JP2019166759A - Resin composite molded body and manufacturing method of resin composite molded body - Google Patents

Abstract

To provide a resin composite molded body in which a member consisting a PBT resin composition high in bond strength between dissimilar materials, and excellent in heat resistance, chemical resistance, electronic properties, and mechanical properties, and a member consisting of a specific thermoplastic elastomer resin composition are bound.SOLUTION: There is provided a resin composite molded body in which a member consisting of a polybutylene terephthalate resin composition (X), and a member consisting of a thermoplastic elastomer resin composite (Y) are bound, the polybutylene terephthalate resin composition (X) contains a non-crystalline resin (x2) of 0.5 to 100 pts.mass based on 100 pts.mass of the polybutylene terephthalate resin composition (X), the thermoplastic elastomer resin composite (Y) contains a thermoplastic elastomer resin (y1) containing a hard segment (a1) consisting of a crystalline aromatic polyester unit, and a soft segment (a2) consisting of an aliphatic polyether unit and/or an aliphatic polyester unit as constitutional components, and the melting point is less than 210°C.SELECTED DRAWING: None

Description

  The present invention relates to a resin composite molded body in which a member made of a polybutylene terephthalate resin composition and a member made of a thermoplastic elastomer resin composition are joined, and a method for producing the resin composite molded body.

  Polybutylene terephthalate resin (hereinafter sometimes abbreviated as PBT resin), which is a thermoplastic hard resin, is excellent in various properties such as heat resistance, chemical resistance, electrical properties, mechanical properties, and molding processability. It is used for many purposes. Specific applications include various automotive electrical parts (various control units, various sensors, ignition coils, etc.), connectors, switch parts, relay parts, coil parts, and the like.

  Among thermoplastic elastomer resins, polyester-based thermoplastic elastomers that have a hard segment composed of crystalline aromatic polyester units and a soft segment composed of aliphatic polyether or aliphatic polyester are vibration-absorbing, impact-resistant and elastic-recoverable. Because of its excellent mechanical properties such as flexibility, low temperature properties, and high temperature properties, it is widely used in the fields of automotive materials, electrical / electronic components, sheets, films, fibers and other industrial materials.

  In recent years, there are various required characteristics for various applications, and it is often impossible to achieve with a single material. There are many cases where a resin composite molded body by bonding with another resin can be put into practical use by satisfying the required performance, and a material that can be bonded with another resin is required. In particular, a resin composite molded body of a thermoplastic hard resin and a thermoplastic elastomer resin can achieve both properties such as strength and rigidity, and properties such as vibration absorption and grip properties, packing, and waterproof sealing properties.

  In the past, bonding methods such as adhesives, screwing, hot plate welding, and ultrasonic welding have been used to produce resin composite molded bodies. However, some problems have been pointed out regarding these joining methods. For example, when an adhesive is used, a process time loss until the adhesive is cured and an environmental load become a problem. Also, screwing increases the labor and cost of fastening, and hot plate welding or ultrasonic welding may cause damage to the product due to heat or vibration. On the other hand, a method of injection fusion using injection molding is preferably used from the viewpoint of high productivity because there is little damage to the product due to heat and vibration accompanying welding.

  As a formation of a resin composite molded body by injection fusion, for example, Patent Document 1 discloses a resin composite molded body made of a polyamide resin composition containing a modified polyester thermoplastic elastomer and a polyester thermoplastic elastomer. However, since the strength of the polyamide resin composition decreases due to moisture absorption, the practicality is insufficient. In addition, a resin composite molded body made of a polyester-based thermoplastic elastomer containing an ABS resin and a PBT resin is disclosed in Patent Document 2, and a resin composite molded body made of a PBT resin, a polycarbonate resin, or an ABS resin and a polyester-based thermoplastic elastomer is disclosed in Patent Document 2. Patent Document 3 discloses a laminate composed of a PBT resin or a polyethylene terephthalate resin and a polyester-based thermoplastic elastomer containing an acrylic ester or methacrylic ester, and Reference 4 discloses a laminate comprising a PBT resin or a polyethylene terephthalate resin and an aromatic vinyl compound. A laminate comprising a polyester-based thermoplastic elastomer containing a diene compound is disclosed.

JP-A-2005-008696 JP 2010-001363 A JP 2004-143349 A JP2011-219526A JP 2011-256252 A

  However, the resin composite molded articles described in Patent Documents 1 to 4 have a problem that the bonding strength is not sufficient. The present invention has been achieved as a result of intensive investigations aimed at solving problems in the prior art. That is, the present invention provides a member made of a PBT resin composition and a member made of a specific thermoplastic elastomer resin composition, which has high bonding strength between different materials and is excellent in heat resistance, chemical resistance, electrical properties, and mechanical properties. An object of the present invention is to provide a resin composite molded body bonded to each other.

  In order to achieve the above object, the resin composite molded body of the present invention is a resin in which a member made of a polybutylene terephthalate resin composition (X) and a member made of a thermoplastic elastomer resin composition (Y) are joined. The composite molded body, wherein the polybutylene terephthalate resin composition (X) contains 0.5 to 100 parts by mass of an amorphous resin (x2) with respect to 100 parts by mass of the polybutylene terephthalate resin (x1). The thermoplastic elastomer resin composition (Y) comprises a hard segment (a1) composed of crystalline aromatic polyester units and a soft segment (a2) composed of aliphatic polyether units and / or aliphatic polyester units. It comprises a thermoplastic elastomer resin (y1) as a component and has a melting point of less than 210 ° C.

  In the resin composite molded body of the present invention, the polybutylene terephthalate resin composition (X) of the above-mentioned polybutylene terephthalate resin composition (X) is made of at least one resin selected from styrene resins and polycarbonate resins. It is characterized by including.

  In the resin composite molded body of the present invention, in the above invention, the hard segment (a1) of the thermoplastic elastomer resin (y1) is derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol. It comprises polybutylene terephthalate units and polybutylene isophthalate units derived from isophthalic acid and / or dimethylisophthalate and 1,4-butanediol.

  In the resin composite molded body of the present invention, the soft segment (a2) of the thermoplastic elastomer resin (y1) is an ethylene oxide addition of poly (tetramethylene oxide) glycol and / or poly (propylene oxide) glycol. And / or a copolymer of ethylene oxide and tetrahydrofuran.

  Moreover, the manufacturing method of the resin composite molded body of the present invention is a method of manufacturing the above-mentioned resin composite molded body of the present invention, wherein the polybutylene terephthalate resin composition (X) or the thermoplastic elastomer resin composition (Y ) Is placed in a mold, and a molten resin composition different from the resin composition constituting the member placed in the mold is injection-fused and joined.

  Moreover, the manufacturing method of the resin composite molded body of the present invention is the above-described manufacturing method, wherein the member disposed in the mold is a member made of a polybutylene terephthalate resin composition (X), A molten resin composition different from the resin composition constituting the arranged member is a thermoplastic elastomer resin composition (Y).

  The present invention relates to a member made of a PBT resin composition and a specific thermoplastic elastomer resin composition, which has high bonding strength between different types of materials and is excellent in heat resistance, chemical resistance, electrical characteristics, and mechanical characteristics. It is possible to provide a resin composite molded body in which a member made of is bonded.

Illustration of L-shaped molded product Illustration of inverted T-shaped mold Diagram showing tensile test direction of composite molded product

  Hereinafter, the present invention will be described in detail. The present invention is a resin composite molded body in which a member made of a polybutylene terephthalate resin composition (X) and a member made of a thermoplastic elastomer resin composition (Y) are joined.

(1) Member made of polybutylene terephthalate resin composition (X) Polybutylene terephthalate (PBT) resin (x1) of polybutylene terephthalate (PBT) resin composition (X) is terephthalic acid or its ester-forming derivative and 1 , 4-butanediol or an ester-forming derivative thereof as a main component, a polymer obtained by a usual polymerization method such as polycondensation reaction, etc., in a range that does not impair the characteristics, for example, about 20 parts by weight or less, etc. The copolymer component may be included. Preferred examples of these polymers and copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene. (Terephthalate / Naphthalate), poly (butylene / ethylene) terephthalate and the like may be mentioned, and these may be used alone or in combination of two or more.

  The polybutylene terephthalate resin (x1) used in the present invention is not particularly limited as long as it can be melt-kneaded. From the viewpoint of fluidity, the melt flow rate (MFR) when measured at 250 ° C. and 1000 gf is 1 g / 10. It is preferably from min to 60 g / 10 min, and more preferably from 5 g / 10 min to 60 g / 10 min.

  The manufacturing method of polybutylene terephthalate resin (x1) used by this invention is not specifically limited, A well-known polycondensation method, ring-opening polymerization method, etc. can be used. Either a batch polymerization method or a continuous polymerization method may be used, and any of a method through a transesterification reaction and a polycondensation reaction and a method by a polycondensation reaction by direct polymerization (direct polymerization method) can be applied. The continuous polymerization method is preferable in that the amount of carboxyl end groups can be reduced and the effect of improving fluidity is increased, and the direct polymerization method is preferable in terms of cost. In order to effectively advance the esterification reaction or transesterification reaction and polycondensation reaction, it is preferable to add a catalyst during these reactions.

  Specific examples of the catalyst include methyl ester of titanic acid, tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester, benzyl ester. , Tolyl esters, or mixed esters thereof, such as organic titanium compounds, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexyldistin oxide, didodecyltin oxide, triethyltin hydroxide, triethyltin Phenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyl Zodichloride, Tributyltin chloride, Dibutyltin sulfide, Butylhydroxytin oxide, Tin compounds such as alkylstannic acid such as methylstannic acid, ethylstannic acid, butylstannic acid, zirconia compounds such as zirconium tetra-n-butoxide, And antimony compounds such as antimony trioxide and antimony acetate. Two or more of these catalysts can be used in combination.

  Among these polymerization reaction catalysts, an organic titanium compound and a tin compound are preferable from the viewpoint of the amount of carboxyl groups of polybutylene terephthalate, and a tetra-n-butyl ester of titanic acid is more preferably used. The addition amount of the polymerization reaction catalyst is preferably in the range of 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the polybutylene terephthalate resin (x1).

  The amount of carboxyl groups of the polybutylene terephthalate resin (x1) used in the present invention is not particularly limited, but is 10 eq / t or more from the viewpoint of improving injection weldability with the thermoplastic elastomer resin composition (Y). Is preferred. Here, the amount of carboxyl groups of the polybutylene terephthalate resin is a value measured by dissolving the polybutylene terephthalate resin in an o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide.

  The non-crystalline resin (x2) of the PBT resin composition (X) generally has glass-like properties and does not show a clear melting point when heated, but only shows a glass transition temperature.

  Examples of the amorphous resin include polycarbonate resin, polyphenylene ether, polyarylate, polysulfone, polyethersulfone, polyetherimide, polyamideimide, and styrene resin. Among these, polycarbonate resins and styrene resins are preferable from the viewpoint of compatibility with the polybutylene terephthalate resin (x1).

  The styrene resin used as the amorphous resin (x2) of the PBT resin composition (X) is arbitrary as long as it is a polymer containing a styrene structural unit, that is, an aromatic vinyl unit.

  For example, (ii) conjugated diene rubbers such as polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, aromatic vinyl such as styrene, α-methylstyrene, dimethylstyrene, vinyltoluene, and acrylonitrile, methacrylonitrile. (C) ABS resin obtained by graft polymerization of other polymerizable monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate, if necessary, AS resin by copolymerization of aromatic vinyl and vinyl cyanide exemplified in (i), (c) HI (high impact) -polystyrene resin by copolymerization of conjugated diene rubber and aromatic vinyl as exemplified above, (d) Illustrated fragrance Polystyrene resin comprising a vinyl, a block copolymer of (e) above aromatic vinyl and diene.

  As the above (e) block copolymer, the structural unit may be either a hydrogenated diene or an unhydrogenated diene. Such dienes include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, 1,3-butadiene, 1,3-pentadiene, and the like. One or two or more hydrogenated or non-hydrogenated conjugated dienes of which 1,3-butadiene and isoprene can be preferably used as non-hydrogenated ones. Specific examples of block copolymers include hydrogenated Examples thereof include unhydrogenated SBS resin (styrene / butadiene / styrene triblock copolymer) and hydrogenated or unhydrogenated SIS resin (styrene / isoprene / styrene triblock copolymer). A styrene triblock copolymer (SEBS resin) is preferably used.

  Further, from the viewpoint of improving the compatibility between the polybutylene terephthalate resin (x1) and the styrene resin and improving the injection weldability with the thermoplastic elastomer resin composition (Y), an epoxy group-containing vinyl copolymer is provided. It is desirable to use

  Furthermore, examples of the epoxy group of the epoxy group-containing styrenic resin include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like. Among them, glycidyl methacrylate is preferable.

  The polycarbonate resin used as the non-crystalline resin (x2) is obtained by a reaction between a dihydroxy compound and a carbonate such as phosgene or diphenyl carbonate. The dihydroxy compound may be an alicyclic compound or the like, but is preferably an aromatic compound (particularly a bisphenol compound).

  Examples of the bisphenol compound include bisphenols [for example, bis (hydroxyaryl) C1-6 alkane; bis (hydroxyaryl) C4-10 cycloalkane; 4,4′-dihydroxydiphenyl ether; 4,4′-dihydroxydiphenylsulfone; 4'-dihydroxydiphenyl sulfide; 4,4'-dihydroxydiphenyl ketone and the like]. Preferred polycarbonate-based resins include bisphenol A type polycarbonate.

  The amorphous resin (x2) used in the present invention is 0.5 to 100 parts by mass when the polybutylene terephthalate resin (x1) is 100 parts by mass. When the content is less than 0.5 parts by mass, the resin composite molded body in which the member made of the polybutylene terephthalate resin composition (X) and the member made of the thermoplastic elastomer resin composition (Y) are joined Injection weld strength is not fully developed. Moreover, when the content exceeds 100 mass parts, the heat resistance of PBT resin composition (X) will fall. Furthermore, it is preferable to contain 3.0 mass parts or more from the point of injection welding strength, and it is more preferable to contain 5.0 mass parts or more. Moreover, it is preferable to contain 50.0 mass parts or less, and it is more preferable to comprise 20.0 mass parts or less.

  In the polybutylene terephthalate resin composition (X) of the present invention, other resin components, reinforcing fibers, inorganic fillers, elastomers, flame retardants, mold release agents, phosphorus-based antiresistants are included within the range not impairing the effects of the present invention. Conventional additives such as an oxidizing agent, a stabilizer, an ultraviolet absorber, a colorant, and a lubricant can be added.

  As the reinforcing fiber, glass fiber, carbon fiber, metal fiber, organic fiber (nylon, polyester, aramid, polyphenylene sulfide, liquid crystal polymer, acrylic, etc.) and the like can be used. The mechanical strength and heat resistance can be further improved by the reinforcing fiber. One or more reinforcing fibers can be used in combination, but most preferably comprises glass fibers.

  Specific examples of the glass fiber include chopped strand type and roving type glass fiber, and are made of a silane coupling agent such as an aminosilane compound or an epoxysilane compound and / or acrylic acid such as urethane or acrylic acid / styrene copolymer. Copolymers, copolymers of maleic anhydride such as methyl acrylate / methyl methacrylate / maleic anhydride copolymer, one or more epoxy compounds such as vinyl acetate, bisphenol A diglycidyl ether and novolac epoxy compounds, etc. A glass fiber treated with a sizing agent containing is preferably used. The fiber diameter of the reinforcing fiber is usually preferably in the range of 1 to 30 μm. From the viewpoint of dispersibility of the glass fiber in the resin, the lower limit is preferably 5 μm. From the viewpoint of mechanical strength, the upper limit is preferably 15 μm.

  Content of the reinforced fiber in this invention is 10-60 weight part with respect to 100 mass parts of polybutylene terephthalate resin (x1). When the content of the reinforcing fiber is less than 10 parts by weight, the mechanical properties of the resin composition are inferior, and when it exceeds 60 parts by weight, the fluidity of the resin composition decreases, which is not preferable.

  In addition, as inorganic fillers, general inorganic fibers such as ceramic fibers, boron fibers, potassium titanate fibers, asbestos, calcium carbonate, highly dispersible silicate, alumina, aluminum hydroxide, talc, clay, mica, glass flakes, Glass powder, glass beads, quartz powder, silica sand, wollastonite, carbon black, barium sulfate, calcined gypsum, silicon carbide, alumina, boron nitrite, silicon nitride, and other granular materials, plate-like inorganic compounds, whiskers, etc. included. These inorganic fillers can be used alone or in combination of two or more as required.

  Elastomers include polyethylene terephthalate / poly (tetramethylene oxide) glycol block copolymer, polyethylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / poly (tetramethylene oxide) glycol block copolymer. Polymer, Polybutylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, Polybutylene terephthalate / decane dicarboxylate / poly (tetramethylene oxide) glycol block copolymer, Polybutylene terephthalate / polyethylene adipate block Copolymer, polybutylene terephthalate / polybutylene adipate block copolymer, polybutylene terephthalate Polyester-elastomer copolymer such as ethylene-poly-ε-caprolactone block copolymer, ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / pentene-1 copolymer, ethylene / propylene / butene-1 copolymer Polymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / 1,4-hexadiene copolymer, ethylene / propylene / dicyclopentanediene copolymer, ethylene / glycidyl methacrylate copolymer Olefin elastomers such as polyesters, urethane elastomers obtained by reacting polyester or polyether polyols with isocyanate compounds, crystalline polyamides such as polyamides 6, 11, 12 and polyoxyethylene, polyoxypropylene, polytetra Polyamide elastomers such as polyethers such as methylene glycol and aliphatic polyesters such as polybutylene adipate, ionomer elastomers obtained by cross-linking the molecular chains of α-olefin and unsaturated carboxylic acid copolymers with metal ions, Copolymers of ethylene and ethyl acrylate, ethylene / methyl acrylate copolymers, ethylene / acrylic acid ester copolymers such as ethylene / butyl acrylate copolymers, ethylene / vinyl acetate copolymers, core shell rubbers, and these These can be used alone or 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 thereof 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.

  Examples of the inorganic flame retardant used in the present invention include magnesium hydroxide hydrate, aluminum hydroxide hydrate, antimony trioxide, antimony pentoxide, sodium antimonate, hydroxytin zinc oxide, zinc stannate, metastannic acid, Examples thereof include tin oxide and zinc borate. Of these, antimony trioxide is preferable.

  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, etc., 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 A benzotriazole ultraviolet absorber represented by a condensate of riazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionate and polyethylene glycol can be given.

  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] siloxa It can also 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 member made of the polybutylene terephthalate resin composition (X) of the present invention can be molded by various methods such as injection molding and extrusion molding. Among these, processing by injection molding or injection fusion is preferable in terms of improving airtightness.

(2) A member comprising the thermoplastic elastomer resin composition (Y) The thermoplastic elastomer resin composition (Y) used in the present invention comprises a hard segment (a1) comprising a crystalline aromatic polyester unit, and an aliphatic polyether. The soft segment (a2) composed of units and / or aliphatic polyester units comprises the thermoplastic elastomer resin (y1) as a constituent component and has a melting point of less than 210 ° C.

  The hard segment (a1) of the thermoplastic elastomer resin (y1) used in the present invention is a polyester formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.

  The thermoplastic elastomer resin (y1) used in the present invention has a melting point of less than 210 ° C. In the present invention, the melting point of the thermoplastic elastomer resin (y1) is measured by a differential scanning calorimeter (DSC), which means that the measured melting point is below 210 ° C. When the thermoplastic elastomer resin (y1) having a melting point of 210 ° C. or higher is used, the bonding strength with the polybutylene terephthalate resin composition (X) is lowered.

  Specific examples of the aromatic dicarboxylic acid mainly constituting the hard segment (a1) of the thermoplastic elastomer resin (y1) include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-monodicarboxylic acid, naphthalene-2,7. -Dicarboxylic acid, anthracene dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, sodium 3-sulfoisophthalate, etc. .

  Furthermore, ester-forming derivatives of aromatic dicarboxylic acids such as lower alkyl esters, aryl esters, carbonates, and acid halides can of course be used equally. In the present invention, the aromatic dicarboxylic acid is mainly used. A part of the aromatic dicarboxylic acid is used as an alicyclic ring such as 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, or 4,4′-dicyclohexyldicarboxylic acid. Or aliphatic dicarboxylic acids such as adipic acid, succinic acid, oxalic acid, sebacic acid, dodecanedioic acid, and dimer acid. Furthermore, ester-forming derivatives of dicarboxylic acids such as lower alkyl esters, aryl esters, carbonates, and acid halides can of course be used equally.

  The aromatic dicarboxylic acid or its ester-forming derivative is preferably terephthalic acid, dimethyl terephthalate, isophthalic acid, or dimethyl isophthalate, and more preferably terephthalic acid and isophthalic acid. Furthermore, it is also preferable to use two or more of the above dicarboxylic acids, and examples thereof include combinations of terephthalic acid and isophthalic acid, terephthalic acid and dodecanedioic acid, terephthalic acid and dimer acid, and the like. By using two or more dicarboxylic acid components, the crystallinity of the hard segment (a1) can be lowered, flexibility can be imparted, and thermal adhesiveness with other thermoplastic resins is improved. .

  Next, the diol that forms an ester with the aromatic dicarboxylic acid or the like will be described. Specific examples of the diol used in the present invention include diols having a molecular weight of 400 or less, such as 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol and the like. Aliphatic diols such as aliphatic diol, 1,1-cyclohexanedimethanol, 1,4-dicyclohexanedimethanol, tricyclodecane dimethanol, and xylylene glycol, bis (p-hydroxy) diphenyl, bis (p- Hydroxy) diphenylpropane, 2,2′-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxy) Ethoxy) phenyl Cyclohexane, 4,4'-dihydroxy -p- terphenyl, and 4,4'-dihydroxy -p- Quarter aromatic diols such as phenyl are preferred. Such diols can also be used in the form of ester-forming derivatives, such as acetyl compounds and alkali metal salts. Two or more of these diol components and derivatives thereof may be used in combination.

  Preferred examples of the hard segment (a1) include those composed of polybutylene terephthalate units derived from terephthalic acid or dimethyl terephthalate and 1,4-butanediol, isophthalic acid or dimethyl isophthalate and 1,4-butanediol, Those composed of polybutylene isophthalate units derived from the above and copolymers thereof are preferred.

  The soft segment (a2) of the thermoplastic elastomer resin (y1) used in the present invention is an aliphatic polyether and / or an aliphatic polyester. Aliphatic polyethers include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (trimethylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, and a combination of ethylene oxide and propylene oxide. And a polymer, an ethylene oxide addition polymer of poly (propylene oxide) glycol, a copolymer glycol of ethylene oxide and tetrahydrofuran, and the like.

  Examples of the aliphatic polyester include poly (ε-caprolactone), polyenanthlactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate. As these soft segments (a2), from the elastic properties of the resulting thermoplastic elastomer resin (y1), poly (tetramethylene oxide) glycol, poly (propylene oxide) glycol ethylene oxide adduct, ethylene oxide and tetrahydrofuran copolymer glycol , Poly (ε-caprolactone), polybutylene adipate, and polyethylene adipate are preferred. Among these, poly (tetramethylene oxide) glycol, ethylene oxide adduct of poly (propylene oxide) glycol, and ethylene oxide / tetrahydrofuran The use of polymer glycols is preferred. The number average molecular weight of these soft segments (a2) is preferably about 300 to 6000 in the copolymerized state.

  In the thermoplastic elastomer resin (y1) used in the present invention, the copolymerization amount of the hard segment (a1) and the soft segment (a2) is usually 5 to 80% by mass of the hard segment (a1) and the soft segment (a2). The hard segment (a1) is preferably 10 to 75% by mass, and the soft segment (a2) is preferably 25 to 90% by mass.

  The thermoplastic elastomer resin (y1) used in the present invention can be produced by a known method. Specific examples include ester-forming derivatives such as lower alcohol diesters of aromatic dicarboxylic acids, excess diol (low molecular weight glycol) and soft low-melting polymer segment (a2) component in the presence of a catalyst. A method of reacting and polycondensing the resulting reaction product, and an esterification reaction of the aromatic dicarboxylic acid, an excess amount of the diol and the soft low-melting polymer segment (a2) component in the presence of a catalyst, and the resulting reaction product Any method such as a polycondensation method may be used.

  Examples of such commercially available thermoplastic elastomer resin (y1) include “Hytrel” manufactured by Toray DuPont Co., Ltd.

  In addition, other resin components, reinforcing fibers, inorganic fillers, and various additives may be added to the thermoplastic elastomer resin composition (Y) of the present invention as long as the object of the present invention is not impaired. it can. For example, known crystal nucleating agents such as talc and molding aids such as lubricants, hindered phenols, phosphites, thioethers, antioxidants that are aromatic amine compounds, UV absorbers, titanium oxide, carbon black, etc. UV blockers, benzophenone-based, benzotriazole-based, hindered amine-based light-proofing agents, hydrolysis-proofing agents, colorants such as pigments and dyes, antistatic agents, conductive agents, flame retardants, reinforcing agents, fillers, plastics An agent, a release agent, a phosphorus-based antioxidant, a stabilizer and the like can be optionally contained.

  The member made of the thermoplastic elastomer resin composition (Y) of the present invention can be molded by various methods such as injection molding and extrusion molding. Of these, processing by injection molding or injection welding is preferable in terms of enhancing airtightness. In the present invention, there is no particular limitation on the method for joining the member made of the polybutylene terephthalate resin composition (X) and the member made of the thermoplastic elastomer resin composition (Y), and the method for heat joining, injection molding or extrusion molding. And the like. Here, as a method of heat bonding, for example, a method of heat bonding by irradiating a laser beam, a method of heat bonding with a hot plate, a method of heat bonding using a high frequency, a heat press by heating a metal press or the like And the like.

  As a specific method for heat bonding, the member made of the thermoplastic elastomer resin composition (Y) and the member made of the polybutylene terephthalate resin composition (X) are stacked so as to contact each other, and first, the thermoplastic elastomer resin composition (Y The member made of the thermoplastic elastomer resin composition (Y) is heated and melted at the joining portion of the member made of the material with the member made of the polybutylene terephthalate resin composition (X). The resin composite molded body can be obtained by bonding to a member made of) and then cooling. Further, it is preferable to pressurize the joint when joining, since joint strength and airtightness are increased.

  In addition, a resin composition that constitutes a member disposed in the injection mold by inserting a member made of the polybutylene terephthalate resin composition (X) or the thermoplastic elastomer resin composition (Y) into an injection mold. A method (two-color molding) in which a melted resin member different from a product is joined by injection fusion (two-color molding) is less preferable because of less product damage due to heat caused by welding and high productivity.

  Furthermore, the resin composite molded body in which the member made of the polybutylene terephthalate resin composition (X) and the member made of the thermoplastic elastomer resin composition (Y) are joined is a member disposed in the mold. Is a member made of polybutylene terephthalate resin composition (X), and a molten resin composition different from the resin composition constituting the member disposed in the mold is a thermoplastic elastomer resin composition (Y). More preferably.

  The method of opening the injection mold and inserting the member made of the polybutylene terephthalate resin composition (X), closing the mold, and injecting and joining the thermoplastic elastomer resin composition (Y) is performed at a low temperature. Welding is possible, product damage due to heat is less, and this is particularly preferable from the viewpoint of high productivity.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of these examples. The present invention can be implemented with appropriate modifications within the scope of the gist of the present invention.

  The effects of the present invention will be described below with reference to examples. In the examples, “%” and “part” are based on mass unless otherwise specified. The physical properties shown in the examples were measured as follows.

[PBT physical property evaluation method]
(1) Tensile properties Using the resin compositions obtained in the examples and comparative examples, test pieces were obtained by injection molding at a cylinder temperature of 260 ° C and a mold temperature of 80 ° C, and conformed to ISO527-1,2. The tensile strength was measured.

(2) Flexural modulus Using the resin compositions obtained in the examples and comparative examples, a test piece was obtained by injection molding at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C., and in accordance with ISO 178, flexural elasticity. Rate was evaluated.

(3) Heat resistance Using the resin composition obtained in each example and comparative example, a test piece was obtained by injection molding at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C., and conformed to ISO 75-1,2. The deflection temperature under load at a flatwise and 1.80 MPa stress was measured.

[Surface hardness (Durometer D)]
The thermoplastic elastomer resin composition (Y) was measured at 23 ° C. according to JIS K7215-1986.

[Mechanical properties]
The thermoplastic elastomer resin composition (Y) was measured for tensile strength at break, tensile elongation at break, and tensile modulus at 23 ° C. according to JIS K7113-1995.

[Heat adhesion strength]
First, using a polybutylene terephthalate resin composition (X) pellet dried at 120 ° C. for 3 hours, an L-shaped molded product having a width of 20 mm, a length of 60 mm, and a thickness of 1 mm shown in FIG. It was produced by injection molding under the condition of a mold temperature of 50 ° C. (B) in FIG. 1 is a view seen from the side, and (b) is a view seen from above. The molded L-shaped molded product (A) was set in an inverted T-shaped mold shown in FIG. Thereafter, the thermoplastic elastomer resin composition (Y) pellets dried at 80 ° C. for 3 hours are subjected to a cylinder temperature of 230 ° C., 250 ° C., a mold temperature of 50 ° C., an injection speed of 30 mm / second, and a minimum holding pressure required for filling + 2 MPa. The molded article (B) made of the thermoplastic elastomer resin composition and the above-mentioned molded article (A) were joined to each other by injection molding at a holding pressure of 2 to obtain a composite molded article. After leaving this at 23 ° C. and 50% RH for 1 day, a tensile test was carried out in the direction shown in FIG. 3 under the condition of a strain rate of 50 mm / min, and the obtained maximum tension was measured as the heat fusion adhesive force. .

[Reference example]
[Polybutylene terephthalate resin composition (X)]
(A) Thermoplastic polyester resin <x1> Polybutylene terephthalate resin, “1100S” manufactured by Toray Industries, Inc. was used.

  As <x2-1> acrylonitrile / styrene copolymer, suspension polymerization of styrene and acrylonitrile was performed to prepare a bead-like modified vinyl copolymer. The weight ratio of each component of acrylonitrile / (B-2) styrene copolymer was 24/76 parts by weight, and the reduced viscosity was 0.79.

  <X2-2> Acrylonitrile / styrene / glycidyl methacrylate copolymer. Styrene, acrylonitrile, and glycidyl methacrylate were subjected to suspension polymerization to prepare a bead-like modified vinyl copolymer. The weight ratio of each component of acrylonitrile / styrene / glycidyl methacrylate copolymer is 23.9 / 75.8 / 0.3% by weight, and the reduced viscosity is 0.49.

  <X2-3> Polycarbonate resin “Taflon” A-1900 (viscosity average molecular weight: 19000) manufactured by Idemitsu Petrochemical Co., Ltd. was used.

  <X3-1> Chopped strand glass fiber having a fiber diameter of about 13 μm, “T-187” manufactured by Nippon Electric Glass Co., Ltd. was used.

  <X4-1> (C) As a glycidyl group-containing copolymer comprising an α-olefin and a glycidyl ester of α, β-unsaturated acid as a copolymerization component, an ethylene / glycidyl methacrylate copolymer (“ROTADER” manufactured by ARKEMA) ( (Registered trademark) AX8840 (trade name), MFR: 5 g / 10 min (190 ° C., 2.16 kgf)).

[Thermoplastic elastomer resin composition (Y-1)]
348 parts of terephthalic acid, 100 parts of isophthalic acid, 390 parts of 1,4-butanediol and 500 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400, and a helical ribbon stirring blade with 0.2 parts of titanium tetrabutoxide The reaction vessel provided was charged. The esterification reaction was carried out while heating at 190 to 225 ° C. for 3 hours and distilling the reaction water out of the system. After adding 0.5 part of N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) (BASF) to the reaction mixture, the temperature was raised to 245 ° C. Then, the pressure in the system was reduced to 27 Pa over 50 minutes, and polymerization was carried out for 2 hours and 45 minutes under the conditions. The obtained polymer (thermoplastic elastomer resin (y1-1)) is discharged into water in the form of strands, cutting is performed, and a thermoplastic elastomer resin composition (in which the thermoplastic elastomer resin (y1-1) is blended) ( Y-1) It was set as the pellet.

  The thermoplastic elastomer resin (y1-1) thus obtained has a melt viscosity index (MFR) (measured according to ASTM D1238-1990) measured at a temperature of 200 ° C. and a load of 2160 g, 13 g / 10 min, and a melting point of 163 The surface hardness measured by durometer D of the thermoplastic elastomer resin composition (Y-1) at 40 ° C. was 40D.

[Thermoplastic elastomer resin composition (Y-2)]
50.5 parts of terephthalic acid, 43.8 parts of 1,4-butanediol and 35.4 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400, 0.04 part of titanium tetrabutoxide and mono-n-butyl -An esterification reaction was performed while charging 0.02 part of monohydroxytin oxide and a reaction vessel equipped with a helical ribbon type stirring blade, heating at 190 to 225 ° C for 3 hours, and allowing reaction water to flow out of the system. After adding 0.2 parts of tetra-n-butyl titanate to the reaction mixture and adding 0.05 parts of a hindered phenol antioxidant (“Irganox 1098” manufactured by Ciba Geigy), the temperature was raised to 245 ° C. Then, the pressure in the system was reduced to 27 Pa over 50 minutes, and polymerization was performed for 1 hour and 50 minutes under the conditions.

The obtained polymer was discharged into water in the form of a strand and pelletized by cutting.
The obtained pellets were charged into a rotatable reaction vessel, the pressure in the system was reduced to 27 Pa, and solid phase polymerization was carried out by rotating at 170 to 180 ° C. for about 24 hours. A thermoplastic elastomer resin composition (Y-2) pellet obtained by blending the thermoplastic elastomer resin (y1-2) was obtained.

  The resulting thermoplastic elastomer resin composition (y1-2) had a melt viscosity index (MFR) (measured in accordance with ASTM D1238-1990) measured at a temperature of 220 ° C. and a load of 2160 g of 8 g / 10 minutes, and a melting point of 208 ° C. The surface hardness of the thermoplastic elastomer resin composition (Y-2) measured by durometer D was 55D.

[Examples 1 to 19]
Tables 1, 2 and 3 show the results of evaluating the thermal fusing power of the polybutylene terephthalate resin composition (X), the thermoplastic elastomer resin composition (Y), and both. The obtained results all showed high heat welding power.

  The determination was performed as follows.

  About Examples 1-3 and 11-13 and the comparative example 1, it was set as x when the heat sealing force in 230 degreeC is 300 N / 20mm or more, and when the heat sealing force is less than 300 N / 20 mm.

  For Examples 4 to 10 and 14 to 19 and Comparative Examples 2 to 5, when the heat fusion force at 230 ° C. is 390 N / 20 mm or more and the deflection temperature under load is 150 ° C. or more, the heat fusion force at 230 ° C. Is 200 N / 20 mm or more and less than 390 N / 20 mm and the deflection temperature under load is 150 ° C. or more, and x is the case when the heat fusion force is less than 200 N / 20 mm or the deflection temperature under load is less than 150 ° C.

[Comparative Examples 1-5]
The polybutylene terephthalate resin composition (X) and the thermoplastic elastomer resin composition (Y) shown in Tables 2 and 3 were evaluated in the same manner as in Examples. As described above, either the heat welding force or the deflection temperature under load became low.

(A) Resin member (B) Other resin composition (C) Tensile test direction

Claims (6)

  A resin composite molded body in which a member made of a polybutylene terephthalate resin composition (X) and a member made of a thermoplastic elastomer resin composition (Y) are joined, wherein the polybutylene terephthalate resin composition (X) Comprises 0.5 to 100 parts by mass of an amorphous resin (x2) with respect to 100 parts by mass of the polybutylene terephthalate resin (x1), and the thermoplastic elastomer resin composition (Y) A thermoplastic elastomer resin (y1) comprising a hard segment (a1) composed of an aliphatic polyester unit and a soft segment (a2) composed of an aliphatic polyether unit and / or an aliphatic polyester unit, and having a melting point A resin composite molded body having a temperature of less than 210 ° C.   The resin composite molded body according to claim 1, wherein the amorphous resin (x2) of the polybutylene terephthalate resin composition (X) includes at least one resin selected from a styrene resin and a polycarbonate resin.   The hard segment (a1) of the thermoplastic elastomer resin (y1) is a polybutylene terephthalate unit derived from terephthalic acid or dimethyl terephthalate and 1,4-butanediol, and / or isophthalic acid or dimethyl isophthalate and 1, The resin composite molded article according to claim 1 or 2, comprising a polybutylene isophthalate unit derived from 4-butanediol.   The soft segment (a2) of the thermoplastic elastomer resin (y1) is composed of poly (tetramethylene oxide) glycol and / or poly (propylene oxide) glycol ethylene oxide adduct and / or a copolymer of ethylene oxide and tetrahydrofuran. The resin composite molded article according to any one of claims 1 to 3, wherein   A method for producing the resin composite molded article according to any one of claims 1 to 4, wherein a member comprising the polybutylene terephthalate resin composition (X) or the thermoplastic elastomer resin composition (Y) is molded as a mold. A method for producing a resin composite molded body comprising: injecting and bonding a molten resin composition different from a resin composition constituting a member disposed in the mold and disposed in the mold.   The resin composite molded body in which the member made of the polybutylene terephthalate resin composition (X) and the member made of the thermoplastic elastomer resin composition (Y) are joined is composed of a member disposed in the mold. It is a member made of butylene terephthalate resin composition (X), and the molten resin composition different from the resin composition constituting the member arranged in the mold is a thermoplastic elastomer resin composition (Y) The method for producing a resin composite molded body according to claim 5.

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