WO2023248679A1 - Composition de résine de polybutylène téréphthalate et article moulé - Google Patents

Composition de résine de polybutylène téréphthalate et article moulé Download PDF

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Publication number
WO2023248679A1
WO2023248679A1 PCT/JP2023/019088 JP2023019088W WO2023248679A1 WO 2023248679 A1 WO2023248679 A1 WO 2023248679A1 JP 2023019088 W JP2023019088 W JP 2023019088W WO 2023248679 A1 WO2023248679 A1 WO 2023248679A1
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Prior art keywords
component
polybutylene terephthalate
parts
weight
terephthalate resin
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PCT/JP2023/019088
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English (en)
Japanese (ja)
Inventor
純樹 田邉
裕介 東城
秀之 梅津
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東レ株式会社
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Priority to JP2023532474A priority Critical patent/JP7401027B1/ja
Publication of WO2023248679A1 publication Critical patent/WO2023248679A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a polybutylene terephthalate resin composition and a molded article formed from the same.
  • the relative dielectric constant and dielectric loss tangent have been reduced for application to high-frequency transmission components such as mobile communication terminals and automotive millimeter-wave sensors based on high-speed communication standards that use high-frequency waves of 1 GHz band or higher. Materials are needed. If the material used for high-frequency transmission components has a particularly high dielectric loss tangent, when a high-frequency signal comes into contact with the material, the high frequency will be converted to heat, resulting in a phenomenon in which communication accuracy such as communication distance decreases due to a decrease in signal strength. ,It has become a challenge.
  • Polybutylene terephthalate resin a type of thermoplastic polyester resin, has excellent processability, mechanical properties, and heat resistance, and is attracting attention as a material suitable for high-frequency transmission parts.
  • a method for reducing the dielectric loss of polybutylene terephthalate resin a method has been disclosed in which a specific aliphatic alcohol is introduced to reduce hydroxyl groups that cause a large energy loss under high frequency, thereby reducing the dielectric loss.
  • a manufacturing method thereof a method is disclosed in which an aliphatic alcohol having 10 to 50 carbon atoms is added in the esterification step of terephthalic acid and butanediol in the polymerization step of polybutylene terephthalate resin.
  • Patent Document 1 Although the method disclosed in Patent Document 1 has been shown to be effective in reducing the dielectric loss tangent in the high frequency band, it is difficult to maintain this effect in a high temperature and humid environment, and the dielectric properties remain stable. There were issues with insufficient durability and weather resistance.
  • Patent Document 2 has a certain effect on reducing the dielectric loss tangent, there is a problem with the stability of dielectric properties in a high temperature and high humidity environment.
  • component (B) acrylonitrile-styrene copolymer resin
  • a polybutylene terephthalate resin composition that satisfies the following condition (i).
  • the ratio of the amount of component (B) to the amount of component (D) is greater than 1 and 15
  • a molded article with stable dielectric properties and improved weather resistance can be obtained in a high temperature and humid environment.
  • the polybutylene terephthalate resin composition of the present invention comprises a polybutylene terephthalate resin (A) in which an aliphatic alcohol having 10 to 50 carbon atoms is combined in an amount of 0.1 to 2.0 mol% based on 100 mol% of terephthalic acid. , 1 to 100 parts by weight of the acrylonitrile-styrene copolymer resin (B) is blended with 100 parts by weight of the polybutylene terephthalate resin (A), and is included in the unit weight of the polybutylene terephthalate resin composition.
  • A polybutylene terephthalate resin
  • B acrylonitrile-styrene copolymer resin
  • 1,4-butanediol is usually used as the butanediol used in the polybutylene terephthalate resin (A).
  • the aliphatic alcohol having 10 or more and 50 or less carbon atoms is contained in an amount of 0.1 to 0.1% by mole based on 100% by mole of the terephthalic acid-derived structural unit (i.e., terephthaloyl group) constituting the polybutylene terephthalate resin (A).
  • the cyano group in component (B) has a carbon number of 10 or more and 50 or more.
  • the main structural unit of the polybutylene terephthalate resin (A) used in the present invention is a structure obtained by condensation polymerization of terephthalic acid and butanediol, and the residue of an aliphatic alcohol having 10 to 50 carbon atoms is terephthalate. It is a polymer compounded in an amount of 0.1 to 2.0 mol% based on 100 mol% of acid.
  • "main structural unit” means that the structure derived from terephthalic acid accounts for 50 mol% or more of the structure derived from dicarboxylic acid, and the structure derived from butanediol accounts for 50 mol% or more of the structure derived from diol.
  • copolymerizable monomers examples include isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4,4'- Aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, and 5-sodium sulfoisophthalic acid, and their ester-forming derivatives, ethylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,5 - C2-C20 aliphatic or alicyclic glycols such as pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol, polyethylene glycol, poly-1,3-prop
  • the number written after "C” in the above represents the number of carbons contained in the group.
  • straight-chain or branched saturated aliphatic groups are preferred from the viewpoint of color tone, as they improve compatibility with component (B), stabilize dielectric properties in high-temperature and humid environments, and have good weather resistance.
  • a saturated aliphatic group having a branch is preferable.
  • the carbon number of the aliphatic group is 10 or more and 50 or less, an effect of improving fluidity can be obtained, and since the fluidity can be further improved, the lower limit of the carbon number is preferably 16 or more, and 20 or more. It is even more preferable.
  • the upper limit of the number of carbon atoms is preferably 36 or less, more preferably 30 or less.
  • Component (A) preferably has a branched saturated aliphatic group having 16 or more carbon atoms and 36 or less carbon atoms at the molecular end, and the concentration of the functional group is 0.005 mmol/g or more and less than 0.20 mmol/g. It is preferable that It is preferable that the functional group concentration of the branched saturated aliphatic group having 16 to 36 carbon atoms is 0.005 mmol/g or more, since fluidity and dielectric properties can be improved, and more preferably 0.010 mmol/g or more. More preferably, it is 0.020 mmol/g or more.
  • the functional group concentration of the aliphatic group present at the molecular terminal of component (A) is a value determined by the integral ratio of the peak derived from the terminal group measured by 1 H-NMR using deuterated hexafluoroisopropanol as a solvent. be.
  • Component (A) is an aliphatic alcohol with a carbon number of 10 to 50, from the viewpoint of increasing compatibility with component (B), stabilizing dielectric properties in high temperature and humid environments, and improving weather resistance.
  • the amount of aliphatic alcohol having 10 to 50 carbon atoms combined with respect to 100 mol% of terephthalic acid is preferably 0.5 mol% or more, and 0.5 mol% or more. More preferably, it is 7 mol% or more. Further, it is preferably 1.8 mol% or less, more preferably 1.6 mol% or less.
  • the hydroxyl group concentration is preferably 0.050 mmol/g or less.
  • the hydroxyl group concentration is more preferably 0.040 mmol/g or less, still more preferably 0.030 mmol/g or less, and still more preferably 0.020 mmol/g or less, from the viewpoint of stabilizing dielectric properties in a high temperature and humid environment.
  • the lower limit of the hydroxyl group concentration is 0 mmol/g.
  • the hydroxyl group concentration of component (A) is a value determined from the integral ratio of peaks derived from end groups measured by 1 H-NMR using deuterated hexafluoroisopropanol as a solvent.
  • the carboxyl group concentration is preferably 0.070 mmol/g or less from the viewpoint of stabilizing dielectric properties in a high temperature and humid environment.
  • the carboxyl group concentration of component (A) is preferably 0.060 mmol/g or less, more preferably 0.50 mmol/g or less.
  • the lower limit of the carboxyl group concentration of component (A) is 0 mmol/g.
  • the carboxyl group concentration of component (A) is a value measured by dissolving component (A) in an o-cresol/chloroform solvent and then titrating with ethanolic potassium hydroxide.
  • the melting point of component (A) is preferably 180°C or higher. By having a melting point of 180° C. or higher, the dielectric properties of the polybutylene terephthalate resin composition can be stabilized in a high temperature and high humidity environment. From the viewpoint of heat resistance, the melting point is preferably 190°C or higher, more preferably 200°C or higher, even more preferably 210°C or higher.
  • the melting point of component (A) is the value of the peak temperature of the endothermic melting peak obtained when the temperature is raised from 25° C. to 20° C./min by DSC (differential scanning calorimetry).
  • the weight average molecular weight (Mw) of component (A) is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.
  • Component (A) preferably has an intrinsic viscosity (IV) of 0.6 dl/g or more in terms of stabilizing dielectric properties in a high temperature/humid environment.
  • the intrinsic viscosity of component (A) is more preferably 0.65 dl/g or more, and even more preferably 0.7 dl/g or more. Further, it is preferable that the intrinsic viscosity of component (A) is 2 dl/g or less, since fluidity is improved.
  • the intrinsic viscosity of component (A) is more preferably 1.7 dl/g or less, still more preferably 1.4 dl/g or less.
  • the intrinsic viscosity of component (A) is a value determined by measurement at 25° C. using orthochlorophenol as a solvent.
  • the dielectric loss tangent of component (A) at 5.8 GHz measured at 23° C. using the cylindrical cavity perturbation method is preferably 0.0060 or less. If this dielectric loss tangent is 0.0060 or less, dielectric loss can be reduced and deterioration of high-frequency signals can be suppressed, resulting in excellent antenna gain and radar accuracy. Suitable for use in materials. More preferably it is 0.0055 or less, still more preferably 0.0050 or less.
  • the dielectric loss tangent of component (A) can be calculated using S-parameter methods such as free space S-para method, corrugated circular waveguide S-para method, balanced disk resonator method, Fabry-Perot open resonator method, and split cylinder cavity resonator. method, split-post dielectric resonator method, cylindrical cavity resonator perturbation method, cut-off cylindrical waveguide method, etc.
  • the method uses the cavity resonance method. Define by the obtained value. Further, in the present invention, values obtained by the cylindrical cavity resonator perturbation method among the cavity resonance methods are used.
  • a known polycondensation method or ring-opening polymerization method can be used to prepare polybutylene terephthalate.
  • a manufacturing method using condensation reaction) or a method of reducing hydroxyl groups by solid phase polymerization (manufacturing method using solid phase polymerization) can be used.
  • the production method using polycondensation reaction may be either batch polymerization or continuous polymerization, and either transesterification reaction, direct polymerization reaction, or direct polymerization reaction can be applied, but from the viewpoint of reducing hydroxyl groups. Batch polymerization is preferred, and direct polymerization is more preferred.
  • component (A) there is a step of mixing terephthalic acid and butanediol to form a slurry, a step of preparing a catalyst solution, and a step of filtering the reactant after esterification through a filter made of metal mesh, etc.
  • the method may include known polyester resin manufacturing steps other than the esterification reaction and polycondensation reaction, such as a filtering step, a step of discharging the molten resin into a water bath and cutting it with a strand cutter, etc.
  • the carbon number It can be produced by adding 10 to 50 aliphatic alcohols at any stage selected from esterification, transesterification, and polycondensation.
  • the resin it is preferable to produce the resin by adding an aliphatic alcohol having 10 to 50 carbon atoms at any stage of the esterification reaction or the transesterification reaction, since a resin with excellent dielectric properties can be obtained.
  • a compound capable of reacting with the hydroxyl group of a diol or its ester-forming derivative (hereinafter sometimes referred to as a "hydroxyl group blocking agent”) is transesterified in the manufacturing process of component (A).
  • a hydroxyl group blocking agent By adding it at any stage of the reaction or polycondensation reaction, the hydroxyl group concentration of component (A) can be reduced.
  • the hydroxyl group blocking agent can reduce the amount of free hydroxyl groups in component (A), and examples of such agents include monofunctional carboxylic acids, acid anhydrides, and isocyanate compounds.
  • Examples of monofunctional carboxylic acids include aliphatic acids having 1 to 50 carbon atoms, such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, stearic acid, oleic acid, linoleic acid, and cyclohexanecarboxylic acid.
  • Examples include aromatic carboxylic acids having 1 to 50 carbon atoms such as carboxylic acids or alicyclic carboxylic acids, benzoic acid, toluic acid, naphthoic acid, anthracenecarboxylic acid, phenylbenzoic acid, chlorobenzoic acid, hydroxybenzoic acid, and phthalic acid. It will be done.
  • acid anhydrides examples include acid anhydrides such as acetic anhydride and benzoic anhydride obtained by dehydration condensation of the above-mentioned carboxylic acid compounds.
  • a phenolic antioxidant in any step of the esterification reaction and polycondensation reaction of component (A) suppresses thermal decomposition of the aliphatic alcohol compound, and the polybutylene terephthalate resin This is preferable in that it can further reduce the number of terminal hydroxyl groups.
  • the phenolic antioxidant preferably used in the present invention is a phenol compound having a t-butyl group, specifically triethylene glycol-bis[3-(3-t-butyl-5-methyl-4 -hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], pentaerythrityl-tetrakis[3-(3,5- di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-tris( 3,5-di
  • the amount of the phenolic antioxidant added is preferably 0.01 to 0.20 parts by weight per 100 parts by weight of component (A).
  • the amount is more preferably 0.02 parts by weight or more, and even more preferably 0.03 parts by weight or more, since it can reduce the number of hydroxyl terminals in the polybutylene terephthalate resin.
  • the upper limit of the amount of the phenolic antioxidant added is preferably 0.15 parts by weight or less, more preferably 0.10 parts by weight or less, from the standpoint of improving the molecular weight.
  • the polymerization reaction catalyst include titanic acid methyl ester, tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester, Organic titanium compounds such as benzyl ester, tolyl ester or mixed esters thereof, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethyldistin oxide, cyclohexahexyldistin oxide, didodecyltin oxide, triethyltin hydroxide, Triphenyltin
  • the polybutylene terephthalate resin composition of the present invention contains 1 to 100 parts by weight of an acrylonitrile-styrene copolymer resin (B) to 100 parts by weight of the polybutylene terephthalate resin (A), and further contains the following: Condition (i) is satisfied.
  • the "unit weight” can be arbitrarily determined as long as it is an amount that allows the above molar ratio ((b)/(a)) to be determined.
  • the aliphatic alcohol that is combined with component (A) is effective in lowering the dielectric loss tangent of component (A), but in a high temperature and humid environment, the desorption of the aliphatic alcohol moiety is promoted.
  • the dielectric loss tangent was not stable, and components derived from the aliphatic alcohol desorbed onto the surface of the molded product bleed out, resulting in poor weather resistance.
  • the present inventors have conducted intensive studies to solve this problem, and have created a composition in which 1 to 100 parts by weight of component (B) is blended with respect to 100 parts by weight of component (A), and the above condition (i) is satisfied.
  • the blending amount of component (B) per 100 parts by weight of component (A) is 20 parts by weight.
  • the amount is preferably at least 27 parts by weight, more preferably at least 27 parts by weight, and most preferably at least 35 parts by weight.
  • the blending amount of component (B) with respect to 100 parts by weight of component (A) is preferably 80 parts by weight or less, more preferably 75 parts by weight or less, and still more preferably 70 parts by weight or less.
  • condition (i) must be satisfied.
  • component (B) contains methacrylic acid as a structural unit other than acrylonitrile and styrene. It is preferred that the structural unit obtained using glycidyl is contained in an amount of less than 5% by weight, more preferably less than 3% by weight, and most preferably less than 1% by weight based on the weight of component (B).
  • titanium oxide fiber titanium carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, calcium sulfate whisker, acicular titanium oxide, glass beads, milled fiber, glass flakes, straw Stenite, silica, kaolin, talc, calcium carbonate, zinc oxide, magnesium oxide, aluminum oxide, mixture of magnesium oxide and aluminum oxide, finely divided silicic acid, aluminum silicate, silicon oxide, smectite clay minerals (montmorillonite, hectorite), Examples include vermiculite, mica, fluoroteniolite, zirconium phosphate, titanium phosphate, and dolomite.
  • the average particle size of the granular, powdered, and layered inorganic fillers is preferably 0.1 to 20 ⁇ m from the viewpoint of impact strength. From the viewpoint of dispersibility of the inorganic filler in the resin, the average particle size is preferably 0.2 ⁇ m or more, and from the viewpoint of mechanical strength, it is preferably 10 ⁇ m or less.
  • the polybutylene terephthalate resin composition of the present invention further contains a polyolefin resin (D) (hereinafter sometimes referred to as "component (D)”) based on 100 parts by weight of the polybutylene terephthalate resin component (A). It is preferable.
  • component (D) it is possible to further suppress the desorption of the aliphatic alcohol moiety of component (A) under high temperature and high humidity environments, and the dielectric properties are stabilized under high temperature and high humidity environments. Weather resistance is improved.
  • the polyolefin resin (D) is a thermoplastic resin that always contains structural units derived from olefins such as ethylene, propylene, butene, isoprene, and pentene.
  • olefins such as ethylene, propylene, butene, isoprene, and pentene.
  • the olefin-derived structural units account for 50 mol% or more of the total structural units.
  • olefin homopolymers such as polyethylene, polypropylene, poly-1-butene, poly-1-pentene, and polymethylpentene, ethylene/propylene copolymers, ethylene/propylene/non-conjugated diene copolymers, Ethylene/butene-1 copolymer, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/butyl acrylate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/butene-1/glycidyl methacrylate copolymer Polymer, ethylene/propylene/glycidyl methacrylate copolymer, ethylene/octene-1/glycidyl methacrylate copolymer, ethylene/acrylic acid ester/glycidyl methacrylate copolymer, ethylene/maleic anhydride copolymer, ethylene/maleic
  • Component (D) is preferably a polyolefin resin copolymerized with ethylene, from the viewpoint of excellent dispersibility with respect to component (A), stable dielectric properties in high temperature and humid environments, and improved weather resistance.
  • ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, and ethylene/butyl acrylate copolymer is preferable.
  • Component (D) is preferably blended in an amount of 1 to 50 parts by weight based on 100 parts by weight of component (A). From the viewpoint of excellent dispersibility in component (A), stable dielectric properties in high temperature and humid environments, and improved weather resistance, the amount of component (D) to be blended is 100 parts by weight of component (A). The amount is more preferably 5 parts by weight or more, and even more preferably 10 parts by weight or more. Moreover, the blending amount of component (D) is more preferably 35 parts by weight or less, even more preferably 30 parts by weight or less, and even more preferably 20 parts by weight or less, based on 100 parts by weight of component (A).
  • the elimination of the aliphatic alcohol moiety in component (A) can be further suppressed, and the dielectric properties are stabilized and weather resistance is improved in a high temperature and humid environment.
  • the ratio of the amount of component (B) to the amount of component (D) is greater than 1 and less than 15. It is preferable to do so. Since the dispersibility is further improved, the lower limit of the blending ratio is preferably 1.5 or more, and more preferably 2 or more. Further, the upper limit of the blending ratio is preferably 10 or less, more preferably 7 or less.
  • the polybutylene terephthalate resin composition of the present invention contains antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, flame retardants, mold release agents, pigments, dyes, and antistatic agents to the extent that the effects of the present invention are not impaired. Any additives such as agents can be blended.
  • the flame retardant examples include phosphorus flame retardants, halogen flame retardants such as bromine flame retardants, salts of triazine compounds and cyanuric acid or isocyanuric acid, silicone flame retardants, and inorganic flame retardants. Two or more types of these may be blended.
  • the blending amount of the flame retardant is preferably 1 to 50 parts by weight per 100 parts by weight of component (A). From the viewpoint of flame retardancy, the lower limit of the blending amount is more preferably 5 parts by weight or more, and from the viewpoint of heat resistance, the upper limit is more preferably 40 parts by weight or less.
  • the mold release agent examples include higher fatty acid ester waxes such as montanic acid and stearic acid, polyolefin waxes, and ethylene bisstearamide waxes. By adding a mold release agent, it is possible to improve the mold release property from the mold during melt processing.
  • the blending amount of the mold release agent is preferably 0.01 to 1 part by weight per 100 parts by weight of component (A).
  • the lower limit of the blending amount is more preferably 0.03 parts by weight or more from the viewpoint of mold releasability, and the upper limit is more preferably 0.6 parts by weight or less from the viewpoint of heat resistance.
  • pigments or dyes By blending one or more pigments or dyes, it is possible to adjust the color to various colors and improve weather resistance (light) resistance and conductivity.
  • the pigment include carbon black and titanium oxide.
  • the amount of pigments and dyes to be blended is preferably 0.01 to 3 parts by weight per 100 parts by weight of component (A).
  • the lower limit of the blending amount is more preferably 0.03 parts by weight or more from the viewpoint of preventing uneven coloring, and the upper limit is more preferably 1 part by weight or less from the viewpoint of mechanical strength.
  • component (A) and component (B) are premixed with various additives as necessary, and the mixture is supplied to a melt kneader and melted.
  • examples include a method of kneading, and a method of melt-kneading by supplying a predetermined amount of each component to a melt-kneader using a quantitative feeder such as a gravimetric feeder.
  • melt kneader for example, a single screw extruder equipped with a "unimelt” or “dalmage” type screw, a twin screw extruder, a triple screw extruder, a conical extruder, a kneader type kneader, etc. can be used. .
  • the above-mentioned premixing include dry blending and mixing using a mechanical mixing device such as a tumbler, ribbon mixer, and Henschel mixer.
  • the inorganic filler (C) may be added by installing a side feeder between the charging part and the vent part of a multi-screw extruder such as a twin-screw extruder.
  • a liquid addition nozzle is installed between the pre-filling part and the vent part of a multi-screw extruder such as a twin-screw extruder, and the additive is added using a plunger pump.
  • a method may be used in which the amount of water is supplied from a metering pump using a metering pump.
  • the polybutylene terephthalate resin composition of the present invention is preferably pelletized and subjected to molding.
  • the pelletizing method include a method in which a polybutylene terephthalate resin composition melt-kneaded using a melt-kneader or the like is discharged in the form of a strand, and then cut with a strand cutter.
  • melt-molding the polybutylene terephthalate resin composition of the present invention By melt-molding the polybutylene terephthalate resin composition of the present invention, molded products in various shapes such as films, fibers, and others can be obtained.
  • melt molding methods include injection molding, extrusion molding, and blow molding, with injection molding being particularly preferably used.
  • injection molding methods include gas assisted molding, two-color molding, sandwich molding, in-mold molding, insert molding, and injection press molding, but any of these molding methods can be applied. can.
  • the molded product of the present invention has stable dielectric properties and improved weather resistance in high-temperature and humid environments, making it suitable as a molded product selected from mechanical mechanical parts, electrical parts, electronic parts, and automobile parts. Can be used. Since the molded article of the present invention has excellent dielectric properties in a high frequency band, it is particularly useful for high frequency transmission parts.
  • mechanical parts, electrical parts, electronic parts, and automobile parts include breakers, electromagnetic switches, focus cases, flyback transformers, molded products for fusers of copiers and printers, general home appliances, and OA. Housings for equipment, variable cap case parts, various terminal boards, transformers, printed wiring boards, terminal blocks, coil bobbins, connectors, relays, disk drive chassis, transformers, switch parts, outlet parts, motor parts, sockets, plugs, capacitors , various cases, resistors, electrical and electronic parts incorporating metal terminals and conductors, computer-related parts, audio parts such as audio parts, lighting parts, telegraph equipment-related parts, telephone equipment-related parts, air conditioner parts, VTRs and televisions. Examples include home appliance parts such as copy machine parts, facsimile parts, optical equipment parts, automobile ignition system parts, automobile connectors, and various automobile electrical parts.
  • high-frequency transmission parts include parts for mobile communication terminals and communication base stations, parts for millimeter wave sensors, antenna base materials for electrical and electronic parts used in in-vehicle communication equipment, connectors, and radar.
  • Radomes are casings (covers) that protect the sources of heat and sensors, and their dielectric properties are stable and weather resistance is improved in high-temperature and humid environments, making them ideal for radomes where robustness is important. It can be used for.
  • the unit average molecular weight is the residue derived from dicarboxylic acid or its ester-forming derivative, diol or its ester-forming derivative, and hydroxycarboxylic acid residue or its ester-forming derivative. This is the value obtained by multiplying the molecular weight by the content ratio of each residue.
  • the term "residue” as used herein includes the structure of a portion constituting an ester bond. For example, for a homopolymer of polybutylene terephthalate, the unit average molecular weight is 220.
  • the obtained square plate was cut to a width of 1 mm in parallel to the flow direction of the resin to obtain a test piece for dielectric property evaluation measuring 80 mm x 1 mm x 1 mm thick.
  • the dielectric properties of these test pieces for dielectric property evaluation were measured at 23°C and 5.8 GHz by the cavity resonator perturbation method using a network analyzer E5071C manufactured by Agilent Technologies and a cavity resonator CP521 manufactured by Kanto Denshi Application Development Co., Ltd. The relative permittivity and dielectric loss tangent were determined.
  • Composition analysis (analysis of amount of aliphatic alcohol residues and amount of cyano groups) 20 mg of a sample of a polybutylene terephthalate resin composition and 5 mg of an internal standard substance (1,4-bis(trimethylsilyl)benzene-d 4 ) were added to 0.7 mL of a 1:1 (volume ratio) mixed solution of deuterium chloroform and deuterium hexafluoroisopropanol. The solution was dissolved and 1 H-NMR measurement was performed using JNM-ECZ500R manufactured by JEOL Ltd. From the obtained 1 H-NMR spectrum, the above 2.
  • the integral value Sb of the peak derived from the aliphatic alcohol moiety derived from the polybutylene terephthalate resin component and its number of hydrogen atoms Hb are determined by the peak attribution method shown in the functional group concentration, and the integral value Sc of the peak derived from the internal standard substance is determined.
  • Polybutylene terephthalate resin in the resin composition according to the following formula using the number of hydrogen atoms Hc, the molecular weight Mc of the internal standard substance, and the mixed amount of the internal standard substance (5 mg 0.5 ⁇ 10 -3 (g)).
  • the dielectric properties of the obtained dielectric property evaluation test piece ( ⁇ ) were measured at 23°C by the cavity resonator perturbation method using a network analyzer E5071C manufactured by Agilent Technologies and a cavity resonator CP521 manufactured by Kanto Denshi Application Development Co., Ltd. , the dielectric loss tangent at 5.8 GHz was determined. Subsequently, the test piece ( ⁇ ) prepared in the same manner as above was placed in a constant temperature and humidity chamber LHL-114 manufactured by ESPEC Co., Ltd., set at a temperature and humidity of 85°C x 85% RH, and incubated for 1500 hours. A pressurized and moist heat treatment was performed to obtain a test piece ( ⁇ ) for dielectric property evaluation.
  • the dielectric loss tangent at 23°C and 5.8 GHz was determined for the test piece ( ⁇ ) under the same conditions as those for the test piece ( ⁇ ) above, and the rate of change in the dielectric loss tangent was determined using the following formula. .
  • a change rate of 30% or less was considered to be excellent in the stability of dielectric properties in a high temperature/humid environment, a rate of change of 25% or less was considered to be better, and a rate of change of 20% or less was judged to be particularly excellent.
  • Rate of change in dielectric loss tangent (%) 100 x (dielectric loss tangent of test piece ( ⁇ ) - dielectric loss tangent of test piece ( ⁇ ))/(dielectric loss tangent of test piece ( ⁇ )).
  • the sample resin composition was molded using a NEX1000 injection molding machine manufactured by Nissei Plastics Co., Ltd., at a mold temperature of 80°C, with a total injection time and pressure holding time of 15 seconds, and a cooling time of 15 seconds. Under the molding cycle conditions, an 80 mm x 80 mm square plate with a test piece thickness of 1 mm was obtained. The obtained square plate was tested using a sunshine weather meter (WEL-SUN-HCH model manufactured by Suga Test Instruments Co., Ltd.), black panel temperature: 63°C, cycle: 120 minutes (18 minutes of rainfall), irradiance: 255 W/m Weathering treatment was carried out under conditions 2 for 200 hours.
  • WEL-SUN-HCH model manufactured by Suga Test Instruments Co., Ltd.
  • the change in color (b value) near the center of the square plate before and after UV irradiation was measured using Spectro Color Meter SE2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. did. It was determined that weather resistance is excellent if the amount of change in color (b value) is 20 or less, more excellent if it is 14 or less, and particularly excellent if it is 12 or less.
  • Polybutylene terephthalate resin (A) Polybutylene terephthalate resin (A) was obtained according to Production Examples 1 to 5 below and evaluated by the above method, and the results are shown in Table 1.
  • 2-hexyl-1-dodecanol as a saturated aliphatic alcohol 49 g (1.5 mol% relative to 100 mol% of terephthalic acid), TBT (tetra-n-butyl titanate) as a polymerization reaction catalyst: a thermoplastic resin to be produced 7.5 x 10 -5 mol per 100 g (0.025 parts by weight per 100 parts by weight of thermoplastic resin) was charged into a reactor equipped with a rectification column, and the mixture was heated at 160°C under a nitrogen stream. The esterification reaction was started. Thereafter, the temperature was gradually raised, and finally the esterification reaction was carried out at a temperature of 225°C.
  • the completion of the esterification reaction was confirmed based on the condition of the distillate, and the reaction time of the esterification reaction was set at 220 minutes.
  • TBT as a polymerization reaction catalyst 7.5 ⁇ 10 -5 mol per 100 g of polyester resin to be produced (0.025 parts by weight per 100 parts by weight of thermoplastic resin) was added, and the temperature was increased.
  • the polycondensation reaction was carried out under conditions of 260° C. and 100 Pa pressure.
  • the completion of the polycondensation reaction was confirmed by checking the viscosity of the reactants, etc., and the reaction time for the polycondensation reaction to obtain a thermoplastic resin was set at 150 minutes, and the reaction was carried out for a total of 330 minutes. Obtained.
  • Inorganic filler (C) (C-1) Glass fiber: Nippon Electric Glass Co., Ltd. glass fiber ECS03T-187, cross-sectional diameter 13 ⁇ m, fiber length 3 mm, treated with epoxy sizing agent was used.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le problème abordé par la présente invention est de fournir une composition de résine de polybutylène téréphthalate qui a une faible tangente de perte diélectrique dans des bandes haute fréquence de 1 GHz et plus, qui maintient des propriétés diélectriques même dans un environnement à haute température et à humidité élevée, et qui a une résistance aux intempéries améliorée, et un article moulé de celle-ci. Le problème est résolu par une composition de résine de polybutylène téréphthalate qui mélange une résine de polybutylène téréphthalate (A) ("composant (A)"), dans laquelle de 0,1 à 2,0 % en moles d'un alcool aliphatique en C10 à 50 sont combinés sur la base de 100 % en moles d'acide téréphtalique, avec 1 à 100 parties en poids d'une résine de copolymère d'acrylonitrile-styrène (B) ("composant (B)") pour 100 parties en poids du composant (A), la composition de résine de polybutylène téréphthalate satisfaisant à la condition (i) ci-dessous. Condition (i) : l'idée principale est que le rapport ((b)/(a)) de la quantité (a) de résidus de l'alcool aliphatique en C10-50 combinés dans le composant (A) et de la quantité (b) de groupes cyano dans le composant (B) contenus dans un poids unitaire de composition de résine de polybutylène téréphthalate est de 5 ou plus.
PCT/JP2023/019088 2022-06-20 2023-05-23 Composition de résine de polybutylène téréphthalate et article moulé WO2023248679A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01234419A (ja) * 1988-03-14 1989-09-19 Kanebo Ltd 低吸水性ポリエステル樹脂
JP2006257338A (ja) * 2005-03-18 2006-09-28 Toray Ind Inc レーザー溶着用樹脂組成物およびそれを用いた複合成形体
JP2007119645A (ja) * 2005-10-28 2007-05-17 Polyplastics Co 難燃性樹脂組成物
JP2007131692A (ja) * 2005-11-09 2007-05-31 Toray Ind Inc レーザー溶着用樹脂組成物およびそれを用いた複合成形体
WO2021020208A1 (fr) * 2019-07-31 2021-02-04 東レ株式会社 Résine polyester thermoplastique, composition de résine polyester thermoplastique, et article moulé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01234419A (ja) * 1988-03-14 1989-09-19 Kanebo Ltd 低吸水性ポリエステル樹脂
JP2006257338A (ja) * 2005-03-18 2006-09-28 Toray Ind Inc レーザー溶着用樹脂組成物およびそれを用いた複合成形体
JP2007119645A (ja) * 2005-10-28 2007-05-17 Polyplastics Co 難燃性樹脂組成物
JP2007131692A (ja) * 2005-11-09 2007-05-31 Toray Ind Inc レーザー溶着用樹脂組成物およびそれを用いた複合成形体
WO2021020208A1 (fr) * 2019-07-31 2021-02-04 東レ株式会社 Résine polyester thermoplastique, composition de résine polyester thermoplastique, et article moulé

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