WO2021187399A1 - Composition de résine et article moulé en résine comprenant ladite composition de résine - Google Patents

Composition de résine et article moulé en résine comprenant ladite composition de résine Download PDF

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Publication number
WO2021187399A1
WO2021187399A1 PCT/JP2021/010284 JP2021010284W WO2021187399A1 WO 2021187399 A1 WO2021187399 A1 WO 2021187399A1 JP 2021010284 W JP2021010284 W JP 2021010284W WO 2021187399 A1 WO2021187399 A1 WO 2021187399A1
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liquid crystal
resin composition
resin
mass
crystal polyester
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PCT/JP2021/010284
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English (en)
Japanese (ja)
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希望 大野
雄二 梅村
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Ｅｎｅｏｓ株式会社
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Priority to CN202180021352.3A priority Critical patent/CN115279832A/zh
Publication of WO2021187399A1 publication Critical patent/WO2021187399A1/fr

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    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • 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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings

Definitions

  • the present invention relates to a resin composition having a low dielectric loss tangent and a low dielectric constant. Furthermore, the present invention relates to a resin molded product made of the resin composition and an electric / electronic component including the resin molded product.
  • the frequency is 10 9 Hz or more gigahertz (GHz)
  • GHz gigahertz
  • This transmission loss consists of a conductor loss caused by a conductor and a dielectric loss caused by an insulating resin composition constituting an electric / electronic component such as a substrate in an electronic device or a communication device.
  • the conductor loss is a frequency used.
  • the dielectric loss of 0.5 is proportional to the first power of the frequency, the influence of the dielectric loss becomes very large in the high frequency band, particularly in the GHz band. Further, since the dielectric loss increases in proportion to the dielectric loss tangent and the dielectric constant of the resin composition, a resin composition having a low dielectric loss tangent and a low dielectric constant is required in order to prevent deterioration of information.
  • liquid crystal polyester resin is excellent in moldability and heat resistance
  • resin molded products for example, injection molded products
  • liquid crystal polyester resin is used for various electronic parts.
  • electronic components have become more integrated, thinner, and shorter due to miniaturization of personal computers and smartphones, and demand for molded products having extremely thin thick parts is increasing.
  • the liquid crystal polyester resin is a thermoplastic resin having both low viscosity and high heat resistance, and is attracting attention because it has a dielectric loss tangent that is an order of magnitude smaller than that of an insulating material for substrates such as polyimide.
  • the applicant has proposed a liquid crystal polyester resin having a low dielectric loss tangent (see Patent Document 1).
  • the present inventor is a resin composition in which a specific liquid crystal polyester resin (A), a fluororesin (B), and an inorganic hollow filler (C) are mixed. Therefore, it was found that the above problems can be solved by adjusting the dielectric loss tangent and the relative permittivity within a specific numerical range.
  • the present invention has been completed based on such findings.
  • Fluororesin (B) and Containing with an inorganic hollow filler (C) Provided is a resin composition having a dielectric loss tangent measured by a cavity resonator perturbation method at a measurement frequency of 10 GHz and having a dielectric loss tangent of 2 ⁇ 10 -3 or less and a relative permittivity of 3.50 or less.
  • the melting point of the liquid crystal polyester resin (A) is preferably 280 ° C. or higher.
  • the liquid crystal polyester resin (A) preferably has a dielectric loss tangent of 1.00 ⁇ 10 -3 or less as measured by the 10 GHz hollow resonator perturbation method.
  • the resin (B) contains a polytetrafluoroethylene resin.
  • the amount of the liquid crystal polyester resin (A) blended with respect to 100 parts by mass in total of the liquid crystal polyester resin (A), the fluororesin (B), and the inorganic hollow filler (C). Is 30 parts by mass or more and 98 parts by mass or less, the compounding amount of the fluororesin (B) is 1 part by mass or more and 50 parts by mass or less, and the compounding amount of the inorganic hollow filler (C) is 1 part by mass or more. It is preferably 30 parts by mass or less.
  • the structural unit (I) derived from the hydroxycarboxylic acid is a structural unit derived from 6-hydroxy-2-naphthoic acid.
  • the composition ratio of the structural unit (I) to the total structural unit of the liquid crystal polyester resin (A) is preferably 30 mol% or more and 80 mol% or less.
  • the structural unit (II) derived from the diol compound is at least selected from the group consisting of 4,4-dihydroxybiphenyl, hydroquinone, methylhydroquinone, and 4,4'-isopropyridene diphenol. It is preferably a structural unit derived from one type.
  • the structural unit (III) derived from the dicarboxylic acid is a structural unit derived from at least one selected from the group consisting of terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid. It is preferable to have.
  • a resin molded product comprising the above resin composition is provided.
  • an electrical / electronic component including the above resin molded product is provided.
  • the present invention it is possible to obtain a resin composition having a low dielectric loss tangent and a low dielectric constant while having the required heat resistance. Further, by using such a resin composition, it is possible to obtain a resin molded product having a low dielectric loss tangent and a low dielectric constant while having the required heat resistance.
  • the resin molded product according to the present invention is used when heated at a high temperature such as in the reflow process. The occurrence of warpage can also be suppressed.
  • the resin composition according to the present invention contains the following liquid crystal polyester resin (A), a fluororesin (B), and an inorganic hollow filler (C), and has a low dielectric loss tangent while having the required heat resistance. And has a low dielectric constant.
  • A liquid crystal polyester resin
  • B fluororesin
  • C inorganic hollow filler
  • the dielectric loss tangent measured by the cavity resonator perturbation method at 10 GHz of the resin composition is 2.0 ⁇ 10 -3 or less, preferably 1.9 ⁇ 10 -3 or less, and more preferably 1.8 ⁇ 10 It is -3 or less.
  • the relative permittivity of the resin composition measured by the 10 GHz cavity resonator perturbation method is 3.50 or less, preferably 3.40 or less.
  • the value is a measured value in the flow direction of the injection-molded product of the resin composition.
  • the injection-molded product is a test piece cut from a flat plate of 60 mm ⁇ 60 mm ⁇ 0.8 mm (thickness) to a width of 60 mm ⁇ 3 mm.
  • the dielectric loss tangent of the resin composition at 10 GHz can be measured by the cavity resonator perturbation method using a network analyzer manufactured by Anritsu and a resonator manufactured by AET.
  • the value of dielectric loss tangent is a value measured at 23 ° C. in an atmospheric atmosphere.
  • the liquid crystal polyester resin used in the resin composition of the present invention contains a structural unit (I) derived from a hydroxycarboxylic acid, a structural unit (II) derived from a diol compound, and a structural unit (III) derived from a dicarboxylic acid. ..
  • a structural unit (I) derived from a hydroxycarboxylic acid a structural unit (II) derived from a diol compound
  • a structural unit (III) derived from a dicarboxylic acid .
  • each structural unit contained in the liquid crystal polyester resin will be described.
  • the unit (I) constituting the liquid crystal polyester resin (A) is a structural unit derived from a hydroxycarboxylic acid, and is preferably a structural unit derived from an aromatic hydroxycarboxylic acid represented by the following formula (I). ..
  • the structural unit (I) may include only one type, or may include two or more types.
  • Ar 1 in the above formula is optionally selected from the group consisting of a phenyl group having a substituent, a biphenyl group, a 4,4′-isopropyridene diphenyl group, a naphthyl group, an anthryl group and a phenanthryl group.
  • a phenyl group, a biphenyl group, and a naphthyl group are preferable, and a naphthyl group is more preferable.
  • the substituent include hydrogen, an alkyl group, an alkoxy group, and fluorine.
  • the number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 5. Further, it may be a linear alkyl group or a branched-chain alkyl group.
  • the number of carbon atoms contained in the alkoxy group is preferably 1 to 10, and more preferably 1 to 5.
  • Examples of the monomer giving the structural unit represented by the above formula (I) include 6-hydroxy-2-naphthoic acid (HNA, the following formula (1)), p-hydroxybenzoic acid (HBA, the following formula (2)), and the like. And these acylated products, ester derivatives, acid halides and the like.
  • the composition ratio (mol%) of the constituent unit (I) to the constituent units of the entire polyester resin is preferably 30 mol% or more, more preferably 35 mol% or more, and further preferably 40 mol% as the lower limit value. It is more preferably 45 mol% or more, and the upper limit value is preferably 80 mol% or less, more preferably 75 mol% or less, still more preferably 70 mol% or less, and further. More preferably, it is 65 mol% or less. When two or more structural units (I) are contained, the total molar ratio thereof may be within the range of the above composition ratio.
  • the composition ratio of the structural unit derived from 6-hydroxy-2-naphthoic acid is preferably higher than the composition ratio of the structural unit derived from p-hydroxybenzoic acid. Further, the composition ratio of the constituent units derived from 6-hydroxy-2-naphthoic acid is preferably more than 50 mol% of the total of the constituent units (I) when two or more kinds of the constituent units (I) are contained. , 70 mol% or more, more preferably 90 mol% or more.
  • the unit (II) constituting the liquid crystal polyester resin (A) is a structural unit derived from a diol compound, and is preferably a structural unit derived from an aromatic diol compound represented by the following formula (II).
  • the constituent unit (II) may contain only one type, or may contain two or more types.
  • Ar 2 in the above formula is optionally selected from the group consisting of a phenyl group having a substituent, a biphenyl group, a 4,4'-isopropyridendiphenyl group, a naphthyl group, an anthryl group and a phenanthryl group. Of these, a phenyl group and a biphenyl group are more preferable.
  • the substituent include hydrogen, an alkyl group, an alkoxy group, and fluorine.
  • the number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 5. Further, it may be a linear alkyl group or a branched-chain alkyl group.
  • the number of carbon atoms contained in the alkoxy group is preferably 1 to 10, and more preferably 1 to 5.
  • Examples of the monomer giving the structural unit (II) include 4,4-dihydroxybiphenyl (BP, the following formula (3)), hydroquinone (HQ, the following formula (4)), and methylhydroquinone (MeHQ, the following formula (5)). ), 4,4'-Isopropyridene diphenol (BisPA, the following formula (6)), and acylated products, ester derivatives, acid halides and the like thereof.
  • BP 4,4-dihydroxybiphenyl
  • HQ hydroquinone
  • MeHQ methylhydroquinone
  • BP 4,4'-Isopropyridene diphenol
  • acylated products ester derivatives, acid halides and the like thereof.
  • the composition ratio (mol%) of the constituent unit (II) to the constituent units of the entire polyester resin is preferably 10 mol% or more, more preferably 12.5 mol% or more, and further preferably 15 as the lower limit value. It is mol% or more, still more preferably 17.5 mol% or more, and the upper limit value is preferably 35 mol% or less, more preferably 32.5 mol% or less, still more preferably 30 mol. % Or less, and even more preferably 27.5 mol% or less. When two or more structural units (II) are contained, the total molar ratio thereof may be within the above composition ratio.
  • the unit (III) constituting the liquid crystal polyester resin (A) is a structural unit derived from a dicarboxylic acid, and is preferably a structural unit derived from an aromatic dicarboxylic acid represented by the following formula (III).
  • the constituent unit (III) may contain only one type, or may contain two or more types.
  • Ar 3 in the above formula is optionally selected from the group consisting of a phenyl group having a substituent, a biphenyl group, a 4,4'-isopropyridene diphenyl group, a naphthyl group, an anthryl group and a phenanthryl group. Of these, a phenyl group and a biphenyl group are more preferable.
  • the substituent include hydrogen, an alkyl group, an alkoxy group, fluorine and the like.
  • the number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 5. Further, it may be a linear alkyl group or a branched-chain alkyl group.
  • the number of carbon atoms contained in the alkoxy group is preferably 1 to 10, and more preferably 1 to 5.
  • Examples of the monomer giving the structural unit (III) include terephthalic acid (TPA, the following formula (7)), isophthalic acid (IPA, the following formula (8)), and 2,6-naphthalenedicarboxylic acid (NADA, the following formula (9)). ), And their acylates, ester derivatives, acid halides and the like.
  • the composition ratio (mol%) of the structural unit (III) to the total structural unit of the polyester resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 10 mol% or more as the lower limit value. It is 12.5 mol% or more, still more preferably 15 mol% or more, particularly preferably 17.5 mol% or more, and the upper limit value is preferably 35 mol% or less, more preferably 32. It is 5.5 mol% or less, more preferably 30 mol% or less, and even more preferably 27.5 mol% or less. When two or more structural units (II) are contained, the total molar ratio thereof may be within the above composition ratio.
  • the composition ratio of the constituent unit (II) and the composition ratio of the constituent unit (III) are substantially equivalent ((constituent unit (II) ⁇ constituent unit (III)).
  • At least the constituent unit of 6-hydroxy-2-naphthoic acid is 45 mol% or more and 75 mol% or less with respect to the constituent unit of the entire polyester resin (A). Is within the range of.
  • a particularly preferable composition of the polyester resin (A) is 45 mol% ⁇ 6-hydroxy-2-naphthoic acid-derived structural unit (I) ⁇ 75 mol% 12 mol% ⁇ Structural unit derived from aromatic diol compound (II) ⁇ 27.5 mol% 3 mol% ⁇ structural unit derived from terephthalic acid Structural unit (III) ⁇ 25 mol% Constituent unit (III) derived from 2 mol% ⁇ 2,6-naphthalenedicarboxylic acid (III) ⁇ 9 mol% Is. If each structural unit is within the above range with respect to the overall structural unit of the polyester resin (A), a polyester resin having a low dielectric loss tangent can be obtained.
  • the liquid crystal property of the liquid crystal polyester resin (A) is a group liquid crystal polyester using a polarizing microscope (trade name: BH-2) manufactured by Olympus Corporation equipped with a hot stage for a microscope (trade name: FP82HT) manufactured by METTLER.
  • the resin (A) can be confirmed by heating and melting it on a microscope heating stage and then observing the presence or absence of optical anisotropy.
  • the melting point of the liquid crystal polyester resin (A) is preferably 280 ° C. or higher, more preferably 290 ° C. or higher, still more preferably 300 ° C. or higher, and even more preferably 305 ° C. or higher as the lower limit value.
  • the upper limit is preferably 370 ° C. or lower, preferably 360 ° C. or lower, still more preferably 355 ° C. or lower, and even more preferably 350 ° C. or lower.
  • the dielectric loss tangent of the liquid crystal polyester resin (A) measured by the cavity resonator perturbation method at 10 GHz is 1.00 ⁇ 10 -3 or less, preferably 0.95 ⁇ 10 -3 or less, and more preferably 0. It is 90 ⁇ 10 -3 or less, more preferably 0.85 ⁇ 10 -3 or less.
  • the relative permittivity of the liquid crystal polyester resin (A) measured by the cavity resonator perturbation method at 10 GHz is 3.7 or less, preferably 3.6 or less.
  • the value is a measured value in the flow direction of the injection-molded product of the liquid crystal polyester resin (A).
  • the injection-molded product is a test piece obtained by cutting a flat plate-shaped test piece having a size of 60 mm ⁇ 60 mm ⁇ 0.8 mm (thickness) into 60 mm ⁇ 3 mm.
  • the blending amount of the liquid crystal polyester resin (A) is based on 100 parts by mass of the total of the liquid crystal polyester resin (A), the fluororesin (B), and the inorganic hollow filler (C).
  • the lower limit is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, further preferably 45 parts by mass or more, still more preferably 50 parts by mass or more, and the upper limit value is preferably. It is 98 parts by mass or less, more preferably 90 parts by mass or less, and further preferably 85 parts by mass or less.
  • the liquid crystal polyester resin (A) can be produced by polymerizing monomers giving the structural units (I) to (III), if desired, by a conventionally known method.
  • the fully aromatic liquid crystal polyester resin according to the present invention can also be produced by two-step polymerization in which a prepolymer is prepared by melt polymerization and further solid-phase polymerization is carried out.
  • the total amount of the monomers giving the above-mentioned structural units (I) to (III) is 100 mol% in a predetermined formulation, if desired. It is preferable to carry out the process under acetic acid reflux in the presence of 1.05 to 1.15 molar equivalents of acetic anhydride with respect to the hydroxyl group.
  • the prepolymer obtained by melt polymerization is cooled and solidified, pulverized into powder or flakes, and then a known solid phase polymerization method.
  • a method of heat-treating the prepolymer resin in an inert atmosphere such as nitrogen or in a vacuum in a temperature range of 200 to 350 ° C. for 1 to 30 hours is preferably selected.
  • Solid-phase polymerization may be carried out with stirring, or may be carried out in a stationary state without stirring.
  • the catalyst may or may not be used in the polymerization reaction.
  • the catalyst to be used conventionally known catalysts for polymerization of polyester can be used, and metals such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate and antimony trioxide can be used. Examples thereof include salt catalysts, nitrogen-containing heterocyclic compounds such as N-methylimidazole, and organic compound catalysts.
  • the amount of the catalyst used is not particularly limited, but is preferably 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the total amount of the monomers.
  • the polymerization reaction device in melt polymerization is not particularly limited, but a reaction device used for the reaction of a general high-viscosity fluid is preferably used.
  • these reactors include, for example, an anchor type, a multi-stage type, a spiral band type, a spiral shaft type, etc., or a stirring tank type polymerization reaction device having a stirring device having various shapes of stirring blades obtained by modifying these, or a stirring tank type polymerization reaction device.
  • Kneader, roll mill, Banbury mixer and the like which are generally used for kneading resins.
  • the fluororesin (B) refers to a synthetic resin obtained by polymerizing an olefin containing fluorine, and refers to all copolymers of a completely fluorinated resin, a partially fluorinated resin, and a fluorinated product.
  • these fluororesins are preferably used as powders.
  • the average particle size of the powdered fluororesin is preferably 0.5 to 70 ⁇ m. The average particle size represents the volume average particle size and can be measured by a laser diffraction method.
  • fluororesin (B) examples include polytetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer resin (PFA).
  • FEP polychlorotrifluoroethylene resin
  • PCTFE polychlorotrifluoroethylene resin
  • ETFE ethylene-tetrafluoroethylene copolymer resin
  • ECTFE ethylene-chlorotrifluoroethylene copolymer resin
  • PVF polyvinyl fluoride resin
  • EPE ethylene-perfluoroalkyl vinyl ether-hexafluoropropylene copolymer resin
  • PTFE polytetrafluoroethylene resin
  • fluororesin (B) Only one type of fluororesin (B) may be used, or two or more types may be used. Further, the fluororesin (B) of the present invention preferably has a lower dielectric loss tangent than the liquid crystal polyester resin (A).
  • the blending amount of the fluororesin (B) is fluorine with respect to a total of 100 parts by mass of the liquid crystal polyester resin (A), the fluororesin (B), and the inorganic hollow filler (C).
  • the blending amount of the resin (B) is preferably 1 part by mass or more as a lower limit value, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and preferably 50 parts by mass as an upper limit value. It is less than or equal to 45 parts by mass or less, still more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less.
  • the blending amount of the fluororesin (B) is about the above numerical range, a resin composition having a low dielectric loss tangent and a low dielectric constant can be obtained while having the required heat resistance.
  • the inorganic hollow filler (C) is a hollow filler containing an inorganic component as a main component.
  • the hollow body includes not only a single hollow portion inside the filler, but also a hollow body having a plurality of bubbles inside and a pumice stone in which the foam inside communicates with the outside.
  • the average particle size of the inorganic hollow filler (C) is preferably 0.5 to 100 ⁇ m, more preferably 1 to 80 ⁇ m, and even more preferably 5 to 50 ⁇ m.
  • the average particle size represents the volume average particle size and can be measured by a laser diffraction method.
  • the inorganic hollow filler (C) include hollow bodies made of inorganic materials such as glass, alumina, silica, zirconia, magnesia, silas, fly ash, borate, phosphate, and ceramics. ..
  • the resin molded product When these inorganic hollow fillers are dispersed in the resin molded product, the resin molded product apparently contains fine bubbles, and the relative permittivity becomes low.
  • These inorganic hollow fillers may be damaged by receiving a history of stress in the manufacturing process of the composition or the manufacturing process of the resin molded product, and therefore, it is preferable that the strength is high. Twice
  • the blending amount of the inorganic hollow filler (C) is 100 parts by mass in total of the liquid crystal polyester resin (A), the fluororesin (B), and the inorganic hollow filler (C).
  • the lower limit value is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and the upper limit value is preferable. Is 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less.
  • the resin composition according to the present invention contains other additives such as a colorant, a dispersant, a plasticizer, an antioxidant, a curing agent, a flame retardant, a heat stabilizer, and an ultraviolet absorber as long as the effects of the present invention are not impaired. It may further contain an agent, an antistatic agent, and a surfactant.
  • the amount of the additive to be blended in the resin composition is preferably 0. It is 01 parts by mass or more, more preferably 0.5 parts by mass or more, and the upper limit value is preferably 5 parts by mass or less, more preferably 1 part by mass or less.
  • the resin molded product according to the present invention comprises the above resin composition.
  • the resin molded product according to the present invention has a low dielectric loss tangent and a low dielectric constant while having the required heat resistance.
  • a resin composition containing the above-mentioned liquid crystal polyester resin (A), fluororesin (B), inorganic hollow filler (C), and optionally other additives is molded by a conventionally known method.
  • the resin composition the all-liquid crystal polyester resin (A), the fluororesin (B), the inorganic hollow filler (C) and the like are melt-kneaded using a Banbury mixer, a kneader, a single-screw or twin-screw extruder or the like.
  • Examples of the above-mentioned molding method include press molding, foam molding, injection molding, extrusion molding, punch molding and the like.
  • the molded product produced as described above can be processed into various shapes depending on the intended use.
  • the shape of the molded product may be, for example, a plate shape or a film shape.
  • the electrical and electronic components according to the present invention include the above resin composition.
  • Examples of electrical and electronic components include antennas used in electronic devices and communication devices such as ETC, GPS, wireless LAN and mobile phones, high-speed transmission connectors, CPU sockets, circuit boards, flexible printed circuit boards (FPC), and stacking.
  • Circuit boards, millimeter-wave and quasi-millimeter-wave radars such as collision prevention radars, RFID tags, capacitors, inverter parts, insulating films, cable coverings, secondary battery insulating materials such as lithium-ion batteries, speaker diaphragms, etc. Can be mentioned.
  • the temperature of the polymerization vessel in the acetic acid distillate state was raised at 0.5 ° C./min, and when the temperature of the melt in the tank reached 310 ° C., the polymer was extracted and cooled and solidified.
  • the obtained polymer was pulverized and pulverized to a size passing through a sieve having a mesh size of 2.0 mm to obtain a prepolymer.
  • the temperature of the prepolymer obtained above was raised from room temperature to 300 ° C. over 7 hours by a heater in an oven manufactured by Yamato Scientific Co., Ltd., and then the temperature was maintained at 300 ° C. for 1 hour. Solid phase polymerization was performed. Then, heat was naturally dissipated at room temperature to obtain a liquid crystal polyester resin A1.
  • a polarizing microscope (trade name: BH-2) manufactured by Olympus Corporation equipped with a hot stage for a microscope (trade name: FP82HT) manufactured by METTLER, a liquid crystal polyester resin sample is heated and melted on a microscope heating stage. It was confirmed that the liquid crystal property was exhibited based on the presence or absence of optical anisotropy.
  • Table 1 shows the structural units (monomer composition) of the liquid crystal polyester resins A1 to A2 obtained above.
  • the melting points of the liquid crystal polyester resins A1 to A2 obtained above were measured by a differential scanning calorimeter (DSC) manufactured by Hitachi High-Tech Science Co., Ltd. in accordance with the test methods of ISO11357 and ASTM D3418. At this time, the temperature is raised from room temperature to 360 to 380 ° C. at a heating rate of 10 ° C./min to completely melt the polymer, and then the temperature is lowered to 30 ° C. at a rate of 10 ° C./min, and further at a rate of 10 ° C./min. The apex of the endothermic peak obtained when the temperature was raised to 380 ° C. was defined as the melting point (Tm 2 ). The measurement results are shown in Table 1.
  • inorganic hollow filler (C) ⁇ Preparation of inorganic hollow filler (C)> The following hollow filler was prepared as the inorganic hollow filler (C).
  • Example 1 The liquid polyester resin A1 obtained above is dry-blended with 85 parts by mass, the polytetrafluoroethylene resin with 10 parts by mass, and the hollow glass with 5 parts by mass, and then a twin-screw kneader (Co., Ltd.) A pellet-shaped resin composition was obtained by kneading the liquid crystal polyester resin A1 with PCM 30) manufactured by Ikekai at a temperature of Tm2 + 20 to 50 ° C., strand-cutting, and pelletizing. When the liquid crystal property of the obtained resin composition was confirmed in the same manner as described above, the liquid crystal property could be confirmed in the melted liquid crystal polyester resin portion.
  • Example 2 The same as in Example 1 except that 75 parts by mass of the liquid crystal polyester resin A1 obtained above, 10 parts by mass of the above polytetrafluoroethylene resin, and 15 parts by mass of the above hollow glass were kneaded. A pellet-shaped resin composition was produced. When the liquid crystal property was confirmed in the same manner as above, the liquid crystal property could be confirmed in the melted liquid crystal polyester resin portion.
  • Example 3 80 parts by mass of the liquid crystal polyester resin A1 obtained above, 10 parts by mass of the above polytetrafluoroethylene resin, 5 parts by mass of the hollow glass, and 5 parts by mass of the milled fiber were kneaded. A pellet-shaped resin composition was produced in the same manner as in Example 1 except for the above. When the liquid crystal property was confirmed in the same manner as above, the liquid crystal property could be confirmed in the melted liquid crystal polyester resin portion.
  • Example 4 Except for kneading 80 parts by mass of the liquid crystal polyester resin A1 obtained above, 10 parts by mass of the polytetrafluoroethylene resin, 5 parts by mass of the hollow glass, and 5 parts by mass of the mica. Produced a pellet-shaped resin composition in the same manner as in Example 1. When the liquid crystal property was confirmed in the same manner as above, the liquid crystal property could be confirmed in the melted liquid crystal polyester resin portion.
  • Example 5 75 parts by mass of the liquid crystal polyester resin A1 obtained above, 10 parts by mass of the above polytetrafluoroethylene resin, 5 parts by mass of the hollow glass, 5 parts by mass of the mica, and the above milled.
  • a pellet-shaped resin composition was produced in the same manner as in Example 1 except that the fiber was kneaded with 5 parts by mass.
  • the liquid crystal property was confirmed in the same manner as above, the liquid crystal property could be confirmed in the melted liquid crystal polyester resin portion.
  • Example 6 The same as in Example 1 except that 75 parts by mass of the liquid crystal polyester resin A1 obtained above, 20 parts by mass of the above polytetrafluoroethylene resin, and 5 parts by mass of the above hollow glass were kneaded. A pellet-shaped resin composition was produced. When the liquid crystal property was confirmed in the same manner as above, the liquid crystal property could be confirmed in the melted liquid crystal polyester resin portion.
  • Example 7 The same as in Example 1 except that 65 parts by mass of the liquid crystal polyester resin A1 obtained above, 30 parts by mass of the above polytetrafluoroethylene resin, and 5 parts by mass of the above hollow glass were kneaded. A pellet-shaped resin composition was produced. When the liquid crystal property was confirmed in the same manner as above, the liquid crystal property could be confirmed in the melted liquid crystal polyester resin portion.
  • Example 1 A pellet-shaped resin composition was produced in the same manner as in Example 1 except that 65 parts by mass of the liquid crystal polyester resin A1 obtained above and 35 parts by mass of the above hollow glass were kneaded. When the liquid crystal property was confirmed in the same manner as above, the liquid crystal property could be confirmed in the melted liquid crystal polyester resin portion.
  • Example 2 The liquid crystal polyester resin A2 obtained above was kneaded with 83 parts by mass, the hollow glass was kneaded with 12 parts by mass, and the milled fiber was kneaded with 5 parts by mass in the same manner as in Example 1 to form pellets. A resin composition was produced. When the liquid crystal property was confirmed in the same manner as above, the liquid crystal property could be confirmed in the melted liquid crystal polyester resin portion.
  • Example 3 A pellet-shaped resin in the same manner as in Example 1 except that 75 parts by mass of the liquid crystal polyester resin A2 obtained above, 15 parts by mass of the above mica, and 10 parts by mass of the above milled fiber were kneaded. The composition was produced. When the liquid crystal property was confirmed in the same manner as above, the liquid crystal property could be confirmed in the melted liquid crystal polyester resin portion.
  • Example 4 The same as in Example 1 except that 30 parts by mass of the liquid crystal polyester resin A1 obtained above, 65 parts by mass of the above polytetrafluoroethylene resin, and 5 parts by mass of the above hollow glass were kneaded. A pellet-shaped resin composition was produced. When the liquid crystal property was confirmed in the same manner as above, the liquid crystal property could be confirmed in the melted liquid crystal polyester resin portion.

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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

La présente invention vise à fournir une composition de résine qui combine des propriétés de résistance à la chaleur et des propriétés de traitement de moulage à l'état fondu qui soutiennent favorablement la comparaison avec des résines de polyester à cristaux liquides, et qui présentent également une faible tangente de perte diélectrique et une faible constante diélectrique. La présente invention concerne par conséquent une composition de résine qui est caractérisée en ce qu'elle contient : une résine de polyester à cristaux liquides (A) qui contient une unité constitutive (I) dérivée d'un acide hydroxycarboxylique, une unité constitutive (II) dérivée d'un composé diol, et une unité constitutive (III) dérivé d'un acide dicarboxylique ; une résine fluorée (B) ; et une charge creuse inorganique (C), la tangente de perte diélectrique mesurée par perturbation de résonateur à cavité à une fréquence de 10 GHz étant d'au plus 2 × 10-3, et la permittivité relative étant d'au plus 3,50.
PCT/JP2021/010284 2020-03-18 2021-03-15 Composition de résine et article moulé en résine comprenant ladite composition de résine WO2021187399A1 (fr)

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US11912817B2 (en) 2019-09-10 2024-02-27 Ticona Llc Polymer composition for laser direct structuring
TW202340372A (zh) * 2021-12-28 2023-10-16 日商住友化學股份有限公司 樹脂組成物及成形體
JP2023114867A (ja) * 2022-02-07 2023-08-18 株式会社有沢製作所 フッ素樹脂組成物、フッ素樹脂フィルム、積層フィルム、及び金属積層板

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WO2020138277A1 (fr) * 2018-12-27 2020-07-02 Ｊｘｔｇエネルギー株式会社 Composition de résine et article moulé en résine comprenant ladite composition de résine

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JP2009114418A (ja) * 2007-10-15 2009-05-28 Toray Ind Inc 液晶性樹脂組成物およびその製造方法
JP2009108190A (ja) * 2007-10-30 2009-05-21 Ueno Fine Chem Ind Ltd 全芳香族液晶ポリエステル
WO2018008612A1 (fr) * 2016-07-04 2018-01-11 Ｊｘｔｇエネルギー株式会社 Résine de polyester à cristaux liquides entièrement aromatique, article moulé et composante électrique/électronique
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