JP2014167042A - Flame-resistant thermoplastic polyester resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-resistant thermoplastic polyester resin composition which has balanced flame resistance, hydrolysis resistance and mechanical characteristics and provides a molding which causes less bleed-out in high-temperature, high-humidity environments and a molding formed by molding the composition.SOLUTION: A flame-resistant thermoplastic polyester resin composition comprises (A) 100 pts.wt. of a thermoplastic polyester resin, (B) 1-70 pts.wt. of a phosphoric ester amide, (c) 1-100 pts.wt. of a flame retardant auxiliary having a 5% heating loss temperature of 300°C or lower.

Description

  The present invention relates to a flame retardant thermoplastic polyester resin composition and a molded article. More specifically, by combining a phosphoric ester amide flame retardant with a specific flame retardant aid, molding that excels in flame retardancy, hydrolysis resistance and mechanical properties, and does not easily bleed out even in high-temperature and high-humidity environments. The present invention relates to a flame retardant thermoplastic polyester resin composition from which a product can be obtained and a molded product obtained by molding the composition.

  Thermoplastic polyester resins are utilized in a wide range of fields such as mechanical mechanism parts, electrical / electronic parts, and automobile parts by taking advantage of their excellent properties such as injection moldability and mechanical properties. However, thermoplastic polyester resins are inherently flammable, so they have general chemical and physical properties for use as industrial materials such as mechanical mechanism parts, electrical / electronic parts, and automotive parts. In addition to balance, flame safety, that is, flame retardancy is required, and high flame retardancy that indicates V-0 of the UL-94 standard is often required. In addition, materials that are used in high-temperature and high-humidity environments are required to have hydrolysis resistance. In recent years, higher levels of hydrolysis resistance are required due to an increase in applications used outdoors such as automobiles and solar cells. Has been.

As a method for imparting flame retardancy to a thermoplastic polyester resin, for example, a base resin and an alumina hydrate represented by a composition formula Al ₂ O ₃ .nH ₂ O (where 0 <n <3) A flame retardant resin composition composed of a flame retardant aid such as a phosphorus-containing compound has been proposed (see, for example, Patent Document 1). However, flame retardancy and hydrolysis resistance were still insufficient.

  Further, a flame retardant resin composition (for example, see Patent Document 2) containing a thermoplastic resin or a thermosetting resin, and a flame retardant composed of phosphoric ester amide and an aromatic compound, a base resin, phosphorus Flame retardant resin compositions containing flame retardants such as containing compounds have been proposed (see, for example, Patent Document 3). However, these techniques still have insufficient flame resistance or sufficient resistance. There was a problem that hydrolyzability could not be obtained.

Japanese Patent Laying-Open No. 2005-162912 (Claims) JP 2001-139823 A (Claims) WO 01/094742 (Claims)

  Since the thermoplastic polyester resin is essentially flammable, it is necessary to add a flame retardant to impart flame retardancy. However, there is a problem that mechanical properties and hydrolysis resistance are lowered by the blending of the flame retardant. The present invention provides a flame retardant heat that is excellent in the balance between flame retardancy, hydrolysis resistance, and mechanical properties by a combination of specific flame retardants, and can obtain a molded product that hardly causes bleed out even in a high temperature and high humidity environment. It is an object to obtain a plastic polyester resin composition and a molded product formed by molding the same.

As a result of repeated studies to solve the above-described problems, the present inventors have blended (A) a thermoplastic polyester resin with a specific amount of (B) phosphoric ester amide, and (C) 5% heat loss temperature. However, the inventors have found that the above-mentioned problems can be solved by blending a specific amount of a flame retardant aid at 300 ° C. or lower, and have reached the present invention. That is, the present invention for solving such a problem is characterized by the following configuration.
(1) (A) 100 parts by weight of a thermoplastic polyester resin, (B) 1-70 parts by weight of a phosphoric ester amide, and (C) 1-100 parts by weight of a flame retardant aid having a 5% heat loss temperature of 300 ° C. or less. A flame-retardant thermoplastic polyester resin composition obtained by blending.
(2) The flame retardant thermoplastic polyester resin composition according to (1), wherein the flame retardant aid (C) having a 5% loss on heating temperature of 300 ° C. or less contains a metal hydrate.
(3) The flame retardant thermoplastic polyester resin composition according to (2), wherein the metal hydrate is aluminum hydroxide.
(4) Water obtained by heating at a temperature of 170 to 300 ° C. in a pressure vessel without adding water to a raw material in which the aluminum hydroxide is mixed with aluminum hydroxide and a reaction retarder that delays boehmite formation. The flame-retardant thermoplastic polyester resin composition according to (3), which is aluminum oxide.
(5) The flame retardancy according to any one of (1) to (4), further comprising (A) 1 to 150 parts by weight of (D) fibrous filler with respect to 100 parts by weight of (A) thermoplastic polyester resin. Thermoplastic polyester resin composition.
(6) A molded product obtained by melt-molding the flame-retardant thermoplastic polyester resin composition according to any one of (1) to (5).
(7) The molded product according to (6), wherein the tensile strength retention after heat treatment at 121 ° C. × 100% RH × 24 hours is 50% or more (8) Flame retardancy is a flame retardancy standard UL-94 V-0 The molded product according to (6) or (7), which conforms to ~ V-2.

  According to the flame-retardant thermoplastic polyester resin composition of the present invention, it is possible to obtain a molded product that has an excellent balance between flame retardancy, hydrolysis resistance, and mechanical properties and is less likely to bleed out even in a high-temperature and high-humidity environment. it can. A molded product obtained by melt-molding the flame-retardant thermoplastic polyester resin composition of the present invention is useful as a mechanical mechanism component, an electric / electronic component, an automobile component, or the like.

  Hereinafter, the present invention will be described in detail.

  The (A) thermoplastic polyester resin in the present invention is composed of (i) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, (b) a hydroxycarboxylic acid or an ester-forming derivative thereof, and (c) a lactone. A polymer or copolymer having one or more selected residues as main structural units. Here, the main structural unit means having 50 mol% or more of one or more residues selected from (A) to (C) in all the structural units, and preferably having 80 mol% or more.

  Examples of the dicarboxylic acid or ester-forming derivative thereof include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malon Examples thereof include aliphatic dicarboxylic acids such as acid, glutaric acid and dimer acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

  Examples of the diol or ester-forming derivatives thereof include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, C2-C20 aliphatic glycols such as cyclohexanediol and dimer diol, long-chain glycols having a molecular weight of 200 to 100,000, such as polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol, 4,4′-dihydroxy Aromatic dioxy compounds such as biphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F, and ester-forming derivatives thereof. .

  Polymers or copolymers containing dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as structural units include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyhexylene terephthalate. , Polyethylene isophthalate, polypropylene isophthalate, polybutylene isophthalate, polycyclohexanedimethylene isophthalate, polyhexylene isophthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / Terephthalate, polybutylene isophthalate / terephthalate, poly Tylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate, polybutylene terephthalate / decane dicarboxylate, polyethylene terephthalate / cyclohexanedimethylene terephthalate, polyethylene terephthalate / 5-sodium sulfoisophthalate, polypropylene terephthalate / 5-sodium sulfo Isophthalate, polybutylene terephthalate / 5-sodium sulfoisophthalate, polyethylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene glycol, polyethylene terephthalate / polytetramethylene glycol, polypropylene Terephthalate / polytetramethylene glycol, polybutylene terephthalate / polytetramethylene glycol, polyethylene terephthalate / isophthalate / polytetramethylene glycol, polypropylene terephthalate / isophthalate / polytetramethylene glycol, polybutylene terephthalate / isophthalate / polytetramethylene glycol , Polyethylene terephthalate / succinate, polypropylene terephthalate / succinate, polybutylene terephthalate / succinate, polyethylene terephthalate / adipate, polypropylene terephthalate / adipate, polybutylene terephthalate / adipate, polyethylene terephthalate / sebacate, polypropylene terephthalate / sebacate, poly Fragrances such as butylene terephthalate / sebacate, polyethylene terephthalate / isophthalate / adipate, polypropylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / succinate, polybutylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / sebacate Group polyester resin, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyneopentyl glycol adipate, polyethylene sebacate, Polypropylene Sebakei , Polybutylene sebacate, polyethylene succinate / adipate, polypropylene succinate / adipate, and aliphatic polyester resins such as polybutylene succinate / adipate and the like. Here, “/” represents a copolymer.

  The hydroxycarboxylic acid or ester-forming derivative thereof includes glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2 -Naphthoic acid and ester-forming derivatives thereof. Moreover, as a polymer or copolymer having these as structural units, aliphatic polyester resins such as polyglycolic acid, polylactic acid, polyglycolic acid / lactic acid, polyhydroxybutyric acid / β-hydroxybutyric acid / β-hydroxyvaleric acid, etc. Etc.

  Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, 1,5-oxepan-2-one and the like. Examples of the polymer or copolymer having these as structural units include polycaprolactone, polyvalerolactone, polypropiolactone, polycaprolactone / valerolactone, and the like.

  Among these, a polymer or copolymer having a main structural unit of dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative is preferable, and aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol. Alternatively, a polymer or copolymer having an ester-forming derivative as a main structural unit is more preferable, which is selected from terephthalic acid, naphthalenedicarboxylic acid or an ester-forming derivative thereof, and ethylene glycol, propylene glycol, butanediol, or cyclohexanedimethanol. A polymer or copolymer having an aliphatic diol or an ester-forming derivative thereof as a main structural unit is more preferable. Among them, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, Aromatic polyester resins such as polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate and polybutylene terephthalate / naphthalate are particularly preferred, and polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polyethylene naphthalate and polycyclohexanedimethylene. At least one aromatic polyester resin selected from terephthalate is most preferred. Moreover, these can also be used by 2 or more types of arbitrary compounding quantities.

  In the present invention, the ratio of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer or copolymer having the dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as the main structural unit is It is preferably 30 mol% or more, and more preferably 40 mol% or more.

  In the present invention, as the (A) thermoplastic polyester resin, a liquid crystalline polyester capable of forming anisotropy upon melting may be used. Examples of the structural unit of the liquid crystalline polyester include an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic and / or aliphatic dicarbonyl unit, an alkylenedioxy unit, and an aromatic iminooxy unit.

  The carboxyl terminal group amount of the thermoplastic polyester resin (A) used in the present invention is preferably 50 eq / t or less, more preferably 30 eq / t or less, in terms of further improving fluidity, hydrolysis resistance and heat resistance. More preferably, it is more preferably 20 eq / t or less, and particularly preferably 10 eq / t or less. The lower limit is 0 eq / t. Here, (A) the amount of carboxyl end groups of the thermoplastic polyester resin is a value measured by dissolving in o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide.

  The amount of hydroxy end groups of the thermoplastic polyester resin (A) used in the present invention is preferably 50 eq / t or more, more preferably 80 eq / t or more, in terms of moldability and fluidity, and 100 eq / t is more preferably t or more, and particularly preferably 120 eq / t or more. The upper limit is 180 eq / t. Here, (A) the amount of hydroxy terminal groups of the thermoplastic polyester resin is the volume of deuterated hexafluoroisopropanol / deuterated chloroform / deuterated pyridine when (A) the thermoplastic polyester resin is polybutylene terephthalate. It can melt | dissolve in ratio 10: 20: 1 mixed solvent, can measure NMR, and can obtain | require from the integrated intensity | strength of the peak of the proton of a terephthalic-acid residue and the proton of 1, 4- butanediol of the obtained chart.

  The viscosity of the thermoplastic polyester resin (A) used in the present invention is in the range of 0.50 to 1.50 dl / g in terms of moldability when the o-chlorophenol solution is measured at 25 ° C. It is preferable.

  The molecular weight of the thermoplastic polyester resin (A) used in the present invention is preferably in the range of more than 8,000 and less than 500,000 in weight average molecular weight (Mw) in terms of heat resistance, and more than 8,000 and less than 300,000. Is more preferable, and more preferably in the range of more than 8000 and 250,000 or less. In the present invention, Mw of (A) the thermoplastic polyester resin is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  The (A) thermoplastic polyester resin in the present invention can be produced by a known polycondensation method or ring-opening polymerization method. Either batch polymerization or continuous polymerization may be used, and any of transesterification and direct polymerization can be applied, but the amount of carboxyl end groups can be reduced and the effect of improving fluidity is increased. In view of this, continuous polymerization is preferable, and direct polymerization is preferable in terms of cost.

  When (A) the thermoplastic polyester resin in the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof The dicarboxylic acid or its ester-forming derivative and the diol or its ester-forming derivative can be produced by an esterification reaction or a transesterification reaction and then a polycondensation reaction. In order to effectively advance the esterification reaction or transesterification reaction and polycondensation reaction, it is preferable to add a polymerization reaction catalyst during these reactions. Specific examples of the polymerization reaction catalyst include titanic acid methyl ester, tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester, Organic titanium compounds such as benzyl ester, tolyl ester, or mixed esters thereof, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexyldistin oxide, didodecyltin oxide, triethyltin hydroxide , Triphenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, Butyltin dichloride, tributyltin chloride, dibutyltin sulfide, butylhydroxytin oxide, tin compounds such as methylstannic acid, ethylstannic acid, alkylstannic acid such as butylstannic acid, zirconia compounds such as zirconium tetra-n-butoxide, And antimony compounds such as antimony trioxide and antimony acetate. Among these, an organic titanium compound and a tin compound are preferable, tetra-n-propyl ester, tetra-n-butyl ester and tetraisopropyl ester of titanic acid are more preferable, and tetra-n-butyl ester of titanic acid is particularly preferable. Two or more of these polymerization reaction catalysts can be used in combination. The addition amount of the polymerization reaction catalyst is preferably in the range of 0.005 to 0.5 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin in terms of further improving mechanical properties, moldability and color tone, The range of -0.2 weight part is more preferable.

  In the present invention, (A) a thermoplastic polyester resin and (B) phosphoric ester amide and (C) 5% heat loss is 300 ° C. or less, a high flame retardancy and excellent mechanical properties, Hydrolysis resistance can be obtained. (A) When the thermoplastic polyester is melted during combustion, (C) 5% reduction in weight of the flame retardant is caused by weight loss of the flame retardant aid, resulting from the cooling effect due to the endothermic reaction and the generation of nonflammable gas The effect of suppressing the initial combustion due to the diluting effect of the combustible gas is exhibited. Further, during initial combustion, (B) phosphoric ester amide moves to the surface of the resin molded product, and an effect of preventing the spread of fire due to formation of a carbonized layer or the like is exhibited. In the present invention, high flame retardancy is obtained by these synergistic effects. Moreover, since high flame retardance is acquired with a small amount of flame retardant by these combinations, the flame retardant blending amount can be reduced, and excellent mechanical properties and hydrolysis resistance can be obtained.

  The (B) phosphoric ester amide is a compound containing a bond of phosphoric ester and phosphoric amide. For example, a compound represented by the following general formula (1) can be used. Two or more compounds represented by the following general formula (1) may be blended.

(In the general formula (1), R ¹ , R ² and R ³ may be the same or different and each represents an optionally substituted alkyl group, cycloalkyl group or aryl group.)

In the general formula (1), examples of the alkyl group represented by R ¹ , R ² , and R ³ include methyl, ethyl, butyl, t-butyl, hexyl, octyl, nonyl, dodecyl, and the like. 1-20 are preferable, as for carbon number of an alkyl group, 1-12 are more preferable, and 1-6 are more preferable. Examples of the cycloalkyl group include cyclohexyl and the like. 5-20 are preferable and, as for carbon number of a cycloalkyl group, 6-12 are more preferable. Examples of the aryl group include phenyl and naphthyl. As for carbon number of an aryl group, 6-20 are preferable. Moreover, all of these alkyl groups, cycloalkyl groups, and aryl groups may have a substituent. Examples of the substituent include a hydroxyl group. Examples of the substituent for the aryl group further include an alkyl group.

  As a commercially available product of (B) phosphoric ester amide represented by the general formula (1), Daikyo Chemical Co., Ltd. Super Bigor FV-1 and the like can be mentioned.

  Moreover, the compounding quantity of (B) phosphoric ester amide is 1-70 weight part with respect to 100 weight part of (A) thermoplastic polyester resin from a viewpoint of the balance of a flame retardance and bleed-out. (B) When the blending amount of phosphoric ester amide is less than 1 part by weight, sufficient flame retardancy cannot be obtained. 2 parts by weight or more is preferable, and 3 parts by weight or more is more preferable. On the other hand, when the blending amount of (B) phosphoric ester amide exceeds 70 parts by weight, bleeding out occurs. 60 parts by weight or less is preferable, and 50 parts by weight or less is more preferable.

  (C) The flame retardant aid having a 5% loss on heating temperature of 300 ° C. or lower is not particularly limited, and for example, a 5% loss on heating in phosphorus-containing compounds, nitrogen-containing compounds, inorganic metal compounds, etc. The thing whose temperature is 300 degrees C or less is mentioned. Two or more of these may be blended. Here, the 5% heat loss temperature in the present invention refers to the temperature at which the weight loss is measured by measuring the weight loss while increasing the temperature from 30 ° C. to 400 ° C. at 30 ° C./min in TGA7 manufactured by PerkinElmer. . When the 5% loss on heating exceeds 300 ° C., (A) the amount of weight reduction of the flame retardant aid at the temperature at which the thermoplastic polyester resin melts at the time of combustion is small, that is, due to the cooling effect accompanying the weight reduction and the generation of nonflammable gas The initial combustion suppression effect such as the combustible gas dilution effect is not sufficiently obtained, and the flame retardancy is not sufficiently exhibited. When a large amount of a flame retardant is blended for improving the flame retardancy, the mechanical properties and hydrolysis resistance of the molded product are lowered. The lower limit of the 5% heat loss temperature is not particularly limited, but is preferably equal to or higher than the melting point of the thermoplastic polyester resin (A) from the viewpoint of further improving mechanical properties. For example, when (A) the thermoplastic polyester resin is polybutylene terephthalate, the 5% heat loss temperature of the flame retardant aid is preferably 260 ° C or higher, more preferably 270 ° C or higher, and further preferably 280 ° C or higher. .

  Examples of phosphorus-containing compounds include organic phosphorus compounds other than phosphate ester amides (phosphate esters, phosphonitrile compounds, organic phosphonic acid compounds, organic phosphinic acid compounds, etc.). In the present invention, among these, And those having a 5% loss on heating temperature of 300 ° C. or lower can be selected and used.

  Examples of the nitrogen-containing compound include amino group-containing triazines, salts of amino group-containing triazines, urea compounds, and the like. In the present invention, those having a 5% heat loss temperature of 300 ° C. or less are selected. It can be selected and used.

  Examples of inorganic metal compounds include metal salts of inorganic acids (boric acid, phosphoric acid, stannic acid, antimonic acid, etc.), metal oxides, metal hydroxides, metal sulfides, etc. Of these, those having a 5% loss on heating temperature of 300 ° C. or lower can be selected and used. From the viewpoint of further improving flame retardancy and mechanical properties, a metal hydrate containing a hydroxyl group or crystal water in the structure of the inorganic metal compound is preferable. Examples of the metal hydrate include aluminum hydroxide, magnesium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, and the like. Is preferably selected and used at a temperature of 300 ° C. or lower. Aluminum hydroxide is more preferable from the viewpoint of further improving flame retardancy, mechanical properties, and hydrolysis resistance.

  Moreover, as aluminum hydroxide, water obtained by heating at a temperature of 170 to 300 ° C. in a pressure vessel without adding water to a raw material in which aluminum hydroxide and a reaction retarder that delays boehmite formation are mixed. Aluminum oxide is preferred. Such aluminum hydroxide has a moderately high 5% heat loss temperature within the range where the above-mentioned flame retardancy effect is exhibited, and can further improve the mechanical properties. As a commercial product of aluminum hydroxide produced by heating at a temperature of 170 to 300 ° C. in a pressure vessel without adding water to a raw material mixed with aluminum hydroxide and a reaction retarding agent that delays boehmite, Aluminum hydroxide “ALH-3L” and “ALH-F” manufactured by Kawai Lime Industry Co., Ltd. are preferably used.

  In addition, the blending amount of the flame retardant aid (C) having a 5% heat loss temperature of 300 ° C. or less is (A) 100 parts by weight of the thermoplastic polyester resin from the viewpoint of flame retardancy, mechanical properties, and hydrolysis resistance. On the other hand, it is 1 to 100 parts by weight. (C) When the blending amount of the flame retardant aid having a 5% heat loss temperature of 300 ° C. or less is less than 1 part by weight, sufficient flame retardancy cannot be obtained. When a large amount of a flame retardant is blended for improving the flame retardancy, the mechanical properties and hydrolysis resistance of the molded product are lowered. 2 parts by weight or more is preferable, and 3 parts by weight or more is more preferable. On the other hand, when the blending amount of the flame retardant aid having (C) 5% heat loss temperature of 300 ° C. or less exceeds 100 parts by weight, the mechanical properties are deteriorated. 90 parts by weight or less is preferable, and 80 parts by weight or less is more preferable.

  In the flame-retardant thermoplastic polyester resin composition of the present invention, (D) a fibrous filler can be further blended, and the mechanical strength and heat resistance can be further improved.

  (D) Examples of the fibrous filler include glass fiber, aramid fiber, carbon fiber, milled fiber, potassium titanate whisker, calcium sulfate whisker, and wollastonite. Two or more of these may be blended. Glass fiber is preferably used from the viewpoint of further improving mechanical strength, heat resistance and productivity. Examples of the glass fiber include chopped strand type and roving type glass fiber. A glass fiber treated with a sizing agent containing a silane coupling agent such as an aminosilane compound or an epoxy silane compound and / or one or more epoxy compounds such as urethane, vinyl acetate, bisphenol A diglycidyl ether, or novolac epoxy compound. Preferably used. The silane coupling agent and / or sizing agent may be used by being mixed with the emulsion liquid. Moreover, the fiber diameter of glass fiber is 1-30 micrometers normally, Preferably it is 5-15 micrometers. In addition, the fiber cross section of the glass fiber is usually circular, but it is also possible to use a fibrous filler having an arbitrary cross section such as an elliptical glass fiber of any aspect ratio, a flat glass fiber and an eyebrow shaped glass fiber, It is characterized by improved fluidity during injection molding and a molded product with less warpage.

  The blending amount of the (D) fibrous filler is preferably 1 with respect to 100 parts by weight of the thermoplastic polyester resin (A) from the viewpoint of fluidity during injection molding and durability of the injection molding machine or mold. -150 parts by weight. (D) If the compounding quantity of a fibrous filler is 1 weight part or more, the effect which improves the mechanical strength and heat-deformation temperature of a molded article will be acquired. 2 parts by weight or more is more preferable, and 3 parts by weight or more is more preferable. On the other hand, if the blending amount of (D) fibrous filler is 150 parts by weight or less, good fluidity can be obtained. 130 parts by weight or less is more preferable, and 100 parts by weight or less is more preferable.

  The flame-retardant thermoplastic polyester resin composition of the present invention can further contain the following components as necessary within a range not impairing the effects of the present invention.

  The flame-retardant thermoplastic polyester resin composition of the present invention preferably further contains a known polyhydric alcohol compound having three or more functional groups and containing one or more alkylene oxide units, such as injection molding. The fluidity during molding can be improved. Here, the polyhydric alcohol refers to a compound having two or more hydroxyl groups. The polyhydric alcohol compound having three or more functional groups and one or more alkylene oxide units has three or more functional groups such as a trifunctional compound, a tetrafunctional compound, and a pentafunctional compound. Any compound that further contains one or more alkylene oxide units is preferably used.

  The functional group is preferably at least one selected from the group consisting of a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, an ester group, and an amide group. It preferably has the above functional group. The same functional group is more preferable in terms of further improving fluidity, mechanical properties, durability, heat distortion temperature, and productivity.

  Examples of the alkylene oxide unit include aliphatic alkylene oxide units having 1 to 4 carbon atoms. Propylene oxide units are more preferred because they are more excellent in fluidity, recyclability, durability, heat distortion temperature and mechanical properties. Moreover, since it is excellent by fluidity | liquidity and mechanical property, 1-5 are preferable for the alkylene oxide unit per functional group.

  The molecular weight or weight average molecular weight (Mw) of the polyhydric alcohol compound having three or more functional groups and containing one or more alkylene oxide units is preferably in the range of 200 to 6000 in terms of fluidity. Here, the molecular weight or weight average molecular weight of the polyhydric alcohol compound in the present invention can be measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent, and converted into polymethyl methacrylate (PMMA). It is.

  As for the compounding quantity of the polyhydric alcohol compound which has a 3 or more functional group and contains one or more alkylene oxide units, 0.1-1 weight part is preferable with respect to 100 weight part of (A) thermoplastic polyester resin.

  The flame retardant thermoplastic polyester resin composition of the present invention may be blended with a thermoplastic resin other than the thermoplastic polyester resin (A), and may improve moldability, dimensional accuracy, molding shrinkage, toughness, and the like. it can. Examples of such thermoplastic resins include low density polyethylene resins, high density polyethylene resins, ethylene copolymers, polypropylene resins, polyamide resins, vinyl resins, polyacetal resins, polyurethane resins, aromatic or aliphatic polyketone resins, Polyphenylene sulfide resin, polyether ether ketone resin, polyimide resin, thermoplastic starch resin, polyurethane resin, methyl methacrylate styrene resin (MS resin), aromatic polycarbonate resin, polyarylate resin, polysulfone resin, polyether sulfone resin, phenoxy resin, Examples include polyphenylene ether resin, poly-4-methylpentene-1, polyetherimide resin, cellulose acetate resin, and polyvinyl alcohol resin. Two or more of these may be blended. In particular, an aromatic polycarbonate resin is preferable from the viewpoint of improving dimensional accuracy and reducing molding shrinkage, and an ethylene copolymer and a vinyl resin are preferable from the viewpoint of improving toughness.

  Examples of the aromatic polycarbonate resin include aromatic homo- or copolycarbonates obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester.

  Examples of aromatic dihydric phenol compounds include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and bis (4- Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2 , 2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, Examples include 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane. Two or more of these can be used.

  The aromatic polycarbonate resin preferably has a weight average molecular weight in the range of 10000 to 1100000 and a glass transition temperature of about 150 ° C. Two or more aromatic polycarbonate resins may be used in combination. An aromatic polycarbonate resin or an aromatic polycarbonate resin oligomer having a weight average molecular weight in the range of 3000 to 1100000 is particularly preferably used. Here, the weight average molecular weight is a value obtained by measuring in terms of polystyrene by gel permeation chromatography using tetrahydrofuran as a solvent.

  Further, those having a melt viscosity index (melt flow index) measured by a melt indexer according to ASTM D1238 under the condition of a load of 1.2 kg at a temperature of 300 ° C. are preferable, particularly mechanical properties. An aromatic polycarbonate resin of 1 to 50 g / 10 min is preferably used from the viewpoint of further improving the viscosity.

  As an example of the above aromatic polycarbonate resin oligomer, “Iupilon” (registered trademark) AL having a weight average molecular weight of about 4000 is commercially available from Mitsubishi Gas Chemical Co., Ltd.

  Moreover, 1-100 weight part is preferable with respect to 100 weight part of (A) thermoplastic polyester resins, and, as for the compounding quantity of aromatic polycarbonate resin, 10-60 weight part is more preferable. By setting the content of the aromatic polycarbonate resin to 1 part by weight or more, the dimensional accuracy of the molded product can be improved, and molding shrinkage can be reduced. On the other hand, when the content of the aromatic polycarbonate resin is 100 parts by weight or less, the heat distortion temperature of the molded product can be further increased.

  In addition to the above aromatic polycarbonate resin, a small amount of an acidic phosphoric acid ester compound may be further blended. (A) Since it is useful for preventing transesterification of the thermoplastic polyester resin and the aromatic polycarbonate resin, the heat distortion temperature, etc. Can be suppressed. The above acidic phosphoric acid ester compound is a general term for partial ester compounds of alcohols and phosphoric acid, a low molecular weight one is a colorless liquid, a high molecular weight one is a white waxy or flaky solid, and (B) phosphoric acid ester It is used in distinction from phosphoric esters of phosphoric flame retardants in which the hydrogen of the amide and phosphoric acid is substituted with an alkyl group or an allyl group. Examples of the acidic phosphate ester compound preferably used include long-chain alkyl acid phosphate compounds such as a mixture of mono and distearyl acid phosphates. Such a compound is, for example, commercially available from ADEKA Corporation under the name “Adeka Stub” (registered trademark) AX-71, and is a flaky solid having a melting point. Two or more of these may be contained.

  Further, the blending amount of the acidic phosphate compound is preferably 0.01 parts by weight or more with respect to (A) 100 parts by weight of the total of the thermoplastic polyester resin and the aromatic polycarbonate resin, and further improves the heat distortion temperature of the molded product. be able to. 0.05 parts by weight or more is more preferable. On the other hand, 2 parts by weight or less is preferable, and higher flame retardancy can be maintained. 1 part by weight or less is more preferable.

  Examples of the ethylene copolymer include ethylene / propylene, ethylene / propylene / non-conjugated diene copolymer, ethylene / ethyl acrylate, ethylene / methyl acrylate, ethylene / butene-1, ethylene / methyl methacrylate, ethylene / Examples thereof include vinyl acetate, an ethylene copolymer and a modified ethylene copolymer obtained by epoxy-modifying a polyethylene resin with an acid anhydride such as maleic anhydride, glycidyl methacrylate and an epoxidizing agent. Further, those having various degrees of crosslinking and those having various microstructures such as a cis structure and a trans structure are exemplified. Examples of the modified ethylene copolymer include ethylene / glycidyl methacrylate, ethylene / ethyl acrylate / glycidyl methacrylate, ethylene / methyl acrylate / glycidyl methacrylate, ethylene / butene-1 / maleic anhydride, ethylene / propylene / maleic anhydride. Ethylene / ethyl acrylate / maleic anhydride, ethylene / methyl acrylate / maleic anhydride, ethylene / methyl methacrylate / maleic anhydride, ethylene / vinyl acetate / maleic anhydride and ethylene or ethylene copolymers with peroxides, etc. Examples include epoxidized epoxidized ethylene copolymers. In particular, ethylene / glycidyl methacrylate and ethylene / butene-1 / maleic anhydride are preferably used because they greatly improve toughness such as impact strength. Examples of commercially available products of ethylene / glycidyl methacrylate and ethylene / butene-1 / maleic anhydride include, for example, “Bond First” (registered trademark) E (ethylene / glycidyl methacrylate) manufactured by Sumitomo Chemical Co., Ltd., Mitsui Oil Examples thereof include MH-5010 and MH-5020 (ethylene / butene-1 / maleic anhydride) manufactured by Chemical Industry Co., Ltd.

  Further, the blending amount of the ethylene copolymer is preferably 0.1 parts by weight or more with respect to 100 parts by weight of the (A) thermoplastic polyester resin, and can improve toughness such as impact strength. 1 part by weight or more is more preferable. On the other hand, 10 parts by weight or less is preferable, and the flame retardancy and the heat distortion temperature can be maintained higher. 5 parts by weight or less is more preferable.

  Examples of the vinyl resin include polymethyl methacrylate, methyl methacrylate / acrylonitrile, polystyrene resin, acrylonitrile / styrene resin (AS resin), styrene / butadiene resin, styrene / N-phenylmaleimide resin, styrene / acrylonitrile / Rubber materials such as vinyl (co) polymers such as N-phenylmaleimide resin, acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / butadiene / methyl methacrylate / styrene resin (MABS resin), high impact polystyrene resin, etc. Styrenic resins modified with polymers, and styrene / butadiene / styrene resins, styrene / isoprene / styrene resins and styrene / ethylene / butadiene / styrene resins as block copolymers And the like.

  Further, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or epoxy group-containing vinyl monomers may be graft-polymerized or copolymerized with the vinyl resin. Among these, a vinyl resin obtained by graft polymerization or copolymerization of an unsaturated acid anhydride or an epoxy group-containing vinyl monomer is preferable.

  The unsaturated acid anhydrides are compounds that share both a vinyl group capable of radical polymerization and an acid anhydride in one molecule, and preferred examples include maleic anhydride.

  In addition, the epoxy group-containing vinyl monomer is a compound that shares both radically polymerizable vinyl group and epoxy group in one molecule, and specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, Examples include glycidyl esters of unsaturated organic acids such as glycidyl itaconate, glycidyl ethers such as allyl glycidyl ether, and the above derivatives such as 2-methylglycidyl methacrylate. Among them, glycidyl acrylate and glycidyl methacrylate are preferably used. it can. Moreover, these can be used individually or in combination of 2 or more types.

  The amount used for graft polymerization or copolymerization of unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or epoxy group-containing vinyl monomers is 0.05% by weight or more based on the vinyl resin. It is preferable that Copolymerization in a large amount tends to decrease fluidity and gelation, and is preferably 10% by weight or less, more preferably 5% by weight or less.

  Further, a vinyl resin that is epoxy-modified with an epoxidizing agent such as peroxides, performic acid, peracetic acid, and perbenzoic acid may be used. In this case, it is preferable that a diene monomer is randomly copolymerized or block copolymerized with the vinyl resin in order to effectively perform the epoxy modification. As examples of diene monomers, butadiene, isoprene and the like are preferably used. Examples of suitable methods for producing these epoxy-modified vinyl resins are disclosed in JP-A-6-256417, JP-A-6-220124 and the like.

  Further, a vinyl resin in which an innermost layer (core layer) having a rubber layer and a vinyl resin covering the inner layer (shell layer) are used as one kind of outer layer (shell layer) is also preferably used, and has a so-called core-shell type structure. A core-shell type rubber is also preferably used.

  Alternatively, a vinyl resin containing a vinyl resin as a branched chain of the graft copolymer may be used. Examples of the resin serving as the main chain include polyolefin, acrylic resin, and polycarbonate resin. Either the branched chain or the main chain may be modified with glycidyl methacrylate or acid anhydride. Specific examples thereof include poly (ethylene / glycidyl methacrylate) -g-polymethyl methacrylate (E / GMA-g -PMMA), poly (ethylene / glycidyl methacrylate) -g-polystyrene (E / GMA-g-PS), poly (ethylene / glycidyl methacrylate) -g-acrylonitrile / styrene (E / GMA-g-AS), poly ( And ethylene-g-acrylonitrile / styrene (Eg-AS), polycarbonate-g-acrylonitrile / styrene (PC-g-AS), etc. ("-g-" represents a graft). As a commercial product of a vinyl resin containing a resin based on a branched chain of a graft copolymer, for example, This Yushi Co., Ltd. "Modiper" (registered trademark). May contain together with these other vinyl resins.

  In addition, from the viewpoint of further improving the toughness of the molded product, the vinyl resin content is preferably 0.1 parts by weight or more and more preferably 1 part by weight or more with respect to (A) 100 parts by weight of the thermoplastic polyester resin. . On the other hand, 10 parts by weight or less is preferable and 6 parts by weight or less is more preferable from the viewpoint of further increasing the heat distortion temperature of the molded product.

  In addition, the flame-retardant thermoplastic polyester resin composition of the present invention preferably further contains a fluorine-based resin, which suppresses melting and dropping of the resin composition at the time of combustion, and further improves flame retardancy. it can.

  The fluorine-based resin is a resin containing fluorine in a substance molecule. Specifically, polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetra (Fluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer, etc. Is mentioned. Among them, polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, and polyvinylidene fluoride are preferable. In particular, polytetrafluoroethylene and (tetrafluoroethylene / ethylene) copolymers are preferred.

  Moreover, the compounding quantity of a fluorine-type resin becomes like this. Preferably it is 0.05-3 weight part with respect to 100 weight part of (A) thermoplastic polyester resins, More preferably, it is 0.15-1.5 weight part. The effect of preventing melting and dropping during combustion is obtained at 0.05 parts by weight or more, and the mechanical properties are further improved at 3 parts by weight or less.

  The flame-retardant thermoplastic polyester resin composition of the present invention further comprises alkaline earth metal soaps such as calcium stearate, barium stearate and zinc stearate, fatty acid esters, fatty acid ester salts (partly salted products) Fatty acid amides such as ethylene bisstearyl amide, polycondensates composed of ethylenediamine and stearic acid and sebacic acid, or fatty acid amides composed of polycondensates of phenylenediamine and stearic acid and sebacic acid, polyalkylene waxes, acid anhydrides A known release agent for plastics such as a modified polyalkylene wax and a mixture of the above-described lubricant and a fluorine resin or a fluorine compound can be blended, and the mold release property at the time of injection molding can be improved. In particular, alkaline earth metal soaps such as zinc stearate and fatty acid ester salts (including partially salted ones) contribute to retention stability in addition to improving mold release during injection molding. Preferably used.

  Moreover, the compounding quantity of a mold release agent becomes like this. Preferably it is 0.01-1 weight part with respect to 100 weight part of (A) thermoplastic polyester resins, and 0.03-0.6 weight part is more preferable. When the amount is 0.01 parts by weight or more, a sufficient releasability effect is obtained, and when the amount is 1 part by weight or less, mechanical properties are further improved.

  In addition, the flame-retardant thermoplastic polyester resin composition of the present invention further comprises (C) a flame retardant aid having a 5% heat loss temperature of 300 ° C. or less and (D) an inorganic filler other than the fibrous filler. It is possible to improve some of the crystallization characteristics, arc resistance, anisotropy, mechanical strength, flame retardancy or heat distortion temperature of the molded product, and in particular, anisotropy is effective. Therefore, a molded product with less warping can be obtained. Examples of the inorganic filler include granular, powdery and layered inorganic fillers. Specific examples include glass beads, glass flakes, kaolin, talc, mica and the like, and two or more of these may be blended.

  In addition, (C) a flame retardant aid having a 5% heat loss temperature of 300 ° C. or less and (D) an inorganic filler other than a fibrous filler include a coupling agent treatment, an epoxy compound, or an ionization treatment. Surface treatment may be performed. Moreover, when mix | blending a granular, powdery, and layered inorganic filler, it is preferable that the average particle diameter is 0.1-20 micrometers from the point of impact strength, and it is more preferable that it is 0.2-10 micrometers. . In addition, the blending amount of (C) flame retardant aid with a 5% heat loss temperature of 300 ° C. or less and (D) inorganic filler other than the fibrous filler is determined by the flowability during molding and the durability of the molding machine and mold. From the viewpoint of properties, 150 parts by weight or less is preferable based on 100 parts by weight of the thermoplastic polyester resin (A) in combination with the blending amount of (D) fibrous filler.

  The flame retardant thermoplastic polyester resin composition of the present invention is an epoxy compound such as a glycidyl ester compound, a glycidyl ether compound and a glycidyl ester ether compound, an oxazoline compound, a carbodiimide-modified isocyanate for the purpose of further improving hydrolysis resistance. Hydrolysis resistance improvers such as compounds and carbodiimide compounds can be included.

  Further, the blending amount of the hydrolysis resistance improving agent is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin from the viewpoint of further improving the hydrolysis resistance. 03-1 weight part is more preferable. The effect of further improving the hydrolysis resistance is obtained at 0.01 parts by weight or more, and the mechanical properties are further improved at 3 parts by weight or less.

  The flame retardant thermoplastic polyester resin composition of the present invention may further contain a hindered phenol antioxidant, a phosphite antioxidant and / or a thioether antioxidant as a stabilizer. Can be provided with extremely good heat aging resistance even when exposed to high temperatures for a long period of time. The blending amount is preferably 0.01 to 2 parts by weight and more preferably 0.03 to 1 part by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin from the viewpoint of improving the heat aging resistance. The effect of improving sufficient heat aging resistance is obtained at 0.01 parts by weight or more, and the mechanical properties are further improved at 2 parts by weight or less.

  The flame-retardant thermoplastic polyester resin composition of the present invention is further prepared by blending one or more types of carbon black, titanium oxide, and various colors of pigments and dyes to adjust the resin to various colors and weather resistance (light It is also possible to improve the property) and conductivity. The blending amount of the pigment or dye is preferably 0.01 to 3 parts by weight and more preferably 0.03 to 1 part by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. 0.01 parts by weight is effective for toning, weather resistance (light), and conductivity, and 3 parts by weight or less improves mechanical properties.

Examples of the carbon black include channel black, furnace black, acetylene black, anthracene black, oil smoke, pine smoke, and graphite. The average particle diameter is 500 nm or less, and the dibutyl phthalate oil absorption is 50 to 400 cm ^3. / 100 g of carbon black is preferably used. Further, it may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane coupling agent or the like.

  Further, as the above titanium oxide, titanium oxide having a crystal form such as rutile form or anatase form and having an average particle diameter of 5 μm or less is preferably used. Aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane cup It may be treated with a ring agent or the like. In addition, the above-described carbon black, titanium oxide, and various color pigments and dyes may be used in various heat treatments in order to improve dispersibility with the flame retardant thermoplastic polyester resin composition of the present invention and to improve handling during production. It may be used as a mixed material which is melt-mixed with or simply mixed with a plastic resin.

  Furthermore, the flame-retardant thermoplastic polyester resin composition of the present invention contains 1 known additives such as ultraviolet absorbers, light stabilizers, plasticizers, and antistatic agents within a range that does not impair the object of the present invention. You may mix | blend a seed or more.

  When the polybutylene terephthalate resin is used as the component (A), the flame-retardant thermoplastic polyester resin composition of the present invention has a molding temperature of 250 ° C. and a mold temperature of 80 ° C. using an IS55EPN injection molding machine manufactured by Toshiba Machine. Tensile ASTM 1 dumbbell with a thickness of 1/8 inch (about 3.2 mm) obtained by injection molding under the molding cycle conditions of 10 seconds for the injection time and pressure holding time under the temperature conditions and 10 seconds for the cooling time. The tensile strength retention before and after the wet heat treatment at a temperature of 121 ° C. and a humidity of 100% RH of the test piece for evaluating physical properties is preferably 50% or more, more preferably 60% or more, and 70% or more. More preferably. The measuring method of the tensile strength retention rate is the same as the measuring method of the tensile strength retention rate of the molded product described later.

  When the polybutylene terephthalate resin is used as the component (A), the flame-retardant thermoplastic polyester resin composition of the present invention has a molding temperature of 250 ° C. and a mold temperature of 80 ° C. using an IS55EPN injection molding machine manufactured by Toshiba Machine. UL94 vertical test of a 1/32 inch (about 0.79 mm) thick combustion test piece obtained by injection molding under the molding cycle conditions of 10 seconds for the injection time and pressure holding time under the temperature conditions and 10 seconds for the cooling time. It is preferable that the flame retardancy in accordance with the evaluation criteria defined in is compatible with V-0 to V-2. The method for evaluating flame retardancy is the same as the method for evaluating flame retardancy of molded products described later.

  The flame-retardant thermoplastic polyester resin composition of the present invention can be produced by a known method. For example, at least the above (A) thermoplastic polyester resin, (B) phosphoric ester amide, (C) a flame retardant aid having a 5% loss on heating temperature of 300 ° C. or less, and a compounding material contained as necessary are premixed. Then, the flame retardant of the present invention is supplied by a method such as supplying to an extruder and sufficiently melting and kneading, or a method using a quantitative feeder such as a weight feeder to supply a predetermined amount of each component to an extruder and sufficiently melting and kneading. A thermoplastic polyester resin composition is produced.

  Examples of the premixing include a dry blending method and a mixing method using a mechanical mixing device such as a tumbler, ribbon mixer, and Henschel mixer. In addition, (D) a method of adding a fibrous filler or an inorganic filler other than the fibrous filler by installing a side feeder in the middle of a former loading part and a vent part of a multi-screw extruder such as a twin screw extruder. It may be. In addition, in the case of liquid additives, a method of adding using a plunger pump by installing a liquid addition nozzle in the middle of the main loading part and the vent part of a multi-screw extruder such as a twin screw extruder and the original loading part For example, a method of supplying with a metering pump may be used.

  In producing a flame-retardant thermoplastic polyester resin composition, for example, a single-screw extruder, twin-screw extruder, tri-screw extruder, conical extruder and kneader equipped with a “unimelt” or “dalmage” type screw. It can be obtained in the form of pellets by discharging into a strand using a kneader of the type and cutting with a strand cutter.

  The molded article of the present invention can be obtained by melt-molding the thus obtained pellet-like flame-retardant thermoplastic polyester resin composition by a known method such as injection molding, extrusion molding, blow molding or inflation molding. As the injection molding method, gas assist molding, two-color molding, sandwich molding, in-mold molding, insert molding and injection press molding are known in addition to the usual injection molding method. it can.

  The tensile strength retention after the heat treatment at 121 ° C. × 100% RH × 24 hours of the molded article of the present invention is preferably 50% or more, more preferably 60% or more, and further preferably 70% or more. 121 ° C x 100% RH x 24 hours after heat treatment of molded products, the higher the tensile strength retention rate, the higher the use at high temperature and high humidity, the outdoor use, the long-term durability required It is useful for such as. Examples of a method for setting the tensile strength retention after wet heat treatment at 121 ° C. × 100% RH × 24 hours in such a range include a method of melt-molding the flame-retardant thermoplastic polyester resin composition of the present invention.

Here, the tensile strength retention after the wet heat treatment at 121 ° C. × 100% RH × 24 hours in the present invention is a test piece for evaluating tensile properties of ASTM No. 1 dumbbell having a thickness of 1/8 inch (about 3.2 mm). Therefore, it can be measured by the following method. In addition, when producing a test piece from a flame-retardant thermoplastic polyester resin composition, for example, using a polybutylene terephthalate resin as the component (A) using an IS55EPN injection molding machine manufactured by Toshiba Machine, a molding temperature ASTM No. 1 with a test piece thickness of 1/8 inch (approximately 3.2 mm) under molding cycle conditions of 250 ° C. and mold temperature of 80 ° C., injection time and holding time of 10 seconds, and cooling time of 10 seconds. A test piece for evaluating the physical properties of a dumbbell is prepared. The tensile strength at break is measured according to ASTM D638 (2005) using the obtained test specimen for tensile property evaluation. The tensile strength at break of three test specimens for evaluating physical properties is measured to obtain an average value, which is the tensile strength before wet heat treatment. Further, the test piece for evaluation of tensile properties is put into an advanced accelerated life test apparatus of EHS-411 manufactured by Espec Co., Ltd. set at a temperature of 121 ° C. and a humidity of 100% RH for 24 hours to perform a wet heat treatment. Similarly, the tensile strength at break of three test pieces for tensile property evaluation after wet heat treatment is measured to determine the average value, and the tensile break strength after wet heat treatment is obtained. From the obtained tensile strength at break, the tensile strength retention can be determined by the following formula.
Calculation formula: Tensile strength retention rate (%) = (tensile breaking strength after wet heat treatment / tensile breaking strength before wet heat treatment) × 100
It is preferable that the flame retardancy of the molded product of the present invention conforms to V-0 to V-2 of flame retardancy standard UL-94. When the flame retardancy of a molded product meets the flame retardancy standard UL-94, it is useful for applications that require high flame retardancy. Examples of the method for setting the flame retardancy standard UL-94 to such a range include a method of melt-molding the flame-retardant thermoplastic polyester resin composition of the present invention.

  Here, the flame retardancy in the present invention can be evaluated from a combustion test piece having a thickness of 1/32 inch (about 0.79 mm) by the following method. In addition, when producing a test piece from a flame-retardant thermoplastic polyester resin composition, for example, using a polybutylene terephthalate resin as the component (A) using an IS55EPN injection molding machine manufactured by Toshiba Machine, a molding temperature A 1/32 inch (approx. 0.79 mm) thick combustion test piece is produced under a molding cycle condition of 250 ° C. and a mold temperature of 80 ° C. with a combined injection time and holding time of 10 seconds and a cooling time of 10 seconds. To do. Using the obtained combustion test piece, the flame retardancy is evaluated according to the evaluation standard defined in the UL94 vertical test. Flame retardancy falls and ranks in the order of V-0> V-1> V-2. Moreover, the material which is inferior in combustibility, does not reach said V-2, and does not correspond to said flame retardance rank shall be outside a specification.

  Molded articles obtained by melt-molding the flame-retardant thermoplastic polyester resin composition of the present invention, taking advantage of the characteristics of having excellent flame retardancy, hydrolysis resistance and mechanical properties, mechanical mechanism parts, electrical and electronic parts, It can be preferably used for automobile parts or housings.

  Specific examples of mechanical mechanism parts, electrical / electronic parts, and automotive parts include breakers, electromagnetic switches, focus cases, flyback transformers, molded products for copiers and printer fixing machines, general household appliances, OA equipment, etc. Housing, variable capacitor case parts, various terminal boards, transformers, printed wiring boards, housings, terminal blocks, coil bobbins, connectors, relays, disk drive chassis, transformers, switch parts, outlet parts, motor parts, sockets, plugs, capacitors, Examples include automobile ignition device parts, automobile connectors, various automobile electrical parts, resistors, and electrical / electronic parts into which metal terminals and conductors are incorporated. Specific examples of the casing include casings for computer-related equipment, audio equipment, lighting equipment, telegraph / telephone equipment, air conditioners, home appliances such as VTRs and televisions, copying machines, facsimile machines, and optical equipment.

  Hereinafter, the effects of the present invention will be described in more detail with reference to examples. The raw material used for an Example and a comparative example is shown below. Here, all parts represent parts by weight, and “/” in the following resin names means copolymerization.

(A) Thermoplastic polyester resin <A-1> Polybutylene terephthalate resin, “Toraycon” (registered trademark) manufactured by Toray Industries, Inc., PBT having an intrinsic viscosity of 1.00 measured at 25 ° C. Used (hereinafter abbreviated as PBT resin).
<A-2> Polyethylene terephthalate resin, “Mitsui PET” J005 manufactured by Mitsui Chemicals, Inc., PET having an intrinsic viscosity of 0.63 measured at 25 ° C. was used.

(B) Phosphoric ester amide <B-1> Phosphoric ester amide, Super Bigor FV-1 manufactured by Daikyo Chemical Co., Ltd. was used.

(C) Flame retardant aid [Flame retardant aid with 5% heat loss temperature of 300 ° C or lower]
<C-1> Aluminum hydroxide produced by heating at a temperature of 170 to 300 ° C. in a pressure vessel without adding water to a raw material in which aluminum hydroxide and a reaction retarder that delays boehmite are mixed, Kawai Lime Industry Co., Ltd. ALH-F, 5% heat loss temperature 283 ° C
<C-2> Aluminum hydroxide, Nippon Light Metal Co., Ltd. BF013, 5% heat loss temperature 268 ° C.
<C-3> Phosphorus-containing nitrogen-containing compound, FP-2200S manufactured by Adeka Co., Ltd., 5% heat loss temperature 296 ° C.
[Flame retardant aid with 5% heat loss temperature exceeding 300 ° C]
<C-4> Boehmite (aluminum hydroxide oxide), Cerasur BMT manufactured by Kawai Lime Industry Co., Ltd., 5% heat loss temperature 400 ° C. or higher <C-5> Magnesium hydroxide, Kyowa Chemical Industry Co., Ltd. Kisma 5E, 5% heat loss 381 ° C
<C-6> Melamine cyanurate, Nissan Chemical Co., Ltd. MC-4000, 5% heat loss temperature 353 ° C.
<C-7> Melamine polyphosphate, Melapur 200/70 manufactured by BASF, 5% heat loss temperature 400 ° C. or more

(D) Fibrous filler <D-1> Chopped strand glass fiber having a fiber diameter of about 10 μm, “3J948” manufactured by Nitto Boseki Co., Ltd. was used.

(E) Other components <E-1> to be blended as necessary, “A-1900” manufactured by Idemitsu Petrochemical Co., Ltd. (hereinafter abbreviated as PC resin).
<E-2> A long-chain alkyl acid phosphate compound, “Adeka Stub” (registered trademark) AX-71 manufactured by Asahi Denka Co., Ltd. was used (hereinafter abbreviated as AX-71).
<E-3> A core-shell rubber composed of a vinyl-based resin, an inner core layer made of silicone acrylic composite rubber, and an outer shell layer made of polymethylmethacrylate, “METABRENE” (registered trademark) SX manufactured by Mitsubishi Rayon Co., Ltd. -005 (hereinafter abbreviated as vinyl resin).
<E-4> An ethylene copolymer, an ethylene / butene-1 / maleic anhydride copolymer, and MH-5020 manufactured by Mitsui Petrochemical Co., Ltd. were used (hereinafter abbreviated as an ethylene copolymer).
<E-5> Polyhydric alcohol compound having three or more functional groups and containing one or more alkylene oxide units, polyoxyethylene pentaerythritol, PNT-60U manufactured by Nippon Emulsifier Co., Ltd. (molecular weight 400, monofunctional The number of alkylene oxide (ethylene oxide) units per group was 1.5 (hereinafter abbreviated as polyhydric alcohol).
<E-6> A hindered phenolic antioxidant, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, “IRGANOX” manufactured by Ciba Geigy (registered) (Trademark) 1010 was used (hereinafter abbreviated as IR-1010).
<E-7> Fluorocarbon resin, polytetrafluoroethylene, “Teflon” (registered trademark) 6-J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., which acts as a melting and dropping (drip) inhibitor during combustion, was used ( Hereinafter, abbreviated as fluororesin).
<E-8> A mold release agent, a partial calcium salt of montanic acid wax, and Rico Wax OP manufactured by Clariant Japan Co., Ltd. were used (hereinafter abbreviated as a mold release agent).
<E-9> Hydrolysis resistance improver, carbodiimide compound, Carbodilite HMV-8CA manufactured by Nisshinbo Co., Ltd. was used (hereinafter abbreviated as hydrolysis resistance improver).
<E-10> Hydrolysis resistance improver, epoxy compound, and Nippon Kayaku Co., Ltd. EOCN-104S were used (hereinafter abbreviated as hydrolysis resistance improver).

  The 5% heat loss temperature of the flame retardant aid is 5% by measuring the weight loss while raising the temperature of the flame retardant aid from 30 ° C. to 400 ° C. at 30 ° C./min in TGA7 manufactured by PerkinElmer. The temperature at which the weight was reduced was determined.

[Evaluation method of each characteristic]
In Examples and Comparative Examples, the characteristics were evaluated by the methods described below.

1. Tensile properties The pellets obtained in each Example and Comparative Example were dried with a hot air dryer for 6 hours and then injection molded using an IS55EPN injection molding machine manufactured by Toshiba Machine, and the specimen thickness was 1/8 inch (about 3.2 mm). A test piece for evaluating the tensile properties of ASTM No. 1 dumbbell was obtained. When the polybutylene terephthalate resin is used as the component (A), the injection molding conditions are a molding temperature of 250 ° C. and a mold temperature of 80 ° C., the injection time and the pressure holding time are 10 seconds in total, and the cooling time is 10 seconds. The molding cycle conditions were as follows. When polyethylene terephthalate resin is used as the component (A), the molding temperature is 270 ° C. and the mold temperature is 80 ° C. The injection time and the holding time are 10 seconds and the cooling time is 10 seconds. . The tensile strength at break and tensile elongation at break were measured according to ASTM D638 (2005) using the obtained test specimens for evaluation of tensile properties. Measurement was performed on three specimens for evaluation of tensile properties, and the average value was obtained. Those having a tensile elongation at break of less than 3% were evaluated as inferior in mechanical properties.

2. Flame retardancy The pellets obtained in each Example and Comparative Example were dried with a hot air dryer for 6 hours, and then injection molded using an IS55EPN injection molding machine manufactured by Toshiba Machine, and had a thickness of 1/32 inch (about 0.79 mm). A combustion specimen was obtained. The injection molding conditions were the same as in item 1 above. Using the obtained combustion test piece, flame retardancy was evaluated in accordance with the evaluation standard defined in the UL94 vertical test. Flame retardancy falls and ranks in the order of V-0>V-1> V-2. Moreover, the material which was inferior in combustibility, did not reach said V-2, and did not correspond to said flame retardance rank was made into the outside of specification.

3. Hydrolysis resistance
The test specimen for evaluation of tensile properties obtained in the above item 1 is put into an advanced acceleration life test apparatus of EHS-411 manufactured by Espec Co., Ltd. set at a temperature of 121 ° C. and a humidity of 100% RH for 24 hours. went. For the three test specimens for evaluation of tensile properties after the wet heat treatment, the tensile break strength was measured in the same manner as in the above item 1 to determine the average value, and the tensile break strength after the wet heat treatment was obtained. The tensile strength retention rate was determined by the following formula, using the tensile strength at break obtained by the above item 1 as the tensile strength before wet heat treatment. When the tensile strength retention was less than 50%, it was evaluated that the hydrolysis resistance was poor.
Tensile strength retention rate (%) = (tensile rupture strength after wet heat treatment / tensile rupture strength before wet heat treatment) × 100

4). Bleed-out The test specimen for evaluation of tensile properties obtained in the above item 1 was subjected to constant temperature and high humidity of “Humiday cabinet” LHL-113 manufactured by Espec Co., Ltd., which was set to a temperature and humidity of 80 ° C. × 95% RH. The tester was put in for 100 hours and subjected to wet heat treatment. The appearance of the test piece for tensile property evaluation after wet heat treatment was visually observed, and bleed out was evaluated according to the following criteria. A molded product that bleeds out is a molded product that greatly impairs the value of the product.
X: A liquid or white powder-like bleed-out is observed in a part of the test piece for tensile property evaluation or everywhere.
◯: No liquid or white powder bleed out is observed on the test specimen for tensile property evaluation.

[Examples 1-18], [Comparative Examples 1-8]
Tables 1 to 3 show (A) a thermoplastic polyester resin, (B) phosphoric ester amide, (C) a flame retardant aid having a 5% heat loss temperature of 300 ° C. or less, and other compounding materials as required. The mixture was mixed at the same composition, and added from the original loading part of a twin screw extruder (manufactured by Nippon Steel Works, TEX-30α) with a screw diameter of 30 mm and L / D35. (D) The fibrous filler was added by installing a side feeder in the middle of the original filling portion and the vent portion. Melting and mixing were performed under extrusion conditions of a kneading temperature of 260 ° C. and a screw rotation of 150 rpm, discharged into a strand, passed through a cooling bath, and pelletized with a strand cutter to obtain pellets of a flame-retardant thermoplastic polyester resin composition. The results of evaluating the obtained pellets by the evaluation method are shown in Tables 1 to 3.

  From the comparison between Examples 4, 6, and 7 and Comparative Examples 1 to 4, (C) Examples 4, 6, and 7 using a flame retardant aid having a 5% heat loss temperature of 300 ° C. or less are excellent in flame retardancy. It was. In addition, the mechanical property is 5% from the comparison between Example 6 using the flame retardant aid having 5% heat loss temperature of 268 ° C. and Example 4 using the flame retardant aid having 5% heat loss temperature of 283 ° C. Example 4 using a flame retardant aid having a high heating weight loss temperature was excellent. In addition, comparison between Example 4 and Example 7 using a flame retardant aid in which both 5% heat loss temperature is 280 ° C. or more shows that Example 4 using metal hydroxide aluminum hydroxide is flame retardant. Excellent balance between mechanical properties and tensile strength retention.

  Moreover, Example 4 which used (B) component and (C) component together from the comparison of Example 4 and Comparative Examples 7-8 of Table 3 was excellent in the flame retardance.

  From the comparison of Comparative Examples 5 to 6 in which Examples 4, 8, and 9 and the component (B) or the component (C) were blended in an amount exceeding the range of the present invention, both the component (B) and the component (C) of the present invention were used. In Examples 4, 8, and 9, the balance of mechanical properties, tensile strength retention, and bleed out was excellent.

  From the comparison between Example 2 and Example 4 in which the component (D) was blended, the tensile strength at break was greatly improved by blending the component (D).

  (A) Example 5 using a PET resin as the thermoplastic polyester resin was also excellent in the balance of flame retardancy, hydrolysis resistance and mechanical properties.

  Moreover, even when it mix | blended the component mix | blended as needed from (E) other than Examples 10-18, it confirmed that the effect of this invention was show | played.

  From the above, the flame-retardant thermoplastic polyester resin compositions described in Examples 1 to 18 are excellent in mechanical properties and hydrolysis resistance while maintaining high flame retardancy (V-2 or higher), and in particular. A flame retardant thermoplastic polyester resin composition suitable for a material requiring flame retardancy and long-term durability was obtained.

Claims (8)

(A) 100 parts by weight of a thermoplastic polyester resin, (B) 1 to 70 parts by weight of phosphoric ester amide, and (C) 1 to 100 parts by weight of a flame retardant aid having a 5% heat loss temperature of 300 ° C. or less. A flame retardant thermoplastic polyester resin composition. The flame retardant thermoplastic polyester resin composition according to claim 1, wherein the flame retardant aid (C) having a 5% loss on heating temperature of 300 ° C or less contains a metal hydrate. The flame retardant thermoplastic polyester resin composition according to claim 2, wherein the metal hydrate is aluminum hydroxide. Aluminum hydroxide obtained by heating at a temperature of 170 to 300 ° C. in a pressure vessel without adding water to a raw material in which the aluminum hydroxide is mixed with aluminum hydroxide and a reaction retarder that delays boehmite formation. The flame-retardant thermoplastic polyester resin composition according to claim 3. The flame-retardant thermoplastic polyester resin composition according to any one of claims 1 to 4, further comprising (D) 1 to 150 parts by weight of a fibrous filler per 100 parts by weight of the thermoplastic polyester resin (A). object. A molded article obtained by melt-molding the flame-retardant thermoplastic polyester resin composition according to any one of claims 1 to 5. The molded article according to claim 6, wherein the tensile strength retention after the heat treatment at 121 ° C x 100% RH x 24 hours is 50% or more. The molded product according to claim 6 or 7, wherein the flame retardancy conforms to the flame retardancy standard UL-94 V-0 to V-2.