer having a specific melt index, and glass fiber in a specific blending amount, a decrease in strength of a weld portion is small. , Excellent mechanical strength,
It has been found that a flame-retardant resin composition having wet heat resistance, heat resistance, fluidity and tracking resistance can be obtained, and the present invention has been completed. That is, the present invention comprises the following components (A) to (F), and their total is 100
The content is a flame-retardant polyester resin composition which is in weight%. (A) thermoplastic polyester resin: 30 to 70% by weight (B) organic phosphorus-based flame retardant: 0.5 to 20% by weight (C) coated stabilized red phosphorus-based flame retardant: 0 to 5% by weight ( D) Melamine / cyanuric acid adduct: 4 to 20% by weight (E) Melt index (MI) value is 190 ° C., 2
Kg load condition (based on JIS K6730)
500 g / 10 min, ethylene unit 30 to 90
% By weight, 10 to 50% by weight of alkyl (meth) acrylate units having 1 to 10 carbon atoms in the alkyl ester, 0 to 40% by weight of carbon monoxide units, and other copolymerizable vinyl monomer units 0 to 10% by weight of a copolymer: 0.5 to 15% by weight (F) Glass fiber: 5 to 50% by weight Further, the present invention provides a method in which the thermoplastic polyester resin as the component (A) is a polyalkylene. The present invention relates to the flame-retardant polyester resin composition according to the above (1), which is a terephthalate resin.

Further, the present invention relates to the flame-retardant polyester resin composition according to the above item (1) or (2), wherein the thermoplastic polyester resin as the component (3) (A) is a polyethylene terephthalate resin. Furthermore, the present invention
(4) The organophosphorus flame retardant as the component (B) is represented by the general formula (I):

[0008]

Embedded image

Wherein R 1 to R 17 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y is a direct bond or a methylene group, an alkylene group having 2 to 3 carbon atoms, —S—,
-SO2-, -O-, -CO- or -N = N-, a divalent linking group, n is 0 or 1, and m is 1 to 10). The invention relates to the flame-retardant polyester resin composition according to the above (1), (2) or (3).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polyester resin (A) used in the present invention is a divalent acid such as terephthalic acid or a derivative thereof having an ester-forming ability as an acid component, and a carbon component as a glycol component. It refers to a saturated polyester resin obtained by using a glycol of 2 to 10 or another dihydric alcohol or a derivative thereof having an ester-forming ability. Among these, a polyalkylene terephthalate resin is preferred because it has a good balance of workability, mechanical properties, electrical properties, heat resistance, and the like. Specific examples of these polyalkylene terephthalate resins include polyethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexane dimethylene terephthalate resin and the like, and among these, heat resistance and chemical resistance tend to be excellent. In this respect, polyethylene terephthalate resin is preferred.

The thermoplastic polyester resin (A) used in the present invention may be copolymerized with other components at a ratio of preferably 20% by weight or less, particularly preferably 10% by weight or less, if necessary. Can be. As components of the copolymer,
Known acid components, alcohol components and / or phenol components, or derivatives thereof having ester-forming ability can be used. Examples of the acid component include divalent or higher valent aromatic carboxylic acids having 8 to 22 carbon atoms, aliphatic carboxylic acids having 4 to 12 carbon atoms, alicyclic carboxylic acids having 8 to 15 carbon atoms, and ester-forming ability. And derivatives thereof.

Specifically, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methaneanthracenedicarboxylic acid, 4-4'-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane- 4,4′-dicarboxylic acid, 5-sodium sulfoisophthalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, maleic acid, trimesic acid, trimellitic acid, pyromellitic acid, 1,3-cyclohexanedicarboxylic acid, Examples thereof include 1,4-cyclohexanedicarboxylic acid and derivatives thereof having an ester-forming ability. These may be used alone or in combination of two or more. Of these, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid are preferred because the obtained resin is excellent in physical properties, handleability, and ease of reaction.

Examples of the alcohol and / or phenol component include dihydric or higher aliphatic alcohols having 2 to 15 carbon atoms, alicyclic alcohols having 6 to 20 carbon atoms and divalent alcohols having 6 to 40 carbon atoms. The aromatic alcohols or phenols described above and derivatives thereof having ester-forming ability are mentioned. Specifically, ethylene glycol, propanediol, butanediol, hexanediol, decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, 2,2′-bis (4-hydroxyphenyl) propane, 2,2′- Compounds such as bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, and derivatives thereof capable of forming an ester;
-Cyclic esters such as caprolactone can also be used. Among these, the physical properties of the obtained resin, handleability,
Ethylene glycol and butanediol are preferred because they are easy to react.

Further, a polyoxyalkylene glycol unit may be partially copolymerized. Specific examples of the polyoxyalkylene glycol include polyethylene glycol,
Polypropylene glycol, polytetramethylene glycol, and their random or block copolymers, and adducts of bisphenol compounds with alkylene glycols (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and their random or block copolymers, etc.) Of modified polyoxyalkylene glycol. Among these, bisphenol A having a molecular weight of 500 to 2,000 is preferred because the thermal stability at the time of copolymerization is good and the heat resistance of a molded article obtained from the resin composition of the present invention is hardly reduced.
Is preferred.

These (A) thermoplastic polyester resins may be used alone or in combination of two or more.
70% by weight, preferably 35-65% by weight. 3
If the amount is less than 0% by weight, the excellent properties inherent to the thermoplastic polyester resin cannot be exhibited. If the amount exceeds 70% by weight, a flame-retardant polyester resin having the excellent properties which is the object of the present invention is obtained. Can not.

The thermoplastic polyester resin can be produced by a known polymerization method such as melt polycondensation, solid phase polycondensation,
It can be obtained by solution polymerization or the like. Further, in order to improve the color tone of the resin during polymerization, phosphoric acid, phosphorous acid, hypophosphorous acid, monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, methyl diethyl phosphate, triethyl phosphate, triisopropyl phosphate, One or more compounds such as tributyl phosphate and triphenyl phosphate may be added.

Further, in order to increase the crystallinity of the obtained thermoplastic polyester resin, various kinds of commonly known organic or inorganic crystal nucleating agents may be used alone or
Two or more kinds may be used in combination. The intrinsic viscosity of these (A) thermoplastic polyester resins (measured at 25 ° C. in a mixed solvent of phenol / tetrachloroethane in a weight ratio of 1/1) is as follows:
It is preferably from 0.4 to 1.2, particularly from 0.6 to 1.
It is preferably 0 dl / g. The intrinsic viscosity is 0.4
If it is less than 1, the mechanical strength and impact resistance tend to decrease, and if it exceeds 1.2, the fluidity tends to decrease, which is not preferable.

The (B) organophosphorus flame retardant used in the present invention is not particularly limited as long as it contains a phosphorus atom in the molecule and has little dispersion and volatilization during molding of the thermoplastic polyester resin. For example, alcohols having a linear or branched aliphatic group, aromatic group, or alicyclic group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, or organic phosphorus such as phenolic phosphate compounds and phosphonate compounds. Compounds, nitrogen-containing organophosphorus compounds and the like.

These (B) organophosphorus flame retardants include:
Typically, phosphate, phosphonate, phosphinate, phosphine oxide, phosphite, phosphonite, phosphinite, phosphine and the like can be mentioned. Specific examples of such an organic phosphorus-based flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (butoxyethyl phosphate), triphenyl phosphate, tricresyl phosphate, and trixylyl phosphate. , Tris (isopropylphenyl)
Phosphate, Tris (phenylphenyl) phosphate, Trinaphthylphosphate, Cresyldiphenylphosphate, Xylyldiphenylphosphate, Diphenyl (2-ethylhexyl) phosphate, Bis (isopropylphenyl) phenylphosphate, Phenylcresylphosphate, Bis (2-ethylhexyl) Phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl 2-acryloyloxyethyl phosphate, diphenyl 2-methacryloyloxyethyl phosphate, triphenylphosphite, tris (nonylphenyl) phospho Phyte, tritridecyl phosphite, dibutyl hydrogen phosphite Ito, triphenyl phosphine oxide, tricresyl phosphine oxide, methanephosphonate diphenyl, such as phenylphosphonic von diethyl,
Further, for example, an organic phosphorus compound such as a condensed phosphate ester represented by the following general formula (I) and the like can be mentioned.

Of these (B) organophosphorus flame retardants, they themselves have low volatility and good thermal stability during molding and hardly impair physical properties such as thermal stability of a thermoplastic polyester resin. For such reasons, general formula (I):

[0021]

Embedded image

(Wherein, R 1 to R 17 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y is a direct bond or a methylene group, an alkylene group having 2 to 3 carbon atoms, —S—,
-SO2-, -O-, -CO- or -N = N-, a divalent linking group, n is 0 or 1, and m is 1 to 10). Those having a main component are preferred. Examples of the alkyl group having 1 to 4 carbon atoms represented by R1 to R17 include methyl, ethyl, propyl, isopropyl, and butyl, and methyl is preferred from the viewpoint of dispersibility. When m increases, the dispersibility in the thermoplastic polyester (A) decreases and the flame retardant effect tends to decrease. m is preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 7.

That is, a dihydroxy compound having at least one substituted benzene ring and a compound obtained by bonding phosphoric acid and each substituted phenol to each other are preferable. Examples of the dihydroxy compound having at least one substituted benzene ring include: Examples include resorcinols, hydroquinones, biphenols, bisphenols, and the like, and examples of each substituted phenol include phenol, cresol, xylenol, ethylphenol, trimethylphenol, and the like.

Specific examples of the condensed phosphoric acid ester include, for example, resorcinol bis (diphenyl) phosphate, methyl resorcinol bis (diphenyl phosphate), methyl resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl) phosphate, bisphenol bis (diphenyl) Phosphate), bisphenol A bis (diphenyl phosphate), bisphenol S bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate), methyl resorcinol bis (dicresyl phosphate), hydroquinone bis (dicresyl phosphate), bisphenol bis
(Dicresyl phosphate), bisphenol A bis (dicresyl phosphate) represented by the following formula (II),
Bisphenol S bis (dicresyl phosphate), resorcinol bis [(di-ethylphenyl) phosphate], methylresorcinol bis [(di-ethylphenyl) phosphate], hydroquinone bis [(di-ethylphenyl) phosphate], bisphenol bis [( Di-ethylphenyl) phosphate], bisphenol A bis [(di-ethylphenyl) phosphate],
Bisphenol S bis [(di-ethylphenyl) phosphate], resorcinol bis [(di-2,6-xylyl) phosphate] represented by the following formula (III), methylresorcinol bis [(di-2,6-xylyl) Phosphate], hydroquinone bis [(di-2,6-xylyl) phosphate] represented by the following formula (IV), bisphenol bis [(di-2,6-xylyl) phosphate], bisphenol A bis [(di-2 , 6-xylyl) phosphate], bisphenol S bis [(di-
2,6-xylyl) phosphate], resorcinol bis [(di-2,4,6-trimethylphenyl) phosphate], methylresorcinol bis [(di-2,4,6
-Trimethylphenyl) phosphate], hydroquinone bis [(di-2,4,6-trimethylphenyl) phosphate], bisphenolbis [(di-2,4,6-
Trimethylphenyl) phosphate], bisphenol A bis [(di-2,4,6-trimethylphenyl) phosphate], bisphenol S bis [(di-2,6-xylyl) phosphate], and condensates thereof.

Among them, the condensed phosphoric acid esters represented by the following formulas (II) to (IV) are excellent in heat stability and wet heat resistance, and have low contamination to metal parts such as molds during molding. And condensates thereof are preferred.

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

These organic phosphorus flame retardants are used alone or in combination of two or more. When two or more kinds are used in combination, the combination is not limited. For example, those having different structures and / or different molecular weights are arbitrarily combined. The amount of the (B) organophosphorus flame retardant added is 0.5 to 20% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 20% by weight in the flame retardant polyester resin composition. Fifteen
% By weight. If the addition amount is less than 1% by weight, the flame retardancy and fluidity tend to decrease, while if it exceeds 20% by weight, the strength of the weld portion, mechanical strength, wet heat resistance and heat resistance decrease. There is a tendency.

The (C) coated stabilized red phosphorus-based flame retardant used in the present invention is a red phosphorus-based flame retardant stabilized by coating the surface by various methods. is there. (Hereinafter, it is abbreviated as (C) stabilized red phosphorus-based flame retardant.) By making the (C) stabilized red phosphorus-based flame retardant coated with red phosphorus, the case where untreated red phosphorus is used is usually used. In comparison, odor generation during molding processing is suppressed,
It is preferable from the viewpoint of improving the moist heat resistance.

The content of red phosphorus in the stabilized red phosphorus flame retardant (C) is preferably at least 20% from the viewpoint of flame retardancy and cost, and more preferably at least 40%. The upper limit of the content of red phosphorus is 99.5% from the viewpoint of improving the odor, and more preferably 99.
0%. The average particle size of the (C) stabilized red phosphorus-based flame retardant is preferably from 0.1 to 500 μm from the viewpoint of flame retardancy and surface properties of a molded product, and more preferably 0.5 to 500 μm.
２００200 μm.

Preferred materials used for the red phosphorus coating treatment include at least one selected from thermosetting resins, metal hydroxides, and metals. It is preferable because the odor can be reduced while keeping the flame retardancy of the resin composition obtained by coating with these. The thermosetting resin is not particularly limited as long as it is a resin capable of coating red phosphorus, and specific examples thereof include a phenol-formalin-based resin, a urea-formalin-based resin, a melamine-formalin-based resin, and an alkyd-based resin. Is mentioned.

The metal hydroxide is not particularly limited as long as it is a compound capable of coating red phosphorus, and specific examples thereof include aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide. The metal may be any metal capable of forming a film capable of coating red phosphorus by electroless plating, and specific examples thereof include Fe,
Examples include Ni, Co, Cu, Zn, Mn, Ti, Zr, Al, and alloys thereof.

The coating formed from the material as described above is:
It may be formed from one kind of material, or may be formed from a material combining two or more kinds. Further, the coating may be a single layer or a double layer or more. These (C)
The stabilized red phosphorus flame retardants may be used alone or in combination of two or more. When two or more types are used in combination, there is no limitation on the combination. For example,
Different coatings and / or different particle sizes can be arbitrarily combined.

The amount of the stabilized red phosphorus flame retardant (C) to be added is 0 to 5% by weight, preferably 0 to 4% by weight.
More preferably, it is 0 to 3% by weight. If the content exceeds 5% by weight, odor tends to be generated during processing, and the cost is increased. The melamine / cyanuric acid adduct (D) used in the present invention includes melamine (2,4,6-triamino-1,3,5-triazine) and cyanuric acid (2,4,6-trihydroxy-1, 3,5-triazine) and / or a tautomer thereof. The melamine / cyanuric acid adduct can be obtained by a method of mixing a melamine solution and a solution of cyanuric acid to form a salt, or a method of forming a salt while adding and dissolving one solution to the other. There is no particular limitation on the mixing ratio of melamine and cyanuric acid, but the resulting adduct is less likely to impair the thermal stability of the thermoplastic polyester resin.
In particular, 1: 1 is preferred. The average particle size of the melamine / cyanuric acid adduct is not particularly limited, but is preferably 0.01 to 2 from the viewpoint of not impairing the strength properties and moldability of the composition obtained.
50 μm is preferred, and particularly preferably 0.5 to 200 μm.

The amount of the melamine / cyanuric acid adduct (D) to be added is 4 to 20% by weight, preferably 5 to 20% by weight.
It is 18% by weight, more preferably 6 to 16% by weight. If the amount is less than 4% by weight, the flame retardancy and the tracking resistance tend to decrease, while if it exceeds 20% by weight, the strength of the weld portion, the mechanical strength and the moist heat resistance tend to decrease.

The value of (E) melt index (MI) used in the present invention is 190 ° C., 2 kg load condition (JIS)
K6730) in the range of 2 to 500 g / 10 m
in, 30 to 90% by weight of ethylene unit, 10 to 50% by weight of alkyl (meth) acrylate unit having 1 to 10 carbon atoms of alkyl ester, 0 to 40% by weight of carbon monoxide unit, and others. A copolymer comprising 0 to 10% by weight of a polymerizable vinyl monomer unit is used for the purpose of improving the strength of the weld portion of the resin, and improving the fluidity and wet heat resistance of the resin.

These (E) copolymers are generally used in combination with ethylene and an alkyl (meth) acrylate, and if necessary, carbon monoxide and / or other copolymerizable vinyl monomers. Can be obtained by radical polymerization in the presence of a radical initiator, but the polymerization method is not limited thereto, and can be polymerized using various known polymerization methods generally known. . The copolymer may be in any copolymer form such as a random copolymer, a block copolymer, and a graft copolymer.

As the alkyl ester in the alkyl (meth) acrylate in the (E) copolymer, one having 1 to 10 carbon atoms is used. When the one having 11 or more carbon atoms is used, the compatibility with the polyester decreases, and the mechanical strength of the obtained composition decreases. Preferably, it has 8 or less carbon atoms, and more preferably 6 or less carbon atoms.

Specific examples of the alkyl (meth) acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, and n
-Propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and the like, and these are used alone or in combination of two or more.

These (E) copolymers may, if necessary,
In addition to the ethylene unit, the alkyl (meth) acrylate unit, and the carbon monoxide unit, the copolymer may contain other copolymerizable vinyl monomer units. Other copolymerizable vinyl monomers include propylene, 1-butene, 1-pentene, isobutene, isoprene, α, ω-non-conjugated diene,
Alkene compounds such as butadiene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3-cyclohexadiene, 1,5-cyclooctadiene, and 1,3-cyclooctadiene; Aromatic vinyl compounds such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, divinylbenzene, maleic acid, maleic anhydride, N-methylmaleimide, N-phenyl Maleimide derivatives such as maleimide and dimethyl maleate; unsaturated nitriles such as acrylonitrile and methacrylonitrile; glycidyl (meth) acrylates such as glycidyl methacrylate; unsaturated amide compounds such as acrylamide; vinyl methyl ether; Ethyl ethers, such as vinyl alkyl ethers, allyl alkyl ethers, such as allyl ethyl ethers, alkyl esters of (meth) acrylic acid alkyl esters having 11 or more carbon atoms, and acrylic acid, methacrylic acid as other vinyl monomers, Examples include, but are not limited to, vinyl acetate, and various copolymerizable components can be used. These are used alone or in combination of two or more.

The value of the melt index (MI) of the copolymer (E) was 190 ° C. under a 2 kg load condition (JIS
K6730) in the range of 2 to 500 g / 10 m
in, preferably 4 to 400 g / 10 min, more preferably 5 to 300 g / 10 min. If the value of the melt index is less than 2, the fluidity and strength of the weld portion of the obtained composition decrease, and if it exceeds 500, the mechanical strength decreases. In the copolymer (E), the ratio of the ethylene unit to the alkyl (meth) acrylate unit, the carbon monoxide unit, and the other copolymerizable vinyl monomer is such that the ethylene unit is 30 to 90% by weight. %, Alkyl (meth) acrylate unit is 10 to 50% by weight, carbon monoxide unit is 0 to 40% by weight, and other copolymerizable vinyl monomer units are 0 to 10% by weight. Preferably, the ethylene unit is 35 to 85% by weight, the (meth) acrylic acid alkyl ester unit is 10 to 40% by weight, the carbon monoxide unit is 0 to 30% by weight, and the other copolymerizable vinyl monomer unit is 0. -7% by weight, more preferably 40-90% by weight of ethylene units, 10-50% by weight of alkyl (meth) acrylate units and 0-2% by weight of carbon monoxide units.
0% by weight, other copolymerizable vinyl monomer units are 0%
~ 5% by weight. When the amount of the alkyl (meth) acrylate unit is less than 10% by weight or more than 60% by weight, the effect of improving the strength of the weld portion is poor. In some cases, the mechanical strength and wet heat resistance of the resulting composition may decrease.
The amount of the (E) copolymer used is 0.5 to 15% by weight, preferably 1 to 11% by weight, more preferably 2 to 15% by weight.
8% by weight. (E) The amount of the copolymer used is 15% by weight.
If the amount exceeds the above range, the mechanical strength and heat resistance of the obtained composition may be reduced. If the amount is less than 0.5% by weight, the effect of improving the strength and fluidity of the weld portion cannot be obtained. These may be used in combination of plural resins having different copolymer components, melt index values, and the like.

As the (F) glass fiber used in the present invention, known glass fibers that are generally used can be used. From the viewpoint of workability, chopped strand glass treated with a sizing agent is used. Preferably, fibers are used.
Further, in order to enhance the adhesion between the resin and the glass fiber, it is preferable that the surface of the glass fiber is treated with a coupling agent, and a material using a binder may be used.

Examples of the coupling agent include γ-
Alkoxysilane compounds such as aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, and as the binder, for example, epoxy resins and urethane resins are preferably used, but not limited thereto. . These glass fibers can be used alone or in combination of two or more. The fiber diameter of these (F) glass fibers is 1 to 20 μm, and the fiber length is 0.01 to 50 m.
m is preferred. When the fiber diameter is less than 1 μm, there is a tendency that the expected reinforcing effect cannot be obtained even when added, and when the fiber diameter exceeds 20 μm, the surface properties and fluidity of the molded article tend to decrease, which is not preferable. . The fiber length is 0.0
If it is less than 1 mm, the expected resin reinforcing effect tends not to be obtained even if it is added, and if the fiber length exceeds 50 mm, the surface properties and fluidity of the molded article tend to decrease, which is not preferable. The amount of use of these (F) glass fibers is 5 to
It is 50% by weight, preferably 7 to 45% by weight, particularly preferably 10 to 40% by weight. (F) If the amount of glass used is less than 5% by weight, sufficient mechanical strength and heat resistance tend not to be obtained, while the amount used is 50% by weight.
Exceeding the range tends to lower the surface properties and extrusion processability of the molded product, which is not preferred.

The flame-retardant polyester resin composition of the present invention may further contain, if necessary, other compounding agents such as an inorganic or organic flame retardant, a flame retardant auxiliary, a reinforcing agent, a hindered phenol compound, Phyt compounds, thioether compounds, deterioration inhibitors such as epoxy compounds, ultraviolet absorbers, release agents, colorants, crystal nucleating agents, antistatic agents, lubricants, plasticizers, other polymers, etc., impair the purpose of the present invention. It can be blended to an extent that it is not.

The method for producing the composition of the present invention is not particularly limited. For example, it can be produced by a method of drying and kneading the above components, other additives, resins, and the like, and then using a melt kneading machine such as a single screw or twin screw extruder. When the compounding agent is a liquid, it can be manufactured by adding the compounding agent to a twin-screw extruder using a liquid supply pump or the like.

The composition of the present invention can be formed into various forms by various molding methods, for example, various molded articles, sheets, pipes, bottles and the like. Moreover, it has a high level of flame retardancy and has a good balance of weld strength, mechanical strength, moist heat resistance, heat resistance, and fluidity, so electronic and electric parts such as home appliances and OA equipment with complicated shapes. It is suitably used for injection molded articles such as housings. In particular, applications that make use of electrical properties such as excellent dielectric strength, arc resistance, and tracking resistance include breaker parts, switch parts, motor parts, ignition coil cases, power module cases, power plugs, power outlets, coil bobbins, It is suitably used for connector terminals, fuse cases and the like.

[0048]

EXAMPLES Next, the composition of the present invention will be described specifically with reference to examples, but the present invention is not limited thereto. Example 1 (A) A thermoplastic polyester resin having a logarithmic viscosity (measured at 25 ° C. in a mixed solvent of phenol / tetrachloroethane at a weight ratio of 1/1, the same applies hereinafter) of 0.65 dl / g is sufficient. 6 dry polyethylene terephthalate (a-1)
0.0% by weight, (B) bisphenol A bis (dicresyl) phosphate (b-1) (trade name: organophosphorus flame retardant)
6.0% by weight of Daihachi Chemical's CR747)
(C) 3% by weight of red phosphorus (c-1) (trade name: Nova Excel 140 manufactured by Rin Kagaku Kogyo Co., Ltd .; red phosphorus content: 95%) surface-coated with a phenol resin as a stabilized red phosphorus flame retardant; (D) Melamine cyanurate (d-1) as a melamine / cyanuric acid adduct (trade name: MC4 manufactured by Nissan Chemical Co., Ltd.)
40) as 10.0% by weight, (E) a copolymer of ethylene and ethyl acrylate (e-1) (Ethyl acrylate ratio: 35% by weight, MI = 25 g / 10 min) (DuPont Mitsui Polychemicals Co., Ltd.) EAFLEX-EE made by company
A A709) was 10% by weight, bisphenol A type epoxy resin (Eicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) was 0.5% by weight as a stabilizer, and tetrakismethylene-3,5-di-t-butyl-4-hydroxy was used. Hydrocinnamate methane (trade name: ADK STAB A manufactured by Asahi Denka Co., Ltd.)
O-60) 0.5% by weight was dry blended. This mixture was supplied to a hopper of a vented 45 mmφ co-rotating twin-screw extruder (trade name: Nippon Steel Works Co., Ltd. TEX44) in which the cylinder temperature was set to 250 to 280 ° C.,
(F) Glass fiber (f-1) (T-1 manufactured by NEC Corporation)
95H / P) 10.0 wt% was added from the middle of the extruder using a side feeder and melt-kneaded to obtain pellets. The obtained pellets were dried at 140 ° C. for 3 hours, and then the following test pieces were molded using an injection molding machine (clamping pressure: 75 tons) at a cylinder temperature of 280 to 250 ° C. and a mold temperature of 100 ° C. did.・ Thickness 6.4mm, 1.6mm bar (each, length: 127m
ASTM No. 1 dumbbell with a thickness of 3.2 mm. ASTM No. 1 dumbbell with a thickness of 3.2 mm filled with resin from both ends of the molded product to form a weld at the center of the molded product. 120 mm × 120 mm , A flat plate having a thickness of 3 mm Using these test pieces, physical properties were evaluated according to the following criteria. Table 1 shows the results.

<Flame Retardancy> The flame retardancy of a 1.6 mm thick bar was evaluated according to the UL-94 standard. Not-V in the flame retardancy evaluation result indicates that the product does not conform to the UL-94 standard. <Mechanical strength> According to ASTM D-638, thickness 3.2
The ASTM No. 1 dumbbell was evaluated for tensile strength. <Strength Improvement Effect of Weld Portion> In injection molding, a resin is filled from both ends of the molded product, and a 3.2 mm thick ASTM No. 1 dumbbell having a weld formed at the center of the molded product is used. The strength was measured in the same manner as in 638, and the strength retention (%) with respect to the tensile strength of the same sample was calculated and evaluated. It can be determined that the higher the strength retention, the greater the improvement in the strength of the weld portion. <Improvement effect of moist heat resistance> ASTM No. 1 dumbbell 121
After treatment for 24 hours at 100 ° C. and 100% RH, AST
The strength was measured in the same manner as in MD-638, and the strength retention (%) for the same sample before treatment was calculated and evaluated. It can be determined that the higher the strength retention, the greater the improvement in wet heat resistance.

<Heat Resistance> According to ASTM D-648, the load deflection temperature [HDT] of a 6.4 mm thick bar was evaluated under a load of 1.82 MPa. <Fluidity> Set temperature 28 according to JIS K-7210
The flow value of Method B was measured at 0 ° C. for a preheating time of 5 minutes. (×
10 ^-2 cc / sec) <Tracking resistance> 20 mm obtained by cutting a flat plate
Using a test piece of × 20 mm and thickness of 3 mm, the IEC standard (P
ub.112), the comparative tracking index [CT
I] was evaluated.

<Surface Properties of Molded Product> Injection molding machine (mold clamping pressure:
75 tons, cylinder diameter: 36 mmφ), cylinder temperature: 280 to 250 ° C, screw rotation speed: 100 rpm
m, back pressure: 0.8MPa, mold temperature 100 ° C, 120 × 1
A flat plate having a thickness of 20 mm and 3 mm was formed.

Criteria A: Surface gloss is present and surface properties are uniform. X: The surface properties are not uniform. <Odor during Extrusion> In the pelletizing step, the odor at a position 1 m away from the extruder die was determined according to the following criteria. ：: Off-flavor is not particularly felt. ×: Strong off-flavor is felt.

Examples 2 to 11 Resin compositions were obtained in the same manner as in Example 1 except that the amounts of the respective ingredients were changed to the amounts shown in Table 1. However, the following compounding agents were used. Table 1 shows the evaluation results. (A) As a thermoplastic polyester resin ・ Polyethylene terephthalate resin having a logarithmic viscosity of 0.75 dl / g (a-2) ・ Polybutylene terephthalate resin having a logarithmic viscosity of 0.85 dl / g (a-3) (B) As an organic phosphorus flame retardant ・ Resorcinol bis (di-2,6-xylyl) phosphate (trade name: PX200 manufactured by Daihachi Chemical Industry Co., Ltd.) (B-
2) ・ Hydroquinone bis (di-2,6-xylyl) phosphate (trade name: PX201, manufactured by Daihachi Chemical Industry Co., Ltd.) (b-
3) Triphenyl phosphate (trade name: TPP manufactured by Daihachi Chemical Industry Co., Ltd.) (b-4) (E) as a copolymer Ethyl acrylate ratio 25% by weight, MI = 275 g
/ 10 min copolymer of ethylene and ethyl acrylate (EVAFLEX manufactured by Mitsui DuPont Polychemicals, Inc.)
-EEA A704) (e-2)-Ethyl acrylate ratio 25% by weight, MI = 20 g /
10 minutes copolymer of ethylene and ethyl acrylate (EVAFLEX manufactured by Mitsui DuPont Polychemicals, Inc.)
-EEA A713) (e-3)-ethylene-n-butyl acrylate-carbon monoxide ethyl acrylate Synthesized according to U.S. Patent No. 4,613,533, ethylene: n-butyl acrylate: carbon monoxide = 7
0: 22: 8, MI = 25 g / 10 min Copolymer (e-4) (Comparative Examples 1 to 11) Except that each compounding agent was changed to the amount shown in Table 2, the same as in Example 1 Thus, a resin composition was obtained. However, the following compounding agents were used. Table 2 shows the evaluation results. (E) As a copolymer: ethyl acrylate ratio 25% by weight, MI = 0.5 g
/ 10 min copolymer of ethylene and ethyl acrylate (EVAFLEX manufactured by Mitsui DuPont Polychemicals, Inc.)
-EEA A714) (e-5)-Ethyl acrylate ratio 25% by weight, MI = 800 g
/ 10 min copolymer of ethylene and ethyl acrylate (EVAFLEX manufactured by Mitsui DuPont Polychemicals, Inc.)
-EEA A715) (e-6)-Linear low density polyethylene with MI = 0.5 g / 10 min (moretech 0168N manufactured by Idemitsu Petrochemical Industries, Ltd.)
(e-7) MI measured at 230 ° C. under a load of 10 kg = 23 g / 1
Polymethyl methacrylate of 0 minutes (Acrypet MD manufactured by Mitsubishi Rayon Co., Ltd.) (e-8) As is clear from comparison between Table 1 of the Examples and Table 2 of the Comparative Examples, the flame retardant of the present invention was used. Polyester resin composition has flame retardancy, mechanical strength, strength improvement of the welded part, wet heat resistance,
It can be seen that heat resistance, fluidity, tracking resistance, and extrudability are all excellent.

[0054]

The flame-retardant polyester resin composition of the present invention is characterized in that the flame-retardant polyester resin composition of the present invention has improved flame retardancy, mechanical strength, strength of a weld portion, wet heat resistance, heat resistance,
It has excellent fluidity, tracking resistance, surface properties of molded products, and extrudability, and does not contain halogen-based flame retardants and antimony compounds. Therefore, the flame-retardant polyester resin composition of the present invention can be suitably used as a molding material for electric and electronic parts, and is industrially useful.

[0055]

[Table 1]

[0056]

[Table 2]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI // (C08L 67/02 73:00 33:08) (C08L 67/02 73:00 65:00)

Claims (4)

[Claims] 1. A flame-retardant polyester resin composition comprising the following components (A) to (F), the total of which is 100% by weight. (A) thermoplastic polyester resin: 30 to 70% by weight (B) organic phosphorus-based flame retardant: 0.5 to 20% by weight (C) coated stabilized red phosphorus-based flame retardant: 0 to 5% by weight ( D) Melamine / cyanuric acid adduct: 4 to 20% by weight (E) Melt index (MI) value is 190 ° C., 2
Kg load condition (based on JIS K6730)
500 g / 10 min, ethylene unit 30 to 90
% By weight, 10 to 50% by weight of alkyl (meth) acrylate units having 1 to 10 carbon atoms in the alkyl ester, 0 to 40% by weight of carbon monoxide units, and other copolymerizable vinyl monomer units Copolymer consisting of 0 to 10% by weight: 0.5 to 15% by weight (F) Glass fiber: 5 to 50% by weight 2. The thermoplastic polyester resin as the component (A) is a polyalkylene terephthalate resin.
The flame-retardant polyester resin composition according to the above. 3. The flame-retardant polyester resin composition according to claim 1, wherein the thermoplastic polyester resin as the component (A) is a polyethylene terephthalate resin. 4. The organophosphorus flame retardant as the component (B) is represented by the general formula (I): (Wherein, R 1 to R 17 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y is a direct bond or a methylene group, an alkylene group having 2 to 3 carbon atoms, —S—, —SO 2 —,
-O-, -CO- or -N = N-, a divalent linking group, n is 0 or 1, and m is 1 to 10). The flame-retardant polyester resin composition according to any one of claims 1 to 3.