JPH11209587A - Flame-retardant polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant polyester resin composition not containing a halogen-based flame retardant and an antimony compound, having excellent flame retardance, mechanical strength, heat resistance, tracking resistance and molding cycle and giving molded products having excellent appearances and dimensional stability. SOLUTION: This flame-retardant polyester resin composition comprises (A) 25-64 wt.% of a thermoplastic polyester resin, (B) an organic phosphorous flame retardant and (C) a melamine-cyanuric acid adduct in a total amount of 15-32 wt.%, (D) glass fibers and (E) an inorganic filler in a total amount of 20-59 wt.%, and (F) 0.01-2 wt.% of a fluororesin compound having an average particle diameter of <=450 μm and a density/bulk density (density/high density) ratio of <=4.0. Therein, the total amount of the components is 100 wt.%, and the components are compounded in a component B/component C ratio of 1/1 to 1/3 and in a component D/component E ratio of 3/2 to 1/4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polyester resin composition used for electric and electronic equipment parts, automobile parts and the like, and more particularly to a bromine- and chlorine-based flame retardant, an antimony compound. The present invention relates to a flame-retardant polyester resin composition containing no.

[0002]

2. Description of the Related Art Thermoplastic polyester resins represented by polyalkylene terephthalate and the like are widely used in electric and electronic equipment parts, automobile parts, and the like because of their excellent properties. In recent years, especially in the field of electrical and electronic equipment components, U.S.A.
L-94 (US Underwriters Laboratory Standard)
In many cases, a high degree of flame retardancy that is compatible with V-0 is required, and therefore, blending of various flame retardants is being studied.

In general, when imparting flame retardancy to a thermoplastic polyester resin, a halogen-based flame retardant is used as a flame retardant in combination with a flame retardant auxiliary 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.

[0004] As one of such flame retardants, inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide are known. However, these inorganic flame retardants are
Since the flame-retarding effect is extremely small, it is necessary to add a large amount in order to obtain a high degree of flame retardancy, and there is a problem that the inherent properties of the resin are impaired.

On the other hand, as other flame retardants containing no halogen, various uses of nitrogenous flame retardants such as organophosphorus flame retardants and triazine compounds such as melamine / cyanuric acid adducts have been studied.

Examples of the organic phosphorus-based flame retardants include triphenyl phosphate, cresyl diphenyl phosphate, and tricresyl phosphate. Under these conditions, there are problems such as volatilization and bleeding of these organic phosphorus-based flame retardants. Therefore, in recent years, organic phosphorus-based flame retardants having relatively high molecular weight such as phosphate ester condensates have been studied. A flame-retardant resin composition using such a phosphorus-based flame retardant is disclosed in JP-B-51-19858.
JP, JP-B-51-39271, JP-B-51-39271
39271 and JP-A-52-102255.

Further, in order to achieve a high level of flame retardancy conforming to UL-94 V-0, various methods of further using a nitrogen-based flame retardant have been studied. Japanese Patent No. 281652 discloses a method in which a polyalkylene terephthalate resin is used in combination with a melamine / cyanuric acid adduct and a phosphorus-based flame retardant. Further, Japanese Unexamined Patent Publication No.
JP-A-70671 and JP-A-6-157880 disclose methods for improving flame retardancy, generation of toxic gas, and corrosiveness by using a specific phosphorus-based flame retardant together with a melamine / cyanuric acid adduct. Have been. However,
These resin compositions have the problem that properties such as mechanical strength, impact resistance, and moisture resistance are impaired.

Therefore, Japanese Patent Application Laid-Open No. 7-196843,
Japanese Patent Application Laid-Open No. 7-233311 discloses that a mechanical strength and resistance to mechanical strength generated when an organic phosphorus-based flame retardant and a triazine compound such as a melamine / cyanuric acid adduct as a nitrogen-based flame retardant are added to a thermoplastic polyester resin. It has been proposed to improve the reduction in impact resistance and moisture resistance by using a compound having two or more functional groups in the same molecule, such as a diepoxy compound.

[0009]

The main fields in which such a flame-retardant polyester resin composition is used include electric and electronic parts. Among these uses, power plug parts and power outlets are particularly preferred. Parts, switch parts, relay parts, and their housing parts are required to have not only high flame retardancy but also high electrical characteristics such as tracking resistance. Conventionally, these parts are mainly small parts, are often incorporated inside products, are rarely seen from the outside, and the surface properties of molded articles are not so much questioned. However, in recent years, in electrical and electronic parts and housing parts, integration of parts as much as possible has been promoted in order to make the products themselves more sophisticated and lower in cost. Due to the integration of these parts, there are cases where they cannot be incorporated inside as in the past, and the surface properties of molded products have been frequently questioned. further,
Due to the integration of the parts, the shape of the molded article naturally becomes more complicated, and as a result, the requirements for the dimensional stability of the molded article have become higher.

[0010] In order to solve these problems, the flame-retardant polyester resin composition obtained by the above-described technique can exhibit properties such as flame retardancy and tracking resistance, but it does not have the surface property of a molded article. In addition, there are problems such as the floating of fillers and the occurrence of uneven patterns, and in the dimensional stability of molded articles, the occurrence of warpage at the time of molding has become a problem, and improvement thereof has been strongly demanded. From the viewpoint of further cost reduction, it has been strongly desired to shorten the molding cycle.However, for example, shortening the cooling time leads to a decrease in the dimensional stability of the molded product. It was a difficult problem.

[0011]

The present inventors have made intensive studies to improve the above-mentioned problems, and as a result, surprisingly, an organic phosphorus-based flame retardant, melamine cyanurate was added to a thermoplastic polyester resin. By adding an acid additive, glass fiber, inorganic filler, and a specific fluororesin in a specific amount and a specific ratio, mechanical strength, heat resistance,
The present inventors have found that a flame-retardant resin composition having excellent surface properties of a molded article, dimensional stability of the molded article, tracking resistance, and molding cycleability can be obtained, thereby completing the present invention.

That is, the flame-retardant polyester resin composition of the present invention comprises a thermoplastic polyester resin (A) 25-6.
4% by weight, total of organic phosphorus-based flame retardant (B) and melamine / cyanuric acid adduct (C) is 15 to 32% by weight, total of glass fiber (D) and inorganic filler (E) is 20 to 59% by weight % And a ratio of density to bulk density (density / bulk density) of not more than 4.0 and a fluororesin (F) having an average particle diameter of not more than 4.0 and 0.01 to 2% by weight.
The total of (F) is 100% by weight, and the weight ratio (B / C) between the components (B) and (C) is 1/1 to 1/1.
3. The weight ratio (D / E) of the components (D) and (E) is 3
/ 2 to 1/4.

A second aspect of the present invention is that the thermoplastic polyester resin as the component (A) in the flame-retardant polyester resin composition is a polyalkylene terephthalate resin.

A third aspect of the present invention is that the polyalkylene terephthalate resin in the second flame-retardant polyester resin composition is a polyethylene terephthalate resin.

A fourth aspect of the present invention is that the organophosphorus flame retardant of the component (B) in the first to third flame retardant polyester resin compositions is represented by the following general formula (I):

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, wherein n is 0 or 1, and m is an integer of 1 to 10). That is.

A fifth aspect of the present invention is that the inorganic filler of the component (E) in the first to fourth flame-retardant polyester resin compositions is selected from talc, wollastonite, dolomite and calcium carbonate. It is at least one inorganic filler.

[0017]

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 as an acid component, or a derivative thereof having an ester-forming ability, and a glycol component as a carbon component. A saturated polyester resin obtained by using 2 to 10 glycols, other dihydric alcohols, or derivatives 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 the polyalkylene terephthalate resin include a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polyhexamethylene terephthalate resin, a polycyclohexane dimethylene terephthalate resin and the like. Polyethylene terephthalate resin is preferred in view of the tendency.

The thermoplastic polyester resin (A) used in the present invention can be copolymerized with other components, if necessary, preferably in a proportion of 20% by weight or less, particularly preferably 10% by weight or less. As the components for copolymerization, known acid components, alcohol components and / or phenol components, or derivatives thereof having ester-forming ability can be used.

As the acid component, 2-8 carbon atoms.
The aromatic carboxylic acid having a valence of 4 or more, an aliphatic carboxylic acid having 4 to 12 carbon atoms, an alicyclic carboxylic acid having 8 to 15 carbon atoms, and derivatives thereof having an ester-forming ability can be given. 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, 1,4-cyclohexanedicarboxylic acid, and derivatives thereof having ester-forming ability are exemplified. These may be used alone or in combination of two or more. Among these, terephthalic acid, because it is excellent in physical properties of the obtained resin, handleability, ease of reaction,
Isophthalic acid and naphthalenedicarboxylic acid are preferred.

The alcohol and / or phenol component includes dihydric or higher aliphatic alcohols having 2 to 15 carbon atoms, alicyclic alcohols having 6 to 20 carbon atoms and dihydric alcohols having 6 to 20 carbon atoms, and dihydric alcohols having 6 to 40 carbon atoms. Aromatic alcohols or phenols having a valency or more, and derivatives thereof having an ester-forming ability are included. Specifically, ethylene glycol,
Propanediol, butanediol, hexanediol, decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, 2,
2′-bis (4-hydroxyphenyl) propane, 2,
2-bis (4-hydroxycyclohexyl) propane,
Compounds such as hydroquinone, glycerin and pentaerythritol, and derivatives thereof having an ester forming ability, and cyclic esters such as ε-caprolactone can also be used. Among these, ethylene glycol and butanediol are preferable because they are excellent in physical properties, handleability, and ease of reaction of the obtained resin.

Further, a polyoxyalkylene glycol unit may be partially copolymerized. Specific examples of polyoxyalkylene glycols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and random or block copolymers thereof, and alkylene glycols of bisphenol compounds (for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, And modified polyoxyalkylene glycols such as random or block copolymers thereof and adducts thereof. Among these, the thermal stability during copolymerization is good,
A polyethylene glycol adduct of bisphenol A having a molecular weight of 500 to 2,000 is preferable because the heat resistance of the obtained molded article is hardly reduced.

These thermoplastic polyester resins (A)
Are used alone or in combination of two or more, and the amount thereof is 25 to 64% by weight, preferably 30% by weight in 100% by weight of the resin composition.
６０60% by weight. If the amount is less than 25% by weight, the excellent properties inherent to the thermoplastic polyester resin cannot be exhibited. If the amount exceeds 64% 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 (A) can be produced by a known polymerization method such as melt polycondensation, solid phase polycondensation, solution polymerization and the like. Also,
To improve the color of the resin during polymerization, phosphoric acid, phosphorous acid, hypophosphorous acid, monomethyl phosphate, dimethyl phosphate,
Trimethyl phosphate, methyl diethyl phosphate, triethyl phosphate, triisopropyl phosphate, tributyl phosphate,
One or more compounds such as triphenyl phosphate may be added. Further, in order to increase the crystallinity of the obtained thermoplastic polyester resin, one or two or more kinds of commonly known organic or inorganic crystal nucleating agents may be used at the time of polymerization.

The inherent viscosity of the thermoplastic polyester resin (A) (phenol / tetrachloroethane is 1
/ 1 in a mixed solvent at 25 ° C) is 0.4 to 1.2.
, And particularly preferably 0.6 to 1.0 dl / g. When the intrinsic viscosity is less than 0.4 dl / g, mechanical strength and impact resistance tend to decrease,
If it exceeds 1.2, the fluidity tends to decrease.

The organic phosphorus-based flame retardant (B) used in the present invention is not particularly limited as long as it contains a phosphorus atom in the molecule and has a small dispersion and volatilization during molding of the thermoplastic polyester resin. No, for example, carbon number 1
12, preferably an organic phosphorus compound such as an alcohol or phenol phosphate compound having 1 to 8 linear or branched aliphatic groups, aromatic groups, and alicyclic groups, a phosphonate compound, a nitrogen-containing organic phosphorus compound, and the like. Is mentioned.

Representative examples of the organophosphorus flame retardant (B) include phosphate, phosphonate, phosphinate, phosphine oxide, phosphite, phosphonite, phosphinite, and phosphine. 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, triphenyl phosphite, tris (nonylphenyl) phosphite, tritridecyl phosphite, dibutyl hydrogen diene phosphite, triphenyl phosphine oxide, tricresyl phosphine oxide, diphenyl methanephosphonate, phenyl phosphite Examples thereof include diethyl fonate and the like, and, for example, an organic phosphorus compound such as a condensed phosphate ester represented by the following general formula (I).

Among these organophosphorus flame retardants, they have low volatility and good thermal stability at the time of molding, and are not liable to impair physical properties such as thermal stability of thermoplastic polyester resin. From the following general formula (I):

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, m is an integer of 1 to 10); Is preferred. Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^{1 to} R ¹⁷ 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 resin (A) decreases, and the flame retardant effect tends to decrease. Therefore, 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, a phosphoric acid and each substituted phenol are preferable, and examples of the dihydroxy compound having at least one substituted benzene ring include resorcinols, Examples include 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), 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) represented by the following formula (III)
-Xylyl) phosphate], methylresorcinol bis [(di-2,6-xylyl) phosphate], hydroquinone bis [(di-2,6-
Xylyl) phosphate], 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], bisphenol bis [(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.

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

Among these, the condensed phosphoric acid esters represented by the above formulas (II) to (IV) are more excellent in thermal stability and less contaminant to metal parts such as molds during molding. And condensates thereof are preferred.

These organophosphorus 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 melamine / cyanuric acid adduct (C) used in the present invention includes melamine (2,4,6-triamino-1,3,5-triazine) and cyanuric acid (2,4).
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. Although there is no particular limitation on the mixing ratio of melamine and cyanuric acid, the resulting adduct is unlikely to impair the thermal stability of the thermoplastic polyester resin,
It is better to be close to equimolar, especially 1: 1. The average particle size of the melanino / cyanuric acid adduct is not particularly limited, but is preferably 0.01 to 250 μm from the viewpoint of not impairing the strength properties and the moldability of the obtained resin composition, and in particular,
0.5 to 200 μm is preferred.

The organophosphorus flame retardant (B) and melamine
The total amount of the cyanuric acid adduct (C) added is 15 to 32% by weight, preferably 17 to 30% by weight, particularly preferably 18 to 28% by weight in the flame-retardant polyester resin composition. %. The total amount of both is 15% by weight
If the total amount is less than 32% by weight, the flame retardancy, the surface properties of the molded article, the tracking resistance, and the molding cycleability tend to decrease.
The surface properties, molding cycleability, and extrusion processability of the molded article tend to decrease, which is not preferable.

The compounding ratio of the organophosphorus flame retardant (B) and the melamine / cyanuric acid adduct (C) is preferably such that (B / C) is 1/1 to 1/3 by weight. Is
5/6 to 4/6. The mixing ratio (B / C) of both is 1
If it is less than / 3, the surface properties and molding cycle properties of the molded article tend to be inferior, while the compounding ratio (B / C) of both is 1
If it exceeds / 1, flame retardancy, mechanical strength and heat resistance are inferior.

Further, as the glass fiber (D) used in the present invention, known glass fibers generally used can be used, but from the viewpoint of workability, chopped glass treated with a sizing agent is used. Preferably, strand glass 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. As the coupling agent, for example, alkoxysilane compounds such as γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, and as the binder, for example, epoxy resin, urethane resin and the like are preferably used. However, the present invention is not limited to these. These glass fibers can be used alone or in combination of two or more.

The glass fiber (D) has a fiber diameter of 1 to 20.
μm and the fiber length are preferably 0.01 to 50 mm. When the fiber diameter is less than 1 μm, there is a tendency that the reinforcing effect as expected is not 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. . Also, there is a tendency that the reinforcing effect as expected is not obtained even if the fiber length is less than 0.01 mm, and if the fiber length exceeds 50 mm, the surface properties of the molded product, the dimensional stability of the molded product, Fluidity tends to decrease, which is not preferable.

The inorganic filler (E) used in the present invention includes talc, wollastonite, dolomite, calcium carbonate, kaolin, mica, glass beads, glass powder,
Ceramic powder, metal powder, calcium carbonate and the like can be mentioned. These inorganic fillers may be used alone or in combination of two or more. These inorganic fillers are used for the purpose of improving tracking resistance, molding cycle properties, and dimensional stability of molded articles. Among these inorganic fillers,
Talc, wollastonite, dolomite, and calcium carbonate are preferred, and talc is particularly preferred, because they tend to have more excellent tracking resistance and molding cycle properties.

The inorganic filler (E) may be a baked product and / or
Alternatively, it may be in any form of an unfired product, and may be an anhydride and / or a hydrate having one or more molecules of crystallinity as long as various physical properties such as thermal stability of the resin composition are not impaired.

Further, the inorganic filler (E) may be treated with a surface treating agent such as a silane coupling agent or a titanate coupling agent. Examples of the silane-based coupling agent include an epoxy-based silane, an amino-based silane, and a vinyl-based silane, and examples of the titanate-based coupling agent include a monoalkoxy-type, a chelate-type, and a coordinate-type. . There is no particular limitation on the method of treating with these surface treatment agents,
It can be carried out in the usual way. For example, the surface treatment agent can be added to the layered silicate and stirred or mixed in a solution or while heating. These different inorganic fillers treated with these surface treatment agents may be used alone or in combination of two or more.

The glass fiber (D) and the inorganic filler (E)
The total amount of both is 20 to 59% by weight in the flame retardant polyester resin composition, preferably 25 to 55%.
%, Particularly preferably 30 to 50% by weight. If the total amount of both is less than 20% by weight, sufficient mechanical strength and heat resistance tend not to be obtained. On the other hand, if the total amount of both exceeds 59% by weight, the surface properties of the molded article and the molding cycle property However, the extrudability tends to decrease, which is not preferable.

The mixing ratio of the glass fiber (D) and the inorganic filler (E) is such that (D / E) is 3/2 to 1 by weight.
/ 4, particularly preferably 1/1 to 1/3.
When the mixing ratio (D / E) of both is less than 1/4, the mechanical strength, the wet heat resistance and the molding cycle property tend to be inferior, while the mixing ratio (D / E) of both is 3 /. If it exceeds 2, the surface properties of the molded article and the dimensional stability of the molded article are inferior, which is not preferable.

The fluororesin (F) used in the present invention is a resin having a fluorine atom in the resin. Specific examples of the fluororesin (F) include polymonofluoroethylene, polydifluoroethylene, and polydifluoroethylene. Examples thereof include trifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / hexafluoropropylene copolymer. In addition, as long as the physical properties such as flame retardancy of the obtained molded article are not impaired, if necessary, the monomers used for producing these fluororesins and other copolymerizable monomers containing no fluorine atom may be used. A copolymer obtained by polymerization in combination may be used. These fluororesins are used alone or in combination of two or more.

The method for producing the fluororesin (F) is not particularly limited, but, for example, tetrafluoroethylene is converted to a free radical catalyst in an aqueous solvent, for example,
It can be obtained by polymerization at a temperature of 0 to 200 ° C. under a pressure of 100 to 1000 psi in the presence of sodium, potassium, or ammonium peroxydisulfide, and emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization And other known polymerization methods. Among them, those obtained from emulsion polymerization are particularly preferable from the viewpoint of the effect of improving the flame retardancy.

In the present invention, the fluororesin (F) needs to have an average particle diameter of 450 μm or less.
More preferably, it is 300 to 430 μm. If the average particle diameter exceeds 450 μm, the surface properties and extrudability of the molded product may be reduced, and a resin composition may not be obtained. In addition,
The average particle size of the fluororesin (F) is 0.3 μm
It means the average particle diameter of the secondary particles formed by agglomeration of the primary particles.

Further, in the present invention, the ratio (density / bulk density) (density / bulk density) of the fluororesin (F) needs to be 4 or less, preferably 3.5 to 4.0. It is. When the (density / bulk density) exceeds 4, flame retardancy may not be obtained in some cases, and the surface properties of the molded article tend to decrease. In addition, the density and the bulk density referred to here are JIS
It is measured by the method described in -K6891 and is usually expressed in units of [g / cm ³ ]. In addition, even if it is the same particle diameter, the small value of (density / bulk density) means that the voids are small in the aggregation of the primary particles forming the secondary particles, and the secondary particles are formed in a denser state. Means that.

The compounding amount of the fluororesin (F) is from 0.01 to 5% by weight, preferably from 0.05 to 2% by weight, more preferably from 100% by weight, based on 100% by weight of the flame-retardant polyester resin composition. , 0.1 to 1% by weight. When the compounding amount is 0.
If the content is less than 01% by weight, the flame retardancy tends to decrease, while if it exceeds 5% by weight, the surface properties, extrudability and the like of the molded article tend to decrease.

The flame-retardant polyester resin composition of the present invention may further contain, if necessary, other compounding agents, for example, an inorganic or organic flame retardant, a flame retardant auxiliary, a reinforcing agent, a hindered phenol compound, Deterioration inhibitors for phyto compounds, thioether compounds, epoxy compounds, etc., UV absorbers,
A release agent, a colorant, a crystal nucleating agent, an antistatic agent, a lubricant, a plasticizer, other polymers, and the like can be blended as long as the object of the present invention is not impaired.

The method for producing the resin composition of the present invention is not particularly limited. For example, the above components (A) to (F), and other additives, resins, etc. are dried and then melt-kneaded with a melt kneader such as a single-screw or twin-screw extruder. can do. 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 resin composition of the present invention can be formed into various forms, for example, various molded articles, sheets, pipes, bottles, etc. by various molding methods. In addition, it has high flame retardancy, excellent dimensional stability, and a good balance with other properties, so it can be used for electronic and electrical parts such as home appliances and OA equipment, and injection molded products such as housings. It is preferably used. In particular, applications that make use of electrical properties such as excellent dielectric breakdown strength, arc resistance, and tracking resistance include breaker parts, switch parts, motor parts, ignition coil cases, power module cases, power plugs, and power outlets. , Coil bobbins, connector terminals, fuse cases, etc.

[0053]

EXAMPLES The resin composition of the present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 As a thermoplastic polyester resin (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, 54.9% by weight of sufficiently dried polyethylene terephthalate (a-1), and melamine cyanurate (trade name: MC440, Nissan Chemical Co., Ltd.) as melamine / cyanuric acid adduct (C) 15% by weight, average particle size 380 μm, density 2.20, bulk density 0.57, (density /
0.5% by weight of polytetrafluoroethylene (f-1) having a bulk density of 3.86, and bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.) 0.3 as a stabilizer % By weight, tetrakismethylene-3,5-di-t-butyl-4-hydroxyhydrocinnamate methane (trade name: ADK STAB AO-
60 (manufactured by Asahi Denka Co., Ltd.) was dry blended. The mixture is brought to a cylinder temperature of 270-28.
It is supplied to a hopper of a vent type 45 mmφ co-rotating twin screw extruder (trade name: TEX44, manufactured by Nippon Steel Works Co., Ltd.) set to 0 ° C., and bisphenol A bis (dicresyl phosphate) is used as an organic phosphorus-based flame retardant (B). )
(B-1) 5% by weight (trade name: CR747, manufactured by Daihachi Chemical Co., Ltd.) of T-195H / P manufactured by NEC Corporation as glass fiber (D) using a liquid addition pump.
6% by weight, and 18% by weight of wollastonite (e-1) (trade name: NYAD325, manufactured by NYCO Co., Ltd.) as an inorganic filler (E) were added and melted in the middle of an extruder using a side feeder. Pellets were obtained by kneading.

After the obtained pellets were dried at 140 ° C. for 4 hours, using an injection molding machine (mold clamping pressure: 50 tons), the cylinder temperature was 280 to 250 ° C. and the mold temperature was 70 ° C. 6.4 mm, 3.2 mm, and 1.6 mm bars (length: 127 mm, width: 12.7 mm, respectively)
In addition, using an injection molding machine (clamping pressure: 75 tons, cylinder diameter: 36 mmφ), cylinder temperature: 280 ° C.
250 ° C, screw rotation speed: 100 rpm, back pressure: 0.
Flat plates having a size of 120 × 120 mm, a thickness of 2 mm and a thickness of 3 mm were formed at 8 MPa and a mold temperature of 90 ° C., respectively. Using these test pieces, physical properties were evaluated according to the following criteria.

<Flame Retardancy> The flame retardancy of a 1.6 mm thick bar was evaluated according to the UL-94 standard. In addition, NOT-V of the flame retardancy evaluation result indicates that it does not conform to the UL-94 standard.

<Mechanical Strength> Tensile strength of a 3.2 mm thick bar was measured according to ASTM D-638.

<Heat resistance> According to ASTM D-648,
The deflection temperature under load [HDT] of a bar having a thickness of 6.4 mm was measured at a load of 1.82 MPa.

<Surface Properties of Molded Product> The surface of a flat plate molded to a thickness of 2 mm was visually observed and the surface of the molded product was touched by hand, and judged according to the following criteria. (Judgment Criteria) A: There is surface gloss and the surface properties are uniform. B: The surface properties are uniform. C: A fine linear pattern is observed. D: The surface properties are not uniform. E: The surface properties are non-uniform, and surface roughness can be confirmed by touching with hands.

<Dimensional Stability of Molded Product> A flat plate molded to a thickness of 2 mm was left at a temperature of 23 ° C. and a humidity of 55% for 24 hours, and the diagonal warpage was measured and evaluated. The diagonal warpage was measured by placing the test piece on a flat surface, fixing one corner, and then measuring the amount by which the diagonal side was lifted using a clearance gauge. Measurement was performed for each of the four corners, and the largest value was taken as the amount of warpage. A large amount of warpage means a large change in the shape of the molded product, and it can be determined that the dimensional stability of the molded product is inferior.

<Tracking Resistance> A 20 mm × 20 mm, 3 mm thick test piece obtained by cutting a flat plate was used.
The comparative tracking index [CTI] was evaluated according to the IEC standard (Pub. 112).

<Molding cycle property> Using an injection molding machine (clamping pressure: 50 tons, cylinder diameter: 36 mmφ), cylinder temperature: 280 to 250 ° C, screw rotation speed:
100rpm, back pressure: 0.8MPa, measuring length: 55m
The cooling time was changed at m, and the evaluation was made by the molding cycle (hour; minute) at the shortest cooling time at which no molding failure occurred. It can be determined that the shorter the molding cycle, the higher the production efficiency and the higher the molding efficiency.

Examples 2 to 6 A resin composition was obtained in the same manner as in Example 1 except that the amounts of the respective components were changed to those shown in Table 1, and similar test pieces were molded. However, those listed in Table 2 were used as other compounding agents. Table 1 shows the evaluation results of Examples 1 to 6 described above.

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[Table 1]

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[Table 2]

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[Table 3]

Comparative Examples 1 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 those shown in Table 3, and the same test pieces were molded. However, those shown in Table 4 were used as the fluorine resin (F) other than the above. Table 3 shows the evaluation results.

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[Table 4]

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[Table 5]

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[Table 6]

As is clear from the comparison between the evaluation results of Examples in Table 1 and the evaluation results of Comparative Examples in Table 3, the flame-retardant polyester resin composition of the present invention has flame retardancy and mechanical strength. It can be seen that heat resistance, surface properties of the molded product, dimensional stability of the molded product, tracking resistance, and molding cycleability are all excellent.

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The flame-retardant polyester resin composition of the present invention is excellent in flame retardancy, mechanical strength, heat resistance, molded article surface properties, molded article dimensional stability, tracking resistance and molding cycle property. And does not contain halogen-based flame retardants or 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.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5: 523 5: 3492 7:14 3:00)

Claims (5)

[Claims] 1. A thermoplastic polyester resin (A) 25 to
64% by weight, total of organic phosphorus-based flame retardant (B) and melamine / cyanuric acid adduct (C) is 15 to 32% by weight, total of glass fiber (D) and inorganic filler (E) is 20 to 59% by weight % And a ratio of density to bulk density (density / bulk density) of not more than 4.0 and a fluororesin (F) having an average particle diameter of not more than 4.0 and 0.01 to 2% by weight.
The total of (F) is 100% by weight, and the weight ratio (B / C) between the components (B) and (C) is 1/1 to 1/1.
3. The weight ratio (D / E) of the components (D) and (E) is 3
/ 2 to 1/4. The flame-retardant polyester resin composition. 2. The flame-retardant polyester resin composition according to claim 1, wherein the thermoplastic polyester resin as the component (A) is a polyalkylene terephthalate resin. 3. The flame-retardant polyester resin composition according to claim 2, wherein the polyalkylene terephthalate resin is a polyethylene terephthalate resin. 4. The organic phosphorus-based flame retardant of the component (B) is represented by the following 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 an integer of 1 to 10). Item 4. The flame-retardant polyester resin composition according to any one of Items 1 to 3. 5. The inorganic filler of component (D) is at least one inorganic filler selected from talc, wollastonite, dolomite and calcium carbonate.
5. The flame-retardant polyester resin composition according to any one of 4.