Flame-retardant polyester resin composition and molded body made thereof

Abstract

To provide a flame-retardant polyester resin composition that has excellent tensile strength, flame retardancy, and moist-heat resistance at room and high temperatures and suppresses aligned crystallization at a gate part to occur in the case of using a limiting gate, and a molding prepared therewith.SOLUTION: A flame-retardant polyester resin composition contains a resin component comprising (A) polyethylenenaphthalate resin (A component) 51-95 wt.% and (B) polyether imide (B component) 5-49 wt.%. Relative to the resin component 100 pts.wt., the polyester resin composition further contains (C) a fibrous filler (C component) 25-150 pts.wt. and (D) a phosphazene compound (D component) 2-20 pts.wt.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a flame-retardant polyester resin composition that is excellent in strength, flame retardancy, and moist heat resistance at room temperature and high temperatures, and that suppresses oriented crystallization at the gate portion that occurs when a limiting gate is used, and a molded article made of the same. [Background technology]

[0002] Polyethylene naphthalate resin is a resin with excellent mechanical properties, heat resistance, chemical resistance, electrical properties, and moldability, and is widely used in the fields of electrical and electronic parts and mechanical parts, etc. In recent years, the fields of electrical and electronic parts and mechanical parts have been advancing in terms of performance and lightness, thickness, and size, and there is a strong demand for resin materials to have high strength at high temperatures in addition to strength at room temperature, and to have thin-wall flame retardancy to maintain product safety.

[0003] Patent Document 1 reports a method of blending a fibrous filler to improve mechanical properties such as the tensile strength of polyethylene naphthalate, and Patent Document 2 reports an example of blending a liquid crystal polymer and a fibrous inorganic reinforcing material with polyethylene naphthalate resin to further increase rigidity. However, polyethylene naphthalate resin is oriented crystallized and embrittled by shear in a suddenly contracted flow path such as the gate part of an injection molded body, so that although high strength is obtained in a tensile test such as a tensile dumbbell piece, there is a problem that sufficient strength is not expressed in the actual product shape. Patent Document 3 exemplifies a method of adding an amorphous copolymerized polyester resin having a glass transition temperature of 80°C or more to suppress the oriented crystallization at the gate part of polyethylene naphthalate resin. However, although the effect of suppressing the oriented crystallization at the gate part is seen by mixing an amorphous copolymerized polyester resin having a glass transition temperature of 80°C or more, the obtained resin composition has a lower heat resistance than polyethylene naphthalate resin, and the strength at high temperatures is reduced.

[0004] In addition, thermoplastic polyester resins have generally been made flame-retardant by using halogen-based flame retardants as flame retardants and antimony trioxide as flame-retardant assistants to obtain resin compositions with excellent mechanical strength and high flame retardancy, but these have problems such as pyrolysis during molding to generate hydrogen halide, corroding the mold and reducing the thermal stability of the resin composition, etc. Furthermore, there is also the problem of generating harmful substances during combustion, and from the viewpoint of reducing the environmental load, it has become desirable to use non-halogen flame retardants.

[0005] Patent Document 4 reports an attempt to blend an organic phosphorus-based flame retardant having a specific structure to impart flame retardancy to a polyethylene naphthalate resin. Patent Document 5 reports an example of blending a phosphoric acid ester compound and glass fiber to impart strength and flame retardancy to a polybutylene terephthalate resin. However, although the flame retardancy is increased by adding a phosphorus-based flame retardant in both cases, there are problems in that the strength is reduced at room temperature and in high temperature ranges, and the resistance to moist heat is greatly reduced. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2001-181489 A [Patent Document 2] JP 2007-277292 A [Patent Document 3] JP 2018-104654 A [Patent Document 4] JP 2014-214180 A [Patent Document 5] JP 2009-96969 A Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a flame-retardant polyester resin composition that is excellent in strength, flame retardancy, and heat and moisture resistance in the room temperature and high temperature regions, and in which the orientation crystallization occurring in the gate portion of an injection molded article is suppressed when a restricted gate is used, and a molded article made therefrom.

Means for Solving the Problems

[0008] As a result of intensive studies to achieve the above object, the present inventors have found that by adding a specific amount of a phosphazene compound as a flame retardant to a resin composition composed of a polyethylene naphthalate resin, a polyetherimide resin, and a fibrous filler, the strength, flame retardancy, and heat and moisture resistance in the room temperature and high temperature regions are improved, and the orientation crystallization occurring in the gate portion of an injection molded article is suppressed when a restricted gate is used, thus completing the present invention.

[0009] That is, the problem of the present invention is achieved by a resin composition containing (C) 25 to 150 parts by weight of a fibrous filler (C component) and (D) 2 to 20 parts by weight of a phosphazene compound (D component) with respect to 100 parts by weight of a resin component composed of (A) 51 to 95% by weight of a polyethylene naphthalate resin (A component) and (B) 5 to 49% by weight of a polyetherimide resin (B component).

Effects of the Invention

[0010] According to the present invention, it is possible to provide a flame-retardant polyester resin composition that is excellent in strength, flame retardancy, and heat and moisture resistance in the room temperature and high temperature regions, and in which the orientation crystallization occurring in the gate portion of an injection molded article is suppressed when a restricted gate is used. The molded article made therefrom can be suitably used for thin-walled molded members for the exterior of electric and electronic devices and for mechanism parts applications that require long-term durability, and is thus industrially useful.

Modes for Carrying Out the Invention

[0011] Hereinafter, the details of the present invention will be further described.

[0012] <Regarding Component A> The polyethylene naphthalate resin, which is component A of the present invention, can be produced using a dicarboxylic acid component mainly composed of naphthalenedicarboxylic acid and / or an ester-forming derivative of naphthalenedicarboxylic acid, and a glycol component mainly composed of ethylene glycol.

[0013] The naphthalenedicarboxylic acid component is mainly composed of 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid, but other dicarboxylic acids can be used in combination as long as the properties are not impaired. Examples of other carboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, and diphenylether-4,4'-dicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid, and oxalic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. One or more of these may be used, and can be selected arbitrarily depending on the purpose. The amount of other carboxylic acids used is preferably 30 mol% or less, more preferably 20 mol% or less, based on the total acid components. The ester-forming derivatives of naphthalenedicarboxylic acid are mainly composed of dimethyl 2,6-naphthalenedicarboxylate and dimethyl 2,7-naphthalenedicarboxylate, but can be used in combination with ester-forming derivatives of other dicarboxylic acids as long as the properties are not impaired. Examples of ester-forming derivatives of other dicarboxylic acids include lower dialkyl esters of aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, and diphenylether-4,4'-dicarboxylic acid, lower dialkyl esters of alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and lower dialkyl esters of aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid, and oxalic acid. One or more of these may be used, and can be selected arbitrarily depending on the purpose. The amount of the ester-forming derivatives of other dicarboxylic acids used is preferably 30 mol% or less, more preferably 20 mol% or less, based on the total dicarboxylic acid ester-forming derivative components.

[0014] A small amount of a trifunctional or higher functional carboxylic acid component such as trimellitic acid may be used, or a small amount of an acid anhydride such as trimellitic anhydride may be used, or a small amount of a hydroxycarboxylic acid or an alkyl ester thereof such as lactic acid or glycolic acid may be used, and these can be selected arbitrarily depending on the purpose.

[0015] The glycol component is mainly composed of ethylene glycol, but other glycol components can be used in combination within the range that does not impair the properties. As the other glycol components, for example, one or more of alkylene glycols such as 1,4-butanediol, 1,3-propylene glycol, 1,2-propylene glycol, neopentylene glycol, hexamethylene glycol, decamethylene glycol, cyclohexanedimethanol, diethylene glycol, triethylene glycol, poly(oxy)ethylene glycol, poly(oxy)tetramethylene glycol, and poly(oxy)methylene glycol may be used, and can be arbitrarily selected depending on the purpose. Furthermore, a small amount of a polyhydric alcohol component such as glycerin may be used. A small amount of an epoxy compound may also be used. The amount of the other glycol components used is preferably 30 mol% or less, more preferably 20 mol% or less, based on the total glycol components.

[0016] The polyethylene naphthalate resin can be produced by a conventionally known production method. That is, it can be produced by a direct esterification method in which a dicarboxylic acid component and a diol component are directly reacted to distill off water, followed by esterification, followed by polycondensation under reduced pressure, or by a transesterification method in which a dicarboxylic acid dimethyl ester and a diol component are reacted to distill off methyl alcohol, followed by transesterification, followed by polycondensation under reduced pressure. In order to further increase the intrinsic viscosity number, solid-phase polymerization can be carried out.

[0017] During the above transesterification reaction, esterification reaction, and polycondensation reaction, it is preferable to use a catalyst and a stabilizer. As the transesterification catalyst, Mg compounds, Mn compounds, Ca compounds, Zn compounds, etc. are used, and examples thereof include acetates, monocarboxylates, alcoholates, and oxides of these. Also, the esterification reaction can be carried out only with dicarboxylic acid and diol without adding a catalyst, but it can also be carried out in the presence of a polycondensation catalyst described later. As the polycondensation catalyst, Ge compounds, Ti compounds, Sb compounds, etc. can be used, and examples thereof include germanium dioxide, germanium hydroxide, germanium alcoholate, titanium tetrabutoxide, titanium tetraisopropoxide, and titanium oxalate. It is preferable to use a phosphorus compound as the stabilizer. Preferred phosphorus compounds include phosphoric acid and its esters, phosphorous acid and its esters, and hypophosphorous acid and its esters. Also, during the esterification reaction, a tertiary amine such as triethylamine, a quaternary ammonium hydroxide such as tetraethylammonium hydroxide, and a basic compound such as sodium carbonate can be added to suppress the by-production of diethylene glycol. Further, various stabilizers and modifiers can be blended into the obtained polyester resin.

[0018] The intrinsic viscosity of component A is preferably 0.5 to 0.9 dl / g, more preferably 0.6 to 0.85 dl / g, and even more preferably 0.65 to 0.80 dl / g. If the intrinsic viscosity of component A is less than 0.5 dl / g, the strength may be inferior, and if it exceeds 0.9 dl / g, the fluidity may be inferior.

[0019] <Regarding component B> The polyetherimide resin, which is the component B of the present invention, is a resin containing a cyclic imide structure, and is not particularly limited as long as it can be used for the purpose of the present invention, but a polyetherimide resin containing an aliphatic or aromatic ether unit and a cyclic imide group as a repeating unit is preferable. In addition, the main chain of the polyimide may contain structural units other than the cyclic imide and ether units, such as aromatic or aliphatic ester units, oxycarbonyl units, etc., as long as the effects of the present invention are not impaired.

[0020] A specific example of the polyetherimide resin that can be preferably used in the present invention is a polyetherimide resin represented by the following formula (1).

[0021] [ka] (In the formula, n represents an integer of 2 or more.)

[0022] R in formula (1) 1 is a divalent aromatic or aliphatic radical containing 6 to 30 carbon atoms, R 2 is a divalent organic group selected from the group consisting of a divalent aromatic residue having 6 to 30 carbon atoms, an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 2 to 20 carbon atoms, and a polydiorganosiloxane group chain-terminated with an alkylene group having 2 to 8 carbon atoms.

[0023] Above R 1 , R 2 Examples of the alkylene groups include aromatic residues and alkylene groups represented by the following formulas (2) to (8).

[0024] [ka]

[0025] [ka]

[0026] [ka]

[0027] [ka]

[0028] [ka]

[0029] [ka]

[0030] [ka] (In formula (8), n represents an integer of 2 or more.)

[0031] In the present invention, the polyetherimide resin represented by the following formula (9) is preferred from the viewpoint of compatibility with polyethylene naphthalate resin.

[0032] [ka] (In formula (9), n represents an integer of 2 or more.)

[0033] An example of this polyetherimide resin is "ULTEM1010" manufactured by SABIC Japan LLC.

[0034] The content of component B is 5 to 49% by weight, preferably 10 to 45% by weight, and more preferably 20 to 40% by weight, based on 100% by weight of the total of components A and B. If the content of component B is less than 5% by weight, the flame retardancy, the effect of suppressing oriented crystallization at the gate when a limiting gate is used, and the effect of improving tensile strength at high temperatures are insufficient, while if it exceeds 49% by weight, the fluidity decreases.

[0035] <Regarding Component C> The fibrous filler which is Component C of the present invention is preferably at least one fibrous filler selected from the group consisting of glass fibers and carbon fibers.

[0036] Examples of suitable glass fibers include glass fibers having a round cross-section, flat cross-section glass fibers having an average value of the major axis of the fiber length cross-section of 5 to 50 μm and an average value of the ratio of the major axis to the minor axis (major axis / minor axis) of 1.5 to 8, and glass milled fibers. Among them, flat cross-section glass fibers having an average value of the major axis of the fiber length cross-section of 10 to 40 μm and an average value of the ratio of the major axis to the minor axis (major axis / minor axis) of 1.5 to 8 are more preferable in terms of tensile strength and dimensional accuracy.

[0037] The glass composition of the above glass fibers is represented by various glass compositions such as A glass, C glass, and E glass, etc., and is not particularly limited. Such glass fibers may contain components such as TiO 、SO 2 、and P 3 、and P 2 O 5 etc. Among these, E glass (alkali-free glass) is more preferable. Such glass fibers are preferably those surface-treated with a well-known surface treatment agent, such as a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent, etc., from the viewpoint of improving mechanical strength. Also, those treated with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, etc. to be bundled are preferable, and epoxy resins and urethane resins are particularly preferable from the viewpoint of mechanical strength. The adhesion amount of the bundling agent of the bundled glass fibers is preferably 0.1 to 3% by weight, more preferably 0.2 to 1% by weight, in 100% by weight of the glass fibers.

[0038] Examples of carbon fibers include metal-coated carbon fibers, carbon milled fibers, vapor-grown carbon fibers, and other carbon fibers, as well as carbon nanotubes. Carbon nanotubes preferably have a fiber diameter of 0.003 to 0.1 μm and may be single-walled, double-walled, or multi-walled, with multi-walled (so-called MWCNT) being preferred.

[0039] Among these, carbon fiber is preferred because of its excellent mechanical strength. As the carbon fiber, any of cellulose-based, polyacrylonitrile-based, and pitch-based carbon fibers can be used. Carbon fibers obtained by a method of spinning without an infusible step, such as a method of spinning or molding a raw material composition consisting of a polymer of aromatic sulfonic acids or their salts formed by methylene bonds and a solvent, followed by carbonization, can also be used. Furthermore, any of general-purpose types, medium elastic modulus types, and high elastic modulus types can be used. Among these, polyacrylonitrile-based high elastic modulus types are particularly preferred.

[0040] In addition, the surface of the carbon fiber is preferably oxidized to enhance adhesion to the matrix resin and improve mechanical strength. The oxidation method is not particularly limited, but suitable examples include (1) a method of treating the carbon fiber with an acid or alkali or a salt thereof, or an oxidizing gas, (2) a method of baking the fiber or carbon fiber that can be carbonized at a temperature of 700° C. or higher in the presence of an inert gas containing an oxygen-containing compound, and (3) a method of oxidizing the carbon fiber and then heat-treating it in the presence of an inert gas.

[0041] The metal-coated carbon fiber is obtained by coating a metal layer on the surface of a carbon fiber. Examples of the metal include silver, copper, nickel, and aluminum, among which nickel is preferred from the viewpoint of the corrosion resistance of the metal layer. As the method for metal coating, known methods such as plating and vapor deposition can be mentioned, and among them, the plating method is preferably used. Also, in the case of such metal-coated carbon fibers, the carbon fibers mentioned above as the original carbon fibers can be used. The thickness of the metal coating layer is preferably 0.1 to 1 μm, more preferably 0.15 to 0.5 μm, and even more preferably 0.2 to 0.35 μm.

[0042] Such carbon fibers and metal-coated carbon fibers are preferably those subjected to a sizing treatment with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, or the like. In particular, carbon fibers treated with a urethane resin or an epoxy resin are suitable in the present invention because of their excellent mechanical strength.

[0043] The content of the C component is 25 to 150 parts by weight, preferably 30 to 140 parts by weight, and more preferably 45 to 120 parts by weight with respect to 100 parts by weight of the resin component composed of the A component and the B component. If the content of the C component is less than 25 parts by weight, the improvement of the tensile strength and flame retardancy is insufficient, and if it exceeds 150 parts by weight, the extrusion processability deteriorates.

[0044] <Regarding the D component> The phosphazene compound used as the D component of the present invention is not particularly limited as long as it does not contain a halogen atom and has a phosphazene structure composed of a phosphorus atom and a nitrogen atom in the molecule. The phosphazene structure referred to here is a structure represented by the formula: -P(R1)=N- [wherein R1 is an organic group], and the phosphazene compound is a compound represented by the general formulas (10) and (11).

[0045]

Chemical formula

[0046]

Chem.

[0047] (wherein X 1 , X 2 , X 3 , X 4 represents a hydrogen atom, a hydroxyl group, an amino group, or an organic group not containing a halogen atom. Further, n represents an integer of 3 to 10).

[0048] In the above formulas (10) and (11), examples of the organic group not containing a halogen atom represented by X 1 , X 2 , X 3 , X 4 include an alkoxy group, a phenyl group, an amino group, an allyl group, etc. As the phosphazene compound, either a linear or cyclic phosphazene compound represented by the above formulas (10) and (11) can be used. From the viewpoint of flame retardancy, a cyclic phosphazene compound is preferable, and a cyclic phenoxyphosphazene is more preferable. Commercially available phosphazene compounds include SPS-100, SPE-100, SPR-100, SA-100, SPB-100, SPB-100L (manufactured by Otsuka Chemical Co., Ltd.), FP-100, FP-110 (manufactured by Fushimi Pharmaceutical Co., Ltd.). In the present invention, it is possible to contain other phosphorus-based flame retardants as long as the function of the phosphazene compound is not impaired.

[0049] The content of component D is 2 to 20 parts by weight, preferably 3.5 to 15 parts by weight, more preferably 5 to 11 parts by weight, based on 100 parts by weight of the resin component composed of components A and B. When the content of component D is less than 2 parts by weight, the flame retardancy and the strength at room temperature decrease. When it exceeds 20 parts by weight, the tensile strength at high temperature decreases.

[0050] <Regarding component E> The hindered phenol stabilizer used as component E of the present invention exhibits an effect of suppressing, for example, deterioration of hue during molding processing and deterioration of hue over long-term use, when blended in the composition. Examples of hindered phenol stabilizers include α-tocopherol, butyl hydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis(4-methylphenyl)propionate, and the like. 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylenebis(6-α-methyl-benzyl-p-cresol) 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-butylidenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6 -tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl 6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,- dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 4,4'-di-thiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylene biphenyl bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,Examples thereof include 5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris(2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl)isocyanurate, and tetrakis[methylene-3-(3’,5’-di-tert-butyl-4-hydroxyphenyl)propionate]methane. All of these are readily available. The above hindered phenol stabilizers can be used alone or in combination of two or more. The content of the E component is preferably 0.0001 to 3 parts by weight, more preferably 0.001 to 1 part by weight, and still more preferably 0.005 to 0.5 part by weight with respect to 100 parts by weight of the resin component composed of the A component and the B component. When the amount of the hindered phenol stabilizer is too small compared to the above range, it is difficult to obtain a good stabilizing effect. When it exceeds the above range, the physical properties of the composition may deteriorate.,

[0051] <Regarding the F component> The resin composition of the present invention is preferably blended with a phosphorus-based stabilizer to the extent that it does not promote hydrolysis. Such a phosphorus-based stabilizer improves the thermal stability during production or molding processing, and improves mechanical properties, color, and molding stability. Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and their esters, as well as tertiary phosphines. Specific examples of the phosphite compound include triphenyl phosphite, tris(nonylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, tris(diethylphenyl)phosphite, tris(di-iso-propylphenyl)phosphite, and tris(di-n-butylphenyl)phosphite. , tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, etc. Furthermore, as other phosphite compounds, those having a cyclic structure that reacts with dihydric phenols can also be used.For example, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, and the like can be mentioned. Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like, and preferably triphenyl phosphate and trimethyl phosphate.

[0052] Examples of the phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis Examples of the phosphonite include (2,4-di-tert-butylphenyl)-3-phenyl-phenyl phosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenyl phosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenyl phosphonite, and bis(2,6-di-tert-butylphenyl)-3-phenyl-phenyl phosphonite. Tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenyl phosphonite are preferred, and tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenyl phosphonite are more preferred. Such phosphonite compounds can be used in combination with phosphite compounds having an aryl group substituted with two or more alkyl groups, and are therefore preferred. Examples of the phosphonate compounds include dimethyl benzene phosphonate, diethyl benzene phosphonate, and dipropyl benzene phosphonate. Examples of tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine.Particularly preferred tertiary phosphine is triphenylphosphine. The phosphorus stabilizer can be used alone or in combination of two or more. Among the phosphorus stabilizers, it is preferred to use an alkyl phosphate compound, such as trimethyl phosphate. In addition, it is also preferred to use such an alkyl phosphate compound in combination with a phosphite compound and / or a phosphonite compound.

[0053] The content of component F is preferably 0.0001 to 3 parts by weight, more preferably 0.001 to 0.5 parts by weight, and even more preferably 0.01 to 0.3 parts by weight, based on 100 parts by weight of the resin component consisting of components A and B. If the amount of the phosphorus-based stabilizer is less than the above range, it is difficult to obtain a good stabilizing effect, and if it is more than the above range, the physical properties of the composition may decrease.

[0054] (Other additives) The resin composition of the present invention may contain various additives such as a mold release agent, a fluorine-containing drip-preventing agent, and carbon black, within the scope of the present invention.

[0055] <Release agent> The resin composition of the present invention may contain a release agent. Specific examples of the release agent include fatty acids, fatty acid metal salts, oxyfatty acids, paraffins, low molecular weight polyolefins, fatty acid amides, alkylenebisfatty acid amides, aliphatic ketones, partially saponified fatty acid esters, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters, fatty acid polyglycol esters, and modified silicones. By blending these, a molded product with excellent moldability can be obtained.

[0056] The fatty acid preferably has 6 to 40 carbon atoms, and specific examples thereof include oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, montanic acid, and mixtures thereof. The fatty acid metal salt is preferably an alkali (earth) metal salt of a fatty acid having 6 to 40 carbon atoms, and specific examples thereof include calcium stearate, sodium montanate, calcium montanate, and the like.

[0057] Examples of hydroxy fatty acids include 1,2-hydroxysteric acid, etc. Examples of paraffins include those having 18 or more carbon atoms, such as liquid paraffin, natural paraffin, microcrystalline wax, and petrolactam.

[0058] The low molecular weight polyolefin preferably has a molecular weight of 5000 or less, and specific examples thereof include polyethylene wax, maleic acid modified polyethylene wax, oxidized polyethylene wax, chlorinated polyethylene wax, polypropylene wax, and the like.

[0059] The fatty acid amide is preferably one having 6 or more carbon atoms, and specific examples thereof include oleamide, erucamide, and behenamide.

[0060] The alkylene bis(fatty acid amide) is preferably one having 6 or more carbon atoms, and specific examples thereof include methylene bis(stearic acid amide), ethylene bis(stearic acid amide), and N,N-bis(2-hydroxyethyl)stearic acid amide.

[0061] The aliphatic ketone is preferably one having 6 or more carbon atoms, such as a higher aliphatic ketone.

[0062] Examples of partially saponified fatty acid esters include partially saponified montanic acid esters, etc. Examples of lower alcohol fatty acid esters include stearic acid esters, oleic acid esters, linoleic acid esters, linolenic acid esters, adipic acid esters, behenic acid esters, arachidonic acid esters, montanic acid esters, isostearic acid esters, etc.

[0063] Examples of fatty acid polyhydric alcohol esters include glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimyristate, pentaerythritol monostearate, pentaerythritol adipate stearate, sorbitan monobehenate, etc. Examples of fatty acid polyglycol esters include polyethylene glycol fatty acid esters, polytrimethylene glycol fatty acid esters, polypropylene glycol fatty acid esters, etc.

[0064] Examples of modified silicones include polyether-modified silicones, higher fatty acid alkoxy-modified silicones, higher fatty acid-containing silicones, higher fatty acid ester-modified silicones, methacryl-modified silicones, and fluorine-modified silicones.

[0065] Among these, fatty acids, fatty acid metal salts, oxyfatty acids, fatty acid esters, partially saponified fatty acid esters, paraffins, low molecular weight polyolefins, fatty acid amides, and alkylene bisfatty acid amides are preferred, and partially saponified fatty acid esters and alkylene bisfatty acid amides are more preferred.Of these, montanic acid esters, partially saponified montanic acid esters, polyethylene wax, acid value polyethylene wax, sorbitan fatty acid esters, erucic acid amide, and ethylene bisstearic acid amide are preferred, and partially saponified montanic acid esters and ethylene bisstearic acid amide are particularly preferred.

[0066] The release agent may be used alone or in combination of two or more kinds. The content of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, based on 100 parts by weight of the resin component consisting of components A and B.

[0067] <Fluorine-containing drip prevention agent> The resin composition of the present invention can contain a fluorine-containing drip-preventing agent. Examples of the fluorine-containing drip-preventing agent include fluorine-containing polymers having fibril-forming ability. Examples of such polymers include polytetrafluoroethylene, tetrafluoroethylene-based copolymers (e.g., tetrafluoroethylene / hexafluoropropylene copolymers, etc.), partially fluorinated polymers as shown in U.S. Pat. No. 4,379,910, and polycarbonate resins produced from fluorinated diphenols. Among these, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

[0068] The molecular weight of the fibril-forming PTFE is extremely high, and it shows a tendency to bond PTFE to each other and become fibrous by external action such as shear force. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million, in terms of number average molecular weight calculated from the standard specific gravity. Such PTFE can be used in the form of a solid or an aqueous dispersion. In addition, such fibril-forming PTFE can be used in the form of a PTFE mixture mixed with other resins to improve dispersibility in resins and obtain better flame retardancy and mechanical properties.

[0069] Examples of commercially available PTFE products having such fibril-forming ability include Teflon (registered trademark) 6-J from Mitsui-Chemours Fluoro Products Co., Ltd., and Polyflon MPA FA500H and F-201 from Daikin Industries, Ltd. Examples of commercially available aqueous dispersions of PTFE include Fluon D series from Daikin Industries, Ltd., and Polyflon F-201 from Mitsui-Chemours Fluoro Products Co., Ltd. A representative example is Teflon (registered trademark) 31-JR manufactured by Teflon Products Co., Ltd.

[0070] The mixed form of PTFE can be prepared by (1) mixing an aqueous dispersion of PTFE with an aqueous dispersion or solution of an organic polymer and co-precipitating the mixture to obtain a co-agglomerated mixture (methods described in JP-A-60-258263 and JP-A-63-154744, etc.), (2) mixing an aqueous dispersion of PTFE with dried organic polymer particles (method described in JP-A-4-272957), or (3) homogeneously mixing an aqueous dispersion of PTFE with a solution of organic polymer particles and extracting the respective media from the mixture. (4) a method of polymerizing a monomer that forms an organic polymer in an aqueous dispersion of PTFE (method described in JP-A-06-220210, JP-A-08-188653, etc.), and (5) a method of homogeneously mixing an aqueous dispersion of PTFE and an organic polymer dispersion, and then polymerizing a vinyl monomer in the mixed dispersion to obtain a mixture (method described in JP-A-11-29679, etc.). Commercially available products of these mixed forms of PTFE include "Metablen A3800" (trade name) and "Metablen A3750" by Mitsubishi Chemical Corporation.

[0071] The proportion of PTFE in the mixed form is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, in 100% by weight of the PTFE mixture. When the proportion of PTFE is within this range, good dispersibility of PTFE can be achieved.

[0072] Examples of styrene monomers as organic polymers used in polytetrafluoroethylene mixtures include styrenes that may be substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and halogens, such as ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethyl-styrene, para-tert-butylstyrene, methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, and vinylnaphthalene, but are not limited thereto. The styrene monomers can be used alone or in combination of two or more types.

[0073] The acrylic monomer used as the organic polymer in the polytetrafluoroethylene mixture includes a (meth)acrylate derivative which may be substituted. Specifically, the acrylic monomer includes a (meth)acrylate derivative which may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, and a glycidyl group, such as (meth)acrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, 2-ethyl ... Examples of the acrylic monomer include, but are not limited to, (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate and glycidyl (meth)acrylate, maleimides which may be substituted with an alkyl group having 1 to 6 carbon atoms or an aryl group, such as maleimide, N-methyl-maleimide and N-phenyl-maleimide, maleic acid, phthalic acid and itaconic acid. The acrylic monomer may be used alone or in a mixture of two or more kinds. Among these, (meth)acrylonitrile is preferred.

[0074] The amount of the acrylic monomer-derived units contained in the organic polymer is preferably 8 to 11 parts by weight, more preferably 8 to 10 parts by weight, and even more preferably 8 to 9 parts by weight, based on 100 parts by weight of the styrene monomer-derived units. If the amount of the acrylic monomer-derived units is less than 8 parts by weight, the coating strength may decrease, and if it is more than 11 parts by weight, the surface appearance of the molded article may deteriorate.

[0075] The polytetrafluoroethylene mixture of the present invention preferably has a residual moisture content of 0.5% by weight or less, more preferably 0.2 to 0.4% by weight, and even more preferably 0.1 to 0.3% by weight. If the residual moisture content is more than 0.5% by weight, it may adversely affect the flame retardancy.

[0076] The process for producing the polytetrafluoroethylene blend of the present invention includes a step of forming a coating layer containing one or more monomers selected from the group consisting of styrene monomers and acrylic monomers on the outside of the branched polytetrafluoroethylene in the presence of an initiator. Furthermore, it is preferable to include a step of drying after the step of forming the coating layer so that the residual moisture content is 0.5% by weight or less, preferably 0.2 to 0.4% by weight, more preferably 0.1 to 0.3% by weight. The drying step can be performed using a method known in the art, such as hot air drying or vacuum drying.

[0077] The initiator used in the polytetrafluoroethylene mixture of the present invention may be any initiator used in the polymerization reaction of styrene-based and / or acrylic monomers without limitation. Examples of the initiator include, but are not limited to, cumyl hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide, hydrogen peroxide, and potassium peroxide. In the polytetrafluoroethylene mixture of the present invention, one or more of the initiators may be used depending on the reaction conditions. The amount of the initiator is freely selected within the range used in consideration of the amount of polytetrafluoroethylene and the type / amount of monomer, and is preferably used in an amount of 0.15 to 0.25 parts by weight based on the amount of the total composition.

[0078] The polytetrafluoroethylene mixture of the present invention is preferably produced by the suspension polymerization method according to the following procedure.

[0079] First, water and a branched polytetrafluoroethylene dispersion (solid concentration: 60%, polytetrafluoroethylene particle size: 0.15 to 0.3 μm) were placed in a reactor, and then acrylic monomer, styrene monomer, and cumene hydroperoxide as a water-soluble initiator were added while stirring, and the reaction was carried out at 80 to 90°C for 9 hours. After the reaction was completed, the water was removed by centrifugation for 30 minutes in a centrifuge, and a paste-like product was obtained. The paste product was then dried in a hot air dryer at 80 to 100°C for 8 hours. The dried product was then pulverized to obtain a polytetrafluoroethylene-based mixture of the present invention.

[0080] Such suspension polymerization does not require a polymerization step by emulsion dispersion in the emulsion polymerization method exemplified in Japanese Patent No. 3469391, and does not require an emulsifier and electrolyte salts for coagulating and precipitating the latex after polymerization. In addition, in the polytetrafluoroethylene mixture produced by the emulsion polymerization method, the emulsifier and electrolyte salts in the mixture tend to be mixed and are difficult to remove, so it is difficult to reduce the sodium metal ions and potassium metal ions derived from the emulsifier and electrolyte salts. Since the polytetrafluoroethylene mixture (B component) used in the present invention is produced by the suspension polymerization method, it does not use such emulsifiers and electrolyte salts, so that the sodium metal ions and potassium metal ions in the mixture can be reduced, and the thermal stability and hydrolysis resistance can be improved.

[0081] In addition, in the present invention, coated branched PTFE can be used as the fluorine-containing drip prevention agent. The coated branched PTFE is a polytetrafluoroethylene mixture consisting of branched polytetrafluoroethylene particles and an organic polymer, and has a coating layer consisting of an organic polymer, preferably a polymer containing a unit derived from a styrene monomer and / or a unit derived from an acrylic monomer, on the outside of the branched polytetrafluoroethylene. The coating layer is formed on the surface of the branched polytetrafluoroethylene. In addition, the coating layer preferably contains a copolymer of a styrene monomer and an acrylic monomer.

[0082] The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. If the polytetrafluoroethylene contained is not branched polytetrafluoroethylene, the drip prevention effect will be insufficient when the amount of polytetrafluoroethylene added is small. The branched polytetrafluoroethylene is particulate and has a particle size of preferably 0.1 to 0.6 μm, more preferably 0.3 to 0.5 μm, and even more preferably 0.3 to 0.4 μm. If the particle size is smaller than 0.1 μm, the surface appearance of the molded article is excellent, but it is difficult to commercially obtain polytetrafluoroethylene having a particle size smaller than 0.1 μm. Also, if the particle size is larger than 0.6 μm, the surface appearance of the molded article may deteriorate. The number average molecular weight of the polytetrafluoroethylene used in the present invention is 1×10 4 ~1×10 7 is preferable, and more preferably 2×10 6 ~9×10 6 Generally, polytetrafluoroethylene having a high molecular weight is more preferable in terms of stability. Either the powder or dispersion form may be used.

[0083] The content of the branched polytetrafluoroethylene in the coated branched PTFE is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight, further preferably 47 to 53 parts by weight, particularly preferably 48 to 52 parts by weight, and most preferably 49 to 51 parts by weight, relative to 100 parts by weight of the total weight of the coated branched PTFE. When the proportion of the branched polytetrafluoroethylene is within this range, good dispersibility of the branched polytetrafluoroethylene can be achieved.

[0084] The content of the fluorine-containing drip prevention agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, and further preferably 0.05 to 0.1 parts by weight, based on 100 parts by weight of the resin component consisting of components A and B. The ratio of the above components indicates the net amount of drip prevention agent, and in the case of mixed PTFE, indicates the net amount of PTFE.

[0085] <Carbon black> Carbon black can be blended into the resin composition of the present invention for the purpose of coloring. The content of carbon black is preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, and even more preferably 0.1 to 1 part by weight, per 100 parts by weight of the resin component consisting of components A and B.

[0086] The carbon black may be added by blending the carbon black as it is when preparing the resin composition, or by using a masterbatch in which the carbon black is blended in advance with a thermoplastic resin. When using a masterbatch, the thermoplastic resin to be used is preferably any one of polyethylene naphthalate resin, polyethylene terephthalate resin, polybutylene naphthalate resin, polybutylene terephthalate resin, and polycarbonate resin, from the viewpoints of compatibility with the resin composition, heat resistance, and flame retardancy.

[0087] In addition, the resin composition of the present invention may contain small amounts of additives known per se to impart various functions to the molded product or improve its characteristics. These additives may be added in normal amounts as long as they do not impair the object of the present invention. Examples of such additives include sliding agents (e.g., PTFE particles), colorants other than carbon black (e.g., pigments and dyes such as titanium oxide), antistatic agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (e.g., fine particles of titanium oxide, fine particles of zinc oxide), ultraviolet absorbers, and infrared absorbers (heat ray absorbers).

[0088] <Method of producing resin composition> Any method can be used to produce the resin composition of the present invention. For example, each component and optionally other components can be premixed, then melt-kneaded, and pelletized. Premixing means can include a Nauta mixer, a V-type blender, a Henschel mixer, a mechanochemical device, an extrusion mixer, and the like. In premixing, granulation can be performed using an extrusion granulator or a briquetting machine, etc. After premixing, the mixture is melt-kneaded using a melt kneader, typically a vented twin-screw extruder, and pelletized using equipment such as a pelletizer. Other examples of melt kneaders include a Banbury mixer, a kneading roll, and a thermostatic stirring vessel, but a vented twin-screw extruder is preferred. Alternatively, each component and optionally other components can be independently supplied to a melt kneader, typically a twin-screw extruder, without premixing.

[0089] <About the molded body> The molded body made of the resin composition of the present invention can be obtained by molding the pellets produced as described above. It is preferably obtained by injection molding or extrusion molding. Injection molding can be performed not only by ordinary molding methods, but also by injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating and cooling mold molding, two-color molding, multi-color molding, sandwich molding, and ultra-high speed injection molding. In addition, molding can be performed using either a cold runner system or a hot runner system. When a molded body is obtained using a cold runner, the gate portion, which is the inlet to the molded body, may be either a restricted gate or a non-restricted gate, but a restricted gate is preferable from the viewpoint of post-processing. A non-restricted gate is a gate in which the flow path cross-sectional area does not decrease at the gate portion, and a restricted gate is a gate in which the flow path cross-sectional area decreases at the gate portion. It is preferable that the restricted gate satisfies the following formula (1).

[0090]

number

[0091] Non-restrictive gates include sprue gates, and restrictive gates include pinpoint gates, side gates, tab gates, overlap gates, film gates, fan gates, disc gates, submarine gates, and the like.

[0092] Examples of molded articles that can utilize the resin composition of the present invention include electrical and electronic parts such as connectors, sockets, relay parts, coil bobbins, optical pickups, oscillators, printed wiring boards, and computer-related parts; parts related to semiconductor manufacturing processes such as IC trays and wafer carriers; parts and housings for home electrical appliances such as computers, VTRs, televisions, irons, air conditioners, stereos, vacuum cleaners, refrigerators, rice cookers, and lighting fixtures; lighting fixture parts such as lamp reflectors and lamp holders; audio product parts such as compact discs, laser discs (registered trademark), and speakers; communication device parts such as ferrules for optical cables, telephone parts, facsimile parts, and modems; copier-related parts such as separation claws and heater holders; mechanical parts such as impellers, fans, gears, bearings, motor parts and cases; automotive parts such as automotive mechanism parts, engine parts, engine room parts, electrical parts, interior parts and the like; cooking utensils such as microwave cooking pots and heat-resistant tableware; thermal insulation and soundproofing materials such as flooring and wall materials, supporting materials such as beams and pillars, building materials such as roofing materials or civil engineering and construction materials; aircraft parts, spacecraft parts, radiation facility components such as nuclear reactors, marine facility components, cleaning tools, optical equipment parts, valves, pipes, nozzles, filters, membranes, medical equipment parts and materials, sensor parts, sanitary fixtures, sporting goods, leisure goods, etc. EXAMPLES

[0093] The following examples are provided to illustrate the present invention, but are not intended to limit the scope of the invention. Physical properties were evaluated by the following methods.

[0094] [Evaluation of resin composition] (1) Extrusion processability The stability during extrusion was evaluated according to the following criteria. ◯: The strands are stable during extrusion and can be pelletized without any problems. Δ: The strands during extrusion were somewhat unstable, but pelletization was possible. ×: The strands are unstable during extrusion, and pelletization is difficult.

[0095] (2) Liquidity The fluidity was evaluated using an Archimedes type spiral flow mold with a flow path thickness of 1 mm and a flow path width of 8 mm. The spiral flow length was measured by drying the pellets obtained by the method described below at 120°C for 8 hours and then evaluating them with an injection molding machine (SE130EV-A manufactured by Sumitomo Heavy Industries, Ltd.) under conditions of a cylinder temperature of 320°C, a mold temperature of 100°C, and an injection pressure of 100 MPa. The spiral flow length must be 50 mm or more.

[0096] (3) Tensile strength at room temperature The pellets obtained by the method described below were dried at 120°C for 8 hours, and then test pieces were made using an injection molding machine (Toshiba Machine Co., Ltd. EC130SXII-4Y) at a cylinder temperature of 320°C and a mold temperature of 80°C. Tensile tests were carried out according to ISO527-1 and 527-2 at a temperature of 23°C and a speed of 5mm / min to measure the tensile strength. The tensile strength must be 180MPa or more.

[0097] (4) Tensile strength at high temperatures The pellets obtained by the method described below were dried at 120°C for 8 hours, and then test pieces were made using an injection molding machine (Toshiba Machine Co., Ltd., EC130SXII-4Y) at a cylinder temperature of 320°C and a mold temperature of 80°C. Tensile tests were carried out according to ISO527-1 and 527-2 at a temperature of 85°C and a speed of 5mm / min to measure the tensile strength. The tensile strength in the high temperature range must be 110MPa or more.

[0098] (5) Moisture and heat resistance The pellets obtained by the method described below were dried at 120°C for 8 hours and then molded into test specimens using an injection molding machine (Toshiba Machine Co., Ltd., EC130SXII-4Y) at a cylinder temperature of 320°C and a mold temperature of 80°C.

[0099] The molded test pieces were subjected to a moist heat treatment at 85℃×85%RH×1000hr, and the test pieces after moist heat treatment were subjected to a tensile test at a temperature of 23℃ and a speed of 5mm / min according to ISO527-1 and 527-2. The tensile breaking strength retention after moist heat treatment was calculated using the following formula. The tensile breaking strength retention must be 60% or more. Tensile breaking strength retention rate (%) = [tensile breaking strength after moist heat treatment / tensile breaking strength before moist heat treatment] x 100

[0100] (6) Flame retardancy The evaluation was carried out by conducting a vertical flame test on a test piece with a thickness of 0.8 mm according to the method (UL94) specified by the U.S. Underwriters Laboratories, Inc. In addition, items that did not fall into the category of V-0, V-1, or V-2 were indicated as "not V."

[0101] (7) Suppression of oriented crystallization The pellets obtained by the method described below were dried at 120°C for 5 hours and then injection molded in a gate simulation mold using an injection molding machine (Toshiba Machine Co., Ltd. EC130SXII-4Y) with a cylinder temperature of 320°C and a mold temperature of 110°C. The gate simulation mold is a mold consisting of two parts: a runner simulation part and a gate simulation part. The runner simulation portion has a shape of 6 mm in height, 13 mm in width, and 5 mm in length, and the gate simulation portion has a width of 13 mm and a length of 125 mm, and the height can be changed arbitrarily. The height of the gate simulation portion is arbitrarily selected, and the S G / S L The value of was changed and the effect of suppressing oriented crystallization was evaluated.

[0102]

number

[0103] The effect of suppressing oriented crystallization was evaluated by measuring the length L of whitening caused by oriented crystals that occurs when the resin is filled up to the end of the 125 mm gate simulation section, as follows: ◎: L=0mm ○: 0mm <L≦50mm △: 50mm <L≦100mm ×: 100mm <L≦125mm

[0104] [Examples 1-25, Comparative Examples 1-9] A mixture of the components excluding component C was fed from the first feed port of a twin-screw extruder in accordance with the contents shown in Tables 1 to 3. This mixture was obtained by mixing in a V-type blender. Component C was fed from the second feed port using a side feeder. For extrusion, a vented twin-screw extruder with a diameter of 30 mm (TEX30α-31.5BW-2V, manufactured by Japan Steel Works, Ltd.) was used, and the mixture was melt-kneaded at a screw rotation speed of 200 rpm, a discharge rate of 20 kg / h, and a vent vacuum of 3 kPa to obtain pellets. The extrusion temperature was 320°C.

[0105] The following materials were used in the examples and comparative examples of the present invention. (Component A) AI: Polyethylene naphthalate resin obtained in Production Example I <Manufacturing example I> 100 parts by weight of dimethyl naphthalenedicarboxylate and 60 parts by weight of ethylene glycol were subjected to an ester exchange reaction in the presence of 0.010 parts by weight (10 mmol%) of cobalt acetate tetrahydrate and 0.030 parts by weight (30 mmol%) of manganese acetate tetrahydrate by a conventional method, 0.012 parts by weight (10 mmol%) of antimony trioxide was added 20 minutes after distillation of methanol, and 0.020 parts by weight (50 mmol%) of orthophosphoric acid was added before the end of the ester exchange reaction, followed by polycondensation reaction at 295°C under high vacuum to obtain a polyethylene naphthalate resin (a) with an intrinsic viscosity of 0.51 dl / g. The obtained polyethylene naphthalate resin (a) was subjected to solid-phase polymerization at a temperature of 227°C and a vacuum degree of 0.5 Torr for 8 hours to obtain a polyethylene naphthalate resin with an intrinsic viscosity of 0.68 dl / g. (B component) BI: Polyetherimide (ULTEM1010 (product name) manufactured by SABIC Japan LLC) (C component) CI: Glass fiber: Flat cross-section chopped glass fiber (manufactured by Nitto Boseki Co., Ltd.: CSG 3PA-830 (product name), long diameter 28 μm, short diameter 7 μm, cut length 3 mm, epoxy-based bundling agent) C-II: Glass fiber: Circular cross-section chopped glass fiber (manufactured by Nitto Boseki Co., Ltd.: CSG 3 PE-944 (product name), diameter 13 μm, cut length 3 mm, epoxy-based bundling agent) C-III: Carbon fiber: PAN-based carbon fiber (Teijin Ltd. IM P303 (product name), fiber diameter 7 μm, cut length 3 mm, epoxy-based bundling agent) (D component) DI: Cyclic phenoxyphosphazene (manufactured by Fushimi Pharmaceutical Co., Ltd.: FP-110T (product name)) D-II: (2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-dibenzyl-3,9-dioxide (manufactured by Teijin Ltd.: FCX-210 (trade name)) D-III: Resorcinol bis(di-2,6-xylyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd.: PX-200 (product name)) (E component) EI: Hindered phenol stabilizer (ADEKA Corporation, Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (ADEKA STAB AO-50)) (F component) FI: Phosphorus stabilizer (Bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite (SONGNOX6260PW) manufactured by Songwon International Japan Co., Ltd.)

[0106] [Table 1]

[0107] [Table 2]

[0108] [Table 3]

[0109] <Examples 1 to 25> Because the composition is within the scope of the present invention, it has been possible to obtain a flame-retardant polyester resin composition and molded article that have excellent strength, flame retardancy, and moist heat resistance at room temperature and high temperatures, and that suppress oriented crystallization at the gate portion that occurs when a limiting gate is used.

[0110] <Comparative Example 1> Since it does not contain component B, it has inferior tensile strength and flame retardancy in the high temperature range, and the effect of suppressing oriented crystallization at the gate portion that occurs when a limiting gate is used was not observed.

[0111] <Comparative Example 2> Since the content of component B exceeded the upper limit, the fluidity was poor.

[0112] <Comparative Examples 3 and 4> Since the content of C component is below the lower limit, the tensile strength and flame retardancy at room temperature and high temperatures are excellent. The results were inferior in quality.

[0113] <Comparative Example 5> Since the content of C component exceeded the upper limit, the extrusion processability was poor.

[0114] <Comparative Example 6> Since the content of component D was below the lower limit, the results showed that the tensile strength and flame retardancy at room temperature were poor.

[0115] <Comparative Example 7> Since the content of D component exceeded the upper limit, the tensile strength in the high temperature range was poor.

[0116] <Comparative Examples 8 and 9> Since component D was not a phosphazene compound, the results showed poor resistance to moist heat.

Claims

1. A flame-retardant polyester resin composition comprising 100 parts by weight of a resin component consisting of 51 to 95% by weight of (A) polyethylene naphthalate resin (component A) and 5 to 49% by weight of (B) polyetherimide resin (component B), and containing 25 to 150 parts by weight of (C) fibrous filler (component C) and 2 to 20 parts by weight of (D) a phosphazene compound (component D).

2. 2. The flame-retardant polyester resin composition according to claim 1, wherein component C is at least one fibrous filler selected from the group consisting of glass fiber and carbon fiber.

3. 3. The flame-retardant polyester resin composition according to claim 1, further comprising 0.0001 to 3 parts by weight of a hindered phenol-based stabilizer (E) (component E) per 100 parts by weight of the resin component.

4. 4. The flame-retardant polyester resin composition according to claim 1, further comprising 0.0001 to 3 parts by weight of a phosphorus-based stabilizer (F) (component F) per 100 parts by weight of the resin component.

5. A molded article comprising the flame-retardant polyester resin composition according to any one of claims 1 to 4.

6. 6. The molded article according to claim 5, wherein the resin composition is molded by passing it through a restricting gate having a narrowing flow path and flowing into the cavity.

7. The molded body according to claim 6, characterized in that the limiting gate satisfies the following formula (1). 0.04≦S Ｇ / S Ｌ <1.0 ・・・(1) (In the formula, S Ｇ is the cross-sectional area of ​​the runner (mm ２ ), S Ｌ is the cross-sectional area of ​​the gate (mm ２ )

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