JP2017179352A - Flame retardant polyethylene terephthalate resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fire retardant resin composition excellent in flowability and capable of providing a molded article excellent in rigidity and flame retardancy and the molded article by molding the same.SOLUTION: There is provided a flame retardant thermoplastic resin composition containing (A) a polyethylene terephthalate resin of 100 pts.wt., (B) a carbon fiber of 1 to 150 pts.wt. and (C) a phosphinic acid metal salt of 10 to 150 pts.wt.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to a flame retardant polyethylene terephthalate resin composition containing a polyethylene terephthalate resin, carbon fiber and a phosphinic acid metal salt, and a molded article obtained by molding it.

  Polyethylene terephthalate resin is utilized in a wide range of fields such as mechanical mechanism parts, electrical / electronic parts, and automobile parts, taking advantage of its excellent mechanical properties. In recent years, thinning of parts for miniaturization and weight reduction of products has progressed, and higher mechanical properties are required. In particular, a material having high rigidity and fluidity is required. Also, for use as industrial materials such as mechanical mechanism parts, electrical parts, electronic parts and automobile parts, in addition to the balance of general chemical and physical properties, safety against flames, that is, flame retardancy Is required, and high flame retardancy showing V-0 of UL-94 standard is required.

  As a method for improving the rigidity of the polyethylene terephthalate resin, it is generally known to blend a fibrous filler such as carbon fiber. As a resin composition containing carbon fiber, a carbon fiber reinforced polyester resin composition composed of a thermoplastic polyester resin, carbon fiber, a phosphorus compound and a polycarbonate resin has been proposed (see, for example, Patent Document 1). However, the resin composition described in Patent Document 1 has insufficient fluidity and flame retardancy.

  On the other hand, as a method for improving the flame retardancy of a thermoplastic polyester resin, it is generally known to add a phosphinic acid metal salt. As such a flame-retardant thermoplastic resin composition, a flame-retardant thermoplastic resin composition containing a thermoplastic resin, phosphinic acid salts and a specific hindered phenol compound (for example, see Patent Document 2), or heat. Flame retardant thermoplastic polyester resin composition (for example, refer to Patent Document 3) containing a thermoplastic polyester resin, a phosphinate, a specific nitrogen compound and a specific phosphorus compound, a thermoplastic polyester resin, a phosphinate, A flame retardant thermoplastic polyester resin composition (for example, see Patent Document 4) formed by blending an acid neutralizing agent and a polyhydric alcohol compound, a polybutylene terephthalate resin, or a specific group including polyethylene terephthalate Flame retardant selected from a specific group including resin, novolak phenolic resin, phosphinic acid metal salt , Reinforcing fillers, flow modifiers and laser weldable resin composition containing a laser absorbing dyes (e.g., see Patent Document 5.) Have been proposed. However, all of the resin compositions described in Patent Documents 2 to 5 have insufficient fluidity, and the molded product obtained from the resin composition has insufficient rigidity.

JP-A-61-89248 International Publication No. 2011/007687 JP 2010-202748 A JP 2010-37375 A JP2013-155279A

  The present invention provides a flame retardant polyethylene terephthalate resin composition that can solve the above-mentioned problems and can provide a molded article having excellent fluidity, rigidity and flame retardancy, and a molded article formed by molding the flame retardant polyethylene terephthalate resin composition. It is in.

The present invention was obtained as a result of intensive studies by the present inventors in order to solve the above-described problems, and has mainly the following configuration.
(1) A flame-retardant polyethylene terephthalate resin composition containing (B) 1 to 150 parts by weight of carbon fiber and (C) 10 to 150 parts by weight of a phosphinic acid metal salt with respect to 100 parts by weight of (A) polyethylene terephthalate resin.
(2) In the molecular weight distribution determined by gel permeation chromatography (GPC) measurement of the (A) polyethylene terephthalate resin, the maximum molecular weight is 100%, and the minimum molecular weight is 0%. The flame retardant polyethylene terephthalate resin composition according to (1), wherein the cumulative peak area is 65% or more of 100% of the total peak area having a molecular weight of 0 to 100%.
(3) The flame-retardant polyethylene terephthalate resin composition according to (1) or (2), further comprising 1 to 100 parts by weight of (E) polyetherimide resin with respect to 100 parts by weight of (A) polyethylene terephthalate resin.
(4) The flame-retardant polyethylene terephthalate resin composition according to any one of (1) to (3), further comprising (D) 1 to 20 parts by weight of a phosphoric acid ester with respect to 100 parts by weight of the (A) polyethylene terephthalate resin. object.
(5) The flame retardant polyethylene terephthalate resin composition according to (4), wherein the (D) phosphate ester has a 5% weight loss temperature of 250 ° C. or higher.
(6) A molded article comprising the flame retardant polyethylene terephthalate resin composition according to any one of (1) to (5).

  The flame retardant polyethylene terephthalate resin composition of the present invention is excellent in fluidity. According to the flame retardant polyethylene terephthalate resin composition of the present invention, a molded product having excellent rigidity and flame retardancy can be obtained.

  The flame-retardant polyethylene terephthalate resin composition of the present invention (hereinafter sometimes referred to as “resin composition”) will be described in detail below.

  The resin composition of the present invention contains (B) 1 to 150 parts by weight of carbon fiber and (C) 10 to 150 parts by weight of phosphinic acid metal salt with respect to 100 parts by weight of (A) polyethylene terephthalate resin. By containing (A) polyethylene terephthalate resin and (B) carbon fiber, a molded product having excellent mechanical properties such as rigidity and strength can be obtained. Moreover, the flame retardance of a molded article can be improved by containing (C) phosphinic acid metal salt. In general, a molded product containing a polyester resin and (B) carbon fiber has high thermal conductivity, and (C) a flame retardant such as a metal phosphinate tends to be insufficient in flame retardancy. However, in the present invention, a molded article excellent in flame retardancy can be obtained by selecting (A) polyethylene terephthalate resin as the polyester resin and combining with (C) metal phosphinate. Furthermore, by combining (A) polyethylene terephthalate resin, (B) carbon fiber, and (C) metal phosphinate, (B) high shear heat generation due to carbon fiber at the time of resin composition production, (C) Since the phosphinic acid metal salt has a catalytic effect that promotes a reduction in the molecular weight of a part of the (A) polyethylene terephthalate resin, the fluidity of the resin composition can be drastically improved. (B) In the case of fibrous fillers other than carbon fibers, since the shear heat generation during the production of the resin composition is relatively low, (C) a catalyst for reducing the molecular weight of a part of polyethylene terephthalate resin by phosphinic acid metal salt Since the effect becomes low, the remarkable fluidity improving effect as in the present invention cannot be obtained. Furthermore, in the case of a flame retardant other than (C) a metal salt of phosphinic acid, a catalytic effect of reducing the molecular weight of a part of the polyethylene terephthalate resin is not achieved, so that a remarkable fluidity improving effect as in the present invention can be obtained. Can not.

  Furthermore, the surface roughness after the high-temperature process of a molded article can be improved by containing 1 to 100 weight part of (E) polyetherimide resin with respect to 100 weight part of (A) polyethylene terephthalate resin. By including (B) carbon fiber in (A) polyethylene terephthalate resin, the solidification rate at the time of molding is increased due to the effect of improving thermal conductivity by (B) carbon fiber, and (A) crystallization of polyethylene terephthalate resin is not effective. It will be enough. In a process that requires high-temperature treatment such as painting due to insufficient crystallization, the components that crystallize during high-temperature treatment increase, and the surface roughness of the molded article increases due to crystal shrinkage. In addition, (B) carbon fiber has a smaller specific gravity than fiber reinforcing materials such as glass fiber, and therefore, when the same weight is contained, the contained volume increases. Therefore, when a molded article formed by molding a composition containing (A) a polyethylene terephthalate resin is subjected to high temperature treatment, the (A) polyethylene terephthalate resin may crystallize and shrink due to the high temperature treatment. When the composition contains (B) carbon fiber, the carbon fiber in the composition occupies a larger volume compared to the composition containing other fiber reinforcement, so that the molded product The surface roughness of increases. Therefore, (A) a molded article obtained by molding a composition containing a polyethylene terephthalate resin by containing (E) a polyetherimide resin having a high glass transition temperature and excellent dimensional stability even in high-temperature processing. ) Shrinkage in the thickness direction due to crystallization of polyethylene terephthalate can be suppressed, and the surface roughness after high temperature treatment can be improved. Note that the high temperature treatment here means a dry heat treatment at 80 ° C. for 1 hour.

  The (A) polyethylene terephthalate resin used in the present invention is obtained by polycondensation of terephthalic acid or an ester-forming derivative thereof and ethylene glycol. Examples of ester-forming derivatives of terephthalic acid include lower alkyl esters of terephthalic acid. As long as the object of the present invention is not impaired, other dicarboxylic acid or its derivative may be copolymerized with terephthalic acid or its ester-forming derivative and ethylene glycol, or other diol may be copolymerized. It may be what you did. Examples of the dicarboxylic acid or derivative thereof used as a copolymerization component include isophthalic acid, adipic acid, oxalic acid, sebacic acid, dodecanedioic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and the like. It is done. Examples of the diol used as the copolymerization component include 1,5-pentanediol, 1,6-hexanediol, and cyclohexanediol. The copolymer component is preferably 20 mol% or less in a total of 100 mol% of terephthalic acid or its ester-forming derivative, ethylene glycol and other copolymer components used as necessary.

  (A) Preferred examples of the polyethylene terephthalate resin include polyethylene terephthalate, polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sebacate), polyethylene (terephthalate / decane dicarboxylate), polyethylene (terephthalate). / Naphthalate) and the like. Here, “/” represents a copolymer component. Two or more of these may be contained.

  The (A) polyethylene terephthalate resin preferably has an intrinsic viscosity measured at 25 ° C. using an o-chlorophenol solvent in the range of 0.36 dl / g to 1.60 dl / g. By setting the intrinsic viscosity to 0.36 dl / g or more, mechanical properties such as strength and toughness of the molded product can be further improved. The intrinsic viscosity is more preferably 0.40 dl / g or more, and further preferably 0.45 dl / g or more. On the other hand, by setting the intrinsic viscosity to 1.60 dl / g or less, the fluidity of the resin composition can be further improved. The intrinsic viscosity is more preferably 1.35 dl / g or less, and further preferably 1.15 dl / g or less.

  Examples of the carbon fiber (B) used in the present invention include carbonaceous fibers and graphite fibers produced using polyacrylonitrile (PAN), pitch, rayon, lignin, hydrocarbon gas, and the like. Two or more of these may be contained. Among these, PAN-based carbon fibers are preferable because they are excellent in the effect of improving mechanical properties such as rigidity and strength. (B) Carbon fiber may be coat | covered with metals, such as nickel, copper, and ytterbium.

  (B) As a shape of carbon fiber, a chopped strand, a roving strand, a milled fiber, etc. are common. (B) The diameter of the carbon fiber is generally 15 μm or less, preferably 5 to 10 μm.

  (B) Although the form of carbon fiber is not particularly limited, a carbon fiber bundle composed of several thousand to several hundred thousand carbon fibers or a milled form obtained by pulverizing the carbon fiber bundle is preferable. Examples of the carbon fiber bundle include those obtained by a roving method using directly continuous fibers, and chopped strands cut to a predetermined length. Among these, chopped strands are preferable. The number of filaments of the carbon fiber strand that is the precursor of the chopped strand is preferably 1,000 to 150,000, which can reduce the manufacturing cost and improve the stability in the production process.

  (B) The strand tensile elastic modulus of the carbon fiber is preferably 150 GPa or more, and more preferably 220 GPa or more from the viewpoint of further improving the rigidity of the molded product. On the other hand, the strand tensile elastic modulus is preferably 1000 GPa or less, more preferably 500 GPa or less, from the viewpoint of further improving the fluidity of the resin composition, the thin-wall moldability, and the mold transferability of the molded product.

  (B) The strand tensile strength of the carbon fiber is preferably 1 GPa or more and more preferably 3 GPa or more from the viewpoint of further improving the strength of the molded product. On the other hand, the strand tensile strength is preferably 10 GPa or less, more preferably 5 GPa or less, from the viewpoint of improving the mold transferability of the molded product.

  Here, the strand elastic modulus and strand strength refer to the elastic modulus and strength of a strand produced by impregnating and curing an epoxy resin to a continuous fiber bundle composed of 1,000 to 150,000 carbon fiber single fibers. This is a value obtained by subjecting the test piece to a tensile test according to JIS R 7601 (1986).

  (B) The carbon fiber may be subjected to surface oxidation treatment, and (A) the adhesion with the polyethylene terephthalate resin can be improved. Examples of the surface oxidation treatment include surface oxidation treatment by energization treatment, oxidation treatment in an oxidizing gas atmosphere such as ozone, and the like.

  In addition, (B) carbon fiber may have a coupling agent or sizing agent attached to its surface, and (A) improved wettability to polyethylene terephthalate resin and (B) handleability of carbon fiber. Can be made. Examples of the coupling agent include amino, epoxy, chlor, mercapto, and cationic silane coupling agents. Two or more of these may be used. Among these, amino silane coupling agents are preferable. Examples of the sizing agent include maleic anhydride compounds, urethane compounds, acrylic compounds, epoxy compounds, phenol compounds, and the like. Two or more of these may be used. Among these, a sizing agent containing a urethane compound or an epoxy compound is preferable.

  When (B) the carbon fiber has a coupling agent, a sizing agent, or the like attached to the surface thereof, the content of the coupling agent and the sizing agent includes the coupling agent and the sizing agent. (B) In the carbon fiber, (A) 0.1 weight% or more is preferable from a viewpoint of improving the wettability of polyethylene terephthalate resin, and 0.5 weight% or more is more preferable. On the other hand, the content of the coupling agent and the sizing agent is preferably 10% by weight or less, more preferably 5% by weight or less from the viewpoint of improving the handleability of the (B) carbon fiber.

  Further, (B) the carbon fiber may be provided with a sizing agent. Examples of a method for producing a chopped carbon fiber by applying a sizing agent to a strand of carbon fiber include, for example, the method described in Japanese Patent Publication No. 62-9541 and the glass fiber chopped strand, Japanese Patent Application Laid-Open No. Sho 62-244606, Examples include the method described in JP-A-5-261729.

  In the resin composition of the present invention, the content of (B) carbon fiber is 1 to 150 parts by weight (1 to 150 parts by weight) with respect to 100 parts by weight of (A) polyethylene terephthalate resin. (B) If the carbon fiber content is less than 1 part by weight, the rigidity and strength of the molded product will be reduced. 10 parts by weight or more is preferable, and 20 parts by weight or more is more preferable. On the other hand, when the content of (B) the carbon fiber exceeds 150 parts by weight, the fluidity of the resin composition and the mold transferability of the molded product are deteriorated. In addition, the productivity of the resin composition is significantly reduced. 100 parts by weight or less is preferable, and 80 parts by weight or less is more preferable.

  The (C) phosphinic acid metal salt in the present invention refers to a metal salt of phosphinic acid and / or diphosphinic acid. Examples of the metal constituting the metal salt include calcium, aluminum, and zinc. Two or more of these may be contained.

  (C) As a phosphinic acid metal salt, the phosphinic acid metal salt shown by following General formula (1) and the diphosphinic acid metal salt shown by following General formula (2) are preferable.

In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Represent. The alkyl group may be linear or branched. M represents calcium, aluminum or zinc. m represents the range of 1-4.

In the general formula (2), each of R ¹ and R ² independently represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Represent. The alkyl group may be linear or branched. R ³ represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 10 carbon atoms, or an arylalkylene group having 7 to 10 carbon atoms. The alkylene group may be linear or branched. M represents calcium, aluminum or zinc. m represents the range of 1-4.

  (C) As a commercial item of a phosphinic acid metal salt, Clariant Japan Co., Ltd. product "Exolit" (trademark) OP1230, OP1240, etc. are mentioned, for example.

  In the resin composition of the present invention, the content of the (C) phosphinic acid metal salt is 10 to 150 parts by weight (10 to 150 parts by weight) with respect to 100 parts by weight of the (A) polyethylene terephthalate resin. (C) The fluidity | liquidity of a resin composition and the flame retardance of a molded article fall that content of a phosphinic acid metal salt is less than 10 weight part. 15 parts by weight or more is preferable, and 20 parts by weight or more is more preferable. On the other hand, when the content of the (C) phosphinic acid metal salt exceeds 150 parts by weight, the productivity, fluidity and toughness of the molded product are lowered. 100 parts by weight or less is preferable, and 70 parts by weight or less is more preferable.

  As described above, the resin composition of the present invention is derived from (B) carbon fiber at the time of producing the resin composition by combining (A) polyethylene terephthalate resin, (B) carbon fiber and (C) phosphinic acid metal salt. (C) Phosphinic acid metal salt in the composition exerts a catalytic effect that promotes lowering the molecular weight of a part of (A) polyethylene terephthalate resin due to the high shear heat generation. Can be improved. The resin composition of the present invention has a molecular weight when the maximum molecular weight is 100% and the minimum is 0% in the molecular weight distribution determined by gel permeation chromatography (GPC) measurement of the (A) polyethylene terephthalate resin. The cumulative peak area of 0 to 10% (0% or more and 10% or less) is preferably 65% or more out of 100% of the total peak area having a molecular weight of 0 to 100% (0% or more and 100% or less). In the present invention, paying attention to the fact that (A) polyethylene terephthalate resin in the resin composition partially contains a component having a low molecular weight, the maximum molecular weight is used as an index of the content of the component having a low molecular weight. The cumulative peak area with a molecular weight of 0 to 10% when the value was 100% and the minimum value was 0% was selected. By setting the cumulative peak area to 65% or more, the fluidity of the resin composition can be further improved. From the viewpoint of further improving the balance between fluidity and rigidity, the cumulative peak area having a molecular weight of 0 to 10% is more preferably 70% or more, and even more preferably 75% or more.

  Here, the cumulative peak area can be obtained by the following method. First, the resin composition was collected so that the content of (A) polyethylene terephthalate resin was 2.5 mg, dissolved in 4 ml of hexafluoroisopropanol (0.005N-sodium trifluoroacetate added), and the resulting solution was Filter through a 0.45 μm filter. Using the obtained filtrate, pump: e-Alliance GPC system (manufactured by Waters), detector: differential refractometer Waters 2414 (manufactured by Waters), column: Shodex HFIP-806M (two) + HFIP-LG, flow rate: Gel permeation chromatography (GPC) is measured under the conditions of 1 ml / min, sample injection amount: 0.1 ml, temperature: 30 ° C., molecular weight reference material: polymethyl methacrylate. From the obtained molecular weight distribution, the ratio of the cumulative peak area of the molecular weight of 0 to 10% to the total peak area of 100% of the molecular weight of 0 to 100% when the maximum value of the molecular weight is 100% and the minimum value is 0% is calculated. To do.

  When (E) a polyetherimide resin is included, the polyethylene terephthalate resin composition is pulverized and then dispersed in a chloroform solvent to extract the (E) polyetherimide resin. From the chloroform solvent, the (A) polyethylene terephthalate component, which is an insoluble component, is recovered and subjected to gel permeation chromatography (GPC) measurement under the above conditions to obtain the molecular weight distribution of the (A) polyethylene terephthalate resin.

  When other components (a thermoplastic resin other than (A) polyethylene terephthalate resin and (E) polyetherimide resin) are included, for example, they are not detected by the gel permeation chromatography (GPC) described above. The GPC conditions shown above can be employed.

  As described above, the cumulative peak area is an index of the content of the component (A) having a reduced molecular weight in the polyethylene terephthalate resin. Therefore, the proportion of the cumulative peak area can be determined by appropriately promoting the reduction in the molecular weight. Can be easily adjusted to the range. More specifically, for example, in the method of setting the content of (B) carbon fiber or (C) metal phosphinate to the above-mentioned preferable range or the resin composition manufacturing method described later, the resin temperature at the time of melt-kneading And a method of adjusting

  The thermoplastic resin composition of the present invention can further contain (E) a polyetherimide resin, and can improve the surface roughness after high-temperature treatment.

  Moreover, (E) polyether imide resin with respect to polyethylene terephthalate resin is blended more than the content of (D) phosphate ester with respect to (A) polyethylene terephthalate resin, which will be described later. Can be suppressed.

  The (E) polyetherimide resin used in the present invention is a polymer containing an aliphatic, alicyclic or aromatic ether unit and a cyclic imide group as repeating units, and is a polymer having melt moldability. There is no particular limitation. Examples thereof include polyetherimides described in U.S. Pat. No. 4,141,927 and Japanese Patent No. 2622678, and polymers described in Japanese Patent No. 2,598,536 and JP-A-9-48852. As long as the effect of the present invention is not impaired, the main chain of polyetherimide contains a structural unit other than cyclic imide and ether units, for example, aromatic, aliphatic, alicyclic ester units, oxycarbonyl units, and the like. May be.

  Among these, from the viewpoint of compatibility with (A) polyethylene terephthalate resin and melt moldability, 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride and m-phenylenediamine, Or the polymer which has a repeating unit shown by following General formula (3) or (4) which is a condensate with p-phenylenediamine is preferable.

(N in the general formula (3) or (4) is usually an integer of 10 to 1000 or more, and may be within the range of the weight average molecular weight described later.)

  (E) Although there is no restriction | limiting in particular in the molecular weight of polyetherimide resin, It is a weight average molecular weight measured by gel permeation chromatography (GPC), Preferably it is 30,000-120,000, More preferably, 40,000-110,000, In particular, it is preferable to use (E) polyetherimide resin in the range of 50,000 to 100,000 because it exhibits more excellent surface roughness. When the weight average molecular weight is 30,000 or more, the surface roughness of the obtained molded product can be further improved. Further, when the weight average molecular weight is 120,000 or less, the productivity is more excellent.

  The weight-average molecular weight referred to here is (E) a solution obtained by taking a polyetherimide resin content of 2.5 mg and dissolving in 4 ml of dimethylformamide (lithium chloride 0.5 wt%). Is filtered through a 0.45 μm filter. Using the obtained filtrate, pump: e-Alliance GPC system (manufactured by Waters), detector: differential refractometer Waters 2414 (manufactured by Waters), column: Shodex KF-805L (two) + KD-G, flow rate 1 ml / It can be obtained by gel permeation chromatography (GPC) measurement under the conditions of min, sample injection amount: 0.1 ml, temperature: 30 ° C., molecular weight reference material: polymethyl methacrylate.

  Moreover, as a glass point transfer temperature (Tg) of (E) polyetherimide resin, 170 degreeC or more is preferable from a viewpoint of surface roughness, and 200 degreeC or more is more preferable. On the other hand, from the viewpoint of productivity and mechanical properties, 300 ° C. or lower is preferable, and 250 ° C. or lower is more preferable.

  (E) As a commercially available product of polyetherimide resin, it is available from SABIC Japan LLC under the trade name “Ultem” (registered trademark), “Ultem 1000”, “Ultem 1010”, “Ultem 1040”, “Ultem 5000”. , “Ultem6000” and “UltemXH6050” series, “ExtemXH” and “Extem UH”. Among them, “Ultem 1000” and “Ultem 1010” represented by the general formula (3) are particularly preferable.

  In the resin composition of the present invention, the content of the (E) polyetherimide resin is 1 to 100 parts by weight (1 to 100 parts by weight) with respect to 100 parts by weight of the (A) polyethylene terephthalate resin. (E) When content of polyetherimide resin is 1 weight part or more, the surface roughness improvement effect after the high temperature process of the molded article formed by shape | molding a resin composition is acquired. 10 parts by weight or more is preferable, and 20 parts by weight or more is more preferable. On the other hand, when content of (E) polyetherimide resin is 100 weight part or less, the fall of productivity of a resin composition, fluidity | liquidity, and the toughness of a molded article are suppressed. 70 parts by weight or less is preferable, and 50 parts by weight or less is more preferable.

  The thermoplastic resin composition of the present invention can further contain (D) a phosphate ester, and can further improve mechanical properties such as strength of a molded product.

  Examples of the (D) phosphate ester used in the present invention include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl Phosphate, tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl Phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid Sulfate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, phenylphosphonic acid Diethyl, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, biphenyl polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, and their condensates Mention may be made of condensed phosphate esters. Two or more of these may be contained.

  Examples of commercially available condensed phosphate esters preferably used as (D) phosphate esters include those manufactured by Daihachi Chemical Industry Co., Ltd., trade names PX-200, PX-201, PX-202, CR-733S, CR- 741, CR747, and the like.

  In the resin composition of the present invention, the content of the (D) phosphate ester is preferably 1 to 20 parts by weight (1 to 20 parts by weight) with respect to 100 parts by weight of the (A) polyethylene terephthalate resin. (D) When the content of the phosphate ester is 1 part by weight or more, mechanical properties such as strength of the molded product can be further improved. 3 parts by weight or more is more preferable. On the other hand, when the content of (D) phosphate is 20 parts by weight or less, the strength of the molded product can be further improved. Moreover, the bleeding out of (D) phosphate ester to the molded article surface can be suppressed, and the surface appearance can be improved. 15 parts by weight or less is preferable.

  Further, the content ratio of (E) polyetherimide resin and (D) phosphate ester ((D) component / (E) component) is preferably 1.0 or less, and 0.8 or less, from the viewpoint of suppressing bleed out. More preferred.

  (D) The 5% weight loss temperature of the phosphate ester is preferably 250 ° C. or higher. When the 5% weight loss temperature is 250 ° C. or higher, decomposition during the production of the resin composition can be suppressed, and moldability can be improved. In addition, the mechanical properties of the molded product can be further improved. (D) The 5% weight loss temperature of the phosphate ester is more preferably 280 ° C. or higher, and further preferably 300 ° C. or higher. Here, the 5% weight loss temperature of (D) phosphate ester is an index representing the heat resistance of (D) phosphate ester, and thermogravimetric analysis (TGA) is performed under a temperature increase condition of 30 ° C./min under a nitrogen stream. ).

  The resin composition of this invention may contain components other than said (A)-(E) as needed in the range which does not impair the effect of this invention. Examples of components other than (A) to (E) include, for example, polyhydric alcohol compounds, thermoplastic resins other than (A) polyethylene terephthalate resin and (E) polyetherimide resin, release agents, and (B) carbon fibers. Other inorganic fillers, hydrolysis resistance improvers, antioxidants, pigments or dyes, (C) flame retardants other than phosphinic acid metal salts, ultraviolet absorbers, light stabilizers, plasticizers, antistatic agents, etc. . Two or more of these may be contained.

  The polyhydric alcohol compound in the present invention refers to a compound having three or more hydroxyl groups. By containing a polyhydric alcohol compound, the fluidity | liquidity of the resin composition at the time of shaping | molding processes, such as injection molding, can be improved more. The polyhydric alcohol compound preferably further has an alkylene oxide unit such as an ethylene oxide unit or a propylene oxide unit. As for content of a polyhydric alcohol compound, 0.1 weight part or more is preferable with respect to 100 weight part of (A) polyethylene terephthalate resin, and can improve fluidity | liquidity more. On the other hand, the amount is preferably 1 part by weight or less, and the bleed out can be further suppressed to further improve the surface appearance.

  Examples of thermoplastic resins other than (A) polyethylene terephthalate resin and (E) polyetherimide include (A) polyester resins other than polyethylene terephthalate resin, aromatic polycarbonate resins, ethylene resins, vinyl resins, fluorine resins, and the like. Can be mentioned. By containing these thermoplastic resins, molding shrinkage can be suppressed, and moldability, dimensional accuracy, toughness, and the like can be further improved.

  (A) Examples of the polyester resin other than the polyethylene terephthalate resin include polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethylene terephthalate. The content of the polyester resin other than (A) polyethylene terephthalate resin is preferably 10 parts by weight or more with respect to 100 parts by weight of (A) polyethylene terephthalate resin, such as mold transferability, moldability, and rigidity and toughness of the molded product. Some of the mechanical properties and the like can be further improved. On the other hand, the amount is preferably 100 parts by weight or less, and the flame retardancy of the molded product can be further improved.

  The weight average molecular weight of the aromatic polycarbonate resin is preferably 10,000 to 1,100,000, and the glass transition temperature is preferably about 150 ° C. The content of the aromatic polycarbonate resin is preferably 5 parts by weight or more with respect to 100 parts by weight of the (A) polyethylene terephthalate resin, can reduce molding shrinkage, and can further improve the flame retardancy and dimensional accuracy of the molded product. . On the other hand, it is preferably 60 parts by weight or less, and the heat resistance of the molded product can be further improved.

  Examples of the ethylene resin include ethylene / glycidyl methacrylate and ethylene / butene-1 / maleic anhydride. The content of the ethylene-based resin is preferably 1 part by weight or more with respect to 100 parts by weight of the (A) polyethylene terephthalate resin, and the toughness of the molded product can be further improved. On the other hand, the amount is preferably 5 parts by weight or less, and the flame retardancy and heat resistance of the molded product can be maintained higher.

  Examples of the vinyl resin include poly (methyl methacrylate), methyl methacrylate / acrylonitrile, polystyrene resin, vinyl (co) polymers such as acrylonitrile / styrene resin (AS resin), and acrylonitrile / butadiene / styrene resin (ABS resin). Styrene resin modified with rubber polymer such as acrylonitrile / butadiene / methyl methacrylate / styrene resin (MABS resin), high impact polystyrene resin, styrene / butadiene / styrene resin, styrene / isoprene / styrene resin, styrene Block copolymers such as / ethylene / butadiene / styrene resin. These vinyl resins may be obtained by graft polymerization or copolymerization of unsaturated acid anhydrides and epoxy group-containing vinyl monomers. Further, a vinyl resin may be included as a branched chain of the graft copolymer. The content of the vinyl resin is preferably 1 part by weight or more with respect to 100 parts by weight of the (A) polyethylene terephthalate resin, and the toughness of the molded product can be further improved. On the other hand, 6 parts by weight or less is preferable, and the heat resistance of the molded product can be further improved.

  Examples of the fluororesin include polytetrafluoroethylene and (tetrafluoroethylene / ethylene) copolymer. The content of the fluorine-based resin is preferably 0.15 parts by weight or more with respect to 100 parts by weight of the (A) polyethylene terephthalate resin, and can further suppress melting and dropping during combustion. On the other hand, the amount is preferably 1.5 parts by weight or less, and the mechanical properties of the molded product can be further improved.

  Examples of the release agent include alkaline earth metal soaps, fatty acid esters, fatty acid ester salts (including partially salted products), fatty acid amides, polyalkylene waxes, acid anhydride-modified polyalkylene waxes, and the above-mentioned And a known release agent for plastics such as a mixture of a lubricant and a fluorine resin or a fluorine compound. By containing a release agent, the release property at the time of injection molding can be improved. As for content of a mold release agent, 0.03 weight part or more is preferable with respect to 100 weight part of (A) polyethylene terephthalate resin, and can improve a mold release property more. On the other hand, the amount is preferably 0.6 parts by weight or less, and the mechanical properties of the molded product can be further improved.

  (B) Examples of the inorganic filler other than carbon fibers include those having a granular, powdery, and layered shape, and examples thereof include glass beads, glass flakes, kaolin, talc, and mica. By containing these inorganic fillers, anisotropy of the molded product can be suppressed, and some of the crystallization characteristics, mechanical strength such as rigidity and strength, flame retardancy, and heat resistance can be further improved. . The inorganic filler may have a coupling agent, a sizing agent or the like attached to the surface, or may be subjected to a surface treatment such as an ionization treatment. (B) The content of inorganic fillers other than carbon fibers is preferably 100 parts by weight or less with respect to 100 parts by weight of (A) polyethylene terephthalate resin, and the fluidity of the resin composition and the durability of the molding machine and mold. It can be improved further.

  Examples of the hydrolysis resistance improving agent include epoxy compounds, oxazoline compounds, isocyanate compounds, and carbodiimide compounds. By containing a hydrolysis resistance improving agent, the hydrolysis resistance of the molded product can be further improved. The content of the hydrolysis resistance improving agent is preferably 0.03 parts by weight or more with respect to 100 parts by weight of the (A) polyethylene terephthalate resin, and the hydrolysis resistance of the molded product can be improved. On the other hand, the amount is preferably 1 part by weight or less, and the mechanical properties of the molded product can be further improved.

  Examples of the antioxidant include hindered phenol antioxidants, phosphite antioxidants, and thioether antioxidants. By containing the antioxidant, even when the resin composition is exposed to a high temperature for a long period of time, extremely good heat aging resistance can be provided. As for content of antioxidant, 0.03 weight part or more is preferable with respect to 100 weight part of (A) polyethylene terephthalate resin, and can improve heat aging property. On the other hand, the amount is preferably 1 part by weight or less, and the mechanical properties of the molded product can be further improved.

  The resin composition of this invention can be obtained by melt-kneading said (A)-(C) and another component as needed, for example. Examples of the melt kneading method include (A) polyethylene terephthalate resin, (B) carbon fiber, (C) phosphinic acid metal salt, and (D) phosphoric acid ester, (E) polyetherimide resin, and other additions as necessary. Examples include a method in which an agent is premixed and supplied to a melt-kneader and melt-kneaded, a method in which a predetermined amount of each component is supplied to a melt-kneader using a quantitative feeder such as a weight feeder, and a melt-kneader is used. .

  Examples of the premixing method include a dry blending method, a mixing method using a mechanical mixing device such as a tumbler, a ribbon mixer, and a Henschel mixer.

  As said melt-kneading apparatus, multi-screw extruders, such as a single screw extruder and a twin screw extruder, etc. are mentioned, for example. From the viewpoint of further improving mechanical properties and productivity, a twin screw extruder is preferred.

  The extruder preferably has one or more vent parts, and removes residual moisture and residual monomers in the resin composition and gas generated during melt-kneading, and (B) carbon fiber and (C) phosphinic acid metal salt The dispersibility can be further improved, and the mechanical properties of the molded product can be further improved. It is more preferable to have two or more vent parts.

  When melt-kneading by an extruder, (B) carbon fiber and (C) phosphinic acid metal salt may be supplied to the extruder from the former part of the extruder, respectively, or the former part and the vent part of the extruder You may supply to an extruder from the side feeder installed between. One of (B) carbon fiber or (C) phosphinic acid metal salt may be supplied to the extruder from the former insertion portion of the extruder and the other from the side feeder. (B) From the viewpoint of suppressing breakage of the carbon fiber and further improving mechanical properties such as rigidity and strength of the molded product, it is preferable to supply the (B) carbon fiber from the side feeder to the extruder. Similarly, when (B) an inorganic filler other than carbon fiber is blended, it is preferably supplied to the extruder from a side feeder installed between the former loading portion and the vent portion of the extruder. In addition, when a liquid additive is blended, it may be supplied to the extruder using a plunger pump from a liquid addition nozzle installed between the original storage part and the vent part of the extruder, or the original storage part For example, it may be supplied to the extruder using a metering pump.

  In the present invention, in order to bring the ratio of the cumulative peak area, which is an index of the content of the low molecular weight component of the (A) polyethylene terephthalate resin, within the above preferred range, In order to appropriately increase the molecular weight, it is preferable to adjust the resin temperature during melt kneading. Specifically, the resin temperature during melt kneading is preferably 280 ° C. or higher, more preferably 283 ° C. or higher, and further preferably 285 ° C. or higher. Here, the resin temperature during melt-kneading in the present invention refers to the temperature of the melt-kneaded product in the die portion of the extruder, and can be measured using a thermometer attached to the die portion of the extruder.

  The resin temperature at the time of melt kneading can be adjusted by, for example, the content of (B) carbon fiber and the extrusion conditions when melt kneading with an extruder. (B) By increasing the carbon fiber content, the resin temperature can be increased by shearing heat generation. Moreover, as extrusion conditions, barrel set temperature, screw rotation speed, etc. are mentioned. Generally, the resin temperature can be increased by increasing the barrel set temperature and the screw rotation speed. (B) From the viewpoint of suppressing breakage of the carbon fiber and further improving mechanical properties such as rigidity and strength of the molded product, it is more preferable to adjust the resin temperature by the barrel set temperature.

  The resin composition of the present invention is preferably molded after being pelletized. Pelletization methods include, for example, single screw extruders, twin screw extruders, triaxial extruders, conical extruders and kneader type melt kneaders equipped with “Unimelt” (registered trademark) or “Dalmage” type screws. And a method of discharging in a strand shape and cutting with a strand cutter.

  By molding the resin composition of the present invention, it is possible to obtain molded products of film, fiber and other various shapes. Examples of the molding method include melt molding methods such as injection molding, extrusion molding, and blow molding, and injection molding is particularly preferably used.

  Examples of the injection molding method include normal injection molding, gas assist molding, two-color molding, sandwich molding, in-mold molding, insert molding, and injection press molding.

  The molded article of the present invention can be suitably used as a molded article for mechanical mechanism parts, electrical parts, electronic parts, and automobile parts taking advantage of the characteristics excellent in rigidity and flame retardancy. Since it is excellent in rigidity, it is particularly useful for housing members.

  Specific examples of mechanical mechanism parts, electrical parts, electronic parts, and automobile parts include breakers, electromagnetic switches, focus cases, flyback transformers, molded products for copiers and printer fixing machines, general household appliances, and OA. Housing components such as equipment, variable capacitor case parts, various terminal boards, transformers, printed wiring boards, relays, disk drive chassis, transformers, switch parts, outlet parts, motor parts, capacitors, various cases, resistors, Electrical and electronic parts with built-in metal terminals and conductors, computer-related parts, audio parts such as acoustic parts, lighting parts, telegraph equipment-related parts, telephone equipment-related parts, air conditioner parts, home appliance parts such as VTRs and TVs, and copying machines Parts, facsimile parts, optical equipment parts, automotive ignition device parts, various automotive electrical components And the like.

Next, the effect of the resin composition of the present invention will be specifically described with reference to examples. The raw materials used in the examples and comparative examples are shown below.
<A-1> Polyethylene terephthalate resin: “Mitsui PET” (registered trademark) J005 (manufactured by Mitsui Chemicals, Inc., intrinsic viscosity 0.63 dl / g measured at 25 ° C. using an o-chlorophenol solvent)
<A′-1> Polybutylene terephthalate resin: “Toraycon” (registered trademark) manufactured by Toray Industries, Inc. (inherent viscosity 0.80 dl / g measured at 25 ° C. using o-chlorophenol solvent)
<B-1> Carbon fiber: “Torayca” (registered trademark) cut fiber TV14-006 manufactured by Toray Industries, Inc.
<B'-1> Glass fiber: Nitto Boseki Co., Ltd. 3J948 (chopped strand shape with a fiber diameter of about 10 μm)
<C-1> Phosphinic acid metal salt: “Exolit” (registered trademark) OP-1240 manufactured by Clariant Japan Co., Ltd.
<E-1> Polyetherimide resin: “Ultem” (registered trademark) Ultem 1010 manufactured by SABIC Japan GK, which can be represented by the general formula (3), Tg = 215 ° C., weight average molecular weight 53,000 <E′− 1> Polycarbonate resin: “Taflon” (registered trademark) A2500 manufactured by Idemitsu Kosan Co., Ltd., Tg = 151 ° C.
<D-1> 1,3-phenylenebis (di2,6-xylenyl phosphate): PX-200 (5% weight loss temperature 320 ° C.) manufactured by Daihachi Chemical Industry Co., Ltd.
<D-2> Triphenyl phosphate ester: Triphenyl phosphate ester manufactured by Ozeki Co., Ltd. (5% weight loss temperature 230 ° C.).

[Measurement method for each characteristic]
In Examples and Comparative Examples, the characteristics were evaluated by the measurement methods described below.

<Resin temperature>
Measure the temperature of the resin composition during melt-kneading using a thermometer attached to the die part of a twin screw extruder (manufactured by Nippon Steel Works, TEX-30α) with a screw diameter of 30 mm and L / D35. And the resin temperature.

<Cumulative peak area>
(1) The pellets obtained in each Example and Comparative Example were collected so that the content of (A) polyethylene terephthalate resin and (A ′) polybutylene terephthalate resin was 2.5 mg, and hexafluoroisopropanol (0 (0.005N sodium trifluoroacetate added) was dissolved in 4 ml, and the resulting solution was filtered through a 0.45 μm filter. Using the obtained filtrate, gel permeation chromatography (GPC) was measured under the following conditions.
Pump: e-Alliance GPC system (manufactured by Waters)
Detector: differential refractometer Waters 2414 (manufactured by Waters)
Column: Shodex HFIP-806M (2) + HFIP-LG
Flow rate: 1 ml / min
Sample injection volume: 0.1 ml
Temperature: 30 ° C
Molecular weight reference material: polymethyl methacrylate (2) The pellets obtained in each Example and Comparative Example containing (E) polyetherimide resin were pulverized and then dispersed in a chloroform solvent. (E) Polyetherimide The resin was extracted. From the chloroform solvent, the (A) polyethylene terephthalate component, which is an insoluble component, was recovered and subjected to gel permeation chromatography (GPC) measurement under the above condition (1) to obtain the molecular weight distribution of the (A) polyethylene terephthalate resin.
(3) In addition, (E ′) polycarbonate resin is not detected by gel permeation chromatography (GPC) under the above conditions, and therefore measured under the above condition (1) to obtain (A) molecular weight distribution of polyethylene terephthalate resin. It was.
From the obtained molecular weight distribution, the ratio of the cumulative peak area of the molecular weight of 0 to 10% to the total peak area of 100% of the molecular weight of 0 to 100% when the maximum value of the molecular weight is 100% and the minimum value is 0% is calculated. did.

<Rigidity, strength, toughness>
After drying the pellets obtained in each Example and Comparative Example for 3 hours with a hot air dryer at a temperature of 150 ° C., using an injection molding machine (SE50EV manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature: 270 ° C., Mold temperature: ISO 3167 type A test piece was injection molded under molding conditions of 40 ° C. Using the obtained ISO 3167 type A test piece, the bending elastic modulus, bending strength and bending deflection were measured at 23 ° C. according to ISO 178, and the rigidity, strength and toughness were evaluated from the results. All measured about six ISO3167 type A test pieces, and calculated | required the number average value.

<Flame retardance>
After drying the pellets obtained in each Example and Comparative Example for 3 hours with a hot air dryer at a temperature of 150 ° C., using an injection molding machine (SE50EV manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature: 270 ° C., Mold temperature: A combustion test piece having a thickness of 1/32 inch (about 0.79 mm) was injection-molded under molding conditions of 40 ° C. A combustion test was performed using the obtained combustion test piece, and the flame retardance was evaluated based on the combustion rank determined 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 did not reach said V-2 was made into the outside of specification.

<Fluidity>
About the pellet obtained by each Example and the comparative example, it melt | dissolved in shear rate 608sec- ^{1 on} condition of cylinder temperature: 270 degreeC and capillary L / D: 20 mm / 1mm using the Toyo Seiki Co., Ltd. capilograph 1C. Viscosity was measured and fluidity was evaluated.

<Surface appearance>
After drying the pellets obtained in each Example and Comparative Example for 3 hours with a hot air dryer at a temperature of 150 ° C., using an injection molding machine (SE50EV manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature: 270 ° C., Mold temperature: ISO 3167 type A test piece was injection molded under molding conditions of 40 ° C. The obtained ISO 3167 type A test piece was subjected to a wet heat treatment for 100 hours in a constant temperature and humidity chamber LHL-113 manufactured by Espec Co., Ltd. set to conditions of temperature: 80 ° C. and humidity: 95% RH. Visual observation was performed, the presence or absence of bleed out was determined according to the following criteria, and the surface appearance was evaluated.
A: No liquid or white powder bleed out is observed in the molded product.
B: A liquid or white powder-like bleedout is observed in a part of the molded product or everywhere.

<Surface roughness>
After drying the pellets obtained in each Example and Comparative Example for 3 hours with a hot air dryer at a temperature of 150 ° C., using an injection molding machine (SE50EV manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature: 270 ° C., Mold temperature: An 80 mm × 80 mm × 1 mm square plate was injection molded under molding conditions of 40 ° C. The obtained 80 mm × 80 mm × 1 mm square plate was subjected to dry heat treatment for 1 hour in a thermostat PHH-202 manufactured by Espec Co., Ltd., which was set at a temperature of 80 ° C., and then used with Tokyo Seimitsu Surfcom 130A. Arithmetic average roughness (Ra) was measured under the conditions of 20 mm, 40 mm, and 60 mm from the top, the measurement direction: TD direction (direction perpendicular to the flow), and the measurement distance: 20 mm, with the plate gate portion as the top. Moreover, the average value of arithmetic average roughness (Ra) of three places was made into surface roughness.

<Examples 1-5, 7-29, Comparative Examples 1-9>
Using a twin-screw extruder with a screw diameter of 30 mm and L / D35 and rotating in the same direction (manufactured by Nippon Steel Works, TEX-30α), (A), (A ′), (C) ˜ (D) was mixed in the ratios shown in Tables 1 to 3, and added from the former loading part of the twin screw extruder. (B) Carbon fiber and (B ′) glass fiber were added to the twin screw extruder from the side feeder installed between the former loading part and the vent part. Melt-kneading was performed under extrusion conditions of barrel set temperature: 260 ° C. and screw rotation speed: 150 rpm, and the mixture was discharged in a strand shape, passed through a cooling bath, and pelletized by a strand cutter.

<Example 6>
Pelletization was performed in the same manner as in Example 5 except that the barrel set temperature was changed to 245 ° C.

  The resin composition obtained by Examples 1-17 was excellent in fluidity | liquidity, and was able to obtain the molded article excellent in rigidity and a flame retardance.

  Compared to Examples 1 to 7, it can be seen that (B) Comparative Example 1 with a low carbon fiber content has low rigidity and strength, and (B) Comparative Example 2 with a high carbon fiber content has low fluidity. Furthermore, compared with Examples 1-2 and 5-7, it turns out that Examples 3-4 in which (B) carbon fiber content exists in a more preferable range are excellent by the balance of fluidity | liquidity and rigidity.

  Compared with Example 4, 8-11, it turns out that the comparative examples 3-4, 9 with little (C) phosphinic acid metal salt content have low fluidity | liquidity and a flame retardance. Further, (C) Comparative Example 5 having a high phosphinic acid metal salt content had low fluidity and toughness, resulting in a decrease in productivity and failure to discharge in a strand form.

  As compared with Examples 1 and 4, it can be seen that (B) Comparative Examples 6 and 7 containing glass fibers instead of carbon fibers have a poor balance between fluidity and rigidity.

  Compared to Example 4, it can be seen that (A) Comparative Example 8 containing polybutylene terephthalate instead of polyethylene terephthalate is inferior in flame retardancy, strength and fluidity.

  Compared to Example 6, it can be seen that Examples 1 to 5 and 7 to 17 in which the ratio of the cumulative peak area is in a preferable range are more excellent in fluidity. Furthermore, it turns out that Examples 4-5, 7, 10-17 which have the ratio of an accumulation peak area in a more preferable range are excellent by the balance of fluidity | liquidity and rigidity.

  Compared with Example 4, it turns out that Examples 12-17 containing (D) phosphate ester are excellent by intensity | strength. Furthermore, compared with Example 14, it turns out that Example 13 containing (D) phosphate ester which has a 5% weight loss temperature in a preferable range is excellent in intensity | strength.

  Compared with Example 18, it turns out that (E) Examples 19-26 and Example 28 containing polyetherimide resin are excellent in surface roughness. Furthermore, compared with Examples 19 to 20 and Examples 23 to 25, Examples 21 to 22, Example 26, and Example 28 in which (E) polyetherimide resin was blended within a more preferable range were particularly rough. It turned out to be excellent.

  From a comparison between Example 28 and Example 29, it was found that bleeding out can be suppressed by setting the content ratio of (E) polyetherimide resin and (D) phosphate to a preferable range.

  Further, compared with Example 26, Example 27 containing (E ′) polycarbonate resin is greatly inferior in the effect of improving the surface roughness.

  The flame-retardant polyester resin composition of the present invention is suitable as a mechanical mechanism component, electrical component, electronic component, and automobile component, taking advantage of the characteristics that can provide a molded product having excellent fluidity and rigidity and flame retardancy. It can be used and is particularly useful for a housing member.

Claims (6)

(A) A flame-retardant polyethylene terephthalate resin composition containing (B) 1 to 150 parts by weight of carbon fiber and (C) 10 to 150 parts by weight of a phosphinic acid metal salt with respect to 100 parts by weight of polyethylene terephthalate resin. (A) In the molecular weight distribution determined by gel permeation chromatography (GPC) measurement of the polyethylene terephthalate resin (A), the cumulative peak area with a molecular weight of 0 to 10% when the maximum molecular weight is 100% and the minimum is 0% The flame retardant polyethylene terephthalate resin composition according to claim 1, wherein is 65% or more of 100% of the total peak area having a molecular weight of 0 to 100%. Furthermore, the flame-retardant polyethylene terephthalate resin composition of Claim 1 or 2 containing 1-100 weight part of (E) polyetherimide resin with respect to 100 weight part of (A) polyethylene terephthalate resin. Furthermore, the flame-retardant polyethylene terephthalate resin composition in any one of Claims 1-3 containing 1-20 weight part of (D) phosphate ester with respect to 100 weight part of (A) polyethylene terephthalate resin. The flame-retardant polyethylene terephthalate resin composition according to claim 4, wherein the (D) phosphate ester has a 5% weight loss temperature of 250 ° C. or higher. A molded product obtained by molding the flame-retardant polyethylene terephthalate resin composition according to any one of claims 1 to 5.