JP5894593B2 - Insert molded body - Google Patents

Description

  The present invention relates to an insert molded body including a resin member composed of a polybutylene terephthalate resin composition.

  An insert molding method is known as a molding method for utilizing the characteristics of a resin and the characteristics of a material of a metal or an inorganic solid (hereinafter sometimes referred to as an insert member). An insert molded body formed by this insert molding method is composed of a resin member and an insert member, and is used as an automobile part, an electric / electronic part, or the like.

  However, the resin member and the insert member are extremely different in expansion and contraction rate (so-called linear expansion coefficient) due to temperature change, so the resin member is thin or has a portion where the change in thickness due to temperature change is large. When the metal member has a sharp corner, there are many troubles that the resin member is cracked immediately after molding or the resin member is cracked due to a temperature change during use.

  For this reason, in order to make it hard to produce the crack of the above resin members, thermosetting resins, such as a phenol resin and an epoxy resin, are widely used as a resin material which comprises a resin member.

  However, when a thermosetting resin is used, the molding cycle becomes longer, and the productivity of the insert molded body is lowered. Further, thermosetting resins lack recyclability. Therefore, it is required to use a thermoplastic resin composition as a resin material constituting the resin member.

  Further, when the insert molded body is used as an automobile part, an electrical part or the like, the insert molded body is required to have flame retardancy.

  Thus, an insert molded body is disclosed in which flame retardancy is imparted to the resin member and the resin member is made of a thermoplastic resin composition (see Patent Document 1).

JP 2007-138018 A

  According to the insert molded article described in Patent Document 1, the resin member is said to be excellent in heat shock resistance. However, when the heat shock resistance of the resin member is further improved, other physical properties are improved. It is difficult to improve heat shock resistance without lowering.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide an insert molded body having a resin member having excellent physical properties and excellent heat shock resistance. There is.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, a polybutylene terephthalate resin composition in which the resin member of the insert molded body contains (A) a polybutylene terephthalate resin, (B) an elastomer, (C) a halogen-based flame retardant, and (D) an antimony compound. It has been found that the above-mentioned problems can be solved by comprising the present invention, and the present invention has been completed. More specifically, the present invention provides the following.

  (1) It is composed of a polybutylene terephthalate resin composition containing an insert member, (A) a polybutylene terephthalate resin, (B) an elastomer, (C) a halogen-based flame retardant, and (D) an antimony compound. An insert molded body comprising a resin member.

  (2) The content of the (D) antimony compound in the polybutylene terephthalate resin composition is 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the (A) polybutylene terephthalate resin (1 ).

  (3) The (B) in the polybutylene terephthalate resin composition, wherein the (B) elastomer includes at least one selected from a styrene-based thermoplastic elastomer and a core-shell elastomer whose main component is an acrylic rubber. The insert molded body according to (1) or (2), wherein the content of the elastomer is 10 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the (A) polybutylene terephthalate resin.

(4) The melt viscosity of the elastomer (B) measured under the conditions of 260 ° C. and a shear rate of 1000 sec ⁻¹ in accordance with ISO 11443 is from 10 Pa · s to 200 Pa · s (1) to (3) The insert molded body according to any one of the above.

  According to the present invention, (B) an elastomer, (C) a halogen-based flame retardant, and (D) an antimony compound are blended with (A) a polybutylene terephthalate resin. It has excellent heat shock resistance while having good physical properties.

  Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited to the following embodiment.

  The insert molded body of the present invention includes a resin member and an insert member. The insert molded body of the present invention exhibits the above-described effects when the resin member is composed of a specific thermoplastic resin composition.

<Resin member>
The resin member is composed of a polybutylene terephthalate resin composition, and the polybutylene terephthalate resin composition includes (A) a polybutylene terephthalate resin, (B) an elastomer, (C) a halogen-based flame retardant, and (D). And an antimony compound.

[(A) Polybutylene terephthalate resin]
(A) The polybutylene terephthalate resin is composed of a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (C ₁ -C ₆ alkyl ester, acid halide, etc.), and an alkylene glycol having at least 4 carbon atoms (1 , 4-butanediol) or a polybutylene terephthalate resin obtained by polycondensation with a glycol component containing an ester-forming derivative thereof. The polybutylene terephthalate resin is not limited to a homopolybutylene terephthalate resin, and may be a copolymer containing 60 mol% or more (particularly 75 mol% or more and 95 mol% or less) of a butylene terephthalate unit.

  (A) The amount of terminal carboxyl groups of the polybutylene terephthalate resin is not particularly limited as long as the object of the present invention is not impaired. In the present invention, the terminal carboxyl group amount of the (A) polybutylene terephthalate resin is preferably 30 meq / kg or less, and more preferably 25 meq / kg or less. When the polybutylene terephthalate resin having a terminal carboxyl group amount in such a range is used, the resin member has particularly excellent heat shock resistance, and (A) by hydrolysis of the polybutylene terephthalate resin in a moist heat environment. It becomes difficult to cause a decrease in strength.

  Further, the intrinsic viscosity of the (A) polybutylene terephthalate resin is not particularly limited as long as the object of the present invention is not impaired. (A) The intrinsic viscosity (IV) of the polybutylene terephthalate resin is preferably 0.60 dL / g or more and 1.2 dL / g or less. More preferably, it is 0.65 dL / g or more and 0.9 dL / g or less. When a polybutylene terephthalate resin having an intrinsic viscosity in such a range is used, the polybutylene terephthalate resin composition is particularly excellent in moldability. The intrinsic viscosity can also be adjusted by blending polybutylene terephthalate resins having different intrinsic viscosities. For example, a polybutylene terephthalate resin having an intrinsic viscosity of 0.9 dL / g is prepared by blending a polybutylene terephthalate resin having an intrinsic viscosity of 1.0 dL / g and a polybutylene terephthalate resin having an intrinsic viscosity of 0.7 dL / g. Can do. (A) The intrinsic viscosity (IV) of the polybutylene terephthalate resin can be measured in o-chlorophenol at a temperature of 35 ° C.

(A) In the polybutylene terephthalate resin, examples of dicarboxylic acid components (comonomer components) other than terephthalic acid and its ester-forming derivatives include, for example, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′- C _{8 to} C ₁₄ aromatic dicarboxylic acids such as dicarboxydiphenyl ether; C _{4 to} C ₁₆ alkyl dicarboxylic acids such as succinic acid, adipic acid, azelaic acid and sebacic acid; C _{5 to} C ₁₀ such as cyclohexane dicarboxylic acid Cycloalkyl dicarboxylic acids; ester-forming derivatives of these dicarboxylic acid components (C ₁ -C ₆ alkyl ester derivatives, acid halides, etc.). These dicarboxylic acid components can be used alone or in combination of two or more.

Among these dicarboxylic acid components, C _{8 to} C ₁₂ aromatic dicarboxylic acids such as isophthalic acid, and C _{6 to} C ₁₂ alkyl dicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid are more preferable.

In the polybutylene terephthalate resin used in the present invention, as a glycol component (comonomer component) other than 1,4-butanediol, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, alkylene glycol C ₂ -C _10, such as 1,3-octanediol; diethylene glycol, triethylene glycol, polyoxyalkylene glycol and dipropylene glycol; cyclohexanedimethanol, alicyclic such as hydrogenated bisphenol a Diols; aromatic diols such as bisphenol A and 4,4′-dihydroxybiphenyl; ethylene oxide 2-mole adducts of bisphenol A, propylene of bisphenol A Of oxide 3 moles adduct, alkylene oxide adducts of C ₂ -C ₄ bisphenol A; or ester-forming derivatives of these glycols (acetylated, etc.). These glycolic component can be used alone or in combination of two or more.

Among these glycol components, ethylene glycol, alkylene glycol C ₂ -C ₆ such as trimethylene glycol, polyoxyalkylene glycols such as diethylene glycol, or alicyclic diols such as cyclohexanedimethanol are more preferred.

  Any of the polybutylene terephthalate copolymers obtained by copolymerizing the comonomer components described above can be suitably used as the (A) polybutylene terephthalate resin. Moreover, you may use combining a homopolybutylene terephthalate polymer and a polybutylene terephthalate copolymer as (A) polybutylene terephthalate resin.

[(B) Elastomer]
In the present invention, the type of (B) elastomer is not particularly limited, and general elastomers such as olefin elastomers, styrene elastomers, polyester elastomers, polyamide elastomers, and core shell elastomers can be used.

  In the present invention, among these elastomers, it is preferable to use a core-shell elastomer whose main component is an olefin elastomer, a styrene elastomer, or an acrylic rubber.

  When an olefin-based elastomer is used, the flame retardancy of the resin member tends to be slightly lowered. However, by using a halogen-based flame retardant and antimony compound, which will be described later, together with an olefin-based elastomer, heat resistance of the resin member is suppressed while suppressing a decrease in the flame retardancy of the resin member due to the use of the olefin-based elastomer. And moldability of the polybutylene terephthalate resin composition can be greatly improved.

  The olefin elastomer is a copolymer mainly composed of ethylene and / or propylene. Specific examples of the olefin elastomer include ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, ethylene-propylene-butene copolymer, ethylene-propylene-diene copolymer, ethylene- Examples thereof include an ethyl acrylate copolymer, an ethylene-vinyl acetate copolymer, and an ethylene-glycidyl methacrylate copolymer.

  When the above copolymer is used, the effect of improving the heat shock resistance of the resin member is small as compared with the case where the following graft copolymer is used. However, since the polybutylene terephthalate resin composition containing the above copolymer has very excellent fluidity, it is preferable in terms of moldability. Here, the “excellent fluidity” means that the flow length measured by the method described in the examples is 40 mm or more when the injection pressure is 75 MPa.

In order to sufficiently improve the fluidity of the polybutylene terephthalate resin composition without impairing the effects of the present invention such as improving the heat shock resistance of the resin member, the melt viscosity of the elastomer is 10 Pa · s or more and 200 Pa · s. It is preferable to adjust to the following. Since the copolymer often has a melt viscosity that satisfies the above range, the copolymer is preferably used as an elastomer from the viewpoint of moldability of the polybutylene terephthalate resin composition. As the melt viscosity, a value measured under conditions of 260 ° C. and a shear rate of 1000 sec ⁻¹ is adopted in accordance with ISO11443.

  As the olefin elastomer, (a-1) an ethylene-unsaturated carboxylic acid alkyl ester copolymer or (a-2) an olefin copolymer comprising an α-olefin and an α, β-unsaturated glycidyl ester. A graft copolymer in which a polymer and (b) one or more of polymers or copolymers composed mainly of repeating units represented by the following general formula (1) are chemically bonded in a branched or crosslinked structure Can also be used. Such a graft copolymer is particularly effective in improving heat shock resistance.

（式（１）中、Ｒは水素原子又はＣ _１ 〜Ｃ _６ のアルキル基を表し、Ｘは−ＣＯＯＣＨ_３、−ＣＯＯＣ_２Ｈ_５、−ＣＯＯＣ_４Ｈ_９、−ＣＯＯＣＨ_２ＣＨ（Ｃ_２Ｈ_５）Ｃ_４Ｈ_９、フェニル基、及びシアノ基からなる群から選択される一種以上の基を表す。）

(In the formula (1), R represents a hydrogen atom or an alkyl group of _C 1 _{~C 6,} X is _{-COOCH 3, -COOC 2 H 5,} -COOC 4 H 9, -COOCH 2 CH (C 2 H 5 And represents one or more groups selected from the group consisting of C ₄ H ₉ , phenyl group, and cyano group.)

  (A-1) Specific examples of the ethylene-unsaturated carboxylic acid alkyl ester copolymer include ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene -Random copolymers, such as vinyl acetate-ethyl acrylate copolymer, are mentioned. Further, (a-1) the ethylene-unsaturated carboxylic acid alkyl ester copolymer may be a copolymer of unsaturated carboxylic acid such as acrylic acid and methacrylic acid within the range not impairing the object of the present invention. Good. These copolymers can be used by mixing two or more kinds.

  Moreover, ethylene, propylene, 1-butene etc. are mentioned as an alpha olefin which is one monomer which comprises the olefin type copolymer of (a-2), In these, ethylene is used more preferably.

（式（２）中、Ｒ１は水素原子、又はＣ _１ 〜Ｃ _６ のアルキル基を表す。） The glycidyl ester of α, β-unsaturated acid, which is another monomer constituting the component (a-2), is a compound represented by the following formula (2), for example, glycidyl acrylate, glycidyl methacrylate, Examples include ethacrylic acid glycidyl ester. Among these glycidyl esters of α, β-unsaturated acid, glycidyl methacrylate is particularly preferably used.

(In the formula (2), R1 represents a hydrogen atom, or an alkyl group of _C 1 _{~C 6.)}

  An olefin copolymer comprising an α-olefin such as ethylene and a glycidyl ester of an α, β-unsaturated acid is obtained by subjecting an α-olefin and a glycidyl ester of an α, β-unsaturated acid to a radical polymerization reaction according to a conventional method. It can be obtained by copolymerization. The preferred ratio of α-olefin and α, β-unsaturated glycidyl ester in the production of the copolymer is 70% by mass or more and 99% by mass or less of α-olefin, and glycidyl of α, β-unsaturated fatty acid. It is 1 mass% or more and 30 mass% or less of ester.

  The polymer or copolymer (b) to be graft polymerized with the olefin copolymer (a-1) or (a-2) is a homopolymer consisting of only one type of repeating unit represented by the formula (1), or It is a copolymer composed of two or more. Specific examples of the polymer or copolymer (b) include polymethyl methacrylate, polyethyl acrylate, polybutyl acrylate, polyacrylic acid (2-ethylhexyl), polystyrene, polyacrylonitrile, acrylonitrile-styrene copolymer. Butyl acrylate-methyl methacrylate copolymer, butyl acrylate-styrene copolymer and the like. Among these polymers or copolymers (b), it is particularly preferable to use a butyl acrylate-methyl methacrylate copolymer. These polymers or copolymers (b) can be prepared by radical polymerization of the corresponding vinyl monomers according to a conventional method.

  The graft copolymer suitably used in the present invention is a branched or olefinic copolymer (a-1) or (a-2) and a polymer or copolymer (b) chemically bonded at least at one point. It is a graft copolymer having a crosslinked structure. When the graft copolymer has such a branched or crosslinked structure, the olefin copolymer (a-1), (a-2), or the polymer or copolymer (b) alone is a polybutylene terephthalate resin composition. The effect of improving the heat shock resistance superior to the case of blending into a product can be obtained. Here, the ratio of (a-1) or (a-2) and (b) constituting the graft copolymer is preferably a mass ratio of 95: 5 to 5:95, and preferably 80:20 to 20 : 80 is more preferable.

  As the styrene elastomer used as the elastomer (B), a block copolymer composed of a polystyrene block and an elastomer block having a polyolefin structure is preferably used. Specific examples of the styrene elastomer include styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene / propylene-styrene block copolymer (SEPS), and styrene-ethylene / butylene-styrene block copolymer (SEBS). And styrene-ethylene / ethylene / propylene-styrene block copolymer (SEEPS).

  The core-shell elastomer used as the elastomer (B) has a multilayer structure composed of a core layer (core portion) and a shell layer that covers at least a part of the surface of the core layer. The core layer of the core-shell elastomer is preferably composed of a rubber component (soft component), and acrylic rubber is suitably used as the rubber component. The rubber component used for the core layer preferably has a glass transition temperature (Tg) of less than 0 ° C. (eg −10 ° C. or less), and −20 ° C. or less (eg −180 ° C. or more and −25 ° C. or less). More preferably, it is -30 degrees C or less (for example, -150 degreeC or more and -40 degrees C or less).

The acrylic rubber used as the rubber component is preferably a polymer obtained by polymerizing an acrylic monomer such as alkyl acrylate as a main component. The alkyl acrylate used as the acrylic rubber monomer is preferably a C _{1 to} C ₁₂ alkyl ester of acrylic acid such as butyl acrylate, and more preferably a C _{2 to} C ₆ alkyl ester of acrylic acid.

  The acrylic rubber may be a homopolymer of an acrylic monomer or a copolymer. When the acrylic rubber is a copolymer of acrylic monomers, it may be a copolymer of acrylic monomers or a copolymer of an acrylic monomer and another unsaturated bond-containing monomer. When the acrylic rubber is a copolymer, the acrylic rubber may be a copolymer of a crosslinkable monomer.

  A vinyl polymer is preferably used for the shell layer. The vinyl polymer includes, for example, at least one monomer selected from an aromatic vinyl monomer, a vinyl cyanide monomer, a methacrylic ester monomer, and an acrylate monomer. Obtained by polymerization or copolymerization. The core layer and the shell layer of the core-shell elastomer may be bonded by graft copolymerization. If necessary, this graft copolymerization can be obtained by adding a graft crossing agent that reacts with the shell layer during polymerization of the core layer, imparting reactive groups to the core layer, and then forming the shell layer. When a silicone rubber is used as the graft crossing agent, an organosiloxane having a vinyl bond or an organosiloxane having a thiol is used, preferably acoxysiloxane, methacryloxysiloxane, or vinylsiloxane.

  The content of the elastomer (B) in the polybutylene terephthalate resin composition is preferably 10 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the (A) polybutylene terephthalate resin. If it is 10 parts by mass or more, the heat shock resistance can be improved, and if it is 30 parts by mass or less, it is preferable because the decrease in flame retardancy is small.

[(C) Halogen flame retardant]
(C) A halogen-type flame retardant is not specifically limited, A general compound can be used. Specifically, halogenated phenyl, halogenated diphenyl ether, halogenated aromatic bisimide compound, halogenated aromatic epoxy compound, low molecular weight organic halogen compound of bisphenol A, halogenated polycarbonate, halogenated polystyrene, halogenated benzyl acrylate compound, etc. Can be illustrated. Here, the halogen is generally preferably bromine. Moreover, you may use the said flame retardant in mixture of 2 or more types.

  Any of the above flame retardants can be used to achieve the object of the present invention, but a halogenated aromatic bisimide compound, a halogenated aromatic epoxy compound, a halogenated benzyl acrylate compound, and a halogenated polycarbonate are particularly preferred.

Here, the halogenated aromatic bisimide compound is represented by the following general formula (3), in which R ₁ is a divalent organic group, generally an alkylene group, an arylene group, etc. Desirable is a lower alkylene group. X is at least one or more halogens, advantageously halogen atoms have at least 25% by weight of the molecule, preferably bromine.

  Suitable halogenated aromatic bisimide compounds include lower alkylene bistetrabromophthalimides, particularly N, N'-ethylenebistetrabromophthalimide.

The halogenated aromatic epoxy compound is, for example, a bisphenol A type epoxy compound represented by the following general formula (4), wherein at least one of X in the formula is a halogen and n is a number of 2 or more. It is. The average degree of polymerization n is preferably 2-30, more preferably 10-20.

  Such a halogenated aromatic epoxy compound is, for example, a halogenated bisphenol A diglycidyl ether obtained by condensing a halogenated bisphenol A alone or, if necessary, bisphenol A together with epichlorohydrin. Bisphenol A or a mixture of bisphenol A and bisphenol A can be obtained by heating to 80 to 250 ° C. in the presence of a catalyst.

  As the halogenated epoxy compound, a brominated epoxy compound is preferably used. In addition, as the halogenated epoxy compound, one having a terminal sealed can be used. Bromophenol is preferably used for end-capping, but tribromophenol is particularly preferably used.

  The content of the (C) halogen flame retardant in the polybutylene terephthalate resin composition is preferably 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the (A) polybutylene terephthalate resin. If it is 10 parts by mass or more, it is possible to impart flame retardancy, and if it is 50 parts by mass or less, it is preferable because the decrease in mechanical properties such as tensile strength and bending strength is small. A more preferable content is 20 parts by mass or more and 40 parts by mass or less.

[(D) Antimony compound]
(D) As an antimony compound, antimony pentoxide and sodium antimonate conventionally used as a flame retardant aid and the like can be used. By using the said antimony compound, the heat shock resistance of the resin member in an insert molded object can fully be improved.

  The content of the (D) antimony compound in the polybutylene terephthalate resin composition is preferably 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the (A) polybutylene terephthalate resin. If it is 1 part by mass or more, flame retardancy can be imparted, and if it is 30 parts by mass or less, mechanical properties such as tensile strength and bending strength, and a decrease in heat shock resistance are preferable. A more preferable content is 10 parts by mass or more and 20 parts by mass or less.

[Other ingredients]
Although the essential component contained in the resin member was demonstrated, the other component may be contained in the range which does not impair the effect of this invention.

  Examples of other components include (E) a filler, (F) a plasticizer, (G) an antioxidant, (H) a lubricant, (I) an anti-drip agent, and the like.

  (E) The filler is an additive used for the purpose of improving the mechanical properties of the resin member. Various fillers such as fibrous and non-fibrous (powdered or plate-like) are used depending on the purpose. These fillers may be used in combination of two or more. Moreover, the usage-amount of (E) filler is also determined according to the objective. Moreover, when using (E) filler, it is preferable to use the filler surface-treated with organic processing agents, such as an aminosilane compound and an epoxy compound, in order to improve the interface property of a filler and resin.

  Examples of the plasticizer (F) include ester plasticizers, phosphate ester plasticizers, and epoxy plasticizers. (F) Two or more plasticizers may be used in combination. (F) The amount of plasticizer used is also determined according to the purpose.

  Examples of (G) antioxidants include phenolic antioxidants, phosphite antioxidants, phosphonite antioxidants, thioether antioxidants, and the like. (G) Two or more kinds of antioxidants may be used in combination. Further, the amount of (G) antioxidant used is not particularly limited, and is determined according to the purpose.

  (H) As the lubricant, for example, fatty acid esters, fatty acid amides and the like can be used. Further, (H) a lubricant may be used in combination of two or more. Further, the amount of (H) lubricant used is not particularly limited, and is determined according to the purpose.

  (I) It is preferable to use an anti-dripping agent when it is required to be flame retardant classification “V-0” of UL standard 94. The anti-drip agent is a fluororesin, and suitable fluororesins include homopolymers or copolymers of fluorine-containing monomers such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, and perfluoroalkyl vinyl ether. And a copolymer of the fluorine-containing monomer and a copolymerizable monomer such as ethylene, propylene, and (meth) acrylate. These fluororesins can be used alone or in combination of two or more. (I) The amount of the anti-dripping agent used is also appropriately determined according to the purpose.

<Method for producing thermoplastic resin composition>
The thermoplastic resin composition can be produced by various methods conventionally known as a method for producing a thermoplastic resin composition. A suitable method for producing the polybutylene terephthalate resin composition is, for example, a method in which each component is melt-kneaded into an extruded pellet using a melt-kneader such as a single-screw or twin-screw extruder.

<Insert member>
As the insert member provided in the insert molded body of the present invention, a general member conventionally used for an insert molded body can be used. Specifically, the insert member may be a metal, an inorganic material, or an organic material. Examples thereof include metals such as steel, cast iron, stainless steel, aluminum, copper, gold, silver and brass, thermally conductive ceramics and carbon materials. Moreover, the metal etc. which the metal thin film was formed in the surface can also be used as an insert member. Examples of the metal thin film include a thin film formed by, for example, plating (wet plating, dry plating, etc.). In addition, an insert member may refer to the composite_body | complex which has several metals, resin, etc. as well as single-piece | units, such as a metal and an inorganic material.

  As a material constituting the insert member, a preferable material can be appropriately selected in consideration of, for example, an application.

  The molding method for producing the insert member is not particularly limited. For example, in the case of metal, a method such as die casting, injection molding, press punching, or the like, such as machining using a conventionally known machine tool Thus, an insert member having a desired shape can be manufactured.

<Method of manufacturing insert molded product>
The insert molded body of the present invention can be manufactured by placing the insert member in a mold and injecting the polybutylene terephthalate resin composition into the mold.

  Since the resin member is excellent in heat shock resistance and flame retardancy, the insert molded body of the present invention obtained as described above is suitably used for various applications such as automotive parts and electronic parts. In particular, even when subjected to intense temperature rise and fall, cracks due to heat shock are unlikely to occur, so it is suitably used as an insert molded product for automotive parts.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Material>
(A) Polybutylene terephthalate resin (inherent viscosity 0.69 dL / g, “300FP” manufactured by Wintech Polymer Co., Ltd.)
(B1) Elastomer: Ethylene ethyl acrylate copolymer (“NUC-6570”, manufactured by Nippon Unicar Co., Ltd.), melt viscosity 37 (Pa · s)
(B2) Elastomer: grafted product of ethylene ethyl acrylate copolymer (“Modiper A5300”, manufactured by NOF Corporation), melt viscosity 307 (Pa · s)
(C) Halogen flame retardant: Halogenated epoxy oligomer flame retardant ("F3100", manufactured by Bromochem Far East Co., Ltd.)
(D1) Antimony trioxide (“PATOX-M”, manufactured by Nippon Seiko Co., Ltd.)
(D2) Antimony pentoxide ("Sun Epoch NA1030", manufactured by Nippon Chemical Industry Co., Ltd.)
(E) Filler: Glass fiber (“CS3J-948”, manufactured by Nitto Boseki Co., Ltd.)
(F) Plasticizer: pyromellitic acid ester (produced by Adeka Sa homogenizer UL100, Ltd. ADEKA)
(G) Antioxidant: tetrakis [methylene-3 (3,5-di -tert- butyl - 4-hydroxyphenyl) propionate] methane ( "IRGANOX1010" bi chromatography er science fiction Japan Ltd.)
(H) Lubricant: Polyglycerin fatty acid ester (I) Anti-dripping agent: Polytetrafluoroethylene ("Fluon CD-076", manufactured by Asahi Glass Co., Ltd.)

  The components shown in Table 1 were dry blended at the ratio (parts by mass) shown in Table 1, and using a twin-screw extruder (TEX-30 manufactured by Nippon Steel Works), the cylinder temperature was 260 ° C. and the discharge amount. The mixture was melt-kneaded under conditions of 15 kg / hr and a screw rotation speed of 150 rpm to produce a pellet of a thermoplastic resin composition. Test pieces are prepared using the obtained pellets, heat shock resistance, tensile strength (TS), tensile elongation (TE), bending strength (FS), bending elastic modulus (FM), fluidity, flame retardancy Evaluated. Specifically, the evaluation was performed by the following method.

<Heat shock resistance>
Insert molding so that the minimum thickness of some resin parts is 1 mm in a mold that inserts an iron core 18 mm long, 18 mm wide, 30 mm high inside a prism with a length of 22 mm, a width of 22 mm, and a height of 51 mm. The body was injection molded to produce a test piece. The process of heating the obtained insert molded body to 140 ° C. after heating it at 140 ° C. for 1 hour 30 minutes, cooling to −40 ° C., cooling it for 1 hour 30 minutes, and then further raising the temperature to 140 ° C. A heat shock resistance test for cycles was performed, and the number of cycles until cracks occurred in the molded product was measured. The number of cycles was defined as the number of failures, and the same test was performed 5 times to obtain the average number of failures. Table 1 shows the average number of failures.

<Mechanical properties>
Based on ISO527-1,2, the tensile strength (TS) and the tensile elongation (TE) were measured. The measurement results are shown in Table 1.

  Moreover, based on ISO178, the bending strength (FS) and the bending elastic modulus (FM) were measured. The measurement results are shown in Table 1.

  Further, Charpy impact strength (Charpy) was measured according to ISO 179 / 1eA. The measurement results are shown in Table 1.

<Fluidity>
Using an injection molding machine (S2000i100B manufactured by FANUC CORPORATION), a cylinder test was performed at a cylinder temperature of 260 ° C., a mold temperature of 60 ° C., and an injection speed of 70 mm / sec. The flow length at 100 MPa and 125 MPa was measured. The results are shown in Table 1.

<Flame retardance>
The test piece (0.75 mm thickness) was subjected to UL-94 standard vertical combustion test by Underwriters Laboratories. The results are shown in Table 1.

  As can be confirmed from Table 1, by using a specific antimony compound and an elastomer in combination, an insert molded body having a resin member excellent in flame retardancy and heat shock resistance is obtained.

  Moreover, it was confirmed from the comparison with Example 1, 2 and Example 3 that the fluidity | liquidity at the time of shaping | molding of the thermoplastic resin composition which comprises a resin member increases by changing the kind of elastomer.

Claims (3)

An insert member;
A resin member composed of a polybutylene terephthalate resin composition containing (A) a polybutylene terephthalate resin, (B) an elastomer, (C) a halogen-based flame retardant, and (D) an antimony compound,
The (C) halogen flame retardant is at least one selected from a halogenated aromatic epoxy compound, a halogenated benzyl acrylate compound, and a halogenated polycarbonate,
Wherein (D) an antimony compound, five Ri Ah with antimony oxide or sodium antimonate, the (D) the content of the antimony compound is the (A) 30 parts by mass or more 10 parts by weight per 100 parts by weight polybutylene terephthalate resin Insert molded body that is less than the part . The (B) elastomer includes at least one or more selected from olefin-based elastomers, styrene-based thermoplastic elastomers, and core-shell elastomers mainly composed of acrylic rubber,
The insert molding according to claim 1, wherein the content of the (B) elastomer in the polybutylene terephthalate resin composition is 10 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the (A) polybutylene terephthalate resin. body. The insert molded article according to claim 1 or 2 , wherein the melt viscosity of the (B) elastomer is 10 Pa · s or more and 200 Pa · s or less, measured under conditions of 260 ° C and a shear rate of 1000 sec ^-1 in accordance with ISO 11443. .