JP2019147883A - Polybutylene terephthalate resin composition and molded article comprising the same - Google Patents

Abstract

To provide a thermoplastic resin composition which is excellent in mechanical strength and metal bonding strength and has both a low dielectric constant and a low dielectric loss tangent.SOLUTION: The thermoplastic resin composition is obtained by blending 100 pts.wt. of the total of (A) 24-85 pts.wt. of a polyalkylene terephthalate resin, (B) 1.0-9.0 pts.wt. of a glycidyl group-containing copolymer containing an α-olefin and a glycidyl ester of an α,β-unsaturated acid, (C) 1.0-9.0 pts.wt. of a copolymer obtained by copolymerizing ethylene and a C3 or higher α-olefin, (D) 3.0-18 pts.wt. of a cyclic olefin resin, and (E) 10-40 pts.wt. of glass fibers.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition having excellent mechanical strength and metal bonding strength, and having a low relative dielectric constant and dielectric loss tangent.

  Polybutylene terephthalate resin is excellent in heat resistance, chemical resistance, electrical characteristics, dimensional stability, etc., so it can be used for various electrical and electronic equipment members, automotive parts such as automobiles, trains and trains, and other general industrial products. Widely used as a manufacturing material.

  In recent years, various parts of automobiles and electrical / electronic devices are often compounded by insert molding of metal parts such as electrodes and structural members in order to provide more advanced functions. From the viewpoint of the strength and waterproofness, there is a demand for improving the bonding strength between resin and metal.

  In addition, such metal composite parts are often used in mobile communication devices such as mobile terminal housings, and resin materials are used to enhance radio wave transmission / reception characteristics important for antennas built into mobile communication devices. It is necessary to have a configuration including a part. Furthermore, since the world's mobile communication systems are in the trend of increasing speed and capacity as a global standard, it has become important to reduce transmission loss in information transmission during communication. It has been demanded.

  For such a problem, for example, Patent Document 1 studies a polybutylene terephthalate resin composition for achieving metal adhesion and low dielectric loss tangent. On the other hand, in order to achieve low dielectric properties, Patent Document 2 describes a polybutylene terephthalate resin composition containing a cyclic olefin resin having a glass transition temperature of 110 ° C. or higher. Patent Documents 3 and 4 describe glass fibers having low dielectric properties. The polybutylene terephthalate resin composition containing is described.

International Publication No. 2017/115757 JP 2013-43942 A International Publication No. 2017/203467 JP 2017-52974 A

However, the methods described in Patent Documents 1 to 4 are insufficient to achieve the low dielectric properties required in the world. In addition, the methods described in Patent Documents 2 to 4 are not satisfactory with respect to metal bondability. Furthermore, even if it tried to combine the method of patent documents 2-4 with patent document 1, it was a subject that metal bondability fell and it became difficult to make compatible.
That is, the subject of this invention is providing the thermoplastic resin composition which was excellent in mechanical strength and metal joint strength, and had low dielectric constant and dielectric loss tangent.

  The inventors of the present invention have reached the present invention as a result of intensive studies and studies in order to solve such problems.

That is, the present invention
(1) (A) 24 to 83 parts by weight of a polyalkylene terephthalate resin, (B) 2.0 to 9.0 parts by weight of a glycidyl group-containing copolymer containing a glycidyl ester of an α-olefin and an α, β-unsaturated acid. Parts, (C) 2.0 to 9.0 parts by weight of a copolymer obtained by copolymerizing ethylene and an α-olefin having 3 or more carbon atoms, (D) 3.0 to 18 parts by weight of a cyclic olefin resin, and (E) a thermoplastic resin composition comprising a total of 100 parts by weight of 10 to 40 parts by weight of glass fiber,
(2) The thermoplastic resin composition according to (1), wherein the (A) polyalkylene terephthalate resin is a polybutylene terephthalate resin,
(3) In the thermoplastic resin composition comprising a total of 100 parts by weight of the component (A), component (B), component (C), component (D), and component (E), (B) α -Blend amount b (part by weight) of olefin and glycidyl group-containing copolymer containing glycidyl ester of α, β-unsaturated acid, (C) Copolymer formed by copolymerizing ethylene and α-olefin having 3 or more carbon atoms. The thermoplastic resin composition according to (1) or (2), wherein the blending amount c (parts by weight) of the polymer and the blending amount d (parts by weight) of the (D) cyclic olefin resin satisfy the following formula (1): ,
0.40 ≦ 0.04b + 0.03c + 0.03d Formula (1)
(4) The thermoplastic resin composition according to any one of (1) to (3), wherein the (E) glass fiber has a relative dielectric constant of less than 5 when measured at a frequency of 1 GHz.
(5) The thermoplastic resin composition for insert molding according to any one of (1) to (4), wherein the thermoplastic resin composition is combined with a metal part and used.
(6) A resin part comprising the thermoplastic resin composition according to any one of (1) to (5), and a metal composite part comprising a metal part,
(7) The metal composite part according to (6), wherein the metal composite part is a communication device part,
Is to provide.

  The thermoplastic resin composition of the present invention is excellent in mechanical strength and metal joint strength and excellent in low dielectric properties. The thermoplastic resin composition of the present invention can be used in combination with a metal part by insert molding, and the metal composite part is useful as a communication device part.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. .

  The (A) polyalkylene terephthalate resin used in the present invention is obtained by an ordinary polymerization method such as a polycondensation reaction mainly comprising terephthalic acid or an ester-forming derivative thereof and an aliphatic glycol or an ester-forming derivative thereof. The copolymer may contain other copolymer components as shown below, for example, about 20 parts by weight.

  Examples of the aliphatic glycol include aliphatic diols such as polymethylene glycol having 2 to 10 carbon atoms such as ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, and cyclohexanedimethanol. Tetramethylene glycol is particularly preferable in terms of density and the like.

  Preferred examples of these polymers and copolymers include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexadimethylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene. (Terephthalate / sebacate), polybutylene (terephthalate / decane dicarboxylate), polybutylene (terephthalate / naphthalate), poly (butylene / ethylene) terephthalate, polyethylene (terephthalate / isophthalate), polypropylene (terephthalate / isophthalate), poly (ethylene) / Cyclohexadimethylene) terephthalate, etc. They may be mixed or two or more of them may be used in Germany.

  The (A) polyalkylene terephthalate resin used in the present invention preferably has an intrinsic viscosity of 0.60 to 1.60, particularly 0.80 when the o-chlorophenol solution is measured at 25 ° C. Those in the range of 1.30 are preferred. When the intrinsic viscosity is 0.60 or more, sufficient mechanical properties can be obtained. On the other hand, when the intrinsic viscosity is 1.60 or less, the moldability is excellent.

  The production method of the (A) polyalkylene terephthalate resin used in the present invention can be produced by a known polycondensation method or ring-opening polymerization method, and may be either batch polymerization or continuous polymerization. And a method through a polycondensation reaction, and a reaction by direct polymerization can be applied, but continuous polymerization can be performed in that the amount of carboxyl end groups can be reduced and the effect of improving fluidity is increased. Direct polymerization is preferred from the viewpoint of cost. In order to effectively advance the esterification reaction or transesterification reaction and the polycondensation reaction, it is preferable to add a polymerization reaction catalyst during these reactions. Specific examples of the polymerization reaction catalyst include methyl ester of titanic acid, Organic titanium such as tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester, benzyl ester, tolyl ester, or mixed esters thereof Compound, Dibutyltin oxide, Methylphenyltin oxide, Tetraethyltin, Hexaethylditin oxide, Cyclohexahexylditin oxide, Didodecyltin oxide, Triethyltin hydroxide, Triphenyl Hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin dichloride, tributyltin chloride, dibutyltin sulfide and butylhydroxytin oxide, methylstannic acid, ethylstannic acid, butylstannic acid, etc. Tin compounds such as alkylstannic acid, zirconia compounds such as zirconium tetra-n-butoxide, antimony compounds such as antimony trioxide and antimony acetate, etc. Among these, organic titanium compounds and tin compounds are preferred, Furthermore, tetra-n-propyl ester, tetra-n-butyl ester and tetraisopropyl ester of titanic acid are preferred, and titanic acid is preferred. Tetra -n- butyl ester is particularly preferred. These polymerization reaction catalysts may be used alone or in combination of two or more. The addition amount of the polymerization reaction catalyst is preferably in the range of 0.005 to 0.5 parts by weight with respect to 100 parts by weight of the polybutylene terephthalate resin in terms of mechanical properties, moldability, and color tone, and is preferably 0.01 to 0.8. A range of 2 parts by weight is more preferred.

  The blending amount of the (A) polyalkylene terephthalate resin in the present invention is 100 weights of the sum of the component (A) and the components (B), (C), (D) and (E) described below. Part to 24 to 85 parts by weight. When the blending amount of the polyalkylene terephthalate resin is less than 24 parts by weight, the fluidity of the resin composition is inferior, and when it exceeds 85 parts by weight, the mechanical properties of the resin composition are deteriorated.

  The (A) polyalkylene terephthalate resin used in the present invention is preferably a polyethylene terephthalate resin, a polypropylene terephthalate resin, or a polybutylene terephthalate resin. It is more preferable to mix two or more of polyethylene terephthalate resin, polybutylene terephthalate resin, and polybutylene (terephthalate / isophthalate) resin, and it is more preferable to mix polyethylene terephthalate resin and polybutylene terephthalate resin.

  Moreover, it is preferable to mix | blend 5-40 weight part of polyethylene terephthalate resin and 60-95 weight part of polybutylene terephthalate resin with respect to a total of 100 weight part of polyethylene terephthalate resin and polybutylene terephthalate resin. When the blending amount of the polyethylene terephthalate resin is 5 parts by weight or more and the blending amount of the polybutylene terephthalate resin is 95 parts by weight or less, sufficient metal bonding strength of the resin composition can be obtained. It is preferable to blend 9 parts by weight or more of polyethylene terephthalate resin and 91 parts by weight or less of polybutylene terephthalate resin. On the other hand, when the blending amount of the polyethylene terephthalate resin is 40 parts by weight or less and the blending amount of the polybutylene terephthalate resin is 60 parts by weight or less, the mechanical strength of the resin composition can be maintained. It is preferable to blend 30 parts by weight or less of polyethylene terephthalate resin and 70 parts by weight or more of polybutylene terephthalate resin.

  Examples of the α-olefin in the glycidyl group-containing copolymer containing (B) the α-olefin and the glycidyl ester of α, β-unsaturated acid used in the present invention include ethylene, propylene, 1-butene, 1-pentene and the like. Of these, ethylene is preferably used. Examples of the glycidyl ester of α, β-unsaturated acid include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate. Among them, glycidyl methacrylate is preferably used. (B) Specific examples of the glycidyl group-containing copolymer include ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / acrylic acid. Examples include an ethyl / glycidyl methacrylate copolymer and an ethylene / vinyl acetate / glycidyl methacrylate copolymer. Among them, an ethylene / glycidyl methacrylate copolymer and an ethylene / methyl acrylate / glycidyl methacrylate copolymer are preferable. These can be used alone or in the form of a mixture.

  The blending amount of the glycidyl group-containing copolymer containing the (B) α-olefin and the glycidyl ester of α, β-unsaturated acid used in the present invention is described below as the component (A) and the component (B) (C ) Component, (D) component, and (E) component is 2.0 to 9.0 parts by weight when the total is 100 parts by weight. When the blending amount is less than 2.0 parts by weight, the relative dielectric constant and dielectric loss tangent of the resin composition are inferior, and when it exceeds 9.0 parts by weight, the mechanical strength of the resin composition is lowered. Furthermore, it is preferable to mix | blend in the range of 2.0-7.0 weight part from the point of a dielectric constant, a dielectric loss tangent, and mechanical strength, and it is more preferable to mix | blend in the range of 2.0-6.0 weight part. preferable.

  The α-olefin having 3 or more carbon atoms in the copolymer of (C) ethylene and α-olefin having 3 or more carbon atoms used in the present invention is propylene, 1-butene, 1-octene, 1-pentene, 3-methyl. Examples include -1-pentene and 1-octacene, and 1-butene and 1-octene are particularly preferable. These can be used alone or in the form of a mixture.

  The copolymerization ratio of the copolymer of ethylene and an α-olefin having 3 or more carbon atoms is 40/60 to 99/1 (molar ratio), preferably 70/30 to 95/5 (molar ratio).

  The blending amount of the copolymer of (C) ethylene and α-olefin having 3 or more carbon atoms used in the present invention is the (A) component, the (B) component, the (C) component and the (D) component described below. When the total of component (E) is 100 parts by weight, it is 2.0 to 9.0 parts by weight. When the blending amount is less than 2.0 parts by weight, the relative dielectric constant and dielectric loss tangent of the resin composition are inferior, and when it exceeds 9.0 parts by weight, the mechanical strength of the resin composition is lowered. Furthermore, it is preferable to mix | blend in the range of 2.0-7.0 weight part from the point of a dielectric constant, a dielectric loss tangent, and mechanical strength, and it is more preferable to mix | blend in the range of 2.0-6.0 weight part. preferable.

  Examples of the (D) cyclic olefin resin used in the present invention include norbornene polymers, vinyl alicyclic hydrocarbon polymers, cyclic conjugated diene polymers, and the like. Among these, norbornene-based polymers are preferable. The norbornene polymer includes a ring-opening polymer of a norbornene monomer (hereinafter also referred to as “COP”), a norbornene copolymer obtained by copolymerizing a norbornene monomer and an α-olefin such as ethylene. And the like (hereinafter also referred to as “COC”). COP and COC hydrogenated products can also be used.

  The norbornene monomer used as a raw material for the norbornene polymer is an alicyclic monomer having a norbornene ring. Examples of such norbornene-based monomers include norbornene, tetracyclododecene, ethylidene norbornene, vinyl norbornene, ethylidetetracyclododecene, dicyclopentadiene, dimethanotetrahydrofluorene, phenyl norbornene, methoxycarbonyl norbornene, methoxy And carbonyltetracyclododecene.

  The COC is obtained by copolymerizing an olefin copolymerizable with the norbornene-based monomer. Examples of such olefin include 2 to 20 carbon atoms such as ethylene, propylene, and 1-butene. And cycloolefin such as cyclobutene, cyclopentene, and cyclohexene; and non-conjugated dienes such as 1,4-hexadiene. The norbornene monomer and the copolymerizable olefin can be used alone or in combination of two or more. Moreover, such a cyclic olefin copolymer can be used individually or in combination. In addition, as the (D) cyclic olefin-based resin, the COP and COC can be used in combination.

  The blending amount of the (D) cyclic olefin resin used in the present invention is 100 weights of the sum of the (A) component, the (B) component, the (C) component, and the (D) component and the (E) component described below. Part to 3.0 parts by weight. When the blending amount is less than 3.0 parts by weight, the relative dielectric constant and dielectric loss tangent of the resin composition are inferior, and when it exceeds 18 parts by weight, the mechanical strength and metal bonding strength of the resin composition are lowered. Furthermore, it is preferable to mix | blend in the range of 4.0-16 weight part from the point of a dielectric constant, dielectric loss tangent, mechanical strength, and metal joint strength, and it is more preferable to mix | blend in the range of 5.0-15 weight part. preferable.

  The glass fiber (E) used in the present invention is a chopped strand type or roving type glass fiber used for a normal PBT reinforcing material, and is a silane coupling agent such as an aminosilane compound or an epoxysilane compound and / or urethane. Glass fibers treated with a sizing agent containing one or more epoxy compounds such as vinyl acetate, bisphenol A diglycidyl ether, and novolac epoxy compounds are preferably used. The silane coupling agent and / or sizing agent may be used in an emulsion solution.

The glass fiber (E) used in the present invention has a fiber diameter of 1 to 15 μm, preferably 5 to 14 μm, more preferably 6 to 13 μm. When the fiber diameter is 1 μm or more, the glass fiber length of the molded product after compounding and molding can be maintained to some extent, the reinforcing effect of the resin can be obtained, and sufficient mechanical strength can be obtained. Moreover, the number of the glass fibers in resin can be maintained simultaneously with the reinforcement effect of resin by setting it as 15 micrometers or less, and sufficient mechanical strength can be obtained.
The (E) glass fiber used in the present invention preferably has a relative dielectric constant of less than 7 when measured at a frequency of 1 GHz, and is less than 5 from the viewpoint of keeping the relative dielectric constant and dielectric loss tangent of the thermoplastic resin composition low. It is preferable.

  The blending amount of (E) glass fiber used in the present invention is (A), (B), (C), (D), and (E) when the total amount is 100 parts by weight. It is 10-40 weight part, Preferably it is 15-35 weight part, More preferably, it is 20-30 weight part. If the blending amount is less than 10 parts by weight, sufficient mechanical strength is not exhibited. On the other hand, if it exceeds 40 parts by weight, the molded appearance, relative dielectric constant, dielectric loss tangent, and productivity are significantly reduced.

The thermoplastic resin composition of the present invention comprises a glycidyl group-containing copolymer containing (B) a glycidyl ester of an α-olefin and an α, β-unsaturated acid in a total of 100 parts by weight of the components (A) to (E). Blending amount b (parts by weight) of the coalescence, (C) blending amount c (parts by weight) of a copolymer obtained by copolymerizing ethylene and an α-olefin having 3 or more carbon atoms, and (D) a cyclic olefin-based resin. The blending amount d (parts by weight) preferably satisfies the following formula (1).
0.40 ≦ 0.04b + 0.03c + 0.03d Formula (1)

  Formula (1) is an empirical formula indicating the dielectric characteristics of the resin composition, and serves as an index for achieving low dielectric characteristics in the resin composition. In the formula (1), when the value of 0.04b + 0.03c + 0.03d is 0.40 or more, the relative dielectric constant and dielectric loss tangent of the thermoplastic resin composition can be lowered. 0.45 or more is more preferable, and 0.50 or more is more preferable. On the other hand, the upper limit of the above value is not particularly limited, but is preferably 0.80 or less and more preferably 0.70 or less from the viewpoint of mechanical strength and metal bonding strength. In this invention, it is preferable to adjust the compounding quantity of (B) component, (C) component, and (D) component so that Formula (1) may be satisfy | filled.

  In the thermoplastic polyester resin composition of the present invention, other resin components, flame retardants, mold release agents, phosphorus antioxidants, stabilizers, ultraviolet absorbers, colorants, as long as the effects of the present invention are not impaired. Conventional additives such as lubricants and small amounts of other polymers can be added.

  As the other resin component, any resin other than the (A) component, the (B) component, the (C) component, and the (D) component may be used, for example, a polybutylene naphthalene dicarboxylate resin, Polyethylene naphthalene dicarboxylate resin, polypropylene terephthalate resin, hydrogenated or unhydrogenated SBS resin (styrene / butadiene / styrene triblock copolymer) and hydrogenated or unhydrogenated SIS resin (styrene / isoprene / styrene triblock copolymer) ), SEBS resin (hydrogenated styrene / butadiene / styrene triblock copolymer), polyethylene resin, polypropylene resin, polymethylpentene resin, cellulose resin such as cellulose acetate, polyamide resin, polyacetal resin, polysulfone resin, polyphenylenesulfur Id resin include polyether Ether ketone resins, resin to be mixed is not necessarily one kind, may be used in combination of two or more.

  Specific examples of flame retardants include brominated flame retardants, phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants, and inorganic flame retardants, each of which can be used alone or in a mixture. Preferably, a mixture of a brominated flame retardant and an inorganic flame retardant can be used.

  Specific examples of the brominated flame retardant used in the present invention include tetrabromobisphenol-A, tetrabrobisphenol-A derivative, tetrabromobisphenol-A-epoxy oligomer or polymer, tetrabromobisphenol-A-carbonate oligomer or polymer, Examples include brominated epoxy resins such as brominated phenol novolac epoxy, poly (pentabromobenzyl polyacrylate), pentabromobenzyl polyacrylate, N, N′-ethylene-bis-tetrabromophthalimide and the like. Of these, tetrabromobisphenol-A-epoxy oligomers or polymers and tetrabromobisphenol-A-carbonate oligomers or polymers are preferred.

  As the inorganic flame retardant used in the present invention, magnesium hydroxide hydrate, aluminum hydroxide hydrate, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, oxidation Tin, zinc borate and the like can be mentioned. Of these, antimony trioxide is preferable.

  Mold 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 Fatty waxes such as derivatives, fatty acids and derivatives thereof may be mentioned.

  Examples of the phosphorus antioxidant include trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, and the like.

  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. In other words, the classification is for convenience and does not limit the action.

  Examples of the ultraviolet absorber include 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, and bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane. Benzophenone-based ultraviolet absorbers typified by, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenylbenzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetra Methylptyl) -6- (2H-benzotriazol-2-yl) phenol], methyl-3- [3- (2H-benzoto 2-yl) can be mentioned -5-tert-butyl-4-hydroxyphenyl] propionate and benzotriazole ultraviolet absorbents typified by a condensate of polyethylene glycol.

  Also, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6) -Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane Tetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl Piperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane Etc. even it can include hindered amine light stabilizers typified, such light stabilizers in combination with the ultraviolet absorber and various antioxidants, exhibit better performance in terms of weather resistance.

  Examples of the colorant include organic dyes, organic pigments, and inorganic pigments.

  Lubricants are (poly) glycerin and (poly) pentaerythritol and caproic acid, enanthylic acid, nonanoic acid, capric acid, octylic acid, lauric acid, myristic acid, behenic acid, palmitic acid, isostearic acid, stearic acid, oleic acid And esters of fatty acids such as aliphatic monocarboxylic acids such as isononanoic acid, alginic acid, and montanic acid.

  Other examples include fluorescent brighteners, phosphorescent pigments, fluorescent dyes, flow modifiers, transesterification inhibitors, inorganic and organic antibacterial agents, photocatalytic antifouling agents, infrared absorbers, and photochromic agents.

  The thermoplastic resin composition of the present invention is usually produced by a known method. For example, (A) polyalkylene terephthalate resin, (B) glycidyl group-containing copolymer containing glycidyl ester of α-olefin and α, β-unsaturated acid, (C) ethylene and α-olefin having 3 or more carbon atoms A copolymer obtained by copolymerizing (D) a cyclic olefin resin, and (E) glass fiber, and further, if necessary, an inorganic filler other than glass fiber, an antioxidant, a lubricant, and, if necessary, other The thermoplastic resin composition of the present invention is prepared by premixing necessary additives and colorants such as pigments and dyes or supplying them to an extruder or the like without premixing and sufficiently kneading them. .

  As an example of the above-mentioned premixing, it is possible to perform dry blending alone, but mixing can be performed using a mechanical mixing device such as a tumbler, a ribbon mixer, and a Henschel mixer. Further, (E) the glass fiber may be added by adding a side feeder in the middle of the original loading part and the vent part of a multi-screw extruder such as a twin-screw extruder. In addition, in the case of liquid additives, a method of adding using a plunger pump by installing a liquid addition nozzle in the middle of the main loading part and the vent part of a multi-screw extruder such as a twin screw extruder and the original loading part For example, a method of supplying with a metering pump may be used.

  In producing a thermoplastic resin composition, for example, a single-screw extruder, a twin-screw extruder, a three-screw extruder, a conical extruder, and a kneader-type kneading equipped with a “unimelt” or “dalmage” type screw. Although a machine etc. can be used, it is not limited to these.

  The thermoplastic resin composition thus obtained is usually injection-molded by a known method to obtain the molded product of the present invention. As the injection molding method, there are known gas assist method, two-color molding method, sandwich molding, in-mold molding, insert molding and injection press molding in addition to the usual injection molding method. Applicable.

  The thermoplastic resin composition of the present invention can be used for various applications such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, household goods and sanitary goods, and is compounded with metal parts by insert molding. Useful for the molded product used.

  Specific applications include air flow meters, air pumps, ignition hobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, inhibitor switches, rotation sensors, acceleration sensors, distributor caps, coils Base, ABS actuator case, air cleaner housing, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes such as automotive underhood parts, torque control lever, register blade, Washer lever, window regulator handle, window regulator handle knob, passing line Automotive interior parts such as levers, sun visor brackets, various motor housings, roof rails, fenders, garnishes, bumpers, door mirror stays, grill apron cover frames, lamp reflectors, lamp bezels, door handles, and other automotive exterior parts, wire harness connectors , SMJ connector, PCB connector, various automotive connectors, electrical connector, relay case, coil bobbin, optical pickup chassis, motor case, laptop housing and internal parts, CRT display housing, and internal parts, printer housing and internal parts, mobile phone Mobile terminal housings and internal parts such as telephones, mobile personal computers and handheld mobiles, recording media (CD, DVD, PD, DD etc.) drive housings and internal parts, mention may be made of electric and electronic parts typified housing and internal parts of copying machines, etc. facsimile housings and internal parts. Furthermore, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, video camera parts, video equipment parts such as projectors, laser discs (registered trademark), compact discs (CDs), DVD-ROMs , DVD-R, Blu-ray disc and other optical recording medium substrates, lighting parts, refrigerator parts, air conditioner parts, and other home / office electrical product parts. Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, optical pickups, oscillators , Various terminal boards, printed wiring boards, speakers, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD chassis, motor brush holders, transformer members, and other electrical and electronic parts, sash doors, blind curtain parts, Piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels, ceiling fishing tackle and other building parts, bearings, levers, cams, latteettes, rollers, water supply parts, toy parts, fans, for cleaning Healing , Motor parts, useful microscope, binoculars, cameras, as machine parts such as watch. Since the resin composition of the present invention has both mechanical strength and metal bonding strength, among them, an ignition bobbin, an ignition case, a clutch bobbin, a sensor housing, an idle speed control valve, a vacuum switching valve, an ECU housing, a vacuum pump case, Especially for automotive parts applications such as inhibitor switches and electrical connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, notebook computer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, and handheld mobiles Useful. Furthermore, since the resin composition of the present invention is excellent in low dielectric properties, a metal composite part by insert molding can be suitably used for mobile communication equipment parts.

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

  Abbreviations and contents of raw materials used in Examples and Comparative Examples are shown below.

[Reference example]
(A) Polyalkylene terephthalate resin A-1: Polybutylene terephthalate resin Inherent viscosity 0.85
A-2: Polyethylene terephthalate resin Intrinsic viscosity 0.65
(B) Glycidyl group-containing copolymer containing α-olefin and glycidyl ester of α, β-unsaturated acid B-1: ethylene / glycidyl methacrylate copolymer “ETX-6” manufactured by Sumitomo Chemical Co., Ltd.
(C) Copolymer formed by copolymerizing ethylene and α-olefin having 3 or more carbon atoms: C-1: ethylene / 1-butene copolymer “Tuffmer TX-610” manufactured by Mitsui Chemicals, Inc.
(D) Cyclic Olefin Resin D-1: Ethylene / Tetracyclododecene Copolymer “Apel APL6013T” manufactured by Mitsui Chemicals, Inc.
(E) Glass fiber E-1: Low dielectric constant circular cross-section glass fiber “ECS303N-3-K / HL” manufactured by CPIC Average fiber diameter 13 μm, dielectric constant (1 GHz) = about 4.5

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

(1) Tensile properties Tensile strength and tensile strain were measured in accordance with ISO527-1, 2: 2012.

(2) Impact characteristics (Charpy impact strength)
The notched Charpy impact strength was measured according to ISO 179: 2010.

(3) Metal bondability (metal bond strength)
The test piece for evaluation has a shape conforming to ISO19095-2: 2015 “Overlapped test specifications (type B)” and uses a SE50DUZ type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. The thermoplastic resin composition was prepared on metal parts by insert molding. The injection conditions were such that the cylinder temperature was 270 ° C., the mold temperature was 140 ° C., the injection speed was adjusted so that the filling time was 0.5 seconds, the holding pressure was 40 MPa, the injection time was 15 seconds, and the cooling time was 15 seconds. In addition, the metal component used the test piece which performed the surface treatment by the TRI technique of Toa Denka Co., Ltd. to the aluminum (A5052) piece.

  Using the prepared test piece, according to ISO19095-3: 2015, the shear joint strength between the resin part and the metal part was measured, and those having a strength of 20 MPa or more were judged as “◯”, and those having a strength of less than 20 MPa were judged as “X”. .

(4) Dielectric characteristics The relative dielectric constant and dielectric loss tangent at a frequency of 2.45 GHz were measured at 23 ° C. by the cavity resonator perturbation method. For the measurement, PNA-L network analyzer N5230A manufactured by Agilent Technologies, Inc. and cavity resonator CP481 manufactured by Kanto Electronics Application Development Co., Ltd. were used.

[Examples 1 to 11]
Change the composition of the resin composition as shown in Table 1, and supply all the components (A), (B), (C), (D) and other additives from the original loading section of the twin screw extruder. (E) The component (E) was supplied from a secondary charging port installed between the main charging port and the tip of the extruder and melt kneaded in a twin screw extruder having a screw diameter of 57 mmφ set at a cylinder temperature of 250 ° C.

  The strand discharged from the die was cooled in a cooling bath and then pelletized with a strand cutter. Each pellet obtained was dried with a hot air dryer at 130 ° C. for 3 hours or more, and then a test piece was prepared and evaluated for tensile strength, impact strength, metal bonding strength, relative dielectric constant, and dielectric loss tangent. The results are also shown in Table 1. All of the obtained compositions were excellent in tensile strength, impact strength, metal bonding strength, and low dielectric properties.

[Comparative Examples 1-8]
Change the composition of the resin composition as shown in Table 2, and supply all components (A), (B), (C), (D), and other additives from the original loading section of the twin screw extruder. (E) The component (E) was supplied from a secondary charging port installed between the main charging port and the tip of the extruder and melt kneaded in a twin screw extruder having a screw diameter of 57 mmφ set at a cylinder temperature of 250 ° C.

  The strand discharged from the die was cooled in a cooling bath and then pelletized with a strand cutter. Each pellet obtained was dried with a hot air dryer at 130 ° C. for 3 hours or more, and then a test piece was prepared and evaluated for tensile strength, impact strength, metal bonding strength, relative dielectric constant, and dielectric loss tangent. The results are also shown in Table 2.

  Since Comparative Examples 1 and 2 did not contain the component (B) and the component (C), respectively, the metal bondability was inferior.

Since the comparative example 3 did not mix | blend (D) component, it was inferior to a dielectric characteristic.
Comparative Examples 4, 5 and 6 were inferior in mechanical strength and metal joint strength because the blending amounts of the component (B), the component (C) and the component (D) were outside the scope of the present invention.

  Comparative Example 7 was inferior in impact characteristics because the blending amount of component (E) was below the range of the present invention.

  Comparative Example 8 was inferior in metal bonding strength and dielectric properties because the amount of component (E) exceeded the range of the present invention.

Claims (7)

(A) 24 to 83 parts by weight of a polyalkylene terephthalate resin, (B) 2.0 to 9.0 parts by weight of a glycidyl group-containing copolymer containing a glycidyl ester of an α-olefin and an α, β-unsaturated acid, C) 2.0 to 9.0 parts by weight of a copolymer obtained by copolymerizing ethylene and an α-olefin having 3 or more carbon atoms, (D) 3.0 to 18 parts by weight of a cyclic olefin resin, and (E) A thermoplastic resin composition comprising a total of 100 parts by weight of 10 to 40 parts by weight of glass fibers. The thermoplastic resin composition according to claim 1, wherein the (A) polyalkylene terephthalate resin is a polybutylene terephthalate resin. In the thermoplastic resin composition comprising a total of 100 parts by weight of the component (A), the component (B), the component (C), the component (D), and the component (E), (B) an α-olefin Blending amount b (part by weight) of glycidyl group-containing copolymer containing glycidyl ester of α, β-unsaturated acid, (C) of copolymer obtained by copolymerizing ethylene and α-olefin having 3 or more carbon atoms The thermoplastic resin composition according to claim 1 or 2, wherein the blending amount c (parts by weight) and (D) the blending amount d (parts by weight) of the cyclic olefin resin satisfy the following formula (1).
0.40 ≦ 0.04b + 0.03c + 0.03d Formula (1) The thermoplastic resin composition according to any one of claims 1 to 3, wherein the (E) glass fiber has a relative dielectric constant of less than 5 when measured at a frequency of 1 GHz. The thermoplastic resin composition for insert molding according to any one of claims 1 to 4, wherein the thermoplastic resin composition is used in combination with a metal part. A metal composite part comprising a resin part comprising the thermoplastic resin composition according to claim 1 and a metal part. The metal composite part according to claim 6, wherein the metal composite part is a communication device part.