JP5347211B2 - Flame retardant polyester resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant polyester resin composition of nonhalogen, having high initial flame retardance and capable of keeping flame resistance after a long heat aging test. <P>SOLUTION: The flame-retardant polyester resin composition having high initial flame retardance and capable of keeping flame resistance after a long heat aging test is obtained by adding an organophosphorus-based flame retardant represented by general formula (1) (wherein, n is an integer of 2-20) and an inorganic compound at a specific ratio. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a flame-retardant polyester resin that does not contain bromine, a chlorine-based flame retardant, and an antimony compound and is excellent in maintaining initial flame retardancy and flame retardancy after long-term heat aging.

  Thermoplastic polyester resins represented by polyalkylene terephthalate and the like are widely used for electric and electronic parts, automobile parts and the like because of their excellent characteristics. In recent years, particularly in home appliances, electricity, and OA-related parts, in order to ensure safety against fire, there are many examples that require high flame retardancy, and therefore, various flame retardant blends have been studied.

When flame resistance is imparted to thermoplastic polyester resins, it is generally difficult to use a halogen-based flame retardant as a flame retardant, and use a flame retardant aid such as antimony trioxide as necessary. A resin composition having a flame effect and excellent mechanical strength, heat resistance and the like has been obtained. Recently, however, regulations on halogenated flame retardants are being issued mainly for products for overseas markets, and non-halogenated flame retardants are being studied.
On the other hand, a technology relating to a resin composition comprising a phosphorus flame retardant having the same structure as the phosphorus flame retardant used in the present invention and a thermoplastic polyester resin (Patent Document 1) has already been disclosed, and polybutylene terephthalate. It is disclosed that a flame retardant property of V-1 to V-0 can be realized based on UL94 in a compression molded product having a thickness of 3.2 mm using a resin.

However, in recent years, particularly in home appliances, electricity, and OA-related parts, high flame retardancy is required to ensure safety against fire, while products are becoming lighter, thinner and smaller. That is, even very thin molded products such as 1/16 inch are required to have V-0 in accordance with UL94 standards, and mechanical properties and heat resistance useful as a structural material requiring heat resistance are also required. In addition, from the viewpoint of long-term reliability of products, for example, it is required that flammability at 1/16 inch should be maintained at V-0 even after a heat aging test at 160 ° C. × 500 hr as a long-term heat resistance acceleration test. Has been. To meet these requirements, the technology disclosed in the patent cannot be achieved, and no materials satisfying the requirements have been obtained at present.
Japanese Examined Patent Publication No. 53-128195

  In view of the current situation as described above, the object of the present invention is V-0 on the basis of UL94 even in a very thin molded product such as 1/16 inch, and after a heat aging test at 160 ° C. × 500 hr. Further, the present invention provides a polyester-based resin composition that is 1/16 inch, can maintain a V-0 flammability on the basis of UL94, and has mechanical properties and heat resistance useful as a structural material.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have made the thermoplastic polyester resin excellent by containing an organic phosphorus flame retardant having a specific structure and an inorganic compound in a specific ratio. A flame-retardant polyester resin composition having flame retardancy and excellent mechanical properties and heat resistance has been completed.

  That is, the first of the present invention is the following general formula (1) with respect to 100 parts by weight of the thermoplastic polyester resin.

(Wherein n is an integer of 2 to 20) represented by 10 to 80 parts by weight of an organic phosphorus flame retardant and 10 to 100 parts by weight of a silicate flame retardant polyester resin composition A flame retardant polyester resin composition having a flame retardancy at 1/16 inch thickness of V-0 based on UL94.

  A preferred embodiment relates to a flame retardant polyester resin composition characterized by being V-0 on the basis of UL94 at a thickness of 1/16 inch even after heat treatment at 160 ° C. for 500 hours.

  A more preferred embodiment relates to the flame retardant polyester resin composition described above, wherein the thermoplastic polyester resin is a polyalkylene terephthalate resin.

A more preferred embodiment relates to the flame retardant polyester resin composition described above, wherein the thermoplastic polyester resin is a polyethylene terephthalate resin.
More preferred embodiments relate to the flame retardant polyester resin composition described above, wherein the inorganic compound is surface-treated with a silane compound, a titanium compound, an alumina compound, a polyether compound or an amine compound.

  The second aspect of the present invention relates to a resin molded article formed entirely or partly from the flame retardant polyester resin composition described above.

  The flame-retardant polyester resin composition of the present invention is V-0 on the basis of UL94 in a very thin molded article such as 1/16 inch, and is 1/16 even after a long-term heat aging test at 160 ° C. × 500 hr. Inflammability based on UL94 standard can be maintained at V-0. Even if it is thin, it is excellent in mechanical strength and rigidity. Therefore, the flame-retardant polyester resin composition of the present invention can be suitably used as a molding material for home appliances, electricity, OA parts and the like, and is industrially useful.

  The thermoplastic polyester resin used in the present invention uses a divalent acid such as terephthalic acid as an acid component or a derivative thereof having ester-forming ability, a glycol having 2 to 10 carbon atoms as a glycol component, and other 2 A saturated polyester resin obtained by using a hydric alcohol or a derivative thereof having ester-forming ability. Among these, a polyalkylene terephthalate resin is preferable in that it has an excellent balance of processability, mechanical properties, electrical properties, heat resistance, and the like. Specific examples of the polyalkylene terephthalate resin include polyethylene terephthalate resin, polybutylene terephthalate resin, and polyhexamethylene terephthalate resin. Among them, polyethylene terephthalate resin is particularly preferable because of excellent heat resistance and chemical resistance. .

  If necessary, the thermoplastic polyester resin used in the present invention is preferably 20 parts by weight or less, particularly preferably 10 parts by weight or less when the thermoplastic polyester resin is 100 parts by weight. Can be copolymerized. As a copolymerization component, a known acid component, alcohol component and / or phenol component, or derivatives thereof having ester forming ability can be used.

  Examples of the copolymerizable acid component include a divalent or higher aromatic carboxylic acid having 8 to 22 carbon atoms, a divalent or higher aliphatic carbonic acid having 4 to 12 carbon atoms, and a divalent or higher carbon number. Examples thereof include 8 to 15 alicyclic carboxylic acids and derivatives thereof having ester forming ability. Specific examples of the copolymerizable acid component include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, bis (p-carbodiphenyl) methaneanthracene dicarboxylic acid, 4-4′-diphenylcarboxylic 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. 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 resulting resin is excellent in physical properties, handleability, and ease of reaction.

  Examples of the copolymerizable alcohol and / or phenol component include dihydric or higher aliphatic alcohols having 2 to 15 carbon atoms, dihydric or higher alicyclic alcohols having 6 to 20 carbon atoms, and 6 to 40 carbon atoms. Examples thereof include aromatic alcohols having a valence of 2 or more, phenols, and derivatives thereof having an ester forming ability. Specific examples of the copolymerizable alcohol and / or phenol component include ethylene glycol, propanediol, butanediol, hexanediol, decanediol, neopentylglycol, cyclohexanedimethanol, cyclohexanediol, 2,2′-bis (4 -Hydroxyphenyl) propane, 2,2'-bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, and the like, and derivatives having ester forming ability, and cyclic esters such as ε-caprolactone It is done. Among these, ethylene glycol and butanediol are preferable because they are excellent in physical properties, handleability, and reaction ease.

  Furthermore, some polyalkylene glycol units may be copolymerized. Specific examples of the polyoxyalkylene glycol include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and random or block copolymers thereof, alkylene glycols of bisphenol compounds (polyethylene glycol, polypropylene glycol, polytetramethylene glycol) , And random or block copolymers thereof) modified polyoxyalkylene glycols such as adducts. Among these, bisphenol A having a molecular weight of 500 to 2,000 is preferable because the heat stability during copolymerization is good and the heat resistance of the molded product obtained from the resin composition of the present invention is hardly lowered. Polyethylene glycol adducts are preferred.

  These thermoplastic polyester resins may be used alone or in combination of two or more.

  The method for producing the thermoplastic polyester resin in the present invention can be obtained by a known polymerization method such as melt polycondensation, solid phase polycondensation, solution polymerization and the like. In order 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 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 organic or inorganic crystal nucleating agents generally well known at the time of polymerization may be added alone or in combination of two or more. May be.

  The intrinsic viscosity of the thermoplastic polyester resin used in the present invention (measured at 25 ° C. in a mixed solution of phenol / tetrachloroethane of 1/1 by weight) is preferably 0.4 to 1.2 dl / g, 0 More preferably, it is 6 to 1.0 dl / g. When the intrinsic viscosity is less than 0.4 dl / g, mechanical strength and impact resistance tend to be lowered, and when it exceeds 1.2 dl / g, fluidity during molding tends to be lowered.

  The organophosphorus flame retardant used in the present invention is represented by the following general formula (1)

(Wherein n is an integer from 2 to 20), the molecule contains a phosphorus atom, and the lower limit of the repeating unit of n is n = 2, preferably n = 3 Particularly preferably, n = 5. There is no particular limitation on the upper limit of the repeating unit of n, but if the molecular weight is excessively increased, the dispersibility tends to be adversely affected. Therefore, the upper limit value of the repeating unit of n is n = 20, preferably n = 15, and particularly preferably n = 13. If it is less than n = 2, the crystallization of the polyester resin tends to be inhibited or the mechanical strength tends to decrease.

  The method for producing the organophosphorus flame retardant used in the present invention is not particularly limited, and is obtained by a general polycondensation reaction. For example, it can be obtained by the following method.

  That is, the following general formula (2)

In a nitrogen gas atmosphere, a required amount of itaconic acid and ethylene glycol of about 2 times moles of itaconic acid are mixed with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide represented by The reaction product of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, itaconic acid and ethylene glycol is obtained by heating at 120 to 200 ° C. and stirring. Antimony trioxide and zinc acetate are added to the obtained reaction product, and a polycondensation reaction is carried out while distilling ethylene glycol while maintaining the set temperature at 245 ° C. under a vacuum of 1 Torr or less. About 5 hours later, when the amount of ethylene glycol distilled extremely decreased, the reaction was regarded as completed. The obtained organic phosphorus flame retardant is a solid having a molecular weight of 4000 to 12000 and has a phosphorus content of 8.3%.

  The organophosphorus flame retardant content in the flame retardant polyester resin composition of the present invention is preferably 10 parts by weight, more preferably 20 parts by weight, and more preferably 30 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin. Part is more preferred. When the lower limit of the organophosphorus flame retardant content is 10 parts by weight or less, the flame retardancy tends to decrease. The upper limit of the organophosphorus flame retardant content is preferably 80 parts by weight, and more preferably 70 parts by weight. When the upper limit of the organophosphorus flame retardant content exceeds 80 parts by weight, the mechanical strength tends to decrease and the moldability tends to deteriorate.

  The present invention is characterized in that an inorganic compound is added to impart long-term flame retardancy and to increase mechanical strength and heat resistance.

  The inorganic compound used in the present invention is not particularly limited. For example, swellable mica, non-swellable mica, silicates such as smectite, talc and kaolin, phosphates such as zirconium phosphate, titanium such as potassium titanate Acid salt, tungstate such as sodium tungstate, uranate such as sodium uranate, vanadate such as potassium vanadate, molybdate such as magnesium molybdate, niobate such as potassium niobate, graphite layered Compounds, metal hydroxides such as magnesium hydroxide, oxides such as silicon oxide, titanium oxide, and alumina, carbonate compounds such as calcium carbonate and barium carbonate, sulfate compounds such as calcium sulfate and barium sulfate, and zinc sulfide , But not limited to, calcium phosphate. These may be used alone or in combination of two or more.

  The preferred structure of the inorganic compound used in the present invention is that the aspect ratio of the inorganic compound is large and the fine dispersion is uniformly finely dispersed in the resin from the viewpoint of improving the long-term flame retardancy by suppressing the bleed-out of the phosphorus-based flame retardant. Is. From the above viewpoint, layered silicates such as swellable mica, non-swellable mica, talc, kaolin and smectite are preferably used.

  The inorganic compound can be subjected to a surface treatment in order to uniformly finely disperse it in the resin. The surface treatment method is not particularly limited, and silane compounds, titanium compounds, alumina compounds, polyether compounds, amine compounds, and the like can be used. Silane compounds and polyether compounds are preferred from the viewpoints of availability, handleability, and the effect of thermal degradation on the polyester resin.

As the silane compound, any one generally used is generally used, and the following general formula (2):
Y _n SiX _4-n (2)
It is represented by N in General formula (2) is an integer of 0-3, Y is a C1-C25 hydrocarbon group which may have a substituent.

  Examples of the substituent when the hydrocarbon group having 1 to 25 carbon atoms in Y has a substituent include a group bonded by an ester bond, a group bonded by an ether bond, an epoxy group, and an amino group. , Carboxyl group, group having carbonyl group at the end, amide group, mercapto group, group bonded by sulfonyl bond, group bonded by sulfinyl bond, nitro group, nitroso group, nitrile group, halogen group, hydroxyl group, etc. Is mentioned. The hydrocarbon group having 1 to 25 carbon atoms may be substituted with one of these, or may be substituted with two or more.

  X in the general formula (2) is a hydrolyzable group or a hydroxyl group. Examples of the hydrolyzable group include an alkoxy group, an alkenyloxy group, a ketoxime group, an acyloxy group, an amino group, an aminoxy group, and an amide group. And a halogen group.

  In the general formula (2), when n or 4-n is 2 or more, n Y or 4-n X may be the same or different.

  In the above general formula (2), as a specific example of the silane compound when Y is a hydrocarbon group having 1 to 25 carbon atoms, for example, a compound having a linear long-chain alkyl group such as decyltrimethoxysilane , Having a lower alkyl group such as methyltrimethoxysilane, having an unsaturated hydrocarbon group such as 2-hexenyltrimethoxysilane, and having an alkyl group having a side chain such as 2-ethylhexyltrimethoxysilane Those having a phenyl group such as phenyltriethoxysilane, those having a naphthyl group such as 3-β-naphthylpropyltrimethoxysilane, and those having an aralkyl group such as p-vinylbenzyltrimethoxysilane. Can be mentioned. Examples of the case where Y is a group having a vinyl group among hydrocarbon groups having 1 to 25 carbon atoms include vinyltrimethoxysilane, vinyltrichlorosilane, and vinyltriacetoxysilane. An example of the case where Y is a group having a group substituted with an ester group is γ-methacryloxypropyltrimethoxysilane. Examples of the case where Y is a group having a group substituted with a group bonded with an ether group include γ-polyoxyethylenepropyltrimethoxysilane and 2-ethoxyethyltrimethoxysilane. An example of the case where Y is a group substituted with an epoxy group includes γ-glycidoxypropyltrimethoxysilane. Examples of when Y is a group substituted with an amino group include γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane. Can be mentioned. An example of the case where Y is a group substituted with a group having a carbonyl group at the terminal includes γ-ureidopropyltriethoxysilane. An example of the case where Y is a group substituted with a mercapto group includes γ-mercaptopropyltrimethoxysilane. An example of the case where Y is a group substituted with a halogen atom includes γ-chloropropyltriethoxysilane. An example of the case where Y is a group having a group substituted with a group bonded with a sulfonyl group includes γ-phenylsulfonylpropyltrimethoxysilane. An example of the case where Y is a group having a group substituted with a group bonded with a sulfinyl group includes γ-phenylsulfinylpropyltrimethoxysilane. An example of the case where Y is a group substituted with a nitro group includes γ-nitropropyltriethoxysilane. An example of the case where Y is a group substituted with a nitroso group includes γ-nitrosopropyltriethoxysilane. Examples of the case where Y is a group substituted with a nitrile group include γ-cyanoethyltriethoxysilane and γ-cyanopropyltriethoxysilane. An example of the case where Y is a group substituted with a carboxyl group includes γ- (4-carboxyphenyl) propyltrimethoxysilane. In addition to the above, a silane compound in which Y is a group having a hydroxyl group can also be used. Such an example includes N, N-di (2-hydroxyethyl) amino-3-propyltriethoxysilane. The hydroxyl group can also be in the form of a silanol group (SiOH).

  In the present invention, a substituted product or derivative of the above silane compound can also be used. These silane compounds may be used alone or in combination of two or more.

  The usage-amount of the silane type compound in this invention can be prepared so that the dispersibility of the inorganic compound in a polyester resin molded object may fully improve. If necessary, a plurality of types of silane compounds having different functional groups can be used in combination. Accordingly, the amount of the silane compound used is not generally limited by numerical values, but the lower limit of the amount of the silane compound used relative to 100 parts by weight of the inorganic compound is 0.1 parts by weight, preferably 0.8. 2 parts by weight, more preferably 0.3 parts by weight, still more preferably 0.4 parts by weight, and particularly preferably 0.5 parts by weight. The upper limit of the amount of the silane compound used relative to 100 parts by weight of the inorganic compound is 200 parts by weight, preferably 180 parts by weight, more preferably 160 parts by weight, still more preferably 140 parts by weight, 120 parts by weight is preferable. If the lower limit of the amount of the silane compound used is less than 0.1 parts by weight, the effect of finely dispersing the inorganic compound may be insufficient. Further, when the amount of the silane compound is 200 parts by weight or more, the effect of fine dispersion does not change, so it is not necessary to use more than 200 parts by weight.

  The polyether compound in the present invention is preferably a compound whose main chain is polyoxyalkylene such as polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer, and the number of repeating units of oxyalkylene is 2. To about 100 is preferable.

  The polyether compound may have an arbitrary substituent in the side chain and / or main chain as long as it does not adversely affect the polyester resin or the inorganic compound. Examples of the substituent include, for example, a hydrocarbon group, a group bonded by an ester bond, an epoxy group, an amino group, a carboxyl group, a group having a carbonyl group at the terminal, an amide group, a mercapto group, and a sulfonyl bond. Functional groups that can form Si—O— bonds such as nitro groups, nitroso groups, nitrile groups, alkoxysilyl groups, silanol groups, halogen groups, hydroxyl groups Etc. One of these may be substituted, and two or more may be substituted.

  The hydrocarbon group is a straight chain or branched chain (that is, having a side chain), saturated or unsaturated, monovalent or polyvalent aliphatic hydrocarbon group, aromatic hydrocarbon group or alicyclic group. It means a hydrocarbon group, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, a naphthyl group, and a cycloalkyl group. In the present invention, the term “alkyl group” includes polyvalent hydrocarbon groups such as “alkylene group” unless otherwise specified. Similarly, the alkenyl group, alkynyl group, phenyl group, naphthyl group, and cycloalkyl group each include an alkenylene group, an alkynylene group, a phenylene group, a naphthylene group, a cycloalkylene group, and the like.

  The composition ratio of the substituents in the polyether compound is not particularly limited, but the polyether compound used in the present invention contains water, a polar solvent compatible with water at an arbitrary ratio, or water. It is desirable to be soluble in a polar solvent. Specifically, for example, the solubility of the polyether compound in 100 g of water at room temperature is preferably 1 g or more, more preferably 2 g or more, further preferably 5 g or more, and particularly preferably 10 g or more. Most preferably, it is 20 g or more. Specific examples of the polar solvent include, for example, alcohols such as methanol, ethanol and isopropanol, glycols such as ethylene glycol, propylene glycol and 1,4-butanediol, ketones such as acetone and methyl ethyl ketone, diethyl ether and tetrahydrofuran. Ethers such as N, N-dimethylformamide, amide compounds such as N, N-dimethylacetamide, and other solvents include pyridine, dimethyl sulfoxide, N-methylpyrrolidone, and the like. Carbonic acid diesters such as dimethyl carbonate and diethyl carbonate can also be used as the polar solvent. These polar solvents may be used alone or in combination of two or more.

  Specific examples of the polyether compound used in the present invention include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol, polyethylene glycol-polytetramethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, Polyethylene glycol monoethyl ether, polyethylene glycol diethyl ether, polyethylene glycol monoallyl ether, polyethylene glycol diallyl ether, polyethylene glycol monophenyl ether, polyethylene glycol diphenyl ether, polyethylene glycol octyl phenyl ether, polyethylene glycol methyl ethyl ether , Polyethylene glycol methyl allyl ether, polyethylene glycol glyceryl ether, polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, polypropylene glycol monomethacrylate, polypropylene glycol monoacrylate, polyethylene glycol-polypropylene glycol monomethacrylate, polyethylene glycol-polypropylene glycol monoacrylate, polyethylene glycol -Polytetramethylene glycol monomethacrylate, polyethylene glycol-Polytetramethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, methoxypolyethylene glycol monoacrylate, octoxypolyethylene glycol- Ripropylene glycol monomethacrylate, octoxy polyethylene glycol-polypropylene glycol monoacrylate, lauroxy polyethylene glycol monomethacrylate, lauroxy polyethylene glycol monoacrylate, stearoxy polyethylene glycol monomethacrylate, stearoxy polyethylene glycol monoacrylate, allyloxy polyethylene glycol monomethacrylate , Allyloxy polyethylene glycol monoacrylate, nonylphenoxy polyethylene glycol monomethacrylate, nonylphenoxy polyethylene glycol monoacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol-polytetramethylene glycol Coal dimethacrylate, polyethylene glycol-polytetramethylene glycol diacrylate, bis (polyethylene glycol) butylamine, bis (polyethylene glycol) octylamine, polyethylene glycol bisphenol A ether, polyethylene glycol-polypropylene glycol bisphenol A ether, ethylene oxide modified bisphenol A di Methacrylate, ethylene oxide modified bisphenol A diacrylate, ethylene oxide-propylene oxide modified bisphenol A dimethacrylate, polyethylene glycol diglycidyl ether, polyethylene glycol ureidopropyl ether, polyethylene glycol mercaptopropyl ether, polyethylene glycol phenyls E sulfonyl propyl ether, polyethylene glycol phenylsulfinyl propyl ether, polyethylene glycol nitro propyl ether, polyethylene glycol nitroso propyl ether, polyethylene glycol cyanoethyl ethers, polyethylene glycol cyanoethyl ether. These polyether compounds may be used alone or in combination of two or more.

  As a polyether compound used by this invention, what has cyclic hydrocarbon groups, such as an aromatic hydrocarbon group and an alicyclic hydrocarbon group, is preferable, and especially the following general formula (3):

(Wherein, -A- is, -O -, - S -, - SO -, - SO 2 -, - CO-, an alkylene group or alkylidene group having 6 to 20 carbon atoms, having 1 to 20 carbon atoms , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are all hydrogen atoms, halogen atoms, or monovalent hydrocarbon groups having 1 to 5 carbon atoms, They may be the same or different.)
What has a unit represented by these is preferable.
Furthermore, the following general formula (4):

(Wherein, -A- is, -O -, - S -, - SO -, - SO 2 -, - CO-, an alkylene group or alkylidene group having 6 to 20 carbon atoms, having 1 to 20 carbon atoms , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are all hydrogen atoms, halogen atoms, or monovalent hydrocarbon groups having 1 to 5 carbon atoms, R ⁹ and R ¹⁰ are each a divalent hydrocarbon group having 1 to 5 carbon atoms, and they may be the same or different from each other. R ¹¹ and R ¹² are each a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and m and n are repeating oxyalkylene units. Indicates number of units, 1 ≦ m ≦ 25, 1 ≦ n ≦ 25, 2 ≦ m + n ≦ 5 In it.) In those represented it is preferable from the viewpoint of dispersibility and thermal stability of inorganic compounds.

  The amount of the polyether compound used in the present invention can be adjusted so that the affinity between the inorganic compound and the polyester resin and the dispersibility of the inorganic compound in the polyester resin composition are sufficiently enhanced. If necessary, a plurality of types of polyether compounds having different functional groups can be used in combination. Therefore, although the amount of the polyether compound used is not generally limited by the numerical value, the lower limit of the amount of the polyether compound used relative to 100 parts by weight of the inorganic compound is 0.1 part by weight, preferably 0.8. 2 parts by weight, more preferably 0.3 parts by weight, still more preferably 0.4 parts by weight, and particularly preferably 0.5 parts by weight. The upper limit of the amount of the polyether compound used relative to 100 parts by weight of the inorganic compound is 200 parts by weight, preferably 180 parts by weight, more preferably 160 parts by weight, still more preferably 140 parts by weight, 120 parts by weight is preferable. When the lower limit of the amount of the polyether compound used is less than 0.1 part by weight, the effect of finely dispersing the inorganic compound tends to be insufficient. Further, when the upper limit value of the amount of the polyether compound used is 200 parts by weight or more, the fine dispersion effect does not change, so it is not necessary to use more than 200 parts by weight.

  The lower limit of the amount of the inorganic compound used in the present invention is preferably 5 parts by weight, more preferably 10 parts by weight, and even more preferably 15 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin. If the lower limit of the inorganic compound content is less than 5 parts by weight, the flame-retardant long-term heat resistance and the effect of improving the rigidity may not be sufficient. The upper limit of the content of the inorganic compound is preferably 120 parts by weight, more preferably 100 parts by weight, and still more preferably 80 parts. When the upper limit value of the inorganic compound content exceeds 120 parts by weight, fluidity may be lowered and thin wall formability may be impaired.

  The flame-retardant polyester resin composition of the present invention can realize high flame retardancy in a very thin molded product.

  As described in the prior art (Patent Document 1), flame retardancy to a polyester resin can be imparted with an organophosphorus flame retardant, but it is limited to thick molded articles such as 3.2 mm thickness. . However, a molded product used for a light and thin product is required to have flame retardancy at a thinner thickness. For this purpose, it is not possible to satisfy the requirements only by combining an organic phosphorus flame retardant with a polyester resin, and this is achieved for the first time by using an inorganic compound in combination. Furthermore, another feature obtained by using an inorganic compound in combination is that the organic phosphorus flame retardant can be stably present in the resin by the inorganic compound, so that it is flame retardant even when exposed to a high temperature of 160 ° C. or more for a long time. It does not decrease the sex. This is a feature that could not be achieved simply by blending only an organophosphorus flame retardant into a polyester resin, and was the first feature that was exhibited by using an inorganic compound together. It is.

  The flame-retardant polyester resin composition of the present invention is preferably V-0 in the UL94 standard with a thickness of 1/16 inch, and V-0 in the UL94 standard with a thickness of 1/32 inch. More preferred.

  The molded body formed from the flame-retardant polyester resin composition of the present invention can maintain the combustibility of the molded product and the surface appearance even when used in an environment exposed to heat for a long period of time in the applications shown below. Therefore, it is preferable that the flame retardancy after the long-term heat aging test is maintained.

  In the flame-retardant polyester resin composition of the present invention, it is preferable that flame retardancy on the basis of UL94 at 1/16 inch thickness is maintained at V-0 after a heat aging test at 160 ° C. for 500 hours. The maintenance after the heat aging test at 180 ° C. for 500 hours is more preferable, and the maintenance after the heat aging test at 200 ° C. for 500 hours is more preferable. When flame retardancy based on UL94 standard at 1/16 inch thickness cannot maintain V-0 in less than 500 hours at 160 ° C, long-term reliability may be hindered in the use of resin molded products. is there.

  If necessary, additives such as glass fibers, pigments, heat stabilizers, antioxidants, and lubricants can be added to the flame retardant polyester resin composition of the present invention.

  The method for producing the flame-retardant polyester resin composition of the present invention is not particularly limited. For example, a polyester resin, an organic phosphorus flame retardant and an inorganic compound are melt-kneaded using various general kneaders. I can give you a way. Examples of the kneader include a single screw extruder and a twin screw extruder, and a twin screw extruder with high kneading efficiency is particularly preferable.

  The flame-retardant polyester resin composition obtained in the present invention has a high flame retardancy even in a very thin molded article, and maintains the flammability after a long-term heat aging test. It is suitably used for complex home appliances, electrical / electronic parts such as OA equipment, and housings.

  Next, the composition of the present invention will be specifically described with reference to specific examples, but the present invention is not limited thereto.

The resins and raw materials used in the examples and comparative examples are shown below.
Polyester resin A1: Polyethylene terephthalate resin (Product name: EFG-70 manufactured by Kanebo Synthetic Fiber)
Polyester resin A2: Polybutylene terephthalate resin (Product name: KP-210 manufactured by KOLON)
Organophosphorous flame retardant B1: produced in Production Example 1 Inorganic compound C1: non-swellable mica (A41S, manufactured by Yamaguchi Mica Co., Ltd.)
Inorganic compound C2: Talc (Nihon Talc, Microace K-1)
Inorganic compound C3: produced in Production Example 2

(Production Example 1)
In a vertical polymerization machine having a distillation tube, a rectification tube, a nitrogen introduction tube and a stirrer, the following general formula (2)

62 parts by weight of itaconic acid and 100 parts by weight of ethylene glycol are added to 100 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide represented by the formula 120-200 under a nitrogen gas atmosphere. The phosphorous compound is obtained by reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, itaconic acid, and ethylene glycol by gradually heating to 10 ° C. and stirring for about 10 hours. Obtained. To the obtained phosphorus compound, 0.1 part by weight of antimony trioxide and 0.1 part by weight of zinc acetate were added, and the temperature was further maintained at 220 to 245 ° C. under a vacuum pressure of 1 Torr or less. Is polycondensed while distilling off. About 5 hours later, the distillation amount of ethylene glycol was extremely reduced, and thus the reaction was considered to be completed. The obtained organic phosphorus flame retardant was a solid having a molecular weight of 7000, and the phosphorus content was 8.3%.

(Production Example 2)
Using a wet mixer, 10 parts of swellable synthetic mica (manufactured by Co-op Chemical Co., Ltd., Somasif ME100) was mixed with 100 parts by weight of pure water. Next, 1.6 parts of a polyether compound (Toho Chemical Co., Ltd., bisol) was added, and the mixture was further treated by continuing the mixing for 15 to 30 minutes. Then, it dried and pulverized.

  The evaluation method in the present example is as follows.

<Flame retardance>
The obtained pellets were dried at 140 ° C. for 3 hours, and then injection molded using an injection molding machine (clamping pressure: 35 tons) under the conditions of a cylinder set temperature of 250 ° C. to 280 ° C. and a mold temperature of 120 ° C. A test piece of 127 mm × 12.7 mm × thickness 1/16 inch was obtained. Based on the UL94 standard V-0 test, the obtained 1 / 16-inch-thick bar-shaped test piece was used to evaluate the flammability at the initial stage and after the heat aging test at 160 ° C. × 500 hr.

<Load deflection temperature>
The obtained pellets were dried at 140 ° C. for 3 hours, and then 127 mm × 12.7 mm × thickness 1 / thickness using an injection molding machine (clamping pressure: 75 tons) under conditions of a cylinder setting temperature of 270 ° C. and a mold temperature of 120 ° C. A 4-inch test piece was prepared. The obtained test specimen was measured for the flexural modulus at room temperature according to ASTM D-790. The higher the elastic modulus, the better. In addition, when the moldability of the material is poor, the test piece having a thickness of 1/4 inch is difficult to solidify, and thus deforms when taken out from the mold. This phenomenon can be judged as good or bad in moldability.

(Example 1-7)
In accordance with the raw materials and formulation composition (unit: parts by weight) shown in Table 1, dry blending was performed in advance. Using a vent type 44 mmφ same-direction twin screw extruder (manufactured by Nippon Steel Works, TEX44), the mixture was supplied from the hopper hole and melt-kneaded at a cylinder set temperature of 250 to 280 ° C. to obtain pellets. .
The evaluation results in Examples 1 to 7 are shown in Table 1.

(Comparative Examples 1 to 4 )
According to the blending composition (unit: parts by weight) shown in Table 1, pelletization and injection molding were carried out in the same manner as in the examples to obtain test pieces, and experiments were carried out using the same evaluation method.
The evaluation results in Comparative Examples 1 to 4 are shown in Table 1.

  From the comparison of Examples and Comparative Examples, the initial flammability and 160 ° C. × 500 at 1/16 inch thickness were determined according to the ratio of the organophosphorus flame retardant and nitrogen compound (C) to the thermoplastic polyester resin in the present invention. It can be seen that the flammability after the heat aging test of time is excellent. Moreover, by using an inorganic compound, the moldability was excellent and the flexural modulus of the obtained molded body was improved.

The flame-retardant polyester resin composition obtained in the present invention has a high flame retardancy even in a very thin molded article, and maintains the flammability after a long-term heat aging test. It is suitably used for complex home appliances, electrical / electronic parts such as OA equipment, and housings.

Claims (5)

The following general formula (1) with respect to 100 parts by weight of the polyalkylene terephthalate resin
(Wherein n is an integer of 2 to 20) represented by 10 to 80 parts by weight of an organic phosphorus flame retardant and 10 to 100 parts by weight of a silicate flame retardant polyester resin composition A flame retardant polyester resin composition having a flame retardancy at 1/16 inch thickness of V-0 based on UL94.   2. The flame-retardant polyester resin composition according to claim 1, wherein the flame-retardant property at 1/16 inch thickness after heat treatment at 160 ° C. for 500 hours is V-0 based on UL94 standard. The flame-retardant polyester resin composition according to claim 1 , wherein the polyalkylene terephthalate resin is a polyethylene terephthalate resin. The flame-retardant polyester resin composition according to any one of claims 1 to 3 , wherein the silicate is surface-treated with a silane compound, a titanium compound, an alumina compound, a polyether compound, or an amine compound. The resin molding in which all or one part is formed from the flame-retardant polyester resin composition in any one of Claims 1-4 .