JP2007314619A - Thermoplastic polyester resin composition and molded product made therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polyester resin composition with low warpage, flame retardancy and heat cyclability, high in mechanical strength and excellent in dimensional stability after subjected to annealing treatment. <P>SOLUTION: The polyester resin composition is obtained by compounding together a total of 100 wt.% of (A) 10-80 wt.% of a thermoplastic polyester resin, (B) 1-15 wt.% of an epoxy group-containing vinyl copolymer, (C) 1-15 wt.% of an ABS resin, (D) 1-20 wt.% of two or more resins selected from the group consisting of (d-1) a maleic anhydride-modified polystyrene resin, (d-2) a rubber-modified polystyrene resin and (d-3) a polycarbonate resin, (E) 0-50 wt.% of glass fiber, (F) 3-20 wt.% of a halogenated epoxy bromine-based flame retardant and (G) 1-10 wt.% of an antimony compound. In this polyester resin composition, the amount of a diene rubber in the ABS resin C is 5-8 pts.wt. based on a total of 100 pts.wt. of the components A to D. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polyester-based resin composition, and more particularly, to a thermoplastic polyester resin composition excellent in flame retardancy, impact properties, and dimensional stability after annealing, and an electrical and electronic molding comprising the same.

  Thermoplastic polyester resins, especially polybutylene terephthalate resin, have excellent properties as engineering plastics such as excellent heat resistance, moldability, chemical resistance and electrical insulation. It is used for applications such as parts, electrical parts, machine parts and construction parts. However, since the thermoplastic polyester resin alone has low mechanical strength and impact strength, a fibrous reinforcing material is usually added to avoid the drawbacks. However, the fibrous reinforcing material has high fiber anisotropy and warpage is remarkable. Therefore, in order to suppress warpage of the molded product made of polybutylene terephthalate resin in order to suppress the occurrence of warping of the system in which the fibrous reinforcing material is added to the thermoplastic polyester resin, ABS resin, AS A method of blending an amorphous resin such as a resin and an isotropic filler such as a milled fiber has been proposed.

  A thermoplastic polyester resin composition obtained by blending a polybutylene terephthalate resin and an AS resin is obtained by blending a thermoplastic polyester and an epoxy group-containing vinyl polymer as described in Patent Document 1, for example. In addition to physical properties, heat resistance and impact resistance, a thermoplastic polyester resin composition excellent in low warpage has been proposed.

  Further, as described in Patent Document 2, for example, a proposal has been made to impart impact resistance and heat resistance by blending a thermoplastic resin, a modified vinyl polymer, and an ABS resin.

  Further, as described in Patent Document 3, for example, a polybutylene terephthalate resin has a fibrous reinforcing material such as glass fiber, a plate-like reinforcing material having a specific shape, flake diameter, and aspect ratio, a specific polymer, these By combining the four, a reinforced PBT resin composition having excellent thermal and mechanical properties and extremely small warpage during molding has been found.

In addition, as described in Patent Document 4, by blending a rubber-modified polystyrene resin, an aromatic polycarbonate resin, and a reinforcing filler with a polybutylene terephthalate resin, the warpage of the molded product is small and the mechanical strength is increased. An excellent composition is proposed.
JP-A-6-287422 JP-A-1-163243 Japanese Patent Laid-Open No. 61-4758 JP 2005-112994 A

  However, the thermoplastic polyester resin composition described in Patent Document 1 has a problem that, by adding an epoxy group-containing vinyl polymer, low warpage is improved, but impact resistance is reduced. . Moreover, although brominated epoxy is used, there is a problem that sufficient fluidity cannot be ensured because it is not designated as having a molecular weight of 2000 to 7000 and end-capped with tribromophenol.

  In addition, the thermoplastic resin composition described in Patent Document 2 has good impact properties by adding ABS resin, but the content of diene rubber is high, and sufficient low warpage and flame retardancy can be obtained. Has the problem of not being able to.

  Further, the thermoplastic resin composition described in Patent Document 3 can reduce the warpage of a molded product by a method of blending an amorphous resin or a filler, but can reduce the tensile strength and bending strength. The above problems may occur and the melt viscosity may increase, which may hinder the production of a molded product by an injection molding method or the like.

  Moreover, since the thermoplastic polyester resin composition described in Patent Document 4 does not contain an epoxy group-containing vinyl polymer, the dimensional stability after heat treatment is poor, and there is a problem in compatibility during molding. Have.

  In addition, when these resin compositions are used in resin molded products for electric and electronic parts, sufficient low warpage, heat cycleability, and flame retardancy cannot be obtained, so heat generated from electric and electronic parts during use is not obtained. As a result, the molded product may be distorted, or cracks may occur in the joint portion with the metal due to heat cycle. Moreover, since the flame retardance is insufficient, there is a problem of safety, and there is a problem that application is hindered.

  The inventors of the present invention have completed the present invention as a result of intensive studies to solve the problems of the prior art. Its purpose is low warping, impact resistance and flame retardancy, good moldability, good mechanical strength, and excellent heat cycle and dimensional stability after annealing. It is to obtain a polyester resin composition.

That is, the present invention
(1) The total of (A) to (G) is 100% by weight,
(A) 10 to 80% by weight of a thermoplastic polyester resin,
(B) (b-1) vinyl cyanide monomer, (b-2) aromatic vinyl monomer, (b-3) an epoxy group-containing vinyl copolymer having an epoxy group-containing vinyl monomer as a structural unit 1-15% by weight of polymer,
(C) 1-15% by weight of ABS resin,
(D) 1 to 20% by weight of two or more resins selected from the group consisting of (d-1) maleic anhydride-modified polystyrene resin, (d-2) rubber-modified polystyrene resin, and (d-3) polycarbonate resin,
(E) 0 to 50% by weight of glass fiber,
(F) 3 to 20% by weight of a halogenated epoxy bromine flame retardant having an average molecular weight of 2000 to 7000, end-capped with tribromophenol, and (G) 1 to 10% by weight of an antimony compound,
(C) A thermoplastic polyester resin composition in which the proportion of the diene rubber contained in the ABS resin is 5 to 8 parts by weight when the total of (A) to (D) is 100 parts by weight,
(2) The thermoplastic polyester resin composition according to (1), wherein (A) the thermoplastic polyester resin is polybutylene terephthalate,
(3) (B) Each monomer of the epoxy group-containing vinyl copolymer is (b-1) 22 to 25% by weight of vinyl cyanide monomer, with (B) being 100% by weight, (b- 2) Reduced viscosity measured with a 0.2% dimethylformamide solution that is 74 to 77% by weight of an aromatic vinyl monomer and (b-3) 0.1 to 0.5% by weight of an epoxy group-containing vinyl monomer ( The thermoplastic polyester resin composition according to (1) or (2), wherein ηsp / C) is 0.7 to 0.9,
(4) The thermoplastic polyester resin composition according to any one of (1) to (3), wherein flame retardance of 1/32 inch thickness according to UL94 is V0,
(5) A molded product formed by molding the thermoplastic polyester resin composition according to any one of (1) to (4),
(6) The molded product according to (5), wherein the molded product is an electric / electronic component, and (7) the molded product according to (6), wherein the molded product is a motor fan case or a fan.

  As described above, the thermoplastic polyester resin composition of the present invention is excellent in flame retardant property, high impact property, high strength, low warpage, heat cycle property, dimensional stability after annealing, and heat resistance rigidity. Taking advantage of such properties, the resin composition can be used as electrical and electronic parts for cases, covers, cooling fan parts, fixing machine parts, electrical parts, and the like.

  The present invention is described in detail below.

  The thermoplastic polyester used in the present invention includes a polymer or copolymer obtained by a polycondensation reaction mainly composed of a dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof). Can be used.

  As the dicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2′-biphenyldicarboxylic acid, 3,3 ′ -Biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-diphenylisopropylidene Dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4′-p-terphenylenedicarboxylic acid, 2 , 5-pyridinedicarboxylic acid, and terephthalic acid Mashiku can be used.

  These dicarboxylic acids may be used by mixing two types of abnormalities. In addition, it is possible to use a mixture of one or more alicyclic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid, sebacic acid and the like, and cyclohexanedicarboxylic acid together with these dicarboxylic acids in a small amount it can.

  Examples of the diol component include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl 1,3-propanediol, diethylene glycol, triethylene glycol and other aliphatic diols, 1,4-cyclohexane. Examples thereof include alicyclic diols such as dimethanol, and mixtures thereof. If the amount is small, one or more long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and the like may be copolymerized.

  Preferred examples of these polymers and copolymers include polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene- In addition to 1,2-bis (phenoxy) ethane-4,4′-dicarboxylate, copolymer polyesters such as polybutylene terephthalate / isophthalate and polybutylene terephthalate / decane dicarboxylate are exemplified. Of these, polybutylene terephthalate can be preferably used. These thermoplastic polyester resins preferably have a relative viscosity in the range of 0.5 to 2.0 when measured with a 0.5% o-chlorophenol solution at 25 ° C. Within the above range, a composition having excellent mechanical properties and excellent moldability can be obtained.

  The thermoplastic polyester resin (A) is at least one acid component selected from terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, etc., and ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, or polyethylene. It is obtained by polycondensation with at least one diol component selected from glycols, polyalkylene glycols such as polytetramethylene glycol, and specifically polybutylene terephthalate, polypropylene terephthalate, polyethylene terephthalate, polyhexylene. In addition to terephthalate (PHT), polyethylene naphthalate, polybutylene naphthalate (PBN), polycyclohexane-1,4-dimethylol terephthalate, polyethylene Sofutareto terephthalate (PET / I), etc. copolymerized polyester such as polybutylene isophthalate-isophthalate (PET / I) can be exemplified. (A) The blending amount of the thermoplastic polyester resin is 10 to 80% by weight, more preferably 20 to 70% by weight, with the total of (A) to (G) being 100% by weight. When the blending amount is less than 10% by weight, the resin component is small and the material becomes brittle, and when it exceeds 80% by weight, the flame retardancy is not sufficiently exhibited.

  In the present invention, it is necessary to use (B) an epoxy group-containing vinyl copolymer. This is because the dimensional stability can be improved by using the epoxy group-containing vinyl copolymer (B).

  (B) The addition amount of the epoxy group-containing vinyl copolymer is preferably 1 to 10% by weight, particularly preferably 5 to 10% by weight, and if less than 1% by weight, the effect of improving dimensional stability is poor, and 15% by weight Exceeding this is not preferable because combustibility is impaired.

  The (B) epoxy group-containing vinyl copolymer used in the present invention includes (b-1) a vinyl cyanide monomer, (b-2) an aromatic vinyl monomer, and (b-3) an epoxy group-containing vinyl. It is a copolymer obtained by polymerizing a monomer as a main component.

  Examples of the (b-1) vinyl cyanide monomer in the (B) epoxy group-containing vinyl copolymer used in the present invention include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, and among others, acrylonitrile. Is preferred.

  Examples of the (b-2) aromatic vinyl monomer include styrene, α-methyl styrene, p-methyl styrene, pt-butyl styrene, and among them, styrene and α-methyl styrene are preferable.

  Furthermore, examples of the (b-3) epoxy group-containing vinyl monomer include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, etc. Among them, glycidyl methacrylate is preferable.

  Further, the epoxy group-containing vinyl copolymer (B) is composed of (B) as a whole by 100% by weight, vinyl cyanide monomer (b-1) 22 to 25% by weight, aromatic vinyl monomer (b-2). ) 74-77 wt% and epoxy group-containing vinyl monomer (b-3) 0.1-0.5 wt% are suitable for mechanical strength and warpage.

  The reduced viscosity (ηsp / C) of the (B) epoxy group-containing vinyl copolymer measured in a 0.2% dimethylformamide solution at 25 ° C. is preferably 0.7 to 0.9. If the reduced viscosity is less than 0.7, the viscosity is low, the dispersion deteriorates, and the warp is adversely affected. Further, when the reduced viscosity is higher than 0.9, the injection pressure required for filling at the time of molding increases, residual stress remains in the molded product, and warpage may occur.

  The (C) ABS resin used in the present invention is a diene rubber (ii), a vinyl cyanide monomer (b), an aromatic vinyl monomer (c), and other copolymerizable monomers as required. A resin composition comprising a graft copolymer composed of (d) and having the total amount of the monomer graft copolymerized with the diene rubber (a) and a copolymer copolymerized with the remaining monomers.

  Examples of the diene rubber (A) used in the present invention include polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, polyisoprene rubber, and the like. Can be used together. In the present invention, polybutadiene and / or styrene-butadiene copolymer rubber is preferably used.

  Examples of vinyl cyanide (b) include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred.

  Examples of aromatic vinyl (c) include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, and the like. Of these, styrene and / or α-methylstyrene is preferably used.

  Examples of other copolymerizable monomers (d) include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, and cyclohexyl methacrylate. Examples include α, β-unsaturated carboxylic acid esters, imide compounds of α, β-unsaturated dicarboxylic acid such as maleic anhydride and itaconic anhydride.

  (C) The amount of the ABS resin added is preferably 1 to 10% by weight, particularly 5 to 9% by weight, with the total of (A) to (G) being 100% by weight. If it exceeds 10% by weight, the moldability, flame retardancy and warpage are impaired.

  The composition ratio of the (C) ABS resin is not particularly limited, but a diene rubber (I) is used from the viewpoint of moldability and impact resistance of the thermoplastic resin composition obtained with respect to 100% by weight of the ABS resin. ) 5 to 85% by weight is preferred, more preferably 15 to 75% by weight. Similarly, the vinyl cyanide (B) is preferably 5 to 50% by weight, particularly preferably 8 to 40% by weight. About aromatic vinyl (c), 10 to 90 weight% is preferable and 17 to 77 weight% is especially preferable.

  Further, when the total of (A) thermoplastic polyester resin, (B) epoxy group-containing vinyl copolymer, (C) ABS resin, and (D) component is 100 parts by weight, the diene rubber content is 5 It is necessary to be -8 parts by weight, and it is preferably 5.5-7.5 parts by weight. If it is less than 5% by weight, sufficient impact properties cannot be obtained. On the other hand, if it is 8% by weight or more, flame retardancy, fluidity, and warpage are reduced.

  (C) There is no restriction | limiting in particular about the manufacturing method of ABS resin, Usually well-known methods, such as block polymerization, solution polymerization, block suspension polymerization, suspension polymerization, and emulsion polymerization, are used. It is also possible to obtain the above composition by blending separately (grafted) copolymerized resins.

  Component (D) used in the present invention is a mixture of two or more selected from the group consisting of (d-1) modified polystyrene resin, (d-2) rubber modified polystyrene resin and (d-3) polycarbonate resin. It is necessary to. This is because the dimensional stability after annealing can be improved by using the component (D).

  (D-1) The maleic anhydride-modified polystyrene resin is a mixture of maleic anhydride and polystyrene. Examples of the mixing method include (1) a method in which both are simply mechanically blended, (2) a method in which a styrene-based monomer and maleic anhydride are graft copolymerized, and the method in (2) is preferable. Examples of the graft copolymerization method include an emulsion polymerization method, a solution polymerization method, and a suspension polymerization method. The content of maleic anhydride in the maleic anhydride-modified polystyrene resin is preferably selected in the range of 1 to 20% by weight. If the amount of maleic anhydride exceeds 20% by weight, it may excessively react with the thermoplastic polyester resin and increase the viscosity by crosslinking.

  (D-1) The MFR of the maleic anhydride-modified polystyrene resin is preferably 0.5 to 15 g / 10 min at 200 ° C. and a load of 5 kg. When the MFR is out of the above range, the melt-kneading with the thermoplastic polyester resin may not be sufficiently compatible and the physical properties of the product may be lowered.

  (D-1) The amount of maleic anhydride-modified polystyrene resin added is 0 to 70% by weight, particularly preferably 0 to 50% by weight, with the total of (D) being 100% by weight. -It is not preferable because fluidity is impaired.

  (D-2) The rubber-modified polystyrene resin is obtained by mixing a rubbery polymer in polystyrene. As a mixing method, (1) a method of mechanically blending the two, (2) a so-called graft copolymerization method in which a styrene monomer is graft copolymerized in the presence of a rubbery polymer, and (3) ( Examples include a so-called graft-blending method in which general-purpose polystyrene produced by another method is mixed with the graft copolymer of 2). From the viewpoint of compatibility and affinity between polystyrene and a rubbery polymer, a graft copolymer obtained by the method (2) or a graft-blend product obtained by the method (3) is preferred.

  (D-2) As a method for producing a rubber-modified polystyrene resin by a graft copolymerization method, a styrene monomer is graft-polymerized in the presence of rubber by an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, or the like. A method is mentioned. Such a rubber-modified polystyrene resin is generally called high impact polystyrene (HIPS).

  (D-2) Specific examples of the rubber-like polymer contained in the rubber-modified polystyrene resin include conjugated diene rubbers such as polybutadiene, styrene-butadiene copolymer, hydrogenated styrene-butadiene block copolymer, Non-conjugated diene rubbers such as ethylene-propylene copolymers are exemplified. Of these, polyptadiene is preferred.

  (D-2) Examples of the styrene monomer constituting the rubber-modified polystyrene resin include styrene, α-methylstyrene, p-methylstyrene, bromostyrene, and the like. Of these, styrene and / or α-methylstyrene is most suitable. Examples of the monomer other than styrene include vinyl monomers such as acrylonitrile and methyl methacrylate.

  (D-2) The amount of the rubber-modified polystyrene resin added is 0 to 50% by weight, particularly 0 to 30% by weight, with the total of (D) being 100% by weight. This is not preferable because the flammability and warpage are impaired.

  (D-2) The content of the rubbery polymer component in the rubber-modified polystyrene resin is preferably in the range of 1 to 40% by weight, more preferably 3 to 30% by weight. When the monomer component other than the styrene monomer is included, (d-2) the sum of the content of the rubber polymer component and the styrene monomer component in the rubber-modified polystyrene resin is 90% by weight or more. Desirably, it is more preferably 95% by weight or more.

  (D-2) The MFR reflecting the molecular weight of the rubber-modified polystyrene resin preferably has a measured value under the conditions of a temperature of 200 ° C. and a load of 5 kg in a range of 0.5 to 15 g / 10 minutes, more preferably 1 The range is from 0 to 10 g / 10 minutes. When the MFR is outside the above range, the melt-kneading with the thermoplastic polyester resin may not be sufficiently compatible and the physical properties of the product may be lowered.

  (D-3) As polycarbonate resin, the carbonate polymer or copolymer which may be branched obtained by making an aromatic dihydroxy compound or this and a small amount of polyhydroxy compound react with phosgene or a carbonic acid diester is mentioned. As the raw material aromatic dihydroxy compound, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4 , 4-dihydroxydiphenyl and the like, preferably bisphenol A.

  In order to obtain a branched aromatic polycarbonate, phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl is used as a part of the aromatic dihydroxy compound. -2,4,6-tris (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-3, 1,3,5-tris (4-hydroxy Phenyl) benzene, polyhydroxy compounds such as 1,1,1-tris (4-hydroxyphenyl) ethane, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin, 5 , 7-dichloroisatin, 5-bromoisatin and the like may be used. The usage-amount of a polyhydroxy compound etc. is 0.1-10 mol% of a dihydroxy compound, Preferably it is 0.1-2 mol%.

  (D-3) In order to adjust the molecular weight of the polycarbonate resin, a monovalent aromatic hydroxy compound may be used. For example, m-, or p-methylphenol, m-, or p-propylphenol, p-tert-butylphenol, p-long chain alkyl-substituted phenol and the like are used. (D-3) The molecular weight of the aromatic polycarbonate resin is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, and preferably 15,000 to 30,000, more preferably. 16,000 to 25,000.

  (D-3) The addition amount of the polycarbonate resin is preferably 0 to 70% by weight, particularly preferably 0 to 45% by weight, with the total of (D) being 100% by weight. During melt-kneading, they are not fully compatible, and the physical properties of the product may decrease, which is not preferable.

  The composition ratio of the component (D) used in the present invention is 1 to 20% by weight, more preferably 4 to 15% by weight, where the total of (A) to (G) is 100% by weight. When (D) is less than 1% by weight, the effects of improving impact strength and reducing molding warpage are not observed, and when it exceeds 20% by weight, sufficient compatibility cannot be obtained, and moldability and mechanical properties may be deteriorated. Yes, not preferred.

  (E) It is possible to use a well-known glass fiber as glass fiber. Although it does not specifically limit as a fiber diameter, 9-15 micrometers is preferable. Specific examples include T-120, T-187, and T-187H manufactured by Nippon Electric Glass Co., Ltd., but are not limited thereto. (E) The compounding quantity of glass fiber is 0 to 50 weight%, More preferably, it is 10 to 40 weight%. By adding glass fiber, sufficient rigidity can be expressed. On the other hand, when the blending amount exceeds 50% by weight, the specific gravity increases, which is not preferable.

  In the present invention, it is necessary to use a halogenated epoxy having a molecular weight of 2000 to 7000 as the (F) brominated flame retardant. Thereby, flame retardancy can be imparted without impairing fluidity. (F) Brominated flame retardants must be end-capped with tribromophenol. This is because the epoxy end of the halogenated epoxy may increase the viscosity of the resin. In addition, by using those end-capped with tribromophenol, it is possible to reduce the amount of flame retardant added for imparting flame retardancy, and it is expected to improve mechanical properties and impact properties.

  (F) The compounding quantity of a brominated flame retardant is 3 to 20 weight% by making the sum total of (A)-(G) 100 weight%, More preferably, it is 5 to 15 weight%. The amount necessary to develop flame retardancy varies depending on the amount of thermoplastic polyester resin, but if it is less than 3% by weight, sufficient combustibility cannot be exhibited. On the other hand, when the blending amount exceeds 20% by weight, impact properties are remarkably lowered.

  (G) Antimony compounds can be used in combination with organic bromine compounds to improve the flame retardancy synergistically. Antimony such as antimony trioxide, antimony pentoxide, sodium antimonate and antimony phosphate An antimony compound which is exemplified by a compound and subjected to a surface treatment or the like can also be used. Of these, antimony trioxide is suitable.

  (G) The compounding quantity of an antimony compound is 1-10 weight% by making the sum total of (A)-(G) 100 weight%, More preferably, it is 3-8 weight%. If it is less than 1% by weight, sufficient combustibility cannot be exhibited. On the other hand, when the blending amount exceeds 10% by weight, the impact property is remarkably lowered.

  The polyester-based resin composition of the present invention usually includes reinforcing materials, fillers, antioxidants, stabilizers, ultraviolet absorbers, colorants, mold release agents, flame retardants, etc., as long as the effects of the present invention are not impaired. And small amounts of other polymers can be added.

  In the present invention, a reinforcing material and a filler can be added in addition to the glass fiber as long as the object of the present invention is not impaired. Examples include carbon fiber, asbestos fiber, rock wool, calcium carbonate, silica sand, bentonite, kaolin, clay, wollastonite, barium sulfate, glass beads, mica and the like.

  Examples of antioxidants include 2,6-di-t-butyl-4-methylphenol, tetrakis (methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, tris Phenol compounds such as (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, sulfur such as dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate And phosphorous compounds such as trisnonylphenyl phosphite and distearyl pentaerythritol diphosphite.

  Stabilizers include benzotriazole compounds including 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, and benzophenone compounds such as 2,4-dihydroxybenzophenone, mono- or distearyl phosphate, trimethyl phosphate And phosphoric acid esters.

  These various additives may have a synergistic effect by combining two or more kinds, and may be used in combination.

  For example, the additive exemplified as the antioxidant may act as a stabilizer or an ultraviolet absorber. Some of those exemplified as stabilizers also have an antioxidant action and an ultraviolet absorption action. That is, the above classification is for convenience and does not limit the action.

Release agents include plant waxes such as carnauba wax and rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as montan wax, petroleum waxes such as paraffin wax and polyethylene wax, castor oil and its Derivatives, fatty acids, and oil-based waxes such as derivatives thereof. Examples of higher fatty acid derivatives include higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, and montanic acid, and monohydric or dihydric or higher alcohols. Esters, partial saponification of these higher fatty acid esters partially with metal oxides such as Ca (OH) ₂ , NaOH, Mg (OH) ₂ , Zn (OH) ₂ , LiOH, Al (OH) ₃ Saponification obtained from esterified esters, higher fatty acids and metal oxides or metal hydroxides Products, higher fatty acids and polyhydric alcohol esters, which are condensed with a dicarboxylic acid such as adipic acid as a binder, mono- or diamides obtained from higher fatty acids and monoamines or diamines.

  Among the flame retardants, the brominated flame retardant is indispensable for imparting flame retardancy. Specific examples of the brominated flame retardant include halogenated polycarbonate (for example, tetrabromobisphenol A carbonate oligomer), halogenated acrylic resin, halogenated epoxy resin, halogenated phenoxy resin, halogenated polystyrene, tetrabromobisphenol A / ethyl. High molecular weight organic halogen compounds such as ether oligomers and halogenated polyphenylene ethers (eg, polydibromophenylene oxide); Decabromodiphenyl ether, hexabromophenol, tetrabromobisphenol A, epoxidized tetrabromobisphenol A, tetrabromobisphenol A / bis (2,3-dibromopropyl ether), tetrabromobisphenol A bis (allyl ether), tetrabromobisphenol A. Brominated bisphenol A such as 2-hydroxyethyl ether, hexabromobenzene, tetrabromophthalic anhydride, tribromophenol, bis (tribromophenoxy) ethane, bis (pentabromophenoxy) ethane, ethylenebistetrabromophthalimide, bromine And low molecular weight organic halogen compounds such as bis (2,3-dibromopropyl ether) of tetrabromobisphenol S and tetrabromobisphenol S. These organic halogen flame retardants can be used alone. Also, two or more of them may be used in combination. Moreover, phosphorus-based and inorganic flame retardants can also be used. As the various polymers, nylon resin, PPS resin, polytetrafluoroethylene, and the like can be added.

  What is necessary is just to implement about the manufacturing method of the polyester-type resin composition of this invention by the method generally known, and does not need to specifically limit. A typical example is a method of melt-kneading at a temperature of 200 to 350 ° C. using a known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll. Each component may be mixed in advance and then melt kneaded. Alternatively, with respect to 100 parts by weight of the total amount of (A) to (G), for a small amount of additive component such as 1 part by weight or less, the other components are kneaded and pelletized by the above method or the like, and then molded. It can also be added before. In addition, although it is better that the water | moisture content adhering to each component is less and it is desirable to dry beforehand, not all the components need to be dried.

  The resin composition of the present invention is generally molded by a known thermoplastic resin molding method such as injection molding, extrusion molding, blow molding, transfer molding, vacuum molding, etc., among which injection molding is preferable.

  The polyester-based resin composition of the present invention is a resin composition excellent in flame retardancy, heat resistance, high impact properties, high strength, and low warpage. Taking advantage of such properties, cases as electrical and electronic parts, It can be used for covers, fixing machine parts, electrical parts, etc. Here, the electric and electronic parts are parts used for electric and electronic devices, and the polyester resin molded product for electric and electronic parts is a polyester resin molded product used for them. In the present invention, these polyester resin molded products for electric and electronic parts are preferably a motor fan case and a fan. Here, the motor fan is a cooling device such as a personal computer, a printer, a game machine, a copying machine, a projector, and a server, and the heat generating part is cooled by air cooling or the like by a fan connected to the motor. Since the polyester resin composition of the present invention is excellent in low warpage and heat cycle properties, when it is used as a motor fan case or fan, there is little initial warpage, and contact between the fan and the case can be prevented. In addition, since there is little distortion caused by heat generation from electrical and electronic parts, motors, etc., there is very little change in dimensions over time. Moreover, the crack of the resin molded product of the joining part with the metal components etc. by a heat cycle can be prevented effectively. Therefore, it can be continuously used for a longer period of time than before.

  Hereinafter, the present invention will be described in more detail with reference to examples.

  The compounding composition used for the Example and the comparative example is shown.

(A-a)
Polybutylene terephthalate resin Inherent viscosity 0.85
PBT resin “Toraycon” 1100S manufactured by Toray Industries, Inc.

(Ba)
(B-1) Acrylonitrile / (b-2) Styrene / (b-3) Glycidyl Methacrylate Copolymer A stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra type stirring blade is disclosed in Japanese Patent Publication No. 45-24151. A solution obtained by dissolving 0.05 part of methyl acrylate / acrylamide copolymer produced by the radical polymerization method in water described in Example 1 of the publication in 165 parts of ion-exchanged water was stirred at 400 rpm, and the system was Replaced with nitrogen gas. Next, a reaction system of the following mixed substances was added with stirring, and the temperature was raised to 60 ° C. to initiate polymerization.
-Styrene: 75.8 parts-Acrylonitrile: 23.9 parts-Glycidyl methacrylate: 0.3 parts-t-dodecyl mercaptan: 0.05 parts-2,2'-azobisisobutyronitrile: 0.4 parts Deionized water: 150 parts

  Specifically, after raising the reaction temperature to 65 ° C. over 15 minutes, the temperature was raised to 100 ° C. over 50 minutes. Thereafter, the reaction system was cooled, the polymer was separated, washed, and dried according to ordinary methods to obtain (B-a). The reduced viscosity is 0.79.

(Bb)
(B-1) Acrylonitrile / (b-2) Styrene Copolymer According to the production method of (Ba), styrene and acrylonitrile were subjected to suspension polymerization to prepare a bead-like modified vinyl copolymer. The weight ratio of each component of (b-1) acrylonitrile / (b-2) styrene copolymer is 24/76 parts by weight, and the reduced viscosity is 0.79.

(Bc)
(B-1) Acrylonitrile / (b-2) Styrene / (b-3) Glycidyl methacrylate copolymer By suspension polymerization of styrene, acrylonitrile and glycidyl methacrylate in accordance with the production method of (Ba), bead-like modification A vinyl copolymer was prepared. (B-1) Acrylonitrile / (b-2) Styrene / (b-3) Glycidyl methacrylate copolymer The weight ratio of each component was 23.9 / 75.8 / 0.3% by weight, and the reduced viscosity was 0. .49.

(Ca)
In the presence of 60 parts of polybutadiene latex (rubber particle size of 0.25 μm, gel content of 80%) (converted to a fixed amount), 40 parts of a monomer mixture composed of 70% styrene and 30% acrylonitrile was emulsion-polymerized. The obtained graft copolymer was solidified with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to prepare a powdered graft copolymer (C-a).

(D-a)
(D-1) Maleic anhydride-modified polystyrene resin Dilark: Maleic anhydride-modified polystyrene, “Dylark (D) D232” manufactured by Nova Chemical Japan, maleic anhydride content 8 to 10% by weight, weight average molecular weight 240 1,000, melt flow rate (temperature 230 ° C., load 2.16 kgf) 2.0 g / 10 min.

(Db)
(D-2) Rubber-modified polystyrene resin HIPS: High impact polystyrene, “Tirelex (R) HT478” manufactured by A & M Co., Ltd., rubber (polybutadiene) content is 8.8 wt%, average rubber particle diameter is 1.8 μm , Number average molecular weight 92,000, weight average molecular weight 230,000, melt flow rate (temperature 200 ° C., load 5 kgf) 1.8 g / 10 min.

(Dc)
(D-3) Polycarbonate resin Toughlon A1900 (made by Idemitsu Kosan Co., Ltd.). Molecular weight 18,500-20,000, melt flow rate (JIS K 7210) 13.5-20.0 g / 10min.

(Ea)
Glass fiber
Fiber diameter 13 μm Glass fiber having a fiber length of 3 mm (T-187 manufactured by Nippon Electric Glass Co., Ltd.).

(F-a)
Brominated flame retardant
Halogenated epoxy ECX30 (Dainippon Ink Co., Ltd.). (Molecular weight 3000, endblocked tribromophenol)

(Fb)
Brominated flame retardant
Halogenated epoxy SR-T2000 (manufactured by Sakamoto Yakuhin). (Molecular weight 4000, no end blocking)

(Fc)
Brominated flame retardant Halogenated polycarbonate FG8500 (manufactured by Teijin Chemicals Ltd.).

(G-a)
Antimony compounds
Suzuhiro Chemical's Fire Cut AT-3.

  The Examples and Comparative Examples were evaluated by the following methods.

  (I) Tensile properties were determined by using a test piece prepared in advance according to ASTM D638 (using a test piece of ASTM No. 1 having a length of 217 mm, a width of a parallel part of 12.7 mm and a thickness of 3.2 mm), and 23 It is measured after being left for 24 hours in an environment of 50 ° C. and 50% RH. The tester uses Autograph UTM-5T manufactured by Shimadzu Corporation, and the tensile speed is 10 mm / min. The test was carried out five times, and the tensile strength and tensile elongation were determined by averaging the individual values.

  (Ii) For flame retardancy, rod-shaped test pieces (125.0 × 13.0 × 0.72 mm thickness) were used. After molding, the sample was allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH, and then measured according to UL94. Ten tests were performed, and a determination was made according to UL94.

  (Iii) The amount of internal warping is 30 mm in width, 30 mm in height, 30 mm in depth, and 1.5 mm in thickness, molded from a side pin gate and left in a 23%, 50% RH environment for 24 hours. The amount of tilt of the side surface to the inner side of the anti-gate side was measured five times with a three-dimensional dimension measuring machine made by MITUTOYO, and the average was taken as the amount of inner warp. See Figure 1 for box molded products.

  (Iv) Dimensional stability after annealing is as follows: Box-shaped molded product (Fig. 1) with a width of 30 mm, height of 30 mm, depth of 30 mm, and thickness of 1.5 mm is molded from the side pin gate, and is 23% and 50% RH environment. After 24 hours underneath, annealed at 130 ° C. for 2 hours. After that, it is left for 24 hours in an environment of 23% and 50% RH, and the amount of the inward side of the side opposite to the gate side is measured five times with a three-dimensional measuring machine made by MITUTOYO, and the average is calculated as the amount of inner warp. did.

  (V) Izod impact strength with a notch was measured as impact strength. Using a test piece (63.5 mm × 12.7 mm × 3.2 mm) prepared in advance according to ASTM D256, a notch was made so as to remain 10 mm, and after molding, 24 hours under an environment of 23 ° C. and 50% RH Measure after standing. A U-F impact tester manufactured by Ueshima Seisakusho was used as a testing machine. The test is carried out 10 times and the notched Izod impact strength is determined by averaging the individual values.

  (Vi) The rod flow length was a rod-shaped mold (width 10 mm, thickness 1 mm) set at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C., molded at 93 MPa, and the flow length at that time was measured. The test was molded 10 times and the rod flow length was determined by averaging the individual values.

  (Vii) The heat cycle property is overmolded to a metal core of 48.6 mm x 48.6 mm x 28.6 mm with a resin molded product thickness of 0.7 mm, and kept at -40 ° C and 85 ° C for 1 hour each. It was allowed to stand and was repeated, and the number of cycles when the number of tests was 5 and all cracked was described. The molding conditions were a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. After molding, the mold was allowed to stand in an environment of 23 ° C. and 50% RH for 24 hours and then placed in a heat cycle tester. The testing machine was TSV-40 manufactured by Tabai Espec Co., Ltd.

  (Viii) In the thickening test, a melt indexer (manufactured by Toyo Seiki Co., Ltd.) was used, and the pellets dried in advance at 130 ° C. for 3 hours were measured under the conditions of a test temperature of 250 ° C. and a load of 1000 g according to ISO 1133. . At that time, when the MFR at the time of 30-minute retention was lower than the MFR at the time of 5-minute retention, “x” was given, and “more” was marked with “◯”.

Examples 1-9
(A) to (G) were blended in combinations shown in Table 1.

  The manufacturing method of each Example is as follows. That is, it was manufactured using a twin screw extruder having a screw diameter of 57 mmφ set at a cylinder temperature of 250 ° C. (A) thermoplastic polyester resin, (B) epoxy group-containing vinyl copolymer, (C) polycarbonate resin, (D) modified polystyrene resin and / or rubber modified polystyrene resin and / or polycarbonate resin, (F) bromine system A flame retardant, (G) antimony compound, and other additives are fed from the source containing part, and (E) when glass fibers are blended, they are melt-kneaded from the side feeder, and the strand discharged from the die is removed. After cooling in the cooling bath, it was pelletized with a strand cutter. Each of the obtained materials was dried with a hot air dryer at 130 ° C. for 3 hours or more, and then molded and evaluated using the evaluation method. The results are also shown in Table 1. All of the obtained compositions had low warpage, mechanical strength, impact characteristics, excellent moldability, heat cycleability, and excellent dimensional stability after annealing.

  Table 1 shows the formulation and evaluation results of Examples 1 to 9.

  Examples 1 to 9 of the polyester resin composition of the present invention are all excellent in the amount of warpage, tensile strength, Izod impact strength, fluidity, combustibility, heat cycleability and dimensional stability after annealing. The result was obtained.

  Tables 2 and 3 show the formulation and evaluation results of Comparative Examples 1 to 13.

Comparative Example 1
(D) Modified polystyrene resin and / or rubber-modified polystyrene resin and / or polycarbonate resin was added in an amount less than the specified range. Others were manufactured and evaluated in the same manner as in Example 1. The amount of warpage and the dimensional stability after annealing were lowered, and the heat cycle property was also lowered.

Comparative Example 2
(C) An amount of ABS resin greater than the specified range was added. Others were manufactured and evaluated in the same manner as in Example 1. The ratio of the diene rubber is also larger than the specified range, the amount of warp and the dimensional stability after annealing are lowered, and the flame retardancy is V2. The fluidity is also low.

Comparative Example 3
(C) ABS resin was added in an amount less than the specified range. Others were manufactured and evaluated in the same manner as in Example 1. The proportion of diene rubber is also smaller than the specified range. A sufficient amount of warp, dimensional stability after annealing, impact value, tensile elongation, and heat cycleability could not be obtained.

Comparative Example 4
(B) An epoxy group-containing vinyl copolymer was added in an amount less than the specified range. Others were manufactured and evaluated in the same manner as in Example 1. Although flammability, mechanical strength, and impact properties are fully expressed, inner warping property and dimensional stability after annealing are reduced.

Comparative Example 5
(B) The epoxy group-containing vinyl copolymer was added in an amount larger than the specified range. Others were manufactured and evaluated in the same manner as in Example 1. The amount of warp, the dimensional stability after annealing, the tensile elongation, and the impact value decreased, the heat cycle property was low, and the flame retardancy was V2.

Comparative Example 6
(D) (Da) modified polystyrene resin and (Db) rubber modified polystyrene resin were added in an amount greater than the specified range. Others were manufactured and evaluated in the same manner as in Example 1. Although the combustibility, the amount of warpage, and the dimensional stability after the annealing treatment are sufficiently expressed, the impact property and the fluidity are lowered.

Comparative Example 7
(D) (Db) rubber-modified polystyrene resin and (Dc) polycarbonate resin were added in amounts greater than the specified range. Others were manufactured and evaluated in the same manner as in Example 1. Although the combustibility, the amount of warpage, and the dimensional stability after the annealing treatment are sufficiently expressed, the impact property and the fluidity are lowered.

Comparative Example 8
Among the components (D), only one (Da) maleic anhydride-modified polystyrene resin was added. Others were manufactured and evaluated in the same manner as in Example 1. Although the combustibility, the amount of warpage, and the dimensional stability after the annealing treatment are sufficiently expressed, the impact property and the fluidity are lowered.

Comparative Example 9
Among the components (D), only one (Db) rubber-modified polystyrene resin was added. Others were manufactured and evaluated in the same manner as in Example 1. Although the combustibility, the amount of warpage, and the dimensional stability after annealing are sufficiently expressed, the tensile strength and bending strength are lowered.

Comparative Example 10
Among the components (D), only one (Dc) polycarbonate resin was added. Others were manufactured and evaluated in the same manner as in Example 1. Although the combustibility, the amount of warpage, and the dimensional stability after the annealing treatment are sufficiently expressed, the impact property and the fluidity are lowered.

Comparative Example 11
(B) Instead of using an epoxy group-containing vinyl copolymer, (b-1) acrylonitrile / (b-2) styrene copolymer was used as (Bb). Others were manufactured and evaluated in the same manner as in Example 1. Although flammability V0 was achieved, sufficient tensile strength, Izod impact strength, and heat cycle could not be obtained.

Comparative Example 12
(Fa) Instead of using a brominated flame retardant, a type (Fb) having no end-capping was used. Flame resistance was V2 due to lack of bromine content.

Comparative Example 13
Instead of using (Fa) brominated flame retardant, (Fc) brominated polycarbonate was used. Others were manufactured and evaluated in the same manner as in Example 1. As a result, sufficient fluidity could not be obtained.

It is a figure which shows the shape of the box formation type | mold product which measured the amount of internal warpage in the Example.

Claims (7)

When the total of (A) to (G) is 100% by weight,
(A) 10 to 80% by weight of a thermoplastic polyester resin,
(B) (b-1) vinyl cyanide monomer, (b-2) aromatic vinyl monomer, (b-3) an epoxy group-containing vinyl copolymer having an epoxy group-containing vinyl monomer as a structural unit 1-15% by weight of polymer,
(C) 1-15% by weight of ABS resin,
(D) 1 to 20% by weight of two or more resins selected from the group consisting of (d-1) maleic anhydride-modified polystyrene resin, (d-2) rubber-modified polystyrene resin, and (d-3) polycarbonate resin,
(E) 0 to 50% by weight of glass fiber,
(F) 3 to 20% by weight of a halogenated epoxy bromine flame retardant having an average molecular weight of 2000 to 7000, end-capped with tribromophenol, and (G) 1 to 10% by weight of an antimony compound,
(C) The thermoplastic polyester resin composition whose ratio of the diene rubber contained in the ABS resin is 5 to 8 parts by weight when the total of (A) to (D) is 100 parts by weight. The thermoplastic polyester resin composition according to claim 1, wherein the thermoplastic polyester resin (A) is polybutylene terephthalate. (B) Each monomer of the epoxy group-containing vinyl copolymer is (b-1) 22 to 25% by weight of vinyl cyanide monomer, and (b-2) aroma. (B-3) Reduced viscosity (ηsp / C) measured with 0.2% dimethylformamide solution (b-3) 0.1 to 0.5% by weight of epoxy group-containing vinyl monomer ) Is 0.7 to 0.9. The thermoplastic polyester resin composition according to claim 1 or 2. The thermoplastic polyester resin composition according to any one of claims 1 to 3, wherein the flame retardance of 1/32 inch thickness according to UL94 is V0. The molded article formed by shape | molding the thermoplastic polyester resin composition in any one of Claims 1-4. The molded article according to claim 5, wherein the molded article is an electric / electronic component. The molded article according to claim 6, wherein the molded article is a motor fan case or a fan.

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