JP2000212412A - Reinforced flame retarded polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition excellent in flame retardancy and mechanical strengths and free from deterioration of appearance and characteristics of a molded article even when used under severe conditions such as a high temperature and high humidity condition by compounding a thermoplastic polyester resin, a vinylic resin, an organic phosphorus-containing flame retardant and a glassfiber in a specific ratio. SOLUTION: There are compounded 20-60 wt.% of a thermoplastic polyester resin, 1.0-30 wt.% of a vinylic resin, 0.5-20 wt.% of an organic phosphorus- containing flame retardant and 5-50 wt.% of a glassfiber. Further added 4-20 wt.% of a melamine-cyanuric acid adduct. As the vinylic resin is preferable a polystyrene in particular. As the organic phosphorus-containing flame retardant is preferable a condensed phosphoric ester of the formula. In the formula, R1 to R17 are each H or a 1-4C alkylene; Y is a direct bond, methylene, 2-3C alkylene, -S-, -SO2-, -O-, -CO- or -N=N-; n is 0 or 1; and m is 1-10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyester resin composition flame-retarded with an organophosphorus flame retardant, which is characterized by a small change in appearance and properties of a molded article under high temperature and high humidity.

[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 (U.S. Underwriters Laboratory Standard), there are many cases where a high level of flame retardancy is required, and therefore, the formulation of various flame retardants is being 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, halogen compounds generated by decomposition of halogen-based flame retardants during resin processing corrode the surfaces of 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, use of a nitrogenous flame retardant such as an organic phosphorus flame retardant or a triazine compound (for example, melamine / cyanuric acid adduct) has been studied. As organic phosphorus-based flame retardants, in addition to triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, etc., due to problems such as heat resistance, organic phosphorus-based flame retardants having relatively large molecular weights such as condensates of phosphate esters in recent years. Flame retardants are being considered. Examples of flame retardant resin compositions using such phosphorus-based flame retardants include JP-B-51-19858, JP-B-51-39271, JP-A-52-102255, JP-A-05-70761, JP-A-05-287
119 and JP-A-06-157880.

[0004]

As a use of such a material having excellent flame retardancy, it is used for electric / electronic parts and housing parts. In these applications, the use environment may be under high temperature and high humidity, and it is required that the appearance and characteristics of the molded product are stable even under such use conditions. In order to solve these problems, in the flame-retardant polyester resin composition obtained from the above-mentioned technology, the organic phosphorus-based flame retardant used as a flame retardant and the organic phosphorus-based flame retardant caused by exposure to high temperature and high humidity conditions Because the substance bleeds on the surface of the molded article, the appearance of the molded article,
In addition, since a problem of causing a significant decrease in characteristics has been caused, improvement thereof has been strongly demanded.

[0005]

The inventors of the present invention have conducted intensive studies to improve the above-mentioned problems, and as a result, surprisingly, the thermoplastic polyester resin has a vinyl resin and an organic phosphorus-based flame retardant, By using glass fiber in a specific compounding amount, it shows excellent flame retardancy and mechanical strength, and the appearance and appearance of the molded product even under severe use environment such as high temperature and high humidity. The inventors have found that a flame-retardant resin composition with reduced deterioration in properties can be obtained, and have completed the present invention. That is, the present invention provides the following components (A) to (D)
And a flame-retardant polyester resin composition having a total of 100% by weight. (A) thermoplastic polyester resin: 20 to 70% by weight (B) vinyl resin: 1.0 to 30% by weight (C) organophosphorus flame retardant: 0.5 to 20% by weight (D) glass fiber: 5 Further, the present invention relates to (2) a flame-retardant polyester resin composition comprising the following components (A) to (E), the total of which is 100% by weight. (A) thermoplastic polyester resin: 20 to 70% by weight (B) vinyl resin: 1.0 to 30% by weight (C) organophosphorus flame retardant: 0.5 to 20% by weight (D) glass fiber: 5 (E) Melamine / cyanuric acid adduct: 4 to 20% by weight Further, in the present invention, the organophosphorus flame retardant as the component (3) (B) is represented by the general formula (I):

[0006]

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—, —SO ₂ —, −
A divalent linking group wherein O-, -CO- or -N = N-,
3. The flame-retardant polyester resin composition according to claim 1, which is a condensed phosphate ester-based flame retardant represented by the following formula:

[0007]

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.

[0008] The thermoplastic polyester resin (A) used in the present invention is preferably 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.

The alcohol and / or phenol component includes dihydric or higher aliphatic alcohols having 2 to 15 carbon atoms, dicyclic or higher aliphatic alcohols having 6 to 20 carbon atoms, and dihydric 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, Compounds such as 2'-bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, and derivatives thereof having ester-forming ability;
Cyclic esters such as ε-caprolactone can also be used. Among these, ethylene glycol and butanediol are preferable because the obtained resin is excellent in physical properties, handling properties and ease of reaction.

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 25-65% by weight. 2
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 above-mentioned thermoplastic polyester resin can be produced by known polymerization methods 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 the thermoplastic polyester resin (A) (measured at 25 ° C. in a mixed solvent of phenol / tetrachloroethane at a weight ratio of 1/1) is from 0.4 to 2.
It is preferably 0, and particularly preferably 0.6 to 1.5 dl / g. If the intrinsic viscosity is less than 0.4, the mechanical strength and impact resistance tend to decrease, and if it exceeds 2.0, the fluidity tends to decrease, which is not preferable.

The vinyl resin (B) used in the present invention is used for the purpose of reducing the thermal conductivity of the composition, and the appearance of the molded article and the change in the surface properties of the molded article when the composition is subjected to high temperature and high humidity. It is used for the purpose of suppressing the composition, but also has the effect of improving the fluidity of the composition. (B) The vinyl resin is selected from the group consisting of aromatic vinyl compounds, unsaturated nitrile compounds, alkyl (meth) acrylates, N-substituted maleimides, unsaturated carboxylic acids and / or anhydrides thereof. It indicates a resin obtained by polymerizing at least one compound. In addition to the compounds selected from the above, other copolymerizable other monomers may be copolymerized. (B) Among the monomers used for polymerization of the vinyl resin, aromatic vinyl compounds include styrene,
Examples thereof include o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, vinyltoluene, and divinylbenzene. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Examples of the alkyl (meth) acrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, methyl acrylate, Ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, acrylic acid 2
-Ethylhexyl, stearyl acrylate and the like. As the N-substituted maleimide, maleimide,
Examples thereof include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and derivatives thereof. Unsaturated carboxylic acids and / or
Or as its anhydride, acrylic acid, methacrylic acid,
Maleic acid, maleic anhydride, fumaric acid and the like are exemplified. Other copolymerizable monomers include vinyl alkyl ethers, unsaturated amino compounds, dialkyl maleate, allyl alkyl ether, diene compounds, vinyl acetate, and the like. Examples of the vinyl alkyl ether include vinyl methyl ether, vinyl ethyl ether, vinyl i-propyl ether, vinyl n-propyl ether, vinyl i-butyl ether, vinyl n
-Amyl ether, vinyl i-amyl ether, vinyl 2-ethylhexyl ether, vinyl octadecyl ether, etc .; unsaturated amino compounds such as acrylamide and methacrylamide; and maleic acid dialkyl esters such as maleic acid diester. n-amyl ester, male i-butyl ester, maleic dimethyl ester, male n-propyl ester, maleic dioctyl ester, maleonyl maleonyl ester, etc. , Allyl n-octyl ether, etc., as diene compounds, dicyclopentadiene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,5-norbonadiene, - cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclohexadiene, 1,
3-cyclooctadiene, and the like. Preferred examples of the (B) vinyl resin include polystyrene, polymethyl methacrylate, styrene / acrylonitrile copolymer, methyl methacrylate / acrylonitrile copolymer, styrene / N-phenylmaleimide copolymer, and styrene / acrylonitrile / N-phenylmaleimide. Copolymers and the like. Among them, polystyrene is preferable because it has a large effect of reducing the thermal conductivity. (B) From the viewpoint of processability, the vinyl resin has a reduced viscosity of 0.2 to
1.2 dl / g (dimethylformamide solution, 30 ° C.,
The concentration is preferably 0.3 g / dl). More preferably, it is 0.3 to 0.9 dl / g. If the reduced viscosity is less than 0.2 dl / g, the mechanical strength is reduced.
If it exceeds 2 dl / g, the fluidity tends to decrease. The amount of the vinyl resin (B) to be added is 1 to 30% by weight, preferably 2 to 25% by weight, and more preferably 5 to 25% by weight.
20% by weight. Heat resistance exceeding 30% by weight tends to decrease, which is not preferable.

The (C) 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 (C) 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.

Among these (C) 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—, —SO 2 —,
-O-, -CO- or -N = N-, a divalent linking group, n is 0 or 1, and m is 1 to 10), and a condensed phosphoric acid ester represented by the formula: Are preferred. Examples of the alkyl group having 1 to 4 carbon atoms represented by R1 to R17 include methyl, ethyl, propyl, isopropyl,
Butyl and the like, 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 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), 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 these, condensed phosphoric acid esters represented by the following formulas (II) to (IV) because of their excellent thermal stability and wet heat resistance and low contamination to metal parts such as molds during molding. And condensates thereof are preferred.

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image These organic phosphorus-based 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 (C) 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. 15% by weight. If the amount is less than 1% by weight, the flame retardancy tends to decrease, while if it exceeds 20% by weight, the mechanical strength, wet heat resistance and heat resistance tend to decrease. The melamine / cyanuric acid adduct (D) used in the present invention is 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. The mixing ratio of melamine to cyanuric acid is not particularly limited, but is preferably close to equimolar, particularly preferably 1: 1 from the viewpoint that the resulting adduct is unlikely to impair the thermal stability of the thermoplastic polyester resin. The average particle size of the melamine / cyanuric acid adduct is not particularly limited, but is preferably 0.01 to 250 μm, particularly preferably 0.5 to 20 from the viewpoint of not impairing the strength properties and moldability of the obtained composition.
0 μm is preferred.

The addition amount of the (D) melamine / cyanuric acid adduct 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 tends to decrease, while if it exceeds 20% by weight, the mechanical strength and the wet heat resistance tend to decrease.

As the glass fiber (E) used in the present invention, a known glass fiber 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 (E) 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 these (E) glass fibers used is 5 to
It is 50% by weight, preferably 6 to 45% by weight, particularly preferably 7 to 40% by weight. (E) If the amount of glass used is less than 5% by weight, sufficient mechanical strength and heat resistance tend not to be obtained, while if the amount used exceeds 50% by weight, extrudability tends to decrease. Yes, not preferred.

The flame-retardant polyester resin composition of the present invention may contain a flame retardant such as red phosphorus and a flame retardant auxiliary for further improving the flame retardancy. In particular, in the case of red phosphorus-based flame retardants, the stabilized red phosphorus-based flame retardants whose surfaces have been coated by various methods usually generate odors during molding compared to the case where untreated red phosphorus is used. It can be preferably used from the viewpoints of being suppressed and improving the moist heat resistance. Further, an epoxy stabilizer, a hindered phenol compound, a phosphite compound, a thioether compound, or the like may be blended as a stabilizer for preventing deterioration. Among them, epoxy stabilizers can be preferably used from the viewpoint of improving mechanical strength and wet heat resistance. Furthermore, ultraviolet absorbers, release agents, colorants, crystal nucleating agents, antistatic agents, lubricants, plasticizers, other polymers,
A toughening agent and the like can be added to such an extent that the object of the present invention is not impaired.

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 excellent flame retardancy, mechanical strength, heat resistance, and suppresses changes in the appearance and surface properties of molded products under high temperature and high humidity, and has low thermal conductivity. It is suitably used for electronic and electric parts, injection molded products such as housings, and the like. In particular, it is suitably used for applications such as electric equipment and electric equipment parts used under high temperature and high humidity.

[0034]

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) As a thermoplastic polyester resin, logarithmic viscosity (phenol / tetrachloroethane in a weight ratio of 1 /
(Measured at 25 ° C. in a mixed solvent of 1);
Polyethylene terephthalate sufficiently dried at dl / g
(a-1) was 43.5% by weight, (B) a styrene resin (trade name: Estyrene G13 manufactured by Nippon Steel Chemical Co., Ltd.) (b-1) as a vinyl resin was 15.0% by weight, (C) ) 8.0% by weight of bisphenol A bis (dicresyl) phosphate (c-1) (trade name: CR747 manufactured by Daihachi Chemical Co., Ltd.) as an organic phosphorus flame retardant, and (E) melamine shear as a melamine / cyanuric acid adduct 15.0% by weight of Nurate (d-1) (trade name: MC440 manufactured by Nissan Chemical Co., Ltd.), and red phosphorus surface-coated with a phenol resin as a stabilized red phosphorus flame retardant (trade name: Rin Kagaku Kogyo Co., Ltd.) Nova Excel 14
0: 95% by weight of red phosphorus), 0.5% by weight of bisphenol A type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) as a stabilizer, tetrakismethylene-3,5-di 0.5 wt% of -t-butyl-4-hydroxyhydrocinnamate methane (trade name: ADK STAB AO-60 manufactured by Asahi Denka Co., Ltd.) was dry-blended. This mixture was supplied to a hopper of a vented 45 mmφ co-rotating twin screw extruder (trade name: TEX44 manufactured by Nippon Steel Works Co., Ltd.) set at a cylinder temperature of 250 to 280 ° C., and (E) glass fiber (e-1) (T-195H / P, manufactured by Nippon Electric Glass Co., Ltd.) 15.0% by weight was added from the middle of the extruder using a side feeder, and the mixture was melt-kneaded to obtain pellets. The obtained pellets are mixed at 140 ° C. for 3 hours.
After drying for an hour, using an injection molding machine (clamping pressure: 75 tons),
Cylinder temperature: 280 to 250 ° C, mold temperature: 100
The following test pieces were formed at a temperature of ° C.・ Thickness 6.4mm, 1.6mm bar (each, length: 127m
ASTM No. 1 dumbbell with a thickness of 3.2 mm, a flat plate with a size of 120 mm × 120 mm and 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> A 3.2 mm thick ASTM No. 1 dumbbell was evaluated for tensile strength in accordance with ASTM D-638. <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> The deflection temperature under load [HDT] of a 6.4 mm-thick bar was evaluated under a load of 1.82 MPa according to ASTM D-648.

<Thermal Conductivity> A 120 × 120 × 3 mm thick flat plate made by Eiko Seiki Co., Ltd.
The thermal conductivity was measured using C-072.

<Appearance of molded product after high temperature / high humidity treatment> 3 mm
After treating the thickness flat plate at 121 ° C. and 100% RH for 24 hours, the surface appearance of the molded product was observed according to the following criteria. ：: No change is observed in the appearance of the molded product. Δ: A powdery bleed product is observed on the surface of the molded product. ×: Liquid bleed is observed on the surface of the molded product.

(Examples 2 to 5 and Comparative Examples 1 to 5) Resin compositions were obtained in the same manner as in Example 1 except that the amount of each compounding agent was changed to the amount shown in Table 1. However, the following compounding agents were used. Table 1 shows the evaluation results.

(A) As a thermoplastic polyester resin: a polyethylene terephthalate resin having an logarithmic viscosity of 0.75 dl / g (a-2) a polybutylene terephthalate resin having an logarithmic viscosity of 0.85 dl / g (a-3) (B) As a vinyl resin ・ Styrene resin (trade name: Estyrene G14 manufactured by Nippon Steel Chemical Co., Ltd.) (b-2) ・ Polymethyl methacrylate resin (trade name: Acrypet MD, Mitsubishi Rayon Co., Ltd.)
(b-3) (C) As organophosphorus flame retardant: Resorcinol bis (di-2,6-xylyl) phosphate (trade name: PX200 manufactured by Daihachi Chemical Industry Co., Ltd.) (c-
2) Hydroquinone bis (di-2,6-xylyl) phosphate (trade name: PX201 manufactured by Daihachi Chemical Co., Ltd.) (c-3) The flame-retardant polyester resin composition of the present invention is excellent in flame retardancy, mechanical strength, wet heat resistance, heat resistance, and high temperature which is a problem in polyester flame-retarded with an organic phosphorus-based flame retardant. Changes in the appearance and properties of the molded product under high humidity were suppressed, indicating that the product was excellent.

[0042]

Industrial Applicability The flame-retardant polyester resin composition of the present invention is excellent in flame retardancy, mechanical strength, wet heat resistance and heat resistance, and is further made of a polyester flame-retarded with an organic phosphorus-based flame retardant. Thus, the change in the appearance and characteristics of the molded article under high temperature and high humidity, which is a problem, is suppressed. 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 the like which is used particularly in a use environment under high temperature and high humidity, and is industrially useful.

[0043]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 57:00) F-term (reference) 4J002 BC01X BC03X BC04X BC06X BC08X BC09X BF01X BF02X BG04X BG05X BG06X BG10X BG13X BH02X BK00 BL BL01X BL02X CE00X CF01W CF03W CF04W CF05W CF06W CF07W CF08W CF10W CF16W CF17W CQ01Y DL008 EU187 EU197 EW036 EW046 EW136 EW146 FA048 FB138 FB148 FD020 FD030 FD050 FD090 FD100 FD13G FD160 FD136 FD136 FD136 G

Claims (4)

[Claims] 1. A flame-retardant polyester resin composition comprising the following components (A) to (D), the total of which is 100% by weight. (A) thermoplastic polyester resin: 20 to 60% by weight (B) vinyl resin: 1.0 to 30% by weight (C) organophosphorus flame retardant: 0.5 to 20% by weight (D) glass fiber: 5 ~ 50% by weight 2. A reinforced flame-retardant polyester resin composition comprising the following components (A) to (E), the total of which is 100% by weight. (A) thermoplastic polyester resin: 20 to 60% by weight (B) vinyl resin: 1.0 to 30% by weight (C) organophosphorus flame retardant: 0.5 to 20% by weight (D) glass fiber: 5 (E) Melamine / cyanuric acid adduct: 4 to 20% by weight 3. The reinforced flame-retardant polyester resin composition according to claim 1, wherein the vinyl resin as the component (B) is at least one vinyl resin selected from a polystyrene resin and a polymethyl methacrylate resin. object. 4. The organic phosphorus flame retardant as the component (C) is a compound 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 —, −
A divalent linking group wherein O-, -CO- or -N = N-,
The reinforced flame-retardant polyester resin composition according to claim 1, wherein n is 0 or 1, and m represents 1 to 10.)